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Studies in Surface Science and Catalysis 45

TRANSITION METAL OXIDES:
Surface Chemi stry and Catal ysi s
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Studies in Surface Science and Catalysis
Advisory Editors: B. Delmon and J .T. Yat es
Vol. 45
TRANSITION
METAL OXIDES:
Surface Chemistry and Catalysis
Harold H. Kung
Chemical Engineering Department, The Technological Institute,
Northwestern University, 2 145 Sheridan Road, Evanston, IL 60208, U. S. A.
E LS EVI E R Amsterdam - Oxford - New York - Tokyo 1989
ELSEVIER SCIENCE PUBLISHERS B.V.
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First edition 1989
Second impression 1991
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0 Elsevier Science Publishers B.V., 1989
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V
To my mentor
Professor Robert L. Burwell, Jr
and my wife
Mayfair
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vii
PREFACE
In the past twenty years there have been rapid advances in the understanding
of surface phenomena as a result of the availability of many new and powerful
techniques to study solids and their surfaces. Clever experimentation coupled
with techniques such as laser Raman spectroscopy, solid state NMR, extended
X-ray absorption fine structure spectroscopy, as well as a host of surface sensitive
electron spectroscopies have provided information on the atomic structure and
composition of surfaces and near surface regions. To date, the bonding
geometries, the positions of adatoms. the orientations of adsorbed molecules, the
structures of overlayers, the extent of relaxation of surface atoms, and even the
atomic positions of surface defects have become accessible. Indeed, many of
these data have been obtained for metallic surfaces, especially transition metal
surfaces where the attention of most surface scientists has been focused. These
data have resulted in significant advances in the understanding of the surface
chemistry and catalytic properties of these materials.
It is anticipated that a similar rapid increase in our level of understanding of
surface phenomena will be forthcoming for transition metal oxides. Indeed, a
growing number of investigators have turned their attention to oxidic materials.
Simultaneously, new catalytic properties of transition metal oxides are being
discovered. New reactions are being reported, such as metathesis, selective
oxidation of butane to maleic anhydride and various photo-enhanced processes,
and new catalytic materials are being synthesized, especially various mixed oxides.
It appears that the level of understanding in the area of surface chemistry and
catalysis of transition metal oxidcs is poised for a quantum leap.
In this book I have attempted to summarize existing information on the
structure, electronic properties, chcrnistry, and catalytic properties of transition
metal oxide surfaces so that it can serve as a uscrul source of information for
investigators i n this field and as a comprchensivc overview of the subject for
graduate students. The book is inlended for surface physicists, chcmists, and
catalytic engineers. By presenting physical, chemical and catalytic properties in
one volume, it is hopcd that the interrclationship among them will become more
apparent.
...
VI U
The subjects in this book can be divided into three sections. The first section
(chapters 1 to 3) deals with the structural, physical, magnetic, and electronic
properties of transition metal oxides. Although the emphasis is on surface
properties, relevant bulk properties are also discussed. The second section
(chapters 4 to 7) covers surface chemical properties. It includes topics that
describe the importance of surface coordinative unsaturation in adsorption, the
formation of surface acidity and the role of acidity in determining surface chemical
properties, the nature and reactivities of adsorbed oxygen, and the surface
chemistry in the reduction of oxides. The third section is on the catalytic
properties (chapters 8 to 14). Various catalytic reactions including decomposition,
hydrogenation, isomerintion, metathesis. selective oxidation, and reactions
involving carbon oxides are discussed. Emphasis is placed more heavily on
reaction mechanisms and the role of catalysts than on kinetics and processes. A
chapter on the preparation of oxide catalysts and one on photo-assisted processes
are also included. Whenever appropriate, relationships among various topics are
indicated.
It would have been impossible to complete this book without the
encouragement and help of a number of people. The most significant of them is
Professor Robert L. Burwell, J r. who provided numerous suggestions and
comments on its content. The constant encouragement and helpful discussions
with Dr. Mayfair C. Kung are also greatly appreciated. The enthusiasm and
dedication of my students have made the study of this subject enjoyable. Much of
our research in this area has been supported by the U. S. Department of Energy
without which I would not have the necessary background to undertake the task.
Finally, permission by various publishers to reproduce the figures and tables in the
text is also gratefully acknowledged.
Harold H. Kung
1988
ix
CONTENTS
PREFACE vii
Chapter 1. INTRODUCTION
References 5
1
Chapter 2. BULK AND SURFACE STRUCTURE OF 6
TRANSITION METAL OXIDE
2.1 Bulk Structure 6
2.2 Shear Structure in Intermediate Oxides of Ti, V, and Mo 12
2.3 Structure, Stability and Reconstruction of Oxide Surfaces 15
2.4 Structure of Supported Oxides 20
References 25
Chapter 3. PHYSICAL AND ELECTRONIC PROPERTIES 27
3.1 Surface Composition 27
3.2 Ionicity of Oxides 28
3.3 Magnetic Properties of Small Oxide Particles 36
3.4 Quadrupole Splittings of Surface Ions 43
3.5 Surface Electronic Structure 46
3.6 Surface Vibration 48
References 50
Chapter 4. SURFACE COORDINATIVE UNSATURATION 53
4.1 Formation of Surface Coordinative Unsaturation 53
4.2 Chemical Properties of Surface Coordinatively
4.3 Adsorption of Small Molecules 61
References 69
Unsaturated Sites 57
X
Chapter 5. SURFACE ACIDITY
5.1 Surface Acid Sites 72
5.2 Formation of Surface Acid Sites 74
5.3 Determination of Acidity 80
5.4 Role of Acid Sites in Catalytic Reactions 88
References 89
Chapter 6. REDUCTION OF OXIDES
6.1 Introduction 91
6.2 Thermodynamics of Reduction 92
6.3 Kinetic Models 93
6.4 Mechanism of Reduction 96
6.5 Effect of Support 98
6.6 Effect of Other Components 100
6.7 Reactivity of Reduced Surfaces 100
6.8 Influence of Reduced Oxides on the Properties of
References 107
Transition Metals 102
Chapter 7. OXYGEN ON OXIDES
7.1 Nature of Adsorbed Oxygen 110
7.2 Detection of Adsorbed Oxygen 11 1
7.3 Reactivity of Adsorbed Oxygen 116
References 119
72
91
110
Chapter 8. PREPARATION OF OXIDES 121
8.1 General Considerations 12 1
8.2 Preparation of Unsupported Single Component Oxides 123
8.3 Preparation of Supported Oxides 129
8.4 Preparation of Multicomponent Oxides 13 1
References 134
Chapter 9. METATHESIS AND ISOMERIZATION
136
9.1 Metathesis 136
9.2 Isomenzation of Alkenes 140
References 144
Chapter 10. DECOMPOSITION, HYDROGENATION AND 146
RELATED REACTIONS
10.1 Decomposition of Alcohols 146
10.2 Decomposition of Nitrous Oxide 153
10.3 Hydrogenation, H-D Exchange of Hydrocarbons, and H2-D2
Scrambling 155
10.4 Reduction of NO 162
References 166
Chapter 11. SELECTIVE OXIDATION REACTIONS I
1 1.1 Introduction 169
11.2 Types of Selective Oxidation Reactions 170
11.3 Features of Catalytic Selective Oxidation 170
11.4 Chemical Factors Affecting Selectivity 175
1 1.5 Oxidation of Propene to Acrolein and Ammoxidation
11.6 Effect of Water on Propene Oxidation 194
References 195
to Acrylonitrile 181
Chapter 12. SELECTIVE OXIDATION REACTIONS II
12.1 Selective Oxidation of Butenes 200
12.2 Selective Oxidation of Butane 210
12.3 Selective Oxidation of Methane 212
12.4 Selective Oxidation of Methanol 217
References 223
Chapter 13. CATALTYIC REACTION BETWEEN
HYDROGEN AND CARBON OXIDES
13.1 Introduction 227
13.2 Alcohol Synthesis on Copper-Zinc Oxide and Other
13.3 Group VIII Metalmetal Oxide Catalysts 236
13.4 Isosynthesis Reaction 240
13.5 Water-Gas Shift Reaction 244
References 248
Cu-based Catalysts 228
xi
169
200
227
Chapter 14. PHOTO-ASSISTED SURFACE PROCESSES 252
14.1 Introduction 252
14.2 Photo-Assisted Adsorption and Desorption 256
14.3 Photocatalysis: Gas Phase Reactions 258
14.4 Photocatalysis: Liquid Phase Reactions 266
14.5 Photocatalysis by Metalmetal Oxide and Oxide/Oxide
References 273
Composites 271
INDEX 277
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Chapter 1
INTRODUCTION
Transition metal oxides are technologically important materials that have
found many applications. For example, in the chemical industry, these oxides are
the functional components in the catalysts used in a large number of processes to
convert hydrocarbons to other chemicals. They are also used as electrode
materials in electrochemical processes. In the electronics industry, they are used
to make conductors in films. The recently discovered high temperature
superconductors are multicomponent transitional metal oxides.
Among these applications, perhaps the use of transition metal oxides as
catalysts is the most technologically advanced and economically important. It is
also anarea in which much progress has been made i n recent years in terms of the
understanding of the fundamental processes that occur, primarily because advances
in instrumentation and experimental techniques have made it possible to study the
chemistry of the interface between the transition metal oxide and the fluid phase in
greater detail than ever before. In particular, developments in surface science
techniques have provided very detailed pictures about the surface structures,
chemical compositions, and electronic properties of the surfaces.
Some of the chemical processes that make use of transition metal oxides are
listed in Table 1-1. As can be seen from the table, many of the processes require
high selectivity for a particular product, and many involve oxidation of the reactant
molecules. I n fact, selective oxidation, ammoxidation, and selective
dehydrogenation probably constitute the most important catalytic uses of transition
metal oxides. The different oxidation states available in these oxides make it
possible to control the selectivity in oxidation with the properties of the oxides.
Some transition metal oxides can also catalyze selective hydrogenation and are
used in some commercial processes. As the demand for specialty chemicals (that
is, specific chemicals for spccific processes) increases in the future, demand for
high selectivity will increase in a wide variety of reactions including amination,
alkylation, aldol condensation, and carbonylation, in addition to those i n Table 1 - 1 .
It is quite possible that transition metal oxides will occupy an increasingly
1
2
Table 1-1 Examples of Chemical Processes in which Transition Metal
Oxides are Catalysts
Process
Oxidation
Dehydrogenation
(nonoxidative)
Dehydrogenation
(oxidative)
Selective oxidation
Selective
Selective reduction
ammoxidation
Metathesis
Water-gas shift
Example
Production of SO3 from SO2
CO oxidation in emission control
Production of styrene from ethylbenzene
Production of formaldehyde from methanol
Production of acrolein from propene,
and butadiene from butenes
and maleic anhydride from benzene or
butane
Production of acrylonitrile from propene
Reduction of NO, selective hydrogenation of
unsaturated ketones
Production of long chain alkenes
Production of hydrogen
important position as catalysts in these chemical processes. Not listed in the table
is the production of methanol by the hydrogenation of CO or C02. The earlier
generation of catalysts for this process are based on zinc-chromium oxide. However,
there is controversy over the current copper-zinc oxide catalyst as to whether the
active component is the oxide or the copper metal.
In addition to being used as catalysts, transition metal oxides are also
precursors for other important catalysts. The cobalt-molybdenum sulfide catalyst
for hydrodesulfurization is an example. This catalyst is prepared by sulfiding
cobalt-molybdenum oxide (often supported on alumina). Another example is the
chromium-based catalyst for ethylene polymerization. The catalyst can be made
from supported chromium oxide as a precursor. Finally, many noble mctal
catalysts are prepared by reduction of the corresponding oxides. In addition, these
metal catalysts are often stored in air and are converted to their oxides during
storage. It is quite conceivable that in these cases, the detailed structures,
morphologies, or other properties of the transition metal oxide precursors could
affect the properties of the final catalysts.
Understanding catalysis requires an understanding of surface chemistry,
which deals with the bonding and reaction of an adsorbate with the surface and the
influence of the surface on the bonding and reaction between adsorbates. I t is
apparent that an important part of any effort toward obtaining such an
undcrstanding is the ability to characterize thc physical and chemical properties of
a surface. In recent years, much progress has been made in the understanding of
INTRODUCTION 3
Table 1-2 Properties that are Important in the Surface Chemistry of Transition
Metal Oxides
Presence of cations and anions in stoichiometric ratios and in
Possibility of covalent and ionic bonding between cations
Presence of a strong electric field normal to the surface
Presence of charged adsorbed species
Presence of surface acidity and basicity
Presence of cationic and anionic vacancies
Ability of cations to undergo oxidation and reduction
High mobility of lattice oxygen and the possibility that
Interaction of the solid with incident photons that leads
well-defined spatial (structural) relationships
and anions
due to the coulombic nature of the ionic lattice
the lattice oxygen are reactants in a reaction
to photo-assisted surface chemical processes
metallic surfaces [l-41. Progress has also been made, but at a slower pace, for the
transition metal oxides because of the higher level of complexity in the
experimental techniques involved. There are significant differences between the
chemistry of transition metal oxides and the corresponding metals. Table 1-2
provides a list of properties that are important in the surface chemistry of transition
metal oxides. Many of themeither do not apply or apply only to a limited extent
to the metals.
Common to many of the properties listed in Table 1-2 is the fact that
transition metal oxides are made up of metallic cations and oxygen anions. The
ionicity of the lattice, which is often less than that predicted by the formal
oxidation states, results in the presence of charged adsorbate species, and the
common heterolytic dissociative adsorption of molecules (that is, a molecule AB is
adsorbed as A+and B3. Surface exposed cations and anions form acidic and
basic sites as well as acid-base pair sites. The fact that the cations often have a
number of commonly obtainable oxidation states has resulted in the ability of the
oxides to undergo oxidation and reduction and the possibility of the presence of
rather high densities of cationic and anionic vacancies. As can be seen throughout
the discussions in this book, these properties have determining effects on the
interaction of molecules with the oxide surfaces.
This book starts with discussions of the structural (Chapter 2) and physical
and electronic properties of transition metal oxides (Chapter 3). Knowledge of
surface structure is as important as knowledge of molecular structure in
understanding surface chemistry. Physical properties of these oxides, especially
those for small crystallites, are often used for identification and characterization
purposes. Sometimes they are used as means to monitor chemical interactions.
4
Surface electronic properties determine the mode of bonding of the adsorbates, and
both surface and bulk electronic properties determine the photo-assisted surface
chemical processes.
Discussions of the surface chemical properties then follow. The importance
of surface coordinative unsaturation in governing the adsorptive properties of
many oxides will be discussed in Chapter 4. The discussion of surface acidity will
be found in Chapter 5, and the nature and reactivities of adsorbed oxygen will be
discussed in Chapter 7. Reduction of transition metal oxides, which is initiated at
oxide surfaces, will be discussed in Chapter 6.
After surface chemistry, the catalytic properties of transition metal oxides
will be discussed. The discussions will begin with the methods of preparation of
oxides and the dependence of the final properties of the oxides on the preparation
methods (Chapter 8). Then various catalytic reactions will be discussed. These
are metathesis and isomerization (Chapter 9), decomposition and hydrogenation
(Chapter lo), selective oxidation (Chapters 11 and 12), reactions of carbon oxides
(Chapter 13), and finally photo-assisted surface processes (Chapter 14). In the last
chapter, photo-assisted surface chemical reactions will be described together with
photo-assisted catalytic reactions.
The emphases of the discussions will be on transition metal oxides.
However, whenever appropriate, nontransition metal oxides will also be discussed,
especially when they are used to illustrate certain concepts or for comparisons. In
particular, properties of ZnO will be discussed rather extensively because ZnO is
among the best understood oxides whose surface chemistry, catalytic, electronic
and structural properties have been studied extensively, and because its behavior is
in many ways similar to many transition metal oxides.
Throughout this book, reference to information obtained from various
experimental techniques will be made. The readers are referred to some excellent
treatises that describe these techniques 11.4-91. The following is a list of standard
acronyms that are often used and their meanings:
AES Auger electron spectroscopy
ELS Electron energy loss spectroscopy
EPR Electron paramagnetic resonance spectroscopy
EXAFS Extended X-ray absorption fine structure
FTIR Fourier transform infrared spectroscopy
HREELS High resolution electron energy loss spectroscopy
IR Infrared spectroscopy
ISS Ion scattering spectroscopy
LEED Low energy electron diffraction
NMR Nuclear magnetic resonance spectroscopy
SEM Scanning electron microscopy
STEM Scanning transmission electron microscopy
TEM Transmission electron microscopy
TPD
TPR
UPS Ultraviolet photoelectron spectroscopy
Temperature programmed desorplion or decomposition
Temperature programmed reduction or reaction
INTRODUCTION 5
UV-vis Ultraviolet-visible absorption spectroscopy
XANES
XPS X-ray photoelectron spectroscopy
X-ray absorption near edge spectroscopy
Other techniques will also be mentioned. They include:
Cyclic voltammetry
Electric conductivity measurement
Magnetization measurement
Mossbauer spectroscopy
Raman or laser Raman spectroscopy
It will be greatly beneficial for the readers to have some general knowledge about
all of these techniques, especially regarding the types of information that are
obtainable, so as to better understand the discussions of the data presented.
REFERENCES
1. G. A. Somorjai, "Chemistry in Two Dimensions: Surfaces," Cornell University
2. 'The Nature of Surface Chemical Bonds." T. N. Rhodin, and G. Ertl, ed., North-
3. S. R. Morrison, 'The Chemical Physics of Surfaces." Plenum Press. NY. 1977.
4. G. Ertl, and I. Kuppers, "Low Energy Electrons and Surface Chemistry,"
5 . "Experimental Methods in Catalytic Research," Vol. 1-3, ed. R. B. Anderson,
6. W. N. Delgass, G. Haller, R. Kellerman. and I. Lunsford, "Spectroscopy in
7. D. P. Woodruff, and T. A. Delchar. "Modem Techniques of Surface Science,"
8. "Electron Spectroscopy for Surface Analysis," Topics in Current Physics,
9. 'The Chemical Physics of Solid Surfaces and Heterogencous Catalysis,
Press, Ithaca, NY, 1981.
Holland Publ. Co., NY, 1979.
Weinheim, Germany, 1985.
et. al., Academic Press, NY, 1968-76.
Heterogeneous Catalysis," Academic Press, N.Y., 1984.
Cambridge University Press, Cambridge, 1986.
vol. 4, ed. H. Ebach, Springer, Berlin, 1977.
D. A. King and D. P. Woodruff ed., Elsevier Scientific Publ., Amsterdam,
1?8l, 1983.
Chapter 2
BULK AND SURFACE STRUCTURE OF
TRANSITION METAL OXIDE
2.1 BULK STRUCTURE
With the exception of some complex oxides of unusual stoichiometries,
multicomponent compounds, and oxides that are only stable at high tcmpcrature
and high pressure, the bulk structures of most transition metal oxides are known.
An examination of the known structures shows that transition metal oxides exist in
many different crystallographic forms. There does not appear to be a simple
generalization that relates the structure to the stoichiometry or the position in the
periodic table. In fact, it is not uncommon to find a certain oxide in more than one
crystal structure at ordinary temperatures as a result of the high activation energy in
the process of transforming from a less thermodynamically stable to a more stable
structure. There is perhaps one generalization, which is the fact that the ionic radii
of transition metals are smaller than that of 02-. Thus the oxygen ions are usually
close-packed with the smaller metal ions situated in the octahedral and tetrahedral
holes among the oxygen ions.
There are many excellent treatise on the subject of crystal structures, such as
the one by Wells [l]. I n this section, structures of some of the oxides that are
commonly used in studies of surface chemistry and catalysis are described. The
structures of the other oxides are necessarily left out.
Oxides commonly studied as catalytic materials belong to the structural
classes of corundum, rocksalt, wurtzite, spinel, perovskite, rutile, and layer
structure. Table 2-1 lists the stable structures of some binary oxides. These arc
the structures often reported for the oxides prepared by common methods under
mild conditions. In some cases, other structures exist. Furthermore, the
structures indicated represent the general type. The positions of the ions may not
be at the ideal positions of the highest symmetry. For example, distortions are
found for FeO, NiO, MnO, and COO from the cubic lattice, and V02, Nb02, Mo02,
W02 from the perfect rutile structure.
The rocksalt structure is made up of a three-dimensional array of alternating
6
U
R
cl
5cr
C
c1
C
Table 2-1 Crystal Structural Classes of Some Common Transition Metal Oxides
v)
Sc2Qcs Ti 0 r* VO r Cr2Q cr MnO r FeO r COO r NiO r CUO s zno w
Ti zQ cr VzO, cr Cr02 t Mn304sp* Fe2Q n,sp Co304 sp cuzo c cl
Ti02 t,a,b VOz t* CI Q or MnzQcs* Fe@4 sp w
MnOz t*,and M
vZo5 a
others
AgzO c CdO r Y 2 4 cs ZrO r NbOz t* Mooz m,(t*) TcOz m.(t) RuOz t RhzQ cr* PdO s
ZrO2 m,tet NbZO5 mt MOO, l,(or) T C Z ~ a Rho2 t
LazQmt H Q m Ta02 t WOz m,(t*) Re02 m,(t) OsO2 t m t Pt304 cub HgO or,and
others
Ta205 or WO, m Re@ cub OsO, m PtOz t
(perovskite)
Re207 a
r =rocksalt s =PtSscructure, w=wurtzite, t =rutile, a =anatase, b =brookite,
c =interpenetrating cristobalite, f =fluoride, cr =corundum, sp =spinel, cs =C structure,
1 =layer, or =orthorhombic, tet =tetragonal, m =monoclinic. cub =cubic,
mt =multiple modifications, * =distorted or defective
8
cations and anions (Fig. 2-la). Each ion is in the center of an octahedron whose
vertices are ions of the opposite type. The structure can be viewed as being made
up of comer-sharing octahedra (Fig. 2-lb). A wurtzite structure is made up of a
three-dimensional net of corner-sharing tetrahedra (Fig. 2-lc,d). Each ion is in
the center of a tetrahedron in which the opposite ions are at the vertices.
The corundum, the rutile, and the spinel structures are made up of layers of
close-packed oxygen ions. If the oxygen ions are modeled by hard spheres,
(neglecting the cations for the moment,) each ion in a close-packed layer is in
contact with six others (see Fig. 2-2). When one such layer is stacked on top of
another such that an ion in this layer is in contact with the maximum possible
number of ions in the other layer, this ion will be sitting above a triangular hole of
the other layer (point B or C), and it will be in contact with three ions in the other
layer. Now consider a case of two close-packed layers stacked in this manner as
in Fig. 2-2. When a third layer is put on top of these two, its ions can take the
positions vertically on top of the ions in the first layer such as above point B, or the
positions above point C. In the former case, the spatial positions of the layers
follow the sequence ababab ... The resulting structure is called hexagonal close-
packing (h.c.p.), and it forms the basis for the corundum and the rutile structure.
In the latter case, the spatial sequence of the layers is abcabca bc... The resulling
s.tructure is called cubic close-packing (c.c.P.), and it forms the basis for the spinel
structure.
Between adjacent layers of oxygen ions in both h.c.p. and c.c.P., the
interstices (holes) are bound by either four or six oxygen ions (Fig. 2-2). They are
commonly referred to as tetrahedral and octahedral holes, respectively. There are
as many octahedral holes as the number of oxygen ions, and half as many
tetrahedral holes as octahedral holes.
In the ideal rutile structure, half of the octahedral holes are filled with cations,
while the tetrahedral holes are empty. Thus the compound has a formula M02
(e.g. TiOz). I n the corundum structure, two-thuds of the octahedral holes are
filled. The tetrahedral holes are empty, and the compound has a formula M203
(e.g. a-FezO3).
An ideal spinel structure would have one-half of the tetrahedral holes and
one-half of the octahedral holes filled, and the formula of the compound is M304
(e.g. Fe304). It is easily seen that for charge neutrality, the cations must be of two
different oxidation states. The most common oxidation states are +2 and +3, and
the formula can be rewritten as MIMJ II04. Both MrI and MI11 can occupy the
tetrahedral or octahedral holes. The equilibrium distribution depends on the
nature of the cation and the temperature. For entropic reasons, increasing the
temperature tends to randomize the distribution. A normal spinel is one in which
all MI ions are in the tetrahedral holes, and all MI1ions in the octahedral holes.
An example is ZnFez04. An inverse spinel has all MI ions in the octahedral holes.
The MI1ions are distributed equally between the octahedral and the tetrahedral
holes. Examples are Fe304 and MgFe200. Mixed spinels have intermediate
distributions, The fact that some of the octahedral or tetrahedral holes arc
unoccupied makes it possible that other ions may occupy these holes when thcse
are exposed on the surface.
OXIDE STRUCTURE
9
Figure 2-1 a. A rocksalt structure; b. Two comer-sharing octahedra, one centered
around ion A. Octahedra centered around ions A and B in FIg. 2-la are edge-sharing;
c. A wurtzite structure; d. Two comer-sharing tetrahedra, one centered around ion C.
Figure 2-2 Close-packed layers of oxide ions. If ions in the third layer are above B, it
is a hexagonal close-packed structure. If these ions are above C, it is a cubic close-
packed stucture. Ions that define octahedral and tetrahedral holes are also shown.
y-Fe2O3 is also a spinel. As suggested by the chemical formula, the
compound has fewer cations than needed to complete an ideal spinel structure.
Indeed, the formula is sometimes written as Fe3(Fe5@)OI2 to represent the fact that
for every twelve oxygen ions (which provide twelve octahedral holes and six
tetrahedral holes), there are three FeIII ions in the tetrahedral holes, and five FeIII
ions in the octahedral holes. Compared to the idcal spinel structurc, the
occupancy of the tetrahedral holes is the same, but the occupancy of the octahedral
holes is 1/6 less. This sixth position is denoted by @ to represent a cation vacancy.
Thus there is one cation vacancy for every three spinel units. When this vacancy
is ordered, the repeating unit is a trispinel.
There is another way to view the spinel and the corundum structures. Instead
of constructing the solid with close-packed layers of oxygen ions, the same
structure can be formed using the octahedral units as building blocks. At the
comers of the octahedral units are the oxygen ions, and at the centers are the
cations. Of course, these cation positions do not have to be completely filled.
The corundum structure is then made up of a three dimensional net of such
octahedra in which some octahedra share comers, edges, or faces, whereas the
spinel structure is made up of octahedra that share comers and edges. Although
not apparent in these cases, it is sometimes more convenient to discuss structures
with networks of octahedra.
The rutile structure is one such case. I n this structure, the sheets of close-
packed oxygen ions are rather distorted. The cations are in the center of octahedra
of oxygen ions, as shown in Fig. 2-3a. Along the c-direction (the vertical
direction), the octahedra are linked by sharing edges (Fig. 2-3b) to form a chain.
Adjacent chains are connected by sharing vertices (Fig. 2-3c). For Ti02, the
octahedra are distorted such that four metal-oxygen distances are of one value, and
the other two are of a different value. For some others like the dioxides of V, Nb,
Mo, and W, the metal-metal distances along the octahedra chain are not regular,
but alternate between a longer and a shorter distance.
Molybdenum trioxide M a 3 has a unique layer structure made up of chains
of octahedra that share comers. Two such chains are connected by sharing two
edges of the octahedra to form a double chain (Fig. 2-4a). These double chains are
then connected together in the third dimension (perpendicular to the plane of the
double chain) by sharing comers to form a sheet-like structure. Thus for each
octahedron, three 0 atoms are shared by three octahedra of the same double chain,
two are shared by two octahedra of adjacent double chains, and one is unshared.
This unshared unit is commonly referred to as a Mo=O unit. Finally, these two-
dimensional sheets are stacked on top of each other with rather weak interaction
between layers (Fig. 2-4b). Vanadium pentoxide V205 also has a layer structure.
The basic units are chains of tetrahedra linked through two comers. Two chains
are then linked by placing a fifth oxygen ion from one chain to each V ion in the
other chain to form a double chain and the basic structure of metavanadates. I n
this manner, each vanadium ion is regarded to have five oxygen neighbors. There
are two V-0 bonds that are shorter where the oxygen is not shared. When
one of these oxygen is shared bctween double chains so that they are linked,
the layer structure of V205 is formed. The oxygen ions in this structure are
OXIDE STRUCTURE
11
0 0 o T i
Figure 2-3 a. A unit cell of rutile TiO,; b. Two edge-sharing octahedra of Ti06 units
from adjacent unit cells; c. A network of octahedra that makes up TiOz.
Figure 2-4 Moo3 structure. a. A double-chain unit; b. Cross-section of the layer structure of
sheets of double-chains. The Octahedra are shown as squares with diagonals.
12
considered to be attached to one, two, or three vanadium ions. The one
attached to one V is the shortest, and is referred to as V=O. The vanadium
ion is considered to be in a distorted octahedron in which the sixth oxygen is
from another layer, and is very far from the vanadium ion.
The last simple structure to be discussed is the perovskite structure.
Compounds of this structure are usually of the formula M1MIIO3. An ideal
perovskite structure is made up of a cubic net of corner-sharing octahedra (Fig.
2-5). The smaller and more highly charged cation, MII sits in the center of an
octahedron, and the larger cation MI sits in the center of the cavity defined by a
cube of eight octahedra. Thus this latter cation is coordinated to twelve oxygen
ions. Usually, the MI1 ions are the transition metal ions, and the MI ions are the
alkali, alkali earth or lanthanide ions. Some examples of perovskites are KTa03,
SrTi03, and LaCoO3. Some compounds have ideal perovskite structures, but many
others, especially those that have large cations, are often distorted.
In addition to those described, there exist many other structures, such as
scheelite, pyrochlore, and wolframite. The variety increases with the number of
components in the compound. The readers are referred to the text by Wells [l ] for
discussions of these structures.
2.2 SHEAR STRUCTURE IN INTERMEDIATE OXIDES OF Ti,
V, AND Mo
Many transition metal ions possess multiple stable oxidation states. This is
evident from the compounds listed in Table 2-1 where a number of oxides of
different stoichiometries are found for many elements. Among these elements,
four have unusually large number of stoichiometries. They are Ti, V, Mo and W.
Table 2-2 lists the known oxides of Ti, V, and Mo that have well-defined three-
dimensional crystal structures. It is evident that many of these oxides differ only
slightly from each other. In fact, their structures are very similar and can be
constructed from the same building blocks. This contributes to the easy
conversion of one oxide to another of adjacent stoichiometry by oxidation or
reduction. The easy oxidation and reduction, and the existence of cations of
different oxidation states in the intermediate oxides have been thought to be
important factors for these oxides to possess desirable properties in selective
oxidation catalysis.
As an example, the structures of M o ~ ~ ~ ~ and M0~0~~have the common
building blocks of a three-dimensional cubic network of comer sharing octahedra
(the Re03 structure, which is also the building block for perovskite). The
structures of these compounds are formed when the positions of some octahedra
are shifted that pairs of octahedra share edges instead of comers (Fig. 2-6). The
shift in the positions are regular along certain directions called shear planes. The
farther is the stoichiometry from Moo3, the higher is the density of shear planes.
OXIDE STRUCTURE
Table 2-2 Intermediate Oxides of Ti, V, and Mo
13
Ti30
Ti20
Ti0
Ti203
Ti305
Ti407
Ti509
Ti02
Figure 2-5 A unit cell of perovskite MIMIIOJ . The MII ion is in the center of a comer-
sharing octahedron.
14
Figure 2-6 Shear structure in molybdenum oxides. a. Re03 structure; b. MogOZ6; c.
MoSOZ3. Each Moo6 octahedron is shown as a half-filled square block.
OXIDE STRUCTURE 15
2.3 STRUCTURE, STABILITY AND RECONSTRUCTION OF
OXIDE SURFACES
The positions of the surface ions may or may not be the same as those
defined by simple extension of the bulk structure, depending on whether the
free surface reconstructs or not. The driving force for reconstruction is to
lower the surface Gibbs energy per unit surface area to attain a thermody-
namically more stable system. However, metastable surface structure can
exist if the energy barrier for reconstruction is too high.
At present, there are few reliable experimental values for surface Gibbs
energies of oxides. Reliable calculated surface energies are also difficult to
find. The uncertainties in the true ionic charge, the degree of covalency, and
other surface properties such as compressibilities have made it difficult to
perform accurate calculations. Therefore, information on the thermal stability
of a certain surface plane comes entirely from experimental data.
Table 2-3 lists the surfaces of transition metal oxides that have been
studied. A surface is regarded stable (in some cases metastable), if it has
been reported to yield a 1x1 LEED pattern at low temperature. A thermody-
namically stable surface structure will not reconstruct on heating, provided that
the temperature is not too high, while a metastable surface would usually
undergo reconstruction. In the absence of knowledge of surface Gibbs
energy, it is useful to develop qualitative guidelines as a first approximation to
compare the stabilities of different surface structures.
Correlations with two effects appear reasonable. One is the polarity of the
surface, and the other is the degree of coordinative unsaturation of a surface
cation.
When a crystal of a binary oxide is cleaved to generate two new surfaces, the
ions in the cleavage plane are partitioned into the two separating solids in such a
manner that charge neutrality is maintained in each solid. The structure of the two
newly created surfaces, however, may or may not be identical. If they are
identical, or if the surface plane contains a stoichiomeuic ratio of cations and
anions, the surface will be dipoleless and it is called a nonpolar surface. If they
are not, the surface will probably (but not necessarily) possess a strong dipole and
the surface is a polar surface. A schematic representation of the two types of
surfaces is shown in Scheme 1.
Examples of nonpolar surfaces are rocksalt (100) surface, rutile (110),
(loo), and (001) surfaces, pervoskite (100) surface, and corundum (047)
surface. Examples of polar surfaces are wurtzite (0001) and (0001) and
rocksalt (111) surfaces. With other factors being identical, a polar surface is
less stable than a nonpolar surface. The presence of a dipole moment
increases the surface Gibbs energy. Comparing a metal-polar and an oxygen-
polar surface, the latter is usually more stable because oxygen ions are more
polarizable than metal ions. Polarization lowers the surface electric field and
the surface energy.
The degree of coordinative unsaturation of a surface cation measures the
number of bonds involving the cation that have to be broken to form a surface.
16
Table 2-3 Stability of Oxide Surfaces
Stabil- Cau 'on coordination Polar or
Surface itya bulk surface nonpolar Ref. Comment
NiO (100) + 6 5
coo (100) + 6 5
MnO (100) + 6 5
TiO, (110) + 6 6 and 5
(100) +/- 6 5
(001) +/- 6 4
SrTiO, (100) + 6 5
(111) +/- 6 3
T$O,(047) + 6 5
vp, (047) + 6 5
v,o, (010) + 6
6 and 5
a-Fe,O, (001) - 6 3
BaTiO (001) - 6 5
(1120) + 4 3
(4041,5031) + 4 3
(Oool) +/- 4 3
(mi) +I- 4 4
MOO, (010) + 6 6
wo, (100) + 6 6
ZnO (13oio) + 4 3
n
n
n
n
n
n
n
P
P
n
n
n
n
P
P
n
n
1-3
3
3
4-6
5
73
22
9
10
10
11
12
13
14-17
16
17,18
18,19
19
20
21
Footnotes:
a) -, +/-, and +represent structures of increasing stability to thermal treatment.
b)reconstruct to (2x2) and (6x6) structures at high temp. (ref. 23).
C)reconstruct to (1x3). (1x5), and (1x7) structures on heating.
d, facet to (011) and then to (114) which is stepped (001) on heating.
e, reconstruct to (2x2). (6 x &)R30" and splitting of spots.
f , reconstruct to (6 x 6.
g, 6-fold "1x1" at low temp., spot-splitting at 300-400°C. (2x2).
h, 6-fold "1x1".
') distorted "1x1".
(5x1), and (6 x aR30" above 700°C.
References:
1. F.P. Netzer and M. Prutton, J. Phys. C., 8, 240 (1975).
2. M.R. Welton-Cook, and M. Prutton, J . Phys. C., 13, 3993 (1980).
3. M. Prutton, J .A. Walker, M.R. Welton-Cook, R.C. Felton, and T.A. Ramsey,
Surface Sci., 89, 95 (1979).
OXIDE STRUCTURE 17
Table 2-3 continued
4. R.H. Tait and R.V. Kasowski, Phys. Rev. B. 20, 5178 (1979).
5. Y.W. Chung, W.J. Lo, and G.A. Somorjai, Surface Sci., 64, 588 (1977).
6. V.E. Henrich, G. Dresselhaus, and H.J. Zeiger, Phys. Rev. Lett., 36, 1335 (1976).
7. V.E. Henrich. and R.L. Kurtz, Phys. Rev. B, 23, 6280 (1981).
8. L.E. Firment, Surface Sci., 116. 205 (1982).
9. W.J. Lo, and G.A. Sornorjai, Phys. Rev. B, 17,4942 (1978).
10. R.L. Kurtz, and V.E. Henrich, Phys. Rev. B. 25. 3563 (1982); 26, 6682 (1982).
11. L. Fiermans, and J. Vennik. Surface Sci., 18, 317 (1969); 9, 187 (1968).
12. R.L. Kurtz, and V.E. Henrich, Surface Sci., 129, 345 (1983).
13. A. Aberdam, and C. Gaub, Surface Sci.. 27, 571 (1971); 27, 559 (1971).
14. M.F. Chung, and H.E. Famsworth, Surface Sci., 22. 93 (1970).
15. J.D. Levine, A. Willis. W.R. Bottoms, and P. Mark, Surface Sci., 29, 944 (1972).
16. S.C. Chang. and P. Mark, Surface Sci.. 45, 721 (1976).
17. W.H. Cheng, and H.H. Kung, Surface Sci., 122, 21 (1982).
18. W.H. Cheng. and H.H. Kung, Surface Sci., 102. L21 (1981).
19. S.C. Chang. and P. Mark, Surface Sci.. 46, 293 (1974).
20. L.E. Firment, and A. Ferretti. Surface Sci., 129. 155 (1983).
21. M.A. Langell, and S.L. Bernasek, J. Vac. Sci. Technol., 17, 1287, 1296 (1980).
22. V.E. Henrich, G. Dresselhaus, and H.J. Zeiger, Phys. Rev. B, 17,4908 (1978).
23. M. Langell. N. Cameron, Surface Sci., 185, 105 (1987).
I l l l l
- M- O - M - 0 - M -
1 " l l I I
- 0- M - O- M - O- \o/ M M \o' \o'
t
0-polar surface
M-polar surface
f
L 1
nonpolar surfaces t cleavage +
Nonpolar surfaces Mewl-polar (lower) and
Ox ygen-polar (upper) Surfaces
Scheme 1
18
The degree of coordinative unsaturation of a surface anion can be similarly
defined. Qualitatively the smaller the number of bonds broken, the more stable is
the surface. Thus with all other factors being identical, a surface is more stable if
its surface cations and anions are more coordinatively saturated. This factor,
together with the surface dipolar factor, qualitatively explains the trends observed
in Table 2-3.
When a metastable surface acquires enough thermal energy to overcome
the barriers for atomic migration, reconstruction by rearrangement of surface
atoms takes place to lower the areal surface Gibbs energy. The structure of a
reconstructed surface is no longer a simple extension of the bulk. At present,
only a few structures of reconstructed surfaces have been analyzed. One
example is the TiOz (001) surface. Upon heating, this surface facets.
Analysis of the LEED pattern shows that the faceted surface is a stepped
surface which is composed of (011) facets at low temperatures, and (114)
faccts at high temperatures [2]. Other examples are the ZnO polar surfaces.
A LEED pattern showing a "1x1" pattern of six-fold symmetry is often
obtained for the ZnO (0001) and (0001) surfaces, although the truncated bulk
structure possesses only a three-fold symmetry. Two possible explanations for
the six-fold symmetry have been proposed. One explanation comes from the
LEED intensity analysis of the Zn-polar surface [3]. It has been found that
the outermost Zn layer relaxes inward by about 0.02 nm (see Table 2-4).
This brings the layer of Zn closer to the layer of 0 atoms, and the surface
behaves like a hexagonal close-packed layer of atoms in the LEED analysis.
The other explanation is that double layer steps are present on these surfaces.
Since adjacent double layers are rotated by 60°, a random occurrence of these
steps would result in a six-fold LEED pattern [4].
It should be emphasized that the stability of these surfaces has been studied
under ultra high vacuum conditions such that the surfaces are presumably clean.
The environment during catalytic reactions or during oxide powder preparation is
either that of an aqueous solution or of gases of atmospheric pressure or higher.
Adsorption of molccules can substantially change the stability of a certain surface
structure. Adsorption often increases the stability of an otherwise unstable
surface.
In vacuo, some surfaces lose oxygen atoms to lower the Gibbs energy of
the system. If the oxygen
atoms are lost such that the anion vacancies form a periodic structure, a
superstructure is observed in the LEED pattern, This phenomenon has been
used to explain the data for a TiOZ (100) surface [5]. Upon heating this
surface to increasingly higher temperature, (1x3), (1x5) and (1x7) patterns arc
formed consecutively. Simultaneous AES data indicate increasing loss of
surface oxygen.
In addition to reconstruction, small relaxations of the surface atoms from
their truncated bulk positions also occur. The bonds of covalent compounds arc
not very compressible, and it would be expected that the anion-cation bond lengths
would remain approximately constant during relaxation [6,7], as is observed for
GaAs (110) [8]. The extent of relaxation also depends on the presence of electron
This is accompanied by reduction of the cations.
OXIDE STRUCTURE 19
Table 2-4 Relaxation of Surface Atoms of Oxides Deduced from LEED Data
Relaxationa Rumpling Ref.
Surface 6M 60 %s,dJ s, -60
NiO (100) 0 to -3% - 5t o 5% a
0 to -3% Oto3% b
coo (100) small b
ZnO (lOi0) 4. 3 f 0.11 4. 1 +_ 0.051 C
ZnO (0001) 4 . 2 1 d
0 0.1 to 0.21 e
coo (111) -15% f
Footnote:
a) negative relaxation is towards the solid.
References:
a) C.G. Kinniburgh, and J .A. Walker, Surface Sci., 63, 274 (1977).
b) M. Prutton, J.A. Walker, M.R. Welton-Cook, R.C. Felfon, J .A. Ramsey.
c) C.B. Duke, A.R. Lubinsky, S.C. Chang, B.W. Lee, and P. Mark, Phys.
d) C.B. Duke, A.R. Lubinsky, Surface Sci.. 50, 605 (1975).
e) R.E. Watson. M.L. Perlman, and J .W. Davenport, Surface Sci.. 115, 117
f ) A. Ignatiev, B. Lee, and M. Van Hove, Proc. 7th Intern. Vacuum
Surface Sci., 89, 95 (1979).
Rev. B, 15, 4865 (1977).
(1982).
Congr.. Vienna. R. Dobrozemsky, et al. ed., 1977, p. 1733.
lone pairs on the surface [9,10]. For example, the oxygen atoms at the (OOOT)
oxygen-polar surface of ZnO have two electrons in the lone-pair orbital pointing
outward from the surface, while the Zn atoms in the (0001) Zn polar surface do not
have such filled orbitals. Surface atom relaxation is expected to be different for
the oxygen and for the Zn atoms, assuming that ZnO is a covalent compound.
For ionic compounds, relaxation of a surface ion is determined by three
factors [l l ]: changes i n h e ionic size because of reduced surface charge
transfer resulting from a reduced Madelung potential at the surface, imbalance
of the ionic forces because of the termination of the lattice, and the residual
influence of covalent bonding. The extent and the direction of relaxation
depend on the relative contributions of these factors. Since the restriction on
bond directions and bond lengths i n an ionic compound is much less severe
than in a covalent coompound, it is possible that both the metal ion and the
oxygen ion relax inward. This difference between covalent and ionic
20
surface
bulk
ionic covalent
SIDE VIEW
Figure 2-7 Side view of a solid showing relaxation of surface atoms in an ionic and a
covalent compound. The dotted circles represent truncated surface lattice positions.
relaxation is schematically illustrated in Fig. 2-7 for the surface atoms of the
zinc oxide (1010) plane [l 11.
Available data on the relaxation of surface atoms of transition metal oxides
are summarized in Table 2-4. For these oxides, the relaxation is of the ionic type,
and both the metal and the oxgyen atoms relax inward. These results are not too
surprising as these oxides are of the first transition period. They are relatively
ionic. Since the ionicity decreases on going to the lower right hand comer of the
periodic table, one would expect the mode of relaxation of the surface atoms of
oxides of F ' t , Pd, Cu, etc. to be different.
It should be emphasized that substantial amounts of defects may exist in
surfaces of oxide crystallite powders prepared by conventional techniques. It
has been reported that steps of different heights exist on surfaces of Moo3
crystallites. These surfaces also reconstruct readily upon thermal heating or
irradiation by electron beams [12]. In fact, single crystal surfaces may also
have well-ordered domains coexisting with disordered regions [ 131.
2.4 STRUCTURE OF SUPPORTED OXIDES
Supported oxides that do not interact strongly with the support form three-
dimensional crystallites whose properties are similar to large bulk crystals.
However, some oxides interact strongly with oxidic supports such that a monolayer
of an oxide of properties different from the bulk oxide is formed. Growth of three-
dimensional crystallites occurs only after a substantial fraction of the surface is
covered by the monolayer. This is often the case for oxides of Cr, Mo, W, V, and
OXIDE STRUCTURE 21
Re supported on alumina, and for vanadium oxide supported on anatase titania.
The absence of three-dimensional crystallites and the presence of monolayer
structure are readily observed by Raman spectroscopy. Figure 2-8 shows the
Raman spectra of vanadia. The spectrum for V205 (curve a) shows intense sharp
peaks at around 996, 703, 530,483, and 406 cm-' [14]. The 996 cm-' band is
assigned to terminal V=O stretch, and the 703 and 530 cm-' bands are assigned to
bridging VC&V symmetric and antisymmetric stretch, respectively. When 2.1
wt.% of vanadia is supported on y-AI2O3 (curve b), the spectrum does not show
any of the prominent V2O5 peaks. Instead, two featureless broad peaks appear;
one centers around 970 cm-' accompanied by a shoulder around 995-1000 cm-',
and the other in the range between 800-830 cm-' [15]. When a larger amount of
vanadia is supported on the alumina (curve c), the intense peaks characteristic of
crystalline V2O5 appear. Interestingly, these characteristic peaks begin to appear
at lower vanadia loadings on a silica support than on alumina [16]. This suggests
that vanadia interacts more strongly with alumina than with silica so that it forms a
monolayer structure with alumina but not with silica. Vanadia also interacts
strongly with anatase Ti02 to form a layer structure [17].
Vanadia supported on anatase Ti02 is a much studied system. It is generally
believed that the vanadia layer structure exposes the (010) plane and the V=O
groups preferentially [ 18-20] because of the excellent match of the vanadate unit
and the anatase structure. It has been proposed that on the (001) plane of anatase,
vanadium exists as monovanadate (V04)"- groups bonded to the surface as [21]:
\ l O l O l O l I \ / \ / \ /
Ti Ti Ti Ti
In this form, the V ion occupies roughly a position which another Ti ion would
occupy if the bulk structure continues. The V-0 bridging bond length of 0.190
nrn is very close to the Ti-0 bond length of 0.193 nm. Indeed, EXAFS studies
show that on anatase, the basic structural unit of vanadium contains two terminal
V=O bonds of a bond length of 0.165 nm, and two bridging V - 0 bonds of 0.190 nm
[221. The Dicture is also consistent with the observation that an average of one
oxygen ion per vanadium can be readily removed on reduction [21]. However,
this model has not been supported by IK data which do not show the expcctcd band-
splitting due to coupling of the two V=O groups [23]. On other crystallographic
planes of anatase, however, there are no sites of such a good match with the
monovanadate groups, and other structures may be present.
On y-AI2O3, EXAFS and XANES studies show that vanadium ions are
present in a more regular tetrahedral coordination than on anatase. Each
vanadium ion is associated with two terminal V=O bonds of 0.167 nm, and two
bridging bonds of 0.182 nrn bond length [21,22]. Upon reduction, each vanadium
22
1500 1000 5bO
Wavenumber cm-l
Figure 2-8 Raman spectra of supported and unsupported vanadia. a. V205; b. 2.1 wt.%
V/y-A1203; c. 4.0 wt.% Vfi- A1203; d. 2.3 wt.% V/SiO2. Curves a-c are from Zi t. Phys.
Chern. Neue Folge, 111, 215 (1978), curve d is from J. Phys. Chem., 84, 2783 (1980).
ion loses 0.6 oxygen atoms readily on the average. A picture that is consistent
with these observations is that the vanadium ions exist as dimcric units on y-AI2O3,
such as pyrovanadate units [21]:
Like vanadia supported on titania or A1203, molybdena on thcse supports also
cxists as well-disperscd units or monolaycr until high loadings. This is illustratcd
by Raman spectroscopy of MoO3/AI203 [24] and M003/ri02 1251. As shown in
Fig. 2-9, the intense and sharp characteristic bands of crystalline Moo3 at 998
OXIDE STRUCTURE 23
I I I I 1
800 1000 1200
Wavenumber cm-’
Figure 2-9 Raman spectra of supported molybdena. a. 12 wt.% MoO3/q-AI2O3; b. 4 wt.%
Mo03/A1203; c. 13.5 wt.% Mo03/Ti02; d. 1.8 wt.% MoO-,/riOZ. Curves a and b are from
J . Phys. Chern., 82, 2002 (1978), and curves c and d are from J. Catal., 94, 108 (1985).
and 821 cm-’ are not present i n samples of low loadings of Moo3. They appcar
only in samples of high loadings. A monolayer structure is formed when the Mo
loading is below about 5 Mo atoms per nm2. Below this value, the ratio of the
intensity of the Mo signal to the A1 signal in XPS and ISS increases linearly with
the Mo loading, consistent with the picture of a well-dispersed phase [26,27]. At
higher loadings, this ratio reaches a plateau. Electron microscopy also shows a
highly dispersed phase of molybdena at low loadings [28,29]. Interestingly,
crystallites of MoS2 on alumina can be redispersed by reoxidation to form a
dispersed phase of molybdena.
One picture that has been proposed to explain these and other evidence is that
the molybdenum ions exist as monomeric MOO^^- units at loadings up to about 1
Mo per nm2. Betwecn 1 to about 4.5 Mo per nm2, heptameric Mq0246p units and
octahedrally coordinated polymeric surface species are also present [30-341. The
heptamer is proposed to be adsorbed as a bilayer with four Mo ions lying next to
the AI2O3 and the remaining three on top [32]. At still higher loadings, crystalline
Moo3 appears.
24
0 500 1000
-1
Wavenumber cm
Figure 2-10 Raman spectra of tungsten oxides. a. WO,; b.
W03/A1203. (From J. Catal.. 90. 150 (1984). copyright Academic Press.)
A12(W04),; c. 10 wt.%
The existence of these well-dispersed or monolayer phases is actually quite
common among supported transition metal oxides. Fig. 2-10 shows another
example of WO3 supported on alumina [35,361. Commonly found in these well-
dispersed phases are the terminal metal-oxygen double bonds. These M=O bonds
usually have characteristic Raman stretching frequencies in the 950-1000 cm-'
region. These peaks are often at somewhat different frequencies and broader than
the corresponding peaks for the crystalline oxides [371. Indeed such M=O groups
have been detected for W6+, Mo6+, V5+, Re7+, and Cr6+oxides on y-AI2O3
[37,38], and Mo6+and V5+ on titania [39,401. The frequencies of these terminal
double bonds vary somewhat depending on the surface coverage of the dispersed
phase and on whether the double bond is interacting with adsorbed water or surface
hydroxyl groups [41 and references thercin].
Nickel oxide also forms a well-dispersed phase on y-A1203 instead of
crystallites of NiO. This well-dispersed two-dimensional phax may actually be Ni
occupying the octahedral and/or the tetrahedral holes at the surface of the alumina
to form a layer of spinel-like NiA1204 [26,27,42].
When Ni is supported together with Mo on y-AI2O3, there is interaction
between Ni and Mo which affects their locations on the support. I t has been
OXIDE STRUCTURE 25
suggested that at low calcination temperatures, the Ni ions interact strongly with
the molybdenum species to partially shield the oxomolybdenum ion. At high
calcination temperatures, the Ni ion migrates to the tetrahedral or octahedral holes
of the alumina, exposing the molybdenum ions [27,43]. Similar incorporation into
the alumina has also been observed in Ni-W/AI2O3 [44] and for Co in the Co-
Mo/A1203 system [451.
REFERENCES
1. A. F. Wells, "Structural Inorganic Chemistry", 4th ed., Clarendon Press,
2. L. E. Firment, Surface Sci., 116, 205 (1982).
3. C. B. Duke, and A. R. Lubinsky, Surface Sci., 50, 605 (1975).
4. V. E. Henrich, H.J .Ziegler. E. I. Solomon, and R. R. Ray, Surface Sci..
5. Y. W. Chung. W. Lo, and G. A. Somorjai. Surface Sci., 65, 419 (1977).
6. J . D. Levine, and S. Freeman, Phys. Rev. B. , 2, 3255 (1970).
7. J . E. Rowe, S . B. Chrisman, and G. Margaritondo, Phys. Rev. k f t . 35, 1471 (1975).
8. A. R. Lubinsky, C. B. Duke, B. W. Lee, and P. Mark, Phys. Rev. Lett.
9. H. C. Gatos, and M. C. Levine, J . Electrochem. Soc., 107, 427 (1960).
London, 1975.
74, 682 (1978).
36. 1058 (1976).
10. H. C. Gatos, J . Appl . Phys., 32, 1232 (1961).
11. C. B. Duke, A. R. Lubinsky, B. W. Lee, and P. Mark, J. Vac. Sci. Technol.,
12. J . M. Dominguez-Esquivel, 0. Guzman-Mandujano, and A. Garcia-Borquez,
13. L. E. Firment, and A. Ferretti. Surface Sci., 129, 155 (1983).
14. I. Beattie, and T. Gibson, J. Chem. SOC. A, 2322 (1969).
15. F. Roozebaum, J . Medema, and P. Gellings, &it. Physik. Chem. Neue Folge,
16. F. Roozebaum, M. Mittelmeijer-Hazeleger, J . Moulijn, J . Medema, V. de Beer,
17. I. Wachs, R. Saleh, S . Chan, and C. Chersich, Appl . Catal., 15, 339 (1985).
18. A. Vijux, and P. Courtine, J . Solid Stare Chem., 23, 93 (1978).
19. G. C. Bond and P. Konig, J . Catal., 77, 309 (1982).
20. Y. Murakami, M. Inomata, K. Mori, T. Ui, K. Suzuki. A. Miyamoto, and T.
13, 761 (1976).
J . Catal., 103, 200 (1987).
111, 215 (1978).
and P. Gellings, J. Phys. Chem., 84, 2783 (1980).
Hattori, in Preparation of Catalysts III. G. Poncelet, P. Grange, and
P. J acobs ed., Elsevier Science Publ., Amsterdam, 1983, p. 531.
21. J . Haber, A. Kozlowska, and R. Kozlowski, J. Catal., 102, 52 (1986).
22. R. Kozlowski, R. Pettifer. and J . M. Thomas, J . Phys. Chem., 87, 5176 (1983).
23. G. Busca, G. Centi, L. Marchetti, and F. Trifio, Langmuir. 2. 568 (1986).
24. H. Knozinger. and H. J eziorowski, J . Phys. Chem., 82, 2002 (1978).
25. Y. Liu, G. Griffin, S . Chan, and I. Wachs, J. Card., 94, 108 (1985).
26. P. Dufresne, E. Payen, J . Grimblot, and J . P. Bonnelle, J. Phys. Chem.,
85, 2344 (1981).
26
27. S. Kasztelan, J . Grimblot, and J . P. Bonnelle, J . Phys. Chem., 91, 1503 (1987).
28. T. Hayden, and J. Dumesic, J . Catal.. 103. 366 (1987).
29. T. Hayden, J . Dumesic. R. Sherwood, and R. Baker, J. Catal., 105, 299 (1987).
30. S. Kasztelan, J . Grimblot. J . P. Bonnelle, E. Payen, H. Toulhoat, and Y. J acquin,
31. L. Wang, and W. K. Hall, J . Cafal.. 77. 232 (1982).
32. W. K. Hall, Proc. 4th Conf. Chemistry and Uses of Mo, H. F. Barry, and
33. H. Weigold, J. Catal., 83, 85 (1983).
34. N. Giordano, J . C. J. Bart, A. Castellan, and G. Martinotti, J . Cafal., 36. 81 (1975).
35. S. Chan, I. Wachs. and L. Murrell, J . Catal., 90, 150 (1984).
36. S. Chan, I. Wachs. L. Murrell. L. Wang, and W. Hall, J . Catal., 88, 5831 (1984).
37. I. E. Wachs. F. D. Hardcastle, and S . S . Chan, Spectroscopy, 1. 30 (1986).
38. S. S. Chan, and I. E. Wachs, J . Catal., 103, 224 (1987).
39. C. P. Cheng and G. L. Schrader, J. Cafal., 60, 276 (1979).
40. K. Y. S. Ng, and E. Gulari, J. Catal., 92, 340 (1985).
41. R. Quincy. M. Houalla, and D. Hercules, J. Catal., 106, 85 (1987).
42. S . Kasztelan, J . Grimblot, and J. P. Bonnelle. J . Chim. Phys., 80, 793 (1983).
43. H. J eziorowski, H. Knozinger, E. Taglauer, and C. Vogdt, J . Cafal., 80, 286 (1983).
44. B. Horrell. D. L. Cocke, G. Sparrow, and J . Murray, J. Cafal., 95, 309 (1985).
45. F. Delannay, E. Haeussler. and B. Delmon, J . Cafal., 66, 469 (1980).
Appl. Cafal., 7, 91 (1983).
P. C. H. Mitchell, ed., 1982, p.224.
Chapter 3
PHYSICAL AND ELECTRONIC
PROPERTIES
3.1 SURFACE COMPOSITION
The surface composition of a single component oxide is determined by the
surface anion to cation ratio, which, for an ideal surface, depends on the
stoichiometry of the oxide and the orientation of the exposed crystal plane. It is
often important to determine whether or not a surface is stoichiometric.
Nonstoichiometry often arises from preferential removal of surface oxygen leading
to a slight reduction of the surface. The extent of nonstoichiometry depends on
the pretreatment of the sample. Stoichiometric surfaces can often be obtained for
surfaces that have low surface areal Gibbs energies (the stable surfaces) by low
temperature annealing. For example, stoichiometric SrTi03 (loo), TiOz (1 lo),
TiOz (100) [l-31, ZnO (1070) [4], and Moo3 (010) [5] surfaces have been
prepared. High temperature annealing in vacuo or ion-sputtering preferentially
removes oxygen, and the cations near the surface are reduced to lower oxidation
states. For oxides that have empty d bands, reduction of the surface to generate
nonstoichiornetry rcsults in the appearance of band-gap states which are readily
detectable by ultraviolet photoelectron spectroscopy and electron energy loss
spectroscopy .
For multicomponent oxides, in addition to the surface anion to cation ratio,
the ratio of the different cations is also of interest. At least two questions are
asked. If the two component oxides form a solid solution, are the surface and the
bulk cation ratios the same? If the component oxides form a bulk compound, does
the surface have the same chemical stoichiometry as the bulk?
Whether the surfacc cation ratio is the same as the bulk ratio depends on a
number of factors. Thesc factors include: (1) the surface tension (or surface Gibbs
energy) of the component oxides. The lower energy component tends to be
segregated to the surface; (2) thc bulk strain of the solid solution due to mismatch
of the ionic sizes or the coordination symmetry. The larger ion tends to be
segregated to the surface, as docs the ion whose preferred coordination symmetry
27
28
differs from that provided by the matrix; (3) the nature of the adsorbate.
Chemisorption lowers the surface energy of the solid. Thus chemisorption tends
to induce surface segregation of the component that binds more strongly with the
adsorbate; (4) formation of a surface compound. Even if the bulk oxide is a true
solid solution, a surface compound of a certain stoichiometry may be formed. The
surface composition is then determined by the surface compound. One driving
force for the formation of a surface compound is the presence of surface adsorbates
that causes the surface cations to have an oxidation state different from the bulk
oxidation state. For example, in the presence of oxygen, the surface chromium
ions in Cr203 have an oxidation state of +6, whereas the bulk ions are +3. In this
case, the adsorbed oxygen are being incorporated as surface lattice oxygen ions.
There are only a few experimental results on solid solutions. In the dilute
solution of ZnO in MgO, the surface is enriched with Zn [6]. This can be
explained by point (2) in that Zn prefers tetrahedral coordination, while the
coordination symmetry in MgO is octahedral. In the solid solutions containing Cr,
which includes CoO-Cr203, NiO-Cr203 [7], and Fq03-Cr203 [8], Cr is enriched
on the surface in the region of low Cr concentrations. The surface cation ratios
seem to remain constant at intermediate Cr concentrations. This phenomenon has
been interpreted as due to the formation of a compound that is segregated onto the
surface, such as CoCrZO4 spinel [7]. The surface enrichment of Sb in the Sn02-
Sb02 solution [9] can be explained by the larger size of Sb than Sn [lo].
In an oxidic multicomponent compound, the surface composition is
constrained by the periodicity of the compound, unless the driving force for surface
segregation is sufficiently large to disrupt the periodicity. I n the limited number
of cases reported, the surface has the same cation ratio as the bulk. For example,
the surface Bi/Mo ratios for Bi2Mo06, Bi2M0209 and Bi2Mo-,OI2 are within 10%
of the bulk values [ll].
3.2 IONICITY OF OXIDES
The formal oxidation states of transition metal oxides range from one in Cu20
to eight in Os04, for example. However, there is little doubt that the true ionic
charges in many transition metal oxides are less than those predicted from formal
oxidation states. Since ionicity affects oxide properties including the surface
electric field gradient, the surface electrostatic potential, and the mode of surface
relaxation, knowledge of its magnitude is important.
Recently, experimental measurements of the degree of charge transfer
between the cation and the anion become available from X-ray diffraction data [ 12-
151, and X-ray photoelectron spectroscopy data [ 16-18]. Some theoretical
calculations are also available that provide charge lransfcr information. These data
are summarized in Table 3-1.
I n the X-ray diffraction technique, electron dcnsity distribctions are deduced
directly from X-ray data. From the distribution maps, boundaries of ions are
assumed to correspond to the point of minimum (local minimum) electron density.
The number of electrons associated with each ion, and thus the true cation charge,
PHYSICAL AND ELECTRONIC PROPERTIES 29
q, is then obtained by summing the electron density within the boundary.
Reliabliliy of the values of q obtained depends on the validity of this method of
partitioning of electrons to the various ions. When properly analyzed, the method
appears to be adequate for electrostatic potential calculations using a point charge
model or a shell model which disregards the nature and spatial orientation of the
electron orbitals.
The method using XP S binding energy shift data was originally proposed by
Siegbhan et al. [17]. The values of q reported here are obtained using the method
of Bagus and Braughton [16]. In this method, it is assumed that the experimental
binding energy of an ion in a solid differs from the binding energy of the ion in the
gas phase by the lattice self-potential at the ion site and the final state extra-atomic
relaxation effect. (The final state extra-atomic relaxation effect is an effect that
affects the kinetic energy of the escaping photoelectron due to the relaxation of the
electrons in the lattice surrounding the ion in response to the removal of the
photoelectron from the ion). Assuming that the final state effects are the same for
the cation and the oxygen ion, the following relationship is obtained [16,18]:
BE(0,XPS) - BE(M,XPS) =
BE(0,gas ion) - BE(M,gas ion) +O(0) - O(M)
(3-1)
The left hand side is the difference in the values of experimental binding energy of
the observed electrons from the oxygen and the metal ion. The first two terms on
the right hand side represent the difference in the binding energy of the same
electrons from the gas phase oxygen and metal ions. The last two terms represent
the difference in lattice self-potential of the oxygen and the cation in the solid.
Since the electron binding energies of the gas phase ions and the term O(0) - @(M)
are unique functions of the true ionic charge, it is in principle possible to calculate
q using this equation. In calculating the values of q listed in Table 3-1, the electron
binding energy calculated for the gas phase ions [19] have been used. The lattice
self-potentials used are listed in Table 3-2.
Assuming that the experimental values of binding energy are accurate, the
accuracy of the ion charge thus obtained still depends on the accuracy of the
calculated binding encrgy for the gas phase ions, the validity of the assumption that
the final state extra-atomic relaxation effects of the oxygen ion and the metal ion
cancel out, and the error introduced by using lattice self-potentials of bulk ions in
calculations involving surface and near surface ions. With these limitations, the
ionic charges thus obtained are at best qualitative and should be used only for
qualitative comparison of ionicity among similar solids.
The seriousness in neglecting the final state effect can best be illustrated
using Si02 and CdO for which the extra-atomic relaxation effect has been included
in the calculation. The charge for Si in Si02 using equation (3-1) is +4. If a
relaxation of about 5 eV is included [20], the charge becomes +2. Similarly for
CdO, a Cd charge of 0.4-0.8 would be obtained without relaxation compared to a
charge of 1.0 with relaxation [21].
A variation of the above method has been used for a number of chromium
compounds [22]. I n this study, the authors make use of the fact that because of
30
Table 3-1 True Cation Charges of Oxides (From J . Solid State Chem.,
52, 191 (1984), copyright Academic Press with update).
Method a
Compound XPS b X-ray Calculation
MgO 1.25- 1.75 1.9 (a), 1.85 (b), 1.5 (c)
CaO 1.8 (c)
SrO 2 (c)
BaO 2 (c)
Ti0 1.52 (o), 1.35" (0)
vo 0-1 (d) 0.66 (1)
MnO 1.5 1.4 (a), 1.51 (b) 1.24 (o), 1.03" (0)
FeO 1.29 (o), 1.03" (0)
coo 1-1.5 1.2 (a), 1.4 (b) 1.16 (o), 0.78" (0)
NiO 1-1.5 0.7 (a), 0.9 (b) 1.2-1.8 (m), 1.9 (n),
1.00 (o), 0.74"(0)
CUO 2
ZnO 1.2-1.7, 1.11" (h)
CdO 1.05" (h)
Ago Ag(1) 0.53" (h)
Ag(II1) 1.87' (h)
a-Fe203 2.7
a-Cr2O3 0.15d (g), 2.6
Ti 02 2.8 2.19" (p)
cro2 0.38d (g)
crO3 0.46d (g)
wo3 1.5
&2O 0.48" (h)
a-A1203 2-2.5 (j)
S i02 4, 2" (i) 1.0 (k)
zrO2 1.2
Moo3 1.5-2
Mg2Si206 (Mg iron) (MI) 1.84 (b)
(M2) 1.79 (b)
LiA1Si206 (Li ion) 0.7 (b)
CaMgSi206 (Mg ion) 1.44 (b)
Mn2Si04 (Mn ion) (Ml) 1.21 (b)
(M2) 1.49 (b)
(A1 ion) 2.4 (b)
(Ca ion) 1.39 (b)
PHYSICAL AND ELECTRONIC PROPERTIES 31
Table 3-1 continued
Footnotes:
a) Letters in the brackets denote references.
b, Unless noted, the charges are calculated using equation 3-1 in text.
The XPS data are from references e and f except when indicated.
') The final state extra-atomic relaxation of the cation has been included
in calculating these values. See text for detail.
d, These are taken directly from reference g using a modified form of
equation 3-1. See text for detail.
') These are for clusters that resemble a surface.
References:
a) S. Sasaki, K. Fujino. and Y. Takeuchi, Proc. J apan Acad., 55, Ser R, 43 (1979).
b) S. Sasaki, K. Fujino, Y. Takeuchi, and R. Sadanaga, Acta Cryst. A36, 904 (1980).
c) G. Vidal-Valef J.P. Vidal, and K. Kurki-Suonio, Acta Cryst., A34, 594 (1978).
d) M. Morinaga, and J .B. Cohen, Acta Cryst., A32, 387 (1976).
e) C.N.R. Rao, D.D. Sarma, S . Vasudevan, and M.S. Hegde, Proc. Royal SOC.
f) D.D. Sarma, and C.N.R. Rao, J . Electron. Spectra. Related Phenom., 20, 25 (1980).
g) T. Dickinson, A.F. Povey, and P.M.A. Sherwood, J. Chem. SOC. Faraday Trans.
h) S.W. Gaarenstroom, and N. Winograd, J. Chem. Phys., 67, 3500 (1977).
i ) F. Bechstedt, Phys. Stat. Sol. B, 91, 167 (1979).
j ) V.I. Nefedov, D. Gati, B.F. Dzhurinskii, W.P. Sergushin. and Ya. V. Salyn,
k) R.F. Steward, M.A. Whitehead, and G. Donnay, h er . Mineralogist, 65, 324 (1980).
1) V.A. Gubanov, B.G. Kasimov, and E.Z. Kuxmaev, J . Phys. Chem. Solid, 36, 861 (1975).
m)A.B. Anderson, Chern. Phys. Lett., 72, 514 (1980).
n) P.S. Bagus, and U. Wahlgren, Mol. Phys., 33. 641 (1977).
o) C. Satoko, and M. Tsukada, IMS Ann. Review, 1979, p. 33; M. Tsukada,
p) M. Tsukada, C. Satoko. and H. Adachi, J. Phys. SOC. J apan, 48. 200 (1980).
London, A367, 239 (1979).
I, 72, 686 (1976).
Russ. I. Inorg. Chem., 20, 1279 (1975).
H. Adachi, and C. Satoko, Prog. Surface Sci., 14, 113 (1982).
reduction by X-ray, XPS data could be recorded for Cr ion and reduced Cr atom
from the same sample. Presumably, since both the Cr ion and the Cr atom are
embedded in the same solid matrix, their extra-atomic relaxation should be the
same. Then using an equation similar to equation (3-1) except that the difference
between two Cr peaks are used instead of between oxygen and chromium, the Cr
ion charge is calculated. It can be scen (Table 3-1) that the ionic charge thus
obtained is smaller than that obtained using equation (3-1).
Finally, the ionic charge provided by some theoretical calculations are
included. These calculations are cluster calculations and the ionic charges are
calculated from the Mulliken populations.
The I t is apparent that different methods yield different ionic charges.
32
Table 3-2 Lattice Self-potential at the Cation Sites of Oxides a
Compound Potential, eV Compound Potential, eV
MO MgO
CaO
Sr O
BaO
MnO
FeO
coo
NiO
CdO
CUO
ZnO
PbO
M02 Ti02
Sn02
Si02
ca2
zrO2
-23.9
-20.9
-19.5
-18.2
-22.7
-23.3
-23.6
-24.2
-21.4
-24.3
-24.0
-20.5
M2O3 a-Cr2O3 -34.9
v2°3 -33.4
a-Fe203 -34.8
a-A1203 -36.6
Ti203 -33.6
Ga203 -35.0
Rh203 -34.1
Pb203 Pb(1) -32.8
Pb(2) -28.1
Nd203 -29.0
-29.7
44. 7 M03 Cr03 -58.5
4 2 . 9 M a3 -58.5
4 6 . 4 to -50.6b wo3 -64.5
-46.2
4 2 . 3
Footnotes:
a) Taken from J . Solid State Chem., 52, 191 (1984); original data from J.Q.
Broughtori and P.S. Bagus, J. Electron Spectros. Relat. Phenom., 20, 261
(1980). and W. Van Cool, and A.G. Piken. J. Mater. Sci., 4. 95 (1969).
b, Value depends on the crystal structure.
differences, in addition to experimental variations, may be due to the fact that
different methads measure ionic charges that are defined differently. Only in the
limit that eleclrons associated with each ion are clearly defined and there is no
overlap of electron density from different ions that the different methods could
yicld the same charge. In spite of this, however, it is worth noting that if the data
are analyzed as exactly as possible with minimal simplification, he ionic charge
does not differ significantly among the different methods.
The values shown in Table 3-1 also confirm the fact that, in general, the trend
of ionicity parallels that derived from electronegativity arguments. Thus the alkali
metal oxides are rather ionic with ionicity increasing with increasing atomic masses
as one goes down a given group. Transition metal oxides near the middle of the
pcriod (groups V1 to IIB) have true ionic charges that arc about half of the formal
PHYSICAL AND ELECTRONIC PROPERTIES 33
charges. Finally, Si02 which is normally thought of as covalent does possess a
cation charge of one.
When the true ionic charge is not available from experimental or theoretical
results, relative ionicity can still be estimated using the electronegativity scale of
Pauling [23], Sanderson [24] or Phillips [251.
The basic assumption in Pauling's ionicity is that if the heat of formation of a
A-B bond, DAB exceeds the arithmetic average of the heats of formation of the
homopolar A-A and B-B bonds, DAA and DBB, the extra energy is due to the
transfer of electron from the less electronegative to the more electronegative atom
in the bond. A scale of elemental electro-
negativities XA and XB can be defined from the relations:
It is, therefore, ionic in origin.
The proportionality factor has the dimension of energy. XA and XD are
dimensionless and increase by 0.5 with valence charge of unity for the first row of
the periodic table. Fractional ionic character f,(A,B) is defined by:
to satisfy the conditions that 0 5 f, 5 1, and f,(A,B) =f,(B,A).
Phillips [25] has proposed that the energy of a bond contains a homopolar, or
covalent, and a heteropolar, or ionic part, the values of which can be defined
accurately in terms of spectroscopic transition energy between bonding and
antibonding states. This proposal stems from the observation that the bonding
states have lower energy, are centered predominantly on the more electronegative
atom, and point towards the nearest-neighbor atoms. The antibonding states are
centered predominantly on the more electropositive atom, and point away from the
nearest neighbors.
The homopolar energy Eh is assumed to depend only on the bond length or
nearest neighbor distance r, and the position in terms of the rows in the Period Table
under concern. The average energy gap between bonding and antibonding state,
E,, is then the geometric sum of Eh and the average ionic energy gap C:
Eg2 =Eh2 +c'
(3-4)
Phillip's ionicity fi is defined as:
The values of E, can be evaluated from the optical properties of the solids such as
the valence electron plasma frequencies or the low frequency electronic dielectric
constants, and Eh can be extrapolated from values of E, of elemental compounds
such as diamond, silicon, germanium and tin using an empirical relation that Eh K
r 0, where r is the interatomic distance, and S an empirical constant with a value of
2.48.
34
Table 3-3 Phillips' Ionicity, f,
MnO 0.887
FeO 0.873
COO 0.858
NiO 0.841
Ge20 0.730
A1203 0.796
Cr2O3 0.777
F%03 0.677
LiNb03 0.825
LiTa03 0.850
(Ta-0)
CU~O 0.56
Ti02 0.686
(Nb-0)
Be0
ZnO
MgO
CdO
CaO
Sr O
0.65.67 0.65-.66 BaO
0.53 0.53 Ge02
0.49 0.51 Sn02
Li20
si02
0.620
0.653
0.839
0.778
0.916
0.928
0.93 1
0.730
0.784 0.57 0.57
0.766
0.570 0.57-.59 0.57-.59
Ge02 0.511 0.53 0.54
A1203 0.796
LiGa03
(Li-0) 0.815
(Ga-0) 0.653
TeOz 0.67 0.63
Footnotes:
a) From B.F. Levine, Phys. Rev. B. 7. 2591 (1973).
b, From B.F. Levine, J. Chem. Phys., 59, 1463 (1973).
') From F. Gervais. Solid State Commun., 18, 191 (1976); I I and L refer
to the polarization directions.
The ionicities defined in this method are obtained from measuremcnts of the
interaction of electrons in the solid with incident photons. Thus they are based on
an effective dynamic charge e that differs from the static charge q by [26]:
e =q +R dq/dr
(3-6)
whcre R is the equilibrium interatomic distance, and dq/dr is the sensitivity of the
static charge transfer to small shifts in the atomic positions. The difference
bctwecn e and q arises from the fact that in the optical measurement of E,, the solid
interacts with an electromagnetic force which draws atoms from their equilibrium
positions. From the viewpoint of electrostatic interaction, the effect of this
movement is equivalent to that of placing on an unperturbed lattice an electric
dipole of magnitude c and a lenglh equaling the change in the interatomic distance.
PHYSICAL AND ELECTRONIC PROPERTIES 35
Since atoms or ions in a solid strongly interact with each other, their
movements are strongly coordinated, giving rise to group vibrations (phonons).
Therefore, it is possible to have different values of dynamic charges (Ze) for a
given solid depending on the type, direction and frequency of the vibration. The
relationship between this dynamic charge and the dielectric constants is given by
Gervais [271:
WLo and WTO are frequencies for the longitudinal and transverse mode, p is the
reduced mass of the ions, q is the dielectric constant of vacuum, and V is the molar
volume. It can be shown that Ze is the actual transverse charge of the ions within
the rigid ion model description.
Phillip's original concept has been developed for simple AB crystals. It is
later extended by Levine to compounds of other structures and stoichiometries,
including oxides, ternary compounds, and compounds containing transition metal
cations [28,29]. The ionicity reported for a number of oxides are listed in Table
3-3. By examining a large number of compounds including halides, halogenides
(sulfides, tellurides, etc.), binary oxides and ternary oxides, it is found that values
of Z/Zo, where Zo is the formal charge, is roughly linearly proportional to exp(f,)
[ 271 :
Z/Zo =0.24 (efi - e)
(3-8)
An examination of the static and dynamic ionic charges in Tables 3-1 and 3-3
suggests that the ionic charges of transition metal oxides seldom equal their formal
charges. I n fact, in most cases, the charge is about half the formal charge.
Furthcrmore, the static and dynamic charges do not differ significantly.
What are the consequences to surface chemistry and catalysis that transition
metal oxides are ionic? Qualitatively, the ionic character results in the presence of
a strong electric field that points outward from the oxide surface. The separation
of charges into cations and anions results in a strongly modulated electronic
potential on theoxide surface. These effects lead to the common phenomenon of
heterolytic dissociative adsorption of molecules. An example is shown for HZ:
(3-9)
Contrary to H adsorbed on metals, the two hydrogen atoms that are dissociatively
adsorbed are not equivalent and carry opposite charges. It is likely that they have
different reactivities. It should be noted that the charges shown in the equation do
not necessarily represent the real charges which are usually unknown.
The ionic character may also increase the sticking probability of polar
molecules, such as ammonia, water, alcohols, acids, ethers and amines. When
these molecules approach the surface, their dipole moments interact with the
electric field at the surface to orient the molecule, thus enhancing the probability of
an attractive bonding interaction.
Since coulombic interaction (that is, charge-charge interaction) is a long-
range interaction, the surface chemistry of an oxide depends not only on the nature
of the cation or anion at the immediate vicinity of a surface adsorbate, but also on
the ionicity of the rest of the oxide matrix. The consequence of this effect in dilute
solid solutions has been explored. It is concluded that the ionicity of the matrix
oxide in a solid solution affects the activation energy of catalytic reactions in
which the rate limiting step involves charge transfer between the oxide and the
surface intermediate [301. This effect is also important in determining whether
new acid sites are formed in oxide solid solutions [31]. This will be discussed in
Chapter 5.
3.3 MAGNETIC PROPERTIES OF SMALL OXIDE PARTICLES
I n some supported transition metal oxide catalysts, the oxide is present as
submicron-size crystallites. They may be so small that detection by X-ray
diffraction is difficult. Recent studies on these particles indicate that some of their
properties differ from those of the bulk oxides. One such property is the magnetic
property which has been used to identify the presence of small crystallites of
oxides and to determine their sizes.
The magnetic properties of an ion or atom are determined by the orientation
and the number of its electron spins. For transition metal oxides, the individual
electrons are so strongly correlated in their motion that the spin of an ion is better
characterized by one total spin (atomic spin) than the individual electron spins.
The atomic spins of neighboring ions may also be strongly correlated with each
other to form a spin sublattice. Depending on the magnitude, the orientation, and
the number of spin sublattices, transition metal oxides possess different internal
magnetic fields, as well as different responses to applied magnetic field.
The readers are referred to
textbooks on the subject, such as that of Cullity [32] or Morrish [33], for a more
