i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 8 ( 2 0 1 3 ) 1 3 7 6 e1 3 8 3

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Hydrogen production by steam reforming of ethanol over

mesoporous NieAl2O3eZrO2 xerogel catalysts: Effect of Zr/Al
molar ratio
Seung Ju Han a, Yongju Bang a, Jeong Gil Seo b, Jaekyeong Yoo a, In Kyu Song a,*
a

School of Chemical and Biological Engineering, Institute of Chemical Processes, Seoul National University, Shinlim-dong, Kwanak-ku, Seoul
151-744, South Korea
b
Department of Environmental Engineering and Energy, Myongji University, Nam-dong, Cheoin-gu, Yongin-si, Gyeonggi-do 449-728, South
Korea

article info

abstract

Article history:

A series of mesoporous NieAl2O3eZrO2 xerogel catalysts (denoted as Ni-AZ-X ) with

Received 18 October 2012

different Zr/Al molar ratio (X) were prepared by a single-step epoxide-driven solegel

Received in revised form

method, and they were applied to the hydrogen production by steam reforming of ethanol.

7 November 2012

The effect of Zr/Al molar ratio of Ni-AZ-X catalysts on their physicochemical properties

Accepted 10 November 2012

and catalytic activities was investigated. Textural and chemical properties of Ni-AZ-X

Available online 6 December 2012

catalysts were strongly influenced by Zr/Al molar ratio. Surface area of Ni-AZ-X catalysts
decreased with increasing Zr/Al molar ratio due to the lattice contraction of ZrO2 caused by

Keywords:

the incorporation of Al3 into ZrO2. Interaction between nickel oxide species and support

Hydrogen production

(Al2O3eZrO2) decreased with increasing Zr/Al molar ratio through the formation of NiO

Steam reforming of ethanol

eAl2O3eZrO2 composite structure. Acidity of reduced Ni-AZ-X catalysts decreased with

Mesoporous NieAl2O3eZrO2 xerogel

increasing Zr/Al molar ratio due to the loss of acid sites of Al2O3 by the addition of ZrO2.

catalyst

Acidity of Ni-AZ-X catalysts served as a crucial factor determining the catalytic perfor-

Zr/Al molar ratio

mance in the steam reforming of ethanol; an optimal acidity was required for maximum

Acidity

production of hydrogen. Among the catalysts tested, Ni-AZ-0.2 (Zr/Al 0.2) catalyst with
an intermediate acidity exhibited the best catalytic performance in the steam reforming of
ethanol.
Copyright 2012, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights
reserved.

1.

Introduction

With increasing demand for new and clean energy, hydrogen

has attracted much attention as a promising energy carrier,
because it possesses high energy density (ca. 120.7 kJ/g) and
burns without emitting any environmental pollutants [1e4].
There are various resources for hydrogen production such as
coal, natural gas, propane, methanol, and ethanol. Among these

resources, ethanol has been considered as a practical resource,

because it is biodegradable, low in toxicity, and free from catalyst poisons such as sulfur [4]. Moreover, ethanol becomes more
abundantly available due to the increasing ethanol production
by bio-chemical processes [5]. Thus, ethanol has served an
environmentally friendly resource for hydrogen production.
Reforming technologies for hydrogen production from
ethanol can be classified into steam reforming, auto-thermal

* Corresponding author. Tel.: 82 2 880 9227; fax: 82 2 889 7415.

E-mail address: inksong@snu.ac.kr (I.K. Song).
0360-3199/$ e see front matter Copyright 2012, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.ijhydene.2012.11.057

i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 8 ( 2 0 1 3 ) 1 3 7 6 e1 3 8 3

reforming, and partial oxidation [6]. Among these technologies,

ethanol steam reforming has been extensively investigated due
to its high hydrogen yield compared to the other reforming
technologies [7]. The target reaction of ethanol steam reforming
is represented in Eq. (1). However, it is known that ethanol
steam reforming reaction is accompanied by several reactions,
including ethanol dehydration (Eq. (2)), ethanol decomposition
(Eq. (3)) followed by methane steam reforming (Eq. (4)), and
ethanol dehydrogenation (Eq. (5)). Among these reactions,
ethanol dehydration reaction is mainly responsible for low
hydrogen yield due to the formation of polymeric carbon
species [8]. On the other hand, water-gas shift reaction (Eq. (6))
is an advantageous reaction in the steam reforming of ethanol
because it enhances hydrogen yield.
o

