Fuel 302 (2021) 121233

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Full Length Article

Effect of the magnesia and alumina in the modified-supported

perovskite-type catalysts for the dry reforming of methane
Pradeep Kumar Yadav , Taraknath Das *, Prasenjit Mondal
Department of Chemical Engineering, Indian Institute of Technology Roorkee, Haridwar, Uttara Khand (UK) 247667, India

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

Keywords: A series of supported perovskite-type catalysts were synthesized. The support (SiO2) was modified with alumina
Synthesis gas and magnesia to prepare the modified-supported catalysts. The synthesized catalysts were assessed for DRM
Dry reforming of methane reaction for the production of syngas. The surface area of the synthesized catalyst increased with addition of ceria
Perovskite catalyst
in a certain ratio (x = 0.05). The surface area did not change significantly as the support-modified with alumina
Modified-support
or magnesia. The nickel-aluminate and nickel-magnesia solid solution were observed in the modified-supported
Raman spectra
perovskite catalysts. It assisted in improving the surface basicity of silica, and increasing the percent conversion
and percent product yield. The optimum ratio of reactant (methane and carbon dioxide) in the feed stream was
suggested to be 1. The ratio of H2/CO increased (>1) as increasing the methane to carbon dioxide ratio suggested
that the methane cracking dominated over DRM. The carbon deposition over the catalyst surface was due to the
methane cracking reaction. The carbon deposited in all catalysts however; the activity of the catalyst was un­
affected. The most effective catalyst was found to be 40LaNi0.75Ce0.05Zr0.20O3/8MgO-SiO2.

1. Introduction La1-xCaxAl1-yNiyO3 [10] La0.9-xCexFeO3 [11] LaNiO3 [12–14] BaCeZrO3

Biogas is the most attractive renewable energy source. The main
constituent in the biogas is methane (55–75%) and carbon dioxide
(24–44%), it can be turned into gaseous fuel or hydrogen rich gas.
Various reforming methods such as steam reforming, dry reforming,
partial oxidation, and tri-reforming are used to convert the biogas
(biological treatment of organic waste) or flue gases (from power plants)
into useful products [1–3]. The dry reforming reactions are the easiest
way to produce the hydrogen or synthesis gas from hydrocarbon is one
of the major feed-stocks for various industrial applications, and
hydrogen uses as a clean fuel. The yield of low H2 to CO ratio ~ 1 is the
suitable feed-stock for the Fischer-Tropsch synthesis for the synthesis of
oxygenated chemicals and hydrocarbons. The DRM (dry reforming of
methane) reaction is highly endothermic and various side reactions such
as water gas shift, methanation, coke gasification, Boudouard reaction,
and oxidations are also taking place. The dry reforming of hydrocarbon
using various catalysts has been reported in the open literature [1–9].
The catalysts use for the dry reforming of methane are active for
example: Ni/MgO-Al2O3, Ni/CaO-Al2O3 [4] Ni-M/La2O3 (M = Co, Fe)
[5] Fe2O3/LaNiO3 [6] LaCeNiO3/SiO2 [7] LaNiAlO3 [8] LaCeNiFeO3 [8]
[15] Rh/LaAlO3, Rh/LaCaAlO3, and Rh/LaCeAlO3 [16] La0.9M0.1Ni0.5
Fe0.5O3 (M = Sr, Ca) [17] BaZr1-xMexO3 [18] LaAl0.25Ni0.75O3 [19] La1-
xAxNiO3-δ [20] LaNiO3/SBA-15 [21] Ni/CeO2 [22] La1-xCexNiO3 [23]
Ni/La1-xMgxAlO3-δ [24] Co/MgO-SiO2 [25] Ni/MgO-SBA-15 [26] Ni/
SBA-15-EG, NiAl/SBA-15 [27] Ni/DMS, Ni/MCM-41, and Ni/Al2O3
[28] Ni/Al2O3 and NiMg/Al2O3 [29] Ni/La2O3-ZrO2 [30] Ni@SiO2@­
CeO2 [31,32] Ir/Ce0.9La0.1O2 [33,34] Ir/Ce0.9M0.1O2 (M = Pr, Zr) [35]
Ir/Ce0.9Pr0.1O2 [36] Ni@SiO2 [37-39] Ni-ZrO2@SiO2 [40] Ni/ZrO2, Ni/
LaZr, Ni/CeZr [41] Ni/CeMn using Mg, La, Zr promoters [42] Ni/ZrO2-
Al2O3, LaCeNiO3, LaNiMgOx [43] Ni/10 wt%MgO-beta Zeolite [44]
NiMgO-CeZrO2 [9,29] NiCe/MgAl [45,46] Ni-Mg/ZSM-5 [47]. The
noble metal (Pt, Pd, Ru, and Rh) based and non-noble metal (Co, Fe, and
Ni) based catalysts are reported to be very active for the dry reforming of
methane reaction [33–36]. The noble metal-based catalysts are superior
coke resistance, higher stability, and activity at the higher reaction
temperature. Considering the high cost, noble metal-based catalysts are
avoided for industrial-scale application. The non-noble metals (nickel)
based catalysts are cheap and most suitable for large-scale commercial
application. However, the coke deposition, nickel-sintering, and strong
metal-support interaction are the challenges in the commercialization of

* Corresponding author at: Heterogeneous Catalysis Laboratory (Reaction Engineering), Department of Chemical Engineering, Indian Institute of Technology
Roorkee, 247667, Haridwar, Uttara Khand (UK), India.
E-mail addresses: taraknath.das@ch.iitr.ac.in, tarak3581@gmail.com (T. Das).

https://doi.org/10.1016/j.fuel.2021.121233
Received 17 March 2021; Received in revised form 24 April 2021; Accepted 5 June 2021
Available online 14 June 2021
0016-2361/© 2021 Elsevier Ltd. All rights reserved.
­
P. Kumar Yadav et al. Fuel 302 (2021) 121233

