Solid State Ionics 101-103 (1997) 655460

Influence of species diffusing at surfaces on reactions of solids and

catalytic processes

B. Delmon
Universite Catholique de Louvain, Unite de Catalyse et Chimie des Mat&iaux Divisb, Place Croix du Sud 2117, B-1348 Louvain-la-
Neuve, Belgium

Abstract

The reactivity of solids focuses on time-dependent modifications. The surface of catalysts also undergoes time-dependent
modifications during the catalytic cycle. The objective of this contribution is to highlight scientific problems of common
interest in the science of solid-state reactivity and in catalysis, especially when the mobility of small chemical species
(hydrogen, oxygen) on surfaces, or ‘spillover’, is involved. This will be illustrated by surface reactions at MoS, edges and
reconstruction of surfaces on MOO,.

Keywords: Spillover; Surface species; Reactivity; Surface reconstruction in catalysis

Materials: MoS,; MOO,

1. Introduction: Special reactivity of surface
mobile species
It is widely recognised that catalysis should benefit
from the scientific knowledge developed in the field
of solid-state chemistry. The corresponding concepts
are used for preparing nano-scale engineered
catalysts. But many solid-state reactivity aspects oc-
curring during the catalytic reaction have been ig-
nored (except sintering). On the other hand, the sci-
ence of the reactivity of solids did not benefit much
from advances concerning the chemical reactions at,
on or in catalysts. The objective of this contribution is
to highlight phenomena of common interest and to
suggest how a joint scientific approach could lead to
accelerated progress in both fields.
The article will focus on the role of atomic species
diffusing on the surface of solids. Of particular
interest for reactions of solids and catalytic phenom-
ena involving hydrogen or oxygen is the case where
atomic surface species possess a high reactivity. The
first experiments suggesting this special reactivity
came from the field of solid-state reactivity. We have
been among the first, or perhaps the first, to show
that a group VIII metal (Ni, Pt, Pd) or Cu, separated
from one oxide, can trigger the reduction by hydro-
gen of this oxide [ 1,2]. The fact that a mobile
hydrogen species was responsible for this effect was
demonstrated by supporting palladium or platinum
on an inert porous powder (alumina or silica, respec-
tively) and mixing this powder with powdered NiO.
The reduction was considerably accelerated, showing
that hydrogen was dissociated on the group VIII
metal, migrated onto the surface of Al,O, or SiO,,
then onto the surface of NiO where it reacted [3].
The striking feature of these phenomena is that a
molecule (e.g. Hz) decomposes to give surface
mobile species which possess a higher reactivity than

0167-2738/97/$17.00 0 1997 Elsevier Science B.Y. All rights reserved.

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656 B. Dehorn I Solid State Ionics 101-103 (1997) 655-660

the molecular form. The dissociation of a molecule
to form atomic species which migrate to other
surfaces received the name of ‘spillover’. The picture
is that of a surface (e.g. that of the noble metals
mentioned above) which gets saturated by disso-
ciated species to the point that these species overflow
across the border between the metal and another
phase, namely ‘spillover’ onto that surface. But it
took very long before the consequences of this high
reactivity began to emerge in the field of catalysis.
A question which is presently coming to the
forefront is whether spillover species can cause a
catalyst to become more active. The group of
Teichner, Pajonk, Blanchi, Gardes, Lacroix and co-
workers showed that Al,O,, SiO, or MgO subjected
during a relatively long time to the action of
spillover hydrogen acquired special catalytic sites
[4-61. But that activity was modest or extremely
modest. On the other hand, synergies very frequently
observed between distinct phases in hydrotreating
and oxidation catalysis led to the idea that active
sites could be continuously created on a catalytic
phase during the catalytic reaction [7-91. This
finding differs from the results mentioned previously
on two grounds: (i) the creation of active sites occurs
on a catalytically active phase, not on a normally non
active or slightly active support; and (ii) this is a
continuous process occurring during the catalytic
reaction, and not the result of some pretreatment. It
turns out that this corresponds to modifications of the
catalyst surface which are very similar, or sometimes
identical, to those occurring during the first steps of
the reaction of a solid.
In this contribution, we shall highlight the simi-
larities between reactions or solids, or more precisely
their initiation by spillover species, and the changes
that catalyst surfaces undergo when irrigated by
spillover species. Our ambition is to show that the
chemistry of solids, on the one hand, and catalysis,
on the other hand, can gain mutual benefits from
their respective advances.
breaking the hydrogen-sulfur (hydrodesulfurization:
HDS) or hydrogen-nitrogen (hydrodenitrogenation:
HDN) bonds, and to hydrogenate unsaturated hydro-
carbons (HYD), are essentially composed of MoS,
(or WS,), which constitute the real active phase,
associated with other sulfides (Co,S,, NiS, and,
recently, more or less sulfided noble metals). These
catalysts are used in the largest group of chemical
processes in the world (more precisely in petroleum
refining), with more than 1.5 billion tons of feed
being treated annually. The special reactivity of
spillover hydrogen H,, explains the activity and
selectivity of sulfide catalysts: H,, controls the local
coordination of active atoms like molybdenum or
tungsten in the sulfide surface.
Fig. 1 represents schematically the edges of the
MoS, layers. In these layers, MO atoms (in black;
their size is actually much larger than in the picture)
are placed between layers of sulfur atoms (open
circles). The edges are catalytically active, the basal
planes are not. The catalytically active MO atoms are
those which have lost some of their sulfur neighbors.
Threefold coordination-unsaturated MO atoms
(CUSMo), namely MO atoms deprived of 3 of their
sulfur neighbors, are responsible for the hydrogena-
tion activity (Fig. 1, left-hand part of the upper slab)
[lo]. The role of the promoter (Co,S,, NiS, sulfided
Pd, Pt, Rh, etc.), or ‘donor’, is to produce spillover
hydrogen H,, which removes sulfur atoms, thus
liberating the necessary coordination positions. This
takes place continuously during the catalytic re-
CUS MO
H2s
t
Hz-

