Sharma 2015

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 x x x ( 2 0 1 5 ) 1 e1 1
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Hydrogen generation by ethanol steam reforming

over Rh/Al2O3 and Rh/CeZrO2 catalysts:
A comparative study
Pankaj Kumar Sharma*, Navin Saxena, Prasun Kumar Roy, Arti Bhatt
Centre for Fire, Explosive and Environment Safety, Brig. S. K. Majumdar Marg, Delhi 110 054, India
article info
abstract
Article history:
Rhodium (Rh) catalysts supported over Al2O3 and CeZrO2 were developed and their activity
Received 30 August 2015
towards hydrogen generation through ethanol steam reforming (ESR) was compared.
Accepted 28 September 2015
Reforming reactions were performed over a range of temperatures (450 Ce600 C) and feed
Available online xxx
flow rates (0.1, 0.2 and 0.3 mL min1) at a constant ethanol-to-water molar ration of 1:6.
Although complete ethanol conversion could be effected, the H2 selectivity was found to be
Keywords:
higher for Rh/CeZrO2 catalyst (62.9%) as compared to Rh/Al2O3 (59.3%) under optimized
Rhodium catalysts
reaction conditions. The average exit flow rate was relatively higher for Rh/CeZrO2 catalyst
Ethanol steam reforming
(263 mL min1) as compared to Rh/Al2O3 catalyst (236 mL min1). In-situ Diffuse Reflec-
DRIFT
tance Infrared Fourier Transform Spectroscopy (DRIFTS) revealed the underlying mecha-
Mechanism
nism responsible for better performance of Rh/CeZrO2 catalyst over Rh/Al2O3 catalyst. Rh/
Coke
CeZrO2 catalyst was found to facilitate the decomposition of acetate intermediates,

through carbonates at lower temperatures. On the other hand, over Rh/Al2O3, reaction
proceeds through formation of both acetate as well as formate species both of which
decompose at much higher temperatures. The amount of coke deposited was also lower in
case of Rh/CeZrO2 catalyst (6.75 mmol gcatalyst 1 ) than over Rh/CeZrO2 catalyst
(10.57 mmol gcatalyst 1 ).
Copyright 2015, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights
reserved.
Introduction
Researchers are engaged worldwide to develop such alternative energy sources which are renewable and environment
friendly. Site specific, intermittent and unstable nature of
most of the renewable energy sources (viz. solar, wind, tidal,
biomass), presently being utilized, have catapulted hydrogen
as one of the most promising source of energy [1]. Due to its
high energy content per unit weight (~120 KJ/g) as well as
carbon free nature in that it ultimately oxidizes to water as the

sole combustion product, hydrogen has been identified as
ideal future energy carrier with high efficiency. In addition to
these properties, the technological advances in its utilization
(particularly in fuel cells) have also made hydrogen more
important as a new fuel [2].
Hydrogen can be generated from a variety of feed stocks by
different methods [3]. Bio-ethanol appears to be the most
promising one due to its low toxicity, easy handling, high
volumetric energy density and readily production from
* Corresponding author. Tel.: 91 11 23907146, 91 11 23907189; fax: 91 11 23819547.

E-mail addresses: [email protected], [email protected] (P.K. Sharma).
http://dx.doi.org/10.1016/j.ijhydene.2015.09.137
0360-3199/Copyright 2015, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.
Please cite this article in press as: Sharma PK, et al., Hydrogen generation by ethanol steam reforming over Rh/Al2O3 and Rh/CeZrO2
catalysts: A comparative study, International Journal of Hydrogen Energy (2015), http://dx.doi.org/10.1016/j.ijhydene.2015.09.137
renewable biomass [4,5]. Out of the several catalytic processes

(viz. steam reforming, partial oxidation and oxidative steam
reforming or auto-thermal reforming) investigated [6] for
hydrogen generation from ethanol, ethanol steam reforming
(ESR) leads to highest hydrogen yield [7,8]. It has therefore
become a research area of interest of researchers worldwide
[9] to develop suitable catalysts and in fact, there is ample
literature on catalytic ESR over different supported oxides
[6,7,9e12].
Catalyst preparation starts with the selection of a proper
support material followed by loading with a suitable active
metal which can be achieved by several methods. Although
various oxides of acidic, basic or redox nature have been utilized for catalysts synthesis, rhodium (Rh) has been reported
to be more active towards hydrogen production by catalytic
ESR reaction as compared to its Ru, Pd, Ni and Pt counterparts
[13,14]. Rh has been shown to be a suitable choice in breaking
CeC bond and thereby rendering increased selectivity towards C1 products (viz. CO2, CO and CH4) during catalytic ESR
[7,15]. Moreover, a recent Density Functional Theoretical (DFT)
study has also quantified the ability of Rh to reduce the activation energy for dissociation of CeH, CeC and CeO bonds,
present in ethanol [16]. This ability in turn has been attributed
to its high lying d band structure with empty d states, which
lowers the CeC bond dissociation barrier by stabilizing the
intermediates [17,18]. Similar to the active metals, support
materials have also been compared [14,19e25] in order to
achieve a suitable catalyst.
The aim of the present work is to compare the catalytic
activity of two Rh catalysts namely Rh/Al2O3 and Rh/CeZrO2,
prepared in the laboratory, for ESR reaction under varying
operating conditions. This comparison has been made based
on ethanol conversion, product distribution, selectivity and
average mass flow rate of exit product gases. Further, in view
of the fact that detailed studies on mechanistic aspects can go
a long way in improving catalyst design by establishing the
role of active metal as well as support in ESR, we have also
identified the nature of intermediates and products formed
over the two different catalyst surface, by performing in-situ
diffuse reflectance infrared Fourier transform spectroscopy
(DRIFTS) under steadyestate reaction conditions at different
temperatures.
Experimental
Materials
Nitrates of cerium (Ce(NO3)3.6H2O), zirconium (ZrO(NO3)2.xH2O) aluminium (Al(NO3)3.9H2O) and rhodium
(Rh(NO3)2.10% w/w in HNO3 solution) were used as the metal
precursors. These metal nitrates (Aldrich), urea (Aldrich) and
ethanol (E. Merck) were used without further purification.
Double distilled water was used throughout the course of the
experimental work.
Catalyst preparation
Mixed CeZrO2 oxide (with a CeO2:ZrO2 molar ratio of 70:30)
was synthesized according to the homogeneous urea co-
precipitation technique described previously for zirconia