Table 1 that eliminate the carbon deposition by activating oxygen species (oxi­
The BET surface area, pore size and pore volume of the synthesized catalysts. dizes C to CO). The ceria improves the dispersion of the active phase in
Catalysts BET surface Pore size Pore volume the alumina-supported catalysts. Moreover, the Ce0.8Zr0.2O2 supported
area (m2/g) (Å) (cm3/g) nickel catalyst is more stable and active than only ceria or zirconia
40LaNi0.75Zr0.25O3/SiO2 83 240 0.3799 supported catalyst. The partial substitution is beneficial that improves
40LaNi0.75Zr0.20Ce0.05O3/SiO2 113 147 0.3913 the oxygen storage capacity [7-9,42,43]. The substitution of B-site metal
40LaNi0.75Zr0.15Ce0.10O3/SiO2 104 146 0.3843 with iron, cobalt, chromium, copper, or other metals in the perovskite
40LaNi0.75Zr0.10Ce0.15O3/SiO2 103 145 0.3735 catalyst improves the structural stability and catalytic activity of the
40LaNi0.75Zr0.05Ce0.20O3/SiO2 100 143 0.3687
40LaNi0.75Ce0.25O3/SiO2 74 140 0.3583
oxides by the synergistic effects. Similarly, the substitution of A-sites
40LaNi0.75Zr0.20Ce0.05O3/ 114 126 0.5240 (using Ca or Sr) improves the stability of the catalyst and suppress the
2Al2O3-SiO2 carbon deposition by increasing the oxygen vacancy (high) [13]. The
40LaNi0.75Zr0.20Ce0.05O3/ 105 130 0.5623 addition of zirconia is also beneficial that minimize the coke formation
4Al2O3-SiO2
[43]. The nickel-aluminate spinel (NiAl2O4) stabilizes nickel as Ni2+
40LaNi0.75Zr0.20Ce0.05O3/ 105 181 0.5901
6Al2O3-SiO2 state, which is hard to reduce. The addition of zirconia leads to the
40LaNi0.75Zr0.20Ce0.05O3/ 105 175 0.4695 reduction of NiO species as nickel-metal and avoid the formation of
8Al2O3-SiO2 inactive NiAl2O4. The catalysts possess smaller (<6 nm) active metal
40LaNi0.75Zr0.20Ce0.05O3/ 103 173 0.4587 superior resistance to carbon formation. Therefore, the carbon forma­
10Al2O3-SiO2
40LaNi0.75Zr0.20Ce0.05O3/2MgO- 119 193 0.5057
tion is strongly dependent on the types of catalyst uses [9,27].
SiO2 The high methane conversion leads to high methane decomposition,
40LaNi0.75Zr0.20Ce0.05O3/4MgO- 113 205 0.5606 high coke formation and catalyst deactivation. Moreover, the carbon
SiO2 deposition over the catalyst surface is due to the methane cracking and
40LaNi0.75Zr0.20Ce0.05O3/6MgO- 103 238 0.5646
Boudouard reactions. The methane cracking is endothermic reaction,
SiO2
40LaNi0.75Zr0.20Ce0.05O3/8MgO- 103 248 0.6656 and the CO disproportionation (Boudouard reaction) is exothermic re­
SiO2 action that favors high and low temperature, respectively. Methane and
40LaNi0.75Zr0.20Ce0.05O3/ 98 242 0.4527 carbon dioxide are very stable molecules with high dissociation energy,
10MgO-SiO2 and it requires high temperature to achieve the equilibrium conversion.
At high temperature, the methane cracking reaction is higher than the
nickel-based catalysts. The supports use for the synthesis of nickel- Boudouard reaction, therefore, increasing the H2/CO ratio and favors
catalysts are alumina, silica, ceria, titania, zirconia, ceria-zirconia, the carbon deposition. It has been reported that the methane conversion
Fe2O3, ZnO, ZSM-5, La2O3, and magnesia [5,6]. The nickel forms the increases, and CO2 conversion decreases with increasing the partial
nickel-aluminate spinel (NiAl2O4) at high temperature. The supported pressure of carbon-dioxide; and the conversion (CH4 and CO2) decreases
nickel-based catalysts are modified using various metal-oxides to avoid with rising partial pressure of methane because of increasing carbon
deactivation due to the coking and sintering. The addition of La2O3, deposition [48]. The optimum temperature considering the carbon
K2O, Al2O3, CaO, MgO, CeO2, and ZrO2 modifies the electronic or deposition and conversion at the feed ratio (1:1) is reported in between
structural properties and also increases the dispersion of nickel particles. 870 and 1040 ◦ C. The optimum CH4/CO2 ratio is reported to be 1.199 at
The addition of these oxides led to the positive catalytic effect (higher reaction temperature 795 ◦ C [49]. Therefore, the feed gas composition is
activity) by increasing metal (nickel) dispersion, increased the surface very crucial to obtain the high conversion (CH4, and CO2), product
basicity, catalyst stability, and lower the coke deposition [9]. selectivity, H2 to CO ratio, and to control the carbon deposition
The addition of MgO in Al2O3 forms the MgAl2O4 spinel phase that [9,42,49–58].
prevents coke formation and increased the CO2 adsorption. The La2O3 The present study aims to increase the methane, and carbon dioxide
interact with nickel forms a new type of synergetic active sites (Ni- conversion, decreased the carbon deposition, and increased the stability
La2O3) which improves the stability and catalytic activity. The sup­ of the catalyst by stopping the deactivation process. Also, to increase the
ported metal catalyst based on silica or alumina pre-coated with MgO or H2/CO ratio. To conduct the above objectives, a series of silica-
CaO performs better (activity, selectivity) than the catalyst without pre- supported perovskite-type catalysts 40LaNi0.75Zr0.25-xCexO3/SiO2 were
coating. Therefore, the nickel supported on magnesium-aluminate synthesized, where the active metal nickel and the other metals Zr-Ce
spinel shows a stable catalytic activity without deactivation for a (by changing ratio). The support silica-modified with alumina and
longer period [43]. The addition of MgO in silica forms an Mg2SiO4 magnesia. The catalysts 40LaNi0.75Zr0.25-xCexO3/SiO2 and the effect of
adlayer silicate type species. It has been reported that the magnesia or modified support (magnesia-silica and alumina-silica) was monitored
lanthanum oxides form a solid solution with active metal oxide (CoO- for the DRM reaction. The synthesized (fresh and used) catalysts were
MgO). Therefore, the magnesia (basic oxides) inhibits the coke deposi­ characterized by using BET surface area analysis, XRD, TEM, H2-TPR,
tion via adsorbed CO2 species on the catalyst surface that react with the CO2-TPD, TGA, and Raman spectra analysis.
deposited coke through reverse Boudouard reaction. The addition of
magnesia improves the catalytic activity, and the 8 wt% MgO coating is 2. Experimental section
optimum for the Ni/SBA-15 catalyst. The addition of magnesia improves
the surface basicity of silica and also decreases the nickel-metal particle Perovskite-type catalysts 40LaNi0.75Zr0.25-xCexO3/SiO2, 40LaNi0.75
size remarkably through the dispersion [9,25,26,29,44]. It also reports Zr0.20Ce0.05O3/ZMgO-SiO2 and 40LaNi0.75Zr0.20Ce0.05O3/ZAl2O3-SiO2
that the addition of iron, improves the stability of the perovskite cata­ (where x = 0, 0.05, 0.10, 0.15, 0.20, 0.25 and Z = 2 wt%, 4 wt%, 6 wt%,
lysts and enhances the metal-support interaction [7,8,43,46]. The 8 wt%, 10 wt%) were synthesized by the sol–gel method. In a typical
addition of a small amount of alumina increases the surface area, im­ experiment, stoichiometric quantities of La(NO3)2⋅6H2O, Ni(NO3)2⋅6H2O
proves the hydrothermal stability of the silica supported nickel catalyst and a known amount of Zirconium (IV) propoxide (Sigma-Aldrich), and
(Ni/AlSBA-15) and the increase the DRM reaction performance [27]. Cerium nitrate added in to a beaker. These were dissolved in millipore
The ceria store and reversibly release a large amount of oxygen. The water under gentle stirring until the formation of a clear solution. The
elimination of lattice oxygen under reducing conditions leads to the citric acid solution was also prepared in a separate beaker, and it was
formation of anionic vacancies (CeO2-x) are the reactive sites. The added to the already prepared precursor solution and mixed gently via
addition of ceria improves the oxygen mobility, and oxygen vacancies stirring. The ratio of citric acid to a precursor solution was unity. The
precursor’s solution stirring gently at 343 K till the solution becomes a

2
 P. Kumar Yadav et al. Fuel 302 (2021) 121233

A # # = Perovskite phase B 40LaNi0.75Zr0.25-xCexO3/SiO2

* = SiO2
* =SiO 2 • = La O 2 3 ο = NiO

•
* ο• 12 nm
Crystal size
Intensity (a.u)

Intensity (a.u)
ο x=0.25
12 nm
LaNi0.75Zr0.20Ce0.05O3
15 nm x=0.20
# # x=0.15
# #
• 17 nm
x=0.10
# #
* ο
ο
16 nm
x=0.05

