Professional Documents
Culture Documents
Preface to Series xi
Preface xiii
Contributors xv
SUPPORTED METALS
2.1 Introduction 17
Characteristics of Supported Metals 18, Conditions
of Characterization of Supported Metals 18
3.1 Introduction 47
Oxides as Catalysts 47, Mechanistic Features of Oxide Catalyzed Reactions 48
3.4 Summary 66
4.1 Introduction 69
4.2 Synthesis Methods 70
4.3 Characterization 71
Structure of the Supported Metal Oxide Phase 71, Surface Coverage
of the Supported Metal Oxide Phase 73, Oxidation States and Local
Structural Environments of Supported Metal Oxide Phases 75, Morphology
of the Supported Metal Oxide Phase 77, Surface Chemistry of
Supported Metal Oxides 77, Characterization Summary 79
vi Contents
5.1 Introduction 89
5.2 Preparation of Bulk TMS Catalysts 90
Binary Sulfides 90, Mixed Metal Sulfides 91
Contents vii
viii Contents
Index 197
Contents ix
This Materials Characterization Series attempts to address the needs of the practical
materials user, with an emphasis on the newer areas of surface, interface, and thin
film microcharacterization. The Series is composed of the leading volume, Encyclope-
dia of Materials Characterization, and a set of about 10 subsequent volumes concen-
trating on characterization of individual materials classes.
In the Encyclopedia, 50 brief articles (each 10 to 18 pages in length) are presented
in a standard format designed for ease of reader access, with straightforward tech-
nique descriptions and examples of their practical use. In addition to the articles,
there are one-page summaries for every technique, introductory summaries to group-
ings of related techniques, a complete glossary of acronyms, and a tabular compari-
son of the major features of all 50 techniques.
The 10 volumes in the Series on characterization of particular materials classes
include volumes on silicon processing, metals and alloys, catalytic materials, integrated
circuit packaging, etc. Characterization is approached from the materials user’s point
of view. Thus, in general, the format is based on properties, processing steps, materi-
als classification, etc., rather than on a technique. The emphasis of all volumes is on
surfaces, interfaces, and thin films, but the emphasis varies depending on the relative
importance of these areas for the materials class concerned. Appendixes in each volume
reproduce the relevant one-page summaries from the Encyclopedia and provide longer
summaries for any techniques referred to that are not covered in the Encyclopedia.
The concept for the Series came from discussion with Marjan Bace of Manning
Publications Company. A gap exists between the way materials characterization is
often presented and the needs of a large segment of the audience—the materials user,
process engineer, manager, or student. In our experience, when, at the end of talks or
courses on analytical techniques, a question is asked on how a particular material (or
processing) characterization problem can be addressed the answer often is that the
speaker is “an expert on the technique, not the materials aspects, and does not have
experience with that particular situation.” This Series is an attempt to bridge this gap
by approaching characterization problems from the side of the materials user rather
than from that of the analytical techniques expert.
We would like to thank Marjan Bace for putting forward the original concept,
Shaun Wilson of Charles Evans and Associates and Yale Strausser of Surface Science
Laboratories for help in further defining the Series, and the Editors of all the indi-
vidual volumes for their efforts to produce practical, materials user based volumes.
xi
xii
xiii
Israel E. Wachs
xiv Preface
xv
Contents
1.1 Introduction
1.2 Preparation of Bulk Alloy or Bimetallic Catalysts
1.3 Bulk Metal Characterization Methods
1.4 Surface Composition–Structure and Catalysis Relationship
1.1 Introduction
Metals and alloys play a key role in catalytic technology, especially in reactions
involving hydrogen transfer and in hydrocarbon conversion reactions. This chap-
ter discusses the characterization of catalytic metals and alloys in their bulk form.