2. The control of metal coordination at the

surface of sulfide catalysts
The sulfided catalysts,
catalysts, used to eliminate
Fig. 1. Schematic representation of the formation, by spillover
hydrogen, of hydrogenation and hydrodesulfurization sites (re-
called hydrotreating spectively: threefold coordinatively-unsaturated sites (CUSMo)
polluting elements by and same type of CUSMo + vicinal SH).
 B. Delmon I Solid State lonics 101-103 (1997) 655-660 651

action, each time an individual reaction in the difference in the relative proportions of MoS, and
successive catalytic cycles ‘goes wrong’ and leaves CoS, at the points of maximum activities is easily
behind a sulfur atom, blocking a coordination un- explained. When the mixture contains little CoS,,
saturation. Thanks to this action, H,, restores the this can only produce a small amount of spillover
correct unsaturation. The HDS sites are probably hydrogen H,,, with the result that the sites created
constituted of a threefold coordination-unsaturated are predominantly the moderately reduced ones,
MO atom of the same kind, situated next to an SH namely HYD sites. With more CoS,, the HDS
group [ 11,121. The formation of this SH group may function becomes comparatively stronger.
be caused by the opening, by reaction with H,,, of an This surface reduction by spillover H,, can be
MO-S-MO bridge on the edge of the MoS, slabs made deeper at higher temperature and lead to a
(Fig. 1, left-hand part of the lower slab). complete reduction, as shown by Chu and Schmidt
A laboratory experiment, where the active phase using scanning tunnelling and atomic force micros-
(MoS,) is supported on particles of a porous oxide copies [ 131. This shows directly the link, or some
(y-Al,O,) and the donor (C,S,) supported on sort of continuity, between the control of catalytic
different particles (carbon) can be made. The two sites and surface reactivity of solids.
powders are mixed by agitating their suspension in
n-pentane and drying. In spite of the physical
separation of the active phases, the activities in the 3. The control of surface structure in selective
hydrogenation of cyclohexene (HYD) and hydro- catalytic oxidation
desulfurization of thiophene (I-IDS) increase by,
respectively, 55% (open arrow) and 65% (black A very large proportion of the functionalized
arrow) because of the action of H,, (Fig. 2). The molecules used as building blocks in the chemical
industry is produced by selective catalytic oxidation
of hydrocarbons on metal oxides. The surface of
these oxides undergoes a continuous reduction-oxi-
dation cycle during the catalytic process (the so-
called Mars-van Krevelen mechanism). For example,
in the case of propene giving acrolein on MOO,
(represented below by Mo,O,,, to suggest that the
catalyst is constituted of relatively big crystallites),
the catalytic cycle is a continuous succession of
reduction and oxidation of the solid, as follows:
Reduction:

CH,=CH-CH, + Mo,O,, -+ CH,=CH-CHO

+ H,O + Mo,O,,_,.