based compositions [26]. Al2O3 was prepared by a combination of homogeneous urea precipitation technique and selfpropagating combustion synthesis (SPCS) technique [27].
Subsequently, Rh (5% w/w) was loaded on the support
following incipient wetness impregnation technique using
an acidic solution of Rh nitrate. Post-impregnation, the
sample was dried in an air oven at 90 C for 12 h and calcined
in a muffle furnace at 600 C for 6 h to yield Rh loaded
catalyst.
Catalyst characterization
Textural properties and porous nature of the as prepared
materials were studied by N2-adsorption-desorption experiments performed at 77 K on a Physisorption Analyzer
(Micromeritics ASAP 2010). Particle size distribution was
determined using a particle size analyser (DIPA 2000,
Donner).
Active metal surface area was determined using pulse CO
chemisorption studies, on a Chemisorption Analyzer (Micromeritics Chemisorb 2920), as per reported procedure [28,29]
and the average crystallite size of Rh-metal was calculated
using this active metal surface area, assuming cubic crystal
structure [29]. Prior to analysis, 50 mg of catalyst was equilibrated at 120 C for 2 h to remove volatiles, after which the
temperature was raised to 400 C in the presence of H2eAr
(10% v/v) for 3 h to ensure complete reduction. Subsequently,
the sample was cooled to 50 C under He purging, following
which a COeHe mixture (10%v/v) pulse was introduced every
2 min until complete saturation.
Temperature programmed reduction (TPR) studies were
performed to establish the reduction behavior of calcined
samples. For this purpose, accurately weighed amount
(~15 mg) of sample was subjected to a temperature program
under reducing atmosphere of H2 at 10 C min1 from 50 C to
1000 C.
In order to quantify the acidity of the prepared catalysts,
temperature programmed desorption (TPD) experiments were
performed on Chemisorption Analyzer using ammonia (NH3)
as the probe molecule. Accurately weighed amount (~50 mg)
of sample was pretreated for 30 min at 300 C to desorb impurities. Subsequently, NH3 was adsorbed into the sample bed
maintained isothermally at room temperature for a period of
120 min. Excess NH3 was eliminated by flowing He over the
sample. NH3 desorption was performed by heating the sample
at 10 C min1 up to 900 C.
Temperature programmed oxidation (TPO) studies were
also performed on the catalyst samples, spent in ESR reactions, by oxidizing the sample (~15 mg) from 50 C to 1000 C
at 10 C min1 under continuous flow of O2eHe (10%v/v)
mixture (25 ml min1).
Powder X-ray diffraction studies were carried out to identify the crystalline phases of prepared materials, on a Philips
PANanalytical Pro-HRXRD diffractometer using CuKa radiation (l 1.54
A). The samples were first pelletized and the data
were collected over the range 2q 20e80 . The average crystallite size were estimated by Scherrer equation using full
width at half maximum (FWHM) of corresponding highest
intensity diffraction peaks.
Performance evaluation of catalysts in ESR reaction

Performance of the prepared Rh/CeZrO2 and Rh/Al2O3 catalysts was evaluated towards ESR reaction at ambient pressure
at different temperatures (450, 500, 550 and 600 C) and feed
flow rates (0.1, 0.2, & 0.3 ml min1) with a feed of 1:6 ethanolto-water molar ratio. The reforming experiments were carried
out in an 8 mm (I.D.) packed bed vertical down-flow stainless
steel continuous flow tubular micro (CFTM) reactor (Microactivity Reference PID, Spain). Approximately 0.2 g of catalyst
(D50 50 mm) thoroughly mixed with ~2.8 g of inert material
(SiC) of same particle size, was loaded in the reactor and the
feed (ethanol water) was introduced into the reactor by
means of an HPLC pump, which regulated the flow rates. Prior
to entering the reactor, the feed solution was passed through
an evaporator (maintained at 200 C) to ensure complete
gasification of the feed stream. Reaction temperature was
measured using a sliding thermocouple placed within the
catalyst bed. Prior to the ESR reactions, catalysts were reduced
under H2 atmosphere (5 mL/min) for 2 h at 600 C. Subsequently, N2 was purged for 30 min at 10 mL/min to remove the
excess hydrogen at the same temperature.
After reforming, the exit stream was passed through a
condenser and gaseliquid separator to separate the gaseous
and liquid products before being subjected to GC analysis. The
composition of the gaseous stream was determined using an
online gas chromatograph (NuCon, India), equipped with a
thermal conductivity detector (TCD) and carbosieve column.
The concentration of ethanol in the liquid condensate was
determined using a Flame Ionization Detector (FID), after
separation through a Porapaq-Q column. The response factors
for all species were calculated, and the system was calibrated
with appropriate standards before each sample run. To evaluate the catalyst performance, ethanol conversion (XEtOH) and
selectivity to a product gas (Sx) were determined as follows:
XEtOH
Sx
MolesEtOH in MolesEtOH out

