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Guczi, L. a al. (Editors), New Frontiers in Corolysb
PIoceedings of the 10th International Congress on Catalysis, 19-24 July, 1992,Budapest, Hungary
43 1993 Elsevier Science Publishers B.V. All rights resewed

HYDROGENATION OF C02 OVER COPPER, SILVER AND GOLD/ZIRCONIA

CATALYSTS: COMPARATIVE STUDY OF CATALYST PROPERTIESAND
REACTION PATHWAYS

A. Baikera, M. Kilob, M.Maciejewskiq S. Menzia and A. Wokaunb

aDepartment of Chemical Engineering and Industrial Chemistry, Swiss Federal Institute of

Technology, ETH-Zentrum, 8092 Zurich, Switzerland
bPhysical Chemistry 11, University of Bayreuth, P.O.Box 101251, D-W8580 Bayreuth,
Germany

Abst;Lact
The hydrogenation of C 0 2 to methanol has been investigated over group IB
metal/zirconia catalysts prepared by coprecipitation, ion exchange and
impregnation. The studies indicate that from these metals copper is most
suitable for CO2 hydrogenation to methanol. The methanol selectivity of all
catalysts is governed by the competition of the simultaneously catalyzed
methanol synthesis and reverse water gas shift reaction. AdZrOz is most
active for the reverse water gas shift reaction and thus exhibits the lowest
selectivity to methanol. Surprisingly, CUlZrO2 and AglZrOs show similar, good
selectivities to methanol. Cqktallization of the amorphous ZrO2 results in
significantly lower activity and selectivity with all catalysts. Thermoanalytical
studies of the crystallization behaviour reveal that the amorphous zirconia is
stabilized by the presence of copper ions, while the presence of metallic Cu, Ag
or Au has no significant effect on the thermal stability of this phase. In situ
diffuse reflectance FTIR studies under reaction conditions show rapid
formation of surface formate on all IB metallzirconia catalysts. However, this
species is not considered to be the immediate precursor to methanol. Methanol
appears to be formed mainly via adsorbed CO, n-bonded formaldehyde, and
surface-bound methylate.

1. INTRODUCTION
Recently, the hydrogenation of C02 to methanol has gained considerable
attention since it may open an ecologically interesting alternative to the
established methanol synthesis from CO/C02 feedstocks. Carbon dioxide
which is formed in all combustion processes and contributes largely t o the
greenhouse effect could be brought into a recycle process. Copper on zirconia
t

1258

catalysts are known to exhibit interesting catalytic properties for methanol

synthesis from C 0 2 11-41.
In the present work we have extended these earlier studies to the other
group 1B metals, silver and gold. A series of metal/zirconia catalysts
containing Cu, Ag and Au were prepared by coprecipitation, ion exchange and
impregnation. Most promising results were obtained with the catalysts
prepared by coprecipitation. These catalysts will be compared with regard to
their structural and catalytic properties. The surface intermediates prevailing
on the catalysts during synthesis conditions are studied using in-situ diffuse
reflectance FTIR spectroscopy.

2.ExPERrMENTAL
Catalysts were prepared from analytical grade Cu(N03)2, AgN03 (Fluka),
HAuC14 and ZrO(NO3)p (Johnson & Matthey) by coprecipitation, ion exchange
and impregnation as described in detail elsewhere 151. The amounts of metal
salts were adjusted to prepare catalysts with atomic ratios IB metal :
zirconium = 1 : 9. Generally the precursors were calcined at 350'C for 3 hrs. To
investigate the effect of the calcination temperature on the structural and
catalytic properties of the final catalysts, some samples were calcined a t
higher temperatures, 450' and 540 OC. The different catalysts are denoted by
referring to the preparation method: coprecipitation (copr), ion exchange
(ionex) and impregnation (impr) and to the calcination temperature (e.g.
Cu(copr, 350)).The catalysts were characterized by means of gas adsorption, X-
ray diffraction (XRD), X-ray fluorescence (XRF), thermal analysis (DTA,TG)
and SEM.Catalytic tests were carried out in a continuous tubular fixed-bed
reactor [3]under the following conditions: reactant mixture, H2/C02(3:1),flow
rate, 90 cm3/min, catalyst weight, 1 g, total pressure 17 bar. In-situ diffuse
reflectance FTIR investigations were performed using a diffuse reflectance
unit equipped with a controlled environmental chamber. Details of the
apparatus and experimental procedures are described in [6].

