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The progress in water gas shift and steam reforming hydrogen production
technologies – A review

Article  in  International Journal of Hydrogen Energy · October 2014

DOI: 10.1016/j.ijhydene.2014.08.041

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Review

The progress in water gas shift and steam

reforming hydrogen production technologies e A
review

Trevor L. LeValley a, Anthony R. Richard a, Maohong Fan a,b,c,*

a
Department of Chemical and Petroleum Engineering, University of Wyoming, Laramie, WY 82071, USA
b
School of Energy Resources, University of Wyoming, Laramie, WY 82071, USA
c
School of Civil and Environmental Engineering, Georgia Institute of Technology, Atlanta, GA 30332, USA

article info abstract

Article history: Hydrogen has been widely considered a clean fuel of the future, with the highest mass
Received 11 March 2014 based energy density of known fuels. Water gas shift (WGS) and steam reforming (SR) are
Received in revised form the major reactions used for hydrogen production, and improved catalysts are essential to
30 July 2014 the future of the WGS and SR processes. Much progress in the different aspects of these
Accepted 4 August 2014 fields has been made recently, which includes approaches to preparation and character-
Available online 11 September 2014 ization, doping and promotion, as well as evaluation of catalysts, especially nanocatalysts.
Significant improvements have been realized in increasing the stability of the catalysts, the
Keywords: overall conversion of raw materials, and the hydrogen production selectivity. This review
Catalysis aims to introduce these hydrogen production processes, to present developments in these
Water gas shift areas, and discusses recent improvements that have made noteworthy impacts.
Steam reforming Copyright © 2014, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights
Carbon emission reduction reserved.
Hydrogen production

existing plants becomes a more viable option [2e5]. The

Introduction
Environmental concerns due to the release of greenhouse
gases have become an important issue which has spurred the
development and implementation of techniques to lessen the
impact of the combustion of fossil fuels [1]. Carbon dioxide
(CO2) sorption is one technology that can be applied to existing
plants producing large quantities of CO2, and as new cost-
effective technologies are developed, implementation into
release of CO2 can also be reduced by using alternative fuels
for energy production methods, with one example being the
use of hydrogen (H2), the production of which will be exam-
ined in this work.
Hydrogen is one of many fuel options for the future, and is
particularly attractive since it can be stored and transported
efficiently, and burns cleanly producing only water as a
byproduct. Although the production of hydrogen from fossil
fuels is unsustainable, a steady supply of renewable fuels