100
MolesEtOH in
for 2 h and subsequently cooled to room temperature under

inert atmosphere of Ar. A background spectrum of the
reduced catalyst was taken at room temperature before
introducing the reactant mixture.
For investigating in situ ethanol steam reforming reactions
over the surface of prepared catalysts, the catalyst surface
was saturated with reactant molecules by bubbling Ar gas
(~20 mL/min) through a saturator filled with the feed (ethanolto-water molar ratio 1:6) for 1 h at room temperature. DRIFT
spectra were then recorded at increasing temperatures 50 C e
600 C, while maintaining a continuous flow of the Ar (~20 ml/
min), through a saturator filled with the feed, over the entire
temperature range. For this purpose, the sample was heated
at 10 C/min and maintained for 5 min at the desired temperature prior to recording of spectra.
Results and discussion

Catalyst characterization
The surface area of the fresh samples of support materials,
before and after metal loading, were determined by performing nitrogen adsorptionedesorption experiments and the
obtained isotherms are presented in Fig. 1. The BET surface
areas of the supports before and after Rh loading are presented in Table 1. It can be observed that there is a substantial
difference in the BET surface areas, Al2O3 possessing
approximately six times larger surface area as compared to
CeZrO2. As expected, loading with Rh leads to a decrease in
the surface area of both the supports, the extent of decrease
being much larger for Al2O3. The pore size distribution was
determined using BarretteJoynereHalenda (BJH) method from
the desorption branch (inset, Fig. 1) and are presented in Table
1, which revealed that the materials exhibit a pore size distribution in the mesoporous range (2e50 nm). It can also be
noted that CeZrO2 and its Rh analog possess pores which are
bigger in size as compared to those of Al2O3 and its Rh analog.
Moles of gas x in gaseous product stream

Total moles of all gases in the gaseous product stream
100
In situ DRIFT analysis

DRIFT spectra were recorded using a Nicolet 8700 spectrometer equipped with a DTGS-TEC detector and the data were
analyzed on OMNIC software. A Harrick reaction chamber
(HVC-DRP) fitted with ZnSe windows served as the reaction
cell for in-situ catalytic ethanol steam reforming experiments.
This chamber, which is used in conjunction with the Praying
Mantis diffuse reflection accessory, allows diffuse reflection
measurements under controlled pressures and a wide range
of temperatures. A thermocouple mounted in this cell allows
direct measurement of sample temperature. Catalyst sample
(~50 mg) was placed inside the reaction cell and typically 128
scans were collected at a resolution of 4 cm1 and a data
spacing of 1.928 cm1 in order to achieve sufficient signal to
noise ratios. Prior to analysis, the sample was reduced under
H2 atmosphere by ramping at 10 C min1 and held at 600 C
Fig. 1 e Nitrogen adsorption-desorption isotherms of as

prepared support materials before and after metal loading
(Inset shows the pore size distribution from the BJH
desorption curve).
Table 1 e Physico-chemical properties of support materials before and after metal loading.
Support/
Catalyst
BET
surface area
(m2g1)
Pore
volume
(cm3g1)
Average
pore size
(nm)
CO
uptake
(mmolg1)
Active metal
dispersion
(%)
Active metal
surface area
(m2gmetal 1 )
Al2O3
Rh/Al2O3
CeZrO2
Rh/CeZrO2
261.64
9.91
42.05
36.81
0.23
0.10
0.160
0.122
3.35
2.62
11.89
10.64
e
102.27
e
351.77
e
25.96
e
93.05
e
114.26
e
409.58
a
b
a
Rh
average
particle size
(nm)
b
CeZrO2
Crystallite
size
(nm)
3.53
e
0.98
e
e
9.86
10.46
Calculated using CO pulse chemisorption.

Calculated using powder XRD.
The cumulative CO uptake, active metal dispersion and

metallic surface area are presented in Table 1. For metallic
surface area calculations, a stoichiometric factor of 1 was
employed, characteristic of linear chemisorption conformation (single CO per metal particle) [29]. It can be seen that the
cumulative CO uptake, active metal dispersion and metallic
surface area are higher for Rh/CeZrO2 catalyst as compared to
that for Rh/Al2O3. The average crystallite size of Rh-metal
(Table 1) was found to be higher for Rh/Al2O3 catalyst as
compared to that for Rh/CeZrO2 catalyst.
The crystalline phases of Al2O3 and CeZrO2 support both
before and after Rh loading were identified by x-ray diffraction
studies of fresh samples, and the patterns are presented in
Fig. 2. PXRD pattern confirms the existence of Al2O3 in the g
phase, (JCPDS file 050-0741), which is reported to exhibit high
surface area [30]. In the PXRD patterns of CeZrO2 and Rh/
CeZrO2, the diffraction peaks at 2q values 28.62, 33.27, 47.87,
56.67, and 77.32 are associated with (111), (200), (220), (311) and
(331) crystal planes of the cubic fluorite structure of CeZrO2.
Absence of the diffraction peaks associated with pure zirconia
together with a downward shift in the 2q values suggests the
formation of a solid solution (JCPDS# 28-0271) where the Ce
lattice positions are replaced with Zr atoms. The appearance
of peaks centered at 2q values 44.37 and 64.57 can be attributed to the formation of some amount of non-stoichiometric
oxides of Ce and Zr (JCPDS#88-2392). The average crystallite
sizes of CeZrO2 as determined using the Scherrer equation
indicates a slight increase in the crystallite size after Rh

