i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 5 8 5 2 e5 8 7 4

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Review Article

Recent advances during CH4 dry reforming for

syngas production: A mini review

Chunsheng Wang a, Yishuang Wang b, Mingqiang Chen a,b,*,

Defang Liang b, Zhonglian Yang b, Wen Cheng a, Zhiyuan Tang a,
Jun Wang b, Han Zhang b
a
School of Earth and Environment, Anhui University of Science and Technology, 232001, Huainan, PR China
b
School of Chemical Engineering, Anhui University of Science and Technology, 232001, Huainan, PR China

highlights graphical abstract

Crystalline oxide catalysts are

greatly robust due to a surface
confinement effect.

New materials of h-BN, clay sup-
ports and MOFs were applied.

Reaction mechanisms were elabo-
rated by advanced in-situ
characterizations.

MDR reaction system was
improved towards low tempera-
ture and high energy efficiency.

Mature MDR integrates robust
catalysts, mechanism control and
system improvement.

article info abstract

Article history: Given the continuing issues of environment and energy, methane dry reforming for syngas
Received 10 September 2020 production have sparked interest among researchers, but struggled with the process
Received in revised form immaturity owing to catalyst deactivation. This review summarizes the recent advances in
26 October 2020 the development of efficient and stable catalysts with strong resistance to coking and
Accepted 28 October 2020 metal sintering, including the application of novel materials, the assessment of advanced
Available online 20 November 2020 characterizations and the compatibility to improved reaction system. One feasible option is
the crystalline oxide catalysts (perovskite, pyrochlore, spinel and LDHs), which feature a
Keywords: fine metal dispersion and surface confinement effect via a metal exsolution strategy and
Methane dry reforming exhibit superior reactivity and stability. Some new materials (h-BN, clays and MOFs) also
Crystalline oxide catalysts extend the option because of their unique morphology and microstructure. It also is
Support elaborated that progresses were achieved in advanced characterizations application,
leading to success in the establishment of reaction mechanisms and attributions to the

* Corresponding author. School of Earth and Environment, Anhui University of Science and Technology, 232001, Huainan, PR China.
E-mail address: mqchen@aust.edu.cn (M. Chen).
https://doi.org/10.1016/j.ijhydene.2020.10.240
0360-3199/© 2020 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 5 8 5 2 e5 8 7 4 5853

In-situ characterizations formed robust catalysts. In addition, the perspective described the upgrade of reaction
Reaction system improvement system to a higher reaction efficiency and milder reaction conditions. The combination of
efficient reaction systems and robust catalysts paves a way for a scaling-up application of
the process.
© 2020 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

Contents

Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5853
Active phases . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5856
Crystalline oxide catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5856
Perovskite catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5859
Spinel catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5859
Pyrochlore catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5860
Layered double hydroxide catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5860
Summary and prospect for crystalline oxide catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5860
New materials for DRM . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5861
Hexagonal boron nitride nanosheet . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5861
Natural clay supports . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5863
Metal organic frameworks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5864
Advanced technologies for revealing DRM reaction mechanism . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5865
In situ DRIFTS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5865
In situ XPS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5866
Temperature program surface reaction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5866
Isotopic labeling experiments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5866
Improvements for DRM reaction system . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5867
Plasma-assisted DRM . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5867
Photo-assisted DRM . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5868
Microwave-assisted DRM . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5869
Summary and outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5869
CRediT author statement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5870
Declaration of competing interest . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5870
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5870
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5870

comparatively mature process to efficiently convert CO2 and

Introduction
Currently, the unmanageable trend of emission growth,
mainly originating from the traditional fossil fuel utilization,
burgeoning shale oil/gas industry and other industrial pro-
cesses, results in a significant wastage of the important car-
bon resource and a severe global climate change [1e3].
According to the relevant reports, it was determined at the
end of 2017 that a total of greenhouse gas (GHS) emission
exceeded to 5.0 metric gigatons equivalent CO2 with an annual
growth of 2.0%, in which CO2 and CH4 occupied the majority
share [4e6]. Despite the success obtained in the researches of
CO2 utilization, such as carbon capture and sequestration, CO2
hydrogenation and electrochemical CO2 reduction, it is hard
to ignore the single material application, limitation of CO2
conversion and potential risks of safety and environment for
the technology [7]. There is an urgent need for a cheap and
CH4 to syngas or other synthetic fuels serving for downstream
chemical industries [8e13]. Reforming is considered the most
reasonable path applied in industries and laboratory studies
to produce syngas, via one of several reforming processes
such as steam reforming of methane (SRM), methane partial
oxidation (SRM), autothermal reforming of methane (ARM), bi-
reforming of methane (BRM) and dry reforming of methane
(DRM) [14,15]. The process option mainly depends on the feed
compositions, target products and reaction conditions, espe-
cially on a tradeoff between its respective merits and demerits
as tabulated in Table 1. SRM brought about an overhigh H2/CO
ratio, which was unsuitable to the F-T synthesis, and the high
steam partial pressure required a high energy consumption
[16,17]. In the case of POM, the process is always faced with
the difficulties to heat control and metal oxidation. As for ARM
and BRM, there is a strict regulation of process parameters, in
particular the feed compositions. Of all technologies, dry
 5854
Table 1 e Comparisons of existing mainstream methane reforming process routes (Modified from Abdulrasheed A et al. [7]).
Reforming type Reaction conditions H2/CO ratio DH (kJ/mol) Merits Demerits

SRM 3e25atm, 250e1000 C 3 228 1.Higher concentration of H2 in the product 1.relatively low energy efficiency

