DEVELOPMENT OF NANOSILICA-BASED

CATALYST FOR SYNGAS PRODUCTION VIA

CO2 REFORMING OF CH4: A REVIEW
Author panel : Chi Cheng Chong a b, Yoke Wang Cheng a b, Mahadi
B. Bahari a, Lee Peng Teh c, Sumaiya Zainal Abidin a d, Herma
Dina Setiabudi a d
Alamat URL :
https://www.sciencedirect.com/science/article/abs/pii/S036031992
0302329

Abstract
The alarming global warming issue has sparked interest in researchers
to mitigate greenhouse gas emissions via CO2 reforming of CH4 (CRM).
Regrettably, the main drawback of CRM is catalyst deactivation because
of coking and metal sintering. Therefore, exceptional resistance towards
coking and sintering is crucial to formulate viable CRM catalysts. This
article reviewed the latest development of nanosilica-based catalysts
(mesoporous nanosilica, dendritic fibrous nanosilica, green nanosilica,
and core@shell nanosilica) for CRM application. The physicochemical
properties of nanosilica supports could be modulated by synthesis
methods to improve their resistance towards coking and sintering.
Furthermore, this review compiled the influence of catalytic
properties of nanosilica supported catalysts, such as active metal
dispersion, crystallite size, acid-basic properties, oxygen
mobility, reducibility, porosity, and morphology on CRM. To conclude,
nanosilica supports with strong metal-support interaction,
homogeneous metal dispersion, appropriate crystallite size, and
moderate acidity/basicity, exhibited satisfactory catalytic activity,
thermal stability, and resistance towards coking and sintering. The
fundamental study and depth understanding on this catalysis field is of
worth in configuring robust catalysts for future industrial applications
success of CRM reaction with superb activity and carbon resistance for
CRM.

Graphical abstract
Introduction
The non-replenishable fossil fuels are unsustainable for the futuristic
huge energy demand urged by the exponentially growing human
population. Apart from non-renewability, unbridled combustion of fossil
fuels also imposes environmental threats by releasing oxides of sulfur
and nitrogen, volatile organic compounds, and greenhouse gases
(CH4 and CO2) into the environment. Indeed, there is an obligation to
source out for an alternative energy reserve as the surrogate for fossil
fuels. Contemporarily, valorization of greenhouse gases into combustible
fuels will be conducive to relieve global warming. To date, there are
several potential CH4- and CO2-utilizing routes, namely carboxylation
[1,2], CO2 methanation [[3], [4], [5]], CO2 splitting [6,7], and reforming
[[8], [9], [10]]. Among the aforesaid pathways, reforming is the most
attractive route since its product is syngas (mixture of H2 and CO) that
versatile for diverse applications. Syngas can largely contribute for
electricity generation, transportation fuel production, and replacement
for gasoline. Moreover, syngas serves as a vital chemical intermediate to
produce hydrogen via water gas shift, methanol via methanol synthesis,
alkanes via Fischer-Tropsch synthesis, aldehydes via hydroformylation,
and ethanol via fermentation [11]. Generally, the common reforming
technologies include steam reforming (SR), partial oxidation (POX),
autothermal reforming (AR), and dry reforming of methane (CRM).

CRM is applauded as a green approach since it converts both greenhouse

gases into valuable syngas. Unlike SR that gives high H2/CO ratio, CRM
able to produce syngas with ideal H2/CO ratio ≈1, which is best suited
for Fischer–Tropsch synthesis despite its higher endothermicity [12].
For CRM, the actual H2/CO ratio of syngas is appreciably influenced by
a secondary reaction known as reverse water gas shift (RWGS) [13].
Nonetheless, CRM technology with countless economic and
environmental merits is not yet ready for industrialization. The main
hindrance of CRM industrialization is the carbon-forming side reactions
(thermal decomposition of CH4 and Boudouard reaction) that deactivate
the reforming catalysts [14,15]. High temperature requirement of CRM
cannot avoid the occurrence of endothermic thermal decomposition of
CH4. Moreover, the absence of steam in CRM worsens coking
deactivation as char gasification (SR of deposited carbon) is not favored.
To investigate the feasibility of CRM, a pilot study on CRM was
attempted by The Linde Group in a pilot dry reformer at Pullach [16]. At
present, commercial reforming catalysts that are less prone to coking are
still underdeveloped. Therefore, promising CRM catalysts must be coke-
resistant to guarantee high catalytic performance and stability.

Although noble metal-based catalysts show outstanding catalytic activity

and coking resistance, their limited availability and high cost render
them inappropriate for industrial applications. Meanwhile, transition
metal-based catalysts, such as cobalt (Co), ruthenium (Ru), iridium (Ir),
nickel (Ni), platinum (Pt), and rhodium (Rh) are acknowledged as viable
CRM catalysts [14,[16], [17], [18]]. Ni-based catalysts are highly
recommended in lieu of noble metal-based catalysts with relatively
cheap price and comparable catalytic activity [5,13,19,20]. However, Ni-
based catalysts are more susceptible to coking and sintering, thereby
induces catalyst deactivation and flow blockage [[21], [22], [23]]. To
confront these issues, the pivotal point of CRM is to enhance metal
dispersion of catalysts by introducing promoters or thermal stable
supports [18,24,25]. The promoters can be classified into textural and
chemical (e.g., alkaline metals or alkaline earth metals) promoters, in
which the former facilitates well dispersion of active metals while the
latter bolsters catalytic activity [26].