extensive discussion. Here we shall give a very brief introduction to magnetism,
and then proceed to discuss magnetic properties of small oxide particles.
Fig. 3-1 shows the types of magnetism commonly found in transition metal
oxides, and the associated spin orientations. The temperature dependence of the
magnetic susceptibility x , which is the magnetization per unit applied field, is
shown in Fig. 3-2.
Diamagnetism is related to changes in the orbital motion of electrons that
occur when atomic systems are placed in a magnetic field. This induced motion of
electrons (or currents) is set up in such a direction as to oppose the change in the
magnetic flux, and persists as long as the magnetic field is present. The magnetic
field produced by the induced current is opposite to the applied field, and the
There are different types of magnetism.
PHYSICAL AND ELECTRONIC PROPERTIES
0
0
0
0
0
0
Diamagnetism
0
P
Antiferromagnetism
Figure 3-1 Types of magnetism in oxides.
direction.
Diamagnetic
p”
“s
Q-
ST
Paramagnetism
Ferrimagnetism
37
Direction of arrows indicates the spin
Paramagnetic
Anti ferromagnetic Ferrimagnetic
a
Figure 3-2 Temperature dependence of magnetic susceptibility for different types of
magnetism, For antifcrromagnetism. the Nee1 temperature is shown. For femmagnetisrn,
saturation magnetization 0, and the Curie temperature T, are shown.
,
38
Table 3-4 Room Temperature Magnetic Properties of Some Common
Transition Metal Oxides a
Paramagnetic Antiferromagnetic Ferrimagnetic Diamagnetic
Ti203 cr203
vo2 Mn203
vo MnO
Nd02 Mn02
FeO
a-Fe203
COO
( 3304
NiO
v203
Footnote:
a) Omitted are the ferromagnetic oxides, such as CrOz, in which there is only one
spin sublattice where the spins are all oriented in the same direction.
magnetic moment associated with the current is a diamagnetic moment.
Paramagnetism is related to the tendency of a permanent magnetic dipole to
align itself parallel to a magnetic field. In transition metal ions, the permanent
magnetic moment is associated with coupled electron spin and orbital motion of
partially filled shells. In a paramagnetic material, these permanent moments are
normally random and uncorrelated, but are aligned in an applied field. The
magnetic susceptibility decreases with increasing temperature because thermal
motion tends to randomize any spins that are aligned by the external field.
In a ferromagnetic material, theinteraction among spins is so strong that the
magnetic moments are aligned parallel to each other. Such an internal interaction
is called exchange field. However, few oxides are ferromagnetic. In a simple
antiferromagnetic material, there are two sets of strongly correlated spins that form
two spin sublattices of equal magnitude but opposite orientations. These two
sublattices cancel each other, resulting in a solid that is like a paramagnet and has
weak magnetization. Below the ordering or Ned temperature, the behavior of an
antiferromagnetic material differs from that of paramagnetic material because at
such low temperatures, the spin sublattice is so rigid that the effect of small
imperfect cancellation of spins becomes evident.
In a ferrimagnetic material, the magnitudes of the two opposing spin
sublattices are different, which result in a net sizable spin. In an applied magnetic
field, these spins align with the external field to yield a saturation magnetization
M,, which can be attained at a relatively low field of about 100 Oe. On increasing
PHYSICAL AND ELECTRONIC PROPERTIES 39
100
(0
0
X
F
8 nm
8 nm
9 nm
-
---
-.-.-
........... 12 nm
-0.-- 14 nm
- 22 nm
-x-x-400 nm
I 1 1
100 200 300
Temperature K
Figure 3-3 Temperature dependence of magnetic susceptibility of a-Fe203 of different
crystallite sizes. (From J. Phys. SOC. Japan, 17, supplement B-1, 690 (1962). copyright
Physical Society of Japan).
temperature, thermal fluctuation randomizes the spin until the Curie temperature is
reached when the spins are totally random that the response of the material is like
that of a paramagnet. Table 3-4 lists the magnetic behavior of some common
transition metal oxides.
The behavior of small oxide crystallites may differ from the bulk behavior
described above because of the large contribution from ions at the surface. The
different magnetic and electric fields experienced by ions in the surface may result
in canting and pinning of surface spins. The surface ions may have different
atomic spins than the bulk ions if they are in a different oxidation state.
Adsorbates may also affect the magnetic behavior.
The magnetic susceptibilities of a number of antiferromagnetic oxides, 01-
Fe2O3, NiO and COO have been measured at different temperatures for different
crystallite sizes [34-391. Fig. 3-3 shows the data for a-Fe203. The large
crystallites (> 14 nm) behave like typical antiferromagnetic materials. The
magnitude of the magnetic susceptibility is very small, and it decreases slowly with
increasing temperature up to about 260K. For the small crystallites, the magnetic
Susceptibility first increases and then decreases with increasing temperature. This
is a typical behavior for superparamagnetic particles. Furthermore, the magnitude
of thc low temperature susceptibility increases with decreasing crystallite size.
This is also demonstrated in Fig. 3-4 which shows the magnetization as a function
of applied field for small crystallites of a-F@03 supported on Si02 [401. The
40
o” 15
N
Y
c
W
5 5
a
I
0
10 2 0 30 40 50
MAGNETIC FIELD KCe
Figure 3-4 Magnetization at 1.7K as a function of applied magnetic field strength: a. 2.5
nm a-FezO,/SiOz; b. 7.5 m a-FezQ/SiOz; c. 9.5 nm a-Fe,Q/Si02; d. 14.5 m a-
Fq@/SiOz; e. 25 m a-Fe2Q. (From J. Phys. Chem., 88, 2525 (1984). copyright Amer-
ican Chemical Society).
magnetization increases with decreasing crystallite size. The shape of the
magnetization curves follows the behavior for superparamagnetic particles, and
can be fitted satisfactorily with the classical Langevin equation:
(3-10)
where M is the instantaneous magnetization, which is the value at the applied field,
Ms is the saturation magnetization, which is the value at an infinitely large applied
field, p is the magnetic moment per particle, H is the applied field, k is the
Boltzmann constant, and T is the temperature.
A quantitative theory to explain the increase in magnetic susceptibility with
decreasing particle size is not available. It has been suggested by Nekl [41] that
spins which lie near the surface tend to orient parallel to the surface. For small
particles, the number of surface spins is a large fraction of the total number of
spins. Since the surface spins have different orientations from those of the bulk
spins, cancellation of the antiparallel spins is no longer perfect. As the particle
size decreases, the contribution of the surface relative to the bulk increases. Thus
the magnetic susceptibility increases.
Let us return to the temperature variation of the magnetic susceptibility for
large particles of a-Fe203 in Fig. 3-3. These particles behave like typical
antiferromagnetic material until a temperature of about 250 K when the
susceptibility suddenly increases before it decreases again on further increase in
temperature. The temperature at which this phenomenon occurs is called the
PHYSICAL AND ELECTRONIC PROPERTIES 41
Table 3-5 Morin Transition Temperature and Lattice Dilation of a-Fe203
(From J . Phys. SOC. J apan, 24, 23 (1968), copyright Physical Society of
J apan).
cr-Fe203 Transition
Particle Temp Lattice Constants
Size (nm) TM (K) a (1) c (1)
80 245 5.0345 13.749
26 227 5.0365fD.0007 13.7901tO.OOO7
20 120 5.0370fD.0007 13.79020.0007
17 5.03739.0007 13.805+0.0007
14 5.04049.0 1 13.83920.01
Morin transition temperature. The increase in susceptibility for a-Fe203 just above
this transition temperature is due to the flipping of the magnetically ordered spin
from an orientation parallel to the c-axis to parallel to the c-plane (basal plane) of
the crystal. The crystal then changes from antiferromagnetic to weakly
ferrimagnetic. For small a-Fe203 crystallites, however, this transition appears to
be absent. This effect has been confirmed by magnetization measurements
[35,36,391 such as those of Fig. 3-3, and by Mossbauer spectroscopy [42,43] which
makes use of the fact that on going from the weakly ferrimagnetic to the
antiferromagnetic state, there is a decrease in the magnetic dipolar field and a
decrease in the magnitude of the magnetic hyperfine splitting in the Mossbauer
spectrum. From these measurements, it has been found that the Morin transition
temperature decreases with decreasing crystallite size until it disappears for very
small sizes (see Table 3-5). The critical size for the disappearance of the transition
temperature has not been firmly established owing to the difficulties in accurate
size determination. One
explanation for this behavior is that the magnetically coupled spins in small
crystallites fluctuate in the basal plane strongly enough that they are no longer
oriented to the c-axis even at low temperatures. Another explanation is that the
spins are pinned at the surface. For small crystallites in which the surface spins
dominate, the magnetization vector does not change direction when the
temperature is changed.
Concurrent with the lowering and disappearance of the Morin transition
temperature, the lattice of small a-Fe203 crystallites is found to dilate [39,43].
The extent of dilation increases with decreasing crystallite size as is shown in Table
3-5. The lattice dilation is probably homogeneous [39,43-451, and results in
clearly observable shifts in the x-ray diffraction peaks. This dilation along the
a-axis may contribute significantly to the lowering of the Morin transition
temperature through the change in the dipolar magnetic field. It should be noted,
For a-F%03, it is estimated to be about 20 nm.
42
Table 3-6 Crystallite Size Dependence of Magnetic Hyperfine Field
Compound Temp (K) Crystallite Hyperfine field (KOe)
size (nm) A site B site
y-Fe203a 77 9.3 sphere 483 508
17.5 sphere 489 513
30.0 sphere 497 517
800 length acicular 508 525
6/1 shape ratio
a-Fe2O3b 296 bulk
83 bulk
296 18
80 18
518
542
503
527
Footnotes:
a) From K. Haneda. and A. Momsh, Phys. Lett.. 64A, 259 (1977).
b, From W. Kiindig, H. Bommel, G. Constabaris. and R. Lindquist, Phys.
Rev., 142, 327 (1966).
however, that this phenomenon of lattice dilation may not be general, and is not
observed for y-Fe203 over the crystallite size range from 9.3 nm to over a few
hundred nm [46].
Another effect observed in small magnetic crystallites is the decrease of
magnetic hyperfine field with decreasing crystallite size. The magnetic hyperfine
field is the magnetic field experienced by the nuclei in an oxide particle. The
nuclear magnetic moment interacts with this field, and the interaction can be
detected by various spectroscopic techniques, especially Mossbauer spectroscopy.
Table 3-6 lists some illustrative data for a- and y-Fe203. There have been three
proposals as to the origin of this decrease. The first one, based on a decrease in the
Curie or Ned temperature with decreasing crystallite size can now be discounted.
Magnetization measurements on small crystallites do not detect changes in these
temperatures. The second interpretation assumes that surface ions have a smaller
hyperfine field than the ions in the bulk. This effect has now been discounted also
by Haneda and Monish [471, at least for y-FezO3. Haneda and Momsh have
prepared y-Fe03 samples with a surface coating enriched in s7Fe. The magnetic
hyperfine field of this enriched sample is found to compare well with the samples
without enrichment. This suggests that the magnetic hyperfine field of the ions at
the surface is the same as the bulk ions.
The third interpretation is that of Mdrup and Topsde [481 who suggest that at
temperatures below the superparamagnetic blocking temperature, thermally
excited oscillations of the magnetization about an energy minimum reduce the
PHYSICAL AND ELECTRONIC PROPERTIES 43
average magnetization and thus the magnetic hyperfine field. The amplitude of
the thermal oscillation depends on the magnitude of the energy barrier for flipping
of the magnetization vector from one easy direction to another, which is expressed
as a product of the anisotropy constant K and the volume of the crystallite. For
small oscillation amplitudes, the hyperline field Hhr(V,T) for a crystallite of
volume V at temperature T is:
where k is the Boltzmann constant. The theory predicts that Hhf decreases linearly
with increasing temperature, and the rate of decrcase depends inversely on the
crystallite size. Furthermore, Hhf is independent of the crystallite size at 0 K.
These predictions have been separately confirmed for Fe304 [48] and 'y-Fe203
crystallites [47].
Although the magnetic hyperfine field of the surface ions is the same as the
bulk ions, there is evidence that under an applied magnetic field, the canting angle
of the surface spins is substantially different from that of the bulk ions. This is the
origin of the much enhanced 2,5 peak in the Mossbauer spectrum of y-Fez03 [49].
Together with the variation in magnetic hyperfine field, the anisotropy
constant also depends on the crystallite size. Table 3-7 shows that the
anisotropy constant K decreases sharply from bulk material to 10 nm size
crystallites. As yet the origin of this decrease is not known. The effect of
such a decrease is that the rate of decrease of the energy barrier for the
flipping of the magnetization vector in a particle and the temperature at which
the particle becomes superparamagnetic (the superparamagnetic blocking
temperature) decrease faster than the volume V of the crystallite, since both of
these are proportional to KV.
3.4 QUADRUPOLE SPLITTINGS OF SURFACE IONS
I t has been observed in Mossbauer spectra of small iron oxide crystallites
that the quadrupole splittings of surface ions are different from the bulk ions.
This is not surprising because the quadrupole splittings are determined by the
electric field gradient at the nucleus, and it is expected that such a gradient at
the surface is different from in the bulk. Fig. 3-5 shows the behavior of
small iron oxide crystallites supported on SiOz [50]. In the fully oxidized
form, the spectrum shows a superparamagnetic doublet due to Fe3+ ions
(curve a). After reduction (curve b), the spectrum consists of two sets of
doublets due to Fe2+ions. The inner doublet shows a quadrupole splitting of
0.91 mm s-l, and the outer doublet, a quadrupole splitting of 1.74 mm spl. I t
is common to assign the outer doublet to Fez+ions of higher coordination
such as those octahedrally coordinated by oxygen ions in the bulk, and the
inner doublet to Fez+of lower coordination, such as those in the surface [50-
521. The assignment is supported by the fact that the inner doublet can be
converted to the outer doublet by adsorption of NH3, CH30H [51], pyridine
44
Table 3-7 Dependence of Anisotropy Constant K on Crystallite Size
Compound Crystallite K erg/cm3 Ref.
size (nm)
Fe3 0 4 6 1.2-1.4 x lo6
10 0.85-0.95 x lo6
12 0.85-0.90 x lo6
large 1.1 x 103
?I-Fe203
6 8 x lo5
95.5 1.2 x 106
epitaxially grown 4.6 x 104
12 3 x 105
single domain powder 3 104
cx-F%03 10 3.5 x 105
12 5-6 x 105
13-18' 4-7 x 104
f
g
h.i
* These values may not beaccurate, see ref. f.
References:
a) L. Bickford, J . Brownlow, and R. Penoyer. Proc. Inst. Elect. Eng..
b) M. Boudart, A. Delbouille, J . Dumesic, S. Khammouma, and H. Topsde,
c) J . Coey, and D. Khalafalla, Phys. Stat. Sol. (A), 11, 229 (1972).
d) A. Morrish, and E. Valtyn, I. Phys. SOC. Jpn.. 17, suppl. B1, 392. (1962).
e) H. Takei, and S , Chiba. J . Phys. SOC. J pn. 21, 1255 (1966).
f) J . Amelse, K. Arcuri, J. Butt, R. Matyi, L. Schwartz, A. Shaxpiro, J .
g) S . Mdrup, and H. Tops&, Appl. Phys., 11, 63 (1976).
h) W. Kiindig, H. Bommel, G. Constabaris, and R. Lindquist, Phys. Rev.,
i ) W. Kiindig, K. Ando, R. Lindquist, and G. Constabaris, Czech. J . Phys.
B104, 238 (1957).
J . Catal., 37, 486 (1975).
Phys. Chem., 85, 708 (1981).
142, 327 (1966).
B17, 467 (1967).
[50], NO [52], CO [53], and H2 0 [54]. It is apparent from these examples
that detecting the changes in quadrupole splittings of surface ions on
adsorption of molecules is one method to investigate the nature of the
adsorption sites.
PHYSICAL AND ELECTRONIC PROPERTIES 45
- 4 - 2 0 2 4
VELOCI TY ( r n r n l s )
Figure 3-5 Room temperature Mossbauer spectra for 0.5 wt.% Fe/SiOz. a. After reduction
in H, at 673K followed by oxidation in 0 2 at 423K; b. After reduction in H2 at 498K; c.
After reduction in Hz at 673K. (From J. Catal., 101, 103 (1986), copyright Academic
Press).
It might be expected that the electric field gradient due to the iorricity of the
oxide matrix is larger at the surface than in the bulk, and would lead to a larger
quadrupole splitting for the surface Fez+ions than the bulk ions, which is contrary
to what has been observed. This is due to the fact that the couloumbic field from
the ions in the oxide matrix is only one contribution to the electric field at the
nucleus. The smaller quadrupole splitting for surface Fez+ions than bulk Fez+
ions has been interpreted as due to the opposing effect of larger crystal field
gradicnt and smaller d electron field gradient at the surface than thc bulk
[52,56,57]. Inner and outer doublcts of Fez+ions have been observed on many
samples of silica-supported small crystallites of reduced iron oxide, although thc
magnitude of the quadrupole splitting differs somewhat from sample to sample.
The prcsencc of inner and outer doublcts has also been observed using MgO, y-
A1203, and Ti02 as supports [%I.
Clearly distinguished inncr and outer doublets of Fe3+ions have not bccn
rcportcd. However, it is well established that the average quadrupole splitting of
46
Table 3-8 Crystallite Size Dependence of Quadrupole Splitting in a-Fe203 at
298K. (From Phys. Rev., 142, 327 (1966), copyright American Physical Society).
Size (nm) Q.S. mms-1
<10
13.5
15.0
18.0
0.98
0.57
0.55
0.44
Fe3+in a crystallite increases with decreasing crystallite size, as is shown in Table
3-8. This increase has been explained by the larger asymmetry in the environment
of surface ions than bulk ions. Some researchers have attempted to fit their
Mossbauer spectra of small crystallites containing Fe3+ions using two sets of
peaks of different quadrupole splittings. The set with a larger quadrupole splitting
is assigned to the surface ions [56,58], which is supported by the observed decrease
in the quadrupole splitting on adsorption of water, methanol, and ammonia [59].
3.5 SURFACE ELECTRONIC STRUCTURE
Knowledge of the detailed surface electronic structure is critical in the
understanding of the chemisorptive and catalytic properties of oxides. The bulk
electronic structures have been studied for a number of oxides [60]. Studies on
surfaces have been concentrated on the detection of electronic states not found in
the bulk that are generated by the presence of the surface. These states are called
surface states. The energy of the surface states of interest in catalysis commonly
lies near the Fermi energy of the solid (or valence states). These surface states are
either partially filled with electrons so that they can both donate and accept
electrons from the molecules interacting with the surface, or close enough to the
filled valence band (or empty conduction band) such that together, they provide a
pair of states to accept and donate electrons to the interacting molecules
simultaneously. Consideration of electron bands in the solid is also important in
photo-enhanced adsorption, desorption, and catalysis. These photo-assisted
processes as well as a short description of electronic bands of oxides will be
discussed in Chapter 14. The readers are referred to standard textbooks in solid
state physics for more in-depth discussions.
The nature and energy of any surface state depend on, among other factors,
the ionicity of the oxides and the position of the ions. The major contributions to
these factors are from ions in the surface region. Therefore, it is expected that
surface structural rearrangements could lead to substantial changes in the surfxe
electronic structure [61,62].
PHYSICAL AND ELECTRONIC PROPERTIES 47
Another effect expected for ionic surfaces is the reduction of the ionic charges
of the surface ions. This results from the downward shift in energy of the surface
orbitals compared to the corresponding bulk orbitals and the enhanced covalency
of the cation-anion bond, as well as the polarization of the surface orbitals by the
surface electric field. The surface-induced changes in the electronic properties are
strongly localized in the outer few layers of the surface regions.
For oxides that are predominantly covalent, the surface coordinative
unsaturation results in the formation of valence orbitals projecting from the surface
that are from the outermost ions (sometimes being referred to as dangling bonds)
[63]. There are two sets of such orbitals. One set is empty and is located mostly
at the cation, and the other is filled and is located at the anion. The separation in
energy of these two sets increases with increasing ionicity of the solid.
The electronic structures of some oxides have been studied by electron
spectroscopies (UPS and ELS). For surfaces of oxides with empty d bands, such as
stoichiometric Ti02 (loo), (001) and (110), SrTiO3 (100) [l-31 and ZnO [@I, no
intrinsic surface states are identified within the bandgap. Similar results have been
observed for W0 3 [65] and Moo3 (010) [66] surfaces. The surface states of these
oxides are close to the conduction or valence bands. For example, the surface states
of ZnO are at -2 eV and -5 eV below the top of the valence band 185,861.
Loss of surface oxygen ions in these transition metal oxides with empty d-
bands causes development of filled electronic states in the band gap. These states
are detected by UP S as emission above the valence band emission (see Fig. 3-6)
[67,68]. It is interesting to note that the intensity of this bandgap emission
decreases when the oxide is annealed in vacuum. The decrease is due to reoxidation
of the surface by oxygen diffusion from the bulk which is taking place faster than
reduction by thermal desorption of oxygen. In a similar manner, this band gap state
can be depopulated by adsorption of O2 [65,67,69,70]. For oxides with empty d
bands, the bandgap surface state has been attributed to the cations at a lower
oxidation state than the bulk, such as Ti3+for Ti02 and SrTi03.
Oxides with partially filled d-bands, such as Ti2O3, V2O3. a-Fe203 [70], Ti 0
[711, MnO [72], FeO [72,73], COO [72,74], NiO [72,75], and CuO [76] have been
investigated. The d states of the cations overlap significantly with the 0 2p bands.
This makes it difficult to detect the presence of any surface states. Deconvolution
of the experimental spectra shows that the bands are derived primarily from the
metal 3d and oxygen 2p levels. The density of states of the 3d band shows two
maxima near the Fermi level, and becomes more pronounced as the number of d
electrons is increased. The absence of large differences between the U P S spectra
of the surfaces of these compounds and the bulk band structures implies that their
surface electronic structures do not differ significantly from the bulk.
The effect of surface roughness has been investigated on Ti02 [77,78]. The
surface states on the atomically rough surface are found to lie deeper in the
bandgap than on the smooth surface. This could result in enhanced reactivity of
the rough surface as compared to the smooth surface.
Most of the studies todate concentrate on studying the surface electronic
structures of the oxides. Only a few have been reported to study the interaction of
molecules with these surfaces. Therefore, there is very limited knowledge of the
48
-1 2 -8 -4 Ef=O
El ect r on Bi ndi ng Energy eV
Figure 3-6 UPS spectra of the clean ordered SrTiQ (1 11) surfaces taken at: a. 27; b. 300; c.
6000C. (From Phys. Rev. B.. 17. 4942 (1978). copyright American Physical Society).
electronic structure of the surface-molecule bonds. The formation of such bonds
is essential in surface chemistry and catalysis, and it requires that the molecule can
physically approach the adsorption site (steric requirement), and surface orbitals of
the appropriate energies and symmetry are available. Since information on the
surface orbitals are not readily available, researchers in this field have made
significant use of the steric requirement. This has led to the concept of
coordinative unsaturation of surface ions, which will be discussed in the next
chapter.
3.6 SURFACE VIBRATION
The lattice vibration of surface atoms which is called the surface optical phonon
vibration modes of some transition metal oxides have been studied using high
resolution electron energy loss spectroscopy (HREELS). These oxides include NiO,
TiOz, ZnO, and SrTi03, all of which exhibit phonon modes that strongly couple with
the incident electron beam. The strong coupling makes it readily possible to detect
not only the fundamental phonon modes but also the overtones. Fig. 3-7 shows a
HREEL spectrum of a ZnO (10iO)surface which possesses a fundamental phonon
mode at 68.8 meV [79]. Fig. 3-8 shows that for a NiO (001) surface whose
fundamental phonon mode is at 69.5 meV [80]. The overtones in both spectra arc
clearly visible. For the large ordered surfaces studied, the surface phonon vibrations
generally lie in the range of 40-100 meV (about 320-800 cm-’), and the strong
PHYSICAL AND ELECTRONIC PROPERTIES 49
286 K
h
127 K
Energy Loss meV
Figure 3-7 Energy-loss sepctrum of 7.5-eV electlons after specular reflection from the
(1070) surface of ZnO. (From Phys. Rev. Lett., 24, 1416 (1970), copyright American
Physical Society).
overtones are in the region where vibrations involving surface adsorbates appear.
This makes it difficult to identify adsorbates.
The frequencies of the surface phonon modes can be described by classical
analyses that apply well to cases where the vibrational wavelength is much larger
than lattice parameters @I ]. It has been shown that the surface phonons that are
excited most strongly in HREELS have small wavevectors parallel to the surface
and long characteristic penetration depths [82]. Thus the energy loss spectra are
rather insensitive to details of the surface structure.
Small differences are observed in the phonon frequencies of different ZnO
surfaces. The observed values are 68.8 meV for the (lOi0) surface, and 67.3 meV
for Lhe(0001) and (000i)surfaces [79]. These values are higher in energy than the
infrared-active optical bulk modes for which the displacement of ions is
pcrpcndicular to the surface. They agree well with the frequencies calculated
from the classical treatment of ionic vibrations in the continuum approximation.
The fundamental modcs of the NiO (100) and (111) surfaces are at about 69.5
mcV [80]. For the SrTi03 (100) surface, surface optical phonon modes at 57 meV
(460 cm-') and 92 meV (740 cm-') have been observed, which are just below the
bulk longitudinal modcs at 474 and 788 cm-' [831.
Recently, a Fourier transform technique has been developed to remove the
combination and overtone structures i n HREEL spectra and retain only the loss
slructure of the fundamental modes [84]. Using this technique, the energy loss
spcclrum of H20 adsorbed on a SrTi03 (100) surface has been observed.
50
-200 0 200 400
Energy Loss meV
Figure 3-8 Specular electron energy loss spectrum of a NiO (001) surface.
Sci.. 152/153, 784 (1985). copyright Elsevier Scientific Publ.).
(From Surf.
REFERENCES
1. R. A. Powell, and W. E. Spicer, Phys. Rev. B. 13, 2601 (1976).
2. V. E. Henrich. G. Dresselhaus, and H. J . Ziegler, J . Vuc. Sci .
3. V. E. Hcnrich, and R. L. Kurtz, J . Vac. Sci. Technof., 18, 416 (1981);
4. W. Gopel. J . Vuc. Sci . Technof., 15, 1298 (1978).
5. L. E. Firment, and A. Ferretti, Surface Sci .. 129 155 (1983).
6. C. Angeletti, A. Chino. V. Indovina. F. Pepe, and M. Schiavcllo,
7. J . Haber, in Surface Properties and Catalysis by Nonmetals”. edited
Technof.. 15, 534 (1978); Phys. Rev. B. 17, 4908 (1978).
Phys. Rev. B, 23, 6280 (1981).
&it. Phys. Chern., Ne w Fofge. 122. 237 (1980).
by J. P. Brunelle, B. Delmon. and E. Deronane, D. Reidel Publishing
Company, 1983, p. 1.
8. M. C. Kung and H. H. Kung, Surface Sci., 104, 253 (1981).
9. Y. M. Gross, and D. R. Pyke, J . Catalysis, 58, 61 (1979).
10. S. Y. Liu, and H. H. Kung. Surfuce Sci ., 110, 504 (1981).
11. D. van Oeffclen, J. van Hoeff, and 0. Schuit, J . Cutuf., 95, 84 (1985);
I. Matsurra, R. Schut. and K. Hirakawa, J . Catul., 63, 152 (1980).
12. S. Sasaki, K. Fujino, and Y. Takeuchi. Proc. Japun Acad., 55 ser R, 43 (1979).
13. S. Sasaki, K. Fujino, Y. Takeuchi, and R. Sadanaga, Actu Cryst.,
14. G. Vidal-Valata, J . P. Vidal, and K. Kurki-Suonio, Actu Crysf., A34, 594 (1978).
A36, 904 (1980).
PHYSICAL AND ELECTRONIC PROPERTIES 51
15. M. Morinaga, and J. B. Cohen. Acta Cryst. A32. 387 (1976).
16. J . Q. Broughton, and P. S . Bagus, J . Electron Spectro. Related Phenom.,
17. K. Sieghban, C. Nordling, A. Fahlman, R. Nordberg, K. Hamrin, J . Hedman.
20, 261 (1980).
G. J ohannson, T. Bergmark, S. E. Karlsson, I. Lundgren, and B. Lingberg,
"ESCA: Atomic, Molecular, and Solid State Structure Studied by Means of
Electron Spectroscopy". Nova Acta Regiae SOC. Sci., Upsalieusis Ser. IV, 1967.
18. P. H. Citrin, and T. D. Thomas, J. Chem. Phys., 57, 4446 (1970).
19. J . Q. Broughton, and P. S. Bagus. J. Electron Spectro. Related Phenom.
20. F. Bechstedt, Phys. Stat. Sol. B, 91, 167 (1979).
21. S. W. Gaarenstroorn, and N. Winograd, J . Chem. Phys. 67, 3500 (1977).
22. T. Dickinson, A. F. Povey, and P. M. A. Sherwood. J . Chem. SOC. Faraday
23. L. Pauling, "The Nature of Chemical Bond", Cornell University Press,
24. R. T. Sanderson, J . Amer. Chem. SOC., 74, 272 (1952); Science, 114. 670 (1951).
25. J . C. Phillips, Phys. Today, 23, 23 (1970).
26. J . P. Suchet, J. Electrochem. SOC., 124, 30C (1977).
27. F. Gervais, Solid State Commun., 18, 191 (1976).
28. B. F. Levine, Phys. Rev. B, 7, 2591 (1973).
29. B. F. Levine. J. Chem. Phys., 59, 1463 (1973).
30. H. H. Kung, J. Catal., 37, 387 (1982).
31. H. H. Kung, J . Solid State Chem.. 52, 191 (1984).
32. B. Cullity, "Introduction to Magnetic Materials", Addison-Wesley, 1972.
33. A. Monish, "The Physical Principles of Magnetism", Wiley, New York, 1965.
34. T. Takada, and N. Kawai, J. Phys. SOC. Japan, 17 supplement B-1, 691 (1962).
35. K. M. Crecr, J. Phys. SOC. Japan, 17 supplemcnt R-I , 690 (1962).
36. Y. Bando. M. Kiyama, N. Yamamoto, T. Takada, T. Shinjo, and H. Takaki,
37. G. J . Muench, S. Arajs, and E. Matijevic, J. Appl. Phys., 52, 2493 (1981).
38. W. J . Schuclc, and V. D. Deetsneek, J . Appl. Phys., 33, 1136 (1962).
39. N. Yamamoto, J. Phys. SOC. Japan, 24, 23 (1968).
40. F. Hong, B. Yang, L. Schwartz, and H. H. Kung, J. Phys. Chem., 88, 2525 (1984).
41. L. Neil, Compt. Rend. 252, 4075; 253, 9; 253, 203 (1961).
42. W. Kundig, H. Bommel, G. Constabaris, and R. H. Lindquist, Phys. Rev.,
43. R. C. Niningcr, J r., and D. Schroeber. J. Phys. Chem. Solidr. 39, 137 (1978).
44. D. Schroeber, and R. Niningcr, J r., Phys. Rev. Lett., 19, 632 (1967);
D. Schrocber, Phys. Leff., 27A. 507 (1968).
45. S. W. Marshall. and R. M. Wi l eni kk, Phys. Rev. Left, 16. 219 (1966).
46. K. Haneda, and A. H. Momsh, Solid Sfate Commun., 22, 779 (1977).
47. K. Haneda, and A. H. Momsh, Phys. Lett., 64.4, 259 (1977).
48. S. Mqhp, and H. Topsde, Appl . Phys., 11, 63 (1976).
49. A. H. Momsh, K. Hancda, and 1'. J. Schurer. J. Phys. Collngue C6,
20, 127 (1980).
Trans. I, 72. 686 (1976).
Ithaca, N.Y., 1962.
J. Phys. SOC. Japan, 20, 2086 (1965).
142, 327 (1966).
supplement 12. C6-301 (1976).
50. G. Connell. and J . Dumesic, J. Catal., 101, 103 (1986).
51. M. Hobson. J r., and H. Gager, J. Colloid Interface Sci., 34, 357 (1970).
52. S. Yuen. Y. Chen, J . E. Kubsh, J . A. Dumesic, N. Topsde, and H.
53. B. Claussen, S. M$rup, and H. Topsde. Surf Sci., 106. 438 (1981).
54. H. Gager. J. Lefelhocz, and M. Hobson, Jr.. Chem. Phys. Lett., 23, 386 (1973).
55. G. Connell, and J . Dumesic. J. Catal.. 102, 216 (1986).
56. G. B. Raupp, and W. N. Delgass, J. Cafal., 58. 337 (1979).
57. R. Ingalls, Phys. Rev., 133, 787 (1964).
58. W. Kiindig, K. J . Ando, R. H. Lindquist, and G. Constabaris. Czech. J . Phys.,
59. H. M. Gager. M. C. Hobson, and J . F. Lefelhocz. Chem. Phys. Lett., 15, 124 (1972).
60. D. W. Bullett, in "Surface Properties and Catalysis by
Tops+, J . Phys. Chem.. 86, 3022 (1982).
B17,467 (1967).
Nonmetals", edited by J. P. Bonnelle, B. Delmon and E. Derouane,
D. Reidel Publishing Company, 1983, p. 47.
61. M. Tsukada, H. Adachi, and C. Satoko, Prog. Surface Sci., 14. 113 (1983).
62. I. Ivanov, and J . Pollmann, Phys. Rev. E, 24, 7275 (1981).
63. M. Tsukada. and T. Hoshino, J. Phys. SOC. Japan, 51. 2562 (1982).
64. W. Gopel, J . Pollmann, I. Ivonav, and B. Riehl, Phys. Rev. E, 26, 3144 (1982).
65. R. D. Bringans. H. Hochst. and H. R. Shank, Phys. Rev. E, 24. 3481 (1981).
66. L. E. Firmenf and A. Ferretti, Surface Sci., 129, 155 (1983).
67. V. E. Henrich, hog. Surface Sci., 9, 143 (1979).
68. V. E. Henrich, Prog. Surface Sci., 14, 175 (1983).
69. M. A. Langell, and S. L. Bernasek, Prog. Surface Sci., 9, 165
70. S. Ferrer, and G. A. Somorjai, Surface Sci., 94.41 (1980);
71. V. Henrich. H. Zeiger, andT. Reed. Phys. Rev. E , 19. 4121 (1978).
72. D. Eastman, and J. Freeouf, Phys. Rev. Lett.. 34, 395 (1975).
73. C. Brundle, Surface Sci., 66, 581 (1977).
74. Y. J ugnet. and T. Duc, J. Phys. Chem. Solid, 40, 29 (1979).
75. G. Wertheim, and S. Hufner, Phys. Rev. Lett., 28, 1028 (1972).
76. C. Benndorf. H. Caw. B. Egert, H. Seidel. and F. Thieme, J.
Electron Spect. Rel. Phenom., 19, 77 (1980).
77. R. B. Kasowski, and R. H. Tait, Phys. Rev. E. 20. 5168 (1979).
78. M. Tsukada, C. Satoko. and H. Adachi, J . Phys. SOC. Japan, 47, 1610 (1979).
79. H. Ibach, Phys. Rev. Lett., 24, 1416 (1970).
80. P. Cox, and A. Williams, Surface Sci., 1521153, 791 (1985).
81. R. Fuchs, and K. Klicwer. Phys. Rev., 6, A2076 (1965).
82. H. Liith, Festk&perprobleme. 21, 117 (1981).
83. A. Baden, P. Cox, R. Egdell, A. Orchard, and R. Willmcr. J. Phys.
84. P. Cox, W. Flavell, A. Williams, and R. Egdell. Surface Sci., 1521153, 784 (1985).
85. R. DOm, H. Luth. and M. Ruchel, Phys. Rev., B16, 4675 (1977).
86. W. Gopcl. J. Pollmann, I . Ivanov, and €3. Reihl, Phys. Rev., B26, 3144 (1982).
(1979); Phys. Rev. E, 23, 1584 (1981).
J . Appl. Phys., 52, 4792 (1981).
C, 14, L1081 (1981).
Chapter 4
SURFACE COORDINATIVE
UNSATURATION
4.1 FORMATION OF SURFACE COORDINATIVE
UNSATURATION
It is generally accepted that surface coordinative unsaturation is important in
surface chemistry. This concept is analogous to that in coordination chemistry
and arises from the fact that because of steric and electronic reasons, only a limited
number of ligands or nearest neighbors can be within bonding distance of a metal
atom or ion. I n most transition metal oxides, the oxygen anions in the bulk form
close-packed laycrs and the metal cations occupy holes among the anions as
described in Chapter 2. In this picture, since the bulk oxide ions are as densely
packed as possible, the oxide ion ligands around a metal cation are thought to have
saturated the coordination sphere of the bulk cation, that is, the bulk cation is
coordinatively saturated.
We have seen in Chapter 2 that in the formation of a surface by cleaving an
oxide crystal, metal-oxygen bonds have to be broken. Therefore the surface
anions and cations have fewer numbcrs of nearest neighbors than the corres-
ponding ions in the bulk. These surface anions and cations are coordinatively
unsaturated (cus). I n most instances, coordinative unsaturation results in ions that
are active in bonding with adsorbates. However, as will be discussed later, not all
surface coordinativcly unsaturated ions are necessarily active and have a high
tendency to form chemical bonds with adsorbates.
There are two approachcs to picture the formation of surface coordinative
unsaturation depending on the way the surface is prepared. The fi st approach
applies to surfaces of microcrystalline samples prepared from aqueous solutions.
The second applies to surfaces formcd from cleaving large single crystal samples.
An oxide or hydrous oxidc sample prepared by precipitation from an aqueous
solution is formed by condensation and polymerization of hydroxylated mctal ions.
For example, a M(II1) metal ion existing as a monomeric unit possesses a saturated
coordination of three hydroxyl and three watcr ligands. Condensation of two
53
54
hydroxyl groups from two different monomeric units links the monomers with a
bridging oxygen to form a dimer. Condensation of more than one pair of hydroxyl
is possible and the dimeric unit has more than one bridging oxygen ion. Bridging
by hydroxyl ions is also possible. These units are schematically shown below:
Monomer
Dimers
Coordinatively unsaturated
sites
Hydroxylated Surface Partially Dehydroxylated Surface
When condensation occurs between many diffcrcnt monomeric units, which
is orten promoted by drying at elevated temperatures, a three-dimensional network
is formed. Depending on the metal and the drying condition, the network may be
amorphous, semicrystalline, or crystalline. A possible configuration of a
hydroxylatcd surface of a network is shown above. In this schematic drawing, thc
number of ligands around a metal ion is set to remain at six, but the number of
ligands for the oxygen ions increases to four in the bulk and three i n the surface.
Other situations are possible, and the coordination number of the metal ions may
change as the solid is formed. Dchydroxylation of this surface may take place
between two adjacent hydroxyl groups, and the surface mctal ions involved would
be coordinated to only five oxygen ions. They bccome coordinatively
unsaturated. The surface oxide ions generated are also coordinativcly unsaturatcd
and have lower coordination numbers than bulk oxide ions or oxide ions of the
COORDINATIVE UNSATURATION 55
surface hydroxyls. Often the M"+(cus) site bchavcs like a Lewis acid, and the
02-(cus) ion is more basic than the bulk ions. Such an acid-base pair site
participates in hcterolytic dissociative adsorption. More extensive coordinative
unsaturation is possible if more dchydroxylation takes place, or if surface lattice
oxygen is rcmoved by reduction. Such a process of dchydroxylation has been
used by Burwell, et al. [2] to describe the formation of a partially dchydroxylated
chromia surface which has surface ions that are coordinatively unsaturated by one
or two ligands.
If dehydroxylation occurs randomly bctwccn pairs of hydroxyl groups, it
would be difficult to achieve complete removal of surface hydroxyl groups. Evcn
after high temperature evacuations, isolatcd surface hydroxyl groups are often
present that show a sharp IR absorption band at high frequencies (?3700 cm-I).
As an example, IR bands of surface hydroxyl groups have bcen identified on
anatase at 3636, 3654, 3672, and 3707 cm-'. The intcnsitics of thcse bands
decrease with increasing evacuation tcrnperature. The rate of decrease is the
fastcst for the lowest frcquency band, whilc thc highest frcqucncy band is almost
unchanged [ 11.
The second approach to picture the formation of surface coordinative
unsaturation is by clcaving a single crystal. Commonly one swts with an
clcctrically ncutral singlc crystal whose faces are bound by nonpolar surfaces. If
thc crystal is bound by polar faces, thcsc faces nccd to be populated with ion
vacancies, hydroxyl groups, or other species so that the crystal does not posscss
any pcriodic dipole momcnt.
Once the crystal is dcfined, it is cleaved (conccptually) into two halves along
the dcsircd direction to expose the planes of intcrcst. The common guidclincs for
the partition of ions along the clcavage planc arc: (1) it rcsults in two half-
crystals that are electrically ncutral; (2) it minimizes the total amount of
coordinativc unsaturation as much as possiblc; (3) it avoids the formation of ions
with an unusually large dcgrce of coordinative unsaturation; and (4) it involves the
brcaking of as small a numbcr of bonds as possible.
Figurc 4-1 shows modcls of three ideal and ordcrcd Ti02 and Ti203 surfaces.
The Ti02 surfaces would be ful l y oxidizcd surfaces cxccpt for the anion vacancics
shown i n Fig. 4-l a and b. If thc anion vacancics arc fillcd by oxidc ions, thcsc
surfaces can be generated theoretically by fracturing a Ti02 singlc crystal along thc
dcsircd dircction, and partitioning the atoms along thc clcavagc planc equally
bctwcen thc two parting faces. I t should be cmphasizcd that thc modcls rcprcscnt
highly ordcrcd surfaccs, and such ideal surfaccs arc not cxpcctcd to cxist ovcr
large macroscopic surfaces in rcality. For cxamplc, the Ti02 (110) surfacc is
pictured as one i n which pcrfcct rows of oxygcn ions sit on altcrnatc rows of Ti
ions in thc surface plane. Although such a configuration minimizes the total
numbcr of coordinative unsaturation and thc number of bonds broken, it has low
entropy. On a rcal surface, thc desire to maximize cntropy rcsults in lcss wcll-
ordcrcd arrangcmcnts.
When a crystal is fractured i n a rcal cxpcriinent, it is oftcn observed that
clcclrons arc emitted from thc surface for somc time. Thcsc arc callcd
cxoelcctrons. I n addition, oxygcn ions arc obscrvcd to be evolvcd. I t is possiblc
56
-LJ
Y Pe
1
Figure 4-la Model of a Ti02 (110) surface. Solid circles are Ti ions, open circles are 0
ions. One type 1 surface lattice oxygen is removed to show an anion vacancy.
Figure 4- l b Model of a Ti02 (100) surface. Shaded circles are surface lattice oxygen ions
under the plane of Ti ions. Other symbols are the same as in Fig. 4-la. One type 1 oxide
ion is removed to show an anion vacancy.
Figure 4-lc Model of a Ti203 (047) surface. Symbols arc the same as in Fig. 4-lb.
COORDINATIVE UNSATURATION 57
that neutral atoms are also evolved without being detected. This further points
out the fact that an ideal perfect surface of macroscopic dimensions may be hard to
obtain.
An inspection of these models shows that different exposed surfaces possess
ions of different degrees of coordinative unsaturation. On the Ti02 (1 10) surface,
two types of Ti ions are present. Half of the Ti ions have six oxygen ion nearest
neighbors and are coordinatively saturated. The other half have five oxygen ion
neighbors.
Similarly, there are two different types of lattice oxygen ions. Type
one is bonded to two Ti cations that are six-fold coordinated, sits above the plane of
the other ions, and, on Sn02 (1 10) [73], has been shown to be more easily removed
than other anions. The other type is bonded to three Ti ions of six- and five-fold
coordination. They are in the surface plane. The Ti02 (100) face has five-fold
coordinated Ti ions, and the (047) face has four-fold coordinated Ti ions.
In addition to these, ions of other types of coordinative unsaturation can be
created by introducing defects on the surface. An example is shown in the Ti 02
(100) surface in Fig. 4-la. An oxygen ion in the row sitting above the surface is
removed, perhaps by reduction. This action exposes two Ti ions of four-fold
coordination. In general, the presence of anion vacancies results in cations of a
lower coordination and in a lower oxidation state. The resulting surface is
commonly chemically more active.
4.2 CHEMICAL PROPERTIES OF SURFACE COORDINATIVELY
UNSATURATED SITES
Coordinatively unsaturated sites are responsible for chemisorption and
binding of molecules to a surface in most instances. Indeed this explains very well
a variety of phenomena including poisoning of a surface, competitive adsorption,
and the common requirement of heating of an oxide to activate it for
chemisorption and catalysis.
Activation of an oxide by heating is needed because of the strong adsorption
of water on oxides. Thus an oxide surface becomes fully covered with adsorbcd
water and hydroxyl groups once it is exposed to the moisture in the atmosphere.
This process is shown by eq. (4-1) and (4-2):
In eq. (4-l), water is adsorbed molecularly to satisfy the coordinative
unsaturation of the metal ion. In eq. (4-2), the coordinatively unsaturated cation
and anion pair adsorbs a water molecule dissociatively as OH- and H+. These
58
a,
c.'
2"
0
N
r
Evacuation Temper at ur e, C
Figure 4-2 Surface hydroxyl content of a ZnO sample evacuated at various temperatures.
(From J . Phys Chem., 84, 2054 (1984), copyright American Chemical Society).
surface ions become coordinatively saturated and unable to adsorb other
molecules. Heating causes removal of water and formation of surface coordinative
unsaturation. The extent of dehydroxylation depends on the temperature, as can be
seen in Fig. 4-2 for ZnO [3], and Fig. 4-3a for Cr203 [2]. These figures are
representative of most oxides.
Referring to Fig. 4-2, it can be seen that water is lost continuously from ZnO
when the temperature is raised. The water that is lost at low temperature are
weakly adsorbed water. I t is probably nondissociatively adsorbed water that is
lost by a process similar to the reverse of eq. (4-l), as well as water held to the
surface by hydrogen bonding. A rapid loss of water occurs around 200 to 350°C
which corresponds to dehydroxylation of the surface by the reverse of eq. (4-2).
Further dehydroxylation of the remaining hydroxyl groups bcyond 400°C is slow.
These hydroxyl groups are probably isolated and difficult to be removed.
Removal of the weakly adsorbed molecular water docs not necessarily
activate the surface, especially if the water molecules are held to the surface by
hydrogen-bonding. This is illustratcd in Fig. 4-3b. The amorphous Cr203
surface only becomes active in chemisorption of CO or O2 and in hydrogenation of
1-hexcne after the oxide is activated above 200"C, although some adsorbed water
is already removed by this temperature (Fig. 4-3a) 121. The chemisorptivc
capacity and the catalytic activity increase rapidly as the degree of dchydrox ylation
increases. The manner in which these quantities incrcasc dcpcnds on the molcculc
and the reaction bccause different requirements of surface sites may bc involved.
For example, the dependence of NH3 adsorption on Cr203 on the activation
temperature is much less than for CO or 02.
COORDINATIVE UNSATURATION
1.2
-
0
0)
e .8
0
v,N
O E
Q : c
cN2
0 2
L u.4
0 0 ,
0 0
o E
J
-
0
59
-
/
-
-
0
I
N
2
3 0 200 300 40(
Act i vat i on Temp. C
300
v,
5
-h
P,
200
D
;
3
P,
..
100 .!
rn
Figure 4-3a Amount of water lost per CPf upon heating from 25OC and the surface area of
amorphous Cr2O3 as a function of temperature of activation with Hz. Data from ref. 2.
Act i vat i on Temp C
300
Figure 4-3b Capacity for 0 2 or CO adsorption and catalytic activity for 1-hexene
hydrogenation as a function of the tcmpcrature of activation of amorphous CrzO3 in H2.
Data from ref. 2.
60
T
Surf ace
normal
Figure 4-4 Adsorption of CO on a: ZnO (0001); b: ZnO (1070) surface.
There is evidence that on a surface where the coordinativc unsaturation is
along a certain direction, (that is, directional valcnce orbital), a molecule
covalently bonded to the surface lies roughly in the direction of thc valence orbital.
The evidence is provided by CO adsorption on ZnO surfaces shown in Fig. 4-4.
Using angle-resolved UP S to monitor the orientation of the adsorbate, it has been
found that CO is adsorbed linearly along the direction of the surface normal of a
ZnO (0001) surface and colinear with the surface valence orbital [4]. On the ZnO
(1010) surface, the axis of the adsorbed CO molcculc is along the direction near the
expected direction of a tetrahedral bond of a surface Zn ion [4,5]. On these two
surfaces, CO are bonded to the surface Zn ions which have thrce oxygcn ion
nearest neighbors instead of four as in the bulk. The situation for the 0-polar
(0001) surface is less clear. The Zn ions in this surfacc have four oxygcn ion
nearest neighbors. They arc coordinatively saturatcd. I n one report, it is said that
adsorption of CO on this surface takcs place only on cations in the surface stcp
defects where coordinatively unsaturated Zn ions are exposed [4,6]. I n another
report, evidence is presented that CO may adsorb to form surface carbonate [721.
I t is further mentioned that the amount of CO adsorbcd on this surface is rcduccd if
the surface is disordercd by ion-bombardment, although one might cxpcct that
such treatment would gencrate more surfacc coordinativcly unsaturated cations.
Furthermore, it is reported that this bchavior is oppositc to that of C02 [72].
It follows that surface ions that are coordinatively unsaturatcd by more than
COORDINATIVE UNSATURATION 61
one ligand may adsorb more than one molecule. This has been observed on
chromia [7,8]. When a sample of reduced chromia is exposed to a mixture I2CO
and 13C0, three IR bands corresponding to Cr(12C0)2, Cr(12CO13CO) and
Cr(13C0)2 are observed. If each Cr ion adsorbs only one CO, only two bands for
Cr12C0 and Cr13C0 are expected.
Direct observation of the interaction between an adsorbate and a surface
cation has been made. For example, UV-vis spcctroscopy shows that on a reduced
Cr2O3/AI2O3 sample, Cr ions of square pyramidal coordination are converted to a
distorted octahedral coordination upon adsorption of ammonia or methanol [9].
When 13C0 is adsorbed on a Coo-MgO solid solution, the EPR signal of Co2+
shows hyperfine interaction with 13C [lo]. The Mossbauer spectrum of reduced
supported iron oxide shows an inner doublet and an outer doublet of Fe2+ions.
Upon adsorption of H2 0 [ll], pyridine [12], NO [13] or other mblecules, the inner
doublet is converted to the outer doublet.
Only in a few cases where surface coordinatively unsaturited oxide ions are
presesnt without any associated coordinatively unsaturated metal ions. The 0-
polar surface of ZnO is one such case. It has been found that without
accompanying M"+(cus) ions, the 02-(cus) ions are not very reactive, particularly
for species that prefer acid-base pair sites. For example, binding of water on the 0-
polar surface is weak. Temperature programmed desorption of water shows a
peak at 190 K from this surface, and a peak at 340 K from the Zn-polar surface
[14]. The 0-polar surface is also less active than the Zn-polar surface in the
catalytic decomposition of 2-propanol [15].
4.3 ADSORPTION OF SMALL MOLECULES
Substantial information is available on the interaction of small molecules
with transition metal oxides and other oxides. At present, most of the information
on the molecular nature of the adsorbate has been obtained by infrared
spectroscopy. Because of the strong infrared absorption by oxides in the region
below about 1000 cm-', there is little information on the surface-adsorbate bond.
Such data may become available as new techniques such as EXAFS and HREELS
become more sophisticated, especially the latter when deconvolution techniques to
rcmove surface phonon spectra are developed.
In general, molecules may interact with an oxide surface in different ways:
(1) Molecular (nondissociative) adsorption in which the interaction is mainly
by o-donation and/or x-bonding interaction.
single surface coordinatively unsaturated ion.
(2) Dissociative adsorption in which a molecule dissociates upon adsorption.
Dissociation of H20 into H+and OH- upon adsorption is an example of
hctcrolytic dissociative adsorption in which the molccule is dissociated
into charged species. This type of adsorption usually requires an
anion-cation coordinativcly unsaturatcd pair site. Homolytic dissociative
adsorption in which ncutral species are formed may also occur but less
This can take place on a
62
frequently.
(3) Abstractive adsorption in which the adsorbate abstracts a species from the
surface (often a proton). This commonly occurs on acidic oxides. If a
proton is abstracted from the surface and the adsorbed species becomes
cationic, the adsorbate could be held to the surface by electrostatic
forces, and coordinatively unsaturated ions might not be involved.
(4) Reductive adsorption in which an adsorbed molecule is oxidized while the
surface is reduced. It may also be abslractive as in the case when a
hydrocarbon molecule is oxidized on adsorption to a carboxylate utilizing
the lattice oxygen while reducing the cation.
In addition to adsorption, a surface may catalyze reactions of the adsorbate.
Examples of various catalytic reactions are discussed in later chapters.
Deprotonation and protonation of an adsorbate are examples of lssociative
and abstractive adsorption, respectively. These are BrQnsted acid-base reactions
between an adsorbate and a surface, and commonly occurs with molecules such as
NH3, pyridine, and alcohols. They will be discussed in greater detail in Chapter 5.
Reductive adsorption is commonly observed on transitional metal oxidcs
which have cations that have readily accessible multiple oxidation statcs. This
type of adsorption must be considcrcd whcn interpreting adsorption data. For
example, adsorption of nitrogen-containing compounds may result in their
oxidation to nitrates or nitrites, and oxidation of adsorbed hydrocarbons to
carbonates or carboxylates also occurs frequently in the absence of gaseous
oxygen.
l at i ce
RN02(ad) + 2 OH(ad)
RC02(ad) + 3 OH(ad)
RCH3 l atti ce 0 ,
(4-3)
(4-4)
Busca and Lorenzelli have summarized the infrared band frcquencies of
carbonate ions, carboxylates, bicarbonates and formates of various compounds
[16]. Because of the many different possiblc ways that these species can bond to a
surface, there are no characteristic bands unique to each species to help thcir
identification. Free carbonate ions possess two dcgcnerale IR-active asymmelric
CO stretching (v3) bands at 1415 cm-’. The splilting between the t wo bands on
adsorption may be used to identify the type of coordination of the carbonatc. If
bonding is to a metal ion that has a high polarizability, the classificauon proposed
by Nakamoto et a]. shown on the ncxt pagc may be uscd [171.
The assignment of v3 splitting largcr than 300 cm-’ is not certain. On oxidcs
of metals having low polarizing powcr, the splitting of v3 is smaller, and the
distinction between a monodcntate and a bidcntatc coordination bccomcs less
clear. Then consideration of thermal stability can help. A moncdcntatc structure
should normally be less stable on a surface than a bidcntatc spccics [16].
Carboxylates show absorption in thc rcgion of 1550-1760 and 1150-1200
cm-’. Sometimes the observation of two bands in thcsc rcgions is confused with
the v3 splitting of a carbonate species. Adsorbcd formate ions show four bands
COORDINATIVE UNSATURATION 63
Coordintation of Carbonates
v3 splitting (cm-') Type of coordination
zero symmetric
100 monodentate
300 bidentate or bridged
symmetric monodentate bidentate bridged
under optimal conditions: C-H stretching at about 2900 cm-', asymmetric C 4
stretching at 155CL1600 cm-', C-H bending at about 1400 cm-', and symmetric
CO stretching at 1345-1385 cm-'.
It is commonly observed that the form of adsorption of a molecule depends
upon the pretreatment of the oxide. This results from different modes of
adsorption requiring different surface sites. Protonation requires surface hydroxyl
groups and thus depends on the extent of surface dehydroxylation. Abstractive
reductive adsorption removes surface oxide ions and thus depends on the oxidation
state of the surface. The presence of adsorbed oxygen could also oxidize
adsorbates. As illustrated earlier, whether a molecule adsorbs nondissociatively
(eq. 4-1) or dissociatively (eq. 4-2) depends on whether cation-anion
coordinatively unsaturated pair sites are available. In what follows, illustrative
examples of the adsorption of hydrogen, hydrocarbons, alcohols, CO and NO are
presented to show the different types of adsorption.
H2
Hydrogen is adsorbed on ZnO both molecularly and dissociatively.
Molecular adsorption has been observed to occur at -195"C, and the adsorbed Hz
shows an IR band at 4019 cm-'. This band is shifted to 3507 and 2887 cm-' for
HD and DZ, respectively [18]. Dissociative adsorption is most likely heterolytic
although there is no direct confirmation of it, and occurs at room temperature:
For Hz, a band assigned to Zn-H at 1712 cm-' and CtH at 3490 cm-' are
observed [19]. I t is interesting that the H atoms bound to Zn-H and 0-H
exchange with D2 present i n the gas phase to form HD in the gas phase, but not
64
-1
1700 1650 1600
Wavenumber cm
Figure 4-5 Effect of increasing CO pressure on the Zn-H strctching band frcquencics (Pll2
=100 Ton). (From J. Catal., 51, 160 (1978), copyright Academic I’ress).
with Zn-D or O-D [20]. This IR-active dissociative form of adsorbed H2 is
involved in the catalytic hydrogenation of alkenes on ZnO.
The frequency of the Zn-H band is affected by coadsorbates. When CO is
adsorbed onto a hydrogen-coverd surface, two new Zn-H bands appcar whosc
intensities vary syslematically with the CO coverage. This is illuslratcd in Fig. 4-5
[21]. The two new Zn-H bands represent Zn-H cornplcxes wilh one or both of its
neighboring Zn ions coordinated to a CO molcculc.
Alkenes
Alkenes are adsorbed both nondissociativcly and dissociatively on ZnO.
Nondissociative adsorption is in the form a x-complex. This has ken observed
for C2H4 [22], propcnc [ 23] , and butenes [24]. Thesc x-complcxes exhibit a C=C
stretching band that is shifted to a lower frequency from the corrcsponding band in
the gas phase by less than 50 cm-’ . These spccics are only weakly adsorbed.
Propcne is also adsorbed on ZnO dissociatively to form x-allyl. The
dissociation is probably heterolytic, and a x-ally1 anion is formcd [23,25]:
C ~ H ~ + -Zn+ 4 CH~-CH-CH; H+ (4-6)
- 1 - - I
Zn
COORDINATIVE UNSATURATION 65
This process is similar to H2 adsorption on ZnO. Upon adsorption of propene in
this form, an 0-H infrared band is obscrvcd but no Zn-H band. Thus the x-ally1
species is adsorbed on the Zn ion. Another band at 1545 cm-' is also obscrvcd
which is assigned to the antisymmctric stretch of thc C-C-C skeleton. This
assignment is substantiated by observing shifts in this band position upon
deutcrating the propene molecule at various positions and noting that the magni-
tudes of the shifts agree with those prcdictcd by group frequency analyses. It is
also supportcd by thc fact that the hydrogen of the G H group formed arises from
thc dlylic H of the propene molecule. This x-ally1 species can be reversibly
removed from the surface on evacuation at slightly elevated temperatures. This
fact strongly suggests that it is not an oxidized surface species. The relative
amount of propene adsorbcd as x-ally1 and as n-complex depends on thc extcnt of
dchydration of the surface [26].
Conclusivc evidence for the formation of n-ally1 from butene when it is
cxposcd to ZnO has not been established. Although an IR band at about 1570-
1580 cm-l has been observed, it cannot be readily removed by evacuation [24].
This, together with the fact that the kinetics of its formation does not appcar to
correlate with the kinetics of butene isomerization, raises the possibility that this
band might be due to a surface oxidized species.
By applying the criterion that x-complex and x-ally1 can be readily dcsorbcd
from the surface, it has also bcen claimcd that a 1600 cm-' band is due to the C=C
strctch of a x-complcx of propcne on Ga-Mo oxide [27], and a 1580 cm-l band to
that on cuprous oxide [28]. Bands at 1400 and 1440 cm-I have bcen assigncd to
the n-ally1 species on thcsc two oxides, respectively. However, definitive
assignmcnt of IR bands cannot be made readily without supplementary information
from other observations, espccially in the absence of close analogs to the adsorbed
spccics. Indccd, thc investigators caution that the 1440 cm-' band mentioned
above may also be assigncd to deformation vibrations of the CH3 group i n
physically adsorbcd propene or a x-complcx. It is also intcrcsting to note that
adsorption of allyl bromide on ZnO rcsults in a surface allyl species with a band at
1470 ern--' instead of 1545 cm-' which is observed on adsorption of propcnc [29].
Only x-complexes have bccn idcntificd on adsorption of ethene and propene on Ni-
Mo-MgO, Co-Mo-MgO 1301, and Ti02 [31]. They havc also been identified on
adsorption of butcncs on a V-P-0 [32], where it is observed that the red-shift in the
C=C stretch on adsorption depends on whether the oxide is oxidized or reduced.
Thc shift is 33 cm-' on an oxidized sample, and 23 cm-' on a reduced sample.
Like alkcncs, terminal alkynes may bc adsorbcd eithcr molecularly or
dissociativcly [33,34]. I t has bcen obscrvcd that acetylene and phcnylacctylcne
are adsorbcd at room tcmpcraturc dissociativcly as acetylide (HCS-) and
phcnylacctylidc, rcspectivcly, on ZnO [34]. Propyne is adsorbcd on ZnO to form
both mcthylacetylide and propagyl spc5cs [33,35-391:
[ CH3 X - C ]
mclhylacctylidc ProPagYl
66
The propagyl species is the intermediate in the isomerization of propyne to
allene. The formation of propagyl species on ZnO has been confirmed using XPS
which shows only one carbon peak for the adsorbed species, instead of two peaks
for the gas phase propyne molecule or the methylacetylide species on a silver
surface [34]. Some of the dissociatively adsorbed species is further oxidized upon
heating, resulting eventually in carbon oxides and water. The extent of
dissociative adsorption depends on the crystallographic orientation of the surface.
On ZnO, dissociative adsorption occurs on the Zn-polar surface, but only
molecular adsorption occurs on the 0-polar surface [341.
Alcohob and Acetone
With few exceptions, alcohols are adsorbed by heterolytic dissociation at
room temperature on a dehydroxylatcd surface with a proton going to a surface
lattice oxygen and an alkoxide to a surface cation. This is again similar to the
other heterolytic dissociative adsorption shown in eq. (4-2), (4-3, and (4-6). The
process on ZnO is shown below:
ROH + Z n 4 -+ RO H
I I
Zn- 0
(4-7)
For example, methoxide has been detected when methanol is adsorbed on
ZnO [40] and Moo3 [41,42]. Similarly, ethoxide is formed from ethanol on
Moo3 [43] and ZnO [44], 1-propoxide is formed from 1-propanol [44] and 2-
propoxide is formed from 2-propanol on ZnO [45]. Methanol has been shown to
be adsorbed dissociatively at as low as 105 K [46].
Oxidation of surface alkoxide commonly occurs. The oxidation of
methoxide to a surface formate is well documented on ZnO [47,48]. The zinc ion
is reduced to zinc metal which can be desorbed from the surface. It also occurs on
Cr2O3 [49]. 2-propoxide on ZnO is oxidized to a surface enolate which eventually
is dcsorbed as acetone [45].
Adsorbed acetone dissociates heterolytically into a surface enolate
species with simultaneous formation of a surface OH group. This reaction:
is observed to occur on both ZnO [45] and NiO [50].
The reversibility of this reaction has been demonstrated. Complete exchange
of the hydrogen atoms of the methyl groups with deuterium has been observed
when a sample of ZnO with adsorbed acetone is exposed to deuterium gas [451.
Thus deuterium is adsorbed dissociatively on the oxide, and the OD group
participates in the reverse reaction.
COORDINATIVE UNSATURATION 67
co
Carbon monoxide is a rather common probe molecule in the study of the
surface chemistry of transition metal oxides. Its behavior on these oxides is quite
different from its behavior on the metals. Adsorption of CO on noble metals is
much stronger than on oxides. CO is adsorbed dissociatively on transition metals
at the left of the Periodic Table. Dissociative adsorption of CO on oxides has not
been reported. Instead, oxidation of CO to C02 or carbonate occurs.
Nondissociative adsorption of CO usually occurs on a surface coordinatively
unsaturated cation. A characteristic feature of this CO is that the species has a
higher infrared absorption frequency than the gas phase frequency of 2143 cm-'. A
value between 2170 amd 2200 cm-' is observed [51]. In constrast, a shift to lower
frequencies is observed on metals. The phenomenon is first noticed on NiO [52].
Explanations of this shift to higher frequencies on oxides have been based on the
assumption that the adsorption involves an interaction between a surface cation and
the carbon end of the CO molecule. This assumption has now been substantiated
by single crystal studies on ZnO [4-61. I n this picture, the C=O stretching
frequency depends on the relative extent of a-donation from CO to the cation,
which would increase the C- 0 bond strength and its frequency, versus back x-
bonding from the cation to the CO molecule, which has the opposite effect. I t is
argued that for cations in a high oxidation state, the cation size is small and its
electron affinity is high. Thus the bonding with CO involves mainly a-donation
and little x-bonding, which results in an increase in the CO stretching frequency.
The importance of x-bonding increases when the cation is in a lower oxidation
state. It has been proposed that the frequency for W'CO is above 2170 cm-',
M'CO i n the region of 2120-2160 cm-', and M"C0 below 2100 cm-' [53].
In addition to the molecular orbital picture of the bonding, the electric field
near an oxide surface could also affect the CO stretching frequency. This effect
has bccn analyzed [54,55]. It is agreed that the interaction of the surface electric
field with the dipole moment of the CO molecule changes the interatomic distance
in the molecule, and thus its force constant and the stretching frequency.
However, quantitative predictions are not yet available.
The mode of adsorption of CO depends on the pretreatment of an oxidc. On
a fully oxidized surface, CO may adsorb reductively to form carbonates [57,58].
CO may also react with surface hydroxyl groups to form formate [59].
The frequency of the CO band can also be affected by coadsorbates. When
CO and COz are coadsorbed on ZnO [56], the CO frequency is shifted from 2183 to
2212 cm-'. The stretching frequency also depends on the pretreatment. ZnO
evacuated at 400°C followed by an oxygen treatment yields a CO band at 2212
cm-*. If the sample is evacuated at 400°C, the band is shifted to 2187 cm-' [60].
The reasons for these shifts are not well understood.
NO
NO is another probe molecule commonly used to study transition metal
oxides. Except for one additional unpaired electron, it has an electronic structure
similar to CO. Thus in many ways its adsorption is similar to that of CO, and
occurs on surface M"'(cus) ions, although its adsorption is often stronger.
68
Table 4-1 Infrared Absorption Peak Positions of Dinitrosyl or Dimeric
Species of Adsorbed NO
Cation Peak Positions, cm-' Peak Separation, cm-1
W+, Cr3+ 1745- 1775, 1865- 1895 120 - 130
reduced MOO, 1695-1713, 1800-1817 100
Fe2+ 1810, 1910 100
reduced WO, 1685, 1795 110
co2+ 1765- 1795, 1840- 1875 80 - 90
NO may be adsorbed in one of the four different forms shown below [ 51] :
Adsorption as neutral species either as a single molecule or as a pair is the
predominant mode observed. In a few cases, charged adsorbed species are
formed. The infrared stretching frequency of adsorbed NO- is lower than the
others, being in the region below 1735 cm-'. The frequency for the othcrs are
mostly in the region 1740-1950 cm-'. In addition to the above species, oxidation of
NO occurs occasionally to form surface nitrate or nitrite species [61-631.
Adsorption in pairs on one M"+(cus) ion is characteristic of NO adsorption,
and it shows in infrared spectroscopy as a pair of absorption bands due to the
symmetric and antisymmetric stretches of the adsorbed NO pair. The absorption
frcqucncies of the pair dcpend on the oxide as well as on the particular sample of a
given oxide. However, the separation between the two peaks is constant for a
given cation and varies less from sample to sample. These separations are listed in
Table 4-1 which is derived from the data summarized i n ref. 51. The high
tendcncy for NO to be adsorbed in pairs is due to the stabilization derived from the
mutual interaction of the unpaired electron on each NO [64]. Whether the pair
exists in the form of a dimcr or dinitrosyl is still unclear.
Dinitrosyl Dimcr
COORDINATIVE UNSATURATION 69
The arguments favoring a dinitrosyl species include the absence of absorption
in the 1250-1350 cm? region, which excludes the presence of a hyponitrite species
(N202-) [&I], the fact that the adsorbed NO pair is stable to quite a high
temperature (on Mo, W, and Cr cations), and the two nitrosyl bands have
approximately the same intensity [65].
Other evidence supports a dimeric form for the adsorbed NO pair. It has
been observed that the ratio of the symmetric and asymmetric stretching from a
N202 dimer is very similar to the coupled nitrosyl bands on a silica-supported
chromia [66]. When a reduced molybdena is first half-saturated with 15N0 and
then exposed to 14N0, no infrared bands attributable to a mixed l 5NW4NO
complex is observed [67,68]. Since isotopic mixing is expected for dinitrosyl
complexes, this observation supports a dimeric species. However, it may also be
explained (though less likely) with a dinitrosyl complex if the adsorption sites
differ greatly in their binding energy for NO or in their accessibility. It should be
noted that the ratio of the intensities of the asymmetric and symmetric stretch of
adsorbed NO pairs is related to the angle between the two M-0 bonds [69].
It has been suggested that linear M-NO groups possess infrared absorption
frequencies higher than 1850 cmpl [70]. Whether a linear group is formed
depends on the degree of coordinative unsaturation of the metal cation. I t appears
that a F e2+40 complex is more linear if the Fe2+ion is less coordinatively
unsaturated than more unsaturated [71].
REFERENCES
1. N. D. Parkyns, in "Chemisorption and Catalysis," ed. by P. Hepple, Elsevier
2. R. L. Burwell, J r., G. L. Haller, K. C. Taylor, and J. F. Read, Adv. Cafaf. . 29,
3. M. Nagao. and T. Morimoto, J . Phys. Chem., 84, 2054 (1984).
4. R. R. Gay, M. H. Nadine, V. E. Henrich, H. J. Zeiger. and E. I. Solomon,
5 . K. L. DAmico, F. R. McFeely, and E. I. Solomon, J . Amer. Chem. Soc.,
6. K. L. DAmico, M. Trenary, N. D. Shim, E. I. Solomon, and F. R. McFeely.
7. A. Zecchina, E. Garrone, and E. Gulielminotti, Cdalysis (London), 6, 90 (1983).
8. B. Rebenstorf' and R. Larsson, Z. Anorg. Al l g. Chem.. 453, 127 (1979).
9. V. A. Shvets, Russ. Chem. Rev., 55, 200 (1986).
Publ. Co., Amsterdam, Netherland, 1971, p. 150.
1 (1969).
J . Amer. Chem. SOC. , 102. 6752 (1980).
105, 6380 (1983).
J . Amer. Chem. SOC., 82, 1504 (1982).
10. V. Indovina, D. Cordischi, and M. Occhiuzzi, J . Chem. SOC. Faraday Trans. I ,
11. H. M. Gager, J. F. Lefelhocz, and M. C. Hobson, J r., Chem. Phys. Left.. 23,
12. G. Connell, and J . A. Dumesic, J . Cafal . , 101, 103 (1986).
13. S. Yuen. Y. Chen, J . E. Kubsh. 1. A. Dumcsic. N. Tops&. and H. Tops&.
77, 811 (1981).
386 (1973).
J . Phys. Chem., 86, 3022 (1982).
14. G. Zwicker, and K. J acobi, Surface Sci., 131, 179 (1983).
15. P. Berlowitz, and H. H. Kung, J. Amer. Chem. Soc., 108, 3532 (1986).
16. G. Busca, and V. Lorenzelli, Mater. Chem., 7, 89 (1982).
17. K. Nakamoto, J . Fugita. S. Tanaka. and M. Kobayashi, J. Amer. Chem. Soc.,
18. C. C. Chang, and R. J . Kokes, J. Amr . Chem. Soc., 93, 7107 (1971).
19. R. P. Eischens, W. A. Plisken, and M. J . D. Low, J. Catal., 1. 180 (1962).
20. S. Naito, H. Shimizu, E. Hagiwara, T. Onishi. and K. Tamaru, Trans. Faraday Soc.,
21. F. Boccuzzi, E. Garrone, A. Zecchina, A. Bossi. and M. Camia. J . Catal.,
22. A. L. Dent, and R. J . Kokes, J. Phys. Chem., 73, 3772, 3781 (1969).
23. A. L. Dent, and R. J . Kokes, J. Amer. Chem. Soc., 92. 6709 (1970).
24. C. C. Chang, W. C. Connor, and R. J. Kokes. J. Phys. Chem., 77, 1957 (1973).
25. T. T. Nguyen, and N. Sheppard, J. Chem. Soc., Chem. Commun., 868 (1978).
26. A. A. Efremov, and A. A. Davydov, Kinet. Catal., 21. 383 (1980).
27. A. A. Davydov, J . Tichy, and A. A. Efremov. React. Kinet. Catal. Lett., 5,
28. V. G. Mikhal’chenko, V. D. Sokolovskii. A. A. Filippova, and A. A. Davydov,
29. A. A. Davydov, A. A. Efremov, V. G. Mikhal’chenko. V. D. Sokolovskii.
30. R. Grabowski, A. A. Efremov, A. A. Davydov, and E. Haber, Kinet. Catal.,
31. A. A. Efremov, and A. A. Davydov, React. Kinet. Catal. Lett., 15, 327 (1980).
32. E. V. Rozhkova, S. V. Gorej, and Ya. B. Gorokhovatskii, Kinet. Katal., 15,
33. R. J . Kokes. Intra-Science Chem. Rep., 6, 77 (1972).
34. J . M. Vohs, and M. A. Barteau, J. Phys. Chem., 91, 4766 (1987).
35. C. C. Chang, and R. J . Kokes. J. Catal., 28, 92 (1973).
36. C. C. Chang, and R. J . Kokes, J. A mr . Chem. Soc., 92, 7517 (1970).
37. J . Saussey, and J . C. Lavalley, J . Chim. Phys., 75, 506 (1978).
38. T. T. Nguyen. J . C. Lavalley, J . Saussey, and N. Sheppard, J. Catal., 61, 503 (1980).
39. T. T. Nguyen, J. Catal.. 61. 515 (1980).
40. A. Ueno, T. Onishi, and K. Tamaru, Trans. Faraday Soc., 67. 3585 (1971).
41. R. P. Groff, J. Catal., 86, 215 (1984).
42. M. Ito, Vib. Surf. (Proc. Intern. Cod.), 2nd, 1980 (published 1982), p. 71.
43. K. Aika. and J . H. Lunsford, J . Phys. Chem., 81, 1393 (1977).
44. M. Nagao, and T. Morimoto. J . Phys. Chem., 84. 2054 (1984).
45. 0. Koga, T. Onishi, and K. Tamaru, J . Chem. Soc. Faraday Trans. I , 76, 19 (1980).
46. W. Hirschwald. and D. Hoffmann, Surface Sci., 140, 415 (1984).
47. S. Akhter, W.H. Cheng, K. Lui, and H. H. Kung, J. Catal.. 85, 437 (1984);
S. Akhter. K. Lui, and H. H. Kung, J . Phys. Chem., 89, 1958 (1985).
48. M. Bowker, H. Houghton. and K. C. Waugh. J . Chem. SOC. Faraday Trans. I,
77, 3023 (1981).
49. K. Yamashita, S. Naito, and K. Tamaru, J. Catal., 94, 353 (1985).
79, 4904 (1957).
67, 1519 (1971).
51, 160 (1978).
353 (1976).
Kinet. Catal., 14, 1099 (1973).
J . Catal., 58, 1 (1979).
22, 794 (1981).
694 (1974).
COORDINATIVE UNSATURATION 71
50. H. N. Rufov, A. A. Kadushin, and S. Z. Roginsky. Proc. 41h Intern. Cong.
51. M. C. Kung, and H. H. Kung, Catal. Rev. , 27,425 (1985).
52. R. P. Eischens, and W. A. Pliskin, Adv. Cafal., 9, 662 (1957).
53. Yu. A. Lokhov, and A. A. Davydov, Kinel. Katal., 21, 1093 (1980).
54. N. S. Hush, and M. L. Williams, J . Molec. Specfrosc.. 50, 349 (1974).
55. R. Larsson, R. Lykvist. and B. Rebenstorf, Z. Phys. Chem. (Leipzig). 263,
56. J. C. Lavalley, J. Saussey, and T. Rais, J . Molec. Catal., 17, 289 (1982).
57. P. G. Harrison, and E. W. White, J . Chem. SOC. Faraday Tram. I , 74, 2703 (1978).
58. E. Guglielminotti, L. Cermti, and E. Borello, Gazz. Chim. Ital., 107, 503 (1977).
59. M. He, and J. G. Eckerdt, J . Cafal., 72, 303 (1981).
60. C. H. Amberg, and D. A. Seanor, Proc. 3rd Intern. Cong. Catal., Amsterdam,
61. P. G. Harrison, and E. W. White, J . Chem. SOC. Faraday Tram I , 74, 2703 (1978).
62. G. Busca, and V. Lorenzelli, J . Cafal., 72, 303 (1981).
63. J . W. London. and A. T. Bell, J . Catal., 31, 32 (1973).
64. A. Zecchina, E. Garrone, C. Morterra, and S. Coluccia, J . Phys. Chem.,
65. A. Kazusaka, and R.F. Howe, J . Cafal., 63, 447 (1980).
66. E. L. Kugler. R. J . Kokes, and J . W. Gryder. J. Catal., 36, 142 (1975).
67. W. S. Millman, and W. K. Hall, J . Phys. Chem., 83, 427, (1979).
68. J . B. Peri, J . Phys. Chem., 86. 1615 (1982).
69. F. A. Cotton, and G. Wilkinson, "Advanced Inorganic Chemistry". 3rd ed.,
Wiley-Interscience, N.Y. 1972, p. 697.
70. J. H. Enemark. and R. D. Feltham, Coord. Chem. Rev. . 138. 339 (1974).
71. S. Yuen, Y. Chen, J . E. Kubsh. J . A. Dumesic, N. Topsde, and H. Topsde,
72. C. Au, W. Hirsch, and W. Hirschwald, Surface Sci .. 197, 391 (1988).
73. D. F. Cox, T. B. Fryberger, and S. Semancik, Phys. Rev. B, 38. 2072 (1988).
Catal.. vol. 3, 1968.
1089 (1982).
1965, p. 450.
79, 978 (1975).
J . Phys. Chem., 86. 3022 (1982).
Chapter 5
SURFACE ACIDITY
5.1 SURFACE ACID SITES
A partially hydroxylated oxide surface has hydroxyl groups and coor-
dinatively unsaturated metal cations and oxygen anions. Each of these species can
participate in an acid-base reaction. Exposed coordinatively unsaturated cations
may act as acceptors for free electron pairs of adsorbed molecules.
M"+(cus) + :B(g) + M"+:B
(5-1)
Such cations are Lewis acid sites. The strength of these acid sites depends on the
charge and size of the cations, both of which may vary with the oxidation number
of the cation. In general, according to the concept of hard and soft acids [l ],
cations of a higher oxidation state are harder. For cations in the same group in the
Periodic Table and of the same oxidation state, those in a later period are softer.
Harder cations are smaller and less polarizable. They will adsorb or bind hard
bases stronger than soft or polarizable bases. Complicating these considerations,
however, is the fact that cations in oxides are usually surrounded by larger and
more polarizable oxygen anions. The harder, smaller and less polarizable cations
are sometimes partially shielded by the oxygen anions so that binding of molecules
to the cations is sterically hindered. As a result, binding is weaker than expcctcd.
Surface hydroxyl groups may act as BrBnsted acid sites. They may dissociate
to protonate adsorbed bases:
The resulting conjugate acids and bases are stabilized on the surface by
electrostatic interaction with each other and with the oxide. As will be discussed
later, the oxide exerts an effect similar to that of an aqueous solution i n slabilizing
charges on the surface.
72
SURFACE ACIDITY 73
Table 5-1 Relative Acidities on Oxide Surfaces a
relative acidity order on M acidb D@(B-H)'
ZnO MgO PKil kcal/mol kcal/mol
1. C~HSSH
2. HCOOH 3.7
3. CH3COOH 1. CH3COOH 4.8
4. HCN 9.3
5. C~HSOH 2. C6H50H 9.9
6. CH3SH 3. CH3SH 12.0
7.f H30H
4. CH30H 15.5
C~HSOH 5. C~HSOH 17.0
9. C~HSCCH 6. C~HSCCH 18.5
7. HCCH 26
33 1.8
345.2
348.5
353.1
351.4
359.0
379.2
376.1
370.3
375.4
83.3
106
105.8
123.8
86.5
90.7
104.4
104.2
132
Footnotes:
a) From R. Spitz, J. Barton, M. Barteau, R. Staley, and A. sleight, J. Phys. Chem.
90, 4067 (1986), copyright American Chemical Society.
b, Homolytic band dissociation energy. From J .E. Bartmess. R.T. McIver, J r., in "Gas
Phase Ion Chemistry", M.T. Bowers, ed., Academic Press, NY 1979, p. 87.
') Hcat of heterolytic dissociation. From D.F. McMillen, D.M. Golden, Ann. Rev.
Phys. Chem. 33, 493 (1982).
An exposed coordinatively unsaturated oxygen ion participates in an acid-
basc reaction as a conjugate Brbnsted base. I t is one element of the pair sites for
hctcrolytic dissociative adsorption (see eq. 4-2). The heterolytic dissociative
adsorption of water, hydrogen, alcohols and alkynes described in Chapter 4 are
cxamplcs where the surface oxygen ions act as conjugate bases. The dissociative
adsorption of bcnzaldchydc and chloroform are other examples. I n general,
transition metal oxides do not have strongly basic sites.
When considering the BrBnstcd acidity of surface hydroxyl groups or basicity
of surface oxygen ions, it is important to know whether it is more appropriate to use
the aqueous solution acidity scale or the gas phase acidity scale. The charged
species are primarily stabilized by the dipoles of water molecules in an aqueous
solution, and by other polarizable spccies in other solutions. I n the gas phase, they
arc stabilized by induction within the molecule. Thus molecules may show
different strengths of acidity and basicity in different media.
While it has long bccn conjectured that the aqueous solution scale is more
appropriate for oxidc surfaces, this has only been demonstrated recently [2]. I n
this study, the adsorption of a series of organic acids that include thiols, alcohols,
acids and alkyncs was studicd (see Table 5-1). The relative strength of adsorption
74
of these molecules was monitored by displacement/ titration experiments. In these
experiments, one molecule was first adsorbed. After evacuation, the oxide was
exposed to a second molecule. The displacement of the first molecule by the
second molecule was followed with FTIR and the extent of displacement was
evaluated from the IR peak intensities. Sometimes deuterated molecules were
used to avoid overlapping peaks. Although this method is not an equilibrium
method and quantitative values of relative acidity could not be obtained, qualitative
ordering could be derived. It was shown that the titration of acids of similar
strengths is completely reversible, but is irreversible for acids of very different
strengths. The results of this study are shown in Table 5-1. The orders of the
strength of adsorption on both ZnO and MgO are the same and follows the same
order as aqueous pK, values. The order does not follow the acid strengths in the
gas phase as measured by the enthalpies of heterolytic dissociation of the probe
molecules, or the bond dissociation energies of these molecules. It may be
concluded that the oxide must function llke an aqueous solution to stabilize the
electric charge on the dissociated molecules.
Although Table 5-1 shows the results of an experiment where the oxide ion of
the solid serves as the conjugate base, the same phenomenon probably applies to
the situation in which the surface hydroxyl groups act as Brdnsted acids, since the
same charge stabilization mechanism is required. Therefore, it is probable that the
