Catalytic Conversion of Greenhouse Gases

Osarieme U Osazuwa, University of Benin, Benin City, Edo State, Nigeria

Chin K Cheng, Universiti Malaysia Pahang, Gambang Kuantan, Pahang, Malaysia
r 2018 Elsevier Inc. All rights reserved.

Introduction

Indisputably, greenhouse gases emission has been unfavourable to the eco-system (Nabgan et al., 2016). Methane (CH4) is a
reactive trace gas readily available which can be obtained from natural and anthropogenic sources (University of Oxford, 1998).
It is the main constituent of natural gas (Zavala-Araiza et al., 2015). CH4 and carbon dioxide (CO2) are the main anthropogenic
gases present in the atmosphere (Lauder et al., 2013). The increased development of industries and the abundance of non-
renewable carbon and H2 sources have led to the growing reservoir of greenhouse gases. Generally, CH4 can be transformed into
more valuable product such as; syngas (H2 and CO) using various reforming techniques which include steam, partial oxidation
and CO2 reforming. In fact, CH4 reforming has become an accepted procedure for producing syngas which is used in the
petrochemical industry (Domínguez et al., 2007; Zahedinezhad et al., 2009). Detailed study have been reported using these
various techniques viz; steam reforming by Antzara et al. (2016), partial oxidation by Jahangiri and Pahlavanzadeh (2012), CO2
reforming by Foo et al. (2012), Osazuwa et al. (2017b) and, (Osazuwa and Cheng, 2017). Combination of CH4 reforming
techniques in order to obtain a much improved product have also being reported previously by, Lim et al. (2010), Koo et al.
(2014), (Choudhary and Mondal, 2006). Apart from the fact that the CO2 reforming of CH4 reaction consumes greenhouse
gases, its products serve as feed for the Fischer-Tropsch synthesis (syngas ratio below 2.0) (Choudhary and Mondal, 2006). The
product (H2) is employed as fuel cells for transmission of clean energy, electricity generation and production systems (Wang
et al., 1996; Hosseini and Wahid, 2016). The need to promote a cleaner environment by minimizing global warming cannot be
over emphasized. To reiterate this need, over 195 countries signed an agreement in 2015 to take part in a combined attempt to
reduce the emission of greenhouse gases. Naturally, CH4 reforming with CO2 (greenhouse gases) is an endothermic reaction
that occurs at a very slow rate if allowed to progress un-catalysed. Therefore, catalytic reforming of CH4 with CO2 is a reaction,
which progresses with H2 and CO formation as products and carbon as unwanted/by products (Pompeo et al., 2009). This
carbon deactivates the catalyst; hence, researchers have tried to develop catalysts with improved performance, which minimizes
catalyst deactivation from carbon formation on the surface or pore of the catalyst. Noble metal based catalyst was reported to
minimize carbon deposition (Hou et al., 2006; Sutthiumporn and Kawi, 2011). However, nickel (Ni) catalyst is more eco-
nomical (Hirose et al., 2011; Yentekakis et al., 2015). Reports have shown that as a result of the cost of noble metals coupled
with the attraction of Ni to carbon, it makes economic sense to enhance the performance of non-noble metal catalyst. Hence,
transition metal based catalyst has shown better performance towards syngas production from CH4 dry reforming (Valderrama
et al., 2005; Gallego et al., 2008b; Rivas et al., 2008; Khajeh Talkhoncheh and Haghighi, 2015). Another effective catalyst for CO2
reforming/ conversion of CH4 is the perovskite, which requires the introduction of metals into the perovskite matrix. Perovskite
possess a structure with superior reduction-oxidation properties that permits very high distribution of metal elements in a
reduced system; hence enhancing the activity of the catalyst (Goldwasser et al., 2005b; Moradi et al., 2012). Moreover, the
perovskite has a wide selection of A and/or B cations, enabling combinations of varying oxidation state of its elements (Tienthao
et al., 2007). Catalytic conversion of greenhouse gases to valuable products can be effectively achieved via CO2 reforming of
CH4. However, catalyst inhibition (deactivation) due to carbon formation has been outlined as the major setback that inhibits
the revolution of CO2 reforming of CH4 to a commercial process. Reports available in literature have attempted to analyse ways
to enhance catalyst activity, catalyst stability, reduce carbon formed and deactivation of catalyst by varying supports, promoters
and combining metals to obtain support on metal oxides and perovskite type catalysts. Furthermore, various modifications have
been carried out to alter the kinetic behaviour of these catalysts in order to improve these aforementioned qualities. This
paper seeks to outline the various methods that have been employed in the catalytic conversion of greenhouse gases into
valuable products. More specifically, the effects of various catalyst type on the overall behaviour (conversion, yield and kinetic)
of greenhouse gases (CH4 and CO2) have been emphasized in this review paper.

