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 4 1 ( 2 0 1 6 ) 3 3 4 9 e3 3 6 2

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Modulating and controlling active species

dispersion over NieCo bimetallic catalysts for
enhancement of hydrogen production of ethanol
steam reforming

Xiaxia Zhao a,b, Gongxuan Lu a,*

a
State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese
Academy of Science, Lanzhou 730000, China
b
University of Chinese Academy of Science, Beijing 100049, China

article info abstract

Article history: In this study, an active NieCo/Al2O3 catalyst for steam reforming of ethanol (SRE) was
Received 3 August 2015 reported. Results indicated that the dispersion of active species can be tuned by prepara-
Received in revised form tion methods, i.e., by stepdstep impregnation method and co-impregnation method
7 September 2015 separately. By comparing the activities and stabilities in the temperature range of 250
Accepted 21 September 2015 e650
C under atmospheric pressure, and correlating the characterization results of H2
Available online 17 January 2016 chemisorption, XRD, HRTEM and TGA, we found the catalytic performance were dependent
on the surface species dispersion over support which could be modulated by preparation
Keywords: process. The ethanol conversion on NieCo/Al2O3, Co/Ni/Al2O3 and Ni/Co/Al2O3 catalysts
Steam reforming of ethanol were 68.7%, 50.9%, 36.6% at 350
C, corresponding to the metal species dispersion data
Hydrogen production 31.5%, 29.1% and 28.0%, respectively. TEM results confirmed these differences corre-
Nickel sponded to the metal particles size of the bimetallic catalysts distribution. Higher dispersed
Cobalt catalyst exhibited higher anti-coking properties and stabilities. Under the optimized con-
High dispersion ditions, the ethanol conversion, H2 and CO2 selectivities were 97.2%, 88.9% and 87.4%,
Anti-coking respectively during a 100 h reaction over NieCo/Al2O3 catalyst at 550
C, LHSV of 7.5 h1
and a C2H5OH/H2O molar ratio of 13.
Copyright 2015, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights
reserved.

hydrogen in near-zero emission way of carbon dioxide, for

Introduction
Hydrogen is one of clean energy carrier and fuel [1]. Presently,
hydrogen is largely produced from steam reforming of natural
gas, liquefied petroleum gas and naphtha, etc [2e4]. However,
due to the huge emission of carbon dioxide in the mentioned
processes, it is urgently to develop new technique producing
example reforming biomass-ethanol, by which the carbon
dioxide formed in the hydrogen production step can be reused
in plant growth cycle [5,6].
The hydrogen can be achieved by several methods,
including pyrolysis, gasification and steam reforming [7e13].
For bio-ethanol is biodegradable, high hydrogen content, low
toxic [14], its steam reforming to hydrogen has received

* Corresponding author. Tel.: 86 931 4968 178.