81struchvalandchemicalppe!rti~ofcatalysts
Structural and chemical properties of the IB metaYzirconia catalysts are
listed in Table 1.The BET surface areas and the specific pore volumes are, as
expected, largest with the samples calcined at 350 OC and decline with higher
calcination temperature. Figure 1 depicts the X-ray diffraction patterns of the
B 1 metal/zirconia catalysts prepared by coprecipitation. The copper catalyst
calcined at 35OoC contained amorphous zirconia, whereas the corresponding
catalysts Ag(copr, 350) and Au(copr, 350) were already partly crystalline. In
catalyst calcined at higher temperature zirconia showed higher crystallinity.
The XRD patterns (Fig. 1) and independent investigations by means of Raman
spectroscopy [71 indicated that the crystalline zirconia adopted mainly
 1259

tetragonal structure. Traces of monoclinic zirconia are indicated in the XRD

patterns of the Ag/ZrOa and AdZrO2 catalysts. Reflections of the group IB
metal were only observed with the gold catalysts. The mean size of the gold
particles as estimated by X-ray line broadening from the Au (111)reflection is
3.4 nm. Gold catalysts containing small Au particles could not be successfully
prepared by impregnation and ion exchange. With these preparations the
mean gold particle sizes were considerably larger (>25 nm). A comparison of
the IB metahirconia samples calcined at 450°C, reveals the higher
crystallinity of the zirconia in the Ag and Au catalysts.
The higher thermal stability of the amorphous zirconia in the copper
catalysts is illustrated by the comparative DTA measurements presented in
Fig. 2. The crystallization temperature of the amorphous zirconia in the IB
metaVzirconia catalysts has been measured under a hydrogen atmosphere
(83% H2 in argon) and under air. Note that under the oxidizing atmosphere
(air) the amorphous zirconia is significantly more stable with respect to
crystallization in the CdZr02 than in Ag/ZrOn and Au/Zr02. This behaviour is
attributed to the presence of copper ions under oxidizing conditions, whereas
Ag and Au are present in the metallic state. This stabilization results in a
shift of the crystallization temperature of about 130K compared to similarly
prepared pure zirconia (688K). Under hydrogen atmosphere only relatively
small differences in the peak temperature of crystallization are observed for
the IB metaVzirconia catalysts, probably due to different residual nitrate
contents. Mass spectroscopic analysis of the gas stream leaving the DTA cell
showed traces of nitric oxide with AdZrOz and Ag/ZrOa indicative for the
decomposition of residual nitrates.

Table 1 Chemical and textural properties of catalysts

Catalysts) ~ t o m i cratiob) BET surfacec? Pore volumec)

IB metaVZr area (m2/g) ..!cm3/g)

Cu(copr,350) 1:10.2 213 0.133

Cu(copr,450) 1:10.2 158 0.136
Cu(copr,540) 1:10.2 76 0.102
Cu(ionex,350) 1:13.7 229 0.181
Cu(imp,350) 1:3.7 142 0.119
Ag(copr,350) 1:9.8 170 0.205
Ag(copr,450) k9.8 72 0.164
Ag(ionex,S!jO) 187 0.159
Ag(imp,350) -- 125 0.106
Au(copr.350) 1:9.6 185 0.156
Au(copr,45O) 1:9.6 83 0.126

alpreparation method and temperature of calcination ("C) are denoted in

parenthesis; bldetermined by X R F ; C)after calcination
1260

Jk Cu(4SO)-

Fig. 1 XRD patterns (CuKa)of IB-metallzirconia

catalysts prepared by coprecipitation. Reflections
due to tetragonal zirconia are marked by circles,
asterisks indicate reflections of Au.
 1261

I 650 700 750 800 850

TEMPERATURE (K)

Fig. 2 Thermpl stability of zirconia phase in IB-metal/

zirconia catalysts prepared by coprecipitation.
Differential thermal analysis (DTA) in air (-1 and under
a hydrogen atmosphere (- 4. Heating rate: 10Kmin-1.
1262