* Corresponding author. Department of Chemical and Petroleum Engineering, University of Wyoming, Laramie, WY 82071, USA. Tel.: þ1
307 766 5633.
E-mail address: mfan@uwyo.edu (M. Fan).
http://dx.doi.org/10.1016/j.ijhydene.2014.08.041
0360-3199/Copyright © 2014, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.
16984 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 9 ( 2 0 1 4 ) 1 6 9 8 3 e1 7 0 0 0
Fig. 1 e Illustration showing the overall process of
methane being converted to CO2 and H2 on a supported
metal catalyst. Many catalysts follow this same general
mechanism.
cannot be guaranteed at this time. Some promising emerging
renewable technologies for hydrogen production include
water splitting and biogas reforming. Water splitting sepa-
rates oxygen and hydrogen from water, breaking these bonds
through various techniques such as photoelectrochemical
splitting, photocatalysis, and electrolysis. Photo-
electrochemical (PEC) water splitting uses a PEC cell which
contains an anode coated with a photocatalyst, a cathode
coated with an electrocatalyst, and an electrolyte which
together generate electron hole pairs which carry out the
oxidation and reduction reactions [6e9]. The use of particulate
photocatalysts for direct conversion is also an important area
of research since it a one-step conversion process using a
single catalyst instead of two as with PEC [10]. As sunlight does
not have a high enough energy density to allow for high en-
ergy activities like transportation, these processes allow for
the storage and later use of the energy derived from the sun.
Another renewable source of hydrogen is biogas reforming,
with bioethanol derived from biomass serving as the typical
biogas [11e13]. The biomass is usually sourced from agricul-
tural byproducts, although some crops are grown solely for
the production of energy. Neither water splitting nor biogas
reforming is a mature technology that can be implemented in
a large scale format. Therefore to facilitate an immediate
reduction of greenhouse gas emissions, the production of
hydrogen from fossil fuels could supplement energy needs in
an environmentally conscious manner.
In order for hydrogen to become a viable fuel option, many
things must occur. Greater quantities must be produced
cleanly and efficiently, infrastructure must be implemented to
distribute hydrogen to customers, and production costs must
be lowered. Implementation of infrastructure by industry is
dependent on a steady and cost-effective supply, so the first
step forward in hydrogen energy production is development
of methods to ensure these demands can be met. To lower
production costs, catalysts must be found that can increase
the activity of the water gas shift (WGS) and steam reforma-
tion (SR) reactions, the main producers of hydrogen, while
also reducing problems found with conventional catalysts
including low conversion during startup and shutdown, high
energy demands, and deactivation [14e16].
Reforming of gaseous fuels is currently the main source of
hydrogen. In 2012, SR of methane (CH4) accounted for 95% of
hydrogen production in the United States [17]. The SR reaction
(R1) uses methane and steam to produce H2 and carbon
monoxide (CO). The CO can be further converted using the
WGS reaction (R2) to produce additional hydrogen by trans-
forming CO and steam into CO2 and H2. These reactions
together create an overall reaction (R3) that converts methane
into carbon dioxide and hydrogen [18,19].
CH4 þ H2 O/CO þ 3H2 (R1)
CO þ H2 O/CO2 þ H2 (R2)
CH4 þ 2H2 O/CO2 þ 4H2 (R3)
Shown in Fig. 1 is a diagram of the overall reaction over a
supported metal catalyst.
To achieve H2 production in large amounts, a catalyst must
be chosen that facilitates activity. Traditional catalysts are
intolerant of poisons and require special activation pro-
cedures [20]. Recently, much research has focused on cata-
lysts which can overcome these issues as well as achieve near
100% theoretical production of hydrogen in the WGS and SR
reactions, meanwhile increasing stability and lowering the
energy input [21,22].
While single metal systems on activated supports have
been widely studied and characterized, a more innovative
method of producing hydrogen through catalysis comes in the
form of bimetallics. Bimetallics can have capabilities which
are very different from those of the individual metals that
comprise them. These properties, as well as extremely
promising results from previous studies, have sparked an in-
crease in the amount of research focusing on bimetallic
compounds. Greater conversions and selectivity variants are
being achieved through the use of bimetallics with dispersed
nano-sized interacting particles. Conversely, the preparation
and characterization of these compounds are more difficult
due to the presence of additional metals [17]. A large number
of metal support combinations have been investigated, some
of which outperformed traditional catalysts by a large margin.
These new catalysts have increased not only the conversion of
desired gasses but also the selectivity, stability, and energy
expenditure required for conversion.
Reforming
Steam reforming can be used with many different feed stocks
including methane, ethane, methanol, ethanol, acetone and
higher hydrocarbons, and much research has been dedicated
to characterization of catalysts using these feed stocks. A
great deal of attention has been focused on methane due to
favorable byproduct formation as compared to other feeds
[17]. An increasing amount of research is being done on
methanol and ethanol, and a number of reaction mechanisms
have been proposed [23]. It has also been found that many
catalysts have activity in SR reactions for various feed stock
combinations [24]. The production of hydrogen through steam
reforming is normally done in multiple stages as can be seen
in the process train shown in Fig. 2.
Conventional SR catalysts are nickel on oxide supports,
which are typically aluminum or magnesium, but these
catalyst often have problems with carbon deposition [19].
 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 9 ( 2 0 1 4 ) 1 6 9 8 3 e1 7 0 0 0
Fig. 2 e Diagram showing the multiple stages for production of CO2 and H2, beginning with steam reforming.
Conventional SR catalysts normally involve steps after the
steam reforming reaction to remove CO. Typical steam
reforming reactions over nickel catalysts are performed at
high temperatures between 750 and 1450  C and 5 and 25 atm
due to the endothermic nature of the reaction [25,26].
Hydrogen production is most often done through reform-
ing, although much research has investigated syngas syn-
thesis producing higher ratios of CO/H2. There are a number of
ways to increase the ratio of CO/H2, but one of the most
common is dry reforming (DR) using CO2 to convert methane
[27e38]. The dry reforming reaction is shown in (R4).
CO2 þ CH4 /2H2 þ 2CO
Another common method is partial oxidation (PO), which
uses oxygen to convert methane [39e41]. Shown in (R5) is the
partial oxidation of methane reaction.
1 endothermic and therefore the reaction proceeds very poorly
O2 þ CH4 /2H2 þ CO
2
Various combinations of these reactions have been
studied for different conditions, feed stocks, and catalysts
resulting in widely varying activities and stabilities, but also
providing tunable H2/CO ratios. The combination of SR and
PO is known as auto thermal reforming (ATR). ATR is
employed in an effort to reduce the energy input of the SR
reaction by the addition of PO, an exothermic reaction [39].
DR and PO have been tested in combination, where oxygen is
added to reduce the energy input to the reaction [42]. The
combination of DR and SR can provide an extremely tunable
CO/H2 ratio depending on the amount of water added. The
addition of H2O to DR reaction can reduce some carbon
deposition problems [27,43]. The combination of the SR, DR,
and PO reactions called tri-reforming, put forth by Song et al.,
had very promising characteristics using CO2 and O2 to
compliment SR reactions, although in practice it was found
to give the best hydrogen output without the addition of O2 or
CO2 [44e47].
A side reaction that can occur during DR is the reverse
water gas shift reaction (RWGS) where CO2 in the feed reacts
with H2, and at high pressures this reaction can become
extremely prevalent. The RWGS reaction is shown in (R6).
CO2 þ H2 /H2 O þ CO
Because the RWGS reaction consumes H2, its occurrence in
DR can lead to lower H2 production, especially when
compared to SR of methane and WGS which can produce
higher concentrations of H2 under lower pressure conditions.
This problem with DR and RWGS has led to speculation that
future hydrogen production will not utilize DR [33].
16985
Steam reforming catalysts
Nickel SR catalyst
Nickel is the most widely studied metal for the SR reaction
because it is cheap and fairly active [48]. The use of nickel
based catalysts for steam reforming reactions has four major
issues as defined by Sehested: activity, sulfur poisoning, car-
bon formation, and sintering. First, Ni SR catalysts must be
active enough to reform the reaction mixture in the catalyst
volume. Second, sulfur containing feeds poison the catalysts
creating H2S compounds blocking active sites on the nickel
surface, so catalysts exposed to sulfur must be tolerant. Third,
(R4)
carbon formation causes a host of problems including block-
ing of active sites, increased pressure drop, and decreased
heat transfer. Fourth, sintering of nickel particles at high
temperatures causes growth and aggregation during opera-
tion, which lowers activity [49]. Steam reforming is extremely
(R5)
at low temperatures. One particular catalyst that was found to
have good performance at relatively low temperatures be-
tween 500 and 600  C is Ni/Zn/Al. Not only does Ni/Zn/Al
provide higher conversion than conventional catalysts in this
temperature range, it also has better stability from carbon
deposition and sintering due to the metal support [50].
Nickel catalysts alloyed with surface gold approximately 1
or 2 atoms deep has shown much better stability due to
decreased carbon formation [51]. Boron has been shown to
increase initial conversion and decrease deactivation of Ni/Al
catalysts by greatly decreasing coke formation resulting in a
stability increase which reduced deactivation after 10 h from
70% to 30%. Boron promoted Ni/Al catalysts have also shown
increased conversion of methane from 56% to 61% and
therefore increased overall activity [52]. Preparation of a Ni/
MgOeAl2O3 catalyst, which has known activity for SR, DR, and
PO of methane, was prepared using hydrotalcite (Mg6A-
l2(OH)16CO3) by Takeguchi et al. The catalyst showed high
activity while maintaining a higher resistance to coke for-
mation than commercial catalysts. The selectivity of coke
formation on this catalyst was as low as 0.2% at a steam to
carbon (S/C) ratio of 0.45 [53].
Nanoscale applications to SR catalysis with Ni have shown
promising results. Nanocrystal NiOeSiO2 supported by
(R6)
alumina was examined for use as an SR catalyst and achieved
conversion of 95.7% when employing a high S/C ratio of 3.5
and a temperature of 700  C with Ni loading of 10%. This
catalyst also showed fair activity for the WGS reaction indi-
cated by the high hydrogen ratio of 3.8 mol/mol methane
reformed [54]. Core-shell structured nanoparticles with a shell
of Ni (11 wt%) and an Si core were found to have moderately
16986 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 9 ( 2 0 1 4 ) 1 6 9 8 3 e1 7 0 0 0
Fig. 3 e Methanol conversion for Ni/Zn/Al catalysts tested
for SR. Ni/Zn ratio remains constant while wt% is
increased. Adapted from [62].
high activity with 85% conversion of methane at 750  C and an
S/C ratio of 3, although at a low S/C ratio of 1, 50% conversion
was obtained. The strong interaction between the metal shell
and the support provides for coking resistance, showing sta-
bility for at least four hours [55]. Nickel on a nanocrystalline
magnesium support has shown high stability and activity for
SR of methane. At an S/C ratio of 1, Ni loading of 7%, and a
temperature of 700  C this catalyst showed an initial activity of
greater than 90%, dropping to around 80% after 50 h which
shows that it is very stable. Higher nickel loading amounts
were found to increase carbon deposition and decrease sta-
bility [56].
Many Ni/Al catalysts have been examined for SR applica-
tions in combination with other metals. Ni/La/Al catalysts
using perovskite structured Ni/La demonstrated near full
conversion of methane at 850  C using an S/C ratio of 1.24, but
also showed very little carbon deposition which indicates that
the catalyst should have very good long-term stability [57]. Ni/
La catalysts have also shown high activity for ethanol refor-
mation and can have improved stability at increased tem-
peratures and high S/C ratios [58]. Ni/Al promoted by Mo was
found to have better stability than pure Ni/Al catalysts in a
study by Maluf and Assaf. When using a Ni/Al molar ratio of 3
with 0.05% Mo and an S/C ratio of 4, a stable conversion of
approximately 85% was obtained. With increased Mo loading
a decrease in catalyst area was found leading to a drop in
conversion. When using an S/C ratio of 2, rapid deactivation of
the catalyst occurred during the first three hours, but then
stabilized near 60% conversion demonstrating the S/C ratio
dependence of this catalyst [59].
Zinc SR catalyst
Zinc catalysts have known activity for SR and have shown
particularly high selectivity for CO2 in SR. Pd doping on ZnO
catalyst was shown to increase selectivity to between 95 and
99.6% for CO2 in SR of methanol with a conversion of 53% [60].
Methanol is often used for SR because of the lower reforming
temperatures [23,61]. Ni/Zn/Al catalysts have also been stud-
ied and are found to be selective against CO and have good
activity in steam methanol reforming. It was found that the
nickel and zinc content heavily influences the reforming re-
action, with higher Ni/Zn wt% showing better performance
[62]. These results are shown in Fig. 3.
Titanium zinc catalysts are another promising material for
methanol reforming and have been found to be active in these
reactions although the activity is dependent on catalyst
composition and zinc oxide dispersion. Ti/Zn showed 96%
selectivity to CO2 at temperatures of 400e450  C [63]. The ac-
tivity of Pd on ZnO was shown to be very high, but also very
dependent on dispersion of the Pd. A 16.7 wt% Pd/ZnO catalyst
with high dispersion showed full conversion of methanol at
300  C with low CO selectivity near 2% [64].
Carbon SR catalyst
The use of carbon in catalysis takes many forms. Activated
carbon (AC) has been studied as an alternative to conventional
catalysts mainly due to its porous structure, tunable surface
chemistry, and low cost [65]. The main disadvantage of acti-
vated carbon is that it cannot be used in hydrogenation re-
actions above 427  C or with oxygen above 227  C. This is due
to the fact that it can be gasified at these temperatures pro-
ducing CH4 or CO2. Activated carbon is often used as a support
for other catalysts due to its naturally high surface area and
porosity.
The use of carbon supports for SR of methanol is possible
because of the lower reaction temperature, typically between
200 and 400  C. SR of methanol can produce unfavorable
byproducts such as dimethyl ether, methyl formate, and
methane which must be selected against to achieve high
production of hydrogen [66]. Ma et al. tested Pt, Fe, Co, and Ni
on Mo/C, all of which exhibited increased activity compared to
Mo/C, with Pt demonstrating the best performance, fair sta-
bility, and 100% conversion of methanol at 200  C and an S/C
ratio of 1. Although deactivation at 200  C reduced conversion
to 60%, at 400  C manageable reduction to 85% occurred [67].
Mo/C catalysts have also been shown to have higher sulfur
tolerance during methanol reforming and are capable of
complete regeneration, although Pt/Mo/C was only able to be
partially regenerated [68]. Another study on Mo/C showed 40%
conversion of CH4 at 700  C, however, Mo/C with aluminum
achieved up to 95% conversion with no deactivation for 6 h at
the same temperature [69]. It has also been suggested by Saito
et al. that Mo/C catalysts are unstable below 8 bar which is not
always a problem because conventional SR catalysts are
typically run at high pressure [70]. A study by Setthapun et al.
examining many metals on Mo/C supports found that Pd/Mo/
C had the highest activity with greater than 99% conversion of
methanol, although selectivity of CO2 never exceeded 70%. It
was also found that noble metal doping achieved high activity
due to catalysis of the methanation reaction, while base metal
doping showed higher selectivity for CO2, which is attributed
to the noble metal catalyzing the methanation reaction [71].
Aluminum SR catalyst
Aluminum has been shown to increase activity for SR, espe-
cially when combined with magnesium. The addition of Mg to
conventional Ni/Al catalysts offers improved activity and
 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 9 ( 2 0 1 4 ) 1 6 9 8 3 e1 7 0 0 0
stability, and is capable of achieving this at low S/C ratios
which is preferable for higher energy efficiency. Ni/Mg/Al
prepared in multibubble sonoluminescence conditions and
tested at 750  C with an S/C ratio of 2 has been shown capable
of conversion as high as 97% with no loss of stability in 50 h.
This preparation method yielded coreeshell structures with a
surface layer of 3 nm [72]. Roh et al. examined Mg/Ni/Al cat-
alysts for combined steam and carbon dioxide reforming of
methane and observed conversion of methane in excess of
90%. The Mg addition also improved stability when compared
to Ni/Al catalyst which showed large amounts of coke for-
mation, causing deactivation with a drop in conversion from
75% to 30% in just over 5 h [73]. Shown in Fig. 4 is the con-
version of methane in the SR reaction for Ni/Al catalysts with
and without Mg, as well as Ni with Mg, Ce, and Zr for
comparison.
A study comparing Ni/Mg/AlO catalyst doped with either Pt
or Rh found that Pt has a greater effect on the activity on an
equivalent loading basis. It is thought that the Mg reacts with
the steam, forming a hydroxide which can then help aid in the
dissociation of CH4 at Pt active sites. Unlike the Pt which is
self-activating, the Rh doped catalysts must be activated by
reduction at high temperatures. Both Rh and Pt doped Ni/Mg/
AlO catalysts showed regenerative traits after reforming [74].
Rh supported Sr-hexaaluminate (SrAl11O19) has very good
stability, but also good activity for SR of methane with 45%
conversion at an S/C ratio of 1.4, 740  C, pressure of 0.4 atm
using 1% Rh [75].
Cerium SR catalyst
Ceria, or cerium oxide, has been researched extensively and
shows great potential for many types of hydrogen production
[76]. Ceria catalysts have been found to be extremely reduc-
ible, and the addition of transition or rare earth metals has
been shown to decrease the activation energy, providing a
ceria catalyst which can become extremely active for the
Fig. 4 e Graph showing the high conversion of methane at
800  C for Mg/Al catalyst doped with nickel as compared to
others tested. Stability can be seen as loss of conversion
over time. Adapted from [73].
16987
production of hydrogen. To achieve high activity in hydrogen
production, ceria catalysts must have small diameter particles
with high surface area, and well dispersed dopant [76]. Ceria
catalysts have increased oxygen storage capacity (OSC), a
measure of how much oxygen a support can lend to the re-
action, higher sulfur tolerance, and are more stable than
many catalysts without the addition of ceria [77]. The high
oxidation potential of ceria catalysts is also beneficial due to
the redox reaction mechanisms involved in (R2) [78].
Nickel and zirconium are two important metals that have
been used in combination with ceria for SR and have shown to
increase catalytic activity greatly. Nickel is used due to its low
cost and activity in SR, and the addition of ceria helps tradi-
tional nickel aluminum and noble metal catalysts by
increasing the rate of carbon gasification, thereby decreasing
deactivation by carbonaceous deposits [18,79]. The use of
zirconia in conjunction with ceria increases OSC, which is
extremely important to the stability of the catalyst [18]. Rh/
Ce.6/Zr.4O2 in the temperature range of 475e700  C, even at
low S/C ratios, provides excellent stability against carbon
formation [18]. Dong et al. examined Ni/Ce/Zr with various
percentages of Ni and found that 15% Ni can achieve methane
conversions of 97% with CO selectivity at 67% and an H2/CO
ratio of 4.7 [80]. At higher Ni percentages, the CeZrO support is
not as prevalent to lend its oxygen to the reaction. The in-
crease in nickel concentration vs. CH4 conversion is shown in
Fig. 5. The stability of Ni/Ce/Zr has been observed to be con-
stant for 12 h leading to an extremely active catalyst [39,80].
Carbon deposition can have a detrimental effect on activity
and is often suspected when high H2 to CO ratios are found in
the effluent stream. It was found by Laosiripojana and Assa-
bumrungrat that Ni/Ce/Zr catalysts with a 3 to 1 ratio of Ce to
Zr have higher stability against carbon formation compared to
Ni/Al catalysts [81]. Xu et al. found Ce/Ni/SiO2/Al2O3 with a Ce/
Ni ratio of 2 to have high H2 yield for over 110 h at a low S/C
ratio of 0.25 without measurable carbon deposition, where
traditional nickel catalysts completely lose activity in less
than 5 h under the same conditions. Ceria protects the nickel
Fig. 5 e Comparison of 3%e30% nickel doped CeeZrO2
catalysts at 750  C. Adapted from [80].
16988 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 9 ( 2 0 1 4 ) 1 6 9 8 3 e1 7 0 0 0