C2H5OH 3H2O / 2CO2 6H2 (DH

298 K

174 kJ/mol)

(1)

C2H5OH 4 C2H4 H2O (DHo298 K 45 kJ/mol)

(2)

C2H5OH 4 CH4 CO H2 (DHo298

(3)

49 kJ/mol)

CH4 H2O 4 CO 3H2 (DHo298 K 205 kJ/mol)

(4)

C2H5OH 4 C2H4O H2 (DHo298 K 68 kJ/mol)

(5)

CO H2O 4 CO2 H2 (DHo298

(6)

41.2 kJ/mol)

Therefore, developing an efficient ethanol steam reforming

catalyst which can not only promote hydrogen production but
also suppress undesired ethanol dehydration reaction is of
great importance. Conventionally, nickel catalysts supported
on alumina (Ni/Al2O3) have been widely used in the steam
reforming of ethanol due to their high dehydrogenation
activity and low cost [9,10]. However, it is known that Ni/Al2O3
catalysts suffer from significant deactivation caused by
carbon deposition on their acid sites during the ethanol steam
reforming reaction [11]. For this reason, many attempts have
been made to increase both catalytic activity and durability of
Ni/Al2O3 catalysts through modification of supporting materials [12]. Alkaline oxides such as MgO and CaO have been
widely used as additives or promoters, because they can
suppress the coking reaction by neutralizing acid sites of Al2O3
[12]. Addition of lanthanide oxides can also increase the
catalytic activity by promoting gasification reaction of dissolved carbon species on the surface of nickel catalysts [13].
Among various metal oxides, ZrO2 is known to be the most
effective additive for Ni/Al2O3 catalysts in the steam reforming of ethanol, because ZrO2 can not only enhance the stability
of the catalysts but also promote adsorption and dissociation
of water on the surface of nickel catalysts [14e16]. On the
other hand, Ni/Al2O3 xerogel catalysts have also been investigated as efficient catalysts for hydrogen production by
reforming reactions due to their high surface area and welldeveloped mesoporous structure [16,17]. Therefore, a systematic investigation on optimizing ZrO2 addition to NieAl2O3

1377

xerogel catalyst for hydrogen production by steam reforming

of ethanol would be worthwhile.
In this work, a series of mesoporous NieAl2O3eZrO2 xerogel catalysts (Ni-AZ-X ) with different Zr/Al molar ratio (X )
were prepared by a single-step epoxide-driven solegel
method, and they were applied to the hydrogen production by
steam reforming of ethanol. The effect of Zr/Al molar ratio on
the physicochemical properties and catalytic activities of
mesoporous Ni-AZ-X catalysts in the steam reforming of
ethanol was investigated.

2.

Experimental

2.1.
Preparation of mesoporous NieAl2O3eZrO2 xerogel
catalysts
A series of mesoporous NieAl2O3eZrO2 xerogel catalysts with
different Zr/Al molar ratio were prepared by a single-step
epoxide-driven solegel method, according to the similar
methods reported in the literatures [18,19]. Known amounts of
aluminum precursor (aluminum nitrate nonahydrate, SigmaeAldrich, 98%) and zirconium precursor (zirconium oxynitrate hydrate, SigmaeAldrich, 99%) were dissolved in
ethanol (58 ml). The total amount of two precursors was
0.04 mol. An appropriate amount of nickel precursor (nickel
nitrate hexahydrate, SigmaeAldrich, 97%) was then dissolved
in the solution containing aluminum and zirconium precursors with vigorous stirring. Propylene oxide (29 ml) as a gelation agent was then added into the resulting solution. Upon
maintaining the solution for a few minutes, deprotonation of
hydrated metal salts and subsequent cross-linking of metal
ion complex occurred for the formation of NieAl2O3eZrO2
composite gel. After the gel was aged for 2 days, it was washed
with ethanol two times in order to minimize the destruction of
pore structure of the catalyst by removing foreign substances
in the gel with ethanol. The product was then dried at 80  C in
a convection oven for 5 days. The resulting powder was finally
calcined at 550  C for 5 h to obtain a mesoporous
NieAl2O3eZrO2 xerogel catalyst. The prepared mesoporous
NieAl2O3eZrO2 xerogel catalysts were denoted as Ni-AZ-X
(X 0, 0.1, 0.2, 0.3, and 0.4), where X represented Zr/Al molar
ratio. Nickel loading of Ni-AZ-X catalysts was fixed at 10 wt%.

