Beruflich Dokumente
Kultur Dokumente
Carbon Monoxide
Geojfrey C Bond
Brunel Uniiersity, Uxbridge, Middlesex, UB8 3PH, UK
The last decade has witnessed a rapid growth of interest in and often contradictory reports on the irnportance of the
the catalytic properties of gold: when it is suitably experimental variables. lt is lirtle wonder, thereore, that
ernployed, and much skill is needed to achieve this, almost all discussions of reaction rnechanisrns are of an
supported gold is capable of catalysing a wide variety of elementary and somewhat speculative nature, because of
reactions under comparatively mild conditions, induding the lack of a firm foundation of reaction kinetics and
oxidation, oxidative dehydrogenation, hydrogenation, spectroscopic data analysis,
and many others. We have recently reviewed this sector of The rnain reason for this review is to try to
catalysis in depth (1), and other review articles have been understand the reasons for the many discrepancies and
published (2, 3): the earlier Gold Bulletin review also contradictions which the literature reveals. These reflect
provides a general survey (4). One of the rnain the very critica! and rnultiple criteria which must be met
conclusions from our previous review (1) was that the way befare high catalytic activity can be obtained, and the
in which gold acts catalytically is substantially different extreme sensitivity of the final catalyst to all stages of its
from that adopted by rnetals of the Platinum Group. preparation and treatment befare use. Although all is as
Probably the greatest surprise has been the ability of yet far from dear, there are enough indicators towards a
appropriately prepared gold catalysts to effect the possible model that will accommodate many of the
oxidation of carbon monoxide at very moderate observations, and a mechanistic concept is tentatively
temperatures: the best have even been reported to advanced later in this paper.
function below arnbient temperature, and to be more
active than conventionally prepared palladium and
platinurn catalysts. Because of the potential for practica! CONSENSUAL OBSERVATIONS
application, as well as intrinsic scientiic interest, the flow
of publications continues unabated. We have recorded Notwithstanding the seemingly confused state of the
sorne 60 publications in 1999, and at least half of these literature, there is a large measure of agreement as to the
concern carbon rnonoxide oxidation, However, a reader principal factors responsible for the activity (or inactivity)
of the recent literature, as well as of the earlier of gold catalysts evaluated for carbon monoxide
publications already reviewed (1), cannot fail to oxidation, and it will be helpful to start by listing these.
experience a sense of conusion at the many rnethods of 1 Unsupported gold in the form of sponge, wire,
preparation and characterization that have been used, the powder, etc, and large supported gold partides are
many different supports, and in particular at the various at best only weakly active for carbon monoxide
Table 1 Kinetics of Carbon Monoxide Oxidation on Supported Gold Catarysts. Rate ex Pco x PO J
Support Method* [Au](%) d(nm) T(range) X y E 02/CO Ref
(K) (kJ mol")
a-Fe203 COP 0.66 4 304 o O.OS 35.1 20 34
(273 - 333)
Notes
1 The first temperature is that at which orders of reaction were measured:the range in brackets is that used for activation energy.
2 A dash means that information was not provided.
3 The quoted OifCO ratio is that used forthe activation energy.
Two FurtherFactors
although activities sometimes increase to begin with, Before attempting harmonization of all these very diverse
before reaching a stable high level, egwhen dried (ie non- observations, two other factors need to be considered:
calcined) materials are used (21). Most authors are quite 1 The reactivity of gold atoms may depend on their
strongly polarized in their views, believing that only Au0 coordination number (CN), stronger
(3, 10) or only Au'" (22, 42) species are responsible for chemisorption being shown theoretically for lower
activity.The mode of action of the atter, and the reasons values of CN (45). The concept of varying electron
for their superiority over Au0, is not explained by those density across steps on model surfaces is well
who believe in them, and no one seems to consider that established ( 46), and the fraction of edge atoms
the presence of both may be necessary. Electrocatalytic will obviously rise as particle size decreases (1, 45).
oxidation studies using gold electrodes (1, 43, 44) 2 The stability of noble metal (Pt, Rh) particles on
strongly suggest that gold atoms having low coordination alumina and titania is attributed to a 'chemical
number (CN) are more electropositive and are thereore glue' of metal cations at the interface between the
more easily oxidized than those of high CN, and this support and the particle (see, for example,
suggests that peripheral gold atoms in small supported reference 47). At small particle sizes the fraction of
particles may readily transorrn into ions. The the metal in ionic form can be quite high.
sirnultaneous presence of both atoms and ions is thereore Structures of this interfacial zone, and changes
not ruled out. with ambient atmosphere, have been elucidated by
EXAFS (47), but similar studies have not yet been
Chemisorption of Reactants ami of Wteter performed with gold on reactive supports.