52 CaCalyticppertiesofcatalysb
The catalytic behaviour of the IB metaVzirconia catalysts is illustrated in
F'igs. 3 and 4. The two significant reactions catalyzed on all IB metaVzirconia
catalysts are the methanol synthesis and the reverse water gas shiR reaction.
Small quantities of methane were detected at higher temperatures over copper
and silver catalysts. Catalysts prepared by coprecipitation or ion exchange
generally exhibited better activity and selectivity t o methanol than
corresponding catalysts prepared by impregnation. Considering the catalytic
behaviour of the copper catalysts (Fig. 3) we note that similar methanol
production rates on a per catalyst weight basis are observed for Cu(copr, 450)
and Cu(ionex, 350). However, the ion exchanged catalyst showed significantly
lower selectivity a t higher temperature (~500K). The influence of the
calcination temperature of the co-precipitated catalysts is significant, as
indicated by the selectivity behaviour of the sample calcined at 54OOC.

"
0 Cu (copr, 350)

-1
O !b Cu (copr, 450)
Cu (copr, 540)
A
O d i O 0 Cu (ionex, 350)
A A
A
6 A Cu (imp, 350)
-2 A Q
A
A

100

- BCI
%
80
x x
A
60 - A 0
A
40 1 ' A

20 1 1 I
X
I
A

Fig. 3 C02 hydrogenation over CdZrO2 prepared by coprecipitation (copr),ion

exchange (ionex) and impregnation (imp). Conditions see experimental part
 1263

Ag (copr, 350)
0%
0 Ag (copr, 450)
A . de
O 0 Ag (ionex, 350)
-2- A Ag (imp, 350)
A 0%
0
A 0 .

v
L.
-3 I
1.8 2.0 2.2 2.4 2.6
-e 1000/T [1/K]

.-
b

.->
U

20
-Q)
480 490 500 510 520 530 540
$ Temperature [K]

Fig. 4 CO2 hydrogenation over Ag/ZrO2 catalysts prepared by coprecipitation,

ion exchange and impregnation. Conditions are given in experimental part.

Noteworthy is also the poor catalytic behaviour of the catalyst prepared by

impregnation (Cu(imp,350)), particularly in the light of its much higher
copper content (cf. Table 1).
The catalytic behaviour of the Ag/ZrOa catalysts (Fig. 4) is rather
surprising. Note that a similar dependence of the selectivity to methanol was
observed as with the best CdZrOz catalysts (Fig. 3). Even the catalyst prepared
by impregnation (Ag(imp, 350))showed remarkable selectivity.
The catalytic behaviour of the AdZrOa catalysts (Fig. 5 ) contrasts the
behaviour observed for the Cu- and Ag/ZrOa catalysts. Although the AdZrO2
catalysts are very active, their selectivity to methanol is relatively low due to
their much higher activity for the competing reverse water gas shift reaction.
As with the co-precipitated CdZrO2 catalysts a significant decrease of the
selectivity to methanol is observed with higher calcination temperature. The
XRD patterns (Fig. 1) indicate that the higher calcination temperature caused
crystallization of the amorphous ZrO2.
 v

0 Au (copr, 350)
0 Au (copr, 450)
-1 - 0

-2 - 0 0
0
0 0

loo?
80 :

60;.
8 0
0.
40 :
0 5 0
20 :
O h S 0

Fig. 6 C 0 2 hydrogenation over Au/ZrO2 catalysts prepared by coprecipitation.

Conditions are given in experimental part.

To identify the species present on the catalyst surfaces under C02

hydrogenation conditions, and to elucidate the catalytic reaction mechanism,
the three catalysts prepared by coprecipitation and calcination at 360°C have
been investigated in situ by diffuee reflectance FTIR spectroscopy. Typical
results are shown in Fig. 6, where the catalysts have been exposed to a static
reaction mixture (COfi2 = 1 : 2) at a temperature of 473 K and a pressure of
2.5 bar. For all three Bysteme, bidentate carbonate species are formed from the
CO2 reactant and surface Oa-, as evidenced by strong absorptions at 1600 - 1660
-
cm-1 and 1300 1360 cm-1. The generation of gaseous CO by the reverse water
gae shift reaction ie recognized by the CO doublet at 2140/2190 cm.1. Adsorbed
(bridge-bonded)CO is obeerved by an intense band at 1950 cm-1 on Cu/ZrO2.
Large concentrations of surface formate are produced over AdZrO2, as
- -
indicated by two comparatively sharp bands at 1680 1600 cm-1 and 1360 1400
 1265

cm-1; corresponding C-H stretches and overtones are observed at 2760, 2880,
and 2960 cm-1. Adsorbed x- bonded formaldehyde is identified by a C-0 stretch
at 1150 cm-1.

