Renewable and Sustainable Energy Reviews 82 (2018) 2570–2585

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Renewable and Sustainable Energy Reviews

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Catalyst design for dry reforming of methane: Analysis review T

a b a a,⁎
Nicolas Abdel Karim Aramouni , Jad G. Touma , Belal Abu Tarboush , Joseph Zeaiter ,
Mohammad N. Ahmada
a
Department of Chemical and Petroleum Engineering, American University of Beirut, Beirut, Lebanon
b
School of Chemical, Biological and Environmental Engineering, Oregon State University, Oregon, USA

A R T I C L E I N F O A B S T R A C T

Keywords: The performance of catalysts used for the dry reforming of methane can strongly depend on the selection of
Methane active metals, supports and promoters. This work studies their effects on the activity and stability of selected
Green House Gas catalysts. Designing an economically viable catalyst that maintains high catalytic activity and stability can be
Dry reforming achieved by exploiting the synergic effects of combining noble and/or non-noble metals to form highly active
Catalysis
and stable bi- and tri-metallic catalysts. Perovskite type catalysts can also constitute a potent and cost effective
substituent. Metal oxide supports with surface Lewis base sites are able to reduce carbon formation and yield a
greater stability to the catalyst, while noble metal promoters have proven to increase both catalyst activity and
stability. Moreover, a successful metal-support-promoter combination should lead to higher metal-support in-
teracrtion, lower reduction temperature and enhancement of the anti-coking and anti-amalgamation properties
of the catalyst. However, the effect of each parameter on the overall performance of the catalyst is usually
complex, and the catalyst designer is often faced with a tradeoff between activity, stability and ease of activation.
Based on the review carried out on various studies, it is concluded that a catalyst design must take into con-
sideration not only the separate effects of the active metal, support and promoter, but should also include the
combined and mutual interactions of these components.

1. Introduction ratios on the conversion levels were investigated and confirmed in

The dry reforming of methane (DRM) is a chemical process that
consists of converting methane and carbon dioxide, identified as the
world's most abundant greenhouse gases (GHG) [1], to syngas (hy-
drogen and carbon monoxide), with a H2/CO molar ratio of 1 [2,3]. As
a result, this process has the potentials to mitigate the environmental
challenges associated with GHG emissions and to convert biogas and
natural gas to syngas [4–6]. Moreover, the lower H2/CO ratio syngas
produced is convenient for the production of hydrocarbons via Fischer-
Tropsch synthesis [7–9], in addition to the synthesis of oxygenated
chemicals [10,11] The reaction governing DRM is:
CH4 + CO2 = 2CO + 2H2 (ΔH298K = +247 KJ mol−1)
Being an extremely endothermic reaction [12,13], DRM requires
high operating temperatures, usually in the range of 900–1273 K, to
achieve the desirable conversion levels. The forward reaction is favored
at low pressures as dictated by stoichiometry. Moreover, it has been
noticed that a CO2/CH4 molar ratio higher than the stoichiometric re-
quirement of 1 can also lead to high syngas yields. The positive effects
of high reaction temperatures, low pressures and high CO2/CH4 molar
several studies [14–16].
Despite its considerable environmental potentials, DRM is not con-
sidered an industrially mature process. The extremely high endothermic
reaction, coupled with rapid carbon formation eventually leads to the
catalyst deactivation. In addition, the long reaction time and the re-
quirement for pure CO2, renders DRM an unpractical process that still
needs further developments [17–21].
In the present article, the performance of different catalysts used in
DRM is intensively discussed. The effect of active metals, supports and
promoters on the quality of the catalysts are investigated. This article
gives a better understanding of catalyst design taking into consideration
the effects of active metals, supports and promoters and their synergic
(1)
effect.
2. Thermodynamics, reaction mechanisms and coke formation
2.1. Thermodynamics
Compared to autothermal (ATR) and steam reforming (SRM), the
dry reforming of methane is the most endothermic reaction. This can be

⁎
Corresponding author.
E-mail address: jz08@aub.edu.lb (J. Zeaiter).

http://dx.doi.org/10.1016/j.rser.2017.09.076
Received 29 December 2016; Received in revised form 9 June 2017; Accepted 19 September 2017
Available online 06 November 2017
1364-0321/ © 2017 Elsevier Ltd. All rights reserved.
N.A.K. Aramouni et al. Renewable and Sustainable Energy Reviews 82 (2018) 2570–2585

Table 1
Possible reactions in dry reforming of methane [13,14].

Reaction ΔH 298 K kJ/mol Ln (Keq) at 573 K Ln (Keq) at 1373 K Favored by

CH4 + CO2 < = > 2CO + 2 H2 247 −20 13 High Temperatures

CO2 + H2 < = > CO + H2O 41 −5 2 High Temperatures
2CH4 + CO2 < = > C2H6 + CO + H2O 106 −19 −5 High Temperatures
2CH4 + 2 CO2 < = > C2H4 + 2CO + 2H2O 284 −36 0 High Temperatures
C2H6 < = > C2H4 + H2 136 −14 4 High Temperatures
CO + 2 H2 < = > CH3OH −90.6 −10 −20 Low Temperatures
CO2 + 3H2 < = > CH3OH + H2O −49.1 −12 −20 Low Temperatures
CH4 < = > C + 2H2 74.9 −6 5 High Temperatures
2CO < = > C + CO2 −172.4 15 −7 Low Temperatures
CO2 + 2H2 < = > C + 2H2O −90 8 −5 Low Temperatures
H2 + CO < = > H2O + C −131.3 12 −6 Low Temperatures
CH3OCH3 + CO2 < = > 3CO + 3H2 258.4 10 40 High Temperatures
3H2O + CH3OCH3 < = > 2CO2 + 6H2 136 20 37 High Temperatures
CH3OCH3 + H2O < = > 2CO + 4H2 204.8 14 37 High Temperatures
2CH3OH < = > CH3OCH3 + H2O −37 3 −1 Low Temperatures
CO2 + 4H2 < = > CH4 + 2H2O −165 14 −10 Low Temperatures
CO + 3H2 < = > CH4 + H2O −206.2 14 −11 Low Temperatures

attributed to the fact that CO2, the oxidizing agent used in DRM, is the
most stable compared to oxygen and steam used in ATM and SRM re-
spectively [18–22].
Although DRM is mainly governed by the reaction between CH4 and
CO2 (reaction 1), several other reactions can also occur during the
process. Nikoo and Amin [14] presented these different reactions
(Table 1), their equilibrium constants as a function of temperature
(Fig. 1) and carried out the corresponding thermodynamics analysis.
The equilibrium composition of the reaction system was analyzed based
on the Gibbs free energy minimization method.
The authors concluded that the main reaction of dry reforming
(reaction 1) is thermodynamically favored at reaction temperatures
higher than 1000 K. Similar conclusions were reached by Bradford and
Vannice [5], Wang et al. [13] and Istadi et al. [23].
Nikoo and Amin [14] identified that methane decomposition (re-
action 8), carbon monoxide disproportionation (i.e. Boudouard reac-
tion) (reaction 9), hydrogenation of carbon dioxide (reaction 10), and
hydrogenation of carbon monoxide (reaction 11) are the four reactions
responsible for carbon formation during DRM. Among these reactions,
it was found that only (reaction 8) is favored at high temperatures,
while the other three are favored when operating at reaction tem-
peratures lower than 800 K. Furthermore, it was found that the Reverse
Water Gas-Shift RWGS (reaction 2), which is the reaction that leads to a
H2/CO ratio less than unity, is dependent on the equilibrium at a cer-
tain temperature range and is usually present during DRM.
On the other hand, Wang et al. [13] reported that the RWGS and
Boudouard reaction will not occur at temperatures exceeding 1093 K,
and that the Boudouard reaction and methane decomposition will be
mostly responsible for the formation of carbon at temperatures ranging
from 830 K to 973 K (Table 2).
Zhang et al. [24] reported an increase of the equilibrium constants
of methane decomposition and RWGS with temperature and its de-
crease for the Boudouard reaction.
Concerning the remaining reactions shown in (Table 1), the oxida-
tive coupling of methane (reaction 3 and 4) were found to be only
possible at very high temperatures. Similarly, the dehydrogenation of
ethane (reaction 5) is also favored at high temperatures. On the other
hand, the reverse of reaction 6 and 7 are more favored at high tem-
peratures. Conversely, reactions 12, 13 and 14 are favored at any
temperature range and reaction 15 is dependent on equilibrium lim-
itations. Finally, due to their exothermic nature and negative ln (K)
values, reactions 16 and 17 have the possibility of occurring at tem-
peratures lower than 800 K.
2.2. Reaction mechanism
The mechanism of methane dry reforming is detailed by
Papadopoulou et al. [25]. It can be summarized in four steps as follows:
1. Dissociative adsorption of methane: although the dissociation en-
ergy of CHx-H bonds is dependent on the surface properties, it is
generally agreed that the dissociation of methane on the catalyst is
the rate determining step. Each partially dissociated CHx species
adsorbs preferentially on a site which completes its tetravalency,
with CH3 adsorbing on top of metal atoms while CH2 adsorbs be-
tween two metal atoms (bridged adsorption). Step sites are more

Fig. 1. Reaction steps for the dry reforming of methane [25]: (a)
Dissociative adsorption of CO2 on the metal and metal-support
interface respectively. (b) Fast desorption of CO and hydrogen. (c)
Formation of surface hydroxyls and oxygen spillover. (d) Surface
hydroxyls and oxygen species oxidize hydrogen depleted S-CHx
species and formation of CO and H2.

