Applied Catalysis A: General 171 (1998) 301±308

In situ IR studies on the mechanism of methanol synthesis over

an ultra®ne Cu/ZnO/Al2O3 catalyst
Qi Suna, Chong-Wei Liub, Wei Panb, Qi-Ming Zhub, Jing-Fa Denga,*
a
Department of Chemistry, Fudan University, Shanghai 200433, China
b
State Key Laboratory of C1 Chemistry and Technology, Tsinghua University, Beijing 100084, China

Received 22 October 1997; received in revised form 4 February 1998; accepted 26 February 1998

Abstract

Methanol synthesis from CO2 and CO/CO2 hydrogenation was carried out under real reaction conditions over an ultra®ne
Cu/ZnO/Al2O3 (Cu/Zn/Alˆ60/30/10, molar ratio) catalyst. The formation and variation of surface species were recorded by in
situ FT-IR spectroscopy. The mechanisms of methanol synthesis and RWGS reaction were discussed. The result revealed that
methanol was formed directly from CO2 hydrogenation for CO2/H2 or CO/CO2/H2 reaction systems. b-HCOOÿ s was the
necessary intermediate for methanol synthesis. A scheme of methanol and RWGS reaction was proposed. # 1998 Elsevier
Science B.V. All rights reserved.

Keywords: Methanol synthesis; Mechanism; In situ; FT-IR

1. Introduction 2. whether CO or CO2 serves as the primary carbon

In industrial processes, methanol is synthesized
from hydrogenation of mixtures of CO and CO2 over
Cu-based catalyst. Addition of a small amount of CO2
to the mixture of CO and H2 can promote methanol
yield remarkably. Because of this attractive promoting
effect, methanol synthesis from CO2 and H2 has
caused considerable attention in recent years [1±7].
However, there is still controversy over some impor-
tant questions, such as:
1. the role of carbon dioxide in the process of
methanol synthesis;
*Corresponding author. Fax: +86 2165 641740; e-mail:
qsun@fudan.edu.cn
source for methanol synthesis;
3. whether the inter-conversion between CO and CO2
via the water-gas shift (WGS)/or reverse water-gas
shift (RWGS) is an indispensable process or not;
and
4. what are the reaction intermediates involved in
methanol synthesis.
By the use of the temperature-programmed-desorption
(TPD) [8±10], IR spectroscopy [11±13], chemical
trapping methods [14] and 14 C or 13 C isotopic tracer
[15,16], various surface species were found on Cu-
based catalyst in the course of methanol synthesis and
some reasonable mechanisms were suggested, but
most of these experiments were carried out at high-
vacuum or atmospheric pressure conditions using
clean Cu single crystal, supported Cu/SiO2 catalyst

0926-860X/98/$19.00 # 1998 Elsevier Science B.V. All rights reserved.