2.2.

Characterization

Nitrogen adsorptionedesorption isotherms of Ni-AZ-X catalysts were obtained with an ASAP-2010 (Micromeritics)
instrument. Chemical compositions of Ni-AZ-X catalysts were
determined by ICP-AES (ICPS-1000IV, Shimadzu) analyses.
Crystalline structures of calcined and reduced catalysts were
investigated by XRD (D-Max2500-PC, Rigaku) measurements
using Cu-Ka radiation (l 1.541 
A) operated at 50 kV and
100 mA. In order to examine the interaction between nickel
species and support, temperature-programmed reduction
(TPR) measurements were conducted in a conventional flow
system with a moisture trap connected to a thermal conductivity detector (TCD) at temperatures ranging from room
temperature to 1000  C with a ramping rate of 5  C/min. For
the TPR measurements, a mixed stream of H2 (2 ml/min) and

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2.3.

Hydrogen production by steam reforming of ethanol

Hydrogen production by steam reforming of ethanol was

carried in a continuous flow fixed-bed reactor under atmospheric pressure. Each calcined catalyst (100 mg) was reduced
with a mixed stream of H2 (3 ml/min) and N2 (30 ml/min) at
550  C for 3 h. Ethanol and water were sufficiently vaporized
by passing through a pre-heating zone, and they were
continuously fed into the reactor together with N2 carrier
(30
ml/min).
Feed
composition
was
fixed
at
C2H5OH:H2O:N2 1:6:24.5. Total feed rate with respect to
catalyst weight was maintained at 23,140 ml/hg. Catalytic
reaction was carried out at 500  C. Reaction products were
periodically sampled and analyzed using an on-line gas
chromatograph (ACME 6000, Younglin) equipped with
a thermal conductivity detector (TCD). Ethanol conversion,
hydrogen yield, and carbon-containing product selectivity
were calculated according to the following equations. Fi,in and
Fi,out are molar flow rates of the specific species (i) at the inlet
and outlet of the reactor, and ni is a stoichiometric factor of
carbon-containing product.
Ethanol conversion %

Hydrogen yield %

Si;carboncontaining



FEtOH;in  FEtOH;out
 100
FEtOH;in

FH2 ;out

 100
3  FEtOH;in  FEtOH;out

Ni-AZ-0.4

Volume adsorbed (A. U.)

N2 (20 ml/min) was used for 100 mg of catalyst sample.

Dispersion of metal species on the reduced catalysts was
examined by TEM-EDX analyses (Tecnai F20, FEI). Prior to the
TEM analyses, each catalyst was preliminarily reduced with
a mixed stream of H2 (3 ml/min) and N2 (30 ml/min) at 550  C
for 3 h. NH3-TPD experiments were conducted to determine
the acid property of reduced catalysts (BELCAT-B, BEL Japan).
0.07 g of each catalyst charged into the TPD apparatus was
reduced at 550  C for 3 h with a mixed stream of H2 (2.5 ml/
min) and Ar (47.5 ml/min). After cooling the catalyst to room
temperature, a mixed stream of NH3 (2.5 ml/min) and He
(47.5 ml/min) was introduced into the reactor at 50  C for
50 min to saturate acid sites of the catalyst. Physisorbed
ammonia was removed at 100  C for 1 h under a flow of He
(50 ml/min). After cooling the sample, furnace temperature
was increased from 50  C to 900  C at a heating rate of 5  C/min
under a flow of He (30 ml/min). The desorbed ammonia was
detected using a TCD (thermal conductivity detector). The
amount of carbon deposition in the used catalysts was
determined by CHNS elemental analyses (CHNS 932, Leco).

Ni-AZ-0.3

Ni-AZ-0.2

Ni-AZ-0.1

Ni-AZ-0

3.1.