*
18 nm
Pure SiO2 ο x=0

10 20 30 40 50 60 70 80 10 20 30 40 50 60 70 80
2-Theta 2-Theta
C 40LaNi0.75Zr0.20Ce0.05O3/ZAl2O3-SiO2 D 40LaNi0.75Zr0.20Ce0.05O3/ZMgO-SiO2
= NiAl2O4 ο = NiO * =SiO * = SiO • = La O
=La2O3 2 # = NiO-MgO 2 2 3 ο = NiO
ο
Crystal size • #
* ο 10 nm ο Z=10 wt.%
* #
ο
ο
• Crystal size
Intensity (a.u)

12 nm ο Z=10 wt.%
Intensity (a.u)

12 nm
Z=8 wt.% 22 nm
Z=8 wt.%
14 nm Z=6 wt.% 18 nm Z=6 wt.%
14 nm Z=4 wt.% 14 nm Z=4 wt.%
15 nm Z=2 wt.% 12 nm Z=2 wt.%
16 nm 16 nm
Z=0 wt.% Z=0 wt.%

10 20 30 40 50 60 70 80 10 20 30 40 50 60 70 80
2-Theta 2-Theta

Fig. 1. XRD patterns of the perovskite-type of catalysts (A) LaNi0.75Zr0.20Ce0.05O3 and SiO2, (B) 40LaNi0.75Zr0.25-xCexO3/SiO2, (C) 40LaNi0.75Zr0.25-xCexO3/ZAl2O3-
SiO2, and (D) 40LaNi0.75Zr0.25-xCexO3/ZMgO-SiO2 (where x = 0, 0.05, 0.10, 0.15, 0.20, 0.25; and Z = 2 wt%, 4 wt%, 6 wt%, 8 wt% and 10 wt%).

gel. A known quantity of silica powder was added slowly with the gel and
mixed thoroughly. The gel was kept in the desiccator overnight, followed
by keeping it in the vacuum oven at 393 K for 12 h to transform the gel
into a cake. The dried cake was pulverized and finally calcined at 1073 K
for 3 h in a muffle furnace. The synthesized material was denoted as
40LaNi0.75Zr0.25-xCexO3/SiO2. Similarly, the support silica was modified
with the precursor of Mg(NO3)2⋅6H2O and Al(NO3)3⋅9H2O by the IWI
method. The modified support denoted as ZMgO-SiO2 and ZAl2O3-SiO2
where, Z was the wt.% of MgO and Al2O3 added to modify the silica. The
above modified supports were used to prepare the supported perovskite
catalysts following the above sol–gel method. The synthesized catalyst
denoted as 40LaNi0.75Zr0.20Ce0.05O3/ZMgO-SiO2 and 40LaNi0.75Zr0.20
Ce0.05O3/ZAl2O3-SiO2.
2.1. Catalyst characterization
The Micromeritics ASAP 2020 porosimeter (USA) equipment was
used to measure the surface properties of the catalyst by obtaining
adsorption–desorption isotherm using liquid nitrogen at 77 K. The sur­
face area was calculated using Brunauer-Emmet-Teller (BET) method in
relative pressure range (p/p0) of 0.05–0.20. The X-ray diffraction
pattern of the synthesized catalyst was recorded with a Bruker AXS
diffractometer D8-Advance in the 2θ = 10–90 angular range. Trans­
mission Electron Microscopy (TEM) analysis of fresh catalysts were
carried out by using FEI Technai G2 20 S-Twin apparatus, with 0.24 nm
to 0.14 nm point and line resolution, respectively, equipped with a LaB6
or W emitter. H2-TPR analysis of the catalyst was conducted to study the
behavior of catalysts and active sites using a Micromeritics Chemisorb
2720 USA instrument equipped with TCD analysis. The same equipment
was used for the CO2-TPD (temperature-programmed desorption)
analysis of the catalyst. About 30 mg of fresh calcined catalyst was
degassed in the U-shaped quartz tube, in the presence of helium flow at
573 K for 3 h, and then cooled to ambient temperature. After pretreat­
ment, a 10% CO2/He gas mixture was used as adsorption gas, while the
temperature was retained at 338 K for 1 h, and then the sample was
flushed with helium-gas flow at 338 K for 1 h. CO2-TPD analysis was
carried out in the presence of helium while increasing the temperature
from ambient to 1273 K with a ramp rate of 10 ℃ min− 1. Raman spectra
were acquired by using an in-via Reflex (Renishaw, UK) instrument. The
spectral range of Raman spectra of the synthesized catalysts were
recorded from 100 to 3000 cm− 1 at ambient temperature. The ther­
mogravimetric (TGA) analysis of the used catalysts was analyzed by TG/
DTA equipment (SII 6300 EXSTAR, Japan).
2.2. Catalytic performance
The DRM reaction was performed in a tubular quartz reactor. Cata­
lytic tests were performed using 100 mg of a fresh catalyst supported