PII S0926-860X(98)00096-9
302 Q. Sun et al. / Applied Catalysis A: General 171 (1998) 301±308
or Cu-based catalyst with low copper content. The
results obtained under these conditions diverge from
the results obtained under real reaction processes. In
this work, a high activity ultrafine Cu/ZnO/Al2O3
catalyst (Cu/Zn/Alˆ60/30/10, molar ratio) prepared
by ``oxalate gel co-precipitation method'' [17±19] was
used as working catalyst to study the mechanism of
methanol synthesis from CO2 and CO/CO2 hydroge-
nation by means of FT-IR spectroscopy under real
reaction conditions (high pressure, high temperature
and feed gas continuously flowing over the catalyst).
A scheme of methanol synthesis formation was
suggested.
2. Experimental
Cu/ZnO/Al2O3 catalyst (Cu/Zn/Alˆ60/30/10,
molar ratio) used in this study was prepared by
``the oxalate gel co-precipitation method'' similar to
that described previously [17±19]. The BET surface
area of the Cu/ZnO/Al2O3 catalyst is 49.7 m2/g, Cu
surface area measured by N2O titration is 36.3 m2/g
and the metallic copper particle size evaluated by
XRD and TEM is 10.7 nm. Infrared experiments were
conducted on a 30 mg wafer of the mixture of the
catalyst and g-Al2O3 (catalyst/g-Al2O3ˆ1/6, weight
ratio) crushed to a powder smaller than 500 mesh
placed inside an in situ reaction cell (shown as in
Fig. 1). Infrared spectra were recorded with a Perkin-
Elmer system 2000 FT-IR spectrometer. A resolution
of 4.0 cmÿ1 was used throughout the investigation and
Fig. 1. Schematic diagram of in situ IR reaction cell: (1) cell body; (2) cell core; (3) window frame; (4) NaCl crystal window; (5) O-ring; (6)
sample fixing ring; (7) sample wafer.
50 scans taken over a 20 s interval were averaged to
achieve a satisfactory signal-to-noise ratio. The ultra-
high purity (>99.999%) gases of H2, CO, N2 and
chemical purity CO2 (>99.9%) were used. The gases
in the in¯ow were puri®ed by passing through a 5 A Ê
molecular sieve-trap. After reduction by H2 at 513 K
for 4 h, the reaction cell packed with the catalyst was
rapidly cooled to room temperature and ¯ushed with a
high-purity N2 for 2 h. After switching N2 with reac-
tion gas (CO2/H2ˆ1/3 or CO/CO2/H2ˆ20/5/75) and
pressurizing slowly to 2.0 MPa, temperature-
programmed-reaction (TPR) experiments (the ¯ow
rate of reaction gas was 30 ml/min and the rate of
temperature increase was 2 K/min) were performed
and IR spectra were recorded synchronously.
3. Results and discussion
Fig. 2 shows part of the IR spectra obtained in
¯owing CO2/H2 reaction gas at 2.0 MPa. It is found
that a few adsorbed CO can be formed easily at room
temperatures. The band at 2079 cmÿ1 is resolved only
at a low temperature range and is attributed to CO
adsorbed on a low Miller-index plane of reduced Cu
[20]. The peaks at 2171 and 2118 cmÿ1 are character-
istic of gaseous CO. With increase in the temperature,
exceeding the level of 313 K, it is found that the
intensity of bands of surface adsorbed CO
(2079 cmÿ1) and gaseous CO (2118 and
2171 cmÿ1) decrease gradually, indicating the
decrease of CO concentration over catalyst surface
 Q. Sun et al. / Applied Catalysis A: General 171 (1998) 301±308 303

Fig. 2. IR spectra for methanol synthesis from CO2/H2 recorded during temperature-programmed-reaction (TPR) process at 2.0 MPa.