loading (Table 1). The PXRD patterns of both Rh/Al2O3 and Rh/
CeZrO2 catalysts are dominated by the patterns of the support
materials only and the peaks pertaining to Rh species could
not be identified, probably due to amorphous nature of the
noble metal oxide.
The TPR profiles of fresh samples of both the support materials before and after Rh impregnation are presented in
Fig. 3. Alumina exhibits negligible H2 consumption in the
temperature range studied [31]. Therefore, the peaks present
in the TPR profile of Rh/Al2O3 catalyst may be assigned solely
to the reduction of different RhOx species present. The first
broad peak with a maximum at 157 C can be assigned to the
reduction of RhOx species of either different sizes or interacting differently with the support [32,33]: the bigger the
particle (or the stronger the interaction with the support), the
higher the reduction temperature. The next broad peak centred at around 410 C has been reported [34] for a Rhhydrotalcite type of material. Finally, a weak hump at very
high temperature, centred at 765 C can be attributed to the
reduction of [Rh(AlO2)y] type of rhodium aluminate species.
The reduction profile of CeZrO2 (Fig. 3) revealed two peaks.
Since ZrO2 is reportedly non-reducible under the conditions
employed in the present investigation [23,35], the first peak
with a maximum at 546 C may be assigned due to reduction
of surface layer of CeO2 and another centred at 761 C due to
reduction of CeO2 in bulk phase [36]. Higher intensity of the
Fig. 2 e Powder XRD patterns of support materials before

and after metal loading.
Fig. 3 e TPR profiles of support materials before and after

metal loading.
It has been reported [38] that the reaction pathway for ethanol
steam reforming, ESR (R1) [C2H5OH 3H2O / 6H2 2CO2] is
rather complex and comprises of several secondary reactions
(R2-R11), as summarized in Fig. 5. Being an endothermic reaction (DH 173.2 kJ mol1 at 298.15 K), ESR (R1) is favored at
high temperatures and low pressures. The reaction temperature can however be lowered by the choice of a suitable
catalyst. Two possible pathways for this reaction are dehydration of ethanol leading to ethylene (R5) and dehydrogenation of ethanol yielding acetaldehyde (R4). Since ethylene is
known to be a very strong coke precursor (R12), it is generally
preferred that the reaction should proceed via dehydrogenation route (R4).
To establish the relationship between process parameters

(temperature, pressure and feed composition) and the product
distribution, equilibrium thermodynamic analysis of ESR was
performed. Based on the results of this analysis and to evaluate the prepared Rh/Al2O3 and Rh/CeZrO2 catalysts for ESR at
various operating conditions, catalytic performance was
investigated under selected conditions of different temperatures (450, 500, 550 & 600 C) and feed flow rates (0.1, 0.2 &
0.3 ml/min) with a feed compositions of 1:6 ethanol-to-water
molar ratio. The results obtained in terms of ethanol conversion and product selectivities as a function of temperature at
different feed flow rates are presented in Table 2.
It can be observed that for ESR reaction catalyzed by both
the catalysts EtOH conversion increases with increasing
temperature and almost complete conversion could be achieved at T > 550 C. From Table 2 it is also clear that increasing
the feed flow rate led to a decrease in ethanol conversion at all
temperatures and this effect is more pronounced at lower
temperatures. Such a decrease in conversion may be understood in terms of progressive decrease in contact time between the reactants and the catalyst with increasing feed flow
rate. At higher temperatures this effect of decreasing contact
time is shrouded to a certain extent by the increased kinetic
energy of reactants.
Under the reaction conditions employed during ethanol
steam reforming, the exit product stream comprised only of
H2, CO2, CO and CH4. It may therefore be concluded that, as far
as EtOH conversion and product distribution is concerned,
both the Rh catalysts act independently of the nature of the
support material as reported earlier [19]. The selectivity of
these products as a function of temperature at different flow
rates (0.1, 0.2 and 0.3 ml.min1) are also presented in Table 2
together with the theoretically calculated values determined
using thermodynamic equilibrium conditions.
Another important observation worth noting from Table 2
is that differences between the predicted and experimental
selectivities are more pronounced at lower temperatures and
at T ~ 600 C, the selectivity values tend to come closer to each
other as well as to the equilibrium values.
Fig. 4 e Ammonia temperature programmed desorption

(NH3-TPD) profiles of support materials before and after
metal loading.
Fig. 5 e Schematic showing different reactions of ESR

process; DHr 0 values (kJ.mol1), given in parenthesis, have
been calculated for gaseous phase of reactants and
products.
low temperature peak indicates that replacement of Ce with

