Journal of Environmental Chemical Engineering 10 (2022) 107710

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Journal of Environmental Chemical Engineering

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Enhanced CH4 selectivity for CO2 methanation over Ni-TiO2 by addition of

Zr promoter
Ammarika Makdee a, Pinit Kidkhunthod b, Yingyot Poo-arporn b, Kingkaew
Chayakul Chanapattharapol a, *
a
Materials Chemistry Research Center, Department of Chemistry, Faculty of Science, Khon Kaen University, Khon Kaen 40002, Thailand
b
Synchrotron Light Research institute (Public Organization), Nakhon Ratchasima 30000, Thailand

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

Editor: Dong-Yeun Koh TiO2 and 10 wt%Ni-ZrxTi1− xO2 (x = 0, 0.1, 0.15, and 0.2) catalysts were synthesized and used for CO2
methanation reaction. The catalyst with 10 mol% Zr addition (10 wt%Ni-Zr0.1Ti0.9O2) exhibited the highest CO2
Keywords: conversion and CH4 selectivity with highly stable property. The role of Zr addition on enhancing CO2 metha­
CO2 methanation nation reaction rate was to tune the electronic property of Ni species by electron transfer from Zr to Ni valence
Zr incorporation into TiO2
state. From the donating effect of Zr, an appropriate metal-support interaction was then improved which led to
Electron movement
higher dispersion of Ni species on catalyst surface which was beneficial to the adsorption of H2 molecules.
Metal-support interaction
Moreover, Zr addition also improved the basicity of the catalyst, which can also promote the adsorption of CO2.
Therefore, an appropriate H2 and CO2 adsorption ability can enhance catalytic activity. The effect of tuning
electronic properties by Zr addition on enhancing the catalytic performance resulted from lowering of C-O
bonding dissociation barrier. Upon CO intermediate was adsorbed on Ni electron rich site, the electron of valence
d state of Ni was transferred to π* anti-bonding of CO molecule and the C-O bonding was then weakened and
easily dissociated to carbon and oxygen to further hydrogenation and formed products.

1. Introduction
It is well known that the increase of greenhouse gas emissions,
especially carbon dioxide (CO2) which is the most abundant in the at­
mosphere and the main contributor to global warming and climate
change, is a global concern. Nowadays, the CO2 concentration in the
atmosphere can be reduced by two main approaches; CO2 capture and
storage (CCS) and CO2 capture and utilization (CCU). CO2 capture and
storage is a process that reduces CO2 concentration by capturing and
storing CO2 in the oceans or mineral carbonates. This involves long-term
separation from the atmosphere [1]. Although CO2 capture and storage
are an important way to rapidly decrease CO2 in the atmosphere, it has a
problem of CO2 leakage, high operation costs and high energy demands.
Therefore, CO2 capture and utilization is now the preferred approach.
CO2 capture and utilization is the technique that captures and uses CO2
as a carbon feedstock to produce useful products and fuels such as car­
bon monoxide (CO), methanol (CH3OH), dimethyl ether (CH3OCH3),
and methane (CH4). Among CO2 conversion processes, CO2 hydroge­
nation to CH4, which is called CO2 methanation or Sabatier reaction
according to Eq. (1), is more interesting for many research groups as it
does not only decrease CO2 concentration but also generates CH4, which
is an important energy carrier source [2]. The generated CH4 can be
directly injected into natural gas pipelines and used as a starting reagent
for the formation of other chemicals. Furthermore, the CO2 methanation
reaction is also considerably faster than other reactions (CO2 hydroge­
nation to hydrocarbons or alcohols) [3] under atmospheric pressure and
low temperature.
CO2 + 4H2 ⇌ CH4 + 2H2O ΔH298 K = − 165.0 kJ/mol (1)
Normally, to increase the reaction rate, increasing the reaction
temperature is usually employed. However, CO2 methanation is an
exothermic reaction which favors to occur at low temperature; thus,
increasing the reaction temperature leads to a reduction of product
formation. Moreover, the CO2 molecule with a fully oxidized state is
inert and highly stable; thus, high energy input is needed to activate this
molecule. Therefore, to overcome the kinetic and thermodynamic lim­
itations, a catalyst must be employed to get high reaction rate at low
temperature. The heterogeneous catalyst for this reaction typically

* Corresponding author.
E-mail address: kingkaew@kku.ac.th (K.C. Chanapattharapol).