E-mail address: gxlu@lzb.ac.cn (G. Lu).
http://dx.doi.org/10.1016/j.ijhydene.2015.09.063
0360-3199/Copyright 2015, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.
3350 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 4 1 ( 2 0 1 6 ) 3 3 4 9 e3 3 6 2
extensive attentions [5,6]. It is known that the over-all ethanol
steam reforming is always accompanied by several side re-
actions, such as ethanol decomposition, ethanol dehydroge-
nation, acetaldehyde decomposition, water-gas shift reaction,
etc. To enhance hydrogen yield in ethanol reforming, the
active sites regarding the cleavage CeC bond in ethanol
molecule and decomposition of the intermediates to desired
species have to be constructed [15,16].
A number of active catalysts for ethanol reforming have
been reported, such as supported VIII metals (e.g., Ni and Co),
for example, Fatsikostas et al. [17] reported that the Ni/La2O3
catalyst exhibited high activity and stability due to formation
of a lanthanum oxycarbonate species (La2O2CO3), which could
react with the surface deposited carbon species formed during
reaction, resulting in inhibition of catalyst deactivation. Yang
et al. [18] showed the significant support effect on ethanol
steam reforming over Ni-based catalysts. Although Ni
exhibited strong ability in cleavage of CeC, OeH, and CeH
bonds, Ni-based catalysts had a strong tendency to sinter and
to form coke in reforming reactions, and its activity loss in CO
removal [19,20]. It is known that Co could catalyze CeC bond
cleavage [21], enhance the water-gas shift reaction which is
important for higher H2 yield [22,23]. Thus, bimetallic NieCo
catalyst shows potential ability for high efficient ethanol-
reforming process.
Since carbon deposition and active Ni sintering were the two
major obstacles in reforming catalyst deactivation [20], tuning
surface active Ni with Co could improve the catalysts perfor-
mance. In fact, bimetallic NieCo catalysts had exhibited
excellent activity for CO2 methanation [24,25], CO hydrogena-
tion [26e28], CH4/CO2 reforming [29], methane partial oxidation
[30] and hydrogen production from liquid reforming [31,32] or
cellulose decomposition [33]. Ishihara's research indicated that
NieCo alloying affects the adsorption ability of H2 and CO,
which improved CO conversion [26]. Takanabe et al. [34] have
reported that the advantages of the bimetallic catalysts are
highly resistant to undesirable metal oxidation. Chen et al. [35]
investigated the effect of the CoeNi ratio on the activity and
stability for methane oxy-CO2 reforming, and found that the
Co/Ni ratio had a strong influence on the catalytic performance,
which could be attributed to the effect of metal particle size and
metal-support interaction. Both supports and active species
affect the catalytic activity and products selectivities for
ethanol steam reforming over NieCo catalysts [36,37].
In this paper, a series of NieCo bimetallic catalysts prepared
by the co-impregnation and sequential impregnation methods
and were investigated for ESR. The results demonstrated that
co-impregnation (NieCo/Al2O3) possessed high active species
dispersion and small crystallite size, as evidenced by H2
chemisorption and TEM results, which effectively improved
catalytic performance and suppressed coke deposition in
compared with stepdstep impregnation catalysts.
Experimental
Catalyst preparation
15 wt.% Ni/g-Al2O3 catalyst (denoted as Ni/Al2O3) was pre-
pared by the impregnation method using Ni(NO3)2$6H2O as a
precursor. Before impregnation, the g-Al2O3 support (183 m2/
g, 0.25e0.35 mm) was calcined at 600
C for 6 h. Ni(NO3)2$6H2O
was dissolved in the distilled water first, and then the solution
was mixed with the calculated amount of g-Al2O3 support.
After impregnation, the catalyst precursor was dried at room
temperature for 24 h and at 110
C for another 24 h. Finally, the
precursor was calcined at 600
C for 3 h. 15 wt.% Co/g-Al2O3
(denoted as Co/Al2O3) catalyst was prepared by the same
procedures using Co(NO3)2$6H2O as a precursor.
7.5 wt.% Ni-7.5 wt.% Co/g-Al2O3 catalyst (denoted as
NieCo/Al2O3) was prepared by the co-impregnation method
using Ni(NO3)2$6H2O and Co(NO3)2$6H2O as precursors. The g-
Al2O3 support was impregnated with aqueous solution con-
taining calculated amounts of Ni(NO3)2$6H2O and Co(N-
O3)2$6H2O. After impregnation, the catalyst precursor was
dried at room temperature for 24 h and at 110
C for another
24 h. Finally, the precursor was calcined at 600
C for 3 h.
7.5 wt.% Co/7.5 wt.% Ni/g-Al2O3 catalyst (denoted as Co/Ni/
Al2O3) was prepared by the sequential impregnation method
using Ni(NO3)2$6H2O and Co(NO3)2$6H2O as precursors. The g-
Al2O3 support was firstly impregnated with aqueous solution
containing an appropriate amount of Ni(NO3)2$6H2O for 24 h,
and dried at 110
C for 24 h. Then, the precursor was calcined
at 600
C for 3 h. The obtained samples were subsequently
impregnated with aqueous solution containing an appropriate
amount of Co(NO3)2$6H2O for 24 h, and dried at 110
C for 24 h,
finally calcined at 600
C for 3 h.
7.5 wt.%/Ni/7.5 wt.% Co/g-Al2O3 catalyst (denoted as Ni/Co/
Al2O3) was prepared by the sequential impregnation method
using Ni(NO3)2$6H2O and Co(NO3)2$6H2O as precursors. The g-
Al2O3 support was firstly impregnated with aqueous solution
containing an appropriate amount of Co(NO3)2$6H2O for 24 h,
and dried at 110
C for 24 h. Then, the precursor was calcined
at 600
C for 3 h. The obtained samples were subsequently
impregnated with aqueous solution containing an appropriate
amount of Ni(NO3)2$6H2O for 24 h, and dried at 110
C for 24 h,
finally calcined at 600
C for 3 h.
Catalytic activity measurements
Catalytic tests were carried out at atmospheric pressure in a
fixed-bed continuous flow quartz reactor (i.d. 8 mm), con-
sisting of a flow controller unit, a reactor unit, and an analysis
unit. The reaction temperature increased from 250 to 650
C at
a 50
C increment. The effluent gas and liquid products were
taken for analysis after stabilizing for 1 h at each investigated
temperature. Typically, 0.5 g catalyst diluted with equal
amount of quartz was used in each run. Prior to the experi-
ment, the calcined catalyst was reduced in situ at 600
C for 2 h
(heating rate 10
C/min) with a 50 vol.% H2/N2 mixture (flow
rate 60 ml/min). The reaction mixture was fed into a pre-
heater by a syringe pump with a given liquid hourly space
velocity and steam to carbon ratio (S/C). The vaporized reac-
tion mixture was fed into the reactor using N2 (30 ml/min) as
the carrier gas. The separation and quantification of the
products were attained on two on-line chromatographs
equipped with thermal-conductivity detectors (TCD) and
flame ionization detectors (FID) respectively. Catalytic per-
formance of a given catalyst was based on ethanol conversion
and H2 selectivity. Ethanol conversion was denoted as XEtOH in
 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 4 1 ( 2 0 1 6 ) 3 3 4 9 e3 3 6 2 3351

the figures. H2 selectivity was defined as the fraction of H2

produced with respect to the theoretical full conversion of Results and discussions
ethanol to H2. Ethanol conversion, H2 selectivity and carbon-
containing product's selectivity were defined as follows: Catalyst characterizations

moles of ethanol consumed As shown in Table 1, the SBET of Ni/Al2O3, Co/Al2O3, NieCo/
XEtOH % 100 
moles of ethanol loaded Al2O3, Co/Ni/Al2O3, Ni/Co/Al2O3 and g-Al2O3 were 136.5, 140.3,
142.0, 140.6, 135.6 and 183.0 m2/g, respectively. A little bit of
decrease of specific area after loading of Ni and Co might

moles of H2 production moles of carbon-containing compounds

SH2 % 100  Scarbon-containing product% 100 
moles of ethanol consumed  6 moles of ethanol consumed  2