Greenhouse Gases

Greenhouse effect is a natural (regular) occurrence modelled to retain gases in the earth crust at equilibrium. However, dis-
turbances to the environment take place when imbalance exists. These disturbances are as a result of artificial greenhouse effect
which enhances the regular greenhouse effect. Artificial greenhouse effect results from burnt fossil fuels, natural gas, coal and
petroleum, while the regular greenhouse effect results from confined heat waves released from the sun. As a result of the heat
energy, the temperature of the greenhouse gases in the atmosphere is increased. Activities of man such as; deforestation, burning of
fossil fuels, coal, oil, industrialization and population increase are responsible for the excess greenhouse gases produced. Com-
ponents of greenhouse gases are; water vapour, nitrous oxide, ozone, CH4 and CO2. CO2 and CH4 are readily available in much

Encyclopedia of Renewable and Sustainable Materials doi:10.1016/B978-0-12-803581-8.11032-X 1

2 Catalytic Conversion of Greenhouse Gases

larger amounts (Lim et al., 2010). The global interest to reduce greenhouse gases has resulted in studies aimed at promoting the
mitigation of the two main gases; CH4 and CO2 into usable products.

Conversion/Reforming of Methane
CH4 can be produced naturally and artificially by organic process and man-made activities, respectively. Conversion/Reforming of
CH4 is the separation of its molecules by combining it with the molecules of a splitting agent. CH4 can be converted via different
methods depending on the quality of the product stream required; steam, partial oxidation and CO2 reforming of CH4 are
amongst the several methods recently reported (Arkatova, 2010).

Steam reforming of CH4

Already commercialized steam reforming is often used industrially and the process is shown in Eq. 1, (Krylov et al., 1998).

CH4 þ H2 O2 CO þ 3H2 ðDH298K ¼ 206kJ=molÞ ð1Þ

Reforming of CH4 via steam produces H2 and CO with ratio of about 3.0. Reports have claimed higher H2: CO ratio is not ideal
for the Fischer Tropsch reaction which produces liquid petrochemicals (Tsipouriari and Verykios, 2001). Low temperature steam
reforming of CH4 using metal oxide (MgO, CaO and La2O3) promoted Ni-Ce0.8Zr0.2O2 catalyst in a compact reformer have been
investigated by Kim et al. (2017). Results from their study showed that metal oxides improved the basic strength of the catalyst,
hence, enhancing the resistance to carbon formation and improving the catalytic activity. Amongst all the catalysts prepared,
Ni-La2O3-Ce0.8Zr0.2O2 catalyst had the highest performance as a result of the high dispersion of Ni, strong basicity of la2O3 and
strong interaction between Ni and La2O3. Enhanced catalytic performance of Ni/a-Al2O3 catalyst modified with CaZrO3 nano-
particles in steam methane reforming have been studied by Lertwittayanon et al. (2017). The effects of loading CaZrO3 nano-
particles (0–15 wt%) were investigated after synthesizing the catalyst using the sequential impregnation method. Results from
their study showed that 15 wt% CaZrO3 nanoparticles provided the highest H2 yield. The activity was linked to the steam
adsorption-dissociation at the sites where O2 vacancies exist on the surface of CaZrO3 nanoparticles. Stability of the modified and
unmodified catalyst was also tested with the modified Ni/a-Al2O3 catalyst showing higher catalytic performance when compared
to the unmodified Ni/a-Al2O3. It was also found that at high S/C ratio of 3.0, excess steam adsorption at the oxygen vacancies on
the CaZrO3 particle occurred resulting in adsorptive competition between steam and CH4, thereby decreasing CH4 dissociation.
Hence, the optimum S/C ratios for the CaZrO3-modified Ni/a-Al2O3 catalysts were lower than those for the unmodified
Ni/a-Al2O3 catalyst as a result of the very good steam reforming capability of the CaZrO3 particles.

Partial oxidation reforming of CH4

In order to produce liquid fuels, syngas ratio less than 2.0 is required (Sutthiumporn and Kawi, 2011; Ruckenstein and Wang,
2002; Khalesi et al., 2008). Syngas with lower ratio are obtained from partial oxidation of CH4 as shown in Eq. 2 (Goldwasser
et al., 2005b).

1
CH4 þ O2 2 CO þ 2H2 ðDH298K ¼  36kJ=molÞ ð2Þ
2

Kaddeche et al. (2017) investigated the partial oxidation of CH4 on co-precipitated Ni-Mg/Al catalyst modified with copper or
iron. The authors used the co-precipitation method to prepare Fe or Cu promoted (Ni/Mg) Al catalysts. The compositional effects
of the catalyst and the pre-treatment conditions were tested on the partial oxidation of CH4. Results from their study revealed that
Fe or Cu promoted (Ni/Mg) Al catalysts had high performance in partial oxidation of CH4. In addition, as the calcination
temperature decreased and Ni and Al contents increased, the results showed increasing activity and selectivity towards the
products. In all reactions, the catalyst promoted with Fe was superior in terms of the CH4 oxidation and for the water-gas shift
reaction. Adding Cu also enhanced the performance of the (Ni/Mg) Al catalyst. The performance was linked to the creation of NiM
(M ¼Cu or Fe) alloy which enhanced the distribution of Ni particles. LaNiO3 and La2NiO4 supported on CeO2 were synthesized
using a microwave assisted co-precipitation method and the activity test was carried out in the partial oxidation of methane by
La Parola et al. (2016). Results from their catalytic study showed that at increased temperature (about 8001C), high CH4 con-
version was obtained with approximately 100% CO selectivity. The LaNiO3CeO2 stimulated CH4 cracking with CO/CO2 evolving
in a large temperature span which was in contrast to LaNiO3 stimulating CH4 cracking in a more limited range of temperature. This
was attributable to the interaction between Ni and Ce, thereby enhancing the catalyst activity in partial oxidation of CH4 reaction.
Partially oxidized CH4 with bi-functional catalyst I and the formation of Ni1/La2O3 during temperature programmed partial
oxidation of methane reaction over LaNiO3 perovskite have been studied by Nguyen et al. (2014). Several characterization
techniques such as XRD, TGA, HRTEM/EDX, and FFT were employed to ascertain the physicochemical properties of the catalyst
pre, during and post reaction. Oxidation of CH4 over LaNiO3 and La2O3, and the syngas production over reduced Ni1/La2O3
catalysts were analysed to understand the transformation of LaNiO3 to Ni1/La2O3 and proposed kinetic model of POM process
over final bi-functional Ni1/La2O3.
 Catalytic Conversion of Greenhouse Gases 3

