Applied Catalysis A: General 263 (2004) 249253

Active Cu/ZnO and Cu/ZnO/Al2 O3 catalysts prepared by homogeneous

precipitation method in steam reforming of methanol
Tetsuya Shishido a,1 , Yoshihiro Yamamoto b , Hiroyuki Morioka c ,
Ken Takaki b , Katsuomi Takehira b,
a

Department of Chemistry, Tokyo Gakugei University, Nukui-Kita 4-1-1, Koganei, Tokyo 184-8501, Japan
Department of Chemistry and Chemical Engineering, Graduate School of Engineering, Hiroshima University,
Kagamiyama 1-4-1, Higashi-Hiroshima, Hiroshima 739-8527, Japan
Hiroshima Prefectural Institute of Industrial Science and Technology, Kagamiyama 3-10-32, Higashi-hiroshima, Hiroshima 739-0046, Japan
b

Received 25 September 2003; received in revised form 9 December 2003; accepted 11 December 2003

Abstract
Cu/ZnO and Cu/ZnO/Al2 O3 catalysts were prepared by homogeneous precipitation (HP) using urea hydrolysis and were applied for
hydrogen production by steam reforming of methanol. The catalysts showed higher activities than those prepared by coprecipitation (CP). It is
suggested that the good catalytic performances of HP-Cu/ZnO and HP-Cu/ZnO/Al2 O3 are due to both highly dispersed Cu metal species and
to high accessibility of the Cu metal species to methanol and steam. The homogeneous precipitation method by urea hydrolysis is preferable
for the preparation of active Cu/ZnO and Cu/ZnO/Al2 O3 catalysts.
2003 Elsevier B.V. All rights reserved.
Keywords: Hydrogen; Homogeneous precipitation; Methanol; Cu/ZnO

CH3 OH + H2 O = CO2 + 3H2 ,

1. Introduction
Hydrogen is forecasted to become a major source of
energy in the future. However, as the major impediment
to the wider use of hydrogen as an energy source are the
difficulties inherent in storage and distribution, one solution to these problems is the on-board hydrogen generation
from a suitable liquid fuel of high energy density. It is
well known that hydrogen can be obtained directly from
methanol according to three different processes: decomposition (Eq. (1)) [14], partial oxidation (Eq. (2)) [5,6] and
steam reforming (SRM: Eq. (3)) [711]
CH3 OH = CO + 2H2 ,

H = +22 kJ mol1

CH3 OH+ 21 O2 =CO2 + 2H2 ,

(1)

H = 192.2 kJ mol1
(2)

Corresponding author. Tel.: +81-824-24-7744;

fax: +81-824-24-7744.
E-mail addresses: stetsuya@u-gakugei.ac.jp (T. Shishido),
takehira@hiroshima-u.ac.jp (K. Takehira).
1 Tel.: +81-42-329-7494; fax: +81-42-329-7494.

0926-860X/$ see front matter 2003 Elsevier B.V. All rights reserved.
doi:10.1016/j.apcata.2003.12.018

H = +49.4 kJ mol1
(3)

Unfortunately, the decomposition and the partial oxidation

produce considerable amount of CO as a byproduct. In the
use of the reformed gas in a fuel cell, even a trace of CO
deteriorates the Pt electrode. On the other hand, the steam
reforming of methanol can produce H2 /CO2 in the molar
ratio of 3/1 and no significant CO below 573 K. Thus, it is
likely that the steam reforming is the most suitable process
to produce hydrogen from on-board methanol for the fuel
cell for the automobile power source.
A large number of catalysts for the steam reforming
of methanol have been reported in the literature [711].
Among these, the majority interestingly use Cu/ZnO-based
system which has also been used in the reverse reaction, i.e.
methanol synthesis from synthesis gas. Since the catalytic
activity of the Cu/ZnO system itself is not high enough,
various modifications have been proposed, such as addition
of a suitable promoter [7] and combination with an effective
component [8,9]. In this paper, we report an effective preparation method of Cu/ZnO and Cu/ZnO/Al2 O3 catalysts, i.e.
the homogeneous precipitation method by urea hydrolysis.