https://doi.org/10.1016/j.jece.2022.107710
Received 17 January 2022; Received in revised form 17 March 2022; Accepted 11 April 2022
Available online 14 April 2022
2213-3437/© 2022 Elsevier Ltd. All rights reserved.
A. Makdee et al.
consists of two main parts: active species and support. For active species,
several works confirmed that noble metals such as Ru and Rh provided
the highest catalytic activity and CH4 selectivity [3–8]. However, they
are very expensive. Therefore, other metals with a lower price have been
employed instead. Ni metal has been widely used as an active species
due to its being inexpensive and having high catalytic activity [4,9–13].
Normally, Ni active species is usually dispersed on high surface area
metal oxide support such as SiO2 Al2O3, zeolite and CeO2 etc. These
supports affect the metal-support interaction, CO2 adsorption, and metal
dispersion on the catalyst surface. Those properties are important factors
to dominate the CO2 methanation catalytic performance. Among metal
oxide supports, TiO2 is now of interested support due to its low price,
low toxicity, and good chemical and thermal stability.
In the past decade, many research groups reported on improving
catalyst properties by many approaches in order to obtain the catalyst
with high catalytic performance, high stability which avoids deactiva­
tion during time on stream. One of the most important issues concerning
catalyst synthesis is that the obtained catalyst must express high CO2
conversion and CH4 selectivity. Since this reaction has a significant
thermodynamic limitation, therefore, at high reaction temperature, CH4
formation is suppressed. Beside thermodynamic limitation at high re­
action temperature, reversed water gas shift reaction (CO2 + H2 ⇌ CO +
H2O ΔH298 K = 41.2 kJ/mol), which is a side reaction, can also occur.
Because this side reaction favors to occur at high temperature, the un­
desired CO product is usually formed and leads to lower CH4 selectivity.
Therefore, to increase the CH4 selectivity at high temperature, CO
methanation is a pathway of interest. The produced CO from side re­
action can convert to CH4 via CO methanation reaction (CO + 3 H2 ⇌
CH4 + H2O; ΔH298 K = − 206 kJ/mol). In order to increase CH4 forma­
tion through CO methanation, dissociation of CO molecules must be
facilitated by lowering its dissociation barrier [14–16]. It has been re­
ported that the addition of the second metal into the catalyst can reduce
the CO dissociation barrier which resulted in high CO2 conversion with
high CH4 selectivity at high reaction temperature. The CO methanation
catalytic activity can be promoted by tuning the interaction between an
active species and the support. Kikkawa et al. [14] reported Pt-Ni/­
γ-Al2O3 for selective hydrogenation of CO2 toward CH4. They found that
Ni-Pt alloy can provide the active site for H2 dissociation at low tem­
perature, which resulted in high CO2 methanation catalytic activity.
This can be described by tuning the interaction between active species
and support. The formation of Ni-Pt alloy can promote the C-O disso­
ciation by increasing the bond strength between the active species on the
catalyst surface and the CO molecule. Upon strongly anchoring the CO
molecule on an active species, the C-O bonding was weakened, which
led to more easily to dissociate to carbon and oxygen atom and further
hydrogenate with nearby H atom to form products. Therefore, the
addition of the second metal into the catalyst to tune the electronic
property of Ni active species is an alternative method. Zr ion is one of the
transition metals that is widely used as the promoter for methanation
reaction [17–20]. It has been reported that the addition of Zr promoted
the thermal stability and catalytic activity of TiO2 [21,22] and also
improved the structural properties of TiO2 in terms of crystallinity and
surface area [23–25]. Moreover, Zr is an earth-abundant and environ­
mentally friendly element. Li et al. [26] reported the effect of Zr addition
on the catalytic activity of anatase and rutile TiO2-supported Co for CO2
hydrogenation reaction. Zr addition improved the adsorptions of CO,
CO2, and H2 in both the capacity and strength on the catalyst surface and
then led to enhancing CO2 conversion.
To the best of our knowledge, this is the first time to report on Zr