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Table 2
Summary of whisker carbon mechanism studies.

Author Proposed works References

Baker et al. Carbon diffusion in nickel is the rate determining step in whisker formation mechanism [35]
Baker et al. The driving force for carbon diffusion is a temperature gradient caused by the dissociation of acetylene on the catalyst surface [33]
Baker et al. diffusion of carbon through the metal particle is confirmed to be rate limiting after comparing activation energies for whisker carbon [36]
growth and carbon diffusion, and finding that they are equal
Lobo Proposed a similar model as Baker (classical model): (1) detachment of a nickel particle, (2) decomposition of adsorbed hydrocarbons [37]
into carbon, (3) diffusion of carbon through the nickel particle, and (4) growth of the whisker.
Rostrup-Nielsen & Trimm Whisker carbon also formed from endothermic surface reactions so the postulate in [baker] is rejected. the driving force for whisker [38]
growth is a concentration gradient of carbon across the nickel particle.
Alstrup Proposed a corrected mechanism in which the rate limiting step is the formation of a metal carbide during the induction period on the [39]
surface of the crystal where carbon decomposition occurs, causing a restructuring of the metal particle. During the steady state carbon
growth period, carbon diffuses through the carbide and a constant carbon gradient is maintained

active for methane adsorption and dissociation than close-packed
surfaces.
2. Dissociative adsorption of CO2: The surface structure and defects
also affect the adsorption and dissociation of CO2, which can occur
in three ways: C-only coordination, C and O coordination (Carbon
and one oxygen adsorb on the catalyst surface and leave one oxygen
atom exposed), or O-only coordination, with both oxygen atoms
bonding with the surface metal. The latter two coordination geo-
metries are more favorable towards dry reforming. This step is
generally considered fast. CO2 tends to adsorb on the metal-support
interface.
3. Hydroxyl groups formation: Little work is done on the surface re-
action mechanisms for dry reforming as compared to steam re-
forming. However, it is known that the water-gas shift reaction is at
quasi-equilibrium, meaning that the surface reactions that are re-
lated to it are quite fast. Most developed models predict hydrogen
migration from the active metal particle to the support where it
forms hydroxyl groups at temperatures below 1073 K.
4. Intermediates oxidation and desorption: Surface oxygen on the
metal particle reacts with S-CHx groups to form S-CHxO or S-CO.
Some authors consider the S-CHxO groups to be precursors to CO
formation while others assert that adsorbed CO2 forms carbonates
that are reduced to CO by carbon on the metal. Other authors claim
that S-CO is formed directly without a formate S-CHxO intermediate.
Just as for steam reforming, there is no clear consensus about the
details of the reaction mechanism on the surface of the catalyst, and
the impact of the catalyst nature and operating conditions is also
very important. However, in many cases, the formation and/or de-
composition of formates S-CHxO to CO and hydrogen is considered
the rate determining step, especially knowing that the desorption of
CO and hydrogen is fast.
A complete list of the possible elementary reaction steps in the dry
reforming reaction are given in Papadopoulou et al. [25].
2.3. Coke formation
Coke deposition on the reforming catalyst is expected due to the
high operating temperatures, which raises the molecular energy enough
to cleave the C-H bonds in methane. It is therefore desirable to un-
derstand the conditions at which carbon forms to minimize its forma-
tion. The majority of catalysts used in the reforming industry consist of
supported nickel, usually on aluminum oxides. The main problem with
these catalysts is that they also catalyze carbon formation reactions
[26,27], resulting in loss of catalyst activity. Predicting the likelihood of
carbon deposition from purely theoretical calculations can be tricky
since the surface phenomena occurring on the nickel crystals cause
substantial deviations from the well-known graphitic carbon thermo-
dynamics [27]. Carbon is formed in three main forms: pyrolytic coke,
whiskers and gum. Coke and whiskers are more commonly formed at
high temperatures while gum is formed at lower temperatures.
Pyrolytic coke is generally formed when heavier hydrocarbons are ex-
posed to high temperatures, while gum is formed as a CHx layer or a few
layers of graphene which encapsulate the catalyst [28].
At high temperatures above 650 °C [26], especially in the presence
of heavy hydrocarbons that undergo pyrolysis and steam cracking,
ethylene produced by the decomposition of higher hydrocarbons causes
a deposition of pyrolytic coke on the catalyst particles, completely en-
capsulating the catalyst pellets and causing a loss in activity and an
increase in pressure drop across the reformer. At low temperatures and
steam to carbon ratios, carbon formed by surface reactions adsorbs on
the catalyst particle and polymerizes forming gum-like carbon that
blocks the catalytic activity of the particle [29]. This type of carbon
deposition is also very important in prereformer treating relatively
heavy feeds (naphtha) since they operate at lower temperatures, in the
range of 350–650 °C. Gum carbon can consist of layers of graphite or
thin films of hydrocarbons deposited on the catalyst [30]. The loss of
catalyst activity alters the reaction profile within the reformer and
therefore modifies the temperature profile due to strong heat effects of
the reactions involved. However, there are different carbon species that
can form based on the thermodynamic conditions and catalyst prop-
erties, and therefore there is no unique description for carbon species
on a catalyst. A classification of surface carbon species has also been
developed based on TPH studies [31]: Cα refers to surface carbide that
can be hydrogenated below 323 K, Cβ (or amorphous carbon) can be
hydrogenated between 373 and 573 K,while Cγ (graphitic carbon) is
only hydrogenated above 673 K.
The most notorious type of carbon deposition on nickel catalysts is,
however, the filamentous carbon also known as whisker carbon. It oc-
curs at higher temperatures, low water content and is greatly influenced
by the presence of aromatics [27]. Carbon issued from the Boudouard
reaction, methane dissociation reaction and other decomposition re-
actions diffuses through the nickel crystal and nucleates on the un-
exposed side [26], creating a strong whisker that grows with a nickel
crystal on top, and eventually pushes the nickel crystal out of the cat-
alyst structure [30]. Rostrup-Nielsen [29] summarized the mechanism
of whisker carbon growth as: Adsorption of CO or hydrocarbons on the
surface, dissociation to give adsorbed carbon that dissolves and diffuses
through the metal particle until it reaches the rear interface, where it
nucleates on the carbon whisker. The growing high strength carbon
fiber pushes out fragments of the active nickel particle as it grows, and
once the fiber reaches the pores of the particle, it can break it. Whisker
carbon can even cause the catalyst pellets to break, potentially with
catastrophic consequences ranging from increased pressure drop and
loss of activity to reactor blockage in steam reformers, and hot spots/
hot bands that can lead to reactor failure [26,29,30,32].
Many authors noted that the thermodynamics of carbon formation
on nickel catalysts deviated from the graphite thermodynamics [26,33],
which brings into question the validity of the graphite assumption for
carbon deposition on supported nickel catalysts. Dent et al. [34] con-
cluded that the equilibrium constants for CO and CH4 decomposition
had smaller equilibrium constants than graphite. Rostrup-Nielsen [26]