CO2 reforming of CH4

The main challenge of partial oxidation of CH4 is the exothermicity of the reaction which creates control difficulties during the
reaction. Hence, CH4 dry reforming with H2: CO ratio less than 2.0 is of higher demand and can be represented by Eq. 3.
CH4 þ CO2 2 2CO þ 2H2 ðDH298K ¼ 247kJ=molÞ ð3Þ
Global industrialization has focused attention on the consumption of CO2. The excessive release of CO2 has further worsen the
critical problems associated with global warming and climate change (Song, 2006). An attractive way atmospheric CO2 can be
effectively minimized is by reforming of CH4 via CO2. Catalytic performance of mesoporous carbons modified with lanthanides in
dry Conversion of methane have been reported by Goscianska et al. (2018). Mesoporous carbon was synthesized using SBA-15
and KIT-6 and sucrose as carbon source. After characterization, the catalysts were tested using 1:1 molar ratio of CH4 and CO2 at
continuous flow in a stainless steel reactor at 6501C under atmospheric influence. From their results, Ce- and La-based catalysts
supported on mesoporous carbons showed better activity and stability when compared to the unmodified catalysts supported on
SBA-15 and KIT-6. Osazuwa and Cheng (2017) studied the catalytic performance of samarium-cobalt trioxides perovskite catalyst
for the conversion of greenhouse gases into cleaner energy. The various outstanding catalytic properties gave way for an excellent
conversion (above 90%) in a 30 h experimental setup with the used catalyst showing evidence of carbon deposits. Syngas
production via methane dry reforming over neodymium sesquioxide supported Co catalyst prepared using the wet-impregnation
technique have been outlined by Ayodele et al. (2016a). Their results showed that conversion of both reactants increased with feed
ratio and reaction temperature, hence, leading to an increased syngas yield of 59.91% and 62.02% for H2 and CO, respectively.
The authors’ proceeded by proposing CH4 and CO2 adsorption, activation of CH4 from CH4 decomposition and gasification of
carbon deposited on the catalyst surface.

Combined steam and CO2 (dry) reforming of CH4

Other researchers have attempted to combine steam and dry reforming process to improve the conversion of greenhouse gases and
enhance the end product of the reaction. In a study, an ideal design for combining steam reforming with dry CH4 reforming and
reusing CO2 as raw material have been investigated by Lim et al. (2010). In order to minimize cost and energy consumption, steam
and dry reforming was combined to reform CH4 for CO2 treatment process. Models for the combined process and the steam
reforming process were established and the cost was obtained for the overall process. Their results showed that the combined
process reduced the net CO2 by 67% when compared to the steam reforming process. The production of syngas via steam and
CO2 reforming of CH4 over Ni-Ce/MgAl2O4 catalysts with enhanced coke resistance have been investigated by Koo et al. (2014).
Ni-Ce/MgAl2O4 catalyst was prepared using the co-impregnation method by adjusting the Ce/Ni ratio in a range 0.0–1.0. In their
study, pre and post catalyst analysis was carried out to determine the effect of Ce addition. It was found that the addition of Ce to
Ni/MgAl2O4 catalyst affected the NiO crystallite size, metal dispersion and reduction degree. Ni-Ce/MgAl2O4 catalyst with
Ce/Ni ratio 0.25 had the smallest NiO crystallite size of 8.3 nm and highest metal dispersion of 4.91%. Ni-Ce/MgAl2O4 with Ce/Ni
ratio of zero had the largest NiO crystallite size of 11.0 nm and lowest metal dispersion of 3.49%. In terms of catalytic activity,
Ni-Ce/MgAl2O4 (Ce/Ni ¼ 0.25) catalyst had the best activity and coke resistance as a results of the improved metal dispersion,
better reducibility and higher surface oxygen transfer. Choudhary and Mondal (2006) combined partial oxidation, CO2 and steam
conversion to syngas catalysed by NdCoO3 perovskite catalyst. The conversion and yield were affected by CO2/H2O feed ratio in
the CO2 and steam reforming process. For the CH4 reforming process via CO2 and partial oxidation, reactants conversion,
H2 selectivity and the net heat of reaction are affected by operating constraints like relative O2 concentration in the feed,
temperature and space velocity. Interestingly, their report showed no carbon deposit on the catalyst for both cases, thereby placing
reduced NdCoO3 as a very good catalyst for carbon-free CO2 combined with steam reforming. Interestingly, CO2 reforming of CH4
reaction proceeds with side reactions such as the reverse water–gas shift reaction (RWGS) represented in Eq. 4.
CO2 þ H2 2 CO þ H2 OðDH298K ¼ 46:1kJ=molÞ ð4Þ
The endothermicity of the RWGS coupled with the formation of H2 and CO (CO2 reforming of CH4) is preferred at high
temperature. In contrary views, some writers have argued that temperature increase does not favour the conversion of greenhouse
gases (forward reaction) because of the negative effects on the catalyst. The resulting effects are catalyst sintering, unsteady
behaviour of the catalyst and catalyst active site engulfment by carbon due to increased CH4 cracking (Luo et al., 2000). In
reforming of CH4 with CO2, carbon is produced as a by-product of CH4 cracking and another side reaction known as the
Boudouard reaction represented as Eqs. 5 and 6, respectively, (Richardson and Paripatyadar, 1990).
CH4 -C þ 2H2 ðDH298K ¼ þ 74:9kJ=molÞ ð5Þ