addition into TiO2 as a zirconia-titania mixed oxide support and which is
then impregnated by Ni to use as a catalyst for CO2 methanation. In this
work, the role of Zr addition on the properties and the catalytic activity
for the CO2 methanation of TiO2-supported Ni catalysts was investi­
gated. The TiO2-supported Ni catalysts with different amounts of Zr
addition were prepared and then characterized using several techniques
including X-ray diffraction (XRD), N2 adsorption-desorption, field
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Journal of Environmental Chemical Engineering 10 (2022) 107710
emission scanning electron microscopy (FE-SEM), H2-temperature pro­
grammed reduction (H2-TPR) CO2-temperature programmed desorption
(CO2-TPD), transmission electron microscopy (TEM) and X-ray absorp­
tion spectroscopy (XAS). The catalytic activities of the prepared cata­
lysts were tested for CO2 methanation reaction in the temperature range
of 100–500 ◦ C. Finally, the role of Zr addition on enhancing the CO2
methanation activity of TiO2-supported Ni was discussed using all of
these characterized results.
2. Experiment
2.1. Catalysts preparation
2.1.1. Preparation of catalyst support
TiO2 support was prepared by the sol-gel method. Ti[OCH(CH3)2]4
was used as a Ti precursor. Ethanol and DI water were employed as
solvents and HNO3 was an acidic catalyst. Ti[OCH(CH3)2]4 was first
dissolved in ethanol, then DI water and HNO3 were added to the Ti
precursor solution and the mixture was continuously stirred for 3 h.
After that, the mixture was dried at 100 ◦ C for 24 h and then calcined
under air at 400 ◦ C (heating rate of 2 ◦ C/min) for 3 h.
ZrxTi1− xO2 (x = 0, 0.1, 0.15, and 0.2) mixed oxide supports were
prepared by using the same procedure as the preparation of TiO2 sup­
port. ZrO(NO3)2.xH2O was used as a Zr source. The calculated amount of
Zr precursor was dissolved in DI water. Afterward, both Zr aqueous
solution and HNO3 were added into the Ti precursor solution. Then, the
mixture was proceeded along with the preparation method as TiO2.
2.1.2. Preparation of 10 wt%Ni-TiO2 and 10 wt%Ni-ZrxTi1− xO2 catalysts
10 wt%Ni-doped TiO2 and ZrxTi1− xO2 catalysts were prepared by
incipient wetness impregnation method. Ni(NO3)2⋅6H2O was used as a
Ni precursor. The desired amount of the Ni precursor was dissolved by
DI water. The solution of the Ni precursor was added to the prepared
supports and then dried overnight at 100 ◦ C and calcined under air at
400 ◦ C (heating rate of 2 ◦ C/min) for 3 h.
2.2. Catalysts characterization
2.2.1. Standard characterization
X-ray diffraction spectra of all catalysts were obtained from PAN­
alytical Empyrean with Cu Kα radiation with the wavelength of 1.5406
Å. The XRD patterns were scanned in the 2θ range of 20–80◦ . The
crystalline size (D) was calculated by using Scherrer’s equation by using
(101) and (200) planes of TiO2 and NiO, respectively. Lattice parameters
(a, b, c) were calculated from Bragg’s equation by using (101), (004),
and (200) planes of TiO2.
N2 adsorption-desorption isotherms at 77 K of the prepared catalysts
were obtained from the BELSORP-miniX instrument. Before the gas
adsorption experiment, the sample was degassed at 150 ◦ C for 60 min.
The obtained isotherm was used to calculate the specific surface area of
the prepared catalysts using the multipoint-BET method.
Three-dimensional morphologies of the prepared catalysts were ob­
tained from an FEI Helios Nanolab G3 CX Dual Beam FIB/SEM instru­
ment. Before scanning, the catalyst was spread on a carbon tape which
was stuck on a specimen stub and coated with gold to avoid the charging
effect.
Inductively coupled plasma-optical emission spectroscopy was used
to determine the metal contents in the prepared catalysts. Before the
measuring of metal content, the catalyst (0.02–0.025 g) was digested by
the mixture of concentrated H2SO4 (5 mL) and 30% H2O2 (1 mL) at high
temperature. The standard solutions in the range of 0–10 ppm were used
to construct the calibration curve. All samples were analyzed by the
optima 100DVICP-OES (PerkinElmer) instrument. The detection wave­
lengths of Zr and Ni were 343.823 and 231.604 nm, respectively.
In order to study the Ni dispersion in the catalyst, transmission
electron microscopy images of the reduced catalysts were obtained from
A. Makdee et al. Journal of Environmental Chemical Engineering 10 (2022) 107710

