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Catalysis Communications 9 (2008) 913918

www.elsevier.com/locate/catcom

Preparation of mesoporous Cu/ZnO catalyst and its application

in low-temperature methanol synthesis
Jun Bao a, Zhenlin Liu b, Yi Zhang b, Noritatsu Tsubaki

b,*

a
b

National Synchrotron Radiation Laboratory, University of Science and Technology of China, Heifei 230026, PR China
Department of Applied Chemistry, School of Engineering, University of Toyama, Gofuku 3190, Toyama 930-8555, Japan
Received 15 May 2007; received in revised form 13 September 2007; accepted 17 September 2007
Available online 5 October 2007

Abstract
A kind of Cu/ZnO catalyst with mesoporosity was prepared by solgel method and characterized by XRD, BET and SEMEDS techniques. The catalyst activity for low-temperature methanol synthesis using alcohol promoter was investigated. The XRD patterns
revealed that the sample was a mixture of ZnO, CuO and Cu2O species. The appearance of low-valence Cu2O was attributed to the fact
that the precursor contained organic groups and its decomposition during the calcination process partly reduced the sample. The Cu/
ZnO particles had large surface area, homogenous elements distribution and exhibited various mesoporous sizes in the range of
210 nm. The pore size distribution results suggested that the surface zinc components of the Cu/ZnO particles might enter and be deposited in the pore of CuO. With 2-butanol as solvent, the Cu/ZnO catalyst showed excellent catalytic activity and very high selectivity for
the low-temperature methanol synthesis from syngas containing CO2.
 2007 Elsevier B.V. All rights reserved.
Keywords: Cu/ZnO catalyst; Mesoporosity; Solgel method; Low-temperature methanol synthesis

1. Introduction
Cu/ZnO-based catalysts are well known to be active for
the synthesis of methanol from CO hydrogenation, and
also used for other catalytic reactions such as the water
gas shift reaction [1], the methanol steam reforming [2]
and synthesis of higher alcohols [3]. Numerous studies have
been carried out to investigate the catalyst structure, the
chemical state of copper and zinc, as well as the reaction
mechanism. Chinchen and co-workers [4] observed that
there was a linear relationship between the catalytic activity
and the metallic copper surface area of the catalyst. They
proposed that the methanol synthesis occurred exclusively
on the surface of metallic copper. Similar result was
reported by Deng et al. [5]. They found that the activity
of methanol synthesis from CO2/H2 on the Cu/ZnO/
A12O3 ternary catalysts increased with increasing the
*

Corresponding author. Tel./fax: +81 76 445 6846.

E-mail address: tsubaki@eng.u-toyama.ac.jp (N. Tsubaki).

1566-7367/$ - see front matter  2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.catcom.2007.09.034

metallic copper surface area until it reached a maximum

at the Cu/ZnO molar ratio of 8. Fujitani et al. [6] reported
that both Cu+ and Cu0 species were essential for methanol
formation and the Cu+/Cu0 ratio determined the specic
activity. Concerning the role of ZnO, it was widely
accepted that the use of ZnO as a support material led to
a highly dispersed copper catalyst. The interaction between
copper and zinc oxide played a vital role in the development of high catalytic activity. Arising from this, one of
the crucial points for preparation of Cu/ZnO-based catalyst was the requirement to produce the possible nest
interdispersion of the metallic elements [7].
Conventional procedure in the preparation of Cu/ZnO
catalyst was the co-precipitation of copper and zinc nitrates
with dierent basic salts. During this preparation, dierent
copper- and zinc-contained phases have been observed
[8,9], which led to dierent types of CuO/ZnO mixtures
on calcination. In the recent years, many eorts have been
developed to prepare Cu-based catalysts with large surface
area, ne particle size and high dispersion, which were