Liquid hourly space velocity (LHSV) was defined as (volu-

metric flow rate of feed solution (cm3/h))/(catalyst bed volume
(cm3)). Steam to carbon ratio (S/C) was defined by the formula:
Table 1 e BET surface area, average pore diameter,
S/C (moles of steam in the feed)/(moles of carbon in the
metallic surface area, metal dispersion of Ni and Co
feed). monometallic and NieCo bimetallic catalysts.
Samples SBETa Pore volumeb Average pore Metal
(m2 g1) (cm3 g1) sizec (nm) dispersiond
Catalyst characterizations (%)
Al2O3 183.0 0.46 10.1 e
Temperature-programmed reduction analysis (H2-TPR) was Ni/Al2O3 136.5 0.32 9.0 27.2
carried out by heating a sample (50 mg) from 25 to 700
C at Co/Al2O3 140.3 0.32 9.1 26.7
NieCo/ 142.0 0.33 9.6 31.5
10
C min1 in 5 vol.% H2eAr mixture (40 mL/min). The
Al2O3
amount of H2 consumed was measured by a TCD. The X-ray
Co/Ni/ 140.6 0.32 9.5 29.1
diffraction spectra (XRD) measurements were performed on a Al2O3
Philips X pert MPD instrument using Cu Ka radiation in the Ni/Co/ 135.6 0.32 9.1 28.0
scanning angle range of 10e80
at a scanning rate of 4
/min at Al2O3
40 mA and 50 kV. a
Obtained from BET method.
X-ray photoelectron spectroscopy (XPS) analysis was per- b
Total pore volume taken from the nitrogen adsorption volume at
formed using a VG Scientific ESCALAB 250Xi-XPS photoelec- a relative pressure (P/P0) of 0.99.
c
tron spectrometer with an Al Ka X-ray resource. The binding Average pore diameter determined from the adsorption data of
the isotherms using BJH method.
energies were calibrated by the C1s binding energy of 284.7 eV. d
Measure by H2 chemisorption at 25
C.
The BET specific surface area of the catalyst was measured
by a Micromeritics ASAP-2010 apparatus at a liquid nitrogen
temperature with N2 as the absorbent at 77 K.
Transmission electron microscopy (TEM) images were ob-
tained using the FEI F20 (Netherlands) high-resolution trans-
mission electron microscopy operating at an accelerating
voltage of 200 kV. The sample for TEM analyses was treated
ultrasonically in ethanol and then transferred as a suspension
to a carbon-coated copper grid.
The amounts of carbon deposition on catalyst surface were
analyzed thermogravimetric and differential scanning calo-
rimetry (TG-DSC) analysis using NETZSCH STA 449F3 instru-
ment. The catalyst was heated from room temperature to
900
C. The ramp rate was 10
C/min and compressed air was
used as the oxidant. The mass loss versus increasing tem-
perature was measured at experimental error about 0.5%.
H2 chemisorption over catalysts was performed on the
Micromeritics Chemisorb 2750. Prior to H2 absorption, 150 mg
samples were put into the quartz tube reactor, and using He
gas purged quartz tube 30 min. These catalysts were reduced
in 5 vol.% H2eHe mixture (40 mL/min) at 600
C for 2 h, then, Fig. 1 e XRD patterns of the Ni/Al2O3, Co/Al2O3, NieCo/
the sample was cooled to room temperature with He gas flow. Al2O3, Co/Ni/Al2O3 and Ni/Co/Al2O3 catalysts reduced at
After this, opening loop of samples was tested. 600
C 2 h.
3352 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 4 1 ( 2 0 1 6 ) 3 3 4 9 e3 3 6 2

because of partial blockage of surface pore by metal oxide
particles [38], NieCo/Al2O3, Co/Ni/Al2O3 present similar SBET,
but NieCo/Al2O3 showed the biggest pore volume and average
pore size among these samples, which might benefit for gas
molecules diffusing during reaction.
In order to recover the metal dispersion state, the metal
dispersions were measured via H2 pulse chemisorption. The
results are presented in Table 1. It was clear that the
dispersion of bimetallic catalysts were higher than mono-
metallic catalysts. The dispersion of NieCo/Al2O3, Co/Ni/
Al2O3 and Ni/Co/Al2O3 catalysts were 31.5%, 29.1% and
28.0%, respectively. The co-impregnation catalyst exhibited
higher metal dispersion compared with sequential impreg-
nation, which was correlated to the higher catalytic per-
formance of NieCo/Al2O3 (discussed in the following
section) [39].

