Journal of CO2 Utilization 46 (2021) 101462

Contents lists available at ScienceDirect

Journal of CO2 Utilization

journal homepage: www.elsevier.com/locate/jcou

A review of different catalytic systems for dry reforming of methane:

Conventional catalysis-alone and plasma-catalytic system
Cong Shi a, Sha Wang a, *, Xiang Ge b, Shengxiang Deng a, *, Bin Chen a, Jun Shen a
a
Institute of Energy and Power Engineering, School of Mechanical and Automotive Engineering, Shanghai University of Engineering Science, Shanghai, 201620, PR China
b
Key Laboratory of Coal Gasification and Energy Chemical Engineering of Ministry of Education, East China University of Science and Technology, Shanghai, 200237,
PR China

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

Keywords: Dry reforming of methane (DRM) uses methane (CH4) and carbon dioxide (CO2) as raw materials to produce
Dry reforming of methane syngas, which has unique economic and environmental benefits. However, DRM reaction still faces the disad­
Catalytic system vantages of catalyst sintering deactivation and carbon formation. In this paper, the research progress of different
Conventional catalysis-alone system
DRM catalytic systems is reviewed. The conventional catalysis-alone system, plasma-catalytic system and some
Plasma-catalytic system
other catalytic systems are discussed. The key factors affecting the performance evaluation of the catalyst in the
conventional catalysis-alone system were given. In particular, whether the plasma-catalytic system can achieve
higher conversion than the conventional catalysis-alone system has become the focus of attention. For this
reason, the reactor structure, discharge mode and the combination with catalyst were discussed. The mechanism
of plasma-catalyst interaction was discussed through literature review. In addition, the possibility of other ap­
plications of DRM plasma-catalytic system is also considered. Finally, the advantages and disadvantages of
conventional catalysis-alone system and plasma-catalytic system are compared. Some other catalytic systems,
such as catalytic membrane reactor and solar driven methane reforming, are also introduced. Considering the
research status of DRM, we can further improve the conversion and energy conversion efficiency by improving
the DRM catalyst and optimizing the design of plasma reactor.

1. Introduction (POM), autothermal reforming (ATR) and methane steam reforming

Because of global warming, people need to take effective measures to
reduce greenhouse gas emissions. More and more people pay attention
to the reduction and utilization of greenhouse gases. At present, an
effective solution is dry reforming of methane (DRM), which can convert
CO2 and CH4 (the main components of greenhouse gases) into syngas.
Moreover, natural gas/shale gas has become the world’s third largest
energy source after oil and coal. The main component of natural gas/
shale gas is CH4, while methane has the characteristics of rich resources,
clean, non-toxic and high calorific value [1,2]. Syngas is a mixture of CO
and H2. Its energy density is about 50% of natural gas [3], which has
been used in urban lighting and industrial scale heating and power
generation [4]. More importantly, syngas can be used as raw materials
to produce a series of other chemicals through Fischer-Tropsch synthesis
(FTS).
At present, there are three mature and widely used methods to
convert natural gas into syngas, namely, partial oxidation of methane
(MSR). However, there are some limitations in MSR. This reforming
reaction needs to adjust the H2/CO ratio [5], and the syngas ratio
generated by MSR is greater than 2, which is not conducive to FTS. POM
has strict requirements on reactor material and is troublesome to oper­
ate. Although syngas from ATR can be regulated for downstream use,
lower H2 production and requirements for control systems may limit its
industrial use. Therefore, the advantages of DRM are particularly
prominent. DRM can achieve almost 100% reactant conversion.
Although DRM has obvious economic and environmental benefits, it is
not a mature industrial process [6]. The main factor hindering DRM
industrialization is catalyst sintering deactivation and carbon formation
[7,8]. But actually, only a few researches involve the experimental
application of DRM in industrial scale. Mortensen et al. [9] summarized
the application experience of industrial scale DRM, and reported that
using traditional nickel catalyst in industrial scale DRM, the output of
syngas is up to 133,000 Nm3/h, but a large amount of steam is needed to
supply together to eliminate the serious carbon formation problem.

* Corresponding author.
E-mail addresses: wangsha_84@163.com (S. Wang), csudsx@126.com (S. Deng).

https://doi.org/10.1016/j.jcou.2021.101462
Received 15 October 2020; Received in revised form 26 December 2020; Accepted 28 January 2021
Available online 9 February 2021
2212-9820/© 2021 Elsevier Ltd. All rights reserved.
C. Shi et al.
Noble metal base, partial sulfur passivated Ni and noble metal have good
potential to promote the successful application of Ni catalyst in
large-scale reforming unit, and only a small amount of steam can be used
as co feed, so it is necessary to continue to strengthen the research of
DRM catalyst. DRM can produce a reasonable ratio of H2/CO, and can
also be used as raw materials for the synthesis of some
oxygen-containing compounds. Moreover, DRM can also be used as
energy storage medium and energy transport. Fig. 1 shows a typical
layout of an industrial scale reforming unit. As shown in the Fig. 1, the
dotted line indicates the optional configuration, and the H2S introduc­
tion is only used for sulfur passivation reforming (SPARG). Carbon di­
oxide can be added to adjust the composition of the feed gas or recycled
from the CO2 removal unit. The actual reforming is carried out in a
primary reformer to convert CH4/H2O/CO2 mixture into syngas. How­
ever, if the reforming unit is likely to form carbon, it is only a matter of
time before it is forced to shut down due to too large pressure drop
[10–12].
In view of this, this paper first introduces the conventional catalysis-
alone system, and then discusses the influence of physicochemical
properties of catalyst on DRM. The design elements of DRM catalyst
were analyzed, including interaction, active metal particle size, basicity,
oxygen storage capacity and carbon deposition. The application of
plasma-catalytic system in DRM is also introduced, including thermal
plasma and cold thermal plasma. The mechanism of plasma catalyst
interaction was discussed through literature review. Secondly, the ad­
vantages and disadvantages of the two catalytic systems were compared.
Finally, the application prospect of non-thermal plasma methane
reforming technology is proposed. In addition, some other catalytic
systems, such as catalytic membrane reactor and solar driven methane
reforming, are introduced. The theoretical significance of this review is
to find out the gap and future direction of research and development,
which will lead to new technologies and methods that can be applied to
methane reforming.
2. Overview of DRM
DRM was proposed at the 10th International catalysis conference.
Fischer and Tropsch studied DRM in 1928, but it was investigated as
early as 1888 [13].
Fig. 1. Typical layout of industrial scale reforming unit. Quoted from Reference [9]. Copyright (2015) Elsevier.
2
Journal of CO2 Utilization 46 (2021) 101462
2.1. Thermodynamics
DRM reaction formula (Eq. (1)) is the main reaction for reforming
syngas. The chemical equilibrium and chemical thermodynamics show
that the reaction is a strong endothermic reaction with the increase of
gas volume. High temperature and low pressure are favorable for the
reaction to proceed in the direction of reforming reaction.
/
CH4 + CO2 →2H2 + 2CO, ΔH298K 0
= 247KJ mol (1)
CO2 and CH4 molecules have high stability and dissociation energy,
so it needs high temperature to realize the equilibrium conversion to
syngas. In addition, the equilibrium conversion of DRM to syngas is
usually affected by the reverse water gas shift (RWGS) reaction (Eq. (2)),
which results in the higher CO2 conversion than CH4 conversion. This is
beneficial to the production of syngas with a H2/CO ratio of 1 or less [14,
15].
/
CO2 + H2 →CO + H2 O, ΔH298K0
= 41KJ mol (2)
In addition, the carbon formation is also one of the important reasons
for deactivation of DRM catalyst. There are two main reasons for the
carbon formation in DRM process [16]: (i) methane decomposition (Eq.
(3)); (ii) Boudouard reaction (CO disproportionation, Eq. (4)).
/
0
CH4 →C + 2H2 , ΔH298K = 75KJ mol (3)
/
0
2CO→C + CO2 , ΔH298K = − 172KJ mol (4)
Wang et al. [17] reported that DRM can be carried out at over 640℃,
accompanied by methane cracking reaction, and RWGS and CO
disproportionation cannot occur above 820℃. While in the temperature
range of 557− 700℃, methane cracking or CO disproportionation will
generate carbon. Nikoo et al. [18] conducted the thermodynamic
equilibrium analysis of DRM with Aspen plus. DRM is a gas-solid cata­
lytic reaction. It is generally believed that gaseous CO2 and CH4 mole­
cules adsorb, activate, decompose and react on the catalyst surface.
However, the main factor affecting the stability of DRM catalyst is the
amount of carbon generated, but it is difficult to describe the carbon
formation process clearly by thermodynamic calculation.
2.2. Catalyst
DRM catalysts mainly include active metals, supports and
C. Shi et al.
accelerators. However, in addition to the composition of the catalyst, the
structure and preparation method of the catalyst will also affect its
performance. It is of great significance for the industrialization of DRM
to develop economically feasible, highly active and stable catalysts.
2.2.1. Active component
At present, the main active components of DRM catalysts are noble
metals (Rh, Ru, Pd, Pt and Ir) and non-noble metals (Ni, Co, Cu and Fe).
Noble metals have high DRM reactivity and high resistance to carbon
[19,20]. However, because non-noble metal catalysts have higher eco­
nomic benefits than noble metal catalysts, they have been studied more
[21,22]. In addition, bimetallic catalysts (Co-Pt, Ni-Co and Ni-Pd) have
attracted more and more attention due to their advantages. Liu et al.
[22] found that Ni-Co bimetallic system had higher activity than pure Ni
or Co. Pan et al. [23] successfully synthesized mesoporous silica sup­
ported Ni-Pd bimetallic catalyst by OA method. Compared with the
single metal catalyst, the presence of Pd increased the proportion of Ni◦
species on the surface of the catalyst. In addition, the doping of Pd and
oleic acid contributes to the formation of uniform nickel nanoparticles,
which improves the anti-sintering performance and significantly pro­
longs the service life of the catalyst. Chen et al. [24] synthesized Co-Pt
bimetallic catalyst by sol-gel combined with supercritical drying
method, showing a conversion rate close to thermodynamic equilibrium,
which is 50% higher than that of single metal Co or Pt catalyst, indi­
cating synergy between Co and Pt.
2.2.2. Support
Supports (SiO2, Al2O3, CaO, La2O3, MgO, CeO2, ZrO2, TiO2) can
provide high specific surface area for the dispersion of active metals, and
their physicochemical properties will affect the performance of the
catalyst [25]. In addition, the structure of the support (porosity [26–28]
and specific surface area [27,29]) also affects the performance of the
catalyst. Li et al. [26] prepared hydroxyapatite (HAP) with different
mesoporous/macroporous ratios by adjusting the heating temperature
(20, 50, 80, 120℃). Then Ni/HAP catalyst was prepared with the above
HAP as support to promote the dry reforming of methane. They found
that different mesoporous/macroporous ratios directly affect the dis­
tribution of nickel particles. With the increase of mesopor­
ous/macroporous ratio, Ni particles preferentially dispersed in
mesoporous channels, and the average particle size gradually decreased.
Xu et al. [29] synthesized ordered mesoporous NiO-CaO-Al2O3 complex
oxides with different Ca contents as DRM catalysts. The catalytic activity
is closely related to the large pore structure and large surface area.
Spinel (AB2O4, such as MgAl2O4, NiFe2O4, NiAl2O4) supports have
excellent high temperature stability [30–32]. Perovskite (ABO3, such as
LaNiO3, LaCoO3) supports have high active metal dispersion [33,34].
Ordered mesoporous materials can obtain well controlled nanoparticles
by embedding active metals into the pores of mesoporous materials [29,
35], which has attracted the attention of scholars all over the world
[36–41].
2.2.3. Promoter
Adding a small amount of promoters in DRM catalyst can improve
the stability of DRM reaction and the ability to resist carbon deposition.
Compared with Rh/SiO2 catalyst, adding V2O5 promoter to Rh/SiO2
catalyst can increase the catalytic activity to 15–20 times [42]. One of
the main ways to improve the anti coking ability of non-noble metal
catalysts is to add basic additives [43]. In addition, rare earth metals (Ce
and La) are more effective than alkaline earth metal (Ca) and alkali
metal (K) promoters. Ce has the highest activity and no obvious deac­
tivation. In addition, rare earth oxide CeO2 has been widely studied as a
promoter. Adding appropriate amount of CeO2 can improve the activity
of the catalyst and reduce carbon deposition [44–46]. The electrode
potential between Ce4+ and Ce3+ is small, and reversible adsorption can
occur under certain conditions, which makes CeO2 have unique redox
properties. In the reaction, CeO2 is used to regulate the concentration of
3
Journal of CO2 Utilization 46 (2021) 101462
oxygen on the catalyst surface: oxygen is stored in oxygen rich condi­
tions, while oxygen is released in oxygen poor conditions. This ability is
beneficial to inhibit the cracking of CH4 and promote the dissociation of
CO2, and enhance the carbon deposition resistance of the catalyst [47].
2.2.4. Preparation method
The amount of additives is affected by the preparation method of
catalyst. The preparation method also affects the structure, composition,
grain size and dispersion of the catalyst, thus affecting its catalytic ac­
tivity, stability and carbon deposition resistance [48,49]. The traditional
preparation methods include impregnation method, co precipitation
method, sol-gel method and hydrothermal synthesis method. Hao, et al.
[50] prepared by sol gel method combined with supercritical drying
method had higher specific surface area, lower bulk density, smaller
nickel particle size, stronger metal-support interaction and higher nickel
dispersion than the impregnated catalyst Ni/Al2O3 catalyst. And it has
higher activity and better resistance to carbon deposition.
In addition, atomic deposition method [51] and plasma technology
[52–54] have also been applied to the preparation of DRM catalyst.
Gould et al. [51] prepared single metal and bimetallic (Ni and Ni-Pt)
catalysts by atomic layer deposition method, which have higher cata­
lytic activity and anti carbon deposition compared with traditional
catalyst preparation methods. Pan et al. [53] prepared Ni/SiO2 catalyst
by argon glow discharge plasma decomposition of nickel nitrate.
Compared with the catalyst prepared by traditional impregnation
method without plasma treatment, the interaction between Ni particles
and SiO2 was enhanced by plasma treatment, and the dispersion of Ni
was better, which significantly enhanced the carbon deposition resis­
tance of the catalyst.
Plasma technology can also be applied to the reduction process of
catalysts [55–57]. Plasma reduction can reduce the size of active grains
on the catalyst. Liu et al. [55] used atmospheric pressure high frequency
cold plasma jet to reduce Ni/γ-Al2O3 catalyst, and calculated the nickel
grain size by Scherrer formula. The results show that the average par­
ticle size of nickel on the catalyst reduced by plasma is 5.9 nm lower
than that of conventional catalyst (impregnation method). The catalyst
using plasma reduction has smaller nickel particle size, which can pro­
mote the dispersion of nickel grains in the catalyst. The reaction activity
of the plasma reduced catalyst is always higher than that of the con­
ventional catalyst. When the plasma reduced catalyst is used for DRM
reaction, almost no water is generated in the reaction, and the amount of
carbon deposition is also very small [57]. The good thermal and
chemical effects of cold plasma can make the reduction process faster,
simpler and more thorough. Moreover, it can prevent the agglomeration
of metal particles and greatly improve the dispersion of nickel compo­
nents on the catalyst [56]. Compared with the conventional catalysts,
the plasma reduced catalyst has smaller particle size and higher
dispersion, and its low-temperature activity, anti-carbon ability and
stability in DRM reaction are significantly improved.
Plasma technology has also been used for the decomposition of metal
precursors [58–64]. Zhou et al. [58] used dielectric barrier discharge
plasma to decompose nickel precursor. Compared with the traditional
calcined catalysts, the high-energy electrons and excited state particles
in plasma can cause the rapid decomposition of metal precursors, which
makes the catalysts have better low-temperature activity and stability.
Hu et al. [64] believe that the treatment of catalyst by atmospheric
pressure cold plasma torch can replace the conventional
high-temperature roasting and high-temperature reduction processes.
They found that the precursor of Ni/γ-Al2O3 catalyst can be decomposed
and reduced to metallic elements within 3 min. This is due to the high
ionization degree of gas in the atmospheric pressure cold plasma jet,
more h particles with strong reduction ability and higher temperature,
so the catalyst precursor can be rapidly decomposed and reduced.
C. Shi et al. Journal of CO2 Utilization 46 (2021) 101462

3. Conventional catalysis-alone system active metal and promoter. The preparation method also affects the MSI
strength of the catalyst [67,78]. Ewbank et al. [67] compared the effects
The research progress of DRM reaction in recent years was reviewed of controlled adsorption (SMSI) and dry impregnation (WMSI) on the
from the perspective of conventional catalysis-alone system. The phys­ performance of the catalysts by changing the preparation methods. In
icochemical properties of DRM catalyst will affect its catalytic perfor­ addition, the total amount of carbon deposited on Ni/Al2O3 (DI) is four
mance. Next, we will focus on the effects of interaction, active metal times that on Ni/Al2O3 (CA). The physicochemical properties of cata­
particle size, basicity, oxygen storage capacity and carbon deposition on lysts are closely related to the preparation methods [78]. The structure
its catalytic performance. of the catalyst also affects the interaction strength [79,80]. Ma et al. [79]
prepared bimodal mesoporous macroporous alumina supported nickel
catalyst. They found that the improvement of catalytic activity is closely
3.1. Interaction
related to the structural characteristics of large surface area, large pore
volume and uniform pore size. Zhang et al. [80] prepared Ni@SiO2 nano
The interactions on DRM catalysts can be divided into two cate­
nickel catalyst with core-shell structure. The MSI with different strength
gories: (1) metal support interaction (MSI). However, the MSI is also
was obtained by calcining the catalyst at different temperatures, which
strong or weak. Strong metal-support interaction (SMSI) has good active
affected its catalytic performance. Table 1 summarizes the influence of
metal dispersion, sintering resistance and carbon resistance [15,65,66].
SMSI on catalyst performance and the influence of different factors on
But, there are few studies on the weak metal-support interaction (WMSI)
catalyst SMSI.
in DRM [67]. In addition, the research on WMSI in other methane
Core-shell structure material is a kind of nano scale functional
reforming methods is relatively less [68]. WMSI is more suitable for
composite materials, which is composed of two or more different ma­
bimetallic catalysts, which can provide better bimetallic synergistic ef­
terials. One nano material can coat other nano materials by chemical
fect [69]. (2) The synergism of bimetallic. The synergistic effect of
bond or other forces. In the core-shell structure, the confinement space
bimetallic helps to enhance dispersion and provide additional active
of the shell can limit the moving range of the internal metal particles and
sites [70–72].
avoid the agglomeration and sintering of the metal particles. Some
characteristics of the shell material, such as oxygen mobility and SMSI,
3.1.1. SMSI
can reduce the formation of carbon deposition, thus improving the
SMSI can affect the dispersion and particle size of active metal, and
stability of the catalyst [81]. Li et al. reviewed the research progress of
then affect the activity and stability of the catalyst. Bu et al. compared
core-shell structure catalysts prepared by different shell materials (SiO2,
the activity and stability of catalysts prepared by different supports in
zeolite, CeO2 and Al2O3) and their application [82,83]. They also pre­
DRM reaction [73]. It is found that SMSI can effectively prevent the
pared a series of core-shell catalysts (Ni@NiPhy@SiO2 [84], Multi-­
movement and agglomeration of nickel at high temperature. SMSI is one
Ni-Core@NiPhy@CeO2 [85], Multi-Ni@NiPhy [86], Ni@SiO2 NTs [87],
of the main reasons for the good stability of DRM catalyst. Li and his
Ni@Ni-Mg Phy [88]). Das and his colleagues have developed a catalyst
colleagues studied the DRM reaction of Ni/CeO2 catalyst in H2 atmo­
with a unique sandwich core-shell structure (Ni-SiO2@CeO2) [89].
sphere at different temperatures [74]. They found that strong
There are two kinds of core-shell structure catalysts mentioned
metal-oxide interactions lead to support-decoration of nickel particles.
above. One is to use active component as the core material, and the outer
In addition, the addition of metal oxides (MgO, Cao and La2O3) [75,76]
coating shell is porous material. The selective diffusion of catalytic
and doping metals (Pt, Fe, Mo) [77] also affected the activity and sta­
products is carried out by using the shell molecular level channels, or the
bility of the catalyst. This may be due to the close interaction between