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J. Bao et al. / Catalysis Communications 9 (2008) 913918

believed to improve the activity of methanol synthesis. Jensen et al. [10] developed the ame combustion of Cu/ZnO/
Al2O3 ternary catalysts from the acetylacetonate vapours
of copper, zinc, and aluminum mixed with the fuel and
air. The obtained particles had large surface area, nanometer size and exhibited excellent high activity, selectivity and
stability in the methanol synthesis from CO, CO2 and H2.
Tanaka et al. [11] prepared a novel Cu/ZnO catalyst from a
solution of copper zinc nitrates dissolved in ethylene glycol.
It was found that the highest selectivity for methanol was
obtained when the molar ratio of copper to zinc was 1.
The active sites were concluded to be copper atoms in contact with crystallites. Deng et al. [12] reported a kind of
ultrane Cu/ZnO/A12O3 catalysts prepared by an oxalate
gel co-precipitation method. The catalyst exhibited a high
activity and optimum methanol selectivity for methanol
synthesis from CO/CO2 hydrogenation. In the present
work, a kind of mesoporous Cu/ZnO catalyst with large
surface area and homogenous elements distribution was
prepared by a solgel method. The obtained sample was
characterized by XRD, BET and SEMEDS techniques,
and its activity for low-temperature methanol synthesis
from syngas using alcohol promoter was investigated.
2. Experimental
2.1. Catalysts preparation
The Cu/ZnO particles were prepared by a solgel
method. Firstly, 5 mmol Cu(Ac)2 H2O and 5 mmol Zn(Ac)2 2H2O were dissolved in 100 ml dehydrated ethanol.
The solution was reuxed at 353 K for 2 h under vigorous
stirring. After cooling to room temperature, the solution
was further cooled to 273 K in an ice-water bath. LiOH
(7 mmol) was dissolved in 50 ml ethanol at room temperature in an ultrasonic bath and cooled to 273 K. Then the
hydroxide solution was added dropwise to the solution
containing copper, zinc acetates under vigorous stirring.
The color of the solution changed from green to dark green
after all the LiOH ethanol solution was added. The transparent sol was kept at 273 K to prevent rapid particle
growth. A greenish precipitate was formed after adding
600 ml hexane to the sol, and the precipitate was separated
from the solution by centrifugation. After being washed
twice with dehydrated ethanol, the precipitate was dried
at 333 K overnight, followed by calcination at 473 K for
2 h. The obtained catalysts were reduced by a ow of 5%
hydrogen in nitrogen at 473 K for 10 h and then passivated
by 1% oxygen in argon at a separate catalyst reduction line.
For comparison, the individual ZnO or CuO samples
were prepared respectively by the same method.
2.2. Characterization methods
X-ray diraction (XRD) patterns were measured using a
Rigaku RINT-2000 diractometer with Cu Ka radiation
(ka = 0.154 nm).