Physicochemical properties of Ni-AZ-X catalysts

0.6

0.8

1.0

Fig. 1 e Nitrogen adsorptionedesorption isotherms of NiAZ-X (X [ 0, 0.1, 0.2, 0.3, and 0.4) catalysts calcined at
550  C.

isotherm measurements as represented in Fig. 1. All the NiAZ-X catalysts exhibited type-IV isotherms with H2-type
hysteresis loops, indicating the presence of well-developed
mesopores [20]. Detailed physicochemical properties of NiAZ-X (X 0, 0.1, 0.2, 0.3, and 0.4) catalysts are summarized in
Table 1. The observed Zr/Al molar ratios of Ni-AZ-X catalysts
were quite similar to the designed values. Surface area of NiAZ-X catalysts decreased with increasing Zr/Al molar ratio.
This might be due to the increased textural density of Ni-AZ-X
catalysts caused by the addition of ZrO2 into NieAl2O3
composite [21]. The lowest surface area of Ni-AZ-0.4 catalyst
could be explained by higher surface energy of Zr4 than Al3;
the coalescence of structure occurred for the minimization of
surface energy, resulting in the decrease of surface area
[22,23]. However, pore volume and average pore diameter of
Ni-AZ-X catalysts showed no consistent trend with respect to
Zr/Al molar ratio.

(7)

(8)

(9)

Results and discussion

0.4

Relative pressure (P/P0)

Table 1 e Detailed physicochemical properties of Ni-AZ-X

catalysts calcined at 550  C for 5 h.
Catalyst

Zr/Al
molar
ratioa

Surface
area
(m2/g)b

Pore
volume
(cm3/g)c

Average
pore
diameter (nm)d

Ni-AZ-0
Ni-AZ-0.1
Ni-AZ-0.2
Ni-AZ-0.3
Ni-AZ-0.4

0
0.07
0.15
0.25
0.39

339
336
320
292
214

0.66
0.62
0.63
0.49
0.28

5.5
5.3
5.7
5.0
3.9

ni  Fi;carbon-containing product

 100
product %
2  FEtOH;in  FEtOH;out

3.

0.2

Textural properties of Ni-AZ-X (X 0, 0.1, 0.2, 0.3, and 0.4)

catalysts were examined by nitrogen adsorptionedesorption

a
b
c
d

Determined by ICP-AES measurement.

Calculated by the BET equation.
BJH desorption pore volume.
BJH desorption average pore diameter.

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XRD and TPR results of Ni-AZ-X catalysts

486

Fig. 2 shows the XRD patterns of Ni-AZ-X (X 0, 0.1, 0.2, 0.3,

and 0.4) catalysts calcined at 550  C. In the Ni-AZ-0 catalyst,
three diffraction peaks indicative of NiAl2O4 phase (solid lines
in Fig. 2) were observed, as reported in the literatures [16,24].
However, the peak intensity of NiAl2O4 gradually decreased
with increasing Zr/Al molar ratio. Instead, the diffraction peak
of tetragonal ZrO2 (1 1 1) (dashed line in Fig. 2) became strong
with increasing Zr/Al molar ratio. It is noticeable that XRD
peak of tetragonal ZrO2 (1 1 1) in the Ni-AZ-X (X 0.1, 0.2, 0.3,
and 0.4) catalysts shifted to the higher diffraction angle than
its original angle (2q 30.2 ), representing the lattice
contraction of ZrO2 caused by the incorporation of Al3 ions
A) is
into ZrO2. This is because the radius of Zr4 ion (0.84 
A) [25]. Thus, it can be
larger than that of Al3 ion (0.54 
inferred that NiOeAl2O3eZrO2 composite structure was
developed in the Ni-AZ-X catalysts by the simultaneous solidestate reaction among NiO, Al2O3, and ZrO2 [26]. Interestingly, diffraction peaks corresponding to NiO (closed circles in
Fig. 2) suddenly appeared in the Ni-AZ-0.4 catalyst. This is
because some Ni2 ions hardly interacted with Al2O3 when an
excess amount of ZrO2 was added into the Ni-AZ-X catalysts.
In order to elucidate the metalesupport interaction in the
Ni-AZ-X (X 0, 0.1, 0.2, 0.3, and 0.4) catalysts, TPR measurements were carried out as shown in Fig. 3. All the catalysts
exhibited a reduction band at relatively high temperature
within the range of 568e638  C. On the other hand, Ni-AZ-X
(X 0.2, 0.3, and 0.4) catalysts showed an additional reduction
band at relatively low temperature ranging from 454  C to
486  C. It has been reported that the band appeared at high
temperature is related to the reduction of nickel oxide species
strongly interacted with Al2O3 [27], while the band appeared at

ZrO2 (1 1 1)

NiAl2O4

Ni-AZ-0.4

Hydrogen consumption (A. U.)

3.2.