from deposition by catalyzing the removal of deposited car- The use of membranes for separation has been extensively
bon with H2O [82]. Deactivation of this catalyst was still researched, and SR reaction conditions mean that membranes
observed through sintering and sulfur poisoning [83]. If the need to be able to withstand high temperatures and pressures.
concentration of hydrogen is too high, the material may be However, as more catalysts are tested and found to have
reduced and lose activity which could become problematic in better behavior at lower temperatures and pressures, thin
industrial scale processes [81]. Roh et al. tested 15 wt % Ni on membranes become a more viable option [92]. The addition of
Ce0.8/Zr0.2 which performed extremely well at 600  C, high a membrane to methanol reforming has shown to increase
space velocity, and an S/C ratio of 1, conditions which would yield to near the theoretical limit for hydrogen production,
cause conventional nickel catalysts to fail [84]. and at low temperatures of around 300  C with 91% recovery of
The addition of Cu to Ni/Ce/Zr was tested as 1% Cu and 10% hydrogen [93].
Ni on ceria/zirconia and was found to have high activity for The addition of a membrane at high pressure can produce
ethanol reformation [85]. Other rare earth metals have also hydrogen at well above the equilibrium value, especially with
been combined with Ceria. Gd doped ceria SR catalysts do not combined SR and WGS reactions and the continued removal
have as high activity as many Ni or other ceria based catalysts, of hydrogen [33]. Shown in Fig. 6 is a comparison of conversion
however Gd/CeO has extremely high stability even with very between a packed bed reactor and a membrane reactor.
low S/C ratios as low as 0.6. Due to the stability at low S/C Catalytic nickel membranes have been used to convert
ratios, this catalyst could be a potential candidate for use in hydrogen while gasses are transported through the mem-
dry methane reforming [86]. La and Sm incorporated with Ce brane. Hydrogen flows faster than any other gas in the
have also been shown to increase thermal stability as well as membrane allowing for high conversion, and due to the
activity [79,87]. removal of the H2 product from the reactor, production of
In a study by Udani et al. copper oxide ceria catalysts were hydrogen above equilibrium values is possible. This mem-
found to have high activity for the steam reformation reaction brane showed good heat and mass transfer, as well as good
of methanol. A mixture of 70% copper to ceria showed higher stability at high temperatures [94].
activity than a commercial catalyst (Synetix 33e5) but less
initial stability with a decrease from 98% conversion of CO to
Microchannel reactors
90% in the first ten hours. After this initial period however, the
catalyst became extremely stable and did not lose conversion
Stationary hydrogen production is conventionally done in
during forty hours of operation [88].
fixed bed reactors with reforming catalysts [95]. One problem
Pd doping of Ce/Al can also increase activity, with the
with fixed bed reactors is the occurrence of low and high
support allowing for high dispersion of the Pd as shown by
temperature zones caused by poor heat transfer which can
Feio et al. While increasing the amount of ceria used can
lead to sintering in the hot areas and low conversion in the
reduce sintering, this can also lead to increased agglomera-
cold areas [96]. Fixed bed reactors also require longer times to
tion, thereby reducing dispersion. Catalysts with at least 12%
reach working conditions after startup [97]. Microchannel re-
ceria by weight have been shown to have higher catalytic
actors with extremely small inner diameters offer improved
activity [89]. In addition, reforming catalysts combining ceria
thermal regulation, which can improve activity, selectivity,
and alumina are more stable because the ceria stabilizes the
and stability, over traditional fixed bed reactors with the same
active phase of the alumina by combining to form CeAlO3 [87].
space velocity. Fabrication costs of typical metal micro-
For steam reforming of acetone, the use of a Co/Ce catalyst
channel reactors are high which necessitates new, less
has been investigated and has shown to have good activity,
but problems with stability. It is important for catalysts to be
selective towards H2 and CO2 to avoid methane formation
through the methanation reaction, which is undesirable;
however, in larger scale operations, methane that is produced
can be fed to a methane reformer or burned to produce energy
for production [90].
As many studies have found, Ce performs well as a base
catalyst for the SR reaction having high activity and stability,
but many conventional Ni/Al catalysts still have better per-
formance. Ce also catalyzes the WGS reaction that proceeds
during SR which gives high H2 to CO ratios and therefore has
its place among SR catalysts.

Product removal

SR being endothermic is greatly dependent on the equilibrium

of the reaction. Because of this, many reactor systems remove
one of the products, maintaining the driving force for the re-
action. For SR, this typically involves removing either hydrogen
via membrane, or CO2 via sorbent. Both methods are effective,
but greatly increase the cost of the reaction system [91].
Fig. 6 e This image shows the fractional methane
conversion in a packed bed reactor and a membrane
reactor against the equilibrium values. Adapted from [33].
 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 9 ( 2 0 1 4 ) 1 6 9 8 3 e1 7 0 0 0 16989

Table 1 e Catalytic metals for the SR reaction used in conjunction with varied supports and some of the specific properties
associated with them.
Catalyst Description T ( C) S/C ratio X (%) Source
Nickel
Ni/Zn/Al Low coke formation of <3.2%. CO selectivity of 99%. 600 2 e [50]
Ni/B/Al Boron improved stability and conversion. 800 1 61 [52]
Ni/Mg/Al Hydrotalcite used for preparation. Used fixed conversion. Very high coke 800 0.75 30 [53]
resistance.
Ni/Si/Al 10% Ni. H2/CH4 ratio of 3.8. 700 3.5 95.7 [54]
Ni/Si Core-shell structure nanoparticles with Si core and 11% Ni. 750 1.3 85 [55]
Ni/Mg Nanocrystalline structure with 7% Ni. Coke resistant and stable to 50 h. 700 1 77 [56]
Ni/La High activity and selectivity toward H2 for ethanol reforming. 800 2 100 [58]
Ni/La/Al Perovskite structured Ni/La. High stability. 850 1.24 100 [57]
NI/La/Ca Perovskite-derived catalyst for glycerol reforming. Deactivation by coking. 550 3 100 [100]
Ni/Al/Mo Ni/Al ratio of 3 and 0.05 wt% Mo. 700 4 85 [59]
Zinc
Pd/Zn Very high selectivity to CO2 in methanol reforming. 886 1 53 [60]
Ni/Al/Zn 8 wt% Ni and 20 wt% Zn had best activity. 500 1.4 100 [62]
Ti/Zn 96% selectivity to CO2. 450 1.1 100 [63]
Pd/Zn Methanol SR. Low CO selectivity of 2%. 300 1.8 100 [64]
Carbon
Fe/C Coal char from gasification cheap, recoverable, heavy deactivation by 500 5 e [15]
sulfur.
Pt/Ce/C Increased activity, decreased deactivation. H2O/ethanol preparation. 350 0.5 90 [101]
Pt/C Nanotubes, promoted by Na, high conversion at high S/C. 400 5 >95 [102]
Pt/Mo/C Carbide, higher activity than traditional catalysts at reaction conditions. 295 5.5 30 [103,104]
Aluminum
Mg/Ni/Al Core-shell structure, 10% Ni. Very good stability over first 50 h. 750 2 97 [72]
Mg/Ni/Al Combined steam and CO2 reforming. Low coke formation. 800 2 90 [73]
Pt/Ni/Mg/Al Very good startup/shutdown activity. 0.5% Pt. 700 2 95 [74]
Rh/Sr/Al 1% Rh on Sr-hexaaluminate. High stability due to structure. Pressure of 740 1.4 45 [75]
0.4 atm.
Cerium
Ni/Zr/Ce CO selectivity of 67%. 15% Ni. Extremely stable due to increased OSC. 750 3 97 [80,84]
Rh/Zr/Ce High conversion at lower temperature with low S/C ratio. 700 4 95.2 [18]
Ni/Si/Al/Ce Low carbon formation, even at lower S/C ratios. 800 1.3 70 [82]
Ni/Cu/Zr/Ce 1% Cu, 10% Ni. Ethanol SR. 400 10 43 [85]
Gd/Ce Good for high temperatures, resistant to carbon deposition. 900 5.5 80 [86]
Pt/Ce/La/Al High activity and stability. 500 3 e [79]
Pt/Ni/Ce Ethanol reforming. High carbon deposition. High byproduct formation. 350 3 100 [105]
2.8% Pt, 9.8% Ni
Cu/Ce 70% Cu, initial minor deactivation stabilized after ~20 h. 300 1.5 100 [88]
Zirconium
Cu/Zn/Zr Methanol reforming. High RWGS activity 260 1.2 100 [106]
Cu/Zn/Ce/Zr Methanol reforming. Lower RWGS activity. Low CO selectivity of 1.4%. No 260 1.2 100 [106]
deactivation for 360 h.
Ni/Ca/Zr Ethanol reforming. Ca deters coking. 500 3 100 [107]

expensive materials to reduce production costs. Ceramic
microchannel reactors were found to have heat transfer co-
efficients fairly similar to metal, but at lower production costs
[98]. Microchannel reactors are also susceptible to hot spots,
but one proposed solution is the use of a stripe configuration
on the combustion catalyst layer, which proved to minimize
these hot spots [99].
Overview and vision of SR catalysts
being produced. Advancements in catalyst preparation,
composition, and reactor conditions, including microchannel
reactors and membranes, allow larger than equilibrium
values of hydrogen from a single reactor. Future catalysts may
be designed and tailored to be selective for CO2 and not CO
reducing the need for two WGS reactors thereby decreasing
costs for the production of hydrogen. In addition, materials
with activity in both reforming and WGS may be combined at
temperatures intermediate to both reactions.

Table 1 is a summary of the aforementioned reforming cata-

lysts along with additional notable catalysts. Water gas shift catalysts
SR of methane has a large role to play in the future of
hydrogen production, due to the availability of natural gas and The WGS reaction is normally used after reforming or gasifi-
the extremely selective and active catalysts that are currently cation processes. Coal gasification, instead of combustion, is
16990 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 9 ( 2 0 1 4 ) 1 6 9 8 3 e1 7 0 0 0
Fig. 7 e Surface plots showing CO conversion versus
temperature for LTSR, HTSR, and the combination of both
[116].
considered to be a preferred method for electricity generation,
with new gasification methods recently emerging [108e112].
The common products of gasification and reforming include
CO, which the WGS reaction converts while producing addi-
tional hydrogen, making WGS very important for increased
hydrogen production. WGS is an overall exothermic system
and catalysts normally involve a few common characteristics
including available oxygen vacancies, activity in the dissoci-
ation of water, and low CO adsorption strength [113]. WGS
catalysts have extremely different characteristics under
different preparation and reaction conditions, and with the
implementation of different promoters. WGS catalysts being
characterized now have the potential to become new indus-
trial catalysts [114].
The WGS reaction is reversible and thermal equilibrium is
reached faster at higher temperatures. Low temperature cat-
alysts provide high conversions, but are kinetically limited so
the reaction proceeds slowly [115]. Due to the equilibrium
constraints, WGS is normally done in two reactors: a high
temperature shift reactor (HTSR) and a low temperature shift
reactor (LTSR). Chen et al. studied WGS as a two part system
using a computer simulation, and it was found that a two
reactor system at a wide variety of temperatures gave higher
conversions than a one reactor system [116]. The result of this
study is shown in Fig. 7.
The most prevalent catalyst used in industry for the high
temperature shift (HTS) reaction is iron/chromium. HTS cata-
lysts normally function between 310  C and 450  C and
25e35 bar [117]. Chromium helps to reduce sintering although
deactivation still occurs necessitating replacement of the
catalyst within 2e5 years [115]. The most prevalent catalyst
used in industry for the low temperature shift (LTS) reaction is
copper/zinc on aluminum oxide. LTS catalysts normally func-
tion between 210  C and 240  C and are capable of converting
nearly all fed CO. Pre-removal of sulfur to below 100 ppb is
required as it can quickly poison the catalyst. Deactivation
causes catalyst life to be limited to 2e4 years [115].
Iron WGS catalyst
For HTS where temperatures exceed 300  C, an iron/chro-
mium catalyst is typically used. The addition of low percent-
ages, about 8%, of chromium to the iron helps to stabilize the
catalyst and to extend catalyst life by decreasing sintering
[118]. Sintering, or aggregation of particles at high tempera-
ture, causes a decrease in surface area and a corresponding
increase in pore size decreasing overall catalyst activity.
Conventional iron chromium catalysts deactivate quickly
during initial use but stabilize after approximately 1000 h
[119]. The concentration leaving a conventional Fe/Cr WGS
reactor can be as low as 3% CO. The concentration of hydrogen
fed to this catalytic system must be minimized due to the
extremely exothermic nature of the reduction reaction which
can cause temperature spiking and subsequent sintering
[115]. While adding chromium increases conversion effi-
ciency, it also increases the toxicity which translates to higher
disposal cost of spent catalyst.
Iron based catalysts have been known to have activity in the
WGS reactions for many years. Iron catalysts often start as Fe2O3
and are reduced to Fe3O4 during the reaction, which is found to
be the active phase [15]. One of the first improvements to iron
catalysts was the use of a less toxic metal while still achieving
the high conversion and stability that chromium provided. The
promotion of varied amounts of Cu, Pb, Ba, Ag, or Hg all show
increased catalytic activity with the order of activity being
Hg > Ag, Ba > Cu > Pb [118]. Thorium, like chromium, decreases
sintering and increases activity but with reduced toxicity
compared to chromium. Because thorium poisons the active
sites of the iron, the optimum amount must be used [120]. Lead
has been shown to increase catalytic activity by many parties
and is often added to iron chromium catalysts in small amounts.
The lead and iron in high oxidation states react together and
produce greater activity in the WGS reaction [121].
A novel type of iron catalyst involving single atom doping
using Ir was investigated by Lin et al. Single atom doping in-
creases the strength of the activity an order of magnitude
higher than with nanoparticle doping. This has implications
for the future because single atom doping not only increases
activity and conversion, but it also uses less metal for doping
which greatly decreases material costs. Single atoms in small
loading situations can provide approximately 70% of the total
activity compared to 30% for clusters of nanoparticles. Single
atom doping may even lead to an increase in OSC for iron
 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 9 ( 2 0 1 4 ) 1 6 9 8 3 e1 7 0 0 0 16991