Fig. 1. Temperature-dependent (a) CO2 conversion, (b) CH4 yield (c) CH4 and CO selectivity of TiO2 and 10 wt%Ni-ZrxTi1− xO2 (x = 0, 0.1, 0.15, and 0.2) catalysts
for CO2 methanation (CO2:H2 ratio = 1:4) (d) Arrhenius plots of 10 wt%Ni-ZrxTi1− xO2 (x = 0, 0.1, 0.15, and 0.2) catalysts and (e) Long-term stability test over 10 wt
%Ni-Zr0.1Ti0.9O2 catalyst at 450 ◦ C for 50 h (CO2:H2 ratio = 1:4).

a FEI/TECNAI G2 20 instrument. Before the scanning process, the obtained from BELCAT II Version 0.3.0.6 instrument. 0.05 g of the
reduced catalyst powder was dispersed in acetone by sonication and prepared catalyst was first pretreated by N2 gas with a flow rate of 50
then dropped on a copper grid. mL/min at 500 ◦ C for 30 min. After that, the mixed gas of H2 and N2 was
H2-temperature programmed reduction profiles of the catalysts were switched and flowed over the pretreated sample during increasing the

3
A. Makdee et al.
reduction temperature from 40 ◦ C to 800 ◦ C with a ramping rate of
10 ◦ C/min. H2 consumption was detected by a TCD detector and the TCD
signal was plotted as a function of temperature.
CO2-temperature programmed desorption profiles of all prepared
catalysts were obtained by using the BELCAT II Version 0.3.0.6 instru­
ment. 0.05 g of the prepared catalyst was first pretreated by He gas with
a flow rate of 50 mL/min at 300 ◦ C for 60 min. After finishing the pre­
treatment process, the temperature was decreased to 50 ◦ C under He
flow and then the gas flow was switched to CO2 with a flow rate of 30
mL/min for 30 min. After that, the excess CO2 and weakly chemisorbed
CO2 were removed by purging He (30 mL/min) for 60 min. The CO2-TPD
was started by increasing temperature from 50 ◦ C to 750 ◦ C with a
heating rate of 10 ◦ C/min under He flow. Finally, the desorbed CO2 was
monitored by a TCD detector and the TCD signal was plot as a function of
temperature. The amount of desorbed CO2 (mmol/gcat.) was calculated
using the peak area.
2.2.2. X-ray absorption spectroscopy (XAS)
X-ray absorption spectroscopy was studied on a SUT-NANOTEC-SLRI
beamline (BL 5.2) [27,28] and a Time-resolved X-ray absorption spec­
troscopy beamline (BL 2.2) at the Synchrotron Light Research Institute
(SLRI), Nakhon Ratchasima, Thailand. For BL 5.2, synchrotron radiation
was tuned by a double crystal monochromator (DCM) equipped with Ge
(220) crystals for Ni K-edge and InSb(111) crystals for Zr L3-edge,
respectively. The monochromatic flux was obtained between 108 and
1010 photons/sec at 100 mA. Additionally, BL 2.2, the bent crystal was
used as an energy dispersive monochromator and Si(111) crystal was
used as a monochromator with an energy range of 2.4–10 keV. The
XANES spectra were obtained by subtracting I1 by I0 with the pre­
processing software before being exported to Athena software. There are
2 experimental sets for investigating the catalyst properties with
different aims as follows;.
(i) Ex-situ X-ray absorption spectroscopy for investigating the elec­
tronic state of Ni, Ti, and Zr of freshly prepared catalysts. The Ni K
edge and Zr L3 edge XANES spectra were obtained from BL 5.2
while Ti K edge XANES spectra were collected at BL 2.2. For Ni K
edge and Zr L3 edge XANES experiment, the spectra were
collected by using fluorescence mode with 4-element silicon drift
as a detector which was placed beside the sample to detect the
fluorescence (IF) signal. For Ti K edge XANES spectra, the
experiment was conducted in a transmission mode with ioniza­
tion chamber as a detector. The ionization chamber was placed in
front of and behind the sample to detect the incident (I0) and
transmitted (I1) X-ray beam.
(ii) In-situ X-ray absorption spectroscopy for monitoring the elec­
tronic state change of Ni during CO2 methanation reaction. This
experiment was carried out at BL 2.2 by monitoring on the Ni K
absorption edge. Firstly, the sample was mixed with boron nitride
(BN) to obtain a homogeneous powder and pressed into a pellet.
The pellet of the sample was placed in an in-situ cell and then
pretreated by heating the sample cell from room temperature to
450 ◦ C (ramp rate of 5 ◦ C/min) under H2 flowing at 24 mL/min.
The spectra were collected at every 10 ◦ C increment during the
