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Catalysis by metals
Pierre Gallezot
Institut de recherches sur la catalyse et l’environnement de Lyon,
UMR 5256 CNRS/Université Lyon1
2 avenue Albert Einstein, 69626 Villeurbanne cedex
[email protected]
1. -
Introduction
Metal catalysis accounts for about 70% of all catalytic processes because it is the
essential tool for the synthesis of chemicals (petrochemicals, bulk, specialities and fine
chemicals), for energy conversion (C1 conversion, H2 production, biomass conversion) and
for environmental remediation (air and water treatments). Usual metal catalysts are
based on group 8-11 elements (Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag). The preparation,
characterisation, and catalytic properties of metal catalysts, supported or unsupported,
possibly promoted by other metals, have been extensively studied for all applications
mentioned above. Because the subject is too wide, this chapter will concentrate on the
most remarkable achievements in France during the 1960–1990 time period. Another
aim of this chapter is to review the advance of catalysis in the presence of gold during
the past ten years. Indeed, it has been discovered recently that gold, considered at
best as a very poor catalyst, could exhibit remarkable catalytic properties in a number
of reactions provided it is in highly divided form.
2. 2.1 -
Advances in the 1960-1990’s
Preparation of metal catalysts
Preparation methods of metal catalysts have been thoroughly studied at the French
Institute of petroleum (IFP) in the 60's and 70's to improve the dispersion of metals
on supports
1,2
. A remarkable achievement was to establish the methods of metal
impregnation of oxide supports, particularly alumina and silica, by cationic exchange and
anionic adsorption, to obtain very small metal particles of homogeneous size and
controlled distribution
3
. These pioneering works served as reference for all the
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subsequent preparations of metal catalysts on oxides, zeolites, and carbon supports.
Well-defined activation and reduction treatments of cation-exchanged zeolites were
established at Institut de Recherches sur la Catalyse (IRC) to control the size and
location of metal clusters in zeolite cages 4.
The scientific bases for the preparation of metal catalysts by oxido-reduction
reactions on metal surfaces were established at the Laboratoire de Catalyse en Chimie
Organique (LACCO) at Poitiers
6
. This method of general application involves the
controlled deposition of metal atoms onto the surface of metal particles resulting in
homogeneous particle size growth or the formation of bimetallic particles of welldefined surface composition.
Bimetallic aggregates were prepared from organometallic precursor either by
decomposition of heteropolynuclear metal complexes or by grafting metal complexes on
the surface of metal particles6, the latter method resulting in controlled surface
composition.
Formulation of Raney nickel catalysts were optimized by P. Fouilloux
7
(Grace-Davison
Award, 1994) and by the CNRS/Rhône-Poulenc joint laboratory from 1987 to 1994.
2.2 -
Characterisation of metal catalysts and adsorbed species
Physical methods (small-angles X-ray scattering, X-ray line broadening analysis,
magnetic granulometry, electron microscopy) were improved and adapted to the study
of metal catalysts at the beginning of the 70's to determine the metal surface area and
particle size distribution. This work conducted by several researchers at IRC resulted
in
remarkable
measurements
8
agreements
between
the
different
methods
of
particle
size
providing the basis for a more rigorous interpretation of particle size
effect in catalytic reactions.
The structural modifications experienced by metal nanoparticles upon adsorption of
reactant molecules under reaction conditions were evidenced by radial electron
distribution method 9. The structure of metal particles was also characterized by
EXAFS as a function of preparation methods
10
. The nuclearity of platinum clusters
encaged in zeolites was evaluated by RMN study of
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129
Xe 11.
2 / 17
In the early 70's it was shown that the IR spectroscopy of adsorbed CO was able to
probe the electronic properties of metals thus allowing to evidence support and
adsorbate effects12. The effect of support acidity on the properties of platinum and
palladium clusters in zeolites was demostrated13. Combined with other methods, the CO
probe allowed a precise description of the surface composition of Ni- or Co-based
bimetallic catalysts 14. It was also possible to follow the disaggregation of palladium and
rhodium particles into monatomic species upon adsorption of NO and CO, respectively15.