order of acid strengths of surface hydroxyl groups on different oxides determined
either by protonation of adsorbed molecules i n a nonaqueous or gaseous
environment or by the isoelectric points in aqueous solutions will be the same.
However, quantitative comparisons between the two methods will probably be
impossible until accurate calculations to evaluate charge stabiliiation become
available. Complicating the matter is the fact that the acid strength of a hydroxyl
group may depend on its environment including the presence of ion vacancies,
impurities, and surface dislocation defects. The importance of surface impurities
has been shown to be a critical factor in the variation of the isoclectric point of a
particular oxide reported in the literature.
5.2 FORMATION OF ACID SITES
Exposed coordinatively unsaturated metal cations and oxygen anions on the
surface are Lewis acid and Brdnsted conjugate base sites, as described above.
Brdnsted acid sites are present only when hydroxyl groups are present. Therefore
the number of such sites depends on the extent of hydroxylation of the surface.
As mentioned in chapter 4, hydroxylation and dehydroxylation involve the
interaction between a water molecule and surface coordinatively unsaturated
metal cations and oxygen anions:
SURFACE ACIDITY 75
It may seem appropriate to relate the appearance of Lewis acidity with
dehydroxylation and disappearance of BrQnsted acidity, and vice versa. In some
cases this can be readily demonstrated. On a ZnO sample that is fully
hydroxylated, significant amounts of BrQnsted acid sites are present, as indicated
by the formation of IW,+ ions on adsorption of ammonia. But when the hydroxyl
density is less than half of the fully hydroxylated surfaces, hardly any w+ is
observed [3]. On alumina-supported molybdena, chromia, rhenium oxide, or
tungsten oxide, adsorption of pyridine results in the formation of pyridinium ions
the amounts of which increases after exposing the oxides to water [4]. A similar
observation has been made using the adsorption of ammonia [ 5] .
In some other cases this interconversion may not be demonstrated so readily.
This may be due to the fact that the surface oxygen anion is very strongly basic
such that its protonated form is only a very weak BrQnsted acid - so weak that it
protonates only strongly basic molecules. It is also possible that in the
dehydroxylated form, the surface cation behaves like a very weak Lewis acid
center because of its nature or because of steric shielding by the neighboring
oxygen ions. Then dehydroxylation would not result in the development of
readily detectable Lewis acidity. For example, anatase TiOz prepared from
titanium tetraisopropoxide possesses Lewis acid sites which are not converted by
the addition of water to Brdnsted acid sites strong enough to protonate pyridine.
However, Lewis acid sites on anatase prepared by the hydrolysis of titanium oxide
sulfate can be converted to Brdnsted acid sites on exposure to water vapor [ 6] .
Since surface coordinatively unsaturated ions are important, it follows that
the presence of cation or anion vacancies and other defects that results in greater
exposure of the ions also affects acidity. However, very little understanding of
this matter is available.
One way to generate new and perhaps stronger acid sites on an oxide is by
incorporation of a second oxide. The mixed oxide of silica-alumina is a classic
example where a high density of new strong acid sites is generated. This situation
is found in many other mixed oxides, as is shown in Table 5-2. Also shown in the
table is the fact that not all mixed oxides develop new acid sites.
Various models have been proposed to predict the formation of new acid sites
in mixed oxides. Tanabe's model applies to dilute mixed oxides where a small
amount of a second oxide is incorporated into the first oxide by cation substitution
[7-91. This model assumes that the generation of new acid sites is caused by an
excess of negative or positive charge in a model structure of a binary oxide. The
model structure is constructed as follows:
i) The coordination number of a cation in the component oxide is maintained
in the binary oxide.
ii ) The coordination number of the oxygen ion in the binary oxide is the
same as in the major component oxide.
As an example, the model structures of a dilute mixed oxide of TiOz and Si02 are
shown in Figure 5-1. I n TiOz, each Ti ion is coordinated to six oxygen ions and each
oxygen ion to three Ti ions. In Si02, each Si ion is four-coordinated and each
oxygen ion is two-coordinated. In the model structure, the coordination numbers
of Ti and Si are maintained, and the coordination number of oxygen is that of the
76
Table 5-2 Formation of New Acid Sites in Some Mixed Metal Oxides. (From J.
Solid State Chem., 52, 191 (1984), copyright Academic Press).
New Acid Sitesb
Matrix Substituting
Oxide Oxide Experimenta Tanabe's Kung's
Model Model
za2 CdO
wo3
+
-
+
+
+
+
+
-
-
+
+
+
+
?
?
+
?
Footnotes:
a) Experimental data extracted from ref. 9 except for those involving WO,
b, +means affirmative, - means negative, ? means dependent on the conditions.
which arc taken from Yamaguchi, et al., J. Catal., 65, 442 (1980).
SURFACE ACIDITY 77
-
I 1 7 - 1
- 0-
I
I
-0
-0 'I
/ T-
(a) Si in Ti 02
I
0
I
I
O 0'
I /
(b) Ti in Si 02
Figure 5-1 Structures used in Tanabe's model for the prediction of formation of new acid
sites in mixed oxides. a. Si in a matrix of Ti02; b. Ti in a matrix of SiOz. (From Bull.
Chem. SOC. J pn., 47, 1064 (1974). copyright Chemical Society of J apan).
major component. The formal charge of each ion is then assumed to be evenly
distributed over the coordinating bonds. In figure 5-la, the +4 charge of the
substituting Si ion is distributed over four bonds, while the -2 charge of an oxygen
ion is distributed over three bonds. Thus each of the bonds surrounding Si bears a
net charge of 4/4 ~ 2/3 (=+1/3). The excess charge at Si is then 4 x 1/3 =+4/3. In
this case, a Lewis acid site is assumed to appear because of the presence of an
excess positive charge. In Fig 5-lb, a similar calculation results in an excess
charge of -2 at the substituting Ti ion site. In this case, a Brbnsted acid site is
assumed to appear, because two protons are assumed to be associated with the site
to maintain charge neutrality. If there is no excess charge at the site of the
substituting ion by such a calculation, as in the case of AI2O3-Bi2O3, there will be
no new acid sites.
This model has been applied to many binary oxides, some of which are shown
in Table 5-2. It has been found that the prediction is accurate over 90% of the
time. The high success rate makes the model very useful, although it is limited by
thc assumptions uscd. One limitation is the need to have a unique coordination
number, which may be difficult to decide in systems of low symmetry. Another
limitation is the use of formal oxidation states which may be quite different from
thc real chargc (see Chapter 3). Since electron deficiency at a site refers to real
charge at a site, the use of formal oxidation states may not be accurate. Finally the
78
-8
0
r
5
p -4
E
z -2-
-6-
U
.-
2 0 -
tl 2 -
= 4 -
w
c
P,
.-
6 -
0. r,
0
-
0.0
-
.)a
0 0 . .
0 . 0
0
0
I I I I I
Averaged El ectronegati vi t y
Figure 5-2 Highest acid strengths and average electronegativities of metal ions of binary
oxides (molar ratio =1) . (From Bull. Chem. SOC. Jpn., 46, 2985 (1973). copyright
Chemical Society of Japan).
model cannot predict acid strength. However, there appars to be a rough
correlation between electronegativity of the cations and the strength of acid sites in
many mixed oxides, as is shown in Fig. 5-2 [lo].
Another model proposed by Kung takes a rather different approach. I n
Tanabe's model, charge compensation at the substituting ion site by neighboring
oxygen ions is important. In Kung's model, changes in electrostatic potential
experienced by the substituting cation due to all the ions in the matrix oxide is
important. Thus Tanabe's model is a localized model, and Kung's model i s a
delocalized model.
I n Kung's model [ l 11, the difference AV between the electrostatic potentials
experienced by a cation A in a matrix BO, and in AO, is given by:
( 5- 3)
where qi is the charge of the ion at a distance ri from the A cation. The subscripts
BO and A 0 denote the matrices BO, and AO,, respectively. When AV is
negative, cation A in matrix BO, experiences a more negative potential than in
SURFACE ACIDITY 79
AO,. I t will be electrostatically more stable. Therefore the electron energy levels
of cation A arc lower in energy in matrix BO, and the cation can accept electrons
inorc rcadily. I t will act as a new Lewis acid site. When AV is positive, A is less
rcadily i n accepting electrons in matrix BO, than in matrix AO,. No new Lewis
acid site is generated at the substituting A cation.
In addition to the changes in the electrostatic potential at site A, when the
oxidation states of cations A and B are different, the overall charge neutrality of the
solid will be maintaincd by a change in the matrix. Two possibilities exist: a
substituting cation A is of a lower formal oxidation state than the matrix cation B, y
<z, and the reverse case of A being of a higher formal oxidation state than B, y >
When y <z, a simple substitution of B ion by A ion would result in a solid
with excess oxygen. This excess can be balanced by: ( 1) development of anion
vacancies; (2) adsorption of protons on the surface; or (3) development of
intcrstitial cation defects. (1) and (2) are intimately related if the solid is prepared
by aqueous precipitation such that the surface is hydroxylated. If the surface stays
hydroxylated, the protons present to balance the excess oxygen will act as new
Brbnstcd acid sites not present in the component oxides. On heating, some of
these protons may be removed as water which is formed with the concurrent
formation of an anion vacancy. The anion vacancy site is a Lewis acid site, and
could act as a BrQnsted acid site after it had been hydrated. The effect of (3) is less
easily prcdictcd. I t could bc important for solids that have open structures. In
most common binary oxides, however, the concentration of interstitial defects is
limited. Whether these defects lead to the formation of acid sites will likely
depend on the nature of the cation.
When y >z, a simple substitution of B ion by A ion would result in a
deficiency of oxygen. The deficiency can be removed by: (1) adsorption of
ncgativcly charged oxygen species onto the A ion; (2) adsorption of OH- onto the
A ion; or (3) formation of cation vacancies. When (1) or (2) operates, the
consequence of electrostatic potential change at the A ion is removed because the
coordinative unsaturation of A is removed by the adsorbed oxygen or OH-. Since it
is not likely that adsorbed oxygen acts as an acid site, new acidity is predicted not
to dcvclop. Adsorbed OH- could provide Brdnsted acidity, but the acidity would
be weak. When (3) operates, new Lewis acid sites could appear because cation
vacancies are clcctron deficient.
A comparison of experimental data and the predicted formation of new acid
sitcs i n binary oxides by Kung's model is summarized in Table 5-2.
It is interesting to note that although Tanabe's and Kung's models employ
very diffcrent approaches, either method gives the same prediction in many cases.
This is bccause Tanabc's model can be mathematically expressed as examining the
diffcrence between the qF/c value of the substituting ion and the surrounding
oxygcn ion, where qp is thc formal oxidation state, and c is the coordination
nunibcr. Although the stoichiometry of an oxide and the qF/c ratio do not have a
fixcd rclationship, this ratio is the same for most oxides of the same stoichiometry.
Sincc the latticc potentials ( i s. , C q,/r,) are about the same for oxides of the same
stoichiomctry and arc diffcrcnt from other stoichiomctries, there is a correlation
L.
80
between the difference in the qF/c values and the value of AV of eq. (5-3). Thus
the two models yield similar conclusions in most cases [111. Although they may
yield similar results, they involve important differences. Tanabe's model is a
localized model such that any new acid sites formed are at the substituting cation
site. Kung's model is a delocalized model. New acid sites can be formed on the
matrix surface far away from the substitution site as well as at the site.
The two models described above apply to dilute oxide solid solutions. That
is, isolated "impurity" cations occupy sites of the host oxide substitutionally.
Cations deposited on an oxide surface but not incorporated substitutionally may
also form new acid sites. A rather detailed study of this latter system has been
reported for Fez+and Fe3+ions deposited on MgO, TiO2. A1203 and SO2, and
Zn2+, Ga3+, Fe3+, M3+, Fez+, Sc3+, and Mg2+deposited on Si02. Mossbauer
spectroscopy and pyridine adsorption have been used to characterize these samples
[12-141. The dependence of the amounts of acid sites in these systems on the
pretreatment temperature indicates that BrQnsted acid sites may be removed by
high temperature evacuation of the oxide, that is, dehydroxylation of the oxide.
Lewis acid sites are present on samples pretreated by evacuation at low
temperatures, and they persist to much higher temperatures.
A model has been proposed by Connell and Dumesic [13,14] to explain the
formation of Lewis acid sites for ions deposited on Si02. The model assumes that
the formal charge on the deposited cation is balanced by the coordinating surface
lattice oxygen ions, and that a cation is coordinatively saturated if' it has a
coordination number four as Si ions have in SO2. If the number of coordinating
oxygen ions is less than four, the deposited cation may be coordinatively
unsaturated and act as a Lewis acid site. I t is further assumed that since oxygen
ions in the Si02 surface have a coordination number of two, the formal charge of
oxygen along each cation to anion bond is negative one. A +2 cation on the Si02
surface requires two coordinating surface oxygen for charge neutrality. For a +3
cation, this number is three. In both cases, the number of coordinating surface
oxygen is less than four, and Lewis acidity is expected to develop at these cation
sites. This model successfully explains the data presented. In addition to the
requirement of coordinative unsaturation of the deposited cation, the formation of a
new Lewis acid site also requires that the matrix oxide is not basic. Finally, the
strength of the acid site is determined by the electronegativity of the cation: more
electronegative cations result in stronger acid sites.
5.3 DETERMINATION OF ACIDITY
Since surface acidity is an important property that often determines the
surface chemistry, various methods have been developed to mcasure its presence
and strength. The most commonly used
method involves spectroscopic investigation of adsorbed probc molecules. This
method is perhaps experimentally the most convenient. With the much improved
spectroscopic techniques available today, rapid determination of the presence of
surface acid sites is possible. The sccond method employs the dctcrmination of
Three methods will be described.
SURFACE ACIDITY 81
isoclcctric point and the third method, titration with indicators.
Adsorption of Ammonia and Pyridine
Infrared spectroscopic investigation of adsorbed probe molecules has been
employed routinely to characterize various oxides [ 15] . The well developed
technique of spectral subtraction, made convenient with computers and Fourier
transform infrared spectroscopy, has made possible the investigation of colored
samples including iron oxide, and samples of low surface areas. Because this is a
dry tcchnique, there is a wide latitude in the pretreatment of the sample, and thus it
is convenient to study the effect of sample pretreatment on the amount and strength
of surface acidic sites.
The most common probe molecules are pyridine and NH3, although other
amines are sometimes used. NH3 and pyridine are bonded to the surface in three
different modes. I n the first mode, the molecules are adsorbed abstractively: it is
protonated by a proton from a surface hydroxyl group. Therefore, it probes
surface Brdnsted acid sites.
C ~H ~N + HM -+C~H~NH+ + 0-4
( 5- 5)
I n the second mode, the electron lone pair of the nitrogen atom adds to the (cus)
cation of the oxide which acts as a Lewis acid. Such bonding involves o-donation
and requires an exposed surface coordinatively unsaturated cation. Hydrogen
bonding is the third mode. It is the weakest mode of interaction. and has not been
uscd to measure the acidity of surface hydroxyl groups, although it can be done in
principle.
The presence of BrBnsted acidity is revealed by the formation of protonated
ammonium or pyridinium ions. These ions possess characteristic vibrational
bands. Likewise, ammonia or pyridine molecules bonded to Lewis acid sitcs or
hydrogen-bonded to the surface also possess characteristic bands. The
characteristic band for a N&+ ion is located at 1400-1480 cm-' [16]. As a
rcfercnce, a detailed table prepared by Tsyganeko [ 171 of NH3 infrared absorption
bands i n solutions of various proton-accepting and proton-donating solvents can be
uscd to help identify the bands. NH3 bonded via the electron lone pair at the
nitrogcn atom to a Lewis acid site possesses an asymmetric and a symmetric
stretching frequency of v,, =3330-3380 cm-' (compared with 3444 cm-' for a
molccule i n the gas phase) and v, =3260-3280 cm-' (3336 cm-' i n the gas phase)
[ 31. Additional hydrogcn-bonding intcraction with neighboring anions would lower
these frcqucnces [ 181. Whcn hydrogen-bonding to a surface hydroxyl group is the
only interaction, the NH3 infrared bands appear near 3400 and 3200 cm-' [3].
For pyridinc, according to Knozinger [ 191, the ring-vibration modes ( 1 9b and
8a modes) arc most affected by the nature of intermolecular interaction via the
nitrogcn atom. These two modes are observed at 1440-1447 and 1580-1600
cm-', rcspectively, for hydrogcn-bonded pyridine, at 1535-1550 and about 1640
cm-' for a pyridinium ion, and at 1447-1464 and 1600-1634 cm-' for pyridine
82
coordinatively bonded to Lewis acid sites.
Although a general classification of the mode of bonding is readily possible,
it has nor becn possible using this method to obtain quantitative information on the
strengths of the acid sites as measured by the proton affinities of the conjugate
bases formcd or the pK,'s of the acid sites. Attempts to determine the strength of
adsorption by temperature programmed desorption of adsorbed NH3 or pyridine
often fail because of oxidation of these molecules by the transition metal oxide.
I t has not been possible either to correlate the vibrational band frcqucncics with
the nature of the metal ion or its coordination [20,21].
Athough ammonia and pyridine have been used to probe similar surface
propcrties, they are not identical. One difference is their sizes. The molccular
cross-sectional area of NH3 is 0.127 nm2, and of pyridine is 0.313 nm2. Thus it may
be possible that more ammonia is adsorbed than pyridine. The larger size of
pyridine may also result in weaker bonding to a Lewis acid cation if steric
crowding is a factor, especially if the cation Lewis site is recessed into the surfacc.
This latter effect has been used to explain the smaller amount of pyridine adsorbed
than NH3 on Cr2O3 [ 181.
Another difference betwecn the two molecules is their relative basic strcngth.
I n an aqueous solution, ammonia is a stronger base with a pKb of around 9
compared to a pKb of about 5 for pyridine [221. However, the basicity of pyridine
in the gas phase is significantly higher [23,24]. I t has been pointed out in section
5.1 that the polarizable surface oxygen ions make molecules on an oxide surfacc
behave as if they were in an aqueous solution. Thus the rclativc basicity i n
aqueous solutions should be more appropriate to describe the relative Brdnstcd
basicity of these two molecules. Indeed, on the oxidized and the reduced
molybdena/alumina, N h + ions are detected. On the other hand, pyridinium ions
are dctected only on the oxidized form [25]. The relative Lewis acidity is
different. For example, pyridine is desorbed more slowly than ammonia from thc
Lewis acid sites of F%03, which suggests that it is adsorbed morc strongly than
Most of the first row transition metal oxides and a fcw of the othcrs have bccn
studicd with these two moleculcs. As shown in Table 5-3, Lewis acid sitcs arc
found on practically all of the oxides studied that have been prctreatcd by hcating
to 400°C or higher in vacuo. On the other hand, Brbnstcd acid sitcs are found only
on V205, Nb205, Moo3, W03, Re207, and Cr2O3/AI2O3 [ l S] .
The density of acid sites dcpends on the sample prctreatmcnt. Figurc 5-3
shows an example of this effect on Nb205 as dctcrmined by pyridinc adsorption
[27]. The sample dried at 100°C possesses a rather large amount of Brdnstcd and
Lewis acid sitcs. Hcating Ihe sample to 300°C in vacuo results in a decrcasc in the
numbcr of BrBnsted acid sites but an increasc in Lewis acid sitcs. Thus thcrc is an
intcrconversion upon dehydration. Further heating to 500°C i n vacuo rcsults i n
sharp dccreascs in both typcs of acid sitcs, which are due mostly to a rapid loss i n
surface arca. The cffcct of evacuation aftcr pyridinc adsorption is also shown in
the figurc. As expcctcd, a highcr evacuation temperature rcsults in smallcr
amounts of pyridinc adsorbed. I t is interesting to note that thc dccrcasc i n the
amount of pyridinc adsorbcd is qiiitc gradual with the incrcasc in evacuation
NH3 [26].
SURFACE ACIDITY 83
Table 5-3 Acid Sites on Various Transition Metal Oxides Determined by
Ammonia or Pyridine Adsorption
Mode of Bonding
Oxidea H-bonding Lewis Acid Brbnsted Acid
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
+
Footnote:
a) Pretreated by evacuation at 400°C or higher.
temperature. This suggests that there is a broad range of strength of interaction of
pyridine with the surface, which implies the presence of sites of a broad range of
acid strength.
Isoelectric Point
A second method to determine the presence of acid sites is by determining the
isoelecuic point of an oxide. This method makes use of the phenomenon that solid
oxide particles in aqueous suspensions are often electrically charged. Charged
particles are formed when there is an imbalance between the densities of adsorbed
H+, OH-, and ionized surface OH groups. They may also be formed by adsorption
of metal hydroxo complexes derived from the hydrolysis products of material
dissolved from the solid, i.e., [Mz+(OH),,]zA species. The presence of a net
charge on the oxide particle can be observed in electrophoresis experiments. The
magnitude of the surface charge depends on the pH of the solution, and there exists
a pH at which there is no net surface charge. This pH is called the isoelectric
point, I t is equivalent to he point of zero charge, and is the pH at which
suspended particles i n H20 do not move in an electric field.
Since the oxide particles arc in an aqueous solution during the determination
of isoelccuic point, much of the variation of surface acidity due to different extents
84
0 200 400 600
Pr et r eat ment Temp. C
Figure 5-3 Relative amounts of a: Lewis acid; b: Brdnsted acid sites of a sample of
Nb2OS.nHzO as a function of pretreatment temperature as determined by the IR absorption
peak intensity of adsorbed pyridine after evacuation at: 1, room temperature; 2. 100°C;
3, 200°C; and 4, 300°C. The surface areas of the sample after pretreatments at various
temperatures are : lOO"C, 164 m2/g; 300"C, 126 m2/g; and 500°C. 42 m2/g. (From Bull.
Chem. SOC. J pn., 56, 2927 (1983), copyright Chemical Society of J apan).
of hydroxylation cannot be studied. However, the isoelectric point is still a rather
sensitive function of the history of the sample. This is because the density of
charges on any oxide surface is quite low. Thus the surface charge could be
significantly altered by the presence of impurity cations or anions on the surface, as
well as surface imperfection such as vacancies and dislocations. I ts value could
also depend on the nature of the ions in the aqueous phase that are used to vary the
pH due to the possibility of specific adsorption of the ions. These factors have led
to wide variations in the reported values of the isoelecuic points of oxides.
Isoelecuic points can be determined in an elcctrophoresis apparatus where
the zeta-potential of a solid is measured as a function of the pH of the solution.
Since zeta-potential is the potential between a charged surface and the electrolyte
solution, its value is zero when the net charge of the surface is zero. Therefore, the
pH at which the zeta-potential is zero is the isoelecuic point, assuming that there
are no adsorption of charged species other than protons and hydroxide ions on the
SURFACE ACIDITY 85
Figure 5-4 Zeta-potential at 22.5'C as a function of pH. Curve 1: NiAl204 and CoA1204;
curve 2: C0304; curve 3: A1203; and curve 4: NiO. (From J . Catal.. 83, 225 (1983).
copyright Academic Press).
surface. Figure 5-4 shows some sample data for a number of oxides [28].
The isoelectric points for a large number of oxides have been determined.
Table 5-4 is an updated summary of the comprehensive data collected by Park
[29,30]. From these data, Park proposes a generalization presented below based
on the stoichiometry of the oxide:
Isoelectric poi nt (IEP)
M2 0 IEP >pH 11.5
MO 8.5 <I EP <12.5
M2°3
6.5 <IEP <10.4
0 <IEP <7.5
M205, M03 IEP <0.5
MO2
Although the expcrimental values of isoelectric point dcpcnd on the hydration
state, purity, and surface imperfection, they are fundamental properties of an
individual oxide whcn thcsc complications are eliminatcd. I t becomes possible to
use isoclcctric points to determine tile fraction of each oxide exposed on the
surface in a system containing two oxides. For example, the isoelectric point of
Moog is 6.25, and of alumina is 8.80. I t has been found that Moo3 supported on
A1203 shows an IEP intermediate between these two values, and there exists a onc-
to-one correlation between the value of IEP and the Mooj surface area detcrmincd
by oxygen chemisorption [31]. I t has now been shown with Co [28], Mo [32], and
V [33] oxides supported on alumina that a supportcd oxide often shows an IEP
86
Table 5-4 Isoelectric Points of Transition Metal Oxides and Hydroxides
7.0
7.3
7.6
11 f 0.2
9.5 f 0.4
12 ? 0.5
6.5 f 0.2
5.2 to 8.5
6.7 rt 0.2
4 to 4.5
7.0
6.2
8.3 to 10.3
11 to 12
4.5 to 6.3
1.4
<0.5
8.7 to 9.2
Table 5-5 Isoelectric Points of Oxides Supported on Alumina
Co-Alb
pure
% Coa pure y-Al2o3 0.6 1.0 1.6 4.4
5.9 Co304 CoA1204
IEP 8.80 8.30 8.05 7.65 7.95 8.05 7.30 2.65
Ni-Alb
% Nia pure y-A1203 2.3 4.5 6.0 9.0 pure NiO NiAI2O4
IEP 8.80 8.15 8.00 7.80 7.60 8.30 2.65
MO-AI' .
% Moa pure y-AI2O3 1.1 4.1 8.8 11.4 13.8 pure Moo3
IEP 8.80 8.65 8.50 8.30 8.00 7.85 6.25
Footnotes:
a) g oxide per 100 g y-Al203.
b, From J . Catal., 83, 225 (1983).
") From Appl. Catal., 4, 371 (1982).
SURFACE ACIDITY
intermediate between the component oxides. Furthermore, the formation of the
aluminates can be easily detected as they have very different isoelectric points
from the component oxides. Table 5-5 shows the data for Co, Ni, and Mo
supported on alumina. For supported vanadia, the EP varies with increasing
vanadium content from 8.25 to 6.80 on a y-alumina support, and from 4.5 to 1.95
on a titania support. The values for pure alumina, vanadia, and titania are 8.80,
1.40, and 6.30, respectively. Among these examples, one may note that the NiO-
A1203 system seems to be anomalous in that the IEPs of the mixed oxides fall
outside the range bracketed by the component oxides. Nonetheless, there is a
monotonic trend as observed in the other oxide systems.
Titration with Indicators
A third method to determine surface acidity is by titration with indicators.
Conceptually the method involves first adsorbing onto the solid a particular
indicator which changes color on protonation. It is important that the adsorption
process is completed without exposure of the pretreated sample to moisture. Thus
careful exclusion of air and an anhydrous organic solution of the indicator is used.
If the surface possesses hydroxyl groups more acidic than the pK, of the indicator,
the indicator becomes protonated and undergoes a change in color. The solid is
then titrated with a strong base such as n-butylamine to deprotonate the indicator.
The amount of n-butylamine needed to completely deprotonate the indicator, as
indicated by a color change, is the amount of surface hydroxyl groups more acidic
than the pK, of the indicator. By using different indicators of different pK,'s, the
distribution of acid strength of an oxide can be determined.
This method has a number of experimental difficulties. The most severe one
is the long time required to attain equilibrium between the surface and the
indicator. During this equilibration time, extreme care is needed to prevent the
oxide from exposure to air, especially moisture and COz. Another problem is that
accurate pK, values of indicators that should be used under these experimental
conditions are not available. Aqueous pK, values are often used as reasonable
approximates.
This method has been extensively employed by Tanabe and coworkers [7,8].
The common indicators used include Methyl Red (pK,=+4.8), 4-dimethylamino-
azobenzene (+3.3), 4-anilinoazobenzene (+1.5), Crystal Violet (+0.8),
dicinnamylidene-acetone (-3.0), benzylideneacetophenone (-5.6), and
anthraquinone (4.2). Table 5-6 shows some exemplary data using this method.
Among these examples, A1203, Ti02 and Zr02 all show a rather narrow
distribution of acid strength. There is a sharp drop in the amount of acid sites of
pK, more acidic than 3.3. On the other hand, mixed oxides show much broader
distributions of acid strength. Most interestingly, new acid sites are developed in
the mixed oxides that are much stronger than those found in the component oxides.
The catalytic importance of strong acid sites has been well documented for silica-
alumina. Acidic mixed oxides involving transition metals may eventually find
technological applications.
88
Table 5-6 Distribution of the Amounts of Acid Sites of Different Acid
Strengths a
Surface
Area
Acid Amounts (mmoVg) at different pK,'s
Oxide mZ/g +4.8 +4.0 +3.3 +1.5 -3.0 -5.6 -8.2
A1203 190 - 0.285 0.075 0
Ti02 38.5 0.057 0.057 0
Zfl2 72.0 -
0.280 0.060 0.060 0
Ti02-Zr02b 230 - 0.475 0.380 0.350 0.375 0.125 0.050
TiO2-Al2O3; 204 0.422 0.422 0.337 0.250 0.220 0.060 0
Zfl2-Al203 320 - 0.590 0.205 0.205 0.045 0.045 0
Footnotes:
a) Taken from Bull. Chem. SOC. J pn., 46, 2985 (1973), copyright Chemical Society
b, The molar ratios are about 1:1.
of J apan.
5.4 ROLE OF ACID SITES IN CATALYTIC REACTIONS
The importance of strong Brbnsted acid sites in hydrocarbon conversions has
been well established [34]. Transition metal oxides are no exceptions. Those
with strong Brbnsted acid sites catalyze cracking and skeletal isomerization of
alkanes. These include Nb205 and TazO5 that are not readily reduced. They also
catalyze carbon-carbon double bond isomerization and alcohol dehydration.
These latter reactions may proceed by other mechanisms not involving acid sites as
well. They are separately discussed in later chapters.
Perhaps the reactions most uniquely catalyzed by transition metal oxides are
metathesis and selective oxidation reactions. The current mechanism of
metathesis does not require acid sites. On the other hand, both Brujnsted and
Lewis acid sites may participate in selective oxidation reactions. For example. it
has been proposed that the oxidative cleavage of butcne to acetic acid and
acetaldehyde proceeds via the formation of carbenium ions [35]:
SURFACE ACIDITY
89
The role of Lewis acid sites in the selective oxidation of alkenes has been
suggested [36-381. The activation of the alkene molecule is assumed to be the
adsorption onto a Lewis acid site. Details of these reactions are discussed in
Chapters 11 and 12 on selective oxidation.
REFERENCES
1. R. G. Pearson, "Hard and Soft Acids and Bases," Dowden. Hutchinson, and Ross
2. R. Spitz, J. Burton, M. Barteau, R. Staley, and A. Sleight, J. Phys. Chem.. 90,
3. T. Morimoto, H. Yanai. and M. Nagao. J. Phys. Chem., 80,471 (1976).
4. K. Segawa, and W. Hall, J. Cutul., 76, 133 (1982).
5. R. Groff, J. Cutul., 86, 215 (1984).
6. T. Kantoh, and S. Okazaki, Bull. Chem. Soc. Jpn., 54.3259 (1981).
7. K. Tanabe, "Solid Acids and Bases, Their Catalytic Applications," Academic Press,
8. K. Tanabe, in "Catalysis Science and Technology", J. R. Anderson and M. Boudart ed.,
9. K. Tanabe, T. Sumiyoshi. K. Shibata, T. Kiyoura, and J. Kitagawa, Buff. Chem. Soc.
10. K. Shibata, T. Kiyoura, J. Kitagawa, T. Sumiyoshi, and K. Tanabe, Bull. Chem. Soc.
11. H. Kung, J. Solid Stute Chem., 52, 191 (1984).
12. G. Connell, and J . A. Dumesic, J. Cutul., 101. 103 (1986).
13. G. Connell, and J. A. Dumesic, J . Cutul.. 102, 216 (1986).
14. G. Connell, and J. A. Dumesic. J. Cutul., 105, 285 (1987).
15. M. C. Kung. and H. H. Kung, Cutul. Rev. Sci . Eng., 27,425 (1985).
16. L. H. Little, "Infrared Spectra of Adsorbed Species," Academic Press, New York. 1966.
17. A. Tsyganeko, D. Pozdnyakov, and V. Filimonov, J. Mol. Struc., 29,299 (1975).
18. K. Morshige. S. Kittaka, S. Katsuragi, and T. Morimoto, J. Chem. Soc. Furuduy
19. H. Krozinger, Adv. Cutul., 25. 184 (1976).
20. N. Gill, R. Nuttall, D. Scaife, and D. Sharp, J. Inorg. Nucl. Chem., 18.79 (1961).
21. A. Zecchina, E. Guglielminotti, L. Cerruti, and S. Coluccia, J. Phys. Chem.,
22. E. P. Parry, J. Cutul., 2, 371 (1963).
23. W. B. Jensen, 'The Lewis Acid-Base Concepts, An Overview," Wiley, New York,
24. M. Taagelpera, W. Henderson, R. Brownlee. J. Beauchamp. D. Holtz. and R. Taft,
25. J . Valyon, R. L. Schneider, and W. K. Hall, J. Cutul., 85, 277 (1984).
26. C. Rochester, and S. Topham. J. Chem. SOC. Faruduy Tr m. I , 75, 1259 (1979).
Publ.. Stroudsburg, PA, 1973.
4067 (1986).
New York, 1970.
Springer-Verlag, New York/Berlin, vol. 2. p. 231, 1981.
Jpn.. 47, 1064 (1974).
Jpn., 46. 2985 (1973).
Trans. I , 78, 2947 (1982).
76, 571 (1972).
1980.
J. Amer. Chem. SOC., 94, 1369 (1972).
90
27. T. Iizuka, K. Ogasawara, and K. Tanabe, Bull. Chem. SOC. Jpn. , 56, 2927 (1983).
28. F. Gil-Llambias. and A. M. Escudey-Castro, J. Cataf., 83, 225 (1983).
29. G. A. Park, Chem. Rev., 65, 177 (1965).
30. G. A. Park, Adv. Chem. Series, 61. 121 (1967).
31. F. Gil-Llambias, and A. Escudey-Castro, J . Chem. SOC. Chem. Commun., 478 (1982).
32. A. Escudey-Castro, L.B. McLeod, and F. Gil-Llambias, Appl. Cataf., 4, 371 (1982).
33. F. Gil-Llambias. A. Escudey-Castro, J . Fierro, and A. Lopez-Agudo, J. Cataf.,
34. H. Pines, 'The Chemistry of Catalytic Hydrocarbon Conversions."
35. Y. Takita, K. Nita, T. Maehara, N. Yamazoe, and T. Seiyama, J. Catof.,
36. D. Dadyburjor, S. J ewur, and E. Ruckenstein, Cutaf. Rev., 19, 293 (1979).
37. H. Kung, Ind. Eng. Chem. Prod. Res. Dev. , 25, 171 (1986).
38. M. Ai, J . Catal., 52, 16 (1978).
95, 520 (1985).
Academic Press, New York, 1981.
50, 364 (1977).
Chapter 6
REDUCTION OF OXIDES
6.1 INTRODUCTION
Reduction of an oxide can be accomplished by removal of lattice oxygen, or
by dissolution of the reductant into the lattice. The former is common to all
oxides, while the latter occurs only i n very selected systems. An example of the
latter is the dissolution of hydrogen in WO3 to form H,W03, tungsten bronze.
Removal of lattice oxygen can be achieved by many different reducing
agents. The common ones include hydrogen, carbon monoxide, ammonia gas, and
hydrocarbons. Usually the thermodynamic driving force is the formation of water
and carbon dioxide. However, while the use of different reducing agents may
involve nearly equivalent thermodynamic driving forces, the kinetics and the
rncchanism of reduction can be very different. The rates of reduction may depend
strongly on the presence of surface defects and bulk grain boundaries, the
orientation of the exposed surface planes, the nature of the support if any, the
presence of hydroxyl groups, and the presence of other metals. When the bulk
structure is anisotropic, the rate of reduction in the bulk is likely anisotropic. For
example, molybdenum oxide has a layer structure, and shear planes are more
readily formed along some directions (see Chapter 2). Reduction along the shear
planes is much more rapid than along other directions.
Reduction in the surface region may be accomplished also by ion sputtering
which usually preferentially removes oxygen atoms. The extent of reduction
obtained by this process depends on the orientation of the surface plane, the nature
of the oxide, and the sputtering conditions [la].
Because of the large number of significant variables, the surface properties of
samples of partially reduced oxides may be quite different and dependent on the
dctails of the reduction process, even for the same overall degree of reduction.
For example, the partial reduction of iron oxide, Fe203, by CO usually results in a
lower oxide in the surface region of a grain and a surface carbonate. Under some
conditions, a carbide may be formed. Reduction by hydrogen, on the other hand,
91
92
results in a hydrogenated surface of reduced oxide. Reduction by hydrocarbon
could lead to a lower oxide with a surface C ~ ~ ~ ~ M C ~ O U S layer, as well as a
hydroxylated surface and surface carbonate. Another example is the reduction of
bismuth molybdate by hydrogen, butene or propene. The catalytic activity of the
partially reduced oxide for propene and butene oxidation has been found to depend
on the reducing agent used (see Chapter 11) [lb].
6.2 THERMODYNAMICS OF REDUCTION
The reaction between a metal oxide MO, and hydrogen to form a lower oxide
MO,-l and water vapor can be represented by the equation:
The Gibbs frce energy change, AG, for this reaction is related to the standard value,
AGO, by:
AG =AGO+ RT tn(PH20/PH2)
(6-2)
If the oxide MO, is reduced totally to the metal M, the last term of this equation
becomes nRT tn(PH20/PH2), and the standard Gibbs free energy change now
refers to the total reduction reaction.
Inspection of the stoichiometric ratios of this reaction in Eq. (6-1) shows that
there is no change in the number of gas phase molecules between the reactants and
the products. Thus the AS contribution to AG is small.
Thermodynamic treatments are quite useful for estimating the extent of
reduction of bulk oxides and large oxide crystallites. Their usefulness is more
limited for well-dispersed oxides on a support or for amorphous oxides, because
the AGO values for these oxides are usually not available, cannot be estimated
reliably from bulk metal-oxygen bond energy, and vary from one sample to the
ncxt. The metal-oxygen bond lengths and bond angles in these oxides may be
quite different frombulk oxides. For example, it has been mentioned in Chapter 3
that the lattice of small a-Fe203 crystallites dilates. The energy associatcd with
the interaction with a support cannot be evaluated accurately either.
If the ratio of the partial pressure of water to hydrogen is known (or
equivalently the gas phase oxygen activity), equations (6-1) and (6-2) permit the
calculation of the MO,-l to MO, ratio. That is, the bulk stoichiometry of the
oxide can be evaluated. However, this does not imply that the surface
stoichiometry is known. At thermodynamic equilibrium, the thermodynamic
activity of the oxygen ion in the surface is the same as that in the bulk. However,
the different electrostatic potcntial and the different numbers of ncighboring ions at
a surface site versus a bulk site make the energy of the surface ions diffcrent from
thc bulk ions. Furthermore, there may be reconstruction of the surface structure.
The result is that at equilibrium, the surface stoichiometry may be somewhat
diffcrent from the bulk stoichiometry. The extent of this possible difference is
REDUCTION 93
currently unknown.
6.3 KINETIC MODELS
The first step in reduction is the activation of the reducing agent. If carbon
monoxide is used, it is most likely first adsorbed onto a coordinatively unsaturated
surface metal ion of the oxide. This is followed by its reaction with the lattice
oxygen to form a surface carbonate with reduction of the metal cations, which
decomposes to carbon dioxide. If hydrogen is used, it is adsorbed by heterolytic
dissociation. A surface hydroxyl group is formed in this process (see Chapter 4).
Desorption of water that is formed by the reaction of a hydroxyl group and a hydride
would results in reduction of the oxide.
Since adsorption of hydrogen and/or carbon monoxide might be enhanced by
the presence of reduced metal oxide which has a higher density of coordinatively
unsaturated metal cations of lower oxidation states, the reduction process could be
autocatalytic, depending on the method of growth of the reduced portion of the
oxide.
Mathematical description of the reduction kinetics is available for bulk oxide
particles which can be modeled as isolated spheres in the absence of any effect due
to support, presence of impurities, or anisotropy. There are two models, the
nucleation model and the contracting sphere model.
I n the nucleation model, surface oxygen ions are removed from the lattice by
reduction, leaving behind an anion vacancy. When the concentration of vacancies
reaches a critical value, the vacancies are annihilated by rearrangement of the
lattice with the eventual formation of small grains of lower oxide or metal (see Fig.
6-1). Such rearrangement can be readily accomplished if the oxide tolerates the
presence of shear planes. The small grains of reduced oxide grows by inward
diffusion of the reduced metal ions and/or outward diffusion of the oxygen ions.
Eventually, these grains of reduced oxides or metal grow to the extent that their
boundaries overlap, resulting in a particle of an oxide core with a shell of reduced
oxide. Further reduction of this particle follows the contracting sphere model.
The time dependence of the degree of reduction, a, in the initial stage of
isothermal reduction by the nucleation model is described by eq. (6-3) [2,3]:
where Vfinal is the final volume of the grain of reduced oxide, C1 and p are
constants related to the time dependence of the volume of a grain, tl is the
induction time, and C2 and q are constants related to the time dependence of the
number of grains.
Figure 6-2 shows the fraction of an oxide reduced with respect to time for the
nucleation model. There are two characteristics for the kinetics of reduction
according to this model: the presence of an induction period, and the possibility
94
nucleus of met al
or reduced met al oxide
met al oxi de
Figure 6-1 Initial stage of reduction of metal oxide by the nucleation model.
Ti me
Figure 6-2 Fraction of oxide reduced as a function of time for the contracting sphere model
(I) and the nucleation model (n).
Figure 6-3 Initial stage of reduction of metal oxide by the contracting sphere model.
REDUCTION 95
of autocatalysis. Both of these characteristics are results of the fact that in the
early stage of reduction, the grain-oxide interfacial area increases with the size of
the grain, and that a grain of reduced oxide activates the reductant more readily
than the fully oxidized oxide. These result in an increase in the rate of supply of
reductant to the oxide, and the corresponding increase in the rate of reduction as
the reduction proceeds. Thus the fraction of oxide reduced as a function of time is
concave upward initially. Eventually when the grains of reduced oxide coalesce,
and the reduction follows the contracting sphere model, the rate of reduction
decreases with time. Thus the reduction curve has a sigmoidal shape.
This nucleation model describes the reduction of NiO with hydrogen. An
induction period is observed when the NiO (100) plane is reduced. As the surface
becomes severely reduced, Ni metal islands exposing primarily the (100) plane are
formed with Ni <010>and <001>directions along the NiO cOlO> and <001>
directions, respectively. The rate of oxygen removal is first order in surface oxide
concentration, and first order in the hydrogen pressure [4]
The contracting sphere model is an extreme case of the nucleation model in
that it is assumed that the number of reduced oxide grains formed on the surface of
the sphere is so large that the boundaries of the grains overlap when the diameters
of the grains are still small versus the radius of the sphere. This situation can be
accurately modeled as a rapid formation of an uniform layer of reduced oxide or
metal on the sphere (Figure 6-3). The thickness of this reduced layer grows
uniformly, resulting in a spherical core of oxide that shrinks with time. Since the
rcduction of the core oxide is accomplished by diffusion of ions and reductant
across the oxide-reduced oxide interface whose area decreases with time, and the
distance of this interface from the surface of the sphere increases with time, the rate
of reduction decreases with time. This results in a characteristic curve for the
extent of reduction shown i n Figure 6-2.
The time dependence of the degree of reduction for isothermal reduction by
the contracting sphere model is described by eq. (6-4) [2]:
k
rodo (‘ O -
P
c,,>t =[ l -
a
- - ( 1 - 3
where k, is the rate constant of reduction per unit area at the oxide-reduced oxide
interface, kd is the diffusivity of reductant through the reduced layer, ro is the
radius of the entire sphere, and C,, C,, are the actual concentration of reductant at
the outer surface of the sphere and the equilibrium concentration. The expression
assumes that the chemical rcaction at the interface is first order with respect to
Cl-C,,, where C, is the reductant concentration at the interface.
Another situation is possible that is i n between the nucleation and the
contracting sphere models. This situation is as follows. Small grains of reduced
oxide are first formed on the surface of an oxide particle as in the nucleation model.
However, these grains of reduced oxide are less active in activating the reductant
molecules than the fully oxidized oxide. Therefore, their presence on the oxide
surface inhibits the rate of reduction bccause it reduces the area of exposed fully
96
oxidized oxide. These grains grow as reduction continues, eventually cover up the
oxide particle. Whence the oxide is reduced by the contracting sphere model.
In this situation, the rate of reduction decreases continuously with increasing
extent of reduction, and the fraction of reduction-versus-time curve should be
qualitatively the same as the one for the contracting sphere model.
The descriptions so far assume that the cations and anions in an oxide have
homogeneous properties. However, the surface chemistry and catalytic properties
depend heavily on the surface condition. In section 4.1, it is shown that a surface
may possess more than one type of surface lattice oxygen. A Ti02 (1 10) surface is
one such example (Fig. 4.1) where there are two types of surface lattice oxygen
ions. Type one is bonded to two six-coordinated Ti cations, and sits above the
plane of the other ions. The other type is bonded to one six- and two five-
coordinated Ti cations and is in the surface plane. Their different positions and
bondings should make them removable with different degrees of difficulty.
Removal of the first type would involve breaking two Ti-0 bonds. Removal of the
second type would involve breaking three Ti-0 bonds, and should be more difficult
than the first type. Indeed, this has been confirmed on the Sn02 (1 10) surface
[67]. Even within each type, it is expected that there will be a gradual increase in
the difficulty in removing the oxygen ions as the reduction increases.
This consideration suggests that unlike the kinetic treatment above which
applies well to bulk reduction, reduction of the surface is likely to proceed with a
rate constant that depends on the orientation of the surface plane, the extent of
reduction, and the density and nature of surface defects. Unfortunately no
quantitative experimental data are available.
6.4 MECHANISM OF REDUCTION
The most heavily studied system is perhaps the reduction of well-dispersed
molybdenum oxide on a support. In the reduction of molybdcnurn oxide
supported on alumina, it has been found that one molecule of water is relcased for
every two hydrogen molecules consumed at low extents of reduction. Thus some
hydrogen is retained by the partially reduced oxide [51. The Mo(V) specics has
been detected by EPR, but its concentration is low compared with thc extent of
reduction [6]. A model of the reduction process that is consistent with these
results is shown in Figure 6-4 [7].
In this model, the well-dispersed supported molybdenum oxidc is present as
an oxide chain. The initial step of reduction is the heterolytic adsorption of
hydrogen molecules followed by reduction of Mo cations and migration of H from
a cation to an oxide ion to form a p-hydroxl group. Thus two p-hydroxyl groups are
formed for one hydrogen molecule adsorbed. The two p-hydroxyl groups may
bridge the same Mo-Mo pair or diffcrcnt pairs as shown in structure 111, and these
two modes probably occur with equal likelihood. On the other hand, dehydration
probably occurs more readily if the p-hydroxyl groups span thesame Mo-Mo pair.
This would explain the observation of one molecule of water released for every
two molecules of hydrogen consumed at low extents of reduction. This i s
REDUCTION
97
I\ / I
- o-o-o o-o-o-
H
0
-1- H2°
(VI)
- o-o-o o-o-o-
Figure 6-4 A possible mechanism for the reduction of supported MOO,
98
illustrated by the conversion of III -t IV. Reduction continues by further adsorption
of hydrogen and dehydration (IV + V + VI).
If the molybdenum species is part of a crystallite instead of the monolayer
shown, diffusion of lattice oxygen from the bulk to the surface occurs. This is
equivalent to the diffusion of anion vacancies fromthe surface into the bulk, and
surface molybdenum oxide can then undergo another cycle of reduction. This
process results in bulk reduction.
The mechanism and the extent of reduction determine whether the reduced
oxide can be rapidly reoxidized. In general, if the reduction preserves the essential
structural feature of the oxidized form, rapid oxidation may be expected. A
rapidly reversible system has been demonstrated for CaMn03 and CaMnO2.5, and
for CazMn04 and Ca2Mn03.s [8]. The reduction of M a 3 to the lower oxides by
the formation of shear planes is also expected to be rapidly reversible.
When there are a number of intermediate oxides between the fully oxidized
state and the metallic state, then during reduction, reduced oxides are normally
formed in the sequence of increasing degree of reduction. For example, in the
reduction of large crystallites of CuO at 250°C in 2% H2/Nz, the oxide is almost
totally reduced to CuzO before metallic Cu appears [9]. However, depending on
the system and the reduction conditions, some intermediate oxides are further
reduced immediately upon formation. For example, one might expect the
reduction of F@03 to proceed via Fe304 and then FeO en route to metallic Fe.
However, when Fez03 is reduced in Hz, F%04 is lirst formed, and Fe304 is then
reduced directly to Fe metal. Little or no FeO is detected [lo].
Even with a given oxide, the reduction sequence can depend on the crystallite
size, the crystallographic form, and the nature of the support. In the example of
CuO mentioned above, much less Cu20 is detected during reduction of small
crystallites, and a majority of CuO appears to be directly reduced to Cu metal [9].
The dependence on crystallographic form is illustrated by Nbz05. The reduction
of p-Nb205 proceeds readily in H2 at 750°C to form Nb02 [ l l ] . However, a-
Nb205 is reduced through a series of complex intermediates, but no Nb02 is
formed [12]. The effect of the support is quite complicated. It is separately
discussed in the next section.
6.5 EFFECT OF SUPPORT
The interaction of an oxide with a support could affect both the
thermodynamics and the kinetics of its reduction. The effect arises partly because
a support can act as a dispersing agent, and small crystallites may be reduced
differently than large crystallites, such as the example of CuO mentioned above.
A support can also interact chemically with the oxide. Often, but not always, such
a chemical interaction increases the resistance of the oxide to reduction.
There are quite a number of examples of increased resistance to reduction
when an oxide is supported. W03 supported on A1203 is more difficult to reduce
than unsupported W0 3 [13,14]. Fe2O3 supported on y-AI2O3 [2], and Pt oxide
supported on y-AI2O3 [15] are similarly less reducible than their unsupported
REDUCTION 99
oxides. It has been reported that a F't+ signal is detected by EPR on a I "fl-Al203
sample even after reduction at 623 K [16].
There are disagreements for some other systems. One report mentions that
V205 supported on Ti02 is less reducible than unsupported Vz05 [17]. Another
lists the ease of reduction as decreasing in the sequence Vh-Al203, VDiO2, V2O5
[18]. I n this case, the influence of impurities present in the support may be
important.
It has been reported that in
temperature programmed reduction, carefully oxidized Rh crystallites on A1203 or
Ti02 that contain only a surface layer of Rh oxide are reduced more readily than
the bulk oxide [19]. In another report, it is mentioned that RhIy-Al203 that is
oxidized at a temperature above 873 K is reduced less readily than a similarly
pretreated bulk oxide [20]. It has been proposed that a high temperature of
oxidation is necessary to induce the strong interaction with the support that leads to
lower reducibility. It is interesting to mention that temperature programmed
reduction of a Rh/Ti02 sample fully oxidized at low temperature shows two
distinct reduction peaks. The lower temperature peak is due to well-dispersed
Rh2O3 on the support, and the higher temperature peak is due to large Rh2O3
crystallites [19]. It appears that in the supported Rh203 system, different
pretreatments lead to different effects of dispersion and chemical interaction on the
rates of reduction.
In some cases, the apparent support effect may be actually due to the reaction
between the oxide and the support to forma new compound. In this case, the
increased resistance to reduction is due to the different properties of the new
compound. This is the case for NiO/A1203. The reduction of this oxide often
shows portions of different rates. It is now understood that the different rates
correspond to the reduction of crystalline NiO, Ni2+bound to alumina, and nickel
aluminate [21-241. The increased resistance to reduction of V205/Mg0 is
likewise due to the formation of Mg3(V04)2 [25].
The reduction of a metallic ion ina zeolite depends on the location of the ion.
It has been reported that a Ni2+ion in a hexagonal prism of faujasite is more
difficult to be reduced than a Ni2+ion in the sodalite cage or supercage [26].
Presumably, the lattice oxide ions of the hexagonal prism stabilize the Ni2+ion
rather effectively.
I t should be noted that while a support affects the reducibility of an oxide, the
presence of an oxide may also cause changes in a support during reduction. For
example, during temperature programmed reduction of a V205/Ti02 (anatase)
sample, reduction of V2O5 and transformation of anatase to rutile are
simultaneously observed [27-291.
When an oxide strongly interacts with a support, the support could determine
the structure of the oxide and its reduction behavior. For example, reduction of
vanadia well-dispersed on anatase Ti02 removes an average of 0.85-0.90 oxygen
atoms per vanadium ion [30]. Reduction of vanadia well-dispersed on A1203
removes an average of 0.6 oxygen atoms per vanadium. Reduction of large
crystallites of V205 removes 0.55 oxygen atoms per vanadium.
The rhodium oxide system is interesting.
100
6.6 EFFECT OF OTHER COMPONENTS
The presence of other components may enhance the rate of reduction of an
oxide by promoting the rate of activation of the reductant. For example, the
presence of a noble metal may enhance the dissociation of hydrogen. The
activated reductant then migrates to the reduction site and reduction is enhanced.
In some cases, migration is by the spillover phenomenon in which the activated
reductant migrates over the support. This mechanism has been used to explain the
results from a physical mixture of F~03&-Al 203 and ptly-AlzO3. Reduction of
FezO3/y-AIzO3 commences at about 430 K in this mixture, much lower than 640 K
without F ' t [2].
The reduction of Re-Pt/Alz03 is another well studied example. The addition
of Pt considerably lowers the temperature required to reduce Rez&. This has been
explained by the surface migration of R%07 to Pt [31,32]. Such migration results
in physical contact between the two components, and hydrogen atoms dissociated
on Pt can migrate readily to R%07. A similar enhanced reduction by the addition
of Pd to R%07/A1203 is also observed [33].
The reduction of Pt is also affected by the physical contact between Pt and
RezO7. In a temperature programmed reduction experiment, the reduction peak for
Pt is moved to a higher temperature in the presence of Rez& than in its absence
WI.
The formation of hydrogen bronze is much facilitated when the oxide is in
contact with a metal that dissociates hydrogen molecules. It has been reported that
HxW03, H,M0O3, and HXV2O5 can be readily prepared by exposing the oxide
deposited with platinum to hydrogen gas [64-661. It is interesting that only part of
the hydrogen incorporated into the bronzes can be removed easily, such as by
evacuation or by consumption in the hydrogenation of ethene [65,66].
6.7 REACTIVITY OF REDUCED SURFACES
Reduced surfaces often possess chemisorptive and catalytic properties
different from stoichiometric surfaces. It has been shown that NO is adsorbed
strongly on Fez+but only weakly on Fe3+[35-371. and strongly on partially
reduced tungsten oxide but not on fully oxidized W6+ [38]. CO has been shown to
adsorb on Cu+ strongly, but on Cu2+ weakly [39]. The reason for the difference
between the oxidized and the reduced ions is probably the different electronic
configurations of the ions, and the lower degree of coordinative unsaturation in the
fully oxidized oxides.
Together with the presence of surface cations with a high degree of
coordinative unsaturation, a reduced surface also has cations of a lower oxidation
state and anion vacancies. Some of these factors lead to the enhanced activity of
the surface to dissociatively adsorb molecules that contain oxygen atoms. The
dissociative adsorption often results in reoxidation of the surface. The data in
Table 6-1 illustrate this effect. I n these experiments, the fully oxidized (i.e.,
stoichiometric) surfaces are prepared either by extensive annealing of the surface
REDUCTION 101
Table 6-1 Chemical Properties of Oxidized and Reduced Single Crystal
Surfaces
Oxidized"
or
Surface Reduced Adsorption Ref.
v203(W'
SrTi03( 1
Reduced
1 Oxidized
Reduced
1) Reduced
SrTi03(100) Oxidized
Reduced
Ti02( 1 10) Oxidized
Reduced
Ti02(100) Oxidized
(1x3) Reduced
Ti02( 100) Reduced
(1x7)
Ads. O2 readily as 02-;
Ads. H20 molecularly.
Ads. O2 readily as 02-;
Ads. H2 0 dissociatively.
Ads. O2 readily as 02-;
Ads. H20 dissociatively.
Ads. O2 readily;
Ads. H20 dissociatively.
Ads. H20 reoxidizes the surface.
Ads. H2 0 molecularly;
Ads. small amount of 02.
Ads. O2 reoxidizes the surface;
Ads. H20 dissociatively.
Does not ads. CO or H2.
Ads. O2 dissociatively
and reoxidizes the surface;
Ads. H20 dissociatively.
Ads. H2 0 molecularly.
Ads. H2 0 dissociatively.
Ads. H2 0 dissociatively.
a
b
a
b
C
C
d
j
e
e
f
g
gh
f
I
1
1
Footnote:
a) Fully oxidized sufaces are stoichiometric surfaces.
References:
a) R.L. Kurtz, and V.E. Henrich. Phys. Rev. B. 25. 3563 (1982).
b) R.L. Kurtz, and V.E. Henrich. ibid. 26, 6682 (1982).
c) R.L. Kurtz, and V.E. Henrich, ibid, 28, 6699 (1983).
102
Table 6-1 continued
d) S. Ferrer. and G.A. Somorjai, Surface Sci.. 97. L304 (1980).
e) V.E. Henrich, et al., J. Vac. Sci. Techno]., 15, 534 (1978).
f) V.E. Henrich. et al., Solid State Commun., 24. 623 (1977).
g) W. Gopel, et al., Phys. Rev. B, 28, 3427 (1983).
h) V.E. Henrich, et al., Phys. Rev. Lett., 36, 1335 (1976).
i) W. Lo. et al., Surface Sci., 71, 199 (1978).
j) by HREELS. R.G. Egdell and P.D. Naylor, Chem. Phys. Lett., 91, 200 (1982).
or by cleavage of a single crystal. Reduction of the surface is achieved by ion-
sputtering or H2 reduction. Adsorption and dissociation of the molecules are
monitored with UPS.
The results in Table 6-1 are supported by other measurements such as
temperature programmed desorption. When adsorbed CI8O2 is desorbed by
heating from a partially reduced TiOz surface, the amount of C1* 0 desorbed
increases with the extent of reduction 1401.
Reduction of a surface does not always lead u, stronger interaction with
molecules. The peak temperature in the temperature programmed desorption of
CO from Ti02 does not change with increasing degree of reduction, although the
amount increases [40]. On ZnO, the differential heat of adsorption of CO is much
lower on a reduced (7 kJ/mole) than on an oxidized surface (44 kJ/mole) [41]. In
contrast to NO which is adsorbed strongly on Fez+but weakly on samples
containing only Fe3+[35-371, pyridine is adsorbed more strongly on samples
containing Fe3+than Fe2+[42]. It is interesting to note that in this study,
Mossbauer spectroscopy detects direct interaction between pyridine and Fe2+of
low coordination, but not that between pyridine and Fe3+. However, pyridine is
shown by infrared spectroscopy to adsorb on Lewis acid sites. Since Fe3+is a
harder and smaller cation than Fez+, it is a stronger Lewis acid.
6.8 INFLUENCE OF REDUCED OXIDES ON THE PROPERTIES
OF TRANSITION METALS
It was first reported about ten years ago that certain transition metal oxides
can have a dramatic effect on the chemisorptive and catalytic properties of metals
when they are in close contact with the metal. This effect was originally tcrmed
Strong Metal-Support Interaction, but is currently referred to as decoration effcct.
The first report of this effect was on the suppression of hydrogen and carbon
monoxide adsorption capacity of noble metals. I t has been found that when a
noble metal is supported on Ti02, the material chemisorbs H2 or CO at a
stoichiometry of roughly one H atom or CO molecule per surface exposed noble
metal atom, if the material is reduced at 200°C. If the material is reduced at
50O0C, its ability to chemisorb H or CO is essentially completely suppressed
[43,44]. This is illustratcd with typical data in Table 6-2. It was later found that
REDUCTION 103
I I
100 300 500 700
C
TA
Figure 6-5 Hydrogen chemisorption on iridium supported on various oxides as a function of
activation in hydrogen for 1 h at each of various temperatures. T, is the activation
tcmperature. and H/M is the atomic ratio of hydrogen adsorbed to iridium in the catalyst.
(From Science, 211, 1121 (1981), copyright American Association for the Advancement
of Science).
Table 6-2 Suppression of H2 Adsorptive Capacity due to Decoration Effect
(From Scicnce, 211, 1121 (1981), copyright American Association for the
Advancement of Science).
2% Metal on
Ti02 Support Reduction at 200°C Reduction at 500°C
H atom adsorbed/rotal metal atoms
Ru 0.23
Rh 0.7 1
Pd 0.93
0s 0.2 1
Ir 1.60
Pt 0.88
0.06
0.01
0.05
0.1 1
0.00
0.00
this effect is not unique to Ti02 as the support. Fig. 6-5 shows the extent of
suppression of the hydrogen chemisorptive capacity as a function of reduction
temperature for various oxide supports. I n general, oxides that are readily
reducible at intermediate temperatures all show this effect. The effect is
reversible. That is. reoxidation with oxygen followed by a low temperature
reduction at 200°C restores most of the adsorptive capacity.
The influence of the decoration effect on the catalytic properties of the metal
depends on the reaction. Some typical examples are shown in Table 6-3. It can
be seen that the decoration effect suppresses the activity of R for benzene
hydrogenation and cyclohexane dehydrogenation, but enhances the activity in CO
hydrogenation. The activity of the Fe catalyst in ammonia synthesis is slightly
decreased, but the activation energy is greatly increased. I n the case of butane
hydrogenolysis, the selectivity and the activity are both altered.
In addition to these examples, it has been shown that CO hydrogenation on Ni
catalysts is also enhanced by the decoration effect, although the extent of
enhancement may vary from very little [48] to rather substantial [49]. In ethane
hydrogenolysis on titania-supported Rh, it has been found that the activity
decreases rapidly with increasing reduction temperature (Fig. 6-6), whereas the
cyclohexane dehydrogenation activity over the same catalyst remains almost
unchanged [ 501.
It is now rather well established that this effect is not due to the formation of
alloys (e.g. R-Ti alloy), the encapsulation of the metal by the support, sintering of
the metal, poisoning of metal by impurities in the support, or simply electron
transfer between the bulk of the support and the bulk of the metal crystallite.
These conclusions follow from a variety of experimental observations. For
example, transmission electron microscopic studies as well as X-ray diffraction
show no evidence of sintering [45,51], and Mossbauer spectroscopy shows that the
bulk of the iron crystallites is the same whether or not the sample is exhibiting the
decoration effect [47], even though the titania support near the metal crystallite is
reduced from Ti02 to TbO, [51,52].
The current picture is that the origin of the effect is the migration of small
particles of reduced titania (or other reduced support) onto the metal crystallites to
"decorate" the metal surfaces. These decorating reduced oxide particles may
partially block the metal surfaces from gas molecules, affect the electronic
structure of the neighboring metal atoms, or provide an oxide-metal interface for
interaction with molecules. Depending on the reaction, one or more of these
effects may participate to affect the observed characteristics of the reaction.
That decoration is the physical picture was first suggested by Dumesic [471
on the Fe/Ti02 system. Using Mossbauer spcctroscopy, it has been observed that
the bulk properties of Fe crystallites are the same whether they are in the decorated
state or not. Thus the effect must be a surface phenomenon. It is then proposed
that titania species cover the iron crystallites. Such a decoration model would
suggest that the extent of the effect should depend on the time allowcd for the
reduced oxide particles to migrate onto the metal crystallites and thc interface
between the metal and the oxide. These have been confirmed. It is observcd that
using the rate of ethane hydrogenolysis as a measure, the extent of the decoration
REDUCTION 105
Table 6-3 Effect of Decoration on the Catalytic Properties of Noble
Metals
Reaction Other
Reaction Catalyst Rate Effects Ref
C6H6 hydrogena- 4.8% Wi O2
tion at 288K 523 K reduced
773 K reduced
C6HI2 dehydroge- 2.7% IrKi02
nation at 523 K 523 K reduced
773 K reduced
CO hydrogenation 1.9% Pt/Ti02
at 524 K 473 K reduced
773 K reduced
NH3 synthesis 1.14 % Fe/Ti02
at 673 K 713 K reduced
798 K reduced
C4Hlo hydro- 4.8% Pfl i 02
genoly sis 623 K reduced
at 623 K
773 K reduced
45
40 mmole/h-g cat.
3.5 mmole/h-g cat.
1400 mmole/h-g cat.
304 mmole/h-g cat.
0.01 11 molecules/s-Pt,
0.076 molecules/s-%
(0.0195 if assumed the
same dispersion as low-
temperature reduced
sample)
45
46
47
0.03 1 ks-l
0.01 1 ks-'
Eact =100 kJ
mole-'
Eact =220 kJ
mole-'
45
Relative product formation rate:
C, =0.65, C2=1.1, C3=0.7, i-C4=0
c1=35, C2=47, C,=25, i-C4=88
effcct depends linearly on the square root of the reduction time [501, which is
characteristic of diffusion processes. For a given reduction time, the
hydrogenolysis activity decreases as the inverse of the particle diameter. Finally,
the increasing suppression of the hydrogenolysis activity as the reduction time
increases is found to parallel a similar suppression by the addition of copper to a
nickcl catalyst, which is interpreted by the braking-up of nickel ensembles on the
surface by copper atoms. Thus the data are consistent with the model that the
surface rnctal ensembles are broken up by reduced titania particles decorating the
surface.
106
Reduct i on Temp- K
Figure 6-6 Ethane hydrogenolysis and cyclohexane dehydrogenation on Rh/Ti02 catalyst
as a function of catalyst reduction temperature. (From J. Catal., 82, 279 (1983). copyright
Academic Press).
Recently, it has been further proposed that the metal-oxide interaction occurs
through the interaction of metal atoms with oxygen ion lattice vacancies in the
reduced oxide. At temperatures sufficiently high to induce the decoration effect,
the oxide support is reduced so that it has a high concentration of anion vacancies.
The high concentration of anion vacancies enhances the diffusion of metal atoms into
the near-surface region of the bulk, and results in the formation of a raft-like
metallic cluster covered by a thin (atomic) layer of the support. When the support
is reoxidized, the anion vacancies are filled, driving the metal atoms back to the
surface [53].
When titania particles are deposited on model catalysts of a Ni (1 11) single
crystal surface 1541 or a F’t foil [ 55, 56] , a similar suppression of the H2 or CO
chemisorption capacity is observed which is similar to that resulting fromhigh
temperature reduction of supported metals. Enhanced catalytic activity in CO
hydrogenation has also been observed on these low surface arca catalysts [54,56].
I n the case of Pt foil, the activation energy is reduced from 126 to 80 W/mole.
Furthermore, a small amount of deposited TiO, particles is found to enhance the
methanation activity of Ni. At an optimum coverage of 8%, (recently there is
doubt about this number because of questions about the calibration method
employed), the activity is four times that of a clean Ni surface. On the other hand,
complete suppression of the chemisorptive capacity rcquires complete coverage of
the metal surface by the oxide particles 156,571.
REDUCTION 107
The extent of election transfer between the metal and the decorating particles
is not established. For example, a study of Pt crystallites supported on a Ti02
single crystal surface by XPS and AES suggests electron transfer from Ti02 to F ' t
[%I, while a XANES study suggests electron transfer fromPt to Ti02 [591.
The influence of the decorating effect on the heat of adsorption depends on
the system. On Pt supported on titania, the effect results in a decrease in the initial
heat of adsorption of H2 from92 to 82 kJ/mole, but no change for CO adsorption
[60]. The integral heats of adsorption of both CO and H2 are substantially reduced
[61]. However, the integral heat of adsorption of CO or H2 on Pd is not affected
[62,63].
REFERENCES
1. a) M. Langell, Surface Sci.. 186, 323 (1987); b) W. Uena. Y. Moro-oka,
2. N. W. Hurst. S. J . Gentry, A. J ones, and B. D. McNicol, Catal. Rev.,
3. J . Haber, J. Less-Common Met., 54, 243(1977); B. Delmon. "Introduction a la
4. R. P. Furstenau, G. McDougall, and M. A. Langell, Surface Sci ., 150, 55 (1985).
5. W. K. Hall, and F. E. Massoth, J. Catal., 34. 41 (1974).
6 . S. Abdo, R. B. Clarkson and W. K. Hall, J. Phys. Chem., 80, 2431 (1976).
7. H. Weigold, J. Caul., 83, 85 (1983).
8. K. R. Poeppelrneier, M. E. hnowi cz. and J . M. Longo, J . Solid State Chem..
9. P. B. Himelfarb, F. E. Wawner, Jr.. A. Bieser, Jr.. and S. N. Vines, J. Catal..
and T. Ikawa, J. Chem. SOC. Faraday Trans. I , 78.495 (1982).
24, 233 (1982).
Cinetique Heterogene", Edition Technip, Paris, 1969.
44, 89 (1982).
83, 469 (1983).
10. E. Unmuth, L. H. Schwartz, J . B. Butt, J. Catal., 61, 242 (1980).
1 1 . K. M. Nimmo, and J . S . Anderson, J. Chem. Soc., Dalton Trans., 2328 (1972).
12. S. K. E. Forghany, and J. S. Anderson, J. Chem. Sw. Dalton Trans., 225 (1981).
13. J . Salvati, J . Phys. Chem., 85, 3700 (1981).
14. I. E. Wachs, C. C. Chersich, and J . H. Hardenbergh, Appl. Cafal.. 13, 335 (1985).
15. R. D. McNicol, H. Charcosset, M. T. Chenebaux, and M. F'rimet, "Scientific Bases
16. T. Huizinga, and R. Prins, J. Phys. Chem.. 87, 173 (1983).
17. I. E. Wachs, S. C. Chan, and R. Y. Saleh, J. Catal., 91. 366 (1985).
18. A. J . Van Hengsbom, J . G. van Omen. H. Bosch, P. J . Gellings, Proc. 8f h Infern.
19. J . C. Vis. H. F. J .van' T Blik. T. Huizinga. J . Van Grondelle, and R. Prim.
20. H. C. Yao, S. J apan, and M. Shclef, J. Catal., 50, 407 (1977).
21. J . Bachelier, J . C. Duchet, and D. Comet, Bull. SOC. Chim. Fr.. 3, 112 (1978).
22. M. Wu, and D. M. Hercules, J. Phys. Chem., 83, 2003 (1979).
23. H. E. Swift, F. E. Lutinski, and H. H. Tobin, J. Catal., 5, 285 (1966).
for the Preparation of Heterogeneous Catal., 11". 1978, paper no. B8.
Cong. Cafal., IV, 297 (1984).
J . Cafal., 95, 333 (1985).
24. P. Dufresne, E. Payen, J . GrimbloS and J. P. Bonnelle, J. Phys. Chem.,
25. M. Iwamoto, T. Takenaka, K. Matsukami, J . Hirata, S. Kagawa. and J . Izumi,
26. H. J .-J iang, PhD thesis, Northwestern University, 1988.
27. G. C. Bond, A. J . Sarkany, and G. D. Parfitt, J. Cataf., 57,476 (1979).
28. A. Vejux, and P. Courtine. J. Solid State Chem., 23, 93 (1978).
29. D. J . Cole, C. F. Cullis, and D. J . Hucknell, J. Chem. SOC.. Farad. Trans. I .
30. J . Haber, A. Kozlowska, and R. Kozlowska, J. Cafaf., 102, 52 (1986).
31. N. Wagstaff, R. Ens. J . Cataf.. 59. 434 (1979)
32. B. H. Isaacs, E. E. Petersen, J . Cataf., 77, 43 (1982).
33. S. B. Ziemecki, G. A. J ones, and J . B. Michel. J. Catal.. 99. 207 (1986).
34. M. S. Nacheff, PhD thesis. Northwestem University, 1988.
35. S. Yuen, Y. Chen, J . E. Kubsh, J . A. Dumesic, N. Topsbe, and H. Topsbe,
36. N. S. Gill, R. H. Nuttall, D. E. Scaife, and D. W. A. Sharp, J. Imrg. Nucl.
37. G. W. Poling, and R. P. Eischens, J . Efectrochem. Soc.. 113, 218 (1966).
38. K. Segawa, and W. K. Hall. J. Catal., 77, 221 (1982).
39. Yu A. Lokhov, Z. Mud, and A. A. Davydov, Kinet. Kataf.. 20, 207 (1979).
40. G. B. Raupp, and J . A. Dumesic. J . Phys. Chem., 89, 5240 (1985).
41. E. Giamello and B. Fubini, J. Chem. SOC. Faraday Trans. I , 79. 1995 (1983).
42. G. Connell. and J . A. Dumesic. J. Catal., 101, 103 (1986).
43. S. J . Tauster, S. C. Fung, and R. L. Carten. J . Amer. Chem. Soc., 100, 170 (1978).
44. S. J . Tauster, S. C. Fung, R. T. K. Baker and J . A. Horsley, Science.
45. P. Meriandeau, 0. H. Ellestad, M. Dufaux, and C. Naccache. J. Catal.,
46. A. Vannice. and C. C. Twu, J . Cataf., 82. 213 (1983).
47. J . Santos, J . Phillips, J. A. Dumesic. J . Catal., 81. 147 (1983).
48. C. H. Bartholomew, R. B. Pannell, and J . L. Butler, J. Catal.. 65, 335 (1980).
49. M. A. Vannice, and R. L. Garten. J. Catal., 56, 236 (1979).
50. D. E. Resasco, and G. L. Haller, J. Catal., 82. 279 (1983).
51. R. T. K. Baker, E. . Prestridge, and R. L. Garten, J . Catal., 56, 390 (1979).
52. R. T. K. Baker, E. B. Prestridge, and R. L. Garten, J . Cataf., 59, 293 (1979).
53. M. G. Sanchez, and J . L. Gazquez, J . Catal., 104, 120 (1987).
54. Y. W. Chung, G. Xiong, and C. C. Kao, J . Cataf., 85, 237 (1984).
55. C. S. KO and R. J . Gorte. J . Cataf., 90, 59 (1984).
56. R. A. Demmin, C. S. KO. and R. J. Gorte, J . Phys. Chem. 89, 1151 (1985).
57. D. J. Dwyer, S. D. Camero. and J . Gland. Surface Sci .. 159, 430 (1985).
58. M. K. Bahl. S. C. Tsai, and Y. W. Chung, Phys. Rev. E. 21, 1344 (1980).
59. D. R. Short, A. N. Mansour, J . W. Cook, J r., D. E. Sayers, and J. R. Katzer,
60. J . M. Hermann, M. Gravell-Rumeau-Maillot, and P. C. Gravelle, J . Cafal.,
85, 2344 (1981).
Appf. Cataf., 16, 153 (1985).
72, 2185 (1976).
J . Phys. Chem., 86, 3022 (1982).
Chem.. 18, 79 (1961).
211, 1121 (1981).
75, 243 (1982).
J . Catal., 82, 299 (1983).
104, 136 (1987).
REDUCTION 109
61. M. A. Vannice, L. C. Hasselbring. and B. Sen, J. Caul., 97, 66 (1986);
62. P. Chow, and M. A. Vannice, J . Cafal., 104. 1 (1987).
63. P. Chow, and M. A. Vannice, J . Cafal., 104, 17 (1987).
64. S. Koobiar, J . Phys. Chern., 68, 441 (1964).
65. J. Marcq, X. Wispenninckx. G. Poncelet, D. Keravis, and J. Fripiat, J. Cafal.,
66. J. Marcq, G. Poncelet, and J. Fripiat, J . Cafal., 87, 339 (1984).
67. D. F. Cox, T. B. Fryberger, and S. Semancik. Phys. Rev. E, 38, 2072 (1988).
85, 2972 (1985).
73, 309 (1982).
Chapter 7
OXYGEN ON OXIDES
7.1 NATURE OF ADSORBED OXYGEN
Depending on the sample history, it is possible that there are oxygen atoms,
either neutral or charged, on an oxide surface that are in positions different from
the positions of surface lattice oxygen ions. These oxygen atoms and ions may
have different charges than the lattice oxygen, have different energics of binding
(or adsorption), and bedesorbed at different temperatures. Adsorbed oxygen on a
stoichiometric surface of a fully oxidized oxide is readily identifiable. It is
ususally desorbed at temperatures lower than the sublimation temperature of
surface lattice oxygen. On a partially reduced surface, adsorbed oxygen may
result in reoxidation of the surface cations to different degrees, depending on the
extent of charge transfer between the reduced center and the adsorbed oxygen. If
the charge transfer is such that an adsorbed oxygen atom acquires the same
elcctron density as a surface lattice oxygen ion, and it occupies a lattice site, the
surface is reoxidized and the adsorbed oxygen becomes a lattice oxygen. If the
charge transfer is less extensive and/or the oxygen species occupies a site diffcrcnt
from a surface lattice site, it is an adsorbed oxygen.
Adsorbed oxygen may be present as atomic or molecular species with various
charges. On transition metal oxides, the most common species are O,O-, 02, and
0 2 , On some basic alkali and alkaline earth oxides, 022- has been reported [l].
On UV-irradiated TiOz, 03- species has been observed with EPR [2]. Various
review articlcs discussing these and other species such as 03- havc appeared in
recent years [2-41.
In general, atomic oxygen spccics are adsorbed more strongly than molccular
species. This is because strong surface-atomic oxygen bonds are needcd to
compensate for the energy required to break the double bond of thc oxygen
molecule. The rate of dissociativc adsorption of oxygen to atomic species is
expcctcd to be lower than that of molccular adsorption. This is because a pair of
neighboring surface sites must be available for the former process. Otherwise
110
SURFACE OXYGEN 111
lattice or surface diffusion of mononuclear oxygen ions (or lattice anion vacancies)
is needed before dissociation of the oxygen molecule can be achieved. This is
consistent with the fact that a saturation coverage of adsorbed atomic oxygen
corresponds to a few atoms per nm2 of surface (see Table 7-1). On the other hand,
molecular adsorption of oxygen can take place on an isolated surface site.
This requirement of the availability of a pair of surface sites can be overcome
by using species such as N20 instead of 02, the decomposition of which would
leave an atomic oxygen on the surface. Indeed, decomposition of N20 at low
temperatures resulting in an adsorbed atomic oxygen (usually detect& as 0-) has
been observed on many oxides [2-41.
7.2 DETECTION OF ADSORBED OXYGEN
One method to detect the presence of adsorbed oxygen is by temperature
programmed desorption after exposing the oxide to 02. Presumably, adsorbed
oxygen is bonded differently on the surface than lattice oxygen, and would be
desorbed at temperatures different from the vaporization temperature. The
temperature programmed desorption profiles of a number of oxides have been
reported [5-81. The general feature of these profiles is schematically shown in
Fig. 7-1. Upon heating of an oxide with adsorbed oxygen from room temperature,
three types of desorption peaks are observed. Type I occurs at a relatively low
temperature and it represents the most weakly adsorbed oxygen. Normally this is
assigned to adsorbed molecular oxygen which usually desorbs below 300°C.
Type I1 which occurs at an intermediate temperature usually results from adsorbed
atomic oxygen, and desorbs below 600°C. The amounts of oxygen desorbed in
type I and I1 are small, of the order of a few percent of a close-packed monolayer.
Type 111occurs at high temperatures and at a rate which may increase continuously
with increasing temperature. The amount of type 111 may be much larger than
those of the other two types. This type results from vaporization of lattice oxygen,
and desorption of metal atoms occurs simultaneously, that is, the metal oxide is
subliming at these temperatures.
Table 7-1 summarizes the desorption temperatures of oxygen from a number
of oxides [51. Except for those noted, oxygen is adsorbed by cooling the oxide in
oxygen from 600°C to 10°C. I n this manner, adsorption is achieved even for
species whose adsorption is activated. It is clear from the table that the schematic
