Solid State Ionics 176 (2005) 2917 2922

www.elsevier.com/locate/ssi

CuZnAl hydrotalcites as precursors of catalysts for the production of

hydrogen from methanol
U. Costantino a,*, F. Marmottini a, M. Sisani a, T. Montanari b, G. Ramis b, G. Busca b,
M. Turco c, G. Bagnasco c
a

CEMIN, Centro di Eccellenza sui Materiali Innovativi Nanostrutturati, Dipartimento di Chimica, Universita` di Perugia, Italy
b
Dipartimento di Ingegneria Chimica, Universita` di Genova, Italy
c
Dipartimento di Ingegneria Chimica, Universita` Federico II, Napoli, Italy

Abstract
The possibility of a wide use of hydrogen as fuel of proton exchange membrane fuel-cells forces to the development of selective catalytic
materials for the oxidative steam reforming of methanol (OSRM) to produce H2 essentially free from CO. Cu/ZnO/Al2O3 catalysts of OSRM
process have been obtained from hydrotalcite-like precursors with nominal formula Cu1
x
y Zny Alx (OH)2(CO3)x/2 (x = 0.23 0.42, y = 0.31
0.58) and prepared by homogeneous precipitation from metal chlorides solutions in the presence of urea. The catalysts were obtained after thermal
decomposition of the hydrotalcites at 450 -C, followed by in situ reduction with H2. X-ray powder diffraction (XRPD) patterns of the precursors
showed the presence of the hydrotalcite phase with minor amounts of a Zn-rich paratacamite phase (Cu2
x Znx (OH)3Cl) whose amount increases
with increasing Cu content. XRPD patterns of thermally treated samples show only the lines of CuO and ZnO phases; Al2O3 and/or aluminates
may be present as amorphous phases. The BET surface areas of the samples are in the range 110 220 m2 g
1 and increase with increasing Al
content. The catalytic activity in the OSRM process is appreciable from about 200 250 -C and methanol conversions up to 90 95% are obtained
at temperatures of 300 400 -C. Hydrogen is the main product, and its yield reaches values up to 2.7 mol/mol of methanol. Carbon monoxide
content is under the detection limit (500 ppm) of the detector.
D 2005 Elsevier B.V. All rights reserved.
PACS: -81.05Zx
Keywords: Hydrotalcites; Cu/ZnO/Al2O3 catalysts; H2 production; Methanol reforming

1. Introduction
Fuel cells with proton exchange membranes (PEMFCs) are
considered one of the most interesting alternatives to the
traditional internal combustion engine for the production of
energy for car-traction [1,2]. Although, on principle, the
PEMFCs can work with different fuels from the simplest
hydrocarbons to alcohols, the present technology is limited to
the employment of H2, but the feeding of the motor-vehicles
with hydrogen could cause problems for the fuel tank
construction, for the filling stations and, above all, for the
safety. Thus, an idea is now spreading to associate the fuel cells
with reactors for hydrocarbons and alcohols reforming. The
reactor should work at a relatively low temperature and be able
* Corresponding author. Department of Chemistry, University of Perugia, Via
Elce di Sotto, 8, 06127 Perugia, Italy. Tel.: +39 075 585 5565.
E-mail address: ucost@unipg.it (U. Costantino).
0167-2738/$ - see front matter D 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.ssi.2005.09.051

to feed the cell with the hydrogen produced during the reaction.
Among the fuels to be reformed, methanol is very attractive for
its low cost, the high H/C ratio and the absence of coke
formation [3]. Recently, an interesting methanol reforming
process, named Oxidative Steam Reforming of Methanol
(OSRM), has been proposed and is under study in various
academic and industrial laboratories [4,5]. OSRM combines
the two reactions:
CH3 OH H2 OYCO2 3H2
CH3 OH 1=2O2 YCO2 2H2

DH- 49:3kJ mol
1

DH-
191:9kJ mol
1

2

endothermic steam reforming (1) and exothermic partial

oxidation (2) and can be carried out in autothermic conditions
if the reactor is fed with mixtures of CH3OH, H2O and O2 in
proper concentration ratio. The reforming process must not