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N.A.K. Aramouni et al.
and Alstrup et al. [33] made similar observations.
Alstrup even proposed an expression for the deviation from the
graphite free Gibbs energy for supported nickel catalysts:
ΔGc = 20.6 + 93/D kJ/mol
With D being the diameter of the largest metal particle catalyzing
filament growth in nm.
The mechanism of whisker growth and its study by different re-
searchers is summarized in Table 2.
Alstrup also noted that the metal particles in typical catalysts are
usually well exposed thermally, which makes the model for the driving
force proposed by Baker et al. [36], unlikely except for large metal
particles which might not be in good thermal contact with the reaction
medium. As a result, the driving force for carbon growth is a combi-
nation of a concentration and a temperature gradient. The deformation
and restructuring of the metal particle with carbon formation has been
observed by Alstrup et al. [33], who noted that the nickel particle be-
comes pear shaped with a conical feature that is longer at higher
temperatures, and concluded the graphite planes may be exerting
friction forces strong enough to deform the metal particle into this
shape.
The mechanism of carbon formation in dry reforming of methane as
explained by Papadopoulou et al. [31] (and references within) corre-
sponds closely to the mechanism discussed by Rostrup-Nielsen, Trimm,
Alstrup and other authors in steam reforming, which leads us to believe
the mechanism of carbon formation in most reforming technologies is
the same, with the exception of the combustion zone in autothermal
reformers where the main carbon type formed is soot.
An interesting observation made by Annesini et al. [32] in their
study of steam/CO2 reforming is that the presence of CO2, even in small
amounts (2%) can drastically affect the carbon limits. At temperatures
below 1000 K, the increasing presence of CO2 in the gas increases the
required steam/carbon ratio to avoid carbon deposition, while the op-
posite effect is observed at temperatures higher than 1000 K.
Rostrup-Nielsen [26] proposed a mathematical formula to predict
the likeliness of carbon formation in the steam reformer that takes into
account the deviation from graphite equilibrium caused by the whisker
structure, by means of evaluating the equilibrium carbon activity aceq:
PCH4
aceq = K c
PH2 2
In which Kc is the equilibrium constant for the methane decom-
position reaction that takes into account the thermodynamic deviation
from ideal graphite structure. A carbon activity lower than 1 is a safe
design criterion to minimize carbon formation in the reformer.
Bengaard et al. [43] observed that step sites on nickel crystals have a
higher affinity for carbon formation: nucleation takes place on these
step sites and layers of carbon form and give carbon whiskers. The
carbon layers formed are thermodynamically stable above approxi-
mately 80 atoms in diameter, and therefore larger crystals are more
prone to carbon deposition [29,40,41]. It is then intuitive that a higher
dispersion of nickel in the support phase will decrease carbon deposi-
tion on the catalyst since they retard the nucleation of carbon whiskers.
A combination of high dispersion catalysts and correct operating con-
ditions should maximize the initiation period and avoid the loss of
catalyst due to coke formation.
A potential research prospect is the development of corrected
thermodynamic studies of carbon formation taking into account the
deviation from graphite thermodynamics proposed by Rostrup-Nielsen
for nickel catalysts that would allow for better knowledge of the risk of
carbon formation, especially towards the end of service of the catalyst
batch suffering from sintering.
3. Heterogeneous catalysts used in DRM
Noble and transition metal based catalysts were extensively
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Renewable and Sustainable Energy Reviews 82 (2018) 2570–2585
investigated to promote the endothermic dry reforming reaction. The
activity and stability of these heterogeneous catalysts, the conversion
rates of methane and carbon dioxide to synthetic gas, the resulting H2/
CO molar ratio, in addition to the morphology and the amount of the
carbon deposited throughout the process, were found to be directly
related to various parameters determined by the selection of the active
metals, supports and promoters [42].
3.1. Effect of active metal
Due to their low cost, availability and high catalytic activity, nickel
and other non-noble metal catalysts were widely used in the dry re-
forming of methane[43–57]. However, despite their apparent con-
venience for industrial applications [58,59], the high coke formation
associated with the use of these catalysts lead to their deactivation and
constitutes a major operational drawback [60,61]. On the other hand,
despite the high resistance to coke deposition exhibited by noble metal
based catalysts, in addition to their noticeable stability and high cata-
lytic activity [62–70], the practical use of these catalysts has been se-
verely hindered by their elevated cost and limited availability [59,71].
The difference in performance can be attributed to the ability of noble
metals, unlike their non-noble counterparts, to disperse on their support
and retain a small particle size. In addition, they tend to reduce the
amount of coke formed during reaction and alter its type. Several ap-
proaches have been investigated in order to overcome deactivation is-
sues. One approach is to create an alloy catalyst (usually bimetallic),
where a noble or non-noble metal is added to another primary metal.
This approach can potentially overcome the deactivation of non-noble
catalysts caused by excessive coke formation, while simultaneously
reducing total cost. It can also increase the dispersion of the metal,
decrease the size of the metal particle and thus retain a good catalytic
activity and stability [24,71–84].
Hou et al. [62] used the impregnation method to prepare different
types of catalysts in order to compare the coke deposition resistance,
activity and stability of noble and non-noble based catalysts. 10 wt%
Nickel and cobalt with Ru, Rh, Pt, Pd, Ir (5 wt%) supported on α-Al2O3,
in addition to Rh (5 wt%) on a meso-porous alumina support (Yas3-8)
were prepared and tested. The conversion rates of methane and carbon
dioxide were measured after 30 and 240 min. The deposited carbon (mg
coke/g cat h) and stability of each catalyst were also reported. The
reaction occurred at 800 °C, with a CH4 flow rate of 25 ml(STP)/min,
CO2 flow rate of 25 ml(STP)/min, in addition to a catalyst amount of
50 mg and a space velocity of 60,000 ml/(g cat h).
All noble metals showed no carbon deposition, except Pd which led
to a carbon deposition of (4.9 mg coke/ g cat h). It was also found that
the carbon deposition under Ni and Co catalysts were considerably high
at (24 mg coke/ g cat h) and (49.4 mg coke/ g cat h) respectively, a
factor repeatedly related to the poor resistance of these non-noble based
catalysts to carbon formation [63–66,85,86]. These numbers strongly
reflect the superior coke resistance ability of noble metal catalysts
compared to their non-noble counterparts. The high coke resistance of
noble catalysts was also confirmed by other studies [63–66].
On the other hand, it was concluded that among the noble metals,
rhodium (Rh) supported catalyst exhibited the highest catalytic activity
and stability, followed by ruthenium (Ru), iridium (Ir), palladium (Pd)
and platinum (Pt). The low stability of Pd and Pt supported catalysts
was attributed to the sintering of the metal particles at high tempera-
tures, while the superior ability of the other noble metals to eliminate
coke deposition was attributed to their high dispersion and small par-
ticle size. These results were also confirmed by Matsui et al. [87] and
Tsyganok et al. [88].
It is worth mentioning that, despite the higher coke formation
witnessed under nickel (Ni) and cobalt (Co) catalysts compared to the
noble metal ones, the non-noble based catalysts achieved higher initial
conversion rates than all other catalysts, except with Rh, thus reflecting
the considerable catalytic activity of transition metal catalysts,
N.A.K. Aramouni et al.
especially supported nickel. However, under different support and re-
action conditions, the catalytic activity of noble metal based catalysts
was found to be higher than those of Ni and Co [50,74,85].
Arandiyan et al. [89] compared the catalytic activity, stability and
surface properties of different perovskite-type oxides catalysts doped
with different noble metals used in the dry reforming of methane reac-
tion. Using the sol-gel method, the authors prepared perovskite catalysts
La0.4M0.6Al0.2Ni0.8O3 (M = noble metal) doped with Ir, Pd, Pt, Rh and
Ru, in addition to LaAl0.2Ni0.8O3. Following an activity performance test
carried out on these catalysts, the authors concluded that CH4 and CO2
conversion were in the order, from the highest to the lowest,
La0.4Rh0.6Al0.2Ni0.8O3 > La0.4Ru0.6Al0.2Ni0.8O3 > LaAl0.2Ni0.8O3 > La0.4
Ir0.6Al0.2Ni0.8O3 > La0.4Pt0.6Al0.2Ni0.8O3 > La0.4Pd0.6Al0.2Ni0.8O3.
These results were largely consistent with the findings of Hou et al.
[62], especially regarding the order of activity of noble metals. The
stability test carried out at 850 °C for 3000 min (Fig. 2) showed that Rh
and Ru catalysts were the most stable, while the Pd catalyst was the
most prone to deactivation. Additionally, the low H2/CO molar ratio
observed for La0.4Pd0.6Al0.2Ni0.8O3 indicated that the reverse water gas
shift reaction (RWGS) occurred favorably under this catalyst. It is be-
lieved that the superior catalytic performance of La0.4Rh0.6Al0.2Ni0.8O3
is due to its good reduction at low temperatures, high surface area and
surface oxygen concentration, which hinders coke formation via the
oxidation of intermediate species.
Several studies have highlighted the importance of maintaining
high dispersion and surface area, in addition to small metal particle size
in order to achieve high catalytic activity, stability and avoid excessive
carbon formation. More importantly, this factor has proved critical for
both noble and non-noble based catalysts [85,88–95].
El Hassan et al. [85] showed that by reducing metal sintering and by
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Renewable and Sustainable Energy Reviews 82 (2018) 2570–2585
Fig. 2. TEM images of the spent (a–c) Co12/SBA-15
and (a′–c′) Rh0.5Co12/SBA-15 catalysts [85].
altering the type of coke formed during DRM reactions, noble metals
are able to provide a superior catalytic activity and stability compared
to their non-noble counterparts. After a reaction time of 550 min, the
conversion levels of CO2 and CH4 were higher under Rh0.5/SBA-15 and
Rh0.5Co12/SBA-15 compared to those reached under Rh-free Co12/SBA-
15 and Co12/SiO2. In order to study the effect of metal sintering and
coke deposition on the performance of the catalysts, the spent Rh0.5/
SBA-15, Rh0.5Co12/SBA-15 and Co12/SBA-15 catalysts were character-
ized by High Resolution Transmission Electron Microscopy (HRTEM)
and Combined Temperature Programmed Hydrogenation and Mass
Spectrometry (TPH-MS).
HRTEM images (Fig. 2a-c) show that during the methane reforming
reaction, a significant amount of cobalt particles present in Co12/SBA-
15 have migrated outside the pores, leading to the sintering of these
nanoparticles and the formation of external particles ranging in size
from 10 to 30 nm. As for the cobalt particles that remained inside the
pores, an important increase in size occurred; the average size of the
cobalt oxides that existed before the reaction was found to be 8.6 nm,
while the reduced Co° species found in the pores after the reaction had
an average size of 11.6. On the other hand, as shown in (Fig. 2a′-c′),
doping the cobalt catalyst with Rh has severely reduced the migration
of active metals to the pores’ exterior and reduced the size increase of
the metal particles inside the pores. These results further support the
claim that noble metals offer superior anti-sintering properties com-
pared to non-noble ones (including nickel), thus leading to more stable
catalysts.
Catalyst deactivation is not only determined by the amount of coke
deposited on the surface. The type of coke formed during the reforming
reaction can also have varying effect on the catalytic stability. The most
reactive carbon among the three types is the Carbide Cα type, it is an
N.A.K. Aramouni et al.
intermediate specie that does not lead to the deactivation of the cata-
lyst. The amorphous Cβ type is less active than Cα and is produced at
low temperatures, whereas the graphitic Cγ type is the least active
among the three types, it is deposited at high temperatures and is di-
rectly linked to catalyst deactivation. El Hassan et al. [85] carried
temperature programmed hydrogenation- mass spectrometry -(TPH-
MS) test to identify different types of carbon deposited on the spent
catalysts. The non-noble based Co12/SBA-15 catalyst had the highest
percentage of the destructive Cγ type compared to the other Rh based
catalysts. Furthermore, comparing the coke types deposited on the
monometallic Co12/SBA-15 and Rh0.5/SBA-15 catalysts, one can notice
that, although the percentage of Cγ did not decrease significantly under
Rh0.5/SBA-15, the increase of the more reactive Cα and the consequent
decrease of the less reactive Cβ on this catalyst explain its superior
stability compared to the non-noble cobalt catalyst. Additionally, it can
be noticed that, doping cobalt with Rh led to a significant decrease of
Cγ type. This justifies the exceptional catalytic performance of the bi-
metallic catalysts Rh0.2Co12/SBA-15 and Rh0.5Co12/SBA-15 compared
to the mono-metallic ones. Finally, among the bimetallic catalysts, it
can be seen that increasing the amount of Rh in the alloy led to the
advantageous increase of Cα type.
It is worth mentioning that, despite the higher coke formation as-
sociated with non-noble metals, maintaining a high dispersion of these
metal particles can delay the catalyst's deactivation time, thus paving
the way for prolonged catalysts stability up to 320 and 600 h [49,95].
Zhang et al. [95] were able to synthesize a highly stable Ni catalyst
supported on SBA-15 zeolite with nickel loadings ranging from 2.5% to
20 wt% . After monitoring the conversion of CH4 and CO2 under re-
action temperatures ranging from 700 to 850 °C it was found that
higher temperatures lead to higher conversion rates and that the cata-
lysts having a Ni loading larger than 10% yielded similar conversion
rates at high temperatures. The authors were able to overcome the
deactivation of nickel catalysts and maintain a conversion rate of CH4
and CO2 close to 90% for 600 h by limiting the sintering of Ni and
ensuring its high dispersion through exploiting the confinement effect
and porosity of the SBA-15 support.
Subsequently, the authors investigated the stability of Ni (12.5 wt
%)/SBA-15 catalyst for 720 h at 800 °C by recording the conversion
rates of CH4 and CO2, in addition to the selectivity of H2 and CO. No
significant change in conversion rates for both CH4 and CO2 nor the
selectivity of H2 and CO were witnessed during the first 600 h. After