2CO-C þ CO2 ðDH298K ¼  172:5kJ=molÞ ð6Þ

Another group of writers have argued that CH4 conversion using CO2 proceeds at elevated temperature in order to crack CH4
and minimize the Boudouard reaction side reaction effect. At elevated temperature, the reverse Boudouard reaction is favourable
and it is shown in Eq. 7.
CO2 þ C-2COðDH298K ¼ 172:5kJ=molÞ ð7Þ
Hence, carbon formation can be minimized by carefully selecting the reaction operating conditions such as; reaction tem-
perature and type of catalyst.
4 Catalytic Conversion of Greenhouse Gases

Catalyst characterization
Catalyst characterization assesses the catalytic physicochemical properties. The need to characterize the catalyst is to ascertain the
connection linking the physicochemical properties and the mechanism of reaction and kinetics as a means of developing a
suitable catalyst to enhance greenhouse gases conversion. In catalytic studies, some physical characterizations include
N2 physisorption, SEM, FESEM and TEM. Physical properties are the textural properties and morphology of the catalyst. N2
physisorption which refer to textural properties such as; pore size, surface area, pore size distribution and pore volume are obtained
by N2 adsorption-desorption isotherms data while the morphology of the catalyst is shown by the scanning electron microscopy
(SEM), field emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM). Some chemical char-
acterizations include; EDX, XPS, XRD, NH3-TPD, CO2-TPD, TGA and FTIR. These chemical characterizations can be sub-divided into
elemental (EDX and XPS) and surface chemical analysis (XRD, TPD, TGA, FTIR). Captured images from SEM, FESEM and TEM are
analysed by the energy dispersive X-ray (EDX) analyser in order to obtain the catalyst elemental composition. X-ray photoelectron
spectroscopy (XPS) is method for elemental and surface analysis due to its increased recognition capability of chemical characteristics
without any known damage to the catalyst morphology (Tao et al., 2014). XPS analysis is aimed at obtaining the composition at the
surface and binding energy of the catalyst. X-ray diffraction (XRD) pattern of the catalyst shows the crystalline structure of the catalyst.
Further computation for the crystalline particle size can be carried out using the Debye-Scherrer equation shown in Eq. 8 (Bradford
and Vannice, 1996) or the more precise Williamson–Hall equation represented in Eq. 9 (Khorsand Zak et al., 2011).
0:9l
Dhkl ¼ ð8Þ
bhkl cosy

kl
bhkl cosy ¼ þ ð4e sinyÞ ð9Þ
Dhkl
where l is the wavelength of Cu-Ka, y is the Bragg diffraction angle, k is a constant (0.9), Dhkl is the crystallite size of the catalyst, the
peak full width with half maximum (FWHM) is bhkl, and e is the strain. Data from XRD can be linearized in the Williamson-Hall
equation to give the y-intercept (y) and slope (s) represented in Eqs. 10 and 11, respectively.
kl
y¼ ð10Þ
Dhkl

s ¼ ð4e sinyÞ ð11Þ

After purging the surface with gases at high temperature, desorbed molecules from a surface are analysed using a technique
known as temperature programmed desorption (TPD). In catalysis, the acidic and basic sites/strength can be determined by the
amount of gases adsorbed in the sites. In addition, the catalyst reducibility can be determined by employing H2- temperature
programmed reduction (H2–TPR). Adsorbed H2, NH3 and CO2 gases on the catalyst surface are estimated using a thermal
conductivity detector. The solid state thermal profile prior to calcination is obtained using thermo gravimetric analysis (TGA).
Furthermore, post reaction (carbon study), the weight loss profile and the derivative weight loss profiles of the catalyst can also be
obtained using the TGA. The TPC uses a flow of N2, while the TPO uses O2. Using infrared light, the functional groups present in
the catalyst can also be identified using the Fourier transform infrared spectroscopy (FTIR). This type of analysis presents the
absorbance spectra showing the chemical bonds and molecular structure of the catalyst.