supports, improving yet another vital component to the WGS carbon support showed higher activity than pure Pt/Ce at high
catalyst [122]. Investigations on using skeletal iron, particle temperatures. The Pt/Ce/C catalyst achieved 90% CO conver-
leeching kinetics, and preparation methods have also sion at 350  C, with little decrease in activity observed over
improved the performance of Fe/Cr catalysts [123]. 120 h [101]. Conversion as a function of temperature for these
catalysts is shown in Fig. 9.
Serrano-Ruiz et al. found that using an impregnation
Zinc WGS catalyst
method for deposition of CeO2 on AC support results in
extremely high particle dispersion with particles sizes
Copper/zinc catalysts are often used for low temperature ap-
remaining very small, between 2 and 4 nm [127]. These highly
plications, usually below 250  C, and have high selectivity for
dispersed ceria nanoparticles on an AC support may have
the WGS reaction allowing for a high conversion especially at
extremely high activity, especially if paired with an additional
low intake concentrations [76,124]. However, they are easily
dopant metal. Carbon nanotubes, doped with Pt and promoted
poisoned by sulfur found in most fossil fuels, are very sensi-
with Na, have also been studied for the LTS reaction. The
tive to temperature, and are pyrophoric in air. Preeactivation
addition of a sodium promoter activates the platinum for the
of Cu/Zn catalysts is a difficult process, which, along with the
WGS reaction, which provides for an extremely high conver-
aforementioned difficulties, has fueled research for alterna-
sion approaching 100% at 300  C with a high S/C ratio of 5 [102].
tive LTS catalysts. Cu/Zn catalysts are normally prepared
Yu et al. studied a catalyst produced by using char, a
using co-precipitation and have been shown to change cata-
product of coal gasification, and doping it with iron. During
lyst activity depending not only on the co-precipitation
the WGS reaction, creation of magnetite (Fe3O4) occurs in the
method but also the co-precipitation time [125].
iron sample which catalyzes the WGS reaction allowing it to
Raney Copper catalysts use Al/Zn supports and are pre-
occur at just above 300  C. This catalyst has the distinct
pared with different techniques than conventional catalysts.
advantage of being cheap to produce and easy to disposed of
While the co-precipitation method is used with conventional
by regasification, during which much of the iron can be
catalysts, impregnation and leeching are used in this instance.
recovered. The main disadvantage is deactivation due to sul-
The catalysts composition, pore size, and surface area are
fur. If H2S is present in large amounts, FeS is formed releasing
dependent on leeching conditions. Although these catalysts
hydrogen gas and causing subsequent deactivation. When the
showed high activity, they have stability issues. It is important
catalyst is being regenerated the sulfur is liberated again,
for all catalysts that conversion remain steady for many
either releasing potentially harmful sulfur compounds into
hours, otherwise the catalysts must be changed frequently to
the air or allowing the continued deactivation of the catalyst.
allow for continuous efficient operation [126]. Fig. 8 shows the
One solution is removal of a portion of the catalyst to prevent
stability of Raney copper catalysts over 800 h with various
sulfur buildup [15].
preparation times, and it can be seen that much of the con-
Carbides have also been examined for WGS catalyst ap-
version is lost within that time with little indication of
plications, with Mo/C garnering much attention. Mo/C cata-
reaching a steady conversion.
lysts were found to have higher activity and better sulfur
resistance than conventional catalysts, with no deactivation
Carbon WGS catalyst

Buitrago et al. examined platinum on carbon supports be-

tween 200 and 350  C and found no activity, but Pt/Ce with

Fig. 9 e Plot showing the conversion against temperature

of Pt catalysts on ceria, carbon, and combined ceria and
Fig. 8 e Stability of Raney copper catalysts prepared carbon supports. The addition of carbon to the PteCe
through a leaching process of various leaching times. catalyst shows higher activity at high temperatures.
Adapted from [126]. Adapted from [101].
16992 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 9 ( 2 0 1 4 ) 1 6 9 8 3 e1 7 0 0 0
for 48 h [33,104]. The addition of Co to Mo/C was studied by
Nagai and Matsuda who found that at 180  C Co/Mo/C was
found to have better activity than conventional LTS catalysts,
but after around 5 h the activity dropped below that of con-
ventional catalysts [128]. When compared to Pt/CeO2 and Pt/
TiO2, Pt/Mo/C catalysts were found to have higher activity,
which is due to an increased number of active sites around the
Pt particles [103]. Deactivation of Mo/C catalyst was examined
using XPS and it is proposed that deactivation is due to
changing states of the Mo molecule on the surface of the
catalyst [129].
Aluminum WGS catalyst
Cu/Zn/Al catalysts used in LTS between 200  C and 240  C can
convert nearly 100% of CO to CO2 though there are large
problems with sintering and poisoning [115]. The rapid
poisoning by sulfur means that a non-sulfur feed must be
used or sulfur must be removed in a costly removal step [115].
Au/Al catalysts have also been previously investigated, but
were shown to have poor activity for the WGS reaction [130].
Nickel based catalysts promoted with potassium on
aluminum supports have demonstrated higher selectivity to-
wards CO2 and are more active than traditional nickel cata-
lysts [131]. Potassium impregnated nickel has also been
shown to reduce the amount of carbon deposition compared
to traditional nickel catalysts. Nickel WGS catalysts often
catalyze the methanation reaction which consumes hydrogen
and therefore severely decreases total hydrogen production
[132]. A potassium promoted nickel catalyst alternatively
produced almost no methane while maintaining high con-
version of CO [131]. Many nickel catalysts are greatly affected
by the pretreatment method. Nickel catalysts pretreated with
an oxidation-reduction process have shown increased
methanation. This is thought to be due to the reorganization
of the catalyst surface structure and the surface oxidative
substances, especially the NiO which subsequently weakens
the CeO bonds allowing active carbon species to form
methane [132].
Rare earth oxides have been known to provide positive
attributes to catalysis for many years [133]. Rare earth metal
oxide catalysts alter the crystal structure allowing for the ac-
tivity and selectivity to be tuned. For example, with the
addition of lanthanum a more energetically favorable crystal
structure can be formed. This change can lower activation
energy and change how the catalyst reacts at different tem-
peratures [133].
Cerium WGS catalyst
The catalytic properties of gold have led to investigations on
its addition to ceria support, although gold was originally
thought to be inactive for the WGS reaction. Early gold cata-
lysts were found to be inactive due to large particle sizes, but
for particles under 5 nm, activity for CO conversion at very low
temperatures on various supports was observed [134]. The
average size of the gold particles is tunable through calcina-
tion at different temperatures which controls sintering
thereby increasing the gold particles to the desired size
[135,136]. Tsubota et al. found that calcination at 400  C
yielded an average gold particle size of 4.6 nm, while calci-
nation at 650  C increased the average particle size to 9.2 nm,
above the active particle size threshold [137].
Variations in ceria particle size can also have a large effect
on the WGS reaction activity. The size of the ceria particles
affects the amount of oxygen storage available to the reaction;
however, small ceria particles with large gold particles are
capable of achieving high conversion where similar sized ceria
particles alone offer almost no conversion. There is a corre-
lation between particle sizes of both the metal and the ceria
support, and the activity. Therefore it is crucial to control both
the size of the metal and the ceria support in all preparation
methods [138]. Deactivation of gold-ceria catalysts was
investigated by Kim and Thompson and it was found that the
catalyst could be fully regenerated through calcination,
removing carbonaceous deposits blocking active sites. Mini-
mization of oxygen deficiency through additional treatment of
the ceria may be able to deter carbonaceous deposit forma-
tion, extending catalyst lifetime [22].
The addition of rare earth metals to ceria catalyst has been
widely studied with much attention focused on lanthanum.
Rare earth metals are well known for their catalytic effects,
and when added to ceria catalyst, provide improved thermal
stability and increased activity [139]. Wang et al. investigated a
ceria/zirconium catalyst doped with rare earth metals La, Nd,
Pr, Sm, and Y and found that all of the metals increased ac-
tivity and selectivity with La, Nd, and Pr performing best [140].
Rare earth metal doping has also been applied to gold/ceria
catalyst, where doping with lanthanum and gadolinium have
both shown increased activity [76].
Another important addition to cerium is zirconium, which
has been investigated for a number of reasons, one being the
formation of carbonate on the surface of the ceria. Hilaire et al.
suggested that the tendency of ceria to stabilize carbonate on
its surface could be inhibited through the addition of another
metal which does not stabilize carbonate formation [141].
These desired properties make zirconium a favorable option.
When Zr is added to Ce, it allows for much higher mobility of
the surface, and more oxygen transfer sites to pass the
reducing effect to molecules deeper in the material [139].
Zirconium facilitates lower-energy bonding between oxygen
molecules when compared to pure ceria. These weakly
bonded oxygen molecules allow for higher reducibility and
thereby higher OSC, which has been found to be integral to
formation of products in the WGS reaction [142].
Ce/Zr catalysts have been doped with many different rare
earth metals, typically showing improved conversion of all
reactants [139]. Studies on Ce/Zr preparation methods include
drying time, preparation temperatures, precipitation steps,
and different starting nitrates of ceria which are typically
ammonia ceria nitrate and ceria nitrate. Changing the starting
material has a considerable impact, varying greatly the
structural properties of the final solid. This could possibly
explain the large variations in results for many of the catalysts
in literature [143].
Hori et al. examined the effect of preparation on OSC and
found that a catalyst with a 25% Zr to 75% Ce ratio, and
precipitated from hydroxides, gave very good results [143,144].
The OSC of these Ce/Zr catalysts with varying ratios of Ce to Zr
is shown in Fig. 10. Jiang et al. found that yttrium and
 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 9 ( 2 0 1 4 ) 1 6 9 8 3 e1 7 0 0 0 16993

lanthanum doping on Cu/Ce/Zr showed an increase in OSC

over pure ceria, and had further improvements with the
addition of an Fe promoter [145]. With an increase in OSC
there is normally a corresponding increase in CO conversion.
An example of this using Pd as Ce/Zr/Pd with other rare earth
metals is shown in Fig. 11.
The sulfur tolerance of Mo and Co on ceria supports was
examined by Roberge et al. for use in dirty coal reforming. Ce/
Co/Mo was found to be more efficient before and after high
concentrations of sulfur than many other catalysts. Conver-
sion was found to be near the equilibrium values for CO
conversion even in sulfur concentrations as high as 500 ppm,
however this catalyst can perform in both sulfur rich and
depleted streams [146]. Results of this study are shown in
Fig. 12. This outcome is an improvement upon a previous Mo
sulfur reliant catalyst test which showed deactivation at low
concentrations of sulfur below 300 ppm [147].
In addition to doping, nanostructuring has been shown to
Fig. 11 e CO conversion vs. temperature for Ce/Zr catalysts
increase activity [148e151]. Synthesis of Au/La/Ce catalysts in
doped with palladium and a rare earth metal. Adapted
nanorod form allows for a decrease in reduction temperature
from [139].
which means higher activity for the WGS reaction, and lower-
energy conversion of CO when compared with nanoparticles,
and with commercial Cu WGS catalysts [152]. Shown in Fig. 13
are TEM images of ceria nanorods with differing percentages techniques of electro catalysis will enable high precision
of lanthanum. Increasing the percentage of La in nano- tunable surface chemistry, allowing for greater control over
structured Au/Ce catalysts showed no appreciable difference composition and material interactions [164]. Future synthesis
up to 25% La, and above this showed a decrease in activity due of materials, including single atom doped catalysts with
to the decrease in exposed ceria surface and therefore extremely weak oxygen vacancies, as well as decreased en-
reducible sites [152]. ergy of dissociating water molecules will allow for extremely
efficient hydrogen production through WGS.
Overview and vision WGS catalyst