desorption profile shown in Fig. 7-1 is oversimplified. For many oxides, there are
more than two desorption peaks below sublimation temperature. For example,
there are three desorption peaks for iron oxide. From their temperatures, one is
probably adsorbed molecular oxygen and two are adsorbed atomic oxygen.
Titanium dioxide appears to have three forms of adsorbed oxygen. The different
forms of adsorbed oxygen reflect interaction with different environment of the
surface. At present, there is little detailed understanding of the differences.
Attempts to gain further understanding of the adsorbed oxygen species is
complicated by the fact that the extent of interaction of the adsorbed species with
the surface (and perhaps also with each other) may depend on the adsorption
112
Table 7-1 Desorption Temperatures and Total Amounts of Oxygen
Desorbed from Metal Oxides a
Desorption Volume Desorbed
Oxides Temp. C" ml(STP)/m2
v205
M003
Biz03
Biz03 .2Mo03
wo3
&02
Fez03
( 3304
NiO
CUO
S iOz
Ti0 (anatase)b
ZnO
Sn02
Cr203
A120zb
?b
450
50,270, 360,540
55, 350,486
30, 165, 380
35,335,425,550
125, 390
65
100
125,1190, 250
190, 320
80, 150
0
0
0
0
0
2.13 x lop2
6.54 x lop2
4.05 x 10-3
3.30 x lop2
1.12 x 10-2
1.42 x 10-1
2.05 x 104
2.99 x 10-5
5.52 x 10-5
2.45 x 104
2.11 x 10-3
Fo o motes:
a) From Iwamoto. et al., J . Phys. Chem., 82, 2564 (1978), coyright American
Chemical Society. Oxygen is adsorbed by cooling the sample in oxygen from
600 to 10°C.
b, Oxygen is adsorbed at room temperature.
') Obtained with a heating rate of 20°C/min.
conditions. For example, the temperature programmed desorption profile of
oxygen adsorbed on a-Fe203 has been shown to depend on the adsorption
temperature. The profile in this figure can be
explained as follows. There are three types of adsorbed oxygen on a-Fe203. The
fist type produces a desorption peak at about 490°C. The second type produces a
peak at about 370°C. The peak temperatures of these two types do not vary with
the adsorption temperature. However, adsorption into these forms is activated and
temperatures close to the desorption temperature are needed for adsorption to
occur. The desorption of the 370°C species is second order in surface coverage,
suggesting that it may be an atomic species [8]. The third type produces a peak
below 200°C whose exact temperature depcnds on the adsorption temperature.
The desorption temperature suggests that this peak is due to adsorbed molecular
This is shown in Fig. 7-2.
SURFACE OXYGEN 113
T-
Figure 7-1 Schematic temperature programmed desorption profile of oxygen born an
oxide. I: from adsorbed molecular oxygen; II: from adsorbed atomic oxygen; III: from
sublimation of lattice oxygen.
0)
m
C
0
w
a
.-
c,
L
n
0
VJ
Q)
a
I I I I I
100 300 500
Temper at ur e, C
Figure 7-2 Effect of adsorption tcmperature on the TPD profile of adsorbed oxygen on a-
Fe203. Adsorption tcmperatures: a. Sample cooled from 600 to 10°C in 0,; b. 10°C; c.
110°C; d. 250°C; e. 400°C. (From Bull. Chem. SOC. J pn., 51. 2765 (1978), copyright
Chemical Society of J apan).
114
Figure 7-3 Room temperature EPR spectrum of adsorbed 0 2 - and Zn' on ZnO. (From J .
Phys. Chem., 82. 2564 (1978), copyright American Chemical Society).
oxygen (type I). The variable temperature of the desorption peak suggests that
there is a broad distribution of adsorption sites. Similar dependence of the
temperature desorption profiles on the adsorption conditions has been observed
also on NiO [91 and Mn02 [51.
The assignment of adsorbed atomic or molecular oxygen species to the
various desorption peaks has been confirmed by EPR measurements on some
oxides. On ZnO, adsorption of oxygen generates an anisotropic signal with
g,=2.052, g2=2.009, and g3=2.003 (Fig. 7-3). This signal is assigned to 02-. The
signal disappears upon evacuation at 20O0C, which coincides with a desorption
peak at 190°C. It appears that the EPR signal and the desorption peak are from the
same species [ 5] . It is interesting that this 02- signal and the Zn' signal are
complementary with each other, showing an electron transfer from Zn+to oxygen:
On anatase TiOz, oxygen adsorption results in three EPR signals that have
been assigned to 0 2 - on three different sites. These three signals disappear upon
heating to temperatures that are coincident with the three temperature programmed
desorption peaks [ 5] . Thus these three desorption peaks are from adsorbed
molccular oxygen.
Direct spectroscopic observation of adsorbed oxygen has been made using IR
and EPR. Because of the lack of a dipole moment, the oxygen molccule in the gas
phase is IR-inactive. However, it is Raman active with a vibrational stretching
frequency of 1552 cm-'. Adsorbed molecular oxygen will have a lower symmetry
than i n the gas phase because of perturbation by the surface, and some weak IR
bands have been assigncd to adsorbed 02. Some of these assignments are
summarized in Table 7-2. The assignment of the charge on the adsorbed oxygen
molecules is generally made by comparison with coordination complexes.
Examples of adsorbed superoxide ion (023 detected by EPR have been given
above for ZnO and Ti02. Adsorbed superoxide ion has been detected on many
SURFACE OXYGEN 115
Table 7-2 IR Detection of Adsorbed Oxygen Molecules on Some
Transition Metal Oxides
Stretching
Oxide Adsorbed Species Frequency, cm-l Ref.
gas phase 0 2
0 2 -
0 2 2 -
NiO singlet O2
0 2 -
Ti02 02-
0 2 h
0 2
cr203 022-
~- F QO~ 0 2 -
022-
singlet O2
1552 a-c
1140
850
1500 d
1140,1060 d
1180-1060 e
16GO- 1580 f
1600-1 700 e
985 g
1460 d
1350,1325,1300,1270 i
1100-900 i
References:
a) J . Shamir. et al. J . Amer. Chem. SOC., 90. 6223 (1968).
b) K. Nakamoto, "IR and Raman Spectra of Inorganic and Coordination Compounds,"
c) N. Sheppard, in "Vibrational Properties of Adsorbates." R. F. Willis, ed..
d) A. Tsyganenko, et al., Spect~os. Lett. 13, 583 (1980).
e) A. Davydov, et al., Kinet. Catal., 14, 1342 (1973).
f) A. A. Davydov, et al., Symposium on "Adsorbirovanny Kislorod v Katalize,"
Wiley-Interscience, NY, 3rd edition, 1978.
Springer-Verlag, Berlin, 1980.
1972, Institute of Catalysis, Acad. of Science, USSR, Novosibirsk.
Preprint No. 19.
g) A. Davydov, et al., Kinet. Catal., 13, 980 (1972).
h) F. Al-Mashta. et al., J . Chem. SOC. Faraday Trans. I, 78, 979 (1982).
oxides including ZnO [5,10-121, Ti02 (5,131, supported V205 [14], supported
Moo3 1151, mixed oxides of COO-MgO [161, and nontransition metal oxides [3,41.
This species is characterized by an anisotropic signal of g1=2.015 to 2.077,
g2=2.002 to 2.012, g3=2.001 to 2.011 [3]. There is a correlation between the
magnitude of g1 and the formal oxidation state of the metal ion: the higher is the
oxidation statc, [he lower is the value of gl because of larger crystal field
inlcractions [3,17]. Interaction of the superoxide ion with the nuclear magnetic
moment of the metal ion may result in hyperfine splitting of the EPR signal [14].
116
Because of the electronegativity of oxygen, electron transfer from the oxide
to adsorbed oxygen commonly occurs, although it may not be a necessary con-
dition for chemisorption. Therefore, adsorption of oxygen becomes much more
facile if the oxide is reduced. It has been shown that chromium oxide reduced at
500°C and evacuated (to dehydroxylate the surface and make some surface
chromium ions coordinatively unsaturated) can adsorb oxygen strongly at as low as
-195°C [MI. Similarly, molybdena reduced at 500°C and evacuated chemisorbs
oxygen at -78°C and below [19]. I n these two cases, adsorption is believed to be
on Cr203 and Ma2. The facile adsorption has made it possible to use oxygen
chemisorption to determine the surface area of supported chromia and molybdena
[20,21]. However, the stoichiometry of adsorbed oxygen and surface cation is not
unity, and an assumption has to be made that this stoichiomeuy is the same for the
supported and the unsupported sample whose surface area can be independently
determined. The nature of the adsorption site is still a subject of investigation
[22]. There is indication that the adsorption site on molybdenum oxide is a surface
Mo2+center based on the competitive behavior between O2 and NO adsorption
~231.
7.3 REACTIVITY OF ADSORBED OXYGEN
Adsorbed oxygen species vary greatly in their reactivities depending on their
nature and the nature of the oxide. Among species that have been identified with
EPR, 0- has been shown to be very reactive. It abstracts an H atom from an
alkane molecule at as low as 77 K. 0 2 - is less reactive, and it forms complexes
with adsorbed alkene molecules. The reactivities of those species not detected by
EPR vary. On iron oxide, for example, the strongly adsorbed oxygen appears to
be unreactive, in contrast to the weakly adsorbed oxygen which degrades adsorbed
alkenes rapidly to combustion products [24].
Most of the studies on the reaction of adsorbed oxygen concerns the EPR-
active 0- species. The common method to generate this species is either by
irradiation of an oxide with y-ray or UV light, or by decomposition of N20 on the
oxide. There does not appear to be any significant difference in the species
produced by either method.
Adsorbed 0- is a very reactive species. It reacts readily with alkanes at low
temperatures on a number of oxides including ZnO, vanadia, and molybdena.
Cleavage of a C-H bond and formation of OH and an alkyl radical is a common
first step of the reaction. In somes cases, partial oxidation products of alkanes are
formed. Examples of these reactions are described below.
Figure 7-4 shows such a reaction on ZnO. Adsorbed 0- is generated by
irradiating ZnO with UV light at 90°K. The presence of this species is detected by
EPR (curve b). On exposure of the sample at 90 K to methane, a new EPR signal
of .CH3 is detected (curve c). Thus 0- abstracts an H atom from methane
according to the equation:
O-(ad) + CH4 -+ .CH3(ad) + OH-(ad) (7-2)
SURFACE OXYGEN
117
___)
A
H
Figure 7-4 EPR spectra taken at 90 K showing reaction of C& with adsorbed 0- on ZnO.
a. ZnO pretreated in 0,; b. Adsorbed 0- on ZnO generated by UV radiation; c. Spectrum
of CH3 after exposure to C&. (From React. Kinet. Cad. Lett., 18, 243 (1981).
copyright Elsevier Scientific F'ubl.)
The same reaction has been detected on silica-supported vanadia, molybdena,
and tungsta [26,27]. When the reaction is conducted at room temperature on
V/Si02, a small amount of C2H, formed by coupling of methyl radicals is detected
in the gas phase. Upon heating the oxide, large quantities of C2H, and CO are
desorbed together with small quantities of CH, and C02. Similar observations have
been made on UV-irradiated Ti02. It has been proposed that the methyl species is
adsorbed as a surface methoxide, at least above ambient temperature [27]:
CH3 + 02- + CH30- + e-
(7-3)
or .CH3 + 0- + CH30-
The formation of ethane, however, should result from the coupling of two methyl
radicals.
When the adsorbed 0- on V/Si02 is exposed to a mixture of methane and
oxygen at room temperature, the 0- EPR signal is immediately replaced by an 03-
signal. Formaldehyde becomes the major reaction product instead of ethane. On
TiOz, CO and C02 are the major products. It is interesting that if ' * 0 2 is present
in the gas phase, the oxygen in the formaldehyde formed is not labeled [27].
Adsorbed 0- reacts readily with ethane also. On Mo03/Si02, the reaction is
instantaneous and proceeds to almost completion at room temperature [28]. Upon
heating, C2H, is desorbed. However, the amount of ethene observed is more than
the amount of 0- detected by EPR. This may indicate the presence of undetected
118
0- which is EPR inactive because of strong magnetic dipolar interaction with the
solid. 0- adsorbed on V/SiO2 also reacts readily with C2H.j. Upon heating, CI&,
C2&, and carbon oxides are the major desorbed species. No coupling product,
butane, is observed [271.
Upon
heating, ethene and methane are the major products. Interestingly, the total
amount of ethene and methane formed is about five times the amount of 0-
detected, as in the case of Mo03/Si02 mentioned above. The reaction mechanism
has been proposed to be:
Adsorbed 0- on Co-MgO also reacts readily with ethane [29].
O-(ad) +C2& + C2HS(ad) +OH-(ad) (7-4)
C2Hs(ad) +02-(lattice) + C2HSO-(ad) +e-(s)
(7-5)
C2HsO-(ad) +2 02-(lattice) + CH3COO-(ad) +H20 +4 e-(s) (7-6)
CH,COO-(ad) +OH-(ad) + C& +C032-(ad)
(7-7)
In addition to alkanes, adsorbed 0- also reacts with HZ, D2, and alkenes.
Reactions of adsorbed 0- with H2 or D2 are also rapid, as is that with various
alkenes. At 10°C the reactivity of 0- with various molecules shows the order D2
<H2 <C21& <CO <CH, [26]. The reactivity also depends on the nature of the
oxide. For H2, D2, and CI&, it decreases in the sequence V205/Si02 >
Mo03/Si02 >W03/Si02 [26,31]. The reaction with H2 results in the formation of
adsorbed OH-. The rate shows a normal deuterium kinetic isotope effect of about
four at -lOO°C. and of about two at 10°C. The reaction with CO results in the
formation of C02- [26,32]. A similar associative reaction of 0- with 0 2 to form
adsorbed 03- has been reported [27.29,30]. On warming and evacuation, the
reaction is reversible and 0- and 02(g) are formed.
The reaction of adsorbed 0- with Cz& is more complex and the detail
depends on the oxide. On Mo03/Si02, exposure of adsorbed 0- to C2H4 at 110 K
results in a new EPR signal that has been assigned to a linear CH2CH20- species.
On warming, the signal is replaced by one that has been assigned to a CHCH2
radical [33]. The assignment to a linear .CH2CH20- species is supported by
deuterium and 13C labelling studies [34]. On W03/Si02, the same reaction at low
temperatures leads to the appearance of a EPR signal that has been assigned to a
cyclic (-CH2CH03 epoxide-like species that has not been clearly identified. On
warming to 90 K, the -CHCH2 species is also formed 1351.
When a sample of Mo03/Si02 is irradiated with W light in the presence of
C2&, 0- is presumably formed by the reaction: Mo6+a2- + Mo5+4-. An
EPR signal assigned to an ethylene oxide species has been observed at 77 K [361
that is formed by:
C2& + 0-(ad) - (H2C- H2)-
(7-8)
\/= 0
SURFACE OXYGEN 119
Under this condition, a small amount of propene is also detected in the gas phase.
On warming, more propene as well as some 1- and 2-butene and formaldehyde are
detected. It is proposed that the adsorbed ethylene oxide decomposes on warming
to form Mo-methylene species, which participate in metathesis at the elevated
temperatures to produce the higher hydrocarbons.
Other surface species have been observed in the reaction of ethene with
adsorbed 0-. On Co-MgO, the reaction at 25°C results in a EPR signal assigned to
.CCHp--OH- [25]. On ZnO at 90 K, a polymeric radical species of R<H2 has
been reported. The EPR signal of this species disappears on exposure to oxygen
or evacuation [371.
Adsorbed 0- also reacts with other alkenes. The reactions with propene and
1-butene result in the formation of methyl radicals and linear -CH2CHO- radicals.
This indicates cracking of the hydrocarbon [34].
There are few studies on transition metal oxides on species of adsorbed
oxygen other than 0-. The associated reaction mechanisms are not well
understood. It has been reported that adsorbed 02- reacts with propene at room
temperature to forma propene-oxygen complex [38]. On desorption. combustion
products are observed fromZnO [39] and copper oxide [40]. The 02- species on
Co-MgO is inactive towards ethane [29].
Adsorbed 03- species on Co-MgO reacts with ethane. On heating, ethene is
desorbed as a product [29].
REFERENCES
1 . F. Blunt, P. Hendra. and I. Mackenzie, Chem. Commun., p. 278 (1969).
2. M. Che, and A.J. Tench, Adv. Cafal., 31, 77 (1982).
3 . J . Lunsford, Adv. Catal., 8, 135 (1973).
4. A. Bielanski, and J . Haber, Adv. Catal., 19. 1 (1979).
5. M. Iwamoto, Y. Yoda, N. Tamazoe. and T. Seiyama, J. Phys. Chem., 82, 2564
6. B. Halpem, and I. Germain. J . Catal., 37. 44 (1975).
7. M. Iwamoto, Y. Yoda. N. Yamazoe. and T. Seiyama, Bull. Chem. SOC. Jpn.. 51,
8. B. Yang, and H. Kung, J. Catal., 75. 329 (1982).
9. M. Iwamoto, Y. Yoda. N. Yamazoe, and T. Seiyama. J. Phys. Chem. Solid,
(1978).
2765 (1978).
80, 1989 (1976).
10. R. Kokes, Proc. 3rd Intern. Cong. Catal., Amsterdam, 1964. p. 484.
1 1 . J . Lunsford and J . J ayne. J. Chem. Phys. 44. 1487 (1966).
12. A. Tench and T. Lawson, Chem. Phys. Lett., 8, 177 (1971).
13. C. Naccache. P. Meriandeau, M. Che, and A. Tench, Trans. Faraday SOC., 67.
14. V. Shvets, V. Vorotyntsev. and V. Kazansky. Kinet. Catal., 10. 356 (1969).
15. K. Seshadri, and L. Petrakis. J. Phys. Chem., 74. 4102 (1970).
16. K. Dyrek, Bull. Acad. Pol. Sci.. Ser. Sci. Chim., 21, 675 (1973).
17. M. Dufaux, M. Che. and C. Naccache, C.R. Acad. Sci., Paris, IS]. 268, 2255 (1969).
506 (1971).
120
18. D. S. McIver, and H. Tobm, J. Phys. Chem., 64. 451 (1960).
19. H.-C. Liu, L. Yuan, and S. W. Weller. J. Catal.. 61, 282 (1980).
20. S. W. Weller, k c . Chern. Res.. 16. 101 (1983).
21. A. Lopez Agudo, F. Llambias, P. Reyes, and J. Fierro, Appl. Cat& 1, 59 (1981).
22. N. K. Nag, J. Catal., 92. 432 (1985).
23. J . Valyon, and W. K. Hall. J. Catal., 84, 216 (1983).
24. B. Yang, and H. Kung, J. Catal., 77, 410 (1982).
25. A. M. Volodin. and A. E. Cherkashin, React. Kinet. Catal. Lett., 18, 243 (1981).
26. N. I. Lipatkina, V. A. Shvets, and V. B. Kazanskii, Kinet. Catal., 19. 979 (1978).
27. S. Kaliaguine, B. Shelimov, and V. Kazansky, J. Catal.. 55, 384 (1978).
28. M. B. Ward, M. J . Lin, and J. H. Lunsford, J . Catal., 50, 306 (1977).
29. K. Aida. M. Tajima, M. Isobe, and T. Onishi, Proc. Int er n. Cong. Catal.,
30. V. B. Kazanski, V. A. Shvets, M. YaKon, V. V. Nikisha, and B. N. Shelimov,
31. V. A. Shvets. and V. B. Kazansky. J . Catal., 25, 123 (1972).
32. A. R. Gonzalez-Elipe, C. Louis, and M. Che, J . Chem. SOC. Farad. Trans. 1,
33. V. B. Sapozhnikov, V. A. Shvets. N. D. Chuvyllcin. and V. B. Kazansky.
34. J . F. Hemidy, and A. J . Tench, J. Catal., 68, 17 (1981).
35. V. A. Shvets, V. B. Sapozhnikov, N. D. Chuvylkin. and V. B. Kazansky.
36. M. Anpo, and Y. Kubokawa, J. Catal., 75, 204 (1982).
37. A. M. Volodin, and A. E. Cherkaskin. React. Kinet. Catal. Lett., 20, 347 (1982).
38. T. Tabasaranskaya, A. A. Kadushin, K. N. Spiridonov, and 0. V. Krylov.
39. A. A. Davydov, A. A. Yefremov, V. G. Mikhalchenko. and V. D. Sokolvoskii,
40. V. Mikhalchenko, V. Sokolvoskii, A. Filippova, and A. Davydov,
8th. vol. ID, 335 (1984).
Proc. 5th Intern. Cong. Catal., (1972), 2, 1423 (1973).
78, 1297 (1982).
Kinet. Catal.. 17. 1251 (1976).
J . Catal.. 52, 459 (1978).
Kinet. Katal., 13, 1370 (1972).
J . Catal., 58, 1 (1979).
Kinet. Katal., 14, 1253 (1973).
Chapter 8
PREPARATION OF OXIDES
8.1 GENERAL CONSIDERATIONS
Oxides can be prepared in the form of single crystals, or polycrystalline or
amorphous samples. For studies where surface atomic arrangements need to be
known, single crystal samples are used from which well-ordered crystallographic
surface planes can be prepared. There are many well established methods to grow
single crystals. The most common method is growth from the melt. In this
method, very high temperatures are required, and the oxygen partial pressure (or
oxygen fugacity) above the melt must be carefully controlled to ensure that the
crystal attains the desired stoichiometry. When the melting point of the oxide is so
high that the oxide decomposes, other lower temperature methods may be
employed, such as vapor transport. Many books are available on the various
methods of crystal growth [l]. In this chapter, we concentrate on methods to
prepare powder samples.
For most practical purposes where a large specific surface area is essential,
polycrystalline or amorphous samples are desirable. Experience has shown that in
general, low temperature processes are necessary to obtain oxides of large surface
areas or small particle sizes. However, methods can be developed such as in the
preparation of aerogels in which high temperatures are used [2a]. A low
temperature treatment does not necessarily lead to the formation of the
thermodynamically most stable phase. Instead, depending on the details of the
preparation procedure, metastable phases and/or amorphous samples may be
obtained. Unfortunately, there is still little understanding of the reasons behind
the formation of a particular phase, and each case has to be treated individually. A
low temperature treatment may also lead to the formation of hydrous oxides from
precursors obtained by aqueous precipitation. The water in the hydrous oxides
can be removed by treatment at elevated temperatures.
Broadly speaking, polycrystalline or amorphous samples of oxides are often
prepared from a solution containing the appropriate precursor compounds. There
121
122
SOLUTION CONTAINING
PRECURSOR CATIONS
/-2 \ \
COPRECIPITATION COMPLEXATION GELFORMATION GALAXING WITH
1 (acid, alcohol addn) I OXIDE PRECURSORS
(AGING) 1
1 DRYING
I
WASHING
(AGING)
1
DRYING .1
1 THERMAL
THERMAL ACTIVATION
ACTIVATION (decomposition)
\ L /
1
(AGING)
1
DRYING
REMOVAL OF 1
VOLATILE COMPDS EXTRUSION OR
1 BALL MILLING
1
(AGING)
1
THERMAL THERMAL
ACTIVATION ACTIVATION
/ (solid-state rxn)
ADDITION OF
3THER ELEMENTS
1
impregnation
malaxing
ball milling
1
(aging)
1
1
DRYING
THERMAL
ACTIVATION
FORMING PROCESS (optional)
\
(tabletting. extrusion)
1
(aging)
1
1
DRYING
THERMAL
ACTIVATION
FINAL OXIDE
1
Figure 8-1 Common methods for the preparation of mixed oxides. (From "Preparation of
Catalysts. III", G. Poncelet, P. Grange, and P. J acobs, ed., Elsevier Publishers, 1983,
p.185. copyright Elsevier Scientific Publishers).
OXIDE PREPARATION 123
are many methods to transform the metal ions in the precursor solution into the
desired oxides. Fig. 8-1 illusuates the most commonly employed methods.
Whether by precipitation, gelation, or complexation, a solid containing the metal
ion of the oxide is first separated from the solution. This precipitate is then
washed and dried, and finally calcined and perhaps reduced to form the desired
oxide. Sometimes other components are added along the process. The oxide at
this point is a powder. It can be formed into pellets or tablets if needed.
However, different techniques of forming an oxide may result in samples of
very different surface properties. This is because the crystallographic form of the
oxide obtained, its morphology, its composition, and its surface structure may vary
depending on the preparation procedure. Any one of these factors can have a
significant effect on the surface property. In this chapter, examples to
demonstrate this will be presented.
The preparation procedure may also determine the pore volume and pore size
and structure of the oxide particles. Although no detailed study is available for
transition metal oxides in general, it is expected that the applicable principles
should be similar to those for alumina, which has been recently reviewed [2]. It is
mentioned that the sedimentation and flocculation of the oxide colloidal particles,
the procedure of drying the wet precipitate agglomerates, the aging process, the
peptising agent, and the nature of any additives are among the factors that affect the
pore size of the oxide. Therefore, attention to details is important in the
preparation.
8.2 PREPARATION OF UNSUPPORTED SINGLE COMPONENT
OXIDES
Single component oxides may be prepared by thermal oxidation of the metal.
Usually, the metal samples arc available in forms that have low surface areas such
as pellets, course powder, or foils. The kinetics of oxidation is slow because
lattice diffusion of metal and oxygen ions is necessary. Therefore, high
temperatures are used to obtain reasonable rates. The result is that the surface
areas of the oxides obtained are low.
For many practical purposes where the available surface area is critical, the
oxides are commonly prepared by the decomposition of precursor compounds
containing the desired metal ion in air or oxygen. Usually, preference is given to
precursor compounds that decompose at low temperatures to minimize sintering of
the resulting oxide which causes low surface area. Carbonates, bicarbonates,
hydroxides, nitrates and oxalates are usually preferred over sulfates for this reason.
The decomposition may also be carried out in vacuo to lower the decomposition
temperatures. The desired precursor compounds can usually be obtained by
precipitation from aqueous solutions of the readily available compounds. When
the readily available compounds of some elements (such as titanium) are not
soluble in water, hydrolysis of nonaqueous solutions or direct vapor phase
oxidation of some compounds may be employed.
The method to prepare aerogels has also been successfully applied to prepare
124
some high surface area transition metal oxides, notably chromia. In this method, a
hydroxide precursor is first precipitated from an alcoholic solution by hydrolysis of
an akoxide, for example, with a controlled amount of water. The alcohol solvent
is then removed by evacuation at a temperature above the critical temperature of
the solvent. An alcoholic solvent is used instead of water because of its lower
surface tension so that the gel structure can be retained from collapsing during
drying. If the hydroxide precursor is prepared by hydrolysis in an aqueous
solution, the water should be first replaced by an alcoholic solvent before
evacuation. Otherwise, dissolution of the oxide in water at the high temperature
may occur [2a].
Crystallographic Phases
It is rather common that different preparation methods result in oxides of
different crystallographic phases. One example that is of significant industrial
interest is the preparation of titanium dioxide (Ti02). Titanium dioxide exists in
three crystallographic forms: rutile, anatase and brookite. The brookite phase is
seldom formed. Although the rutile phase is generally considered the most stable
form, there are thermochemical data which indicate that anatase may be more
stable than rutile [3].
Common titanium compounds are not soluble in water. Very pure Ti02 can
be prepared by hydrolysis of prepurified TiCb. Ti(1V) sulfate, or Ti akoxides.
The resulting solid is best regarded as hydrous titanium oxide. Subsequent
calcination in air produces Ti02. Normally, rutile is the predominant form, but
anatase is often present in minor amounts. The anatase form can be produced by
hydrolysis of Ti halides at temperatures around 600°C, or via low temperature
calcining (-700°C) of precipitated titanic acid H2Ti03 .nH20 [4].
Ti02 can also be prepared by vapor phase oxidation of TiC12. TiH2 can also
be used [5].
ZrO2 crystallizes in the monoclinic and tetragonal forms. The absorption of
mechanical energy by the Zr02 particles finely dispersed in A1203 when they
transform from the tetragonal to the monoclinic form is the reason for the enhanced
fracture toughness of such alumina. Davis has investigated the final crystallo-
graphic phase of ZrOz as a function of the pH of the precipitation mixture [6]. The
results are shown in Fig. 8-2. The hydrous Zr02 precipitates are prepared by
adding WOH . NaOH or KOH rapidly to a zirconyl nitrate solution to bring it to a
desired pH. The gel is then calcined to 600°C to yield Zr02. Precipitation at a pH
of 3-4 or 13-14 results in a nearly 100% tetragonal phase. On the other hand, at
pH 7-10, over 90% of the ZrOz is in the monoclinic phase.
The phases obtained by hydrothermal treatment of amorphous hydrous z102
gel depends on the other salts present in the mixture. Only the monoclinic phase is
produced using KF or NaOH, while a mixture of both phases is produced using
LiCl, KBr or no salt [7]. Monoclinic Zr02 is also obtained by heating stabilized
colloidal zirconyl nitrate in concentrated nitric acid [8].
Molybdenum trioxide also exists in two different crystallographic forms,
orthorhombic and hexagonal. If the oxide is prepared by th addition of HN03 to
an aqueous solution of ammonium heptamolybdate to form a precipitate which is
OXIDE PREPARATION 125
.I NHiOH
"1 dKOH NaOH
0 8 i
-
z
0
0,
0,
C
0
' 0 4
06
c
-
c
P
LL
0 2
2 4 6 8 1 0 4 2 4 4
PH
Figure 8-2 Fraction of tetragonal zirconia in materials obtained by calcining at 6OO0C gels
precipitated from solutions with NH40H. NaOH, or KOH versus h a 1 pH of the solution.
(From J. h e r . Ceram. Soc., 67, C-168 (1984). copyright American Ceramic Society).
heated to above 300"C, the orthorhombic form is produced predominantly. If the
precipitate is heated to below 250"C, hexagonal Moo3 is obtained predominantly
[91.
Morphology of Oxide Crystallites
The preparation method determines the morphology of the final product as
well as its crystallographic phases. I n general, the higher the temperature of
calcination, the coarser and the more crystalline is the final powder. Some
examples of preparing different morphologies are described bclow.
ZnO is the first example [lo]. If ZnO is prepared at high temperature by
ignition of zinc in an oxidizing atmosphere, a three dimensional crystalline sample
of a low surface area is obtained. Electron microscopy shows that thc sample
consists of crystallites of about 700 nm long and 300 nm wide, exposing the
prismatic face on the long side, and the polar faces on the short side. Small
crystals grown from vapor transport are needles of hexagonal cross-section, about
0.1 cm long and 0.001 cmin diameter. The long side exposes the prismatic face.
A powder preparcd from ZnC03 precipited from a nitrate solution with sodium
carbonate followed by washing and conversion to oxide by calcining has a high
surface area about 36 m2gp1. The resulting oxide contains hexagonal platelets about
15 nm across. The polar face represents about 33% of the exposed surface. A
powder prcpared by the decomposition of zinc acetate contains particles grown
126
mostly along the (0001) orientation, while that by the decomposition of zinc
formate mostly contains particles grwon along the (1 120) direction [ 111.
The surface area of ZnO prepared by the decomposition of ZnC03 precipi-
tated from a nitrate solution depends on the calcination procedure. If the water
trapped in the prccipitate is removed efficiently during heating of the precipitate
(ZnC03), a high surface area sample (above 30 m2g-') is obtained. Otherwise,
the surface area is much lower (10 m2gA1 or lower),
Haematite a-Fe203 is another example [12]. It is reported that the di sh-
bution of the exposed planes depends on the precipitation method and the
temperature of oxygen pretreatment. Precipitation at high pH from aqueous ferric
nitrate leads to the formation of geothite (a-FeOOH) with a smaller amount of
haernatite. Mainly haematitc is formed at low pH [13-151. Precipitation from a
ferric chloride solution leads to the formation of P-FeOOH, particularly when the
precipitate is aged in contact with a solution containing chloride ions [14-171.
Subsequent heating of these different precipitates results in a-Fe203 particles that
possess different proportions of hydroxyl groups of different IR absorption
frequencies. The latter is an indication that different amounts of various crystal
faces result from the various preparations [ 121.
In addition to preparing oxides with the cxposure of different crystallographic
planes in the crystallites of different samples, it is also possible to prepare oxide
particles of different macroscopic shapes by careful aging of a solution of a
particular composition at a particular temperature and for a particular time [18].
Table 8-1 summarizes the examples in the literature which show that depending on
aging conditions, spherical, cubic, spindle or disk-like a-Fe203 can be obtained.
It is noted, though, that each of the uniformly shaped macroscopic particles consists
of many subparticles. That is, the macroscopic particles are not single crystals.
At this point, except for the fact that slow aging is required, there is little
understanding of why different but uniform shapes are obtained under different
conditions. In general, if the hydrolysis products consist of discrete well-defined
ionic complexes, crystal growth occurs, yielding particles of fixed stoichiometry
and most often of well-defined crystal habits. If the hydrolysis results in the
formation of polymeric metal complexes, spherical particles are produced.
Indeed, low temperature hydrolysis has been a method to produce high
surface area oxide gels. For example, chromia gel has been produced by the
hydrolysis of chromium nitrate in an urea solution. Heating the solution to
decompose the urea permits slow and uniform hydrolysis throughout the solution.
The gel precipitates after boiling the solution for a few hours [19]. Drying at low
temperatures results in a high surface-area gel. Evacuation may help the drying.
Use of organic instead of aqueous solvents results in gels of larger pores because of
the lower surface tension of organic solvents. Other hydrolysis methods can also
be used. For example, hydrolysis of tris(2,4-pentanedionate) chromium
(Cr(a~ac)~) followed by precipitation with ammonium hydroxide, or hydrolysis of
chromium ethoxide by water and ammonium hydroxide has been successfully
attempted [20]. Such chromia gel is mostly amorphous to X-ray diffraction. Only
a small fraction is crystalline.
OXIDE PREPARATION 127
Table 8-1 Examples of the Dependence of the Morphology of an Oxide on
the Preparation Method.
Material and Aging solution Aging temp. Reference1
Morphology ture and time
spherical 0.032 M FeClz 100"C,
(- 0.1 to 0.5 p)
hematite (a-Fq03)
sol
+0.005 M HCl 2 weeks
cubic (- 1 pn) FeC13 in HzO. 100°C. days
a- Fez03 HzO-ethanol, or
HzO-methanol soh.
disklike 0.0040 M Fe(NQ)3 50°C. 1 h
(- 1 x 10 pm)
a-FqO, +1.20 M NaOH
+0.20 M triethanolamine
+0.50 M Hz02
spindle a-FeZO3 Fe3++NaHzQ 100°C. days
spherical amor- Crz(S04h 75°C
phous chromium
hydroxide
Cr3++KHZPO4 but 75°C
not in the presence
of (Cl , NO3- or
acetate)
spherical rutile TiC14, S04z- 98"C, days
spherical (<1 pm) Soh. of FeS04 and
Ni,Fq-x04 KOH in OZ-free soh.
well-formed 0.02 M Fe(NQh 25OoC, 2 h
crystallites +0.40 M TEA
Fc304 +2.4 M NaOH
+0.85 M NzH4
E. Matijevic and
P. Scheiner, J.C.I.S.
63, 509 (1978).
S. Hamada, E. Matijevic,
J.C.I.S.. 84, 274 (1981).
E. Matijevic, Acc. Chem.
Res., 14, 22 (1981).
M. Ozaki, S. Kratohvil,
and E. Matijevic J.C.I.S.
102, 146 (1984).
R. Demchak. and Matijevic.
J.C.I.S. 31, 257 (1969).
E. Matijevic. A. D. Lindsay,
S. Kratohvil. M. E. J ones,
R. I. Larson, N. W. Caycy,
J.C.I.S., 36. 273 (1971).
E. Matijevic, M. Budnik,
L. Meites, J.C.I.S.,
61, 302 (1977).
A. E. Regazzoni, and
E. Matijevic. Corrosion,
38, 212 (1982).
R. S. Sapieszko. E. Matijevic
J.C.I.S.. 74, 405 (1980).
128
Table 8-1 continued
polyhedra
CUO
needle ZnO
(- 1 x 50 pm)
(- 20 Pm)
VzOs leaflets
crystalline
cobalt oxide
crystalline
Zr02 (16 nm)
mixture of
monoclinic
and tetragonal
monoclinic 6 nm
ZrOz
spherical (-1 pm)
A1hydroxide sol
ferrous hydride gel
containing excess
FeS04
0.040 M CU(NO:,)~
+0.20 M HEDTA
+1.20 M NaOH
0.040 M Zn(NQ)z
+0.20 M TEA
+1.2 M NaOH
+0.85 M N2H4
0.040 M Na3V04
+0.20 M HEDTA
+1.20 M NaOH
+0.85 M N2H4
acetate
amorphous hydrous
Zr Oz in distilled water
with or without added
KF, NaOH. LiCI. or
KBr
90°C
100"C,
70 min
25OoC. 2 h
25OoC, 3 h
200°C
stabilized colloidal 150°C.
zirconyl nitrate in 14 days
HN03
0.002 M AIz(SO3)3 97"C, 48 h
E. Matijevic, J.C.I.S.,
58, 374 (1977).
E. Matijevic, Am. Chem.
Res.. 14, 22 (1981).
ibid.
ibid.
T. Sugimoto. E. Matijevic
J. Inorg. Nucl. Chem.,
41, 165 (1979).
E. Tani, M. Yoshimura,
S . Somiya, J. Amer.
Ceram. SOC., 66, 11 (1983).
P. Morgan, J. Amer. Ceram.
SOC., 67. C-204 (1984).
R. Brace and E. Matijevic,
J. Inorg. Nucl. Chem.,
35, 3691 (1973).
Footnote:
a) J.C.I.S. stands for J . Coll. Interface. Sci.
OXIDE PREPARATION 129
8.3 PREPARATION OF SUPPORTED OXIDES
There are a number of reasons to use supported oxides instead of unsupported
ones. One reason is to increase the surface area. Often oxides are prepared by
calcination at relatively high temperatures that result in significant sintering or loss
of surface area. A suitable support can reduce sintering. Sometimes a support is
used as a heat conduction medium. This may be particularly important in
oxidation reactions which have large heats of reaction. A support of high thermal
conductivity helps to remove the heat from the reaction site, and reduces hot spots
which usually degrade selectivity. Silicon carbide has been used for this purpose.
In a number of systems, the support provides a template for the oxide to form in a
certain desirable morphology, such as the exposure of one predominant plane.
V2O5 supported on anatase Ti02 is a well known example [21,22]. V205 forms a
layer structure on TiO2, preferentially exposing the (010) plane which contains the
V=O groups believed to be important in oxidation reactions. In this regard, the
exact nature and structure of the support can be critical. As described in Chapter
2, V2O5 forms a layer structure much more readily on anatase TiOz than Si02 [21].
Similarly, Moo3 forms a monomolecular layer structure on A1203 but not on SiO,
[231.
I t is common that an oxide support interacts strong with the oxide. The
formation of a layer structure on the support is a result of such strong interaction.
The reducibility of the oxide is often affected by a strongly interacting support (see
Chapter 6). The strong interaction may also cause morphological changes in the
support. The surface area of V205 supported on anatase Ti02 is much smaller
than that of the original support, whereas that of Moo3 supported on the same Ti02
has the same surface area [24].
Supported oxides are often prepared by impregnation or ion-exchange of a
precursor compound onto the support. Ion-exchange can be used for oxides that
have precursor compounds that dissolve in water and formionic complexes that
contain the desired metal. This requirement usually excludes the preparation of
supported Ti or Zr oxides by ion-exchange. Schematically, the process involves
ionization of surface hydroxyl groups of the support in the aqueous solution. The
desired ion is then attached to the ionized hydroxyl group by electrostatic forces.
The process for high pH is:
S-OH + OH- + S- 0 - + H20 (8-1)
The corresponding process at low pH is:
S-OH + H+ 4 S-OH,' (8-3)
S 4 H 2 + + (M)"- --+S-OH,+(M)"-
(8-4)
In these equations, S-OH stands for the hydroxyl group of the support, and
130
(I@"+ Or "- is the ionic complex. For most metals, cationic amine complexes are
readily available. For Mo and V, the anionic 0x0 complexes are often used [25].
Subsequent calcining of the ion-exchanged material produces the oxide. This
method produces highly dispersed oxides because electrostatic repulsion keeps the
complexes apart. The loading obtainable is also low for the same reason.
In impregnation, a solution of the salt containing the desired cation is added
to the support. If the volume of the solution is just enough to fill the pore volume
of the support, the method is called impregnation by incipient wetness. Excess
solution may also be used. The solvent is eventually removed by drying, and the
oxide is formed after calcination.
Impregnation is the most widely used method because it is applicable to
practically all oxides. The possible use of either aqueous or nonaqueous solvent is
the major factor of the versatility of the method. The loading can be varied over a
wide range by changing the concentration and the amount of solution used. The
loading as well as the details of the drying and calcination conditions affect the
dispersion of the final oxide.
The pH of the ion-exchange or impregnation solution is one of the factors that
determine the nature of the final oxide. In addition to changing the extent of
protonation or dissociation of surface hydroxyl groups, different pH's may also
change the species in the solution. For example, at pH c 1, vanadyl cation (VO,')
is the major species in solution. At pH 4, the major species is a three-dimensional
decavanadate, [HVI 0028]s-. At pH 7, two-dimensional tetra- and trivanadate
species are present, and at pH 9 and 12, divanadate and monovanadate species are
formed, respectively [26]. At high pH's, dissolution of the support may occur.
Special techniques are sometimes used for better wetting of the support by the
oxide precursors. For example, spraying in vacuo a solution of the precursor onto
the support has been attempted [27] to prepare silica-supported Fe203-Mo03.
Precursors may also be introduced in the gas phase. For example, alumina-
supported V205 has been prepared by treating the A1203 with a stream of N2
containing VOC13. The VOC13 is then hydrolyzed with steam diluted with N2 [21].
The process can be repeated to increase loading. Organometallic compounds may
also be used in the gas phase method. For example, cyclopentadienyl zirconium
can be used as precursor for Zr02, and x-ally1 chromium for Cr203. In these cases,
the Zr or Cr precursors are anchored onto the surface by the hydrolysis reaction of
the organometallic complexes with the surface OH groups. Since this hydrolysis
reaction involves specific interaction between the compound and the surface OH
groups, the compound may also be introduced in an inert solvent. Contacting a
solution (normally a thoroughly dehydrated hydrocarbon or ether solution) of the
compound with the solid support often works well. With this technique, Ti02
supported on A1203 can be prepared using a heptane solution of TiCI4 or
Ti(OC3H7)4 [28], and Nb205 supported on Si02 using a hexane solution of
Nb(OC2Hs)s [291.
Repeated ion-exchange, repeated impregnation, or a combination of ion-
exchange and impregnation are sometimes employed to increase the final loading.
I t may be noted that because of the pH of the impregnation solution, sometimes ion-
exchange occurs during impregnation. This happens when alumina is impreg-
OXIDE PREPARATION 131
nated with a solution of ammonium heptamolybdate of low pH. A highly dis-
persed molybdenum oxide is thus obtained [30].
It is important to recognize the possibility that the support, which is almost
always another oxide, may react with the oxide. Among the common supports,
Si02 may form silicate with many oxides, especially those in the first transition
period, A1203 may form aluminates, and Ti02 titanates. In fact, the formation of
new compounds is often thermodynamically favorable but kinetically limited.
Thus high temperature calcination enhances their formation. In some cases, such
as supported NiO, this leads to the apparent increase in the resistance to reduction
of the oxide [31].
For TiO,, there is the additional complication that phase transformation of
titania may be enhanced by the presence of a second oxide. It has been reported
that the transformation of anatase to rutile is enhanced by the presence of vanadium
oxide [32]. In another study, vanadia-titania catalysts were prepared by
coprecipitation. It was shown that the different precipitation conditions and
different subsequent treatments led to widely different fractions of titania being in
the rutile form [33].
Like unsupported oxides, the crystallographic form of a supported oxide may
depend on the preparation method. This has been reported to be the case for a
silica-supported iron oxide. A sample prepared by hydrolysis of a mixed solution
of ethyl silicate and iron (111) nitrate in ethylene glycol consists of very small
crystallites of y-Fe203 on theSiOz support, but one prepared by impreg- nation of
silica gel with aqueous iron (111) nitrate consists of a-F@03 particles with a broad
size distribution [34].
8.4 PREPARATION OF MULTICOMPONENT OXIDES
Since the number of possible compounds that can be formed increases rapidly
with the number of components, multicomponent oxide systems can be very
complex. Since catalysts are often prepared at as low a temperature as feasible to
preserve the surface area, the formation of compounds is often kinetically
controlled instead of thermodynamically controlled (that is, the compounds
observed may not be the most thermodynamically stable ones). Thus the overall
chemical composition of the oxide can be used only as a guideline for the possible
compounds present. I t is not uncommon to find in a mixture of compounds some
of stoichiometries quite different from the overall composition. However, this may
be desirable in some cases when a multi-phase is necessary for the desired
selectivity and activity of a catalyst. Nonetheless, this behavior makes it more
difficult to reproduce the properties of a catalyst, whose behavior is vulnerable to
small changes in the preparation procedure.
In general, the various methods shown in Fig. 8-1 are used to prepare
multicomponent oxides. The most desirable method would be one which results
in a solid of a reasonable surface area, the desired stoichiometry, the desired
number of phases, and, very importantly, the desired spatial distribution of these
phases. The latter is important in catalytic reactions where the diffusion of
molecules is critical to selectivity. There is not yet a universally most desirable
preparation method for all oxides.
The traditional ceramics preparation technique of ball-milling the appropriate
ratio of the component oxide powders followed by high temperature calcination to
bring about compound formation is seldom used in the preparation of high surface
area samples. This is because the reaction rates between component oxides are
usually small. Thus a high temperature and a long heating time are needed which
cause the formation of low surface area compounds. To overcome this problem,
instead of mixing component oxides, precursor compounds that contain the desired
metals and decompose at low temperatures are used. Carbonates and oxalates are
among the precursor compounds. For example, CaMn03 and Ca2Mn04 can be
prepared by the oxidative decomposition at 1000°C of CaMn(C03)2 and
Ca2Mn(C03)3, respectively [35]. High surface area solid solutions of NiO-MgO
and Coo-MgO are obtained by impregnating Mg(OH)2 with Ni or Co nitrate. The
mixture is then thermally decomposed and annealed in vacuo at 1000°C [36].
Intermetallic compounds have also been used as precursors.
Although the ion-exchange method may be used to prepare multi-component
oxides, the need to know the ion adsorption coefficients so as to control the
stoichiometry of the final product makes the method less convenient to use.
Impregnation does not have this limitation. A solution containing the desired ratio
of the compounds can often be made. By virtue of the method, all solute deposits
onto the support. Repeated ion-exchange, repeated impregnation, or a
combination of ion-exchange and impregnation can also be used.
In these methods, the desired final compound is formed without the necessity
of very severe heating because the metal ions are already brought into intimate
mixing in the precursors. To achieve good intimate mixing of the metal ions in the
precursors is also the goal of many other techniques. Freeze-drying, for example,
involves spraying a solution that contains decomposable compounds of the desired
metal ions into liquid nitrogen. Because of the rapid freezing, the precursor
compounds form very small particles and little segregatory crystallization takes
place. Upon drying in vacuo such that the solvent is removed without melting the
solid (which sometimes may exist as a glassy solid), the intimate mixing of the
precursor compounds is preserved. Among many examples, Zn ferrite has been
prepared with this technique [37].
Spray-drying employs a similar principle as freeze-drying. Here, a solution of
precursor compounds is sprayed into a hot chamber. The solvent is rapidly
evaporated, and the precursor compounds form fine particles. Again, because of
the speed of the drying process, segregation of the components is minimized.
Both spray-drying and freeze-drying are commonly employed techniques. They
are applicable to systems that have precursor compounds that are soluble i n a
common solvent.
A variation to freeze-drying and spray-drying is to make use of complexation.
In the preparation of a Cu-Co-Al-Zn oxide, an organic acid (citric, malic, tartaric,
glycolic, or lactic) is first added to the metal nitrate solution. The solution is then
evaporated in vacuo to yield a glassy amorphous material. This is then calcined
WI.
OXIDE PREPARATION 133
1 I I I 1 I I
0 0.4 0.8
2-
Amount of CO Added X i [ M"+]
3
Figure 8-3 Neutralization curve of a nitrate solution of Cu", A13+, and ZnZf (0.35 M) with
0.4 M sodium carbonate. (From the same source as Figure 8-1, copyright Elsevier
Scientific Publisher).
One advantage of the techniques mentioned thus far, except ion-exchange, is
that all of the starting material is recovered in the solid. Thus the overall
stoichiometry of the final compound is known with certainty during preparation.
Such is not the case with another commonly employed technique of
coprecipitation.
I n coprecipitation, a precipitation agent which is often hydroxide or car-
bonate of ammonium or sodium is added t~ a solution containing the precursor
compounds. Hydroxides or carbonates of the metal ions are precipitated out of the
solution. They are filtered, washed, and then calcined to form the oxide. The
homogeneity and the degree of atomic mixing of the metal ions in the precipitates
depend on the solubility products of the compounds involved. As an example, a
Cu-Zn-A1 oxide catalyst is prepared by coprecipitation of a solution containing Cu,
Zn, and A1 nitrates with sodium carbonate. The precipitation curves of Cu, Zn,
and A1 hydroxycarbonates are shown in Fig. 8-3 [39]. It can be seen that the
precipitation curves are so differcnt that if Na2C03 is added slowly to the solution
of nitrate mixture, Al , Cu, and Zn hydroxycarbonates would precipitate out quite
independently. I n such a situation, it is advisable to add the nitrate solution slowly
into a sodium carbonate solution. I t is also interesting to note that the precipitation
point for A1 and Cu hydroxycarbonates shown in Fig. 8-3 are much lower than
those if the hydroxycarbonates are precipitated separately from a solution
containing only one metal salt.
When properly performed, coprecipitation can result in a fairly well mixed
134
precursor mixture. This is particularly me if the precipitate compound contains a
mixture of metal ions. I n the example of the Cu-Zn-A1 oxide above, the
compounds (Cu,Zn)2(OH)2C03, (Cu,zn)dOH)6(CW2, and (Cu,Zn)gA12(OH)16-
C03 can be formed [39,40]. These compounds provide intimate mixing of the
metallic ions. Upon calcination, well mixed CuO and ZnO, as well as possibly
Cu+ dissolved in ZnO are formed.
One more example will be mentioned to demonstrate the importance of the
pH in the stoichiometry of the final oxide obtaincd. In the preparation of the
NiMo04-Mo03 system, the amount of Moo3 in the final oxide depends on the pH
of the solution during the addition of ammonium heptamolybdate solution to the
nickel nitrate solution. If the pH is 6, stoichiometric NiMo04 is formed. If the
pH is 5 or lower during the addition, and then raised to 5. 5 at the end of the
addition, excess Moo3 is formed. The amount of excess Moo3 increases with
decreasing pH [41].
There are variations to the simple coprecipitation technique. For example,
coprecipitation can be performed in the presence of a suspension of another
precursor. This is used as one of the methods to prepare a Ag-Mn-Co oxide [42].
Thus a Ag and Co carbonate mixture is precipitated out in a solution containing a
MnOz suspension. Other variations such as precipitation of Ag-Mn oxide in a
C0C03 suspension can also be used.
REFERENCES
1. M. M. Faktor. and I. Garrett, "Growth of Crystals from the Vapor," Chapman
and Hall Ltd., London. 1974; D. Elwell, and H. J. Scheel." Crystal Growth
from High-Temperature Solutions," Academic Press Publ., New York, 1975.
2. D. L. Trimm. and A. Stanislaus. Appl . Cafal., 21, 215(1986).
2a."Aerogels", ed. J . Fricke. Springer-Verlag Publ.. Berlin, 1986.
3. F. A. Cotton and G. Wilkinson, "Advanced Inorganic Chemistry," 4th Edition,
J ohn Wiley & Sons, N.Y. 1980. p. 695.
4. "Handbook of Preparative Inorganic Chemistry", Ed. by G. Braucr (Engl.
transl.) Vol. 2, 2nd edition, Academic Press, 1965.
5. V. A. Lavrenko, V. Zh. Shemet, S. K. Dolukhanyan, CA 98382827k
6. B. H. Davis, J . Amer. Ceram. Soc., 67. C-168 (1984).
7. E. Tani, M. Yoshimura. S . Somiya, J . Amer. Ceram. Soc., 66, 11 (1983).
8. P. E. D. Morgan, J . Amer. Ceram. Soc.. 67, C-204 (1984).
9. J .-M. Tatibouet and J . E. Germain, C. R. .4cad. Sci. Paris C. 290. 321 (1980).
10. M. Bowker, H. Houghton. K. C. Waugh, J . Cafal., 84, 252 (1983).
11. G. Djega-Mariadasson and L. Davignon. J . Chem. SOC. Faraday Trans. 1.
12. C. H. Rochester and S. A. Topham, J . Chem. Soc., 1073 (1979).
13. R. J . Atkinson. A. M. Posner. and J . P. Quirk. J. Inorg. Nuclear Chem.,
14. P. J. Murphy, A. M. Posner. and J . P. Quirk, J . Colloid Interface Sci.,
78, 2447 (1982).
30, 2371 (1968).
56, 270, 284, 312 (1976).
OXIDE PREPARATION 135
15. T. G. Spiro, S. E. Allerton, J . Renner, A. Terzie, R. Bils, and P. Saltman,
16. A. L. Mackay, Mineral. Mag., 32, 545 (1960).
17. K. Kauffman, F. Hazel. J . Coffoid Inferface Sci., 51. 422 (1975).
18. E. Matijevic, Acc. Chem. Res., 14, 22 (1981) and reference within.
19. R. L. Bunvell, Jr., A. B Littlewood. M. Cardew. G. Pass, C. R. H. Stoddart,
20. K. C. Taylor, PhD Thesis, Northwestern Univ.. 1968.
21. Y. Murakami, M. Inomato, K. Mori, T. Ui, K. Suzuki, A. Miyamoto, T. Hattori.
Proc. 3rd Intern. Symp. on Scientific Basis for the Preparation of Heterogeneous
Catalysts, G. Poncelet, P. Grange and P. A. J acobs, ed., 1983. p. 531.
22. G. C. Bond and P. Konig, J. Cafaf.. 77, 309 (1982).
23. N. Giordano, A. Castellan. J . C. J . Bart,, A. Vaghi. and F. Campadelli.
24. M. Del Arm, M. J . Holgado, C. Martin, and V. Rives, J . Catal.. 99. 19 (1986).
25. L. Wang and W. K. Hall, J . Card., 66, 251 (1981).
26. M. Pope, and B. Dale, Quarr. Rev. (London). 22, 527 (1968).
27. M. Carbucicchio and F. Trifiro, J . Cataf., 62. 13 (1980).
28. G. B. McVicker and J . J. Ziemiak. J. Cafaf., 95, 473 (1985).
29. E. J . KO, R. Bafrali, N. T. Nuhfer, and N. J . Wagner, J . Cafal., 95. 260 (1985).
30. M. Houalla, C. L. Kibby, L. Petrakis, D. M. Hercules, J. Caraf., 83, 50 (1983).
31. M. Houalla, Proc. 3rd Intern. Symp. on Scientific Basis for the Preparation
J . Amer. Chem. Soc.. 88, 2721 (1966).
J . Amer. Chem. Soc., 82, 6272 (1960).
J. Cafal., 37, 204 (1975).
of Heterogeneous Catalysts, G. Poncelet, P. Grange, and P. A. J acobs, ed.,
1983, p. 273, Elsevier Science Publ.
32. G. C. Bond, and A. Sarkany, J . Cafaf., 57, 476 (1979).
33. W. E. Slinkard and P. B. DeGrooS J . Calaf.. 68. 423 (1981).
34. T. Ida, H. Tsuika. A. Ueno, K. Tohji, Y. Udagawa, K. Iwai. and H. Sano.
35. H. S. Horowitz and J . M. Longo. Mat. Res. Buff., 13, 1359 (1978).
36. A. P. Hagan, M. G. Lofthouse, F. S. Stone and M. A. Trwethan, in "Scientific
Bases for the Preparation of Heterogeneous Catalysts, II", B. Delmon, P.
Grange, P. J acobs, and G. Poncelet, ed., Elsevier Scientific Publ., 1979, p. 417.
84, 382 (1980).
17, 241 (1982).
III", G. Poncelet, P. Grange and P. A. J acobs, ed., Elsevier Scientific Publ.,
1983. p. 185.
Kobylinski, J . Cafaf., 56, 407 (1979).
J . Catal.. 106, 428 (1987).
37. H. H. Kung, S . Kundalkar, M. C. Kung. and W. H. Cheng J . Phys. Chem.,
38. Ph. Courty, D. Durand, E. Freund, and A. Sugier, J . Mofec. Cataf.,
39. Ph. Courty and Ch. Marcilly, "Scientific Basis for the Preparation of Catalysts,
40. R. G. Herman, K. Klier, G. W. Simmons, B. P. Finns, J. B. Bulko, andT. P.
41. U. Ozkan and G. L. Schrader, J. Card.. 95, 120 (1985).
42. M. Haruta and H. Sano, "Scientific Bases in the Preparation of Catalysts, III",
G. Poncelet, P. Grange, and P. A. J acobs, ed., Elsevier Scientific Publ., 1983,
p.225.
Chapter 9
METATHESIS AND ISOMERIZATION
9.1 METATHESIS
In fro ductio n
When a mixture of two alkenes is exposed to a metathesis catalyst, the
substituents of the two alkenes are interchanged to form new alkenes according to
the reaction:
Usually, both the E and the Z isomer of each of the four products shown are
obtained. These products can be predicted by assuming that each alkene molecule
is dissociated into two (R)2C fragments by breaking the C=C bond. These
fragments recombine with other fragments to form the products. One must
emphasize that the actual reaction mechanism is quite different from this picture.
Since the discovery of highly selective catalysts for metathesis, this reaction has
been used to prepare specific alkenes, particularly internal alkenes, from more
commonly available ones.
Metathesis does not always result in the production of new alkene molecules
with a different carbon chain length or with a diffcrent position of the carbon-
carbon double bond. When this happens, the reaction is dcgenerative
(nonproductive). Reactions (9-2) and (9-3) are two examples of degenerative
mctathesis:
136
METATHESIS AND ISOMERIZATION &37
CH2=CHCH3 + CD2=CDCD3 ---+CH2-CDCD3 + CDZ=CHCH2 (9-2)
(9-3)
Concurrent with reaction (9-2), productive metathesis occurs that produces cthene
and butene as products:
CH2=CHCH3 + CD2XDCD3 + CH2=CD2 + CD3CMHCH3 (9-4)
It can be seen that according to reaction (9-3), metathesis is also a route for cis-
trans isomerization.
Co-Mo oxide supported on A1203 is the first transition metal oxide
heterogeneous metathesis catalyst reported [ 11. Since then, many other oxidic
catalysts have been discovered [2,3], including MoO3-Cr2O3/AI2O3. Mo03/Si02,
W03/Si02, W03/A1P04, Re207/A1203, Ta20s/Si02, Nb20s/Si02, and Te03/Si02.
Among these, those based on Moo3, W03 and R%07 are the most active and
selective, with Re207 being active at close to room temperature. Progress on this
reaction has been reviewed [2,3]. Some nonoxidic catalysts are also very active,
especially those prepared from molybdenum hexacarbonyl.
Mechanism
I t is generally accepted that metathesis proceeds via a metallocarbene
intermediate. For example, consider the metathesis of a mixture of propcne and
propene-d6. The reaction of propene-d6 with the catalyst results in the
metallocarbenes I and 11:
MqD2 MXDCD3
Addition of propene to I generates a metallocyclobutane the decomposition of
which leads to cithcr dcgencrative (eq. 9-5) or productive (eq. 9-6) metathesis,
depending on the orientation of the propene molecule. Analogous reactions can
be written for species 11.
Dcgencrative:
CH3
I
138
Productive:
One characteristic of this mechanism is the retention of the identity of the
CR2 fragments. Indeed, when the center carbon of propene is labeled, the label is
found in the product butene but not in ethene [4]. A mixture of C2H, and C2D4
yields exclusively C2HzD2 as the product. No isotopic mixing is detected [5].
Similarly, the products from a mixture of propene-d,, and propene-4 are almost
exclusively ethene-d,,, d2 and 4, propene-d,,, d2, 4, and 4, cis-2-butene-4, 4,
and d8, and trans-2-butene-d,,, 4, and ds [6]. Thus the reaction proceeds via
transalkylidenation and not transalkylation.
Another possible mechanism, which involves a cyclobutane intermediate (eq.
9-7) has not received much support. Cyclobutane only reacts very slowly over a
metathesis catalyst.
H2C=CH2 + D2C=CD2 + H2yTDZ --+2 H2C=CD2
(9-7)
H2C-CD2
There are other evidence that support the involvement of some organometallic
species (such as I or II) in this reaction. It has been observed that prereduction of
the catalyst by propene or butene produces a very active catalyst, otherwise an
induction period is observed before the catalyst becomes active. Strong evidence
for the metallocarbene intermediate is provided by homogeneous catalysis where
the intermediate is isolated and shown to be an active catalyst [7,8]. It appears
that the carbene-intermediate mechanism can explain all of the available data on
metathesis, including that of cyclopropane which may proceed by first isomerizing
to propene [9,10], and stereospecific metathesis of terminal alkenes [ 131.
The rate of metathesis depends on the substituents around the double bond
due to different degrees of steric hindrance and different polarities of the
intermediates. The sample data shown in Table 9-1 show that on reduced
M003/A1203, butenes and propene react much faster than ethene [l l ]. I t has also
been found that degenerative metathesis of' propene and 1-butene is about ten timcs
faster than productive metathesis [6], and the rate of degenerative metathesis of
cis-2-butene is slower than that of 1-butene [ll]. This latter observation is
different from those reported in homogeneous systems where the activity sequence
in decreasing ordcr is: degenerative metathesis of terminal alkene >cross
metathesis of terminal and internal alkenes >metathesis of internal alkene >and
productive metathcsis of terminal alkene [12]. I n a mixture of alkenes, the alkene
with a higher metathesis rate tends to suppress the metathesis of the alkenc of a
METATHESIS AND ISOMERIZATION 139
Table 9-1 Relative Rates of Metathesis and Isomerization on Reduced
M0 0 3 / y - A1 ~ 0 ~ ~
Relative Initial Rates
Catalyst Productive Degenerative
Reactant Activated byb Metathesis Metathesis Isomerization'
ethene none 0
1.2
12.7
CZH,
c-2-butene
propene none 1.3 0
c3H6 9.4 53.5
c-2-butene 6.2 47.5
1 -bu tene none 0 0 64.6
1-butene 4.0 32Sd 24.7
c-2-butene 1.7 26.0d 27.4
c-2-butene none 0 29.8
c-2-butene 0 81.9" 1.9
Foomotes:
a) From J. Engelhardt. et al., J. Catal., 70, 364 (1981). copyright Academic Press.
b, Catalyst has been preoxidized and then reduced by the hydrocarbon indicated.
') By mechanism other than metathesis.
d, Measured by the formation of 1-butene-dz and 4 from a mixture of 1-butene-4
e, Measured by the formation of c-2-butene-d4 and t-2-butene from a mixture of
and de.
c-2-butene-6 and d8.
slower rate [ 1 I].
Nature of Catalyst
Oxides of molybdenum, tungstcn, and rhenium are among the most active
oxide catalysts for metathesis. However, the oxide must be reduced first before it
is active as is illustrated in Table 9-1. A fully oxidized catalyst has very low
activity, but the activity increascs with the time of contact with the alkene. In the
case of molybdenum oxide, reduction of the catalyst by alkenes has been directly
confirmed by the color change of the catalyst and the detection of the EPR signal of
Mo5+[l 11. Indeed, molybdenum oxide on a variety of supports but contains only
Mo6 is inactive for metalhesis 1141. Similar observations have been made on
+. .
140
W03/Si02 [3]. Exposure of the catalyst to oxygen which reoxidizes the catalyst
also poisons it [23.
The induction period of the fully oxidized catalyst can be eliminated by
prereduction with alkenes. It has been found that propene and butenes are much
more effective activation agents than ethene [11,15]. This is because ethene does
not reduce the oxide as effectively as the other alkenes. For example, a
Mo0,/A1203 catalyst possesses a Mo5+spin concentration of 0.09 x 1014 after
reduction with ethene, and 1.0 x 1019, 2.0 x 1019, and 2.4 x 1019, respectively, after
reduction with propene, 1-butene, and c-2-butene at 60°C [ l l ] . Reduction by
other agents such as HZ, CO or NH3 is also possible but not as effective as propene
or butene [15]. Perhaps this is because of the fact that the active catalyst is a
surface metallocarbene which can be formed during the reduction by alkenes. I t is
known that carbonaceous residue is retained by the catalyst after reduction [9].
However, only a small fraction of the adsorbed CH3 and CH2 groups after
reduction are associated with the active sites. It has also been reported that
treatment with halogenated alkenes also greatly enhances the metathesis activity
[161.
Although reduction of the catalyst is important for the activity, the activity
does not necessarily correlate with the extent of reduction. It has been found that
on a Md3/A1203 catalyst, the metathesis activity is independent of the extent of
reduction beyond an equivalent of 0.3 e/Mo [17]. Furthermore, poisoning of the
catalyst by pyridine and water shows that the amount of active sites is an order of
magnitude less than the number of anion vacancies generated by reduction or the
number of hydrogen atoms retained in the reduction step.
The activity also depends on the type of support. For molybdena, using
A1203 or Ti02 as support generates active catalysts, using SO2, Zr02, Cr2O3, or
ZnO generates less active catalysts, and using Co304, NiO, MgO, Ge02, or SnO2
generates inactive catalysts [141. In the case of Co304, NiO, and SnOz,
prereduction reduces the support but not Moo3. I n the case of MgO, a magnesium
molybdate compound is probably formed in which the Mo6+is more difficult to
reduce. Attempts to correlate the activity with the acidity of the catalyst have not
been successful [ 101.
9.2 ISOMERIZATION OF ALKENES
Introduction
Isomerization is perhaps one of the least demanding reactions in terms of the
requirements for the active site. Thus many oxides and metals are active
isomerization catalysts. Indeed, practically all transition metal oxides possess
isomerization activity. However, the activity and the selectivity vary among
different oxides. I n general, there are two types of isomerization reactions
involving alkenes: double bond migration and cis-trans isomerization.
There are four well recognized mechanisms for isomerization: by
metathesis, via carbanion intermediate, via carbenium ion intermediate, and via a
radical-like (i.e. nonionic) alkyl intermediate. In the case of double bond
METATHESIS AND ISOMERIZATION 141
migration, sometimes the product can be either a cis or trans-alkene. The cis/trans
ratio differs substantially between the carbanion and carbenium ion mechanism,
being ten or higher for the former, and close to unity for the latter. Double bond
migration cannot be achieved by metathesis. Except for the charge on the alkyl
intermediate, the mechanism via a free radical-like alkyl intermediate is similar to
that for the carbenium ion intermediate. Therefore, this mechanism will not be
discussed further.
The cis/trans ratio is often used as an indication of the reaction mechanism.
It should be noted that the pretreatment condition may alter this ratio for some
oxides. For example, the cis/uans-2-butene ratio from 1-butene on a Cr2O3
catalyst pretreated by evacuation ranges from 2 for evacuation at 300-45OoC,
which suggests the involvement of carbenium ion intermediates formed with
surface hydroxyl groups, to as high as 50 for evacuation at 750°C. which suggests
involvement of carbanion intermediates when the surface is dehydroxylated
[18,26]. The cis-2-hexene/trans-2-hexene ratio from 1-hexene is 0.5 if the catalyst
is activated with hydrogen, which may leave adsorbed hydrogen on the surface to
form BrBnsted acid sites for the cationic reaction mechanism [27].
The effect of prereduction of a M a 3 catalyst is different from a Cr2O3
catalyst. On a reduced Md3/AI2O3 catalyst, the metathesis activity is high and
isomerization by metathesis is the major mechanism for cis-trans isomerization
[11,19]. On a fully oxidized Mo03/A1203 catalyst, isomerization proceeds mainly
by a cationic intermediate. In this latter case, the contribution of A1203 to the
isomerization activity has not been identified.
Isomerization by Metathesis
In section 9-1, it is pointed out that degenerative metathesis may lead to cis-
trans isomerization, and that the CR2 fragment is retained in the process. The
latter is a characteristic of isomerization by metathesis which is illustrated by the
data in Table 9-2. Here, a mixture of cis-2-C4Ds and cis-2-C4H8 is passed over a
reduced molybdena catalyst. The deuterium content of the product mixture is
analyzed. The product trans-2-butene contains essentially only &, 4 and ds
species. This can be readily understood if the CR2 fragment is retained during
isomerization as in metathesis. In contrast, the formation of 1-butene which
involves double bond migration must involve a different mechanism. The
deuterium distribution in this molecule is much broader [19]. The much broader
deuterium distribution in all products froman oxidized molybdena catalyst also
points to a different reaction mechanism. I t will be shown later that these
reactions proceed via carbenium ion intermediates.
The activity for isomerization by metathesis increases drastically when the
catalyst is reduced, as is discussed in the last section. However, reduction also
suppresses isomerization by other rncchanisms. This is shown in Table 9-1. For
example, a ful l y oxidized MoO3/y-AI2O3 catalyst is very active in isomerizing cis-
2-butene to I-butene and trans-2-butene. Reduction of the catalyst greatly
suppresses the formation of I-butene, and the formation of trans-2-butene is now
primarily by metathesis. The cis to trans-2-butene isomerization is suppressed by
the presence of propene or l-butene, and less effectively by ethene [ll]. The
142
Table 9-2 Deuterium Distribution in the Isomerization of a Mixture of
cis-2-C4H8 and trans-t-CdH8'
Deuterium Distribution %
cis-2-butene 47.1 0 0 0 0 0 1.1 5.9 45.9
(reactant)
oxidized cis-2-butene 55.8 9.1 1.2 0.4 0.8 0.3 0.9 5.7 25.9
Moo3/ trans-2-butene 28.3 18.6 3.2 1.1 2.2 0.6 3.4 18.6 24.2
y-A1203 l-butene 30.2 23.6 4.3 1.0 0.7 1.0 4.7 16.6 17.9
reduced cis-2-butene 28.3 1.9 0.6 2.0 28.3 1.5 0.7 3.7 33.1
Moo3/ trans-2-butene 26.6 1.7 0.7 3.1 38.9 2.3 0.5 2.9 23.3
y-Al2O3 l-butene 59.5 7.1 2.4 2.4 9.5 2.4 2.4 4.8 11.9
Foomote:
a) From J. Goldwasser, et al., J . Catal., 70. 275 (1981), copyright Academic Press.
reaction is poisoned by H20 and pyridine, and partially by NH3 [17].
Isomerization v i a Carbenium Ion Intermediate
In this mechanism, a proton is added to one carbon of the double bond of an
alkene as in abstractive adsorption to forman adsorbed carbenium ion. Loss of a
different proton from the same carbon may result in cis-trans isomerization, and
loss of a proton from adjacent carbon may result in double bond migration.
Reaction (9-8) illustrates this mechanism:
+
-
R1 CH=CH-CH2R2
I
*
+H
Since a proton needs to be supplied by the catalyst, the catalyst must
possess BrQnsted acid sites (see Chapter 5 for a discussion of acid sites).
Practically all acidic catalysts that possess BrQnsted acid sites can catalyze
isomerization by this mechanism.
METATHESIS AND ISOMERIZATION 143
According to the mechanism, if the reactant is a perdeuterated alkene, one
deuterium atom in the molecule is equilibrated with the surface proton pool each
time it undergoes isomerization. Multiple exchange is also possible if the
molecule undergoes more than one reaction cycle before desorption. This would
result in a broad isotopic distribution i n the product. This is illustrated in Table
9-2 by the products from a fully oxidized MoO3/AI2O3 catalyst and by 2-butene
from the reduced molybdena catalyst. The formation of a product alkene-d,
requires at least one reaction cycle, alkene-d2 at least two reaction cycles, and so
on. Thus the larger is the difference between the deuterium content of the reactant
and the product, the larger is the number of reaction cycles the molecule has
undergone. In support of the fact that these product distributions are results of a
cationic intermediate mechanism, 1 -butene yields only cis- and trans-2-butene as
products on the fully oxidized Mo03/A1203 with a cis/trans ratio of 1.9 which is
characteristic of such a mechanism.
The isomerization of 1-butene to 2-butenes on TiOz-supported W03 has been
shown to proceed via a carbenium ion intermediate. The reaction rate parallels the
density of acid sites as determined by titration with indicators. The cis/trans ratio
of the product 2-butene is 1.7 [6], which is a typical value for this mechanism.
The isomerization of cyclopropane to propene also shows a qualitative correlation
with the acidity among various supported W03. Thus W03/Si02 and W03/Mg0
which have low acidity are inactive.
Since an acid site is required, its removal should render the catalyst inactive.
Indecd, molybdena catalysts are poisoned by H20, NH3 and pyridine which
interact strongly with the acid sites, while NO, CO, or CO2 are not poisons [17].
Reduction of the molybdena catalyst reduces the activity for isomerization by this
mechanism, in agreement with the decrease i n the amount of pyridine adsorbed
(that is, acidity) [l l ]. On the other hand, preadsorbed hydrogen on a reduced
catalyst enhances the activity two to five times. For comparison, the metathesis
activity is not affected by the presence of preadsorbed hydrogen [20], but is
poisoned by CO [21.
Preadsorbed hydrogen also greatly enhances the isomerization activity of
Co304. If preadsorbcd deuterium is used, it is incorporated into the isomer product
to form a dl species. However, its incorporation is inefficient, and the
preadsorbed deuterium is preferentially released back to the surface after
isomerization. Exactly how this is accomplished is not clear. The enhanced
activity cannot be maintained as the preadsorbed hydrogen is consumed to
hydrogenate the alkene [21,22].
Isomerization via Carbanion Intermediate
Double bond migration can also be achieved by first abstraction of an allylic
hydrogen from the alkene molecule to form a x-ally1 species. Addition of
hydrogen back to the molecule but at the opposite end of the allylic bond results in
isomerization. This process is shown in reaction (9-9) in which the lost hydrogen
is shown as a proton:
144
The heterolytic dissociative adsorption of alkenes has been described in Chapter 4.
In this step, the catalyst provides a basic coordinatively unsaturated surface lattice
oxygen ion to accept the proton from the molecule. The x-ally1 anion is bonded to
a surface coordinatively unsaturated cation. This mechanism has been shown to
be operative on ZnO and Cr2O3 pretreated by evacuation where the cis-2-
butene/trans-2-butene ratio from 1-butene is 10, and 2 to 50, respectively [18].
The interaction of alkenes with ZnO has been studied in detail (see Chapter
4). Infrared spectroscopy shows that propene is adsorbed both as a x-complex
with a C==C stretching band at 1620 cm-' and as a x-ally1 species with a C 4 4
antisymmetric stretching band at 1545 cm-' [23]. The assignment of the bands
has been confirmed using various isotopically labeled propene molecules. The
formation of x-ally1 is accompanied by the formation of surface OH groups.
These adsorbed species can be removed readily by evacuation. The idea of x-
ally1 intermediates based on propene adsorption data has been used to interpret
data in the reactions of butenes, although some of the adsorbed butenes cannot be
removed by evacuation, and behave kinetically differently from the isomerization
reaction [ 181.
It is interesting to note that reaction (9-9) may proceed either by
intramolecular or intermolecular H-transfer. The relative contributions of these
two pathways have been evaluated on Cr2O3 [24]. Using CD2=CH-CH3 and
CD2=C(CH3)2 as reactants, intramolecular H-transfer would yield
CD2H<H=CH2 and CD2H-C(CH3)=CH2, respectively, as the only initial
products, whereas intermolecular H-transfer would yield propene-dl and d3 and
isobutene-dl and d3 products. It is found that the ratio of intrdintermolecular H-
transfer is 1.4 for amorphous Cr2O3 and 3.9 for crystalline Cr2O3 for propene.
Both inter- and intramolecular H-transfer take place on ZnO also [25]. I t has been
further suggested that the intermolecular pathway proceeds via the x-complex and
not the x-ally1 intermediate.
REFERENCES
1. R. L. Banks, and G. C. Bailey, Ind. Eng. Chem. Prod. Res. Develop., 3, 170 (1964).
2. G. C. Bailey, Cafal. Rev., 3, 37 (1969).
3. J . C. Mol, and J . A. Moulijn. Adv. Catal.. 24. 131 (1975).
4. J . C. Mol, J . A. Molijn. and C. Boelhouwer, Chem. Commun., 663 (1968).
5 . J . C. Mol, F. R. Visser, and C. Boelhouwer, J . Cafal.. 17. 114 (1970).
METATHESIS AND ISOMERIZATION 145
6. K. Tanaka, K.-i Tanaka, and K. Miyahara, J. Chem. Soc. Chem. Commun.,
7. D. J . Cardin. M. J . Doyle. and M. F. Lappea J . Chem. Soc. Chem. Commun.,
8. R. H. Grubbs, and C. R. Hoppin, J . Amer. Chem. Soc., 101, 1499 (1979).
9. M. Lo J acono, and W. K. Hall, J . Colloid Interfnce Sci., 58, 76 (1977).
10. T. Yamaguchi, Y. Tanaka. and K. Tanabe. J. Catal., 65, 442 (1980).
11. J . Engelhardt. J . Goldwasser, and W. K. Hall, J . Catal., 70, 364 (1981).
12. J . McGinnis, T. J . Katz. and S . Hurwitz, J. Amer. Chem. Soc., 98, 605 (1976).
13. C. P. Casey, and H. E. Tuinstra, J . Amer. Chem. Soc.. 100, 2270 (1978).
14. K. Tanaka, K. Miyahara. and K.-i Tanaka, Proc. 7th Intern. Cong. Catal.,
15. A. A. Olsthoorn, and C. Boelhouwer. J. Catal., 44, 207 (1976).
16. E. S. Davis, D. A. Whan, and C. Kambell, J . Chem. Soc. Chem. Commun.,
17. E. A. Lombardo, M. Lo J acono, and W. K. Hall, J . Catal.. 64. 150 (1980).
18. C. C. Chang, W. C. Connor. and R. 1. Kokes, J . Phys. Chem.. 77. 1957 (1973).
19. J . Goldwasser. J . Engelhardt. and W. K. Hall, J . Catal., 70, 275 (1981).
20. J . Engelhardt, and D. Kallo, J . Caul., 71, 209 (1981).
21. T. Fukushima, and A. Ozaki, J. Catal., 32, 376 (1974).
22. T. Fukushima, and A. Ozaki, J. Catal., 41, 82 (1976).
23. A. L. Dent, and R. J . Kokes, J . Amer. Chem. Soc., 92, 6709 (1970).
24. G. L. Haller, and C. S . J ohn, Proc. 7th Intern. Cong. Catal.. Tokyo, J apan,
25. A. L. Dent, and R. J . Kokes, J . Amer. Chem. Soc.. 92, 6718 (1970).
26. N. E. Cross, and H. F. Leach, J. Catal., 21, 239 (1971).
27. R. L. Burwell, Jr., G. L. Haller, K. C. Taylor, and J. F. Read, Adv. Catal.,
314 (1979).
927 (1972).
Tokyo, J apan, 1980, paper B47.
1202 (1971).
1980, paper B20.
29, 1 (1969).
Chapter 10
DECOMPOSITION, HYDROGENATION AND
RELATED REACTIONS
10.1 DECOMPOSITION OF ALCOHOLS
There are three common reactions of alcohols on transition metal oxides:
catalytic dehydration to the corresponding alkenes, catalytic dehydrogenation to
ketones or aldehydes, and oxidation to carboxylates or carbon oxides with
reduction of the oxide. In some cases, formation of hydrocarbon by coupling and
bimolecular dehydrogenation is the major catalytic reaction.
Dehydrogenation may be carried out both oxidatively in the presence of
oxygen or other oxidants, and nonoxidatively. In the nonoxidative route,
hydrogen is the other product. In the oxidative route, water is the byproduct.
Examples of the oxidative route include the highly selective oxidative
dehydrogenation of methanol to formaldehyde (see chapter 12) and ethanol to
acetaldehyde [l] on molybdate catalysts. Ordinarily, an oxidant is needed to
prevent reduction of the oxides. In this chapter, the nonoxidative route is
discussed.
Methanol
and dissociatively to form a surface methoxide:
It was discussed in Chapter 4 that methanol is initially adsorbed heterolytically
CH3O H
I I
CH30H + M a + M -- 0 (10-1)
Adsorbed methoxide has been shown to result from adsorption of methanol
on ZnO at room temperature by use of infrared spectroscopy [2,31 and XPS (41.
Molecularly adsorbed methanol may also be present. On heating, the undisso-
ciated methanol and possibly some methoxide are desorbed as unreacted methanol,
146
DECOMPOSITION AND HYDROGENATION 147
the latter via the reverse of reaction (10-1). The remaining methoxide reacts via
two pathways:
In the lower temperature catalytic pathway (10-2), adsorbed methoxide reacts to
form formaldehyde, CO and H2. In the higher temperature pathway (10-3), it is
oxidized by the zinc cation to an adsorbed formate which is decomposed to CO,
C02, H2 and H20 [4-61. In this pathway, the ZnO surface is reduced which results
in the evolution of Zn atoms into the gas phase at a temperature lower than the
ordinary sublimation temperature of ZnO [7]. These two pathways are readily
observed in a temperature programmed decomposition experiment (Figure 10- 1).
These two pathways are also observed under (quasi-)steady state conditions.
Methanol is decomposed on ZnO into H2 and HCHO in the temeprature range 453-
513 K, and into HCHO, CO, C02, and H2 over 563-613 K [8]. Reduction of ZnO
during the reaction is detected, and the formation of a "metallic silver mirror'' on
the reactor used for methanol decomposition has been mentioned.
In this reaction, formaldehyde is formed by C-H bond dissociation in the
adsorbed methoxide. Indeed, when CH3180H is used, only HCH180 and Cl 80
are detected in the lower temperature pathway [7]. On the other hand, the
formation of an adsorbed formate in the higher temperature pathway results in
scrambling between the oxygen atom in methanol with those in the surface, and a
mixture of C1602, Cl60l8O, Cl 60 and Cl 80 is observed [7,8]. Since C02 is not
formed by the reaction of CO with the surface, it must be a primary product in
methanol decomposition [8]. The formate is formed above 400 K and can be
detected by IR [2] and X P S [4], but it decomposes at a much higher temperature
[4,6]. C-H bond breaking is involved in the overall kinetics of methanol
decomposition. I t has been observed that there is no H/D kinetic isotope effect for
CH30H and CH30D, but there is a normal kinetic isotope effect for CH30D and
CD30D [8]. Finally, it has been observed in temperature programmed
decomposition studies that this surface formate, whcther it is formed by the
oxidation of methanol or formaldehyde, or by the dissociative adsorption of
formic acid, decomposes at the same temperature [4,6].