710 h, the conversion rate of CH4 decreased by approximately 50%,
while that of CO2 decreased by 25%. This in turn suggested to the
authors that two active centers exist for the activation of CH4 and CO2.
The size of Ni particles did not significantly increase before the reaction
and after 710 h, thus indicating that Ni was confined to the pores of the
support and did not sinter throughout the reaction. Moreover, it was
concluded that coke formation (measured at 14.8 wt% after 710 h) and
not nickel sintering led to the deactivation of the catalyst after 600 h.
The sharp decrease of the SBA-15's pore diameter from 6.64 nm after
reduction at 750 °C to 5.66 nm after 710 h of reaction, and the decrease
of the BET- specific surface area from 409.4 m2/g to 319.0 m2/g, led the
researcher to conclude these variations were caused by coke formation.
In another study [49], Zeng et al. were able to enhance the catalytic
activity and stability of non-noble Co/ γAl2O3 catalyst via the addition
of mixed rare earth (MRE) oxides promoters. The addition of these
promoters offered a beneficial synergetic effect that decreased the size
of Co3O4 particles and increased the interaction between the cobalt
species and its support, which lead to an increase in the anti-sintering
ability of the metallic cobalt particles. Additionally, these promoters
increased the ratio of active carbon and improved the anti-coking
performance of the catalyst. It was observed that this 0.5MRE/Co cat-
alyst achieved a CH4 and CO2 conversion of 75% and 84% respectively
after 320 h at 800 °C.
Appendix I presents the conversion percentages of methane and
carbon dioxide under noble and non-noble monometallic catalysts as
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Renewable and Sustainable Energy Reviews 82 (2018) 2570–2585
reported by different studies. Appendices II and III present the con-
version levels under nickel and other non-noble monometallic catalysts
respectively, while Appendix IV presents these values under various
noble monometallic catalysts. Additionally, the support, promoter, re-
action temperature, reaction time, catalyst preparation method and
reactor type under each run are also presented.
One can observe that the performance of nickel and cobalt as active
metals is very close, although nickel is slightly more active [62] and
especially over a La-Al support [96]. The presence of Co increases the
catalyst stability, as can be shown by the longer reaction times dis-
played for Co-based catalysts (Appendix III) as compared to Ni-based
catalysts (Appendix II). However, using a noble metal yields better re-
sults, and the noble metals rank in the following order: Rh > Ru >
Ir > Pt > Pd. Noble metals improve catalyst performance drastically,
both as active metals and promoters, but their loading is very critical,
with optimal concentrations usually low, and typically below 0.5% wt
as promoters. Silver and gold are not as successful as the former noble
metals in dry reforming: even on the excellent Mg-doped alumina
support and at 800 °C, a 2% Au catalyst yields only 0.8% CO2 conver-
sion and 0.3% methane conversion [97]. Furthermore, the synergetic
effect observed in bimetallic formulations is not always apparent when
using noble metals. For example, Rh/La2O4 gives a better conversion
than Rh-Pt/La2O4 [74].
Several researchers have investigated the ability of alloy-catalysts
(usually bimetallic) to overcome the operational and economical lim-
itations imposed by noble and non-noble based catalysts respectively.
This approach in designing the catalyst has the potential to tackle the
deactivation problem witnessed for non-noble catalysts attributed to
their sintering and low coke deposition resistance, in addition to
overcoming the high cost and unavailability of coke resistant noble
catalysts. The addition of small amounts of noble metals (Rh, Ru, Ir, Pt,
Pd, Au) or non-noble metals (Ni, Co, Cu, Fe) to conventionally non-
noble based catalysts enhanced the catalytic activity and stability of the
resultant bimetallic catalyst in comparison to its original monometallic
derivatives. This amelioration of the catalytic performance and coke
resistance is achieved by increasing the dispersion of the active metal
particles and decreasing their size, enhancement of the catalyst re-
ducibility, decreasing the rate of coke formation, altering the type of
coke deposited on the catalyst's surface, in addition to creating a sy-
nergic effect between the metals involved [62,72,75,85,91,96–103].
Different studies have investigated the effects of adding small
amounts of noble metals to a non-noble based catalyst
[61,86,97,104–108]. Hou et al. [62] investigated the coke formation
and conversion rates of CH4 and CO2 under Ni catalyst supported on
meso-porous alumina (Yas3-8). The reaction conditions were as follow:
800 °C, CO2/CH4 = 50/50 ml/min, 1 atm, 50 mg catalyst, space velo-
city 120,000 ml/g cat h and 4 h on stream. The Ni/Yas3-8 led to a CH4
and CO2 conversion levels of 62% and 68.4% respectively, while the
coke formation rate was measured at (17.2 mg coke/g cat h). Subse-
quently, the author added a small amount of Rh to this Ni based catalyst
corresponding to Rh/Ni = 0.1. This new bimetallic catalyst Rh0.1Ni/
Yas3-8 was able, under the same reaction conditions, to eliminate the
formation of coke while increasing the conversion rates of methane and
carbon dioxide to 69% and 75% respectively. The authors concluded
that the higher stability and activity of the bimetallic catalyst can be
attributed to the synergic effects of Ni and Rh. Moreover, they ex-
plained the elimination of coke deposition to the formation of Rh-Ni
clusters, having a Ni covered surface, thus enhancing the dispersion of
the nickel particles and favoring the formation of more reactive inter-
mediate carbonaceous species.
Moreover, Tomishige et al. [102] have investigated the catalytic
performance of Pt modified Ni/Al2O3 catalysts compared to the Ni and
Pt monometallic catalysts. After carrying out a methane reforming re-
action with CO2 and O2 in a fixed-bed reactor at atmospheric pressure,
the authors concluded that Pt(0.3)/Ni(10)/Al2O3 (prepared by a se-
quential impregnation method) showed a superior performance than Pt
N.A.K. Aramouni et al.
(0.3) + Ni(10)/Al2O3 (prepared by co-impregnation), Ni(10)/Al2O3, Pt
(0.3)/Al2O3 and Pt(10)/Al2O3 respectively. The authors attributed
these results to the ability of surface Pt atoms on the nickel catalyst to
enhance the catalyst reducibility.
El Hassan et al. [85] showed that doping a small amount of Rh (up
to 0.5 wt%) on Co (12 wt%)/SBA-15 catalyst can achieve a higher
catalytic activity and stability. The authors concluded that the addition
of rhodium promotes the reducibility of the cobalt nanospecies under
hydrogen and participates in the reaction thus improving catalytic
performance. Moreover, the authors showed that the presence of small
amounts of Rh can alter the nature of the coke formed on the catalyst
and reduce the amount of the destructive Cγ type. Jozwiak et al. [107]
investigated the activity and stability of silica supported monometallic
Ni, Rh and bimetallic Ni–Rh catalysts used for the dry reforming of
methane. The results showed that under a reaction condition of 700 °C,
24 h and contact time of 3.33 × 10−5 g h cm−3, the addition of Rh to
Ni/SiO2 catalyst can increase its activity and stability. It was found that
the conversion rate of methane was highest and the loss of activity was
lowest under bimetallic catalysts.
The presence of another metal as a support doping agent or as a
support can have different effects based on the metal: noble metals such
as Ru, Rh and Pt promoting nickel or cobalt can improve the catalyst
activity and stability, but other metals, especially Ca, Mn and Sn [44]
are poisons to the catalyst, causing a large decrease in activity and
increased carbon formation. Potassium in small amounts causes a de-
crease in activity but also a decreased carbon formation rate [109].
However, manganese and potassium do not poison noble metals as
much as nickel, and Yttrium has even shown to improve the activity of
palladium catalysts [65]. In addition, it can be concluded from
Appendix V that Sr is a weak promoter for nickel and cobalt catalysts.
The addition of mixed rare earth metals (MREs) to cobalt/alumina
catalysts enhances the coke resistance and increases the ratio of active
carbon deposited on the catalyst [49]. It is also observed that the ad-
dition of MRE oxides causes an increase in CO2 conversion that is higher
than the increase in methane conversion, meaning that the MREs in the
amounts used promote the reverse water-gas shift reaction. Iridium
based catalysts also promote the reverse water gas shift reaction and
therefore exhibit a CO2 conversion higher than that of methane [110],
while platinum based catalysts seem to inhibit this reaction, showing a
much larger methane conversion [102].
On the other hand, titanium has shown questionable performance in
a catalyst formulation, be it as an active metal or oxide support
[90,108,111–113]. Although Takanabe et al. [100] found TiO2 sup-
ported Ni-Co catalysts to be highly stable, the maximum methane
conversion they obtained using these catalysts was approximately 50%
at 1023 K, which is way below the equilibrium conversion. Usman et al.
[42] highlighted the good performance of TiO2 as a support in main-
taining dispersion and reducing carbon deposition rates. However,
conversions obtained on titanium catalysts or catalysts supported on
TiO2 have shown quite low conversions even at high temperatures, as
shown in the appendices. (Appendix V) presents the results of several
studies comparing the reaction yields of dry reforming of methane
under mono, bi and trimetallic catalysts. It can be noticed that the
majority of these studies reported higher conversion levels under alloy
catalysts than their corresponding monometallic ones. Moreover,
(Appendix VII) presents the conversions under bimetallic catalysts
formed by the addition of noble and non-noble metals.
Alloy catalysts are not restricted to noble - non noble bimetallic
catalysts. Several studies have developed alloy catalysts based on two
non-noble metals [96,101,114,115], two noble metals [74,116] or tri-
metallic catalysts [117,118].
Al Fatesh [101] prepared Ni (10 wt%), Co (10 wt%) monometallic
catalysts and Ni (5 wt%) + Co (5 wt%) bimetallic catalyst supported on
γ-Al2O3 by the impregnation method. Sr was used as a promoter with
loadings ranging from 0 to 1 wt, and concluded that the bimetallic
catalysts offered a better catalytic activity and stability compared to the
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Renewable and Sustainable Energy Reviews 82 (2018) 2570–2585
monometallic ones. This was ascribed to the interaction of the two
species. The highest catalytic activity was experienced under Ni-Co,
followed by 5Ni5CoSr0.25, 5Ni5CoSr0.75, 5Ni5CoSr0.5, 10Co, 5Ni5CoSr1
and finally 10 Ni. Moreover, Sr promoted bimetallic catalysts exhibited
higher stability (small decrease of methane conversion) and smaller
amounts of coke deposition compared to the other catalysts, while all
bimetallic catalysts led to smaller deactivation factors and carbon de-
position amounts than the two monometallic ones. The enhancement
offered by the Sr promoters was attributed to their high basicity and
better metal-support interaction, thus reducing the sintering of active
metal particles.
Fan et al. [91] compared the methane conversion rates under Ni/
MgO-ZrO2, Co/MgO-ZrO2 and Ni-Co/MgO-ZrO2. It was reported that
the bimetallic Ni-Co catalyst achieved the highest methane conversion
rate of 80%, higher than the ones witnessed under the monometallic Ni
and Co catalysts, at 70% and 71% respectively. The increase in the
catalytic activity of the bimetallic compound compared to the mono-
metallic ones was attributed to the synergic effect of Ni and Co, in
addition to better metal dispersion and smaller particle size. Appendix
VI presents the conversion levels of methane and carbon dioxide under
bimetallic catalysts consisting of two non-noble metals.
As for bimetallic catalysts formed by the addition of two noble
metals, Du et al. [116] investigated the catalytic performance of Pt, Ru
and Pt-Ru catalysts supported on γ-Al2O3. After carrying out the me-
thane reforming reaction for 1 h at 700, 800 and 900 °C, the authors
showed that the Pt-Ru/γ-Al2O3 bimetallic catalyst exhibited superior
catalytic activity and selectivity (lower CO/H2 molar ratio) compared
to its corresponding monometallic ones under all the investigated re-
action temperatures. Moreover, the authors tested the stability of the
Pt-Ru/γ-Al2O3 for 500 h at 800 °C. At the end of the test, the authors
measured the conversion of CH4 and CO2 at 94% and 96% respectively.
Moreover, the author found that this catalyst led to a molar ratio of CO/
H2 close to 1, thus indicating that the side reactions accompanying the
dry reforming of methane reaction were limited to a large extent. Ad-
ditionally, the spent catalysts were subjected to a thermo-gravimetric
(TG) test to investigate the carbon deposited on their surfaces. It was
shown that the mass loss for the bimetallic catalyst occurred at lower
temperature ranges than the monometallic ones. Consequently the Pt-
Ru/γ-Al2O3 catalyst will be able to generate more active carbon species
during the reaction, thus enhancing its stability compared to the other
catalysts. Finally, the authors attributed the enhanced catalytic per-
formance and stability of Pt-Ru/γ-Al2O3 to the anti-agglomeration of
the active bimetallic particles.
On the other hand, Wu et al. [117] investigated the effects of adding
small amounts of Au and Pt to Ni (4 wt%) catalyst supported on Al2O3
and Al2O3−10 wt%MOx(M = Ce or Mg) oxides. It was concluded that
the addition of 0.2 wt% of Au and Pt to Ni catalyst leads to the for-
mation of bi and trimetallic catalysts having a superior catalytic activity
and stability as compared to monometallics. This was attributed to the
formation of nanosized nickel particles that synergistically interact with
Au and Pt. The activity was however only slightly increased by using
trimetallic Ni-Au-Pt catalysts.
Trimetallic catalyst formulations do not always follow the same
trends that are shown when comparing monometallic catalysts with
bimetallic catalysts: Synergetic effects are less noticeable and some-
times even hindered as in the case of the Ni-Pt-Au /Al2O3 system [117]
where the Ni-Pt catalyst showed a slightly better conversion than the
Ni-Au-Pt catalyst in some cases. The use of more than one noble metal
in a trimetallic formulation is therefore not always desirable both due
to economic barriers and low technical advantage. Furthermore, due to
the already intricate interactions between three metallic species
yielding generally good catalyst properties, the effect of the support
material is less apparent in trimetallic catalysts (Appendix V).
Perovskite-type catalysts were also investigated for the dry re-
forming of methane [89,119–121]. De Caprariis et al. [119] in-
vestigated methane dry reforming under three ternary perovskite type
N.A.K. Aramouni et al. Renewable and Sustainable Energy Reviews 82 (2018) 2570–2585