i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 5 8 5 2 e5 8 7 4
CH4/H2O ¼ 1-5 2. High efficiency of operation 2. Relatively high requirement for reaction units
3. Industrial maturity 3.The target products unsuitable for F-T
synthesis
POM 100 atm, 950e1100  C 2 22.6 1.Higher tolerance for sulfides 1.High cost of pure O2 feed
CH4/O2 ¼ 2 2.Short contact time 2.Possible uncontrolled combustion
phenomenon
3.More efficient in energy efficiency
4. High conversion/selectivity
ARM CH4/H2O/O2 ¼ 1/1/0.5 1 or 2 based negative value 1.More efficient in energy efficiency 1.Lower H2 yield
on feed depended on feed
composition composition
2.Short contact time 2.An upper limit of H2O/O2 ratio
3.Lower coke deposition 3.Possible uncontrolled combustion
phenomenon
4.Flexible and adjustable feed composition
BRM CH4/H2O/CO2 ¼ 3/2/1 2 220
650-900  C 1.Lower coke deposition 1. Relatively high requirement for reaction units
2.Flexible and adjustable feed composition 2.high cost of CO2 separation from target
products
DRM 1 atm, 650e900  C 1 247 1.Simultaneous conversion of the two GHG 1.Challenge to catalyst deactivation due to coke
and metal sintering
CH4/CO2 ¼ 1 2.Production of clean energy and fuel 2.Harsh requirement for CO2 activation
3.Ideal H2/CO for F-T synthesis
plasma-assisted 400  C 1.High energy efficiency of ionization activation 1. Expensive glow discharge systems
for reactants
2.relative mild thermodynamic conditions 2.Ambiguous reaction mechanism
photo-assisted 400  C 1.Break through the limit of thermodynamics and 1. Catalysts restricted in photocatalytic materials
reduce energy consumption
2. Few relative studies
microwave-assisted 800  C 1.instantaneous heating 1.Uncontrolled hot spot effect
2.relatively easy experimental setup 2.Difficulty in monitoring the catalyst bed
temperature
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 5 8 5 2 e5 8 7 4
reforming, as the most promising chemical process, operated
at equal CO2 and CH4 conversions and converted the two
major GHG into syngas with a proper H2/CO ratio close to 1
[16e18]. Moreover, the DRM process features more practical
than other processes since it avoids the complex product
separation from the outflow and extends to the production of
biogas (CO, CO2 and CH4) for clean and renewable energy
development [17]. Thus, the process may availably reduce the
overall environment footprint of syngas and its derived fuels
and chemicals production if can be optimized and matured to
the maximum extent.
However, the DRM, a strongly endothermic and reversible
reaction, is still considered as an immature process since it is
thermodynamically feasible above 640  C and optimal around
850  C [17,19]. The thermodynamical property has dominated
the most proper reaction temperature, pressure and feed
composition for the optimization of the reaction process.
Meanwhile, there is an inherent difference in the activation
barrier of two reactants, signifying that the activation rate of
p-bond in the chemical inert CO2 mismatches with the one of
s-bond in CeH of active CH4 in terms of kinetics [20]. The side
reactions would inevitably occur and its extent was measured
on the basis of the deviation of actual products from the
standard stoichiometry. The presence of reverse water gas
shift reaction (RWGS) for water production can be deduced by
the higher stoichiometric conversion of CO2 than CH4 and a
H2/CO ratio below 1 [21,22]. While the Boudouard reaction and
CH4 decomposition mainly for coke formation were favored in
the case of a higher stoichiometric conversion of CH4 than
that of CO2 [23,24]. The DRM is mainly dominated by the re-
action between CH4 and CO2 and accompanied with several
side reactions. Except the feed ratio and pressure, the ther-
modynamic property, influenced the optimal reaction tem-
perature and the level of side reactions. The reaction system
equilibrates as a function of temperature, as itemized in Table
2.
Apparently, as with any effort into catalyst study, this re-
quires an understanding of the molecular-level details that
control the DRM mechanism. The catalysts are essential to
maximize syngas production as it could tune and enhance the
structure sensitive reaction involved rate-determining steps
[20]. The key lies in the fact that the CeH activation prefers on
the highly under-coordinated metal sites, especially on the
metal particles with small size, while the CO2 activation
significantly depends on defect sites or strong basic sites
[25e27]. The catalysts work via providing a specific reaction
path that decreases the activation energy and reaction tem-
perature and contributes to a steady reaction state approxi-
mating to the thermodynamic equilibrium. Hence, the design
Table 2 e Reactions in the DRM (Modified from Abdullah B et al. [18]).
Num Reactions
Main reaction Methane dry reforming
Side reaction decreasing H2/CO < 1 Reverse water gas shift reaction
Side reactions favoring coke formation Methane decomposition
CO disproportionation
CO2 hydrogenation
CO hydrogenation
5855
and exploration of high active and selective catalysts with a
long life-span have been still the focal point in recent DRM
researches. Whereas, the stability of catalysts is always trap-
ped in the deactivation issues of metal sintering and coke
deposition. During the harsh DRM conditions, the metal par-
ticles dispersed on the catalyst surface inevitably ripened,
migrated and aggregated. The CH4 decomposition easily
occurred on bulk metal particles, resulting in severe carbon
accumulation and metal particle encapsulation. The metal
sintering and coke deposition would further hinder the sur-
face oxygen spillover from the CO2 activation at metal-
support interface or other basic sites, which attenuates the
gasification of carbonous species and the DRM process [28].
The common supported catalysts, whether cheap transi-
tion metal based (Ni or Co) or efficient noble metal based (Ir,
Pd, Pt, Rh and Ru), inevitably face with a trade-off between the
catalytic activity, selectivity and stability as they always suffer
an unavoidable deactivation issues [15]. To overcome the
dilemma, long-term and massive endeavor has been devoted
to develop efficient and stable catalysts and eliminate or
control the two deactivation sources [7,17,19,29,30]. The
contemporary concept of catalyst design principally consists
in an understanding of the intrinsic role and property of each
catalyst component (active metal, promoter and support). It
takes a consideration into the complex synergistic effect from
the combined and mutual interaction of these components
[15]. The synergistic effect, deeply affecting important physi-
cochemical properties and reactions mechanism of catalysts,
must be subtly tuned for an optimal reforming performance
by advanced catalytic materials and analytical characteriza-
tions. These concepts were concretized by combining bi- or
tri-metal based, selecting supports with definite structure and
morphology, doping promoters with basic and redox property,
improving synthesis methods, regulating metal-support
interaction (MSI) or redox property and specifying the reac-
tion mechanism [7,17,19,29,30]. However, as highlighted the
abovementioned points, it is hard to realize a robust and
efficient catalyst and control the DRM mechanism basing on
the optimization of single synthesis variable in laboratory
studies.
In the end, we provide perspectives and highlight the
challenges of future researches on a long-term operation and
a scale-up application of DRM, for instance, the synthesis of
robust catalyst, the definition of reaction mechanism, the
tendency of the low temperature process and the improve-
ment of energy efficiency. This review summarizes research
progress in recent three years in the aspect of: (1) the devel-
opment of perovskite, pyrochlore, spinel and hydrotalcite
catalysts; (2) the application of new catalytic materials (h-BN,
Equations DH (kJ/mol) Mostly favored by
CH4þCO242COþ2H2 247 above 727  C
CO2þH24CO þ H2O 41 under 820  C
CH44Cþ2H2 74.9 above 527  C
2CO4C þ CO2 172.4 557  C~700  C
CO2þ2H24Cþ2H2O 90 under 527  C
CO þ H24C þ H2O 131.3 under 527  C
5856 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 5 8 5 2 e5 8 7 4
clay supports and MOFs) and (3) the probe of reaction mech-
anism by advanced characterizations, such as, in situ DRIFTS,
in situ XPS, TPSR and isotopic labeling experiments. Mean-
while, it also comprises of a brief introduction of improved
DRM processes without the thermodynamic limit, such as
plasma-, photo- and microwave-assisted types, and an
outlook for the future DRM development.
Active phases
It is generally established in literature that DRM proceeds via a
bi-functional mechanism such that nonvalent metal sites are
for CH4 dehydrogenation while basic sites for CO2 dissociation
are on basic support or promoters [31]. Catalysts with main
active metal phases including noble metals (Pt, Pd, Rh, Ir, and
Ru) and transition metals (Ni and Co) have been intensively
investigated towards a highly active and stable catalyst
configuration [17,32]. Different metals possess different met-
allicity and electron structure and further exhibit different
cleavage capacity of CeH and catalytic behavior for DRM. The
order of catalytic activity of main active metals is
Ru ~ Rh > Ni ~ Ir > Pt > Pd > Co [33]. Noble metal-based cata-
lysts are common in the heterogeneous hydrogenation/
dehydrogenation reactions all the time but still restricted for a
widespread and scale-up application due to the expensive
cost [12]. Although in the cheapest Ru-based catalysts, the
metal loading generally was less than 3 wt% [34]. In single
noble metal-based catalysts, minor even trace metal loading
provided a fine metal dispersion and sometimes sub-
nanoparticle size (2e3 nm), which brought about a high
initial activity and a coke-free feature at relatively low tem-
perature (700  C) [12], while gradually deactivated due to
metal sintering. However, Ni- and Co-based catalysts as cheap
alternatives have fascinated more researchers even if noble
metal catalysts intrinsically performed better in terms of
catalytic activity and coke-resistance [35]. Horlyck et al. [36]
ascertained the roles of Ni and Co in NiCo/Al2O3 catalysts with
10 wt% metal loading for DRM selectivity and demonstrated
that Ni was more active towards CH4 decomposition and Co
preferred to cause the Boudouard reaction. This was due to
the carbon affinity of Ni and Co from the electron deficiency of
3d orbitals. Analogously, Bian et al. [35] synthesized a series of
10 wt% NieCo phyllosilicates catalysts and investigated the
effect of Ni content on catalytic behavior. Decoupling NiCo
alloy synergy elucidated that Co was responsible for coke
removal via its oxidation and combined with Ni of the high
CH4 activity to provide a coke-resistance function. Therefore,
apart from metal sintering, remarkable coke deposition pre-
vails in Ni and Co-catalysts, which is a major obstacle to the
catalyst long-time running.
One strategy to facilitate CO2 dissociation and suppress
coke deposition is the modification of DRM catalysts by basic
promoters such as alkali and alkaline metals and rare earth
metals [37e41]. These promoters not only provide sufficient
basic sites but also regulate the catalyst microstructure and
the synergy or interaction among the catalyst components.
Rosset et al. [37] investigated the effects of Li, Na and K on
NieAl LDH-derived catalysts and found that acidity of the
catalysts decreased as the order of alkali metal cation size:
NiLi > NiNa > NiK. Meanwhile, Sun et al. [38] synthesized Mg
or Ca modified CoeCe/AC-N catalyst to obtain a stronger MSI
and a better metal dispersion. Additionally, Sr was selected by
Figueira et al. [39] as a basic promoter to prepared
CeSr@MWCNT/Co catalyst. Rare earth metals (La, Ce, Pr, Nd,
Sm and Y) have been favored by researchers in the last decade
and presented a prominent promotion effect due to the
introduction of abundant active surface adsorbed oxygen
species, the high oxygen mobility and the oxygen storage/
transfer capacity [41e43]. Bahari et al. [42] compared the in-
fluence of CeO2, La2O3, Y2O3, and Sm2O3 addition on the Co/
mesoporous Al2O3 (MA) catalysts and YCo/MA with a fine Co
dispersion and a stronger MSI showed the highest activity
owing to a superior oxygen storage capacity. The prominent
promotion and stabilizing effect of Y was also confirmed by
the works of Swirk’s group [43e47]. Other than alkali and
alkaline metals and rare earth metals, some reducible tran-
sition metal oxides such as ZrO2, TiO2, MnO2 and MoO3 have
been used as promoters to improve catalytic behavior and
reduce coke deposition since their high oxygen mobility and
the surface migration/decoration to metal sites [48e51].
Typically, Abdullah et al. [52] elaborated the structural effect
of Zr promoter on Ni/SBA-15 catalyst and 1 wt% Zr addition
significantly improved the Ni metal dispersion by the strong
metal-support interaction (SMSI) and the stabilizing effect and
avoided coke formation.
Crystalline oxide catalysts
Crystalline oxide catalysts have been fine options of the
catalyst configuration recently, as compared with the tradi-
tional precipitation or impregnation catalysts. The latter fea-
tures with metal precursors accumulating at the internal and
external surface of metal oxides or other ordered mesoporous
materials. Whereas in the former, the active metal atoms
were dispersed and accommodated in the bulk phase within a
well-defined crystalline structure, such as, perovskite, pyro-
chlore, spinel and layered double hydroxide (LDHs), as shown
in Fig. 1 [7,53e57]. Fig. 1 displayed the crystalline structure and
metal coordination environment of the crystalline oxides.
This characteristic of ordered solid solution assisted crystal-
line oxide catalysts away from some problems including the
crystal nucleation during a preparation process and the metal
aggregation during a calcination/reduction treatment. When
being in a reductive environment, the active metal restricted
in the host lattice would migrate from the bulk to surface and
form metal nanoparticles with a smaller size and a SMSI, as
described in Fig. 2. The schematic diagram and TEM images
clearly visualized the metal exsolution considered as a surface
confinement effect. The reduction phenomenon is generally
termed as metal exsolution. The exsolved metal nanoparticles
embedded in the surface of crystalline oxide parent perform
well in terms of the catalytic activity and stability due to su-
perior resistance to coking and metal sintering. Meanwhile, in
the polynary crystalline oxide systems, the incorporation of
multivalent metals and incompatibility of doped metal ion
radius necessarily resulted in the crystalline structure change
or lattice distortion, which brought about improvements in
surface redox property, basicity, oxygen mobility and oxygen
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 5 8 5 2 e5 8 7 4 5857