In a more advanced application of IR spectroscopy carried out at LCS (Caen), the
percentage of (100) and (111) faces and the atomic discontinuities present on the
surface of palladium particles were determined 16.
Because of the high sensitivity of neutron spectroscopy to hydrogen, this method was
able to reveal the adsorption modes of hydrogen on Raney nickel catalysts and to
identify the nature of the active species in hydrogenation reactions 17.
The effects of poison adsorption on the activity of metal catalysts for various
reactions were studied in details at Poitiers. It was clearly demonstrated that poison
molecules adsorbed on metals are selective for different reactions
18
. The catalyst
deactivation due to poisoning by sulfur, carbonaceous deposits, or p-electron metals was
thoroughly studied and a scale of relative toxicity of poisons was established
19
.
The
resistance of metals to sulfur poisoning was interpreted by electronic effects produced
by supports or surface ligands 20.
2.3 -
Structure and reactivity of model metal surfaces
Surface science teams in Nancy, Strasbourg, Paris, Lyon, and Marseille contributed a
great deal to the knowledge of the structure of metal surfaces and adsorbed species.
Early works at LRIGS (Nancy) on the interaction of small molecules with platinum
crystal faces resulted in the detection of the precursor states of chemisorbed species
21
. The LMSPC at Strasbourg demonstrated the specific reactivity of edges and corner
platinum
atoms
compared
to
dense
hydrogenolysis/isomerisation reactions
crystal
faces
in
hydrocarbon
22
. The various states of sulfur adsorption on
metals, and their effect on catalytic properties were studied in details by the Oudar's
group in Paris 23.
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In the late 70's, HREELS spectroscopy was developed at IRC to study the activation of
carbon monoxide and unsaturated hydrocarbons (acetylene, ethylene, benzene) on Ni, Pt
and Pd single crystals and alloys
24
. It was demonstrated that the surface of the binary
alloy Pd8Ni92(110) reconstructs with the segregation of palladium on surface. This
catalyst was 20 to 30 more active than palladium in butadiene hydrogenation and yielded
100% selectivity to butane
25
. The deposition of ultra-thin palladium layer (1-4 atomic
layers) on Ni(110) surfaces led to similar results 26.
2.4 -
Contribution of theoretical chemistry to metal catalysis
French theoretical chemists contributed greatly to the modelling of naked or
adsorbate-covered metal surface, and more recently to the interpretation of reaction
selectivities. Theoretical studies were first conducted with a physicical approach by
Friedel's school
27
. Chemists at Orsay using Hückel's method got quite comparable
results on the electronic occupancy of metal d-orbitals as a function of surface
geometry
28
. The theoretical group at IRC/ENS-Lyon succeeded in the description of
active sites and molecular reactivity in relation with experimentalists. Using the
extended Hückel method it was possible to account for the higher selectivity to butene
of palladium compared to platinum in butadiene hydrogenation
29
. The selectivity to
unsaturated alcohol in the hydrogenation of  -unsaturated aldehydes was interpreted
from the adsorption modes of molecules and metal surface composition
30
. An accurate
description of the molecular interactions on metal surfaces, for instance in the case of
the dissociative adsorption of NO on rhodium 31, was obtained with the DFT theory.
2.5 -
Hydrogenation catalysis on metals
Along the way paved by the pioneering work of Sabatier, French laboratories
contributed markedly to develop fundamental and applied studies on catalytic
hydrogenation. Kinetic laws were established at IFP in 1957 to interpret the selectivity
of metals in competitive hydrogenation of unsaturated hydrocarbons
32
. The effects of
sulfur adsorption33, particle size34, and various additives35 were studied by the kinetic
analysis of hydrogenation reactions. Academic research conducted by the Germain's
group greatly contributed to unravel the mechanism of hydrogenation and exchange on
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metals
36
. The effect on activity and selectivity of the adsorption modes of molecules,
particularly steric effects, were studied
37
. A kinetic analysis of the competitive
hydrogenation of unsaturated hydrocarbons was used at Poitiers and IRC to the probe
steric
38
and electronic effects39 on reaction activity and selectivity in combination with
theoretical studies40.