Fig. 2 e TEM and HRTEM images of catalysts reduced at 600
C 2 h. (a) and (d) NieCo/Al2O3, (b) and (e) Co/Ni/Al2O3, (c) and (f)
Ni/Co/Al2O3.
 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 4 1 ( 2 0 1 6 ) 3 3 4 9 e3 3 6 2 3353

The X-ray diffraction (XRD) patterns of monometallic (Ni/
Al2O3 and Co/Al2O3) and bimetallic (NieCo/Al2O3, Co/Ni/Al2O3
and Ni/Co/Al2O3) samples, pretreated in H2 at 600
C for 2 h,
are showed in Fig. 1. For Ni/Al2O3 catalyst, the diffraction
peaks located at 2q 44.5, 51.8 and 76.5
indicated the exis-
tence of the characteristics of Ni metal phase (JCPDC Card No.
70-0989), the peaks located at 2q 37.3, 45.7, 60.8 and 66.9

could be assigned to characteristics of Al2O3 phase (JCPDC
Card No. 29-0063), while the peaks at 31.7, 37.3 and 44.5
were
assigned to the diffraction of NiAl2O4 bulk phase (JCPDC Card
No. 65-3102). For the Co/Al2O3 catalyst, the diffraction peaks
located at 2q 44.2, 51.4 and 75.7
indicated the existence of
the characteristics of Co metal phase (JCPDC Card No. 89-
4307), while the peaks at 19.1, 31.5 and 37.3
could be assigned
to the diffraction of CoAl2O4 bulk phase (JCPDC Card No. 03-
0896). For NieCo bimetallic catalysts, we found that the
diffraction peaks of bimetallic catalysts were relatively broad
and weak compared with monometallic catalysts, indicating
metal particles were in highly dispersion state over catalysts
[40]. In addition, the peaks were located at 2q 44.4
could be
assigned to the diffraction of Ni and Co particles. The char-
acteristic peaks of spinel compounds NiAl2O4 and CoAl2O4
were quite weak, and were hard to be identified due to their
similar morphology and structural characteristics [41]. How-
ever, for Ni/Co/Al2O3 catalyst, the intensities of typical
diffraction peaks of active species were weaker than the in-
tensities of other two bimetallic catalysts, which might imply
that the active species were high dispersion. Those results
were further supported by TEM images (Fig. 2). The Ni and Co
particle sizes were almost same in those three bimetallic
catalysts, however, the particle distribution results indicated
that the portion of smaller size was higher in NieCo/Al2O3
catalyst than other two samples, which was correlated to its
higher dispersion measurement results. In fact, the peak
located at 2q 44.4
, which was assigned to the diffraction of
Ni and Co in NieCo/Al2O3 catalyst, were relatively broad and
weak compared with the Co/Ni/Al2O3 catalysts. Generally, the
big crystallites would correspond to lower the active species