Table 1
Comparison of DRM catalysts with SMSI.
Catalyst Reaction conditions Conversion Time Remarks Reference
(%) on

GHSV or Feed gas Temperature CH4 CO2 stream

Flow rate ratio
1
NiMA-BN-M-R 25 L g− CH4/CO2 1073K 85 95 20h SMSI can effectively prevent the movement and agglomeration of [73]
h− 1 = 1/1 nickel at high temperature. It showed good stability in 100 h-DRM
reaction.
1
Ni/CeO2 48,000 h− CH4/CO2 773K 31 43 10h The strong metal-oxide interaction results in the support-decoration of [74]
= 1/1 nickel particles. Within 3 h, the conversion of CH4 decreased rapidly,
but the amount of carbon deposition decreased.
1
Ni-MgO- 48,000 h− CH4/CO2/ 1073K 95 96 40h There is a close interaction between Ni and MgO. Catalyst exhibited [75]
Ce0.8Zr0.2O2 N2 = 1/1/ equilibrium CH4 and CO2 conversion within 200 h, but no deactivation
3 was observed.
1
Pt/FeMo/Ni/ 12 L g− CH4/CO2 973K 81 86 10h Mo and Fe promoters improved the anti-coking ability of the catalyst. [77]
Al2O3-CeO3 h− 1 = 1/1 The catalyst has good activity and selectivity, and the carbon
deposition is very low.
Ni/Al2O3 (CA) 1 CH4/CO2 49 60 The preparation method will affect the strength of metal-support
22,000 h− 973K 10h [67]
Ni/Al2O3 (DI) = 1/1 98 80 interaction. The catalytic performance was stable for at least 9 h.
CaZrNiOx
CH4/CO2/ 79.5 88
(HDP) 60,000 cm3 CaZrNiOX (HDP) has better catalytic activity and stability than Ni/
N2 = 2/2/ 1123K 20h [78]
Ni/CaZrOx g− 1 h− 1 CaZrOX (IMP) in the reaction time of 100 h.
1 49.2 64.8
(IMP)
Ni/MM-A 1 73 83 The structure of the catalyst will affect the strength of metal-support
30 L g− CH4/CO2
973K 100 h interaction. The Ni/MM-A catalyst showed strong catalytic stability [79]
Ni/M-A h− 1 = 1/1 70 81
after 100 h life test, and there was no obvious deactivation after 100 h.
1 CH4/CO2/ Ni@SiO2-600(b) (the best coupling of size effect and metal-support
60 L g−
Ni@SiO2 N2 = 3/3/ 973K 2.6(a) 2.9 41.6h interaction) catalyst showed the highest performance, stability and [80]
h− 1
4 lowest carbon deposition.

(a) Reaction rates of CH4 and CO2 (mmolg−Ni1 s− 1).

(b) The samples were calcined in muffle furnace for 2 h (600 ℃) to form catalyst Ni@SiO2-600.

4
C. Shi et al. Journal of CO2 Utilization 46 (2021) 101462

components in the reaction system that are not conducive to the target
reaction are blocked to improve the activity and life of the catalyst. The
other is to wrap the active component in the shell layer to increase the
specific surface area and enhance the diffusion in the reaction system. In
addition, the shell and core can be used as bifunctional catalysts, which
can significantly improve the conversion of consecutive reactions.
The above literature review shows that SMSI contributes to the
anchoring and dispersion of active particles, providing active sites and
improving catalytic performance. Nickel based core-shell catalyst has
some advantages of anti-sintering and anti-carbon deposition in DRM
reaction, but there are still some problems to be solved. As far as the
core-shell structure catalyst is concerned, the existing structure is mostly
double-layer, while the core-shell structure of multilayer and free core is
rarely reported. From the relationship between the core and the shell,
the mechanism of the strong and weak force is not mature. Therefore, we
should continue to explore new structural forms of core-shell materials
in future research. In order to control the catalytic activity and stability,
we need to further improve the mechanism of strong and weak inter­
action between core and shell.
3.1.2. The synergism of bimetallic
In recent years, the application of bimetallic catalysts in DRM has
become a new development direction. Bimetallic catalysts exhibit
unique properties and excellent catalytic performance different from
single metal catalysts due to their adjustable physicochemical proper­
ties, electronic and geometric effects between bimetallic catalysts
[90–96]. At present, Pt [97,98], Pd [99], Rh [100], Au [101], Ru [102]
or other metals such as Cu [103], Co [91,104,105], Fe [72], Mn [106],
Sn [92], In [90] have been used as the second metal of Ni based bime­
tallic catalysts. The second metal may form alloy phase with Ni or exist
as independent phase as dopant, which changes the electronic structure
and geometric structure of active metal, thus changing the activity and
stability of the catalyst. In addition, the synergistic effect of bimetallic
helps to enhance the dispersion and provide additional active sites,
showing high activity and stable reaction performance in the DRM
process.
Noble metals usually help to improve the reducibility of Ni, thus
increasing the number of active centers in the catalyst [19,20]. There­
fore, the noble metal as the second metal of Ni based bimetallic catalyst
has high reducibility, and the alloy still exists in the metal state even
though oxygen exists under atmospheric pressure and pressure [107].
Wu et al. [101] studied the effects of the addition of very low concen­
trations of Au and Pt on the catalytic performance of Ni based catalysts
supported on Al2O3 and Al2O3-MOX (M = Ce or Mg) oxides. The results
show that the addition of a small amount of Au and Pt in Ni based
catalyst can form a synergistic effect, which leads to the decrease of NiO
species and particle size, and improves the catalytic performance of
bi-/trimeric catalyst. Diéguez and his colleagues found that bimetallic
catalysts (Pt-Ni/γ-Al2O3) exhibited higher activity and less carbon
deposition than single metal catalysts (Ni/γ-Al2O3, Pt/γ-Al2O3) [97].
This is related to the formation of Pt-Ni alloy. The high content of Pt on
the surface of Pt-Ni alloy leads to the metal particle size (10 nm) smaller
than that of single metal Ni catalyst (25 nm).
The addition of other metals (Cu, Co, Fe, Mn, Sn, In) can also
significantly improve the anti-carbon ability of the catalyst. These
metals have become a research hotspot due to their price advantages.
According to the existing research, the influence of the second metal on
the catalytic performance of bimetallic catalysts was summarized. It
should be noted that excessive addition of the second metal may reduce
the activity of the catalyst. The effects of bimetallic synergism on the
performance of the catalysts are summarized in Table 2.
(1)Ni-Cu. Ni and Cu alloying can inhibit the decomposition of CH4,
Cu provides a place for CO2 dissociation, thus producing more active
oxygen suitable for carbon gasification, thus reducing the carbon
deposition and improving the catalytic stability [103].
(2)Ni-Co. The promotion effect of Co is mainly attributed to its
strong affinity for oxygen species. Therefore, the presence of Co en­
hances the adsorption of CO2, which helps to inhibit carbon deposition
by enhancing carbon removal. In addition, the strong synergistic effect
between Ni and Co helps to disperse the active sites of the metal alloy,
thus improving the catalytic performance of the catalyst [91,104,105].
(3)Ni-Fe. Fe has excellent redox properties. Theofanidis et al. [72]
studied the catalytic performance of bimetallic catalyst (Fe-Ni/M­
gAl2O4) for DRM. They believe that CO2 oxidizes Fe to FeOx, and CH4
activates at the Ni active site to form H2 and carbon species. The latter is
reoxidized by lattice oxygen from FeOx to produce Co. In addition, the
formation of Ni-Fe alloy can enhance the interaction between Ni and Fe.
(4)Ni-Sn. Guharoy et al. found that Sn atoms occupy the C

Table 2
Comparison of DRM catalysts with the synergistic effect of bimetal.
Catalyst Reaction conditions Conversion Time Remarks Reference
(%) on

GHSV or Feed gas Temperature CH4 CO2 stream

Flow rate ratio

Ni/Al2O3 60 70
CH4/CO2/ There is a synergistic effect between Ni and Pt, which improves the
Pt/Al2O3 1 65 76
6000 h− He = 1/1/ 973K 14h conversion of DRM. A small amount of Pt can be used to prolong the service [97]
Ni-Pt/
3 69 76 life of Ni/Al2O3 catalyst.
Al2O3
Ni-Pd/ 1 Different Ni/Pd ratios have little effect on the catalytic activity of the
19.8 L g− CH4/CO2 =
La2O3- 973K 73 78 2h catalysts, but the performance of all bimetallic catalysts is better than that of [99]
h− 1 1/1
ZrO2 single metal Ni or Pd catalysts.
1 Alloying Ni with Cu inhibits CH4 decomposition. Cu provides active sites for
Ni-Cu/Mg 60 L g− CH4/CO2/
873K 51 58 25h CO2 dissociation. The optimum performance of the catalyst is related to the [103]
(Al)O h− 1 N2 = 1/1/2
synergistic effect between Ni and Cu.
Ni/Al2O3 10 \
1 The strong bimetallic interaction resulted from the formation of well
Co/Al2O3 114 L g− CH4/CO2/ 22 \
873K 24h dispersed NiCo alloy can improve the catalytic performance by inhibiting the [91]
Ni-Co/ h− 1 N2 = 1/1/1
34 \ boudouard reaction of CO and the selectivity of Ni for methane cracking.
Al2O3
1 Sn can increase the potential barrier of coke nucleation. Sn can also promote
Ni-Sn/ 60 L g− CH4/CO2/
973K 30 75 20h the oxidation of key reaction intermediates on the catalyst surface. Ni Sn [92]
Al2O3 h− 1 N2 = 1/1/6
bimetallic catalyst showed good stability in 20h-DRM.
Pt/CeO2 27 \ The presence of Co and Pt further increases the abundance of O* through
1
12 L g− CH4/CO2/ significantly enhanced CO2 activation and higher O* binding strength. The
Pt-Co/ 873K 12 h [93]
h− 1 Ar = 1/1/2 42 \ O* modified surface of Pt-Co/CeO2 promoted the reforming reaction with a
CeO2
higher entropy contribution to compensate for its higher activation barrier.

5
C. Shi et al.
nucleation center near Ni atom, which can increase the potential barrier
of coke nucleation [92]. Although this does not completely prevent
carbon deposition, it does slow down carbon formation and affects the
type of carbon formed on the catalyst surface. Sn also promotes the
oxidation of key reaction intermediates (such as CHO) on the catalyst
surface, thus facilitating the formation of final products.
(5)Ni-In. Németh et al. found that the presence of In can change the
chemisorption and dissociation of methane [90]. The effect of In on
methane decomposition has two aspects: Changing the surface
structure of adsorption sites to prevent the complete dissociation of
methane. ②Compared with single metal catalyst, it has electronic effect
on Ni, which leads to stronger hydrogen chemisorption.
(6)Pt-Co. The Pt-Co/CeO2 bimetallic catalyst was prepared by Xie
et al. [93]. CeO2 is favorable for CO2 activation and provides O* for
Pt/CeO2 surface. The presence of Co and Pt further increases the
abundance of O* through significantly enhanced CO2 activation and
higher O* binding strength. The O* modified surface of Pt-Co/CeO2
promoted the reforming reaction with a higher entropy contribution to
compensate for its higher activation barrier.
In addition, the research on polymetallic catalysts needs to be
strengthened. Kim et al. [106] developed the precursor of trimetallic
catalyst (LaNi0.34Co0.33Mn0.33O3). The effect of Mn is to improve the
stability of the catalyst, while Co is an additional active component to
increase the reaction rate. In the trimetallic catalyst, MnO mediates the
strong interaction between metal and support, which contributes to the
synergy among the three metals, thus maintaining high activity and
stability under harsh DRM conditions.
The above literature review shows that the synergistic effect of
bimetallic catalysts can enhance the dispersion, provide additional
active sites and improve the sintering resistance. Among the bimetallic
catalysts, the selection of different active metal combinations will
strongly affect the performance of the catalysts. In addition, specific
crystal faces or reaction surfaces can be exposed preferentially or
selectively by interfacial constraints. It can enrich and regulate the
active sites, regulate the adsorption and activation of reactants and in­
termediates, and improve the conversion and selectivity of reforming
reaction [108]. However, the structure of bimetallic particles and the
promotion mechanism of different metals are not mature and need
further study. The research on polymetallic catalysts also needs to be
strengthened.
3.2. Active metal particle size
The performance of the catalyst is not only related to the strength of
metal-support interaction, but also affected by the size of active metal
particles [80]. DRM reaction requires high temperature, and high tem­
perature will lead to the sintering of small size active metal particles,
and eventually increase with the deposition of carbon. Many researchers
[109,110] proposed that carbon deposition in reforming reaction pro­
cess obviously depends on the size of metal particles. In addition, SMSI
can maintain small size active metal particles at high temperature
[111–113]. Smaller nickel particles have stronger ability to inhibit
carbon deposition [114–117]. However, the effect is limited. Indepen­
dent observation of the active metal particle size of dry reforming
catalyst can provide valuable insights for researchers to design better
catalysts [117].
The results show that the smaller the active metal particle size, the
higher the activity of the catalyst [117,118]. In addition, promoter
[119], support [80,117,120,121], preparation method [122] and pre­
treatment [123] can also affect the active metal particle size of the
catalyst, thus affecting the activity of the catalyst. Han et al. [119]
evaluated the dependence of CH4 and CO2 conversion on Ni particle size
and support, respectively. It was found that the smaller the Ni particle
size, the higher the CH4 turner frequency. In the MSR reaction, there are
similar conclusions about the active metal particle size [118]. The size of
active particles and the amount of carbon deposition can also be reduced
6
Journal of CO2 Utilization 46 (2021) 101462
by introducing suitable promoter into the catalyst [119]. Kang et al.
[119] prepared Ni-La0.7Sr0.3Cr0.5Mn0.5O3-δ(LSCM) and Cu/Ni-LSCM
catalysts, and compared their catalytic performance for DRM reaction.
The experimental results show that when a certain amount of Cu is
added into the catalyst, the grain size, active particle size, carbon fiber
diameter and carbon deposition amount of Ni decrease. When the active
metal particle size is the same, the CH4 conversion of the catalyst is also
affected by the support [117,120,121]. Tian et al. [121] encapsulated
uniform nickel nanoparticles (about 2 nm) into the through channel of
MCM-41 via ethanol induced capillary effect. After 200 h of reaction
time, no obvious Ni-NP agglomeration was observed. In contrast, the
unconfined Ni/MCM-41 deactivates rapidly within 12 h, and the size of
Ni particles increases to 16.7 nm after 60 h, and the catalyst surface is
covered by carbon nanotubes. In addition, the introduction of Ni can
well adjust the pore size distribution of the support, and larger Ni spe­
cific surface area can provide more reaction sites for methane activation
[122]. Zhou et al. [123] found that pretreatment of the precursor can
affect the size and distribution of active metal particles in DRM catalyst,
thus affecting its performance. The effect of active metal particle size on
the performance of DRM catalyst is summarized in Table 3.
The above literature review shows that smaller nickel particles have
stronger ability to inhibit carbon deposition. However, in order to design
a more reasonable DRM catalyst, other factors need to be considered.
3.3. Basicity
In the DRM reaction, methane decomposition occurs in the acidic
part of the support, so basicity is the key feature of the catalyst’s ability
to resist carbon deposition. Alkali metals [96] (Na, K) and alkaline earth
metals [96,124–126] (Mg) can be used as supports or promoters, which
can reduce the acidity of the supports to a certain extent. In addition,
some modified catalysts also have high basicity [126,127]. Sengupta
et al. [126] studied the modification effect of CaO and MgO on the
support. The experimental results show that the Al2O3 supported Ni and
CaO modified Ni-Co catalysts have extra base sites, which improve the
chemisorption capacity of the catalysts for H2 and CO2, thus improving
the activity and carbon resistance of the catalysts. MgO has a strong
interaction with active metals, which has a negative effect on the cata­
lytic activity. Li et al. [127] reported a new method of modifying
Ni/Al2O3 with La2O2CO3. They found that LA can cover the acidic sites
of Al2O3, increase the basicity of the catalyst, promote CO2 adsorption
and activation, and inhibit carbon deposition.
Increasing the basicity of the catalyst can accelerate the activation of
the intermediate acid CO2 and oxidize the carbon on the catalyst surface
[128–130]. The presence of active CO2 on the catalyst surface will
inhibit the decomposition of CH4 to produce carbon, thus improving the
anti deactivation ability [131]. Ballarini et al. [96] investigated the
catalytic performance of Pt catalysts with different metal loading in the
dry reforming of methane using alkaline (Na and K) or alkaline earth
metal (Mg) doped Al2O3 as supports. The experimental results show that
the presence of alkaline metals or alkaline earth metals improves the
thermal stability of γ-Al2O3 and the acidity of support, while the cata­
lysts doped with alkaline earth metals can maintain higher specific
surface area and better Pt dispersion. Carbon is deposited on the surface
of metal particles and supports, and the carbon deposition amount of
support with stronger acidity (A-Mg) is greater, which increases with the
increase of activity [132]. Dama et al. [124] synthesized perovskite type
oxides substituted by alkaline earth metals and evaluated them as pre­
cursors of DRM catalysts. The results show that the types of alkaline
earth metals that replace the a site of perovskite oxides play an impor­
tant role in the structure, basicity, oxygen defects and Ni dispersion of
perovskite oxides. In addition, basicity plays an important role in the
activation and maintenance of reforming reaction. Vasoncelos et al.
[125] prepared Ni based catalysts from two hydroxyapatites with
different physicochemical properties. The catalyst with high basicity
and high alkali density shows good performance in all cases. The effect
 C. Shi et al.
Table 3
Comparison of DRM catalysts with active metal particle size.
Catalyst Reaction conditions Conversion(%) Time Remarks Reference
on

GHSV or Feed gas Temperature CH4 CO2 stream

Flow rate ratio
36.7(2.6
62.4
nm)(a)
36.8(5.2
61.6 In the case of higher reaction temperature, as long as the particle size is small and the interaction with the basic
CH4/CO2/ nm)
Ni/SiO2@SiO2 \ 1073K 100 h support can maximize the activity. After 100 h, the amount of CO absorption increases slightly because the silica [117]
N2 = 9/9/2 18.8(9.0
35.4 coating becomes more open after high temperature reaction.
nm)
12.6(17.3
26.6
nm)
Ni-La0.7Sr0.3Cr0.5Mn0.5O3-
923K 7 8
1 1 CH4/CO2/ After 13 h-DRM, the addition of appropriate amount of Cu reduced the grain size of Ni, the size of active
10 L g− h− 13 h [119]
δ
7

Cu/Ni- Ar = 1/1/8 particles, the diameter of carbon wire and the amount of carbon deposited.
923K 73 60
La0.7Sr0.3Cr0.5Mn0.5O3-δ
1 1 CH4/CO2 = The introduction of proper amount of Mg controls Ni particle size, which contributes to suppressing the carbon
NiO-MgO-Al2O3 15 L g− h− 973K 78 83 100 h [120]
1/1 formation. There was no deactivation after 100 h long-term stability test.
1 1 CH4/CO2 = A new method for the preparation of Ni/MCM-41 catalyst can effectively prevent the sintering and high-
Ni/MCM-41 45 L g− h− 973K 71 81 200 h [121]
1/1 temperature coking of metal nanoparticles. It can maintain high activity and stability for 200 h-DRM.
Ni-MA(EISA) 85.9 78.1
W/FCH4 = 1 g CH4/CO2/ 6h The introduction manner of Ni can well regulate the pore size distribution of the support, and the larger surface
Ni/MA(IMP) 1023K 81.3 74.8 [122]
h mol− 1 O2 = 4/2/1 area of Ni can provide more reaction sites for methane activation.
Ni-MA(EISA) 86 78 100 h
Ru0.003Ni0.067Mg0.93O-
75 80
CR(b) 1 1 CH4/CO2 = The pretreatment of precursors can affect the size and distribution of active metal particles in DRM catalyst, thus
86 L g− h− 1033K 100 h [123]
Ru0.003Ni0.067Mg0.93O- 1/1 affecting its performance. The catalyst of direct reduction has higher stability in 100 h-DRM.
79 83
DR(c)

(a) Four different sizes (2.6, 5.2, 9.0, and 17.3 nm) of Ni nanoparticles.
(b) CR indicating calcination and reduction.
(c) DR representing directly reduced.