7Au(350)

cu(350) l0l i
35 0 3000 2500 2000 1500 1000 51 3
wavenumber / cm-'
Fig. 6 In-situ FTIR investigation of CO2 hydrogenation over IB-metal/zirconia
catalysts. Conditions: 473 K, reaction time 40 min; pressure, 2.5 bar C02/H2
1:2.
Over Ag/ZrO2 and CdZrO2, where the surfaces were covered by high
concentrations of surface formate prior to the catalytic run shown,formate is
seen to disappear, and methanol is formed as evidenced by C-0 and C-H
stretches at 1050,2830,and 2950 crn-1, respectively.

4. DISCUSSION

The comparative activity and selectivity studies of CO2 hydrogenation over IB

metayzirconia catalysts demonstrate that AglZrOn (Fig. 4) exhibits similar,
good selectivity t o methanol as CdZrOa (Fig. 3). Furthermore, similar
activation energies were found for these catalysts for methanol synthesie (- 40
kJ/mol) as well as for the reverse water gas shift reaction (-85 kJ/mol).
1266

Noteworthy is also the high activity of AdZrO2 for the reverse water gas shift
reaction. The catalytic behaviour of the silver catalysts is surprising and seems
to support Frost’s metalloxide junction effect theory [81. Frost obtained active
catalysts with Ag and Au supported on thoria. However, his findings stand in
contrast with the results of Shaw et al. [91 who studied the activity and
structure of methanol synthesis catalysts derived from silver, copper, and
cerium alloys and concluded that, at least for methanol synthesis catalysts
derived from these intermetallic precursors, the identity of the transition metal
appears to be crucial. Although the catalytic results of our study seem to be in
agreement with Frost prediction, some doubts still remain about the origin of
the catalytic methanol synthesis activity observed. A significant influence of
contaminants originating from the precursor materials used can not be
completely ruled out. A thorough search for possible contaminants is presently
undertaken and will hopefully provide a more conclusive answer with regard
t o the origin of the methanol synthesis activity observed for Ag/ZrO2 and
AdZrO2. Another important aspect to be clarified is the role of residual nitrate
ions which originate from the metal nitrate precursors. The presence of
residual nitrate ions has been evidenced by DTA coupled with mass
spectrometry as mentioned above.
Another observation, which has been made in earlier [4,8] as well as in the
present study, is the importance of the metal-to-zirconia contact area. The
catalytic properties of the catalysts strongly depend on this interfacial contact,
which is probably best realized in catalysts prepared by coprecipitation and
calcined at temperatures low enough to avoid crystallization of the amorphous
zrO2.
As regards the reaction pathway of methanol synthesis the mechanisms
proposed in the literature are controversial. In several investigations [1,lO-121,
it has been suggested that C02 rather than CO is the precursor of methanol.
However, more recently considerable doubts have been formulated concerning
the generalization of these results to other catalytic systems. Jennings et al
[13,14] have studied methanol synthesis catalysts derived from binary rare
eartWcopper precursors and from ternary rare earth/Cu/Ti, Zr o r A1
precursors and their results obtained with 14CO2 indicate that methanol is
formed by hydrogenation of CO; the mechanism therefore differs from that
which has been suggested for methanol synthesis over the mostly studied
conventional CdZnO/Al203 catalyst.
The reaction pathway derived from the observed correlations of surface and
gas phase species, both in this and previous studies [4,6,151 is summarized in
Fig. 7. Upon adsorption of CO2 and H2, surface formate is produced by a rapid
reduction step. On the one hand, formate is reduced t o methane without
further observable intermediates. On the other hand, formate is in equilibrium
with adsorbed CO over CdZrOz. Although the latter species is not observed
with Ag/ZrO2 and AdZrO2 under the conditions of the experiment presented
in Fig. 6, all three catalysts showed a high activity for catalyzing the water gas
shiftireverse water gas shift reaction. From adsorbed CO, a second major
reaction route leads to adsorbed a-bonded formaldehyde, surface-bound
methylate, and finally the methanol product. Note that over AdZrO2, no traces
of methane production were observed in spite of high surface formate
concentrations.
 1267