Table 2 summarizes the catalysts talked about in this section,
as well as additional noteworthy catalysts.
Ceria, due to its high OSC, has great potential for use in
future industrial catalysts. The combination of ceria and other
metals has made catalysts that have unique properties, with
some having activity in both steam reforming and WGS. New
General problems with reforming and WGS
catalysts
SR and WGS reactions are affected by many variables
including reaction conditions such as temperature and pres-
sure, S/C ratio, feed stock used, reactor characteristics, and

Fig. 10 e Comparison of oxygen storage for Ce/Zr catalysts Fig. 12 e Three different catalysts tested over a range of
using two different preparation methods with varying temperatures and sulfur feed amounts. Adapted from
percentages of Ce. Adapted from [144]. [146].
16994 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 9 ( 2 0 1 4 ) 1 6 9 8 3 e1 7 0 0 0
Fig. 13 e TEM images of CeO2 nanorods with varying amounts of La [152].
residence time; and physical parameters such as catalyst
composition, dopant dispersion, sintering, and poisoning.
These factors all affect how a catalyst performs and can give
widely varying results [165]. The same catalyst can yield very
different results due to these variations, and in an effort to
account for these factors, a parameter known as characteristic
time was proposed by Liao and Erickson to quantify the per-
formance of a reactor. The characteristic time is related to
physical and reaction parameters so variations in these at-
tributes are captured. The characteristic time could serve as a
consistent evaluation parameter for reactor systems, avoiding
the problems of variations in reported values between studies
[166].
Coking is a major problem for SR and WGS processes and is
considered in all highly optimized catalyst systems. Coking
can come in many forms and occurs through varied mecha-
nisms depending on reaction conditions. The addition of
sulfur or tin in small amounts has been shown to decrease
carbon deposition through reduction of active spots for carbon
formation. Another method involves increasing the rate of
coke gasification so that the formation rate is less than or
equal to the rate of gasification. Rare earth metal oxides have
demonstrated the ability to increase the rate of coke gasifi-
cation as well as increasing the activity of the catalysts mak-
ing them an important area of study for catalysts in the
production of hydrogen [167]. Coking can also be minimized
by increasing the S/C ratio, a method that has been employed
by many researchers. While many coking reduction methods
are effective, they typically increase production costs, a major
factor in industrial applications. Some catalysts are able to be
regenerated by blowing hot air through the bed. Imple-
mentation of this type of regeneration in continuous opera-
tion of plants requires the use of a regeneration scheme such
as swing bed, moving bed, and fluidized bed regeneration
processes [168]. A novel method for SR catalyst regeneration is
a two zone fluidized bed where a small amount of oxygen is
fed to the lower zone of the bed regenerating active sites, and
methane is fed to the top zone for conversion. Since the bed is
fluidized, catalyst between zones is interchanged. The selec-
tivity is extremely high in the regenerative zone allowing
carbonaceous deposits to be removed, resulting in no net coke
formation and better methane conversion compared to a
regular fluidized bed reactor with the same reaction condi-
tions [169].
Most SR and WGS catalysts are intolerant of sulfur
which poisons the catalyst and decreases activity. To in-
crease sulfur resistance, doping has been successful with a
number of metals which have shown decreases in sulfur
poisoning. Some of these sulfur resistant metals are shown
in Fig. 14.
Conversely, small amounts of sulfur cannot only increase
activity, but can also decrease coking by adsorbing to the
surface, though a balance must be found between sulfur-
occupied activating sites and reduction of carbon deposition
[167].
As the activity of the WGS reaction decreases at lower
temperatures, the amount of CO in the effluent increases. This
is especially problematic for fuel cell applications that require
very low CO levels. The use of a catalyst that operates at very
low temperatures, but remains active at higher temperatures,
could mitigate this problem [63].
Sintering caused by hot spots is a common cause for
deactivation. A study looking at the deactivation of a Pd/Ce
catalyst found that a change in particle size (sintering) was
responsible and not over reduction of the ceria support. This
was tested by saturating the catalyst with oxygen after
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Table 2 e Summary containing a selection of catalytic metals and supports used for the WGS reaction.
Catalyst Description T ( C) S/C ratio X (%) Source
Iron
Cr/Fe 25e35 bar, deactivates quickly, at 1500 h it stabilizes, must be replaced 300e450 e 97 [115,119]
within 2e5 years. ~ 8% Cr.
Cr/Fe Promotion by Hg > Ag, Ba > Cu > Pb all increase activity compared to 400 6 37.4 [118,121]
traditional catalysts. 50 vol% H2 added. Pressure of 400 psi.
Th/Cu/Fe Reduced toxicity compared to Cr, selectivity for CO2 of 85.3%. 370 0.6 e [120]
Cu/Co/Cr/Fe Chloride precursors. H2 selectivity 85%, 8% Cr, 2% Cu, 2% Co, balance Fe. 380 2 78 [114]
Ir/Fe Single atom, decreased dopant, high stability. 2.4% doped Ir. 300 5 93 [122]
Zinc
Raney Cu Leeching preparation, extremely tunable pore size and surface area. Slow 200 22.5 100 [126]
deactivation for 400 h then rapid deactivation.
Carbon
Fe/C Coal char from gasification is cheap. Good recoverability, heavy 275e425 5 e [15]
deactivation by sulfur. 2.66% Fe deposition.
Pt/Ce/C Decreased deactivation. 40% Ce deposition. 350 20 90 [101]
Pt/C Nanotubes, promoted by Na. 1% Pt deposition. 300 5 >95 [102]
Pt/Mo/C Carbide, higher activity than traditional catalysts. 295 5.5 30 [103,104]
Aluminum
Cu/Zn/Al Intolerant of sulfur, must be replaced within 2e4 years. <250 e >99 [115]
Ni/Al Unpromoted: 25.1% methanation, promoted by K: 0.19% methanation. 350 3 >98 [131,132]
Cerium
Au/Ce Urea precipitation. Deactivation was seen. Low deposition. 250 2.3 90 [22,76]
Pt/Ce Activity > Au/Ce. Increased activity with increased dopant, 5% Pt. 300 33.3 90 [153,154]
Pd/Ce High activity, promotion by iron increased oxygen transfer. 200 1 e [20]
Rh/Ce Kinetic rates equivalent to Pd and Pt doped ceria. 300 0.75 <1 [155]
Au/La/Ce Increased OSC, and stability, nanorods lowered energy input. 25% La, 4% Au >300 5 >95 [76,152]
balance Ce.
Pt/La/Ce Increased OSC and activity compared to PtCeO2. Constant ratio of 0.2 La to 325 3 93 [156]
0.8 Ce. 5% Pt deposition.
Cu/Zr/Ce Increased reduction. Promotion by 3% Fe, 60% Ce, 40% Zr. 400 1 75.9 [145]
Pd/La/Zr/Ce Extremely high conversion due to the addition of O2. 270 e 100 [139]
Pt/Mg/Ce Increased OSC, activity, stability, and decreased methanation. 300 10 50 [157]
Pd/Ni/Ce 100% selective towards H2. 88% Ce, 2% Pd, 10% Ni. 380 e 99 [158]
Ru/Si/Ce No increase in OSC, decreased methanation. 85% Ce, 10% Si, 5% Ru. 100% 280 27.5 99 [159]
selective toward H2.
Cu/Ce 100% CO2 selectivity, high space velocity, stable for 20 h. 400 2 73 [160]
Ni/La/Ce High conversion. 5% Ni, 10% La, balance Ce. 400 5 >95 [161]
Cu/La/Ce High conversion, no activation, high stability. 5% Cu, 10% La. 300 5 100 [161]
Cu/Ni/Ce 100% hydrogen selectivity. 75% Ce, 10% Cu, 15% Ni. 320 27.5 100 [78]
Mo/Co/Ce High activity in high and low concentration sulfur feeds. 375 1 80 [146]
Zirconium
Cu/Zr Deposition precipitation preparation followed by Cu leeching. 6.1% Cu. 270 0.4 >85 [162]
Pt/Ti/Zr Increased dispersion due to Ti loading. 20% Ti, 0.97% Pt. 300 1.42 78 [163]

accelerated aging (deactivation) and repeating the conver-

sion test, which found no subsequent increase in conver-
sion. This result suggests that sintering is the cause of the
catalyst deactivation, since O2 saturation caused no reac-
tivation [170].
In most hydrogen production, large amounts of CO2 are
produced. Saxena et al. combined the production of H2 and the
sequestration of carbon by using a modified SR reaction which
is shown as (R7) [171].

2NaOH þ CH4 þ H2 O/Na2 CO3 þ 4H2 (R7)