The fraction of adsorbed methanol on ZnO that is adsorbed weakly depends
on the extent of surface dehydroxylation [9]: it increases with increasing hydroxyl
contcnt of the surface. The density of strongly adsorbed methanol increases
proportionally with decreasing hydroxyl content, and reaches a limiting value of
four molecules per nm2 on a totally dehydroxylated surface. The fraction of
strongly adsorbed spccics that reacts by dehydrogenation versus that which reacts
by the oxidation pathway dcpends on the condition of the surface. A more
148
a
Z
8
0 100 200 300 400 500
TEMP C
Figure 10-1 TPD spectrum of CH30H decomposition on a Zn-polar surface. (From J.
Phys. Chem., 90, 3184 (1986), copyright American Chemical Society).
reduced surface favors dehydrogenation [6].
The activity of the ZnO surface towards decomposition of methanol under
ultra-high vacuum conditions depends on the surface crystallographic orientation
Temperature programmed decomposition studies show that the Zn-polar surface is
the most active. The prismatic surfaces containing step defects or anion vacancies
are also active, but the 0-polar surface is very inactive [4,6,10,11]. It has now
bcen demonstrated that the catalytic activities of the Zn-polar surface for methanol
decomposition at low (mtorr) and near atmospheric pressure are also much higher
than the other ZnO surfaces [98,99].
The methanol decomposition pathways are somewhat different on other
oxides. On NiO, CO, H2 and H20 are the only products detected [12]. On a
highly dehydroxylated anatase TiOz surface, adsorbed methanol decomposes in
TPD studies to form dimethyl ether, ethane and methane as the major products at
high methoxide coverages, and mostly dimethyl ether and ethane at low coverages
[13]. Dimethyl ether is formed by bimolecular dehydration, which is proposed to
occur between methoxy groups on adjacent Ti cations:
YcH3 YCH3 + p, + H3COCH3
T i T i Ti Ti
(1 0-4)
Ethane is proposed to be formed from two Ti-CH3 species the presence of which is
detected by IR. Methane is formed fromisolated Ti-CH3 species. If a Ti02
DECOMPOSITION AND HYDROGENATION 149
surface is first covered with methoxy species, exposure to ethene yields propene, 1-
butene and t-2-butene, while exposure to ethanol yields propene, c-2-butene.
methyl ethyl ether, and C5 oligomer. The appearance of these products is
consistent with the presence of Ti XH3 groups on the surface. In this aspect, the
surface of Ti02 is similar to a Ziegler-Natta oligomerization catalyst. It is
possible that the dissociative adsorption of methanol to form Ti XH3 and OH(ad)
occurs on an oxygen vacancy and a surrounding reduced Ti ion. It should be
mentioned that methane has been reported as a minor product of reaction of
methanol on ZnO [6] and Cr2O3 [14], suggesting the possible presence of surface
methyl species.
Oxidation of surface methoxide to formate is also found on chromium oxide
[14]. Decomposition of formate then yields CO, COz, and HZ. Methane and
dimethyl ether are the other products.
Catalytic decomposition of methanol on CuO and Cu20 yields C02, H20 and
H2 as initial products and methyl formate at a later stage. Methyl formate, CO,
and H2 are also products on CuCr204, but in this case, reduction of the oxide to
metallic copper dispersed on Cr2O3 occurs [15].
2 -Propano1
The decomposition of 2-propanol is another well-studied reaction. The two
most common reaction pathways are dehydrogenation (10-5) and dehydration (10-
6):
CH3CHOHCH3 CH3COCH3 + H2 (10-5)
(10-6)
+H+
CH3CHOHCH3 ------) [CH3,HCH3]+
OH2
Sincc dehydrogenation is the preferred pathway on basic oxides, while dehydration
is preferred on acidic (BrQnsted) oxides [16], this reaction has been used as a probe
for the acidicbasic properties of an oxide [17]. Indeed, the predominant reaction
is dehydrogenation to acetone on oxides such as CaO and MgO, and dehydration to
propene on oxides such as A1203 and V205. However, the situation is less definite
on transition metal oxides. It has been shown that dehydrogenation is
predominant on Cr2O3, Mn02, FezO3, C0304. NiO, CuO. and ZnO some of which
are considered acidic (see Chapter 5). Furthermore, anatase and rutile Ti02 give
different selectivities: dehydrogenation is predominant on rutile, and dehydration
on anatase [611.
The detailed mechanism of the reaction on ZnO has been studied. Infrared
spectroscopy shows that 2-propanol is adsorbed heterolytically as 2-propoxide
with the simultaneous formation of surface hydroxyl groups [18]. At 363 K,
transformation of the surface alkoxide to an adsorbed acetone occurs. Further-
more, a surface enolate species is detected suggesting a rapid interconversion
between acetone and enolate:
CH 3
(10-7)
The dehydrogenation to acetone is the predominant reaction under catalytic
conditions, accounting for 90% of the products.
The interconversion of acetone and enolate on ZnO has been independently
confirmed with adsorbed acetone [l8,19]. It has also been observed on NiO
[20,21]. This process has also been confirmed with deuterium-labeling studies.
When a mixture of 2-propanol-& and dg is decomposed on ZnO, H/D mixing does
not occur in 2-propanol, but it occurs in the product acetone [19].
At 160°C, the normal H/D isotope effect at the secondary C-H bond suggests
that the breaking of this secondary C-H bond is rate limiting in 2-propanol
decomposition. In contrast, deuteration of the methyl groups does not affect the
reaction rate [19]. Use of a mixture of C3H70D and C3D70D with monitoring the
evolution of D2, HD, and H2 has shown that the product H2 is formed exclusively
from the a-C-H and &H of 2-propanol [22].
The dehydrogenation of 2-propanol to acetone on ZnO is a totally reversible
reaction, and acetone is readily hydrogenated to 2-propanol.
At low pressures, dehydrogenation is first order in 2-propanol, and becomes
zeroth order at higher pressures (2 P a and above) [22,23]. At low pressures, the
reaction rate depends on the orientation of the exposed surface plane. At about
2OO0C, the rate of reaction is much faster on the Zn-polar surface than the 0-polar
surface (Fig. 10-2) [23,24]. Interestingly, the activation energy is higher on the
Zn-polar than the 0-polar surface. The reaction has also been studied on a stepped
prismatic surface. The rate is higher if the alcohol molecules impinge on the
surface in the direction up the step than down the step. At a higher pressure of
alcohol and using powder samples. a different conclusion has been made that the
reaction rate is proportional to the number of surface coordinatively unsaturated Zn
ions independent of the crystallographic plane [25]. At the moment, the reasons
for the differences between the low-pressure single-crystal study and the higher-
pressure powder study are not understood. It is possible that a reaction that is
structure sensitive at low pressure, i.e., low surface coverage, may become
structure insensitive at high coverage, i.e., high surface coverage [26].
The high selectivity for dehydrogenation observed under catalytic conditions
on ZnO is not observed in temperature programmed decomposition studies [27-291
where a selectivity as low as 60% dehydrogenation has been observed. It is
further found that the ratio of dehydrogenation to dehydration depends on the
pretreatment of the ZnO sample.
A Zr(OH),
The selectivity for this reaction depends on the oxide used.
DECOMPOSITION AND HYDROGENATION 151
M
I
0
7
v; 3. 55
I
W
+J
v1
\
W
.-
2. 84
U
W
0
E
d
c 2. 13
0
c,
u
u
0
.4
a
1. 42
W
c
0
c,
W
U
0.71
L
0
Q-
L L
2
I
/ d
100 1 80 260 340
Temper at ur e C
Figure 10-2 Rate of reaction measured as turnover frequency for acetone production as a
function of temperature for the Zn-polar ( 1) and the 0-polar surfaces (2) of ZnO.
sample treated with H2Te04 is 100% selective for acetone production [30]. On
the other hand, TiOz [31,341 and Se-treated Ti02 [30] samples are quite selective
for dchydration. The activation energy of the reaction depends on the promoters.
For example, on an alkali-promoted VzOs catalyst, the activation energy varies
from 1.6 to 38 kcal/molc depending on the alkali ion used [32]. The interaction of
the hydroxyl group of the alcohol with the alkali ion was used to explain this
obscrvation. In other instances, the band theory of oxides [I61 or the geometric
rcquircmcnt of surface atoms [331 have been invoked to explain similar
obscrvations.
Rcccntly, it has been reported that on the Cu-CuO system, dchydrogcnation
of 2-propanol docs not take place on Cu metal, Cu20, or CuO. However, the
activity on a prcrcduced Cu20 or prcoxidizcd Cu is very high. It is also high for a
physical mixture of Cu and CuO. The results suggest that there is a synergistic
cffcct bctween oxidized and metallic Cu that lcads to high activity [42], but Lhc
exact cause has yet to be found.
152
Other Alcohols
The decomposition of other alcohols has been less extensively studied. The
patterns of their reactions are similar to 2-propanol. On anatase Ti02, dehydration
of ethanol to ethene and 2-methyl-2-propanol (tert-butyl alcohol) to 2-
methylpropene (isobutene) are the major reactions r31.351. In the reaction of
ethanol, small amounts of ether and butenes are detected, which indicate
bimolecular dehydration and oligomerization of ethene. The latter is due to the
formation of Ti-C2H5 species [13]. Infrared spectroscopy detects the presence of
surface alkoxides.
Dehydration of ethanol to ethene is also the major reaction on Cr2O3 [36] and
Mo03/Si02 [37]. Small amounts of C€&, C2H6 and C3€& are also produced on
Mo03/Si02. This may be due to the formation of Mwalkyl or Mmarbene species
after some of the surface Moo3 is reduced by the reaction with the alcohol. On
niobia, the products from ethanol decomposition at 400-550 K range from 50%
diethyl ether and 50% ethene on Nb.L05/Si02 prepared by impregnation, to 50%
ether and acetaldehyde and 50% ethene on unsupported Nb2O5, to over 99% ethene
on a thin layer of niobia on Si02 [43].
The decomposition of various alcohols has also been studied on ZnO using
temperature programmed decomposition technique. As mentioned earlier, for
reasons not yet fully understood, the dehydration pathway is more prominent using
this technique than under catalytic conditions. It has been observed that 90% of
ethanol is decomposed to ethene, about 3040% of 1-propanol, 2-propanol, and 1-
butanol to the corresponding alkenes, and 17% of 2-bum01 to butenes [38]. The
remaining products are the corresponding aldehydes and ketones. A high
selectivity for dehydration of ethanol has also been observed on ZnO single crystal
surfaces [39]. In contrast, catalytic decomposition of ethanol on ZnO powder is
predominantly dehydrogenation to acetaldehyde [401.
I n the temperature programmed decomposition studies, the dehydrogenation
products (aldehydes and ketones) are evolved about 10-15°C lower than the
dehydration products (alkenes). This indicates higher activity for dehydro-
genation on ZnO, which may account for the much higher selectivity for
dehydrogenation under catalytic conditions. It is also observed that branched
alcohols decompose about 50°C lower than straight chain alcohols. I f this implies
that the adsorbed species from a branched alcohol is less stable, it would indicate
that the transition state in the dehydrogenation reaction of surface alkoxides on
ZnO might have a carbenium ion character [39].
2-butanol decomposition has been studied on mixed iron oxides. The
selectivity depends on the oxide components. Dehydrogenation to methyl ethyl
ketone is the only reaction observed on FQO~. It is also the predominant reaction on
Fe203-Zn0. However, dehydration to butenes is the predominant reaction on
Fe203-Ti02, while both reactions proceed about equally on F+03-Zr02.
Reduction of these catalysts results in a much enhanced production of butane,
presumably formed by nucleophilic substitution of OH- i n butanol by H- that is
lcft on the surface from the dchydrogenation of butanol [411.
DECOMPOSITION AND HYDROGENATION 153
10.2 DECOMPOSITION OF NITROUS OXIDE
The decomposition of nitrous oxide produces only nitrogen and oxygen:
2N20 --+ 2N2 + 0 2 (10-8)
Because of its apparent simplicity, this reaction has been used as a probe for the
properties of solids. However, an unequivocal correlation between reaction
kinetics and properties of the catalyst depends on a firm establishment of the
reaction mechanism for which more than one has been proposed over the years.
One of the most popular mechanism is as follows [16,44]:
N20(g) + V,- N20-(ad) (10-9)
N20-(ad) - N2(g) + 0-(ad) (1 0- 10)
2 0-(ad) --+02(g) + 2 V,- (10-11)
In this mechanism, nitrous oxide is first adsorbed on a surface anion vacancy V,-
with a trapped electron. This step involves electron transfer from the solid to the
adsorbate. The adsorbed N20- decomposes quite readily to gaseous N2, leaving
an adsorbed 0- on the surface. Recombination of 0- to form gaseous oxygen and
two anion vacancies completes the cycle.
There is experimental evidence to support this mechanism. Stoichiomeuic
decomposition of N20 to N2(g) and adsorbed oxygen can be accomplished at a
temperature lower than the catalytic decom osition temperature [45,46]. The
species 0- has been detected by EPR on Md or V205 supported on SO2 [47,48]
and UV-irradiated Ti02 [49] and ZnO [50] upon decomposition of N20. This
evidence further suggests that the recombination of adsorbed oxygen is the slow
step in the reaction. Indeed, the rate expression for a large number of oxides,
including NiO, ZnO, Fe2O3, Cr203, Ti02, CuO, Rh2O3, Mn02, Ir02, and many
nontransition metal oxides has the general form [44,51]:
P
(10-12)
which can be derived from the reaction sequence assuming that the step of
N20-(ad) decomposition is irreversible, but the adsorption of N20 and desorption
of oxygen are reversible. This expression implies that the reaction is inhibited by
gaseous oxygen as is observed.
This reaction mechanism suggests electron transfer between the adsorbates
and the solid. Electron transfer is involved in the formation of 0-(ad) which has
been mentioned above. For semiconducting oxides, electron transfer affects the
electrical conductivity. I t has bun observed that the electrical conductivity of
ZnO changes when subjected to the reaction condition, which supports the presence
154
of electron transfer [62]. Changes in electrical conductivity during oxygen
chemisorption are also well known. In these cases, the conductivities are strong
functions of the oxygen partial pressures which may reflect changes in the
concentration of anion vacancies.
The involvement of electron transfer in the reaction mechanism suggests
possible correlations between the semiconducting properties of oxides and their
activities in this reaction. Indeed, the most active oxides which include Cu20,
COO, Mn2O3, and NiO are all p-type semiconductors, the least active oxides which
include ZnO, CdO, Ti02, Fe2O3, and Cr2O3 are n-type semiconductors, and the
oxides that are intermediate in activity which include CuO, MgO, CaO, and Ce02
are insulators [63]. Essentially the same classification is obtained if activation
energy is used as the criterion instead of activity [HI: the p-type semiconducting
oxides have the lowest activation energy, and the n-type semiconducting oxides
have the highest activation energy. A linear correlation between the activation
energy and the electrical conductivity has been reported [ 55] .
The higher activity of p-type semiconducting oxides is explained by the fact
that oxygen recombination and desorption is a slow step. Since electron is
transferred into the solid in this step, its rate is enhanced by the availability of holes
in the solid. Thus p-type semiconductors are more efficient than n-type
semiconductors or insulators. Alternatively, the different positions of the Fermi
levels in the two types of semiconductors may be the reason for the different rates
of electron transfer in this step [65].
Since the oxygen desorption step is slow, there have been attempts to
correlate the kinetic parameters of this reaction with those of isotope exchange
between gaseous oxygen and the oxide surface. There appears to be a strong
correlation in the preexponential factor and the activation energy for these two
processes (Fig. 10-3 and 10-4) [441.
The apparent success in correlating semiconducting and catalytic properties of
oxides has led to attempts to study the effect of dopants on the reaction. Studies
using doped NiO [MI, doped ZnO [51], and doped Fe203 [52]. have been
conducted, yet they were not always successful. Some complications encountcred
in these studies include the fact that the activation energy is found to depend on thc
outgassing temperature of the oxide, the oxide is oxidized during reaction [531, and
a new compound is formed between the dopant and the oxide [52,541. It has also
been reported that the activation energy depends on the crystallite size of the oxide.
On iron oxide, the value for very small crystallites is lower than for large
crystallites [56].
Recently an alternate mechanism involving reduction and oxidation of the
oxidc has been proposed on iron-exchanged zeolites [57]:
N20 + O’-(S) N2 + 0 2 + VS-- + C(S) (10- 13)
NzO + V,- + e-(s) --+N2 + O’-(s)
(10- 14)
0 2 +2 v,- +2 c-(s) --+2 02-(s) (10-15)
DECOMPOSITION AND HYDROGENATION 155
68
84
68
-
84 -
0
1 1
84 126 168 kJ/mol e
1 1
84 126 168 kJ/mol e
Act i vat i on Energy for N 0 Decomp.
2
Figure 10-3 Correlation between the activation energies for NzO decomposition and those
for the oxygen-exchange reaction on various oxides. (From J. Catal.. 19. 32 (1970),
copyright Academic Press).
In this mechanism, the evolution of oxygen is a result of reaction (10-13) in which
N20 reacts with a surface lattice oxide ion to yield N2, 0 2 and an anion vacancy.
The anion vacancy is filled and the oxide is reoxidized either by N20 (eq. 10-14) or
by gaseous oxygen if present. This mechanism is supported by the following
observation. When N2I60 is decomposed over a Fe-exchanged Y-zeolite loaded
with l 8 0 , the gaseious O2 is composed of 80% 1602 and 20% 180160 [%I. The
substantial amount of l8O in the gaseous oxygen product suggests the involvement
of lattice oxygen and the redox mechanism. Interestingly, when the same reaction
is run over Fe-exchanged zeolite M (mordenite), no l8O is detected in the product.
Thus either the number of active sites is very small on this catalyst or the redox
mechanism is not operative.
10.3
AND H2-Dz SCRAMBLING
HYDROGENATION, H-D EXCHANGE OF HYDROCARBONS,
Transition metal oxides are generally not very active catalysts for
In fact, except for reduced oxides of chromium, vanadium, hydrogenation.
156
MgO Gab / 0 Ca
- ; / ; s ; Hf ' OZ"
Th
0
Sr
1 I
2.0 5.0
'O%o A1
Figure 10-4 Correlation between the preexponential factor of the rate constants for the N20
decomposition Al and the oxygen-exchange reaction AB. (From the same reference as
Figure 10-3).
copper, and molybdenum, cobalt oxide, zinc oxide and a few others, other oxides
can be considered inactive for hydrogenation when compared with the noble
metals. The relatively low activity even among the more active oxides has been
advantageously used for selective hydrogenation. For example, copper chromite
is used in the selective hydrogenation of nitrobenzene to aniline in which the
functional group but not the benzene ring is hydrogenated [59].
Attempts have been made to explain the activity pattern of transition metal
oxides. When examining the activities of oxides of the first transidon period for
ethene hydrogenation. it is found that the highly active Cr203 and Co304 are
separated by the inactive MnO and the nearly inactive Fez03 [60]. (For example,
what is in effect a layer of MnO on Si02 will remove O2 from a mixture of H2 and
propene without forming any ropane.) This pattern is shown in Fig. 10-5. It is
explained by the fact that Mn2' and Fe3+are in the very stable 3d5 configuration.
It is difficult to excite a 3d5 ion into a state that would bind an adsorbate strongly.
It should be noted that an active oxide must have surface coordinatively
unsaturated ions to adsorb an alkene molecule, dissociatively adsorb hydrogen
molecule, and bind the surface alkyl relatively strongly. An inactive oxide may
fail because it does not meet one or more of these requirements.
The dependence of hydrogenation activity on the position of the oxide in the
DECOMPOSITION AND HYDROGENATION
60
30
157
-
-
n
0
N
Ni O
Ti02 Cr203 Fe203
" 2 ' 3 MnO Co304 ZnO
Figure 10-5 Activity pattern in the hydrogenation of ethene. Figures in parentheses denote
reaction temperatures. (From J. Catal., 7, 359 (1967). copyright Academic Press).
Periodic Table as shown in Fig. 10-5 has also been observed in the H2-D2
scrambling [67], dehydrogenation of propane [68], disproportionation of
cyclohexene [68], and isomerization of butene [69]. While the correlations and
the explanation based on crystal field theory are appealing, the data are for only a
limited number of oxides, and the effect of preparations and pretreatments of the
oxides have not been taken into account [69]. An oxide may show very different
catalytic activity for different degrees of surface hydroxylation, extents of surface
reduction, or calcination temperatures, among many variables.
Instead of comparing under one set of conditions, comparison can also be
made of the maximum activity of each oxide [69]. It is found that (i) for a given
element, the activity of a lower oxide is higher than a higher oxide; (ii) the activity
of oxides at their highest common oxidation state increases from right to left within
each period; (iii) all trends observed for hydrogenation apply to double-bond
migration, exchange of hydrocarbons with deuterium, and H2-D2 scrambling.
Unfortunately these conclusions are based on a limited number of oxides, and they
should be tested with more data when available.
The mechanism of hydrogenation is believed to be stepwise addition of H
atoms to an adsorbed alkene, first to forma surface alkyl species and then an
158
alkane. The sequence is similar to that found on metals. The reversibility of the
individual step depends on the oxide, and can be probed by following the
incorporation of deuterium atoms in the hydrocarbon molecule upon deuteration.
The most detailed investigation of the hydrogenation mechanism has been
conducted on ZnO and CrzO3. For ethene hydrogenation on ZnO, the adsorption
and the kinetic data, and the deuterium distribution in ethane lead to the mechanism
[ 701 :
H2C=CH 2 I Y zHS
I + *
C2H4 +Zn-O __L Zn-0 - Zn-0 (10-16)
H
I
+ Zn-O + C2&
+ *
-
The adsorption of ethene as a x-complex is confirmed by IR spectroscopy. This
step is reversible and the adsorbed ethene can be removed readily by evacuation.
Hydrogen is adsorbed dissociatively and heterolytically to form Zn-H+ and &H-.
Addition of H to an adsorbed ethene forms a surface a-alkyl. Addition of the
second H completes the hydrogenation. These two steps are irreversible because
if ethene is deuterated with D2, the product contains 99.9% ethane-d2 [71].
Reversibility of the addition of the first H would lead to deuterium incorporation in
the reactant ethene, and reversibility of the addition of the second H would lead to a
broad distribution of deuterium content in ethane, neither of which is observed.
This mechanism applies to well dehydroxylated Cr203 [71,72] and Co304 1731.
Conclusions concerning the mechanism of ethene hydrogenation are
substantiated by results of hydrogenation using H2 and D2mixtures. On both ZnO
and Cr203, the product ethane consists of mostly 4 and d2 species. Small
amounts of ethane-dl can be attributed to the simultaneous H2-D2 scrambling
reaction that produces HD in the gas phase [71]. On Co304, the production of HD
is substantial. Thus the ethane product shows a broad distribuiton of 4, d, , and d2
species which parallels the relative concentrations of H2. HD, and D2 in the gas
phase [73].
It is interesting to note that although C2H4 does not exchange with D2 on
Co304, intermolecular H-D exchange between C2H4 and C2D4 occurs rapidly. In
a mixture of C2H4, C2D4, and H2, ethylene is rapidly randomized to yield a broad
distribution of 4. dl, d2, d3, and 4 species. Thus, this intermolecular exchange
process is more rapid than hydrogenation [73].
This mechanism and the similarity between ZnO and Cr2O3 do not extend to
propene. When propene is deuterated on ZnO, deuterium is incorporated into the
reactant propene, and the product propane shows a wide distribution in the
deuterium content as shown in Table 10-1 [74]. The data can be explained by the
reversible formation of x-ally1 upon dissociative adsorption of propene (eq. 10- 17).
If the surface x-ally1 forms propene by picking up a surface deuterium atom instead
of a hydrogen atom, deuterium is incorporated into propene. The broad
DECOMPOSITION AND HYDROGENATION 159
Table 10-1 Deuterium Distribution in Propene Hydrogenation
ZnO, C3& +D2 at 25°C (ref. a)
propene 84.4 14.1 1.6 0 0
propane 12.2 20.9 55.6 11.3 0
Cr2O3, C3& +D2 at -11°C (ref. b)
propane <4% 94 1.5 0.1
References:
a) A. L. Dent, and R. J . Kokes, J . her . Chem. SOC., 92, 6718 (1970).
b) A. B. Littlewood, and R. L. Burwell. Jr., J . h e r . Chem. SOC.,
82, 6287 (1960).
distribution of deuterium in propane may be due to the rapid reversibility of this
step and/or subsequent steps of the formation of surface alkyl.
CH2-CH-CH, H
A
C3& + Z n O d - 1 - - -
Zn
(1 0- 17)
In contrast to ZnO, deuteration of propene on CrzO3 activated at 450°C leads
almost exclusively to propane-d2 [71,72]. Thus the reaction on Cr2O3 probably
proceeds as in eq. (10-16) without the formation of n-allyl.
The situation for the hydrogenation of 1 -butene, 2-pentene, cyclopentene, and
l-hexene on Cr203 is similar to that of propene. In all cases except pentene,
alkane-d2 accounts for 90% or more of the hydrogenated products. For 2-pentene,
the product is 78% pcntane-d2 [72]. The deuterium distribution becomes broader
when the reaction temperature is raised from about 30" to 130°C. but the amount of
alkane-d2 is still higher than that expected from a statistical distribution of
deuterium atoms.
The nearly exclusive production of butane-d2 on Cr2O3 permits the
determination of whether the two hydrogen atoms are added on the same or
opposite sides of the carbon-carbon double bond. I t is found that using D2 and cis-
2-butene, meso-2-3-dideuterobutane appears as nearly the only product as shown in
eq. (10-18) [75]. Thus D2 is added cis to the double bond.
160
From IR spectroscopy, it has been shown that on ZnO. reversibly adsorbed
hydrogen participates in hydrogenation [771. If HD is used as a reactant, it is
adsorbed primarily in form I at room temperature and in form 11below -40°C.
H D
I I
Zn 0
D H
I 1
Zn 0
I 11
When the selective hydrogenation of buta-1,3-diene to l-butene is carried out at
these two temperatures, the same distribution of 75% [3-Dl]but-l-ene and 25% [4-
Dl]but-l-ene is obtained in spite of the different forms of adsorbed HD [78]. I t is
not known whether this is a result of the different reactivity of Zn-H versus O-H
and Zn-D versus O-D that happens to compensate each other, or the fact that the
catalytically active sites do not distinguish the two forms, or that butadiene is
adsorbed in different forms at the two temperatures.
The fact that the deuterium distribution in the alkane product follows closely
the D2, HD, and H2 distribution in the gas phase for those oxides that have been
carefully studied suggests that either the mobility of adsorbed H (and D) species is
very low or the density of active sites is very low. Few quantitative
determinations of the density of active sites have been reported. The density is
known to depend on the degree of dehydroxylation. A chromia gel activated
below 200°C is inactive. Activity is obtained at highcr temperature of activation,
and the chromia is very active after 450-500°C activation in an inert atmosphere
(see Fig. 4-3b) [72,76]. The deuterium distribution in alkane depends on the
activation condition. The amount of alkane-d2 increases with increasing
temperature of activation, while the spread of distribution decreases. For
example, CrzO3 activated at 215°C yields only 26% hexane-d2 in the deuteration of
1 -hexene, while activation at 400°C yields 90% hexane-d2. The broad distribution
resulting from low activation temperatures cannot be explained by rapid
isomerization because the ratio of hydrogenation to isomerization does not change
significantly with activation temperature. It might suggest that surface hydroxyl
groups could exchange with adsorbed deuterium and surface alkyl species readily.
It is most likely that the active sites involve surface coordinatively
unsaturated cations. These active sites can be poisoned by water [70,76,77], 02,
CO [73,76], and, for Co304, by irreversibly adsorbed H2 [73]. Different alkenes
compete for active sites. On C%04, the rate of propene hydrogenation is greatly
reduced by the presence of ethene. On a molybdena catalyst, the active sites are
the reduced Mo(cus) ions. Interestingly, these sites are poisoned by NO and CO,
DECOMPOSITION AND HYDROGENATION 161
but not NH3 or pyridine [91].
Deuterium exchange of alkenes via a x-ally1 intermediate (reaction 10-17) is
known to occur on ZnO. Table 10-1 shows the data that support this. Appar-
ently, the reversible formation of x-ally1 is much more rapid relative to
hydrogenation on ZnO than on CrzO3. Since negligible amounts of hexene-dl are
formed when 1-hexene is passed over chromia with D2 at lower temperatures,
although at 200°C small amounts can be detected [72]. The same applies to a
mixture of D2 and butene [72]. Isotope exchange between D2 and propene has
also been reported on rutile Ti02 [79].
Deuterium exchange of alkanes has been studied extensively on Cr203
[75,76,80]. Chromia gel develops significant activity after activation in N2 or H2
above 300°C to remove higher oxides. The activity is poisoned by exposure to air
(presumably moisture) or 0 2 . The predominant reaction is the exchange of one
hydrogen atom per period of adsorption. Thus the initial products are alkanes-dl .
There is only very minor amounts of multiple exchange the extent of which
increases with increasing temperature. The primary carbon in propane and hexane
exchanges faster than the secondary carbon. Thus 2.2-dimethylpropane
exchanges faster than propane. The faster exchange of primary than secondary
carbon can be explained by the involvement of intermediates with some carbanion
character.
The situation for cyclic alkanes is less clear. At 200°C on chromia, the rate
of exchange per H atom in the molecule follows the order: cyclopropane >>
ethylcyclobutane >cyclooctane 2 hexane >cycloheptane >2.2-dimethylbutane >
cyclohexane = cyclopentane = methane >ethane. The order is somewhat different
at different temperatures because the values of activation energy are different.
Another reaction related to hydrogenation and deuterium exchange is H2-D2
scrambling:
H2 + D2 + 2HD (10-19)
which may occur on a surface with the following mechanism:
H H D D
M O M 0
H2 + D2 + 2M-O + I I I I + 2HD + 2M-0 (10-20)
This mechanism is supported by the detection of Zn-H and &H IR vibrational
bands when H2 is adsorbed on ZnO [771. On other oxides where such an
observation has not been made, such as Cr203, there are suggestions that the
reaction may proceed without total dissociation of H2 and D2 [81].
This reaction is known to occur on many oxides including nontransitional
oxides, in particular MgO. Across the first transition period, the activity of the
oxides shows the two peaks of high activity similar to that shown in Fig. 10-5.
except that Co304 and NiO are more active than Cr203 [67]. Reduced vanadia
and molybdena are also quite active. In contrast, a reduced anatase Ti02 is less
active and the reaction shows a higher activation energy than a reoxidized or an
162
outgassed sample [821.
The H2-D2 scrambling reaction is usually suppressed by the presence of
alkenes. For example, butenes suppress greatly this reaction on reduced M a 3
[83]. ethene suppresses this on Co304 [73], CrzO3 and to a lesser extent ZnO [71].
Thus it is likely that hydrogenation and this reaction take place on the same active
sites.
10.4 REDUCTION OF NO
NO reduction is an important process because it is one of the reactions in
environmental pollutant control. In particular, reduction of NO by NH3 or CO is
very desirable as it removes two atmospheric pollutants simultaneously:
2N0 +2NH3 + 1/202+ 2N2 + 3H2O (10-21)
NO + CO --j 1/2N2 +CO2 (10-22)
Reduction can also be achieved with H2:
NO + H2 + 1/2N2 + H2O (10-23)
The formation of N2 and H20 are not the only possible reactions in a mixture of
NO and NH3. There are at least three competing reactions:
The extent of these competing reactions depends on the reaction conditions such as
temperature, composition of the reaction mixture, and the catalyst. For example,
in the reaction between NO and NH3 on V205, a higher partial pressure of oxygen
greatly enhances the production of N2 over that of N20 so that N2amounts to over
90% of the nitrogen-containing products [97] (see Fig. 10-6). On copper oxide,
the product is 99% N2 when the oxide is fully oxidized, and becomes 75% N2 and
25% N20 when the oxide is partially reduced [92]. The product is 60% N2 and
40% N20 over unsupported Cr2O3. but it is 75% N2 and 25% N2O on a
Cr203/A1203 [%I. On Moo3, the ratio depends on the morphology of the oxide
particle [90].
A number of oxides has been reported to be active for NO reduction with
NH3. CuO [921. A1203-supported Fez03 [931, 0 2 0 3 [941, and VZOS [951, 7302-
supported VzOs [84]. Moo3 [851. Fe203 [861, and Nb2Os [87] are reported to be
active. Some, such as supported or unsupported V205, are active even for trace
amounts of NO and NH3 and in the presence of air or oxygen. The activity of
DECOMPOSITION AND HYDROGENATION 163
1.0
0.5
0
O2 Concent rat i on, 96
Figure 10-6 Effect of 0 2 concentration on the production rates of N2 and NZO at 250°C
over VzOs. Inlet concentrations of NO and NH3 are lo00 ppm. W/F =0.33 g-h/rnole.
(From J. Catal., 62, 140 (1980), copyright Academic Press).
these oxides depends on the support. V205 supported on Ti02 is more active than
on A1 2 0 3 or Si02 [84]. Moo3 supported on Ti02 is the most active, followed by
other supports like Zr02. A1203 and finally SO2 [85]. On Fer03, the activity
sequence follows: Si02 >A1203 >Zr02 >Ti02-Zr02 >active carbon >MgO >
Si02-Ti02 >Ti02 >Sn02. In this case, the activity difference among the first four
supports parallels their different surface areas [86]. For Nb2O5. Ti02 support
provides a catalyst that is much more active than A1203 and Zr02, which are more
active than Si02 [87]. It has also been reported that sulfate enhances the catalytic
reaction for Nb205/Ti02 and Fe2O3/ZrO2 [861.
The activity of the catalyst depends on the oxidation state. The active state
of vanadium oxide is V2O5. This state is maintained when there is 1% or more of
O2 in the feed under the condition shown in Fig. 10-6 [97]. In the absence of
oxygen, the catalyst is reduced to V204. The active state of Cr203/A1203 is also
nearly fully oxidized [96]. On the other hand, the activity of copper oxide
increases when CuO is reduced [92].
The mechanism of the reaction has been elucidated mostly by use of isotope
labeling techniques and infrared spectroscopy. On V205, adsorption of NO only
occurs i n the presence of O2 with the formation of an adsorbed *- N02- species
characterized by an IR band at 1632 cm-'. Adsorption of N H 3 occurs on BrBnsted
acid sites to form NI-&+. The adsorbed NO2- and w+ react on the surface to
form N2 which is detected in the gas phase [95]. These observations lead to the
proposed mechanism:
NO +O-(ad) + N02-(ad) (10-27)
164
C
0
CI
.-
CI C E '
0,
0
C
I
(b)
0 20 40 60
Ti me, s
Figure 10-7 Concentration profiles at the inlet and outlet of the reactor. a. Inlet
rectangular pulse of a mixture of NO and NH3. b. Concentration profiles of N2 produced by
the reaction of rectangular pulse of the NO and NH3 mixture with unsupported V205 at
various temperatures. (From J. Phys. Chem.. 85, 2367 (1981). copyright American
Chemical Society).
*-OH- + NH3 -+ *a2%+ (1 0-28)
*-027W&+ + N02-(ad) - N2 + 2 H20 + *a2- (10-29)
*a2- + H20 + 2* 4H- ( 10- 30)
While gas phase oxygen enhances the reaction rate, the reaction proceeds
without oxygen. Under such a condition, the V=O groups in V205 are reduced
[88]. When NO gas is introduced onto the catalyst with NH3 preadsorbed as
W+ at 100°C or higher, w+ disappears and products N2 and H2O are formed
[97]. The consumption of V=O in this reaction has been used to determine the
surface density of V=O. In this technique, a rectangular pulse of NO and NH3 is
passed over a catalyst and the production of N2 is monitored (see Fig. 10-7). The
evolution of N2 shows a large peak at the beginning which is assumed to be due to
DECOMPOSITION AND HYDROGENATION 165
the reaction with surface V=O (reaction 10-31). This is followed by a long tail
which represents regeneration of consumed surface V 4 by lattice oxygen. The
reaction sequence is:
V 4 + N H 3 + NO + V-OH ,I- N2 + H2O (10-31)
2V-H + [O] + 2 V 4 + H20 (10-32)
The Occurrence of reaction (10-32) has been questioned recently because it
was observed that the same profile of N2 evolution was obtained using a
V205Di02 catalyst on which V2O5 presumably forms a monolayer on the support.
Since there should not be lattice diffusion of oxygen to reoxidize surface V 4 H
groups as in reaction (10-32), the long tail is proposed to be due to reaction on a
reduced surface site [89]:
3 V 4 + 2NH3 --+3V 0 + N2 + 3H2O (10-33)
VO + NO -----) V=O + 1DN2 (10-34)
Here, VO represents a vanadium ion associated with an oxygen vacancy.
Analogous equations can be written if it represents a V-OH group.
When 15NH3 is used as a reactant with 14N0, isotopically labeled N2 and
N20 are produced. On Cr203/A1203, the product consists of 15N14N, 14N14N, and
14N20 but no 15Ni4N0. The ratio 15N14NP4N20 ranges from 1.5 to 3. On
CrzO3, 15N14N and 14N20 are the major products, no 14N2 and only a small
amount of 15N14N0 are found. The ratio 15N14NP4N20 is slightly below 2 [97].
This ratio is also about 2 on FezO3/Al2O3. The mechanism proposed to account
for this is:
2Cr=O + NO + 1 5 NH3 -+Cr+NO + Cr4Hl 5NHz (10-35)
-+15N14N + H20 +C d + Cr-OH
H
2Cr-OH + 2N 0 --j 2Cr-U-NO (10-36)
--+ 2 0 + N20 + H2O
A combination of reactions (10-35) and (10-36) gives a 15N14NP4N20 ratio of
two. The production of 14N2 is assumed to bedue to decomposition of l4NzO.
When the same reaction is studied on copper oxide, only 15N14N is produced
on fully oxidized CuO. The catalyst is reduced at the same time. Other products
begin to appear as the extent of reduction increases. On Cu20, 15N14N 9 14N 2,
15Ni4N0 and 14N20 are formed in the ratio 73:16:9:3 [92].
166
REFERENCES
1. T. Ono, M. Anpo, and Y. Kubokawa, J. Phys. Chem., 90,4780 (1986).
2. A. Ueno, T. Onishi, and K. Tamaru, Trans. Faraduy Soc., 67, 3585 (1971).
3. 0. Koga, T. Onishi, and K. Tamaru, J. Chem. Soc. Faraday Trans I , 76, 19 (1980).
4. J . M. Vohs and M. A. Barteau, Surface Sci ., 176, 91 (1986).
5. M. Bowker, H. Houghton. and K. C. Waugh, J. Chem. Soc. Faraday Tram. 1,
6. S. Akhter. W. H. Cheng, K. Lui, and H. H. Kung, J. Catal., 85.437 (1984).
7. K. Lui, M. Vest, P. Berlowitz, S. Akhter, and H. H. Kung, J. Phys. Chem.,
8 . K. M. Tawarah, and R. S. Hansen, J. Caral., 87, 305 (1984).
9. M. Nagao, and T. Morimoto, J . Phys. Chem., 84,2054 (1984).
77, 3023 (1981).
90, 3183 (1986).
10. G. Zwicker, K. J acobi. and J. Cunningham, Intern. J. Mass Spectros. Ion
11. S. Akhter, K. Lui, and H. H. Kung, J. Phys. Chem., 89, 1958 (1985).
12. F. Steinbach, and D. Hofer, Surface Sci., 79, 311 (1979).
13. J. Canigosa, G. Munuera. And S. Castanar. J. Cutal.. 49, 265 (1977).
14. K. Yamashita, S. Naito, and K. Tamaru, J. Catal.. 94, 353 (1985).
15. A. Iimura, Y. Inoue, and 1. Yasumori, Bull. Chem. Soc. Japun, 56. 2203 (1983).
16. 0. V. Krylor, "Catalysis by Nonmetals", Academic Press Publ., 1970.
17. M. Ai, J. Catal., 40, 327 (1975).
18. 0. Koga, T. Onishi, K. Tamaru, J. Chem. SOC. Faraday Trans. 1, 76, 19 (1980).
19. K. Nagai, and K. Miyahara, J. Res. Inst. Catalysis, Hokkuido Univ.,
20. A. A. Kadushin, Kinet. Katal., 8, 1356 (1967).
21. Y. Kubokawa, T. Ono. andN. Yaw, J. Catal., 34, 117 (1974).
22. E. Akiba, M. Soma, T. Onishi. and K. Tamaru. Zed. Phys. Chem. Neue
23. P. Berlowitz, and H. H. Kung, J. Amer. Chern. Soc., 108, 3532 (1986).
24. M. Vest, P. Berlowitz, and H. H. Kung, submitted.
25. G. Djega-Mariadassou, and L. Davignon, J . Chem. Soc. Faraday Trans. 1 ,
26. M. Boudart, Ind. Ens. Chem. Fundamental, 25, 656 (1986).
27. K. Lui, S. Akhter, and H. H. Kung. in "Solid State Chemistry in Catalysis",
ACS Symposium Series 279, R. K. Grasselli and J . F. Brazdil ed.. ACS.
Washington, 1985, p. 205.
28. M. Bowker, H. Houghton, and K. C. Waugh. J. Chem. Soc. Faraday Truns. I ,
81. 3073 (1985).
29. K. C. Waugh. M. Bowker, R. W. Petts, H. D. Vandervell. and J. OMalley.
Appl. Catal., 25. 121 (1986).
30. M. Hino. and K. Arata, J. Chem. SOC. Chem. Commun., 1037 (1984).
31. I. Carrigosa, and G. Munuera, J . Catal.. 49, 174 (1977).
32. Y. Kera and M. Negoro. J . Catal., 99, 198 (1986).
33. A. A. Balandin. Adv. Catal., 10, 96 (1958).
34. P. J ackson, and G. D. Parfitt, J . Chem. Soc. Faraday Trans. I , 68, 1443 (1972).
Processes, 6, 213 (1984).
23, 110 (1975).
Folge, 109, 103 (1980).
78, 2447 (1982).
DECOMPOSITION AND HYDROGENATION 167
35. I. Carrizosa, and G. Munuera, J. Caral.. 49, 189 (1977).
36. L. M. Roev, and A. N. Terenin, Dokl. Akad. Nauk SSSR, 124, 373 (1959).
37. M. B. Ward, M. J . Lin, and J . H. Lunsford, J. Catal.. 50. 306 (1977).
38. M. Bowker, R. W. Petts, and K. C. Waugh, J. Calal., 99. 53 (1986).
39. W. Mokwa. D. Kohl, and G. Heiland. Surfnce Sci., 117, 659 (1982).
40. K. Thomke, Z. Physik Chem. (NF) 109, 101 (1978).
41. T. J in, H. Hattori. and K. Tanabe. Bull. Chem. SOC. Japan, 56, 3208 (1983).
42. J . Cunningham. G. H. Al-Sayyed. J. A. Cronin. J . Fierro, C. Healy, W. Hirschwald,
M. Ilyas, and J. Tobin, J. Caral., 102, 160 (1986).
43. K. Asakura, and Y. Iwasawa, Chem. Lerr., 859 (1986).
44. E. R. S. Winter, J. Catal., 15. 144 (1969).
45. T. A. Egerton, F. S. Stone, and J . C. Vickerman. J. Catal.. 33, 229 (1974).
46. T. A. Egerton, F. S. Stone, and J. C. Vickerman, J. Catal., 33, 307 (1974).
47. V. A. Shvets, and V. B. Kazanskii. J. Catal.. 25, 123 (1972).
48. V. A. Shvets, V. M. Vorotyntsev. and V. B. Kazanskii. Kinet. Catal..
49. V. A. Shvets, and V. B. Kazanskii, Kinet. Cataf.. 12. 332 (1971).
50. J . H. Lunsford, Catal. Rev., 8, 135 (1973).
51. Ph. Roussel, and S. J. Teichner. Catal. Rev., 4, 133 (1972).
52. D. Cormack. R. J . Bowser. R. Gardner. and R. L. Moss, J. Catal.. 17, 230 (1970).
53. M. Schiavello. M. Valigi, and F. Pep, J. Chem. SOC. Faraday Trans. 1.
54. D. Cormack, D. Poynter. C. J . Burlace, and R. Moss, J . Catal., 26, 135 (1972).
55. K. V. Ramanujachary, N. Kameswari. and C. S. Swamy. J. Catal.. 86, 121 (1984).
56. D. Patel. MS thesis, Northwestern University, 1985.
57. C. Fu. V. Korchak, and W. K. Hall, J . Catal., 68. 166 (1981).
58. I. Leglise, J . Petunchi, and W. K. Hall, J. Catal.. 86, 392 (1984).
59. C. L. Thomas, "Catalytic Processes and Proven Catalysts". Academic Press,
60. D. L. Harrison, D. Nicholis, and H. Steiner, J. Cafal., 7, 359 (1967).
61. J . Cunningham, B. K. Hodnett, M. Ilyas, J . Tobin. and E. L. Leahy, Chem.
62. C. Wagner, J . Chem. Phys., 18, 69 (1950).
63. R. M. Dell, F. S. Stone, and P. F. Tiley, Trans. Faraday SOC., 49, 201 (1953).
64. E. R. S. Winter, J . Caral., 19, 32 (1970).
65. K. Hauffe, Adv. Catal., 7. 213 (1955).
66. R. I. Bickley and F. S. Stone, in "Electronic Phenomena in Chemisorption and
Catalysis on Semiconductors." ed. K. Hauffe and Th. Wokenstein, 1968. p138.
67. D. A. Dowden, and D. Wells, Proc. 2nd Intern. Congr. Catal., Paris, p. 1499 (1961).
68. G. M. Dixon, D. Nichols, and H. Steiner. Proc. 3rd Intern. Congr. Catal.,
69. Yu. S. Khodakov. and Kh. M. Minachev, Bull. Acad. USSR, Chem. Sci., 31,
70. A. L. Dent, and R. J . Kokes, J . Phys. Chem., 73, 3781 (1969).
71. W. C. Connor, and R. J. Kokes, J . Phys. Chem., 73. 2436 (1969).
72. A. B. Littlewood and R. L. Burwell, Jr.. J . Amer. Chem. SOC.. 82. 6287 (1960).
10, 356 (1959).
71, 1642 (1975).
N.Y. (1971).
SOC. London. Faraday Disc., 281 (1981).
Amsterdam, p. 815 (1964).
24 (1982).
168
73. K. Tanaka, H. Nihira, and A. Ozaki, J . Phys. Chem., 74,4510 (1970).
74. A. L. Dent, and R. J . Kokes. J . Amer. Chem. SOC.. 92, 6718 (1970).
75. R. L. Bunvell, Jr.. A. B. Littlewood, M. Cardew, G. Pass, and C. T. H. Stoddart,
76. R. L. Bunvell, J r., G. L. Haller. K. C. Taylor, and J. F. Read, Adv. Cataf..
77. A. L. Dent, and R. J. Kokes, J. Phys. Chem.. 73. 3772 (1969).
78. K.-i Tanaka, K. Aomura, T. Okuhara, and K. Miyahara. J . Chem. SOC.
79. I. J . S. Lake, and C. Kemball, Tram. Faruday Soc., 63. 2535 (1967).
80. G. Pass, A. B. ittlewood, and R. L. Burwell, J r., J. Amer. Chem. Soc.,
81. R. L. Burwell. Jr., and K. S . Stec. J. Colloid Inferface Sci .. 58. 54 (1977).
82. T. Iwaki, K. Katsuta, and M. Miura, J . Cafaf. . 68, 492 (1981).
83. J . Goldwasser. and W. K. Hall, J. Cataf.. 71. 53 (1981).
84. M. Inomata, A. Miyamoto. and Y. Murakami, J. Phys. Chem., 85, 2372 (1981).
85. S. Okazaki, M. Kumasaka, J . Yoshida, K. Kosaka, Ind. Eng. Chem. Prod.
86. T. Iizuka, H. Ikeda, T. Terao, K. Tanabe, Awf . J . Chem., 35, 927 (1982).
87. S. Okazaki. and T. Okuyama. Buff. Chem. Soc. Jpn, 56, 2159 (1983).
88. A. Miyamoto, Y. Yamazaki. M. Inomata, and Y. Murakami, J . Phys. Chem.,
89. J. van Ommen, and J . Ross, Appf. Cataf.. 25, 239 (1986).
90. A. Baiker, P. Dollenmeier, and A. Reller, J. Cataf.. 103, 394 (1987).
91. E. A. Lombardo, M. Lo J acono, and W. K. Hall, J . Cataf., 64. 150 (1980).
92. K. Otto and M. Shelef, J. Phys. Chem., 76, 37 (1972).
93. E. Echigoya, H. Niiyama, and A. Ebitani, Nippon Kagaku Kaishi, 222 (1974).
94. H. Niiyama, K. Murata, A. Ebitani, and E. Echigoya, J. Cataf.. 48. 194 (1977).
95. M. Takagi, T. Kawai. M. Soma, T. Onishi, and K. Tamaru, J. Cataf., 50, 441 (1977).
96. H. Niiyama, K. Murata. and E. Echigoya, J . Catal., 48, 201 (1977).
97. M. Inomata, A. Miyamoto, and Y. Murakami, J . Catuf., 62, 140 (1980).
98. M. Vest, PhD thcsis, Northwestern University, 1988.
99. K. Lui, PhD thesis, Northwestem University, 1988.
J . Amer. Chem. SOC., 82, 6272 (1960).
29, 1 (1969).
Faraday Trans. I , 77, 1697 (1981).
82, 6281 (1960).
Res. Dev., 20, 301 (1981).
85, 2366 (1981).
Chapter 11
SELECTIVE OXIDATION REACTIONS I
11.1 INTRODUCTION
Selective oxidation of hydrocarbons is a very important industrial process
that uses catalysts commonly based on transition metal oxides which are often
vanadium and molybdenum oxides. Because of their industrial importance and
the fact that they pose challenging scientific questions, selective oxidation catalysis
has been rather extensively studied. A common feature among these reactions is
that the desired products are often not the most thermodynamically favorable ones.
For example, selective oxidation of hydrocarbons are usually carried out with
oxygen or air. The most thermodynamically favorable products are water and
carbon dioxide. The desired products, on the other hand, are alcohols, aldehydes,
ketones, acids, anhydndes, or alkenes and dienes. Furthermore, for each hydro-
carbon reactant, there are many possible products of various degrees of oxidation
before carbon oxides are formed. Depending on the application, one or more of
these partial oxidation products are desired. Therefore it is a challenge to
understand the factors that account for the activity and the selectivity of a catalyst
and to develop a practical catalyst.
The discussions here will concentrate on the chemical factors that determine
activity and selectivity, with emphasis on the latter. Readers are urged to
recognize that physical factors, such as pore size and heat and mass transfer can be
very important. Local heating in a reactor is common because of the high heats of
reaction in oxidation. It can lead to a drastic decline in selectivity as carbon oxides
are generally favored at higher temperatures. Severe mass transfer limitations in
catalyst pores result in concentration of partial oxidation products to be higher in
catalyst pores than would be the case in the absence of mass rransfer limitations.
Therefore, selectivity to total oxidation is enhanced. Similar enhancement is also
observed at high conversions.
If we confine our discussions just to the chemical effects, variations in
activity and selectivity among oxide catalysts are due to different chemical
169
170
bondings between the solid and the reactants and the reaction intermediates.
There is as yet no universal rule that applies to all selective oxidation processes,
perhaps because there are at least two different types of selective oxidation
reactions (see next section). It is likely that the rate-limiting and the selectivity-
determining steps differ for the two types of selective oxidation reactions. In this
chapter, a summary of the current understanding of the role of a catalyst in these
reactions is given. This is followed by descriptions of some selective oxidation
reactions that are fairly well understood. The latter will be continued in the next
chapter.
11.2 TYPES OF SELECTIVE OXIDATION REACTIONS
Selective oxidation reactions can be classified into two types: those that
involve only dehydrogenation, and those that involve both dehydrogenation and
oxygen insertion into the hydrocarbon molecule. Table 11-1 summarizes the
common oxide-catalyzed selective oxidation reactions and the catalysts.
In dehydrogenation reactions, a hydrocarbon molecule is converted into a
more unsaturated hydrocarbon by breaking C-H bonds and forming C=€ bonds.
Often gaseous oxygen is used as an oxidant to yield water as a byproduct. This
provides the thermodynamic driving force for the dehydrogenation process and
permits the reaction to be conducted at a lower temperature than a simple
dehydrogenation without oxygen. Sometimes other oxidants are used instead of
oxygen, including iodine, bromine, and nitrous oxide. Among these, only iodine
has had found commerical applications. In these dehydrogenation reactions, the
carbon skeletons of the hydrocarbon molecules remain intact.
There are many examples of reactions involving both dehydrogenation and
oxygen insertion. Oxygen is needed as an oxidant both for the formation of
oxygenates and in the formation of water in the dehydrogenation steps. The
general features of these reactions are that C-H bonds are broken, and C 4 bonds
are formed. Exceptions to these include the oxidation of ethylene to ethylene
oxide in which no C-H bonds are broken, and ammoxidation reactions such as the
reaction of propene to form acrylonitrile in which C-N bonds are formed. In some
cases, such as the oxidation of benzene to maleic anhydride, the carbon skeleton is
broken. In others, the carbon skeleton remains intact. The selectivity is
determined in part by the ability of the oxide to catalyze the formation of C-0
bonds without excessive breaking of C-C bonds which leads to combustion.
11.3 FEATURES OF CATALYTIC SELECTIVE OXIDATION
In selective oxidation reactions, gaseous oxygen is consumed in the formation
of oxygenates and water, and almost always some carbon oxides. The reaction
pathway of oxygen is as follows. Gaseous oxygen is oxidatively adsorbed on the
oxide as 0-, 02-, or incorporated as lattice 0’- species. The solid is oxidized in
this step, and the electrons acquired by the adsorbed oxygen could be from reduced
SELECTIVE OXIDATION I 171
Table 11-1 Common Oxide-Catalyzed Selective Oxidation Reactions.
(From Ind. Eng. Chem. Prod. Res. Devel., 25, 171 (1986). copyright
American Chemical Society).
Reaction Catalyst
Oxidative Dehvdrogenation
ethylbenzene -+styrene
isopentane, isopentene -+isoprene
butane. butene --+butadiene
methanol ----j formaldehyde
Dehvdrogenation and Oxvgen Insertion
butane, butene --+maleic anhydride
propene -+acrolein
@ropene and NH3 -+ acryloniuile)
propene --+acrolein, acrylic acid,
benzene -+maleic anhydride
o-xylene, naphthalene --+phthalic
anhydride
methane --+methanol, formaldehyde
ethylene -+ ethylene oxide
acetaldehyde
methyl ethyl ketone -+biacetyl
methyl ethyl ketone -+acetaldehyde,
butane, butene -j acetaldehyde,
acetic acid
acetic acid
V-Ti-0
Sn-Sb-0
Bi-Mo-0, promoted Fe-0
promoted V- 0
Fe-Mo-0, M a3
v-P-0
Bi-Mo-0
Bi-Mo-0, U-Sb-0, Fe-Sb-0,
Bi-S b-Mo-0
Co-Mo-Te-0, Sb-V-Mo-O
V-P-0, V-Sb-P-0
promoted V- 0
Mo-0. V-0
Fe-Mo-0 (also catalyzed
by promoted Ag)
Co-0 (promoted by Ni, Cu)
V-Mo-0
V-Ti-0
surface cations or anion vacancies with trapped electrons. When an oxygen atom
is incorporated into a product molecule which is then desorbed, the electrons are
returned to the solid. Therefore, in one catalytic cycle, electrons are removed
from and then returned to the solid. I n other words, the solid has undergone an
oxidation-reduction cycle. If the oxygen species that is incorporated into the
molecule is a lattice oxygen atom, the sites for adsorption of oxygen and for
oxygen incorporation into the molecule may be different, and migration of oxide
172
Figure 11-1 Schematic representation of the redox cycle in a selective oxidation reaction
involving lattice oxygen. $'s are anion vacancies.
ions in the solid between the two sites would occur. This situation is shown
schematically in Fig. 11-1, which was first proposed by Mars and van Krevelan [l],
and is commonly referred to as the Mars and van Krevelan mechanism. One
should emphasize that there can be many possible variations from this scheme. For
example, alkene adsorption may take place on a partially reduced cation, or the
hydrocarbon molecule may adsorb with heterolytic dissociation.
This mechanism which involves lattice oxide ions have a number of conse-
quences. Since some cations in the solid continually undergo alternate oxidation
and reduction during the reaction with a consequent change in the local cation-
anion ratio in the solid, the catalyst must be able to accommodate these changes
reversibly and easily. For example, in molybdenum oxide, this is achieved by the
ready interconversion of corner-sharing and edge-sharing M06 octahedra as
examplified by the formation of shear planes, and in vanadium phosphorous oxide
by the ready interconversion between two crystallographic structures.
Another consequence is the interesting feature that many reactions proceed
with the same initial activity and selectivity in the presence or absence of gaseous
oxygen. That is, a catalytic reaction and a noncatalytic surface reaction give the
same initial rate and selectivity. Table 11-2 summarizes some of the known
examples. In the absence of gaseous oxygen, oxidation of the hydrocarbon is by
the cation in the solid. Usually, the reaction rate and the selectivity for partial
oxidation products decrease with increasing extent of reduction of the oxide,
although the rate of decrease depends on the particular oxide. For some oxides,
such as a-iron oxide, however, the selectivity is improved initially when the
catalyst is reduced before it deteriorates. In this case, the presence of surface
anion vancancies may be important.
SELECTIVE OXIDATION I 173
Table 11-2 Examples Where the Rate andor Product Distribution Have
Been Shown to be Similar in the Presence and Absence of Gaseous Oxygen
Reaction Catalyst
Ammoxidation of propene Bi-Mo-0
Oxidation of propene Bi-Mo-0
Oxidation of butene Bi-Mo-0, Fe-SbO, Bi-W-0, Sn-Sb-0
Sb-Mo-0, Sn-P-0, U-Sb-0, Ni-Sn-P-K,
V-P-0, Fe-0
CH30H oxidation M a3
Although the catalysts in Table 11-2 sustain their activities and selectivities
even after a substantial extent of reduction of the oxide, some other oxides do not.
Cobalt molybdate is an example. When propene is oxidized in the absence of
oxygen on this catalyst, acrolein is formed with the consumption of the first surface
layer of lattice oxygen. As the degree of reduction increases, the acrylic acid yield
as well as the oxidation activity decrease rapidly [2]. Experiments using isotopic
gaseous oxygen further show that only a few (3 to 6) layers of lattice oxygen are
involved in the oxidation of propene [3].
The incorporation of lattice oxygen into selective oxidation products has now
been demonstrated for quite a number of systems. However, it must be recognized
that this is not universal. This is illustrated by the selective oxidation of propene
over a Sn-Mo oxide catalyst [4]. Passage of a mixture of propene, oxygen-160,
and water-I80 over the catalyst yields acrolein, acetone, acrylic acid, acetic acid,
and carbon oxides as products. There is a substantial incorporation of in
acetone, but much less in acrolein. Thus the sources of oxygen in these two major
products are different.
It has been observed that the proximate origins of oxygen atoms used in the
formation of water during the oxidative dehydrogenation of butene to butadiene
and in the selective oxidation of propene to acrolein are different on a Bi2Mo06
catalyst. Ueda, et al. [5] have shown that the conversion of consecutive propene
or butene pulses at 4OO0C decreases in the absence of gaseous oxygen until the
catalyst becomes inactive eventually. Fromthe total amount of propene reacted,
the extent of reduction required to deactivate the catalyst for the propene reaction
can be calculated. If the catalyst is first prereduced to the same extent by the
butene dehydrogenation reaction or by hydrogen and then propene pulses are
passed over the catalyst, the conversion of propene is found to be essentially the
same as for a fresh catalyst. Thus the reduction by butene or H2 does not remove
the oxygen important in the oxidation of propene. This conclusion is confirmed
by l80 labeling experiments [5]. I n these experiments, a catalyst is first reduced
by butene pulses and then reoxidized with 1802. The reoxidized catalyst is then
174
10 20 30 40
React i on Ti me, mi n
Figure 11-2 '*O concentration of acrolein formed on "0 labeled BizMoOB catalyst in the
oxidation of propene with ''Oz at 400°C. The oxidation of propene was carried out after
pretreating the catalyst by propene and "02 (open circles) or 1-butene and I8O2 (closed
circles). (From J. Chem. SOC. Farad. Trans. I, 78, 495 (1982), copyright Royal Society
of Chemistry).
used for propene oxidation. The l80 content in acrolein is found to increase in the
first couple pulses. These results are shown in Fig. 11-2. If the catalyst is
reduced with propene instead of butene and then reoxidized, the l80 content in
acrolein decreases with the pulse number. Thus the proximate source of lattice
oxygen for the formation of water in dehydrogenation must be different from that
used for insertion into propene.
Reduction of Bi2Mo06 followed by reoxidation with l8OZ also causes shifts
in Raman bands related to the M M bonds at 725, 803, and 844 cm-'. The
magnitude of the band shifts are much larger if the reduction is with propene than
with 1-butene, consistent with the above conclusion that different oxygen species
are involved in the two reactions [6,7].
Another interesting feature in selective oxidation catalysis is the influence of
water. Water is often added with the feed as a diluent to reduce the tendency of
SELECTIVE OXIDATION I
175
coking of a catalyst. Less understood is the effect of water in the feed changing
the surface hydroxyl concentration and the acidity and basicity of the catalyst. A
high concentration of surface hydroxyl groups enhances the possibility of reaction
of surface intermediates with hydroxyl groups. For example, in the oxidation of
methane with N2 0 over a silica-supported molybdena catalyst, methanol is
produced at a much higher rate in the presence of water [8.9]. Similarly, in the
oxidation of ethane with N20 over a supported Moo3 catalyst, the presence of
water results in a higher yield of acetaldehyde primarily at the expense of ethene
[10,11]. I n general, the presence of water vapor enhances the selectivity for
alcohols and saturated ketones in the oxidation of alkenes. For example, propene
is first hydrated to 2-propanol which is then oxidatively dehydrogenated to acetone
when propene is passed over a Sn-Mo-0 catalyst with water and oxygen [12]. In
the absence of water and at a higher temperature, no acetone is formed. Instead,
acrolein is produced with 45% selectivity [13]. One of the most interesting
observations in this regard is the selective formation of acetic acid and
acetaldehyde from butene in the presence of oxygen and water over a V-Ti-0
catalyst [ 141, whereas maleic anhydride is a major partial oxidation product over
many vanadia catalysts when the feed does not contain water.
11.4 CHEMICAL FACTORS AFFECTING SELECTIVITY
Past effort by many research workers has provided significant understanding
of heterogeneous catalytic selective oxidation processes. Some of the efforts have
been to find correlations between activity and selectivity and properties of the
catalysts. The following correlations have been proposed:
a) Presence of cation vacancies: Correlations have been found between the
rates of production of selective oxidation products in the oxidation of
butene and propene on schcelite catalysts derived from PbMo04 [15] and
the presence of cation vacancies. Later work concluded that the cation
vacancies associated with Bi ions are the important species [16].
b) Metal-oxygen bond strength: Since the discovery that lattice oxygen
is incorporated into the product acrolein in propene oxidation, it has
been proposed that an optimal M a bond strength is required for high
selectivity in oxidation. More recently, correlations have been made
between selectivitjj and the M-O bond strengths measured as the rates of
change of the hats of reduction of oxides with the degree of reduction
[17], or measured as a function of M a bond lengths [18].
c) Ability to form shear structures: The ability of a catalyst to form
shear structures facilitates the oxidation and reduction cycle that a
catalyst undergoes during reaction without the need for major structural
changes [19].
d) Optimal density of active oxygen: The active site must not contain too
many or too few active oxygen ions that can participate in the reaction.
Too many would lead to excessive oxidation, and too few would lead to
176
an inactive catalyst [201.
e) Acid-base properties of the oxide: Reactants and products of oxidation
reactions can be classified as Lewis acids or bases according to their
ionization potentials. Whether a catalyst contains strong or weak Lewis
acid or base sites will determine the strength of interaction of the
reactants and products with the solid [21], which in turn determines
whether a reactant can be readily adsorbed (and presumably activated)
or a product can be readily desorbed.
f) Electron binding energy of lattice oxygen: A correlation has been
observed between the electron binding energies of lattice oxygen in four
catalysts as determined by XPS and their activities for selective
oxidation [22]. This correlation is based on the concept that the electron
binding energy can be used as a measure of the basicity of the lattice
oxygen, and that for the same cation, a more basic lattice oxygen ion
could more easily abstract an allylic H atom from an alkene. This last
point will be discussed further later.
g) Crystallographic plane: Different surface planes have different atomic
arrangements, which may show different activities and selectivities. For
example, different selectivities have been observed on different
crystallographic planes of MoOj in the oxidation of methanol and ethanol
[23,24]. However, only a phenomenological explanation is presently available.
h) Presence of M=O bonds: It has been noted that terminal MLO bonds are
present on many selective oxidation catalysts such as Moo3, molybdates
[25,26], and VzOs [27]. Thus it has been suggested that their presence is
important. However, not all selective catalysts contain such M=O bonds,
whereas some nonselective catalysts do. This will be discussed further
later.
desorption to determine which oxide adsorbs oxygen weakly, a correlation
has been found that for simple binary oxides, those that are selective
in oxidation do not have weakly adsorbed oxygen [28]. This observation
is consistent with those which show that weakly adsorbed oxygen causes
combustion of adsorbed hydrocarbons [29].
i) Absence of weakly adsorbed oxygen: Using temperature programmed
Further discussions of these correlations are found in the sections that
describe individual reactions. The existence of so many correlations indicates the
complexity of the problem. Because selective oxidation is a multistep process and
there are different types of selective oxidation reactions, the important step that
determines activity may well be different from the step that determines selectivity,
and these steps may be different for different reactions. Even for the same
reaction, the critical step may depend on the oxide and operating conditions. In
other words, because of the diversity of this area, it is unlikely that one corrclation
is sufficient to explain all processes under all conditions on all catalysts. To
expand on this, consider the examples of the oxidation of propene to acrolein and
of butcne to butadiene. Under industrial operating conditions, the rate-limiting
step for both reactions is the breaking of the allylic C-H bond (first C-H bond
SELECTIVE OXIDATION I
177
breaking). A successful correlation would be rate versus factors that affect the
rate of breaking of this bond. At lower temperatures, however, the desorption of
acrolein [30] or butadiene [31] are rate limiting. In this case, a successful
correlation for the rate would be with factors that affect rates of desorption of these
products, Since selectivity is determined by factors other than those that
determine rate, these correlations would not be successful for selectivity.
That selective oxidation is a multi-step sequence of reactions is well
recognized. The need for every step to proceed rapidly on a good catalyst is also
known. Grasselli and coworkers have identified three major functions of a
catalyst for the oxidation and ammoxidation of propene [6,32]: allylic hydrogen
abstraction, oxygen insertion, and oxidation-reduction of the catalyst. Different
cations important for each function have been identified. An active and selective
catalyst must then contain cations for every function. We shall discuss this in
detail later.
Approaching from a different point of view, Haber analyzed the question of
selectivity by considering the types of oxygen available for the reaction [33]. He
proposes that the reactivity of an oxygen depends on whether it is electrophilic or
nuclcophilic. Electrophilic oxygen species, such as adsorbed 02- and 0- are very
active. They attack hydrocarbon molecules at the regions of high electron
densities. Saturated aldehydes are formed which readily undergo total oxidation.
Nucleophilic oxygen species, such as lattice oxygen are less reactive and are
suitable for partial oxidation. In a reaction that makes use of nucleophilic oxygen,
activation of the hydrocarbon molecules is the rate-determining step, whereas in a
reaction that uses electrophilic oxygen, adsorption of oxygen to form the
electrophilic species is the rate-limiting step. In Haber's model, a selective
oxidation catalyst should be capable of adsorbing and activating a hydrocarbon
molecule for nucleophilic attack by oxygen. It should be able to insert
nucleophilic lattice oxygen efficiently into the hydrocarbon molecule, and be able
to replenish rapidly the lattice oxygen consumed. It should not generate
electrophilic oxygen species.
Haber's treatment, while generally plausible, is not universal. For example,
the statement that electrophilic 02- or 0- are not suitable for selective oxidation
needs qualification. In the recent examples of selective oxidation of methane on
Si02-supported M a 3 134-361 and V205 [37,38] catalysts, N20, which decom-
poses rcadily to adsorbed 0-, is an effective oxidant. In another example, the
oxidation of ethylcne to ethylene oxide, the standard heat of reaction is -24.7
kcal/mole. Thus the heat of adsorption of the oxygen involved must be smaller
than this value. I n other words, it must be a relatively weakly adsorbed oxygen.
Another approach to understanding selective oxidation is to analyze each step
in the reaction sequence individually, and consider the factors that affect each step.
This approach makes it possible to understand why changes in some catalyst
propcrtics would rcsult in the observed changes in the reaction characteristics when
the ratc-limiting and the selectivity-determining steps are known.
To illustrate this approach the oxidation of butane to maleic anhydride is used
as an cxamplc. A simplificd scheme for the sequential oxidation of butane is
shown in Fig. 11-3. This reaction contains all the essential features of most
178
0
CO +C02 +H20
Figure 11-3 A simplified scheme for the oxidation of butane.
selective oxidation reactions. Step 1 involves the activation of an alkane. Step 2
involves the activation of an alkene. Steps 3 and 4 involve insertion of oxygen
into the hydrocarbon. The chemical transformations involved in these steps have
been analyzed, and the catalyst properties important in these steps have been
postulated [391. A summary of the results are presented below.
a) Alkane activation (step 1). Because alkane molecules are very inert and interact
only very weakly with most catalysts, it is believed that the transition state in the
breaking of the first C-H bond in alkane activation is reactant-like. The energetics
of the process favors the dissociation of the C-H bond in a manner similar to the
production of free radicals. Furthermore, because of the strong C-H bonds in
alkanes, this reaction step requires a very reactive weakly adsorbed oxygen species
to be energetically favorable. Weakly adsorbed 02- and 0- species are some of
the possible candidates. Once the first C-H bond is broken, a weakly adsorbed
alkyl radical or a surface alkyl species would be formed, and breaking of the
second C-H bond to form an alkene should proceed easily.
b) Alkene activation (step 2). Unlike alkanes, the C=C bonds of alkenes can
interact strongly with the cations of a catalyst. The strong bonding makes
possible charge delocalization between the adsorbate and the cation. Since the
charge on the cation in the solid can be much better stabilized by electrostatic
forces in the solid than charges on the adsorbate outside the solid, it becomes
possible that the allylic C-H bond breaking in this step is achieved with charge
transfer between the x-ally1 and the surface cation:
(1 1-1)
RCH-C HXH2
- - - - I - - -
RCH=CHCH3 + Mn+02- --+[
M 0 2 -
This step which is heterolytic dissociative adsorption of alkene is enhanced if (i) the
cation can readily undergo reduction; (ii) the surface oxygen is a strong Brdnsted
base; and (iii) he cation is a soft acid.
Following the allylic C-H bond breaking, a second C-H bond must also be
SELECTIVE OXIDATION I 179
broken to form diene. Breaking of the second C-H bond can be homolytic and
does not need to be accompanied by charge separation. It can be enhanced by
weakly adsorbed highly reactive oxygen species.
In both dehydrogenation of alkane to alkene and alkene to diene, the products
must desorb rapidly. Since unsaturated hydrocarbons are soft basic ligands,
desorption is facilitated by hard acid cations. For this step, the solid is preferably
ionic, and the cation is in a high oxidation state.
At this point, it becomes apparent that different, and sometimes opposite,
properties are desirable for different steps. Take for instance the desirable
properties of a cation in the dehydrogenation of alkene to diene. It is desirable for
the activation of an alkene to have a soft cation, but for the desorption of diene to
have a hard cation. Therefore, to determine the role of a promoter or in seeking
meaningful correlations, it is important to be able to identify the critical factor (i.e.
catalyst property) in the rate-limiting step.
c) Oxygenate formation (steps 3 and 4). The formation of oxygenates from a
diene or an alkene involves breaking C-H bonds, forming C-O bonds (i.e. oxygen
insertion), and desorption of the oxygenates. In the oxygen insertion step, it is
important that the appropriate number of oxygen atoms be incorporated into the
molecules. Excess incorporation or incorporation at the wrong position leads to
undesirable combustion. There are at least two important oxide properties that
affect this step: geometric effect and metal-oxygen bond energy.
The geometric effect states that an ideal active site must not have too many or
too few oxygen ions or atoms that can participate in the reaction [6,32,40]. Too
many would lead to excessive oxidation, too few would lead to an inactive
catalyst. This concept points to the importance of the crystal structure and the
surface atomic structure.
The importance of metal-oxygen bond strength has long been recognized. It
is generally believed that too weak bonds result in nondiscriminative C 4 bond
formation which leads to combustion, and too strong bonds lead to unavailability
of lattice oxygen that could participate in the reaction. Since the M-O bond
strength usually increases with the degree of reduction of the oxide, one concept is
that there is an optimal value for the rate of increase in the heat of reduction of an
oxide with the extent of reduction near the steady state of the oxide [17].
Both the geometric and the M-O bond strength effects are short-ranged. An
efficient way for a promoter to affect them is by the formation of a compound.
The beneficial effects in the formation of bismuth molybdate, vanadium
pyrophosphate, etc. could be i n part due to this reason. A correlation mentioned
carlier that krminal M=O groups are important may also be another manifestation
of the geometric and M a bond strength effect.
The lattice oxygen that is used for C 4 bond formation must be replenished
to maintain the catalyst at the optimal steady state. The ability of an oxide to form
shcar structure facilitates this reduction-oxidation process [9]. However, this is not
a necessary condition for selective oxidation catalysts, as some of them (e.g. silver
metal, copper oxide) are not known to form shear planes.
After the desired oxygenates are formed, they must be desorbed. Many
180
Table 11-3 Desirable Surface Properties in Selective Oxidation Reactions.
(From Ind. Eng. Chem. Prod. Res. Devel., 25, 171 (1986), copyright American
Chemical Society).
Reaction Properties
Alkane activation:
C-H bond dissociation Highly reactive surface oxygen
(weakly adsorbed oxygen and/or
surface lattice defects).
Alkene activation:
C-H bond dissociation (i) Surface oxygen strong Brbnsted base
(ii) Cation readily undergoes reduction
(iii) Cation soft acid
Diene (or alkene) desorption Cation hard acids
Water desorption Cation soft acids
Oxygenate formation:
Oxygen insertion (i) Limited number of available oxygen
(ii) d AH,/& too large for further reduction
Oxygenate desorption Cation soft acids
Prevent combustion: (i) Short residence time of surface
intermediates
(ii) Weak adsorption of desired product
(iii) No weakly adsorbed oxygen
(iv) No combustion site
oxygenates are adsorbed via the electron lone pair of oxygen. They are hard
bases. Thus desorption is easier from soft than from hard cations.
d) Combustion reaction. This is an undesirable reaction and should be minimized.
This can be achieved by (i) shortening he surface residence time of surface
intermediates, especially the desired products; (ii) eliminating weakly adsorbed
oxygen species which are very reactive; (iii) eliminating active sites that only lead
SELECTIVE OXIDATION I 181
to combustion products. Property (ii) has been discussed earlier. For (i), very
reactive oxygen is desirable for activating the strong C-H bonds of alkanes, but is
undesirable for other processes. (iii) is self-explanatory. A summary of the
desirable properties of a catalyst for each of the steps described is presented in
Table 11-3.
11.5 OXIDATION OF PROPENE TO ACROLEIN AND
AMMOXIDATION TO ACRYLONITRILE
Catalytic partial oxidation of propene can result in a number of products such
as acetone, propionaldehyde, and acrolein. In the presence of ammonia,
ammoxidation to acrylonitrile is also possible. Among these reactions, the
catalytic oxidation to acrolein:
CH3CHxH2 + 0 2 300-4500c) CH2=CHCH0 + H20 (11-2)
and the ammoxidation to acrylonitrile:
CH3CHKH2 + NH3 + 3/22? (11-3)
400-4600c+ CH2=CHCN + 3H20
are commercially very important and the most studied and understood. We shall
discuss them i n this section.
There have been successive generations of commercial catalysts for these
reactions based on molybdates, cuprous oxide or antimonates. Bismuth
molybdates, tin antimonates and uranium antimonates were the catalysts in the
recent past. Work on tin antimonates has been recently reviewed [41]. The latest
catalysts are the multicomponent molybdate catalysts, M.2+Mb3+Bi,Moy0, (I@+
= Ni, Co, Mg, Mn, and M3+= Fe, Cr, Al, Ce) that are based on bismuth molybdate,
multicomponent antimonate catalysts, M,MbF%SbyO,, and Ce-Te-Mo oxide.
Experience has shown that a catalyst that is active and selective for propene
ammoxidation to acrylonitrile is also excellent for oxidation to acrolein.
The selectivity for acrolein or acrylonitrile over the commercial catalysts are
very high, usually in excess of 80% even at high conversions. In the oxidation
reaction, the byproducts include carbon dioxide, carbon monoxide, acetaldehyde,
formaldehyde, propionaldehyde, propionic acid, formic acid, and acetic acid.
Since most of the selective catalysts are based on molybdates, the published
work has concentrated on the molybdate system. In particular bismuth molybdate,
which exists as Bi2Mo06 (y phase), Bi2Mo3012 (a phase), and Bi2M0209 (p
phase), has been heavily studied. In this system, the y phase is the most selective
and active, while the a phase is inferior to the other two.
182
Reaction Mechanism
Based on work by various workers, detailed mechanisms for both oxidation
and ammoxidation over bismuth molybdate have been proposed by Burrington, et
al. 142,431. They are shown in Fig. 114.
In these mechanisms, the surface active site is a Bi-Mo pair site (I) that is
composed of a Bi-O group responsible for allylic H abstraction, and a
molybdenum dioxo group for oxygen insertion or diimido group for nitrogen
insertion. The molybdenum cation is believed to be the propene adsorption site,
although the discussions later would suggest that this assignment of sites is not yet
universally accepted. The oxidation reaction proceeds via dissociative adsorption
of propene to produce a x-ally1 species (III). Under reaction conditions, whether
dissociation of propene occurs on adsorption (I + I11 directly) or propene is first
adsorbed molecularly as a II; complex and allylic H abstraction follows (I + I1 +
111) is not clear. This step is followed by the formation of a C-0 bond (I11 + IV),
and a second hydrogen abstraction in the form of a 1.4 shift in species IV to
produce adsorbed acrolein and Mo-OH. Desorption of the product and
reoxidation of the catalyst complete the cycle.
In the ammoxidation cycle, a surface molybdenum diimido species (VI) is
formed by the reaction of &ox0 groups with ammonia (I -+VI). Propene is
activated in the same way as in the oxidation to acrolein. The reaction proceeds
via dissociative adsorption of propene (VI + VIII), formation of a C-N bond (VIII
-+ IX), and a second and a third hydrogen abstraction to form acrylonitrile. The
reduced surface site is reoxidized, and then reconverted to the diimido species to
complete the cycle. It has also been suggested that the diimido species is important
at high propene pressure (10 Pa), and a monoimido species is important at low
propene pressure (4 Pa) [431.
In both oxidation and ammoxidation, the first step of the reaction is the
dissociative adsorption of propene to form an adsorbed symmetrical x-ally1 species
(I + I n and VI + VIII). The involvement of a symmetric x-ally1 species has been
convincingly shown 6rst by Adams and Jennings on bismuth molybdate and
cuprous oxide catalysts [44,45]. When propene labeled with deuterium at either
end is oxidized, deuterium atoms are found only at the end carbons of acrolein, and
the distribution of deuterium is the same regardless of which deuterated propene is
used.
CH2=CH-CH2D
or -- Bi -Mo-o CH@CH=CHD + CDHH=CH2 (11-4)
CD2=CH-CH3
Experiments using carbon labeling also substantiate this conclusion. It is
found that the carbon labels at either end of propene is always equally distributed
in the end carbons of acrolein. This has been confirmed over bismuth molybdates
[46-48] as well as cuprous oxide [49], uranium antimonate [50], tin-antimony
oxide [ 51] , and supported rhodium, ruthenium [52] and gold [53] catalysts.
In principle, the symmetric distribution of labeled carbon or deuterium in
S
E
I