Outstanding results were obtained by research teams at Rhône-Poulenc
41
on the
hydrogenation organic compounds such as the hydrogenation of nitroaromatic
derivatives to phenylhydroxylamine on Pt/C catalysts
42
and the hydrogenation of  -
unsaturated aldehydes to unsaturated alcohols using water-soluble metal-TPPTS
complexes in bi-phasic medium
43
. Selective bimetallic Ru/Sn catalysts were developed
for the vapour-phase hydrogenation of carboxylic acids to aldehydes, e.g., for the
synthesis of prenal and fluoral
44
. Remarkable progress in the selective hydrogenation
of dinitrils was achieved by the CNRS-Rhône-Poulenc joint laboratory on triphasic
reactor from 1987 to 1994
45
.
Heterogeneous catalysis applied to organic reactions was developed at Poitiers, Lyon
and Montpellier during the 80's and 90's and successful international congresses on
this topic were held in Poitiers in 1988, 1990 and 1992, and in Lyon in 1999. Because of
the diversity of organic reactions it is not possible to detail all the results obtained in
this area; some are available in reviews on chemo- and regioselective hydrogenations
and on enantioselective hydrogenation
46
47
. From the 1990's the catalytic hydrogenation
of renewable resources, e.g., carbohydrates
48
and triglycerides derivatives
49
to
produce valuable intermediates and specialty chemicals were also developed in the same
laboratories. A detailed review on this research field is given in chapter X.
2.6 -
Hydrogenolysis and isomerisation reactions
During the 1960's and 1970's fundamental studies were devoted to hydrocarbon
isomerisation reactions on metal surfaces. The work carried out by Gault's team
demonstrated that the isomerisation of saturated hydrocarbons on metals occurs
either via bond shift or cyclic mechanisms
50
. In addition to these mechanisms taking
place on metal sites, hydrocarbon isomerisation may proceeds via a bifunctionnal
mechanism involving metals and the acid sites of supports
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51
. Studies using isotope
5 / 17
labelling
evidenced
the
detailed
mechanism
of
bifunctional
isomerisation
52
.
Isomerisation and exchange reactions of olefins on metals were also subject to detailed
studies by microwave spectroscopy53.
In the 1970's many investigations focused on hydrogenolysis reactions and a vivid
debate arose on the respective merits of geometric effects (ensemble theory) and
electronic (ligand) effects. The ensemble theory developed in the case bimetallic
catalysts was supported by the kinetic analysis of hydrogenolysis reactions and
magnetic characterization of catalysts
54
. Hydrogenolysis properties of metals were
interpreted by electronic effect associated with the coordination of surface atoms, e.g,
by the presence of a second metal or of adsorbed molecular species 55.
During the same period of time considerable R&D effort was devoted to hydrocarbon
reforming to develop bimetallic catalysts that favour isomerisation with respect to
hydrogenolysis reactions56. The role of metallic additives (Sn, Re, Ge,…) acting as
selectivity promoters was interpreted from experimental and theoretical studies on the
segregation topology of additives57.
Hydrogenolysis of C-Cl bonds is an important reaction for the preparation of various
specialities
chemical.
chlorofluorocarbons
59
Hydrodechloration
of
polychloroaniline
58
and
of
were achieved on Pd/C catalysts. Hydrodechloration was also
used in environmental chemistry, e.g., for the destruction of chloroaromatics pollutants
in water on Ru/C catalysts
60
. Hydrogenolysis of C-OH bonds in polyols obtained from
bioresources (carbohydrates, glycerol) has been used to obtained valuable chemicals
61
.
Hydrogenolysis reactions of esters to alcohols have been extensively studied on
bimetallic catalysts allowing to minimize cracking reactions 62.
2.7 -
Hydrogen and synthesis gas production
Metal catalysts are extensively used to convert fossil or renewable raw materials to
hydrogen or synthesis gas. In the late 1970's new interest, triggered by the increase of
oil price, arose for the conversion of syngas to hydrocarbons (Fischer-Tropsch
synthesis) and alcohols
63
. Presently, the research is again active on steam reforming of
natural gas to produce hydrogen for fuel cell application and synthesis gas for the
production synthetic fuels via Fischer-Tropsch reaction 64.