and gas phase, and the rato-vibrational spectrum of

H2O (1600±1800 cmÿ1) begins to arise and increase.
Meanwhile, monodentate formate species (m-
HCOOÿ) are observed at 1585 cmÿ1. The results
indicate that CO species are formed from dissociative
adsorption of CO2 over catalyst surface. With the
temperature increasing further (higher than 323 K),
during the increase of the intensity of peak at
1585 cmÿ1, the intensity of another peak at
1593 cmÿ1 due to bidentate carbonate species
…b-CO2ÿ3 † also increases more rapidly. Up to about
493 K, it is found that these two peaks weaken again.
Fig. 3 shows the process of formation and change for
CH3O and CH3OH species at various temperatures. It
is found that several peaks at 2857 and 2940 cmÿ1,
which are characteristic of b-HCOOÿ s , are present at
lower temperatures, e.g. 313 K. As the temperature is
raised further, the intensity of the peaks at 2857 and Fig. 3. Formation and variation of methoxy group and methanol
during temperature programmed reaction (TPR) process at 2.0 MPa
2940 cmÿ1 is also increased and reaches a steady-state
for methanol synthesis from CO2‡H2.
concentration above 413 K. However, the peaks at
2918 and 2965 cmÿ1, assigned to CH3Os and CH3OH
species, respectively, occur and are ampli®ed gradu- CO species (COs and gaseous CO) and that of
ally until the temperature is raised above 433 K. Such m-HCOOÿ s decrease, and CH3Os as well as product
a result reveals that, although some adsorbed and CH3OH increase due to the increase of b-HCOOÿ s .
gaseous CO are present at low temperature, no CH3Os From these results, it is concluded that methanol is
(adsorbed methoxy species) or CH3OH were formed, formed directly from hydrogenation of CO2, and that
and b-HCOOÿ s species also could be ignored. While methanol formation from hydrogenation of carbon
the temperature is higher than 393 K, the amount of monoxide formed via RWGS is negligible. The key
304 Q. Sun et al. / Applied Catalysis A: General 171 (1998) 301±308
intermediate species for methanol synthesis from CO2
hydrogenation is bidentate formate …b-HCOOÿ s †
instead of monodentate formate …m-HCOOÿ s †.
Further, when we switch feed gas CO2/H2 with pure
H2, all the band intensities of CO, CO2, m-CO2ÿ 3 , m-
HCOOÿ become weaker slowly, but CH3Os and
CH3OH could still be clearly detected due to the
existence of surface formate b-HCOOÿ at 2940
cmÿ1. When b-HCOOÿ (2940 cmÿ1) fades away,
no methanol species could be observed by IR. The
above experimental observation and analysis strongly
indicate that the process of the hydrogenation of
bidentate formate …b-HCOOÿ s † is the rate-limiting step
for methanol synthesis from CO2 hydrogenation. This
result is in agreement with previous reports [11,21].
TPR-IR experiments were also conducted with H2/
CO/CO2 feed gas. Fig. 4 shows the spectra obtained
when the temperature was increased from 293 K with
the rate of 2 K/min at a pressure of 2.0 MPa and gas
¯ow rate of 30 ml/min. It is found that a sharp peak at
2006 cmÿ1 ascribed to absorbed CO (carbonyl band)
Fig. 4. IR spectra for methanol synthesis from CO/CO2/H2 recorded during temperature-programmed-reaction (TPR) process at 2.0 MPa.
varied from weak to intense in the temperature range
293±343 K and then to weak again with the increase of
temperature. It is coincident with the variation of the
peak at 1634 cmÿ1 due to the bending mode of H2O
physisorbed on Cu. However, no formate or carbonate
species appear under these conditions. As the tem-
perature increases to above 353 K, the peak at
2006 cmÿ1 disappears and a broader peak at
1972 cmÿ1 grows rapidly and then decreases gradu-
ally. Moreover, the bands at 1591 and 1601 cmÿ1,
which are characteristic of m-HCOOÿ and b-CO2ÿ 3
species, respectively, increase gradually and reach the
maximum at 493 K. Furthermore, when the tempera-
ture is increased again, two bands of 1591 and
1601 cmÿ1 diminish. This variation is similar to the
change of CO2‡H2 in the TPR-IR experiment. How-
ever, it is also found that, besides the bands of 2855
and 2940 cmÿ1 (ascribed to bidentate formate
b-HCOOÿ s and CH3Os, respectively), product CH3OH
is also detected upon the temperature of 443 K. This
indicates that the necessary intermediate is still
 Q. Sun et al. / Applied Catalysis A: General 171 (1998) 301±308 305