3
­
 P. Kumar Yadav et al.
Fig. 2. The TEM images and SAED patterns of the catalysts 40LaNi0.75Zr0.20
Ce0.05O3/SiO2 (A, B), 40LaNi0.75Zr0.20Ce0.05O3/6Al2O3-SiO2 (C, D) and
40LaNi0.75Zr0.20Ce0.05O3/8MgO-SiO2 (E, F) catalysts.
over quartz wool bed. A total flow rate of reactant gas mixture of 100 ml
min− 1 consisting of CH4:CO2:N2 = 1:1:2 was fed to the reactor using
individual mass flow controllers (AALBORG). The product was analyzed
using a Gas Chromatograph (NewChrom 6700) equipped with a meth­
anizer and TCD (Thermal Conductivity) detector. The detailed experi­
mental setup can be found in the open literature [59].
3. Results and discussion
3.1. BET surface area analysis
The BET surface area of the synthesized catalysts 40LaNi0.75Zr0.25-
xCexO3/SiO2, 40LaNi0.75Zr0.20Ce0.05O3/ZMgO-SiO2 and 40LaNi0.75Zr0.20
Ce0.05O3/ZAl2O3-SiO2 (where x = 0, 0.05, 0.10, 0.15, 0.20, 0.25 and Z =
2 wt%, 4 wt%, 6 wt%, 8 wt%, 10 wt%,) were shown in Table 1.. The BET
study suggested that the surface area of the catalyst 40LaNi0.75Zr0.25O3/
SiO2 was 83 m2/g. The surface area increased by increasing the degree of
ceria content in the catalysts 40LaNi0.75Zr0.20Ce0.05O3/SiO2. The addition
of ceria (small), the segregated phase NiO dispersed gradually and the
surface area increased. Further increasing ceria content, the surface area
decreased. The highest specific surface area was ~ 113 m2/g with the
catalyst 40LaNi0.75Zr0.20Ce0.05O3/SiO2. The pore size decreased and pore
volume increased accordingly. The surface area for the catalyst
40LaNi0.75Ce0.25O3/SiO2 was very low 74 m2/g. The decreased surface
area was due to the blockage of mesopore present in the catalyst (sup­
port). The BET surface area of the calcined catalysts 40LaNi0.75Zr0.20
Ce0.05O3/ZAl2O3-SiO2 by adding the wt.% of alumina was shown in
Table 1.. The study revealed that the addition of alumina in silica slightly
increased the surface area of the catalyst 40LaNi0.75Zr0.20Ce0.05O3/
2Al2O3-SiO2 (~114 m2/g). The increased of surface area was due to the
4
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­
­
Fuel 302 (2021) 121233
dispersion of nickel and the increased of pore volume. The surface area
gradually decreased further increasing the alumina content in the catalyst.
The pore size and pore volume increased up to the catalyst possessed 6 wt
% of Al2O3 in SiO2. Further, increasing the wt.% of alumina the pore size
and pore volume decreased. An unexpected effect is also reported. The
addition of alumina that incorporated in to the Ni3+ ions in the perovskite
lattice (LaNiZrCeO3) and form a modified perovskite-type phase and
NiAl2O4 spinel. The catalyst 40LaNi0.75Zr0.20Ce0.05O3/2MgO-SiO2
possessed the highest surface area (119 m2/g). The surface area gradually
decreased by increasing the magnesia content in the MgO-modified silica-
supported catalysts. The addition of magnesia that incorporated in to the
Ni2+ ions in nickel-oxide lattice (NiO) and form a solid solution (NiO-
MgO). Therefore, the shrinkage of perovskite lattice would be expected by
Al3+ and Mg2+. The excessive addition of Al+3 or Mg2+ the form a NiAl2O4
spinel or solid solution (NiO-MgO) decreased the surface area. Thus,
addition of ceria by substitution of zirconia till x = 0.05, the surface area
of the catalyst increased. However, the study also suggested that the
addition of a small amount of magnesia or alumina was beneficial, and it
modify the support (silica) increased the surface area of the catalysts [25].
3.2. X-ray diffraction study
The X-ray diffraction patterns of the catalysts LaNiZrCeO3, SiO2,
40LaNi0.75Zr0.25-xCexO3/SiO2, 40LaNi0.75Zr0.20Ce0.05O3/ZMgO-SiO2
and 40LaNi0.75Zr0.20Ce0.05O3/ZAl2O3-SiO2 (where x = 0, 0.05, 0.10,
0.15, 0.20, 0.25 and Z = 2 wt%, 4 wt%, 6 wt%, 8 wt%, 10 wt%,) were
obtained and are shown in Fig. 1. Fig. 1A, it revealed that the bulk
perovskite-phase (LaNiZrCeO3) was highly crystalline. The addition of
support, Fig. 1B revealed that the perovskite-phase was highly dispersed
in the catalysts 40LaNi0.75Zr0.25-xCexO3/SiO2 (x = 0, 0.05, 0.10, 0.15,
0.20, 0.25). The detailed study may be available in the open literature
[60]. The La2O3, NiO, and SiO2 were observed with the catalyst
40LaNi0.75Zr0.25-xCexO3/SiO2. The broad peak in the 2θ range 15◦ to 25◦
due to the SiO2 appeared. The diffraction peaks at 2θ values 37.5, 43.6,
and 63.1◦ corresponded to the (1 1 1), (2 0 0) and (2 2 0) planes of the NiO
phase. In addition to ceria, the nickel oxide gradually dispersed as
crystallite size gradually decreased. The peak position at 29◦ and 43.6◦
suggested by the species La2O3. The intensity of these bands gradually
decreased by increasing the ceria content. The study suggested that the
addition of ceria in the catalyst assisted in the dispersion of nickel oxide.
The analysis of Fig. 1C suggested that the addition of alumina in the
modified supported-catalysts 40LaNi0.75Zr0.20Ce0.05O3/ZAl2O3-SiO2,
the similar phenomena observed. With the addition of alumina, the
nickel oxide dispersed as the crystallite size gradually decreased. The
dispersion of nickel oxide was highest with the catalyst modified with
10 wt% Al2O3. At the same time, the formation of NiAl2O4 was observed
in the catalyst. Further increasing the loading of alumina, the dispersed
nickel oxide transformed into nickel aluminate and the intensity of the
species gradually increased. The magnesia-modified catalysts are shown
in Fig. 1D. The analysis of Fig. 1D suggested that similar phenomena and
the presence of NiO, La2O3, and SiO2 species were observed. The in­
tensity of the peaks due to nickel oxide gradually increased as increased
the addition of magnesia in the catalyst up to the loading 8 wt%. Further
increasing the loading of magnesia, the crystallite size (nickel oxide-
magnesia solid solution) decreased. Thus, the study suggested that
with the addition of support (SiO2) dispersed the perovskite phase and
form a highly dispersed supported perovskite catalyst. Furthermore, the
addition of modified-support (alumina-silica), the size of nickel oxide
gradually decreased and formed a new species nickel-aluminate. With
the addition of modified-support (magnesia-silica) the crystallite size of
nickel oxide (nickel oxide-magnesia solid solution) increased. It also
suggested that NiAl2O4 or NiO-MgO solid solution and a highly disperse
perovskite-phase formed by the addition of alumina or magnesia in the
supported perovskite catalysts [61–64].
P. Kumar Yadav et al. Fuel 302 (2021) 121233

40LaNi0.75Zr0.25-xCexO3/SiO2 940 A 40LaNi0.75Zr0.20Ce0.05O3/ZAl2O3-SiO2 1078 B

611 1004
Different loading of Al2O3 1087
x=0.25
1037
x=0.20 637 Z=10 wt.% 865

TCD Signal (a.u)

TCD Signal (a.u)

1044 Z=8 wt.% 1087

647 873
x=0.15
1074 Z=6 wt.% 1087
x=0.10 651
Z=4 wt.% 885

x=0.05 656
942 1044 Z=2 wt.% 867
x=0 663

400 500 600 700 800 900 1000 1100 1200 400 500 600 700 800 900 1000 1100 1200
Temperature, K Temperature, K
40LaNi0.75Zr0.20Ce0.05O3/ZMgO-SiO2 C
1077

1090
Different loading of MgO
Z=10 wt.% 832
1067
880
TCD Signal (a.u)

Z=8 wt.%
832 1055
Z=6 wt.%

1055
855
Z=4 wt.%

Z=2 wt.% 861

400 500 600 700 800 900 1000 1100 1200

Temperature, K

Fig. 3. The H2-TPR profile of catalyst (A) 40LaNi0.75Zr0.25-xCexO3/SiO2, (B) 40LaNi0.75Zr0.25-xCexO3/ZAl2O3-SiO2 and (C) 40LaNi0.75Zr0.25-xCexO3/ZMgO-SiO2.
(where x = 0, 0.05, 0.10, 0.15, 0.20, 0.25 and Z = 2 wt%, 4 wt%, 6 wt%, 8 wt% and 10 wt%).