Bulk element compositions of catalysts were analyzed by

an energy dispersive X-ray spectrometer (Shimadzu, EDX700).
Scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS) analysis were performed on JEOL
JSM-6360LV scanning electron microscope equipped with
JED-2300 energy dispersive X-ray analysis system.
BET surface area, pore-size distribution and pore volume were determined by the adsorption method (Quantachrome AUTOSORB-1) employing N2 as the adsorbent.
2.3. Catalytic activity test
The catalytic performance of the prepared Cu/ZnO catalyst for methanol synthesis using 2-butanol as solvent was
measured [13]. A closed typical batch reactor with inner
volume of 85 ml and a stirrer was employed in the experiment. The stirring speed was carefully checked to eliminate
the diusion resistance between dierent phases. The standard reaction conditions were: catalyst weight, 1.0 g; initial
pressure, 3.0 MPa; alcohol solvent, 20 ml 2-butanol; stirring speed, 2000 r/min; reaction time, 4 h; feed gas, CO/
CO2/H2/Ar = 32.5/5.15/59.31/3.04. At rst the 2-butanol
solvent and catalyst were added into the reactor. Then
the reactor was closed and the air inside the reactor was
purged by the pressurized reactant gas of 1.0 MPa for three
times. Pressurized reactant gas was introduced and then the
reaction took place at the desired temperature. After reaction, the reactor was put into a cooling pool with ice-water
and then the gas was collected inside the reactor with a
plastic bag. All products were analyzed quantitatively by
gas chromatograph (Shimadzu GC-8A, equipped with a
methanator) with inner standard method [14].
3. Results and discussion
3.1. XRD results
Fig. 1 shows the XRD patterns of the samples and their
precursors. For individual ZnO sample, all the diraction
peaks of the precursor precipitate can be assigned to pure
ZnO, indicating that the precursor sol was ZnO. The chemical reaction during the preparation can be described as
below [15]:
Zn(Ac)2 + 2LiOH ! 2LiAc + ZnO(sol) + H2 O
The addition of hexane promoted the aggregation and
precipitation of ZnO sol particles. After calcination, the
diraction peaks of ZnO became stronger, reecting a better crystallization. The CuO precursor precipitate showed
a complex diraction pattern, in which several strong peaks
appeared at around 2h = 10 and no any diraction characteristics of CuO were observed. After being calcined at
473 K, the diraction peaks of the sample were indexed
to the CuO and Cu2O species. The appearance of lowvalence Cu2O indicated that the CuO precursor contained
organic groups and its decomposition during the calcina-

J. Bao et al. / Catalysis Communications 9 (2008) 913918

915

Table 1
Bulk element composition of Cu/ZnO sample
Test no.

CuO (wt%)

ZnO (wt%)

Cu/Zn
atomic ratio

Average Cu/Zn
atomic ratio

1
2
3

48.008
51.479
49.861

51.992
48.521
50.139

1:0.95
1:1.09
1:1.02

1:1.02

zinc precursor sol in the solution were precipitated simultaneously when the hexane was added. Combining with the
XRD results, it suggested that the copper and zinc species
in the solution were not separated; there existed some interaction between them.
3.3. SEMEDS results
Fig. 2 shows the SEM images of the prepared Cu/ZnO.
The particle size was about 12 lm. The surface element
distribution in a dened red line1 in Fig. 2b was analyzed
by the EDS technique and the results are shown in
Fig. 3. From the gures, it can be seen that the copper
and zinc had a homogeneous distribution on the surface.
The surface Cu/Zn atomic ratio in the dened line was
1.02, the same to that of the bulk phase, proving the homogeneous distribution of both Cu and Zn at either surface or
bulk phase.
Fig. 1. XRD patterns of samples and their precursors.

tion process partly reduced the sample. The complex diffraction pattern of the precursor might be due to the existence of organic groups. For Cu/ZnO particles, its
precursor exhibited very weak diraction intensity and
only a broad peak around 2h = 33.35 was observed, which
may be assigned to ZnO. The diraction peaks that
belonged to the CuO precursor were not observed in the
Cu/ZnO precursor. These ndings suggested that the Cu/
ZnO precursor may not be a simple mixture of CuO precursor and ZnO. The calcined Cu/ZnO sample contained
ZnO, Cu2O and CuO species. After reduction, only ZnO
and metal copper were detected.
3.2. EDX results
During the preparation, the initial molar ratio of copper
and zinc in the ethanol solution was 1:1. The addition of
hexane promoted the aggregation and precipitation of precursor sol particles. If the deposition rates of copper and
zinc precursors were dierent, the Cu/Zn atomic ratio in
the obtained precipitates might not be 1:1. For identication purpose, the bulk element compositions of the calcined
Cu/ZnO were analyzed by EDX technique and the results
are listed in Table 1. It can be seen that for the sample, only
copper, zinc and oxygen elements were detected and the
Cu/Zn atomic ratio were 1:1.02, almost the same as the initial ratio in the solution. This indicated that the copper and