Fig. 1 e The crystalline structure schematics of (A) perovskite (ABO3), (B) pyrochlore (A2B2O7), (C) spinel (AB2O4) and (D)
hydrotalcite-like precursor ([M2þ1-x M3þx (OH)2]xþ[An¡x/n·yH2O]x¡). Reconstructed from Ref. [7,53e55].

Fig. 2 e The above diagram represents the process of metal exsolution. The below TEM-EDS images confirmed the exsolved
metal particle embedding in the support. Collected from Ref. Zhang et al. [56] and Ref. Carrillo et al. [57].

vacancy formation [58e60]. Besides producing an active and a proper redox or regenerative treatment because of a re-
coke-resistant catalyst, the reversibility of active metal exso- dissolution of active metal into the bulk parent and a self-
lution and the catalyst regenerability would be achieved after reconstruction of the initial crystalline structure [61]. Hence,
 5858
Table 3 e Highlights of recent advancements in crystalline oxide catalyst development for DRM.
Catalysts Preparation Reactor Temperature Time(h) CH4 CO2 H2/CO Key findings Ref.
method type ( C) conversion % conversion %
LaAl0.25Ni0.75O3 impregnation/ fixed-bed 800  C ~36 h ~75% ~75% ~0.8 Mesoporous perovskite formation by using an SBA-15 hard [33]
hardtemplate quartz reactor template;
the incorporation of Si into perovskite strengthening the
surface basicity
Mg(Ni, Al, Zr)O co-precipitation fixed-bed 750  C 5h ~85% ~90% ~0.9 The Zr addictive rearranging Ni crystallites into smaller [53]
quartz reactor aggregates;
The textural properties, reducibility of Ni species, materials