Fig. 3 e HAADF-STEM (high-angle annular dark field scanning transmission electron microscopy) image and elemental
mapping images of catalysts reduced at 600
C 2 h. (a) NieCo/Al2O3, (b) Co/Ni/Al2O3, (c) Ni/Co/Al2O3.
3354 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 4 1 ( 2 0 1 6 ) 3 3 4 9 e3 3 6 2
dispersion and lead to lower the catalytic performance. Thus
metallic species with smaller particle size would be beneficial
for ethanol steam reforming reaction [42].
More detail results of metal dispersion were given in im-
ages of Figs. 2 and 3. All bimetallic catalysts were reduced at
600
C for 2 h. The results showed that the nickel and cobalt
particles were rather uniformly dispersed in the NieCo/Al2O3
and Co/Ni/Al2O3 samples. However, some aggregation was
taken place over Ni/Co/Al2O3 catalyst. It seems that the Ni and
Co element distribution follows the order NieCo/Al2O3 > Co/
Ni/Al2O3 > Ni/Co/Al2O3. These results implied the particle
sizes distribution and active species dispersion were depen-
dent on the preparation method and calcination process. The
average size of Ni and Co particles on NieCo/Al2O3 was about
4e7 nm (Fig. 2a). The d-spacings of 0.204 nm and 0.176 nm
could be indexed to as the (111) and (200) crystalline plane of
face-centered cubic Ni lattice, respectively. The d-spacing of
adjacent fringe for Co nanocrystals was 0.205 nm, that could
be indexed to the (111) crystalline plane of face-centered cubic
Co lattice (Fig. 2d). For Co/Ni/Al2O3 and Ni/Co/Al2O3, the
average particle sizes were 5e8 and 7e10 nm, respectively
(Fig. 2b,c). The d-spacings of Ni (111) and Co (111) were also
given in Fig. 2e and f, which suggested that crystalline features
of Ni and Co particles on Co/Ni/Al2O3 and Ni/Co/Al2O3 were
similar to that on NieCo/Al2O3. These results were in accor-
dance with those results of XRD characterization.
H2-TPR measurements were carried out to investigate the
reducibility of the Ni/Al2O3, Co/Al2O3, NieCo/Al2O3, Co/Ni/
Al2O3 and Ni/Co/Al2O3 catalysts and the interaction between
impregnated metal particles and support [35]. TPR results of
catalysts calcined at 600
C for 3 h are presented in Fig. 4.
Three H2 consumption peaks appeared in all the catalysts,
however, the corresponding temperature of reduction peaks
were different. For Ni/Al2O3 catalyst, three reduction peaks
appeared at 285
C, 426
C, 567
C, which could be assigned to
the reduction of amorphous NiO, crystal NiO and NiAl2O4,
respectively [43,44]. The reduction profile of the Co/Al2O3
catalysts was composed of a small shoulder at 283
C, a
Fig. 4 e H2-TPR profiles of the Ni/Al2O3, Co/Al2O3, NieCo/
Al2O3, Co/Ni/Al2O3 and Ni/Co/Al2O3 catalysts calcined at
600
C 3 h.
principal peak at 356
C and a prolonged tail peak at 588
C,
which might be attributed to the reduction of Co3O4 to CoO,
and the subsequent reduction of CoO and CoAl2O4, respec-
tively [45,46]. For NieCo/Al2O3 catalyst, three reduction peaks
appeared at 258
C, 280
C, 551
C, which were likely assigned
to the reduction of NiO, Co3O4 and spinel (NiAl2O4 and
CoAl2O4), respectively. For Co/Ni/Al2O3 catalyst, three reduc-
tion peaks appeared at 258
C, 294
C, 552
C, which were likely
assigned to NiO, Co3O4 and spinel (NiAl2O4 and CoAl2O4),
respectively. And for the Ni/Co/Al2O3 catalyst, three reduction
peaks appeared at 277
C, 349
C, 580
C, which could be
attributed to the reduction of NiO, Co3O4 and spinel (NiAl2O4
and CoAl2O4), respectively. Obviously, compared with the
monometallic catalysts, the bimetallic catalysts promoted the
dispersion and reducibility of the metal oxides by modifying
the interaction between the active phase and the support [24].
In addition, co-precipitation method could result in higher
dispersion than other two bimetallic samples, which corre-
sponded to lower reduction peaks. According to the XRD
patterns (Fig. 1), relatively broad and weak peaks of bimetallic
catalysts compared with the monometallic catalysts, sug-
gested that the dispersion of active species in bimetallic cat-
alysts were high over Al2O3 support surface [40], as a result,
the shift of the reduction peaks of the bimetallic catalysts to
lower temperature was observed [47]. This conclusion was
further supported by TEM images, that active particles were
small and uniformly dispersed in the NieCo/Al2O3 and Co/Ni/
Al2O3 catalysts while the somehow agglomeration occurred
on Ni/Co/Al2O3 sample. That explained the NieCo/Al2O3 and
Co/Ni/Al2O3 catalysts exhibited lower reduction temperature
compared with Ni/Co/Al2O3 catalyst.
In order to further clarify the reduction of NiO at low
temperature, we used the different precursors and precipita-
tion methods to prepare the catalyst by different impregna-
tion strategies. One step impregnation and multiple
impregnation (impregnated three time, each time 5 wt.% of Ni
was loaded) catalysts using Ni(NO3)2$6H2O as a precursor were
denoted as sample a and b. For comparison, one step
impregnation using (CH3COO)2Ni$4H2O as a precursor was
Fig. 5 e H2-TPR profiles of the (a), (b) and (c) catalysts
calcined at 600
C 3 h.
Fig. 6 e XPS spectra of catalysts reduced at 600
C 2 h. (a) Ni2p3/2 peak of Ni/Al2O3, (b) Ni2p3/2 peak of NieCo/Al2O3, (c) Ni2p3/2
peak of Co/Ni/Al2O3, (d) Ni2p3/2 peak of Ni/Co/Al2O3, (e) Co2p3/2 peak of Co/Al2O3, (f) Co2p3/2 peak of NieCo/Al2O3, (g) Co2p3/2
peak of Co/Ni/Al2O3, (h) Co2p3/2 peak of Ni/Co/Al2O3.
3356 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 4 1 ( 2 0 1 6 ) 3 3 4 9 e3 3 6 2