oxides BaZr(1-x)MexO3 using noble metals Rh, Ru and Pt as active Table 3

species. Performing the DRM reaction at atmospheric pressure and Textural properties of the supports [123].
under reaction temperatures ranging from 850 to 1150 K, the authors
Support BET surface area Pore volume Average pore size
showed that BaZr0.8649Rh0.1351O3 displayed the highest catalytic ac- (m2/g) (cm3/g) (nm)
tivity followed by BaZr0.8649Ru0.1351O3 then BaZr0.9272Pt0.0728O3. The
higher activity of Rh and Ru based catalysts compared to BaZrPtO3 was SiO2 239 (235a) 0.76 12.8
TiO2 9 (7a) 0.030 13.8
connected to their higher reducible nature. Moreover, the low carbon
Al2O3 167 (161a) 0.60 14.3
formation rates witnessed under Rh and Ru perovskites at 0.0019 and MA 145 (142a) 0.58 15.9
0.0027 g coke/ g cat h respectively, compared to the Pt perovskite at ZrO2 25 (21a) 0.10 15.2
0.0094 g coke/ g cat h, justified the lack of deactivation witnessed MgO 29 (23a) 0.093 12.6
under the Rh and Ru catalysts after a 65 h long stability test and the a
Specific surface area of catalysts after loading NiO.
10% drop of activity for the Pt catalyst after the same duration.
Valderrama et al. [120] produced perovskite-type oxides based on
La_Sr_Co (La1−xSrxCoO3). The authors concluded that despite the ex-
treme reaction conditions, the catalysts led to high activity and stability Table 4
due to the formation of nano-sized Co0 particles over the SrO and La2O3 Metal dispersion in catalysts [123].
phases which were highly dispersed in the La2O2CO3_SrO solid matrix.
Catalyst Metal Specific surface area Particle Carbon
Moreover, the Sr promoter has also proved its ability to stabilize the dispersion % of metal size nm deposition (mgC.
cobalt metallic particles. It was observed that, under a reaction tem- (gcat h)−1)
perature of 800 °C for 30 h in a tubular quartz reactor, the use of A(m2/g A(m2/g
La0.9Sr0.1CoO3 has led to conversion levels of 86% and 91% for me- car) Ni)

thane and carbon dioxide, respectively. Appendices V and IX present NiO/SiO2 10.3 5.5 68.4 9.9 3.0
the reaction yields witnessed under bimetallic catalysts formed by the NiO/TiO2 2.0 1.1 13.5 49.9 24.7
addition of two noble metals, in addition to perovskite and trimetallic NiO/Al2O3 3.1 1.7 20.6 32.7 16.3
catalysts, respectively. NiO/MA 7.6 4.0 50.6 13.3 1.7
NiO/ZrO2 4.4 2.4 29.5 22.9 21.0
NiO/MgO 3.0 1.6 20.4 33.0 4.2
3.2. Effect of the support selection