i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 5 8 5 2 e5 8 7 4
basicity
and thus their catalytic activity of the obtained samples in DRM
being dependent on the amount of introduced Zr
La0.46Sr Sol-gel fixed-bed 700  C 100 h ~34% ~36% ~0.56 Varying the reduction temperature to adjust the Ni crystallite [57]
0.34Ti0.9Ni0.1O3 combustion quartz reactor size
and obtain a bimodal size distribution; the small exsolved Ni
particles (~2.5 nm) contributing to coke resistance
LaCu0.55Co0.45O3 sol-gel U shaped tubular 700  C 55 h ~63% ~61% 1 Stable and small CoCu alloy formation; metal-perovskite [63]
fixed-bed interaction enhancing the resistance to coking and metal
quartz reactor sintering; the lattice oxygen species in perovskite favoring
the activation of CeH
LaNi0.2RexFe0.6O3þd sol-gel fixed-bed 750  C 1h ~40% ~50% ~0.8 Binary Re-Ni-Fe alloy formation via a solid phase [67]
quartz reactor crystallization path; Re improving the activity of Ni;
The SMSI inhibiting the evaporation of Re at DRM conditions
CoeAl spinel sol-gel fixed-bed 750  C 24 h ~80% ~87% ~0.9 Amorphous CoeAl oxide formation under 500  C calcination [69]
quartz reactor and crystal CoeAl spinel formation with embedded Co0
particles
under 750  C reduction.
Co/MgeAl-Ox co-precipitation fixed-bed 750  C 15 h e e ~1 The incorporation of Mg into spinel provoking an inverse [70]
quartz reactor structure and
change the basicity and reducibility of catalyst; Co being active
with
MgeAl-Ox support due to a close CoeMg interaction
Ni/Al2O3 atomic “clam 700  C 60 h ~60% ~45% e The NiAl2O4 slowly reduced at DRM condition and releasing the [71]
layer deposition -type” furnace activity
to prolong the life-span
Ru/Sm2Ce1.8O7d Sol-gel fixed-bed 700  C 24 h ~70% ~70% e The Ru incorporation resulting in the lattice construction and [61]
combustion quartz reactor oxygen
vacancy rearrangement; The catalyst restoring the initial
pyrochlore
structure via a redox treatment 700  C
Co/Mg(Al)O co-precipitation fixed-bed 750  C 200 h 86.70% 92.70% 0.85 Co/Mg(Al)O being a potential catalyst for low-temperature CH4 [83]
quartz reactor eCO2
reforming
Ni3Fe1Cu1-MA co-precipitation fixed-bed 650  C 20 h ~15% ~35% ~0.5 Stable NieFeeCu alloy inhabiting the dealloy phenomenon; the [85]
quartz reactor addition
enhancing the interaction among metals and restricting the Fe
segregation
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 5 8 5 2 e5 8 7 4
the catalysts with superior performance and unique charac-
teristics were compiled in Table 3. There are eleven Ni-, Co-
and Ru-based crystalline oxide catalysts prepared by different
methods and modified by various promoters. In the reaction
conditions of 600e800  C and CH4/CO2 ¼ 1, Co/Mg(Al)O cata-
lyst synthesized by co-precipitation method presented the
highest conversion of CH4 and CO2 at 700  C, which were
86.70% and 92.70%, respectively. Meanwhile, the catalyst
successfully stood a 200 h stability test. Without regard to the
influence of preparation methods and promoters, the crys-
talline oxide catalysts with a good sintering and coke resis-
tance, gave relatively high activity and robust stability, which
resulted from the fine metal dispersion and SMSI.
Perovskite catalysts
Perovskites are generally regarded as a combination of two or
more simple oxides with a cubic structure and a high melt
point, which requires a calcination temperature above 750  C
to drive the solid phase reaction [33,62]. They have a formula
of ABO3, where A site (12-fold coordination) represents the
rare earth and alkaline-earth metals with a larger ion size,
taking charge of the thermal stability and basicity, and B site
(6-fold coordination) is for the transition metals with a small
ion radius and reducibility, providing the metal sites and
catalytic activity [63,64]. The perovskite catalysts are common
in the contemporary DRM studies due to its unique charac-
teristics: (1) high oxygen storage capacity and oxygen mobility
from the bulk lattice; (2) flexible composition by a partial
substitution to A or B site with other elements; (3) tunable
redox property by a control of their valency, oxygen vacancy
and stoichiometry [65,66]. Carrillo et al. [57] prepared a double
perovskite-type catalyst La0.46Sr0.34Ti0.9Ni0.1O3 via a gel com-
bustion method, possessing a bimodal size distribution of Ni
metal nanoparticles. The superior coke resistance of the
catalyst was closely correlated to the small Ni particles
(~2.5 nm) with a SMSI. The homogeneous alloy phase could be
obtained by a metal exsolution of LaCu0.55Co0.45O3 perovskite
and a simultaneous reduction of the two metals in the B site,
as referred to the work of Touahra et al. [63]. Similarly,
Zubenko’s group prepared a non-stoichiometric LaNi0.2Rex-
Fe0.6O3þd precursor with a substitution of multivalent Re to its
B site. The metals in the B site jointly exsolved, leading to alloy
particles formed and socketed into the support [67]. The so-
called solid-phase crystallization induced a SMSI and
restricted evaporation of Re, thus enhancing catalytic activity
and stability. However, it is hard to ignore the intrinsic
shortcoming of perovskites, which was expressed as bulk
particles with a lower surface area (<10 m2/g) and difficulties
to the sufficient exposure of metal sites and the internal and
external mass transfer. In order to overcome this problem,
Ruan et al. [33] attempted to synthesize a mesoporous
LaAl0.25Ni0.75O3 perovskite by using SBA-15 as a hard template
agent. After a removal of the hard template, the perovskite
maintained a good mesoporous structure (above 200 m2/g).
SBA-15 effectively inhibited the phenomenon of perovskite
aggregation via its confined channels, thus favoring a higher
metal dispersion. Additionally, the residue and incorporation
of about 5.7% atomic Si in the perovskite lattice were
5859
unavoidable, provoking the lattice distortion and basicity
strengthening, which promoted the MSI and the adsorption
and dissociation of CO2 for the sake of the resistance to coke
and metal sintering.
Spinel catalysts
The spinels are enthralling bulk catalysts derived from a
group of binary crystalline oxide with a form of AB2O4. The
divalent transition metals (Ni, Co and Cu) were introduced to
the A site in tetrahedron center for providing metal sites, and
the trivalent Al was accommodated in the B site in octahedron
center for supporting robust thermal stability [68]. The spinel
preparation was similar with the perovskite in term of ther-
mal treatments and difficult to obtain a pure or stoichiometric
phase due to a spinel structure inversion. The non-
stoichiometry or partial substitution of A site metals may
cause the occupation of Al ions on the A site instead of the
normal octahedral B site. Whereas in the reduction process,
the exsolution of A site metals also triggered the lattice ion
rearrangement and oxygen vacancy arose at the crystallite
surface. The spinel was inert for DRM unless properly reduced
at high temperature. The A site metals reduced and segre-
gated to the surface and became small metal crystallite
embedded in the depleted A site metal spinel for a “stabilized”
state. Obviously, the reducibility was significantly vital for the
catalytic activity and subjected by the specific composition
and morphology such as crystallinity, surface area and A site
metal coordination environment. Recently, Wong et al. [69]
conducted DRM on a series of amorphous CoeAl oxides with a
lower Co loading prepared by the sol-gel method. Upon 750  C
reduction temperature, the oxides were crystallized and the
exsolved Co particles were formed embedded on Co deficient
spinel, which controlled the Co particle size and provided a
balance between the catalyst reducibility and the SMSI. The
effects of metal coordination environment on the MSI, surface
basicity and intrinsic activity were probed by Alabi et al. [70].
The XANES technique was used to characterize the metal
coordination in the Mg incorporated CoeAl and NieAl spinels.
The results showed that octahedral Mg and an inverse spinel
structure appeared, leading to a higher Co metal dispersion, a
strong MgeCo interaction and basicity, which were respon-
sible for a better conversion rate and a resistance to deacti-
vation. The synthesis method also plays a vital role in the
homogeneous distribution and coordination of metals, thus
affecting the catalyst properties. Boukha et al. [71] thoroughly
characterized and compared two typed of NieAl spinel pre-
pared by the co-precipitation and co-dissolution methods,
thus found that the latter was more pure or homogeneous and
had an inverse structure (Ni1-xAlx [NixAl2-x]O4). The octahedral
Ni was more reducible than tetrahedral one, producing ho-
mogeneous and monodispersed Ni crystallite to minimize the
acidity of Al substrate and enhance the efficiency and stability
of DRM. The novel synthesis method such as atomic layer
deposition was likewise applied to NieAl spinel preparation as
reported by Littlewood’s group [72]. About 2 wt% Ni was
coated on the commercial Al2O3 substrate and formed a sur-
face layer of NiAl2O4, which reduced under DRM conditions,
thus slowly releasing and increasing catalytic activity.
5860 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 5 8 5 2 e5 8 7 4
Pyrochlore catalysts
The cubic pyrochlore-type oxides catalysts (A2B2O7) have
attracted attention of researchers due to its superior thermal
stability, oxygen ions conductivity and massive oxygen va-
cancies, especially in the case of the rare earth composite
oxides materials [73]. In the cubic structure (Fd3m), the A site
(8-fold coordination) is normally a trivalent rare earth metal
with a large radius, and the B site holds a transition metal with
a small radius [74,75]. It is intensely reported that the partial
substitution of A or B site dramatically improved the catalytic
performance of materials, originating from the changes in
crystalline structure, physicochemical properties and activity-
structure relationship [76]. The isomorphic substitution not
only arouses the electron transfer effect and subsequently
prevents the exsolved metal sintering, but also alters the A-O
and BeO bond energy and provokes the lattice distortion and
lattice oxygen release. Typically, in the report of Müller et al.
[61], the defective fluorite type solid solution Sm2RuxCe2xO7
exhibited a complex defect structure and crystalline compo-
sition by means of in situ XAS-XRD and ex situ XAS. The
exsolved Ru particles with a small size (1e2 nm) were
anchored on the C type solid solution Sm2Ce1.8O7d via a
process of phase transformation and oxygen vacancy rear-
rangement. It is also underlined that the original pyrochlore
structure can be restored more than twice by the re-
dissolution of the exsolved Ru particles during an air oxida-
tion above 700  C, meaning an ideal self-reconstruction
property and catalyst regenerability.
Layered double hydroxide catalysts
The LDHs were expressed as the formula of [M2þ1-x M3þx
(OH)2]xþ[Anx/n$yH2O]x, and deemed as a classical two-
dimensional anionic clay with intercalated anions and
brucite-like layers. The weak bonding of interlayer renders
LDHs with flexible structure and expanding properties. The
LDHs with layer structures were generally synthesized by urea
hydrolysis, co-precipitation, hydrothermal synthesis, and sol-
gel methods and can host various type of di-, tri- or even
tetravalent cations, where M are metal cations, An represents
the compensation anion in interlayers, i.e., carbonate, bicar-
bonate and nitrate, and y is the hydration degree [77,78].
Generally, the di- and trivalent metals were selected from Ni,
Co, Zn, Cu, Mg, Al, Ce, La, Fe and the noble metals, respec-
tively. Depending on the diverse metal ion assembly and
calcination treatments, the LDHs as a catalyst precursor
would inevitably decompose into a solid solution or an oxides
mixture containing spinel or periclase phase as reported by
Daza et al. [79e81]. There is a fine tunability for the essential
features such as metal particle size, MSI, acidity/basicity and
surface area [82]. Jiang et al. [83] produced a hydrotalcite-
derived Co/Mg(Al)O catalyst with an excellent activity and
stability for the low temperature DRM (500  C), which achieved
about 18.2% and 29.5% of CH4 and CO2 conversions at equi-
librium, respectively. It originated from the small metal par-
ticles (~10 nm) separating from the Co/Al incorporated MgO
solid solution. The similar low temperature activity and
resistance to coking and metal sintering also be observed on
the Zr promoted Mg(Ni, Al)O mixed oxides catalyst as reported
by De˛bek et al. [53]. The incorporation of Zr remarkably
modified the texture, basicity and reducibility and Ni species
distribution in the obtained material. De˛bek’s group also
explored the influence of Ce/Zr molar ratio on the catalytic
performance of NiMgAl LDHs derived catalysts [84]. The Ce/Zr
ratio dominated the catalysts properties (basicity, reducibility,
texture etc.) and brought about an increase in strong basic
sites for a stability improvement. Meanwhile, the
hydrotalcite-like precursor was a proper choice for realizing
the stable and homogeneous alloy catalyst. For instance, a
steady NieFeeCu alloy catalyst was reported by Jin et al. [85]
and it featured a good resistance to dealloy phenomenon. The
alloy phase stability was powerfully supported by a close
interaction of Cu with Ni and Fe. For overcoming the poor
thermostability and the heat/mass transfer limitations of
LDHs, it is also worth to note that some new design of LDHs
derived catalysts, such as LDHs layers confined or grown on
other matrix (h-BN and FeeCreAl-Nanofiber) and 3D LDHs
synthesis, like yolk-core structure [78].
Summary and prospect for crystalline oxide catalysts
Crystalline oxide catalysts are easily prepared, low-cost and
reproducible. There is no a boundary between active metals
and support due the active metals accommodating in the host
lattice. As compared with the supported catalysts prepared by
the traditionally industrialized methods (precipitation or
impregnation), it commendably avoids the concentration
gradient of metal precursors and subsequent metal aggrega-
tion, low metal dispersion, improper MSI and unsatisfied
catalytic life-span. During a reducing atmosphere, the active
metal in the host lattice spontaneously exsolved to surface
and formed fine nanoparticles, where the base of nano-
particles firmly embedded on surface of the support or resid-
ual parent with a SMSI. Meanwhile, the unreducible metals or
rare earth metals in the host lattice inevitably rearranged to
adapt to the absence of active metal, leading to an oxygen
vacancy formation and oxygen transfer improvement. This
reduction strategy both minimized the metal particle size for
obtaining more active sites and achieved a synergistic effect
between the active site and support having surface oxygen
transfer. This type catalysts markedly revealed superior cat-
alytic activity and stability even if in a low temperature con-
dition. However, some inherent shortages such as low surface
area, poor reducibility and low atom utilization, existed in the
catalytic material. These issues are ascribed to the nature of
an ordered solid solution formed by a solid phase reaction at a
high calcination temperature. The compact and non-porous
solid solution was difficult to provide a large contact area for
reaction medium access and metal dispersion for a better
mass transfer and catalytic efficiency. In term of reducibility,
the more pure or large-sized the solid solution is, the more
unreducible the active metal in the bulk is, in which a pure
bulk NiAl2O4 is completely reduced above 900  C. In order to
obtain fine metal particles, the metal exsolution process
necessarily remains partial active metal remaining in the
parent to sustain the SMSI at the expense of a 100% atom
utilization. It is quite adverse for non-noble metals due to its
low intrinsic catalytic activity and requirement for high metal
loading as compared with the noble metals.
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The contemporary catalyst design and synthesis are al-
ways an art, which balances various physicochemical prop-
erties to realize a compromise among catalytic activity,
selectivity and stability via a control of different synthesis
variables. The modification of synthesis method and catalyst
configuration is crucial for the studies of crystalline oxide
catalysts. Some reports have provided new insight into the
improvement in this type of catalyst, for instance, meso-
porous catalyst preparation using a hard template (SBA-15 or
A520-MOF), incorporation of proper noble metals or Cu for a
better reduction behavior via hydrogen spillover effect and Ce
incorporated hydroxyapatite serving as a support of single-
atom Ni-based catalyst [33,86].
New materials for DRM
Recently, some new materials for the catalytic studies, espe-
cially for DRM, were introduced to develop a novel and
promising catalyst and overcome the poor durability of the
base metal catalysts, which extends the options for the ma-
terial of catalysts preparation instead of being restricted to the
traditional metal oxides. Among them, two-dimensional
hexagonal boron nitride (h-BN) nanosheets, low-cost nature
clay and metal organic frameworks (MOFs) were prominent in
the attempts of application of new materials in the robust
catalysts with a strong resistance to coking and metal sin-
tering [87e101]. No matter 2D h-BN nanosheets or MOFs have
been continually applied in the field of electrochemistry due
to their electrical conductivity, but itself is of deficiency in the
catalytic reforming activity. So do the economic and envi-
ronmental clay in the aspect of catalytic activity. When active
metals were doped with these inert materials, the metals
interacted with the support in the form of charge transfer,
surface defects anchoring, metal-support interface and sur-
face nanostructure reconstruction. These MSI phenomena or
components synergies have a positive effect on the catalytic
performance by optimizing the metal reducibility and
dispersion, catalyst redox property and reactants adsorption
and activation. This perspective paves the way of the design of
Ni- or Co-based catalysts for a superior activity and
deactivation-resistance. Some of the latest reports investi-
gated how to explore the new materials for their application in
DRM, are shown in Table 4.
Fig. 3 e Proposed DRM reaction mechanism over 2D interface confined Ni/h-BN catalyst. Collected from Ref. Zhang et al.
[88e91].
5861
Hexagonal boron nitride nanosheet
The 2D h-BN, an analogy of ultra-thin graphene prevailing in
heterocatalysis, possesses outstanding features, such as high
chemical and thermal stability and regulable 2D interface, in
charge of functions of surface chemistry and catalysis [88e90],
it has been demonstrated that h-BN with well-defined 2D
layers serves as a suitable support by confining metal parti-
cles. A surface defect engineering via ball-milling introduced B
or N atom defects (Bv or Nv), which well confined Ni nano-
particles and formed a defect-modified interface. In the
support-metal interface, the defects of Bv and Nv, acting as an
electron acceptor (Lewis acid) and electron donor (Lewis base),
respectively, could strongly influence the MSI via electron
transfer mechanisms and thus modify the electronic structure
of Ni to favor the adsorption and activation of CH4 and CO2.
The promotional mechanisms were strongly evidenced by the
results of in-situ DRIFTS, partial density of states and DFT
calculation, and termed by the authors as a taming 2D inter-
facial electronic effect, as depicted as Fig. 3. On that basis, the
authors explored a defect-confined Ni-based catalysts with
abundant terminal sites of exposed B atoms by sonication-
assisted alcoholysis and chemical peeling techniques. The
oxygen-terminated defect of armchair BN could serve as a
metal anchor site and a strong basic site for CO2 activation,
and provoked the regeneration of more B terminate sites and
BeO. The surface BeOH ceaselessly participated in the con-
version of carbonate species and CHx* species into formyl
species, and regenerated by the combination of new formed
*H and *O with the B terminal, thus continuously promoting
the CO formation and preventing coke deposition. The details
in reaction path and mechanism was highlighted in Fig. 3.
Meanwhile, a 2D nanocomposite catalyst (h-BN/(Ni,Mg)Al2O4)
was rationally designed and originally prepared by a
confinement strategy. The h-BN substrate provided an inter-
face confinement for a LDHs patch and prevented the collapse
of the LDHs derived (Ni,Mg)Al2O4 mixed sheets. The interface-
confined periclase phase derived the SMSI, suppressing the
sintering of highly dispersed Ni. The interface confinement
and the SMSI primarily contributed to the excellent activity
and stability of the catalyst and the regenerated catalyst.
These reports for 2D h-BN confined Ni-based nanocomposites
clearly exhibited that the catalytic properties of catalysts
directly depended on the extent and form with which the
 5862
Table 4 e The comparison of catalysts derived from h-BN, clay supports and MOFs.
Materials Unique features Catalysts Preparation Temperature Time CH4comversion CO2comversion H2/CO Ref.
method ( C) (h) % %
h-BN Ultrathin 2D nanosheets, rich-defect Ni/h-BNNS ball milling and 750  C 120 h ~88% e ~0.9 [88]
on the surface, interface confinement, impregnation
the BeOH at the h-BN edges acting as