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Dehydrogenation and oxidation reactions
Metal catalysts have been widely used for vapour phase dehydrogenation of
hydrocarbons. Thus, the dehydrogenation of isobutane to isobutene and the synthesis
of paracymene on bimetallic catalysts prepared by surface organometallic chemistry
were carried out by the LCOMS in Lyon
65
. Vapour phase dehydrogenation at short
contact time for the synthesis of 2-coumaranone was studied at IRC
66
and developed
by Clariant.
Vapour phase oxidation reactions on silver catalysts have been used for a long time for
industrial epoxidation of ethylene and oxy-dehydrogenation of methanol. Liquid phase
oxidations with air of alcohol and aldehydes on platinum and palladium promoted with
bismuth were developed in the 90's. Thus, oxidation reactions of glyoxal, glycerol,
carbohydrates and fine chemicals were conducted at IRC 67.
Research teams in Lyon and Poitiers have carried out a pioneering work to develop
catalytic wet air oxidation applied to the treatment of organic pollutants in water
68
.
The treatments of waste water by advanced oxidation methods and photocatalysis are
described in chapters X and Y, respectively.
3. -
Gold catalysis
Gold was hardly considered as a metal with useful catalytic properties until the end of
the 1980’s when Haruta et al
69
demonstrated that 5nm large gold particles are active
for CO oxidation at low temperatures. Studies on gold catalysis started in France in the
early 1990’s. A recent review on gold catalysis has been published
3.1 -
70
.
Preparation of gold catalysts
The first investigations carried out in France were devoted to bimetallic catalysts
where gold acted as a promoter of activity or selectivity for metals such as palladium or
platinum. Thus, it was shown that the activity and selectivity in methyl cyclohexane
dehydrogenation of Pt-Au catalysts prepared by co-impregnation increased with the
gold concentration
71
. Bimetallic Au-Pd, Au-Pt, and Au-Fe catalysts supported on HY
zeolite were prepared by autoreduction of adsorbed Au[(H2NCH2CH2NH2)2]3 complex
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72
.
7 / 17
Bimetallic Au-Pd
73
, Au-Pt
74
75
and Au-Cu
catalysts were prepared by surface redox
reactions to study the effect of gold on the base metal. Heteronuclear organometallic
complexes were decomposed to prepare Pt-Au catalysts used for NO reduction by
propene
76
. Pd-Au/Nb2O5 catalysts were prepared by photoassisted reduction and used
in the gas phase oxidation of ethanal 77.
Gold nanoparticles were prepared by autoreduction of Au [(H2NCH2CH2NH2)
complexes adsorbed in NaHY zeolites
2]
3+
78
. Homogeneous 2nm particles were obtained in
zeolite exchanged mainly with Na+ cations, whereas 3-4 nm particles were formed in
NaHY zeolite. 1.5 nm-large gold particles were obtained by reduction with hydrogen
plasma of Au[(H2NCH2CH2NH2)2]3+ complexes in NaHY zeolite
79
.
Preparation methods based on vaporisation of gold and deposition of metal vapours on
solid supports or into liquids have been designed to prepare model catalysts. Thus, the
ablation of gold metal targets with a laser beam and condensation of metal vapours in
liquids leads to a suspension of 10-20 nm colloidal gold particles
80
. Gold metal vapour
produced in a Knudsen cell at high temperatures under UHV conditions were condensed
on TiO2 microspheres resulting in the deposition of 2nm particles
81
. The Au-Au
interatomic distances in gold particles interacting with the (110) TiO2 anatase surface
were contracted and elongated along the [110] and [100] directions, respectively. Gold
particles of controlled size were prepared by laser vaporisation and condensation on
various oxide supports (Al2O3, ZrO2, TiO2)
82
. The device described in Figure 1 was
designed to collect metal vapours homogeneously on the surface of oxide powder
yielding supported gold catalysts that can be tested in conventional catalytic reactors.