Fig. 7 Possible reaction pathway of C02 hydrogenation over IB-metaVzirconia

catalysts

1 Y. Amenomiya, Appl. Catal. 30 (1987)57.

2 B. Pommier and S.J. Teichner, in M.J. Phillips and Ternan (Eds),
Proc. 9th Int. Congr. Catal., Calgary, 1988,Vol. 2,1988, p.610
3 D. Gasser and A. Baiker, Appl. Catal. 48 (1989) 279.
4 R. A. K6ppe1, A. Baiker, Ch. Schild and A. Wokaun, Stud. Surf. Sci. 8z
Catal., 63 (1991)59.
5 R.A. Koppel, Ph D Thesis, ETH-Zurich, 1990; S. Menzi, diploma work,
ETH-Ziirich, 1991; R. A. Koppel, A. Baiker and A. Wokaun, Appl.
Catal., in press.
6 C. Schild, A. Wokaun, and A. Baiker, J. Mol. Catal., 63 (1990) 223.
7 C. Schild, A. Wokaun, R.A. Koppel, and A. Baiker, J. Catal., 130
(1991)657.
8 J.C. Frost, Nature, 334 (1988) 577.
9 E.A. Shaw, T. Rayment, A.P. Walker, J.R. Jennings and R.M.
Lambert, J. Catal., 126 (1990)219.
10 G.C. Chinchen, M.S. Spencer, K.C. Waugh, and D. Whan, J. Chem.
SOC.,Faraday Trans. 1,83 (1987)2193.
11 B. Denise, 0.Cherifi, M.M. Bettahar and R.P.A. Sneeden, Appl. Catal.
48 (1989) 365.
12 R. Burch, R.J. Chappell and S.E. Golunski, J. Chem. SOC., Faraday
Trans 1,85 (1989)3569.
13 J.R. Jennings, R.M. Lambert, R. M. Nix, G. Owen and D.G. Parker,
Appl. Catal., 50 (1989) 157.
14 G.Owen, C.M. Hawkes, D. Lloyd, J.R. Jennings, R. M. Lambert and
R.M. Nix, Appl. Catal., 58 (1990) 69.
15 R.A. Koppel, A. Baiker, Ch. Schild and A. Wokaun, J. Chem. SOC.,
Faraday Trans., 87 (1991) 2821.
DISCUSSION
Q: K. C. Waugh (United Kingdom)
Have you confirmed your suggestion that CO is the precursor to methanol on these
zirconia supported catalysts by doing labelled CO experiments ?
A: A. Baiker
Spectroscopic assignments have been confirmed using deuterated reference
compounds. Experiments with labelled CO and CO are presently being pursued.
However, we feel that even with the use of labelled cadon oxides we shall still face the
problem of interference between methanol synthesis and water gas shift reaction. A
possible way of dissecting these reactions is presently considered by the use of a special
gradientless reactor which allows fast control of the concentrations of the relevant
species. This permits to maintain equilibrium between the components of the water gas
shift reaction, while the changcs of surface species are monitored. We hope that this
strategy will resolve the question with respect to the immediate precursor.
Another aspect which deserves further attention is the pressure dependence of the
concentrations of the surface intermediates, which we are presently investigating in an
improved spectroscopic chamber. I would like to reemphasize that all spectroscopic
results presented so far have bccn collected at a pressure of 3 bar.
Q: H. L. Krauss (Germany)
1) What is the cxperimental note for the existence of a n-bonded form of aldehyde ?
2) Did you try to find Cu in higher oxidation states then zero by reflexion UV-VIS
spectroscopy - especially with respect to the border 1B metal-to-supporting ZrO, ?
A: A. Baiker
1) The C - 0 stretching vibration of x-bonded formaldehyde has been assigned on the
basis of adsorption expcriments with formaldehyde as well as protonated and
perdcutereated methanol (cf. our rcf. 6).
2) UV-VIS reflectance spectroscopy is difficult for thcsc very strongly absorbing
materials, which appear visually black. However, we have investigated the oxidation
state of copper in copper/zirconia catalysts prepared from glassy metal alloys using XPS
and AES. These investigations revealed that the vast majority of the surface exposed
copper is present in metallic form with traces of Cu(I). More detailed information is
given [ 11.
[l] Ch. Schild, A. Wokaun and A. Baiker, Surj Sci., 269/270, 520 (1992)
Q: R. Prins (Switzerland)
Can you say something about the possibility that formate bound to the Zr02 reacts
with spilled-over H atoms to form methoxy and finally methanol ?
This would explain why you need a basic support and a metal which can split H,