i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 5 8 5 2 e5 8 7 4
active site
Ni/d-BN sonication-assisted 750  C 125 h ~86% ~92% 1.06 [89]
alcoholysis and
chemical peeling
NiMgAl/d-BN co-precipitation 750  C 20 h ~85% ~95% ~1.1 [90]
Kaolin Hydrated layered aluminosilicate, Ni/ATK or Ni/BTK ions exchange 700  C 20 h ~45% ~58% ~0.8 [93]
low-cost and environmental
Attapulgite Fiber-like and rod cluster morphology, NieAl/Attapulgite co-precipitation 700  C 120 h ~100% ~95% ~1.0 [94]
Fe in the frameworks alloying with
supported Ni species
Halloysite hollow nanotube structure, halloysite Ni/Halloysite molten salt and 750  C 15 h ~90% e ~1.1 [95]
nanosheets with defects from an sheets impregnation
exfoliation process
Illite lamellar structure, Fe in the 10Ni15Ce/Illite co-impregnation 800  C 25 h ~70% ~70% ~0.9 [96]
frameworks alloying with
supported Ni species
MIL-53 high surface area (>1000 m2/g), Ni/AlMIL incipient wetness 650  C 100 h ~75% ~80% ~1.1 [98]
inserting the Ni precursor in the impregnation
frameworks as a template and
support precursor
UiO-67 high surface area (>2000 m2/g), PtNP@UiO-67 impregnation <400  C e ~54% ~43% ~1.0 [99]
stabilizing and behaving well in
the DBD-plasma DRM conditions
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 5 8 5 2 e5 8 7 4
Fig. 4 e The TEM images of the clay supports corresponding to (A) sepiolite, (B) halloysite, (C) attapulgite, (D) kaolin, (E) illite
and (F) montmorillonite. Collected from Ref. [92e97,102].
support interacts with active metal or other constituent
components. Doing so requires profound, comprehensive and
progressive understanding of the synergy effect of the catalyst
components at atomic and electronic levels using state-of-
the-art experiment design, material characterization and
DFT calculation. It has strong use for reference to the re-
searchers of developing defect-rich 2D catalytic material
whether in the actual operation or theoretical foundation.
Natural clay supports
Till now, among these support materials preferentially
considered for DRM, mesoporous supports such as molecular
sieves, metal oxides and carbon materials were commonly
investigated. However, the structure degradation, phase
transformation, recycling issue and price factor on the sup-
ports are always enormous challenges in the application of
these materials in large-scale commercialization. Further-
more, the complicated synthesis procedure with various
chemical reagents at a laboratory level inevitably involved
with the pollution risk and precluded their further application.
Thus, there is an urgent voice for a cheap, environmental and
highly stable catalyst. One material that fit this definition, but
that was not deeply explored yet in nature clay minerals, for
instance, sepiolite, montmorillonite, attapulgite, illite, kaolin
and halloysite [92e97,102]. The TEM images for their specific
morphology and fine metal dispersion were shown in Fig. 4.
These highly hydrated and crystalline silicate clays generally
feature as lamellar-like or fibrous-like morphology due to its
unique 2:1 or 1:1 type microstructure. For instance, raw
5863
sepiolite (SEP), defining as Mg8Si12O30(OH)4(OH2)4$8H2O in
theory, actually possesses a Si/Al tetrahedral double chains
bridged by Mg/Al in octahedral coordination and assembles a
sandwich-like structure that has some Kþ or other heteroatom
trapped in Si/Al tetrahedral interstices to keep charge balance
[102]. The unique microstructure renders the clays with many
special properties, such as ion adsorption capacity, chemical
and thermal stability and unique interlayer space. But the
clays are almost inactive or passivated since it naturally
formed. The clays must be activated via chemical (acid or al-
kali), thermal and mechanical treatments prior to act as a
catalyst support for the purpose of purification, opening
interlayer space and providing metal anchoring sites.
The exploration of kaolin as Ni-based catalyst support was
carried out by Ayodele et al. [93], in which the key factors were
chemical activation and calcination temperature. The results
manifested that acid activation facilitated an increase of Si/Al
ratio in kaolin and transformed the morphology from stacked
layered sheets into disordered arrangement for an increased
porosity, while alkali treatment converted the kaolin into a
zeolitic material. As the calcination temperature increased,
there was a loss of basicity and an increase of Ni particle size
in the catalysts, cumulatively affecting the conversion rate
and syngas yield. Liu’s group also focused on the modification
effect of various promoters (La, Al, Cu and Fe, etc.) on Tunisian
clay supported Ni based catalysts [103,104]. Similarly, Chen
et al. [94] prepared an Al promoted Ni/attapulgite catalyst with
a high Ni dispersion and a strong interaction among Ni, Al2O3
and attapulgite. The catalyst achieved a best activity for DRM
at 700  C and reached a CH4 conversion of roughly 100% and
5864 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 5 8 5 2 e5 8 7 4
H2/CO molar ratio of 0.98 under a 140 h test. In order to further
improve the basicity and MSI of the clay catalysts, the basic
promoters or active metals were homogeneously incorporated
into the clay microstructure and dispersed within the clay
matrix through a pillar method just as that the montmoril-
lonite with high interlayer space confined and immobilized Ni
particles [92,97]. It is also worth to note that the combination
of the molten-salt exfoliation method and ball milling effec-
tively transformed the halloysite with hollow nanotube fea-
tures into a few-layer material and exposed more active sites
and defects. Lu et al. [95] found that abundant surface defects
in the tailored halloysite nanosheets confined Ni particles
together via a charge transfer and boosted the CO2 activation
and *O species formation, thus leading to a highly dispersed
Ni particles with a SMSI and a strong coke-resistance.
The Si-rich or Al-rich clays have intensively attracted the
attention of researchers due to its special morphology and
physicochemical properties. The necessary pretreatments for
the clay endow it the possibility of working as a proper DRM
catalyst support. For utilizing the clay support in depth, a
surface reconstruction strategy of the clay was proposed to
synthesize an order mesoporous structure using the clay Si
source or produce a CoeAl spinel phase using the clay Al
source. In the perspective of economy and industrial potential
of catalytic materials, take the case of attapulgite, the unit
price was about 200 USD per ton, which was only 1/200 of the
unit price of SBA-15 [105]. The spinel catalysts and ordered/
hierarchical porous material were synthesized by common
solid-phase reaction method and hydrothermal method,
respectively. The greater effort of researchers should be
devoted to this orientation due to a consideration to the cat-
alytic performance and the cost of scale-up application. This
economic and environmental strategy could accurately tune
the nanostructure and ingredient of the clay supported cata-
lysts, which is significantly beneficial to the catalytic activity
and stability.
Fig. 5 e (A) Schematic diagram of the MIL-53 MOF preparation route of the NieAl catalyst; (B) The combination of the DBD
plasma reactor with PtNP/UiO-67 catalyst. Reconstructed from Karam et al. [98] and Vakili et al. [99].
Metal organic frameworks
Metal organic frameworks (MOFs) are fascinating and versa-
tile porous materials for its infinite possibility of the frame-
works design. The regular assembly of metal clusters
connecting to the another by multifunctional organic linkers
constructed a highly porous hybrid structure. By the devel-
opment of MOFs with superior properties, such as high
porosity (>1000 m2/g) and high adsorption ability, catalysts
based on MOFs have shown a good performance in the het-
erocatalysis, such as liquid phase hydrogenation and oxida-
tion or CO catalytic oxidation [98e101]. However, considering
the thermal condition of DRM (>600  C), the MOFs with a poor
thermal stability (<400  C) rapidly degraded along with a
structure collapse and unlikely survived, and therefore the
support precursor seems to be a suitable choice for the use of
MOFs in DRM. In the work of Karam et al. [98], as depicted in
Fig. 5, the MIL-53 (1130 m2/g) as a support precursor and a hard
template intimately mixed with the Ni precursor at the step of
impregnation, in which the Al-OH groups and pores in the
MOF framework anchored the Ni precursor. After a 500  C
calcination in air, a porous NieAl solid solution formed and
enabled a fine dispersion and an immobilization of Ni species
within the porous lamellar g-Al2O3, leading to an outstanding
catalytic stability with no loss of activity during a 100 h reac-
tion. The report revealed the MOF could be used as a sacrificial
template and porous host to stabilize metal species and obtain
fine Ni particles, which was analogous to the non-porous
perovskite or LDHs [101]. But what is interesting is that the
MOFs material directly serves as a chemically and thermally
stable support in a particular case. Vakili et al. [99] performed
the plasma-assisted dry reforming over PtNP@UiO-67 catalyst
(Fig. 5), breaking through the thermodynamical limit of the
DRM by the energetic electron activation of reactant mole-
cules rather than the traditional thermal activation. The
highly porous UiO-67 (>2000 m2/g) was stable under plasma
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 5 8 5 2 e5 8 7 4
conditions and favored to a dispersion of fine Pt particles.
More importantly, the UiO-67 facilitated the plasma formation
and surface discharges in the discharge zone, coupling with
the Pt particles to enhance the CH4 and CO2 conversion and
syngas production.
Advanced technologies for revealing DRM
reaction mechanism
The activation of CH4 on metal sites and activation of CO2 on
basic sites or defects smoothly propel the process of DRM and
keep a balance between the dissociation rates of reductant
and oxidant in the reaction medium. This calls for a profound
and detailed understanding of, among others, (1) the reactants
how to preferentially interact with surface sites of catalysts;
(2) the fast evolution to key intermediate species from the
reactants adsorbed on active sites and (3) the persistent for-
mation of target products through the combination and con-
version of the adsorbed intermediate species. Although these
mechanisms are more currently studied and understood by
means of some ex situ characterizations under a static
perspective, an increasing attention is focused on a more ac-
curate and real-time tracking for the evolution of reaction
species on catalyst surface by in situ characterizations under a