,
E
C
T
I
V
E

O
X
I
D
A
T
I
O
N

I

1
8
3

184
acrolein can be due to the abstraction of a hydrogen atom to form rc-ally1 or the
addition of a hydrogen atom to form a 2-propyl species:
When the reaction is studied over a deuterated catalyst, the 2-propyl route
would yield approximately 50% monodeuterated acrolein, while the rc-ally1 route
would yield 0%. Experimentally, it is found that very little deuterium is
incorporated in the acrolein. thus confirming the rc-ally1 route [46].
This rc-ally1 intermediate behaves like an adsorbed radical. Martin and
Lunsford have detected with electron spin resonance the desorption of rc-ally1
radicals from a bismuth molybdate catalyst [54,55].
In the oxidation of para-substituted phenylpropene @-XC6&CH2CH~H2),
the rates of oxidation of these compounds over bismuth molybdate at 320°C
relative to the unsubstituted phenylpropene (X=H). rXhH are 1.55, 1.98 and 3.03 for
X = CH3, C1, and WH3, respectively. These rates compare well with the rates of
decomposition of psubstituted phenyl azoethanes (p-XC6&CH(CH3)-N=b-
(CH3)CH@-XC6&)). These azocompounds decompose into allyl radicals. The
good agreement suggests that adsorbed ally1 radicals are formed in the oxidation of
phenylpropenes [56].
Other evidence is also consistent with this adsorbed n-ally1 radical
intermediate, but the data may also be interpreted as involving a n-ally1 cation
intermediate. The rates of oxidation of various alkenes depend on the type of
allylic hydrogen. The relative rates over bismuth molybdate at 460°C for alkenes
with a tertiary, a secondary and a primary allylic hydrogen are 75, 14, and 1 [57],
which parallel the order of stability of the rc-ally1 cations or radicals, and the order
of the C-H bond energies. Exposure of the catalyst to propene results in the
reduction of Mo6+to Mo5+which can be followed by EPR [ 58] . Therefore, there
is electron transfer from the surface intermediate to the cation. I f the allylic
hydrogen is abstracted frompropene as a proton, the electron transfer would result
in an adsorbed x-ally1 radical (see eq. 11-1). If the hydrogen is abstracted as a
hydrogen atom, the electron transfer would result i n a rc-ally1 cation.
The oxidation products of propene on bismuth molybdate have also been
compared with those of n-ally1 radicals generated by the decomposition of
azopropene [59], and n-ally1 cations generated by the decomposition of allyl iodide
[60]. Both azopropene and allyl iodide yield selective oxidation products similar
to propene, but azopropene produces more C02, acetaldehyde and benzene, and
less acrolein than allyl iodide. While this evidence seems to support an allyic
cation intermediate, the effect of iodide is not clear nor is the consequence of
azopropene and ally1 iodide.
Above 400°C. the ratc-limiting step in the catalytic oxidation of propene over
bismuth molybdate is the abstraction of the allylic hydrogen. This makes it
SELECTIVE OXIDATION I 185
difficult to study by kinetics alone the steps subsequent to the first hydrogen
abstraction, and there is no conclusive evidence as to whether the abstraction of the
second hydrogen precedes or follows oxygen or nitrogen insertion.
In one report, it is claimed that the details of the next step depends on the
catalyst [61]. On bismuth molybdate, the oxidation of (E)-propene-l-dl yields a
product mixture that contains 1:l: 1 (E)-acrolein-3-dl, (Z)-acrolein-3-dl, and
acrolein-dl .
(E)-propene-1-dl (Ei)-acrolein-3-dl (Z)-acrolein-3-dl acrolein-1-dl
This can be explained by rapid interconversion of x-ally1 and 0-ally1
intermediates, which equilibrates the (E) and (Z) spccies:
The ratio of these products is 1:1:1.6 over cuprous oxide. Thus the x-ally1
and the 0-ally1 intermediate do not equilibrate as rapidly on this catalyst [62].
It is not yet established whether the abstraction of the second H precedes or
follows 0 or N insertion to the adsorbed sc-allyl. The H-D kinetic isotope effect in
acrolein production on bismuth molybdate is consistent with the assumption that
abstraction of the second hydrogen precedes oxygen insertion. This is shown by
the results [44,45] of experiments which monitor the deuterium content in the
various positions of acrolein (CH@CH=C(DJ -Q2 and C(D,H)O-CH<H2) during
the oxidation of CH2=CH-CH2D and CHD=CH-CH3. The experimental results
are compared with the calculated values which are based on the relative probability
of a deuterium atom being abstracted relative to that of a hydrogen atom,
assuming that the abstraction of the second hydrogen precedes oxygen insertion.
The results agree well. The kinetic isotope effect, kH/kD, for the second hydrogen
abstraction at 450°C is found to be 1.82, while kH/kD for the overall reaction of
acrolein production is 2.4 at 320°C [63].
A different conclusion is obtained for the second hydrogen abstraction in the
oxidation of allyl alcohol (CH2=CH-CD20H) [63]. Heterolytic dissociative
adsorption of allyl alcohol on a bismuth molybdate catalyst produces 0-0-ally1
molybdate (species IV i n Fig. 11-4):
186
This species is the same as the one that would be formed by oxygen insertion to a
surface n-allyl. Thus the acrolein produced from allyl alcohol would represent
the result of a mechanism in which oxygen insertion precedes abstraction of the
second hydrogen. The interpretation of the results, however, is complicated by the
isomerization of allyl alcohol which equilibrates the two ends of the molecule:
H H
H2C=C-CD20H C- HOHzC-C=CDz (11-7)
The results of the oxidation and ammoxidation of a mixture of 1,l-d2-ally1 alcohol
and pyridine (the latter is added to suppress the isomerization) have been compared
with those of propene-l,l-dz. Although there are some differences, similarity
between results with the two reactants is large enough to indicate that 0 or N
insertion precedes the second H abstraction.
In addition to the surface reactions shown in Fig. 11-4, it has also been
established that at 45OoC over bismuth molybdate, desorbed allyl radicals react
with gas phase oxygen to form peroxide species, which undergo a homogeneous
gas phase reaction with propene to form propene oxide [64,65]:
It is believed that these surface-initiated homogeneous reactions would become
important at high propene to oxygen ratios and in reactors having large post-
catalytic volumes. This hydroperoxide species, however, does not participate in
the surface reaction on Bi-Mo-oxides, although it is a possible intermediate over
USb301o [MI.
The detailed mechanisms for the production of the side products (products
other than acrolein or acrylonitrile) are less clear. The same kinetic isotope effect,
kH/kD. is observed in the formation of acrolein and carbon dioxide on Bi2M03012
and BizM006 [66]. This suggests that the same rate limiting-step applies to the
formation of both products. There are indications based on isotope labeling
experiments that carbon dioxide arises mostly from further oxidation of acrolein at
the vinyl group [65,67], whereas formaldehyde is derived from the carbonyl group
of acrolein [68].
On Bi3FeMo2012, however, the kH/kD ratio is smaller for C02 than for
acrolein. Thus there may be an additional mechanism leading to combustion on
this catalysts [66].
Kinetics
Propene oxidation proceeds readily above 300°C. On bismuth molybdate
SELECTIVE OXIDATION I 187
Table 11-4 Activation Energies for the Oxidation of Propene, 1-Butene, and
the Reduction of Oxides by Propenea
Oxidation of redn by propene
Catalyst propene kJ/mole 1-butene kJ/mole kJ /mole
Bi2Mo06 59 46 65
Bi2MozO9 63 46 67
Bi2(M004)3 71 46 67
Bi203 59b
Footnotes:
a) From J . Peacock, et al.. J. Catal., 15, 398 (1969), copyright Academic Press.
b, From W. Martin, and J . Lunsford, J. h e r . Chem. SOC., 103, 3728 (1981).
However, a value of 92 kJ/mole has been quoted in another report
(M. White. and J . Hightower, J. Catal., 82, 185 (1983)).
and cobalt molybdate, the reaction is close to fist order in propene and zeroth
order in oxygen. The ammoxidation reaction requires a higher temperature (over
400OC). For a given propene and oxygen concentration in the feed, the relative
rates of production of acrylonitrile versus acrolein increases with the NH3/propene
ratio [42,59].
The activation energies for the oxidation of propene for different Bi-Mo-
oxides are shown in Table 11-4 [58]. Also shown in the table are the activation
energies for the oxidation of 1-butene and the reduction of the oxides by propene.
Since abstraction of the allylic hydrogen from propene is believed to be the rate-
limiting step in the oxidation of propene, the similar activation energies for this
reaction over Bi203 and Bi-Mo oxide of various BWo ratios suggest that Bi is the
site for propene adsorption and formation of n-allyl. This suggestion is supported
by the fact that the activation energy for the production of gas phase n-ally1
radicals frompropene on Bi203 is 67 kJ/mole, which is close to the value for
propene oxidation [69]. It is also supported by the observed constant activation
energy for the oxidation of 1-butene, which is also believed to proceed via the
formation of n-methylallyl, and for the reduction of the oxides by propene,
assuming that its rate-limiting step is allylic hydrogen abstraction from propene.
Callahan, et al. have also determined the activation energy for the oxidation
of propene [70], and reported values of 80-88 kJ/mole for various molybdates.
These values are the same for ammoxidaton of propene over the same catalysts,
which suggests that the rate-determining steps are identical in both reactions. The
differences in the activation energies between these values and those in Table 11-4
have not been explained.
On the multicomponent catalyst (M,MbBi,Mo,O,) at about 440°C, the
188
Table 11-5 Kinetic Isotope Effect in the Oxidation of Propene over Bi-Mo
Oxide. (From J. Caul., 87, 363 (1984), copyright Academic Press).
Reactant Relative Rate of Oxidation
1 .oo
0.85
0.98
0.55
difference in the activation energies between C02 formation and ammoxidation of
propene is 39 kJ/mole, and C02 formation and selective oxidation to acrolein is 5
kJ/mole. This implies a 34 kJ/mole difference in the overall process for nitrogen
versus oxygen insertion [42].
The activation energy for propene oxidation over cobalt molybdate ranges
from 51 to 67 kJ/mole [71,72]. The activation energy for acrolein formation is 37
kl/mole. There are reports that the rate of propene reaction is retarded by the
presence of the products acrolein and acrylic acid [73].
The kinetic isotope effect for propene oxidation over a Bi-Mo oxide catalyst
has been determined by Adams and Jennings using C3H, and C3D6 [44,45]. In
these studies, it is assumed that the first and second H abstraction have the same
isotope effect. Then the value of kH/kD is deduced from the data. This value
depends on the temperature. It is 2.3 k 0.4 at 365"C, and 1.8 f 0.3 at 475°C.
These values are very close to the theoretical values for the dissociation of a C-H
or versus a C-D bond. It is further found that the isotope effect is much larger if
the D atom is located in the CH3 group than in the CH2 group. This is illustrated
in Table 11-5.
Using [2,3,3,3-&]-propene, Krenze and Keulks have observed kH/ kD values
of 1.7 to 1.8 at 450°C and 1.5 to 2.2 at 350°C over Bi2M03012, Bi2M006, and
Bi3FeMo2OI2 [66]. The close
agreement of this value on Biz03 and Bi-Mo oxides again suggests that the
abstraction of the allylic H to form an adsorbed x-ally1 species is the rate-
determining step, that Bi ion is involved in this step, and the intermediate is a rc-
allyl. The isotope effect on the activation energy in the formation of desorbed gas
phase x-ally1 radicals from Bi2O3 has been determined over 365475°C to be 67
kJ/mole for C& and 74 kJ/mole for C3D6 [541.
Ammoxidation exhibits a similar kinetic isotope effect as oxidation when
investigated using [3,3,3-d3]-propene. This shows that the two reactions have the
same rate-limiting steps [44,45].
On Bi203, the value is 1.7 at 400°C [54].
SELECTIVE OXIDATION I 189
Nature of Catalysts (Bismuth Molybdate)
According to the mechanism in Fig. 11-4, the catalyst provides the function
for allylic hydrogen abstraction, C-O or CbJ bond formation, and activation of
gaseous oxygen. In addition, the catalyst undergoes redox cycles during the
reaction. Grasselli and Bunington have summarized these requirements and
assigned individual components in multicomponent oxides based on bismuth
molybdate and other selective oxidation catalysts to these functions [59]. Their
summary is shown in Table 11-6.
These assignments are very helpful towards understanding the role of the
catalysts. Although the emphasis in these assignments is on the nature of the
cations, it is understood that the oxide ions bonded to these cations are just as
imponnat.
For bismuth rnolybdate, the oxide ion bonded to Bi is proposed to be
responsible for allylic hydrogen abstraction. The similar kinetic parameters
already mentioned earlier for this catalyst and bismuth oxide support this proposal.
The x-ally1 species is proposed to adsorb on a Mo ion. This is supported by some
but not all evidence. For example, it has been observed that propene oxidation on
bismuth oxide yields hexadiene, which can be produced by coupling of two ally1
radicals [74,75]. Thus n-ally1 is produced and presumably can adsorb on Bi ions.
lSO-labeled bismuth molybdate can be prepared such that l80 is concentrated
either in the Mo layer or i n the Bi202 layer. When propene is oxidized over this
oxide, the oxygen label in acrolein is consistent with the view that propene is first
oxidized by the Bi202 layer [76]. This implies that propene is adsorbed on a Bi
ion.
On the other hand, unsupported Moo3 can oxidize propene to acrolein. Thus
adsorption of x-ally1 on Mo ion is possible. Furthermore, as mentioned earlier,
adsorption of propene on Bi-Mo-0 results in the formation of MoS+ ions [ 58] ,
which suggests that electron transfer from adsorbed x-ally1 to Mo ions occurs.
There are data which suggest that Bi ions in conjunction with cation
vacancies are important. Sleight and coworkers [77] have shown that in the
oxidation of propene and butene on PbMo04, the rate of production of selective
oxidation products increases with the amount of cation vacancies introduced when
Pb is substituted by Bi to produce Pbl-3xBi2x@xMo04. Later work by Brazdil, et al.
shows that the important species are cation vacancies associated with Bi ions [16].
In the Pb0.84-3xB~.08Na,,08La2x@xMo04 system, the Bi content can be kept
constant, and cation vacancies can be introduced by the incorporation of La. It is
found that with increasing cation vacancy density, the rate of ammoxidation of
propene and the acrylonitrile yield increase, while the selectivity remains
constant. However, in the Pb-La-Mo-0 system that does not contain bismuth, the
yield and selectivity for acrylonitrile are both low and independent of the density of
cation vacancies. Thus cation vacancies are important only when they are
associated with Bi ions.
Although the current view is that sites involving Bi are responsible for allylic
hydrogen abstraction, there are data that suggest other possibilities. For example,
when l-butene is oxidized over BiOCl and BiOBr, which have the same type of
(Bi2022+)n layer structure as Bi2Mo06, butadiene is formed very selectively. The
190
Table 11-6 The Functions of Various Components in the Selective Oxidation
Catalysts. (From Ind. Eng. Chem. Prod. Res. Devel., 23, 393 (1984), copyright
American Chemical Society).
Function
Catalyst allylic H alkene chemisorption redox coupleb
abstraction' and 0-insertion
Multicomponent Bi3+(5d106s26p0) Mo6+(4d05s0) Fe2+/Fe3+
bismuth
molybdate
TezMo07, Te4+(4d1 5s2 5p0) Mo6+(4d0 5s') ~e3+/ ~e4+
(Te,Ce ,Mo)O,
Fe,S b,O, Sb3+(d1 O5s25po) S6+(5S05PO) Fe2+/Fe3+
USb3010 u5+(5S26d07S0) s bs +( 5s05pO) u5+/u6+
Footnotes:
a) The lattice oxide ions bridging these cations and Mo6+ or Sb5+are for allylic
b, For activation of gaseous oxygen.
H abstraction.
catalyst activity is not high, and no isomerization of butene occurs. I n contrast,
the h2Md6 catalyst that has MOO^^-),, layers is active in isomerization of
butene, but not active in selective oxidation. These results lead to the conclusion
that butene adsorption and allylic hydrogen abstraction take place on the Mo
layers, while oxidation takes place using the lattice oxygen of the Bi layer [78].
The formation of carbon-oxygen bond (0 insertion) is a critical step in the
production of oxygenates. The mechanism in Fig. 11-4 shows that the surface
lattice oxygen is the active species in this step. On bismuth molybdates, it is now
well established that at the higher operating temperatures of about 45OoC, lattice
oxygen accounts for nearly 100% of the oxygen incorporated into acrolein and
carbon dioxide [66,79-811. When a mixture of propene and 1802 are passed over a
catalyst containing l 60, the acrolein and C02 produced initially contain practically
only l 60, which can only come from the lattice. Exchange between the lattice
oxygen and gaseous oxygen or acrolein can be independently determined to be too
slow to account fo the results under similar conditions. It is further shown that in
some catalysts, all of the lattice oxygen can participate in the reaction due to rapid
diffusion of lattice oxygen.
SELECTIVE OXIDATION I 191
The extent of lattice versus adsorbed oxygen as being the proximate origin of
oxygen for the C-O bond formation at a lower temperature of about 350" is not
unequivocally established. One report shows that all acrolein is formed from
lattice oxygen [66], whereas another one shows that the contribution from adsorbed
oxygen increases with decreasing temperature [81].
That lnttice oxygen is the major proximate source of oxygen in the formation
of acrolein has now been demonstrated for Sn-Sb-0, U-Sb-0 [82,83]. and Sn-
Mo-0 [84], in addition to Bi-Mo-0. This property is not universal. In the case of
cuprous oxide, acrolein is formed with adsorbed oxygen [85]. There is also IR
evidence that adsorbed propene reacts with 02- on ZnO to form an adsorbed
acrolein [86,87].
The formation of a C-O bond using lattice oxygen implies reduction of the
cations in the oxide, which must be reoxidized for a steady state operation.
Indeed, exposure of bismuth molybdate to propene causes the reduction of Mo6+to
MoS+[88], which can be detected by EPR. Coupled with the earlier discussion
that the B i 4 group is involved in allylic hydrogen abstraction, it is possible that
during catalysis, the oxygen neighboring bismuth is removed in water formatkn,
the lattice oxygen at the molybdenum center is removed in the formation of
acrolein. Both oxygen species are replenished by the diffusion of lattice oxygen,
and eventually the lattice is reoxidized by gaseous oxygen.
According to this picture, there must be an inlet and an outlet in the catalyst
for oxygen. One outlet is the oxygen species in the inolybdooxo group (Mo=O).
The inlet is a pair of oxygen vacancies (I$), perhaps in an ensemble with Bi ions,
and the reoxidation proceeds as [89-911:
(Bi++)202- + O2 - (~i3+02-)~02- (11-9)
In addition to isotopic studies, the involvement of the lattice oxygen can also
be demonstrated by monitoring the vibrational spectra of the oxide. Molybdenum
oxide, molybdates and vanadates possess characteristic bands in the 800- lo00
cm-' region that can be assigned to terminal M=O vibrations (see Chapter 2). The
frequencies of these bands depend on the oxygen isotope, and possibly on the metal
oxidation state of the cation. For example, the shift in this band has been
interpreted as due to the transformation of Mo6+=0 to Mo5+=0 on adsorption of
butadienes [92]. Broadening and shifts of bands in this region of a bismuth
molybdate catalyst have been observed after it is used in the oxidation of propene
with lSO2 [93,941. From the magnitudes of the shifts, it was concluded that
practically all of the lattice oxygen in Bi2M006 (y phase) and Bi2M0209 (p phase)
are involved in the reaction, while much less is involved in Bi2M03012 (a phase)
[93]. This is probably due to the much slower diffusion of lattice oxygen in the a
phase than in the other two phases.
These results support the scheme in Fig. 11-4 that M H groups are involved
in the reaction. That the presence of M H groups is important for high
selectivity on molybdates has been pointed out by Trifib. It has been observed
that the molybdates of Bi, Fe, Co and Mn, which show strong infrared absorption
in the 920-970 cm-' region, are selective oxidation catalysts, while molybdates of
192
Ca, Pb, and Tl, which do not show strong absorption in that region (implying no
M d bonds) are nonselective catalysts [96,97]. In addition, the higher activity
of bismuth molybdate than Fe, Co or Mn molybdates is correlated with its slightly
weaker Mo=O bond, as indicated by a lower vibrational frequency. However,
the presence of M d groups is not a sufficient condition. Na and K molybdates
have Mo=O groups, but are nonselective catalysts [981.
The selectivity of bismuth molybdate for acrolein depends little on the partial
pressure of gaseous oxygen. The selectivity on Co, Fe(I1) and Mn molybdate,
however, decreases with increasing oxygen partial pressure. This has been
correlated with the octahedral coordination of Mo in Bi-Mo-0, and tetrahedral
coordination in the other molybdates [99]. No direct correlation between the
amount of Mo=O and the activity or selectivity of the catalyst has been reported.
It has also been suggested that molybdates that contain isolated or comer-sharing
Moo6 octahedra as in Mo17047 and BizMO06 [loO,lOl] are more active or
selective catalysts than those with edge-sharing octahedra as in Bi2M03012. or
those with layer structures as in Moo3 [1021.
In the scheme in Fig. 11-4, the active site is shown as a cluster of bismuth ion
and molybdenum dioxo (I) or diimido (IV) species. Experimental results
correlating XP S intensities of bismuth and molybdenum in Bi-Mo-0 with catalytic
activity support the view that the active sites consist of bismuth-molybdenum pairs
[103,104]. There is no direct evidence to support the presence of dioxo species.
The involvement of diimido species is supported by data in ammoxidation that the
acrylonitrile/acrolein ratio increases linearly with the [NH3]2/[propene] ratio [42].
which fits the model in which substitution of two Mo=O species by two MwNH
occurs at the active site.
Other Molybhtes
Cobalt molybdate CoMd4 is also a selective oxidation catalyst for the
production of acrolein. It has two polymorphic modifications: a high
temperature (>4O0-45O0C) p and a low temperature a form [105]. Excess M a 3
is required for high selectivity for acrolein in the Co-Mo-0 system. It has been
reported that excess Moo3 stabilizes the a modification [ 1061 whereas excess
Co304 stabilizes the p form [107]. Although the matter has not been discussed, it
is also possible that excess Moo3 is the active site for the reaction, as is observed in
the Ni-Mo oxide system [108]. It has also been reported that with Ni-Mo oxides,
only samples containing more Moo3 than needed for NiMo04 produce acrylic acid
in propene oxidation [110].
When excess Moo3 is present in Co-Mo-0, acrolein can be produced from
propene in the absence of gaseous oxygen [lo91 until an equivalent of one
monolayer of lattice oxygen is consumed, The acrylic acid yield, however,
decreases rapidly with increasing degrees of catalyst reduction, and the rate of
reaction is slower in the absence than in the presence of gaseous oxygen.
The dependence of the activity and selectivity on the surface crystallographic
orientation of Moo3 has been studied recently. Volta, et al. have studied the
reaction over a series of Mo03/graphite catalysts prepared with different
calcination times and temperatures [ 11 1,1121. These catalysts have different
SELECTIVE OXIDATION I 193
distributions of exposed crystal faces. A linear correlation is observed between
the yield ratio of acroleiqK02 and the ratio of (100)/(010) surface areas. It is
concluded that acrolein is produced on the (100) face of Moo3, and C02 is
produced on the (010) face. Other explanations of these data have been advanced
[ 113,1141. In one report, it was concluded that acrolein was produced on the (010)
face, and combustion, on the (100) and the (101) faces. This latter assignment is
supported by the observation that the yield of acrolein in the oxidation of ally1
halides is proportional to the surface area of the (010) face of Moo3 [114].
Another example of crystal-face specificity has been reported for the
multicomponent Mnl -x4xV2-2xM02x0,j catalyst [ 1151.
Effect of Modifiers to Molybdates
Various modifiers have been used to further improve the activity and
selectivity of bismuth molybdates. These have led to the development of the
multicomponent catalysts. However, detailed understanding of the chemical
effects of the additives is lacking. In many cases, only observations of the effect
are reported.
When Ce is substituted for some Bi in Bi2(M00~)~, high catalytic activities in
propene ammoxidation are observed at Bi/Ce ratios that correspond to the
maximum solubility of Bi in Ce(Mo04) and of Ce in Bi2(Mo04),. A high activity
is also observed at a Ce concentration that correspnods to the point of equal
solubility of Ce in Bi molybdate and Bi in Ce molybdate [116,117]. Substitution
of Bi by La is less effective than by Ce [95]. This is interpreted as due to the fact
that Ce undergoes redox (e- +Ce4+ + Ce3+) more readily than La or Bi, and
more effectively facilitates the reoxidation and reconstruction of the Bi-Mo-0
phase.
Thcre are reports that addition of Fe203, CrzO3, CuO, Te02 or Se02
facilitates the formation of the a and p phases of bismuth molybdates during the
preparation of the catalysts [118]. Addition of BiP04, F%MqO12, or Cr2M03012
to Bi2M03012 also increases the formation of the a phase [119].
The current industrial multicomponent catalyst, Me,F%B&M%PiK,O, where
Me= Ni, Co, or Mg is essentially a Me-Bi-Fe molybdate promoted by P and K. In
some recent publications, it is suggested that the primary components of this
catalyst are femc molybdate and Bi3(Fe04)(M00~)~ [ 120,1211.
Alkali metals are promoters in the supported Moo3 system. At low alkali
metal concentrations, the promoting effect decreases as Cs>Rb >K >Na >Li [92].
This trend is inversely related to the electronegativity of the alkali metal.
Addition of V [I221 or Sn [123] to Moo3 does not produce a selective
catalyst for acrolein in propene oxidation. On the other hand, Te02-Mo03 is very
active and selective both for propene oxidation to acrolein [124,125] and for
ammoxidation [126]. Ce-Mo-Te oxide is also an active and selective ammoxid-
ation catalyst. A catalyst prepared by coprecipitation of all the components
consists of essentially a ternary (Ce,Mo,Te) oxide, a-Ce2Mo4OI5 and/or p-
Ce2M03013 [127]. Ni-Mo-0 and Cu-Mo-0 have also been reported to have
reasonable selectivities [128,129,130].
In the Co-Mo-0 system, a small amount of Te has been found to be an
194
effective promoter in the oxidation of both propene [128] and butene [131]. Te is
found to be enriched at the surface [105]. Addition of Fe, Bi and V also increases
the activity and selectivity in acrolein production [105]. In general the Co-Mo-0
system produces more acrylic acid than the Bi-Mo-0 system.
11.6 EFFECT OF WATER ON PROPENE OXIDATION
When water is added to a feed of propene and oxygen, 2-propanol is often
formed either as the major product or as the initial product which is then
dehydrogenated to acetone.
On a Mo03/Al203 catalyst [132], acetone is produced with 83% selectivity at
300°C. This
contrasts sharply the situation for acrolein production where the proximate source
of the oxygen atom in acrolein is a lattice oxide ion. If D20 is used, the deuterium
atoms rapidly exchange with the hydrogen atoms of the end carbons of the reactant
propene to form (DIH)3C-CH=C(D,H)2. The hydrogen at the center carbon does
not undergo exchange. When deuterated propene is used, no kinetic isotope effect
is observed if the deuterium atoms are at the end carbons, as would be expected if
the exchange of these atoms with hydrogen atoms in water is rapid. A kH/kD ratio
of 2.2 is observed if the deuterium atom is at the center carbon. This behavior of
the kinetic isotope effect is opposite that observed in acrolein production.
It has been proposed that the reaction proceeds via a carbenium ion
intermediate [132]:
If H21S0 is used, the l 8 0 atom is incorporated into acetone.
MoS++ H20 -+MoS+OH- + H+(ad) (11-10)
H+(ad) + C3H, + C3H7+(ad)
C3H7+(ad) + Mo5+OH- + Mo5++ C3H70H
C3H70H + 1/202 + (CH3)ZCO + H2O
In this mechanism, a surface coordinatively unsaturated MoS+is assumed to be the
active site. However, there is no direct evidence for the presence of MoS+ in the
catalyst.
Whether desorbed 2-propanol is a significant product is questionable at
temperatures higher than about 30O0C when the equilibrium concentration of 2-
propanol is small. Under these conditions, it is possible that acetone is formed
from a surface alkoxide [ 1341:
H3qHp- h
b
H
-H 0
I
H
0
C& + J F=== ? -+(CH&CO + J (11-11)
*
SELECTIVE OXIDATION I 195
The mechanism in eq. (1 1-10) explains the data over a Sn-Mo oxide catalyst
at 150°C [133]. On this catalyst, 2-propanol has been shown to be the only
product at low conversions. Acetone begins to appear as the conversion increases.
The reaction rate at high conversions is suppressed by methyl ethyl ketone.
In the presence of water, propene can also be oxidized to acetone on a VzOs
catalyst at 200°C [135]. As the temperature increases, the acetone yield
decreases, whereas the yields for acetic acid and C02 increase. Over a V-P oxide
(VP about unity), selective production of acrylic acid is observed. Addition of Te
suppressess the selectivity for combustion such that at 80% conversion, a
combined selectivity to acrylic acid, acetic acid, and acrolein in excess of 60% is
obtained. Decreasing the water partial pressure in the feed decreases the selectivity
for acrylic acid and acetic acid, but increases that for acrolein [135].
REFERENCES
1. P. Mars and D. van Krevelen. Chem. Eng. Sci. Suppl.. 3, 41 (1954).
2. B. Grzybowska, and A. Mazurkiewicz, Bull. Acad. Polon, Sci. Ser. Sci. Chim.
27, 149 (1979).
3. G. W. KeuLks, and L. D. Krenzke, Proc. 6th Intern. Cong. Catal., London,
Paper B-20. 1976; J . Catal., 61, 316 (1980).
4. Y. Moro-oko. Y. Takita, and A. Ozaki, J . Catal., 27, 177 (1972).
5. W. Ueda, Y. Moro-oka, and T. Ikawa, J . Chem. SOC. Faraday Trans.
I, 78. 495 (1982).
6. R. K. Grasselli, Appl. Cafal.. 15, 127 (1985).
7. R. K. Grasselli, J . F. Brazdil, and J . Burrington, Proc. 8th Intern. Cong. Catal..
5, 369 (1984).
8. R. S. Liu, M. Iwamoto. and J . H. Lunsford, J. Chem. SOC. Chem. Commun.,
78 (1982).
9. H. F. Lin, R. S . Liu, K. Y. Liew, R. E. J ohnson, and J . H. Lunsford,
J. Amer. Chem. SOC., 106, 4117 (1984).
10. L. Mendelovici. and J . H. Lunsford, J. Catal., 94. 37 (1985).
11. M. B. Ward, M. J . Lin. and J . H. Lunsford, J. Catal.. 50. 306 (1977).
12. Y. Takita. Y. Moro-Oka. and A. Ozaki, J . Catal., 52, 95 (1978).
13.T. Ono, T. Ikehata, and Y. Kubokawa, Bull. Chem. SOC. Jpn., 56, 1284 (1983).
14. W. E. Slinkard and P. B. DeGroot, J . Catal., 68, 423 (1981).
15. A. W. Sleight, and W. J . Linn, Ann. New York Acad. Sci., 272
16. J . F. Brazdil, L. C. Kartisek. R. K. Grasselli. J. Catal.. 81, 142 (1983).
17. W. M. H. Sachtler. G. J . H. Dorgels, V. Farenforf and R. J. H. Voorhoeve.
18. I . Ziolkowski, J . Catal.. 80, 263 (1983).
19. I. Haber, J. J enas. M. Schiavello, and R. J . Tilley, J . Catal., 82, 395 (1983).
20. R. K. Grasselli, and T. D. Bumngton, Adv. Catal., 30, 133 (1980).
21.M. Ai, and T. Ikawa, J . Catal.. 40, 203 (1975).
22 (1976).
Proc. 4th Intern. Cong. Catal., 1, 355 (1970).
196
22. R. A. Zhdan. A. P. Shepelin, Z. G. Osipova, and V. D. Sokolovski, J . Catal.,
23. J. M. Tatibouet, J. E. Germain, and J . C. Volta, J. Catal., 82, 240 (1983).
24. J. M. Tatibouet, and J. E. Germain. J . Catal., 72. 375 (1981).
25. F. Tdi ro, Chim. Ind. (Milan), 56, 835 (1974).
26. P. C. H. Mitchell and F. Trifiro, J. Chem. SOC. (A), 3183 (1970).
27. K. Mori, M. Inomata, A. Miyamoto. and Y. Murakami, J. Phys. Chem..
28. M. Iwamoto, Y. Yoda, N. Tamazoe, and T. Seiyama, J. Phys. Chem.,
29. B. L. Yang, M. C. Kung. and H. H. Kung, J. Catal., 89, 172 (1984).
30. G. Keulko, and Z. Yu, Proc. 8th Int ern. Cong. Catal., Vol. III, p. 289, 1984.
31.M. C. Kung, W. H. Chang, and H. H. Kung. J . Phys. Chem., 83, 1737 (1979).
32. R. K. Grasselli. and J . D. Burrington, Ind. Eng. Chem. Prod. Res. Devel.,
33. J. Haber, in "Solid State Chemistry in Catalysis", ed. by R. K. Grasselli
34. R. S. Liu, M. Iwamoto, and J. H. Lunsford, J. Chem. Soc.. Chem. Commun.,
35. M. M. Khan, and G. A. Somorjai, J. Catal., 91, 263 (1985).
36. H. F. Lin, R.-S. Liu. K. Y. Liew. R. E. Johnson, and J. H. Lunsford,
37.K. J. Zhen, M. M. Khan, C. H. Mak, K. B. Lewis. and G. A. Somorjai,
38. M. Iwamoto, J apanese patent JP5892630.
39. H. H. Kung, Ind. Eng. Chem. Prod. Res. Develop., 25. 171 (1986).
40. J . L. Callahan, and R. K. Grasselli. AZChE J., 9. 755 (1963).
41.F. J . Berry, Adv. Catal., 30, 97 (1981).
42. J. D. Burrington, C. T. Kartisch. and R. K. Grasselli. J . Catal., 81,489 (1983).
43. J. D. Burrington, C. T. Hartisch, and R. K. Grasselli, J. Catal., 87, 363 (1984).
44.C. R. Adams, and T. J . J ennings, J. Catal., 2, 63 (1963).
45. C. R. Adams, and T. J. Jennings, J. Catal., 3, 549 (1964).
46. C. C. McCain, G. Cough, and G. W. Godin, Nature (London). 198, 989 (1963).
47.W. M. H. Sachtler. Rec. Trav. Chim. Pays-Bas., 82, 243 (1963).
48. W. M. H. Sachtler, and N. K. DeBoer, Proc. 3r d. Int. Cong. Catal., I. (1965) p.252.
49. H. H. Voge, C. D. Wagner, and D. P. Stevensen. J. Catal., 2, 58 (1963).
50. R. K. Grasselli, and D. D. Suresh, J . Catal., 25. 273 (1972).
51. G. W. Godin. C. C. McCain, and E. A. Porter, Proc. 4th Int. Cong. Catal.,
52.N. W. Cant, and W. K. Hall, J . Cdal. . 22. 310 (1971).
53.N. W. Cant, and W. K. Hall, J. Phys. Chem., 75. 2914 (1971).
54. W. Martir, and J. H. Lunsford, J . Amer. Chem. Soc., 103, 3728 (1981).
55. D. Driscoll, and J . H. Lunsford. J. Phys. Chem., 89, 4415 (1985).
56. J. D. Burrington. C. T. Kartisch, and R. K. Grasselli, J. Org. Chem.,
57. C. R. Adams, Proc. 3rd Int ern. Cong. Catal. I , 1965, p. 240.
58, 8 (1979).
87, 4560 (1983).
82, 2564 (1978).
23, 393 (1984).
and J. F. Brazdil, American Chemical Society Symp. Series no. 279. 1985. p. 1.
78, (1982).
J. Amer. Chem. Soc., 106,4117 (1984).
J . Catal.. 94, 501 (1985).
I, (1971) p.271.
46, 1877 (1981).
SELECTIVE OXIDATION I 197
58. J. M. Peacock, A. J . Parker, P. G. Ashore. and J . A. Hockey. J . Cafal.,
59. R. K. Grasselli, and J . D. Burrington. Ind. Eng. Chem., Prod. Res. Devel.,
60. B. Grzybowska, J . Haber, and J . J anus, J. Calal., 49, 150 (1977).
61.M. Imachi, R. L. Kuczkowski, J . T. Groves, and N. W. Cant, J. Cotal.,
62. HA . Choi, J .-T. Lin, and R. L. Kuczkowski, J. Cafal., 99, 72 (1986).
63. J. D. Burrington, C. T. Kartisch, and R. K. Grasselli, J . Cafal., 63, 235 (1980).
64. C. Daniel, and G. W. Keulks, J . Catal., 24, 529 (1972).
65. C. W. Keulks, M. P. Rosynek, and C. Daniel, Ind. Eng. Chem. Prod. Res. Dev.,
66. J . D. Krenze. and G. W. Keulks, J. Cafal., 61. 316 (1980).
67. G. W. Keulks, and M. P. Rosynek, Amer. Chem. Soc. Div. Petrol. Chem. Prepr.,
68. A. P. Gershkov, J. K. Kolchin, I. M. Gribov, and L. YaMargolis, Kinef. Katal.,
69. J . D. D~i.scoll, and J . H. Lunsford, J. Phys. Chem., 87. 301 (1983).
70. J . L. Callahan, R. K. Grasselli, E. C. Milberger, H. A. Strecker, I d .
71.M.V.C. Sastri, B. Viswanathan, V.C. Bhuvana, Proc. 7th Inter. Cong. Catal.,
72. Y. Moro-oka, S. Tan, and A. Ozaki, J. Catal., 12, 291 (1968).
73.0. M. Vinogradov, G. F. Vitnov, I. V. Luiksaar, and 0. V. Altshuler,
74.H. E. Swift, J . E. Bozik. and J . A. Ondrey. J. Catal., 21. 212 (1971).
75. K. Bruckmann. J . Haber. and J . J anus. Bull. Acad. Pol. Sci., Ser. Sci. Chim.,
76.T. Osubo, H. Mirura, Y. Morikawa, T. Shirasaki, J. Cafal.. 36. 240 (1975).
77.K. Aykan, D. Halvorson. A. W. Sleight, D. B. Rogers, J. Catal., 35, 401. (1975).
78. H. Miura, Y. Arai. K. Sugiyama, and T. Matsuda. J . Cafal., 68, 264 (1981).
79. G. W. Keulks, J. Catal., 19. 232 (1970).
80.R. D. Wragg, P. G. Ashore, and J . A. Hockey, J. Cafal.. 22. 49 (1971).
81.K. M. Sancier, P. R. Wentrcek. and H. Wise, J. Catal., 39, 141 (1975).
82. J . R. Christie, D. Taylor, and C. C. McCain, J. Chem. SOC. Faraduy Trans. I ,
83. P. Pendleton, and D. Taylor, J. Chem. Soc. Faraduy Trans I , 72, 1114 (1976).
84. Y. Moro-oka, Y. Takifa, and A. Ozaki, J . Cafal., 27. 177 (1972).
85. M. Akimoto, M. Akiyama, and E. Echigoya, Bull. Chem. Soc. Jpn., 49. 3367 (1976).
86. B. L. Kugler, and R. J . Kokes, J. Cafal.. 32, 170 (1974).
87. B. L. Kugler, and J . W. Gryder, J . Catal., 44, 126 (1976).
88. J . M. Peacock, M. J . Sharp, A. J . Parker, P. G. Ashore, and J . A. Hockey,
89. W. Linn. and A. W. Sleight, J. Cafal., 41, 134 (1976).
15, 398 (1969).
23. 393 (1984).
82. 355 (1983).
10, 138 (1971).
14, C55 (1969).
9, 1068 (1968).
Eng. Chem. Prod. Res. Dev., 6, 134 (1970).
Tokyo, (1980). B-32.
Kinet. Katal., 16, 671 (1975).
20, 813 (1972).
72, 334 (1976).
J. Catal., 15, 379 (1969).
90. D. A. G. van Ocffclcn. J. H. C. Van Hoolf, and G. C. A. Schuit. J . Carol .,
91. T. Osuba. H. Miura. Y. Morikswa, T. Shirosaki. J. Cdal . , 36. 240 (1975).
92. M. Aki moto. and E. Echigoya. J. Coral., 35, 278 (1974).
93. E. V. Hocfs. J . R. Monnicr. and G. W. Keulks, J. Cdah, 57, 331 (1979).
94. R. K. Grassclli, Appl. Carol ., 15, 127 (1985).
95. R. K. Grasselli. J . F. Rraxdil, J. D. Burrington. Infern. Cong. Cu d . , 8rh. V
96. F. Trifiro. P. Cent014 I . Pasquon. P. Ji ru. Pr cx. 41h Irucrn. Cong. Carol.,
97. P. C. H. Mitchell, and F. Trifiro. 1. Uhem. Soc. A , 3183 (1970).
98. L. Burlamncchi, G. Martini, and F. Trifiro, 1. Cu d . . 30. 393 (1973).
99. F. Trifiro. C. Capuio, and P.L. Villa, J . Less Common Meroh, 36. 305 (1974).
100. Dh. A. Hatist. C. J . Kapteyus. B. C. Lippcns. and C. C. A. Schuit, J. CafuL,
101. G. Rlassc. 1. Inorgvi. Nuclear Chem., 28, 1124 (1966).
102. D. B. Dadyburjor, S. S. Jewur. and E. Ruckenstein, Catal. Rev., 19. 293 (1979).
103. R. K. Grassclli, J . B. Burrington, and J. E. Brardil. 1. Chem. Soc., Fmoday Disc.,
104. I . Marsurra R. Schul K. Hirakawa. J. Cdd. , 63, 152 (1980).
105. B. Crzybowska. A. Miv.urkicwicc and J. Sl~~zynski, Appl. Carat..
106. T. C. Alkhazav, K. Yu A&hamov, and N. Kh. Allakhvcrdovc, Ki nel . Karol.,
107. P. Boutny, J.C. Daumas, R. Montarnal. P. Co d n c , and C. Pannclicr,
108. U. Ozkan, and G. L. Schreder, 1. Cuhl. , 95, 120 (1985).
109. B. Crzybwska, and A. MazurkiewicL Bull. Acad. Polon. Sci. Ser. Sci . Chbn..
27. 149 (1979).
110. C. Mwzocchia. F. DiKenzo, P. Centola, R. Del Rosso. in “Proc. 4t h Inrrernniional
Conierence in rhe Chmi sr r y and Uses oj Mol ybdenum“ , Climax Molybdenum
Co., Coldcn. Colo. 1982.
1 1 1 . J . C. Volla. M. Forissicr, F. Thmbald. and T.P. Pham, 1. C k m . SOC., Farad.
Disc.. 72, 225 (1981).
112. J.C. Volta. and 8. Moraweck, J. Chem. SOE. Chcrn. Commw.. (1980) 338.
113. J. Ziokowski, 1. Card, 80, 263 (1983).
114. K. 8riickmw K. Grabowski. 1. Hah. A. Ma~urkiewicr, J. Sloczynoki, and
T. Wiltowski. 1. Curd.. 104. 71 (1987).
115, J . Xiotkowski. and J . Janass. 1. Caful., 81, 298 (1983).
116. J . F. Brazdil, and R. K. Grussclli. 1. Coral.. 79, 104 (1983).
117. 1. F. Rwdi l , L. C. Glaesa. R. G. Tcllcr and R. K. Grassclli,
118. M. Ai. and S. Sumki. 1. Cord., 30. 362 (1973).
119. Ph. A. Batist. C. G. M. van der Moesdijk, I . Matsurra, and G. C. A. Schuit,
120. O.V. Krylov. Yu. V. Maksirnov, and L. Ya. Margol i s, J . Caiol.. 95. 289 (1985).
95. 84 (1985).
(1984) p. 369.
1. 310 (1969).
7, 33 (1967).
72, 203 (1982).
13, 223 (1985).
15, 1492 (1974).
Bul l . Soc. Ch h . F r me ( 1 968) 481 1 .
Reprints ACS Division of Perroleurn Chemisrry, 28, 1285 (1983).
1. Carol., 20, 40 (1971).
SELECTIVE OXIDATION I 199
121. T. S. R. Prasada Rao, and K. R. Krishnamurthy, J. Carol., 95, 209 (1985).
122. T. Ono, Y. Kubokawa, Bull. Chem. SOC. Jpn., 55, 1748 (1982).
123. T. 0x10, T. Ikehara, Y. Kubokawa, Bull. Chem. SOC. Jpn. 56, 1284 (1983).
124. Y. Amaud, J . Guidof J.Y. Robin, M. Romand, J . E. Germain, J. Chim. Phys..
125. T. V. Andrushkevich. G.K. Boreskov. L.L. Kuznetsova, L.M. Plyasova, Y. N.
126. J. C. J . Bart, and N. Giordano, J. Cafal., 64, 356 (1980).
127. J . C. J . Bart, N. Giordano, Ind. Eng. Chem. Prod. Res. Dev., 23, 56 (1984).
128, Ph. J aeger, and J.E. Germain. Bull. SOC. Chim. France, 11-12, I(1982) 407.
129. J . Haber. Kinet. Carol.. 21, 100 (1980).
130. C. Mazzochia, P. Centola, R. Del Crosso, G. Terzaghi, and I. Pasguon, Chim. I d . ,
131. P. Forzatti, P.L. Villa, D. Ercoli. G. Gasparini, and F. Trifiro,
132. N. Giordano. A. Vaghi, J . Bart, and A. Castellan. J. Catal., 38, 11 (1975).
133. Y. Takita, Y. Moro-oka, and A. Ozaki, J. Catal., 52, 95 (1978).
134. J . Buiten. J. Catal., 10, 188 (1969); 13, 373 (1969); 27, 232 (1972).
135. M. Ai. J . Catal., 101, 473 (1986).
73, 651 (1976).
Tyurin, and Y. M. Shchekochikhin, Kinet. Katal., 15,424 (1974).
55, 687 (1973).
Id. Eng. Chem. Prod. Res. and Devel., 16, 26 (1977).
Chapter 12
SELECTIVE OXIDATION CATALYSIS I1
12.1 SELECTIVE OXIDATION OF BUTENES
The selective oxidative dehydrogenation of butenes to butadiene (eq. 12-l),
and the selective oxidation of butenes to maleic anhydride (eq. 12-2) are both
industrially important reactions:
C4Hg + 3 0 0 - 4 0 0 0 c > c4H, + H20 (12-1)
C4Hg + 3 0 2 4 0 0 - 5 0 0 0 c ) C4H203 + 3H2O (1 2-2)
Other important reactions of butenes include the production of acetaldehyde and
acetic acid catalyzed by promoted vanadium oxides supported on rutile Ti02 [l]
and other vanadates, and the oxidation of 2-methylpropene (isobutene) to
methacrolein (2-methylprop-l-en-3-al) or ammoxidation to methacry lonitrile (2-
cyanopropene) catalyzed by molybdates and cuprous oxide:
(12-3)
0 2
C4Hg =@ CH3COOH, CH3CHO
( 12-4a)
(12-4b)
Selective oxidative dehydrogenation (eq. 12-1) can be carried out on many
catalysts including molybdates. vanadates. ferrites, uranium-antimony oxide, tin-
200
SELECTIVE OXIDATION II a01
antimony oxide and other antimonates. Selectivities for butadiene in excess of
85% have been obtained using these catalysts. Maleic anhydride can be produced
selectively on catalysts based on vanadium oxide and/or molybdenum oxide,
especially those promoted by phosphorous. A selectivity for maleic anhydride of
higher than 70% has been reported in a number of patents [2].
Reaction Mechanism
i) Oxidative Dehydrogenation:
water involves stepwise abstraction of two hydrogen atoms:
It is likely that the oxidative dehydrogenation of butene to butadiene and
(12-5)
This mechanism has been proposed by analogy to propene oxidation in which
dissociative adsorption of propene to formadsorbed x-ally1 is well established (see
Chapter 11). Adsorbed x-bonded butene (C4H8(ad)) and x-ally1 (C4H7(ad)) on
ferrites have been observed using infrared spectroscopy at room temperature [3,4].
It has also been shown that on ferrites, adsorbed butadiene is produced below
200°C. and the desorption of butadiene is rate limiting [5,6]. However, data at
ordinary catalytic temperatures of about 350°C are not available.
Butene isomerization accompanies dehydrogenation, but there are few studies
on this reaction during oxidation. Isomerization by reversing the allylic hydrogen
abstraction step (step I1 in eq. 12-5) is a possibility. On MgF%04 [8] and
CoF%04 [9], it has been proposed that isomerization and dehydrogenation take
place on separate sites [7] based on the fact that when a mixture of trans-2-C4D8
and trans-2-C4H8 is oxidized over the catalysts, there is no H/D isotope mixing
found in butadiene. Such mixing is expected if step I1 is readily reversible on the
oxidation sites. Isomerization also shows a smaller deuterium isotope effect than
oxidation [8,9], but its implication on the mechanisms has not been explored.
ii) Oxygenate Formation:
postulated to be [lo]:
The primary route for the oxidation of butene to maleic anhydride has been
(12-6)
(ad or g)
\ /-nd
202
Other possible intermediates that have been suggested include 45-
dihydrofuran and 2.5-dihydrofuran [11,121. Methyl vinyl ketone, acetic acid,
acetaldehyde, and carbon oxides are among the common side products [13]. This
mechanism is supported by the following results using V-P oxides (V/P 1. 1/1) as
catalysts. When used as the reactant feed under similar reaction conditions.
butene, butadiene, crotonaldehyde, and furan all yield substantial amounts of
maleic anhydride [13,14]. The selectivity for maleic anhydrik increases in the
sequence: butene c butadiene c furan. In the oxidation of 1-butene, substantial
conversion begins at -220°C. The major product below 250°C is butadiene
which becomes negligible at 280°C. As the temperature increases, the yield of
maleic anhydride increases and reaches a maximum at 300-330°C. This supports
butadiene as both an intermediate and a precursor for maleic anhydride. The CO
and C02 production increases with increasing temperature continuously. Small
amounts of furan, acetaldehyde, methyl vinyl ketone, and crotonaldehyde are also
observed between 250-330°C [141.
The product distribution on the V-P oxide also depends on the oxygen partial
pressure. At low butene/02 ratios or at low conversions, maleic anhydride and
COX are the only detectable products. At high 0 2 conversions, other intermediate
oxidation products appear, including butadiene [141. I n the absence of gaseous
oxygen, butadiene is the major product until the catalyst is too extensively reduced
to be active [15,161.
Selective production of mdeic anhydride from butene, butadiene, and furan
(with selectivity increasing in this order) has also been reported for NiMo04
containing 15% excess Moo3 [17,18]. The reaction sequence (12-6) probably
applies to this catalyst.
Kinetics
i) Oxidative dehydrogenation:
On most catalysts, the oxidative dehydrogenation of butene to butadiene
shows a positive order in butene and zero order in oxygen. In addition, a negative
order in butadiene, indicative of product inhibition, is often reported, especially at
lower temperatures. The order in butene depends both on the temperature and the
pressure. It usually decreases with increasing butene pressure or decreasing
temperature. For example, on bismuth molybdate, the rate is first order in butene
over the temperature range 343-500°C [19]. The rate depends on the butene
isomer. At 460°C. the rate for 1-butene is several times greater than for cis-2-
butene, which is greater than for trans-2-butene [19]. Below 4OO0C, butadiene
inhibits the reaction. In contrast, water or carbon dioxide has little effect on the
reaction. The same kinetics is observed on Fe-promoted Bi-Mo oxide [20].
Unlike bismuth molybdates or ferrites, the reaction on the scheelite
Pbl -3xBi2x$x(Mo04) system shows a zeroth order in butene and a positive order in
oxygen [211.
The formation of butadiene shows a deuterium isotope effect. The ratio of
rate constants kH/?.D is 3.9 at 300°C and 2.6 at 400°C on MgFe204 (8), and 2.4 at
430°C for CoFe204 [9]. The large isotope effects indicate that the breaking of
C-H (C-D) bonds is involved in the slow step of the reaction. This conclusion is
SELECTIVE OXIDATION LI 203
supported by the relative reaction rates of various substituted butenes [22]. On a-
Fe203, the relative rates at 270°C are 1.3 : 1.0 : 0.9 : 0.7 for
F 7
C
I
C=C-C<<, C=G<<, C=C<<, and C-C=C<, respectively. These relative
rates parallel the expected relative strengths of allylic C-H bonds in these
compounds, suggesting that breaking of these bonds to form allylic species is
involved in the slow reaction step. When the reactivities are normalized to per
hydrogen atom at the allylic position, they are found to be 1.4, and 12 for primary,
secondary and tertiary allylic C-Hs.
The activation energy for the reaction of butene on the scheelite
Pbl-3xBi2x@n(Mo04) system [21] is 147 kJ/mole, which is close to the 139 kJ /mole
for propene oxidation. This value does not depend on the concentration of cation
vacancies, although the selectivity and the rate both increase with increasing values
of x. The rate of isomerization increases with increasing x, and the ratio of
isomcrization to oxidation is constant for a given temperature.
The values of the activation energy depend strongly on the catalyst and the
reaction conditions. For a- and y-Fez03, the values are about 105 and 63 kJ
mol-', respectively, at about 300°C [22]. For Bi3(Fe04)(Mo04),, the value
decreases from 209 kJ mol-l below 400°C to 75 kJ mo1-l above 400°C due to a
change in the rate-limiting step from butadiene desorption at low temperature to
surface reaction at high temperature [23]. A similar decrease from 160 to 40 kJ
mole-' has also been reported on Fe-promoted bismuth molybdates, and on defect
scheelite systems such as Pbo.s~Ce+os$o.04 Moo4 and Bi0.93@0.07V0.79 M00. 2~04
for which the activation energy decreases from about 147 to about 63 kJ /mole
above 400°C [21].
The reported activation energy for bismuth molybdate varies widely. It
ranges from 109 [19] to 168 kJ/mole [24] at about 400°C. The value also
decreases from high to low temperature, in contrast to the other oxides mentioned
earlier. In one report [21], it decreases from 159 to 59 kJ/mole. One interpretation
assumes that the rate-limiting step at low temperatures is the desorption of
butadiene, and the rate-limiting step at high temperatures is allylic hydrogen
abstraction. This interpretation is consistent with the results from butene and
butadiene on bismuth molybdate [25]. When compared under identical
conditions, the activation energies for 1-butene oxidation are the same for a, p and
y-bismuth molybdates (see Table 11-4).
ii) Oxygenate Formation:
The kinetics of the oxidation of butene to maleic anhydride on V-P-0 has
been reported [26,27]. At about 380°C and for a butene pressure of about 1 P a in
air, the rate of disappearance of butene follows the expression [27]:
k€l kO ' H '0
k, ' 0 -t % kH ' H
rate = (12-7)
Where kH and are constants, PH and PO are the partial pressures of butene and
oxygen, and % is the average number of oxygen molecules required per
hydrocarbon molecule oxidized. This rate expression suggests inhibition by
reactants at high butene partial pressures. This has been observed [30]. Below
1% concentration of butene, the reaction rate follows a first order kinetics [13,27].
1-Butene and 2-butene show similar behavior. The activation energy is around 84
kJ/mole [27]. Isomerization of butenes accompanies oxidation [28a].
Nature of Catalysts
i) Catalysts for Oxidative Dehydrogenation:
Bismuth molybdates, which are selective for the oxidation of propene to
acrolein, are also selective for oxidative dehydrogenation of butenes. These
oxides have been discussed in detial in Chapter 11, and will not be repeated here.
However, it is interesting and important to point out two differences between
oxidative dehydrogenation of butene and oxidation of propene to acrolein on these
catalysts. The first difference is that the lattice oxygen involved in the formation
of water during butene oxidation is different from that incorporated into propene to
form acrolein [28] (see section 11-3). The second difference is that, although
acrolein is produced with high yield and selectivity from propene on bismuth
molybdate, selective dehydrogenation is the dominant reaction for butene. Little
furan, maleic anhydride, or oxygenates are produced.
On unsupported [29] and graphite-supported Moo3 catalysts [31], oxidative
dehydrogenation of butene has been shown to be crystal-face specific. A linear
correlation is observed between the ratio of the surface areas of the (100)/(010)
faces and the ratio of butadiene to C02 production in the oxidation of 1-butene. It
has been established that butadiene is mostly formed on the (100) plane, and COX
on the basal (010) plane.
On many selective oxidative dehydrogenation catalysts, the reaction proceeds
with the same initial activity and selectivity in the absence and presence of gaseous
oxygen (see Table 11-2). This implies that the formation of water involves lattice
oxygen, although there has been no study to determine the proximate origin of the
oxygen atoms in the product water under steady state conditions in the presence of
gaseous osxygen. It has been
reported that the selectivity for butadiene is higher in the absence than in the
presence of gaseous oxygen [541.
It has been observed that fenites of the spinel structure are more selective
than those of the corundum structure, especially at higher temperatures (near
400°C) [7,32]. The difference is particularly evident when comparing a-Fe203
(corundum) with y-Fe203 (spinel) [22]. In one report, the much higher selectivity
for butadiene on y-Fe203 has been explained by two factors: adsorbed n-ally1 or
butadiene on y-Fe203 is much less susceptible to degradation by gaseous oxygen,
and the activation energy for desorption of butadiene is lower on y-Fe203 [32].
This latter effect might be due to the fact that surface coordinatively unsaturated
cations derived from the bulk tetrahedral Fe3+ions which are present only in the
spinel structure bind butadiene less strongly than those derived from the bulk
octahedral Fe3+ions. Indeed, a rough correlation has been reported between the
Fe-Te oxide does not fit this generalization.
SELECTIVE OXIDATION II
fraction of bulk tetrahedral Fe ions and the production rate of butadiene on the Cr
substituted MgFe204 [33]. Another explanation has been advanced that the
diffusion of lattice cation is faster in a spinel than in a corundum because of the
presence of rows of unoccupied octahedral holes in a spinel. The rapid diffusion
allows rapid reduction and reoxidation of the oxide during reaction [9].
When a femte catalyst is reduced, such as from Fez03 to Fe304, the oxide is
no longer active for dehydrogenation, although it is still active for cis-trans
isomerization and double bond migration. This has led to the suggestion that Fez+
is responsible for isomerization [34,35]. Reoxidation of Fe304 at low
temperatures (<300°C) produces y-F%03 which is a highly active and selective
catalyst for oxidative dehydrogenation of butenes [34]. Probably because of this
conversion, prereduction of iron oxide also increases significantly the selectivity in
the dehydrogenation of ethylbenzene to styrene [36].
In addition to the crystal structure, the selectivity also depends on the
crystallite size. On a series of a-Fe203 with a crystallite size ranging from about
2.5 nm to 60 nm, theselectivity for butadiene decreases from about 80% to about
55% [37]. The exact reason for this dependence is not fully understood.
Mossbauer effect, X-ray, and magnetic characterization of the samples show only
the presence of a-F%03. This rules out the possiblity that the effect is due to the
presence of other bulk phases. One explanation for the effect is that the reaction is
crystal-face specific, and different proportions of various crystal faces are present
on crystallites of different sizes. Another explanation is that smaller crystallites
supported on silica are more difficult to be reduced than larger crystallites [38,39]
and the different redox properties result in different catalytic properties. It is
interesting that on the same series of oxides, the activation energy in N20
decomposition is found to be lower on the sample that contain very small
crystallites [40]. Since desorption of oxygen is the rate-limiting step in N20
decomposition, this observation may indicate different reactivites of adsorbed
oxygen on different iron oxide samples.
The activities and selectivities of a series of iron-containing compounds have
been correlated to their heats of adsorption of l-butene. On a-F%03, Fe304,
Fe4Bi209, FeSb04, FeAs04 and FeP04 [41], it has been found that oxides that
have high AH's of adsorption are nonselective, and combustion is the major
reaction. Oxides that have low AH's are active for isomerization, and high
selectivity for oxidative dehydrogenation are found for oxides of intermediate AH's
(FeSbO, and FeAs04). For these two oxides, two forms of adsorption of 1-butene
are observed: a fast and weak and a slow and strong adsorption.
V-Mg oxides have also been found to be selective for this reaction. It has
been proposed that the active site is associatcd either with octahedrally
coordinated bulk vanadium ions that are exposed on the surface [42] or with
surface V043- complexes [43]. It has also been reported that the activity
correlates wilh the intensity of an EPR signal assigned to V02+ [44]. Addition of
Na' ions to a silica-supported vanadia catalyst increases the selectivity for
butadiene substantially, but decreases the activity [45].
206
ii) Catalysts for Oxygenate Formation
The V-P-0 catalyst has been studied extensively and the results have been
recently reviewed [2,46]. It is established that a selective catalyst must maintain a
P/V ratio between 0.9 to 1.3. V20~/Si02 without phosphorous is slightly inferior
to those with phosphorous in selectivity for maleic anhydride from butene,
although it is totally nonselective for butane oxidation (unlike V-P-0) [47].
V2O5/riO2 shows high selectivities for acetic acid and acetaldehyde when used in
the oxidation of butene in air and steam [l].
It has been
proposed that in these catalysts, the ability of the V ion to undergo redox cycles is
very important. When a catalyst is quenched from reaction conditions, V(1V) is
found to be the major component, but V(II1) is also present when the catalyst is
used under conditions selective for butadiene production (lower temperature,
higher butene/02 ratio), while V(V) is present when the catalyst is selective for
maleic anhydride production (higher temperature, lower butene/02 ratio). These
results are shown in Fig. 12-1 [46]. The data on the valence state of vanadium were
obtained by chemical analyses and they were confirmed by diffuse reflectance
measurements of the catalysts. Based on these findings and the fact that the states
of the catalysts are interconvertible, the scheme in Fig. 12-2 has been proposed.
In this scheme, the V(II1)-V(1V) couple is involved in the oxidative
dehydrogenation of butene to butadiene, and the V(1V)-V(V) couple is involved in
the oxidation of adsorbed butadiene to maleic anhydride. Depending on the
reaction conditions (temperature and butene/O2 ratio), the catalyst surface can be
in one of these states: (i) a reduced state (V(II1) and V(1V)) in which the main
product is butadiene; (ii) a state with contemporary presence of V(II1). V(IV), and
V(V) in which the main product is maleic anhydride, and (iii) a strongly oxidized
state (V(1V) and V(V)) in which the main products are carbon oxides. In addition
to changing the product selectivity, the different reaction conditions and surface
valence states also affect the catalyst life. For example, deactivation is much more
rapid in higher butene/02 ratios and at higher temperatures [55].
The role of phosphorous has now been understood: it forms compounds with
vanadium which facilitate the redox processes among the various oxidation states
of vanadium, and help maintain the vanadium ions in the optimal distribution of
valence states.
In various V-P oxide preparations, a number of phases have been identified,
including a-VOPO,, P-VOPO,, (V0)2P2@.2H20, P-(V0)2P207, an amorphous
V(1V) phase, a B-phase and more recently y-VOP04, and Y -(VO)~P~O~ [561. An
interesting aspect of these phosphorous compounds is their ability to vary their
degrees of condensation, which allows the solid to accommodate a change in the
valence state of V [46]. In earlier studies, the resulting crystalline phase after
calcination has been found to depend on the method of preparation. If the catalyst
is prepared in an aqueous medium by reduction of V205, a mixture of a-VOP0,
and P-(VO2)P20, (vanadyl pyrophosphate) is obtained [48-511. During butane
oxidation, the P-vanadyl pyrophosphate phase is the predominant phase present at
about 40O0C, and the a-VOPO, phase is the predominant phase at 420°C [14,521.
If the catalyst is prepared in an organic medium by the reduction of V205 or
Selective V-P-0 catalysts contain P/V ratios near unity.
SELECTIVE OXIDATION II 207
v
>
0
I
250 300 350
Temperat ure, C
Figure 12-1 Effect of reaction temperature on: a. The selectivity of main products
(butadiene BD, maleic anhydride MA, and COX) in 1-butene oxidation; b. The valence
state of vanadium. Catalyst V-P-0 with V/P =0.99 containing 100% VOV) before use;
feed 0.6 % 1-butene, 12 % 02. (Ind. Eng. Chem. Prod. Res. Devel., 24, 221 (1985).
copyright American Chemical Society).
VOP04 with HCl or alcohol, it contains vanadyl pyrophosphate [15]. p-VOP04 is
a slightly less selective catalyst than a-VOP04. Both p-VOP04 and (V02)P207
have been tested in the pure form to produce maleic anhydride, and are found to
interconvert slowly during butene oxidation [53].
I t has been proposed that the active catalyst consists of p-(VO)2P2O7 and a-
VOP04 which can readily interconvert by reduction and oxidation under reaction
conditions [52,57]. This interconversion is regarded as crucial in the reaction
mechanism because it interconverts V(IV) and V(V). The active p-(VO)2P207
phase may be nonstoichiomeuic. At high temperatures under oxidizing
208
C4H
Figure 12-2 Catalytic cycle of butene oxidation on a V- P- 0 catalyst.
conditions, a-VOp04 converts to p-VOP04, which cannot be easily reconverted to
the pyrophosphate phase. This causes a loss of the redox ability of the catalyst and
the low selectivity.
A more recent crystallographic study [ 56] of the V-P-0 system shows that
vOHp04.#20 is the precursor prior to calcination. If VOHP04-#120 is
obtained by reduction in an organic medium, a 6-VOPO, form is formed on
calcination which successively converts to y and p-VOP04. Under nitrogen, y-
VOP04 is reduced reversibly to y-(V0)2P207. Repeated cycles of oxidation-
reduction slowly converts this y-VOP04/y-(VO)2P20, couple into the p-VOP04/p-
(V0)2Pz07 couple.
Calcination of VOHP04.+H20 obtained in an aqueous medium produces a-
VOPo4 which exists in two forms: a1 and all. a1 is converted to p-(V0)2P20, by
reduction at 76OoC, a11 is converted to y-(V0)2P207 when heated under nitrogen at
700°C.
Crystallographic considerations shows that the interconversion of y-VOP04 to
y-(VO)2P207 requires very small displacements of atoms [ 56] . The reduction of p-
VOW4 to form p-(VO)2P207 involves crystallographic shear planes, and would
be more difficult. Thus, p-VOP04, once formed, makes the catalyst less
selective.
p-(VO)2P207 contains double chains of edge-sharing VO6 octahedra linked
by pyrophosphate (V2@4-) units. The axial V-O bond lengths within an
octahedra are not equivalent. One of the V-O bonds can be viewed as a vanadyl
( V 4) group [ 59] . An IR band at 963 cm-' assigned to V=O has been observed
on this compound. A V=O stretching band at 1001 cm-I has also been observed
on p-VOP04 [60].
SELECTIVE OXIDATION II 209
The presence of V-0 might be important. There is a correlation between the
density of V- 0 groups and the activity in butene and butane oxidation on
unsupported V2O5 catalysts [47]. The activity per V=Q depends on the method of
preparation of V205. Interestingly, butene is oxidized to maleic anhydride with
about 45% selectivity on the catalysts, but butane is oxidized only to carbon
oxides.
In the NiMo04-Mo03 system, excess Moo3 is found to be essential for the
selective production of maleic anhydride from butene at 480°C. Pure Moo3 or
pure NiMoO, produces butadiene at about 20-25% selectivity but no maleic
anhydride. NiMo04 containing excess Moo3, however, produces maleic
anhydride with up to 35% selectivity [17,611. A similar synergistic effect is also
observed for the selective oxidation of butadiene to maleic anhydride [18].
Spectroscopic investigations lead to the conclusion that the selective catalysts are
Moo3 particles whose surfaces are decorated with NiMoO, particles that
effectively block the combustion sites of Moo3. Furthermore, NiMo04, being
effective in producing butadiene, also serves to supply butadiene to Mo03 which
produces furan and maleic anhydride more selectively from butadiene than from
butene.
The production of maleic anhydride on Moo3 is crystal-face specific [29,31].
A correlation has been found between the ratio of the (lOO)/(OlO) areas and the
ratio of maleic anhydride to C02 production in the oxidation of 2-methylpropene.
Effect of Promoters
There are claims that many promoters are effective, and summaries of these
are found in a number of review articles and monographs [2,7,61a,62].
Unfortunately, there is relatively little understanding of the promoting effects.
In the oxidative dehydrogenation of butenes on ferrites, the promoting effects
of Mg, Cr, Co, Zn, Bi, Mo, P, Sb, and V have been studied. The addition of Cr,
Mg, or Zn increases the resistance of the ferrites to reduction [35]. In addition, Co,
Zn and Mg form spinel ferrites with Fe2O3, which is a more desirable structure
than corundum for this reaction.
The promoting effect of Mo, V and P has been interpreted as due to changes
in the acidity and basicity of the oxide [41,63]. This interpretation is based on the
idea that butene and butadiene are both Lewis bases as indicated by their rather low
ionization potentials. The Lewis acidity or basicity of a selective catalyst must not
be too strong so that it is sufficiently acidic to adsorb butene, yet sufficiently basic
to prevent strong adsorption of butadiene which would poison the active sites.
Addition of Mo, V and P increases the acidity of iron oxide, which is presumably
too basic. In the case of Sb and As, the promoting effect is a result of the
formation of FeAs04 and FeSb04 [41].
The effect of the support in supported F%03 has been investigated [64].
Si02, Ti02, A1203 and their mixed oxides have been used as supports, and the
activity per gram of catalyst varies widely over two orders of magnitude, but the
selectivity for butadiene remains in the range 65-88%.
The V-P oxide catalyst deactivates by the loss of phosphorous during
operation. This problem can be reduced by operating at a lower temperature or by
210
stabilizing the composition of the catalyst with the addition of alkali metals. Li
has been claimed to be effective for this purpose [2]. The rate-limiting step in
butene oxidation on this catalyst is believed to be C-H bond breaking. Thus
promoters such as Fe, Cr, Mg, and Zn that have dehydrogenation activities have
been reported to enhance the catalytic acitivity.
In a number of studies on vanadium oxide catalysts [65-681, it is reported that
there is an optimal concentration of promoters beyond which the selectivity
decreases rapidly. This may be due to possible changes in the crystalline phases
and/or in the redox potential of the vanadium ions in the solid when too high
concentrations of promoters are added. This interpretation is consistent with the
fact that the effects of some promoters depend on the feed composition, especially
the hydrocarbon to oxygen (or air) ratio and the conversion. Perhaps different
gas phase compositions are needed to obtain the optimal distribution of oxidation
states of vanadium in the presence of different promoters.
Alkali promotion has also been reported for vanadium oxide. In one report,
sodium addition significantly increases the selectivity for butadiene on a
V205/SiOz catalyst but decreases the selectivity to maleic anhydnde [69].
12.2 SELECTIVE OXIDATION OF BUTANE
In all studies reported, butane is less reactive than butene and higher reaction
temperatures are required. It is reasonable to expect that the oxidation of butane
proceeds via dehydrogenation to form butene, which is then reacted to form
butadiene, maleic anhydnde, or other oxidation products as discussed in the last
scction. It is important to note, however, that because butane is less reactive and
requires a higher temperature for reaction, some catalysts such as ferrites that are
highly selective for butene oxidation are not as selective for butane oxidation.
The most often studied reactions of butane are the oxidative dehydrogenation
to butenes and butadiene (eq. 12-8) and oxidation to maleic anhydride (eq. 12-9):
Nature of Catalysts
A number of oxides have been reported to be quite selective in oxidative
dehydrogenation. Among these are NiO, Moo3, and c0304[70], and mixed
oxides of Co-Mo, Ni-Mo, Mg-Ni [71], and Mg-V [72]. A selectivity for
dehydrogenation in excess of 60% at a conversion of 20% or more has been
obtained with some of these mixed oixdes.
Among the mixed oxides, Mg-Mo oxide and Mg-V oxide have been studied
quite extensively. High selectivities (60+%) for dehydrogenation (butenes and
SELECTIVE OXIDATION II 211
butadiene) on Mg-Mo oxide have been observed both in the presence [71] and in
the absence of gaseous oxygen in the feed [73]. Analyses of the selective catalysts
show that they are mixtures of MgMo04, MgO, and an unidentified phase.
The selectivity for oxidative dehydrogenation on a Mg-V oxide is as high as
80% at low conversions [74]. It decreases to about 50% when the conversion
increases to 40% [72]. Detailed analyses of the catalyst show that the active phase
is magnesium orthovanadate (Mg3(V04)2). This conclusion is confirmed by the
similarity in the catalytic behaviors of a stoichiomeuic Mg orthovanadate and a
mixed Mg-V oxide. Interestingly, neither Mg pyrovanadate (Mg2VzG) nor Mg
metavanadate (MgV206) is selective for this reaction [74]. On the other hand,
other orthovanadates including LuV04 and SmV04 are about as selective as
Mg3(V04)2 [751.
The differences among the various vanadates have led to the suggestion that
the bonding of oxygen in the oxide lattice is a factor that determines selectivity.
The oxygen ions in an orthovanadate are bridged between a vanadium ion and
another cation such as Mg, Lu, or Sm. If this other cation is not easily reducible,
the bridging oxygen ion cannot be readily removed from the lattice, and the
catalyst is selective. In a metavanadate or a pyrovanadate, there are oxygen ions
bridging between two vanadaium ions. Since V5+ions are easily reducible, the
bridging oxygen ions are readily removable, and the catalysts show high
combustion activities.
The selective oxidation of butane to maleic anhydride is quite demanding and
only a few catalysts have been reported to have high selectivities. Molybdenum-
phosphorous oxide and V-P-0 are among the few. Of these two, V-P-0 has been
very extensively studied as described in section 12.1. Selectivities as high as 78%
for maleic anhydnde at low conversions of butane and 65% at high conversions
have been reported in the patents [2].
Although the active phases in V-P-0 in butane oxidation are believed to be
the same as those in butene oxidation, some differences have been reported
between the behavior of this catalyst in the two reactions. It has been found that
although p-VOP04 transforms into (V0)2P207 during butene oxidation, the
transformation is much slower during butane oxidation [53]. The areal activities
of V-P-0 catalysts prepared either by aqueous reduction of V2O5 with H3P04 or by
reduction with H3P04 in an organic medium are the same in butene oxidation, but
are different in butane oxidation [76]. This observation may indicate different
rate-limiting steps in the two reactions.
The participation of lattice oxygen in a V-P-0 catalyst in butane oxidation has
becn demonstrated. It has been found that only the first one to five layers of lattice
oxygen are involved [14,15]. This is very different from the behavior of bismuth
molybdates in propene oxidation (see Chapter 11). It has been porposed that the