Catalyst Type for Conversion of Greenhouse Gases

Good catalysts are required to stimulate the process of CH4 dry reforming and improve the product under favourable conditions
(Lombardo and Ulla, 1998). At high temperature and under reducing conditions, the formation of syngas is favoured. Hence,
several researchers reduce the catalyst with H2 to aid finely dispersed metal particles of the catalyst (Zhu et al., 2014). In CH4
reforming reactions, the ability to synthesize a catalyst with high performance is of great interest. Hence, it is desirable to obtain a
deactivation free catalyst that can effectively combine greenhouse gases (CH4 and CO2) to produce valuable products. Researchers
have tried to obtain this kind of catalyst by supporting and promoting the active site of the catalyst (Su et al., 2014). CH4 cracking
during the CO2 reforming of CH4 is a major source of carbon. Carbon formation during the reforming process has been the major
drawback and it is still under investigation up till date (Sutthiumporn et al., 2012). Noble metals show good performance and
more importantly are have less affinity for carbon during methane dry reforming (Hou et al., 2006). The use of noble metals is
however to advisable due to their high cost and unavailability. To substitute for noble metals, attention have shifted to Group VII
transition metals like Nickel (Ni) (Wang et al., 1996). These type of metals are active and selective towards CH4 dry reforming
(Valderrama et al., 2005; Rivas et al., 2008; Khajeh Talkhoncheh and Haghighi, 2015; Pichas et al., 2010). Additionally, the low
cost of transition metals is another advantage over noble metals (Yentekakis et al., 2015). In terms of superior activity, an effective
catalyst for methane dry reforming is the Ni-based catalyst (Gallego et al., 2008a). However, the active site of Ni-based catalyst are
readily attacked by carbon, (Gallego et al., 2008b; Ashcroft et al., 1991). Supported cobalt (Co) catalysts (Ruckenstein and Wang,
2000) and Co-La based perovskite catalyst have also been applied in methane dry reforming (Valderrama et al., 2013). In
summary, Ni-based catalyst have shown superior catalytic properties in CO2 reforming of CH4, supported Co catalyst have been
reported to exhibit better stability towards the reaction as a result of its superior ability to withstand carbon attacks and extreme
 Catalytic Conversion of Greenhouse Gases 5

temperature changes (Ferreira-Aparicio and Guerrero-Ruiz, 1998). In addition, Co catalyst have also being reported to show good
catalytic properties in methane dry reforming (Budiman et al., 2012).

Supported Metal Catalyst for Conversion of Greenhouse Gases

SBA-15 supported mesoporous Ni and CO catalysts with high coke resistance for CO2 reforming of CH4 have been investigated by
Erdogan et al. (2018). In their study, wet-impregnation method was used to synthesize the mesoporous SBA-15 supported Ni and CO
and Ni-Co catalysts. From the activity results, it was found that bimetallic 4Ni-1Co@SBA-15 catalyst had good activity with CH4
conversion 73% and CO2 conversion of 89% with reaction temperature of 7501C. Coke formation was decreased when Co was
combined with SBA-15 supported Ni catalyst. Durability and activity enhancement of Zirconia supported Ru catalyst for methane dry
reforming have been studied by Whang et al. (2017). In their study, a small amount of Ru (0.13 wt%) supported on ZrO2-SiO2 showed
good performance for methane dry reforming reaction carried out at 8001C. Ru size increased (6.3 nm) after Ru was placed on the SiO2
support. In contrast, the size of Ru reduced to 1.4 nm when Ru was incorporated on the ZrO2-SiO2 support. Upon testing in methane
dry reforming reaction, the Ru/ZrO2-SiO2 catalyst showed no carbon deposit while the filamentous carbon was deposited on the Co-
Ru/ZrO2-SiO2 catalyst. Nickel catalyst particles incorporated on ceria-zirconia were synthesized by different methods and their catalyst
performance were evaluated in methane dry reforming by Wolfbeisser et al. (2016). The catalyst which they prepared by surfactant
assisted co-precipitation was inactive for methane dry reforming due to the engulfment of Ni particle by ceria-zirconia particles. In terms
of the catalytic activity, it was found that the catalyst prepared without surfactant was similar to that of Ni-ZrO2. Ni-ZrO2 did not show a
better performance when compared to ceria-zirconia supported Ni catalyst even though filamentous carbon was reduced during the
reaction. In summary, the authors linked the catalyst activity to the method of preparation and phase composition. The effects of
support on the activity of Ni-based catalyst in dry methane reforming have been reported by Zhang et al. (2015). It was found that
support significantly affected NiO species. According to the authors, SiO2, TiO2 and ZrO2 as support have a weak attraction to NiO.
These could lead to catalyst inactivity as a result of accumulation of active metal species. In contrast, Al2O3 and MgO showed strong
interaction with NiO leading to phase modification ot NiAl2O4 and NiO-MgO, hence, making the reduction process difficult to attain.
Therefore, NiO supported on MgO-modified Al2O3 exhibited the best catalytic performance (100 h stability) in methane dry reforming.
The effects of phosphorus addition to Rh-supported catalysts for conversion of methane with CO2 have been studied by Cimino et al.
(2017). Three types of these catalysts were prepared; (i) dispersed phosphorus and rhodium on La-stabilized g-Al2O3; (ii) stabilizing
g-Al2O3 with phosphorus and then dispersing rhodium; (iii) dispersing rhodium on AlPO4 support and Rh incorporated on La-
stabilized g-Al2O3 was used a catalyst reference. It was found that the addition of phosphorus to the supports increased the catalyst
acidity and suppressed CO2 activation leading to reduction in activity and carbon resistance during methane dry reforming reaction.