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T. Shishido et al. / Applied Catalysis A: General 263 (2004) 249253

We performed the SRM over Cu/ZnO and Cu/ZnO/Al2 O3

catalysts and found that the catalysts prepared by the homogeneous precipitation by urea hydrolysis are more highly
efficient and more stable for SRM than those prepared by
coprecipitation.

was placed at the center of the catalyst bed. The catalysts

were reduced at 623 K for 20 min in 14.3 vol.% H2 /N2 flow
(total flow rate: 35 ml-NTP min1 ). The feed gas composition was MeOH/H2 O/N2 = 10/12/30 ml-NTP min1 in the
steam reforming. The products were analyzed by on-line
TCD gas chromatographs with Porapak-Q and Molecular
Sieve 5A columns.

2. Experimental
2.1. Catalyst preparation

3. Results and discussion

Cu/ZnO and Cu/ZnO/Al2 O3 catalysts were prepared by

two methods, i.e. coprecipitation (CP) and homogeneous
precipitation method by urea hydrolysis (HP). CP-Cu/ZnO
and CP-Cu/ZnO/Al2 O3 catalysts were prepared by coprecipitation, i.e., the aqueous solution of metal nitrates was
dropped into aqueous solution of Na2 CO3 with vigorous stirring and the pH was adjusted at 7 with NaOH. The obtained
precipitate was dried at 353 K, followed by calcination at
573 K for 3 h. Both HP-Cu/ZnO and HP-Cu/ZnO/Al2 O3 catalysts were prepared by homogeneous precipitation by urea
hydrolysis [1214] as follows: urea was mixed into a solution of metal nitrates at room temperature, and the urea
was hydrolyzed by heating the mixture at 363 K. During the
hydrolysis of urea, hydroxide ions are generated in the homogeneous solution (Eq. (4)).

Fig. 1 shows the XRD patterns of CP- and HP-Cu/ZnO

catalysts before (A) and after (B) calcination. Before the
calcination, both CP- and HP-Cu/ZnO catalysts clearly
showed the diffraction lines due to aurichalcite ((Cu,
Zn)5 (CO3 )2 (OH)6 , ICDD 17743), wherein the copper is
atomically mixed with zinc [16,17]. After the calcination,
auricalcite decomposed to CuO and ZnO phases. The width
of diffraction lines of CuO and ZnO phases in HP-Cu/ZnO

CO(NH2 )2 + H2 O 2NH4 + HCO3 + OH

(4)

It is expected that the homogeneity of the precipitate will be

higher than that prepared by conventional coprecipitation,
since there is no gradient in concentration of precipitants
in the solution. The precipitates were then filtered, washed
with distilled water, dried in air at 353 K and finally calcined
at 573 K for 3 h.

0.5

(a)

(b)

10

2.2. Characterization

15

20

25
2 / degree

30

35

1.0

(a)

2.3. Catalytic reactions

The steam reforming and oxidative steam reforming of
methanol were carried out using a fixed-bed flow reactor at
atmospheric pressure using 200 mg of catalysts. The catalysts were diluted with 200 mg of quartz granules. The thermocouple was introduced from the top of the reactor, and

40

CuO
ZnO

(B)

Intensity / kcps

The structures of catalysts were characterized by XRD

(Rigaku RINT2550VHF). Inductively coupled plasma (ICP)
analyses were measured by Shimadzu ICPS-100V. BET
measurements were conducted using N2 at 77 K with a
Micromeritics Flowsorb2300 instrument. The copper metal
surface areas were determined by N2 O decomposition at
363 K as reported by Evans et al. [15], assuming a reaction
stoichiometry of two Cu atoms per oxygen atom and a Cu
surface density of 1.63 1019 Cu atom/m2 . Scanning
electron micrographs (SEM) were obtained over on a JEOL
JSM6340F.

Aurichalcite

Intensity/kcps

(A)

(b)

25

30

35

40
45
2 / degree

50

55

60

Fig. 1. XRD patterns of Cu/ZnO catalysts before (A) and after (B)
calcination. (a) CP-Cu/ZnO, (b) HP-Cu/ZnO.

T. Shishido et al. / Applied Catalysis A: General 263 (2004) 249253

251

Table 1
Activity and selectivity for steam reforming of methanol over Cu/ZnO and Cu/ZnO/Al2 O3 catalystsa
Catalystb

Cu/(Cu + Zn)c

Reaction
temperature (K)

Conv. of
MeOH (%)

Selectivity (%)
CO2

CO

Rate of H2 production
(cm3 min1 g1 )

CP-Cu/ZnO

0.3

473
523
573

12.1
46.4
84.9

100.0
99.6
95.2

0.0
0.4
4.8

18.2
69.6
127.4

HP-Cu/ZnO

0.3

473
523
573
473
523
573
473
523
573

32.4
89.2
100.0
37.5
94.2
100.0
27.0
85.6
100.0

100.0
97.3
95.6
100.0
99.6
94.3
100.0
99.3
95.4

0.0
2.7
4.4
0.0
0.4
5.7
0.0
0.7
4.6

48.6
133.8
150.0
56.3
141.3
150.0
40.5
128.4
150.0

473
523
573

47.4
97.3
100.0

100.0
99.0
92.7

0.0
1.0
7.3

71.1
146.0
150.0

0.5

0.7

HP-Cu/ZnO/Al2 O3 d

a
b
c
d

0.5

MeOH/H2 O/N2 = 10/12/30 ml-NTP min1 .