active surface of V-P-0 is a layer of VOP04, and scrambling of lattice oxygen
occurs rapidly, creating a pool of five exchangeable oxygen atoms per surface V
ion [ 58] . When one of the five oxygen atoms is consumed in the reaction, the
vacancy is filled by reoxidation by gaseous oxygen. The replenished oxygen atom
scrambles rapidly with the remaining four oxygen atoms in the surface layer. This
picture is consistent with the observation that i n a pulse experiment, 90% of the
212
reaction products contain oxygen atoms already present in the catalyst, and 10%
contains oxygen from gaseous oxygen.
Finally, if the catalyst is first treated with D20, nearly 2f3 of the product
maleic anhydride contains two deuterium atoms in a pulse experiment. Thus the
reaction proceeds with exchange of H atoms in the surface intermediate (such as a
x-allyl) and surface OD groups.
Mechanism
The mechanism and the kinetics of butane oxidation to maleic anhydride on a
V-P-0 catalyst have been studied. By studying the deuterium isotope effect at
different positions of a butane molecule on the p-(VO)2P2@ catalyst, it has been
demonstrated that the first step of the reaction is the production of adsorbed butyl
species [58]. At 400°C. a sizable isotope effect, kH/kD of 2.1 to 2.2 is observed for
C-H (C-D) bonds at the secondary carbons of a butane molecule, but there is
almost no isotope effect at the two primary carbons. The kH/ kD values of 2.1 to 2.2
are close to the theoretical maximum value of 2.27 for a homolytic dissociation of a
C-H bond based on the difference in zero point energy of the C-H and C-D bonds,
which is 4.4 kJ/mole. Thus the dissociation of a methylene C-H bond of butane to
form an adsorbed sec-butyl species is the rate-limiting step in the reaction.
It is likely that the
formation of an adsorbed butyl species is followed by a second C-H bond breaking
which results in an adsorbed butene molecule. The butene molecule then reacts in
the same manner as described in the last section. An in situ FTIR study identified
maleic acid on the catalyst together with some unidentified alkenic species, in
addition to butane, adsorbed maleic anhydride, and adsorbed carbon dioxide [1201.
Little mechanistic information is provided by the kinetics [58,77-791.
There is no information on the subsequent steps.
12.3 SELECTIVE OXIDATION OF METHANE
The selective oxidation of methane is one of the most challenging processes
because the C-H bond in methane is the strongest among all hydrocarbons, and
because the selective oxidation products are generally more reactive than methane
such that high yields of products are difficult to obtain.
This reaction has received considerable attention recently because of the
abundant reserve of natural gas in the world, and two recent review articles have
appeared on this subject [80,81]. I n the review by Pitchai and Klier [81], different
methods to oxidize methane are mentioned. These methods include partial
oxidation to methanol or formaldehyde, oxidative dimerization to acetylene,
ethene, and ethane, oxidative methylation, and others. The first two processes,
oxidation of methane to methanol or formaldehyde and oxidative dimerization will
be discussed here.
Formatwn of Methanol or Formaldehyde
A large number of oxides can act as catalysts for the oxidation of methane to
methanol or formaldehyde using oxygen [80,81]. Oxides of zinc, lead, nickel,
SELECTIVE OXIDATION 11 213
chromium, copper, iron, silver, cobalt, molybdenum, manganese, vanadium as well
as mixed oxides containing these have been claimed to be active and selective. In
general, however, the conversions are low, thus the yields of methanol and
formaldehyde are low. Among these oxide, vanadium oxide, and especially
molybdenum oxide are the more thoroughly investigated.
The first extensive report on the use of Moo3 and mixed oxides of Moo3 with
Fe2O3, ZnO, U02, or V0 2 is in a patent by Dowden and Walker [82]. In a highly
oxygen-lean feed of about 97% CH, and 3% oxygen, and at a low methane
conversion of a few percent, a selectivity of methanol of up to 75% is achieved
with Mo03-U02. 3MoO3-F~O3 shows a methanol selectivity of 6396, and a
formaldehyde selectivity of 8%. A later patent claims CuO-Moo3 to be about as
effective as the other molybdates [83].
Selective oxidation to methanol and formaldehyde at a much higher
conversion is reported by Iwamoto [84] and by Lunsford and coworkers on silica-
supported Moo3 catalysts using N20 as the oxidizing agent [ 85] . In the latter
report, CH30H and formaldehyde are produced with 55.1% and 23.9% selectivity,
respectively, at a conversion of 12.5%. The feed is 72 torr CH,, 277 torr N20 and
266 torr H20, the reaction temperature is 580°C and the catalyst is 1.7 weight %
Mo03/SiOz. Water is found to be essential for the high selectivity to the formation
of partial oxidation products. Higher partial pressures of water increase the
selectivity. At low water partial pressures, the activity increases with increasing
water partial pressure, but becomes constant for P H ~ ~ >75 tom. Later work show
that below 5OO0C, methanol is formed almost exclusively [86.87]. Above 5OO0C,
HCHO selectivity continues to increase and HCHO becomes the major partial
oxidation product above about 550°C. Up to this temperature, no CO or C02 is
detected even at a methane conversion of 1.9%. At higher temperatures, CO
formation becomes considerable. At 580°C. the selectivity to partial oxidation
products increases with increasing PcH4/ P~20 ratio in the feed, and reaches 100%
when the ratio is 1.2. Although the conversion to methanol increases as PHz0
increases from 0 to 260 torr, the conversion to HCHO stops increasing for P H ~ ~
larger than 40 torr, and the conversion to CO decreases slightly. The activity of
the catalyst also increases with PHZo up to 50 tom. beyond which there is no further
effect. The steam reforming of methane and the water-gas shift reactions are
negligible under these reaction conditions.
Selective production of formaldehyde is also observed using oxygen as the
oxidant over a M a3 catalyst supported on silica-alumina [81]. Formaldehyde,
CO and C02 are the only products reported. No methanol is formed. The
selectivity for HCHO increases with increasing CH4/02 ratio, reaching a value of
46% at 600°C and a CH,/02 ratio of 17. As with N20 as the oxidant, addition of
water to the feed is beneficial. The selectivity for HCHO increases with the
amount of water added, although the CH, conversion decreases. At 6OO0C, a
HCHO selectivity of over 90% is achieved with water in the feed and a C&/O2
ratio of 9.
From these reports, a number of interesting differences is observed between
using 0 2 and using N20 as the oxidant. Methanol is not produced using O2 but is
produced using N20. With increasing temperature, the selectivity for the partial
214
oxidation products increases using 0 2 , but decreases using N2O. The CH,J02
ratio required to obtain high selectivity to partial oxidation is much higher than the
CH,/N20 ratio.
The need to have water in the reaction mixture for high selectivity could limit
the long term stability of the molybdenum oxide catalysts. Water reacts with
Moo3 to form a volatile molybdenum hydroxide species 1811:
This could lead to loss of molybdenum under reaction conditions.
At 540°C. the production of CH30H in CH, oxidation with N20 on Moo3/
Si02 is roughly first order in CH, and H20 and zeroth order in N20 [87]. The
production of HCHO is zeroth order with respect to all reactants. At 580°C. the
overall conversion of CH, is zeroth order in CHq and first order in N20 [86]. For
some reasons, the rate constant is lower for P N ~ O <80 torr than for higher PNz0.
Between 480 and 520°C the activation energy for methanol production is 170
kJ/mole. Above 520". subsequent oxidation of methanol becomes rapid, making it
difficult to estimate the true activation energy. The activation energy for HCHO
production is 344 kJ/mole from 480 to 540°C. and 168 kJ/mole from 540 to 590°C
[87]. The activation energy for the disappearance of methane is 176 kJ/mole from
The following sequence of reactions has been proposed for HCHO production
550 to 594OC [86].
[ 861 :
MO' +N20
MoV'O- + CH, + MoV1 OH- + CH3
MoV'02- + CH? + MoVOCH3-
MoVOCH3- + H2 0
MoV'OH- + MoVOH- + MoV + MoV'02- + H2O
MoV'O- + N2
Mo'OH- + CH30H
and for the combustion reaction, the overall reaction is:
8MoV' + 4 0 2 - + C&
2MoV +N20 - 2MoV' + N2 + 02-
8 MoV + 2 H20 + C02
(12- 1 1)
(12-12)
(12- 13)
(12- 14)
(12-15)
(12-16)
(12-17)
Bands in the C-H stretching region assigned to methoxy (peaks at 2955,2928, and
2857 cm-') are observed by IR when a reduced MoV'/Si02 catalyst, reoxidized by
N20, is exposed to CH, at 25°C. The production of methyl radicals on the
catalyst on exposing CH, to a reduced catalyst that is reoxidized by N20 has also
bccn demonstrated by EPR [86].
The active site is postulated to consist of oxomolybdenum clusters such as the
SELECTIVE OXIDATION I1 215
following species (4 is an anion vacancy):
This species could be the one on the right hand side of eq. (12-15). Oxide ions of
silica could make up some of the oxide ions in this species.
Selective oxidation of methane by N20 can also be carried out using a
V205/Si02 catalyst [88,89]. In fact, with catalysts of comparable loadings and at
comparable conversions, a supported V205 catalyst produces methanol and
formaldehyde selectively at 460-500°C. a temperature lower than that required for
Mo03/Si02 [881.
The selectivities for CH30H and HCHO decrease with increasing
temperature. They also decrease with increasing contact time due to secondary
reactions of these molecules to form carbon oxides. At 500°C. replacing N20
with O2 reduces the selectivities for partial oxidation products from nearly 100% to
less than 20%, and combustion to carbon oxides becomes the dominant reaction.
Addition of a small amount of O2 to N20 enhances the conversion with some loss
in selectivity.
At 500°C with a small amount of oxygen in the feed stream, the kinetic
orders are found to be:
rate (CH30H) a [CHJ '/2[N20]1/2 [H20]1/2 (1 2- 18)
rate (CH20) a [CI-LJ1/2 [N20]1/3 (12-19)
rate (CO) a [CIl,]1/2 [N20]' [H20]-' ( 12-20)
Over the temperature range 460-5Oo0C, the activation energies for the formation of
HCHO, CH30H, and CO are 92, 168, and 197 kJ /mole, respectively.
It should be mentioned that in addition to the direct observation using EPR of
the presence of methyl radicals at low temperatures on these catalysts, the
importance of this species in this reaction is inferred from the fact that the addition
of dimethyl ether, which decomposes to produce CH3 and CH30 species, decreases
the required reaction temperature substantially [80]. Similarly other hydrocarbons
such as ethane can also be used as initiators [81].
Oxidative Dimerization
Many oxides possess some catalytic activities for oxidative dimerization of
methane [90-931. Using a high CIl,/02 ratio and at low conversions, many rare
earth oxides show good selectivities for C2 products (primarily ethane and ethene).
Carbon selectivities for Cz better than 80% are obtained, and Sm2O3 and Dy203
show selectivities better than 90%. Exceptions to this are Ce02 and TbO,. Among
the other oxides, the basic oxides Bi2O3 and CaO also show good selectivities.
On the other hand, acidic oxides such as silica-alumina, hydrogen-Y zeolite, and
216
ZSM-5 zeolite are nonselective. Thus far, only a few transition metal oxides are
selective for this reaction. Based on data reported, it appears that only a few
oxides that can undergo oxidation-reduction readily are selective.
Addition of alkali metals sometimes improves the activity and selectivity of a
catalyst.
Addition of Li to MgO has been shown to be very effective. A C2
selectivity of 89% has been obtained at a CH, conversion of 5% [91]. Li-ZnO is
also quite active and selective, and a C2 selectivity of over 65% has been obtained
WI .
This oxidative dimerization reaction has been studied in detail on the Li-
promoted MgO and L a203 [91,93], and interesting similarities and differences are
detected between the two systems. On Li-promoted MgO, the products are
ethane, ethene, and C02. Only small amounts of CO, methanol, and formaldehyde
are detected. For 02/CH, ratios less than unity, a lower ratio leads to a higher C2
selectivity but a lower methane conversion at 720°C. C21-& is the major C2
product at 620"C, but C2H4 becomes dominant at 720°C. The total C2 selectivity
increases with increasing temperatures up to 7OO0C, beyond which it decreases.
The apparent activation energy for the reaction is 230 kJ/mole over 560 to 660°C.
Methyl radicals are detected downstream from the catalyst bed of Li-MgO.
Thus ethane is formed by the coupling of two methyl radicals in the gas phase,
Ethene is then formed by the oxidative dehydrogenation of ethane. These steps
are:
c2H6 + Wad) + C2Hs(ad) + OH-(ad) (12-22)
.C2HS(ad) + 02-(s) --+ C2H50-(ad) + e-(lattice) (12-23)
CzHsO-(ad) 4 C2&(g) + OH-(ad) (12-24)
The rate-limiting step is likely the catalytic production of methyl radicals. C02 is
formed from methane at low conversions by the oxidation of surface methoxy
groups and gas phase peroxide CH3O2. species. This peroxide species is formed by
the reaction of a gaseous methyl radical and an oxygen molecule, and its
equilibrium concentration decreases with increasing temperature. This latter effect
is a major reason why very high temperatures (700°C or higher) are required for
substantial yields of C2 products.
On Li-MgO, the active site is postulated to be a Li'O-center that is produced
when Li is incorporated into the MgO matrix. Methane reacts at this center to
form methyl radicals:
Li+O- + CH, --+ Li'OH- + CH3 ( 12-25)
The active site is regenerated by the desorption of water to produce Li+@
(where @ denotes an anion vacancy), which then reacts with oxygen to form the
active site. The presence of this Li'O- center is detected by EPR. In addition,
SELECTIVE OXIDATION II 217
LiC03 is also present in the catalyst, and might contribute to the reaction.
On La2O3, C2 products are also produced via the gas phase coupling of
methyl radicals. C02 is formed by the oxidation of these radicals. But at high
methane conversions, combustion of C2& is extensive and accounts for the low
selectivity to C2 products. Under oxygen-lean conditions, increasing temperature
decreases the COX selectivity, and increases Cz& selectivity, while C2&
selectivity remains roughly constant.
The active site on La203 is probably different from that on Li-MgO. In
particular, no 0- species has been detected with EPR on La203. Instead, a signal
that can be assigned to 02- is detected [93]. Experiments at temperatures below
200°C show that 02- is much less reactive toward alkanes than 0-. At the reaction
temperature of about 70O0C, this species may become active, or it may acquire an
electron fromthe lattice to become two 0- species which are active. Without
more evidence, the active site has been tentatively assumed to be some form of
sorbed oxygen, such as 02-.
Selective production of C2 products has also been reported in reactions
(noncatalytic) of methane with oxides [95,96]. Si02-supported manganese oxide,
I n203, Ge02, PbO, and Sb2O3 show selectivities higher than 70% when methane is
passed over themin the absence of gaseous oxygen at about 700°C. The oxides
are reduced i n the process, and the conversion of methane drops rapidly as the
reduction procecds. Reoxidation of the reduced oxides regenerates the initial
activity. Ethane and ethene are the major products, and a few percent of other
higher hydrocarbons including benzene and toluene are detected. If the reaction
is carried out under catalytic conditions using a methane/oxygen mixture, the
selectivities for C2 products are somewhat lower.
Fromthe change in product distribution as a function of contact time, it is
concluded that ethane is the primary product on supported manganese oxide.
Ethcne, higher hydrocarbons, and COX are all secondary products. One pathway
to form higher hydrocarbons is methylation of alkenes, which has been demon-
strated to occur under reaction conditions by passing a mixture of methane and
alkenes over the oxide. Evolution of methyl radicals into the gas phase has also
been detected.
Silica-supported manganese oxide is among the best oxides reported for this
reaction. Mn7SiOI2 has been detected as a component on this oxide. After use,
MnSi03 is formed. It has also been found that silica is a better support than
alumina for manganese oxide because of higher selectivity for C2 products.
Addition of sodium phosphate further improves the performance.
Of all the process reported, this cyclic noncatalytic oxidation-reduction
process appears to be the most promising for commercialization. The process has
now been successfully demonstrated in a pilot-plant scale test by ARCO.
12.4 SELECTIVE OXIDATION OF METHANOL
The selective oxidation of methanol to formaldehyde can be carried out
effectively on many catalysts based on vanadium oxide and molybdenum oxide.
218
As in other oxidation reactions, the activity and selectivity depend on the nature of
the support and the presence of other components that form compounds with V or
Mo oxides.
The commercial process is carried out at 200-300°C over an iron molybdate
catalyst containing excess Moo3. For example, the commercial Harshaw catalysts
is a 3:l mixture of Mo03 and Fe2(Mo04)3. The process runs at 400°C under
methanol-lean conditions with methanol conversion of 95-99% and selectivities of
On a M a3 or Fe2(Mo04), catalyst at 200-300°C, pulse reaction studies
show that dimethyl ether, formaldehyde and water are the primary reaction
products [98]. In a flow reactor, the selectivity to various products typically
depends on the conversion in the manner shown in Fig. 12-3 [99]. At low
conversions, formaldehyde is the main product, followed by dimethoxymethane
and dimethyl ether. With increasing conversion, the selectivity for formaldehyde
increases, that for dimethoxymethane drops rapidly, while that for dimethyl ether
drops slowly. Methyl formate is formed as the major secondary product at
intermediate conversions. Selectivity for CO is low except at high conversions,
whereas C02 is never a major product. At higher temperatures and lower
conversions, the selectivities for CO and HCHO both increase while those for all
other products decrease.
Addition of a small amount of water increases the selectivity for HCHO, but
suppresses the activity [99,10O]. In the absence of water, the reaction rate at low
partial pressures shows a small positive order in oxygen, and an order near 0.5 in
methanol [99]. In one paper [loll, the order in both components drops to zero
above 180 torr, but an order of 0.5 has been reported at 318 torr in another paper
[loo]. Over 162-251°C. the activation energy is 70 M/mole on F%(MoO~)~,
75-88 kJ/mole on Ma3, and 79 Id/mole on the mixed Fe-Mo oxide [99,100].
Between 220 and 300°C over MOO3, Fe2(M0O4), and their mixture, the ratio
of rate constants for CH30D and CH30H varies from 0.83 to O.%, while the ratio
for CD30D and CH30H varies from 0.15 to 0.37 [102]. Thus deuteration of the
methyl group shows a much larger kinetic isotope effect than the 0- H group.
This indicates that the breaking of the C-H bond is rate limiting. This conclusion
is supported by temperature programmed desorption results which show that the
desorption temperatures of formaldehyde, methanol and water are shifted to
slightly higher temperatures when CD30H is adsorbed instead of CH30H [l03].
The slower rate for CH30D than CH30H is attributed to the slower
dchydroxylation rate of surface OD groups than OH groups, which results in a
slower rate of regeneration of active sites. CH30H and CH30D give similar
products, but CD30D gives much more dimethyl ether and less formaldehyde than
CH30H, consistent with the expectation that the formation of formaldehyde
involves C-H bond breaking as a rate-limiting step.
It has been shown by Mossbauer spectroscopy that the Fe ions in FQ(MoO~)~
and Fe2(M004)3.M003 can be reduced by methanol at catalytic temperatures
[104]. This suggests the possibility that the catalyst undergoes oxidation and
reduction during reaction and that lattice oxide ions are involved. Using a feed
that contains *02, no 80-labeled water is found initially. The amount of H2'*0
91-94% [97].
SELECTIVE OXIDATION 11
'-O I
219
Fr act i on of Methanol Converted
Figure 12-3 Product distribution in methanol oxidation on a Fe-Mo-0 catalyst as a function
of methanol conversion. Products are CO, methylformate MF, dimethyl ether DME,
dimethoxymethane DMM, and formaldehyde F. (From Proc. 4th Intern. Cong. Chem.
Uses Molydenum, p.411 (1982), copyright Climax Molydenum).
increases with time, and l80 is detected in the catalyst after use. These results
support the possibility that lattice oxygen participates in the reaction, although
oxygen-exchange between water and lattice oxygen would lead to the same
observations.)
A proposed reaction mechanism on Mo03 is shown in Fig. 12-4 [105]. In
this mechanism, methanol is adsorbed dissociatively on a dioxomolybdenum
species. Abstraction of a hydrogen atom from the methyl group of an adsorbed
methoxy is accomplished by an adjacent dioxomolybdenum species. Desorption
of formaldehyde and water, and reoxidation by gaseous oxygen complete the cycle.
The product water is formed initially with the oxygen atom from the surface.
The reaction of adsorbed methanol has been studied with IR spectroscopy.
One report claims that dissociatively adsorbed methanol is observed at 100 K on
Moo3 and ferric molybdate [106]. Another claims that methanol initially
chemisorbs on M a3 molecularly and, with increasing coverage, reacts in a
bimolecular process to formchemisorbed methoxy and water [103]. Whether the
catalyst is reduced is the process has not been addressed. Methoxy is also formed
by exposing an oxidized M a 3 (pretreated with 0 2 at 250°C) to methanol at 100°C
[ 106,1071. Temperature programmed desorption of adsorbed CD30H yields
CD30D as one of the products [103]. This species must be formed by the
recombination of a surface methoxy and a deuterium atom from surface OD group
that is formed when a C-D bond is dissociated.
N20 can also be used as the oxidant instead of 0 2 on Md3/Si 02. However,
the resulting activity and selectivity for formaldehyde are lower. I n fact, the
selectivity decreases rather sharply with increase in temperature beyond 200°C
220
o+Mo:'OH
4 %
Figure 12-4 Mechanism for methanol oxidation to formaldehyde on MOO,. (From J. Catal..
92. 127 (1985), copyright Academic Press).
[loo]. Inspite of these differences, the orders of the reaction in O2 or N20 are the
same. These observations have led to the conclusion that adsorbed 0- species is
not involved in the selective oxidation reaction.
Nature of Catalysts
The commercial Fe-Mo oxide catalyst consists of Fe2(M00~)~ and Moo3.
The M a3 is required to maintain high activity and selectivity. It has been
claimed that a catalyst with a Fe/Mo ratio of about 1.7 shows the maximum activity
[108,109]. It has been suggested in the past that the activity is due to the
Fe2(M004)3 phase and Moo3 serves as a structural promoter to increase the
surface area and as a source to replenish the Mo lost during operation
[104,110,111]. Recent papers report little difference in the kinetic order
dependence on methanol and oxygen, the areal activities, the product distributions,
and the activation energy among samples of pure Moo3. pure F%(M0O4),, and
MoO~/ F~~(MOO~)~ of comparable surface areas [99,104]. Thus, it is possible that
the excess MOO, is also an active phase.
FeMo04, F ~P M O ~~O ~~ and
Fe4(SiMo12040)3 show activities and selectivities comparable to Moo3,
Fe2(Mo04)3, and their mixtures. Bismuth molybdates and aluminum molybdates
show good selectivities but lower activities. Other molybdates such as chromium
molybdate, cobalt-nickel molybdate, Co-P-Mo-0 and Ru-P-Mo-0 show poorer
Other molybdate catalysts have been tried.
SELECTIVE OXIDATION II 22 1
selectivities [991.
The initial oxidation state of Mo is not very important. It has been found that
at steady state, M a2, Mo205, and Moo3 are all active and highly selective for
formaldehyde. However, Mo2O5 appears to be somewhat more active. X P S
investigations of catalysts used in a pulse reaction study show a rough correlation
between the amount of formaldehyde formed and the intensity of the Mov signal.
Since the catalyst undergoes a redox cycle during reaction, it is suggested that
Mo(IV), Mo(V), and Mo(V1) are involved in the reaction cycle [loo], although the
mechanism described in Fig. 124 uses only Mo(V) and Mo(V1).
The reaction on Moo3 is crystal-face specific. Under ultra high vacuum
conditions, an ordered (010) surface of Moo3 does not adsorb methanol.
Methanol is adsorbed much more readily after this surface is reduced and
disordered by ion bombardment [ 1031. Presumably, ion bombardment generates a
higher density of surface Mo ions that are extensively coordinatively unsaturated,
reduced Mo ions, or other high energy defect structures.
Such structure sensitivity has also been demonstrated on crystalline samples
of Moo3 [112,113]. The selectivity for oxidation to formaldehyde or methylal
versus dehydration to dimethyl ether depends on the ratio of the crystal faces
exposed:
+CH30H
- 2 v CH20 CH2(mH3)2
CH30H (12-26)
+CH+ (cH~)~o
-H 20
Fig. 12-5 shows this dependence. The selectivity for formaldehyde versus
methylal varies linearly with the ratio of the basal (010) plane to the side (100)
plane, and the selectivity for ether versus oxidation to formaldehyde is proportional
to the ratio of the apical (001) and (101) planes to the basal plane. These results
are opposite to what would be expected fromresults mentioned earlier that an
ordered (010) surface does not adsorb methanol. This is probably due to the fact
that in these catalytic studies, the (010) faces of the crystals used have high
densities of defects such as steps, which provide active sites for the reaction. The
very different pressures of methanol used in these two types of studies may also
contribute. Structure sensitivity is also observed in ethanol oxidation [112,114]
and in the reaction of methanol in the absence of oxygen [106,112]. In the latter
case, the dependence of activity on the crystal faces is somewhat different from
that in the presence of oxygen.
The results of these studies suggest that the basal (010) plane of Moo3 is very
selective for dehydrogenation, and it is much more active in the presence than in
the absence of oxygen. The active site is probably associated with the terminal
Mo=O groups. In the absence of 02, the C-H bond breaking occurs on this
surface, but water is not formed. The hydrogen accumulates on the surface to
formbronze H, Md3. The apical (001) and (101) or (701) surfaces are active in
dehydrogenation and dehydration both in the presence and in the absence of
222
100)
%(001) and (101)/%(010)
Figure 12-5 Dependence of selectivity in methanol oxidation on Moo3 catalyst. a. Ratios
of formaldehyde and methylal selectivities versus area ratios of basal (010) to side (100)
faces of MoQ; b. Ratios of dimethyl ether and formaldehyde selectivities versus area
ratios of apical (001) and (101) to basal (010) faces. (From J. Catal., 72. 375 (1981).
. , *. 3 * n \
SELECTIVE OXIDATION II 223
oxygen. The (100) face catalyzes dehydrogenation in the presence of gaseous
oxygen when MoSO groups exist. In the absence of oxygen, this face catalyzes
dehydration where the active sites are proposed to be the exposed Mo cations
which act as Lewis acid sites.
In addition to the dependence on the crystal face orientation, the selectivity in
methanol oxidation also depends on the polymorphic crystalline form of Mo03
[115]. The orthorhombic formis less active and catalyzes mainly the oxidation to
methylal. The hexagonal form is more active, and the main reaction is
dehydration to dimethyl ether.
In addition to molybdenum oxides, vanadium oxides are also selective in the
production of formaldehyde. Under optimal conditions, 87% yield of
formaldehyde is obtained with an unsupported V2O5, and a Ce02-supported V2O5
shows a nearly 100% selectivity at low conversions [116]. On other supports, the
selectivity decreases in the order: a-A1203 (83%) >Ti02 (rutile) =zirconia >Ti02
(analase) [116,117]. In general, the selectivity decreases rapidly with increasing
temperature because of increase in conversion.
When VzOs is used in a solid solution with other oxides (A1203, Sn02, or
Ti02), the selectivity for HCHO is very low at low vanadium concentrations. At
high concentrations, the selectivity increases up to almost 100% [118]. V2O5
supported on A1203 or TiOz shows poor selectivity. On V2OS/Al2O3, dehydration
dominates; on V205/ri02, combustion dominates [ 1191.
REFERENCES
1. W. E. Slinkard, and P. B. DeGroot, J. Cafal., 68. 423 (1981).
2. R. K. Hodnett. Caul. Rev., 27, 373 (1985).
3. E. N. Amirbekov. F. V. Aliev, L. I. Lafer, A. M. Rubinshtein. and V. I. Yakevson,
4. E. N. Amirbekov. F. V. Aliev, L. I. Lafer. A. M. Rubinshtein, and V. I. Yakevson.
5. M. C. Kung, W. H. Cheng. and H. H. Kung. J . Phys. Chem., 83. 1737 (1979).
6. H. H. Kung. B. Kundalkar, M. C. Kung, and W. H. Cheng, J. Phys. Chem.,
7. H. H. Kung and M. C. Kung. Adv. Cafal.. 33, 159 (1985).
8. M. A. Gibson. and J. W. Hightower, J . Cafal., 41, 420 (1976).
9. W. R. Cares, and J . W. Hightower. J. Cafal., 23, 193 (1971).
I zv. Akad. Nauk SSSR, Ser. Khim., 7. 1344 (1979).
I zv. Akad. Nauk. SSSR, Ser. Khim.. 11, 2250 (1979).
84. 382 (1980).
10. F. Cavani, G. Centi, I. Manenti, and F. Trifiro. Ind. Eng. Chem. Prod. Res. Dev..
11. G. Busca, F. Cavani, G. Centi. and F. Trifire, J . Cafal., 99, 400 (1986).
12. G. Busca, G. Centi, and F. Trifiro, Appl. Cafal., 25. 265 (1986).
13. M. Ai. Bull. Chem. SOC. Jpn.. 43, 3490 (1970).
14. G. Centi, G. Fornasari, and F. Trifiro, J. Cofal., 89, 44 (1984).
15. F. Cavani, G. Centi, and F. Trifiro, Appl. Cafal.. 9, 191 (1984).
16. D. Brkic. and F. Trifiro, Ind. Eng. Chem. Prod. Res. Dev., 18, 333 (1979).
17. U. Ozkan, and G. L. Schrader, J . Cafal., 95, 137 (1985).
24. 221 (1985).
224
18. U. Ozkan, and G. L. Schrader. J. Catal.. M, 147 (1985).
19. C. Adams, H. Voge, C. Morgan, and W. Armstrong, J. Catal., 3, 379 (1964).
20. Ph. A. Batist, C. G. M. van de Maesdijk, I. Matsuura, and G. C. A. Schuit,
21. A. W. Sleight, and W. J. Lm, Ann. New York Acad. Sci., 272, 22 (1976).
22. M. Misono, K. Sakata, F. Ueda. Y. Nozawa, and Y. Yoneda, Bull. Chem. Soc. Jpn.,
23. W. J . Linn, and A. W. Sleight, J. Catal., 41. 134 (1976).
24. Ph. Batist. B. Lippens, and G. C. A. Schuit, J. Catal.. 5. 55 (1966).
25. I. Matsuma, and G. C. A. Schuit, J . Catal., 20, 19 (1971).
26. P. Sunderland, Ind. Eng. Chem. Prod. Res. Devel., 15, 90 (1976).
27. R. L. Varrna, and D. N. Saraf, J. Catal., 55, 361 (1978).
28. W. Ueda, Y. Moro-oka, T. Ikawa. J. Chem. Soc. Faraday Trans I . 78. 495 (1982).
28a. M. Ai, P. Bontry, R. Montarnal, and G. Thomas, Bull. Sm. Chim. Fr., (8-9),
29. J . M. Tatibouet, Ch. Phichitkul, and J . E. Germain, J . Catal., 99, 231 (1986).
30. F. Cavani, G. Cemti, I. Manenti, A. Riva, and F. Trifiro, Ind. Eng. Chem.
Prod. Res. Devel.. 22, 565 (1983).
31. J . C. Volta, J . M. Tatibouet, C. Pitchitkul, and J . E. Germain, Proc. 8th Intern.
Congr. Catal., (Berlin 1984), Dechema, Frankfurt, IV, 451 (1984).
32. B. L. Yang, M. C. Kung. and H. H. Kung, J . Catal.. 89, 172 (1984).
33. R. J . Rennard, and W. L. KeN, J. Catal., 21, 282 (1971).
34. M. Misono. Y. Nozawa. and Y. Yoneda, Proc. 6th Intern. Cong. Catal., 1976,
35. F. E. Massoth, and D. A. Scarpiello, J. Cataf., 21, 294 (1971).
36. E. H. Lee, Catal. Rev., 8, 285 (1974).
37. B. L. Yang. F. Hong. and H. H. Kung. J. Phys. Chem., 88, 2531 (1984).
38. G. B. Raupp, and W. N. Delgass, J . Catal., 58, 337 (1979); M. C. Hobson.
39. J . A. Amelse, J . B. Butt, and L. H. Schwartz, J. Phys. Chem., 82, 558 (1978).
40. D. Patel, MS Thesis, Northwestern University , 1985.
41. I. Matsuma, Proc. 6th Intern. Congr. Catal., London, Paper B-21. 1976.
42. I. Kozlov, Izv. Akud. Nauk. SSSR, Ser. Khim. Nauk., 3, 10 (1983).
43. V. Fenin, V. Shvets, and V. Kazanski, Kinet. Katal., 20. 952 (1979).
44. A. Simakov, and S. Veniaminov. React. Kinet. Catal. Lett., 28, 67 (1985).
45. R. Fricke. W. Hanke, H. J erschkewitz, B. Parlitz, and G. Ohlmann. Appl. Catal.,
46. F. Cavani. G. Centi, I. Manenti, and F. Trifiro. Ind. Eng. Chem. Prod. Res. Dev..
47. K. Mori, A. Miyamoto, and Y. Murakami, Appl. Catal., 6, 209 (1983).
48. B. K. Hodnett, and B. Delmon, Appl. Catal.. 9. 203 (1984).
49. B. K. Hodnett, Ph. Permanne. and B. Delmon. Appl. Catal., 6. 231 (1983).
50. E. Borde, and P. Courtine, J . Catal., 57, 236 (1979).
51. L. Morselli, A. Riva, F. Trifiro, M. Zucchi. and G. Emig. Chim. I nd. (Milan),
10. 791 (1979).
52. G. Poli, I Resta, 0. Ruggeri. and F. Trifiro, Appl. Catal., 1, 395 (1981).
J . Catal., 20, 40 (1971).
53, 648 (1980).
2783 (1970).
I, 386 (1977).
and H. M. Gager, J. Catal.. 16. 254 (1970).
9, 235 (1984).
24, 221 (1985).
SELECTIVE OXIDATION 11 225
53. T. P. Moser, and G. L. Schrader. J . Cataf., 104, 99 (1987).
54. Y. N. Shyr, and G. L. Price, Ind. Ens. Chem. Prod. Res. Devef., 23, 536 (1984).
55. R. L. Varam, and D. N. Saraf. Indian Chem. Eng., 20, T44 (1978).
56. E. Bordes, and P. Courtine, J . Chem. Soc. Chem. Commun., 294 (1985).
57. G. Centi, I. Manenti. A. Riva, and F. Trifiro, Appf. Cufal., 9, 177 (1984).
58. M. A. Pepera, J. L. Callahan. M. J. Desmond, E. C. Milberger, P. R. Blurn,
59. Y. E. Gorbunova, and S . A. Linde, Sov. Phys. Dokl., 24, 138 (1979).
60. T.P. Moser, and G.L. Shrader, J . Cataf., 92, 216 (1985).
61. U. Ozkan, and G. L. Schrader. J . Cataf., 95, 120 (1985).
61a. D. J . Hucknall, "Selective Oxidation of Hydrocarbons", Academic Press, London,
1974.
62. D. B. Dadybiujor. S . S. J ewar. and E. Ruckenstein. Catal. Rev., 19, 293 (1979).
63. M. Ai. J . Cataf., 52, 16 (1978).
64. E. Rodenas, T. Iizuka, H. Katsumata, and K. Tanabe, React. Kinet. Cataf. Len.,
65. M. Brutovsky, and S . Gerej, Czech. Chem. Commun., 47, 403 (1982).
66. M. Brutovsky, S. Gerej. F. Vasilco, and J. Gerejova. Czech. Chem. Commun.,
67. B. K. Hodnett, and B. Delrnon, J . Chem. Soc., Chem. Commun., 373 (1983).
68. B. K. Hodnett, and B. Delmon, Appf. Cataf.. 6. 245 (1983).
69. R. Fricke, W. Hanke. H.-G. J erschkewitz, B. Parlitz. and G. i)hlmann,
70. V. A. Levin, T. V. Vernova, and A. L. Tsailingol'd, Kinet. Kataf., 13, 504 (1972).
71. G. A. Stepanov, A. L. Tsailingol'd, V. A. Levin, and F. S . Pilipenko, Stud. Surf.
72. M. A. Chaar, D. Patel, M. Kung, and H. H. Kung. J. Cataf., 105, 483 (1987).
73. V. A. Doroshenko, L. P. Shapovalova, A. I. Zelenina, D. N. Tmenov. 0. M.
Taranukha, and I. S . Lushnik, Kinet. Catal., 24, 749 (1983).
74. D. Patel. M. Kung, and H. Kung, Proc. 9th Intern. Cong. Cufaf.. 4, 1554 (1988).
75. D. Patel, PhD thesis, Northwestern University, Evanston, 1988.
76. G. Busca, G. Centi. F. Triliro, and V. Lorenzelli, J . Phys. Chem.. 90 1337 (1986).
77. A. Escardino. C. Sola, and F. Ruiz. An. Quim., 69, 385 (1973).
78. F. Cavani, G. Centi, and F. Trifiro, Appl. Cataf., 15, 151 (1985).
79. K. WoNfahrt, and H. Hofmann, Chem. Ing. Techn., 52, 811 (1980).
80. N. R. Foster, Appf. Cataf., 19, 1 (1985).
81. R. Pitchai, and K. Klier, Catal. Rev., 28. 13 (1986).
82. D. A. Dowden, and G. T. Walker, U.K. Patent 1,244,001 (1971).
83. H. J . F. Stroud, U.K. Patent 1,398,385 (1975).
84. M. Iwamoto, Jpn. Patent 58 92,629 (1983).
85. R. S. Liu, M. Iwamoto. and J. H. Lunsford. J . Chem. Soc., Chern. Commun., 78 (1982).
86. H. F. Lin, R. S. Liu. K. Y. Liew, R. E. J ohnson, and J. H. Lunsford, J. Amer. Chem.
SOC., 106, 4117 (1984).
87. M. M. Khan, and G. A. Somorjai. J. Cataf.. 91, 263 (1985).
88. K. J .Zhen. M. M. Khan, C. H. Mak, K. B. Lewis and G. A. Sornorjai, J . Cafaf.,
and N. J. Bremer, J. Amer. Chem. Soc.. 107, 4883 (1985).
19, 341 (1982).
47, 1290 (1982).
Appf . Card. , 9. 235 (1984).
Sci. Catal., 7 (part B, New Horizon Catal.), 1293 (1981).
94, 501 (1985).
226
89. M. Iwamoto, J pn. Patent 58 92,630 (1983).
90. K. Otsuka, K. J inno, and A. Morikawa, J. Catal., 1000, 353 (1986).
91. T. Ito, J .-X. Wang, C.-H. Lin, and J . H. Lunsford, J. Amer. Chem. Soc.,
92. K. Otsuka. K. J inno, and A. Morikawa, Chem. Lett., 499 (1985).
93. C. H. Lin, K. D. Campbell, J .-X. Wang, and J . H. Lunsford, J. Phys. Chem.,
94. I. Matsuura, Y. Utsumi, M. Nakai. and T. h i , Chem. Lett., 1981 (1986).
95. J . A. Sofranko, J. Leonard, and C. A. J ones, J. Catal., 103, 302 (1987).
96. C. A. J ones, J . J . Leonard, and J . A. Sofranko, J. Catal.. 103, 311 (1987).
97. R. Pearce, and W. R. Patterson, "Catalysis and Chemical Processes." J ohn Wiley and
98. C. J . Machiels, in "Catalysis under Transient Conditions," ACS Symposium series,
99. C. J . Machiels, and A. W. Sleight, Proc. 4th Intern. Conference Chem. Uses of
100. T.-J . Yang, and J. H. Lunsford, J. Catal., 103, 55 (1987).
101. N. Pernicone, F. Lazzeria, G. Liberti, and G. Lanzavecchia, J . Catal.. 14. 293
(1969).
102. C. J . Machiels, and A. W. Sleight, J. Catal., 76, 238 (1982).
103. U. Chowdhry, A. Ferretti. L. E. Firment, C. I. Machiels, F. Ohuchi. A. W. Sleight,
and R. H. Staley. Appl. Surjme Sci., 19, 360 (1984).
104. M. Carbucchio, and F. Trifiro, J. Catal., 45, 77 (1976).
105. J. N. Allison. and W.A. Goddard, III, J. Catal., 92. 127 (1985).
106. M. Ito, Vib. Surf. [Proc. Intern. Cod. 2nd, 19801, publ., 1982, p.71.
107. R. P. Groff, J . Catal., 86, 215 (1984).
108. N. Pernicone. C. Liberty, and L. Ersini, Proc. 4th Intern. Cong. Catal. 1969 p.366.
109. B. Popov, K. Osipova. V. Malakhov, and A. Kolchin. Kinet. Catal., 12. 1464 (1971).
110. N. van Truong, P. Tittarelli, and P. Villa, Proc. 3rd Int. Conference Chem. Uses
ofMolybdenwn. H. F. Bany, P. C. H. Mitchell, ed.. 1979, p.161.
111. G. Alessandrini, L. Cairati, P. Forzatti. P. Villa, and F. Trifiro, J . Less-Common
Met.. 54. 373 (1977).
112. J. M. Tatibouet, and J. E. Germain, J. Catal., 72, 375 (1981).
113. J. M. Tatibouet. J. E. Germain, and J . C. Volta, J . Cafal., 82, 240 (1983).
114. J. M. Tatibouet, and J. E. Germain. J. Chem. Res.. ( S ) , 268 (1981);
(M), 3070 (1981).
115. J . M. Tatibouet, and J. E. Germain. CR. Acad. Sci.. Paris C. 290, 321 (1980).
116. F. Roozeboom. P. D. Cordingley, and P. J . Cellings, J. Catal., 68. 464 (1981).
117. A. J. van Hengstrom, J . G. van Ommen, H. Bosch, and P. J . Gellings, Proc. 8th
Intern. Congr. Catal., IV, 297 (1984).
118. P. J. Pornonis, and J. C. Vickerman, Faraday Disc., Chem. SOC., 72, 247 (1982).
119. J . Kuenski. A. Baker. M. Glinski, P. Dollenmeier, and A. Wokann. J. Catal.,
101, 1 (1986).
120. R. W. Wenig, and G. L. Schrader, J . Phys. Chem.. 90, 6480 (1986).
107, 5062 (1985).
90, 534 (1986).
Sons, NY 1981, p. 263.
no. 178, ed. A. T. Bell, L. L. Hegedus, 1982. p. 239.
Molybdenum, H. F. Barry and P. C. H. Mitchell, ed., 1982, p. 411.
Chapter 13
CATALYTIC REACTIONS BETWEEN
HYDROGEN AND CARBON OXIDES
13.1 INTRODUCTION
CO and C02 can be hydrogenated on transition metal oxides to alcohols and
hydrocarbons. Since the oxides of the Group VIII transition metals have lower
hydrogenation activities, they may show higher selectivities for higher
hydrocarbons and alkenes. Transition metal oxides also have a lower tendency to
dissociate CO than their metals. Thus, they often produce alcohols more
selectively. In addition, some transition metal oxides produce branched products
quite selectively, especially 2-methylpropane, 2-methylpropene, and 2-
methylpropanol. However, in some of the systems that have been extensively
studied, such as Cu-Zn oxide, rhodium or palladium oxide, it has been
controversial as to whether the active components are the metal or the oxide.
The water-gas shift reaction, which is the reaction between carbon monoxide
and water to form hydrogen and carbon dioxide, also involves hydrogen and
carbon oxides. This reaction is readily reversible, and the reverse reaction, known
as reverse shift reaction, is between hydrogen and carbon dioxide.
Various aspects of earlier work on these reactions catalyzed by oxides have
been rcviewed [l]. For example, it has been discussed in these earlier reviews that
catalysts based on ZnO, such as Zn-Cr oxide are effective in the hydrogenation of
CO to methanol, which can also be catalyzed by copper catalysts. Higher alcohols
can beproduced by promoting these catalysts with alkali ions. On the other hand,
ZrO2 and Tho2 are effective for the production of branched products. Since
these earlier reviews, new catalysts have been discovered and significant progress
in understanding the reaction mechanisms has been made. The discussions here
will emphasize the more recent developments.
221
228
13.2
OTHER CU-BASED CATALYSTS
ALCOHOL SYNTHESIS ON COPPER-ZINC OXIDE AND
Methanol Synthesis
Copper-zinc oxides are very active and selective catalysts for the production
of methanol from a feed mixture containing CO, C0 2 and H2 [2-51. Highly
selective catalysts can be made with a C a n ratio between about 3/7 to 7/3. Often
the catalysts are suppported, and A 1 2 0 3 is the support in the commercial catalyst.
At present, it is controversial as to whether the active phase is highly dispersed
copper metal supported on ZnO or Cu(1) ion in a ZnO matrix. This will be
discussed further later.
Highly active and selective catalysts to produce methanol from a CO and H2
mixture have been reported using other copper compounds. I n particular, rare
earth-copper intermetallics appear to be quite effective 121. For these catalysts,
the active phase is believed to be metallic copper.
There has been a large volume of work reported on the study of this reaction,
and a very comprehensive review has been published [2]. The readers should
refer to this review for detailed discussions regarding this reaction.
Methanol can be produced by the hydrogenation of CO or C02:
CO + 2H2 + CH30H (13-1)
CO2 + 3 H2 + CH30H + H2O (1 3-2)
Industrially a mixture of CO, C02 and H2 is used as the feed. The high activity of
Cu-Zn oxide has made it possible to synthesize methanol at a lower temperature
(c30O0C) and a lower pressure (c10 MPa) than those used for the older generation
of catalysts such as Zn-Cr oxide.
Kinetics and Mechanism of Methanol Synthesis
Typical industrial reaction conditions for a copper-zinc oxide catalyst are 200
to 275°C and 5 to 10 MPa total pressure. A typical feed consists of a mixture of
CO (8 to lo%), C02 ( 5 to 6%), and the balance being Hz. At this temperature, the
methanol synthesis catalyst is also an active catalyst for the water-gas shift
reaction:
CO + H20 .I- C02 + H2 (13-3)
The rate of methanol production depends on the partial pressures of the
various components. On Cu-Zn oxide, the rate from a C02/H2 mixture is faster
than froma C0/H2 mixture [6-81. In a mixture of CO, C02, and H2, the ratc
depends both on the CO/C02 ratio and the conversion. At low conversions, the
rate increases with increasing C02 content [6]. At high conversions, the rate first
increases rapidly with the addition of a small amount of C02 to a HdCO feed, but
decreases on further addition beyond an optimal concentration [9,10]. This
behavior is shown in Fig. 13-1. A small amount of water in the feed also enhances
CO HYDROGENATION 229
2
0 30
m
a
20
c
z
W
0
W
a 10
a
I I
0 10 20 30
PERCENT Co p IN SYNGAS, CO+c o 1=3O
Figure 13-1 Effect of COz partial pressure on the rate of methanol production on a Cu-Zn
oxide catalyst. (From J. Catal.. 74, 343 (1982), copyright Academic Press).
the rate of methanol production froma mixture of Hz and CO (Fig. 13-2) [ll],
although high concentrations actually suppresses the rate [6,11].
The behavior shown in Fig. 13-1 can be interpreted possibly by two factors.
The first is that methanol is formed faster by the hydrogenation of COz than by CO.
Thus addition of C02 enhances the rate at low C02 partial pressures. The
apparent suppression of the rate at high C02 partial pressures is probably due to
limitation by the approach to chemical equilibrium. However, it may also be due
to poisoning of the catalyst by carbonate formation, oxidation of the catalyst, or
the presence of a high partial pressure of water due to the reverse water-gas shift
reaction and the hydrogenation of COz.
The behavior shown in Fig. 13-2 can be similarly explained. In the absence
of water, CO hydrogenation is the only reaction possible. Addition of a small
amount of water results in the formation of C02 by the water-gas shift reaction, and
the rate of methanol production is enhanced. Excess water results i n suppression
of the rate because water competes effectively for the active sites.
That C02 is the main source of carbon for methanol has been confirmed by
isotope labeling experiments, first by Rozovskii and coworkers [12-141, and later
by others [15-171. These results can be summarized as follows. If the carbon
atom of a carbon dioxide molecule in a feed is labeled, and the feed is passed over a
230
0 20 40 60 80
Wat er Addi t i on, mol /h X l o3
Figure 13-2 The dependence of methanol synthesis rate on the quantity of water added to the
binary H&O =70/30 vol% synthesis gas with GHSV =6120 l(STP)/kg cat/hr at 7.5 MPa
and temperature of 1: 190DC, 2: 215"C, 3: 22SoC, and 4: 235°C. Catalyst weight =2.45 g.
(From F'roc. 8th Intern. Congr. Catal., II. 47 (1984), copyright Elsevier Scientific hbl . ) .
Cu-Zn oxide catalyst under conditions that are close to the industrial ones, the
carbon label of the methanol molecule is identical to that of carbon dioxide when
thc conversion is low (high space velocities). As the conversion increases (lower
space velocities), the carbon label begins to appear in carbon monoxide, and the
fractions of carbon dioxide and methanol in the reactor outlet that contain the label
decrease. These results are shown in Fig. 13-3 [15,16].
Since water is formed in the experiments shown in Fig. 13-3 by reactions
(13-2) and (13-3), these results suggest that the presence of a small amount of
water has little effect on the main source of carbon for methanol. However, there
are indications that a large amount of water suppresses the rate of hydrogenation of
C02 such that the contribution from CO hydrogenation becomes significant [17].
The effect of C02 on the rate of methanol synthesis from CO differs on other
catalysts. On CuCr02, addition of a small amount of C02 to a CO and H2 feed
actually decreases the rate of production of methanol by about 25%, probably due
to competition by C02 for the adsorption site of H2. Further addition does not show
any more effect [18]. On a Cu/Th02 catalyst, addition of C02 to the C0/H2 feed
CO HYDROGENATION 23 1
a
0
m
5 0.8
CT
\
\
\
\
. ,exi t CO
\
\
%
--
i nl et CO -I
'1 ----
0 1'0 2b
Space Vel oci t y (h-l X
Figure 13-3 Variation of specific radioactivity of the products with space velocity in the
reaction of CO:C02:H2 =10:10:80 over Cu/Zn/Al/oxide. Total pressure =5 MPa, 25O"C,
and the feed contained 14C02. (From Appl. Catal., 30, 333 1987). copyright Elsevier
Scientific hbl .).
has no effect on the rate of methanol production, although it prevents the
deactivation of the catalyst that occurs at low HJCO ratios [19]. On 21-0~.
methanol is produced as a minor product froma HJCO feed only if a small amount
of water is also present [20]. In this case, it is believed that water is needed to
form surface hydroxyl groups which react with CO to form surface formate
species, which are believed to be intermediates in the formation of methanol on this
oxide.
The detailed mechanism of methanol formation on a Cu-Zn oxide catalyst has
been investigated by a number of workers, but no agreements have been reached.
An earlier infrared study has reported the observation of two bands at 2270 and
2661 cm-' which have been assigned to a formyl species [21]. In a later i n situ
study, these two bands were not observed. Instead, a surface formate, which can
be hydrogenated to adsorbed formaldehyde and then to adsorbed methoxy was
observed [22]. This surface formate could be formed by the hydrogenation of a
surface carbonate. A carbonyl species with a vibrational frequency of 2090 cm-'
was also observed which was assigned to CO adsorbed on copper. A surface
formate adsorbed on copper metal has also been identified in the reaction of COz
with H2 [231.
The presence of surface formate has also been confirmed by chemical
trapping with dimethyl sulfate [7]. The presence of surface formyl and
formaldehyde species are inferred from results of chemical trapping with
diethylamine, methyldiethylamine [ 111, and isopropylamine [24]. In these
experiments, the chemical trapping agent is injected into the feed stream of CO and
H2 under reaction conditions for methanol synthesis. The extra products are then
analyzed so as to deduce from them the nature of the adsorbed species that have
reacted with the trapping agent, For example, in the study using isopropylamine
as the trapping agent, methylisopropylamine is formed. Since condensation
between methanol and the amine is slow under the reaction condition, it is
proposed that methylisopropylamine is formed by the reaction of isopropylamine
with adsorbed formaldehyde:
H
R1 R2N C h H
I
M
-H 11.
R1R2NCH20H
+
M
H20 11-H20
R 1 R2NCH3
+
H2 H2O
____) (13-4)
+
M
The result of this experiment therefore supports the presence of surface formyl
and/or adsorbed formaldehyde species, which is formed by the reaction of
adsorbed CO and adsorbed hydrogen.
Based on these results, a likely mechanism for the formation of methanol
from C02 is as follows:
H
+H 2
H I
* + 4 + COz(ad) + * +
-*-OH - H>C4 H &
(13-5)
*
+H CH3 I +H
-- 0 -4 CH30H
J
Nature of Copper-Zinc Oxide Catalyst in Methanol Synthesis
There are two proposals for the nature of the active component in copper-zinc
oxide. Thcy arc Cu(1) ions stabilized in a matrix of ZnO, and highly dispersed
copper metal on a ZnO support. In the former model, the Cu(1) ions are proposed
to be sites for the adsorption of CO, whereas the ZnO matrix is for the adsorption
of H2. This model was first advanced by Klier [3,25]. The data that support this
CO HYDROGENATION 233
model include the following:
a) Optical diffuse reflectance results show that the active catalysts possess a
new absorption band that is not characteristic of ZnO, copper metal, or cupric
oxide.
b) Electron microscopic and surface analyses show intimate contact between
copper and ZnO.
c) The active catalysts contain a copper phase that is amorphous to X-ray
diffraction.
d) The methanol synthesis activity has been reported to be directly correlated
to the amount of strongly adsorbed CO [3], and only Cu(1) species are
known to adsorb CO strongly [26]. In one in-situ infrared spectroscopic
study of the catalyst using CO and H2, a carbonyl species at 2130 cm-I was
observed whose intensity was linearly proportional to the methanol synthesis
activity [27]. In another study, a band at 2093 cm-I was observed that
appears to be involved in the synthesis reaction [lo]. These band frequencies
suggest adsorption on an oxidized formof copper.
e) XPS studies of an active catalyst show that Cu(1) is stabilized by ZnO [28].
f ) CuCr02, which contains Cu(I), is active in methanol synthesis [18,29].
In this catalyst, the activity could be correlated to the amount of Cu(1)
detected by XP S .
I n the second model, copper metal is believed to be the active component.
Zinc oxide serves to stabilize the copper metal in a state of high dispersion, thereby
maintaining a large surface area of copper. Under high pressures, the reactants for
methanol synthesis COz and H2 adsorb on copper. Participation of zinc oxide in
the activation of H2 is also possible. The evidence that support this model
include:
a) The methanol synthesis activity has been found to be linearly proportional
to the surface area of copper [15,16,30], which, for example, can be
determined by the stoichiomeuic decomposition of nitrous oxide.
b) Cu/Si02 is also an active and selective catalyst for methanol synthesis
[27,31]. The activity is comparable to Cu-Zn oxide [27], but it decreases
with time on stream due to sintering of copper [31]. Similarly, highly
active Cu/A1203, Cu/MgO, Cu/MnO and Coho2 catalysts have been report-
ed [15,32]. It is not known that Cu(1) can be stabilized by these supports.
It is unlikely that the question of the active site can be resolved readily
because at present it is quite difficult to characterize a catalyst under reaction
conditions. Since the state of the catalyst, especially the oxidation state of copper,
responds rapidly to the gas composition, there will be uncertainties in the
applicability of the data from various characterization techniques to the working
catalyst.
Effect of Promoters on Cu-Zn Oxide
The performance of a Cu-Zn oxide catalyst can be improved by the addition
of promoters. Aluminum is a structural promoter that significantly increases the
thermal stability of the catalyst. Many other promoters have been mentioned,
including boron, chromium, manganese, rare earth, and some alkaline metal ions
234
ethanol
600
E 6t
met hyl
/- f or mat e
I
7
Nomi nal Cs Conc. mole %
Figure 13-4 Yields of methanol, methyl formate, and ethanol as a function of Cs loading on
a Cu/Zn/O catalyst. Reaction conditions: Hz/CO = 2.333, P =7.6 MPa, GHSV =6120
l(STP)/kg cat-h, 523 K. (From J. Chem. SOC. Chem. Commun.. 193 (1986). copyright
Royal society of Chemistry).
[ 2] , but there is little understanding of their functions.
Potassium, barium, and cesium ions are among the alkali and alkali earth
promoters. The effect of the addition of Cs has been studied in detail [33,34]. It
has been observed that the rate of methanol production by the hydrogenation of CO
is greatly increased by adding a small amount of Cs to the catalyst. This is shown
in Fig. 13-4. Addition of a large amount of Cs, however, blocks the catalyst
surface and causes decline of the activity.
It is proposed that Cs participates in the synthesis reaction in the following
manner [34]:
(13-6)
CO HYDROGENATION 235
In addition to methanol, Cs promotion also enhances the production of C2
compounds such as ethanol and methylformate (Fig. 13-4). as well as higher
alcohols [33,34].
Whether CO or methanol is the carbon source for ethanol and methylformate
produced on a Cs-Cu-Zn oxide has been investigated by isotopic labeling
experiments [34]. By using a mixture of 13CH30H and 12C0/H2 as the reactant, it
is found that the 13C label in methylformate resides almost exclusively in the
methyl group. In ethanol and propanol, the carbon atoms are about equally
labeled.
These labeling data can be explained by the following. Methylformate is
formed by CO insertion into the surface-oxygen bond of a methoxide, which might
be bound to a Cs ion:
CH3 co Y H 3
-H20 I
CSOH + CH3OH e==k 0 ' -+w=O (13-7)
+H20 Cs@ @c s
+HzO
r-- CSOH + HCOOCH3
-H20
--2
The nearly equal extent of labeling of the carbon atoms in ethanol and propanol
suggests that CO insertion is not involved in their formation. It is proposed that
they are formed by coupling of alcohol molecules. For example, the overall
reaction for the formation of ethanol is:
2CH30H CH3CH20H + H2O (13-8)
which might proceed via an aldehydic intermediate:
(13-9)
Higher alcohols are then produced by analogous coupling reactions.
Promotion of a Cu-Zn oxide catalyst by both Co and A1results in a catalyst
that produces almost as much ethanol as methanol at 563 K and 6 MPa pressure
using a feed of HJCO ratio of two [35]. Higher alcohols are also produced the
amounts of which decrease with increasing chain length.
236
Unlike Cs, promotion by potassium enhances the production of branched
alcohols [36]. This will be described in the section on isosynthesis.
13.3 GROW VIII METALMETAL OXIDE CATALYSTS
A number of group VIII metal oxides have been reported to be active in the
hydrogenation of carbon oxides. Rather extensive work has been performed on
systems based on Pd, Rh, and Fe. These will be discussed here. However, in all
of these cases, it is not yet settled whether the active component in the catalyst is
the metal or the metal oxide.
Methanol Production on Palladium Catalysts
I t is well known that Pd catalyzes CO hydrogenation to methane. However,
the production of methanol on Pd has also been known for a long time [37].
Recently, it has been found that methanol can be produced with high selectivity
[38,39]. Since then, it has been found that the methanol selectivity depends on the
support used. For example, methanol is produced almost exclusively on Pd
supported on La2O3. On other supports, the selectivity for methanol decreases as:
La203 >Si02(II) >ZrOz >ZnO - MgO >Ti02 >A1203 2 Si02(I), and the product
on Pd/Si02(I) is practically exclusively methane [40]. It is interesting that the
selectivities are quite different on the two different sources of silica, Si02(I) and
Si02(II). This difference for different SO2 supports has later been confirmed
[41]. In general, basic oxide supports favor methanol production. Different
promoters, such as Na [39,42], Mg, and L a [43] also enhance the selectivity for
methanol.
The reasons behind the dependence of the selectivity for methanol versus
methane on the nature of the promoter or the support are not well understood. One
proposal is that methanol is formed via a formate intermediate. The role of the
alkali ion promoter is to stabilize the formation of the formate [42], which has been
detected by infrared spectroscopy on a Na-promoted Pd catalyst. By isotopically
labeling this formate species and following its reaction, its participation in
methanol production is established. However, this proposal has not been
supportcd by other evidence. In one study, chemical trapping experiments on a
Mg-promoted catalyst did not detect any surface formate. Instead, a good
correlation between the activity for methanol production and the concentration of a
surface formyl species was obtained [44]. In another study, a surface formate
species was detected only on a Pd/La203 catalyst but not on a Pd/SiO2 catalyst,
although the kinetics of methanol synthesis on both catalysts were very similar
P51.
Another factor that might determine methanol selectivity is the morphology
of the Pd crystalliks. It has been suggested that a Pd(100) surface in a Pd/La203
catalyst is more active than a Pd(ll1) surface, and for a fixed morphology,
Pd/La203 is more active than Pd/SiO [461
Yet another proposal is that Pd ion is involved in methanol production. I t
has been found that the rate of methanol production can be correlated to the amount
3 . -
CO HYDROGENATION 237
of Pd extractable by acetylacetone on the promoted catalysts [43]. Since
acetylacetone extracts Pd' ions, this correlation strongly suggests that on these
promoted catalysts, methanol formation is associated with an oxidized Pd center.
The role of a promoter or a suitable support is to stabilize the Pd ion in a reducing
atmosphere. Indeed, Pd' has been detected by EPR on MgO and La203-supported
catalysts [471.
This last proposal is also supported by the effect of oxygen treatment and
isotope labeling results [42]. When Pd is supported on 2 3 0 2 or TiO2, the catalyst
pretreated with oxygen at 723 K followed by a low temperature reduction results in
a higher methanol production rate than one without the oxygen pretreatment. The
effect is removed by a high temperature reduction. It is suggested that Zr02 and
Ti02 can stabilize a certain form of surface oxygen at or near Pd that results in the
active site for methanol production. The effect of oxygen treatment, however, is
absent if the catalyst is promoted with Na, because the special active site is already
stabilized by the alkali ion promoter.
When C1*O is used as a feed over a Na-promoted Pd catalyst, the methanol
produced initially is CH3160H [42]. The amount of such l60 product is much
smaller on catalysts without Na promotion. Thus there is a surface oxygen species
present on catalyts active in methanol production that is stabilized by the alkali ion
promoter.
+
Rhodium Catalysts
Some catalysts based on rhodium oxide have been found to hydrogenate CO
to produce hydrocarbons, methanol and higher oxygenates. The product
distribution depends on the reaction conditions, the presence of promoters, and the
pretreatment of the catalyst 1481.
Table 13-1 lists some examples where the production of oxygenates has been
reported. Among the first rhodium oxide-based catalyst studied was a surface-
oxidized rhodium foil [49a]. At a pressure of 0.6 ma, and a HJCO ratio of 3 to
1/3, up to about 10% oxygenates were produced, which are primarily methanol,
ethanol, and acetaldehyde. Decreasing the HJCO ratio or the reaction
temperature shifted the product distribution towards higher molecular weight
hydrocarbons, and higher ethylene to ethane ratios. Lowering the temperature
also increased the oxygenate yield, while decreasing the HJCO ratio favored the
production of acetaldehyde at the expense of methanol and ethanol. About the
same product distribution was obtained using a H2/C02 feed instead of a HJCO
feed [49b], but the reaction rate was higher.
In comparison. the products from Rh metal that has not been preoxidized
contain no oxygenates but a larger fraction of methane. Furthermore, the activity
of the surface-oxidized rhodium, as measured by the methane turnover number,
(that is the rate of methane production pcr exposed rhodium metal atom before
oxidation), is about ten timcs that of rhodium [49a,b]. The use of a H2/C02 feed
on Rh metal instead of HJCO results in a higher C b selectivity at the expense of
longcr chain hydrocarbons [49b].
Rho2, Rh203, and Rh203.5H20 have been studied as catalysts [50]. I t has
been found that under thc reaction conditions of 300°C, 0.6 MPa of 1:l CO/H2,
238
Table 13-1 Product Distribution in CO Hydrogenation over Rhodium Oxides
Products. wt %
Catalyst 'PC H2/CO' CH, C2H, C,H, C,+ CH,OH C,H,OH MeCHO Oxyge- ref.b
nates
oxidized 300 3/1
Rh foil 300 1/3
and 250 3/1
Rh(ll1) 250 1/3
heavily 300 3/1
oxid. Rh( 11 1)
R$O,. 300 1/1
5Hz0
LaRhO, 300 1/1
225 1/1
8 0 4
7 7 -
2 i
56 15 3 22 - 3 1
60 5
6 17 -
12 i
35 10 2 48 - 10 1
70 4 6 10 - 10 i
29 22(C2) 25 3 tr 16 11
...
16 9(C,+) 17 14 31 111
12 6(C,+) 40 13 23 111
...
Footnotes:
a) 0.6 MPa total pressure.
b, References:
i) D.G. Castner, R.L. Blackadar, and G.A. Somorjai. J. Catal., 66, 257 (1980).
ii) P.R. Watson, and G.A. Somorjai, J . Catal.. 72. 347 (1981).
iii) P.R. Watson, and G.A. Somorjai. J . Catal., 74, 282 (1982).
only Rh203.5H20 resists complete reduction to the metal. The selectivity for
methane on this catalyst is much lower than on a Rh metal or oxidized Rh metal
(see Table 13-1). Almost all Cz+ hydrocarbons are alkenes, and a significant
quantity of oxygenates is produced. I n addition to the products shown, a small
amount of propanal and butanal are produced. At the same temperature and total
pressure, the C b yield increases with an increasing HJ CO ratio, but the product
distribution changes little with total pressure. Increasing the temperature
increases the CH, selectivity.
Addition of C 2b to the feed enhances the production of C~HSCHO. This
can be explained by the general scheme for the formation of aldehyde via
carbonylation of surface hydrocarbon species:
+co +(z+l )H
M-C,H, ---+ M - C O - C , H , A M + C,H,+,CHO (13-10)
CO HYDROGENATION 239
Addition of C2H4 to the feed increases the surface concentration of M-C2& (or M-
C2H5) which, upon carbonylation and hydrogenation, yields propanal.
Results using LaRh03 as the catalyst follow the trend described thus far. At
225 and 30O0C, 0.6 MPa and using a 1/1 C0/H2 mixture, about 80% of the
products were oxygenates, of which ovTr half were acetaldehyde and ethanol.
Among the hydrocarbons, methane was the dominant product. The higher
hydrocarbons were mostly alkenes. In comparison, LaRh03 supported on a-
A1203 produced methanol very selectively [2]. The surface condition of Who 3
during reaction is not known. In one study, surface analyses by AES showed that
the LaRh03 surface contained some Rh metal, but most of the rhodium was in the
+1 state [51]. In another study, surface analyses by XPS showed the presence of
Rh metal and Rh(II1). No Rh(1) was detected [52].
The higher rates of oxygenate and alkene production on rhodium oxides can
be explained by the lower hydrogenation activity and CO dissociation ability of the
oxides than the mctal. On going from heavily oxidized metal to rhodium oxide
and LaRh03, the degree of oxidation and the stability of the oxide increases. (This
has been shown by temperature programmed reduction studies [52]). Concurrently
one sees an increase in the selectivity for higher hydrocarbons, alkenes, and
oxygenates. The increase in oxygenate production is also a result of the higher
concentration of adsorbed molecular CO on the oxides that leads to a greater rate of
CO insertion into a surface MXH, species to produce Cz+oxygenates, and to
more direct hydrogenation of CO to methanol.
It should be noted that the discussions above do not explain the higher
activity due to surface oxidation, especially in methane production. This
phenomenon is not yet satisfactorily explained.
The role of oxidized Rh appears to be also important in other supported Rh
catalyst. On a Rh/MgO catalyst that has a high selectivity for methanol and other
oxygenates, a Rh(I1) EPR signal has been detected [47]. Isotope labeling
experiments show that adsorbed oxygen and/or surface lattice oxygen on a Na-
promoted Rh/Si02 is incorporated into the product acetaldehyde, and that the C 4
bond is formed by CO insertion into a surface CH, species [421.
However, the participation of rhodium oxide has not been universally
accepted. Recently, it has been reported that the product distributions are similar
on a Rh/Si02, reduced Rh2O3, and prereduced or unprereduced LaRh03 catalyst.
This has led to the suggestion that Rh metal is the active component [52].
Iron Catalyst
Recently, it has been suggested that iron oxide is active in CO hydrogenation
because the catalytic activity of an iron foil is increased ten times when the foil is
preoxidized in dry oxygen before exposure to a C0/H2 mixture [531. This high
activity decreases with time as the surface oxide is reduced. Subsequently, it was
reported that the pseudo-steady state CO hydrogcnation activity of an unsupported
catalyst whose precursor is a-Fez03 is higher, if the iron oxide has not been
prereduced, than if it is prercduced to a-Fe [54]. The bulk of the unprereduced
catalyst is converted to Fe304 at pseudo-steady state. However, there is no
information on the surface conditions. The a-Fe catalyst is converted to iron
240
carbide during reaction, and the used catalyst contains more surface graphitic
carbon than the used unprereduced catalyst. These results show that bulk Fe304 is
at least as active in CO hydrogenation as bulk metallic iron or iron carbide.
Most of the observations above have been confinned in another study [55].
In particular, the pseudo-steady state bulk compound of a a-Fe203 catalyst is
confinned to be Fe304. Some X-iron carbide is also present. If the a-Fe203 is
prereduced to Fe before reaction, the pseudo-steady state catalyst contains x -
carbide and small amounts of €'-carbide and a-Fe. However, the product
distributions over these two catalysts are the same. This has led to the conclusion
that neither F@03 nor Fe304 are active for hydrocarbon synthesis. It is proposed
that the superior catalytic acitivity of the unprereduced a-FezO3 catalyst is due to
the formation of very small crystallites of a-Fe and X-iron carbide under reaction
conditions, which are the active phases.
13.4 ISOSYNTHESIS REACTION
It has been found that on some basic oxides, especially Zr 02 and Tho2 [56-
601, and some rare earth oxides such as La203 and Dy2O3 [61], branched alcohols
and hydrocarbons are produced quite efficiently, particularly 2-methylpropane, 2-
methylpropene, and 2-methylpropanol. Table 13-2 shows some sample data for
Zr02 [58]. At the low conversions shown, alcohols, ether, and hydrocarbons are
the major products, and substantial amounts of 2-methylpropane and 2-
methylpropene are produced. These two branch-chain molecules are among the
major hydrocarbon products also at much higher conversions of CO, although then
the predominant reaction producct is COz, which is formed by the water-gas shift
reaction [W]. The reaction that leads to the production of these branched products
is called the isosynthesis reaction. In addition to the oxides mentioned above,
some alkali-promoted ZnO [56] and potassium-promoted Cu-Zn oxide [36] also
produce branched products.
The formation of alcohols and hydrocarbons in the isosynthesis reaction are
closely related. For example, on Th02, branched alcohols are produced in
substantial yields below about 375°C. At higher temperatures (425-450°C),
branched C4 hydrocarbons are formed. Above 50O0C, methane, ethane, and
propane are the principal products [62].
A mechanism for chain growth and chain branching in the isosynthesis
reaction on Zr02 is shown in Fig. 13-5 [58,63]. It is based on analogous
compounds and reaction mechanisms involving coordination complexes. An
important intermediate in this mechanism is the bound aldehyde (species I). The
lowest member of the bound aldehyde is the bound formaldehyde (R=H), which
can be formed by hydrogenation of adsorbed CO or surface formate. The
hydrogenation of adsorbed CO may take place by insertion of CO into a metal-
hydrogen bond. A model for this step is the reaction of CO with [(Cp)2ZrHCIl, to
give [(Cp)2ZrC1]2(p-CH20) [a]. This latter compound has a bridging
formaldehyde moiety in which the oxygen atom of the formaldehyde bridges the
two metal atoms and the mcthylene fragment is bound to one Zr and the 0 atom.
CO HYDROGENATION 241
Table 13-2 Product Distributions in CO Hydrogenation on Zr02 (425°C.
3.5 MPa total pressure, CO/H2 =l/l). (From J. Catal., 109, 284 (1988),
copyright Academic Press).
CO conversion %
Product Selectivity (mole %)
methane
methanol
dimethy lether
ethane and ethene
propane and propene
linear C4's
branched C4's.
linear C5's
branched C5'sb
C4 alkenes/C4 alkanes (mole ratio)
catalyst 1
0.6
42.8
4.1
16.8
11.8
3 .O
4.6
13.1
0.5
2.3
16.4
catalyst 2
0.4
41.9
5.9
10.4
11. 1
4.7
5.9
16.2
0.4
3.5
20.2
Foomotes:
a) The ratio of 2-methylpropene/branched C4's is greater than 0.93.
b, Monomethylated butanes only.
C2 compounds are formed by insertion of CO into a bound formaldehyde to
form a cyclic acyl species (I -+TI). Hydrogenation of species II (I1 -+I V) would
eventually lead to a linear alcohol that is one carbon longer.
The acyl species @I) has an isomeric structure (HI), which permits 1,2-H shift
to form an enediolate (I11 -+V). The formation of enediolate by a similar process
has been suggested in complexes of thorium, uranium, and hafnium [65,66].
Chain branching results when the enediolate is hydrogenated to form a bound diol
(V -+VI) which dissociates to form an enolate and a surface hydroxyl (VI 4 VII).
The latter step is similar to what would be involved in the catalytic dehydration of
alcohols. Species VII has a resonance structure VIII which is a q3-enolate.
Addition of H to VIII leads to a bound aldehyde structure OX). Insertion of CO
into this species like the step I -+I1 complctcs the cycle for chain branching.
The validity of this mechanism, especically the importance of the bound
aldehyde structure, has been tested by monitoring the incorporation of propanal
and acetone into the isosynthesis products. I t has been found that on ZrOz [58],
addition of propanal to a feed of CO and H2 increases theyields of 1-butene, 2-
mcthylpropene, and 2-methyl- 1-propanol. By using 13C-labeled propanal, it is
confirmcd that these products can indeed be formed from propanal. Similarly,
when acetone is added, the yields of I-butene, 2-methylpropene, and 2-methyl-l-
2
4
2