568

572
464

Ni-AZ-0.3
585
454

Ni-AZ-0.2
590

Ni-AZ-0.1

638

Ni-AZ-0

200

400

600

Temperature

800

1000

(oC)

Fig. 3 e TPR profiles of Ni-AZ-X (X [ 0, 0.1, 0.2, 0.3, and 0.4)

catalysts calcined at 550  C.

low temperature is associated with the reduction of nickel

oxide species weakly interacted with ZrO2 [28,29]. It is
noticeable that reduction peak temperature of nickel oxide
species interacting with Al2O3 decreased with increasing Zr/Al
molar ratio, while that of nickel oxide species interacting with
ZrO2 increased with increasing Zr/Al molar ratio. In other
words, reducibility of nickel oxide species in the Ni-AZ-X
catalysts increased with increasing Zr/Al molar ratio. From
these results, it can be inferred that the addition of ZrO2
suppressed the interaction between nickel oxide and support
(Al2O3 or Al2O3eZrO2) through the formation of NiOeAl2O3eZrO2 composite structure.

NiO
Ni (1 1 1) Ni (2 0 0)

Ni (2 2 0)

Ni-AZ-0.4
Ni-AZ-0.4

Ni-AZ-0.2

Ni-AZ-0.1

Intensity (A. U.)

Intensity (A. U.)

Ni-AZ-0.3
Ni-AZ-0.3

Ni-AZ-0.2

Ni-AZ-0.1

Ni-AZ-0
Ni-AZ-0

20

30

40
50
60
2 Theta (degree)

70

80

Fig. 2 e XRD patterns of Ni-AZ-X (X [ 0, 0.1, 0.2, 0.3, and

0.4) catalysts calcined at 550  C.

20

30

40

50

60

70

80

2 Theta (degree)
Fig. 4 e XRD patterns of Ni-AZ-X (X [ 0, 0.1, 0.2, 0.3, and
0.4) catalysts reduced at 550  C.

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Fig. 5 e TEM images of (a) Ni-AZ-0, (b) Ni-AZ-0.2, and (c) Ni-AZ-0.4 catalysts reduced at 550  C, and EDX maps with
distribution of (I) Ni, (II) Al, and (III) Zr.

Fig. 4 shows the XRD patterns of Ni-AZ-X (X 0, 0.1, 0.2, 0.3,

and 0.4) catalysts reduced at 550  C. All the reduced catalysts
showed diffraction peaks corresponding to metallic Ni (solid
lines in Fig. 4). Furthermore, diffraction peaks indicative of
NiO and NiAl2O4 were not observed, indicating that nickel
species in all the Ni-AZ-X catalysts were completely reduced
into metallic nickel during the reduction process employed in
this work.
TEM images of Ni-AZ-0, Ni-AZ-0.2, and Ni-AZ-0.4 reduced
at 550  C, and EDX maps with distribution of Ni, Al, and Zr are
represented in Fig. 5. It was observed that density of Al
decreased while that of Zr increased with increasing Zr/Al
molar ratio, in accordance with ICP-AES analyses (Table 1). It
is noteworthy that Al and Zr were homogeneously distributed
throughout the catalysts without any significant aggregation
regardless of the different Zr/Al molar ratio.

3.4.

This can be explained by the fact that acidity of the catalysts is

mainly related to Al2O3 surface, because large amount of acid
sites exists in Al2O3 rather than ZrO2 [24,30e34]. This result
can also be deduced by the fact that the addition of ZrO2

Ni-AZ-0.4

NH3 desorbed (A. U.)

3.3.
Crystalline structure and metal dispersion of
reduced Ni-AZ-X catalysts

Ni-AZ-0.3

Ni-AZ-0.2

Ni-AZ-0.1

Ni-AZ-0

Acidity of reduced Ni-AZ-X catalysts

Fig. 6 shows the NH3-TPD profiles of Ni-AZ-X (X 0, 0.1, 0.2,

0.3, and 0.4) catalysts reduced at 550  C. Acidity of reduced NiAZ-X catalysts was calculated from peak area as summarized
in Table 2. It was observed that acidity of the catalysts
monotonically decreased with increasing Zr/Al molar ratio.

100

200 300 400 500 600 700 800 900

Temperature (oC)

Fig. 6 e NH3-TPD profiles of Ni-AZ-X (X [ 0, 0.1, 0.2, 0.3,

and 0.4) catalysts reduced at 550  C.

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200

Table 2 e Acidity of reduced Ni-AZ-X catalysts.