Zr renders a larger fraction of the lattice reducible at lower
temperatures [36]. In the TPR profile of Rh/CeZrO2 (Fig. 3), it
can be observed that the reduction of Rh takes place at much
lower temperature (~80 C) and the broad hump near 742 C
can be attributed to the reduction of bulk CeZrO2 [37]. It appears that the dispersed RhOx species interact very weakly
with the CeZrO2 support, which permits easy reduction of the
supported species resulting in the formation of metallic Rh.
The NH3-TPD profiles of Al2O3 and CeZrO2 are presented in
Fig. 4. The profiles are indicative of the considerable heterogeneity of the surface in terms of different acidic site types
and densities. The appearance of peak maxima for Al2O3 at
comparatively higher temperature indicates the presence of
acidic sites of higher strength in comparison to CeZrO2. In
addition, the acidity of Al2O3 (1.99 mmol g1) was found to be
1.5 times larger than that of CeZrO2 (mmol.g1), which indicate that Al2O3 contains acidic sites of not only higher
strength but also of higher density as compared to that of
CeZrO2. The acidity of Rh/Al2O3 (2.51 mmol g1) was found to
be much higher as compared to that of Rh/CeZrO2 catalyst
(mmol.g1).
Performance evaluation of Rh/Al2O3 and Rh/CeZrO2

catalysts towards ESR
49
93
145
65
129
189
66
140
202
85
170
263
3.34
18.99
69.65
8.01
7.92
21.14
65.79
5.14
22.94
59.53
2.75
14.78
43
73
125
58
121
177
62
126
180
75
158
236
23.95
1.23
24.08
50.74
30.45
26.57
22.78
22.35
18.93
17.6
14.01
13.34
12.26
7.53
7.37
7.4
1.55
2.62
3.44
2.17
2.55
3.35
3.3
4.18
4.69
5.03
5.84
6.55
26.72
27.0
26.58
27.59
26.68
26.8
25.6
25.0
25.0
24.5
24.4
24.0
41.28
43.81
47.2
47.88
51.83
52.25
57.09
57.48
58.05
62.7
62.79
62.9
99.05
96.04
90.04
99.2
96.42
95.1
99.87
99.62
97.21
99.91
99.97
99.99
30.56
25.4
22.74
23.72
21.86
19.67
11.36
13.13
15.25
10.05
8.11
8.41
b
600
550
500
450
Feed composition (EtOH-to-water molar ratio of 1:6).

Average mass flow rate of exit gases.
1.86
4.44
6.06
1.45
6.44
7.7
6.24
7.84
8.49
8.7
7.99
8.5
28.68
27.15
26.29
28.01
26.95
25.81
27.7
26.53
25.2
23.2
24.74
24.15
38.9
43.01
44.91
46.74
44.75
46.82
54.7
52.5
51.06
58.05
59.1
59.26
98.77
98.21
85.25
99.46
99.23
96.16
99.68
99.52
99.48
99.96
99.88
99.96
0.1
0.2
0.3
0.1
0.2
0.3
0.1
0.2
0.3
0.1
0.2
0.3
Rh/
CeZrO2
Rh/
Al2O3
SCH4 (%)
SCO (%)
SCO2 (%)
SH2 (%)
SCO2 (%)
XEtOH (%)
SH2 (%)
SCO2 (%)
SCO (%)
SCH4 (%)
XEtOH (%)
SH2 (%)
Rh/CeZrO2
Rh/Al2O3
Feed
flow rate
(mL/min)
Temp.
( C)
Table 2 e Activity and selectivity of Rh/Al2O3 and Rh/CeZrO2 towards ethanol steam reforming.
SCO (%)
SCH4 (%)
Thermodynamic equilibrium
AMFR
(mL/min)
In line with thermodynamic predictions, with increasing

temperature, selectivity towards H2 and CH4 should increase
and decrease respectively, irrespective of the type of catalyst
used for reforming. At 600 C, selectivity to H2 reaches its
maximum value while selectivity to CH4 reaches its minimum
value for all flow rates and the main products remain to be CO2
and CO together with H2, implying that most of the H-atoms of
ethanol participate in hydrogen production. Our study indicates that both the catalysts exhibit their optimal performance at 600 C~.
Further, thermodynamic analysis predicts that the selectivity to CO2 should decrease while to CO should increase with
increasing temperature. The same is evident from the experimental results of both the catalysts at all flow rates. This
concomitance indicates that as the temperature increases, in
view of the exothermic nature of WGS (R10) reaction, both the
catalysts prepared favors reverse of WGS reaction (R10) converting CO2 to CO, the extent of which being slightly higher for
Rh/Al2O3 catalysts.
The absence of any C2 product, particularly ethylene over
both the catalysts is indicative of the fact that during these
reaction conditions dehydrogenation route (R4) of ESR is being
favored over dehydration (R5) route and this may be attributed
to the inherent lower acidity of the both the supports prepared
as discussed above in characterization section under TPD. The
absence of acetaldehyde in the product stream may be
attributed to comparatively faster decomposition (R6) or
transformation (R7) of acetaldehyde as compared to its formation through dehydrogenation step (R4). The absence of
both ethylene as well as acetaldehyde in the reformer exit
stream lead to conclude that primarily ethanol steam
reforming (R2), which is a combination of ethanol decomposition (ED) (R3) and water gas shift (WGS) (R10) reaction, prevails over the surface of these catalysts. The increase in
selectivity towards H2 (Table 2) with increasing temperature,
at all flow rates, can be attributed to methane steam reforming
(MSR) (R8) reaction together with ED (R3) reaction. A simultaneous decrease in selectivity to CH4 (Table 2) supports this
fact.
Highest ethanol conversion (XEtOH) and selectivity towards
H2 (SH2) were obtained for both Rh/Al2O3 and Rh/CeZrO2 catalysts under optimal temperature of 600 C and flow rate of
0.3 ml.min1. It can be observed that although complete
conversion of ethanol is effected over both the catalysts, the
hydrogen selectivity of Rh/CeZrO2 is slightly higher (62.9%) as
compared to Rh/Al2O3 (59.3%), which suggests the superiority
of the former. This superiority is further supported by the
values of exit flow rates of exit gases summarized in Table 2,
which reveals that the amount of product gases is ~10% higher
in the presence of Rh/CeZrO2. In view of the complete conversion of ethanol over the surface of both the catalysts, it can
be concluded that the reactants undergo transformation to
other undesired carbonaceous species, e.g. coke, in the case of
Rh/Al2O3.
Reaction mechanism using in-situ DRIFT spectroscopy