The performance of a catalyst is not only a function of the active

metal and promoter, but also of the support [122]. Support materials
provide certain textural and physicochemical properties that play an
important role in keeping the catalyst well-dispersed and resistant to
carbon. Highly porous, high surface area supports are desirable to give
high activity and good dispersion. Furthermore, the interaction be-
tween the active species and the support material affects the stability
and reducibility of the catalyst. An appropriate selection of the support
must exploit its textural and chemical properties, such as surface area,
pores characteristics, thermal stability, redox properties, oxygen sto-
rage capacity and surface basicity, to enhance the metal-support in-
teraction, increase the dispersion of active metal particles, prevent their
sintering, facilitate the reduction of the catalyst, in addition to reducing
or eliminating the formation of carbonaceous species.
Wang and Ruckenstein [111] compared the performance of Rh
(0.5 wt%) catalysts supported on reducible (CeO2, Nb2O5, Ta2O5,
TiO2, and ZrO2) and irreducible (γ-Al2O3, La2O3, MgO, SiO2, and
Y2O3) metal oxides. Under the same reaction conditions, the conver-
sion rates of CH4 and CO2 varied widely according to the support em-
ployed, thus reflecting the important influence of the support type on
the catalytic activity and stability. Moreover, it can be noticed that the
catalysts supported on irreducible oxides generally led to higher con-
version rates and H2/CO ratios than their reducible counterparts.
After 0.5 h on stream, the conversions rates, H2 and CO yields ob-
tained under the irreducible oxides decreased in the following order
SiO2 ≈ MgO ≈ γ-Al2O3 > Y2O3 > La2O3. However, due to the deac-
tivation of the Rh/SiO2 catalyst, 50 h after the start of the reaction, the
order changed to γ-Al2O3 ≈ MgO > Y2O3 > SiO2 ≈ La2O3. As for the
reducible oxides supported catalysts, after 0.5 h on the DRM reaction,
the conversions and yields decreased in the following order
Ta2O5 > > TiO2 > > ZrO2 > Nb2O5 > CeO2, and it changed after
50 h to ZrO2 > Ta2O5 > CeO2 > > TiO2 > > Nb2O5. The authors at-
tributed the deactivation of SiO2, Y2O3 and Ta2O5 to metal sintering,
while the high stability exhibited by MgO and La2O3 was attributed to
the strong metal-support interaction created by the production of
LaRhO3 and MgRh2O4 compounds. Additionally, although no chemical
compounds were created between the alumina support and the rhodium
metal, the authors attributed the stability of γ-Al2O3 and the lack of Rh
sintering to the strong metal-support interaction.
Zhang et al. [123] investigated the effect of SiO2, TiO2, Al2O3, MgO-
modified Al2O3 (denoted as MA), ZrO2 and MgO supports on the cat-
alytic performance of Ni based catalysts. The surface area and other
textural properties are presented in Table 3, while Table 4 shows the
metal dispersion and the amount of coke deposited on each catalyst.
The authors attributed the high initial metal dispersion on SiO2 to its
large surface area. On the other hand, the strong interaction between
NiO and alumina, resulting in the formation of the difficultly reduced
NiAl2O4 spinel, led to the low metal dispersion in NiO/Al2O3. However,
the MgO modification of alumina was found to be critical in increasing
the metal dispersion in NiO/MA. This was attributed to the ability of
MgO to weaken the strong NiO-alumina interaction and facilitate the
reduction of NiO. Finally, the low metal dispersion on TiO2, ZrO2 and
MgO supports was attributed to their small surface areas.
The authors carried out the DRM reaction at 750 °C in a tubular
fixed-bed continuous-flow reactor and measured the progress of CH4
and CO2 conversion levels with time under the different catalysts. Due
to its large surface area and considerable initial metal dispersion level,
the NiO/SiO2 catalyst exhibited initial high catalytic activity. However,
metal sintering resulting from the weak NiO-SiO2 interaction occurred
with time, leading to the subsequent deactivation of this catalyst. On
the other hand, the poor catalytic performance of NiO/TiO2 was at-
tributed to its small surface area and the weak metal-support interac-
tion, leading to the agglomeration of the NiO particles. As for the Al2O3
support, the poor catalytic activity was ascribed to the very strong NiO-
alumina interaction and the formation of NiAl2O4 spinel, leading to
difficulties in reducing this catalyst. However, modifying alumina with
MgO has enhanced the catalytic activity, stability and anti-coking
capability. The authors concluded that the reaction between Mg2+ and
unsaturated Al3+ ions on the catalyst surface has weakened the metal-
support interaction, thus enhancing the dispersion of the metal particles
on the support and lowering the reduction temperature. As for NiO/
ZrO2, the authors justified its high initial activity to the weak metal-
support interaction which may have facilitated the reduction of the
catalyst. However, it was found that this property may subsequently
lead to the quick deactivation of the catalyst by allowing the sintering