Acidity (mmol-NH3/g)a

Ni-AZ-0
Ni-AZ-0.1
Ni-AZ-0.2
Ni-AZ-0.3
Ni-AZ-0.4

131
124
101
86
79

a Calculated from peak area of NH3-TPD profiles in Fig. 6.

decreased surface area of the catalysts (Table 1), resulting in

the decrease of acid sites of the catalysts [35].

160
Hydrogen yield (%)

Catalyst

120

3.5.
Hydrogen production by steam reforming of ethanol
over Ni-AZ-X catalysts

Ni-AZ-0.4

80

Ni-AZ-0.3
Ni-AZ-0.2
Ni-AZ-0.1

40

Ni-AZ-0

0
0

Fig. 7 shows the hydrogen yields with time on stream over NiAZ-X (X 0, 0.1, 0.2, 0.3, and 0.4) catalysts in the steam
reforming of ethanol at 500  C. Both Ni-AZ-0 and Ni-AZ-0.1
catalysts experienced a catalytic deactivation resulting from
the significant carbon deposition on the catalyst surface
(Table 3). However, Ni-AZ-X (X 0.2, 0.3, and 0.4) catalysts
showed a stable performance with time on stream. It is
believed that the addition of ZrO2 improved the catalytic
stability by inhibiting coke formation [12].
Detailed catalytic performance of Ni-AZ-X (X 0, 0.1, 0.2,
0.3, and 0.4) catalysts in the steam reforming of ethanol at
500  C after a 900 min-reaction is summarized in Table 3.
Complete conversion of ethanol was achieved in all the
catalysts under the conditions of high reaction temperature
and excess amount of steam. This is in good agreement with
the previous reports [6,36]. Selectivity for C2H4 over Ni-AZ-X
catalysts decreased in the order of Ni-AZ-0 (9.8%) > Ni-AZ-0.1
(1.6%) > Ni-AZ-0.2 (0%) Ni-AZ-0.3 (0%) Ni-AZ-0.4 (0%). This
can be explained by the fact that large amount of acid sites in
the supports promoted the dehydration of ethanol to ethylene
via one-step elimination mechanism [37]. The amount of
carbon deposition decreased in the order of Ni-AZ0 (28.8%) > Ni-AZ-0.1 (21.5%) > Ni-AZ-0.2 (3.5%) > Ni-AZ-0.3
(2.6%) > Ni-AZ-0.4 (1.3%) (Table 3). This might be because ZrO2
in the Ni-AZ-X catalysts hindered both ethanol dehydration
reaction (Eq. (2)) and ethylene formation reaction related to
coking [38]. It was also observed that CO/CO2 molar ratio
increased with increasing Zr/Al molar ratio (with decreasing
acidity) in the order of Ni-AZ-0 (0.045) < Ni-AZ-0.1 (0.049) z NiAZ-0.2 (0.053) Ni-AZ-0.3 (0.053) < Ni-AZ-0.4 (0.240). This

200

400

600

800

1000

Time (min)
Fig. 7 e Hydrogen yields with time on stream in the steam
reforming of ethanol over Ni-AZ-X (X [ 0, 0.1, 0.2, 0.3, and
0.4) catalysts at 500  C. All the catalysts were reduced at
550  C for 3 h prior to the reaction.

result indicates that water-gas shift reaction (Eq. (6)) was

suppressed with increasing Zr/Al molar ratio (with decreasing
acidity). It has been reported that the increased surface acidity
promotes the water-gas shift reaction by increasing the
number of adsorbed CO species [39]. Therefore, it can be
inferred that an excess amount of ZrO2 hindered water-gas
shift reaction in the steam reforming of ethanol.
Fig. 8 shows the hydrogen yields over Ni-AZ-X (X 0, 0.1,
0.2, 0.3, and 0.4) catalysts in the steam reforming of ethanol
obtained after a 900 min-reaction, plotted as a function of Zr/
Al molar ratio and acidity of the catalyst. Hydrogen yields
showed a volcano-shaped curve with respect to Zr/Al molar
ratio and acidity of the catalyst. Hydrogen yield decreased in
the order of Ni-AZ-0.2 > Ni-AZ-0.3 > Ni-AZ-0.1 > Ni-AZ0.4 > Ni-AZ-0. Among the catalysts tested, Ni-AZ-0.2 catalyst
exhibited the best catalytic performance in terms of hydrogen
yield. Although acidity of the catalyst was not the sole factor
determining the catalytic performance in the steam reforming
of ethanol, it greatly affected the reaction path and stability
[6,12]. Relatively more acidic catalysts (Ni-AZ-0 and Ni-AZ-0.1)
exhibited low hydrogen yield because undesired ethanol