b-HCOOÿ ÿ
s species instead of m-HCOOs or other
species. It is noteworthy that the intensity of bands
of the rato-vibrational spectrum of H2O at 1600±
1800 cmÿ1 is obviously weaker for CO/CO2‡H2 sys-
tem than that for CO2/H2. So the addition of CO could
inhibit the reaction of RWGS. Namely, the formation
of water species could be suppressed and the forma-
tion rate of methanol could be enhanced by the addi-
tion of CO into CO2/H2 feed gas. Fig. 5 shows the
methanol formation rates for feed gases containing
only CO2 and H2, containing only CO and H2 as well
as containing CO/CO2 mixture and H2. It is found that
both the methanol formation rates for the individual
CO and CO2 hydrogenation are much lower than that
for CO/CO2 mixture hydrogenation, and the methanol
formation rate for CO hydrogenation is lower than for
CO2 at 499 K. It is clear that the addition of CO into
CO2/H2 feed gas promotes the formation rate of
methanol signi®cantly. Especially, we found that the
variation of the amount of water is very signi®cant for Fig. 5. Methanol synthesis rate for CO/H2, CO2/H2 and CO/CO2/
H2 feeds over the ultrafine Cu/ZnO/Al2O3 catalyst. Pˆ2.0 MPa,
CO2/H2 and CO/CO2/H2 reaction systems. After addi- space velocityˆ4500 hÿ1.
tion of CO into CO2/H2, only a trace of water was
detected and the amount is three orders of magnitude
lower than that of CO2/H2 reaction system. This result According to the above analysis, some suggestions
was also found in this in situ IR±TPRS experiment and for methanol synthesis from CO/CO2/H2 could be
in previous kinetic and catalytic activity testing [19]. proposed:
According to the Arrhenius equation, ln(TOF) of 1. The procedures of dissociative adsorption and
methanol formation is proportional to the inverse hydrogenation of CO2 are two parallel competitive
temperature. By plotting the formation rate from reactions. At low temperatures, the formation of
kinetic and activity testing versus 1/T (Fig. 6), an
apparent activation energy could be determined from
the slope. The slope is measured at the temperature
ranging from 433 to 453 K, where the rates of both
methanol synthesis and RWGS start to increase
rapidly before the conversion signi®cantly alters the
gas-phase composition. The activation energy for
methanol synthesis is 20.7 kcal/mol and that for
RWGS reaction is 22.73 kcal/mol. After the addition
of CO into CO2/H2 feed gas, however, the activation
energy for methanol synthesis is decreased to
6.52 kcal/mol, although there is no signi®cant change
in the activation energy for RWGS reaction. It is clear
that the addition of CO into CO2/H2 feed gas could
lead to the decrease of the activation energy for
methanol synthesis. As a result, the rate of methanol
formation is increased and the methanol selectivity is Fig. 6. Arrhenius plot ln(TOF) for methanol formation and RWGS
promoted to a large extent. This is in agreement with reaction versus the inverse reaction temperature (1/T) over Cu/
the results from this in situ IR experiment. ZnO/Al2O3 catalyst for CO2‡H2 (&,*) and CO/CO2‡H2 (~).
306 Q. Sun et al. / Applied Catalysis A: General 171 (1998) 301±308
CO (corresponding to the bands of 2007 cmÿ1)
along with the adsorbed Os by dissociative
adsorption is a prior process. These adsorbed
oxygen species (Os) combine with nascent hydro-
gen (Hs) to form hydroxy species (OHs) and then
to H2O, so the peak at 1634 cmÿ1 is observed. As
temperature increases, the rate of CO2 adsorption/
hydrogenation increases and the process of
dissociative adsorption of CO2 is suppressed, so
the bands of 1634 and 2007 cmÿ1 diminish
gradually and then disappear.
2. With the increase of temperature, the bands at 1591
and 1601 cmÿ1 (ascribed to m-HCOOÿ s and
m-CO2ÿ 3 species, respectively) increase gradually,
and then diminish after reaching the maximum,
while the bands at 2857 …b-HCOOÿ s †, 2918 and
2940 cmÿ1 (CH3Os) increase gradually along with
the variation of the intensity of the band at
2965 cmÿ1 (CH3OH). This indicates that the for-
mation of CH3Os and CH3OH species are accom-
panied by the formation of bidentate formate
…b-HCOOÿ ÿ
s †, and b-HCOOs species is a key inter-
mediate, which undergoes stepwise hydrogenation
to form CH3Os then to CH3OH. The rate-limiting
step for methanol synthesis over the ultrafine Cu/
ZnO/Al2O3 catalyst is the hydrogenation of
b-HCOOÿ s .
3. The effects of addition of CO to the CO2/H2 feed
gas are ascribed to the inhibition of the RWGS
reaction (or enhancement of the WGS reaction).
Water produced via methanol synthesis from CO2
hydrogenation is consumed by the fast water-gas
shift reaction that simultaneously provides CO2,
which is the feed gas for methanol synthesis. As a