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U. Costantino et al. / Solid State Ionics 176 (2005) 2917 2922

produce CO, since this by-product, even in ppm amounts,

damages the fuel cell operation [6]. Hence, the ideal OSRM
catalysts should possess, beside high chemical, thermal and
mechanical endurance to operate for long time with many
working cycles in the presence of water vapour and oxygen, a
high surface area and chemical properties (redox, acid base) to
selectively activate the reagents for CO2 and H2 production.
Literature data indicate that good catalysts are obtained with
systems based on metallic copper well dispersed into zinc and/
or aluminium oxides [7 9]. A relatively simple way to obtain
such systems consists in preparing catalyst precursors constituted of Cu, Zn, Al hydroxycarbonates with hydrotalcite
structure [4,5,10]. The hydrotalcite-like compounds, also
known as anionic clays or lamellar double hydroxides, are
practically the unique example of lamellar solids having
lamellae with positive charges balanced with exchangeable
anions accommodated in the interlayer region. Their general
formula is [M(II) 1
x M(III) x (OH) 2 ](A x /n )Im H 2 O, where
M(II) = Mg, Zn, Ni, Cu, Mn; M(III) = Al, Cr, Fe; x = 0.2 0.4;
An- is the intercalated anion of charge n; m = mol/mol of cointercalated water. The structure of the lamellae is of brucite
type and comes out from the linkage through corners of
M(OH)6 octahedra where M is the bivalent or trivalent metal.
More than one bivalent or trivalent metal can be introduced in
the brucite layer to achieve a large variety of composition
[11,12]. In any case, the brucite layer is constituted of metal
cations interdispersed at atomic level and ternary hydrotalcites
of the type Cux Zn0.67
x Al0.33(OH)2(CO3)0.17, calcined and
reduced with a hydrogen flow can lead to catalysts containing
Cu highly dispersed on ZnO and Al2O3. In this line, previous
works [4,5] have shown that thermal decomposition and
reduction of ternary hydrotalcites produces catalysts that show
high catalytic performances in terms of methanol conversion
and high selectivity to produce H2 and CO2.
It was thus of interest to prepare Cu Zn Al hydrotalcite
precursors with different composition in order to obtain new
catalysts for the OSRM process. In this work a series of
hydrotalcite precursors with nominal formula Cu1
x
y Zny Alx (OH)2(CO3)x/2 (x = 0.23
0.42, y = 0.31
0.58) have been
prepared by homogeneous precipitation from metal chlorides
accomplished by urea hydrolysis [13]. The materials have been
characterised by chemical and thermal analyses, X-ray powder
diffraction (XRPD) and BET surface areas and the catalysts
thereby obtained have been used in OSRM process with the
aim to obtain information on the effect of Cu, ZnO and Al2O3
molar ratio on the efficiency of the reaction.

then suspended in a 0.05 M Na2CO3 solution (about 20 mL/g

of precipitate) for 1 day, in order to exchange chloride ions,
eventually present in the hydrotalcite materials, with carbonate
anions. After equilibration with the Na2CO3 solution the solids
were recovered, washed with deionised water and finally dried
at room temperature over P4O10. The catalysts were obtained
by heating the precursors in dry airflow at rate of 2 or 10 -C
min
1 up to 450 -C and maintaining it at this temperature for
12 h. Then the samples were reduced in situ with 2% H2/He
mixtures. The reducing treatments were effected before
characterization measurements. The metal ions contents were
obtained by ion chromatography, after dissolution of the
samples in concentrated HCl. Carbonate and water contents
were evaluated from thermo gravimetrical analysis.
2.2. Instrumentation and catalytical characterisation
XRPD patterns of the samples were recorded with a
computer controlled Philips PW1710 diffractometer using
Cu Ka Ni-filtered radiation (40 kV, 30 mA). XRPD patterns
at programmed temperatures have been taken in a HT A.
Paar diffraction camera. TG analyses were performed in air
by a Netzsch STA449C Thermal Analyser at a heating rate
of 5 -C min
1.
N2 adsorption desorption isotherms were obtained at
196
-C, on samples previously degassed at 100 -C, using a
computer controlled Micromeritics 2010 apparatus. The IR
spectra were recorded with a Nicolet Protege 460 Fourier
Transform instrument.
A Micromeritics 2900 apparatus equipped with a TCD
detector was employed for Temperature Programmed Reduction/Oxidation (TPR and TPO) measurements. TPR measurements were carried out on calcined samples at a rate of 10 -C
min
1 using a 5% H2/Ar mixture. Catalytic activity measurements are carried out in a laboratory flow apparatus with a
fixed bed reactor. A gas-chromatograph (GC) HP 5890,
equipped with a Porapak-molecular sieve double-packed
column and a TCD detector, is employed for the analysis of
H2, CO, CO2, O2, CH4, CH3OH, H2O. From concentrations
and volume of effluent stream, total and partial conversions are
calculated. The tests were carried out at T = 200 400 -C,
feeding with H2O/CH3OH/O2 mixtures at 1.1:1:0.12 molar
ratio and space velocity, GHSV = 0.6  106 or 1.2  106 h
1.
3. Results and discussion
3.1. Precursors preparation and characterisation