Promoted Metallic Catalyst for Conversion of Greenhouse Gases

Samaria-doped Ni and Co/SBA-15 catalysts for methane reforming with CO2 has been reported by Taherian et al. (2017). It was
found that samaria doped Ni/SBA-15 gave the best CH4 conversion (about 58% at 7001C). However, samaria-doped Co/SBA-15
has very low conversion of methane (about 25% at 7001C). The author related the effects of samaria on Ni/SBA-15 to reduced NiO
particles, increased dispersion of NiO and reduced carbon formation. The undesired influence of samaria on Co/SBA-15 catalyst
was as a result of Co oxidation and Co particles sintering at elevated temperatures. Károlyi et al. (2018) reported methane dry
reforming over Ni-in/SiO2 catalyst free of carbon deposit. Findings from their study showed that carbon deposit on Ni/SiO2 can be
completely eradicated from the process of greenhouse gases conversion by the addition of indium as promoter to the catalyst.
Characterizations such as TPR, CO2-TPD and XPS suggested the interaction between the two metals. According to their report,
indium diluted the nickel surface thereby minimizing the formation of carbon species and carbon nanotubes on the catalyst
surface in-situ the conversion of methane with CO2 reaction. Promotional effect of Gd over Ni/Y2O3 catalyst for methane dry
reforming have been investigated by Al-Fatesh (2017). The effects of calcination temperatures, activation temperature and time
were studied. It was found that a maximum H2 yield of 82.8% was obtained at calcination temperature of 8001C, activation
temperature of 8001C and reaction temperature of 7001C. In order to inhibit carbon formation, the catalyst was promoted by Gd.
Interestingly, 1 wt% of Gd altered the carbon formation mechanism and reduced the carbon deposited. This property of Gd was
linked to the superior basicity of the Gd when compared with non-promoted Ni/Y2O3 catalyst. Dispersed Gd-doped Ni/ZSM-5
catalyst for enhanced carbon-resistant for dry reforming of methane have been reported by Sarkar et al. (2016). Adding Gd forms
GdNi5 alloy on the ZSM-5 support with particle size ranged 2–10 nm. It was found that Gd enhanced the mass transfer effects of
the reactants and products, respectively, while hindering accumulation of the Ni nanoparticles. According to the authors, Gd
releases O2 to oxidize the carbon deposited on the Ni sites. The Gd promoted Ni/ZSM-5 catalyst was able to withstand 100 h of
reaction runs without catalyst deactivation. Interestingly, Ni/ZSM-5 catalyst deactivated during the methane dry reforming reaction
due to Ni metal sintering. Ghods et al. (2016) studied the effects of alkaline earth promoters on the catalytic performance of Ni
catalyst supported on mesoporous magnesium silicate in methane dry reforming reaction. The catalysts were characterized by N2
adsorption, X-ray diffraction, TPR-TPO techniques. It was found that modifying the catalyst decreased the specific surface area and
the distribution of the pore sizes. TPR also showed a decrease in the temperature of reduction of the catalyst. From their results,
promoting the catalyst with MgO gave the highest catalytic performance. Ni/MgSiO3 catalysts modified by different contents of
MgO were synthesized and results showed that deposited carbon on the catalyst surface decreased with increase in MgO content.
6 Catalytic Conversion of Greenhouse Gases