3.3. TEM analysis 3.4. H2-TPR analysis

The TEM images and SAED analysis of the calcined catalysts
40LaNi0.75Zr0.20Ce0.05O3/SiO2, 40LaNi0.75Zr0.20Ce0.05O3/6Al2O3-SiO2,
and 40LaNi0.75Zr0.20Ce0.05O3/8MgO-SiO2 were obtained and shown in
Fig. 2. TEM images were taken at higher magnification with selected
area electron diffraction pattern (SAED). The TEM image of (Fig. 2A)
and corresponding SAED (Fig. 2B) patterns of the catalyst
40LaNi0.75Zr0.20Ce0.05O3/SiO2 suggested the formation of a poly-
crystalline material. However, the material was distributed uniformly
in the catalyst. The same catalyst synthesized by using the modified-
supports (6Al2O3-SiO2 and 8MgO-SiO2) the TEM image and SAED pat­
terns are shown in (Fig. 2C and D), and the (Fig. 2E and F) respectively.
The analysis of Fig. 2D and F suggested the formation of polycrystalline
material in the catalysts. The formation of NiAl2O4 and perovskite phase
in the alumina-modified (6Al2O3-SiO2) catalysts. The formation of NiO-
MgO (solid solution) and the perovskite phase in the magnesia-modified
(8MgO-SiO2) catalysts. Thus the study suggested that the catalyst pre­
pared by modified supports possessed more polycrystalline feature that
assisted to the dispersion of nickel oxide.Fig. 3.Fig. 4.Fig. 5.Fig. 6.Fig. 7.
Fig. 8.
The H2-TPR profile of all the calcined catalysts 40LaNi0.75Zr0.25-
xCexO3/SiO2, 40LaNi0.75Zr0.20Ce0.05O3/ZMgO-SiO2 and 40LaNi0.75Zr0.20
Ce0.05O3/ZAl2O3-SiO2 (where x = 0, 0.05, 0.10, 0.15, 0.20, 0.25 and Z =
2 wt%, 4 wt%, 6 wt%, 8 wt%, 10 wt%) were obtained and are shown in
Fig. 3. The TPR profile of catalyst 40LaNi0.75Zr0.25-xCexO3/SiO2 shown
in Fig. 3A exhibited the three peaks, the position at 663 K, 942 K, and
1044 K for the catalysts × = 0. The first peak 663 K represented a direct
reduction of the Ni2+ species to Ni. The peak at 942 K was due to the
nickel-zirconia phase and the 1044 K was due to the perovskite phase in
the catalyst. The peak position at 663 K gradually decreased to the lower
temperature as increased the ceria content (x = 0, 0.05, 0.10, 0.15, 0.20,
and 0.25). The peak position increased to 1074 K for the catalyst
40LaNi0.75Zr0.20Ce0.05O3/SiO2. Further increased the ceria (as x), the
peak position shifted to lower reduction temperature. The peak at 611 K
associated with the reduction of the most easily reducible surface-
capping oxygen of the nickel oxide. The peak position at 940 K was
attributed to the reduction of bulk oxygen present in the perovskite
(dispersed) phase (nickel-ceria) in the catalyst. The study suggested that
a different types of oxides species (Ni-Ce or Ni-Zr) and a perovskite
phase formed in the catalyst 40LaNi0.75Zr0.25-xCexO3/SiO2. Addition of

5
 P. Kumar Yadav et al. Fuel 302 (2021) 121233

3.5. The CO2-TPD analysis

40LaNi0.75Zr0.20Ce0.05O3/ZMgO-SiO2
Different wt. % The surface basicity of the catalyst 40LaNi0.75Zr0.20Ce0.05O3/ZMgO-
loading of MgO 1190 SiO2 (Z = 0 wt%, 2 wt%, 4 wt%, 6 wt%, 8 wt%, 10 wt%) were analyzed
386 868 by the CO2-TPD analysis. The desorption temperature and the CO2 up­
CO2 concentration in (a.u)

Z = 10 take reflected the amount, and strength of the basic sites on the catalytic
1190
surface. The CO2 desorption curves were shown in Fig. 4. Fig. 4 sug­
805 1328 gested that the various peaks at 386 K, 925 K, 1190 K, and 1240 K
386 Z=8 930
corresponded to the catalyst 40LaNi0.75Zr0.20Ce0.05O3/SiO2. The CO2-
1190
386 930 desorption peaks categories into three different regions: first peak α <
Z=6 500 K, second peak β < 1100 and third peak γ > 1100 K. The peak at 386
1190 K attributed to the weak basic sites (–OH) on the surface of the catalyst.
386 925
Z=4 The desorption peaks around 500–1100 K attributed to the medium
1190 basic sites (associated with the metal–oxygen ion pairs) on the surface of
386 the catalyst. The desorption peak at 1190 K and one shoulder peak at
Z=2
925 1190 1240 1240 K associated with the strong basic sites (unsaturated O2–) on the
386 Z=0 surface of the catalyst [29,72,73]. The study suggested that all the cat­
alysts possessed the weak and strong basic sites. These basic sites were
400 500 600 700 800 900 1000 1100 1200 1300 gradually increased as increasing the wt.% of magnesia. The new band
Temperature, K at 805 K was due to the adsorption of carbon dioxide over the surface of
lanthanum oxides. The amount of medium, and strong basic sites was
Fig. 4. The CO2-TPD profiles of the catalyst 40LaNi0.75Zr0.25-xCexO3/ZMgO-
highest with the catalyst 40LaNi0.75Zr0.20Ce0.05O3/8MgO-SiO2. Further,
SiO2, where Z = 0 wt%, 2 wt%, 4 wt%, 6 wt%, 8 wt%, and 10 wt% of MgO
increasing the wt.% of MgO content (or Z value) in the catalyst, the
in SiO2.
intensity of the medium, and strong basic sites decreased. Thus, the
study suggested that the catalyst synthesized using 8 wt% of MgO
ceria (x = 0.05) the reduction temperature of the perovskite-phase
possessed the highest medium and strong basic sites.
moved to higher temperature (1074 K) in the catalyst [65-70].
The analysis of the catalysts synthesized by using the modified-
3.6. Raman spectra analysis
support (ZAl2O3-SiO2) were obtained and shown in Fig. 3B. The anal­
ysis of the Fig. 3B suggested that the presence of peaks position at 620 K,
The Raman spectra of the fresh perovskite-type catalysts
867 K, and 1087 K for the catalyst (Z = 2 wt% Al2O3). The study sug­
40LaNi0.75Zr0.25-xCexO3/SiO2 (where x varied as x = 0, 0.05, 0.10, 0.15,
gested that the catalyst 40LaNi0.75Zr0.20Ce0.05O3/2Al2O3-SiO2 possessed
0.20, 0.25), 40LaNi0.75Zr0.20Ce0.05O3/ZAl2O3-SiO2, and
three different types of reducible (oxygenated compound) species. The
40LaNi0.75Zr0.20Ce0.05O3/ZMgO-SiO2 (where Z = 0 wt%, 2 wt%, 4 wt%,
peak position at 620 K suggested the reduction of surface Ni2+ species to
6 wt%, 8 wt%, and 10 wt%). are shown in Fig. 5. The analysis of Fig. 5A
Ni. With the addition of modified-support (2Al2O3-SiO2) the peak
revealed that the vibrational bands appeared at 496 cm− 1 and 983 cm− 1.
appeared at 867 K and 1087 K. The peak position at 867 K was due to the
The band at 496 cm− 1 suggested the nickel-oxide species and band at
NiAl2O4 species and the peak at 1087 K was due to the perovskite-phase.
983 cm− 1 suggested the support silica in the zirconia (x = 0) dominated
[61,65-68]. Further increased the wt.% of Al2O3 (ZAl2O3-SiO2)
catalysts. The band intensity gradually increased by increasing the ceria
modified-catalysts the peak at 620 K disappeared and the peak 867 K
content in the catalysts, and a new band appeared at 519 cm− 1. The band
shifted to 885 K. Increased addition of alumina, the reduction peaks
496 cm− 1 shifted towards the right at 604 cm− 1 till x = 0.20. Further
shifted to lower temperature (1078 K).
increasing ceria, the band shifted at 561 cm− 1. The band 496 cm− 1 was
The study suggested that the formation of nickel oxide species and
due to the zirconia dominated nickel-oxide, and the band 561 cm− 1 was
other two different types of oxides species that reduced at higher tem­
due to the ceria dominated nickel oxides in the catalysts. The bands 519
peratures. The H2-TPR analysis for the catalyst 40LaNi0.75Zr0.20
cm− 1 and 604 cm− 1 were due to both the ceria and zirconia dominated
Ce0.05O3/ZMgO-SiO2 was obtained and shown in Fig. 3C. In Fig. 3C the
nickel oxide. The Raman spectra of the catalysts 40LaNi0.75Zr0.20
peaks at due to the surface nickel oxide was absent in the modified
Ce0.05O3/ZAl2O3-SiO2 were obtained and shown in Fig. 5B. The analysis
supported-catalysts (magnesia-silica). The major peaks appeared at 861
of Fig. 5B suggested the band at 983 cm− 1 confirmed the silica. The band
K and 1055 K. These peaks suggested to the formation of NiAl2O4 species
at 519 cm− 1 and 604 cm− 1 confirmed the ceria and zirconia dominated
that reduced at 861 K, and the perovskite oxide species reduced at 1055
nickel oxide species in the catalysts. The intensity of bands gradually
K for the catalyst 40LaNi0.75Zr0.20Ce0.05O3/2MgO-SiO2. Further
decreased as increasing the wt.% of Al2O3 in the catalysts. The bands at
increased addition of magnesia in the modified supported catalysts, the
480 cm− 1 and 604 cm− 1 were almost disappeared in the alumina-
reduction peaks of perovskite phase moved to higher temperature till z
modified catalyst (10 wt%). Thus, the study suggested that the nickel
= 8 wt%, then it decreased. The hydrogen consumption was also
oxide gradually dispersed with formation of NiAl2O4 as increased the wt.
measured for each sample and it was observed that the order of
% of Al2O3 in the catalyst. The Raman spectra of the perovskite-type
consumed hydrogen as 218.34 (ml/gcat) 40LaNi0.75Zr0.20Ce0.05O3/
oxide catalysts 40LaNi0.75Zr0.20Ce0.05O3/ZMgO-SiO2 (Z = 2 wt%, 4 wt
8MgO-SiO2 > 64.35 (ml/gcat) (40LaNi0.75Zr0.20Ce0.05O3/6Al2O3-SiO2)
%, 6 wt%, 8 wt%, 10 wt%) were obtained and shown in Fig. 5C. The
> 50.24 (ml/gcat) (40LaNi0.75Zr0.20Ce0.05O3/SiO2) [71]. The details
analysis of Fig. 5C revealed that the band appeared at 983 cm− 1 con­
hydrogen consumption of all catalysts is not shown here for brevity.
firms the support silica. The band at 519 cm− 1 and 604 cm− 1 suggested
Thus, the study suggested that the nickel oxide was highly dispersed or
the nickel oxide species in the catalyst 40LaNi0.75Zr0.20Ce0.05O3/SiO2.
absent, and the perovskite-phase were more stable in catalysts by
The addition of magnesia in the catalyst, the peak 519 cm− 1 shifted to
addition of magnesia. The addition of modified support a NiAl2O4
534 cm− 1 and a new band appeared at 384 cm− 1 with the loading 4 wt%
(spinel), and NiO-MgO (solid solution) formed along with the perovskite
magnesia. The intensity of the peaks was gradually increased by
phase in the modified-supported catalyst (ZAl2O3-SiO2 and ZMgO-SiO2)
increasing the magnesia content in the catalyst. The band at 384 cm− 1
respectively, therefore, the catalyst reduced at higher temperature. The
confirms the La2O3 in the catalyst. The band 604 cm− 1 was due to the
magnesia modified-supported catalyst possessed more reducible nickel;
zirconia-ceria dominated nickel oxides, and the band at 534 cm− 1 was
therefore, it consumed more hydrogen.
nickel-oxide-magnesia solid solution. Thus, the study suggested that the