Journal of CO2 Utilization 46 (2021) 101462

C. Shi et al. Journal of CO2 Utilization 46 (2021) 101462

of basicity on catalyst performance is also summarized in Table 4.
The above literature review shows that in DRM process, because CO2
is acidic gas, the adsorption capacity of alkaline support is higher than
that of acid support. However, it is usually beneficial to have a medium
surface acid-base center [133], because excessive acidity of the support
can lead to carbon deposition through enhanced CH4 decomposition
reaction [134]. In addition, too high basicity can promote boudouard
reaction, promote the oxidation of active metals, and lead to the deac­
tivation of the catalyst. In the design of high basicity support, we should
also pay attention to the negative effects of high basicity.
3.4. Oxygen storage capacity
Oxygen storage capacity is also one of the important factors for
carbon deposition resistance of DRM catalyst. The oxygen defects in the
support are the potential sites for CO2 activation and C–O bond frac­
ture, and increase the free oxygen content on the catalyst surface. Free
oxygen oxidizes C to CO and forms carbonate intermediate products on
the alkaline reduction support, thus eliminating the formation of carbon
[135]. In addition, the atmosphere in which the catalyst is prepared also
affects the oxygen storage capacity of the catalyst [136]. Zhu et al. [136]
calcined Ni-Ce/SiO2 catalysts in different atmospheres (Ar, H2, CO2, O2)
and applied them to DRM. The results show that the catalyst calcined in
Ar atmosphere has higher oxygen storage capacity, the fluidity and ac­
tivity of oxygen on the catalyst surface are significantly improved, and
the catalyst is more stable. However, the catalyst calcined in H2 atmo­
sphere will lose the oxygen storage capacity of CeO2 and inhibit the
elimination of carbon whiskers, resulting in poor stability of the catalyst.
When the catalyst was calcined in CO2 and O2, the surface oxygen
mobility and activity decreased, and the carbon removal was inhibited.
The high oxygen storage capacity of CeO2 helps to eliminate carbon
and inhibit carbon deposition [44,137–139]. Many studies have shown
that CeO2 has large oxygen storage capacity, which can promote the
formation of oxygen vacancies and improve the oxygen mobility
[139–145]. However, CeO2 usually loses its oxygen storage capacity
under high temperature treatment and reduction atmosphere [137,142,
146]. In addition, promoter [45,147,148] and modified catalyst [149]
can also affect it. The promoter can improve the physical and chemical
properties of the support and catalyst, and improve the stability of the
catalyst under thermal reduction treatment [147,148]. It can also in­
crease the surface concentration of active sites [45]. Wang et al. [147]
doped Pr or Zr into CeO2 matrix and studied Ir catalyst supported on Ce
composite oxide. The experimental results show that doping Pr or Zr can
improve the oxygen storage capacity of the catalyst, make carbon
vaporize rapidly at the interface of metal support, and effectively reduce
the carbon deposition on the catalyst surface. CeO2 modified catalyst
can also inhibit carbon deposition and improve catalyst activity [149].
Chein et al. [149] improved the catalytic performance of DRM catalyst
by CeO2 modification of Ni/Al2O3 catalyst and the addition of O2 into
the reactant. The effect of oxygen storage capacity on catalyst perfor­
mance is summarized in Table 5.
In the process of catalyst development, researchers also found that
perovskite type composite oxide (ABO3) has the advantages of good
catalytic activity and high thermal stability. Perovskite has a wide
tolerance range for the composition ion radius in the lattice composi­
tion, so the cations with appropriate ionic radius can be used to partially
or completely replace the A site and B site ions without causing great
damage to the original perovskite structure [150]. The substitution of
low valence ions (such as Sr2+, Eu2+, Ba2+) to A site will increase the
concentration of oxygen defects in bulk phase, while the high or variable
valence ions (such as Ce4+) will reduce the concentration of oxygen
defects [151], which makes perovskite composite oxides have a certain
advantage in catalytic activity and stability. Bian et al. [152] summa­
rized that the substitution of A site can produce more active moving
surface oxygen sites, which can vaporize the carbon species on the
catalyst surface, thus improving the carbon resistance. Pichas et al.
[153] studied the performance of La2-xSrxNiO4 perovskite oxide catalyst
in DRM reaction. They found that a small amount of Sr increased carbon
deposition on the surface of the catalyst, while a high amount of Sr
inhibited coking and increased CO2 conversion and CO production. Sr
also can increase the basicity of the catalyst surface. Sutthumporn et al.
have also shown that the substitution of Sr can significantly increase the
lattice oxygen content [154], which may be due to the breaking of the
oxidation state equilibrium between Sr2+ and La3+.

Table 4
Comparison of DRM catalysts with basicity.
Catalyst Reaction conditions Conversion Time Remarks Reference
(%) on

GHSV or Feed gas Temperature CH4 CO2 stream

Flow rate ratio

Pt/Al2O3-K 64 81 The acidity of the support is inhibited by doping alkaline metal, but
the properties of the support will change during the high temperature
CH4/CO2
\ 1023K 2.25h heat treatment (1000℃). After doping alkaline earth metal, there are [96]
Pt/Al2O3-Mg = 1/1 58 74
still some acid centers in the support. It is estimated by TPO analysis
that the carbon content of all catalysts is less than 1 wt%.
CaZr0.8Ni0.2O3-δ has high activity and is stable even after 500 h.
CH4/CO2/
1 Probably, the oxygen defects created due to Ni substitution might
CaZr0.8Ni0.2O3-δ 28,800 h− N2 = 1/1/ 1073K 95 96 500 h [124]
have also been helpful for the removal of coke formed thus imparting
1
durability to the catalyst.
Ni/Ca-HA1(a) 1 CH4/CO2/ 60 70 Ni/Ca-HA2 catalyst has better catalytic performance than Ni/Ca-HA1
15.9 L g−
N2 = 1/1/ 973K 7h catalyst, which is due to the stronger basicity, higher density of basic [125]
Ni/Ca-HA2 h− 1 80 81
3 sites and higher specific surface area of Ca-HA2 support.
Ni-Co/Al2O3 14 15
Ni-Co/CaO- 0.14 kg h CH4/CO2/ Cao modified catalyst has extra basic sites, which improves the
15 16
Al2O(b)
3 kg− 1 mole N2 = 1/1/ 873K 3h chemisorption capacity of H2 and CO2. MgO has a strong interaction [126]
Ni-Co/MgO- CH4 3 with Ni and Co, which has a negative effect on the catalytic activity.
8 13
Al2O3
La2O2CO3 modified Ni/Al2O3 can regulate the interaction between Ni
1 CH4/CO2/ and Al2O3. La can cover the acidic position of Al2O3, increase the
Ni/La2O2CO3- 240 L g−
N2 = 3/3/ 923K 61 69 50h basicity of catalyst, promote the adsorption and activation of CO2, and [127]
Al2O(c)
3 h− 1
14 inhibit carbon deposition. The catalyst has good stability after 50h-
DRM.

(a) Two hydroxyapatites (HA), Ca-HA1 (SBET = 7 m2 g− 1, d50 = 5.2 μm) and Ca-HA2 (SBET = 60 m2 g− 1, d50 = 6.1 μm).
(b) Modifying the support of Al2O3 with CaO and MgO.
(c) Modification of Ni/Al2O3 by La2O2CO3.

8
 C. Shi et al. Journal of CO2 Utilization 46 (2021) 101462

The above literature review shows that improving the oxygen stor­
Reference
age capacity of the catalyst can promote the carbon removal, which is
one of the effective means to improve the performance of the catalyst. In

[136]

[147]

[148]

[149]

[153]
[45]
addition, the substitution of A site in perovskite can produce more
active moving surface oxygen sites, which can vaporize the carbon
The catalyst calcined in Ar atmosphere has a higher oxygen storage capacity, and the mobility and activity of oxygen on

catalyst is calcined in CO2 and O2 atmosphere, the mobility and activity of surface oxygen are reduced, and the removal

mechanism on metal surface. The addition of Pr, Zr and Nb doped ceria into Pt/Al2O3 catalyst can significantly reduce
the surface of the catalyst are significantly improved, and the catalyst is more stable. However, the catalyst calcined in
high temperature H2 atmosphere will lose the oxygen storage capacity of CeO2 and the catalyst stability is poor. When the

The modification of Ni/Al2O3 catalyst with CeO2 can inhibit carbon deposition. The stability test for 36 h showed that the
stability of the catalyst under thermal reduction treatment. Zr-rich catalysts show high activity and strong resistance to

Ir/Ce0.9M0.1O2 (M = Pr, Zr) catalyst has stronger metal support interaction and better oxygen storage capacity, which
Compared with the samples without zirconia, Ni/CeO2-ZrO2 catalyst showed higher activity. Zr improves the texture

A small amount of Sr increased carbon deposition on the surface of the catalyst, while a high amount of Sr inhibited
species on the surface of the catalyst, thus improving the carbon resis­

Pt/CePr/Al2O3 has the highest oxygen storage/release capacity, which promotes the occurrence of carbon removal

coking and increased CO2 conversion and CO production. Sr also can increase the basicity of the catalyst surface.
of carbon is inhibited. The Ni-Ce/SiO2 catalyst calcined in Ar atmosphere has better catalytic stability after 30 h. tance. However, the substitution of reducible elements at B site and
simultaneous substitution of A and B sites need more detailed study.

3.5. Carbon deposition

In catalytic chemical reactions, deactivation of catalyst is inevitable,

especially in the case of higher reaction temperature [7,155]. According
to thermodynamics, the carbon deposited on the catalyst surface mainly
comes from the boudouard reaction and CH4 decomposition, which is
easier to form under DRM conditions [156]. The type and quantity of
activity of CeO2 modified Ni catalyst was higher than that of pure Ni catalyst. carbon deposited on the catalyst surface are closely related to the
properties of the support [157]. Therefore, designing a reasonable
support is one of the effective means to solve the problem of carbon
effectively reduces the carbon deposition on the catalyst surface.

deposition on catalyst.
Many studies have shown that there are three types of carbon
deposition on supported nickel catalysts [158–161]: amorphous carbon
carbon deposition. It remained stable after 24h-DRM.

(polymerized) Cα, filamentous carbon Cβ and graphite carbon Cγ. Cα

comes from the decomposition of hydrocarbons and is an active species
to form syngas. Cβ and Cγ are formed on the surface of the catalyst and
need the participation of metal active sites. The activity of Cγ is the
worst, which can lead to catalyst deactivation [160,161]. Cα and Cβ are
converted into Cγ after a long time reaction, resulting in the rapid
deactivation of the catalyst. In addition, two types of carbon, filamen­
tous and encapsulated carbon, may be formed on nickel catalyst [158,
the loss of catalyst activity.

159]. Guo et al. [160] found that Cγ was the least active species for H2
and O2, but its activity for CO2 was unexpectedly high. The unique
reactivity of CO2 with different types of coke can be attributed to the
formation of carbonate, bidentate acid and formate on the surface of
MgAl2O4. These surface species promote the oxidation of Cγ, thus
Remarks

(a) Ni-Ce/SiO2 catalysts were prepared by calcination in four different atmospheres (Ar, CO2, O2, H2).

improving the stability of Ni/MgAl2O4 catalyst. Because the Ni particles

at the end of the carbon nanofibers can still contact with the reactants,
the filamentous carbon is not considered to affect the catalytic activity
Time on

stream

200 h

of the catalyst [162–166]. Although there is carbon deposition in the

30 h

24h

24h

18h

48h

reaction process, the catalyst will not be deactivated, but the accumu­
lation of carbon on the catalyst surface will increase the pressure drop of
Conversion(%)

the bed or block the reactor [158,167,168]. Based on the formation

13.6
13.9
CO2

0.98(Ar)(b)

35

52

57
71
76
21
51
55
68

87
0.95(CO2)

mechanism of filamentous carbon, the diameter of carbon nanotubes

0.91(H2)
0.97(O2)

depends on the size of metal Ni particles [162]. Smaller Ni particles and

10.2
11.6
CH4

more uniform dispersion can reduce the deposition of carbon on the

20

38

43
54
57
16
38
43
57

51

catalyst surface and effectively inhibit the growth of filamentous car­

Temperature

bon. Large pore size has little effect on the growth of filamentous
carbon.
(b) Stability = CH4 conversion at 30 h/CH4 conversion at 1 h.
1073K

1023K

1073K

1073K
973K

673K
Comparison of DRM catalysts with oxygen storage capacity.

Xu et al. [166] found that there were four carbon species on

Ni/La2O3/γ-Al2O3 and Ni/La2O3/α- Al2O3 catalysts, which existed in
CH4/CO2 = 1/1

CH4/CO2 = 1/1

CH4/CO2 = 1/1

CH4/CO2 = 1/1

CH4/CO2 = 1/1

CH4/CO2 = 1/1

three types (Cα, Cβ, Cγ). The amount and type of carbon deposition are
Feed gas ratio

different depending on the size of Ni particles in the catalyst and the

structural characteristics of the support. The formation and morphology
(c) CeO2 modification on Ni/Al2O3 catalyst.

of filamentous carbon are closely related to the size of Ni particles.

When Ni particles are less than 15 nm, they can inhibit the formation
Reaction conditions

and deposition of filamentous carbon, reduce the amount of carbon

GHSV or Flow rate

− 1

deposition, and produce more active Cα species, so that the catalyst has
F = 60 mL min

− 1

better activity and stability. The smaller the grain size of graphite car­
h−

h−

h−

70 cc min
1

bon is, the easier carbon monoxide can be produced by gasification with
30 L g−

18 L g−

30 L g−

carbon dioxide, thus prolonging the service life of the catalyst [124].
Generally speaking, the activated carbon generated from methane
Ni/CeO2-Al2O(c)

decomposition is easy to be gasified into CO, and excess carbon species

Pt/CeNb/Al2O3

3
Ir/Ce0.9Pr0.1O2
Ir/Ce0.9Zr0.1O2

Pt/CePr/Al2O3
Pt/CeZr/Al2O3
Ni/CeO2-ZrO2

are deposited on the catalyst. Therefore, carbon deposition is generally

Ni-Ce/SiO(a)
2

LaSrNiO4
Pt/Al2O3

the result of the equilibrium of activated carbon formation and gasifi­

Ni/CeO2

La2NiO4
Catalyst

Ir/CeO2
Table 5

cation. In addition, smaller nickel particle size can inhibit the nucleation
and growth of coke [169]. Further study [170] shows that when the

9
C. Shi et al. Journal of CO2 Utilization 46 (2021) 101462

positive ion, negative ion, excited atom or molecule, ground state atom
Table 6
or molecule and photon. Whether the gas is partially ionized or fully
Classification of plasma.
ionized, the total number of negative charges is equal to the total
Classification Temperature(K) Example number of positive charges, which is generally quasi neutral, so it is
High temperature plasma (thermal Tg=Ti=Te = 106- Nuclear fusion, called plasma. Plasma is considered as the fourth state of matter except
equilibrium) 109(a) Laser fusion solid, liquid and gas. At present, some plasma gas conversion methods
Electric arc,high have been reported, such as CO2 pyrolysis [172–174], DRM [172,
Thermal plasma Tg≈Ti≈Te = 3 ×
frequency
Low (local equilibrium) 103− 4
discharge
[175–177] and nitrogen fixation [178–180].
temperature According to different standards, plasma has different classification.
Te(>104)>> Glow discharge,
plasma Cold plasma
Ti≈Tg≈3 × 102- Microwave No matter what standard is selected, the plasma temperature should be
(nonequilibrium)
103 discharge considered. Plasma is a multicomponent system, which presents the
(a) Tg: Heavy particle temperature; Ti: Ion temperature; Te: Electron temperature of multiple states, electron temperature (Te), ion temper­
temperature. ature (Ti) and gas temperature (Tg). According to the system tempera­
ture, the plasma is divided into high temperature plasma and low
radius of Ni is less than 7 nm, it can effectively inhibit carbon deposition. temperature plasma, as shown in Table 6. High temperature plasma is
Wu et al. [101] suggested that there was a strong correlation between generally used in nuclear technology. Low temperature plasma can be
the catalytic activity and the type/number of carbonaceous species. The divided into hot plasma and cold plasma. The gas temperature of hot
catalyst with the best performance is the one with the best combination plasma is close to that of electron, and the system is in equilibrium, so it
of the two parameters (high amount of carbon nanotubes and low total is called equilibrium plasma. The advantage of thermal plasma is that
carbon). Guharoy et al. [92] showed the difference of carbon deposition the thermodynamic equilibrium of electrons and heavy particles can be
between single metal catalyst and bimetallic catalyst by SEM image. achieved through a large number of collisions between electrons and
Comparing the images of new catalyst and waste catalyst, it can be found heavy particles [181]. On the contrary, although the electron tempera­
that the single metal catalyst is completely covered by carbon after DRM ture of cold plasma is high, its gas temperature is very low, which can be
reaction, while the bimetallic system is only partially covered by fila­ kept at room temperature. The system is in thermodynamic
mentous carbon species. non-equilibrium state, so it is also called non-equilibrium plasma. The
The above literature review shows that the support is one of the key advantage of cold plasma is that the gas can be activated by electron
factors affecting the carbon deposition of the catalyst. Therefore, it is an impact excitation, ionization and dissociation reactions, rather than
urgent need to develop a more reasonable support. In addition, it is heating the whole reactor [182,183].
necessary to further study the effect of different types of carbon depo­ Next, the research progress of cold and hot plasma in plasma-
sition on the catalytic performance. catalytic system is introduced.