3.4. BET and pore structure

The pore size distributions of the prepared ZnO, CuO
and Cu/ZnO particles are shown in Fig. 4 and their physical properties are summarized in Table 2. The individual
ZnO had the largest surface area and exhibited two kinds
of pore with size of 3.9 and 6.2 nm. The CuO sample
had the lowest surface area and the smallest pore volume.
Its pore size distribution curve indicated that the sample
had three kinds of pore with average diameters around
2.7, 4.1 and 7.1 nm. The formation of various pore size
may be related to the decomposition of organic groups
existed in the precursor. The specic surface area and pore
volume of Cu/ZnO sample was 66.2 m2/g and 0.11 ml/g,
respectively, falling in between those of CuO and ZnO
samples. It should be noted that the Cu/ZnO particle also
exhibited three types of mesopores in the range of 210 nm
and its pore size distribution curve was very similar with
that of CuO sample. The pores originated from individual
ZnO were not observed. These results suggested that the
pores of Cu/ZnO particle were mainly formed by CuO
species. The zinc components might be well dispersed
inside the pores of CuO. As a result, the Cu/ZnO exhibited only the feature of pore structure of copper
components.

1
For interpretation of color in Figs. 2 and 3, the reader is referred to the
web version of this article.

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J. Bao et al. / Catalysis Communications 9 (2008) 913918

Fig. 2. SEM images of Cu/ZnO particles: (a) 6000 magnication and (b) 2000 magnication.

Fig. 3. EDS line scanning: element distributions in a dened line (red line in Fig. 2).

Table 2
Physical properties of ZnO, CuO and Cu/ZnO samples

Fig. 4. Pore size distributions of the ZnO, CuO and Cu/ZnO samples.

3.5. Activity of catalysts

The activity of the prepared Cu/ZnO catalyst for the
methanol synthesis from syngas using alcohol as promoter

Sample

Surface area
(m2/g)

Pore volume
(ml/g)

Pore size
(nm)

ZnO
CuO
Cu/ZnO
Sud-Chemie cat.

74.9
20.2
66.2
52.8

0.13
0.08
0.11
0.16

3.9, 6.2
2.7, 4.1, 7.1
2.9, 3.6, 8.7
8.3

was investigated. The synthetic route is a new method of

low-temperature methanol synthesis that developed by
the present authors [16]. The method allows using conventional solid catalysts and syngas containing CO2 and/or
H2O directly from an industrial reformer, and can be operated at signicantly low-temperature and low pressure. In
previous studies, the eects of dierent alcohol solvents
have been investigated and the 2-butanol was found to be
most helpful for the methanol formation [13]. Table 3
shows the batch reaction results of the prepared Cu/ZnO
at dierent temperatures with 2-butanol as solvent. For
comparison purpose, a commercial Cu-based catalyst
(Sud-Chemie, Co.) for methanol synthesis was also tested
under the same conditions. The physical properties of commercial catalyst are also listed in Table 2. The analysis
results showed that only CO and CO2 were the carbon-containing gas components after reaction, and only methanol
and 2-butyl formate were the liquid products. The 2-butyl
formate was the key intermediate, which was formed by the
esterication of formic acid by 2-butanol and can be further hydrogenated to produce methanol and 2-butanol.
Through the path, the temperature and pressure of metha-

J. Bao et al. / Catalysis Communications 9 (2008) 913918

917

Table 3
Batch reaction results for methanol synthesis with 2-butanol as solvent
Catalyst

Reaction temp. (K)

CO conversion (%)

CO2 conversion (%)

Total carbon conversion* (%)

Methanol

2-Butyl formate

Sud-Chemie cat.