2. Experimental
2.1. Synthetic procedures and chemical analyses
The hydrotalcite precursors were obtained with urea method
[13]. Aqueous solutions, obtained by mixing solutions 0.5 M of
AlCl3, ZnCl2 and CuCl2 in the proper volume ratio, were added
of solid urea until the molar ratio urea/Al(III) was 6 and then
refluxed for 3 days. The precipitates obtained were separated
from the mother solutions, washed with deionised water and

The Cu Zn Al precursors of the OSRM catalysts have

been prepared with the urea method. This method generally
allows the preparation of different hydrotalcite-like compounds
having a high crystallinity degree and a narrow particle size
distribution [13]. However, the presence of Cu2+ cations makes
the synthetic procedure more complex, at least for two reasons.
First, Cu2+ ions show the Jahn-Teller effect that favours the
formation of distorted octahedral structures [14], secondarily
Cu2+ ions can be depleted by ammonia originated from urea

U. Costantino et al. / Solid State Ionics 176 (2005) 2917 2922

2919

Table 1
Metal content, phase analysis and surface area of Cu/Zn/Al hydrotalcite precursors (the surface area of the precursors, previously heated at 450 -C is also reported)
Sample

C1u
C2u
C3u(NA)
C11u
C3u(bis)
C4u
PTAC*

Solid composition (% metals molar ratio)

Cu

Zn

Al

9
11
18
24
45
60
75

48
52
33
43
31
20
25

43
37
49
33
23
19

% Htlc phase

% PTAC* phase

Surface area (m2/g)

100
100
85
65
56
40
0

0
0
15
35
44
60
100

216
216
134
48.7
67
116.1
10.8

Precursor

Oxides
254

125
9.4

PTAC* = paratacamite Cu2
x Znx (OH)3Cl.

These data seem to indicate that the brucite sheet of wellcrystallised hydrotalcites is not able to accommodate more than
one copper atom every six different metal atoms. If one
considers that every metal centre in the brucite sheet is
surrounded by six others metal centres, it may be deduced
that the brucite layer seems not to tolerate the presence of two
contiguous distorted Cu(OH)6 octahedra. It may be recalled
that hydrotalcite samples with a higher Cu content can be
prepared by the classical precipitation procedure, but the
samples obtained have a low degree of crystallinity and the
attempts to prepare more crystalline samples produce the
segregation of other Cu-rich phases [16].

12000

PTAC

10000

C4u

Intensity (a.u.)

hydrolysis. The preparation of Cu Zn Al precursors has

required modification of the original urea method. In particular,
the molar ratio urea/Al(III) has been decreased from 10 to 6
and addition of the CuCl2 solution has been carried out drop by
drop as the Zn Al hydrotalcite starts to be formed. These
modifications allowed to obtain materials having a Cu content
near, even if always lower, to that of the starting solutions.
Table 1 reports the composition, expressed as % molar ratio of
the metal ions content, the phase analysis and the BET surface
area of the samples prepared. The XRPD patterns of the
precursors are reported in Fig. 1. The patterns clearly indicate
the good crystalline order of the samples. It may be also seen
that most of them are biphasic and pure hydrotalcite phases
(PDF No. 14-0191) were obtained when the Cu-content was
lower than 15% (samples C1u and C2u). At higher Cu-content,
a new phase, identified as Zn-rich paratacamite (PDF N. 501558) of formula Cu2
x Znx (OH)3Cl, starts to be formed. The
relative amount of the two phases has been evaluated by
quantitative Rietveld procedure, using GSAS program [15].
Table 1 shows the increase of paratacamite phase amount with
the increasing Cu-content and, correspondingly, a decrease of
BET surface areas of related samples. It may be observed that
pure paratacamite sample, prepared with the urea method, has a
very low surface area when compared with that of pure
hydrotalcite phase (sample C1u).