realistic or simulative DRM condition. There is a surging trend
in the contemporary studies, i.e., the techniques of in situ
DRIFTS, in situ XPS, TPSR and isotopic labeling are used to
establish an authentic reaction mechanism model. These
techniques powerfully elaborate the activity-structure rela-
tionship, the causes for outstanding catalytic behaviors and
the insight into design rules of highly efficient and stable
catalyst.
Fig. 6 e In situ DRIFTS spectra of (A) CO2-TPD, (B) DRM reaction at 500  C for 10 min and (C) DRM reaction at 400e700  C on
NiMgAl/d-BN catalyst. (D) and (E) The DRM reaction mechanism and path. Reconstructed and modified from Bu et al. [90].
5865
In situ DRIFTS
In situ DRIFTS is a sensitive and efficient measurement for
probing the surface characteristics and mechanism pro-
cess of DRM over a specific catalyst. The test methods are
diverse, for instance, (1) monitoring the catalyst surface
reaction proceeding under DRM conditions; (2) the
temperature-programmed surface reaction after CH4 or
CO2 saturation adsorption and (3) the reaction of adsorbed
CH4 at catalyst surface with CO2 flow at a specific tem-
perature [17,106]. Therefore, the surface function groups,
active sites, key intermediate species and reaction path
could be ascertained by an analysis about bands evolutions
of relevant adsorption species in a time- or temperature-
spectra. Typically, Bu et al. [89] deduced a possible reac-
tion mechanism mainly by observing the evolution of key
intermediates over h-BN supported catalysts in an in-situ
DRIFTS spectra. As revealed by Fig. 6, the eOH species
(~3750 cm1) on the NiMgAl/d-BN catalyst surface could
transform the *CHx into *CHxO or formyl when the eOH
species rapidly consumed and regenerated. At the same
time, the adsorbed CH4 was dehydrogenized on Ni0 sites.
Whereas in the CO2 activation and surface oxygen
mobility, the two key intermediates like monodentate or
bidentate carbonates (~1520 cm1 or ~1625 cm1) remained
the strong adsorption state under a fluctuant temperature
and reaction time, indicating a good adsorption and acti-
vation capacity of the catalyst for CO2. As the temperature
increased, the bands of CO (~2170 and 2130 cm1) gradually
strengthened due to the fact that the carbonate reacted
with *H and decomposed to formate and *O, and the
formate further dissociated to CO and *OH. Meanwhile, the
*O/*OH species constantly combined with the *C or surface
5866 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 5 8 5 2 e5 8 7 4
coke formed from the CH4 dehydrogenation and *CHxO
disassociation to form *CHxO, which then decomposed
into CO and *H. The authentic formate/carbonate reaction
path was summarized in Fig. 6(E) and well accepted. It is
note that a quantitative analysis conducted over a com-
bination of in situ DRIFTS and mass spectroscopy is
benefited for a more incisive understand of the reaction
mechanism.
In situ XPS
In situ XPS is generally considered as a means, providing a
surface-sensitive information regarding to element
chemical states and surface species on catalysts during a
specific atmosphere [18,27,107]. The researchers often
omit the latter function. Senanayake’s groups observed the
CO2 adsorption and activation on the Ce3þ and Ru sites for
the Ru/CeO2 system by the analysis of temperature-
resolved spectra in Fig. 7(A) [18]. Likewise, in the Co/CeO2
system, the identical phenomenon on the catalyst surface
with a slight oxidation also appeared due to the CO2
dissociation [27]. All of those show that in situ XPS offered
the possibility of monitoring the reaction on catalytic
surfaces. Wu et al. [107] employed the characterization to
test the surface reactivity of Ni/Al2O3 and NiCo/Al2O3 cat-
alysts. As the temperature-programmed experiments
implemented with a frequent atmosphere switchover, the
comparison of Co and Ni sensitivity to CO2 and CH4 was
shown in Fig. 7. Average valence states of Ni and Co in
these catalysts would fluctuate sharply because of the H2
or CH4 reduction and the CO2 oxidation. By observing quick
responses of valence states to gas reactants switchover, it
implied that, in NiCo/Al2O3 catalyst, the gap of valence
state in Ni species was more pronounced. The results
confirmed the alloy catalyst with a stronger CO2 dissocia-
tion capacity and the Ni as a main component for CH4/CO2
activation.
Fig. 7 e (A) Ce 3d and C 1s þ Ru 3d regions of the in-situ AP XPS spectra of the Ru/CeO2 catalyst. (B) Average valence state
change of Ni and Co in Ni/Al2O3 and NiCo/Al2O3 catalysts within different treatment steps. Collected from Senanayake et al.
[18] and Wu et al. [107].
Temperature program surface reaction
TPSR is commonly conducted over an apparatus like TPD
or a tailored reactor with a mass analyzer to investigate
the reactant dissociation behavior on catalyst surface
under a CH4 flow or consecutive CH4/CO2 alternating pul-
ses [83,108e111]. In the CH4-TPSR experiment (Fig. 8), the
estimation of CH4 dissociation capacity was through the
analysis of the peak and temperature window of CH4
consumption. But so do the subsequent product signals
such as CO, CO2, H2 and H2O. They are used for detecting
the contribution of surface active sites or species to the
CH4 dissociation. Zhang et al. [108] ranked the CH4 disso-
ciation capacity of a series of rare-earth metal oxides
(REMO) modified Ni/ZrO 2 catalysts by CH4-TPSR. They
found that the surface adsorbed oxygen species (SAOS)
from REMO promoters significantly accelerated the CH4
dissociation and gasified the residual carbon after CH4
dissociation. In term of the catalyst oxygen mobility, as
shown in Fig. 8, Theofanidis et al. [109] used a special
reactor for monitoring the CO2 flow formed during dozens
of CH4 pulse. It has verified that the incorporation of Fe
into MgAl2O4 endowed the material with redox properties,
which was based on the coke gasification capacity by
surface mobile lattice oxygen.
Isotopic labeling experiments
Isotopic labeling experiments, were operated on a reaction
unit with a mass spectroscopy or an apparatus such as FT-IR
and DRIFTS by utilizing the ultra-high purity labelled carbon
(13CO2 or 13CH4) and labelled oxygen (C18O2) to replace the
normal gas reactants. In Fig. 9, trails of the labelled atoms in
gas products or surface adsorbed species were exhibited by
mass profiles or FT-IR spectra [20,112]. In order to propose
an authentic DRM mechanism on the Ni/La2Zr2O7 catalyst,
Kumar et al. [112] carried out a series of isotopic labeling
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 5 8 5 2 e5 8 7 4
experiments and displayed a bifunctional mechanism, i.e.,
CH4 dissociated on Ni sites into *C and H2 and contributed to
the major coke, while the activation of CO2 occurred at ox-
ygen vacancies or metal-support interface and ruled out the
possibility of lattice oxygen involving reaction. Furthermore,
to detect the rate-determining step, Vogt et al. [20] switched
12
CH4 and 13CH4 to observe the blue shift of the adsorbed CO
and *CO peaks in the relevant FT-IR spectra on Ni/SiO2
catalysts due to the substitution of 13C to 12C in the two
species. No matter what size of Ni particles in the catalyst,
after the switching of 13CH4 flow, the peak of adsorbed *12CO
peaks was still obvious, indicating that the desorption of
*CO species adsorbed on Ni particles is more of kinetically
limiting factor.
Improvements for DRM reaction system
DRM is widely recognized as a strongly endothermic process
with a harsh thermodynamic condition and a complex redox
environment that prompts researchers all the time to focus on
the development of highly active and stable catalysts.
Although plenty of superior catalysts for DRM were reported in
the latest studies, the irreversible deactivation tendency
contributed by metal sintering and coke deposition seems to be
unavoidable. There is a synergy between the catalyst deacti-
vation issue and harsh reaction conditions. Therefore, viewed
from another angle, some researchers attempted to improve
the DRM system and make the reaction conditions milder and
towards to low temperature, such as plasma-, photo- and
microwave-assistant DRM [99,113e136]. These attempts
significantly increase the DRM reaction efficiency, alleviate the
catalyst deactivation to maximize the life-span during rela-
tively mild reaction conditions and open up new prospects of
the maturation and commercialization of DRM process.
Fig. 8 e (A) The signal profiles of CH4, H2, CO2, CO and H2O in the CH4-TPSR test over REMO modified Ni/ZrO2 catalysts. (B)
MgFexAl2¡xO4 oxygen mobility test: CO2 flow during CH4 pulses at 993 K. Collected from Zhang et al. [108] and Theofanidis et al. [109].
5867
Plasma-assisted DRM
Non thermal plasma is a promising choice to break through
the thermodynamic limit compared with the traditional
thermal activation of DRM, in which the dielectric barrier
discharge (DBD) plasma reactor was common in relevant
studies due to its simple structure without a vacuum condi-
tion [113]. In a typical DBD plasma reactor (Fig. 10), a HV
electrode is fixed at the coaxial center of a quartz or dielectric
tube and a ground electrode is coated on the outer layer of the
tube [114]. There is a space between the two electrodes for
discharge and catalysts packing. When operating at specific
voltage and AC frequency, the Ar gas of universal carrier
would ionize and release Ar plasma and high-energy elec-
trons. The energetic electrons collided with bulk gas CH4/CO2
molecules, leading to nonselective bond cleavage of the mol-
ecules and formation of reactive ions and free radicals. The
details in the DBD plasma system have been reviewed by
Khoja et al. [113]. With respect to the essential step of DRM, Tu
et al. [114e116] engaged in the research of plasma catalytic
CO2 conversion and considered CO2 dissociation as an ener-
getically inefficient process with a thermodynamic equilib-
rium limit of about 40e50%. As a novel and disruptive
technology, it liberates the DRM from a high temperature
environment and eliminated the deactivation dilemma of
active metal sites due to the aging and sintering. Vakili et al.
[99] originally applied the MOFs-based catalyst into the
plasma system and the combination exhibited outstanding
catalytic performance and an energy efficiency of ~55%. This
was due to the stable MOFs catalyst with well-developed
porous structure, favoring the filamentary microdischarge
and surface discharge and inhibiting the formation of C2 or C3
species. Chung et al. [117] selected a series of perovskite-type
photocatalysts to couple with the plasma system and revealed
that plasma could modify the photocatalyst surface and
5868 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 5 8 5 2 e5 8 7 4