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N.A.K. Aramouni et al.
of the metal particles. Finally, the authors ascribed the good catalytic
performance of the MgO supported catalyst to the ability of MgO's basic
sites to enhance the chemisorption of the acidic CO2 gas on the catalyst
surface, thus reducing the carbon deposition and enhancing the cata-
lyst's anti-coking capabilities by the gasification of the formed carbo-
naceous species. Finally, the authors concluded that MgO-modified
alumina can be considered as the most stable and active support; the
performance of the tested catalysts decreased in the following order
NiO/MA (Al2O3-MgO) > NiO/SiO2 ≈ NiO/MgO > NiO/Al2O3 > NiO/
ZrO2 > NiO/TiO2.
Naeem et al. [124] compared the performance of Ni (5 wt%) cata-
lysts supported on γ-Al2O3 (SBET = 180 m2 /g), CeO2 (SBET = 40 m2 /g)
and ZrO2 (SBET = 35 m2 /g). These catalysts were prepared by the
polyol method. The authors concluded that, owing to its advantageous
combination of high thermal stability, redox potential, reducibility and
surface acidity, the Ni-Zr catalyst provided the best catalytic perfor-
mance. On the other hand, Ni-Ce was the least active catalyst and led to
the highest coke formation. This was directly related to the low Ni
dispersion % on its surface and its large Ni crystal size, favoring the
formation of coke. Moreover, the authors showed that Ni-Al was the
most coke resistant catalyst, a property resulting from the high metal
dispersion on its surface, small Ni particle size, in addition to its basic
surface allowing for the gasification of the carbonaceous species.
The catalytic activity and stability of Ni-Pd bimetallic catalysts
supported on S105 (93% ZrO2 + 7% La2O3), La2O3, ZrO2, SiO2, Al2O3
and TiO2 were investigated by Steinhauer et al. [108]. Carrying out the
DRM reaction at 500, 600 and 700 °C for 2 h each, the authors showed
that the effect of the support was not prominent at low temperatures.
However, the difference in conversion rates and H2, CO yields increased
at high temperatures. The catalytic activity of the catalysts decreased in
the following trend according to the supports ZrO2-La2O3,
La2O3 > ZrO2 > SiO2 > Al2O3 > TiO2. This varying catalytic perfor-
mance was mainly attributed to differences in metal-support interaction
and metal dispersion level. Moreover, the authors attributed the re-
duced activity of Al2O3 and TiO2 supported catalysts to the blockage of
active sites. The poor performance of TiO2 and the beneficial effect of
composite supports were in agreement with the findings of Zhang et al.
[123].
On the contrary, studying the catalytic performance of supported
Iridium (Ir) catalysts, Nakagawa et al. [125] ranked the activity of the
supported catalysts as follow TiO2 ≥ ZrO2 ≥ Y2O3 > La2O3 > MgO
≥ Al2O3 > SiO2. The authors showed that carbon deposition was only
present on Al2O3 and SiO2 supported catalysts. The authors attributed
the effects of the support to the activation of CO2 with the metal oxides
support. Moreover, the low stability of Al2O3 and SiO2 supported cat-
alysts was believed to be caused by the deposition of carbonaceous
species on their surfaces.
Hongjing Wu et al. [117] investigated the performance of mono-
metallic and trimetallic Ni based catalysts supported over Al2O3 and
modified Al2O3. The sol-gel method was used to prepare the Al2O3 and
Al2O3−10 wt% MOx (M = Ce or Mg) supports. It was found that the
modified AlCe and AlMg supports have offered an important enhance-
ment to the catalytic activity and stability compared to their un-
modified counterpart. The authors reported that the strong metal-sup-
port interaction between NiO and CeO2 species has enhanced the
reducibility of Ni-Al and prevented metal sintering. Moreover, the in-
teraction of CeO2 and Al2O3 to create CeAlO3 was also found to be
beneficial for the catalytic performance. This was attributed to CeAlO3
species’ ability to prevent carbon formation via catalyzing CO2 de-
composition and thus creating active oxygen atoms necessary to oxidize
the carbon derived from methane decomposition. As for the Ni-AlMg
catalyst, the authors concluded that the metal-support interaction was
enhanced after doping Al with MgO, thus allowing to retain a small Ni
particle size and avoid metal sintering. Moreover, the authors con-
cluded that the Ni-AlMg catalyst offered a superior coke resistance
compared to Ni-Al due to the presence of basic MgO sites on the
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Renewable and Sustainable Energy Reviews 82 (2018) 2570–2585
catalyst's surface, thus enhancing CO2 chemisorption and leading to a
faster gasification of carbonaceous species.
Interestingly, doping Al2O3 with MgO and CeO2 did not enhance the
catalytic activity or stability when trimetallic NiAuPt was employed
due to good performance of the active metals combination. These re-
sults strongly reflect the dominant effect of metal selection on the
catalytic performance compared to the effect of the support. Although
doping Al2O3 with MgO and CeO2 has enhanced the catalytic activity of
monometallic Nickel catalysts [117], different results were observed
when operating under Rh catalysts [84]. Asmaa Drif et al. [126] have
investigated the catalytic activity and stability of monometallic Rh
catalysts supported over alumina and various MxOy - Al2O3 oxides (M
= Zr, Mg, Ni, Ce, La). For the DRM reaction, the highest hydrogen
yields were observed under Rh/NiO-Al2O3 > Rh/Al2O3 > Rh/MgO-
Al2O3 ≈ Rh/CeO2-Al2O3 > Rh/ZrO2–Al2O3 > Rh/La2O3-Al2O3. The
authors attributed the superior catalytic performance of Rh/NiO-Al2O3
to the high dispersion of Rh over the catalyst surface and the formation
of NiAl2O4 spinel structure.
On the other hand, several studies have investigated the DRM re-
action under mesoporous supports such as SBA-15 and ZSM-5
[85,95,127–131]. As previously mentioned, Zhang et al. [95] were able
to enhance the stability of monometallic Ni catalyst by using the tex-
tural properties of SBA-15 to confine the nickel particles inside the
pores, thus avoiding their sintering. It was found that coke formation
and not metal amalgamation was responsible for the catalyst deacti-
vation after a DRM reaction time of 600 h. El Hassan et al. [85] com-
pared the catalytic activity and stability of Co catalyst supported on
SiO2 and SBA-15. It was found that Co12/SBA-15 exhibited higher
catalytic activity and stability than Co12/SiO2. This was mainly attrib-
uted to the occlusion of the cobalt particles inside the mesopores of the
support, thus enhancing the catalyst's anti-agglomeration properties
and the metal-support interaction. Appendices X and XI present a
comparison of the catalytic activity and stability under different sup-
ports and promoters respectively.
Although many single-metal supports such as γ-Alumina perform
very well, it is apparent that mixed and/or structured supports have
properties that make them attractive to use in methane reforming.
Zeolites are a highly potent group of materials to consider [132,133],
and it is apparent that zeolites with a higher Si/Al ratio, which are more
basic, give better conversions [128]. The reason to their good perfor-
mance is the confinement of active metal particles inside their pores,
ensuring a higher resistance to sintering, in addition to their basic
character that decreases carbon deposition. Promoting a zeolite-sup-
ported catalyst with a noble metal does not have a huge effect on the
conversion [105] (Appendix V), but gives a higher stability to the active
metal particles inside the pores [85]. Additionally, other basic metal
oxides, such as those of cerium or magnesium enhance the surface re-
actions and promote carbon gasification [134,135], adding to the sta-
bility of the catalyst. They are especially effective when used in mod-
erate amounts (~10%) on an already potent support such as alumina
[24,88,93], which is less basic, with a point of zero charge at pH = 8
approximately. Ceria shows a slightly better performance than mag-
nesia when doping alumina [117]. Another interesting observation
concerning alkaline metal oxides doping alumina is that small amounts
of CaO increase the catalyst activity and stability while larger CaO
loadings have the opposite effect of increasing the carbon formation on
the catalyst and decreasing the CO2 conversion [136]. Alumina doped
with La proves to be a potent support for Ni catalysts, but not for Co
catalysts [96].
Apart from the choice and loading of active metal, the preparation
method of the catalyst also plays an important role in achieving sa-
tisfactory dispersion and good metal-support interaction while mini-
mizing the formation of spinel that is difficult to reduce. In general,
catalysts synthesized by the sol-gel method give better results than
those synthesized by impregnation, which in turn perform better than
catalysts synthesized by co-precipitation [47,137,138]. For
N.A.K. Aramouni et al.
Table 5
Summary of catalyst properties.
multimetallic catalysts prepared by impregnation, the order of im-
pregnation also plays a role in determining the catalyst performance,
with sequential impregnation being more advantageous than co-im-
pregnation [102]. Based on the results [107] for Rh-Ni/SiO2 catalysts, it
can be said that the choice of noble metal precursor for incipient wet-
ness impregnation does not greatly affect the performance of the cat-
alyst, mostly due to the uncontrolled nucleation of metal particles on
the support taking place during solvent evaporation and not during
impregnation. This is not the case for strong electrostatic adsorption or
deposition-precipitation methods.
Table 5 summarizes the properties of each type of support and ac-
tive metal and highlights the effect of their combinations. A typical,
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Renewable and Sustainable Energy Reviews 82 (2018) 2570–2585
well-performing catalyst is proposed as an example for each combina-
tion.
For any catalyst to have a potential in industrial applications, many
parameters must be met: It is desirable for the synthesis method to be
quick, require a minimal number of steps and amount of solvent and
employ inexpensive precursors. The catalyst must be highly active,
resistant to coking and durable, a parameter which is often overlooked:
although it is highly interesting to synthesize catalysts that yield high
conversions in laboratory experiments, a commercially viable catalyst
must have the ability to retain its performance over a long period of
time before it gets deactivated. Hence, Table 6 compiles the catalysts
showing the longest time on stream.
 Table 6
Catalyst durability ranking.

References Reason Reactor Preparation Metal weight% Time (h) Temperature (°C) Metal - support - CH4 CO2
type methoda Promoter weight % promoter conversion conversion
% %
N.A.K. Aramouni et al.

[118] Co-O affinity accelerated the gasification of coke intermediates, counteracts coke FBR ST 0.075–7.425–92.5 mol% 1000 800 Co0.075Ni7.425Mg92.5O 69 75
formation – n/a – n/a
[95] Ni was confined to the pores of the SBA−15 mesoporous support and did not FBR Imp. 12.5 600 800 Ni – SBA−15 – n/a 90 89
sinter throughout the reaction
[116] – Bimetallic particles suppress agglomeration of active metals FBR IWI 0.75–2.25 500 800 Pt-Ru – γAl2O3 – n/a 94 96
– Formation of active amorphous carbon species on the catalyst's surface
[49] – Mixed rare earths promoters decreased the size of Co3O4 particles and FBR Imp. 20 320 800 Co – γ-Al2O3 – MRE 75 90
increased the metal-support interaction, increased the anti-sintering ability of 0.025
cobalt particles.
– MRE promoters increased the ratio of active carbon and improved the anti-
coking performance of the catalyst.
[49] Mixed rare earths promoters decreased the size of Co3O4 particles and increased FBR Imp. 20 280 800 Co – γ-Al2O3 – n/a 66 76
the metal-support interaction, increased the anti-sintering ability of cobalt
particles.
– MRE promoters increased the ratio of active carbon and improved the anti-
coking performance of the catalyst.
[139] – CeAlO3 phase suppressed coke formation without damaging the catalytic quartz IWI 10 250 800 Ni – γ-Al2O3 – CeO2 79 88
activity reactor 5
– CeAlO3 inhibited the growth of graphitic carbon, decomposed CO2 and
formed active surface oxygen
[139] – CeAlO3 phase suppressed coke formation without damaging the catalytic quartz IWI 10 250 800 Ni – γ-Al2O3 – CeO2 78 86
activity reactor 10
– CeAlO3 inhibited the growth of graphitic carbon, decomposed CO2 and

2580
formed active surface oxygen
[109] – CeAlO3 phase suppressed coke formation without damaging the catalytic quartz IWI 10 250 800 Ni – γ-Al2O3 – CeO2 77 85
activity reactor 15
– CeAlO3 inhibited the growth of graphitic carbon, decomposed CO2 and
formed active surface oxygen
[139] – CeAlO3 phase suppressed coke formation without damaging the catalytic quartz IWI 10 250 800 Ni – γ-Al2O3 – n/a 80 90
activity reactor
– CeAlO3 inhibited the growth of graphitic carbon, decomposed CO2 and
formed active surface oxygen
[98] – Strong resistance of the basic MgO against Ni sintering FBR CP 15–10 200 800 Ni- MgO – Ce0.8Zr0.2O2 95 96
– Strong interaction between Ni and MgO – n/a
[110] – Pr6O11 or ZrO2 doping of CeO2 matrix lead to better metal-support FBR DP 2 200 750 Ir – Ce0.9Pr0.1O2 – n/a 56 75
interaction, avoid Ir aggregation
– Stronger metal-support interaction and improved oxygen storage capacity
reduce carbonaceous deposits on the catalyst's surface
[110] – Pr6O11 or ZrO2 doping of CeO2 matrix lead to better metal-support FBR DP 2 200 750 Ir – Ce0.9Zr0.1O2 – n/a 53 72
interaction, avoid Ir aggregation
– Stronger metal-support interaction and improved oxygen storage capacity
reduce carbonaceous deposits on the catalyst's surface
[118] Co -O affinity accelerated the gasification of coke intermediates, counteracts coke FBR ST 0.075–7.425–92.5 mol% 140 800 Co0.075Ni7.425Mg92.5O 73 80
formation – n/a – n/a
[118] Co -O affinity accelerated the gasification of coke intermediates, counteracts coke FBR ST 0.225–7.275–92.5 mol% 140 800 Co0.225Ni7.275Mg92.5O 68 76
formation – n/a – n/a
[118] Co -O affinity accelerated the gasification of coke intermediates, counteracts coke FBR ST 5.0–5.0–90 mol% 140 800 Co5Ni5Mg90O – n/a – 84 84
formation n/a
[118] Co -O affinity accelerated the gasification of coke intermediates, counteracts coke FBR ST 7.5–92.5 mol% 140 800 Ni7.5Mg92.5 O – n/a – 71 78
formation n/a
(continued on next page)
Renewable and Sustainable Energy Reviews 82 (2018) 2570–2585
 Table 6 (continued)

References Reason Reactor Preparation Metal weight% Time (h) Temperature (°C) Metal - support - CH4 CO2
type methoda Promoter weight % promoter conversion conversion
% %

[130] FBuR IWI 5–25 120 800 98 95

N.A.K. Aramouni et al.