A: A. Baiker
Therefore is no doubt that the interface between Zr02 and the IB metal is crucial for
the activity of these catalysts and the spillover of hydrogen may indeed play an important
role. Our spectroscopic measurements do not give evidence for a correlation between
surface bound formate and the methanol product; however, the route you described
cannot generally be excluded.
Q: K. Kochloefl (Germany)
1) Do you have data concerning the methanol yield (kg CHgOH/h/cat) to make a
comparison with commercial Cu/Zn0/Al2O3 mcthanol synthesis catalysts '?
 1269

2) What was the degree of reduction of Cu in the case of catalyst (CuErOi) prepared
by the coprecipitation method (Cu(O)/Cu(I)tCu(II)) ?
A: A. Baiker
1) In comparative tests using microreactors we found that the best copper/zirconia
catal sts exhibited similar specific methanol production rates as commercial
Cu$O/A120 catalysts. We should add that these tests were performed at low pressure
conditions of 1? bar.
2) After precipitation the copper in the Cu/ZrOZ catalyst is mainly present in the
form of CuO. This is transformed to metallic copper in the reduction process. XPS and
AES of samples exposed to air during the transfer to the UHV system ive evidence for
the presence of some Cu(I) on the surface, which is quantitatively re fuced to metallic
copper upon exposure to hydrogen.
Q: W. HiSlderich (Germany)
1) The BET surface area differs with preparation method. Does the surface area have
no influence on the catalyst performance when you compare the various catalysts ?
2) In the case of amo hous alloys (CuErO ) you might have an even better
2
interaction between Cu and rOp than in the case of the coprecipitated material. Which
material is better ? Can you comment on this ?
A: A. Baiker
1) In earlier investigationswe have found that there exists no correlation between the
activity of copper/zirconia catalysts with their BET surface. A correlation was however
e
observed between the s ecific metal surface area and the activity for families of similarly
prepared catalysts [2]. nfortunately, your question can only be conclusively answered
for copper/zirconia catalysts, since reliable methods for the determination of specific
silver or gold surface areas ark not available. Assumin that the dispersion of the
f
IB metals is not largely different on the prepared catalysts, t e given reaction rates should
provide a reasonable qualitative comparison of activities, since the IB metal/Zr atomic
ratio was about the same with all catalysts (cf. Table 1).
2) First of all I should mention that the motivation to prepare copper/zirconia
catalysts emerged from earlier studies, where we investigated the potential of glassy
metal alloys for catalysis. The first copper/zirconia catalysts were prepared from glassy
copper/zirconia alloys by in situ activation. These catalyst were found to be highly active,
however, they cannot easily be brought in a form which is technically applicable.
P
Consequently we were forced to search for other methods which emit to prepare
copper/zirconia with large interfacial contact areas. Coprecipitatedcata yst were found to
meet this requirement. In fact, catalytic activities could be reached which are comparable
to those obtained with catalysts derived from correspondingglassy metals.
[2] R. Burch, S.Chalker, P. Loader and J. M.Thomas, Appl. Caral., ?34,77(1992)
Q: P. E. Hojlund-Nielsen(Denmark)
1) Do you agree that it is essential that the supporting oxide is a semiconducting
oxide 1
2) Do you think that there is an accumulation of negative charge, at the metal in the
metal-semiconductor interface '?
3) Have you alone any studies using CO (carbon monoxide) in the reaction gas ?
A: A. Baiker
1) We have not observed a correlation between the semiconductive character of the
carrier .materials and the catalyst performance in methanol synthesis.
2) As you know such a correlation has been proposed by Frost (ref. 8 of our paper).
Although other factors may influence the catalytic behavior, Frost's suggestion has
1270