6
­
­
 P. Kumar Yadav et al. Fuel 302 (2021) 121233

Fesh 40LaNi0.75Zr0.25-xCexO3/SiO2 A Fresh 40LaNi0.75Zr0.20Ce0.05O3/ZAl2O3-SiO2 B

561 Different wt.%
loading of Al2O3
983 480 604 983 Z = 10
x=0.25
604
519 Z=8
x=0.20

Intensity (a.u)
Z=6
519
Intensity (a.u)

604 604
519
x=0.15 Z=4
604
519 Z=2
x=0.10 519604
x=0.05
496
x=0 Z=0

300 600 900 1200 1500 1800-1 2100 2400 2700 3000 300 600 900 1200 1500 1800 2100 2400 2700 3000
-1
Raman Shift (cm ) Raman Shift (cm )
Fresh 40LaNi0.75Zr0.20Ce0.05O3/ZMgO-SiO2 C
534

604 Different wt.% loading

384 of MgO with SiO2
983
Z=10 wt.%
Intensity (a.u)

Z=8 wt.%
519 Z=6 wt.%
Z=4 wt.%
519 604 Z=2 wt.%

Z=0 wt.%

300 600 900 1200 1500 1800 2100 2400 2700 3000
-1
Raman Shift (cm )

Fig. 5. The Raman spectra of the perovskite-type catalysts (A) 40LaNi0.75Zr0.25-xCexO3/SiO2 (where × varied as x = 0, 0.05, 0.10, 0.15, 0.20, 0.25), (B)
40LaNi0.75Zr0.20Ce0.05O3/ZAl2O3-SiO2, and (C) 40LaNi0.75Zr0.20Ce0.05O3/ZMgO-SiO2 with different values of Z where Z = 0 wt%, 2 wt%, 4 wt%, 6 wt%, 8 wt%, and
10 wt%.

formation of NiO-MgO solid solution and it gradually increased as up to 10 h.

increasing the loading of magnesia (wt.%) in the catalysts.
3.7. The effect of Zr to Ce ratio using catalysts 40LaNi0.75Zr0.25-xCexO3/
SiO2 for DRM reaction
The DRM reaction was performed over the catalysts 40LaNi0.75Zr0.25-
xCexO3/SiO2 (x = 0, 0.05, 0.10, 0.15, 0.20, 0.25) by changing the ratio of
Zr to Ce were obtained and shown in Fig. 6. The percentage conversion
of CH4 and CO2 are shown in Fig. 6A, and the corresponding product (H2
and CO) yield are shown in Fig. 6B. In Fig. 6A, it revealed that the
percent conversion of CH4 and CO2 gradually increased as increasing the
ceria content and decreasing the zirconia content till the catalyst
40LaNi0.75Zr0.20Ce0.05O3/SiO2. The conversion of CH4 and CO2
decreased further increasing the ceria content in the catalyst. The yield
of product (H2 and CO) gradually increased till the catalyst
40LaNi0.75Zr0.20Ce0.05O3/SiO2, then it decreased with increasing more
addition of ceria in the catalyst. The study suggested that the highest
percent conversion, and product yield of (H2 and CO) obtained with the
catalyst 40LaNi0.75Zr0.20Ce0.05O3/SiO2. The ratio of H2 to CO was
consistent close to unity (0.92) for all the catalysts throughout operation
3.8. Effect of alumina in the Modified-Supported (ZAl2O3-SiO2) catalysts
The DRM reaction was performed over the catalysts
40LaNi0.75Zr0.20Ce0.05O3/ZAl2O3-SiO2 (Z = 0, 2 wt%, 4 wt%, 6 wt%, 8
wt%, 10 wt%) by changing the weight percent of Al2O3 in SiO2 were
obtained and shown in Fig. 7. The percent conversion is shown in
Fig. 7A, and the corresponding product (H2 and CO) yield are shown in
Fig. 7B. Fig. 7A revealed that the percent conversion of CH4 and CO2
gradually increased till the 6 wt% Al2O3 added in silica, and further
increased the wt.% of alumina, the percent conversion decreased. The
yield of product (H2 and CO) gradually increased as increasing the wt.%
of Al2O3 till the 6 wt% of Al2O3 added in silica, and further increased the
wt.% of alumina, the percent conversion decreased. Thus, the study
suggested that the addition of alumina in a certain wt.% (Z = 6 wt%) in
the silica, the percent conversion (CO2 and CH4) and the product (H2,
CO) yield were increased and beneficial. The catalyst 40LaNi0.75Zr0.20
Ce0.05O3/6Al2O3-SiO2 was the most active. The ratio of H2 to CO was
consistent close to unity (0.79) for the most active catalyst throughout
operation up to 10 h.