denoted as sample c. Ni loading amount was 15 wt.%, and

their H2-TPR profiles were presented in Fig. 5. The first
reduction peak of sample a was centered at 285
C, while the
corresponding peaks of sample b and c were centered at 261
C
and shoulder at 226
C. Such low temperature shift reflected
reducibility and dispersion variation in these three samples,
i.e., multiple impregnation led to better reducibility and
dispersion. Using organic precursor also helps Ni species
dispersion. The corresponding metal dispersion data for a, b
and c by H2 chemisorption were 27.2%, 30.3% and 33.8%,
respectively. As indicated of results of H2-TPR in Fig. 5 and the
dispersion of a, b and c catalysts, it was indicated that
reduction temperature of Ni species was inversely dependent
on the metal dispersion. The metal dispersion of the Ni/Al2O3
and NieCo/Al2O3 catalysts were 27.2% and 31.5%, the lowest
reduction temperature of bimetallic catalysts corresponded to
high dispersion of Ni species.
In general, weak chemical interaction between metal ox-
ides and support leads to the lower temperature reduction
peaks observed, and this interaction could be tuned by addi-
tion of second component [24]. According to the XRD patterns
(Fig. 1), the bimetallic catalysts diffraction peaks were rela-
tively broad and weak compared with the monometallic cat-
alysts, suggesting bimetallic catalysts possessed a high
dispersion of active species over the Al2O3 support surface
[40]. In addition, Fig. 2 showed the TEM images of the bime-
tallic catalysts, Ni and Co species were small and uniformly
dispersed in the NieCo/Al2O3 and Co/Ni/Al2O3 catalysts while
the agglomerative phenomenon occurred on Ni/Co/Al2O3
sample. In fact, we observed the shift of the reduction peaks to
lower temperature on NieCo/Al2O3 and Co/Ni/Al2O3 catalysts.
The XPS measurements were also conducted to get the
catalyst surface information. All the samples were reduced at
600
C for 2 h. The XPS results of Ni2p spectra are shown in
Fig. 6aed. The binding energies at 852.3, 857, 869.9 and
875.3 eV were assigned to Ni2p3/2 (Ni), Ni2p3/2 (NiAl2O4), Ni2p1/2
(Ni), and Ni2p1/2 (NiAl2O4), respectively [48], suggesting that
Ni0 (Ni) and Ni2 (NiAl2O4) were Ni species on the catalyst
surface. It was clearly that metallic Ni was main Ni species,
which was supported by XRD results. The XPS results of Co2p
spectra were present in Fig. 6eeh. Correspondently, the
binding energies at 777.8, 780.7, 793 and 797.5 eV were
assigned to Co 2p3/2 (Co), Co 2p3/2 (CoAl2O4), Co 2p1/2 (Co), and
Co 2p1/2 (CoAl2O4), respectively. That indicated that metallic
Co and CoAl2O4 were surface Co species. Among them,
metallic Co is the main Co species. For NieCo/Al2O3, Co/Ni/
Al2O3 and Ni/Co/Al2O3 catalysts, the atomic ratios between Co
and Ni were 1.14, 1.25, and 0.52, respectively, indicating that
the Co atoms had enriched on the surface of the NieCo/Al2O3
[24], which was resulted from surface segregation during the
reduction process.
Coking behaviors of NieCo bimetallic catalysts for steam
reforming ethanol were studied by TG method. The TG curves
for the endurance-tested NieCo bimetallic catalysts were
shown in Fig. 7. As shown in Fig. 7, the initial step of weight
reducing occurred over temperature at about 100
C. Previous
reports [49] ascribed this phenomenon to thermal desorption
of H2O and/or adsorbed CO2. The oxidation of coke to CO and
CO2 occurred mainly at about 400e650
C [50]. From the TG, it
was observed that the order of the loss of weight of coke was
Fig. 7 e TG results of the endurance-tested (a) NieCo/Al2O3,
(b) Co/Ni/Al2O3 and (c) Ni/Co/Al2O3 catalysts.
NieCo/Al2O3 < Co/Ni/Al2O3 < Ni/Co/Al2O3. The amount of coke
might come from the Boudouard reaction and methane
decomposition [51]. The TG results revealed that the NieCo/
Al2O3 catalyst showed better carbon resistance, which could
result from high metal dispersion [39]. In addition, hydrogen
spillover could also account for above results. Hydrogen
spillover led to the reaction of surface carbon and hydrogen,
forming CH4 or CO2 [52]. This could clean the catalyst surface
and improve NieCo/Al2O3 catalyst stability. The NieCo/Al2O3
catalyst exhibited better catalyst stability owing to its high
resistance to coke formation partially, which was in accor-
dance with the stability experiment of the NieCo/Al2O3 cata-
lyst (Fig. 12).
Catalytic activity and stability
The activities of the catalysts were determined in terms of
conversions of ethanol and selectivities to the products as
shown in Fig. 8. For the steam reforming of ethanol, the
monometallic catalysts were also active, but it was clear that
they were inferior to bimetallic catalysts, both in terms of
conversions of ethanol and selectivities to the desired prod-
ucts. For bimetallic catalysts, they all showed good activity
and selectivity. However, the catalytic performances were
different for the bimetallic catalysts prepared by different
preparation methods. It could be seen that the ethanol con-
version followed the order NieCo/Al2O3 > Co/Ni/Al2O3 > Ni/
Co/Al2O3 in the temperature range of 250e450
C. However,
the conversions of bimetallic catalysts reached nearly 100% at
temperature above 450
C. As for H2 (Fig. 8b), at the reaction
temperature below 350
C, H2 selectivity of Ni/Co/Al2O3 cata-
lyst was superior to NieCo/Al2O3 and Co/Ni/Al2O3 catalysts,
which could be attributed to high activity of Ni for the cracking
of CeC bonds [53]. But when the temperature exceed 350
C,
the order of the H2 selectivity followed the order as NieCo/
Al2O3 > Co/Ni/Al2O3 > Ni/Co/Al2O3. Besides, the NieCo/Al2O3
catalyst produced the least amounts of by-products such as
 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 4 1 ( 2 0 1 6 ) 3 3 4 9 e3 3 6 2 3357

Fig. 8 e Ethanol conversions, H2, CO2, CO and CH4 selectivities versus reaction temperature. Catalysts: Ni/Al2O3, Co/Al2O3,
NieCo/Al2O3, Co/Ni/Al2O3 and Ni/Co/Al2O3 catalysts, S/C 13, LHSV 7.5 h1, P 1 atm.