This reaction is performed through gasification of methane

and sodium hydroxide from approximately 1150 to 1350  C
using no catalyst to create a no carbon emission process with
NaCO3 produced as a byproduct. The high reaction tempera-
ture and need for a large supply of NaOH are the main de-
terrents to large scale use [171].
Fig. 14 e Graph plotting seven different metals and their
resistance to sulfur poisoning. Graph shows the ratio of
hydrogen to hydrogen sulfide. Once hydrogen sulfide is
removed, sulfur problems occur less frequently. Adapted
from [83].
16996 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 9 ( 2 0 1 4 ) 1 6 9 8 3 e1 7 0 0 0
Conclusion
Advancements in catalysis technologies and methods have
improved the state of SR and WGS. The synthesis methods of
nano-sized particles including impregnation, co-sputtering,
and chemical vapor deposition, allow for highly dispersed
dopants and high activity. The addition of metallic or bime-
tallic species to a catalyst can improve selectivity, durability,
and activity. Many typical problems with catalysts can be
mitigated through the addition of these metals including coke
formation, active oxidation, sintering, and segregation [48].
WGS and SR reactions are affected by reaction conditions,
catalysts type and composition, residence time, temperature,
and feed conditions, which can change the overall conversion
and selectivity [172]. As research is done to characterize more
catalysts with varied compositions, an increasing amount of
materials and supports are being discovered that can increase
activity for these reactions. Future combinations of materials
which are active at lower temperatures and can achieve high
conversion at low S/C ratios would increase feasibility of large
scale hydrogen production.
Acknowledgments
The authors would like to thank the National Science Foun-
dation and University of Wyoming EENanotechnology Pro-
gram (NSF-40243) for financial support.
references
[1] Edmonds JA, Chandler WU, Wuebbles D. Greenhouse gases:
what is their role in climate change? Dahlem workshop on
limiting greenhouse effect: options for controlling
atmospheric CO sub 2 accumulation. Berlin (Germany, F.R.);
1990. p. 41. p. Medium: ED; Size: Pages.
[2] He L, Fan M, Dutcher B, Cui S, Shen Xd, Kong Y, et al.
Dynamic separation of ultradilute CO2 with a nanoporous
amine-based sorbent. Chem Eng J 2012;189e190:13e23.
[3] Dutcher B, Fan M, Leonard B, Dyar MD, Tang J, Speicher EA,
et al. Use of nanoporous FeOOH as a catalytic support for
NaHCO3 decomposition aimed at reduction of energy
requirement of Na2CO3/NaHCO3 based CO2 separation
technology. J Phys Chem C 2011;115:15532e44.
[4] Zhang BT, Fan M, Bland AE. CO2 separation by a new solid
KeFe sorbent. Energy Fuels 2011;25:1919e25.
[5] Cui S, Cheng W, Shen X, Fan M, Russell A, Wu Z, et al.
Mesoporous amine-modified SiO2 aerogel: a potential CO2
sorbent. Energy Environ Sci 2011;4:2070e4.
[6] Antoniadou M, Sfaelou S, Dracopoulos V, Lianos P.
Platinum-free photoelectrochemical water splitting. Catal
Commun 2014;43:72e4.
[7] Hamann TW. Water splitting: an adaptive junction. Nat
Mater 2014;13:3e4.
[8] Zhang P, Zhang J, Gong J. Tantalum-based semiconductors
for solar water splitting. Chem Soc Rev 2014;43:4395e422.
[9] Wang D, Zhang Y, Wang J, Peng C, Huang Q, Su S, et al.
Template-Free Synthesis of Hematite Photoanodes with
Nanostructured ATO Conductive Underlayer for PEC Water
Splitting. ACS Appl Mater Interfaces 2014;6:36e40.
[10] Moriya Y, Takata T, Domen K. Recent progress in the
development of (oxy)nitride photocatalysts for water
splitting under visible-light irradiation. Coord Chem Rev
2013;257:1957e69.
[11] Oakley JH, Hoadley AFA. Industrial scale steam reforming of
bioethanol: a conceptual study. Int J Hydrogen Energy
2010;35:8472e85.
[12] Khila Z, Hajjaji N, Pons MN, Renaudin V, Houas A. A
comparative study on energetic and exergetic assessment
of hydrogen production from bioethanol via steam
reforming, partial oxidation and auto-thermal reforming
processes. Fuel Process Technol 2013;112:19e27.
[13] Cormos C-C. Renewable hydrogen production concepts
from bioethanol reforming with carbon capture. Int J
Hydrogen Energy 2014;39:5597e606.
[14] Tanksale A, Beltramini JN, Lu GM. A review of catalytic
hydrogen production processes from biomass. Renew
Sustain Energy Rev 2010;14:166e82.
[15] Yu J, Tian FJ, McKenzie LJ, Li CZ. Char-supported nano iron
catalyst for water-gas-shift reaction: hydrogen production
from coal/biomass gasification. Process Saf Environ
2006;84:125e30.
[16] Joensen F, Rostrup-Nielsen JR. Conversion of hydrocarbons
and alcohols for fuel cells. J Power Sources 2002;105:195e201.
[17] Wei Z, Sun J, Li Y, Datye AK, Wang Y. Bimetallic catalysts for
hydrogen generation. Chem Soc Rev 2012;41:7994e8008.
[18] Halabi MH, de Croon MHJM, van der Schaaf J, Cobden PD,
Schouten JC. Low temperature catalytic methane steam
reforming over ceriaezirconia supported rhodium. Appl
Catal A 2010;389:68e79.
[19] XU J. Methane steam reforming, methanation and water gas
shift: I. Intrinsic kinetics. AlChE J 1989;35.
[20] Wang X, Gorte RJ. The effect of Fe and other promoters on
the activity of Pd/ceria for the water-gas shift reaction. Appl
Catal A 2003;247:157e62.
[21] Aksoylu AE, Freitas MMA, Figueiredo JL. Bimetallic PteSn
catalysts supported on activated carbon. II. CO oxidation.
Catal Today 2000;62:337e46.
[22] Kim CH, Thompson LT. Deactivation of Au/CeOx water gas
shift catalysts. J Catal 2005;230:66e74.
[23] Palo DR, Dagle RA, Holladay JD. Methanol steam reforming
for hydrogen production. Chem Rev 2007;107:3992e4021.
[24] Koh ACW, Chen L, Leong WK, Ang TP, Johnson BFG,
Khimyak T, et al. Ethanol steam reforming over supported
ruthenium and ruthenium-platinum catalysts: comparison
of organometallic clusters and inorganic salts as catalyst
precursors. Int J Hydrogen Energy 2009;34:5691e703.
[25] Simpson AP, Lutz AE. Exergy analysis of hydrogen
production via steam methane reforming. Int J Hydrogen
Energy 2007;32:4811e20.
[26] Nguyen LQ, Abella LC, Gallardo SM, Hinode H. Effect of
nickel loading on the activity of Ni/ZrO2 for methane steam
reforming at low temperature. React Kinet Catal Lett
2008;93:227e32.
[27] Huang TJ, Jhao SY. NieCu/samaria-doped ceria catalysts for
steam reforming of methane in the presence of carbon
dioxide. Appl Catal A 2006;302:325e32.
[28] Tang M, Xu L, Fan M. Effect of Ce on 5 wt% Ni/ZSM-5
catalysts in the CO2 reforming of CH4 reaction, Int J
Hydrogen Energy.
[29] Pompeo F, Gazzoli D, Nichio NN. Stability improvements of
Ni/a-Al2O3 catalysts to obtain hydrogen from methane
reforming. Int J Hydrogen Energy 2009;34:2260e8.
[30] Jang WJ, Jeong DW, Shim JO, Roh HS, Son IH, Lee SJ. H2 and
CO production over a stable NieMgOeCe0.8Zr0.2O2 catalyst
 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 9 ( 2 0 1 4 ) 1 6 9 8 3 e1 7 0 0 0
from CO2 reforming of CH4. Int J Hydrogen Energy
2013;38:4508e12.
[31] Jeong DW, Jang WJ, Shim JO, Roh HS, Son IH, Lee SJ. The
effect of preparation method on the catalytic performance
over superior MgO-promoted NieCe0.8Zr0.2O2 catalyst for
CO2 reforming of CH4. Int J Hydrogen Energy
2013;38:13649e54.
[32] Asencios YJO, Assaf EM. Combination of dry reforming and
partial oxidation of methane on NiOeMgOeZrO2 catalyst:
effect of nickel content. Fuel Process Technol 2013;106:247e52.
[33] Oyama ST, Hacarlioglu P, Gu Y, Lee D. Dry reforming of
methane has no future for hydrogen production:
comparison with steam reforming at high pressure in
standard and membrane reactors. Int J Hydrogen Energy
2012;37:10444e50.
[34] Reddy GK, Loridant S, Takahashi A, Deliche
re P, Reddy BM.
Reforming of methane with carbon dioxide over Pt/ZrO2/
SiO2 catalystsdeffect of zirconia to silica ratio. Appl Catal A
2010;389:92e100.
[35] Xu L, Liu Y, Li Y, Lin Z, Ma X, Zhang Y, et al. Catalytic CH4
reforming with CO2 over activated carbon based catalysts.
Appl Catal A 2014;469:387e97.
[36] Liu H, Wang B, Fan M, Henson N, Zhang Y, Towler BF, et al.
Study on carbon deposition associated with catalytic CH4
reforming by using density functional theory. Fuel
2013;113:712e8.
[37] Liu H, Teng B, Fan M, Wang B, Zhang Y, Gordon Harris H.
CH4 dissociation on the perfect and defective MgO(0 0 1)
supported Ni4. Fuel 2014;123:285e92.
[38] Xu L, le Duan, Tang M, Liu P, Ma X, Zhang Y, et al. Catalytic
CO2 reforming of CH4 over Cr-promoted Ni/char for H2
production. Int J Hydrogen Energy 2014;39:10141e53.
[39] Escritori JC, Dantas SC, Soares RR, Hori CE. Methane
autothermal reforming on nickeleceriaezirconia based
catalysts. Catal Commun 2009;10:1090e4.
[40] Ashcroft AT, Cheetham AK, Foord JS, Green MLH, Grey CP,
Murrell AJ, et al. Selective oxidation of methane to synthesis
gas using transition metal catalysts. Nature 1990;344:319e21.
[41] Tsipouriari VA, Zhang Z, Verykios XE. Catalytic partial
oxidation of methane to synthesis gas over Ni-based
catalysts: I. Catalyst performance characteristics. J Catal
1998;179:283e91.
[42] Jahangiri A, Aghabozorg H, Pahlavanzadeh H. Effects of Fe
substitutions by Ni in LaeNieO perovskite-type oxides in
reforming of methane with CO2 and O2. Int J Hydrogen
Energy 2013;38:10407e16.
[43] Huang B, Li X, Ji S, Lang B, Habimana F, Li C. Effect of MgO
promoter on Ni-based SBA-15 catalysts for combined steam
and carbon dioxide reforming of methane. J Nat Gas Chem
2008;17:225e31.
[44] Garcı́a-Vargas JM, Valverde JL, de Lucas-Consuegra A, Go  mez-
Monedero B, Dorado F, Sa  nchez P. Methane tri-reforming over
a Ni/beSiC-based catalyst: optimizing the feedstock
composition. Int J Hydrogen Energy 2013;38:4524e32.
[45] Song C, Pan W. Tri-reforming of methane: a novel concept
for catalytic production of industrially useful synthesis gas
with desired H2/CO ratios. Catal Today 2004;98:463e84.
[46] Jiang Ht, Li Hq, Zhang Y. Tri-reforming of methane to
syngas over Ni/Al2O3 e thermal distribution in the catalyst
bed. J Fuel Chem Technol 2007;35:72e8.
[47] Chen WH, Lin MR, Lu JJ, Chao Y, Leu TS. Thermodynamic
analysis of hydrogen production from methane via
autothermal reforming and partial oxidation followed by
water gas shift reaction. Int J Hydrogen Energy
2010;35:11787e97.
[48] Dal Santo V, Gallo A, Naldoni A, Guidotti M, Psaro R.
Bimetallic heterogeneous catalysts for hydrogen
production. Catal Today 2012;197:190e205.
16997
[49] Sehested J. Four challenges for nickel steam-reforming
catalysts. Catal Today 2006;111:103e10.