In order to find out the possible reason behind the apparent
differences in the activity of Rh/Al2O3 and Rh/CeZrO2 catalysts, the sequence of reactions was followed by identifying
the intermediates and products formed over the surface of

both catalysts using in-situ DRIFT spectroscopic technique
during catalytic ESR reaction conditions. Different vibrational
modes of these species were assigned based on reported
studies. The changes in the DRIFT spectra, as a function of
temperature are presented in Fig. 6 (a and b).
A broad band (3650e3050 cm1) in the form of a hump is
observed in the DRIFT spectra (50 C), the intensity of which is
higher for Rh/CeZrO2. This band indicates the presence of
adsorbed water [39] on the surface of the catalysts. Disappearance of this band above 100 C is suggestive of either
thermal desorption of this water from the catalyst's surface or
its participation in reforming reactions. In the case of Rh/Al2O3
catalyst, this ease of water desorption may be an indicative
[40] of the lower acidity of the prepared Al2O3 support.
Weak absorptions centered at 1253 cm1 (Rh/Al2O3 catalyst) [41,42] and 1226 cm1 (Rh/CeZrO2 catalyst) [43] can be
attributed to the angular vibration [d(OH)] of physically
adsorbed ethanol molecules held to the Lewis acid sites of the
surfaces of both catalysts. This band disappears at temperatures close to 300 C. In view of the dipoleedipole interactions,
ethanol molecules are expected to exhibit acidebase interaction between H atoms of ethanol and OH sites (and/or coordinatively unsaturated O-sites) available on the support
surface. As a result of this interaction EtOH molecules further
undergo dissociation to result in surface ethoxide and water
(and/or hydroxyl species) [42,44e46]. The presence of these
ethoxide species was confirmed by the appearance of absorption peak at ~1086 cm1 and ~1052 cm1 in Rh/Al2O3
catalyst [22] and at ~1093 cm1 and ~1053 cm1 in Rh/CeZrO2
catalyst [41,47e50], which is indicative of ethoxide linkage

with the surface in both mono-dentate as well as bi-dentate
fashions, respectively. On increasing the temperature, these
bands gradually decrease in intensity and completely disappear above 400 C (Rh/Al2O3 catalyst) or 300 C (Rh/CeZrO2
catalyst). This may be attributed either to further transformation of ethoxides into other surface species or partly to
their thermal desorption in the form of ethanol from the
surface.
Other medium intensity bands observed in the case of Rh/
Al2O3 catalyst at lower temperatures may be assigned to CeH
stretching and bending vibrational modes of surface ethoxide/
ethanol species: 2972 cm1 [nas(CH3)], 2926 cm1 [nas(CH2)],
2896 cm1 [ns(CH3)], 1417 cm1 [ds(CH3)] and 1385 cm1 [u(CH2)]
[51]. Similarly in the case of Rh/CeZrO2 catalyst, weak intensity bands observed at 50 C may be assigned to CeH
stretching and bending vibrational modes of ethoxide/ethanol
species: 2980 cm1 [nas(CH3)], 2932 cm1 [nas(CH2)], 2902 cm1
[ns(CH3)], 2879 cm1 [ns(CH2)], 1457 cm1 [das(CH2)], 1420 cm1
[ds(CH3)] and 1388 cm1 [u(CH2)]. Intensity of these CeH bands
decreases in both the catalysts with increasing temperature
and finally disappears above 300 C.
For Rh/Al2O3 catalyst, bands pertaining to surface acetate
([na(OCO)] and [ns(OCO)] vibrations at 1552 and 1454 cm1,
respectively) [51] and formate ([na(OCO)] and [ns(OCO)] vibrations at 1586 and 1341 cm1, respectively) [52] are visible at
50 C. On the contrary, there appears a band pertaining to
surface acetyl (at 1635 cm1) species together with acetate
species ([na(OCO)] and [ns(OCO)] vibrations at 1582 and
1436 cm1, respectively) in the case of Rh/CeZrO2 catalyst. It
Fig. 6 e In-situ DRIFT analysis during ethanol steam reforming over (a) Rh/Al2O3; and (b) Rh/CeZrO2 catalysts.
appears that the presence of Rh over the surface of CeZrO2