result, the limitation of thermodynamic equili-
brium for CO2 hydrogenation to CH3OH is
removed and leads to a higher methanol yield
(methanol synthesis formation rate) and selectivity.
This result has been discussed in kinetic terms
previously [19].
From Fig. 6, it is also found that with the addition of
CO into CO2/H2 feed gas, apparent activation energy
for methanol synthesis is decreased. It led to the
promotion of methanol formation rate and selectivity.
One explanation is the following: in the absence of
CO, H2O is formed earlier via RWGS reaction and it
prohibits the reaction of methanol synthesis; when CO
is introduced, relative high coverage of CO leads to the
reduction of dissociative adsorption of CO2 on the
catalyst surface and the inhibition of RWGS reaction.
Therefore, the reaction of methanol synthesis can take
place quickly. Moreover, the Os species formed via
b-HCOOÿ s hydrogenation to H2COs is consumed by
the adsorbed COs to form [CO2]s rapidly. Thus, a
direct result is that methanol formation rate and
selectivity is increased. From such an analysis, it is
easy to illustrate the pathway of methanol synthesis
and RWGS reaction by the scheme shown in Fig. 7: In
the absence of CO, the process of dissociative adsorp-
tion for CO2 could take place easily over the catalyst
surface [22] and there is a strong tendency for pathway
(I) to happen; even if the reaction occurs via pathway
(II), this surface (O=C±OH)s could dissociate to form
COs and OHs easily due to the absence of CO in gas
phase. However, when CO is introduced into CO2/H2
feed gas, the process of dissociative adsorption for
CO2 is inhibited due to the high coverage of CO. The
reaction tends to take place via pathway (II) to form
O=C±OHs, which then isomerizes to form other inter-
mediate species b-HCOOÿ s , but could not dissociate to
form COs and OH easily. The direct result is that IR
band absorption intensity at 1600±1800 cmÿ1
ascribed to the rato-vibrational spectrum of H2O in
CO/CO2/H2 system is much weaker than that in
CO2‡H2 system, and methanol formation rate and
selectivity are promoted significantly.
On the other hand, if the conclusions that b-HCOOÿ s
species are a key intermediate and hydrogenation of
b-HCOOÿ s is the rate-limiting step for methanol synth-
esis are true, it seems to be ambiguous to explain the
fact of the lowering of apparent activation energy after
introducing CO gas into CO2/H2 mixture. Although
we did not make further study on the adsorption/
desorption species and hydrogenation activity of those
adsorbed species on this ultra®ne Cu/ZnO/Al2O3 cat-
alyst, some previous research works have given some
powerful hints which could be helpful to explain the
above divergency. Fujita et al. [23], found that two
types of adsorbed formate species, HCOO±Cu and
HCOO±Zn, can be formed and hydrogenate to form
CH3O±Zn and then methanol, but the rate constant of
the hydrogenation of HCOO±Cu is about 10 times
greater than that of the hydrogenation of HCOO±Zn
and the activation energy of the former is lower than
that of the latter. Based on this result, we can easily
explain the mechanism of methanol synthesis and the
 Q. Sun et al. / Applied Catalysis A: General 171 (1998) 301±308
Fig. 7. Scheme for mechanism of methanol synthesis and RGWS/GWS reaction from CO2/H2 and CO/CO2/H2 over ultrafine Cu/ZnO/Al2O3
catalyst.
fact of the lowering of apparent activation energy after
introducing CO into CO2/H2 mixture. For CO/H2
reaction system, a mount of Os or OHs is formed with
CH3O±Zn being formed from HCOO±Cu hydrogena-
tion, as shown in Fig. 7. The adsorbed Os or OHs could
inhibit the hydrogenation of HCOO±Cu, so, under
steady-state condition, methanol formation rate is
low and apparent activation energy is high. However,
after introducing CO into CO2/H2 system, CO reacts
quickly with Os to form CO2 and remove the adsorbed
Os from the equilibrium system. As a direct result, the
hydrogenation of HCOO±Cu is promoted and metha-
nol formation rate is accelerated as well as the appar-
ent activation energy of methanol synthesis is lowered.
4. Conclusion
The mechanism of methanol synthesis and RGWS
reaction was studied by using in situ IR technique. The
experimental results indicate that methanol was
307
formed directly from CO2 hydrogenation both for
CO2 and CO/CO2 hydrogenation. b-HCOOÿ s is the
key intermediate for methanol synthesis and hydro-
genation of b-HCOOÿ s is the rate-limiting step for
methanol synthesis. The addition of CO to CO2/H2
system not only affects the reaction pathway but also
lowers the apparent activation energy of methanol
synthesis.
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