increasing of temperature. Next, the temperature was kept at
450 ◦ C for 90 min and the spectra were collected every 10 min.
After the pretreatment step, the temperature was reduced to
100 ◦ C and the mixed feed gas of H2 (24 mL/min) and CO2 (6 mL/
min) was then switched over the sample to start the CO2
methanation reaction. The reaction temperature was kept at
100 ◦ C for 20 min and the spectra were collected every 10 min at
this point. After that, the reaction temperature was increased to
150 ◦ C (ramp rate of 5 ◦ C/min) and the spectra were collected
every 10 ◦ C of increment. When the reaction temperature reached
150 ◦ C, the spectra were collected every 10 min during holding
for 20 min. Then, the reaction temperature was increased every
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Journal of Environmental Chemical Engineering 10 (2022) 107710
50 ◦ C until it reached 500 ◦ C and the spectra were recorded as
described above.
2.3. CO2 methanation catalytic activity test
The catalytic activities of all prepared catalysts were tested for CO2
methanation reaction in a continuous flowed fixed-bed reactor. The
catalyst (50 mg) was placed between two layers of quartz wool in the
Pyrex tube. The Pyrex tube was placed inside the controllable temper­
ature furnace. The K-type thermocouple was placed at the top of the
catalyst to detect the reaction temperature. The feed gases flow rate was
controlled by mass flow controllers. Before starting CO2 methanation,
the catalyst was reduced at 450 ◦ C under H2 with a flow rate of 50 mL/
min for 90 min. After that, the feed gas was changed to the mixture of
CO2, H2, and He with a flow rate of 6, 24, and 10 mL/min, respectively.
The mixed feed gas was passed through the catalyst under a reaction
temperature of 100–500 ◦ C. Finally, the remaining reactants and prod­
ucts were analysed by online Agilent Technologies 6890 N gas chro­
matograph with a HEYSEP D packed column and TCD was used as a
detector. The percentages of CO2 conversion, CH4 yield, and CH4
selectivity and the rate of CO2 reaction were calculated by using the
following equations:
(
[CO2 ]out
)
% CO2 conversion = 1 -
[CO2 ]out + [CH4 ]out + [CO]out
× 100
(2)
(
[CH4 ]out
)
% CH4 yield = × 100 (3)
[CO2 ]out + [CH4 ]out + [CO]out
(
CH4 yield
)
% CH4 selectivity = × 100 (4)
CO2 conversion
CO2 conversion x FCO2, in
CO2 methanation rate = (5)
W
where [CO2]out, [CH4]out, and [CO]out are outlet concentrations of CO2,
CH4, and CO, respectively. FCO2, in is inlet molar flow rate of CO2 and W
is the sample weight [29].
3. Results and discussion
3.1. Catalytic activity for CO2 methanation reaction
The catalytic activities of the prepared catalysts were tested for CO2
methanation reaction in the temperature range of 100–500 ◦ C. Fig. 1(a)–
(c) show the percentages of CO2 conversion, CH4 yield, and products
(CO and CH4) selectivity as a function of reaction temperature, respec­
tively. It is clearly seen that the CO2 conversion and CH4 yield of all
prepared catalysts was enhanced with increased reaction temperature
from 100 to 450 ◦ C and then slightly decreased after the reaction tem­
perature reached 500 ◦ C. The reduction of CH4 selectivity at high tem­
perature was due to the formation of the reversed-water gas shift side
reaction, which produced an undesired product (CO). The bare TiO2
catalyst was not active for this reaction. After impregnating Ni onto
TiO2, the CO2 conversion was dramatically enhanced, which resulted
from the existence of an active site which was reactive toward both
reactant molecules (H2 and CO2). Upon incorporating Zr into TiO2 and
then impregnating it with Ni species, the CO2 methanation catalytic
performance was shifted toward lower reaction temperature with
improving the CO2 conversion percentage. The highest CO2 methana­
tion catalytic activity was obtained by Zr addition only 10 mol% (10 wt
%Ni-Zr0.1Ti0.9O2), with CO2 conversion of 68.0% at 450 ◦ C. However,
the catalytic activity decreased with further increased Zr content. CH4
selectivity of 10 wt%Ni-Zr0.1Ti0.9O2 was higher than 96% in a wide
range of reaction temperatures (150–350 ◦ C) when compared with other
A. Makdee et al. Journal of Environmental Chemical Engineering 10 (2022) 107710