induces successive removal of hydrogen atoms from ethoxide,
which in turn produces intermediates, particularly acetaldehyde and acetyl species, which on oxidation gives rise to
surface acetate species. For the Al2O3 supported catalysts ESR
reaction has been reported [53e55] to follow either acetate
driven or formate driven route which is governed by the
acidity of catalyst. Presence of both acetates and formate intermediates in the present case indicates that the nature of
catalyst favors both the routes.
Another visible difference in the DRIFT spectra of two
catalysts at 50 C is the presence of a weak intensity band at
2018 cm1 attributed to the linearly adsorbed CO species
[n(CO)linear] on the surface of Rh/CeZrO2 catalyst. Presence of
these species at such low temperatures clearly reveals higher
activity of Rh/CeZrO2 catalyst in the decomposition of ethanol
to form CO, CH4 and H2 after CeH and CeC bond fissions as
compared to its Rh/Al2O3 counterpart.
On increasing the temperature to 100 C, no appreciable
change in the DRIFT spectra of Rh/Al2O3 catalyst are apparent,
except slight increase in the intensity of bands corresponding
to surface acetates and formates. Similarly in case of Rh/
CeZrO2 catalyst, the intensity of acetate and linearly adsorbed
CO species increases but that of acetyl absorption decreases.
The [n(CO)linear] band blue shifts from 2018 cm1 to 2028 cm1
and a new band emerges at 1800 cm1, which may be attributed to the stretching vibrations of bridged CO species,
[n(CO)bridge]. This is again suggestive of ethanol decomposition
to H2, CO and CH4 through acetyl and/or acetaldehyde
intermediates.
In the presence of Rh/Al2O3 catalyst, at 200 C, intensity of
CeH vibrations related with ethoxide/ethanol decreases while
those of acetates and formates increase slightly with minor
shift in their positions. A new band, at 1407 cm1, develops
which may be assigned to CeH vibrations related with acetate
species. Important development appears in terms of new
bands at 2028, 1817 and 1675 cm1. Of these bands the former
two can be assigned to stretching vibrations of linearly
adsorbed and bridge-bonded surface CO species [51,55]
[n(CO)linear], [n(CO)bridge], respectively while the latter at
1675 cm1 has been attributed to [n(CO)acetyl] of acetyl species
[51]. Another noticeable observation at this temperature is the
appearance of vibrational bands pertaining to gaseous
methane (3019 cm1) and CO2 (2361 and 2322 cm1). Under
similar conditions, in the presence of Rh/CeZrO2 catalyst, the
intensity of bands pertaining to both linearly and bridged CO
species sharply increases. The acetyl band disappears
completely and the acetate bands become clearly visible
although with reduced intensity.
In the presence of Rh/Al2O3 catalyst, at 300 C, intensity of
various bands increases including CeH vibration of acetate
species. This band loses its intensity above 500 C with other
symmetric and asymmetric stretching vibrations of surface
acetate species. Further, increasing the temperature to 400 C
increases the intensity of gaseous methane and CO2 bands.
Intensity of linearly adsorbed CO vibration decreases and in
addition to bridge-bonded CO species, there appears multicoordinated CO species in the form of medium intensity
band at 1930 cm1. Two new bands also emerge at 3733 and
1768 cm1, which can be assigned to n(OeH) vibration of type
IIa hydroxyls [56] and n(CO) vibration of surface acetaldehydes

[51] respectively.
In the presence of Rh/CeZrO2 catalyst, at 300 C, bands
associated with gaseous methane (at 3016 cm1) [57] and CO2
(at 2362 and 2323 cm1) starts appearing together with a
decrease in acetate bands at 1582, 1436 and 1388 cm1. The
appearance of gaseous CH4 and CO2 may be a result of acetate
decomposition. The [n(CO)bridge] band red shifts from
1800 cm1 to 1779 cm1 and a new band in the form of
shoulder at 1868 cm1 appears, indicating presence of multicoordinated CO species [n(CO)multi]. At 400 C, intensity of
gaseous methane and CO2 bands increases, while the acetate
bands completely disappear. Additional bands at 1481 and
1365 cm1 were observed, which may be attributed to the
presence of surface carbonate CO3 2 species. It can be
concluded that surface acetates, post de-methanation,
convert into surface carbonates which on decomposition
gives rise to gaseous CO2 species. It is particularly interesting
to note the presence of three different kinds of surface CO
species on the catalyst surface.
In the DRIFT spectrum recorded at 500 C (not shown in Fig.
6), over Rh/Al2O3 catalyst, the acetyl band disappears instantaneously. The intensity of bands pertaining to gaseous
methane, surface acetates and formates decreases slightly.
Whereas, the intensity of bands representing gaseous CO2 and
type IIa hydroxyls increases. But over Rh/CeZrO2 catalyst, the
intensity of gaseous methane and CO2 bands decreases
slightly. At the same time the intensity of other bands associated with surface carbonate and CO species, remain largely
unaffected.
Increasing the temperature to 600 C brings a further increase in gaseous CO2 and type IIa hydroxyl bands in case of
Rh/Al2O3 catalyst. It also decreases the intensity of bands of
surface acetates, formates and gaseous methane. The only
observable species are CH4, CO2, and linearly adsorbed CO,
other than some carbonaceous species in the form of weak
bands in the region 1500e1400 cm1. Whereas over Rh/
CeZrO2, at 600 C, the intensity of bands associated with surface carbonate and CO species slightly decrease and the band
at 3016 cm1 [n(CH4)] disappears completely, which is indicative of higher activity of Rh/CeZrO2 catalyst in MSR reaction
(R8 or R9). A simultaneous decrease in intensity of gaseous
CO2 bands may be indicative of similar activity of this catalyst
in reverse WGS reaction (R10) predominating at higher temperatures. These facts support the decreasing selectivity towards CO2 and CH4 with increasing temperature during
ethanol steam reforming reaction over Rh/CeZrO2 catalyst.
Stability test and coke analysis