increase the lifespan of electron-hole pairs for a higher syngas
production rate. NiTiO3 photocatalyst reached the 75.7% and
70.4% of CH4 and CO2 conversions at the conditions of 16 kV,
20,000 Hz and CH4/CO2 ¼ 1 and the highest energy efficiency of
18.5 mol/kWh was also achieved. The plasma-catalyst inter-
face or interaction was a vital contributor to facilitate the
formation of reactive intermediates and promote the system
efficiency. The catalysts were still the key to plasma system,
but the application of abundant catalysts to the plasma sys-
tem was not definitely instructive for the best choice of cata-
lysts. It relies on the reactor specification and reaction
conditions. The perovskite catalysts such as NiTiO3 and low
dielectric constant materials with specific morphology and
developed porous structure such as MOFs seems more suit-
able to the plasma system due to their plasma sensitivity.
Currently, the research hotspots mainly consist of the selec-
tion of packing materials or catalysts, the effect of catalysts on
discharge characteristics, the kinetic study and the increase in
of the system energy efficiency [27,119,120,127].
Photo-assisted DRM
The photocatalytic DRM could be an effective approach to
syngas production with an ultrahigh conversion beyond the
thermal system limitations [128,129]. Photo energy, originated
from photoexcitation of electron-hole pairs, drives DRM over
various semiconductors or light-harvesting catalytic mate-
rials. The lights with different wavelength finally converted
into a stable chemical energy [130,131]. Cho et al. [131]
believed that the visible-light-sensitive photocatalyst support
must be chosen from the P-type metal oxides with a narrow
bandgap and a high conduction band, such as ZnFe2O4,
CaFe2O4, and Cu2O. Whereas, Miyauchi et al. [130] reported a
Rh/SrTiO3 catalyst that can effectively enhance the DRM
process under the conditions of a UV-irradiation and a
controlled reaction temperature (<200  C). The study demon-
strated that the photogenerated hole contributed to methane
oxidation on SrTiO3 and the photoelectron facilitated CO2
reduction on Rh (Fig. 10). Isotopic analysis also deduced that
lattice oxygen species (O2) acted as an intermediate
throughout the reaction driving methane dry reforming.
Overall, the finds of Rh/SrTiO3 catalysts can be extended to the
DRM catalyst development for syngas production with a low
energy consumption via photon energy. Kulandaivalu et al.
[136] summarized the photocatalytic materials such as solid
basic oxides (ZrO2, MgO and b-Ga2O3), TiO2, ZnO2, g-C3N4 for
DRM and proposed the criterions of more light adsorbing
materials experimented to future studies: (1) proper band
structure matching the reduction potentials of intermediates,
(2) simultaneous activation of CH4 and CO2, (3) high light