Oxidation:
I I
0’ Mn03n_2 + 0, -+ Mo,O,,.
0 0.5 1

MoS2
1
y- A'24 CoSx
I
Carbon During each cycle, two oxygen atoms are removed
from the surface. The structure of MOO, is built
Fig. 2. Catalytic synergy in the hydrogenation of cyclohexene from comer-sharing octaedra, similar to those found
(HYD) and hydrodesulfkization of thiophene (HDS) contained in in the suboxides of MOO,, exhibiting shear struc-
the same feed. The catalyst was obtained by mixing MoS,
hues. The catalytic cycle therefore corresponds to a
supported on y-alumina and cobalt sulfide supported on micropor-
ous carbon. The independently prepared powders were suspended
cyclic structural change of the surface between
in n-pentane and agitated until all the n-pentane was evaporated ‘clusters’ of two comer-sharing octaedra pairs and
(reaction at 300°C at a total pressure of 3 MPa) [18]. ‘clusters’ of two edge-sharing octaedra pairs (upper
658 B. Delmon / Solid State Ionics 101-103 (1997) 655460

CH3 - CH = CH2 CH2 = CH- CHO

I lH2o

Fig. 3. Transformation of corner-sharing to edge-sharing octaedra arrangements of MOO, and back, during the catalytic oxidation of

part of Fig. 3). Unfortunately, reduction of MOO, by prediction was then that any factor which would
hydrocarbons is usually more rapid than reoxidation, favor the establishment of this dynamic or wobbly
and MOO, forms, by development of shear struc- state, such as the presence of O,,, could trigger
tures, suboxides (e.g. Mo,O, , ) which are less active progressive changes in surface structure or morphol-
and less selective. The industrial catalysts retain their ogy, namely lead to a reconstruction. Indeed, scan-
activity for months or years because they contain ning electron microscopy (SEM) shows that the
several oxides, e.g. o-Sb,O,, in addition to the edges of MOO, crystallites, initially flat (Fig. 4),
catalytically active ones. reconstruct during the oxidation of isobutene to
A crucial experiment we did was to use simple methacrolein, and acquire a stepped morphology. But
physical mixtures of separately prepared powders of
MOO, and ol-Sb,O,. Such mixtures exhibit a strong
catalytic synergy. MOO, and other catalytic oxides,
which normally get reduced during catalytic reaction,
remain in a high oxidation state in the presence of
o-Sb,O, [9,14,15]. We could show, using ‘*O-la-
belled a-Sb,O,, that ‘*O can migrate to MOO, [16].
We could also show that O,, coming from cx-Sb,O,
is able to accelerate the reoxidation of previously
reduced MOO, [ 16,171. This demonstrates that O,, is
indeed mobile and that it possesses a high reactivity.
Our interpretation of the favorable role of O,, in
catalytic oxidation reaction is that this species, due to
its high reactivity, reacts with clusters of edge
sharing octaedra pairs, thus preventing the nucleation
of shear structures.
These results indicate that the surface of oxidation
catalysts are in a special metastable state, existing
only as long as the catalytic reaction goes. This is a
dynamic or wobbly state, with structures continuous- Fig. 4. MOO, crystallite on which small aggregates of a-Sb,O,
ly being created and destroyed. Based on that, our have been deposited: SEM picture on the freshly prepared sample.
 B. Delmon / Solid State Ionics IOl- 103 (1997) 655-660 659

understand this wobbly state, and can help to create

Fig. 5. MOO, crystallite on which small aggregates of a-Sb,O,
have been deposited: SEM picture after having worked cata-
lytically in the oxidation of isobutene to methacrolein for 3 h [19]
in the usual oxidation conditions [9]. No change is observed in the
same conditions if o-Sb,O, is absent [19].
it. On the other hand, new results on this wobbly
state coming from catalytic science provide the
science of the reactivity of solids with new data and
new problems to solve. In this context, the surface
mobility of small chemical species, especially spill-
over, deserves special attention. It controls the
‘wobbly state’. This implies that the presence or not
of spillover species constitutes a new parameter to
control reactivity, in addition to temperature, reactant
concentrations or pressures, reaction pressure, mag-
netic or electric fields, etc. The behavior of catalysts
during the catalytic reaction, and all the dynamic
processes involving spillover species, provide new
insights into solid-state reactivity. In a broader
context, the catalytic reaction is a dissipative process
that can operate almost indefinitely, thus generating
otherwise metastable structures lasting during a long
period. Considering together catalysts as they react
catalytically and the other aspects of the reactions of
solids, a broader field opens to the science of the
reactivity of solids.

this occurs only when these crystallites are in contact

with a source of spillover oxygen (namely when References
o-Sb,O, is present) (Fig. 5). Atomic force micro-
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