7
­
P. Kumar Yadav et al. Fuel 302 (2021) 121233

100 100
A 40LaNi0.75Zr0.25-xCexO3/SiO2 CH4 B 40LaNi0.75Zr0.25-xCexO3/SiO2 YH2
CO2 YCO
90 90

% Yield of H2 and CO
% Conv.of CH4 & CO2

80 80

70 70

60 60

50 50
x=0 x = 0.05 x = 0.10 x = 0.15 x = 0.20 x = 0.25 x=0 x=0.05 x=0.10 x=0.15 x=0.20 x=0.25
Catalysts Catalysts

Fig. 6. (A) The percent conversion of CH4 and CO2 and (B) product yield of CO and H2 during the DRM reaction over the catalysts during the DRM reaction over the
catalysts 40LaNi0.75Zr0.25-xCexO3/SiO2 by changing the ratio of Zr to Ce. The ratio was varied as (x = 0.25, 0.20, 0.15, 0.10, 0.05, 0).

100 100
A 40LaNi0.75Zr0.20Ce0.05O3/ZAl2O3-SiO2 CH4 40LaNi0.75Zr0.20Ce0.05O3/ZAl2O3-SiO2 YH2
B
98
CO2 95 YCO
96
90
% Yield of H2 and CO
% Conv. of CH4 and CO2

94
85
92

90 80

88
75
86
70
84
65
82

80 60
Z=0 Z=2 Z=4 Z=6 Z=8 Z = 10 Z=0 Z=2 Z=4 Z=6 Z=8 Z = 10
Catalysts Catalysts

Fig. 7. (A) The percent conversion of CH4 and CO2 and (B) product yield of CO and H2 during the DRM reaction over the catalysts 40LaNi0.75Zr0.20Ce0.05O3/ZAl2O3-
SiO2; where Z = 0 wt%, 2 wt%, 4 wt%, 6 wt%, 8 wt% and 10 wt% of Al2O3 with SiO2. The DRM reaction was conducted for 10 h (time on stream study) with
each catalyst.

3.9. Effect of magnesia in the modified-supported (ZMgO-SiO2) catalysts operation up to 10 h.

The DRM reaction were performed over the catalysts
40LaNi0.75Zr0.20Ce0.05O3/ZMgO-SiO3 (Z = 0, 2 wt%, 4 wt%, 6 wt%, 8 wt
%, 10 wt%) by changing the weight percent of magnesia in silica are
shown in Fig. 8. The percent conversion shown in Fig. 8A and the cor­
responding product (H2 and CO) yield shown in Fig. 8B. In Fig. 8, it
revealed that the conversion of CH4 and CO2 gradually increased by
increasing the loading of magnesia (Z = 8 wt% of MgO) in the catalyst.
Further increased the wt.% of MgO the percent conversion decreased.
The yield of product (H2 and CO) also gradually increased till the 8 wt%
of MgO content and then it decreased further increasing addition of
magnesia in the catalyst. The study suggested that the highest percent
conversion (CH4 and CO2) and highest product yield (H2 and CO) were
obtained with the catalyst 40LaNi0.75Zr0.20Ce0.05O3/8MgO-SiO2. The
H2-TPR and CO2-TPD analysis were consistent as the catalyst was more
stable and possessed more medium basic sites. The ratio of H2 to CO was
consistent close to unity (0.89) with the most active catalyst throughout
4. The effect of CH4 and CO2 ratio in the feed
The DRM reaction was performed over the catalyst
40LaNi0.75Zr0.20Ce0.05O3/8MgO-SiO2 by changing the ratio of CH4: CO2
in the feed stream and the data are shown in Fig. 9. The symbol and the
dotted line indicated the experimental data point trend of the conver­
sion, yield, and H2/CO ratio with gradual change of CH4/CO2 ratio in the
feed. The reaction was conducted at total flow rate 100 ml/min and the
ratio of CH4 to CO2 were gradually increased and it was varied as 0.1 to
9.0. The analysis of Fig. 9A suggested that the conversion of CH4 and
CO2 increased as increasing the ratio of CH4 to CO2 upto the 1. Further
increasing the ratio of CH4 to CO2, the percent conversion of CH4 and
CO2 gradually decreased. However, the percent conversion of methane
decreased more rapidly than the carbon dioxide. The analysis of Fig. 9B
suggested yield of H2 and CO. The yield of H2 and CO were gradually
increased as increasing the CH4/CO2 ratio till 1.5. Further increased the