Fig. 9 e DRM over Ni/La2Zr2O7 catalyst at 750  C under continuous flow of (A) 12CH4 before labelled 13CO2 introduction and (B)
12
CH4 before labelled C18O2 introduction. (C) TPO results of spent Ni/La2Zr2O7 catalysts. (D) Overview of CO and adsorbed *CO
peaks in FT-IR spectra during a pulsed experiment from 12CH4 to 13CH4 over Ni/SiO2 catalysts with different metal particle
sizes (500  C, 4:1 ratio of CH4/CO2 and atmospheric pressure). Collected from Kumar et al. [112] and Vogt et al. [20].
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 5 8 5 2 e5 8 7 4
Fig. 10 e (A) The schematic diagram of a DBD reactor. (B) The mechanism of photocatalytic DRM over Rh/SrTiO3 catalyst.
Collected from Wang et al. [118] and Shoji et al. [130].
adsorption efficiency, in particular visible light. Meanwhile,
precious Pt, Ag, Au, Rh, Ru and Ir could serve as effective
oxidation sites to photocatalytic CO2 reforming of CH4 due to
their role as an electron accepter. Despite the excellent per-
formance in photocatalytic system, the foremost challenges
in photo-assisted DRM have been identified as follow: (1) the
current reports only being restricted to the level of laboratory
microreactor; (2) the sensitivity of catalysts to the specific light
source and (3) a high energy consumption (100e1200 W) and a
low energy efficiency (<20%).
Microwave-assisted DRM
The microwave-assistant DRM has rapidly drawn attention
recently due to the instantaneity of microwave heating, the
decrease of reactant molecules activation energy and the
preservation of catalytic stability by coke deposition removal
[128e135]. The heating mechanism primarily depends on the
composition of the catalytic materials, which underlines the
importance of the material selection [132]. Li et al. [135]
selected bio-char modified by various additives as a proper
catalyst for the DRM due to its microwave susceptibility and
thermal stability. Similarly, a Ni/SiC catalyst stood out from
the work of Nigar et al. [133] and was able to achieved a 90%
conversion without an obvious deactivation in an activity test
at 800  C. Nguyen et al. [130] reviewed the guidelines of cata-
lyst design and summed up two types of catalysts including
carbon- and metallic-based catalysts. The desirable choice for
highly active and stable catalysts is either via in-situ growth of
5869
carbon films on metal-based catalysts (chemical vapor depo-
sition or pulsed laser deposition) or graphene supported metal
single atom catalysts (SACs). These strategies required the
reservation of microwave adsorption capacity of doped mag-
netic metals (Ni, Co and Fe, etc.) and the use of supports with a
high surface area and a heat dissipation property. However,
the development of microwave-assistant DRM still faces with
some dilemmas, such as the accurate measure of catalyst bed
temperature under microwave irradiation, the suppression of
the hot spot effect and the shortage in scaling-up ability.
Summary and outlook
In the foreseeable future, DRM is a promising and competitive
pathway for a conversion of the two greenhouse gases to
syngas as a valuable chemical feedstock, but not an industri-
ally mature process. As abundant studies have shown, a
profound understanding of the reaction mechanism and
structure-activity relationship was established at atomic level
by advanced characterizations. DRM is a heterocatalysis and
structure-sensitive reaction. CH4 dehydrogenation and sub-
sequent carbonaceous species conversion orderly proceed at
metal sites, which matched with a catalyst surface oxygen
spillover of CO2 dissociation at basic sites in terms of kinetics.
Given the strong endothermy and harsh reaction conditions of
DRM, many researchers attempted to seek a proper catalyst
with a superior activity, selectivity and stability, such as the
crystalline oxide catalysts (perovskite, pyrochlore, spinel and
5870 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 5 8 5 2 e5 8 7 4
LDHs). This type of catalysts could provide a high metal
dispersion and a surface confinement effect via a metal
exsolution strategy and the SMSI, and then constitute a potent
and cost-effective candidate due to a subtle synergy among
catalyst components. Meanwhile, some new materials (h-BN,
clays and MOFs) are also introduced to the catalyst design and
significantly extend options for the preeminent catalyst
formulation owing to their unique morphology and nano-
structure. However, only the continuous exploration of an
optimal catalyst is not enough to ensure a high conversion of
DRM in a long-term run although the catalysts with a finite
life-span possess a strong resistance to deactivation. Of
particular strategy is the improvement of traditional DRM,
such as plasma-, photo- and microwave-assistance instead of
the direct external heating, which dramatically break through
the thermodynamical limitation towards the low temperature
reaction. The combination of the robust catalysts and the
improved DRM systems seems a comprehensive method for
propelling the process maturation and commercialization.
In the quest for the process maturation and commer-
cialization, subsequent researches should focus on the
development of bimetallic or trimetallic Ni- and Co based
catalysts, especially the ones modified by trace of noble
metals, as these catalysts have proved a superior activity
and high resistance to deactivation owing to the synergy or
alloying effect. For given active metals, the consideration of
catalyst regenerability also ought to take up more share in
the rational design of catalyst configuration, such as the
self-reconstruction property of crystalline oxide catalysts.
The regenerability is an important indicator for catalysts in
a scaling-up application. But few relative researches have
been conducted in the aspect of a better understanding the
reaction and deactivation mechanisms and a maximization
of the catalyst life-span. In contemporary DRM catalyst
design and exploration, there is a comprehensive set of
characterization methodologies such as in-situ spectrum
technologies and in-situ electron microscope technologies
for giving detail information concerning the active sites, the
synergy effect among catalyst components and the contri-
bution factors to catalytic behavior. Parallel to these,
another advance in DRM studies is the reactor improvement
in a fix bed reactor system for increasing reaction efficiency
and operating stability. Solar reactor and membrane reactor
would be promising choices with emphasis on the promo-
tion of energy efficiency and the integration of target
product generation and separation.
CRediT author statement
Chunsheng Wang: Data curation, Writing-original draft,
Validation, Visualization, Investigation. Yishuang Wang:
Investigation, Data curation, Validation, Confirmation of
manuscript. Mingqiang Chen: Conceptualization, Writing-
review & editing, Supervision, Project administration.
Defang Liang: Investigation, Data curation. Zhonglian Yang:
Investigation. Wen Cheng: Validation, Resources. Zhiyuang
Tang: Investigation. Jun Wang: Investigation, Supervision.
Han Zhang: Investigation, Supervision.
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 funds of National Natural
Science Foundation of China (Grants No. 51876001 and No.
51906001) and China Postdoctoral Science Foundation Grant
(2018M642505).
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