[50] Nieva MA, Villaverde MM, Monzo  n A, Garetto TF, Marchi AJ.
Steam-methane reforming at low temperature on nickel-
based catalysts. Chem Eng J 2014;235:158e66.
[51] Besenbacher F, Chorkendorff I, Clausen BS, Hammer B,
Molenbroek AM, Nørskov JK, et al. Design of a surface alloy
catalyst for steam reforming. Science 1998;279:1913e5.
[52] Xu J, Chen L, Tan KF, Borgna A, Saeys M. Effect of boron on
the stability of Ni catalysts during steam methane
reforming. J Catal 2009;261:158e65.
[53] Takeguchi T, Watanabe H, Murayama T, Takahashi H,
Ueda W. Quantitative analysis of coke formation during
steam reforming of methane on a nickelehydrotalcite
catalyst under practical operation conditions. Chem Lett
2013;42:124e6.
[54] Bej B, Pradhan NC, Neogi S. Production of hydrogen by
steam reforming of methane over alumina supported nano-
NiO/SiO2 catalyst. Catal Today 2013;207:28e35.
[55] Majewski AJ, Wood J, Bujalski W. Nickelesilica core@shell
catalyst for methane reforming. Int J Hydrogen Energy
2013;38:14531e41.
[56] Andache M, Rezaei M, Kazemi Moghadam M. A
nanocrystalline MgO support for Ni catalysts for steam
reforming of CH4. Chin J Catal 2013;34:1443e8.
[57] Hufschmidt D, Bobadilla LF, Romero-Sarria F, Centeno MA,
Odriozola JA, Montes M, et al. Supported nickel catalysts
with a controlled molecular architecture for the catalytic
reformation of methane. Catal Today 2010;149:394e400.
[58] Fatsikostas AN, Kondarides DI, Verykios XE. Production of
hydrogen for fuel cells by reformation of biomass-derived
ethanol. Catal Today 2002;75:145e55.
[59] Maluf SS, Assaf EM. Ni catalysts with Mo promoter for
methane steam reforming. Fuel 2009;88:1547e53.
[60] Lorenz H, Friedrich M, Armbrüster M, Klo € tzer B, Penner S.
ZnO is a CO2-selective steam reforming catalyst. J Catal
2013;297:151e4.
[61] Brown LF. A comparative study of fuels for on-board
hydrogen production for fuel-cell-powered automobiles. Int
J Hydrogen Energy 2001;26:381e97.
[62] Men Y, Yang M. SMSI-like behavior and Ni promotion effect
on NiZnAl catalysts in steam reforming of methanol. Catal
Commun 2012;22:68e73.
[63] Pinzari F, Patrono P, Costantino U. Methanol reforming
reactions over Zn/TiO2 catalysts. Catal Commun
2006;7:696e700.
[64] Chin YH, Dagle R, Hu J, Dohnalkova AC, Wang Y. Steam
reforming of methanol over highly active Pd/ZnO catalyst.
Catal Today 2002;77:79e88.
[65] Rodrı́guez-reinoso F. The role of carbon materials in
heterogeneous catalysis. Carbon 1998;36:159e75.
[66] Choi Y, Stenger HG. Fuel cell grade hydrogen from methanol
on a commercial Cu/ZnO/Al2O3 catalyst. Appl Catal B
2002;38:259e69.
[67] Ma Y. Low-temperature steam reforming of methanol to
produce hydrogen over various metal-doped molybdenum
carbide catalysts. Int J Hydrogen Energy 2014;39:258e66.
[68] Lausche AC. Understanding the effects of sulfur on Mo2C
and Pt/Mo2C catalysts: methanol steam reforming. Appl
Catal A 2011;401:29e36.
[69] Christofoletti T, Assaf JM, Assaf EM. Methane steam
reforming on supported and non-supported molybdenum
carbides. Chem Eng J 2005;106:97e103.
[70] Saito M, Anderson RB. The activity of several molybdenum
compounds for the methanation of CO2. J Catal
1981;67:296e302.
[71] Setthapun W, Bej SK, Thompson LT. Carbide and nitride
supported methanol steam reforming catalysts: parallel
16998 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 9 ( 2 0 1 4 ) 1 6 9 8 3 e1 7 0 0 0
synthesis and high throughput screening. Top Catal
2008;49:73e80.
[72] Kim HW, Kang KM, Kwak HY, Kim JH. Preparation of
supported Ni catalysts on various metal oxides with core/
shell structures and their tests for the steam reforming of
methane. Chem Eng J 2011;168:775e83.
[73] Roh HS, Koo K, Jeong J, Seo Y, Seo D, Seo YS, et al. Combined
reforming of methane over supported Ni catalysts. Catal
Lett 2007;117:85e90.
[74] Li D, Nishida K, Zhan Y, Shishido T, Oumi Y, Sano T, et al.
Superior catalytic behavior of trace Pt-doped Ni/Mg(Al)O in
methane reforming under daily start-up and shut-down
operation. Appl Catal A 2008;350:225e36.
[75] McGuire NE, Sullivan NP, Kee RJ, Zhu H, Nabity JA, Engel JR,
et al. Catalytic steam reforming of methane using Rh
supported on Sr-substituted hexaaluminate. Chem Eng Sci
2009;64:5231e9.
[76] Fu Q, Deng W, Saltsburg H, Flytzani-Stephanopoulos M.
Activity and stability of low-content goldecerium oxide
catalysts for the wateregas shift reaction. Appl Catal B
2005;56:57e68.
[77] Kobayashi M, Flytzani-Stephanopoulos M. Reduction and
sulfidation kinetics of cerium oxide and Cu-modified
cerium oxide. Ind Eng Chem Res 2002;41:3115e23.
[78] Shinde VM, Madras G. Water gas shift reaction over multi-
component ceria catalysts. Appl Catal B
2012;123e124:367e78.
[79] Mortola VB, Damyanova S, Zanchet D, Bueno JMC. Surface
and structural features of Pt/CeO2eLa2O3eAl2O3 catalysts
for partial oxidation and steam reforming of methane. Appl
Catal B 2011;107:221e36.
[80] Dong WS, Roh HS, Jun KW, Park SE, Oh YS. Methane
reforming over Ni/CeeZrO2 catalysts: effect of nickel
content. Appl Catal A 2002;226:63e72.
[81] Laosiripojana N, Assabumrungrat S. Methane steam
reforming over Ni/CeeZrO2 catalyst: influences of CeeZrO2
support on reactivity, resistance toward carbon formation,
and intrinsic reaction kinetics. Appl Catal A
2005;290:200e11.
[82] Xu J, Yeung CMY, Ni J, Meunier F, Acerbi N, Fowles M,
et al. Methane steam reforming for hydrogen
production using low water-ratios without carbon
formation over ceria coated Ni catalysts. Appl Catal A
2008;345:119e27.
[83] Hulteberg C. Sulphur-tolerant catalysts in small-scale
hydrogen production, a review. Int J Hydrogen Energy
2012;37:3978e92.
[84] Roh HS, Eum IH, Jeong DW. Low temperature steam
reforming of methane over NieCe(1x)Zr(x)O2 catalysts under
severe conditions. Renew Energy 2012;42:212e6.
[85] Furtado AC, Alonso CG, Canta ~ o MP, Fernandes-
Machado NRC. Bimetallic catalysts performance during
ethanol steam reforming: influence of support materials.
Int J Hydrogen Energy 2009;34:7189e96.
[86] Ramı́rez-Cabrera E, Atkinson A, Chadwick D. Catalytic
steam reforming of methane over Ce0.9Gd0.1O2x. Appl Catal
B 2004;47:127e31.
[87] Duarte RB, Safonova OV, Krumeich F, Makosch M, van
Bokhoven JA. Oxidation state of Ce in CeO2-promoted Rh/
Al2O3 catalysts during methane steam reforming: H2O
activation and alumina stabilization. ACS Catal
2013;3:1956e64.
[88] Udani PPC, Gunawardana PVDS, Lee HC, Kim DH. Steam
reforming and oxidative steam reforming of methanol over
CuOeCeO2 catalysts. Int J Hydrogen Energy
2009;34:7648e55.
[89] Feio LSF, Hori CE, Damyanova S, Noronha FB, Cassinelli WH,
Marques CMP, et al. The effect of ceria content on the
properties of Pd/CeO2/Al2O3 catalysts for steam reforming
of methane. Appl Catal A 2007;316:107e16.
[90] Sun J, Mei D, Karim AM, Datye AK, Wang Y. Minimizing the
formation of coke and methane on Co nanoparticles in
steam reforming of biomass-derived oxygenates.
ChemCatChem 2013;5:1299e303.
[91] Oliveira ELG, Grande CA, Rodrigues AE. Methane steam
reforming in large pore catalyst. Chem Eng Sci
2010;65:1539e50.
[92] Abashar MEE. Coupling of steam and dry reforming of
methane in catalytic fluidized bed membrane reactors. Int J
Hydrogen Energy 2004;29:799e808.
[93] Katiyar N, Kumar S, Kumar S. Polymer electrolyte
membrane fuel cell grade hydrogen production by
methanol steam reforming: a comparative multiple reactor
modeling study. J Power Sources 2013;243:381e91.
[94] Ryi SK, Park JS, Kim DK, Kim TH, Kim SH. Methane steam
reforming with a novel catalytic nickel membrane for
effective hydrogen production. J Memb Sci 2009;339:189e94.
[95] Düsterwald HG, Ho € hlein B, Kraut H, Meusinger J, Peters R,
Stimming U. Methanol steam-reforming in a catalytic fixed
bed reactor. Chem Eng Technol 1997;20:617e23.
[96] Amphlett JC. Simulation of a 250 kW diesel fuel processor/
PEM fuel cell system. J Power Sources 1998;71:179e84.
[97] De Wild PJ, Verhaak MJFM. Catalytic production of hydrogen
from methanol. Catal Today 2000;60:3e10.
[98] Murphy DM, Manerbino A, Parker M, Blasi J, Kee RJ,
Sullivan NP. Methane steam reforming in a novel ceramic
microchannel reactor. Int J Hydrogen Energy
2013;38:8741e50.
[99] Jeon SW, Yoon WJ, Baek C, Kim Y. Minimization of hot spot
in a microchannel reactor for steam reforming of methane
with the stripe combustion catalyst layer. Int J Hydrogen
Energy 2013;38:13982e90.
[100] Wu G, Li S, Zhang C, Wang T, Gong J. Glycerol steam
reforming over perovskite-derived nickel-based catalysts.
Appl Catal B 2014;144:277e85.
[101] Buitrago R, Ruiz-Martı́nez J, Silvestre-Albero J, Sepúlveda-
Escribano A, Rodrı́guez-Reinoso F. Water gas shift reaction
on carbon-supported Pt catalysts promoted by CeO2. Catal
Today 2012;180:19e24.
[102] Zugic B, Bell DC, Flytzani-Stephanopoulos M. Activation of
carbon-supported platinum catalysts by sodium for the
low-temperature water-gas shift reaction. Appl Catal B
2014;144:243e51.
[103] Schweitzer NM, Schaidle JA, Ezekoye OK, Pan X, Linic S,
Thompson LT. High activity carbide supported catalysts for
water gas shift. JACS 2011;133:2378e81.
[104] Patt J, Moon D, Phillips C, Thompson L. Molybdenum
carbide catalysts for wateregas shift. Catal Lett
2000;65:193e5.
[105] Palma V, Castaldo F, Ciambelli P, Iaquaniello G, Capitani G.
On the activity of bimetallic catalysts for ethanol steam
reforming. Int J Hydrogen Energy 2013;38:6633e45.
[106] Zhang L, Pan L, Ni C, Sun T, Zhao S, Wang S, et al.
CeO2eZrO2-promoted CuO/ZnO catalyst for methanol
steam reforming. Int J Hydrogen Energy 2013;38:4397e406.
[107] Nichele V, Signoretto M, Pinna F, Menegazzo F, Rossetti I,
Cruciani G, et al. Ni/ZrO2 catalysts in ethanol steam
reforming: inhibition of coke formation by CaO-doping.
Appl Catal B 2014;150e151:12e20.
[108] Popa T, Fan M, Argyle MD, Slimane RB, Bell DA, Towler BF.
Catalytic gasification of a powder river basin coal. Fuel
2013;103:161e70.
[109] Monterroso R, Fan M, Zhang F, Gao Y, Popa T, Argyle MD,
et al. Effects of an environmentally-friendly, inexpensive
composite ironesodium catalyst on coal gasification. Fuel
2014;116:341e9.
 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 9 ( 2 0 1 4 ) 1 6 9 8 3 e1 7 0 0 0
[110] Monterroso R, Fan M, Argyle MD, Varga K, Dyar D, Tang J,
et al. Characterization of the mechanism of gasification of a
powder river basin coal with a composite catalyst for
producing desired syngases and liquids. Appl Catal A
2014;475:116e26.