– Accelerated reduction of surface carbonaceous species due to the creation of Ni-Mo – SBA−15 –
La2O2CO3 species 2 La2O3
– La2O3 increased the support's surface area, increased Ni–Mo-La interaction,
improved Ni dispersion and retarded Ni sintering
[130] – Accelerated reduction of surface carbonaceous species due to the creation of FBuR IWI 5.0–25.0 120 800 Ni-Mo – SBA−15 – n/a 84 96
La2O2CO3 species
– La2O3 increased the support's surface area, increased Ni–Mo-La interaction,
improved Ni dispersion and retarded Ni sintering
[140] – Large number of whisker carbons were found on the spent Ce0.01- FBR BUA 3.71 mol% 100 760 Ni – MgO – Ce 71 83
Ni0.10Mg0.90O catalyst 0.58 mol%
– Addition of CeO2 accelerated the growth of Ni particles, decreased coke
resistance
[140] – Co-O affinity enhanced the gasification of intermediate Cα FBR BUA 3.44 mol% 100 760 Ni – MgO – Co 73 90
0.51 mol%
[129] – Addition of CeO2 increased the support's surface area and pore volume; Ni FBuR IWI 5–25 100 800 Ni - Mo – SBA−15 – 90 97
and Ce-Mo contained in the pores, avoided carbon deposition and metal 2 CeO2
sintering
– Addition of CeO2 (high oxygen storage capacity) improved the catalyst's
reducibility
[129] – Addition of CeO2 increased the support's surface area and pore volume; Ni FBuR IWI 5.0–25.0 100 800 Ni - Mo – SBA−15 – n/ 79 96
and Ce-Mo contained in the pores, avoided carbon deposition and metal a
sintering
– Addition of CeO2 (high oxygen storage capacity) improved the catalyst's
reducibility

2581
[123] Mg2+ ions react with unsaturated Al3+, reduce metal-support interaction, FBR IWI 8 100 750 NiO – MA (Al2O3- 87 89
increase metal dispersion, decrease reduction temperature MgO) – n/a
[98] Basic MgO surface sites are conductive to the adsorption of acidic CO2, surface FBR IWI 8 100 750 NiO – MgO – n/a 74 76
enriched with CO2, carbon deposition on the catalyst is inhibited
[110] Pr6O11 or ZrO2 doping of CeO2 matrix lead to better metal-support interaction, FBR DP 2 100 750 Ir – Ce0.9Pr0.1O2 – n/a 57.5 76
avoid Ir aggregation
– Stronger metal-support interaction and improved oxygen storage capacity
reduce carbonaceous deposits on the catalyst's surface
[87] Pr6O11 or ZrO2 doping of CeO2 matrix lead to better metal-support interaction, FBR DP 2 100 750 Ir – Ce0.9Zr0.1O2 – n/ 54 72
avoid Ir aggregation a
– Stronger metal-support interaction and improved oxygen storage capacity
reduce carbonaceous deposits on the catalyst's surface
[84] Encapsulation of Ni-Co particle (10.1 ± 2.2 nm) by an amorphous SiNx shell FBR Comm 10 100 800 4Ni−3.6Co – Si3N4 – 70 83
n/a

a
The abbreviations are detailed in the nomenclature at the end of the article.
Renewable and Sustainable Energy Reviews 82 (2018) 2570–2585
N.A.K. Aramouni et al.
Fig. 3. Conversion versus time on stream for multiple catalysts.
3.3. Catalyst durability-activity tradeoff
It is obvious that industrial applications require active and durable
catalysts. It is shown that active catalysts require a fine dispersion and
good surface oxygen mobility, which comes at the expense of higher
sintering risk. Furthermore, a good metal-support interaction, crucial
quality for a catalyst resistant against sintering, is often accompanied
by the formation of a spinel structure that is difficult to reduce, leading
to less active catalysts. The catalyst designer has then to find a com-
promise that gives a catalyst with an acceptable performance.
Fig. 3 shows CO2 and methane conversions reached by the most
durable catalysts (Table 6) considered in this study. The durability is
designated by the time on stream, irrespective of the composition or
operating temperature. The general trend is indeed a lower conversion
obtained for the most stable catalysts, showing effectively the trade-off
between activity and stability.
4. Conclusion
Dry reforming of methane is not an industrially mature process
given the operational constraints exhibited by the various catalysts
involved. As several studies have shown, satisfactory catalytic ac-
tivity and stability are dictated in large part by active metal dis-
persion, adhesion to support and resistance to sintering, but also by
low carbon formation. While a good catalyst cannot fully eliminate
the formation of coke, it can favor the formation of more reactive
intermediate carbonaceous species over that of the destructive
Carbon Gamma type (Cγ).
The rapid deactivation and high coke formation associated with
non-noble based monometallic catalysts, coupled with the expensive
price of the more coke resistant and stable noble monometallic ones,
dictate that new and innovative approaches must be investigated to
overcome these limitations. Consequently, an economically potent
catalyst is expected to be based on an inexpensive non-noble metal,
while adding a small yet influential amount of noble and/or other non-
noble metals to enhance its catalytic properties, as bimetallics have
shown better performance. Additionally, trimetallic catalysts can also
lead to similar outcomes. Nevertheless, despite their superior perfor-
mance, noble-noble bimetallic catalysts are not viable candidates due to
price and scarcity concerns. On the other hand, several studies have
shown that Perovskite-type catalysts can also exhibit a very good per-
formance.
For a given active metal, choosing an appropriate support can en-
hance the metal-support interaction, thus leading to a reduction of
metal sintering, while too strong a metal-support interaction comes at
the expense of catalyst reducibility, thus leading to lower catalytic ac-
tivity. In that case, an adequate doping of the support with another
species can ensure that the metal-support interaction is strong enough
to avoid metal sintering, and weak enough to ensure low reduction
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Renewable and Sustainable Energy Reviews 82 (2018) 2570–2585
Fig. 4. Summary of catalyst design tradeoffs.
temperatures (MgO doping of NiO/Al2O3). Additionally, the anti-coking
abilities of the catalyst can be enhanced by the presence of basic sites on
the surface of the catalyst or by doping the support with species that
can catalyze CO2 decomposition (formation of CeAlO3 under Ni-AlCe).
Finally, Co, Zr or MRE doping can also lead to better metal-support
interaction and enhanced anti-coking capabilities. Moreover, meso-
porous and composite can perform better than reducible and irre-
ducible metal oxides due to their peculiar properties.
Although these general guidelines for the influence of supports and
promoters are generally valid, it can be noticed that different studies
have reported varying degrees of success for a given support or pro-
moter. This can be attributed to the fact that the influence of a given
support or promoter, and thus the validity of the aforementioned fac-
tors, is extremely dependent on the active metal species involved. This
confirms the dominant influence of metal selection on the overall cat-
alytic performance. Moreover, accurately defining an optimum choice
of active metal, support and promoter cannot be achieved separately,
given the intertwining influence of all these components, as summar-
ized Fig. 4.
Based on the results of this study, it is recommended to further in-
vestigate the alloying and synergetic effect of nickel and cobalt with the
excellent promoting effect of rhodium in trace amounts in a trimetallic
Ni-Co-Rh catalyst. Alternatively, a cheaper catalyst with strong poten-
tial would confine Ni and Co particles in the mesopores of SBA15
zeolite. No such combinations have been reported in literature to the
knowledge of the authors.
It is further desirable to tackle the issue of catalyst design based
on an understanding of its deactivation mechanism. In summary,
there is a need for a catalyst that is active with a small particle size,
good metal-support interaction but nonetheless good reducibility,
and a certain tolerance to carbon formation, especially to avoid the
formation of whisker carbon. As explained in this work, whisker
carbon presence is due to the solubility of carbon in the non-noble
metal crystals and its diffusion through the metal lattice. Future
works should then investigate the prevention of carbon diffusion
into the (non-noble) active metal crystallites while maintaining
acceptable activity. Furthermore, the deviation from graphitic
thermodynamics determined experimentally should be in-
corporated into modeling works on reforming processes to study the
effect of the particle size on the carbon limits.
N.A.K. Aramouni et al.
Acknowledgments
The authors would like to thank the Lebanese National Council for
Scientific Research (LCNRS) (102909) for their funding of this work.
Appendix A. Supplementary material
Supplementary data associated with this article can be found in the
online version at http://dx.doi.org/10.1016/j.rser.2017.09.076.
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