Perovskite Catalyst for Conversion of Greenhouse Gases

The perovskite is a mineral with the configuration of CaTiO3 (Zhu et al., 2014). It was named after the Russian mineralogist, Count Lev
Aleksevich Von Perovski but was actually discovered by Gustav Rose in 1839 (Screen, 2007). ‘A’ depicts a rare earth or alkaline earth
metal, while ‘B’ depicts the transition metals in the general formula ABO3 or A2BO4 (Mishra and Prasad, 2014). The perovskite structure
is cubical with ‘A’ cation being 12-fold coordinated and ‘B’ cation 6 fold coordinated with O2 anions (Peña and Fierro, 2001;
Goldwasser et al., 2003). The framework of the perovskite is a ReO3 type framework configured by adding ‘A’ cations to the BO6
octahedral structure (Peña and Fierro, 2001). Various isomorphic solids can be prepared from the perovskite for catalytic studies. The
properties and oxidation states of A and B sites are the basis for the catalytic nature of the perovskite. In catalytic studies, perovskites with
higher surface area are desirable; however, other factors have played significantly affected the performance of the catalyst. Furthermore,
the method of preparation plays an important role in the physical properties of the perovskite. Perovskites prepared using the solid state
synthesis method is a very stable solid at extreme temperatures in catalytic reactions. Nonetheless, this synthesis route fails for perovskite
employed in surface related studies but are applied mainly in electronic and electrical applications (Labhasetwar et al., 2015). As catalyst,
the stability and activity of the perovskite is controlled by the ‘A’ cation and ‘B’ cation, respectively (Mishra and Prasad, 2014; Zhong
et al., 1997). In another perspective, Zhang (1990) reported that ‘A’ metals influences the amount of adsorbed O2, while ‘B-site’
influences the quality of adsorbed O2. Peña and Fierro (2001) stated that partially substituting the ‘A’ site with rare earth cations can
alter the structural defects and oxidation state such as ionic vacancies. For the ‘B’ site partial substitution enhances the structural stability
and catalytic performance of the catalyst. This claim was supported by Goldwasser et al. (2005a) who also reported that the activity of
the catalyst could be enhanced by substituting the A and/or B sites leading to slight crystalline structural changes. About 90% of the
metals on the periodic table can be incorporated into the A and/or B ionic sites of the perovskite, hence resulting in different
stoichiometry and crystalline shapes (Zhu et al., 2014). The major drawback of the perovskite is it relatively low surface area, therefore
researchers have focus attention on ways to improve the surface area of the perovskite (Lombardo and Ulla, 1998). The solid state
properties of perovskites has further beamed more search light on the use application of perovskite in catalysis (Lombardo and Ulla,
1998). Very recently, more author are using perovskite as catalyst in methane dry reforming by incorporating rare earth or alkaline earth
metal into the ‘A’ site and a transition metal into the ‘B’ site (Goldwasser et al., 2005b; Hayakawa et al., 1999). Perovskites meets the
requirement to be applied in catalysis for reforming reactions because it provides a platform for its constituent’s metals to be stable and
well dispersed (Goldwasser et al., 2003; Tomishige et al., 2002). The structure of the perovskite is significant in formulating a catalyst that
can resist carbon formation during methane dry reforming. La-Ni based perovskites have been reportedly employed for syngas
production from methane dry reforming however, for this type of catalyst, structural differences/defects were often observed post
reaction as a result of the carbon deposited which leads to catalyst deactivation (Lombardo and Ulla, 1998; Gallego et al., 2006;
Jahangiri et al., 2013; Zheng et al., 2015). Perovskite type oxides LaFe1-xCoxO3 for chemical looping steam methane reforming to syngas
and H2 production have been investigated by Zhao et al. (2016). LaFe1-xCoxO3 with x¼0.1, 0.3, 0.5, 0.7, 1.0 were employed as O2
carriers and in effects of Co on the perovskite characteristics were analysed. It was found that the optimal Co required was 0.3. Although,
moderate sintering occurred, LaFe1-xCoxO3 catalyst was able to regenerate in twenty redox reactions. Syngas ratio of 2.0 was obtained
with 85% conversion, 43% of CO selectivity and 50% of H2 selectivity. In the steam oxidation cycle, H2 production of approximately 4
mmol g1 O2 carriers was produced. Dama et al. (2018) prepared and investigated alkaline earth metal substituted perovskite catalyst
for methane dry reforming. From characterizations carried out, it was found that the perovskite A site was responsible for the structure,
basicity, O2 deficiency and Ni dispersion. Results showed that calcium promoted perovskite (CaZr0.8Ni0.2O3-δ) showed better CH4 and
CO2 conversion rate with stability maintained even after 500 h of reaction. In terms of carbon formation, their studies revealed that the
type of carbon formed depends on the basicity of the perovskite, metal to support interaction, Ni crystallite size, surface hydroxyl groups
and O2 defects. In summary, the authors successfully proved that CaZr0.8Ni0.2O3-δ was a very good catalyst for methane dry reforming in
terms of its activity and stability. The effects of incorporation of perovskite type oxides into a mesoporous SBA-15 silica support in
methane dry reforming have been reported by Rivas et al. (2010). It was found that incorporating the perovskite into the SBA-15
mesoporous silica increases reactants conversion and selectivity for syngas production but a decrease in reactants conversion were
observed when another cation was added to the perovskite active site. A comparative study on methane dry reforming on LaNiO3
perovskite catalysts supported on mesoporous SBA-15, MCM-41 and silica carrier have been studied by Wang et al. (2013). It was found
that the pore structure had a direct impact on the catalyst activity and stability. More specifically, LaNiO3/MCM-41 had higher activity
due to more uniformly dispersed Ni particles in the catalyst. LaNiO3/SBA-15 showed better stability when compared with LaNiO3/
MCM-41 as a result of the stable silica structure which resisted the accumulation of Ni particles. Furthermore, it was reported that the
hexagonal matrix of LaNiO3/SBA-15 was retained even after reaction unlike the LaNiO3/MCM-41 matrix which was completely
modified resulting in metal agglomeration.

Catalyst Deactivation in the Conversion of Greenhouse Gases

Efforts have being put in place to enhance the catalyst for conversion of greenhouse gases (CO2 and CH4) particularly, for Ni-based
catalyst so as to minimize catalyst deactivation due to carbon attacks. In methane dry reforming, catalyst deactivation are triggered by
carbon formation which causes reactor pressure build up, carbon attack on metal site and agglomeration of the active metal, thereby
reducing and eventually blocking the catalyst pores. Several combinations of La-Ni-Co have been used as catalyst by Yang et al. (2013),
González et al. (2005) and Valderrama et al. (2010) try to minimize catalyst deactivation during the conversion of greenhouse gases
(CO2 and CH4). Due to the increased rate of carbon formation when using transition metals especially Ni catalyst in CO2 reforming of
CH4, rare earth metal oxide rich in lattice O2 such as CeO2, La2O3, TiO2 and SiO2 or mixed supported oxide such as ZrO2-SiO2, La2O3-
 Catalytic Conversion of Greenhouse Gases 7