Table 3 e Catalytic performance of Ni-AZ-X catalysts in the steam reforming of ethanol at 500  C after a 900 min-reaction.
Catalyst

Ethanol
conversion (%)

Hydrogen
yield (%)

Selectivity
for C2H4 (%)

CO/CO2
molar ratio

Amount of carbon
deposition (wt%)a

Ni-AZ-0
Ni-AZ-0.1
Ni-AZ-0.2
Ni-AZ-0.3
Ni-AZ-0.4

100
100
100
100
100

104
123
137
130
119

9.8
1.6
0
0
0

0.045
0.049
0.053
0.053
0.240

28.8
21.5
3.5
2.6
1.3

a Determined by CHNS elemental analysis.

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140

140

Ni-AZ-0.2

b
Ni-AZ-0.3

Ni-AZ-0.1
Ni-AZ-0.4

110

Hydrogen yield (%)

Hydrogen yield (%)

Ni-AZ-0.3

130
120

Ni-AZ-0.2

130
Ni-AZ-0.1

120
Ni-AZ-0.4

110

Ni-AZ-0

Ni-AZ-0

100

100

90

90
0

0.1

0.2

0.3

0.4

Zr/Al molar ratio

70

80

90

100

110

120

130

140

Acidity of catalyst ( mol-NH3/g)

Fig. 8 e Hydrogen yields over Ni-AZ-X (X [ 0, 0.1, 0.2, 0.3, and 0.4) catalysts in the steam reforming of ethanol obtained after
a 900 min-reaction, plotted as a function of (a) Zr/Al molar ratio and (b) acidity of the catalyst.

dehydration reaction occurred on the acid-rich surface,

resulting in a severe coke formation [37,38]. On the other
hand, relatively less acidic catalysts (Ni-AZ-0.3 and Ni-AZ-0.4)
showed low hydrogen yield due to low reactivity for water-gas
shift reaction [39].
In the aspect of textural properties and reducibility, it was
revealed that the addition of ZrO2 decreased surface area and
increased reducibility of the catalysts. As these two factors
affect the catalytic activity in an opposite way, it is believed
that high surface area of Ni-AZ-0 and Ni-AZ-0.1 compensates
low reducibility, and high reducibility of Ni-AZ-0.3 and Ni-AZ0.4 compensates low surface area [40]. Consequently, it is
concluded that catalytic performance of Ni-AZ-X catalysts
was well correlated with acidity regardless of the effect of
textural properties and reducibility. Among the catalysts
tested, Ni-AZ-0.2 catalyst with an intermediate acidity
showed the maximum hydrogen yield.

4.

Conclusions

A series of mesoporous NieAl2O3eZrO2 (Ni-AZ-X ) xerogel

catalysts with different Zr/Al molar ratio (X) were prepared by
a single-step epoxide-driven solegel method. The prepared
catalysts were applied to the hydrogen production by steam
reforming of ethanol. The effect of Zr/Al molar ratio on the
catalytic performance was investigated. It was found that all
the Ni-AZ-X catalysts exhibited a mesoporous structure.
Surface area of the catalysts decreased with increasing Zr/Al
molar ratio due to the incorporation of ZrO2. Reducibility of NiAZ-X catalysts increased with increasing Zr/Al molar ratio
through the formation of NiOeAl2O3eZrO2 composite structure. Acidity of Ni-AZ-X catalysts monotonically decreased
with increasing Zr/Al molar ratio. In the hydrogen production
by steam reforming of ethanol, hydrogen yields over Ni-AZ-X
catalysts showed a volcano-shaped curve with respect to Zr/
Al molar ratio and acidity of the catalysts. Among the catalysts
tested, Ni-AZ-0.2 catalyst with an intermediate acidity
exhibited the best catalytic performance. It is concluded that
an optimal Zr/Al molar ratio of NieAl2O3eZrO2 xerogel catalyst was required for maximum production of hydrogen by
steam reforming of ethanol.

Acknowledgments
This work was supported by the Global Frontier R&D Program
on Center for Multiscale Energy System funded by the
National Research Foundation under the Ministry of Education, Science and Technology, Korea (20110031575).

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