3.2. Catalysts preparation and characterisation

As already mentioned, OSRM catalysts are obtained by
calcination and subsequent reduction of the precursors. It was
thus of interest to study the thermal behaviour of the
precursors. Fig. 2 shows the weight loss curves of the samples
prepared as a function of temperature. For sake of comparison,
the TG curve of the sample of paratacamite, prepared by the
urea method, is also reported. Thermal decomposition of
paratacamite occurs in two well differentiated steps. The first
one, attributed to the loss of condensation water, is sharp and
occurs at 300 -C. The second step, occurring between 450- and

C3ubis

8000

C11u
6000
C3u
4000
C2u
2000
C1u
0
5

10

15

20

25

30

35

40

2
Fig. 1. XRPD patterns of the indicated samples, conditioned at room temperature over P4O10. See Table 1 for the abbreviations.

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U. Costantino et al. / Solid State Ionics 176 (2005) 2917 2922

C1u
C2u
C3u
C3uNA
C4u
Ptac

100
C3uNA
95

% weight loss

90
85
80
75
70

C4u

65

C1u

60

C3u
C2u

55

PTAC
0

200

400

600

800

1000

1200

Temperature (C)
Fig. 2. Weight loss curves as a function of temperature of the indicated samples. Heating rate of 5 -C min
1 in air flow.

650 -C, is broad and can be attributed to the loss of chlorine,

very likely as HCl. At 700 -C only a mixture of Zn and Cu
oxides are present. The weight loss curve of the hydrotalcite
phase is represented by the curve of the C1u sample. It is
constituted by two broad weight losses, the first occurring
between room temperature and about 200 -C is mainly
attributed to the loss of co-intercalated water, the second loss,
between 200- and 450 -C, is attributed to the loss of
constitutional water and carbon dioxide and leads to the
formation of metal oxides and aluminates. The TG curves of
the other precursors show the typical features of the thermal
decomposition of hydrotalcite and paratacamite phases. The
loss below 150 -C can be attributed to the loss of water co-

intercalated with carbonates in the hydrotalcite phase, while the

loss over 450 -C to the decomposition of the paratacamite
phase. The losses between 150 and 450 -C can be ascribed to
the loss of condensation water of hydrotalcite and of
paratacamite overlapping with the loss of carbonates. The total
weight loss of the precursors is very near to that calculated for
the thermal transformation of the precursors into CuO, ZnO
and Al2O3 metal oxides. It is, however, difficult to deduce the
formula of the mixed phase precursors since Cu and Zn are
vicariant metals both in hydrotalcite and paratacamite phases.
The thermal decomposition of the precursor has been also
monitored by recording the XRPD patterns in a HT diffraction
camera. The structure of the hydrotalcite phase collapses at

Fig. 3. XRPD patterns at room temperature of the indicated samples, previously heated at 450 -C.

U. Costantino et al. / Solid State Ionics 176 (2005) 2917 2922

2921

Fig. 4. FT-IR adsorption spectra of CO adsorbed at
160 -C over C3u catalyst, pre-treated under vacuum at 300 -C. Surface species after contact with the gas (a),
after evacuation at
160 -C (b), after evacuation at
140 -C (c). The spectrum of the catalyst after thermal treatment has been subtracted. Inset (c) (a) subtraction
spectrum.