443
453
463

13.54
23.81
15.67

8.40
14.77
9.72

12.84
22.57
14.86

98.77
98.89
100.00

1.23
1.11

Cu/ZnO

443
453
463

17.66
32.10
19.79

10.96
19.91
12.28

16.74
30.43
18.76

62.20
97.75
100.00

37.80
2.25

Selectivity (%)

Reaction conditions: P = 3.0 MPa, catalyst weight; 1.0 g, alcohol solvent; 20 ml 2-butanol, stirring speed; 2000 r/min, reaction time; 4 h, feed gas; CO/
CO2/H2/Ar = 32.5/5.15/59.31/3.04.
*
Total carbon conversion = CO conversion 32.5/(32.5 + 5.15) + CO2 conversion 5.15/(32.5 + 5.15).

nol synthesis reaction can be decreased greatly. From the

Table 3, it can be seen that the reaction temperature had
a large eect on the catalysts activity. At 443 K, the prepared Cu/ZnO catalyst exhibited a low conversion and
the methanol selectivity was only 62%, which reected that
the Cu/ZnO catalyst had a low hydrogenation activity
under this conditions. When the temperature rose to
453 K, the carbon conversion of the catalyst increased to
30% rapidly and the methanol selectivity was high up to
98%. Further increasing the temperature to 463 K, the
methanol selectivity reached 100% but the conversion
decreased remarkably. The results indicated that increasing
the reaction temperature can greatly facilitate the hydrogenolysis of 2-butyl formate, leading to a very high selectivity for methanol. The optimum reaction temperature for
the prepared Cu/ZnO under the present conditions was
453 K. The decrease of conversion at higher temperature
may be due to the limitation of thermodynamic because
methanol synthesis is an extremely exothermic reaction.
The catalytic activity of the commercial Cu-based catalyst
showed similar changes when increasing the temperature.
Compared with the commercial catalyst, the solgel
derived Cu/ZnO catalyst exhibited better performances
for the low-temperature methanol synthesis, except that
the selectivity at 443 K was lower.
It is well known that for the Cu/ZnO-based catalysts for
the methanol synthesis, the catalytic activity strongly
depends on the surface area and the interaction between
copper and zinc oxide. Large surface area can improve
the dispersion of copper (metallic copper or Cu+), which
is recognized as an essential component of the active sites
[12]. The intense interaction between copper and zinc is
in favor of the formation of CuZnOx species. The sites
of particular reactivity are suggested to exist at the Cu
ZnOx interface [17]. For the present Cu/ZnO catalyst prepared by the solgel method, its specic surface area was
up to 66.2 m2/g, much higher than that of the conventional
co-precipitated sample with the same composition [16]. The
homogenous elements distribution as revealed by the
SEMEDS results suggested that the Cu/ZnO catalyst
had a high interdispersion of the metallic elements, which
helped to create more CuZnOx species. Furthermore, as

claried by the pore size distribution shown in Fig. 4, the

surface ne zinc crystallites were actually well-dispersed
in the pores of CuO. This structure contributed to inhibit
the aggregation of metal copper during the reduction process, maintaining a high copper dispersion and large Cu
ZnOx interface. These characteristics exhibited by the
solgel derived Cu/ZnO catalyst may be responsible for
its excellent catalytic performances in the low-temperature
methanol synthesis.
4. Conclusion
A mesoporous Cu/ZnO catalyst with large surface area
and homogenous elements distribution was prepared by a
solgel method. The precursor precipitate contained
organic groups and its decomposition during the calcination partly reduced the sample and formed a mixture of
CuO, ZnO and low-valence Cu2O species. The physical
adsorption results indicated that Cu/ZnO particles exhibited various mesoporous sizes in the range of 210 nm
and the surface zinc components were mainly deposited
in the pore of CuO. In the low-temperature methanol synthesis from syngas using 2-butanol as solvent, the prepared
Cu/ZnO catalyst showed excellent catalytic performances.
This might be due to the fact that the solgel derived Cu/
ZnO particles had a large surface area and homogenous
elements distribution, which helped to improve the copper
dispersion and created more CuZnOx species.
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