Table 1
Catalytic system based on TiO2 support by using Ni as active metal for CO2 methanation.
Catalysts Ni doping CO2 methanation conditions CO2 CH4 Ref.
preparation methods conversion (%) selectivity (%)

15%Ni/TiO2- Conventional Fixed-bed reactor (id: 8 mm), 350 ◦ C, 1 atm, 1.0 g catalyst, pretreated at 450 ◦ C under 80 95.5 [30]
IMP impregnation 100 mL/min H2 +N2 for 4 h, H2:CO2:Ar = 12:3:5, total flow rate = 40 mL/min− 1, GHSV
= 2400 h− 1
10%NiO/TiO2- incipient Fixed-bed reactor, 450 ◦ C, 1 atm, 50 mg catalyst diluted by 0.1 silica carbide, pretreated 60 91.7 [31]
C wetness at 700 ◦ C under 40 mL/min H2 for 1 h, H2:CO2 = 4:1, GHSV = 60,000 h− 1
impregnation
15%Ni/ impregnation Fixed-bed reactor (id: 6 mm), 400 ◦ C, 1 atm, 9 g catalyst, pretreated at 600 ◦ C under 57 97 [32]
TiO2@SiO2 10 L h− 1 H2 + 20 L h− 1 N2 for 2 h, H2:CO2 = 4:1, total flow rate of 25 L h1
10%Ni-Ce/ incipient wetness Fixed bed reactor (id: 6 mm), 450 ◦ C, 1 atm, 50 mg catalyst, pretreated at 450 ◦ C under 65 95 [33]
TiO2 impregnation 40 mL/min H2 for 1.5 h, H2:CO2:He = 24:6:10, total floe rate = 40 mL/min, GHSV
= 4250 h− 1
12%Ni/TiO2 sol–gel Fixed bed reactor (id: 6 mm), 450 ◦ C, 1 atm, 50 mg catalyst, pretreated at 450 ◦ C under 40 97 [34]
40 mL/min H2 for 1.5 h, H2:CO2:He = 24:6:10, total floe rate = 40 mL/min
10%Ni/TiO2- impregnation Fixed bed reactor, 340 ◦ C, 6.1 bar, 200 mg catalyst diluted by 1800 mg silicon carbide, 42.6 79 [35]
anatase pretreated at 400 ◦ C under N2 +H2 atmosphere for 4 h, N2:H2:CO2 = 1:4:1
10%Ni-TiO2 incipient Fixed bed reactor (id: 6 mm), 450 ◦ C, 1 atm, 50 mg catalyst, pretreated at 450 ◦ C under 55 83 This
10%Ni-Zr/ wetness 40 mL/min H2 for 1.5 h, H2:CO2:He = 24:6:10, total floe rate = 40 mL/min, GHSV 68 94 work
TiO2 impregnation = 4250 h− 1

Fig. 2. (a) XRD patterns of ZrxTi1− xO2 (x = 0, 0.15, and 0.2) supports (b) Magnification of (101) peak at ~25.4◦ for ZrxTi1− xO2 (x = 0, 0.15, and 0.2) supports (c)
XRD patterns of TiO2 and 10 wt%Ni-ZrxTi1− xO2 (x = 0, 0.1, 0.15, and 0.2) catalysts (d) Magnification of (101) peak at ~25.4 ◦ for all synthesized catalysts.

prepared catalysts. Furthermore, the addition of optimal Zr content can
reduce the formation of undesired CO product. Table 1 presents the
catalytic activity for CO2 methanation by using the catalysts based on
Ni-doped TiO2 in this work compared with other works.
The kinetic study in a terms of apparent activation energy (Ea) was
also carried out to investigate the role of the catalysts in enhancing the
reaction rate. To avoid the mass and heat transfer effect, the kinetic
experiment was studied in the temperature range of 190–280 ◦ C in
which the CO2 conversion was less than 10%. To determine the apparent
activation energy, an Arrhenius plot, which shows a relationship be­
tween ln (rate) and the reciprocal of absolute temperature was con­
structed as shown in Fig. 1(d). The slope of this plot was used to

5
A. Makdee et al. Journal of Environmental Chemical Engineering 10 (2022) 107710

Table 2
Crystalline size, unit cell parameters, surface area, and metals content of all prepared catalysts.
Catalyst Crystalline size (Å) Lattice parametersa BET surface areab (m2/g) Metal contentc
d
NiO TiO2e a = b (Å) c (Å) 3
cell volume (Å ) Ni (%wt) Zr (%mol)

TiO2 – 92.5 3.790 9.551 137.2 86.36 – –

10 wt%Ni-TiO2 129.3 95.6 3.789 9.538 136.9 56.20 8.71 –
10 wt%Ni-Zr0.1Ti0.9O2 148.0 67.9 3.807 9.624 139.5 84.05 8.79 7.34
10 wt%Ni-Zr0.15Ti0.85O2 192.3 73.5 3.815 9.658 140.6 103.12 8.90 14.51
10 wt%Ni-Zr0.2Ti0.8O2 201.4 81.6 3.821 9.668 141.2 135.75 8.83 16.34
a
Calculated from (101), (004), (200) planes of TiO2 by using Bragg’s equation.
b
Calculated by using Multipoint BET method.
c
Calculated from ICP-OES results.
d
Calculated from (101) plane of TiO2 by using Sherrer’s equation.
e
Calculated from (200) plane of NiO by using Sherrer’s equation.

calculate the apparent activation energy. The calculated apparent acti­

vation energies of 10 wt%Ni-ZrxTi1− xO2 (x = 0, 0.1, 0.15, and 0.2) were
79.34, 76.04, 77.18 and 79.99 kJ/mol, respectively. It is clearly seen
that 10 wt%Ni-Zr0.1Ti0.9O2 exhibited the lowest apparent activation
energy (76.04 kJ/mol) which was in agreement with the highest cata­
lytic activity for CO2 methanation.
The long-term stability of the best catalyst (10 wt%Ni-Zr0.1Ti0.9O2)
for CO2 methanation reaction was also investigated because metallic Ni
can be sintered under exothermic conditions and carbon deposition can
also be formed on the catalyst surface, which led to catalyst deactiva­
tion. In this work, a long-term stability test was investigated at 450 ◦ C
for 50 h and the results are shown in Fig. 1(e). The percentages of CO2
conversion, CH4 yield, and CH4 selectivity were almost stable without an
obvious decrease of those values in the range of stability test (50 h). This
indicated that 10 wt%Ni-Zr0.1Ti0.9O2 catalyst had great stability.