4. Plasma-catalytic system 4.2. Thermal plasma-catalytic system

The progress of DRM reaction in recent years was reviewed from the
perspective of plasma-catalytic system.
4.1. Plasma
Plasma is a conductive fluid composed of electrons, ions, free radi­
cals and neutral particles. This concept was first introduced by Irving
Langmuir in 1928 [171]. Because the mass of ions and neutral particles
in plasma is much larger than that of electrons, electrons are called light
particles, while ions and neutral particles are called heavy particles.
Plasma is actually ionized gas, including six typical particles: electron,
Fig. 2. Thermal plasma treatment system. 1. Ar, 2. CH4, 3. CO2, 4. Gas inlet I,
5. Gas inlet II, 6. Gas inlet III, 7. DC power supply, 8. Cathode, 9. Plasma
generator, 10. First anode, 11. Contactor, 12. Second anode, 13. Graphite tube
reactor, 14. Collector, 15. Gas outlet. Quoted from Reference [185]. Copyright
(2009) Elsevier.
Thermal plasma is a continuous and uniform plasma produced by
arc. Thermal plasma has the characteristics of high enthalpy content,
high temperature (0.5− 1 eV for heavy particles and electrons), high
electron density (1019-1020 m− 3), large processing capacity, easy
amplification and high energy conversion efficiency. It has obvious
thermal and chemical effects. It has been widely used in industry [184].
Tao et al. [185] applied bipolar thermal plasma to DRM for the first
time to study how to expand the process flow and reduce energy con­
sumption. In addition, no oxidation of cathode and anode or carbon
deposition in the plasma generator were observed. Fig. 2 shows the
thermal plasma treatment system they used. They used two ways to
score research. (i) The feed gas (CH4 and CO2) enters the discharge area
between 10 (first anode) and 12 (second anode) from 5 (gas inlet II); and
(II) feed gas (CH4 and CO2) simultaneously enters the discharge area
between 10 (first anode) and 12 (second anode) from 5 (gas inlet II) and
6 (gas inlet III). The first method has high conversion rate and selec­
tivity, but the energy conversion efficiency is low due to the high energy
utilization rate; the second method has high energy conversion effi­
ciency due to the large feed gas dosage, but the conversion rate and
selectivity are low. In addition, the oxidation of cathode and anode or
carbon deposition in plasma generator were not observed in both
methods. Tao et al. [186] also carried out DRM experiments using
thermal plasma alone and synergistic effect of thermal plasma and in­
dustrial catalyst. Under the same experimental conditions, the conver­
sion of CH4 and CO2, the selectivity of H2 and CO (10–20% higher) and
the specific energy of the reaction were increased by using thermal
plasma catalyst than without catalyst. In order to reduce the energy
consumption of bipolar thermal plasma DRM process, on the basis of Tao
et al. [185,186], Xu et al. [187] also studied the synergistic effect of hot
plasma and industrial Z107Ni/Al2O3 catalyst. Under the conditions of
CH4/CO2 = 4/6, 14.4 kW input power and 5m3/h feed gas, the con­
version of CH4 and CO2 is 77% and 62%, the selectivity of H2 and CO is
88% and 97%, respectively. The optimal specific energy is 193 kJ/mol