[111] Popa T, Fan M, Argyle MD, Dyar MD, Gao Y, Tang J, et al. H2
and COx generation from coal gasification catalyzed by a
cost-effective iron catalyst. Appl Catal A
2013;464e465:207e17.
[112] Howaniec N, Smolin  ski A. Steam co-gasification of coal and
biomass e synergy in reactivity of fuel blends chars. Int J
Hydrogen Energy 2013;38:16152e60.
[113] Ammal SC, Heyden A. Origin of the unique activity of Pt/
TiO2 catalysts for the wateregas shift reaction. J Catal
2013;306:78e90.
[114] Dufour J, Martos C, Ruiz A, Ayuela FJ. Effect of the precursor
on the activity of high temperature water gas shift
catalysts. Int J Hydrogen Energy 2013;38:7647e53.
[115] Rhodes C, Hutchings GJ, Ward AM. Water-gas shift reaction:
finding the mechanistic boundary. Catal Today
1995;23:43e58.
[116] Chen WH, Lin MR, Jiang TL, Chen MH. Modeling and
simulation of hydrogen generation from high-temperature
and low-temperature water gas shift reactions. Int J
Hydrogen Energy 2008;33:6644e56.
[117] Kung MC, Kung HH. The surface cation densities of iron
oxide-chromium oxide solid solutions. Surf Sci
1981;104:253e69.
[118] Rhodes C, Peter Williams B, King F, Hutchings GJ. Promotion
of Fe3O4/Cr2O3 high temperature water gas shift catalyst.
Catal Commun 2002;3:381e4.
[119] Keiski RL, Salmi T. Deactivation of the high-temperature
water-gas shift catalyst in nonisothermal conditions. Appl
Catal A 1992;87:185e203.
[120] Rangel Costa JLs, Se rgio Marchetti G, do Carmo Rangel M. A
thorium-doped catalyst for the high temperature shift
reaction. Catal Today 2002;77:205e13.
[121] Topsøe H, Boudart M. Mo € ssbauer spectroscopy of CO shift
catalysts promoted with lead. J Catal 1973;31:346e59.
[122] Lin J, Wang A, Qiao B, Liu X, Yang X, Wang X, et al.
Remarkable performance of Ir1/FeOx single-atom catalyst in
water gas shift reaction. JACS 2013;135:15314e7.
[123] Leoni TM, Wainwright MS. Kinetics of formation of chromia
promoted skeletal iron catalysts for the water gas shift
reaction. Catal Today 2011;178:103e9.
[124] Chinchen GC, Denny PJ, Jennings JR, Spencer MS,
Waugh KC. Synthesis of methanol: part 1. Catalysts and
kinetics. Appl Catal 1988;36:1e65.
[125] Taylor SH, Hutchings GJ, Mirzaei AA. The preparation and
activity of copper zinc oxide catalysts for ambient
temperature carbon monoxide oxidation. Catal Today
2003;84:113e9.
[126] Mellor JR, Coville NJ, Sofianos AC, Copperthwaite RG. Raney
copper catalysts for the water-gas shift reaction: I.
Preparation, activity and stability. Appl Catal A
1997;164:171e83.
[127] Serrano-Ruiz JC, Ramos-Ferna  ndez EV, Silvestre-Albero J,
Sepúlveda-Escribano A, Rodrı́guez-Reinoso F. Preparation
and characterization of CeO2 highly dispersed on activated
carbon. Mater Res Bull 2008;43:1850e7.
[128] Nagai M, Matsuda K. Low-temperature wateregas shift
reaction over cobaltemolybdenum carbide catalyst. J Catal
2006;238:489e96.
[129] Moon D, Ryu J. Molybdenum carbide wateregas shift
catalyst for fuel cell-powered vehicles applications. Catal
Lett 2004;92:17e24.
[130] Lenite BA, Galletti C, Specchia S. Studies on Au catalysts for
water gas shift reaction. Int J Hydrogen Energy 2011;36:7750e8.
16999
[131] Hwang KR, Lee CB, Park JS. Advanced nickel metal catalyst for
wateregas shift reaction. J Power Sources 2011;196:1349e52.
[132] Kim SH, Nam SW, Lim TH, Lee HI. Effect of pretreatment on the
activity of Ni catalyst for CO removal reaction by wateregas
shift and methanation. Appl Catal B 2008;81:97e104.
[133] Capitan MJ, Centeno MA, Malet P, Carrizosa I, Odriozola JA,
Marquez A, et al. Drifts, XPS, XAS, and ab initio study of
lanthanide oxides supported on.gamma.-Al2O3. J Phys
Chem 1995;99:4655e60.
[134] Haruta M, Yamada N, Kobayashi T, Iijima S. Gold catalysts
prepared by coprecipitation for low-temperature oxidation
of hydrogen and of carbon monoxide. J Catal
1989;115:301e9.
[135] Haruta M. Size- and support-dependency in the catalysis of
gold. Catal Today 1997;36:153e66.
[136] Liu X, Wang A, Yang X, Zhang T, Mou CY, Su DS, et al.
Synthesis of thermally stable and highly active bimetallic
AueAg nanoparticles on inert supports. Chem Mater
2009;21:410e8.
[137] Tsubota S, Cunningham D, Bando Y, Haruta M. Preparation
of nanometer gold strongly interacted with TiO2 and the
structure sensitivity in low temperature oxidation of CO.
Stud Surf Sci Catal 1995;91:18.
[138] Fu Q, Weber A, Flytzani-Stephanopoulos M. AueCeO2
catalysts for low-temperature wateregas shift. Catal Lett
2001;77:87e95.
[139] Wang Q, Zhao B, Li G, Zhou R. Application of rare earth
modified Zr-based ceria-zirconia solid solution in three-way
catalyst for automotive emission control. Environ Sci
Technol 2010;44:3870e5.
[140] Wang Q, Li G, Zhao B, Zhou R. The effect of rare earth
modification on ceriaezirconia solid solution and its
application in Pd-only three-way catalyst. J Mol Catal A
Chem 2011;339:52e60.
[141] Hilaire S, Wang X, Luo T, Gorte RJ, Wagner J. A comparative
study of wateregas-shift reaction over ceria supported
metallic catalysts. Appl Catal A 2001;215:271e8.
[142] Dutta G, Waghmare UV, Baidya T, Hegde MS, Priolkar KR,
Sarode PR. Reducibility of Ce1xZrxO2: origin of enhanced
oxygen storage capacity. Catal Lett 2006;108:165e72.
[143] Letichevsky S, Tellez CA, De Avillez RR, Da Silva MIP,
Fraga MA, Appel LG. Obtaining CeO2eZrO2 mixed oxides by
coprecipitation: role of preparation conditions. Appl Catal B
2005;58:203e10.
[144] Hori CE, Permana H, Ng KYS, Brenner A, More K,
Rahmoeller KM, et al. Thermal stability of oxygen storage
properties in a mixed CeO2eZrO2 system. Appl Catal B
1998;16:105e17.
[145] Jiang L, Li C, Li Z, Zhang S. Effect of additives on the activity
of CuO/Ce0.6Zr0.4O2 catalysts for the wateregas shift
reaction. Chem Eng Technol 2013;36:1891e8.
[146] Roberge T, Blavo S, Holt C, Matter P, Kuhn J. Effect of
molybdenum on the sulfur-tolerance of ceriumecobalt
mixed oxide wateregas shift catalysts. Top Catal
2013;56:1892e8.
[147] Cheah S, Carpenter DL, Magrini-Bair KA. Review of mid- to
high-temperature sulfur sorbents for desulfurization of
biomass- and coal-derived syngas. Energy Fuels
2009;23:5291e307.
[148] Zhou K, Xu R, Sun X, Chen H, Tian Q, Shen D, et al.
Favorable synergetic effects between CuO and the reactive
planes of ceria nanorods. Catal Lett 2005;101:169e73.
[149] Mai HX, Sun LD, Zhang YW, Si R, Feng W, Zhang HP, et al.
Shape-selective synthesis and oxygen storage behavior of
ceria nanopolyhedra, nanorods, and nanocubes. J Phys
Chem B 2005;109:24380e5.
[150] Si R, Flytzani-Stephanopoulos M. Shape and crystal-plane
effects of nanoscale ceria on the activity of AueCeO2
17000 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 9 ( 2 0 1 4 ) 1 6 9 8 3 e1 7 0 0 0
catalysts for the wateregas shift reaction. Angew Chem Int
Ed 2008;47:2884e7.
[151] Lin K, Chowdhury S. Synthesis, characterization, and
application of 1-d cerium oxide nanomaterials: a review. Int
J Mol Sci 2010;11:25.
[152] Liang S, Veser G. Mixed lanthana/ceria nanorod-supported
gold catalysts for wateregas-shift. Catal Lett 2012;142.
[153] Jacobs G, Ricote S, Davis BH. Low temperature water-gas
shift: type and loading of metal impacts decomposition
and hydrogen exchange rates of pseudo-stabilized
formate over metal/ceria catalysts. Appl Catal A
2006;302:14e21.
[154] Jacobs G, Graham UM, Chenu E, Patterson PM, Dozier A,
Davis BH. Low-temperature wateregas shift: impact of Pt
promoter loading on the partial reduction of ceria and
consequences for catalyst design. J Catal 2005;229:499e512.
[155] Bunluesin T, Gorte RJ, Graham GW. Studies of the water-
gas-shift reaction on ceria-supported Pt, Pd, and Rh:
implications for oxygen-storage properties. Appl Catal B
1998;15:107e14.
[156] Kalamaras CM, Petallidou KC, Efstathiou AM. The effect of
La3þ-doping of CeO2 support on the wateregas shift
reaction mechanism and kinetics over Pt/Ce1xLaxO2d.
Appl Catal B 2013;136e137:225e38.
[157] Duarte de Farias AM, Barandas APMG, Perez RF, Fraga MA.
Wateregas shift reaction over magnesia-modified Pt/CeO2
catalysts. J Power Sources 2007;165:854e60.
[158] Shinde VM, Madras G. Nanostructured Pd modified Ni/CeO2
catalyst for water gas shift and catalytic hydrogen
combustion reaction. Appl Catal B 2013;132e133:28e38.
[159] Shinde VM, Madras G. Synthesis of nanosized
Ce0.85M0.1Ru0.05O2d (M ¼ Si, Fe) solid solution exhibiting
high CO oxidation and water gas shift activity. Appl Catal B
2013;138e139:51e61.
[160] Jeong DW, Jang WJ, Shim JO, Han WB, Roh HS, Jung UH,
et al. Low-temperature wateregas shift reaction
over supported Cu catalysts. Renew Energy 2014;65:102e7.
View publication stats
[161] Li Y, Fu Q, Flytzani-Stephanopoulos M. Low-temperature
wateregas shift reaction over Cu- and Ni-loaded cerium
oxide catalysts. Appl Catal B 2000;27:179e91.
[162] Zhang Y, Chen C, Lin X, Li D, Chen X, Zhan Y, et al. CuO/
ZrO2 catalysts for wateregas shift reaction: nature of
catalytically active copper species. Int J Hydrogen Energy
2014;39:3746e54.
[163] Hwang KR, Ihm SK, Park SC, Park JS. Pt/ZrO2 catalyst for a
single-stage wateregas shift reaction: Ti addition effect. Int
J Hydrogen Energy 2013;38:6044e51.
[164] Calle-Vallejo F, Koper MTM, Bandarenka AS. Tailoring the
catalytic activity of electrodes with monolayer amounts of
foreign metals. Chem Soc Rev 2013;42:5210e30.
[165] Chen WH, Hsieh TC, Jiang TL. An experimental study on
carbon monoxide conversion and hydrogen generation
from water gas shift reaction. Energy Convers Manage
2008;49:2801e8.
[166] Liao C, Erickson PA. Characteristic time as a descriptive
parameter in steam reformation hydrogen production
processes. Int J Hydrogen Energy 2008;33:1652e60.
[167] Trimm DL. Catalysts for the control of coking during steam
reforming. Catal Today 1999;49:3e10.
[168] Rostrup-Nielsen JR. Industrial relevance of coking. Catal
Today 1997;37:225e32.
[169] Perez-Moreno L, Soler J, Herguido J, Mene ndez M. Stable
hydrogen production by methane steam reforming in a two
zone fluidized bed reactor: experimental assessment. J
Power Sources 2013;243:233e41.
[170] Wang X, Gorte RJ, Wagner JP. Deactivation mechanisms for
Pd/Ceria during the wateregas-shift reaction. J Catal
2002;212:225e30.
[171] Saxena S, Kumar S, Drozd V. A modified steam-methane-
reformation reaction for hydrogen production. Int J
Hydrogen Energy 2011;36:4366e9.
[172] Lu X, Wang T. Wateregas shift modeling in coal gasification
in an entrained-flow gasifier. Part 1: development of
methodology and model calibration. Fuel 2013;108:629e38.