3.2. Catalyst characterization

XRD patterns of TiO2 and 10 wt%Ni-ZrxTi1− xO2 (x = 0, 0.1, 0.15,

and 0.2) catalysts are revealed in Fig. 2(a). The diffraction peaks of bare
TiO2 were observed at around 25.4, 37.8, 48.2, 54.1, 55.1, and 62.8◦
which corresponded to the (101), (004), (200), (105), (211), and (204)
crystallographic planes of anatase structure, respectively (JCPDS file
number 21–1272) [36–39]. All modified catalysts exhibited all above
diffraction peaks corresponding to anatase TiO2, which indicated that
the structure of those catalysts remained unchanged after the addition of
both Ni and Zr. Fig. 2(a) illustrates XRD patterns of bare TiO2 compared
with modified supports (ZrxTi1− xO2; x = 0.15, and 0.20). Only high Zr
addition samples were selected to investigate a clearly shifting of the
diffraction peaks in Fig. 2(a). It is seen that upon addition of Zr into TiO2,
the diffraction peaks corresponding to zirconium oxide phase were not
observed. Moreover, the diffraction peaks were shifted to lower
diffraction angle (Fig. 2(b)) which indicated to an expansion of the host
lattice. This can indicate that Zr incorporated into TiO2 lattice formed as
a solid solution. The incorporation of larger Zr4+ (0.072 nm) ions into
smaller Ti4+ (0.060 nm) sites inside TiO2 host lattice would lead to
distortion and enlargement of the host supporting material lattice.
Increased Zr content in the catalysts resulted in more shifting of (101)
crystallographic plane to lower diffraction angle, which indicated a
higher amount of substitution of Ti4+ by Zr4+. Moreover, upon
impregnating Ni onto bare TiO2 and titania-zirconia mixed oxide sup­
port, an additional diffraction peak at around 43.4◦ which corresponded
to (200) plane of cubic NiO (JCPDS file number 47-1049) [39,40] was
observed as shown in Fig. 2(c). The existence of NiO diffraction peak
together with no shifting of TiO2 characteristic peak for 10 wt%Ni-TiO2
in Fig. 2(d) when compared with other catalysts can indicate that added
Ni species formed on catalyst surface as NiO.
Table 2 summarized the cell parameters, cell volumes, and crystal­
line sizes of all prepared catalysts. There was no significant difference
between the cell parameters of bare TiO2 and 10 wt%Ni-impregnated
Fig. 3. N2 adsorption-desorption isotherms of TiO2 and 10 wt%Ni-ZrxTi1− xO2
(x = 0, 0.1, 0.15, and 0.2) catalysts (solid symbol: adsorption branch, open
symbol: desorption branch).
TiO2 which confirmed that NiO was dispersed on the catalyst surface. In
contrast, unit cell enlargement occurred upon the addition of Zr into the
TiO2 lattice. Larger unit cell expansion of host lattice was observed with
increased Zr loading. This indicated that Zr ion incorporated into TiO2
lattice to form a solid solution, which can be evidenced by the absence of
XRD peaks of ZrO2 even though the Zr content reached 20 mol%. The
TiO2 crystalline size tended to decrease upon the addition of Zr, which
was probably due to the inhibition of TiO2 crystal growth by the co-
addition of Zr during the synthesis procedure. Upon increased Zr con­
tent, the crystalline size of TiO2 was slightly increased. On the other
hand, NiO crystalline size was further increased with increased Zr
amount.
N2 adsorption-desorption isotherms of TiO2 and 10 wt%Ni-impreg­
nated mixed oxide catalysts are shown in Fig. 3. All catalysts exhibited
the type IV isotherm with hysteresis loop, which indicated the meso­
porous structure [38,41]. The calculated specific surface area of TiO2
and 10 wt%Ni-ZrxTi1− xO2 (x = 0, 0.1, 0.15, and 0.2) catalysts by BET
method are shown in Table 1. It can be seen that the BET surface area
decreased from 86.36 m2/g to 56.20 m2/g after 10 wt%Ni was added on
TiO2, which was probably due to a partial blockage or collapse of
mesopores during the impregnation process [11]. The surface area of
impregnated 10 wt%Ni on mixed oxide support was higher than that on
bare TiO2, which corresponded to higher surface area of supporting
material due to their low crystalline sizes as mentioned in XRD results.
However, upon further increasing Zr content, the surface area was still
increased, which was opposite to their crystalline size. This was prob­
ably due to the formation of the interparticle cavities (self-assembled