certainly provided a stimulus to test the other IB metals besides the established copper
catalvsts.
--J -
3) CO hydrogenation has been studied over all IB metal/zirconia catalysts and results
obtained with copper/zirconia are presented in [3].
[3] W. Ueda, J . Mol. Car., 63,243 (1990)
Q: D. L. Trimm (Australia)
How did you assess active surface area '? Was "EM of any use ? Is the concept of
turnover number meaningful to the comparison between catalysts ?
A: A. Baiker
The active surface area is difficult to assess, all experimental observations made so
far indicate that the active surface is the interfacial contact area between IB metal and
ZrO? Although "EM can provide information about the dispersion and particle size
distribution of the IB metal, it does not allow a useful quantitative assignment of the
active interfacial area. Thus, at the moment, we can only give relative values for the
activities of the IB metal catalysts, based on comparing catalysts with the same metal
loadings. Although the concept of comparing turnover numbers is frequently useful to
compare the activities of catalysts, it ma not be useful in the present case, since the
reaction appears to occur at the metalixide interface and not on the pure metal.
Furthermore, presently, only copper surface areas can be measured with some reliability,
whereas no established chemisorption methods exist for the measurement of the surface
area of supported silver and gold particles.
Q: M. Haruta (Japan)
The results reported are very interesting in that all three IB metals are active for the
hydrogenation of CO, when supported on Zr02 Our experiences concerning the
preparation of supported gold catalysts have shown that coprecipiation could produce
small hemispherical but not spherical particles having a flat plane strongly attached to the
support oxides. This structure might create a large interfacial area between metal and
support oxides leading to high activity and selectivity. We have been studying the effect
of support oxides for gold in this reaction and have obtained the results that ZnO and
Fe20 are much better than ZrO;! for methanol synthesis.
&uld you tell us in more detail what motivated you to select ZrO, as a support for
this comparative study ?
A: A. Baiker
As pointed out in the paper, our most active goldhirconia catalysts were also
preparcd by coprecipitation. This seems to be in agreement with your work. There is no
doubt that the high activity of this catalyst is related to the exceptionally large interfacial
contact area between the gold particles and the zirconia support.
Concerning the suitability of ZnO and Fe203 as a support for the gold particles,
I can not make a comparison with the zireonia support used by us, since we have not
tested these support materials.
The reasons for selecting ZrO as a support for this comparative study were:
(i) copper/zirconia has earlier been g u n d to exhibit good activity and selectivity in the
hydrogenation of CO to methanol (our ref. 3); (ii) we wanted to use a support which has
no intrinsic activity Z r CO hydrogenation under the conditions used. note that a major
aspect of the work was to c i r i f y whether gold and silver exhibit catalytic activity for the
hydrogenation of CO, when brought on a suitable support.
Q: J. J. Rooney (Ireland)
We have found [4] that norbornadiene hydrogenation is a very useful chemical probe
for various methane synthesis catalysts.
Thus norbornadiene hydrogenates to give norbornene, nortricyclene and norbornane
on I.C.I. Cu/ZnO catalyst, and on Cu and Au on MgO.
 1271

d? +
co
The formation of nortricyclene reveals a dipolar mechanism operating via metal ions
and involving molecular H2

There is no reaction on Ag dispersed on SiO, or MgO, but significant hydrogenation

to nortricyclene occurs on Ag/Zr02 catalysts.
This parallels methanol synthesis activity from CO and H2 and reveals that Ag+ ions
are the active sites in both cases.
If the mechanism at the ion is also analogous then one can appreciate the sensitivity
of the rate to electron donation or withdrawal by the surrounding matrix.
 1272

The electron occupations and the energetics of the relevant molecular orbitals in the
[2+2] activated complex are then crucial factors.
[4] V. Amir-Ebrahimi, J. J. Rooney,J. Mol, C a t 4 67, 339 (1991)
A: A. Baiker
Thank you for this interesting comment. It would indeed be very interesting to study
the norbornadiene hydrogenation over the IB metal/zirconia catalysts and to compare
their catalytic behavior in this reaction with the one in methanol synthesis.

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