Aside from the choice and loading of active metal, the type of supports is
also essential for satisfactory metal dispersion and good metal-support
interaction. The textural and physicochemical properties of supports are
vital to keep the catalyst resistant to coking [12,16,26]. High porosity and
surface area of supports generally allow good metal dispersion, which is
conducive to high catalytic activity and stability. Furthermore, the
interaction between active metals and supports may alter the stability
and reducibility of catalysts. The redox properties (surface acidity and
basicity) of supports are likely to influence the likelihood of side
reactions’ occurrence [27]. High thermal stability of support can impede
the sintering of active metals, whereas high oxygen storage capacity
suppresses coking by promoting the oxidation of deposited carbon [28].
For selective catalysis, other remarkable features of supports may
include chemical composition, wall thickness, and pore size [17].
Over these years, countless review articles [12,14,[16], [17], [18],29,30]
pertinent to CRM have been published with emphasis on catalyst type,
catalyst synthesis, Ni-based catalysts, influence of process parameters,
mechanistic and kinetic study, and coke suppression. To the best of
authors’ knowledge, there is no single review article that is solely
devoted to development and application of nanosilica-supported
catalysts in CRM. The recent employment of nanosilica supports in CRM
had received extensive attention by virtue of its high porosity (surface
area and pore volume) and tunable pore diameter [31,32]. Highly porous
nanosilica tends to furnish myriad catalytic sites for the adsorption of
CH4 and CO2, thereby securing a superior catalytic activity in CRM.
Today, multiple nanosilica supports are developed and applied in CRM,
specifically mesoporous nanosilica, dendritic fibrous nanosilica, green
nanosilica, and core@shell nanosilica. To fill the research gap, this
article meticulously reviewed the application of nanosilica catalysts in
CRM from the perspective of catalytic properties, synthesis routes,
catalytic performance, and resistance towards catalyst deactivation.
Additionally, this article has detailed the influence of active metal
dispersion, crystallite size, acidity and basicity, oxygen mobility, surface
area, and morphology of nanosilica supported catalysts on CRM.

Thermodynamic and mechanism of CRM

For CRM, understanding of its thermodynamic and mechanism is
beneficial to mitigate the coking issue and optimize the syngas yield by
tuning operating conditions, such as reaction temperature, partial
pressure, weight hourly space velocity, and feed ratio. The primary
reaction, CRM (Eq. (1)) is an endothermic reaction that favors high
temperature. Since CH4 and CO2 are highly stable reactants, the
endothermicity of CRM can be linked with high dissociative energies of
CH3–H (435 kJ/mol) and CO–O 

Synthesis method of nanosilica supports for modulation of

physicochemical properties
Mesoporous nanosilica, such as Mobil Composition of Matter No. 41
(MCM-41), mesoporous silica nanosphere (MSN), and Santa Barbara
Amorphous-15 (SBA-15) are widely used in CO2 reforming of
CH4 because of their interesting physicochemical properties. Regardless
of synthesis routes, there are three main elements in the preparation of
mesoporous nanosilica, namely silica precursor, surfactant, and catalyst
(either acid or base). Conventionally, mesoporous nanosilica is
synthesized via sol-gel

Nanosilica supported catalysts for syngas production via CRM

Table 1 summarizes the common types of nanosilica supports used in
CRM, together with their preparation details, textural properties, and
catalytic performance. Through sol gel method, Tian et al. [57] prepared
nanosized MCM-41 (diameter: 50 nm–200 nm) by using
cetyltrimethylammonium chloride (CTAC) and tetraethyl orthosilicate
(TEOS) as surfactant and silica source, respectively. After the
impregnation of 10 wt% of Ni, the Ni/MCM-41 could attain high
conversion of CH4 and CO2 (���4 = 72% and ��

Influence of catalytic properties of nanosilica supported

catalysts on CRM
The activities of metal-based catalysts are markedly influenced by the
textural and physicochemical properties of the supports, which have
been attributed to the active metals dispersion, crystallite size, acidity,
basicity, oxygen mobility, and surface area, as illustrated in Fig. 14.
Typically, the support itself is catalytically inactive, but it will partake in
the reaction when interacting with the active sites to increase the active
metal dispersion, strengthen the metal-support

Conclusion and outlook

CO2 reforming of CH4 (CRM) is an alluring process to convert
greenhouse gases (CH4 and CO2) to value-added syngas, but it is
underdeveloped due to significant catalyst deactivation (coking and
sintering). CRM is a highly endothermic reaction that occurs at
temperatures of >700 °C. Endothermic nature of CRM triggers the
occurrence of C-forming thermal decomposition of CH4, which can clog
the pores of supports and mask the active metals. Undesirable coking
deactivation reduces the accessibility