CP: co-precipitation, HP: homogeneous precipitation using urea hydrolysis.
Metal composition was calculated from the amount of reagents.
Cu/Zn/Al = 45/45/10 mol%, metal composition was calculated from the amount of reagents.

was larger than those in CP-Cu/ZnO, indicating that the

particle size of CuO and ZnO in HP-Cu/ZnO is smaller
than that in CP-Cu/ZnO. After the reduction, CuO was reduced to Cu metal, whereas the ZnO phase still remained.
The XRD patterns of CP- and HP-Cu/ZnO/Al2 O3 catalysts before calcination also showed the diffraction lines
due to aurichalcite. After the calcination, both CuO and
ZnO phases were observed. On the contrary, no diffraction lines of any Al compounds, such as Al2 O3 , CuAl2 O4
and ZnAl2 O4 were observed, suggesting that Al species
were highly dispersed in the HP-Cu/ZnO/Al2 O3 . After the
reduction, CuO was reduced to Cu metal.
The catalytic activities of the Cu/ZnO and Cu/ZnO/Al2 O3
catalysts prepared by CP- and HP-methods for the steam
reforming of methanol are summarized in Table 1. In all
the reactions, the effluent gas contained H2 and CO2 as the
major component, together with a small amount of CO. No
other products, such as dimethyl ether, methyl formate and

methane, could be obtained over any of the catalysts tested.

The methanol conversion and hydrogen production rate increased with increasing the reaction temperature. The physical properties and TOF values are shown in Table 2. The
TOF values were calculated from the surface area of metallic Cu and the production rate of hydrogen. The actual Cu
loadings which are measured by ICP analyses are consistent
with the Cu loadings estimated from the amount of reagents.
Although the content of copper in CP-Cu/ZnO (Cu/Zn =
30/70) was equal to that in HP-Cu/ZnO (Cu/Zn = 30/70),
the conversion of methanol and the production rate of hydrogen on CP-Cu/ZnO were lower than those on HP-Cu/ZnO,
indicating that the preparation method influences the catalytic activity. The HP-Cu/ZnO showed higher values of both
BET and Cu metal surface areas as well as the higher activity
than those of CP-Cu/ZnO. SEM observation of HP-Cu/ZnO
(Cu/Zn = 30/70) revealed the presence of spherical fine
particles (ca. 10 m in diameter) as shown in Fig. 2 at a

Table 2
Physical properties and TOF values for steam reforming of methanol over Cu/ZnO and Cu/ZnO/Al2 O3 catalysts
SBET c (m2 g-cat1 )

SCu0 d (m2 g-cat1 )

TOFe (102 s1 )

Catalyst

Cu/(Cu + Zn)a

Conv. (%)b

CP-Cu/ZnO

0.3

12.1

40.7

16.0

2.78

HP-Cu/ZnO

0.3
0.5
0.7

32.4
37.5
27.0

107.9
76.4
62.5

41.0
41.6
23.7

2.90
3.30
4.17

HP-Cu/ZnO/Al2 O3

0.5

47.4

97.5

47.0

3.70

a
b
c
d
e

Metal composition was calculated from the amount of reagents.

Reaction temperature 473 K.
BET surface area.
Cu metal surface area was determined by N2 O decomposition method [15].
Hydrogen molecules produced per surface Cu atom per second at 473 K.

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T. Shishido et al. / Applied Catalysis A: General 263 (2004) 249253

Fig. 2. SEM images (5000) of the HP-Cu/ZnO (a) and the CP-Cu/ZnO (b).

magnification of 5000. Judging from the SEM observation

in Fig. 2(a), one can conclude that the spherical fine particles consist an assembly of small thin plates and possess
a developed porous structure. Although some aggregates of
spherical fine particles were observed when the magnification was low (not shown), every particle still showed a quite
spherical morphology. On the other hand, CP-Cu/ZnO afforded rather massive precipitation (Fig. 2(b)).