10
C. Shi et al.
and the energy conversion efficiency is 66%. Compared with the steam
reforming process, the experimental results are very close to the in­
dustrial requirements. Kim et al. [188] studied the treatment of hot
plasma by plasma tube, and determined the optimal operation condi­
tions of DRM reaction. Although thermal plasma can achieve
high-efficiency reforming reaction of DRM, it has some disadvantages,
such as low energy utilization, high equipment material requirements
and high operation cost.
The above literature review shows that although thermal plasma can
realize the efficient reforming reaction of DRM, it still has the disad­
vantages of low energy utilization, high equipment material re­
quirements and high operation cost. In order to improve the energy
utilization and reduce the application cost, it is necessary to further
optimize the DRM thermal plasma reaction system.
4.3. Cold plasma-catalytic system
In cold plasma, the total kinetic temperature of gas is kept low, while
the energy of electrons is very high. The typical electron temperature is
1− 10 eV, which is enough to break down inert molecules and produce
highly active substances: free radicals, excited atoms, ions and mole­
cules [189,190]. Therefore, the synthesis gas can be prepared by plasma
discharge at low temperature, and DRM reaction can be carried out
under normal pressure and low temperature by cold plasma [191,192].
However, the basic relationship between plasma chemistry and selected
plasma conditions and reactor parameters is still poorly understood.
Therefore, more and more researchers begin to pay attention to the cold
plasma technology rather than the traditional catalytic technology.
The generation modes of cold plasma are: dielectric barrier discharge
(DBD) [193–199], corona discharge [200,201], glow discharge [202,
203], spark discharge [52,204], microwave discharge [205–208],
sliding arc discharge [209–211], radio frequency (RF) discharge [212].
In this section, the related researches on different discharge modes are
summarized, and their advantages and disadvantages in DRM reaction
are introduced.
(1)DBD. Khoja et al. [193] studied the DRM reaction over supported
Ni-Al2O3-MgO catalyst in a DBD plasma reactor. They found that the
energy efficiency (EE) of DRM catalyzed by plasma and catalyst is higher
than that of DRM catalyzed by plasma only, which indicates the syner­
gistic effect between catalyst and plasma. On this basis, Khoja and his
colleagues also synthesized Ni/La2O3MgAl2O4 catalyst and carried out
DBD plasma DRM test [194]. In addition, Khoja et al. [199] also sum­
marized the research status and latest progress of DBD plasma for DRM,
mainly discussed the challenges faced by DBD plasma technology, the
interaction between catalyst and plasma, and the research progress of
Fig. 3. Schematic diagram of fixed bed pyrolysis device. (1: gas cylinder, 2: valve; 3: mass flow control; 4: pressure gauge; 5: mass flow indicator; 6: temperature
controller; 7: furnace; 8: reactor; 9: plasma generator; 10: oscilloscope; 11: regulator; 12: cold trap; 13: gas flowmeter; 14: gas chromatograph). Quoted from
Reference [227]. Copyright (2017) Elsevier.
11
Journal of CO2 Utilization 46 (2021) 101462
plasma catalyst in improving the yield and selectivity of DRM.
(2)Corona discharge. Nguyen et al. [200] studied the DRM reaction
under corona discharge under different process parameters. The exper­
imental results show that the conversion of CH4 and CO2 increases with
the increase of applied peak voltage or pulse frequency, but decreases
with the increase of total flow rate.
(3)Glow discharge. Li et al. [202] studied the DRM reaction by
atmospheric pressure glow discharge plasma. This process can effec­
tively convert CH4 and CO2 into syngas. The maximum conversion of
CH4 and CO2 is 98.52% and 90.30% respectively, and the highest con­
version rate is 12.21 mmol/kJ. Compared with other plasma processes,
it has the advantages of large capacity and high conversion.
(4)Spark discharge. Zhu et al. [52] studied the kinetics of DRM
reaction in a kilohertz discharge plasma, and thus established the kinetic
equation of DRM reaction in spark discharge plasma.
(5)Microwave discharge. Fidalgo et al. [208] studied the
microwave-assisted DRM reaction using activated carbon as catalyst and
microwave acceptor. Compared with conventional heating and micro­
wave heating, microwave heating can improve the conversion of CH4
and CO2.
(6)Sliding arc discharge. Indarto and his colleagues have studied
the conversion of methane in sliding arc plasma [210].
(7)RF discharge. Putra et al. [212] proposed a method for preparing
hydrogen by decomposing methane hydrate with 27.12 MHz RF plasma.
DBD and corona discharge produce low electron density and limited
reaction volume, which limits the processing capacity. Glow discharge is
a low-voltage discharge (less than 10 mbar), but the electron energy is
very high during the discharge process. Because of its low pressure
characteristics, it is not suitable for chemical synthesis. Microwave
discharge has large discharge space and uniform discharge, but its in­
dustrial application is limited due to its complex equipment and high
price. The reactor with sliding arc discharge is difficult to expand, which
is far from the industrial requirements. RF discharge works at high
frequency (GHz) and very low pressure to achieve non-equilibrium
conditions. This discharge is not suitable for chemical synthesis.
In addition, scholars at home and abroad have carried out a lot of
research on the combination of cold plasma and heterogeneous catalysis
[213,214]. The combination of plasma and solid catalyst can improve
the conversion of CH4 and CO2, the selectivity of products, and the
stability, sintering resistance and carbon resistance of the catalyst
[215–218]. Although there are many studies on plasma catalysis
[193–198], the interaction mechanism between plasma and catalyst is
relatively less. The interaction between plasma and catalyst can produce
synergistic effect, which is mainly manifested in the destruction of
volatile organic compounds by plasma catalytic system. The plasma
C. Shi et al.
catalytic system is superior to the traditional single catalytic system. Tu
et al. [195] also found that the way in which the catalyst was filled in the
discharge gap affected the conversion of CH4 and CO2. This may be due
to the filling mode changing the discharge mode. Galen et al. [198] also
found that the mode of catalyst filling affected the synergistic effect
between plasma and catalyst. In addition, there are some negative ef­
fects in the plasma catalytic system [195,219], but the reasons for this
phenomenon have not been discussed and are not clear. The under­
standing of the interaction and synergistic effect between plasma and
catalyst is also uncertain.
The above literature review shows that the reaction of methane
initiated by cold plasma has enough energy under normal temperature
and atmospheric pressure. At present, the design of plasma power supply
and plasma reactor is not mature enough. It is necessary to further
improve the efficiency of energy utilization and the stability of the
system.
4.4. Coupling of DRM cold plasma-catalytic system and pyrolysis
technology
DRM can also be used to improve the yield and quality of tar during
coal pyrolysis. The yield of coal tar is further improved by coupling coal
pyrolysis with CH4 activation, such as MSR [220], DRM [221–224],
methane aromatization [225], DRM by cold plasma [226,227]. At pre­
sent, the research on the integrated process of cold plasma and pyrolysis
technology is relatively less [227].
Wang et al. [222] studied the thermal decoupling of DRM and coal
and the coupling process of DRM and coal catalytic pyrolysis. It was
found that the tar yield was increased by 80% at 750℃ compared with
that in nitrogen atmosphere. This is due to the interaction between the
free radicals formed by DRM and the free radicals generated by the
pyrolysis of coal structure. DRM is usually carried out above 700℃,
which is higher than the optional temperature of coal pyrolysis
(500− 650℃). In order to solve the problem of temperature mismatch,
He et al. [226] activated methane by dielectric barrier discharge plasma
and combined it with coal pyrolysis. The results show that the tar yield
at 400℃ is about twice as high as that under N2 condition, and the high
tar yield is the result of active substances participating in tar formation
in mixed gas plasma. Jin et al. [227] studied the integrated process of
coal pyrolysis and DRM reaction by spark discharge plasma technology
(cold plasma). Compared with the pyrolysis of nitrogen or carbon di­
oxide and methane, the combination of spark discharge plasma DRM
and coal pyrolysis can produce more tar. Fig. 3 is the schematic diagram
of the fixed bed pyrolysis device. In quartz tube reactor, stainless steel
tube is used as high voltage electrode and stainless steel rod as
grounding electrode. Considering the integrated process of coal pyrol­
ysis with DRM and adjustable discharge gap, the two electrodes were
Fig. 4. Comparison of the conversion efficiency between plasma and plasma
catalysis. Quoted from Reference [176]. Copyright (2012) Elsevier.
12
Journal of CO2 Utilization 46 (2021) 101462
fixed in the cylinder vertically and coaxial respectively and sealed. Lv
et al. [223] studied the dry reforming reaction of methane and ethane
mixture of low-carbon alkanes on Ni/La2O3. At 600℃, the tar yield was
20.6 wt.%, which was 1.18 and 1.09 times higher than that under N2 and
DRM conditions, respectively. Compared with industrial Ni/Al2O3,
Ni/La2O3 has higher gas reforming conversion and tar yield, and less
carbon deposition.
In addition, DRM can also promote the upgrading of coal tar. Wang
et al. [224] used activated carbon supported nickel (Ni/AC) catalyst for
in-situ catalytic cracking and DRM of coal tar. At 650℃, compared with
unmodified tar, the content of light tar on Ni/AC catalyst increased to
96.5%, and the yield of light tar increased from 8.0% to 12.2%.
The above literature review shows that the integrated process of cold
plasma and pyrolysis technology has a significant effect on improving
the yield of pyrolysis products. However, the research on the mechanism
of integration process is not mature and needs further research. In
addition, in addition to coupling with coal pyrolysis, it is feasible to
couple cold plasma technology with biomass [228] and oil shale py­
rolysis, which has certain research value.
4.5. Mechanism of plasma-catalyst interaction
The coupling of plasma and catalyst can overcome the disadvantages
observed when plasma is used alone (high energy consumption and
unnecessary by-product formation [229,230]). The plasma-catalytic
system has higher conversion efficiency than that of plasma alone (see
Fig. 4), which may be due to the plasma-catalyst interaction. This
interaction depends on the discharge behavior induced by the catalyst
and the activity of the catalyst excited by plasma. Due to the short
lifetime of the active particles in the excited state at atmospheric pres­
sure, the effect of the catalyst placed at the end of the plasma discharge
region or isolated from the discharge region is even worse than that of
the catalyst or plasma alone. When the catalyst is placed in the plasma
discharge area, the synergistic effect is greater than the sum of the
plasma and catalyst alone under the same conditions [176,231].
The way in which the catalyst is placed in the plasma discharge area
will change the physical and chemical properties of the plasma and the
catalyst, thus affecting the plasma-catalyst interaction [195]. When the
catalyst is filled in the discharge area, the discharge area will be reduced
and the discharge mode will be changed, which is not conducive to the
plasma catalytic reaction. When the catalyst is partially filled with the
discharge area, the plasma field changes from micro discharge to mixed
form of solid surface discharge and micro discharge. The catalyst is
activated by high energy electron bombardment and forms active par­
ticles with large lattice defects. The excited species were selectively
adsorbed on the surface of the catalyst and reacted to produce the target
product. The other active state particles which were not selectively
adsorbed formed the product by free binding.
The physical and chemical properties of the catalyst (such as con­
ductivity, electromagnetism, basicity and structure) will affect the syn­
ergistic effect between the catalyst and the plasma, thus affecting the
reactant conversion, product selectivity and species [232,233]. Liu et al.
[232] found that, compared with the absence of catalyst,
Mo-Zn/HZSM-5 zeolite catalyst increased the electron temperature of
plasma by 2.28 times, but the gas temperature remained unchanged. At
the same time, the electron concentration is reduced by 58%. In addi­
tion, when the zeolite catalyst exists in the plasma discharge region, the
plasma electron concentration decreases and the ionization degree also
decreases, resulting in the increase of plasma resistance and the
discharge parameters are seriously affected. Kim et al. [233] reviewed
the research progress of interaction between cold plasma and catalyst in
recent years. The plasma induces a series of interactions on the catalyst
surface (such as: providing active components, local heating and surface
charging). The electrical properties of the catalyst will greatly change
the nature of plasma generation.
Plasma can increase the temperature of the catalyst surface, thus
C. Shi et al.
affecting the desorption of species adsorbed on the catalyst surface
[234]. Zhang and his colleagues found that the catalyst was easy to be
activated in a high-power plasma field, and the activation temperature
of the catalyst could be reduced by the high-energy electron bombard­
ment excited by the plasma field, thus showing a better synergistic effect
[234].
The reactor structure and electrode material are also important
factors affecting the synergistic effect of plasma and catalyst. Wang et al.
[235] found that different reactor structures have different electric field
intensity and energy distribution, which leads to different reaction
mechanism. The main product in glow discharge plasma is C2H2, while
the content of C2H4 and C2H6 is less and the amount of carbon deposit is
more. The main products in dielectric barrier discharge plasma are C2H6
and C3H8, while the contents of C2H4 and C2H2 are less and the amount
of carbon deposit is very small. Spiess et al. [236] studied the effect of
electrode materials on CH4 conversion and H2 selectivity.
The DRM reaction of plasma synergetic catalyst is an extremely
complex catalytic reaction process, and researchers have not yet formed
a unified understanding of the mechanism of plasma synergistic catalyst.
Most researchers believe that the synergetic mechanism of plasma and
catalyst is the combination of free radical reaction and catalytic reac­
tion, that is, CH4 molecules are decomposed into excited free radicals
CH3, CH2, CH, C and H in the plasma field, and CO2 molecules dissociate
into living state substances CO and O. These free radicals are selectively
adsorbed on the surface of the catalyst to produce products [237–240].
However, the violent uncontrollability of plasma chemical reaction re­
sults in a variety of reaction products, such as syngas, hydrocarbons,
aldehydes, alcohols, ketones and organic acids [241,242]. Kado et al.
[238] believe that the electron energy provided by plasma can directly
decompose CH4 into C atoms, and the electron density in the discharge
region makes the excited free radicals CH3, CH2 and CH dehydrogenate
to form C atoms. These excited C atoms can combine with H atoms to
form C2H2. The formation of C2H2 also comes from the decomposition
and recombination of excited C, CH3, CH2, CH, C2 hydrocarbons and
C2H2.
The catalyst mainly adsorbs the excited free radicals on the active
sites of the catalyst surface. However, the active state of CH4 under the
action of plasma will compound with free radical CHX (x = 1–3) on the
catalyst surface, and the complex reaction between free radical CHX also
occurs on the catalyst surface. There is a competitive relationship be­
tween the two complex reactions, and the inhibition degree of different
kinds of catalysts on the complex reaction of H atom and free radical
CHX is different. Somer et al. [243] showed that the adsorption capacity
of excited state CHX on different Ni lattice planes (Ni(111)、Ni(100)、
Ni(111)s1 and Ni(111)s2) was CH > CH2>CH3 (where Ni(111)s1 and Ni
(111)s2 are defective Ni(111) surfaces produced by electron bombard­
ment). The steric hindrance produced by C–H bond will hinder the
bonding of free electrons with Ni atom surface. The steric hindrance
increases with the increase of the number of C–H bonds, while the
adsorption capacity of catalyst surface decreases with the increase of
steric hindrance.
In situ DRIFTS characterization is a reliable means to understand the
reaction between plasma and catalyst surface. Vakili et al. [244] studied
plasma assisted DRM reaction in a DBD reactor with different fillers
(ZrO2, UiO-67 MOF and PtNP@UiO-67). In situ DRIFTS characterization
was used to explain the interaction between the catalyst and plasma. In
situ DRIFTS characterization indicated that there were surface reactions
on Pt NPs. The results showed that the dissociated CO2 adsorbed on the
solid surface with different coordination degree of carbonate, and then
decomposed into formate. The adsorbed formates were further decom­
posed into CO and OH on Pt NPs, and tended to be stable with the re­
action going on. The dehydrogenation of adsorbed C2H4 on Pt NPs was
C2H3 intermediate. The peak strength of adsorbed C2H3 is very weak
because it is rapidly dehydrogenated to C2H2 [245]. Therefore, it was
proved that the PtNP@UiO-67 catalyst enhanced the surface reaction of
plasma assisted DRM.
13
Journal of CO2 Utilization 46 (2021) 101462
The above literature review shows that the interaction between
plasma and catalyst can improve the conversion of reactants, reduce the
types of by-products and improve the selectivity of target products. The
research on the interaction mechanism of plasma and catalyst is rela­
tively less, mainly because the physical changes and chemical reactions
of plasma and catalyst in the process of interaction are quite complex,
and the mechanism of interaction varies greatly for different reactors,
catalysts and gas temperatures. We can optimize the energy efficiency
by studying the plasma-catalyst interaction mechanism.
5. Comparison of two catalytic systems
The disadvantages of the conventional catalysis-alone system of
DRM include: the need for large-scale unit; the cost and modification of
catalyst; the size and weight requirements; the limitation of rapid re­
action; and the limitation of heavy hydrocarbon reforming. Compared
with the conventional catalysis-alone system, plasma-catalytic system
has potential advantages. The conversion efficiency of conventional
catalysis-alone system is lower than that of thermal plasma and cold
plasma jet [14,186,202]. Compared with the conventional
catalysis-alone system, plasma-catalytic system has the characteristics of
electron induced chemical and thermochemical reactions. It can obtain
higher conversion without catalyst and no need to worry about carbon
deposition.
The main drawback of plasma-catalytic system is its dependence on
electric energy. Thermal plasma has the advantages of high enthalpy
content, high temperature, high electron density, large processing ca­
pacity, easy amplification and high energy conversion efficiency. It has
obvious thermal and chemical effects. Although thermal plasma can
achieve high-efficiency reforming reaction of DRM, it has some disad­
vantages, such as low energy utilization, high equipment material re­
quirements and high operation cost. The non-equilibrium characteristics
of cold plasma, such as high electron energy and low ion and gas tem­
perature, are very effective for chemical reactions. On the one hand,
electrons have enough energy to excite, dissociate and ionize the reac­
tant molecules. On the other hand, the reaction system can keep low
temperature or even close to room temperature, which can reduce the
energy consumption of the reaction system and save investment. Low
temperature plasma technology is a very effective method of molecular
activation. It has enough energy to activate methane molecules at room
temperature and atmospheric pressure to initiate chemical reactions.
Single cold and hot plasma assisted DRM reaction has high energy
consumption and leads to the formation of non selective products. This