Oxide
powder
Gold bar
Ar
He
Gold
clusters
Laser Nd: YAG
Figure 1 Device for the preparation of supported
catalyst in powder formby laser vaporisation
A number of investigations on the preparation of gold particles supported on various
oxides were conducted with new preparation methods. Thus, different preparation routes
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giving highly divided gold in Au/TiO2 catalysts were designed by the group of Catherine
Louis in Paris VI
83-87
. The aim was to prepare 2 nm-large gold nanoparticles with a
concentration of gold on the support higher than that obtained with the depositionprecipitation method developed by Haruta
69
. Using a cationic adsorption method they
succeeded to obtain 2 nm particles, but with a concentration of gold not exceeding 2wt%.
In contrast, using urea as basic agent in the deposition-precipitation method, 1.5 nm gold
particles were obtained in Au/TiO2 catalysts loaded with up to 7 wt% gold 83 (Figure 2).
Figure 2 TEM image of 7.1w% Au/TiO2 catalyst obtained by deposition-precipitation with
urea and particle size distribution (average size 1.7 nm).
The mechanisms of gold particle formation by the deposition-precipitation method using
either sodium hydroxide or urea were compared to interpret the different efficiency
of both methods for gold fixation on the support
84
. The influence of thermal
treatments and storage conditions on gold particle sizes in Au/TiO2 prepared by
different methods were studied
85
. The effects of thermal pre-treatment conditions
were monitored by infrared spectroscopy of CO adsorbed at low temperatures
86
.
Another method based on the dry impregnation of oxides supports (alumina, silica,
titanium dioxide) by aqueous solutions of HAuCl4 followed by successive washing with
ammonia solutions and drying was designed
87
. Gold particles obtained by this method
were slightly larger than in the case of deposition-precipitation method with urea
(Figure 3).
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Figure 3 Distribution of gold particle size on 4wt% Au/TiO2 catalysts prepared by
deposition-precipitation with urea (continuous line) and by dry impregnation followed by NH3
washing (dashed line))
Gold particles supported on alumina were prepared by anionic exchange of the hydroxyl
group of the support with AuCl4- anions
88
. 5 to 30 nm particles were detected after
water washing whereas washing with ammonia solutions resulted in 1 - 5 nm particles.
The structure of gold complexes grafted on the alumina surface and the mechanism of
particle growth were investigated
89
. Particles of 1 to 3 nm were obtained in 3.1wt%
Au/Al2O3 catalysts after optimisation of the preparation conditions. The anionic
exchange method was extended to other supports (TiO2, ZrO2, CeO2)
90
.
The morphology of gold particles prepared by deposition-precipitation with KOH was
studied on various TiO2 supports 91. Figure 4 shows gold particles on the surface of TiO2
film covering the surface of a SBA15 mesostructured alumina. This catalyst exhibited a
remarkable activity CO oxidation particularly in the presence of hydrogen.
Figure 4 Gold particles obtained by deposition-precipitation with KOH on
a film of TiO2 covering the surface of a mesostructured silica SBA-15
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3.2 -
Oxidation reactions on gold catalysts
CO oxidation
CO oxidation withh oxygen in the presence of gold catalysts was the subject of many
invetigations during the past years. The main challenge is to oxidize CO in the presence
of hydrogen in order to eliminate the traces of CO which could poison platinum
catalysts used for hydrogen oxidation at the anode of fuel cells (PROX catalysis).
The activities of Au/TiO2 catalysts prepared by deposition-precipitation with either
NaOH or urea were compared for CO oxidation
92
. It was shown that the activity
expressed per mol of gold increased with the percentage of gold present in the
catalysts and reached a maximum at 200°C calcination temperature where gold was
completely reduced to metallic state. At higher calcination temperatures, the activity
decrease was interpreted by the faceting of gold particles which decreased of the
number of low-coordinated surface atoms.
The structure and oxidation state of gold particles in Au/TiO2, Au/Al2O3 and Au/SiO2
catalysts were characterised by in situ EXAFS and XANES spectroscopies during CO
oxidation
93
. These studies showed a modification of the electronic structure of
alumina-supported gold particles occurring upon CO adsorption which was interpreted as
a retro-donation of gold d-electrons to the * orbitals of CO.