Many catalytic applications require catalysts with high surface area to provide ade-
quate contact between the reactants and the catalyst. Therefore, a large number of
catalytic processes rely on supported-metal catalysts, in which the metal particles
are well dispersed on a high surface area support material. However, unsupported
bulk metals or alloys are sometimes employed in the form of films, foils, wires, or
powders. Because of their high catalytic activity, platinum group metals find the
widest application. The reactions of hydrocarbons on Pt surfaces include hydro-
genation and dehydrogenation; hydrogenolysis of C–C, C–S, and C–N bonds;
isomerization; and cyclization reactions.
On an industrial scale, ammonia is oxidized to nitric acid in the presence of a
Pt–Rh wire gauze or Pd–Au alloy wires. Palladium–gold alloys are very effective
catalysts for the selective hydrogenation of unsaturated hydrocarbons, such as the
hydrogenation of acetylene to ethylene. Catalytic hydrogenation can also be accom-
plished over Raney nickel or cobalt catalysts. Silver gauze or granular silver screened
such as metal chlorides are reduced in flowing hydrogen gas or in hydrazine solu-
tions4 or some other suitable reducing medium. To ensure that the resulting alloy is
homogeneous, one evaporates the solvent until a dry halide salt mixture is obtained,
keeping the reduction temperature as low as possible to prevent sintering and keep-
ing the surface area of the powder as large as possible. Nonnoble metal alloy catalysts
are usually made from their corresponding carbonates, nitrates, or hydroxides, which
are first calcined to convert them into an oxide mixture and then reduced in flowing
hydrogen to generate an alloy. Reduction of the precursor salt mixtures can also be
carried out in aqueous or nonaqueous solutions, with sodium borohydride, hydra-
zine, formaldehyde, or hypophosphorous acid as reducing agents. One often finds
traces of sodium and boron impurities in these types of catalysts. Like monometallic
catalysts, alloy catalysts can be prepared by the evaporation of suitable metals. This
preparation technique is frequently used to make alloy films of high purity.
Metal catalysts, such as Raney nickel or cobalt catalysts, are widely used for cata-
lytic hydrogenation reactions. These Raney-type catalysts are prepared from Ni–Al
or Co–Al alloys; they are activated by leaching the aluminum out of the alloy in
a sodium hydroxide solution at a pH of approximately 14.5 The leaching process
leaves behind a porous skeleton of Ni or Co, with a greater surface area than the
original alloy. Amorphous alloys, such as Fe–Ni,6 AuZr,7 or FeB,8 can be prepared
by methods including vapor deposition, sputtering, electroplating, chemical plating,
and rapid quenching of melts. These amorphous alloys represent nonequilibrium
X-ray diffraction is a powerful method used in the determination of the bulk crystal-
lographic structure of catalytic materials; it is also widely used for the characteriza-
tion of bulk metals and alloys.10 From X-ray diffraction patterns, lattice spacings for
the various crystallographic planes in a metal or alloy can be determined with great
accuracy. One can determine all metallic or intermetallic phases present in a bulk
metal sample in a straightforward manner by comparing the unknown X-ray diffrac-
tion pattern with known patterns of metals and alloys. In substitutional alloys that
form a continuous series of solid solutions, the lattice spacings vary with composi-
tion, as demonstrated in Figure 1.3 for a series of copper–nickel alloys.11
X-ray diffraction lines are generally very narrow for bulk samples in the form of
single crystals, thin films, or powders with large grains, with the actual width of a
where K is a constant that depends on the crystal geometry and is often set equal to
1. The parameter β represents the line broadening after correcting for instrumen-
tal contributions to a finite line width. Various procedures exist for separating the
instrumental contribution from the broadening due to the particle size, including a
method based on a Fourier transform.12, 13 In bulk samples, lattice strain can con-
tribute some additional broadening of the lines.