CO and CH4 compared with other two bimetallic catalysts.
These results could also be assigned to its high metal disper-
sion, small metal particle size and large SBET of NieCo/Al2O3
catalyst. Because the dispersion of surface species and its
particles size on the support may play an indispensable role in
its catalytic performance [39,54], we identified the co-
impregnation catalyst (NieCo/Al2O3) possessed the best cat-
alytic performance. Then we tested the influences of reaction
temperature, LHSV, S/C and stability test on this catalyst.
Typical experimental results of NieCo/Al2O3 catalyst at
different temperatures were presented in Fig. 9, in which the
conversion of ethanol and selectivity to each product were
shown as a function of reaction temperature ranged from 250
to 650
C. It could be seen that the catalyst showed activity for
the reforming reactions even at the initial lower reaction
temperature of 250
C, where ethanol conversion attained
about 40%, along with a certain amount H2, CO2, CO and CH4
as the products. At 350
C, the conversion of ethanol was
3358 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 4 1 ( 2 0 1 6 ) 3 3 4 9 e3 3 6 2

Fig. 9 e Effects of reaction temperature on the steam Fig. 10 e Influence of LHSV on the conversions of ethanol
reforming reactions. Catalyst: NieCo/Al2O3, S/C 13, and selectivities to the products at 550
C. Catalyst: NieCo/
LHSV 7.5 h1, P 1 atm. Al2O3, T 550
C, S/C 13, P 1 atm.