Interestingly, although both CP- and HP-Cu/ZnO have

the same crystal structure of auricalcite in the XRD observations, the obtained morphologies were quite different,
resulting in the significant difference between BET results
and Cu metal surface areas. On the contrary, the TOF value
on HP-Cu/ZnO was almost identical to that on CP-Cu/ZnO.
This result suggests that the property of active site is little
affected by the preparation method for Cu/ZnO catalyst. A

T. Shishido et al. / Applied Catalysis A: General 263 (2004) 249253

Conversion of methanol /%

100

90

80

70

60

50
0

10

15

20

25

Time on stream /h
Fig. 3. Time course of the steam reforming of methanol over the Cu/ZnO
and the Cu/ZnO/Al2 O3 catalyst. () HP-Cu/ZnO/Al2 O3 (45/45/10), ()
HP-Cu/ZnO (30/70), () CP-Cu/ZnO/Al2 O3 (45/45/10) and () Commercial Cu/ZnO/Al2 O3 . Reaction temperature, 523 K; catalyst, 0.2 g;
MeOH/H2 O/N2 = 10/12/30 ml-NTP min1 .

253

for 24 h. On the other hand, the HP-Cu/ZnO/Al2 O3 showed

high enough and stable enough activity compared to the
HP-Cu/ZnO. Ross et al. reported that the addition of Al
on Cu/ZnO increased the sustainability, resulting in no noticeable deactivation at any temperature during the steam
reforming reaction [7]. Furthermore, the HP-Cu/ZnO/Al2 O3
showed higher activity and stability than CP-Cu/ZnO/Al2 O3
(Cu/Zn/Al = 45/45/10) and a commercial Cu/ZnO/Al2 O3
catalyst (Cu/Zn/Al = 42/46/12) in this reaction.
As a conclusion, the homogeneous precipitation method
by urea hydrolysis is preferable for the preparation of the
active Cu/ZnO and Cu/ZnO/Al2 O3 catalysts for hydrogen
production by steam reforming of methanol (SRM). The
high activities of the catalysts prepared by the homogeneous
precipitation method may be due to the highly dispersed
Cu metal particles and the high accessibility of Cu metal
particles to methanol and steam. The activity and stability
were improved by the addition of Al species to Cu/ZnO
system.

Acknowledgements
well-mixed copper-zinc hydroxide may be formed by the
homogeneous precipitation. Thus, it is likely that highly dispersed Cu metal particles were formed after the reduction,
and this highly dispersed Cu metal species may show the
high accessibility to methanol and steam. These are reasons
why the high activity for the steam reforming of methanol
was obtained over HP-Cu/ZnO even at low temperature, as
shown in Table 1. Here, we point out that the homogeneous
precipitation method by urea hydrolysis is a hopeful candidate as the preparation method of active Cu/ZnO catalysts
for hydrogen production via steam reforming of methanol.
An increase in the Cu content in HP-Cu/ZnO catalyst up
to 50 mol% (Cu/Zn = 50/50) resulted in increases in the
conversion of methanol, the production rate of hydrogen
and Cu metal surface area. When the Cu content exceeded
50 mol%, methanol conversion, the formation rate of hydrogen and the Cu metal surface area all gradually decreased
with increasing Cu content. These results strongly suggest
that the Cu metal surface area, viz., the dispersion of Cu
metal species, affects the catalytic activity.
HP-Cu/ZnO/Al2 O3 (Cu/Zn/Al = 45/45/10) showed
higher activity than that on HP-Cu/ZnO (Cu/Zn = 50/50)
as well as higher values of both BET and Cu metal
surface area. This indicates that the aggregation of Cu
species was inhibited by the addition of Al species to
Cu/ZnO system. The TOF value of HP-Cu/ZnO/Al2 O3
(Cu/Zn/Al = 45/45/10) is larger than that of HP-Cu/ZnO
(Cu/Zn = 50/50). This result suggests that the property
of the active site is also influenced by the presence of Al
species. Moreover, the stability of the Cu/ZnO catalyst was
also improved by the addition of Al. Fig. 3 shows the time
course of the steam reforming of methanol at 523 K. The
activity of the HP-Cu/ZnO catalyst was low even at the
beginning of the reaction and declined during the reaction

The authors sincerely appreciate the financial support by

the Hiroshima Industrial Technology Organization. The authors also thank Mrs. E. Tanabe and M. Honda for their kind
support with the SEM and ICP experiments.
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