It is, however, generally agreed that the carbon
monoxide which is oxidizable is reversibly adsorbed on Classes of Support
the gold (either Au" or Au'") (19, 37, 38): if it is on lt remains now to draw these threads together and in a
the support it is as a strongly held spectator (37, 38) or very speculative way to imagine what structures may
as a stable carbonate ion (3, 10, 38, 41). The route for exist in gold catalysts that are active for carbon
oxygen appears to involve its adsorption as a rnolecule monoxide oxidation, and by what mechanisms the
or superoxide molecular ion (02-) on anion vacancies reaction may occur. lt has been very sensibly suggested
in the surface of the supports, if these are easy to form that it may be necessary to consider each type of
(37, 38). Although several authors suggest that lattice catalyst by itself, and although for example Au/FeOx
oxide ions (02-) are the oxidant (40), there is little catalysts made and pretreated in different ways may
direct evidence for this, and very clear indications that exhibit sorne different characteristics these must be
the active species is an oxygen rnolecule (2, 10, 37, 38) considered in the framework of a single model. We will,
or 02-. No dissociation of oxygen occurs except by therefore, adopt the following classification of supports:
reaction with carbon monoxide (37). 1 FeOx (and perhaps other easily reducible oxides such
Various results have been reported for the effect of as Co304, NiO, CuO, etc, for which detailed
water on the reaction (10, 22, 25, 37, 38). lt sornetimes information is lacking)
increases the rate, perhaps by ensuring that sorne or all of
calcination,
-111 red:uctioo
OXI atlOO
2 Ti02 (and perhaps other less easily reducible oxides complete reduction, due to excessive calcination or use
such as Zr02) of hydrogen, is harmful because the glue is lost from
3 MgO (and perhaps other strongly basic supports) the interface and sintering can then occur easily
4 Ah03, Si02. (Figure 1): but equally the total absence of Au0 is
We have already said something about alumina and undesirable, as it is needed to provide a locus for the
silica as supports and there is only a little inormation chernisorption of the carbon monoxide, and a partially
available about magnesia (23, 25): we will, thereore, reduced support surface may contain anion vacancies
focus on the more commonly studied iron oxide and which assist oxygen adsorption,
titania supports. Iwasawa's Au/FeOx are more active than Thus, the sense of inicial activity changes will depend
his Au/Ti02 catalysts (2), probably because FeOx is the on the Auill ! Au'' ratio at the outset and on the 02/CO
more easily reducible support and because the disordered ratio used. We believe that not only reduction but also
structure noted above facilitates the formation of anion oxidation of the gold phase can occur during reaction,
vacancies near gold particles: the reverse is, however, true and we have noted the very widely varying reaction ratios
for coprecipitation catalysts (3), which may suggest that that are used to measure activity (Table 1). This model
anion vacancies are oflesser importance in this case. can be reined to assign various tendencies for carbon
monoxide to chernisorb on Au0 atoms of different CN
Possible Reaction Mechanisms (45). Large gold particles may possess only relatively small
We suggest that many of the reported observations can interfacial areas and few atoms having low CN and thus
be understood on the basis of a model in which the show only dirninished activity.
active catalyst contains both gold atoms andions (which It has been suggested in the case of magnesia (25) that
we will take to be Aulll), and that the latter form the the mechanism may start by a support hydroxyl ion
'chernical glue' which binds the particle to the support attacking a carbon monoxide molecule on the gold
(see Figure 1). Each particle is, therefore, bounded by a (Au0 ... CO). We think this may occur more generally, and
ring of Auill ions, The structure is not, however, fixed: propose a 'periphery' mechanism as follows. The
the AuIIll/Au0 ratio may change (i) during calcination, Au0 ... CO is attacked by an hydroxyl group either on a
when depending on temperature a certain fraction of support cation or on a peripheral Auill ion, forming a
the Auill will autoreduce as oxygen is lost (20, 22), (ii) carboxylate group attached to the latter. This is in turn
during reduction by hydrogen if perforrned (40), and attacked by a superoxide ion, which must be responsible
(iii) during reaction, where initial changes in reactivity for oxidizing two carboxylate ions: the hydroxyl group
may reflect changes in this ratio (10, 20 - 22). Thus returns whence it carne and is ready to re-engage in the
Figure 2 A representation of the early stagesof the oxidation of carbon monoxide at the periphery of an active gold particle. At the lefa,
a carbon monoxide molecule is chemisorbed on a low CN gold aiom, andan hydroxyl ion has moved ftom the support to an
Aum ion, creating an anion vacancy.At the right they have reacted to forma carboxylategroup, andan oxygen molecule
occupies the anion vacancy as 02. This then oxidizes the carboxylategroup by abstracting a hydrogen atorn,forming carbon
dioxde, and the resulting hydroperoxide ion H02' then oxidizes a [urther carboxylate speciesforming another carbon
dioxde and restoring two hydroxyl ions to the support su,face. This completes the catalytic cycle. No atternpt is made to
suggestthe chargescarried by the reactngspecies.
ACKNOWLEDGEMENTS
POTENTIAL APPLICATIONS FOR We thank Donka Andreeva, Alfons Baiker, Masatake
CATALYSISBY GOLD Haruta, Graham Hutchings, Yasuhiro Iwasawa, Ben
Nieuwenhuis and Walter Vogel for providing reprints and
Practica! applications for gold catalysts will naturally preprints of their papers.
require reliable rnethods of manufacture and a secure
knowledge of their long-term rnechanical and catalytic
stability as well as their performance criteria, including ABOUTTHEAUTHORS
activity and durability under practica! operating
conditions. Nevertheless, there is no reason why such Geoffrey Bond held academic posts at Leeds and Hull
inforrnation should not become available in due course Universities before joining Johnson Matthey ple in 1962
and the poten tial of these catalysts for pollution as Head of Catalysis Research. In 1970 he was appointed
control, fuel cell, sensor, and chernical processing Professor in Brunel University's Chemistry Department,
applications could then be realized. and is now an Emeritus Professor at that University.
It is possible that gold could be usefully incorporated David Thompson has a special interest in catalysis by
into automobile catalysts: the price of palladium is gold, having previously held catalysis research posts in
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