is because the chemical reactions in the whole process are so complex
that we can’t get a very selective product from it. Therefore, we can
improve the selectivity of the products by combining plasma activation
with heterogeneous catalysts. In addition, we believe that further study
of plasma combined with photocatalysis is an effective way to realize
selective chemical reactions. Kang et al. [246] studied the photocatalytic
degradation of toluene by plasma combined with nano-TiO2 under at­
mospheric pressure. The degradation rate of toluene was only 40% in
single plasma, but less than 40% in single photocatalysis. However, the
degradation rate of toluene reached 70% in plasma-TiO2 photocatalytic
system. Unfortunately, this method is only widely used in VOCs treat­
ment, and rarely reported in methane reforming.
At present, there are some negative effects in the plasma catalytic
system [195,219], but the reasons for this phenomenon have not been
discussed and are not clear. The understanding of the interaction and
synergistic effect between plasma and catalyst is also uncertain. Brom­
berg et al. [247] carried out a comparative experiment on the two kinds
of plasmas, both of which can obtain high hydrogen yield, but in the case
of cold plasma, the energy consumption is significantly reduced.
A large number of studies have shown that the plasma process can
carry out the reaction which is not possible in thermodynamics at room
temperature, and can obtain higher conversion than the traditional
thermal method. However, further optimization of plasma processes is
C. Shi et al.
very difficult because we do not know enough about them. For thermal
processes, most of the key quantities are known and can be used to
predict yields. However, this prediction method is usually not suitable
for plasma process. In most cases, plasma process parameter studies
report only one or a set of finite residence time conversions or gas
compositions. In this case, the kinetic or maximum yield interpretation
is slightly thin, which makes it difficult to determine the synergy be­
tween the plasma and the filler material (catalyst).
6. Other catalytic systems
This section introduces the research progress of some other catalytic
systems.
6.1. Catalytic membrane reactor
Membrane catalytic reaction technology can complete the catalytic
reaction and product separation at the same time, and can filter the
reactants at the same time. For the membrane reactor, the main prin­
ciple is the selective permeation of raw materials or the selective sepa­
ration of reaction products [248]. Thus, the conversion rate of the whole
process can be improved, the positive movement of raw materials can be
realized, and the material balance and thermodynamic balance of the
reaction system can be changed or broken, so that the conversion per­
formance of the reaction is better than that of the traditional reaction
device. Membrane reactors can be divided into two types according to
different separation mechanisms. (1)Dense metal film. Through the
formation of metal hydride and diffusion transfer process, dense metal
membrane can provide the maximum hydrogen selectivity, but its low
permeability and low gas permeability flow rate are the defects of the
metal membrane, and sulfur and carbon will make the membrane toxic
failure [249]. (2)Porous ceramic membrane. Porous ceramic membrane
has good mechanical properties and thermal stability, but in addition to
hydrogen, the membrane also has a certain permeability to other gases
[250].
Many scholars use membrane reactor instead of traditional fixed bed
or fluidized bed reactor in reforming process, such as POM [251,252],
ATR [253], MSR [254–256], DRM [257,258]. In addition, there are
related studies that combine the two reforming reactions to carry out the
combined reforming, such as the coupling of POM and MSR [259], and
the coupling of DRM and POM [260]. Compared with the traditional
fixed bed and fluidized bed technology, membrane reactor has many
advantages, such as higher energy efficiency, lower capital and oper­
ating costs, compact equipment components, lower maintenance costs,
easy to expand the scale and so on.
The above literature review shows that the membrane reactor can
obtain pure reactants (such as oxygen permeable membrane) or pure
products (such as hydrogen permeable membrane) by osmosis, and
improve the reaction efficiency. Although a lot of research has been
done on membrane reactor, no commercial membrane reactor has been
used in dry reforming reaction.
6.2. Solar driven methane reforming
There are two forms of solar driven methane reforming: solar ther­
mal catalysis and solar photocatalytic [261]. Solar thermal catalysis uses
concentrated solar radiation (through a concentrating system). Solar
photocatalysis is the use of solar radiation in the photon energy can be
absorbed by a variety of semiconductors, surface generated electrons
and holes, and reacts with reactants to form chemical products. In the
process of solar thermochemistry, the selection of catalyst and the
design of reactor play an important role [262].
Cavity reactor is one of the most common solar thermochemical re­
actors. It usually places a concentrating structure at the entrance of
sunlight. Jin et al. [263] reported the design of an efficiency enhanced
solar driven methane reforming reactor. The sunlight is focused by a disc
14
Journal of CO2 Utilization 46 (2021) 101462
collector, and then the sunlight is further converged by the composite
parabolic concentrator through the quartz window, and finally enters
the cavity to drive the reforming reaction. When the reactor is working,
the reactants are fed into the reaction chamber by carrier gas or screw
feeding device, so that they are evenly distributed in the reaction
chamber. The sunlight through quartz glass is irradiated on the reactants
in the reaction chamber after secondary concentrating, and the reactants
receive the heat of sunlight and have endothermic reaction. Finally, the
products are sent out of the reactor by carrier gas.
Membrane reactor is also widely used in solar thermochemical pro­
cess. Wang et al. [264] proposed a solar driven methane reforming
reactor with Pd membrane as hydrogen permeation membrane. The
inner tube of the reactor is made of hydrogen permeable membrane
material, and the outer tube is made of conventional stainless steel tube.
Water and methane continue to flow into the inner tube at a certain ratio
of substances, and then the reactants react in the inner tube. The pro­
duced hydrogen is immediately transferred to the annular region be­
tween the inner and outer tubes and is recovered at the outlet. In
addition, there are many forms of reactors, such as rotary reactor [265],
fluidized bed reactor [266].
The design of solar driven methane reforming reactors is based on
ideal environmental conditions. The actual solar energy supply is
intermittent, such as alternating day and night, cloudy days or cloud
cover. These practical factors will affect the stable output and conver­
sion of solar energy to a certain extent. In order to alleviate this problem,
Gokon et al. [267] designed a solar driven methane reforming reactor
with buffer outer wall. However, there is no commercial solar driven
methane reforming reactor.
7. Summary
In this paper, the research progress of different DRM catalytic sys­
tems are reviewed. The conventional catalysis-alone system, plasma-
catalytic system and some other catalytic systems are discussed. The
conventional catalysis-alone system of DRM still has a series of prob­
lems, such as the need for large-scale unit; the cost and modification of
catalyst; the size and weight requirements; the limitation of rapid re­
action; and the limitation of heavy hydrocarbon reforming. Although
plasma-catalytic system of DRM can achieve higher conversion rate.
However, it is very difficult to further optimize the plasma process. The
interaction mechanism between plasma and filler (catalyst) needs
further study. In addition to producing syngas (H2 and CO) and pro­
ducing a series of chemicals, we should also consider the possibility of
DRM application in other aspects in the future work. In addition, most of
the other catalytic systems discussed are still in the laboratory research
stage, and how to apply them to practical engineering is also a problem
to be solved.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgments
This work was supported by the National Natural Science Foundation
of China (Grant No.51704194), the Shanghai Sailing Plan (Grant
No.19YF1418000) and the Shanghai University of Engineering Science
innovation training program for college students (Grant No.cs2001010).
References
[1] X.L. Wang, L.J. Zhu, Y.C. Liu, S.R. Wang, CO2 methanation on the catalyst of Ni/
MCM-41 promoted with CeO2, Sci. Total Environ. 625 (2018) 686–695.
C. Shi et al.
[2] Y. Liu, Y. Wu, Z. Akhtamberdinova, X.P. Chen, G.D. Jiang, D. Liu, Dry reforming
of shale gas and carbon dioxide with Ni-Ce-Al2O3 catalyst: syngas production
enhanced over Ni-CeOx formation, ChemCatChem. 10 (2018) 4689–4698.
[3] R.A.M. Esfahani, L. Osmieri, S. Specchia, S. Yusup, A. Tavasoli, A. Zamaniyan, H2-
rich syngas production through mixed residual biomass and HDPE waste via
integrated catalytic gasification and tar cracking plus bio-char upgrading, Chem.
Eng. J. 308 (2017) 578–587.
[4] P.J. Woolcock, R.C. Brown, A review of cleaning technologies for biomass-
derived syngas, Biomass Bioenerg. 52 (2013) 54–84.
[5] S.T. Oyama, Novel catalysts for advanced hydroprocessing: transition metal
phosphides, J. Catal. 216 (2003) 343–352.
[6] N.A.K. Aramouni, J.G. Touma, B.A. Tarboush, J. Zeaiter, M.N. Ahmad, Catalyst
design for dry reforming of methane: analysis review, Renew. Sust. Energ. Rev.
82 (2018) 2570–2585.
[7] O. Muraza, A. Galadima, A review on coke management during dry reforming of
methane, Int. J. Energ. Res. 39 (2015) 1196–1216.
[8] S. Aroraa, R. Prasad, An overview on dry reforming of methane: strategies to
reduce carbonaceous deactivation of catalysts, RSC Adv. 6 (2016)
108668–108688.
[9] P.M. Mortensen, I. Dybkjær, Industrial scale experience on steam reforming of
CO2-rich gas, Appl. Catal. A Gen. 495 (2015) 141–151.
[10] K. Aasberg-Petersen, T.S. Christensen, I. Dybkjaer, J. Sehested, M. Østberg, R.
M. Coertzen, M.J. Keyser, A.P. Steynberg, Chapter 4 - Synthesis gas production for
FT synthesis, Stud. Surf. Sci. Catal. 152 (2004) 258–405.
[11] T.S. Christensen, Adiabatic prereforming of hydrocarbons - an important step in
syngas production, Appl. Catal. A Gen. 138 (2) (1996) 285–309.
[12] P. O’Connor, T. Takatsuka, G.L. Woolery, Deactivation and testing of
hydrocarbon-processing catalysts, American Chemical Society 634 (1996).
[13] M.C.J. Bradford, M.A. Vannice, CO2 reforming of CH4, Cata Rev. 41 (1999) 1–42.
[14] X.M. Tao, M.G. Bai, X. Li, H.L. Long, S.Y. Shang, Y.X. Yin, X.Y. Dai, CH4-CO2
reforming by plasma-challenges and opportunities, Prog. Energy Combust. Sci. 37
(2011) 113–124.
[15] A.M. Gadalla, B. Bower, The role of catalyst support on the activity of nickel for
reforming methane with CO2, Chem. Eng. Sci. 43 (1988) 3049–3062.
[16] W.J. Jang, D.W. Jeong, J.O. Shim, H.M. Kim, H.S. Roh, I.H. Son, S.J. Lee,
Combined steam and carbon dioxide reforming of methane and side reactions:
thermodynamic equilibrium analysis and experimental application, Appl. Energy
173 (2016) 80–91.
[17] S.B. Wang, G.Q. Lu, G.J. Millar, Carbon dioxide reforming of methane to produce
synthesis gas over metal-supported catalysts: state of the art, Energ. Fuel 10
(1996) 896–904.
[18] M.K. Nikoo, N.A.S. Amin, Thermodynamic analysis of carbon dioxide reforming
of methane in view of solid carbon formation, Fuel Process Technol. 92 (2011)
678–691.
[19] A.T. Ashcroft, A.K. Cheetham, M.L.H. Green, P.D.F. Vernon, Partial oxidation of
methane to synthesis gas using carbon dioxide, Nature. 352 (1991) 225–226.
[20] S. Kawi, Y. Kathiraser, J. Ni, U. Oemar, Z.W. Li, E.T. Saw, Progress in synthesis of
highly active and stable nickel-based catalysts for carbon dioxide reforming of
methane, ChemSusChem. 8 (21) (2015) 3556–3575.
[21] Y. Turap, I. Wang, T.T. Fu, Y.M. Wu, Y.D. Wang, W. Wang, Co-Ni alloy supported
on CeO2 as a bimetallic catalyst for dry reforming of methane, Int. J. Hydrogen
Energ. 45 (2020) 6538–6548.
[22] A. Liu, S. Praserthdam, S. Phatanasri, Investigation on the increased stability of
the Ni-Co bi-metallic catalysts for the carbon dioxide reforming of methane,
Catal. Today 358 (2020) 37–44.
[23] C. Pan, Z.L. Guo, H. Dai, R. Ren, W. Chu, Anti-sintering mesoporous Ni-Pd
bimetallic catalysts for hydrogen production via dry reforming of methane, Int. J.
Hydrogen Energ. 45 (32) (2020) 16133–16143.
[24] L. Chen, Q.Y. Huang, Y.C. Wang, H. Xiao, W.F. Liu, D.C. Zhang, T.Z. Yang,
Tailoring performance of Co-Pt/MgO-Al2O3 bimetallic aerogel catalyst for
methane oxidative carbon dioxide reforming: effect of Pt/Co ratio, Int. J.
Hydrogen Energ. 44 (36) (2019) 19878–19889.
[25] M. Usman, W.M.A.W. Daud, H.F. Abbas, Dry reforming of methane: influence of
process parameters-a review, Renew. Sust. Energ. Rev. 45 (2015) 710–744.
[26] B. Li, X.Q. Yuan, B.T. Li, X.J. Wang, Impact of pore structure on hydroxyapatite
supported nickel catalysts (Ni/HAP) for dry reforming of methane, Fuel Process
Technol. 202 (2020), 106359.
[27] P.H. Tu, D.N. Le, T.D. Dao, Q.T. Tran, T.C.D. Doan, Y. Shiratori, C.M. Dang,
Paper-structured catalyst containing CeO2-Ni flowers for dry reforming of
methane, Int. J. Hydrogen Energ. 45 (36) (2020) 18363–18375.
[28] X.L. Liu, H.L. Wang, G.H. Ye, X.G. Zhou, F.J. Keil, Enhanced performance of
catalyst pellets for methane dry reforming by engineering pore network structure,
Chem. Eng. J. 373 (2019) 1389–1396.
[29] L.L. Xu, H.L. Song, L.J. Chou, One-pot synthesis of ordered mesoporous NiO-CaO-
Al2O3 composite oxides for catalyzing CO2 reforming of CH4, ACS Catal. 2 (2012)
1331–1342.
[30] E. Cho, Y.H. Lee, H. Kim, E.J. Jang, J.H. Kwak, K. Lee, C.H. Ko, W.L. Yoon, Ni
catalysts for dry methane reforming prepared by A-site exsolution on mesoporous
defect spinel magnesium aluminate, Appl. Catal. A Gen. 602 (2020), 117694.
[31] R. Benrabaa, H. Boukhlouf, A. Löfberg, A. Rubbens, R.N. Vannier, E. Bordes-
Richard, A. Barama, Nickel ferrite spinel as catalyst precursor in the dry
reforming of methane: synthesis, characterization and catalytic properties, J. Nat.
Gas Chem. 21 (5) (2012) 595–604.
[32] F.F. De Sousa, H.S.A. De Sousa, A.C. Oliveira, M.C.C. Junior, A.P. Ayala, E.
B. Barros, B.C. Viana, J.M. Filho, A.C. Oliveira, Nanostructured Ni-containing
spinel oxides for the dry reforming of methane: effect of the presence of cobalt
15
Journal of CO2 Utilization 46 (2021) 101462
and nickel on the deactivation behaviour of catalysts, Int. J. Hydrogen Energ. 37
(4) (2012) 3201–3212.
[33] Y.Z. Ruan, Y.F. Zhao, Y. Lu, D. Guo, Y.J. Zhao, S.P. Wang, X.B. Ma, Mesoporous
LaAl0.25Ni0.75O3 perovskite catalyst using SBA-15 as templating agent for
methane dry reforming, Microporous Mesoporous Mater. 303 (2020), 110278.
[34] F. Touahra, R. Chebout, D. Lerari, D. Halliche, K. Bachari, Role of the
nanoparticles of Cu-Co alloy derived from perovskite in dry reforming of
methane, Energy. 171 (2019) 465–474.
[35] L.A.S. Hoyos, B.M. Faroldi, L.M. Cornaglia, A coke-resistant catalyst for the dry
reforming of methane based on Ni nanoparticles confined within rice husk-
derived mesoporous materials, Catal. Commun. 135 (2020), 105898.
[36] A. Sápi, T. Rajkumar, M. Ábel, A. Efremova, A. Grósz, A. Gyuris, K.B. Ábrahámné,
I. Szenti, J. Kiss, T. Varga, Á. Kukovecz, Z. Kónya, Noble-metal-free and Pt
nanoparticles-loaded, mesoporous oxides as efficient catalysts for CO2
hydrogenation and dry reforming with methane, J. CO2 Util. 32 (2019) 106–118.
[37] B.T. Li, Y. Luo, B. Li, X.Q. Yuan, X.J. Wang, Catalytic performance of iron-
promoted nickel-based ordered mesoporous alumina FeNiAl catalysts in dry
reforming of methane, Fuel Process Technol. 193 (2019) 348–360.
[38] K. Li, X. Chang, C.L. Pei, X.Y. Li, S. Chen, X.H. Zhang, S. Assabumrungrat, Z.
J. Zhao, L. Zeng, J.L. Gong, Ordered mesoporous Ni/La2O3 catalysts with
interfacial synergism towards CO2 activation in dry reforming of methane, Appl.
Catal. B Environ. 259 (2019), 118092.
[39] A. Mourhly, M. Kacimi, M. Halim, S. Arsalane, New low cost mesoporous silica
(MSN) as a promising support of Ni-catalysts for high-hydrogen generation via
dry reforming of methane (DRM), Int. J. Hydrogen Energ. 45 (20) (2020)
11449–11459.
[40] J. Goscianska, R. Pietrzak, J. Matos, Catalytic performance of ordered
mesoporous carbons modified with lanthanides in dry methane reforming, Catal.
Today 301 (2018) 204–216.
[41] B. Erdogan, H. Arbag, N. Yasyerli, SBA-15 supported mesoporous Ni and Co
catalysts with high coke resistance for dry reforming of methane, Int. J. Hydrogen
Energ. 43 (2018) 1396–1405.
[42] M. Sigl, M.C.J. Bradford, H. Knözinger, M.A. Vannice, CO2 reforming of methane
over vanadia-promoted Rh/SiO2 catalysts, Top. Catal. 8 (3) (1999) 211–222.
[43] M.S. Fan, A.Z. Abdullah, S. Bhatia, Catalytic technology for carbon dioxide
reforming of methane to synthesis gas, ChemCatChem. 1 (2009) 192–208.
[44] C.E. Daza, C.R. Cabrera, S. Moreno, R. Molina, Syngas production from CO2
reforming of methane using Ce-doped Ni-catalysts obtained from hydrotalcites by
reconstruction method, Appl. Catal. A Gen. 378 (2) (2010) 125–133.
[45] A. Kambolis, H. Matralis, A. Trovarelli, Ch. Papadopoulou, Ni/CeO2-ZrO2
catalysts for the dry reforming of methane, Appl. Catal. A Gen. 377 (1–2) (2010)
16–26.
[46] N. Wang, W. Chu, L.Q. Huang, T. Zhang, Effects of Ce/Zr ratio on the structure
and performances of Co-Ce1-xZrxO2 catalysts for carbon dioxide reforming of
methane, J. Nat. Gas Chem. 19 (2) (2010) 117–122.
[47] J.A.C. Ruiz, F.B. Passos, J.M.C. Bueno, E.F. Souza-Aguiar, L.V. Mattos, F.
B. Noronha, Syngas production by autothermal reforming of methane on
supported platinum catalysts, Appl. Catal. A Gen. 334 (1–2) (2008) 259–267.
[48] F. Menegazzo, M. Signoretto, F. Pinna, P. Canton, N. Pernicone, Optimization of
bimetallic dry reforming catalysts by temperature programmed reaction, Appl.
Catal. A Gen. 439-440 (2012) 80–87.
[49] P.S. Lau, K.M. Ng, Carbon dioxide reforming of methane by solid state synthesis
supported catalysts, Int. J. Hydrogen Energ. 39 (34) (2014) 19513–19518.
[50] Z.G. Hao, Q.S. Zhu, Z. Jiang, B.L. Hou, H.Z. Li, Characterization of aerogel Ni/
Al2O3 catalysts and investigation on their stability for CH4-CO2 reforming in a
fluidized bed, Fuel Process Technol. 90 (1) (2009) 113–121.
[51] T.D. Gould, M.M. Montemore, A.M. Lubers, L.D. Ellis, A.W. Weimer, J.
L. Falconer, J.W. Medlin, Enhanced dry reforming of methane on Ni and Ni-Pt
catalysts synthesized by atomic layer deposition, Appl. Catal. A Gen. 492 (2015)
107–116.
[52] B. Zhu, X.S. Li, J.L. Liu, X.B. Zhu, A.M. Zhu, Kinetics study on carbon dioxide
reforming of methane in kilohertz spark-discharge plasma, Chem. Eng. J. 264
(2015) 445–452.
[53] Y.X. Pan, C.J. Liu, L. Cui, Temperature-programmed studies of coke resistant Ni
catalyst for carbon dioxide reforming of methane, Catal. Lett. 123 (1) (2008)
96–101.
[54] S.Y. Shang, G.H. Liu, X.Y. Chai, X.M. Tao, X. Li, M.G. Bai, W. Chu, X.Y. Dai, Y.
X. Zhao, Y.X. Yin, Research on Ni/γ-Al2O3 catalyst for CO2 reforming of CH4
prepared by atmospheric pressure glow discharge plasma jet, Catal. Today 148
(3–4) (2009) 268–274.
[55] G. Liu, W. Chi, H.L. Long, X.Y. Dai, Y.X. Yin, A novel reduction method for Ni/
γ-Al2O3 catalyst by a high frequency cold plasma jet at atmospheric pressure,
Chinese J. Catal. 28 (7) (2007) 582–584.
[56] W. Hua, L.J. Jin, X.F. He, J.H. Liu, H.Q. Hu, Preparation of Ni/MgO catalyst for
CO2 reforming of methane by dielectric-barrier discharge plasma, Catal.
Commun. 11 (11) (2010) 968–972.
[57] C.J. Liu, K.L. Yu, Y.P. Zhang, X.L. Zhu, F. He, B. Eliasson, Characterization of
plasma treated Pd/HZSM-5 catalyst for methane combustion, Appl. Catal. B
Environ. 47 (2) (2004) 95–100.
[58] R. Zhou, N. Rui, Z.G. Fan, C.J. Liu, Effect of the structure of Ni/TiO2 catalyst on
CO2 methanation, Int. J. Hydrogen Energ. 41 (47) (2016) 22017–22025.
[59] Y. Zhang, W. Wang, Z.Y. Wang, X.T. Zhou, Z. Wang, C.J. Liu, Steam reforming of
methane over Ni/SiO2 catalyst with enhanced coke resistance at low steam to
methane ratio, Catal. Today 256 (2015) 130–136.
C. Shi et al.
[60] Z.G. Fan, K.H. Sun, N. Rui, B.R. Zhao, C.J. Liu, Improved activity of Ni/MgAl2O4
for CO2 methanation by the plasma decomposition, J. Energy Chem. 24 (5)
(2015) 655–659.
[61] X.Y. Jia, X.S. Zhang, N. Rui, X. Hu, C.J. Liu, Structural effect of Ni/ZrO2 catalyst
on CO2 methanation with enhanced activity, Appl. Catal. B Environ. 244 (2019)
159–169.
[62] X.S. Zhang, N. Rui, X.Y. Jia, X. Hu, C.J. Liu, Effect of decomposition of catalyst