[
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1

I

N

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n

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I

u
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N

I
-

u

7

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:
T

m

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n

(
Y

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,

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L

-

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1

CO HYDROGENATION 243
CH3 I
z; j o
CH2
I
CH
\
( 1 )
*
- H
L
-
+ H
CH 3
I
CH3-CH
I
CH20H
+ H
1
7
- H
1
CH 3
I )o
* I
CH3-CH
I
CH
Z r
( XI 1 1
I,
CH3 I
0
I
Zr
( XI )
+
Figure 13-6 Aldol condensation mechanism in the formation of branched products on Z Q .
(From the same source as Figure 13-5. copyright Academic Press).
butene are increased.
The enhanced yields of these products support the participation of surface
species of the bound aldehyde structure (I and IX). A bound propanal would
produced 1-butene by the reaction sequence I + I1 + I V 4 butanol, which is
dehydrated to 1-butene. The same reaction sequence for a bound acetone would
produce 2-methylpropanol, which on dehydration would result in 2-methyl-
propene. The production of 1-butene from acetone is interesting. It can be
accounted for if the steps leading from species II to IX are all rapidly reversible.
I t has also been shown that when 2-propanol is added to the reaction feed,
there is little enhancement in the yields of the C4 products [%I. Thus 2-propanol
cannot be converted easily into an intermediate for chain growth or chain
branching. This rules out the possibility that acetone is first hydrogenated to 2-
propanol before i t is converted to the C4 products.
The enhanced production of 2-methylpropene or 2-methylpropanol from
propanal, or 2-methyl-1 -butene from acetone cannot be explained by this
mechanism. However, these are important products. In the experiments where
propanal was added, it was observed that the yields of 2-methyl-1-propanol and 2-
methylpropanal were both increased substantially in a parallel fashion. I t was
244
concluded that these oxygenates were the primary products. They were
subsequently converted to 2-methylpropene by dehydration and hydrogenation
[%I. The enhanced yields of these products suggest the presence of a parallel
mechanism, which is also suggested by other evidence. If the mechanism i n Fig.
13-5 is the only process on the catalyst, it would predict a statistical distribution of
products with respect to the number of carbon atoms in the molecules. In
particular, the amount of each product would decrease in a proportional manner as
the carbon number increases, (that is, it would follow the Anderson-Schultz-Flory
distribution). The data in Table 13-2 shows that this is not the case. The amounts
of C4 products are substantially more than those of C3 and C5.
To account for these observations, an additional mechanism has been
proposed. This mechanism is shown in Fig. 13-5. It involves alkylation of an q3-
enolate by a nearby methoxide group at the P-carbon. This is a condensation
reaction, and it is assumed that during synthesis from CO and H2, this reaction is
faster for the C2 species than for the C3 or C4 species, and has no equivalent i n the
C1 reactions [63].
The participation of this condensation reaction has been confirmed. I t has
been observed that when '3C-melhanol is added to the CO/H2 feed, 13C is
incorporated into 2-methylpropene, 2- and 3-methyl-1 -butene, and 2-methyl-2-
butene. Interestingly, no 13C incorporation is observed i n the C4 or C5 linear
products [ S S ] . Since it has been shown that methanol adsorbs as methoxide on the
catalyst [67], the incorporation of 13C into the branched products supports the
condensation mechanism.
This mechanism explains the production of 2-methylpropanol and 2-
methylpropene from propanal. Condensation of a methoxide with a bound
propanal results in these products. The production of 2-methyl-1-butene from
added acetone can be understood also. Condensation of a methoxide with a bound
acetone would produce 2-butanol or 2-butanone. CO insertion to a bound 2-
butanone followed by the reaction sequence leading from I to IV would produce 2-
methyl-1-butene.
13.5 WATER-GAS SHIFT REACTION
The water-gas shift reaction is an industrial process to generate hydrogen from
steam and carbon monoxide:
CO + H20 + C02 + H2
The reaction is carried out between 1 to 3 MPa. The commercial catalysts are of
two types. An iron-chromium oxide catalyst, sometimes promoted by other
oxides such as A1203, or supported on Si02, is used at a higher temperature of 600-
725 K. A newer catalyst, based on copper-zinc oxide, promoted by Cr, Co, A!,
and Ni, is used at a lower temperature of about 500 K. The advantage of the
copper-zinc oxide catalyst over the iron-chromium oxide catalyst is that the
catalyst is much more aclive and can be used at lower temperatures where the
CO HYDROGENATION 245
equilibrium is more favorable to the formation of H2. The disadvantages are
sensitivity to poisoning by sulfur and chlorine, and shorter catalyst life.
The copper-zinc oxide catalyst used for this reaction is essentially the same as
the one used in methanol synthesis. In fact, during methanol synthesis, the water-
gas shift reaction proceeds at a comparable rate. Thus the readers are referred to
section 13.2 for discussions of this catalyst. When this catalyst is used for water-
gas shift, methanol production becomes thermodynamically unfavorable because
of the high water and low hydrogen partial pressures.
It is believed that the mechanism of the reaction over copper-zinc oxide
involves a surface formate that is formed by the insertion of CO into a surface
hydroxyl group:
CO(g) + CO(ad) (13-1 la)
H20(g) + OH-(ad) +H+(ad) (13-llb)
CO(ad) +OH-(ad) + HCOO-(ad) ( 13- 1 1 C)
HCOO-(ad) _L C02(ad) +H-(ad) (13- 1 Id)
A correlation between the ability to form a surface formate and the water-gas
shift activity of a catalyst has been observed [68]. On Cu-Zn oxide, this
mechanism has been discussed for methanol synthesis (similar to reaction 13-6). A
surface formate has been identified by chemical trapping [7] and by infrared
spectroscopy for the reaction of H2 +C02 [22,23]. Further support comes from
the fact that the rate for formic acid decomposition is comparable to that for water-
gas shift reaction [69].
In spite of the fact that a surface formate is probably involved as an
intermediate in both the water-gas shift and the methanol synthesis reaction, there
are no indications that these two reactions are necessarily correlated. In fact, the
relative activities for the two reactions on different catalysts could be quite
different.
The iron-chromium oxide is a mixture of Fe304 and Cr203 under reaction
conditions. It is generally agreed that the addition of Cr greatly helps retain the
surface area of the catalyst. There is no evidence that chromium chemically
affects the iron oxide. The mechanism with which the Cr promoter functions is not
firmly established. I t has been suggested that Cr2O3 forms a protective layer
around the a-Fe203 particles (which has the same corundum structure as Cr2O3)
during calcination, thereby prevcnting particle growth of the iron oxide [70].
Indeed, determination of the surface composition of an Fe203-Cr203 solid solution
has suggested the formation of a surface compound which might serve as the
protective laycr [71]. I t has been shown on another system of Fe304 supported on
246
Si02 that the formation of a surface shell of iron-silicon oxide on a Fe304 particle
stabilizes the particle from sintering during oxidation-reduction [72].
There are two proposed mechanisms for the iron-chromium oxide catalyst.
One mechanism involves a surface formate as shown in eq. 13-11 173,741. The
other is a redox mechanism in which a surface oxygen species is involved as is
shown below:
(13-12)
sl ow p
L
- M +CO2
sl ow 0, p
-2
- M +H2
In this mechanism, the active site is proposed to be an anion-cation pair
O P
site ( \M ). CO first adsorbs weakly on the coordinatively unsaturated metal
cation of this site. This weakly adsorbcd molecule then reacts with surface oxy-
gen i n the site to form a bidcntate carbonate, which decomposes into C02 leaving
an anion vacancy in the site (M ). The anion vacancy is the site for the adsorp-
tion of water. The oxidized surfacc site is regcncratcd by thc desorption of H2
[751.
Support for this redox mechanism (also called rcgencrative mcchanism) has
been provided by chemisorption expcriments undcr catalytic conditions which
show that: (1) H2 adsorbs dissociatively and H2 0 adsorbs associatively, and the
isotherm for concurrent adsorption of bolh molcculcs follow the form for
competitive adsorption [75]; (2) whcn a Fe3O4 catalyst is exposed to a mixture of
CO and C02, thc adsorption isotherms of thcse molecules also follow the form for
competitive adsorption. Furthermorc, thc saturation coverage of CO corrcsponds
directly to thc coverage of anion vacancics, while changes i n the C02 saturation
coverage correlate with changcs in the covcragc of the reducible oxygcn spccics
on thc surface 1761; (3) by following the CO-C02 isotopic exchange reaction using
13C-labeling 1771, it is concludcd that CO and C02 arc indistinguishable once
adsorbcd on thc catalyst as is prcdictcd by rcaction (13-12); (4) the rates of
production of CO from thc rcaction of C02 with a catalyst surfacc, of C02 froin
CO as mcasurcd hy thc chcinisorption cxpcrirncnts, and of 1-12 from H20 and H2O
/O
CO HYDROGENATION 247
0 50 100 150 200
Fe 0 Par t i cl e Si ze, nm
3 4
Figure 13-7 The F q04 particle size dependence of the water-gas shift activity of magnetite.
Open circles represent unsupported Fe304 (except that the smallest particle-size sample is
a commercial catalyst) and solid circles represent silica-supported catalysts. (From J.
Catal., 76, 93 (1982). copyright Academic Press).
from H2 are comparable to the rate of th water-gas shift reaction under similar
conditions [78]; and (5) it is observed that the rate of the wixr-gas shift reaction
corresponds to the rates at which H20 oxidizes and CO reduces the surface of Fe304
[79,80].
I t has been further proposed that the active site consists of octahedrally
coordinated Feions of magnetite that are exposed on the surface. The proposal is
based on the following observations [75]. I t is found that, the rate of the water-gas
shift reaction per surface Fe ion (the amount of exposed surface Fe ions is
dctcrmined by NO adsorption) is relatively ilJ dependent of the crystallite size of
unsupported Fe304 (see Fig. 13-7) 1811. Hovever, the rate per surface Fe ion
decreases sharply with decreasing crystallite size on Si02-supported magnetite
catalysts. On the other ha. neither unsupported nor supported catalysts show
crystallite-six dependence when the number of active sites is determined by
CO/C02 adsorption (which measures the amount of removable oxygm on the
catalyst surface). I t is further shown that Si ions substitute into the magnetite
248
lattice at the surface of the crystallites in the Si02-supported catalysts. The Si ion
substitution occurs at the tetrahedral sites [72].
The data in Fig. 13-7 can beexplained as follows. The catalytically active
site consists of a surface-exposed Fe cation in an octahedral site and the
surrounding oxygen anions. Then the apparent crystallite-size effect on the
supported samples is due to the following. In a Si02-supported catalyst, Si4+
substitution in the magnetite surface causes all of the Fe ions to be in the octahedral
sites as well as a decrease in the electron density at these ions. The latter effect
perturbs the balance between Fez+and Fe3+at these sites and reduces their ability
to undergo oxidation and reduction, as is required in the regenerative mechanism.
This effect is manifested in a decrease in the amount of reducible oxygen on the
surface as determined by CO/CO2 chemisorption, and a corresponding decrease in
catalytic activity. Since the Si subsitution is confined to the surface, its effect is
larger for smaller crystallites, and affects more strongly the more weakly adsorbed
gases such as CO and C02. On the other hand, it does not affect the adsorption of
more strongly adsorbed gases such as NO. This might be due to surface
reconstruction induced by NO adsorption on cations that are inaccessible to more
weakly adsorbed gases [81,82].
REFERENCES
1 . "Catalysis. vol. 3," P.H. Emmett ed., Reinhold, New York, 1955.
2. G. C. Chinchen, P. J. Denny, J. R. J ennings, M. S. Spencer, and K. Waugh.
3. K. Klier, Adv. Catal., 31, 243 (1982).
4. P. J . Denny, and D. A. Wan, "Catalysis". vol. 2. Chem. SOC., London, 1978, p.46.
5. H. H. Kung, Cataf. Rev., 22. 235 (1980).
6. G. Liu, D. Wilcox, M. Garland, and H. H. Kung, J . Cataf., 90, 139 (1984).
7. R. Kieffer, E. Ramaroson. A. Deluzarche, and Y. Trambouze, React. Kinet. Cataf.
8. B. Denise, and R. P. A. Sneeden, J . Mofec. Cutaf.. 17. 359 (1982).
9. K. Klier. V. Chatikavanij. R. G. Herman, and G. W. Simmons. J. Cataf..
Appf. Cataf.. 36, 1 (1988).
Lett., 16, 207 (1981).
74, 343 (1982).
10. R. Bardet, J. Thivolle-Cazat, and Y. Trambouze, J. Chim. Phys., 78, 135 (1981).
1 1 . G. A. Vedage, R. Pitchai, R. G. Herman. and K. Klier. Proc. 8th Intern.
12. Yu. B. Kagan, A. Ya. Rozovskii. L. G. Liberov, E. V. Slivinskii, G. I. Lin,
Congr. Catal.. vol. II, 47 (1984).
S. M. Loktev, and A. N. Bashkirov. Dokf. Akud. Nauk. USSR, Chemistry Section,
224, 598 (1975).
13. A. Ya. Rozovskii, Kinet. Cataf., 21, 78 (1980).
14. A. Ya. Rozovskii, Yu. B. Kagan, G. I. Lin, E. V. Slivinskii. S. M. Loktev.
L. G. Liberov, and A. N. Bashkirov, Kinet. Cataf., 16, 706 (1975).
15. G. C. Chinchen, P. J. Denny, D. G. Parker, G. D. Short, M. S. Spencer, K. C. Waugh,
and D. A. Wan, Preprint Div. Fuel Chemistry, Amr . Chem. SOC.. 29, 178 (1984).
CO HYDROGENATION 249
16. G. C. Chinchen. P. J. Denny, D. G. Parker. M. S. Spencer, and D. A. Whan,
17. G. Liu, D. Willcox, M. Garland. and H. H. Kung, J. Catal., 96, 251 (1985).
18. I. R. Monnier, G. Apai, and M. I. Hanrahan, J. Catal., 88, 523 (1984).
19. F. P. Daly. J. Catal.. 89. 131 (1984).
20. N. J ackson, and J . Ekerdt, J. Catal., 101. 90 (1986).
21. I. Saussey, 1.-C. Lavalley. I. Lamotte, andT. Rais, J . Chem. Soc. Chem. Commun.,
22. J . F. Edwards, and G. L. Schrader. J. Phys. Chem.. 88, 5620 (1984); I. Catal.,
23. Y. Amenomiya, and T. Tagawa. Proc. 8th Infern. Congr. Catal., II, 559 (1984).
24. G. A. Vedage, R. G. Herman, and K . Klier, J . Catal.. 95,423 (1985).
25. R. G. Herman, K. Klier, G. W. Simmons, B. P. Finn, J . B. Balko, andT. P.
26. Y. Y. Huang, J. Catul., 30, 187 (1973).
27. C. Visser-Luirink, E. R. A. Matulewicz, I. Hart. and J. C. Moi. J. Phys. Chem..
28. Y. Okamoto. K. Fukiro. T. Imanaka, and S. Teranishi, J. Phys. Chem.,
29. J . R. Monnier. M. Hanrahan. and G. Apai. J. Catal., 92, 119 (1985).
30. K. Fukino, T. Imanaka, and S. Teranishi, Proc. 8th Intern. Cong. Catal., 11.
31. J . B. Friedrich. M. S. Wainwright, and D. J . Young, J. Catal., 80. 1 (1983).
32. E. G. Baglin. G. B. Atkinson, and L. J . Nicks, I&EC Proc. Res. Develop., 20, 87
33. J. Nunan, K. Klier, C.-W. Young, P. B. Himelfarb, and R. G. Herman,
34. J . Nunan, C. Bogdan, K. Klier. K. Smith, C. Young, and R. Herman, J. Catal.,
35. Ph. Courty, D. brand, E. Freund, and A. Sugier. J. Molec. Cutal.. 17. 241 (1982).
36. K. J . Smith, and R. B. Anderson, C w d . J . Chem. Eng.. 61.40 (1983).
37. German patent 293787 (1913).
38. M. L. Poutsma. L. F. Elek, D. A. Ibarbia. A. P. Risch, and J. A. Rabo, J . Catal.,
39. Y. Kikuzono, S. Kagami, S. Naito, T. Onishi, and K. Tamaru. Faraday Disc.,
40. Y. A. Ryndin, R. F. Hicks, A. T. Bell, and Y. I. Yermakov, J. Catal., 70, 287 (1981).
41. F. Fajula, R. G. Anthony, and J. H. Lunsford. J . Cutal.. 73, 237 (1982).
42. S. Naito, H. Yoshioka. H. Orita, and K. Tamaru, Proc. 8th Intern. Congr. Catal.,
43. J . M. Driessen. E. K. Poels, J . P. Hindermann, and V. Ponec, J. Catal., 82, 26 (1983).
44. J . P. Hinderman, A. Kienncmann, A. Chakor-Alami, and R. Kieffer, Proc.
45. R. F. Hicks, and A. T. Bell, J. Catul.. 91, 104 (1985).
46. R. F. Hicks, and A. T. Bell. J . Catal.. 90, 205 (1984).
Appl. Catal., 30. 333 (1987).
278 (1982).
94, 175 (1985)
Kobylinski, J. Catal.. 56, 407 (1979).
87, 1470 (1983).
87, 3740, 3747 (1983).
159 (1984).
(1981).
J . Chem. Soc. Chem. Commun.. 193 (1986).
113, 410 (1088).
52, 157 (1978).
Chem. SOC., 72, 135 (1981).
HI, 207 (1984).
8th Infern. Congr. Coral.. II. 163 (1984).
250
47. E. K. Poels, P. J . Mangus, J. V. Welzen, and V. Ponec, Proc. 8th Intern. Congr.
48. T. Wilson, P. Kasai. and P. Ellgen, J. Catal., 69, 193 (1981);
49a. D. G. Castner, R. L. Blackadar, and G. A. Somorjai. J. Cataf.. 66, 257 (1980).
49b. B. A. Sexton, and G. A. Somorjai, J. Cataf., 46, 167 (1977).
50. P. R. Watson, and G. A. Somorjai, J. Catal., 72, 347 (1981).
51. P. R. Watson, and G. A. Somorjai, J. Catal., 74, 282 (1982).
52. H. J . Gysling, J. R. Monnier, and G. Apai, J . Catal., 103, 407 (1987).
53. D. J . Dwyer, and G. A. Somorjai. J. Cataf., 52, 291 (1978).
54. J . P. Reymond, P. Meriaudeau, and S. J. Teichner, J. Cataf., 75, 32 (1982).
55. R. A. Dictor, and A. T. Bell, J. Cataf., 97, 121 (1986).
56. G. Natta, U. Columbo. and I. Pasquon, "Catalysis", P.H. Emmett ed..
57. H. Storch. N. Golumbic, and R. Anderson, 'The Fischer-Tropsch and Related
58. S. C. Tsang, N. J ackson, and J . Ekerdt, J. Cataf., 109, 284 (1988).
59. C. Chang. W. Lang. and A. Silvestri, J. Cataf., 56. 268 (1979).
60. T. Maehashi, K.4. Maya. K. Domen, K. Aika, and T. Onishi. Chem. Lett.
61. R. Kieffer, J . Varela, and A. Deluzarche, J. Chem. Soc. Chem. Cornmum.,
62. H. Pichler, and K.-H. Ziesecke, Bur. Mines Buff. , 448 (1950).
63. T. J . Mazanec, J. Cataf., 98, 115 (1986).
64. S. Gambarotta, C. Floriani, A. Chiesi-Villa, and C. Guastini, J. Amer. Chem. Soc.,
65. J. Manriquez. P. Fagan, T. Marks, C. Day, and V. Day, J. Amer. Chem. Soc.,
66. D. Roddick. M. Fryzuk. P. Seidler. G. Hillhouse, and J . Bercaw, Organometalfics,
67. N. J ackson, and J . Ekerdt, J. Catal., 101, 90 (1986).
68. D. G. Rethwisch, and J . A. Dumesic, Appl. Catal., 21. 97 (1986).
69. T. Van Henvijnen, and W. A. de J ong, J. Cataf., 63, 83. 94 (1980).
70. F. Domka, and M. 2. Laniecki, Anorg. Af l g. Chem., 435. 273 (1977).
71. M. Kung, and H. Kung, Surface Sci., 104. 253 (1981).
72. C. R. F. Lund, and J. A. Dumesic, J . Phys. Chem., 85, 3175 (1981);
73. S. Oki, and R. Mezaki. J. Phys. Chem., 77. 447 (1973).
74. S. Oki, J. Happel. M. Hinatow, and Y. Kaneko. Proc. 5th Intern. Congr. Catal.,
75. C. Lund, J. E. Kubsh. and J. A. Dumesic, ACS Symp. Series no. 279, "Solid State
76. J . E. Kubsh, Y. Chen, and J. A. Dumesic, J. Cataf., 71, 192 (1981).
77. M. Tinker, and J . Dumesic, J . Cataf.. 103. 65 (1987).
78. J . E. Kubsh, and J. A. Dumesic. AlChE J ., 28, 793 (1982).
79. G. K. Boreskov, T. M. Yur'eva. and A. S . Sergeeva, Kinet. Kafaf., 11, 1476 (1970).
Cataf., II. 61 (1984).
M. Kawai, M. Uda, and M. Ichikawa, J . Phys. Chem., 89, 1654 (1985).
Reinhold Publ., vol. V, 131 (1957).
Synthesis." Wiley, N.Y., 1951.
Chem. SOC. Jpn., 747 (1984).
763 (1983).
105, 1690 (1983).
100, 7112 (1978).
4, 97 (1985).
86. 130 (1982).
1973, p. 173.
Chemistry in Catalysis," ed. R. K. Grasselli, and J . F. Brazdil, 311 (1985).
CO HYDROGENATION 251
80. G. K. Boreskov, Kinet. Kufal.. 11, 374 (1970).
81. C. Lund, and J. Dumesic, J. Cafal., 76, 93 (1982).
82. K. Segawa, Y. Chen, J. Kubsh, W. Delgass, J. Dumesic. and W. K. Hall, J. Cnfal..
76, 1 1 2 (1982).
Chapter 14
PHOTO-ASSISTED SURFACE PROCESSES
14.1 INTRODUCTION
A general picture of the bulk electronic band structure of the valence
electrons of transition metal oxides may be described as follows: the 0 2p orbitals
overlap to form a filled valence band, and the s and d orbitals of the cations overlap
to form the conduction band. The conduction band is at a higher energy than the
valence band and separated from it for most transition metal oxides at their highest
oxidation states. The separation between the two bands is the band gap (Fig. 14-
la). At thermal equilibrium, the Fermi energy (that is, the electrochemical
energy) of the valence electrons in the solid is between the conduction band energy
and the valence band energy. The conduction band is populated with only a few
electrons that are thermally excited into the band from the valence band. This
excitation also leaves holes (unoccupied electron orbitals) in the valence band.
The density of electrons in the conduction band can be increased by incorporating
donor ions in the solid that donate valence electrons to the conduction band, and
the density of holes in the valence band can be increased by acceptor ions that
accept electrons from the valence band. The presence of these donor or acceptor
ions also causes a corresponding adjustment of the Fermi energy such that at
thermal equilibrium, the density of electrons in the conduction band, n, and of
holes in the valence band, p, are given by:
where E,, Ef. E, are the lowest energy of the conduction band, the Fermi energy,
and the highest energy of the valence band, rcspectively. N, and N, are constant.
N, is related to the effective mass and mobility of an electron in the conduction
band, and N, is related to the effective mass and mobili, y of a hole in the valence
252
PHOTO-ASSISTED PROCESSES
1
/Ill/ conduction band
253
I- - - - - - - -
band gap
valence band
Figure 14-1 Energy level diagram of a semiconducting oxide. a. In vacuum; b. In contact
with a solution containing a A-/A redox couple; c. As in b but under illumination. The
photo-generated hole migrates to the surface to accept an electron from A-; the
photo-generated electron migrates to the bulk of the solid and to a counter-electrode.
band. k is the Boltzmann constant, and T is the temperature.
This simple picture applies to the bulk of an ideal oxide. As discusscd in
Chapter 3, truncation of the solid to form surfaces might generate surface
254
electronic states. In addition, the position of the Fermi energy may be different
under different situations such as when the oxide is in contact with another
medium, when there are adsorbates on the oxide surface, or when the surface is
partly reduced. These situations could result in a surface region of the solid that is
very different from the bulk, and a potential gradient is developed between the
surface and the bulk. Associated with this potential gradient is a distribution of
densities of electrons and holes (Fig. 14-lb). Absorption of light of energy larger
than the band gap energy by the solid also changes these populations. Depending
on the solid, the light intensity and its wavelength, photo-excitation could increase
the population of electrons and holes by thousands or millions times. When these
photo-generated holes and electrons migrate to the surface, light-induced surface
chemistry becomes noticeable.
A photo-enhanced surface electron transfer process is schematically
illustrated in Fig. 14-1. The energy level diagram of an oxide neglecting any
surface effects is shown in Fig. 14-la. When this sample is placed in water which
contains a redox couple A-/A, electron transfer between the solid and the solution
occurs until the electrochemical potential of the valence electrons in the solid
equals that in the solution. If the redox couple A-/A is the only species that can
exchange electrons with the solid, the electrochemical potential of the solution is
defined by the standard redox potential of this couple and the relative
concentrations of A- and A. Fig. 14-lb shows the situation where before the solid
contacts the solution, the Fermi energy of the solid is higher than the
electrochemical energy of the elcctrons in the solution, and after contact, electrons
flow out of the solid to the solution so as to establish equilibrium (that is,
equalization of electrochemical potcntial) across the interface. The outflow of
electrons from the solid results in a net positive charge near the surface in the solid,
which eventually sets up a potcntial barrier to stop the electron flow. Equilibrium
is then established. The region of the solid near the surface that has a net charge is
called the depletion layer.
When the solid absorbs a photon of light of an energy larger than the band
gap, an electron is excited from the valence band to the conduction band (Fig. 14-
lc). Because of the upward-bending of the electron bands near the surface. the
photo-generated hole tends to migrate to the surface, while the electron tends to
migrate to the bulk. This results in anincreased hole concentration at the surface,
which facilitates surface reactions involving electron transfer to the solid, such as
oxidation reactions. This situation persists as long as the solid is illuminated and
there is a mechanism to remove the electron that has migrated to the bulk. Flow of
electrons from the oxide via an external circuit to a counter electrode is one way to
remove them.
If there are no mechanisms to remove the electrons from the bulk, continuous
illumination will result in accumulation of elcctrons and holes near the surface, to
the extent that the bending of the electron bands is removed. The photo-generated
elcctrons become available at the surface i n significant concentrations, which
facilitate surface reactions that involve transfer of elcctrons from the solid, such as
reduction reactions.
Recently thcrc has becn a strong intercst to replace the external circuit that
PHOTO-ASSISTED PROCESSES
A A-
D-
3
P t
Ti O2
255
Figure 14-2 Schematic diagram showing a Ti02 particle deposited with Pt. Absorption of
a photon generates an electron-hole pair. a. The hole migrates to the Ti02 surface to
accept an electron from a donor species, and the electron migrates to thz Pt surface to be
donated to an acceptor species. b. The energy level diagram of this system under
illumination.
connccts the counter electrode and the irradiated oxide by direct contact of the two
elcctrodes. Platinum deposited on TiOz is the most popular system that has been
investigated. In this system, the photo-generated holes are consumed in the
surface reaction at Ti02. The photo-generated electrons migrate to platinum where
they are consumed in a reaction at the platinum surface. The complete oxidation-
reduction cycle can be accomplished on one composite particle. This is
schematically shown in Fig. 14-2.
I t is seen from this description that the photo-effect is significant only when a
large concentration of photo-gcnerated holes and/or electrons are present at the
oxide surface. Since most of the light is absorbed by the region of an oxide up to a
256
few hundred nanometers from the surface, these holes and electrons must have
sufficiently long lifetimes to reach the surface. Therefore, reduction of an oxide
and the presence of lattice defects and impurities which shorten the lifetime of
these holes and electrons will reduce the photo-effect. The lifetime also depends
on the effective masses of these carriers, which depend on the band structure of the
solid. For
example, photo-enhanced processes are readily observed on ZnO and Ti02, but are
much weaker on V205.
It is also apparent that light of an energy larger than the band gap energy is
needed to produce photo-effects. I t is possible to generate photoelectrons with
light of a lower energy if there are discrete energy levels (commonly called traps)
in the band gap. Absorption of a photon may excite an electron from the trap to
the conduction band. Similarly, it is possible to generate photo-holes by exciting
electrons from the valence band into the unfilled inter-band gap traps. However,
these processes are normally not efficient. The concentration of these traps are
limited so that the possible densities of photo-generated holes and electrons are
also limited. These traps usually act as electron-hole recombination centers that
shorten the lifetime of the photo-generated carriers.
The description for the scheme shown in Fig. 14-1 is for an n-type
semiconducting oxide. An analogous scheme can be readily drawn for a p-type
semiconducting oxide, whose Femi energy is much closer to the valence band than
n-type semiconductors. Because of the position of the Fermi energy, it is common
that electrons flow into a p-type oxide from an external redox couple. This results
in a bending of the electron bands in a direction opposite to those shown in the Fig.
A side effect that occurs on illumination is heating of the oxide. A majority
of electrons and holes recombine nonradiatively. The energy released heats up the
oxide. In many experiments, light sources are used that give a broad spectral
distribution. Some light of energy less than the band gap energy is absorbed by
the phonon mode of the oxide and heats up the solid. The extent of heating
depends on the oxide and the light source used. A temperature rise to 60°C from
room temperature has been reported [ 19] .
Thus the magnitude of the photo-effect depends on the oxide.
14-1.
14.2 PHOTO-ASSISTED ADSORPTION AND DESORPTION
As described in the last scction, absorption of light of energy larger than thc
band gap energy increases the surface concentrations of electrons and holes of a
semiconducting oxide significantly and enhances rate processes such as adsorption
and dcsorption that involve electron transfer.
Photo-assisted adsorption and desorption of oxygen is the most studied
process in this category [ 1,23:
Adsorption: e- + O2 + 02-(ad) (14-3)
Desorption: h+ + 02-(ad) --+02(g) (14-4)
PHOTO-ASSISTED PROCESSES 257
Both adsorption and desorption can be enhance by irradiation. Which
process dominates depends on the experimental conditions and the nature and
pretreatment of the oxide. It is commonly found that the relative rates of these two
processes depend on the pressure of oxygen. Band gap illumination of ZnO at
room temperature results in photo-assisted adsorption of oxygen at low pressures.
The effect decreases with increasing pressure, and eventually becomes photo-
assisted desorption at high pressures [3]. However, the effect of pressure is
opposite at 400°C: photo-assisted desorption at low pressures, and adsorption at
high pressures. Theeffect is not well understood.
A similar pressure dependence has been reported on Ti02 at 500°C [41. At
low pressures of oxygen, irradiation enhances desorption; at high pressures, it
enhances adsorption.
Detection of photo-assisted adsorption can be made by following changes in
the conductivity of the sample. Since such adsorption changes the concentration
of charged species on the surface and consumes photoelectrons or holes, it changes
the conductivity of the sample. It has been found that the surface returns only
slowly to the equilibrium state after the light is turned off, thus the enhanced
adsorption due to irradiation must be retained for a long time, and these species
are practically irreversibly adsorbed. Their desorption can be enhanced by
heating the sample [51.
The nature of the adsorbed species has been deduced from the dependence of
photoconductivity 0 with pressure. Up to lo2 Pa of oxygen, 0 shows a -1/2 power
dependence on the pressure on ZnO and ZrOz [ 10.1 11. There are indications that
the order changes to -1 at higher pressures on ZnO [12]. On anatase TiOz, the
order dependence changes from -1/2 to -1 as the pressure increases [lo]. An
order of -1 has been reported on a single crystal rutile TiOz sample [13].
Furthermore, cr increases linearly with light intensity.
The following processes have been proposed to explain the order dependence
[lo]:
02(ad) + e- + 02-(ad) (14-7)
O(ad) + e- + 0-(ad) (14-8)
The order in oxygen changes from -1/2 to -1 when thc dominant reactions change
from (14-6) and (14-8) to (14-5) and (14-7). Other processes have been excluded.
The reaction 02-(ad) +e- + 2 0-(ad) would lead to only a -1 order in oxygen,
and the react. m: 02(ad) +2 e- + 022-(ad) + 2 0-(ad) would lead to a half order
dependence on light intensity.
The surface condition is important. It has been shown that the amount of
oxygen photo-adsorbed on Ti02 increases with the amount of hydroxyl groups on
the surface [6]. A similar observation has been reportcd that dehydroxylation of
258
the surface reduces photo-adsorption of oxygen on TiO2, which can be restored by
rehydrating the surface [7,14]. It is believed that hydroxyl groups are important in
trapping photo-generated holes, making photo-electrons available for chemi-
sorption:
OH- + h+ -+.OH(ad) (14-9)
In this case, the fate of the hydroxyl radical is unclear. In the presence of
hydrocarbon molecules, the radical may participate in oxidation reactions, as will
be discussed later.
In addition to photo-enhanced adsorption or desorption of oxygen, photolysis
of the lattice resulting in evolution of lattice oxygen has been reported on ZnO
[8,9]. On the other hand, photo-decomposition of Ti02 has not been observed
The photo-response of a sample depends on its pretreatment, especially if the
pretreatment results in a slightly reduced or fully oxidized sample. Reduction
usually leads to n-type semiconductivity, and the extent of reduction determines
the density of conduction electrons and the lifetime of photocarriers. For some
oxides, severe oxidation may lead to excess lattice oxygen and p-type conductivity.
Coupled with the effect of surface hydroxylation, it is not surprising that there are
conflicting reports in the literature on the effect of illumination.
Doping of an oxide changes its semiconducting properties and response to
irradiation. Addition of Li to ZnO enhances photo-adsorption of oxygen, while
addition of Ga or A1 reduces it [3,4].
Ti02 and ZnO are among those that demonstrate large photo-effects. Under
the same conditions where these two oxides show photo-adsorption behavior,
adsorption of oxygen on V205 does not show any response to light, and W03
shows only a weak response [lo]. This behavior parallels their photo-enhanced
catalytic oxidation activities which will be discussed next.
[91.
14.3 PHOTOCATALYSIS: GAS PHASE REACTIONS
A large number of gas phase catalytic reactions have been found to be greatly
enhanced by illuminating an oxide with light of band gap energy. These reactions
include:
oxidation of hydrocarbons
oxidation of alcohols
oxygen isotope exchange
oxidation of CO, NH3
H2-D2 exchange
In general, these reactions proceed readily at elcvated temperatures in the dark.
Thus most of the studies of light enhancement have bcen conducted near room
temperature. Product selectivities are generally different between thermal and
light-assisted reactions.
PHOTO-ASSISTED PROCESSES 259
Table 14-1 Partial Oxidation Products in the Gas Phase Photocatalytic
Oxidation of Hydrocarbons at Low Conversions.
Hydrocarbon Oxide Partial Oxidation F’roducts
Major Minor
ethane
propane
propene
2-methylpropane
2-methylpropene
2,2-dimethyl-
propane
butane
2-methylbutane
2,2-dimethylbutane
2-methyl- 1 -butene
3-methyl- 1-butene
3-methyl-2-butene
pentane
2-methy lpentane
toluene
p-alkyltoluene
Ti02
Ti02
Ma3
wo3
wo3
Ti02
Ti02
Ti02
Ti02
Ti02
Ti02
Ti02
Ti02
Ti02
Ti02
Ti02
Ti02
TiOz
Ti02
ethanal
acetone
acetone
acetone
ethanal, acrolein
ethanal, acrolein
acetone
acetone
acetone
butanone
acetone
3,3-dimethylbutan-
2-one
butanone, ethanal
acetone
acetone, ethanal
pentan-2-one,
pentan-3-one
2-methylpentan-
3-one,
4-methylpenta.n-
2-one,
acetone
phenol
substituted benz-
aldehyde
propanal, ethanal
propanal
propene oxide,
acetone, propanol
2,2-dimethylpropanal
butanal, propanal,
ethanal
butanone, ethanal,
3-methylbutanone
butanone, acetone,
3,3-dimethylbutanal,
propanal, ethanal
acrolein, acetone
pentanal, butanal,
propanal, ethanal
2-methylpentanal,
propanal, ethanal
Oxidation of Hydrocarbons
Oxidation of hydrocarbons is among the most studied reactions. In
particular, the oxidation of alkanes have been studied heavily. Table 14-1 lists thc
partial oxidation products for a number of alkanes. It is clear from the data using
260
Table 14-2 Selectivities for Ketone and Aldehydes for Different Alkanes.
(From Farad. Disc. Chem. Soc., 58, 185 (1974). copyright Royal Society
of Chemistry).
Alkanes
% Selectivity (excluding Cod
Ketones Aldehydes
n-alkanes 56 20
alkanes possessing one or two 61 19
neoalkanes 43 14
tertiary carbon atoms
TiOz as the catalyst that photocatalytic oxidation produces a wide range of
products. In addition, combustion is usually a significant reaction, especially at
conversions higher than a few percent. However, there are some notable
exceptions. The oxidation of 2-methylpropane to acetone on Ti02 proceeds with
up to 75% selectivity [15], and the oxidation of 3-methyl-1-butene to acetone
proceeds with 87% selectivity [16].
In general, ketones and aldehydes are the partial oxidation products for the
hydrocarbons shown in Table 14-1, as well as for hexane, heptane, octane [17] and
p-alkyltoluenes [52]. It should be noted that cracking of the carbon chain to
products of lower carbon numbers is a common process. No dehydrogenation
products (alkenes, dienes, etc.) have been reported as significant, although they
have been suggested as reaction intermediates. The production of ketones is more
preferred than aldehydes at low conversions. Teichner and coworkers have
calculated the average selectivities for a large number of hydrocarbons, and
grouped these values according to their structures [17]. These values are shown in
Table 14-2. Apparently neoalkanes are more susceptible to combustion than
other alkanes. Combustion is also theonly reaction reported for butenes [15].
The reactivity also depends on the nature of the alkane. In particular, the
reactivity of various types of carbon atoms on Ti02 follows the sequence:
The reactivity do not seem to follow the ionization potential of the hydrocarbons
Although Ti02 has been the most extensively studied, and it shows the
highest quantum efficicncy, it is not as sclcctive as W03, Moo3 or some
nontransition metal oxides such as antimony oxide and tin oxide [ 18,191.
In the formation of ketones and aldchydes on Ti02, it has been proposed that
the first step of the reaction is the formation of an alcohol. If a primary alcohol is
formed, it may dehydrogenate to an aldchyde. Dehydrogcnation of a secondary
alcohol would form a ketone. A primary, secondary, or tertiary alcohol may also
~71.
PHOTO-ASSISTED PROCESSES 26 1
dehydrate to forman alkene, which could then be oxidatively cleaved to shorter
chain ketones and aldehydes [161. These reactions are illustrated below for 2-
methylbutane:
CH3
I
CH3
I
CH3
I
CH3CH2CHzCH3 0 CH3CHCH2CH2OH 5 CH3CHCH2CHO
(14- 10)
-H2
-H20 1
CH 3
I
CH 3
I
CH3CHCH=CH2 CH3CHCHO +COz (14-11)
H2d
CH 3
I
CH3
I 0
( 14- 12)
CH3
I
CH3CHCH2CH3 0 CH3CHCHCH3 CH3CHCCH3
I
OH 6
-H20 J
CH 3
I
CH3CHCH=CH2 ::& CH3CHCHO +COz (14-13a)
2
+
CH 3
I 0
CH3C=CHCH3 CH3COCH3 +C02 (14-13b)
2
OH
HZ CH3COCH3 +CH3CH0
This mechanism has been substantiated by studying the photo-oxidation of the
appropriate alcohols and alkenes. Oxidation of 3-methyl-1-butanol yields 52% 3-
methylbutanal, 20% 2-methylpropanal and acetone: 3-methyl-2-butanol yields
39% ethanal, 34% acetone, 17% 3-methyl-2-butanone, and 10% 2-methylpropanal;
and 2-methyl-2-butanol yields 50% acetone and 42% ethanal. Oxidation of 3-
methyl- I-butene yields 87% acetone and small amounts of 2-methylpropanal,
acrolein and ethanal; and 2-methyl-2-butene yields 35% acetone, 29% ethanal, and
some unidentified products. These results support the mechanism illustrated
above.
262
Another mechanism for the production of alcohols and ketones involves a
peroxy intermediate. This is illustrated for the oxidation of propane [20]:
C3Hs + O-(ad) + 0 2 + C3H700. + OH-(ad) (14- 15)
The peroxy species then further reacts to form an aldehyde.
In the photocatalytic oxidation of propane on silica-supported Mo03, it is
determined by varying the residence time that acetone, propanal, and propanols are
primary products. As the residence time increases, the secondary products C02,
CH3CH0 and methanol increase. The production rates of all primary products
show a nearly first order dependence on light intensity, while the secondary
products show an order dependence that is substantially larger than unity [19].
Since acetone appears as a primary product, its production cannot be via an
alcohol intermediate as suggested earlier. The following mechanism has been
proposed for Moo3:
C3Hs + 0-(ad) -+C3H70+ + e-(lattice) (14- 16)
n-C3H70. + O2 -+C2HsCHO + H02- (14- 17)
n-C3H70. + C3Hs -+n-C3H70H + C3H7 (14-18)
i-C3H70. + O2 + (CH3)2CO + HO2. (14- 19)
i-C3H70- + C3H8 -+(CH3)2CHOH + C3H7 (14-20)
Since a C-H bond is stronger than a C&H bond, it is not clear how efficient are
reactions (14-18) and (14-20) for the production of propanols. It is possible that
there are other routes to produce these alcohols.
Although most oxidation reactions produce a broad distribution of partial
oxidation products, the oxidation of 2-methylpropane (isobutane) on anatase Ti02
produces almost exclusively acetone [21]. The following accounts for up to 95%
of the reaction of 2-methylpropane:
CH3
I
CH3-CHXH3 + 5/2 0 2 + CH3COCH3 + C02 + 2 H20 (14-21)
Since the activity in the photocatalytic oxidation of hydrocarbons is
proportional to the light intensity, and the reaction only proceeds in the presence of
oxygen, it has been assumed that photo-adsorbed oxygen and photo-generated
holes are both important. The detailed roles of these species, however, have not
been unequivocally identified. The photo-adsorbed 0-(ad) species is often
assumed to be the species that activates alkanes by the abstraction of a hydrogen
atom [21]:
CnHzn+2 + 0-(ad) -+ .C,,H2"+, + OH-(ad) (14-22)
PHOTO-ASSISTED PROCESSES 263
or 0-(ad) + h+ -+O(ad) (14-23)
An alternate activation mechanism involves surface OH species that are formed
when a surface hydroxyl group captures a hole:
OH-(ad) + h+ + .OH(ad) (14-25)
or 02-(ad) + .OH(ad) + 0-(ad) + 02H(ad) (14-27)
Reactions (14-27) and (14-28) have been suggested because the reaction requires
gaseous oxygen and does not take place with N20 as the oxidant [17]. This has
been taken to indicate that 02-(ad) is necessary. The participation of OH groups,
however, may not be important on TiO2. It has been shown that a highly
dehydroxylated anatase sample photo-oxidizes 2-methylpropane as actively as a
partially dehydroxylated sample [22].
On the other hand, using isotopically labeled oxygen, it has been observed on
silica-supported vanadia that lattice oxygen participates in the photo-oxidation of
propene to acetaldehyde [32]. Since the photo-activity of vanadia is relatively
poor, and the participation of lattice oxygen in thermal oxidation reactions on
vanadia is well established, it is not clear if this observation applies to titania or
other oxides. The fact that lattice oxygen does participate in CO oxidation on
titania suggests that this may be important in some cases [33].
The participation of photo-adsorbed oxygen is also supported by the fact that
the activity in photocatalytic oxidation over various oxides can be broadly
correlated with their photo-adsorption properties [10,18]. Thus TiOz and Zr02,
which are very active in photo-assisted adsorption of oxygen, are also very active
in photocatalytic oxidation of propene. V205, which does not demonstrate photo-
assisted adsorption of oxygen, is quite inactive. The different selectivities on
different oxides for partial oxidation products seem to parallel the trend in thermal
oxidation. However, these correlations are at best qualitative.
Changes i n oxide morphology after reaction have been reported. On silica-
supported molybdena, isolated tetrahedrally coordinated Mo6+ions crystallizes to
Moo3 crystallites after being used in the photocatalytic oxidation of cyclohexane
1231. Similar crystallization has also been reported for silica-supported V2O5
[24]. It is interesting that V2O5 is inactive in the oxidation of propene, but
V205/Si02 is active in the oxidation of cyclohexane.
Oxidation of Alcohols
Photocatalytic oxidation of alcohols at room temperature in the presence of
oxygen proceeds readily on a number of oxides. For example, the oxidation of 2-
264
propanol on rutile Ti02 results almost exclusively in acetone [14,25]. A small
amount of acetaldehyde is also produced which may be formed from the photo-
oxidation of propene which is a dehydration product of 2-propanol. Continual
exposure of the reaction mixture to illuminated Ti02 results in further oxidation of
acetone to formic acid, and eventually C02 and water. However, the rate of
oxidation of acetone is slow [171.
Other selective oxidation of alcohols have been reported. On Ti02 butanol is
oxidized to butanal, and 2-butanol to butanone [26], although there is a report that
acetaldehyde is also a significant product from 2-butanol [30]. Thus oxidative
cleavage of the carbon chain may occur. In some cases, this is the predominant
reaction. For example, 2-methyl-2-propanol is oxidized to acetone quite
selectively [26], 3-methyl-2-butanol is oxidized to ethanal and acetone, and 2-
methyl-2-butanol to acetone and ethanal. 3-Methylbutanol is oxidized primarily
to 3-methylbutanal but there is a substantial production of 2-methylpropanal as
well [16]. From the product distributions in the reactions of the appropriate
alkenes, it has been suggested that oxidation of alcohol is the first reaction step for
primary alcohols. For secondary and tertiary alcohols, the first step is dehydration
to the corresponding alkenes, which are then oxidized by the photo-generated
adsorbed oxygen 1271.
Photo-enhanced oxidative dehydrogenation of 2-butanol and 2-propanol to
the corresponding ketones have also been observed on MnOz and ZnO [30,31].
The photo-activity declines with time. Illumination has no effect on V205. Cr2O3,
Fe2O3. Co3O4. NiO, or CuO.
Photo-oxidation of methanol at 403 K on anatase Ti02 results in methyl
formate up to about 60% conversion [281. It is proposed that an adsorbed
methoxy is photo-oxidized to an adsorbed formate, which reacts with another
methoxy to form methyl formate. The reaction rate at room temperture is very
low, although formaldehyde is readily oxidized [22]. When the titania is
impregnated with Moo3, the quantum efficiency decreases with increasing
molybdena content to about 10% of the molybdena-free value when there is about
a monolayer equivalent of molybdena. The rate of production of methyl formate
is low, and the major product is dimethoxymethane. It is proposed that an
adsorbed methoxy is first oxidized to an adsorbed formaldehyde which condenses
with adsorbed methoxy groups to form dimethoxymethane [28]. The photo-
oxidation of methanol to methyl formate has also been reported for ZnO [29].
Oxygen Isotope Exchange
over Ti02 and ZnO. Both the homophasic exchange reaction:
Light-enhance oxygen isotope exchange reaction has been studied in detail
and the hcterophasic exchange reaction:
(14-29)
l8O2(g) + l6O(lattice) 4 l60l8O(g) + ls0(lattice) (14-30)
PHOTO-ASSISTED PROCESSES 265
proceed readily at roomtemperature under band gap illumination.
Exposure of oxygen to an illuminated Ti02 at 77 K results in the appearance
of an EPR signal assigned to 03-(ad). This species is thermally unstable and
decomposes to adsorbed 0- and O2 on warming to 137 K, but its intensity can be
correlated with the catalytic activity for homophasic exchange of oxygen over the
sample at 137 K [34]. Thus this species has been proposed as a reaction
intermediate in the homophasic exchange reaction which proceeds as:
l802(g) + l60-(ad) + 03J ad) -----) l60l8O(g) + l80-(ad) (14-31)
There is evidence that isotopic scrambling between adsorbed 0 2 (or 0 2 3
species does not contribute to this reaction. On a Ti02 sample previously exposed
to 1802 and 1602, it has been found that equilibrium distribution of isotopic oxygen
species in the gas phase can be obtained rapidly when the sample is illuminated.
However, the isotopic composition of the adsorbed oxygen is very different from
the gas phase composition at the end of the reaction [35]. In fact, it is similar to
the composition of adsorbed oxygen froma sample that has not been used for the
reaction. This has been found by thermally desorbing the adsorbed oxygen after
reaction. Thus adsorbed O2 species are not involved in the homophasic exchange
reaction.
Monatomic oxygen species are also involved in the heterophasic isotope
exchange reaction on Ti02. When anatase Ti02 is exposed to l S02 under
illumination, 160180 first appears in the gas phase followed by 1602 in a manner
characteristic of stepwise reactions: 1802 * l60l8O + 1602. Thus the reaction
proceeds as [36]:
1802(g) + 160(ad) + l6OI8O(g) + lS0(ad) (14-32a)
160180(g) + 160(ad) + 1602(g) + I80(ad) (14-32b)
Both homophasic and heterophasic reactions occur simultaneously on an
illuminated oxide [37,38]. The homophasic reaction proceeds faster than the
hctcrophasic reaction on ZnO pretreated with oxygen or prereduced. This
contrasts the thermal reaction for which the homophasic reaction is greatly
suppressed by pretreating the oxide with oxygen. The extent of surface
hydroxylation may be important also. The photocatalytic activity of a partially
dehydroxylated TiOz is higher than a fully hydroxylated sample [21].
Other photo-oxidation reactions compete with the photocatalytic oxygen
isotope exchange reaction. In the presence of 2-methylpropane, oxygen isotope
exchange is completely suppressed on Ti02 until the oxidation of the hydrocarbon
is complete [36]. On ZnO, CO oxidation suppresses the oxygen isotope exchange
reaction [33,39]. These results suggest that these reactions either proceed on the
same sites or involve a common intermediate. Indeed, on TiO2, the activity per
unit area for oxygen isotope exchange correlates with that for 2-methylpropane
oxidation [36], and the participation of 0-(ad) in both reactions has been
suggested.
266
Other Reactions
Many other photocatalytic reactions have been observed [2,40]. Oxidation
of CO [41] and NH3 [42], H2-D2 exchange [43], decomposition of NO [26] and
N20 [a], and reduction of N2 [45] have been reported. In the oxidation of NH3
over Ti02, N2 and N20 are the products observed in addition to H20. From
conductivity measurements, it appears that the species involved in this reaction,
NH3, N2 and N20 do not compete for photo-generated electrons with adsorbed
oxygen. The decomposition of NO produces N2 as the product at low NO
pressures, and N20 at high NO pressures. Adsorbed oxygen is the other product at
room temperature.
The photo-enhanced H2-D2 exchange reaction has been analyzed in detail [2].
It is assumed to proceed by heterolytic dissociative adsorption of hydrogen.
Participation of lattice oxygen in CO oxidation has been demonstrated for
Ti02 [33]. Using a mixture of CO and the photo-enhanced production of
C1602 is much larger than C1601s0 at the beginning of the reaction.
Photo-reduction of N2 to form NH3 has been successfully demonstrated by
passing N2 saturated with water vapor over illuminated W03 [45]. No N2H4 is
formed. If the tungsten oxide is slightly reduced before the reaction, it is
reoxidized during the reaction. The reverse reaction, decomposition of ammonia,
is also photocatalyzed. Photo-reduction of N2 also occurs on illuminated anatase
TiO2. Ammonia and traces of N2H4 are formed [461. Rutile Ti02 doped with Fe is
quite effective in this reaction.
14.4 PHOTOCATALYSIS: LIQUID PHASE REACTIONS
In gas phase photocatalytic reactions, charged reaction intermediates must
remain adsorbed on the surface. On the other hand, charged species can readily
exist in the liquid phase. Thus it becomes possible to remove an electron from an
anion in the solution to form a neutral species by a photoelectrode, or inject an
electron into a neutral species to form an ion. The resulting species could then
further react in solution.
Oxidation Reactions
The oxidation of oxalate and formate ions to C02 by an illuminated ZnO in an
aqueous suspension has long been reported [471. Hydrogen peroxide is a by-
product:
C2Od2- + 0 2 + 2 H2O ---+ 2 C02 + 2 OH- + H202 (14-33)
HCOO- + 0 2 + H20 - C02 + OH- + H202 (14-34)
Under similar conditions, 2-propanol is oxidized to acetone:
(CH3)ZCHOH +0 2 (CHj)ZCO +H202 (14-35)
PHOTO-ASSISTED PROCESSES 267
The oxidative decarboxylation of acetate ions can be effected with
illuminated mile TiOz. In the absence of oxygen, ethane is a product which is
formed by coupling of two methyl radicals [48]:
CH3COz- + h+ - CH3 + COz (14-36)
2CH3 - Cz& (14-37)
The production of ethane is greatly suppressed by the presence of oxygen.
Presumably the methyl radicals react to form methanol and formaldehyde [49].
Photo-assisted oxidation has also been demonstrated at a TiO, electrode for
hydroquinone, p-aminophenol, I-, Br-, C1-, Fez+, Ce3+, and CN- ions. Many of
these species are oxidized at potentials negative of their standard redox potential
POI .
It is interesting to note that in the photo-assisted decarboxylation of a
dicarboxylate on TiOz, the reaction stops at the monoacid form. Perhaps this is
due to the displacement of the monoacid from the surface by the diacid [Sl]:
C02H Ti Oz, hu
+ COz (14-38)
O C 0 2 H -- C H 3 C N 0- COzH
Photo-assisted oxidation of hydrocarbons has been studied rather extensively
[511. In an aqueous suspension of TiOz, substituted toluene reacts to form both
oxidation and coupling products [55,56]:
(14-39)
R
This contrasts sharply the relatively selective production of substituted
benzaldehyde in the gas phase reaction [52]. Cyclohexene is likewise oxidized to
a mixture of cyclohexenol and cyclohexenone [51].
Oxidative cleavage of 1 ,l-diphenylethylene to benzophenone can be achieved
efficiently with TiOz [53]:
(14-40)
268
Substituted naphthalene is photo-oxidized with cleavage on one of the benzene
rings. For example [51]:
(14-41)
Amines can also be photo-oxidized. On ZnO, aniline is oxidized to
azobenzene, and toluidines are oxidized to the corresponding azo compounds.
The relative rates depend on the substituent, and the order meta >ortho >para-
toluidine >aniline has been observed [54].
The mechanism of liquid phase photo-assisted oxidation of hydrocarbons
with TiO, has been investigated in detail [51]. Several observations support the
involvement of a radical cation intermediate:
RH + h+ ---+RH+ (14-42)
Stilbene radical cation is observed spectroscopically after a Ti02 colloidal
suspension in acetonitrile containing trans-stilbene has been flashed with a
nitrogen laser [55]. Efficient photo-conversion of diphenylelhylene is achieved
only in solvents of high dielectric constants. This is consistent with the
involvement of a highly polar transition state. When para-substituted diphenyl-
ethylene is oxidized with Ti02, a linear Hammett plot with a negative slope is
obtained between the relative rate of reaction and the substitution parameter 1561.
The relative rates of reaction of other substituted diphenylcthylene molecules also
show reduced reactivity with decreased K- electron density of the double bond.
Thus these relative rates reflect the stability of the one-electron oxidation product,
consistent with the proposed involvement of radical cations.
Subsequent reactions of the radical cations may involve capture by triplet
molecular oxygen. They may also involve attack by superoxide. In either case,
the reactions are not photo-assisted. If the hydrocarbon molecule is an alkene,
dioxetane is then formed which would be cleaved to a ketone or an aldehyde [51].
The oxidation of water has been studied extensively. Earlier work has been
on the formation of hydrogen peroxide 12,471. The reaction mechanism can be
either:
H20 + 0-(ad) --+ HOO-(ad) + H(ad) (14-43)
HOO-(ad) + H+(ad) + H202 (14-44)
or H20 + 0-(ad) + OH-(ad) + OH(ad) (14-45)
OH-(ad) +OH(ad) ---+ Hz02 +e-(lattice) (14-46)
PHOTO-ASSISTED PROCESSES 269
Adsorbed electron acceptors retard the reaction. Thus adsorbed 0, [57] or
adsorbed bicarbonate [58] slow the reaction.
Recently, the interest has been shifted to the photo-assisted electrochemical
oxidation of water to oxygen. It has been discovered that band gap illumination of
a Ti02 anode substantially reduces the applied potential required for the evolution
of oxygen, as shown in Fig. 14-3 [59]. Many other oxides have been subsequently
shown to demonstrate a similar effect [60,61,68,69]. They include W03 [62], n-
Fez03 [63,64], and mixed oxides such as SrTi03 [65], KTa03 [66] and others. In
the absence of other more readily reducible species, proton is reduced to hydrogen
at the cathode when a sufficiently high potential is applied. Thus the net reaction
is the decomposition of water:
2 H20 + 2 H2 + 0 2 (14-47)
With the more efficient photo-anodes such as those listed above, the external
potential needed to achieve this reaction is substantially less than the
thermodynamic value of 1.23 V when the photo-anode is illuminated. Therefore,
such a system serves to convert light energy into chemical energy. However, only
the large band gap oxides such as SrTi03 and KTa03 can sustain the reaction
without any applied external potential. In fact, it appears that the magnitude of the
applied potential is roughly inversely correlated with the width of the band gap
[611.
The oxidation reaction at the anode may involve the photo-production of OH
radicals which form H202 [671:
Hydrogen peroxide decomposes to water and oxygen in a basic solution. The
reduced titania is reoxidized by water to regenerate the hydroxylated surface. In
fact, if deuterated water is used in the reoxidation, D, is evolved 1671:
Reduction Reactions
Photo-assisted reduction of metal complexes to metallic particles deposited
on the oxide can be achieved in a number of systems. The reduction is
accompanied by oxidation of another species. For example, copper ions can be
reduced to copper metal deposited on illuminated Ti02 or W03 particles in water
and oxygen is produced [701.
270
cu I I
E
0
+
c 1.0
2
L
3
0
0
.-
U
2 0
a
I V(SCE) I
-0.5 1
Figure 14-3 Anodic current as a function of voltage (versus SCE) at a semiconducting
anode in a pH 4.7 electrolyte. The potential for the evolution of oxygen from the oxidation
of water is lowered by illumination. a. Anode illuminated with strong light; b. with
weak light; c. No illumination. (After Nature, 238, 37 (1972), copyright Mcmillan
Publisher).
Ti 02, hu
Cu2+ + H20 -- CU + 1/2 0 2 + 2 H+
(14-50)
I n the presence of acetate, acetate is oxidized to C02:
Cu2++ 2CH3COO- Cu + C2& +2C02 (14-51)
Copper can also be deposited on KTa03 and SrTi03 [71]. The deposition of Pt
from a solution of hexachloroplatinic acid and carbonate onto irradiated Ti02 has
also been achieved. The carbonate is converted to C02 [72]. Other platinum
complexes can likewise be used [73]. The reduction of chloroplatinic ion is
accompanied by a release of proton that has been quantitatively detected. In the
reduction of dinitrodiaminoplatinum, N20 and N2 are evolved. Transmission
electron microscopy shows that platinum is initially deposited as very small
particles distributed over the Ti02 particles. Deposition of other metals, including
Pd, Ag, Rh. Au, and Ir on Ti02 and on other oxides including ZnO, Nb2OS and
Tho2have been reported [73, and references therein]. The rate of deposition
depends on the strength of adsorption of the metal ion and the quantum efficiency
for reduction. For the reduction of Ag+- the adsorption of the ion on ZnO is
weaker than on Ti02, but the quantum efficiency for reduction is higher. The
relative rates of deposition on the two oxides also depend on the concentration of
the ions in the solution [74].
There are reports on the photo-assisted reduction of water by oxides. p-Type
PHOTO-ASSISTED PROCESSES 27 1
Fez03 has been successfully used with n-type Fe03 to decompose water. Water
is reduced to H2 at the p-type iron oxide [75]. p-LuRh03 has also been reported as
effective in this reduction [76].
14.5 PHOTOCATALYSIS BY METALMETAL OXIDE AND
OXIDE/OXIDE COMPOSITES
It can be Seen fromthe examples described above that some oxide particles or
electrodes are quite efficient in effecting photo-assisted electron transfer. For an
n-type semiconducting oxide, this has resulted in enhancement in many oxidation
reactions. However, for an effective photocatalyst, every step of the catalytic
cycle must proceed efficiently. This requirement may not be met by many oxides.
For example, photo-oxidation on Ti02 is commonly observed; but photo-reduction
on this oxide is much less known. Thus electron transfer out of Ti02 is more
difficult than into the oxide. Therefore, attempts have been made to deposit metal
or another oxide on a semiconducting oxide that will facilitate electron transfer in
the difficult direction. Noble metals and RuO2 have been used as deposits for this
purpose.
Sometimes a composite of n- and p-type semiconducting oxides are used
when a single oxide does not generate sufficient photoelectrochemical driving
force to complete a desired reaction. Then a composite of two appropriate
semiconducting oxides could be used to supply a combined photoelectrochemical
driving force. Successful decomposition of water using visible light has been
achieved using such devices.
Such composite systems have been used in the oxidation of ethanol. Ethanol
is oxidized in a water mixture by an irradiated Wi02 to acetaldehyde and acetic
acid. Hydrogen is also evolved [77]:
CH3CH20H hu, CH3CH0 + H2
CH3CHO + H20 -!% CH3COOH + H2
(14-52)
(14-53)
After prolonged irradiation, methane and C02 are observed due to the
decarboxylation reaction of acetic acid [78].
CH3COOH C& +C02 (14-54)
A side reaction may also occur via the reaction of acetaldehyde with OH radical,
which eventually leads to combustion:
CH3CHO + 3 H2O 5 HzO + 2 C02 (14-55)
Photo-assisted decarboxylation of acids takes place efficiently on Wanatase
Ti02 in the absence of oxygen. Wanatase is more effective in this reaction than
Wrutile, possibly because anatase has a slightly larger band gap than rutile. The
272
Table 14-3 Products in the Photo-assisted Decarboxylation of Acids
on m i 0 2
Acid Major Products Minor Products
acetic cH4, co2 C2&. H2
propionic C2&. co2 c2H4, H2
n-butyric propane, C02 H2
n-valeric n-butane, C02 H2
pivalic isobutane. C02 isobutene. H2
adamantane- 1 - adamantane, C02
adipic butane, C02 valeric acid
carbox ylic
products of the reaction are listed in Table 14-3 [78,8S]. These products can be
accounted for by a general reaction scheme:
h+ + RC02- Re + CO2 (14-56)
e- +RCOOH - H(ad) + RCOO-
e- +R. + RCOOH - RH +RCOO-
2 H(ad) - H2
R. + H(ad) - RH
It is of significance to note that H2 is a product in these reactions because Pt is an
excellent catalyst for the recombination of H atoms. Pd or Ru02 can be used
instead of R, but the efficiency in H2 evolution follows the order: Wi 02 2
Pd/Ti02 >RuOJI’iO2 >>Ti02 1791.
Complete decarboxylation of adipic acid, HOOC(CH3)4COOH, to C4H1 0 can
also be achieved with illuminated mi 02 [85]. Oxidation of alkanes, including
hexane, cyclohexane, heptane, nonane, and decane in an aqueous solution results in
practically complete combustion [86].
The photo-decomposition of water has been studied extensively. Pt/SrTi03
is an efficient catalyst [80], more efficient than Wrutile Ti02. This is because
SrTi03 has a smaller electron affinity and therefore a larger band bending at the
surface [81]. For the Pt/TiO2 system, anatase is more efficient than mile. A
small amount of Nb205 doping further enhances the efficiency [82]. Platinked
PHOTO-ASSISTED PROCESSES 273
KTa03 also decomposes water on illumination [711.
Oxide/oxide composites have been used for this reaction. A NiO/SrTi03
composite, prepared by impregnation with Ni(NO3)2 followed by reduction and
reoxidation at 500°C decomposes water effectively upon irradiation. Nearly
stoichiometric amounts of H2 and O2 are produced [83]. The reduction step is
necessary to produce metallic Ni to form a NiO/Ni/SrTi03 interface in which Ni
serves as an ohmic contact. The activity in NaOH is higher than in water, perhaps
because hydrogen peroxide decomposes more efficiently in basic than neutral
solutions.
Another system reported to be successful is a n-Fe203/pF%03 composite
[75,84]. p-Fe203 is made by Mg doping. The actual material in the composite is
a mixture of MgO, p-Fe203 and MgFe204. The activity of the system declines
slowly with time. It can be regenerated by oxygen treatment of the oxide.
REFERENCES
1. S. Baidyarov, W. Bottoms, and P. Marks, Surface Sci., 28, 517 (1971).
2. Th. Wokenstein, Adv. Catal.. 23, 157 (1973).
3. F. Romero-Rossi, and F. Stone, Proc. 2nd Infern. Cong. Catal., 1970, paper 70.
4. T. Kwan, in "Electronic Phenomena in Chemisorption and Catalysis on
5. K. Tanaka, and G. Blyholder, J. Phys. Chem., 76. 3184 (1972).
6. A. BoonstTa and C. Mutsaers. J . Phys. Chem., 79. 1694 (1975).
7. F. Stone, Coloq. Quim. Fis. Processos Superficies Solides, 1965, p. 109.
8. R. Collins, and D. Thomas, Phys. Rev., 112, 388 (1958).
9. J . Cu~i ngham. E. Finn, and N. Samman, Farad. Disc. Chem. Soc., 58, 160 (1974).
Semiconductors," p. 184, de Gruyter, Berlin, 1969.
10. J .-M. Herrmann. J. Disdier. and P. Pichat. J . Chem. Soc. Farad. T r m . I,
11. W. Doerffler, and K. Hauffe. J . Catal., 3, 156 (1964).
12. H. Degn. and J. Nabbs, Appl. Phys. Lef f . , 26. 526 (1975).
13. R. Keezer, J. Appl. Phys., 35, 1866 (1964).
14. R. Bickley. and R. J ayanty, Faraday Disc. Chem. Soc., 58, 194 (1974).
15. F. Formenti, F. J uillet, P. Meriaudeau. and S. Teichner. Chem. Tech.. 1, 680 (1971).
16. N. Djeghri, and S. Teichner, J . Cafal., 62, 99 (1980).
17. N. Djeghri, M. Formenti. F. J uillet, and S . Teichner. Farad. Disc. Chem. Sm.,
18. P. Pichat, J .-M. Herrmann, J . Disdier, and M.-N. Mozzanega, J . Phys. Chem..
19. K. Marcinkowska. S . Kaliaguine, and P. Roberge, J . Catal., 90, 49 (1984).
20. V. Kazansky. Kinet. Katal.. 19, 279 (1978).
21. J .-M. Herrmann. J . Disdier, and M.-N. Mozzanega, and P. Pichat, J. Catal.,
22. M. Formenti. F. J uillet, P. Mariaudeau. and S. Teichner, Proc. 5th Intern. Cong.
23. A. Mahay, S. Kaliaguine, and P. Roberge, C a d . J . Chem. Eng.. 60. 2719 (1982).
24. D. Nguyen. P. Roberge. S. Kaliaguine. Canad. J . Chem. Eng., 57, 288 (1979).
77, 2815 (1981).
58, 185 (1974).
83, 3122 (1979).
60, 369 (1979).
Cafal., 11. p. 1011 (1972).
214
25. R. Brickley, G. Munuera, and F. Stone, J. Cataf.. 31, 398 (1973).
26. P. Pichat. H. Courbon, J. Disdain, M. Mozzanega, and J. Hemnann, Proc. 7th
27. A. Walker, M. Formenti, P. Meriaudeau, and S. Teichner, J. Catal., 50, 237 (1977).
28. Y. Liu, G. Griffin. S. Chan, and I. Wachs, J. Cataf.. 94. 108 (1985).
29. G. Schwab, F. Steinbach, H. Noller, and M. Venugopalan, 2. Naturforsch. A,
30. J . Cunningham, B. Hodrett, M. Ilyas. J. Tobin, and E. Leahy, Faraday Disc. Chem.
31. J . Cunningham, and B. Hodnett, J. Chem. SOC. Farad. Tram. 1, 77, 2777 (1981).
32. S. Yoshida, T. Tanaka, M. Okada. and T. Fundabiki, J. Chem. SOC. Faraday Tranr. 1,
33. S. Sato. T. Kadowaki, and K. Yamaguti. J. Phys. Chem., 88, 2930 (1984).
34. V. Nikisha, B. Shelimov. and V. Kazanskii, Kinet. Cataf., 15, 599 (1974).
35. K. Tanaka, J. Phys. Chem., 78, 555 (1974).
36. H. Courbon, M. Formenti, and P. Pichat. J. Phys. Chem., 81, 550 (1977).
37. J . Cunningham, and E. Goold, J. Chem. SOC. Farad. Trans. 1. 78, 785 (1982).
38. J . Cunningham, E. Goold, and E. Leahy, J. Chem. SOC. Farad. Trans. 1,
39. K. Tanaka, and K. Miyahara, J. Phys. Chem., 78, 2303 (1974).
40. S. Morrison, 'The Chemical Physics of Surfaces." Plenum Press. N.Y. 1977,
41. C. Schwab, F. Steinbach. H. Noller. and M. Venugopalan, 2. Naturforsch. A
42. H. Mozzanega. J .-M. Hemnann, and P. Pichat, J . Phys. Chem.. 83. 2251 (1979).
43. Th. Freund, J. Catal., 2, 289 (1964).
44. K. Tanaka, and G. Blyholder, J. Phys. Chem., 75, 1037 (1971).
45. E. Endoh, J. Leland, and A. Bard, J. Phys. Chem., 90, 6223 (1986).
46. G. Schrauzer, and T. Guth, J. Amer. Chem. SOC., 99. 7189 (1977).
47. Th. Freund, and W. Comes, Catal. Rev., 3, 1 (1969).
48. B. Kraeutler, and A. Bard, J. Amer. Chem. Soc.. 99. 7729 (1977).
49. B. Kraeutler, and A. Bard, J. h e r . Chem. Soc., 100, 5985 (1978).
50. S. Frank, and A. Bard, J. Amer. Chem. Soc., 99,4667 (1977).
51. M. Fox,Acc. Chem. Res., 16, 314 (1983).
52. M. Mozzanega, J. Herrmann, and P. Pichat, Tefrahedron Letf.. 2965 (1977).
53. M. Fox, and C. Chen, J. Amer. Chem. Soc., 103, 6757 (1981).
54. H. Kasturirangan, V. Ramakrishnan, and J. Kuriacose. J. Cataf., 69, 216 (1981).
55. M. Fox, B. Lindig, and C. Chen, J. Amer. Chem. SOC.. 104. 5828 (1982).
56. M. Fox, and C. Chen, Tefrahedron Left., 24, 547 (1983).
57. G. Korsunovsky, Dokl. Akad. Nauk. SSSR, 113, 853 (1957).
58. G. Calvert. K. Theurer. T. Rankin. and W. MacNevin, J. Amer. Chem. SOC..
76, 2575 (1954).
59. A. Fujishima, and K. Honda, Nature, 238, 37 (1972).
60. H. Gerischer, in "Solar Energy Conversion, Topics in Applied Physics."
vol. 31. B. 0. Seraphin ed.. Springer, NY, 1979.
61. H. Kung, H. J arrett, A. Sleight, and A. Ferretti, J. Appl . Phys., 48. 2463 (1977).
Intern. Cong. Catal.. XI. p. 1498 (1980).
19, 445 (1964).
SOC., 281 (1981).
80, 119 (1984).
75,305 (1979).
chapter 9.
19, 445 (1964).
PHOTO-ASSISTED PROCESSES 275
62. M. Butler, R. Nasby, and R. Quinn, Solid Sfate Commun.. 19, 101 1 (1976).
63. K. Hardee, and A. Bard, J . Electrochem. Soc., 123, 1024 (1976).
64. R. Nasby, and R. @inn, Mater. Res. Bull., 11. 985 (1976).
65. M. Wrighton, A. Ellis, P. Wolczanski, D. Morse, H. Abrahamson, and D. Ginley,
66. A. Ellis, K. Kaiser, and M. Wrighton, J . Phys. Chem.. 80, 1325 (1976).
67. G. Somorjai, H. Hendewerk, and J . Turner, in "Catalysis and Surface Science."
H. Heinemann and G. Somorjai, ed., Marcel Dekker, NY, 1985, p. 381.
68. L. Harris, and R. Wilson, Ann. Rev. Mot. Sci., 8, 99 (1978).
69. A. Nozik. Adv. Hydrogen Energy. Hydrogen Energy Syst., 3, 1217 (1979).
70. H. Reiche, W. Dunn, and A. Bard, J. Phys. Chem., 83, 2248 (1979).
71. M. Wrighton, P. Wolczanski. and A. Ellis, J. Solid Stare Chem.. 22, 17 (1977).
72. B. Kraeutler, and A. Bard, J . Amer. Chem. Soc., 100, 4317 (1978).
73. J . Henmann, J . Disdier. and P. Pichat, J . Phys. Chem., 90, 6028 (1986).
74. P. Fleichaner, H. Kan, and J. Shephard, J. Amer. Chem. Soc., 94, 283 (1972).
75. C. Leygraf. M. Hendewerk, and G. Somorjai. J. Cutul., 78, 341 (1982).
76. H. J arrett, A. Sleight, H. Kung. and J. Gillson. J . Appl. Phys., 51, 3916 (1980).
77. T. Sakata, and T. Kawai, Chem. Phys. Lett.. 80, 341 (1981).
78. B. Kraeutler. and A. Bard. J. h e r . Chem. Soc., 100, 5985 (1978).
79. T. Sakata. K. Hashimoto, and T. Kawai, J . Phys. Chem., 88, 5214 (1984).
80. F. Wagner, and G. Somorjai, J . Amer. Chem. Soc., 102, 5494 (1980).
81. J . Mavroides. J . Kafalas, and D. Kolesar. Appl. Phys. Letf., 28, 241 (1976).
82. E. Bargarello, J . Kiwi, E. Pellizzetti, M. Visca, and M. Gratzel,
83. K. Domen, A. Kudo, and T. Onishi, J. Cutul., 102, 92 (1986).
84. Ch. Leygraf, M. Hendewerk, and G. Somorjai, J . Phys. Chem., 86, 4484 (1982).
85. I. Izumi, F. Fan, and A. Bard, J. Phys. Chem., 85. 218 (1981).
86. I. Izumi, W. Dunn, K. Wilbourn, F. Fan, and A. Bard, J. Phys. Chem.,
J . Amer. Chem. SOC.. 98, 44 (1976).
J . Amer. Chem. Soc.. 103, 6324 (1981).
84. 3207 (1980).
This Page Intentionally Left Blank
INDEX
Acetone, adsorption, 66
Acid sites, formation, 74, 75-80
Acidity, 72
-, determination, 80, 83, 87
-, effect of pretreatment, 82
-, selective oxidation, 175
-, strength, 74. 78
Acrolein, from propene. 181
Acrylonitrile, from propene, 18 1
Adsorbed oxygen, 110
-, desorption, 11 1
-, detection, 11 1
-, photo-adsorption, 256
-, photo-desorption, 256
-, reactivity, 116, 118
-, selective oxidation, 176
-, superoxide, 114
Adsorption, 61
-, abstractive, 62
-I and cus, 57
-, heterolytic dissociative, 3, 35, 57, 61
-, homolytic dissociative, 61
-, molecular, 57, 61
-, pretreatment effect, 63
-, reductive, 62
AES, 4
Aerogel, preparation, 124
-, IR, 114
-, types, 110
Alcohol, adsorption, 66
-, decomposition. 146
-, photo-oxidation, 261, 263
Aldol condensation, in isosynthesis, 243
Alkane, activation, 178
-, deuterium exchange, 161
-, photo-oxidation, 259
-, reaction with adsorbed oxygen, 116
Alkene, activation, 178
-. adsorption, 64
-, deuterium exchange, 161
-, hydrogenation, 156
-, reaction with adsorbed oxygen, 118
Alkyne, adsorption, 65
Alumina, isoelecmc point. 85
Ammonia, adsorption, 81
-, photo-oxidation, 266
Anion vacancies, surface, 55-57
Anisotropy constant, 43
Antiferromagnetism, 35
--, crystallite-size effect, 39
-, temperature effect, 39
Antimonoy-tin oxide, propene oxidation,
181
Band gap. 252
Bi-Fe-Mo-0, propene oxidation, 186
Bismuth molybdate, 189, 204
-, butene oxidation, 173, 204
277
278
-, propene oxidation, 173, 181. 182.
Brdnsted acid, 72
-, formation, 75
Butane oxidation, 210
Butadiene, from butane, 210
-, from butene, 200
Butene, adsorption, 65
.-, dehydrogenation, 201, 203
-, hydrogenation, 159
-, oxidation, 88, 189, 200
185, 187, 188
Carbon-oxygen bond, formation, 179
Carbanion, in isomerization, 143
Carbenium ion, in isomerization, 142
Carbonate, adsorbed, 62
Carboxylate, adsorbed, 62
Catalytic processes, 2
Chromia (see chromium oxide)
Chromium-iron oxide, 209, 244
Chromium oxide, adsorbed oxygen, 116
-, butene hydrogenation, 160
-, butene isomerization. 141, 144
-, CO adsorption, 58, 61
-, dehydroxylation, 55, 58
-, deuterium exchange, 161
-, methanol decomposition, 149
-, NO reduction, 165
-, preparation, 126
-, propene hydrogenation, 159
CO, adsorption, 58, 67
-, copper catalysts, 228, 230, 232
-, hydrogenation, 228
-, in C02 hydrogenation, 228
-, iron catalyst, 239
-, Pd catalyst, 236
-, Rh catalyst, 237
Cobalt molybdate. propene oxidation,
Cobalt oxide, ethene hydrogenation, 158
-, isomerization, 143
Conduction band, 252
Contracting sphere model, 95
COZ, hydrogenation, 228
Coordinative unsaturation, 53
.-, conjugate base, 72
188, 192
-, effect on structure, 15
-, formation, 53. 55
-. Lewis acid, 72
Copper oxide, methanol decomposition,
-, NO reduction, 162
-, propanol decomposition, 151
-, reduction, 98
Copper-thorium oxide, 230
Copper-zinc oxide, 228, 232, 245
Corundum structure, 10
Cubic close-packing, 8
Curie temperature, 39
Cuprous oxide, propene oxidation, 182.
Cus (see coordinative unsaturation)
149
185
Decarboxylation, 267, 271
Decomposition, methanol, 146
-, water, 269, 272
Decoration effect. 102
Dehydrogenation, butane, 210
-, butene. 200
Dehydroxylation, 54
-, Cr24, 58
-, zno, 58
Diamagnetism, 36
Dimerization, 215
Dissociative adsorption, 3, 35
Electronic structure, bulk, 252
-, surface, 46
ELS, 4
EPR, 4
Ethane, from carbon oxides, 235
-, from methane, 215
Ethanol, from carbon oxides, 235, 238
-. photo-oxidation, 271
Ethene. from carbon oxides, 235
-, from methane, 215
-, hydrogenation, 156
EXAFS. 4
Fez& (see iron oxide)
Fermi energy, 252
Femmagnetism. 38
INDEX
279
Ferrites (see iron oxide)
Formaldehyde, from methane, 212
-, from methanol, 217
Formate, 62, 147, 245
m, 4
Hexagonal close-packing, 8
HREELS, 4
Hydrogerb adsorption, 63
-, reaction. adsorbed oxygen, 11 8
Hydrogen-deuterium scrambling, 161
Hydrogenation, 155
Hydroperoxide, in propene oxidation, 186
Hydroxyl, Brdnsted acid, 72
-, in photo-assisted processes, 257
Impregnation, 130
Indicators, 87
Ion-exchange, in preparation, 129, 132
Ionic charge, effect on structure, 15
Ionicity, determination, 28
-, Pauling's, 33
-, Phillip's, 33, 34
-, values, 30
IR, 4
Iron-molybdate, methanol oxidation, 218,
Iron oxide, alcohol decomposition, 152
-, anisotropy constant, 43
-, butene dehydrogenation, 201, 203, 204
-, CO hydrogenation, 239
-, lattice dilation, 41
-, magnetic hyperfine field, 42
-, magnetic properties, 39
-, Morin transition, 41, 42
-, oxygen desorption, 11 1
-, preparation, 126, 131
-, quadrupole splitting, 43, 46
-, reduction, 98
-, structure, 10
-, water decomposition, 273
-, water-gas shift, 246
Isoelectric point. 83
Isomerization, akenes, 140
-, carbenium ion, 142
-, effect of reduction, 141
220
-, metathesis, 141
Isosynthesis, 240
ISS, 4
Lanthanum oxide, methane coupling, 217
Lattice oxygen, in selective oxidation,
170, 177, 190, 211
-, in photo-oxidation, 263
Lattice self-potential, 29, 32
LEED, 4
Lewis acid, 72
-, formation, 75
Magnetic properties, 36, 38
Magnetic hyperfine field, 4143
Magnesium oxide, methane coupling, 216
Maleic anhydride, from butane, 210
-. from butene, 200
Manganese oxide, methane coupling, 217
Metathesis, 136
-, degenerative, 137
-, isomerization, 141
-. mechanism, 137
-. productive, 137
-, substituent effect, 138
-, support effect, 140
Methane, dimerization, 215
-, oxidation, 212
Methanol, decomposition, 146
-, from carbon oxides, 228, 231
-, from methane, 212
-, oxidation, 217
-, photo-oxidation, 264
Methyl formate, from carbon oxides, 235
Methyl radical, 116. 216
Mixed oxides, acidity, 75
-, alkane reaction, 118
-, reduction, 100
Molybdenum-nickel oxide, butene
oxidation, 202, 209
Molybdenum oxide, adsorbed oxygen, 11 6
-, alcohol adsorption, 66
-, alkane reaction, 117, 118
-, alkene isomerization, 141. 143
-, butene oxidation, 204
-, ethanol decomposition, 152
-, isoelectric point, 85
-, methane oxidation, 213
-, methanol oxidation, 218, 221
-, metathesis, 138, 139
-, photo-oxidation 260
-, preparation, 124, 131
-, propene oxidation, 189, 192. 194
-, reduction, 96
-, shear structure, 12
-, structure, 10, 22
Molybdenum-tin oxide, propene oxidation,
173
Morin transition temperature. 41
Multicomponent oxidation catalyst, 187
Ne61 temperature, 38
Nickel oxide, acetone adsorption, 66
-, reduction, 95
-, structure, 6, 24
-, support effect, 99
-, surface phonon. 48
-, water decomposition, 273
Niobium oxide, ethanol decomposition,
-, reduction, 98
Nitric oxide, adsorption, 67
-, reduction, 162
Nitrous oxide. decomposition, 153
NMR. 4
Nonpolar surface, 15
Nucleation model, 93
152
Oxidation, photo-assisted, 259
-, selective (see selective oxidation)
Oxide, properties, 3
-, structure, 6
Oxide catalysts, 2
Oxygen, adsorbed (see adsorbed oxygen)
-, isotope exchange, 264
--, on chromia, 58, 11 6
-, on iron oxide, 11 1
-, on zinc oxide, 114, 116
-, photo-adsorption, 256
-, photo-desorption, 256
Palladium, CO hydrogenation, 236
Paramagnetism, 38
Perovskite. structure. 12
Phonon, 48
-, and ionicity, 35
Photo-assisted processes, 256
-. adsorption, 256
-, desorption. 256
-, oxidation, 259, 263
-, reduction. 269
Photoelectrons, 254
Photo-holes, 254
-, radicals, 186
Polar surface, 15
Preparation, 121
-, complexation, 132
-, coprecipitation, 133
-, crystallographic phase, 124
-, freeze-drying. 132
-, impregnation, 130
-, ionexchange, 129. 132
-, morphology, 125
-, pH effect, 130
-, special techniques, 130
-, spraydrying, 132
Propene. adsorption, 64
-, ammoxidation, 181
-, hydrogenation, 158
-, metathesis, 137
Propene oxidation, 173. 181
-, kinetics, 185, 186
-, mechanism, 182
-, promoters, 193
-, water effect, 194
Promoters, butene oxidation, 209
-, COX hydrogenation, 233
-, propene oxidation, 193
Propanol decomposition, 149
Pyridine. adsorption, 8 1
n-allyl, 64. 178, 182
Quadruple splitting, 43, 46
Reconstruction, surfaces, 15
Reduced oxide, effect on metal, 102
-, properties, 100
Reduction, 91
28 1
-, bronze formation, 100
-, kinetics, 93
-, mechanism, 96
-, mixed oxides, 100
-, support effect, 98
-, thermodynamics, 92
Relaxation, surfaces, 18
Rhodium, CO hydrogenation, 237
Rhodium oxide, support effect in
reduction of, 99
Rocksalt structure, 6
Rutile structure, 8, 10
Scheelites, in oxidation, 189, 203
Selective oxidation, 169
-, oxygen source, 173
-, redox mechanism, 170
-, selectivity in, 175
-, types, 170
-, water effect. 174
SEM, 4
Shear structure, 12
-, in selective oxidation, 175, 179
Solid solutions, surface composition, 28
Spinel structure, 8, 10
STEM, 4
Strontium titanate. surface phonon, 49
Structure, supported oxide. 21
Structure sensitivity, alcohol
decomposition, 148
Supported oxide, preparation, 129
-, structure, 21
Surface, anion vacancies, 55-57
--, Composition, 27
-, electronic structure, 46
-, polar and nonpolar, 15
-. reconstruction, 15
-, relaxation, 18
-, structure, 15
Surface vibration, 48
TEM, 4
Thorium oxide, isosynthesis, 240
Til03, surface structure, 55
Titanium oxide, acidity, 75
--, adsorbed oxygen, 114
-, alcohol, decomposition, 152
-, -, photo-oxidation, 261, 264
-, alkane, photo-oxidation, 260
-. ammonia oxidation, 266
-, decarboxylation, 267, 271
-, methanol decomposition, 148
-, 0, isotope exchange, 265
-, photo-adsorption. 257
-. photo-desorption. 257
-, photo-oxidation, 267
-, photo-reduction, 269
-, preparation, 124, 131
-, propanol decomposition, 151
-, reduced. decoration effect, 102
-, reduction, 96
-, structure, 10
-, surface electronic structure, 47
-. surface structure. 18, 55
-. water decomposition, 269, 272
-, water oxidation, 268
Titration, acidity, 87
TPD, 4
TPR, 4
Tungsten oxide, alkane, photo-oxidation,
-, alkene isomerization, 143
-, reduction, support effect, 98
-, supported, structure, 24
_ -
, , reactivity, 101
260
UPS, 4
uv-vis. 4
Vacancies, in selective oxidation, 175, 189
-, surface, 55-57
Valence band, 252
Vanadates, butane oxidation, 21 1
-. butene oxidation, 205
Vanadia (see vanadium oxide)
Vanadium oxide, isoelectric point. 85
-, methane oxidation, 215
-. methanol oxidation, 223
-, NO reduction, 162
.-, propanol decomposition. 151
-, propene oxidation, 195
-, reduction, support effect, 99
282
- structure, 10
- supported, structure, 21
- butane oxidation, 21 1
- butene oxidation, 202, 203
~ propene oxidation, 195
V-P-0, 206
Water, adsorption, 57
- in COX hydrogenation, 230
- in selective oxidation, 174
- photodecomposition, 269
- photo-oxidation, 269
Water-gas shift, 244
WO, (see tungsten oxide)
Wurtzite structure, 8
XANES. 4
XPS, 4
Zinc oxide, acetone adsorption, 66, 150
-, acidity, 75
-, adsorbed oxygen, 114, 11 6
-, alcohol, adsorption, 66
-, -, decomposition, 152
-, alkane reaction, 116
-, alkene isomerization. 144
-, butene, adsorption, 65
-, -, hydrogenation, 160
-, CO adsorption, 60, 67
-, dehydroxylation, 58
-, deuterium exchange, 161
-, ethene hydrogenation, 158
-, hydrogen adsorption, 63
-, methanol decomposition, 146
-, O2 isotope exchange, 265
--, photo-adsorption, 257
-, photo-desorption, 257
-, photo-oxidation, 266, 268
-, preparation, 125
-, propanol decomposition, 149
-, propene adsorption, 64
-, propene hydrogenation, 158
--, surface electronic smcture, 47
-, surface phonon, 48
-, surface structure, 18
zirconium oxide, isosynthesis. 240
-. preparation, 124
283
STUDIES I N SURFACE SCIENCE AND CATALYSIS
Advisory Editors: B. Delmon, Universite Catholique de Louvain, Louvain-la-Neuve, Belgium
J .T. Yates, University of Pittsburgh, Pittsburgh, PA, U S A .
Volume 1
Volume 2
Volume 3
Volume 4
Volume 5
Volume 6
Volume 7
Volume 8
Volume 9
Volume 10
Volume 11
Volume 12
Volume 13
Volume 14
Preparation of Catalysts I. Scientific Bases for the Preparation of Heterogeneous
Catalysts. Proceedings of the First International Symposium, Brussels, October 14-
17, 1975
edited by B. Delmon, P.A. J acobs and G. Poncelet
The Control of the Reactivity of Solids. A Critical Survey of the Factors that
Influence the Reactivity of Solids, with Special Emphasis on the Control of the
Chemical Processes in Relation to Practical Applications
by V.V. Boldyrev, M. Bulens and B. Delmon
Preparation of Catalysts II. Scientific Bases for the Preparation of Heterogeneous
Catalysts. Proceedings of the Second International Symposium, Louvain-la-Neuve,
September 4-7, 1978
edited by B. Delmon, P. Grange, P. J acobs and G. Poncelet
Growth and Properties of Metal Clusters. Applications to Catalysis and the
Photographic Process. Proceedings of the 32nd International Meeting of the Societe
de Chimie Physique, Villeurbanne, September 24-28, 1979
edited by J . Bourdon
Catalysis by Zeolites. Proceedings of an International Symposium, Ecully (Lyon),
September 9- 1 1, 1980
edited by B. Imelik, C. Naccache, V. Ben Taarit, J .C. Vedrine, G. Coudurier and
H. Praliaud
Catalyst Deactivation. Proceedings of an International Symposium, Antwerp,
October 13-15, 1980
edited by B. Delmon and G.F. Froment
New Horizons in Catalysis. Proceedings of the 7th International Congress on
Catalysis, Tokyo, J une 30-J uly 4, 1980. Parts A and B
edited by T. Seiyama and K. Tanabe
Catalysis by Supported Complexes
by Vu.1. Yermakov, B.N. Kuznetsov and V.A. Zakharov
Physics of Solid Surfaces. Proceedings of a Symposium, Bechyhe, September 29-
October 3, 1980
edited by M. LazniEka
Adsorption at the Gas-Solid and Liquid-Solid Interface. Proceedings of an
International Symposium, Aix-en-Provence, September 21-23, 198 1
edited by J . Rouquerol and K.S.W. Sing
Metal-Support and Metal-Additive Effects in Catalysis. Proceedings of an
International Symposium, Ecully (Lyon), September 14-1 6, 1982
edited by B. Imelik, C. Naccache, G. Coudurier, H. Praliaud, P. Meriaudeau,
P. Gallezot, G.A. Martin and J .C. Vedrine
Metal Microstructures in Zeolites. Preparation - Properties - Applications.
Proceedings of a Workshop, Bremen, September 22-24, 1982
edited by P.A. J acobs, N.I. J aeger, P. J irG and G. Schulz-Ekloff
Adsorption on Metal Surfaces. An Integrated Approach
edited by J . Benard
Vibrations at Surfaces. Proceedings of the Third International Conference,
Asilomar, CA, September 1-4, 1982
edited by C.R. Brundle and H. Morawitz
284
Volume 15 Heterogeneous Catalytic Reactions Involving Molecular Oxygen
by G. I. Golodets
Volume 16 Preparation of Catalysts Il l . Scientific Bases for the Preparation of Heterogeneous
Catalysts. Proceedings of the Third International Symposium, Louvain-la-Neuve,
September 6-9, 1982
edited by G. Poncelet, P. Grange and P.A. J acobs
Volume 17 Spillover of Adsorbed Species. Proceedings of an International Symposium, Lyon-
Villeurbanne, September 12-1 6, 1983
edited by G.M. Pajonk, S.J . Teichner and J .E. Germain
Volume 18 Structure and Reactivity of Modified Zeolites. Proceedings of an International
Conference, Prague, J uly 9-1 3, 1984
edited by P.A. J acobs, N.I. J aeger, P. J irP, V.B. Kazansky and G. Schulz-Ekloff
Volume 19 Catalysis on the Energy Scene. Proceedings of the 9th Canadian Symposium on
Catalysis, Quebec, P.Q.. September 30-October 3, 1984
edited by S. Kaliaguine and A. Mahay
Villeurbanne (Lyon), September 25-27, 1984
edited by 8. Imelik, C. Naccache, G. Coudurier, Y. Ben Taarit and J .C. Vedrine
Volume 2 1 Adsorption and Catalysis on Oxide Surfaces. Proceedings of a Symposium,
Uxbridge, J une 28-29, 1984
edited by M. Che and G.C. Bond
Volume 22 Unsteady Processes in Catalytic Reactors
by Yu.Sh. Matros
Volume 23 Physics of Solid Surfaces 1984
edited by J . Koukal
Volume 24 Zeolites: Synthesis, Structure, Technology and Application. Proceedings of an
International Symposium, Portoroi-Portorose, September 3-8, 1984
edited by B. Driaj, S. HoEevar and S. Pejovnik
Volume 25 Catalytic Polymerization of Olefins. Proceedings of the International Symposium
on Future Aspects of Olefin Polymerization, Tokyo, J uly 4-6, 1985
edited by T. Keii and K. Soga
Bowness-on-Windermere, September 15-1 9, 1985
edited by D.A. King, N.V. Richardson and S. Holloway
Volume 27 Catalytic Hydrogenation
edited by L. Cervenq
Volume 28 New Developments in Zeolite Science and Technology. Proceedings of the 7th
International Zeolite Conference, Tokyo, August 17-22, 1986
edited by Y. Murakami, A. lijima and J .W. Ward
Volume 29 Metal Clusters in Catalysis
edited by B.C. Gates, L. Guczi and H. Knozinger
Volume 30 Catalysis and Automotive Pollution Control. Proceedings of the First International
Symposium, Brussels, September 8-1 1, 1986
edited by A. Crucq and A. Frennet
Volume 3 1 Preparation of Catalysts IV. Scientific Bases for the Preparation of Heterogeneous
Catalysts. Proceedings of the Fourth International Symposium, Louvain-la-Neuve,
September 1-4, 1986
edited by B. Delmon, P. Grange, P.A. J acobs and G. Poncelet
Volume 32 Thin Metal Films and Gas Chemisorption
edited by P. Wissmann
Volume 33 Synthesis of High-silica Aluminosilicate Zeolites
by P.A. J acobs and J .A. Martens
Volume 34 Catalyst Deactivation 1987. Proceedings of the 4th International Symposium,
Antwerp, September 29-October 1, 1987
edited by B. Delmon and G.F. Froment
Volume 20 Catalysis by Acids and Bases. Proceedings of an International Symposium,
Volume 26 Vibrations at Surfaces 1985. Proceedings of the Fourth International Conference,
285
Volume 35
Volume 36
Volume 37
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Volume 39
Volume 40
Volume 4 1
Volume 42
Volume 43
Volume 44
Volume 45
Keynotes in Energy-Related Catalysis
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Methane Conversion. Proceedings of a Symposium on the Production of Fuels and
Chemicals from Natural Gas, Auckland, April 27-30, 1987
edited by D.M. Bibby, C.D. Chaney, R.F. Howe and S. Yurchak
Innovation in Zeolite Materials Science. Proceedings of an International
Symposium, Nieuwpoort, September 13-1 7, 1987
edited by P.J . Grobet, W.J . Mortier, E.F. Vansant and G. Schulz-Ekloff
Catalysis 1987. Proceedings of the 10th North American Meeting of the Catalysis
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edited by J .W. Ward
Characterization of Porous Solids. Proceedings of the IUPAC Symposium (COPS I),
Bad Soden a. Ts., April 26-29, 1987
edited by K.K. Unger, J . Rouquerol, K.S.W. Sing and H. Kral
Physics of Solid Surfaces 1987. Proceedings of the Fourth Symposium on Surface
Physics, Bechyne Castle, September 7-1 1, 1987
edited by J . Koukal
Heterogeneous Catalysis and Fine Chemicals. Proceedings of an International
Symposium, Poitiers, March 15-17, 1988
edited by M. Guisnet, J . Barrault, C. Bouchoule, D. Duprez, C. Montassier and
G. Perot
Laboratory Studies of Heterogeneous Catalytic Processes
by E.G. Christoffel, revised and edited by 2. Paal
Catalytic Processes under Unsteady-State Conditions
by Yu. Sh. Matros
Successful Design of Catalysts - Future Requirements and Development.
Proceedings of the Worldwide Catalysis Seminars, J uly, 1988, on the Occasion of
the 30th Anniversary of the Catalysis Society of J apan
edited by T. lnui
Transition Metal Oxides: Surface Chemistry and Catalysis
by H.H. Kung
Volume 46 Zeolites as Catalysts, Sorbents and Detergent Builders. Applications and
Innovations. Proceedings of an International Symposium, Wurzburg, F R G ,
September 4-8, 1988
edited by H.G. Karge and J . Weitkamp
Volume 47 Photochemistry on Solid Surfaces
edited by M. Anpo and T. Matsuura
Volume 48 Structure and Reactivity of Surfaces. Proceedings of a European Conference
Trieste. Italy, September 13- 16, 1988
edited by C. Morterra, A. Zecchina and G. Costa
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