The catalysts prepared were evaluated for their application in
ESR for a period of 20 h time-on-stream and both were found
to exhibit negligible variation in activity in terms of ethanol
conversion and product selectivities. Quantitative and qualitative determination of the coke deposited over the surface of
both the spent catalysts (after 20 h of ESR at 600 C,
0.3 mL min1 and EtOH:H2O::1:6) was performed using TPO
analyses, the results of which are presented in Fig. 7. The TPO
profiles of spent Rh/Al2O3 and Rh/CeZrO2 catalysts exhibit a
broad peak, attributed to the oxidation of coke deposited, with
Fig. 7 e TPO profiles of coke deposited after 20 h run of ESR

reaction over the surface of rhodium catalysts supported
over CeZrO2 and Al2O3 materials.
conditions employed, ethylene was not detected in the product stream, irrespective of the nature of support system used.
Further, formation of different products has been explained
on the basis of in situ DRIFT study. Our studies revealed that
the ethanol molecules, in the presence of Rh, follow dehydrogenation route, after dissociative adsorption on the catalyst's surface in the form of ethoxides. These successively
dehydrogenate into acetaldehyde and acetyl species over the
surface of both the catalysts. In the presence of Al2O3, these
acetaldehyde and acetyl species through acetate or formate
driven route directly convert into H2, CO, CO2 and CH4. However, in the presence of Rh/CeZrO2, acetaldehyde and acetyl
species first oxidise into acetates, which on decomposition
through surface carbonates convert into H2, CO, CO2 and CH4.
The prepared catalyst was found to be stable up to 20 h in
catalytic ethanol steam reforming for hydrogen production.
Acknowledgement
a maximum roughly at 586 C and 615 C, respectively. The
temperature range associated with the oxidation is indicative
of the amorphous nature [26] of coke deposited mainly on the
support [58]. Total consumption of oxygen associated
with these peaks was 10.57 mmol gcatalyst 1 and
6.75 mmol gcatalyst 1 , for spent Rh/Al2O3 and Rh/CeZrO2 catalysts, respectively, which clearly indicates that the amount of
coke deposited over Rh/Al2O3 catalyst is larger (1.5 ) than for
spent Rh/CeZrO2 catalyst, which in turn may be attributed to
the comparatively acidic nature of Al2O3 [59]. Comparatively
lower amount of coke deposited on the surface of spent Rh/
CeZrO2 may also be ascribed to the oxygen storage capacity
(OSC) of the ceria, which has been reported to aid the gasification of coke deposited over active sites by activating the
oxidationereduction cycle. Further, the presence of zirconia
reportedly increases the OSC of ceria [36]. Coke formation
during catalytic ESR reportedly occurs by either decomposition of ethylene (R12) or dissociation of CO (R11), i.e Boudouard
reaction (Fig. 5) [60]. The absence of ethylene in the product
stream as well as during DRIFT studies, indicates the larger
contribution of Boudouard reaction (R11) towards coking
irrespective of the nature of support. The larger amount of
coke formed over the surface of Rh/Al2O3 also supports the
higher amount of gaseous products formed over Rh/CeZrO2 as
discussed earlier (Table 2).
Conclusion
The catalytic activity of Rh loaded over two different supports,
Al2O3 and CeZrO2, towards ethanol steam reforming was
studied. Both the Rh catalysts are efficient systems for
hydrogen generation by ESR reaction at 600 C. Complete
conversion of ethanol (99.9%) could be effected over the surface of both the catalysts, however the amount of gaseous
products, comprising primarily of H2, CO, CO2 and CH4 was
found to be higher in the case of Rh/CeZrO2. Further, the
amount of coke deposited over Rh/Al2O3 was Rh/CeZrO2 as
established by TPO studies. Under the experimental
The authors are grateful to Director, CFEES for providing the

laboratory facilities. The authors are also thankful to Akhilesh
Pandey, SSPL, Delhi for carrying out XRD analyses.
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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 x x x ( 2 0 1 5 ) 1 e1 1

Available online at www.sciencedirect.com

Hydrogen generation by ethanol steam reforming

Received 30 August 2015

Accepted 28 September 2015

Available online xxx

Ethanol steam reforming

CeZrO2 catalyst was found to facilitate the decomposition of acetate intermediates,

carbon free nature in that it ultimately oxidizes to water as the

* Corresponding author. Tel.: 91 11 23907146, 91 11 23907189; fax: 91 11 23819547.

renewable biomass [4,5]. Out of the several catalytic processes

precipitation technique described previously for zirconia

Performance evaluation of catalysts in ESR reaction

MolesEtOH in MolesEtOH out

for 2 h and subsequently cooled to room temperature under

Results and discussion

Moles of gas x in gaseous product stream

In situ DRIFT analysis

Fig. 1 e Nitrogen adsorption-desorption isotherms of as

Calculated using CO pulse chemisorption.

The cumulative CO uptake, active metal dispersion and

indicates a slight increase in the crystallite size after Rh

Fig. 2 e Powder XRD patterns of support materials before

Fig. 3 e TPR profiles of support materials before and after

To establish the relationship between process parameters

Fig. 4 e Ammonia temperature programmed desorption

Fig. 5 e Schematic showing different reactions of ESR

low temperature peak indicates that replacement of Ce with

Performance evaluation of Rh/Al2O3 and Rh/CeZrO2

Feed composition (EtOH-to-water molar ratio of 1:6).

In line with thermodynamic predictions, with increasing

Reaction mechanism using in-situ DRIFT spectroscopy

the intermediates and products formed over the surface of

catalyst [41,47e50], which is indicative of ethoxide linkage

appears that the presence of Rh over the surface of CeZrO2

IIa hydroxyls [56] and n(CO) vibration of surface acetaldehydes

Stability test and coke analysis

Fig. 7 e TPO profiles of coke deposited after 20 h run of ESR

The authors are grateful to Director, CFEES for providing the

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[12] Barroso M, Gomez M, Arrua L, Abello M. Effect of the

studied by temperature-programmed reduction-oxidation

zinger H, Ratnasamy P. Catalytic aluminas: surface

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