temperatures higher than 180 -C, while the characteristic peak

of paratacamite is not present at temperatures higher than 260
-C, in agreement with the TG data. Over 320 -C, very weak
reflections typical of the copper and zinc oxides start to appear.
To have a better insight of the phases formed at temperatures
higher than 320 -C, the XRPD patterns, taken at room
temperature, of samples previously heated for three hours in
an oven at 450 -C have been collected (see Fig. 3). The patterns
show diffraction peaks attributable to CuO and ZnO and only
broad reflections attributable to zinc (or copper) aluminates.
Reflections of Al2O3 are absent. From these data, it appears
that treatment at 450 -C is suitable for obtaining catalysts for
OSRM. In fact, this temperature is sufficiently high for the
formation of metal oxides, but low enough to avoid sintering
phenomena that could cause loss of surface area. Subsequent
characterisation has been carried out on the C3u sample. TPR
signals showed that the reduction of Cu(II) species to Cu(0)
occurs in two steps in the 250 400 -C temperature range, and
give evidence that the heating rate employed in the thermal
treatment influences the crystal size and the homogeneity of the
CuO phase. Correspondingly, TPO measurements gave evidence that oxidation of Cu phase occurs in several steps in the
temperature range 200 350 -C, suggesting that in the reaction
conditions Cu(0), Cu(I) and Cu(II) can be present simultaneously. This was confirmed by IR measurements. Fig. 4
reports the IR spectra of carbon monoxide adsorbed at
160
-C on the catalysts, pre-treated at 300 -C. The adsorption of
CO gives rise to a complex band characterised by a maximum
at 2128 cm
1 with a shoulder at 2135 cm
1 and two weaker
bands at 2163 and 2187 cm
1. According to previous works
[17,18], the observed features can be assigned to CO adsorbed
on the Zn-aluminate support (2187 cm
1), on Cu2+ sites (2163

Fig. 5. Methanol conversion (a) and hydrogen yield (b) as a function of

temperature in the OSRM process catalysed by the indicated catalysts.
GHSV = 0.6  106 h
1.

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U. Costantino et al. / Solid State Ionics 176 (2005) 2917 2922

cm
1, decreasing in intensity by reduction), on Cu+ centres

(2135 cm
1, stable to out gassing at
110 -C) and on Cu
metal deduced from the presence of a component at 2128
cm
1, (see inset of Fig. 4), labile even at
110 -C.
3.3. Preliminary catalytic activity measurements
Preliminary catalytic activity tests indicated that the
catalysts, obtained from precursors listed in Table 1, have a
good activity and selectivity, giving almost complete CH3OH
conversion with high yield to H2 and absence of CO (detection
limit = 500 ppm) under conditions of interest for OSRM
process. The activity strongly depended on space velocity:
for GHSV = 1.2  106 h
1, CH3OH conversion was low and O2
conversion negligible at T < 300 -C, for GHSV = 0.6  106Ih
1
CH3OH conversion was markedly higher, reaching 100% at
T  350 -C. Fig. 5a and b reports the methanol conversion and
the H2 yield, respectively as a function of temperature at
GHSV = 0.6  106 h
1, for three different catalysts. Results
obtained with a sample of paratacamite, previously calcined
and reduced at 450 -C, are also shown for comparison. It may
be seen that all the three catalysts produce a complete methanol
conversion at temperatures lower than 400 -C. Of particular
interest is the behaviour of samples C2u and C3u that produce
an almost complete methanol conversion at temperatures lower
than 350 -C and a H2 yield (see Fig. 5b) close to the value 2.76
mol/mol of methanol expected on the basis of feed composition
assuming total conversion of O2 and CH3OH. It is interesting
to note the poor catalytic efficiency of calcined paratacamite
sample. Catalysts obtained by precursors containing a large
amount of paratacamite phase, such as the sample C3u bis,
show indeed a lower catalytic activity when compared with that
of obtained by hydrotalcite-rich precursors. The catalytic
activity of sample C2u and a study of the reaction path under
OSRM conditions have been objects of a recent work [15].

This has allowed to obtain products with fairly high Cu

content, however the contemporary formation of Cu Zn
oxychloride (paratacamite phase) could not be avoided, it
seems in fact that the layer of brucite type does not tolerate
more than 15% of Cu(II) cations in octahedral coordination,
due to the Jahn Teller distorsion. However, the Cu/ZnO/Al2O3
catalysts thereby obtained gave preliminary good results, in
terms of CH3OH conversion and H2 yield, together with low
CO production and this is a further stimulus to investigate the
hydrotalcite system as efficient precursor of very selective
OSRM catalysts.
Acknowledgements
The authors acknowledge MUIR in the framework of
Programmi di Ricerca di Interesse Nazionale, 2004 no. 031878.
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method, modified to introduce Cu(II) into the brucite sheets.

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