precursor on Ni/CeO2 activity for CO methanation, Chinese J. Catal. 40 (4)
(2019) 495–503.
[63] Z. Wang, Y. Zhang, E.C. Neyts, X.X. Cao, X.S. Zhang, B.W.L. Jang, C.J. Liu,
Catalyst preparation with plasmas: how does it work? ACS Catal. 8 (3) (2018)
2093–2110.
[64] S.J. Hu, H.L. Long, Y. Xu, S.Y. Shang, Y.X. Yin, Reduction mechanism of Ni/Al2O3
catalyst reduced by cold plas ma jet for carbon dioxide reforming of methane,
Chinese J. Catal. 32 (2) (2011) 340–344.
[65] E.L. Saché, L. Pastor-Pérez, D. Watson, A. Sepúlveda-Escribano, T.R. Reina, Ni
stabilised on inorganic complex structures: superior catalysts for chemical CO2
recycling via dry reforming of methane, Appl. Catal. B Environ. 236 (2018)
458–465.
[66] N. Wang, K. Shen, L.H. Huang, X.P. Yu, W.Z. Qian, W. Chu, Facile route for
synthesizing ordered mesoporous Ni-Ce-Al oxide materials and their catalytic
performance for methane dry reforming to hydrogen and syngas, ACS Catal. 3
(2013) 1638–1651.
[67] J.L. Ewbank, L. Kovarik, F.Z. Diallo, C. Sievers, Effect of metal-support
interactions in Ni/Al2O3 catalysts with low metal loading for methane dry
reforming, Appl. Catal. A Gen. 494 (2015) 57–67.
[68] R. Kumar, K. Kumar, K.K. Pant, N.V. Choudary, Tuning the metal-support
interaction of methane tri-reforming catalysts for industrial flue gas utilization,
Int. J. Hydrogen Energ. 45 (2020) 1911–1929.
[69] D. Pakhare, J. Spivey, A review of dry (CO2) reforming of methane over noble
metal catalysts, Chem. Soc. Rev. 43 (2014) 7813–7837.
[70] K. Sutthiumporn, T. Maneerung, Y. Kathiraser, S. Kawi, CO2 dry-reforming of
methane over La0.8Sr0.2Ni0.8M0.2O3 perovskite (M=Bi, Co, Cr, Cu, Fe): roles of
lattice oxygen on C-H activation and carbon suppression, Int. J. Hydrogen Energ.
37 (2012) 11195–11207.
[71] M.S. Aw, M. Zorko, P. Djinović, A. Pintar, Insights into durable NiCo catalysts on
β-SiC/CeZrO2 and γ-Al2O3/CeZrO2 advanced supports prepared from facile
methods for CH4-CO2 dry reforming, Appl. Catal. B Environ. 164 (2015) 100–112.
[72] S.A. Theofanidis, V.V. Galvita, H. Poelman, G.B. Marin, Enhanced carbon-
resistant dry reforming Fe-Ni catalyst: role of Fe, ACS Catal. 5 (2015) 3028–3039.
[73] K.K. Bu, S. Kuboon, J. Deng, H.R. Li, T.T. Yan, G.R. Chen, L.Y. Shi, D.S. Zhang,
Methane dry reforming over boron nitride interface-confined and LDHs-derived
Ni catalysts, Appl. Catal. B Environ. 252 (2019) 86–97.
[74] M.S. Li, A.C.V. Veen, Tuning the catalytic performance of Ni-catalysed dry
reforming of methane and carbon deposition via Ni-CeO2-x interaction, Appl.
Catal. B Environ. 237 (2018) 641–648.
[75] W.J. Jang, D.W. Jeong, J.O. Shim, H.S. Roh, I.H. Son, S.J. Lee, H2 and CO
production over a stable Ni-MgO-Ce0.8Zr0.2O2 catalyst from CO2 reforming of
CH4, Int. J. Hydrogen Energ. 38 (2013) 4508–4512.
[76] W.J. Jang, D.W. Jeong, J.O. Shim, H.M. Kim, W.B. Han, J.W. Bae, H.S. Roh, Metal
oxide (MgO, CaO, and La2O3) promoted Ni-Ce0.8Zr0.2O2 catalysts for H2 and CO
production from two major greenhouse gases, Renew. Energ. 79 (2015) 91–95.
[77] A. Jawad, F. Rezaei, A.A. Rownaghi, Highly efficient Pt/Mo-Fe/Ni-based Al2O3-
CeO2 catalysts for dry reforming of methane, Catal. Today 350 (2020) 80–90.
[78] J.H. Park, I. Heo, T.S. Chang, Dry reforming of methane over Ni-substituted
CaZrNiOx catalyst prepared by the homogeneous deposition method, Catal.
Commun. 120 (2019) 1–5.
[79] Q.X. Ma, Y.X. Han, Q.H. Wei, S. Makpal, X.H. Gao, J.L. Zhang, T.S. Zhao,
Stabilizing Ni on bimodal mesoporous-macroporous alumina with enhanced coke
tolerance in dry reforming of methane to syngas, J. CO2 Util. 35 (2020) 288–297.
[80] L.J. Zhang, F.G. Wang, J.Y. Zhu, B.L. Han, W.Q. Fan, L. Zhao, W.J. Cai, Z.C. Li, L.
L. Xu, H. Yu, W.D. Shi, CO2 reforming with methane reaction over Ni@SiO2
catalysts coupled by size effect and metal-support interaction, Fuel. 256 (2019),
115954.
[81] S. Das, J. Pérez-Ramírez, J.L. Gong, N. Dewangan, K. Hidajat, B.C. Gates, S. Kawi,
Core-shell structured catalysts for thermocatalytic, photocatalytic, and
electrocatalytic conversion of CO2, Chem. Soc. Rev. 49 (10) (2020) 2937–3004.
[82] Z.W. Li, Z.G. Wang, S. Kawi, Sintering and coke resistant core/yolk shell catalyst
for hydrocarbon reforming, ChemCatChem. 11 (1) (2019) 202–224.
[83] Z.W. Li, M. Li, Z.F. Bian, Y. Kathiraser, S. Kawi, Design of highly stable and
selective core/yolk-shell nanocatalysts-a review, Appl. Catal. B Environ. 188
(2016) 324–341.
[84] Z.W. Li, B. Jiang, Z.G. Wang, S. Kawi, High carbon resistant Ni@Ni
phyllosilicate@SiO2 core shell hollow sphere catalysts for low temperature CH4
dry reforming, J. CO2 Util. 27 (2018) 238–246.
[85] Z.W. Li, S. Kawi, Facile synthesis of Multi-Ni-core@Ni phyllosilicate@CeO2 shell
hollow spheres with high oxygen vacancy concentration for dry reforming of CH4,
ChemCatChem. 10 (14) (2018) 2994–3001.
[86] Z.W. Li, S. Kawi, Multi-Ni@Ni phyllosilicate hollow sphere for CO2 reforming of
CH4: influence of Ni precursors on structure, sintering and carbon resistance,
Catal. Sci. Technol. 8 (2018) 1915–1922.
[87] Z.W. Li, Z.G. Wang, B. Jiang, S. Kawi, Sintering resistant Ni nanoparticles
exclusively confined within SiO2 nanotubes for CH4 dry reforming, Catal. Sci.
Technol. 8 (2018) 3363–3371.
16
Journal of CO2 Utilization 46 (2021) 101462
[88] Z.W. Li, Y. Kathiraser, J. Ashok, U. Oemar, S. Kawi, Simultaneous tuning porosity
and basicity of Nickel@Nickel-Magnesium phyllosilicate core-shell catalysts for
CO2 reforming of CH4, Langmuir. 30 (48) (2014) 14694–14705.
[89] S. Das, J. Ashok, Z. Bian, N. Dewangan, M.H. Wai, Y. Du, A. Borgna, K. Hidajat,
S. Kawi, Silica-Ceria sandwiched Ni core-shell catalyst for low temperature dry
reforming of biogas: coke resistance and mechanistic insights, Appl. Catal. B
Environ. 230 (2018) 220–236.
[90] M. Németh, G. Sáfrán, A. Horváth, F. Somodi, Hindered methane decomposition
on a coke-resistant Ni-In/SiO2 dry reforming catalyst, Catal. Commun. 118 (2019)
56–59.
[91] J. Horlyck, C. Lawrey, E.C. Lovell, R. Amal, J. Scott, Elucidating the impact of Ni
and Co loading on the selectivity of bimetallic NiCo catalysts for dry reforming of
methane, Chem. Eng. J. 352 (2018) 572–580.
[92] U. Guharoy, E.L. Saché, Q. Cai, T.R. Reina, S. Gu, Understanding the role of Ni-Sn
interaction to design highly effective CO2 conversion catalysts for dry reforming
of methane, J. CO2 Util. 27 (2018) 1–10.
[93] Z.H. Xie, B.H. Yan, S. Kattel, J.H. Lee, S. Yao, Q.Y. Wu, N. Rui, E. Gomez, Z.Y. Liu,
W.Q. Xu, L. Zhang, J.G.G. Chen, Dry reforming of methane over CeO2-supported
Pt-Co catalysts with enhanced activity, Appl. Catal. B Environ. 236 (2018)
280–293.
[94] D.G. Araiza, D.G. Arcos, A. Gómez-Cortés, G. Díaz, Dry reforming of methane over
Pt-Ni/CeO2 catalysts: effect of the metal composition on the stability, Catal.
Today (2019). Available online 7 June.
[95] A.A. Ibrahim, A.S. Al-Fatesh, W.U. Khan, S.O. Kasim, A.E. Abasaeed, A.
H. Fakeeha, G. Bonura, F. Frusteri, Enhanced coke suppression by using
phosphate-zirconia supported nickel catalysts under dry methane reforming
conditions, Int. J. Hydrogen Energ. 44 (2019) 27784–27794.
[96] A. Ballarini, F. Basile, P. Benito, I. Bersani, G. Fornasari, S. de Miguel, S.C.
P. Maina, J. Vilella, A. Vaccari, O.A. Scelza, Platinum supported on alkaline and
alkaline earth metal-doped alumina as catalysts for dry reforming and partial
oxidation of methane, Appl. Catal. A Gen. 433-434 (2012) 1–11.
[97] M.G. Diéguez, E. Finocchio, M.Á. Larrubia, L.J. Alemany, G. Busca,
Characterization of alumina-supported Pt, Ni and PtNi alloy catalysts for the dry
reforming of methane, J. Catal. 274 (1) (2010) 11–20.
[98] B.T. Egelske, J.M. Keels, J.R. Monnier, J.R. Regalbuto, An analysis of electroless
deposition derived Ni-Pt catalysts for the dry reforming of methane, J. Catal. 381
(2020) 374–384.
[99] B. Steinhauer, M.R. Kasireddy, J. Radnik, A. Martin, Development of Ni-Pd
bimetallic catalysts for the utilization of carbon dioxide and methane by dry
reforming, Appl. Catal. A Gen. 366 (2) (2009) 333–341.
[100] A. Horváth, G. Stefler, O. Geszti, A. Kienneman, A. Pietraszek, L. Guczi, Methane
dry reforming with CO2 on CeZr-oxide supported Ni, NiRh and NiCo catalysts
prepared by sol-gel technique: relationship between activity and coke formation,
Catal. Today 169 (1) (2011) 102–111.
[101] H.J. Wu, G. Pantaleo, V.L. Parola, A.M. Venezia, X. Collard, C. Aprile, L.F. Liotta,
Bi- and trimetallic Ni catalysts over Al2O3 and Al2O3-MOx (M=Ce or Mg) oxides
for methane dry reforming: Au and Pt additive effects, Appl. Catal. B Environ.
156-157 (2014) 350–361.
[102] N.A.K. Aramouni, J. Zeaiter, W. Kwapinski, J.J. Leahy, M.N. Ahmad, Eclectic
trimetallic Ni-Co-Ru catalyst for the dry reforming of methane, Int. J. Hydrogen
Energ. 45 (35) (2020) 17153–17163.
[103] K. Song, M. Lu, S. Xu, C.Q. Chen, Y.Y. Zhan, D.L. Li, C. Au, L.L. Jiang,
K. Tomishige, Effect of alloy composition on catalytic performance and coke-
resistance property of Ni-Cu/Mg(Al)O catalysts for dry reforming of methane,
Appl. Catal. B Environ. 239 (2018) 324–333.
[104] H.Q. Wang, X.L. Dong, T.T. Zhao, H.R. Yu, M. Li, Dry reforming of methane over
bimetallic Ni-Co catalyst prepared from La(CoxNi1-x)0.5Fe0.5O3 perovskite
precursor: catalytic activity and coking resistance, Appl. Catal. B Environ. 245
(2019) 302–313.
[105] C.Z. Wang, N.N. Sun, N. Zhao, W. Wei, Y.X. Zhao, Template-free preparation of
bimetallic mesoporous Ni-Co-CaO-ZrO2 catalysts and their synergetic effect in dry
reforming of methane, Catal. Today 281 (2017) 268–275.
[106] W.Y. Kim, J.S. Jang, E.C. Ra, K.Y. Kim, E.H. Kim, J.S. Lee, Reduced perovskite
LaNiO3 catalysts modified with Co and Mn for low coke formation in dry
reforming of methane, Appl. Catal. A Gen. 575 (2019) 198–203.
[107] Z.F. Bian, S. Das, M.H. Wai, P. Hongmanorom, S. Kawi, A review on bimetallic
Nickel-based catalysts for CO2 reforming of methane, Chemphyschem. 18 (22)
(2017) 3117–3134.
[108] J.F. Weaver, C. Hakanoglu, A. Antony, A. Asthagiri, Alkane activation on
crystalline metal oxide surfaces, Chem. Soc. Rev. 43 (22) (2014) 7536–7547.
[109] L.D. Li, D.H. Anjum, H.B. Zhu, Y. Saih, P.V. Laveille, L. D’Souza, J.M. Basset,
Synergetic effects leading to coke-resistant NiCo bimetallic catalysts for dry
reforming of methane, Chemcatchem. 7 (3) (2015) 427–433.
[110] H.S. Bengaard, J.K. Nørskov, J. Sehested, B.S. Clausen, L.P. Nielsen, A.
M. Molenbroek, J.R. Rostrup-Nielsen, Steam reforming and graphite formation on
Ni catalysts, J. Catal. 209 (2) (2002) 365–384.
[111] W.J. Jang, J.O. Shim, H.M. Kim, S.Y. Yoo, H.S. Roh, A review on dry reforming of
methane in aspect of catalytic properties, Catal. Today 324 (2019) 15–26.
[112] V.M. Gonzalez-DelaCruz, J.P. Holgado, R. Pereñíguez, A. Caballero, Morphology
changes induced by strong metal-support interaction on a Ni-ceria catalytic
system, J. Catal. 257 (2008) 307–314.
[113] Y.H. Wang, H.M. Liu, B.Q. Xu, Durable Ni/MgO catalysts for CO2 reforming of
methane: activity and metal-support interaction, J. Mol. Catal. A-Chem. 299
(2009) 44–52.
[114] Y.H. Hu, Solid-solution catalysts for CO2 reforming of methane, Catal. Today 148
(3–4) (2009) 206–211.
C. Shi et al.
[115] Y.H. Hu, E. Ruckenstein, Catalytic conversion of methane to synthesis gas by
partial oxidation and CO2 reforming, J. Adv. Catal. Sci. Technol. 48 (2004)
297–345.
[116] G. Jones, J.G. Jakobsen, S.S. Shim, J. Kleis, M.P. Andersson, J. Rossmeisl,
F. Abild-Pedersen, T. Bligaard, S. Helveg, B. Hinnemann, J.R. Rostrup-Nielsen,
I. Chorkendorff, J. Sehested, J.K. Nørskov, First principles calculations and
experimental insight into methane steam reforming over transition metal
catalysts, J. Catal. 259 (1) (2008) 147–160.
[117] J.W. Han, J.S. Park, M.S. Choi, H. Lee, Uncoupling the size and support effects of
Ni catalysts for dry reforming of methane, Appl. Catal. B Environ. 203 (2017)
625–632.
[118] J. Wang, J. Zhang, H.X. Zhong, H.Z. Wang, K.D. Ma, L.W. Pan, Effect of support
morphology and size of nickel metal ions on hydrogen production from methane
steam reforming, Chem. Phys. Lett. 746 (2020), 137291.
[119] D.W. Kang, J. Yu, W.H. Ma, M. Zheng, Y.F. He, P.F. Li, Synthesis of Cu/Ni-
La0.7Sr0.3Cr0.5Mn0.5O3-δ and its catalytic performance on dry methane reforming,
J. Rare Earth. 37 (2019) 585–593.
[120] L.L. Xu, H.L. Song, L.J. Chou, Carbon dioxide reforming of methane over ordered
mesoporous NiO-MgO-Al2O3 composite oxides, Appl. Catal. B Environ. 108-109
(2011) 177–190.
[121] J.Q. Tian, H.C. Li, X. Zeng, Z.C. Wang, J. Huang, C. Zhao, Facile immobilization of
Ni nanoparticles into mesoporous MCM-41 channels for efficient methane dry
reforming, Chinese J. Catal. 40 (2019) 1395–1404.
[122] Q.X. Ma, L.S. Guo, Y. Fang, H.J. Li, J.L. Zhang, T.-S. Zhao, G.H. Yang,
Y. Yoneyama, N. Tsubaki, Combined methane dry reforming and methane partial
oxidization for syngas production over high dispersion Ni based mesoporous
catalyst, Fuel Process Technol. 188 (2019) 98–104.
[123] H.B. Zhou, T.T. Zhang, Z.J. Sui, Y.A. Zhu, C. Han, K. Zhu, X.G. Zhou, A single
source method to generate Ru-Ni-MgO catalysts for methane dry reforming and
the kinetic effect of Ru on carbon deposition and gasification, Appl. Catal. B
Environ. 233 (2018) 143–159.
[124] S. Dama, S.R. Ghodke, R. Bobade, H.R. Gurav, S. Chilukuri, Active and durable
alkaline earth metal substituted perovskite catalysts for dry reforming of
methane, Appl. Catal. B Environ. 224 (2018) 146–158.
[125] B.R.D. Vasconcelos, D.P. Minh, E. Martins, A. Germeau, P. Sharrock, A. Nzihou,
Highly-efficient hydroxyapatite-supported nickel catalysts for dry reforming of
methane, Int. J. Hydrogen Energ. 45 (36) (2020) 18502–18518.
[126] S. Sengupta, G. Deo, Modifying alumina with CaO or MgO in supported Ni and Ni-
Co catalysts and its effect on dry reforming of CH4, J. CO2 Util. 10 (2015) 67–77.
[127] K. Li, C.L. Pei, X.Y. Li, S. Chen, X.H. Zhang, R. Liu, J.L. Gong, Dry reforming of
methane over La2O2CO3-modified Ni/Al2O3 catalysts with moderate metal-
support interaction, Appl. Catal. B Environ. 264 (2020), 118448.
[128] Z.Y. Hou, P. Chen, H.L. Fang, X.M. Zheng, T. Yashima, Production of synthesis gas
via methane reforming with CO2 on noble metals and small amount of noble-(Rh-)
promoted Ni catalysts, Int. J. Hydrogen Energ. 31 (2006) 555–561.
[129] C. Carrara, J. Múnera, E.A. Lombardo, L.M. Cornaglia, Kinetic and stability
studies of Ru/La2O3 used in the dry reforming of methane, Top. Catal. 51 (2008)
98–106.
[130] P. Chen, H.B. Zhang, G.D. Lin, K.R. Tsai, Development of coking-resistant Ni-
based catalyst for partial oxidation and CO2-reforming of methane to syngas,
Appl. Catal. A Gen. 166 (1998) 343–350.
[131] K. Fujimoto, K. Omata, T. Nozaki, O. Yamazaki, Y. Han, Selective synthesis of
liquid hydrocarbons from carbon dioxide and methane, Energ. Convers. Manage
33 (1992) 529–536.
[132] L.V. Mattos, E.R. De Oliveira, P.D. Resende, F.B. Noronha, F.B. Passos, Partial
oxidation of methane on Pt/Ce-ZrO2 catalysts, Catal. Today 77 (3) (2002)
245–256.
[133] Z.W. Li, S. Das, P. Hongmanorom, N. Dewangan, M.H. Wai, S. Kawi, Silica-based
micro- and mesoporous catalysts for dry reforming of methane, Catal. Sci.
Technol. 8 (2018) 2763–2778.
[134] J. Ashok, Z. Bian, Z. Wang, S. Kawi, Ni-phyllosilicate structure derived Ni-SiO2-
MgO catalysts for bi-reforming applications: acidity, basicity and thermal
stability, Catal. Sci. Technol. 8 (2018) 1730–1742.
[135] P. Djinović, J. Batista, A. Pintar, Efficient catalytic abatement of greenhouse
gases: methane reforming with CO2 using a novel and thermally stable Rh-CeO2
catalyst, Int. J. Hydrogen Energ 37 (2012) 2699–2707.
[136] J.Q. Zhu, X.X. Peng, L. Yao, X.J. Deng, H.Y. Dong, D.M. Tong, C.W. Hu, Synthesis
gas production from CO2 reforming of methane over Ni-Ce/SiO2 catalyst: the
effect of calcination ambienc, Int. J. Hydrogen Energ 38 (2013) 117–126.
[137] C.E. Daza, A. Kiennemann, S. Moreno, R. Molina, Dry reforming of methane using
Ni-Ce catalysts supported on a modified mineral clay, Appl. Catal. A Gen. 364
(2009) 65–74.
[138] S. Damyanova, B. Pawelec, K. Arishtirova, M.V. Martinez Huerta, J.L.G. Fierro,
The effect of CeO2 on the surface and catalytic properties of Pt/CeO2-ZrO2
catalysts for methane dry reforming, Appl. Catal. B Environ 89 (2009) 149–159.
[139] F. Pompeo, D. Gazzoli, N.N. Nichio, Stability improvements of Ni/α-Al2O3
catalysts to obtain hydrogen from methane reforming, Int. J. Hydrogen Energ. 34
(2009) 2260–2268.
[140] X.L. Cai, X.F. Dong, W.M. Lin, Effect of CeO2 on the catalytic performance of Ni/
Al2O3 for autothermal reforming of methane, J. Nat. Gas Chem. 17 (2008)
98–102.
[141] Ş. Özkara-Aydınoğlu, A.E. Aksoylu, Carbon dioxide reforming of methane over
Co-X/ZrO2 catalysts (X=La, Ce, Mn, Mg, K), Catal. Commun. 11 (2010)
1165–1170.
17
Journal of CO2 Utilization 46 (2021) 101462
[142] V.B. Mortola, S. Damyanova, D. Zanchet, J.M.C. Bueno, Surface and structural
features of Pt/CeO2-La2O3-Al2O3 catalysts for partial oxidation and steam
reforming of methane, Appl. Catal. B Environ. 107 (2011) 221–236.
[143] D.W. Jeong, W.J. Jang, J.O. Shim, H.S. Roh, I.H. Son, S.J. Lee, The effect of
preparation method on the catalytic performance over superior MgO-promoted
Ni-Ce0.8Zr0.2O2 catalyst for CO2 reforming of CH4, Int. J. Hydrogen Energ. 38
(2013) 13649–13654.
[144] D.W. Jeong, H.S. Potdar, J.O. Shim, W.J. Jang, H.S. Roh, H2 production from a
single stage water-gas shift reaction over Pt/CeO2, Pt/ZrO2, and Pt/Ce(1− x)Zr(x)O2
catalysts, Int. J. Hydrogen Energ. 38 (2013) 4502–4507.
[145] D.W. Jeong, H.S. Potdar, H.S. Roh, Comparative study on nano-sized 1wt% Pt/
Ce0.8Zr0.2O2 and 1wt% Pt/Ce0.2Zr0.8O2 catalysts for a single stage water gas shift
reaction, Catal. Lett. 142 (2012) 439–444.
[146] T.T. Zhang, Z.X. Liu, Y.A. Zhu, Z.C. Liu, Z.J. Sui, K. Zhu, X.G. Zhou, Dry reforming
of methane on Ni-Fe-MgO catalysts: influence of Fe on carbon-resistant property
and kinetics, Appl. Catal. B Environ. 264 (2020), 118497.
[147] F.G. Wang, L.L. Xu, J. Yang, J. Zhang, L.Z. Zhang, H. Li, Y. Zhao, H.X. Li, K. Wu,
G.Q. Xu, W. Chen, Enhanced catalytic performance of Ir catalysts supported on
ceria-based solid solutions for methane dry reforming reaction, Catal. Today 281
(2017) 295–303.
[148] R.O.D. Fonseca, R.C. Rabelo-Neto, R.C.C. Simões, L.V. Mattos, F.B. Noronha, Pt
supported on doped CeO2/Al2O3 as catalyst for dry reforming of methane, Int. J.
Hydrogen Energ. 45 (2020) 5182–5191.
[149] R.Y. Chein, W.Y. Fung, Syngas production via dry reforming of methane over
CeO2 modified Ni/Al2O3 catalysts, Int. J. Hydrogen Energ. 44 (2019)
14303–14315.
[150] G. Saracco, G. Scibilia, A. Iannibello, G. Baldi, Methane combustion on Mg-doped
LaCrO3 perovskite catalysts, Appl. Catal. B Environ. 8 (2) (1996) 229–244.
[151] S. Ponce, M.A. Peña, J.L.G. Fierro, Surface properties and catalytic performance
in methane combustion of Sr-substituted lanthanum manganites, Appl. Catal. B
Environ. 24 (3–4) (2000) 193–205.
[152] Z.F. Bian, Z.G. Wang, B. Jiang, P. Hongmanorom, W.Q. Zhong, S. Kawi, A review
on perovskite catalysts for reforming of methane to hydrogen production, Renew.
Sust. Energ. Rev. 134 (2020), 110291.
[153] Ch. Pichas, P. Pomonis, D. Petrakis, A. Ladavos, Kinetic study of the catalytic dry
reforming of CH4 with CO2 over La2− xSrxNiO4 perovskite-type oxides, Appl. Catal.
A Gen. 386 (1–2) (2010) 116–123.
[154] K. Sutthiumporn, S. Kawi, Promotional effect of alkaline earth over Ni-La2O3
catalyst for CO2 reforming of CH4: role of surface oxygen species on H2
production and carbon suppression, Int. J. Hydrogen Energ. 36 (22) (2011)
14435–14446.
[155] F.R. Shamskar, M. Rezaei, F. Meshkani, The influence of Ni loading on the activity
and coke formation of ultrasound-assisted co-precipitated Ni-Al2O3 nanocatalyst
in dry reforming of methane, Int. J. Hydrogen Energ. 42 (7) (2017) 4155–4164.
[156] W.D. Zhang, B.S. Liu, C. Zhu, Y.L. Tian, Preparation of La2NiO4/ZSM-5 catalyst
and catalytic performance in CO2/CH4 reforming to syngas, Appl. Catal. A Gen.
292 (2005) 138–143.
[157] M.A. Alsaffar, B.V. Ayodele, S.I. Mustapa, Scavenging carbon deposition on
alumina supported cobalt catalyst during renewable hydrogen-rich syngas
production by methane dry reforming using artificial intelligence modeling
technique, J. Clean. Prod. 247 (2020), 119168.
[158] I. Luisetto, S. Tuti, C. Battocchio, S.L. Mastro, A. Sodo, Ni/CeO2-Al2O3 catalysts
for the dry reforming of methane: the effect of CeAlO3 content and nickel
crystallite size on catalytic activity and coke resistance, Appl. Catal. A Gen. 500
(2015) 12–22.
[159] X.J. Chen, J.G. Jiang, K.M. Li, S.C. Tian, F. Yan, Energy-efficient biogas reforming
process to produce syngas: the enhanced methane conversion by O2, Acs Appl.
Energy Mater. 185 (2017) 687–697.
[160] J.J. Guo, H. Lou, X.M. Zheng, The deposition of coke from methane on a Ni/
MgAl2O4 catalyst, Carbon. 45 (6) (2007) 1314–1321.
