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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
*
1566-7367/$ - see front matter 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.catcom.2007.09.034
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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).
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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
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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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.
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
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Table 3
Batch reaction results for methanol synthesis with 2-butanol as solvent
Catalyst
CO 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).
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