68.7%, but it reached 100% with the temperature increase to decrease in CH4 selectivity was observed, however, along with
above 450
C. CO and CH4 were the main gaseous by-products the increase of LHSV, the CO selectivity increased remarkably,
among products. The temperature below 350
C, CO2 selec- which increased progressively from 4.4% at 3.8 h1 to 28.8% at
tivity decreased from 78.1% to 42.0% while CO and CH4 15 h1. As the LHSV increased, the velocity of steam and
selectivity gradually increased as increase of temperature. ethanol through the catalyst bed became larger and then the
The phenomenon might be caused by the decomposition of contact time of reactants which contacted with catalyst active
ethanol (CH3 CH2 OH/CH4 CO H2 ) and reverse water gas sites became shorter. Thus, the thermodynamic equilibrium
shift reaction (RWGS:CO2 H2 4CO H2 O), due to the low ef- of SRE was not achieved, resulting in lower ethanol conver-
ficiency of the catalyst for steam reforming at low reaction sion and desired products (H2 and CO2) selectivities. In addi-
temperature. As for CH4, when the temperature from 350 to tion, at higher LHSV the lower contact time, which was not
650
C, the CH4 selectivity decreased owing to the steam conducive to the adsorption and activation of steam and
reforming of CH4 (CH4 H2 O/3H2 CO). When the tempera- ethanol, therefore, the shift reaction could not work suffi-
ture exceeded 350
C, the catalyst exhibited good steam ciently, resulting in large amount of CO. As for CH4, we
reforming performance and promoted water gas shift reaction considered it come from methanation of carbon oxides. When
(CO H2 O4CO2 H2 ). Therefore, CO2 selectivity increased
and CO selectivity decreased, especially, at 550
C the H2 and
CO2 selectivity reached maximum value 92.2% and 85.2%,
respectively, while the CO selectivity reached minimum value
9.7%. However, when the temperature continuously increased
to 650
C, H2 and CO2 selectivity decreased while CO selectivity
increased, which were mainly attributed to reverse water gas
shift reaction (RWGS:CO2 H2 4CO H2 O), for water gas shift
was exothermic reaction and high temperature had negative
effect on the reaction. Although the domination of steam
reforming above 550
C suppresses the production of CH4, the
production of CO becomes significant, which also negatively
affects H2 production. In conclusion, at 550
C, the NieCo/
Al2O3 catalyst exhibited the best performance in terms of
catalytic activity and the desired products selectivities. Thus,
the following experiments would be carried out at 550
C.
The effects of LHSV on the catalytic performances of
NieCo/Al2O3 catalyst were investigated at 550
C, S/C 13.
Results were illustrated in Fig. 10. It could be observed that
LHSV affected the catalytic activity and selectivities signifi-
cantly. With LHSV increasing from 3.8 to 15.0 h1, ethanol Fig. 11 e Effects of S/C on the conversions of ethanol and
conversion decreased from 100% to 91.9%, together with a distribution of the products at 550
C. Catalyst: NieCo/
significant decrease in H2 and CO2 production. A slightly Al2O3: T 550
C, LHSV 7.5 h1, P 1 atm.
 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 4 1 ( 2 0 1 6 ) 3 3 4 9 e3 3 6 2
increased the LHSV, the limited catalyst surface was mainly
adsorbed by steam and ethanol. Consequently, the H2 and
carbon oxides had little chance to contact with the active sits
of catalyst to form CH4, leading to lower CH4 selectivity as the
increase of LHSV. These results showed that the proper LHSV
was 7.5 h1.
S/C was another key parameter ethanol steam reforming
reaction, influence of which on the steam reforming reaction
was investigated at 550
C. Results were given in Fig. 11. The
conversion of ethanol was totally converted during the whole
S/C ratios, but the selectivity of CO and CH4 decreased with the
increase of S/C ratios, conversely, the selectivities of H2 and
CO2 increased at higher S/C ratios [55,56]. At lower S/C ratios,
steam reforming rates was low [57] and large amounts of
byproducts were produced. The H2 selectivity was relatively
low owing to the significant amount of CO and CH4 generation.
It was clear that 1 mol of CH4 will result in 4 mol loss of H2,
similarly, 1 mol of CO will result in 1 mol loss of H2 [58].
Increasing S/C ratios remarkably promoted the efficiency of
steam reforming. The H2 and CO2 selectivities increased sub-
stantially. Meanwhile, the amounts of the by-products (CO
and CH4) decreased. At high S/C ratios, the high partial pres-
sure of steam in reactor promoted the adsorption of steam on
the active sites, and consequently suppressed the decompo-
sition of ethanol. The high steam pressure also promoted the
Fig. 12 e Stability tests of (a) NieCo/Al2O3, (b) Co/Ni/Al2O3 and (c) Ni/Co/Al2O3 catalysts: T 550
C, S/C 13, LHSV 7.5 h1,
P 1 atm.
3359
WGS reaction to remove the CO intermediate, resulting in
higher H2 and CO2 selectivity. In addition, the high steam
pressure inhibited methanation of carbon oxides, leading to
lower CH4 selectivity. Based on the above the results, it was
conclusion that properly increasing S/C ratio had a positive
effect on the catalytic activity and selectivities of the desired
products (H2 and CO2). Because using a large amount of steam
could be not conducive to steam reforming reaction. Vagia's
research [59] indicated that high excess of steam had a
negative influence on the energy consumption and on the size
of the units during the steam reforming reaction. Thus, the
optimum S/C was 13, meaning the entire catalyst works
efficiently.
Developing stable catalysts is one of the major issues in
steam reforming reactions [60]. To assess the stability of
NieCo/Al2O3, Co/Ni/Al2O3 and Ni/Co/Al2O3 catalysts, endur-
ance test was performed at severe experimental conditions
(T 550
C, LHSV 7.5 h1 and S/C 13) for 100 h. The results
were presented in Fig. 12. The complete ethanol conversion
was achieved on the NieCo/Al2O3 catalyst up to a period of
40 h, and after 40 h, the ethanol conversion decreased slightly.
But in general, the ethanol conversion keeps above 95%. The
H2, CO2, CO and CH4 selectivities remained constant about
90%, 88%, 8% and 1%, respectively during the reaction time
and no significant drop in selectivities were observed.
3360 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 4 1 ( 2 0 1 6 ) 3 3 4 9 e3 3 6 2
Conversely, Co/Ni/Al2O3 and Ni/Co/Al2O3 catalysts deacti-
vated drastically after 60 h and 30 h, respectively. The two
catalysts lost about 10.9% and 19% of their initial ethanol
conversion at the end of the test, respectively. And finally the
conversion reached about 89.1% and 81%, respectively. As for
the Co/Ni/Al2O3 catalyst, The CO and CH4 selectivities were
about 17.5% and 5.4%, respectively. As for Ni/Co/Al2O3, The CO
and CH4 selectivities were approximately at 28.8% and 11.3%,
respectively. Based on above results, it was found that the Co/
Ni/Al2O3 and Ni/Co/Al2O3 catalysts generated significant
amounts of CH4 and CO compared with NieCo/Al2O3 catalyst,
leading to large amounts of coke [51]. It was well known that
metal particle dispersion and size could have influence on
catalytic performance. High metal dispersion and small par-
ticle size could be resistance to carbon deposition. The TEM
(Fig. 2) and H2 chemisorption (Table 1) results showed that the
NieCo/Al2O3 catalyst possessed higher metal particle disper-
sion and smaller metal size. Therefore, with 100 h, the NieCo/
Al2O3 catalyst exhibited excellent catalyst stability owing to
lower carbon deposition. In addition, NieCo/Al2O3 catalyst
could also produce hydrogen spillover, which could also
inhibit carbon deposit and clean the catalyst surface to
improve NieCo/Al2O3 catalyst stability [52].
Conclusions
A series of bimetal NieCo catalysts had been prepared by co-
impregnation and sequential impregnation methods.
Comparing catalytic performance with characterization re-
sults, it was observed that the dispersion of catalyst surface
active species influenced remarkably catalytic behaviors. High
metal dispersion, low metal particle size and high SBET were
observed in co-impregnation catalyst (NieCo/Al2O3), rather
than sequential impregnation catalysts. These properties
could improve catalytic performance of SRE. In addition, the
deactivation of catalysts in SRE was attributed to the carbon
deposition that covers the active sites. High metal dispersion,
low metal particle size and high SBET could suppress carbon
deposition and thus improve the catalyst stability in SRE.
Temperature, liquid hourly space velocity and S/C had also
remarkable affected on the conversion of ethanol and distri-
bution of the products, especially at higher space velocity and
lower S/C ratios. Appropriate increase of the S/C ratios could
remarkably improve the catalytic activity and selectivity. At
an optimized experimental condition of T 550
C,
LHSV 7.5 h1 and S/C 13, the NieCo/Al2O3 catalyst
exhibited excellent catalytic performance and, most impor-
tantly, good long-term stability for hydrogen production.
Acknowledgments
This work has been supported by the 973 Program and 863
Program of Department of Sciences and Technology China
(Grant Nos. 2013CB632404 and 2012AA051501); by the National
Natural Science Foundation of China (Grant Nos. 21373245 and
21433007).
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