[161] Z.L. Zhang, X.E. Verykios, Carbon dioxide reforming of methane to synthesis gas
over supported Ni catalysts, Catal. Today 21 (2–3) (1994) 589–595.
[162] S. Tang, L. Ji, J. Lin, H.C. Zeng, K.L. Tan, K. Li, CO2 reforming of methane to
synthesis gas over sol-gel-made Ni/γ-Al2O3 catalysts from organometallic
precursors, J. Catal. 194 (2) (2000) 424–430.
[163] K. Asai, K. Takane, Y. Nagayasu, S. Iwamoto, E. Yagasaki, M. Inoue,
Decomposition of methane in the presence of carbon dioxide over Ni catalysts,
Chem. Eng. Sci. 63 (20) (2008) 5083–5088.
[164] J.G. Zhang, H. Wang, A.K. Dalai, Development of stable bimetallic catalysts for
carbon dioxide reforming of methane, J. Catal. 249 (2) (2007) 300–310.
[165] N. Nichio, M. Casella, O. Ferretti, M. González, C. Nicot, B. Moraweck, R. Frety,
Partial oxidation of methane to synthesis gas. Behaviour of different Ni supported
catalysts, Catal. Lett. 42 (1) (1996) 65–72.
[166] J.K. Xu, W. Zhou, J.H. Wang, Z.J. Li, J.X. Ma, Characterization and analysis of
carbon deposited during the dry reforming of methane over Ni/La2O3/Al2O3
catalysts, Chinese J. Catal. 30 (11) (2009) 1076–1084.
[167] L. Ji, S. Tang, H.C. Zeng, J. Lin, K.L. Tan, CO2 reforming of methane to synthesis
gas over sol-gel-made Co/γ-Al2O3 catalysts from organometallic precursors, Appl.
Catal. A Gen. 207 (1–2) (2001) 247–255.
[168] K. Takanabe, K. Nagaoka, K. Nariai, K. Aika, Titania-supported cobalt and nickel
bimetallic catalysts for carbon dioxide reforming of methane, J. Catal. 232 (2)
(2005) 268–275.
[169] S.H. Zhang, S. Muratsugu, N. Ishiguro, M. Tada, Ceria-doped Ni/SBA-16 catalysts
for dry reforming of methane, ACS Catal. 3 (8) (2013) 1855–1864.
C. Shi et al.
[170] G.S. Gallego, F. Mondragón, J. Barrault, J.-M. Tatibouët, C. Batiot-Dupeyrat, CO2
reforming of CH4 over La-Ni based perovskite precursors, Appl. Catal. A Gen. 311
(2006) 164–171.
[171] I. Langmuir, Oscillations in ionized gases, Proc. Natl. Acad. Sci. 14 (8) (1928)
627–637.
[172] R. Snoeckx, A. Bogaerts, Plasma technology-a novel solution for CO2 conversion?
Chem. Soc. Rev. 46 (19) (2017) 5805–5863.
[173] T. Butterworth, R. Elder, R. Allen, Effects of particle size on CO2 reduction and
discharge characteristics in a packed bed plasma reactor, Chem. Eng. J. 293
(2016) 55–67.
[174] I. Michielsen, Y. Uytdenhouwen, J. Pype, B. Michielsen, J. Mertens, F. Reniers,
V. Meynen, A. Bogaerts, CO2 dissociation in a packed bed DBD reactor: first steps
towards a better understanding of plasma catalysis, Chem. Eng. J. 326 (2017)
477–488.
[175] Y. Uytdenhouwen, S. Van Alphen, I. Michielsen, V. Meynen, P. Cool, A. Bogaerts,
A packed-bed DBD micro plasma reactor for CO2 dissociation: Does size matter?
Chem. Eng. J. 348 (2018) 557–568.
[176] X. Tu, J.C. Whitehead, Plasma-catalytic dry reforming of methane in an
atmospheric dielectric barrier discharge: understanding the synergistic effect at
low temperature, Appl. Catal. B Environ. 125 (2012) 439–448.
[177] I. Michielsen, Y. Uytdenhouwen, A. Bogaerts, V. Meynen, Altering conversion and
product selectivity of dry reforming of methane in a dielectric barrier discharge
by changing the dielectric packing material, Catalysts. 9 (1) (2019) 51.
[178] B.S. Patil, Q. Wang, V. Hessel, J. Lang, Plasma N2-fixation: 1900-2014, Catal.
Today 256 (2015) 49–66.
[179] M.D. Bai, X.Y. Bai, Z.T. Zhang, B. Mingdong, B. Xiyao, Z. Zhitao, Synthesis of
ammonia in a strong electric field discharge at ambient pressure, Plasma Chem.
Plasma P. 20 (4) (2000) 511–520.
[180] A. Mizuno, Industrial applications of atmospheric non-thermal plasma in
environmental remediation, Plasma Phys. Contr. F. 49 (2007) A1–A15.
[181] C.B. Laflamme, J.W. Jurewicz, D.V. Gravelle, M.I. Boulos, Thermal plasma reactor
for the processing of gaseous hydrocarbons, Chem. Eng. Sci. 45 (8) (1990)
2483–2487.
[182] S. Samukawa, M. Hori, S. Rauf, K. Tachibana, P. Bruggeman, G. Kroesen, J.
C. Whitehead, A.B. Murphy, A.F. Gutsol, S. Starikovskaia, U. Kortshagen, J.-
P. Boeuf, T.J. Sommerer, M.J. Kushner, U. Czarnetzki, N. Mason, The 2012
Plasma Roadmap, J. Phys. D Appl. Phys. 45 (25) (2012), 253001.
[183] E. Tatarova, N. Bundaleska, J.P. Sarrette, C.M. Ferreira, Plasmas for
environmental issues: from hydrogen production to 2D materials assembly,
Plasma Sources Sci. T. 23 (6) (2014), 063002.
[184] P. Fauchais, A. Vardelle, Thermal plasmas, IEEE Trans. Plasma Sci. IEEE Nucl.
Plasma Sci. Soc. 25 (6) (1997) 1258–1280.
[185] X.M. Tao, M.G. Bai, Q.Y. Wu, Z.J. Huang, Y.X. Yin, X.Y. Dai, CO2 reforming of CH4
by binode thermal plasma, Int. J. Hydrogen Energ. 34 (23) (2009) 9373–9378.
[186] X.M. Tao, F.W. Qi, Y.X. Yin, X.Y. Dai, CO2 reforming of CH4 by combination of
thermal plasma and catalyst, Int. J. Hydrogen Energ. 33 (4) (2008) 1262–1265.
[187] Y. Xu, Q. Wei, H.L. Long, X.Q. Zhang, S.Y. Shang, X.Y. Dai, Y.X. Yin, CO2
reforming of CH4 by synergies of binode thermal plasma and catalysts, Int. J.
Hydrogen Energ. 38 (3) (2013) 1384–1390.
[188] S.C. Kim, Y.N. Chun, Production of hydrogen by partial oxidation with thermal
plasma, Renew. Energ. 33 (7) (2008) 1564–1569.
[189] A.M. Harling, D.J. Glover, J.C. Whitehead, K. Zhang, Novel method for enhancing
the destruction of environmental pollutants by the combination of multiple
plasma discharges, Environ. Sci. Technol. 42 (12) (2008) 4546–4550.
[190] L. Yu, X.D. Li, X. Tu, Y. Wang, S.Y. Lu, J.H. Yan, Decomposition of naphthalene by
dc gliding arc gas discharge, J. Phys. Chem. A 114 (1) (2010) 360–368.
[191] L. Yu, X. Tu, X.D. Li, Y. Wang, Y. Chi, J.H. Yan, Destruction of acenaphthene,
fluorene, anthracene and pyrene by a dc gliding arc plasma reactor, J. Hazard.
Mater. 180 (1–3) (2010) 449–455.
[192] S. Paulussen, B. Verheyde, X. Tu, C.D. Bie, T. Martens, D. Petrovic, A. Bogaerts,
B. Sels, Conversion of carbon dioxide to value-added chemicals in atmospheric
pressure dielectric barrier discharges, Plasma Sources Sci. T. 19 (3) (2010)
34015–34016.
[193] A.H. Khoja, M. Tahir, N.A.S. Amin, Cold plasma dielectric barrier discharge
reactor for dry reforming of methane over Ni/γ-Al2O3-MgO nanocomposite, Fuel
Process Technol. 178 (2018) 166–179.
[194] A.H. Khoja, M. Tahir, N.A.S. Amin, Process optimization of DBD plasma dry
reforming of methane over Ni/La2O3MgAl2O4 using multiple response surface
methodology, Int. J. Hydrogen Energ. 44 (2019) 11774–11787.
[195] X. Tu, H.J. Gallon, M.V. Twigg, P.A. Gorry, J.C. Whitehead, Dry reforming of
methane over a Ni/Al2O3 catalyst in a coaxial dielectric barrier discharge reactor,
J. Phys. D Appl. Phys. 44 (2011), 274007.
[196] J. Sentek, K. Krawczyk, M. Młotek, M. Kalczewska, T. Kroker, T. Kolb, A. Schenk,
K.H. Gericke, K. Schmidt-Szałowski, Plasma-catalytic methane conversion with
carbon dioxide in dielectric barrier discharges, Appl. Catal. B Environ. 94 (2010)
19–26.
[197] M.H. Pham, V. Goujard, J.M. Tatibouët, C. Batiot-Dupeyrat, Activation of
methane and carbon dioxide in a dielectric-barrier discharge-plasma reactor to
produce hydrocarbons-influence of La2O3/γ-Al2O3 catalyst, Catal. Today 171
(2011) 67–71.
[198] H.J. Gallon, X. Tu, J.C. Whitehead, Effects of reactor packing materials on H2
production by CO2 reforming of CH4 in a dielectric barrier discharge, Plasma
Process. Polym. 9 (2012) 90–97.
[199] A.H. Khoja, M. Tahir, N.A.S. Amin, Recent developments in non-thermal catalytic
DBD plasma reactor for dry reforming of methane, Energ. Convers. Manage. 183
(2019) 529–560.
18
Journal of CO2 Utilization 46 (2021) 101462
[200] H.H. Nguyen, A. Nasonova, I.W. Nah, K.S. Kim, Analysis on CO2 reforming of CH4
by corona discharge process for various process variables, J. Ind. Eng. Chem. 32
(2015) 58–62.
[201] G.B. Zhao, S. John, J.J. Zhang, L. Wang, S. Muknahallipatna, J.C. Hamann, J.
F. Ackerman, M.D. Argyle, O.A. Plumb, Methane conversion in pulsed corona
discharge reactors, Chem. Eng. J. 125 (2006) 67–79.
[202] D.H. Li, X. Li, M.G. Bai, X.M. Tao, S.Y. Shang, X.Y. Dai, Y.X. Yin, CO2 reforming of
CH4 by atmospheric pressure glow discharge plasma: a high conversion ability,
Int. J. Hydrogen Energ. 34 (1) (2009) 308–313.
[203] D.G. Cheng, X.L. Zhu, Y.H. Ben, F. He, L. Cui, C.J. Liu, Carbon dioxide reforming
of methane over Ni/Al2O3 treated with glow discharge plasma, Catal. Today 115
(1–4) (2006) 205–210.
[204] S.L. Yao, E. Suzuki, N. Meng, A. Nakayama, A high-efficiency reactor for the
pulsed plasma conversion of methane, Plasma Chem. Plasma P. 22 (2) (2002)
225–237.
[205] L.Z. Li, J. Chen, K. Yan, X.M. Qin, T. Feng, J.W. Wang, F. Wang, Z.L. Song,
Methane dry reforming with microwave heating over carbon-based catalyst
obtained by agriculture residues pyrolysis, J CO2 Util. 28 (2018) 41–49.
[206] L.Z. Li, J. Chen, S. Wang, Y.D. Tan, B. Meng, G.F. Zou, F. Wang, Z.L. Song, C.
Y. Ma, Utilization of biochar for a process of methane dry reforming coupled with
steam gasification under microwave heating, J. Clean. Prod. 237 (2019), 117838.
[207] T.S. Kim, S. Song, K.M. Chun, S.H. Lee, An experimental study of syn-gas
production via microwave plasma reforming of methane, iso-octane and gasoline,
Energy. 35 (6) (2010) 2734–2743.
[208] B. Fidalgo, A. Domínguez, J.J. Pis, J.A. Menéndez, Microwave-assisted dry
reforming of methane, Int. J. Hydrogen Energ. 33 (16) (2008) 4337–4344.
[209] M.J. Gallagher, R. Geiger, A. Polevich, A. Rabinovich, A. Gutsol, A. Fridman, On-
board plasma-assisted conversion of heavy hydrocarbons into synthesis gas, Fuel.
89 (6) (2010) 1187–1192.
[210] A. Indarto, J.W. Choi, H. Lee, H.K. Song, Effect of additive gases on methane
conversion using gliding arc discharge, Energy. 31 (14) (2006) 2986–2995.
[211] H. Lee, H. Sekiguchi, Plasma-catalytic hybrid system using spouted bed with a
gliding arc discharge: CH4 reforming as a model reaction, J. Phys. D Appl. Phys.
44 (2011), 274008.
[212] A.E.E. Putra, S. Nomura, S. Mukasa, H. Toyota, Hydrogen production by radio
frequency plasma stimulation in methane hydrate at atmospheric pressure, Int. J.
Hydrogen Energ. 37 (21) (2012) 16000–16005.
[213] H.L. Chen, H.M. Lee, S.H. Chen, Y. Chao, M.B. Chang, Review of plasma catalysis
on hydrocarbon reforming for hydrogen production-Interaction, integration, and
prospects, Appl. Catal. B Environ. 85 (2008) 1–9.
[214] T. Nozaki, W. Fukui, K. Okazaki, Reaction enhancement mechanism of the
nonthermal discharge and catalyst hybrid reaction for methane reforming, Energ.
Fuel. 22 (2008) 3600–3604.
[215] J.V. Durme, J. Dewulf, C. Leys, H.V. Langenhove, Combining non-thermal plasma
with heterogeneous catalysis in waste gas treatment: a review, Appl. Catal. B
Environ. 78 (2008) 324–333.
[216] J.C. Whitehead, Plasma catalysis: a solution for environmental problems, Pure
Appl. Chem. 82 (2010) 1329–1336.
[217] C.J. Liu, J.Y. Ye, J.J. Jiang, Y.X. Pan, Progresses in the preparation of coke
resistant Ni-based catalyst for steam and CO2 reforming of methane,
ChemCatChem. 3 (2011) 529–541.
[218] C.J. Liu, J.J. Zou, K.L. Yu, D.G. Cheng, Y. Han, J. Zhan, C. Ratanatawanate, B.W.
L. Jang, Plasma application for more environmentally friendly catalyst
preparation, Pure Appl. Chem. 78 (6) (2006) 1227–1238.
[219] H.K. Song, J.W. Choi, S.H. Yue, H. Lee, B.K. Na, Synthesis gas production via
dielectric barrier discharge over Ni/γ-Al2O3 catalyst, Catal. Today 89 (2004)
27–33.
[220] C. Dong, L.J. Jin, Y. Li, Y. Zhou, L. Zou, H.Q. Hu, Integrated process of coal
pyrolysis with steam reforming of methane for improving the tar yield, Energ.
Fuel. 28 (12) (2014) 7377–7384.
[221] J.H. Liu, H.Q. Hu, L.J. Jin, P.F. Wang, S.W. Zhu, Integrated coal pyrolysis with
CO2 reforming of methane over Ni/MgO catalyst for improving tar yield, Fuel
Process Technol. 91 (4) (2010) 419–423.
[222] P.F. Wang, L.J. Jin, J.H. Liu, S.W. Zhu, H.Q. Hu, Isotope analysis for
understanding the tar formation in the integrated process of coal pyrolysis with
CO2 reforming of methane, Energ. Fuel. 24 (8) (2010) 4402–4407.
[223] J.N. Lv, D.C. Wang, M.Y. Wang, Y. Li, L.J. Jin, H.Q. Hu, Integrated coal pyrolysis
with dry reforming of low carbon alkane over Ni/La2O3 to improve tar yield, Fuel.
266 (2020), 117092.
[224] M.Y. Wang, L.J. Jin, H.B. Zhao, X.Y. Yang, Y. Li, H.Q. Hu, Z.Q. Bai, In-situ
catalytic upgrading of coal pyrolysis tar over activated carbon supported nickel in
CO2 reforming of methane, Fuel. 250 (2019) 203–210.
[225] L.J. Jin, X. Zhou, X.F. He, H.Q. Hu, Integrated coal pyrolysis with methane
aromatization over Mo/HZSM-5 for improving tar yield, Fuel. 114 (2013)
187–190.
[226] X.F. He, L.J. Jin, D. Wang, Y.P. Zhao, S.W. Zhu, H.Q. Hu, Integrated process of
coal pyrolysis with CO2 reforming of methane by dielectric barrier discharge
plasma, Energ. Fuel. 25 (9) (2011) 4036–4042.
[227] L.J. Jin, Y. Li, Y.Q. Feng, H.Q. Hu, A.M. Zhu, Integrated process of coal pyrolysis
with CO2 reforming of methane by spark discharge plasma, J. Anal. Appl. Pyrol.
126 (2017) 194–200.
[228] L. Liu, Z.K. Zhang, S. Das, S. Kawi, Reforming of tar from biomass gasification in a
hybrid catalysis-plasma system: a review, Appl. Catal. B Environ. 250 (2019)
250–272.
[229] B.M. Penetrante, J.N. Bardsley, M.C. Hsiao, Kinetic analysis of non-thermal
plasmas used for pollution control, J. Appl. Phys. 36 (1997) 5007–5017.
C. Shi et al.
[230] T. Yamamoto, Optimization of nonthermal plasma for the treatment of gas
streams, J. Hazard. Mater. 67 (2) (1999) 165–181.
[231] Q. Wang, B.H. Yan, Y. Jin, Y. Cheng, Dry reforming of methane in a dielectric
barrier discharge reactor with Ni/Al2O3 catalyst: interaction of catalyst and
plasma, Energ. Fuel. 23 (8) (2009) 4196–4201.
[232] C.J. Liu, J.X. Wang, K.L. Yu, B. Eliasson, Q. Xia, B.Z. Xue, Y.H. Zhang, Floating
double probe characteristics of non-thermal plasmas in the presence of zeolite,
J. Electrostat. 54 (2) (2002) 149–158.
[233] H.-H. Kim, Y. Teramoto, N. Negishi, A. Ogata, A multidisciplinary approach to
understand the interactions of nonthermal plasma and catalyst: a review, Catal.
Today 256 (2015) 13–22.
[234] A.J. Zhang, A.M. Zhu, J. Guo, Y. Xu, C. Shi, Conversion of greenhouse gases into
syngas via combined effects of discharge activation and catalysis, Chem. Eng. J.
156 (3) (2010) 601–606.
[235] J.G. Wang, C.J. Liu, B. Eliassion, Density functional theory study of synthesis of
oxygenates and higher hydrocarbons from methane and carbon dioxide using cold
plasmas, Energ. Fuel. 18 (1) (2004) 148–153.
[236] F.J. Spiess, S.L. Suib, K. Irie, Y. Hayashi, H. Matsumoto, Metal effect and flow rate
effect in the hydrogen production from methane, Catal. Today 89 (1–2) (2004)
35–45.
[237] C.H. Lin, S.H. Lee, C.M. Hsu, C.T. Kuo, Comparisons on properties and growth
mechanisms of carbon nanotubes fabricated by high-pressure and low-pressure
plasma-enhanced chemical vapor deposition, Diam. Relat. Mater. 13 (11–12)
(2004) 2147–2151.
[238] S. Kado, K. Urasaki, Y. Sekine, K. Fujimoto, T. Nozaki, K. Okazaki, Reaction
mechanism of methane activation using non-equilibrium pulsed discharge at
room temperature, Fuel. 82 (18) (2003) 2291–2297.
[239] M.H. Rafiq, H.A. Jakobsen, J.E. Hustad, Modeling and simulation of catalytic
partial oxidation of methane to synthesis gas by using a plasma-assisted gliding
arc reactor, Fuel Process Technol. 101 (2012) 44–57.
[240] A. Indarto, J.W. Choi, H. Lee, H.K. Song, Methane conversion using dielectric
barrier discharge: comparison with thermal process and catalyst effects, J. Nat.
Gas Chem. 15 (2) (2006) 87–92.
[241] S.Y. Savinov, H. Lee, H.K. Song, B.K. Na, Decomposition of methane and carbon
dioxide in a radio-frequency discharge, Ind. Eng. Chem. Res. 38 (7) (1999)
2540–2547.
[242] C.J. Liu, R. Mallinson, L. Lobban, Nonoxidative methane conversion to acetylene
over zeolite in a low temperature plasma, J. Catal. 179 (1) (1998) 326–334.
[243] W. Somers, A. Bogaerts, A.C.T. van Duin, E.C. Neyts, Plasma species interacting
with nickel surfaces: toward an atomic scale understanding of plasma-catalysis,
J. Phys. Chem. C. 116 (39) (2012) 20958–20965.
[244] R. Vakili, R. Gholami, C.E. Stere, S. Chansai, H. Chen, S.M. Holmes, Y.L. Jiao,
C. Hardacre, X.L. Fan, Plasma-assisted catalytic dry reforming of methane (DRM)
over metal-organic frameworks (MOFs)-based catalysts, Appl. Catal. B Environ.
260 (2020), 118195.
[245] T. Cao, R. You, X.Y. Zhang, S.L. Chen, D. Li, Z.H. Zhang, W.X. Huang, An in situ
DRIFTS mechanistic study of CeO2-catalyzed acetylene semihydrogenation
reaction, Phys. Chem. Chem. Phys. 20 (14) (2018) 9659–9670.
[246] M. Kang, B.J. Kim, S.M. Cho, C.H. Chung, B.W. Kim, G.Y. Han, K.J. Yoon,
Decomposition of toluene using an atmospheric pressure plasma/TiO2 catalytic
system, J. Mol. Catal. A-Chem. 180 (1–2) (2002) 125–132.
[247] L. Bromberg, D.R. Cohn, A. Rabinovich, N. Alexeev, Hydrogen manufacturing
using low current, non-thermal plasma boosted fuel converters, Energy for the
21st century: hydrogen energy, Fuel Chem. Division Am. Chem. Soc. (2001).
[248] Z.G. Wang, T.J. Chen, N. Dewangan, Z.W. Li, S. Das, S. Pati, Z. Li, J.Y.S. Lin,
S. Kawi, Catalytic mixed conducting ceramic membrane reactors for methane
conversion, React. Chem. Eng. 5 (2020) 1868–1891.
19
Journal of CO2 Utilization 46 (2021) 101462
[249] J. Galuszka, R.N. Pandey, S. Ahmed, Methane conversion to syngas in a palladium
membrane reactor, Catal. Today 46 (2–3) (1998) 83–89.
[250] L. Paturzo, F. Gallucci, A. Basile, G. Vitulli, P. Pertici, An Ru-based catalytic
membrane reactor for dry reforming of methane—its catalytic performance
compared with tubular packed bed reactors, Catal. Today 82 (1–4) (2003) 57–65.
[251] H.X. Luo, Y.Y. Wei, H.Q. Jiang, W.H. Yuan, Y.X. Lv, J. Caro, H.H. Wang,
Performance of a ceramic membrane reactor with high oxygen flux Ta-containing
perovskite for the partial oxidation of methane to syngas, J. Membrane Sci. 350
(1–2) (2010) 154–160.
[252] X.F. Zhu, Q.M. Li, Y.F. He, Y. Cong, W.S. Yang, Oxygen permeation and partial
oxidation of methane in dual-phase membrane reactors, J. Membrane Sci. 360
(1–2) (2010) 454–460.
[253] F. Borgognoni, S. Tosti, Pd-Ag multi-membranes module for hydrogen production
by methane auto-thermal reforming, Int. J. Hydrogen Energ. 37 (2) (2012)
1444–1453.
[254] Y.Z. Chen, Y.Z. Wang, H.Y. Xu, G.X. Xiong, Hydrogen production capacity of
membrane reformer for methane steam reforming near practical working
conditions, J. Membrane Sci. 322 (2) (2008) 453–459.
[255] S.K. Ryi, J.S. Park, D.K. Kim, T.H. Kim, S.H. Kim, Methane steam reforming with a
novel catalytic nickel membrane for effective hydrogen production, J. Membrane
Sci. 339 (1–2) (2009) 189–194.
[256] F. Borgognoni, S. Tosti, M. Vadrucci, A. Santucci, Pure hydrogen production in a
Pd-Ag multi-membranes module by methane steam reforming, Int. J. Hydrogen
Energ. 36 (13) (2011) 7550–7558.
[257] N.N. Gavrilova, V.N. Sapunov, V.V. Skudin, Intensification of dry reforming of
methane on membrane catalyst, Chem. Eng. J. 374 (2019) 983–991.
[258] A.D. Fontana, B. Faroldi, L.M. Cornaglia, A.M. Tarditi, Development of catalytic
membranes over PdAu selective films for hydrogen production through the dry
reforming of methane, Mol. Catal. 481 (2020), 100643.
[259] Z.X. Chen, Y.B. Yan, S.S.E.H. Elnashaie, Novel circulating fast fluidized-bed
membrane reformer for efficient production of hydrogen from steam reforming of
methane, Chem. Eng. Sci. 58 (19) (2003) 4335–4349.
[260] V.R. Choudhary, K.C. Mondal, T.V. Choudhary, Partial oxidation of methane to
syngas with or without simultaneous steam or CO2 reforming over a high-
temperature stable-NiCoMgCeOx supported on zirconia-hafnia catalyst, Appl.
Catal. A Gen. 306 (2006) 45–50.
[261] Z.W. Li, Q. Lin, M. Li, J.X. Cao, F. Liu, H.Y. Pan, Z.G. Wang, S. Kawi, Recent
advances in process and catalyst for CO2 reforming of methane, Renew. Sust.
Energ. Rev. 134 (2020), 110312.
[262] Q.B. Liu, H.G. Jin, H. Hong, J. Sui, J. Ji, J.G. Dang, Performance analysis of a mid-
and low-temperature solar receiver/reactor for hydrogen production with
methanol steam reforming, Int. J. Energ. Res. 35 (1) (2011) 52–60.
[263] J. Jin, X. Wei, M.K. Liu, Y.H. Yu, W.J. Li, H. Kong, Y. Hao, A solar methane
reforming reactor design with enhanced efficiency, Appl. Energy 266 (2018)
797–807.
[264] H.S. Wang, M.K. Liu, H. Kong, Y. Hao, Thermodynamic analysis on mid/low
temperature solar methane steam reforming with hydrogen permeation
membrane reactors, Appl. Therm. Eng. 152 (2019) 925–936.
[265] E.J. Sheu, A.F. Ghoniem, Receiver reactor concept and model development for a
solar steam redox reformer, Sol. Energy. 125 (2016) 339–359.
[266] S. Bellan, T. Kodama, K. Matsubara, N. Gokon, H.S. Cho, K. Inoue, Thermal
performance of a 30kW fluidized bed reactor for solar gasification: a CFD-DEM
study, Chem. Eng. J. 360 (2019) 1287–1300.
[267] N. Gokon, S. Nakamura, T. Hatamachi, T. Kodama, Steam reforming of methane
using double-walled reformer tubes containing high-temperature thermal storage
Na2CO3/MgO composites for solar fuel production, Energy. 68 (2014) 773–782.