8
P. Kumar Yadav et al.
100
A B
98
96
% Conv. of CH4 and CO2
94
92
90
88
86
40LaNi0.75Zr0.20Ce0.05O3/ZMgO-SiO2
84
CH4
82 CO2
80
Z=0 Z=2 Z=4 Z=6 Z=8
Catalysts
Fig. 8. (A) The percent conversion of CH4 and CO2 and (B) product yield of CO and H2 during the DRM reaction over the catalysts 40LaNi0.75Zr0.20Ce0.05O3/ZMgO-
SiO2; where Z = 0 wt%, 2 wt%, 4 wt%, 6 wt%, 8 wt% and 10 wt% of MgO with SiO2. The reaction was conducted for 10 h (time-on-stream) with each catalyst.
ratio of CH4 to CO2, the product yield was decreasing gradually. The
analysis of Fig. 9C suggested that the H2/CO ratio gradually increased as
increasing the ratio CH4 to CO2 in the feed stream. The H2/CO ratio
crossed the stoichiometry value 1.0 (>1), while the CH4 to CO2 ratio
crossed the range of 2. Thus, the study suggested that the optimum ratio
of CH4 to CO2 was 1.0 to obtain the highest percent conversion of CH4
and CO2. And it was ~ 2 to obtain the highest product (H2, CO) yield.
The H2/CO ratio was ~ 1 when the CH4/CO2 ratio fixed the value 1 to 2.
5. TGA and Raman spectra analysis of the used catalysts
The thermo gravimetric analysis (TGA) were performed to investi­
gate the carbon deposition of the used catalysts. The mass loss profiles of
the used catalysts 40LaNi0.75Zr0.20Ce0.05O3/ZMgO-SiO2 at different
loading of magnesia (Z = 2 wt%, 4 wt%, 6 wt%, 8 wt%, 10 wt%,) were
obtained and presented in Fig. S1. Fig. S1 revealed that the percent
weight loss was highest with the catalyst (z = 0) possessed no magnesia.
The addition of magnesia (2 wt% magnesia-modified silica) in the
catalyst, the carbon deposition or weight loss decreased. As increased
the wt% of magnesia, the percent weight loss gradually decreased. Thus,
the study suggested that the addition of magnesia (MgO-modified silica)
was beneficial to suppress the carbon deposition during the DRM
reaction.
The Raman spectra of the used catalysts 40LaNi0.75Zr0.25-xCexO3/
SiO2 were obtained and shown in Fig. S2. The used catalysts were
analyzed after conduction of the DRM reaction at 1073 K for 10 h. The
analysis of Fig. S2A suggested that the formation of new bands appeared
at 1345 cm− 1, 1586 cm− 1, and 2686 cm− 1 suggested to the formation of
carbon in the used catalyst of 40LaNi0.75Zr0.25O3/SiO2. These bands
were suggested to the D, G, and 2D vibration modes of carbonaceous
materials and graphite in samples. The D band related to the disorder-
induced Raman scattering and G band was due to the stretching of the
C–C bond of sp2 carbons. The 2D band was due to the second-order
Raman band of isolated carbonaceous materials assigned to both over­
tone and combination bands. The intensity of the bands was gradually
decreased till x = 0.05. Further increased addition of ceria by substi­
tution of zirconia the carbon formation gradually increased. Thus, the
study suggested that the catalyst with an optimum ratio of Zr to Ce was
beneficial and the catalyst 40LaNi0.75Zr0.20Ce0.05O3/SiO2 possessed less
carbon deposition during DRM reaction. Also, the absent of any bands at
519 cm− 1 suggested that the nickel oxide (Ni-Ce or Ni-Zr spinel oxides)
Fuel 302 (2021) 121233
100
95
90
% Yield of H2 and CO
85
80
75
70
40LaNi0.75Zr0.20Ce0.05O3/ZMgO-SiO2
65 YH2
YCO
60
Z = 10 Z=0 Z=2 Z=4 Z=6 Z=8 Z = 10
Catalysts
in the catalysts was reduced into nickel metal during the DRM reaction
at high temperature (1073 K). The Raman spectra of the used catalysts
40LaNi0.75Zr0.20Ce0.05O3/ZAl2O3-SiO2 were obtained and shown in
Fig. S2B. The analysis of Fig. S2B suggested that the carbon deposition
was gradually increased as increased the wt% of alumina addition
(modified the support). However, the highest percent conversion ob­
tained with the catalysts possessed 6 wt% of alumina-modified silica.
The study also suggested that the carbon deposition did not affect the
percent conversion of methane and carbon dioxide (the data is not
shown here for brevity). The analysis of the Raman spectra of the used
catalysts 40LaNi0.75Zr0.20Ce0.05O3/ZMgO-SiO2 were obtained and
shown in Fig. S2C. The study suggested that the formation of various
carbonaceous materials as discussed above. A weak band at 519 cm− 1
were obtained and suggested the nickel oxide present in the used cata­
lyst. However, the intensity of carbon formation was low in case of MgO-
modified SiO2 supported catalysts.
Furthermore, the most active catalyst 40LaNi0.75Zr0.20Ce0.05O3/
8MgO-SiO2 studied for the DRM reaction by changing the CH4/CO2 ratio
and the obtained Raman spectra are shown in Fig. S3. The analysis of the
spectra in Fig. S3 suggested that the carbon formation gradually
increased as increasing the methane to carbon dioxide ratio till 1. The
carbon deposition decreased further increasing the ratio till 1.5. The
carbon formation again increased as increasing the CH4 to CO2 ratio.
The ordered carbon material (G-band) formation gradually increased
with increasing the flow rate of methane in the feed gas. Thus, the study
suggested that the high CO2 flow in the feed gas was beneficial to
minimize the formation of (SP2 graphitic) carbon in the catalyst. The
Raman spectra study suggested that the conversion of methane and
carbon dioxide gradually increased and the deposition of carbon also
increased. The carbon formation increased as increasing the methane
cracking reaction, however removal of the deposited-carbon decreased
due to the slow reverse Boudouard reaction. The study also suggested
that the H2 to CO ratio gradually increased as increasing the CH4 to CO2
ratio. The study suggested that the DRM reaction increased till the ratio
reached to 1, and it decreased further. The cracking of methane reaction
dominated (CH4 to CO2 ratio > 1) over DRM, as results the H2 to CO
ratio increased which was beyond the stoichiometry (H2:CO::1). The
reverse Boudouard reaction also took place simultaneously. Thus, the
optimum ratio of CH4 to CO2 for the DRM reaction suggested to be 1
under the present operating conditions.
9
P. Kumar Yadav et al. Fuel 302 (2021) 121233

100 100
A 40LaNi0.75Zr0.20Ce0.05O3/8MgO-SiO2 B
90 90 YH2
YCO
% Conversion of CH4 and CO2

80 80

% Yield of H2and CO
40LaNi0.75Zr0.20Ce0.05O3/8MgO-SiO2
70 70
CH4
60
CO2 60
Total flow rate: 100 ml/min
50 CH4: 5 ml/min to 45 ml/min 50
CO2: 45 ml/min to 5 ml/min
40
N2: 50 ml/min 40
30
30
20
20
10
0 1 2 3 4 5 6 7 8 9 10 0 1 2 3 4 5 6 7 8 9 10
CH4/CO2 Ratio CH4/CO2 Ratio
1.4
C
1.2

40LaNi0.75Zr0.20Ce0.05O3/8MgO-SiO2
1.0
H2/CO Ratio

H2/CO
0.8

0.6

0.4

0.2

0.0
0 1 2 3 4 5 6 7 8 9 10
CH4/CO2 Ratio

Fig. 9. (A) The percent conversion of CH4 and CO2, (B) product yield of H2 and CO, and (C) H2/CO ratio during the DRM reaction over the catalysts
40LaNi0.75Zr0.20Ce0.05O3/8MgO-SiO2. The reaction was conducted for 6 h on stream. The flow rate of CH4 and CO2 was varied from 5 ml/min to 45 ml/min. The N2
gas flow rate is constant 50 ml/min.

6. Conclusions
A series of perovskite catalysts were prepared considering Ni (75 wt
%) and Zr-Ce (25 wt%) (changing the ratio). The support silica-modified
with alumina and magnesia. All the synthesized catalysts were tested for
the DRM reaction. The surface area of the synthesized catalyst increased
with addition of ceria a certain ratio (x = 0.05). However, the surface
area did not change significantly as the silica-modified with alumina or
magnesia. The increased of surface area was due to the dispersion of the
nickel oxide and increased the pore volume. An excess zirconia/ceria
prevents the formation of perovskite structure and produced the segre­
gated phases of (La2O3, NiO, and CeO2) in the silica-supported catalyst.
The formation of NiAl2O4 or NiO-MgO solid solution were observed in
the alumina or magnesia-modified catalysts. All catalysts possessed
polycrystalline phases. Addition a small amount of ceria with zirconia
increased the stability of the catalysts, and the stability further increased
by addition of alumina (6 wt%) or magnesia (8 wt%) in a certain ratio.
The nickel oxide gradually dispersed (as NiAl2O4) as increasing the
addition of alumina, and by formation of NiO-MgO solid solution as
increasing the addition of magnesia. The alumina-modified silica and
magnesia-modified silica assisted in increasing the percent conversion
and product yield. The carbon deposition observed in all catalysts during
the DRM reaction however; the activity of the catalyst was unaffected.
The ratio of reactant (methane and carbon dioxide) in the feed stream
was very crucial and the optimum ratio was 1 to obtain the highest
conversion and product yield using the DRM reaction. The ratio of H2/
CO gradually increased as increasing the methane to carbon dioxide
ratio suggested the methane cracking reaction dominated over the DRM
reaction and the deposition of carbon was due to the methane cracking.
CRediT authorship contribution statement
Pradeep Kumar Yadav: Conceptualization, Investigation, Formal
analysis. Taraknath Das: Project administration, Resources, Supervi­
sion. Prasenjit Mondal: .
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.

10
P. Kumar Yadav et al. Fuel 302 (2021) 121233

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