Investigations on CO oxidation reaction combining surface science studies and catalytic
activity measurements were conducted on model catalysts prepared by laser
vaporisation
82,94
. The activity of gold on TiO2 and ZrO2 supports was much higher than
that on Al2O3 suggesting that these oxides participate in the mechanism of CO
oxidation (Figure 5). The activity of these catalysts was also compared in CO oxidation
in the presence of hydrogen. Surprisingly, it was observed that the CO oxidation
activity was much higher in the presence of hydrogen and did not depend on the nature
of the support. To interpret these results it was suggested that in PROX condition CO
molecules adsorbed on gold were oxidised by adsorbed H-O-O species formed by the
reaction of dissociated hydrogen on gold surface with gas-phase oxygen via an EleyRideal mechanism. The mechanims of deactivation-reactivation of Au/TiO2 catalysts
were studied by thermodesorption measurements
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95
. PROX catalysts exhibiting an
11 / 17
activity comparable to that of Au/ZrO2 can be prepared by oxidation of a Zr0.5Au0.5
alloy obtained by arc melting of Zr and Au under argon
96
.
Conversion de CO (%)
100
90
80
Au/ γ -Al 2O 3
Au/TiO 2
70
60
Au/ZrO 2
50
40
30
20
10
0
0
100
200
300
Température (°C)
400
500
Figure 5 Comparison of gold catalysts on different supports in CO oxidation
CO oxidation in the presence of light hydrocarbons was studied under the conditions of
cold starting of car exhaust catalysts
97
. The CO conversion in the presence of
Au/Al2O3 catalysts prepared by anionic exchange was not affected by ethylene which
was oxidised at 250°C, but acetylene poisoned CO oxidation. The oxidation of saturated
hydrocarbons occurred only above 450°C, i.e. well above in cold start conditions. The
activity of Au/Mg4Al2 catalysts prepared by anionic exchange of hydrotalcite with
AuCl4- was measured as a function of different preparation parameters
98
.
The study of CO oxidation in the presence of hydrogen (CO/H2 = 0.07) on Au/Fe2O3
catalysts showed that particles smaller than 5nm were selective for CO oxidation
whereas large gold particles were little active and no selective
99
.
Other reactions
There is a growing interest for wet air oxidation (WAO) as a technique for treating
organic wastes in water by total oxidation with air or oxygen. The presence of catalysts
allows operate at lower temperature and pressure for achieving total oxidation. In the
presence of Au/TiO2, Au/CeO2 and Au/CeO2-ZrO2 catalysts prepared by depositionprecipitation with NaOH or urea, a total oxidation of succinic acid to CO2 was achieved
at 190°C, acetic acid being the only detected intermediate
100
. The activity was larger
as the particle size decreased (Figure 6) and the nature of the support was also playing
a large role because the activity of Au/CeO2-ZrO2 and Au/CeO2 catalysts was twice
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12 / 17
that of Au/TiO2 and matched that of a ruthenium catalyst. A more complete account on
catalytic wet air oxidation is given in chapter X.
15
50
40
30
10
5%Au/CeO2-ZrO2
5
20
10
0
0
0
2
4
temps (h)
6
0
8
2
4
taille particules (nm)
6
Figure 6 Wet air oxidation of succinic acid at 190°C :a- product distribution vs. time (‹
succinic acid, „ acetic acid) ; b- Influence of gold particle size on the activity of Au/TiO2
catalysts.
The stereoselective epoxidation of trans-stilbene in methylcyclohexane solution with
tert-butylhydroperoxyde was carried out on Au/TiO2 catalysts
101
. It was shown that
both gold and TiO2 support play a role in the activation mechanism leading to a 90%
selectivity to the epoxide at 60% conversion.
Crotonaldehyde hydrogenation was studied on Au/TiO2 catalysts prepared by
deposition-precipitation with urea
102
. The selectivity to unsaturated alcohol is close to
70% at conversions not exceeding 50%, and it does not depend upon the particle size.
However the intrinsic activity increased as particle size decreased and attained a
maximum for 2 nm-large particles. Au/TiO2 catalysts containing 2 nm particles are also
very selective in the hydrogenation of butadiene into 1-butene
103
. Ni-Au/SiO2 and Ni-
Au/TiO2 bimetallic catalysts are active and selective in the hydrodechloration of 2,4dichlorophenol 104.
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