The total surface area of bulk metal catalysts is most commonly measured by the
Brunauer–Emmet–Teller (BET) method,18 for which commercial instruments are
available. The BET method is based on physical adsorption of gases such as nitro-
gen or krypton. Bulk metal catalysts tend to have fairly low surface areas, except
perhaps Raney-type powders. The pore volume and pore size distribution of the
Surface Composition
Many techniques are available for the surface characterization of bulk metals and
only a brief overview will be given here. Metal surfaces can be probed by either a
particle beam or by electromagnetic or thermal energy. The output signal can consist
in the emission of particles or photons of discrete energy, which can then be analyzed
by suitable detectors. Many surface characterization techniques require an ultrahigh
vacuum (UHV); however, it is very difficult to maintain clean metal surfaces during
analysis. Even in a vacuum of 10–9 torr there are enough residual gas molecules in the
analysis chamber of a typical spectrometer that it will take only about 15 minutes for
the sample surface to be covered with a monolayer of adsorbate, if one assumes that
every collision of a gas molecule with the surface results in adsorption.
A key characteristic of a bulk metal catalyst is the relationship between its bulk
composition and its surface composition. In ideal bimetallic systems it is possible
to derive thermodynamically the equilibrium surface composition as a function of
the bulk composition and temperature. The heat effects of surface segregation can
be determined from the “broken bond” model, in which it is assumed that each
metal atom in the bulk forms a certain number of bonds with nearest neighbor
atoms: 8 for bcc metals and 12 for fcc metals. Metal atoms on the surface have
fewer nearest-neighbors, and several bonds are “broken,” depending on the crys-
tal face exposed. Metals with lower sublimation energy and, consequently, weaker
metal–metal bonds tend to segregate in the surface, where less energy is used by not
forming the weaker bonds. Segregation is also more prevalent on rougher surfaces
with higher index planes, since there is a greater number of bonds not formed on
where I(A) and I(B) are Auger signal intensities for elements A and B in the alloy,
respectively, divided by the Auger signal intensity of the pure metals A and B; R* is
a correction factor for back scattering; ρA and ρB represent the planar densities of
elements A and B, respectively; N1 is the fraction of the total signal emanating from
the first layer; x1 is the molar ratio of A in the top layer; and xbulk is the molar ratio
on the bulk of the alloy. Figure 1.5 compares experimental Auger spectroscopy data
for the surface composition of Pt–Cu alloys with predicted surface compositions for
ideal alloys. Note the significant deviations from ideal behavior.
Samples for XPS and Auger electron spectroscopy should have flat surfaces; thin
metal foils are ideal. Powder samples must be pressed into the shape of a thin wafer.
To study a clean, reduced metal surface, it is necessary to transfer a sample of the
metal from a pretreatment chamber operated at higher pressures into the analysis
chamber, which runs at UHV, without exposing the sample to ambient air. Commer-
cial transfer devices with appropriate interlock and pump systems are available.
In XPS, the effective depth of the analyzed layer is about 2–4 nm, and for Auger
electron spectroscopy, about 1–3 nm. It is possible to sputter the surface with high
energy argon ions that remove atoms from the surface, so that depth profiles can
be acquired. Depth profiling can give valuable information about the location of
impurities and is a very useful method for studying compositional changes between
the surface and the subsurface. The spatial resolution of XPS is not very good, the
signal arising from an area about 10 000 nm across. Much better spatial resolution
can be achieved in a scanning Auger microprobe (SAM), where the signal emanates
from an area as small as 20 nm across. In samples with a non-uniform distribution
of metal components, XPS tends to give an average surface composition, whereas
the SAM pinpoints the local variations in surface composition. The SAM can also
reveal the oxidation state of the surface, which can be very important because many
metals have a tendency to undergo surface oxidation when exposed to ambient air.
Gas–Surface Interactions
The main technique used in determining the surface structure of single crystals is
low energy electron diffraction (LEED). The first layer of atoms on a surface may
have a structure which deviates from the bulk structure, which is indicated by the
appearance of extra diffraction spots in LEED patterns—diffraction spots other
than those characteristic for the bulk structure. Surface structure analysis by LEED
has provided strong evidence that the surface atoms in many metals and alloys are
located in new equilibrium positions. In experiments with Pt single crystals, it was
found that the rates of many hydrocarbon conversion reactions vary, depending on
the type of crystallographic face exposed.29 The information gained from studies
on well-defined single-crystal surfaces can be used to better interpret the catalytic
References
REFERENCES 15