SiO2, (Sutthiumporn and Kawi, 2011; Ayodele et al., 2016b), can be used as support for the metallic catalyst. The carbon deposited is
gasified by Lattice O2 released by this oxides, hence, purging the metallic active surface. Recently, researchers have focused attention
not only on producing an efficient catalyst but also to reducing carbon deposit on the catalyst surface in the course of the CH4
reforming reaction. An efficient means of merging transition metals and rare earth oxides is by hosting the metals in the perovskite
structure (Moradi et al., 2014). Studies have shown that the superior solid-state properties of the perovskite have presented this type of
catalyst as a very good candidate for methane dry reforming (Lombardo and Ulla, 1998). The performance of cobalt aluminate as an
O2 rich catalyst for methane dry reforming have been reported by Wong et al. (2017). The catalyst was synthesized via sol-gel method
as an O2 carrier which inhibits the carbon formation rate. Employing this catalyst, the authors successfully obtained a novel
mechanism for syngas production via the catalyst reduction by CH4 and regeneration with CO2. They conducted a stability test using
the best cobalt aluminate catalyst with 33.33% of Co content. It was found that the catalyst was stable for up to 30 h with 97.2% and
99.7% H2 and CO yield, respectively with only 1.9% CH4 converted to carbon. Re-alloy catalysts with improved stability in CO2
reforming of CH4 reactions have been investigated by Zubenko et al. (2017) Perovskite precursors (LaFeO3) were promoted with Ni
and Re. Reducing the perovskite catalyst ex-solved Re-alloy nanoparticles which showed good performance in methane dry reforming.
The authors carried out a 70 h reaction study with no carbon deposits or metal particle sintering. Son et al. (2014) studied coke
formation over Ni/g-Al2O3, Co- Ni/g-Al2O3 and Mg-Co- Ni/g-Al2O3 catalysts for CO2 reforming of CH4. The effects of promoting the
catalyst with Mg and Co have been analysed to know the value on coke deposits. Amongst all the catalyst employed for the study, Mg-
Co-Ni/g-Al2O3 catalyst had the highest performance with CH4 conversion over 95% for 200 h and minimal coke formation. The
increased activity resulted from the addition of Mg and Co which enhanced the cracking of CH4 and dissociation of CO2. High carbon-
resistance Ni/CeAlO3-Al2O3 catalyst for CH4/CO2 reforming was investigated by Chen et al. (2013). After reduction at 9001C, CeAlO3
phase was formed. In their study, it was found that the catalyst showed good activity with or without CeAlO3 for 250 h at 8001C and
WHSV of 20,000 mLh1gcat1. However, as the CeAlO3 phase increased, carbon formation progressively dropped from 0.92 to 0.29
gcat1. They concluded that CeAlO3 can minimize the formation of graphitic carbon on the metallic surface with the formation of
amorphous carbon being independent of the CeAlO3 phase. This phase (CeAlO3) was also responsible for breaking down CO2 to
release O2 species which aided gasification. Carbon gasification from Fe-Ni catalyst supported on MgAl2O4 after methane dry
reforming was reported by Theofanidis et al. (2016). Gasification was obtained using a transient response technique known as
temporal analysis of products (TAP). After the reaction, graphitic and amorphous carbons were formed. The oxidation of CO2
removed some of the carbon species located in the active metal sites. The carbon species removal involves: (1) CO2 dissociation on the
Ni site closely followed by carbon oxidation by surface O2. (2) CO2 oxidation by Fe and carbon oxidation by the lattice O2 from Fe
oxide. The carbon species oxidation by O2 which was observed in the TPO analysis and the isothermal test included two steps: (1)
Surface carbon oxidation by lattice O2 and (2) the movement of particles to the carbon species deposited away from the active metallic
sites followed by the lattice O2 oxidation of Fe and /or NiO.

Kinetics of conversion of greenhouse gases (methane dry reforming reaction)

The kinetics and mechanism of syngas production from the mitigation of CH4 using CO2 over SmCoO3 perovskite catalyst
operated in the temperature ranged 973–1073 K was investigated by Osazuwa et al. (2017a). The authors carried out detailed study
of the mechanism of the reaction and postulated a model for the process. The reaction mechanism predicts CH4 adsorption on the
Co1, CH4 decomposition and carbon formation. They reported that the mechanism also predicted the formation of Sm2O2CO3
which reacted with carbon to form CO.

Conclusions

Various methods exist for the conversion of greenhouse gases to more valuable products. Amongst these methods are the steam
reforming, partial oxidation and CO2 reforming of CH4. In terms of the amount of greenhouse gases converted (CO2 and CH4)
and the usefulness of its products (syngas) in the formation of other petrochemicals, CO2 reforming of CH4 is more advantageous.
In order to increase this conversion, various support have been used, promoters have been added, bi-metallic catalyst have been
developed and even recently perovskite have been employed to mitigate greenhouse gases in various reforming processes.
Decomposition of CH4 on the metallic surface, dissociation of CO2 on the support, the reduction-oxidation perovskite mechanism
coupled with the effects of dopants in inhibiting carbon formation on the surface of the catalyst by introducing O2 species
describes the reaction mechanism. Comparing supported catalyst, with particular interest on Ni-based and Co-based supported
catalyst, reports show that perovskite oxides show greater superiority in preventing catalyst deactivation during the conversion of
greenhouse gases (CH4 and CO2) as a result of the abundance of O2 species in its structure.

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