6
A. Makdee et al.
TiO2 10wt%Ni-TiO2
10wt%Ni-Zr0.15Ti0.85O2
Fig. 4. FE-SEM images of TiO2 and 10 wt%Ni-ZrxTi1− xO2 (x = 0, 0.1, 0.15, and 0.2) catalysts.
Fig. 5. H2-TPR profiles of TiO2 and 10 wt%Ni-ZrxTi1− xO2 (x = 0, 0.1, 0.15 and
0.2) catalysts.
NPs) [42] of the catalyst.
Fig. 4 presents the FE-SEM images of TiO2 and 10 wt%Ni-ZrxTi1− xO2
(x = 0, 0.1, 0.15, and 0.2) catalysts with the same magnification of
200000x. It can be seen that the morphologies of TiO2, 10 wt%Ni-TiO2,
and 10 wt%Ni-Zr0.1Ti0.9O2 showed an agglomeration of spherical par­
ticles to form a rough surface with the average particle size in the range
of 13–15 nm. For 10 wt%Ni-Zr0.15Ti0.85O2 and 10 wt%Ni-Zr0.2Ti0.8O2,
the particles clearly exhibited an almost spherical shape with particle
sizes of 26.7 and 30.1 nm, respectively. The 10 wt%Ni-Zr0.2Ti0.8O2
catalyst showed the largest particle size. However, the highest surface
area was found for this catalyst, which was probably due to the forma­
tion of the highest interparticle cavities.
7
Journal of Environmental Chemical Engineering 10 (2022) 107710
10wt%Ni-Zr0.1Ti0.9O2
10wt%Ni-Zr0.2Ti0.8O2
To investigate the reduction behavior and interaction of NiO with the
support of the prepared catalysts, H2-TPR profiling was performed.
Fig. 5 shows the H2-TPR profiles of TiO2 and 10 wt%Ni-ZrxTi1− xO2
(x = 0, 0.1, 0.15 and 0.2) catalysts. For TiO2, only a small peak was
observed at 619.6 ◦ C, which indicated that TiO2 catalyst was hardly
reduced in the temperature range of 50–800 ◦ C. When Ni was impreg­
nated onto TiO2 support (10 wt%Ni-TiO2), two main reduction peaks at
340.5 ◦ C and 471.3 ◦ C were found. Those two reduction peaks were
attributed to the reduction of NiO to metallic Ni (Ni2+ → Ni0). It has been
reported that different reduction temperature of Ni2+ to Ni0 was related
to its binding strength to supporting material or metal-support interac­
tion [30,43,44]. The strength of interaction between Ni and support can
be categorized into three regions. The first low reduction temperature
ranges around 250–300 ◦ C was attributed to the reduction of bulk NiO
particle without interaction with the support. The second reduction
temperature range around 300–600 ◦ C was assigned as the reduction of
NiO with moderately binding strength to the support. Finally, the last
high reduction temperature (above 600 ◦ C) was assigned as the reduc­
tion of NiO with a strong binding strength to the support [44]. There­
fore, those two reduction peaks on 10 wt%Ni-TiO2 were attributed to
moderately binding strength between NiO and TiO2. Moreover, those
two reduction peaks were also indicated to two difference kinds of
interaction between NiO and TiO2; i.e., the reduction temperature
around 340.5 ◦ C and 471.3 ◦ C were related to lower and higher binding
strength between them, respectively. Incorporation of Zr into TiO2 lat­
tice resulted in shifting those two reduction peaks toward higher tem­
perature (360–376 ◦ C for low reduction temperature side and
476–492 ◦ C for high reduction temperature side). Normally, the
reduction temperature of the NiO can indicate the interaction between
NiO and catalyst support, i.e., higher reduction temperature implied to
higher or stronger interaction between them. However, it can be seen
that the amount of H2 consumption for those two reduction peaks in
Fig. 5 were significantly varied upon addition of Zr. Therefore, the
amount of H2 consumption of those two reduction peaks, which were
A. Makdee et al. Journal of Environmental Chemical Engineering 10 (2022) 107710

Table 3
The dispersion of Ni species expressed by AH/(AH+AL) ratio which calculated from H2-TPR results and the desorbed CO2 amount from CO2-TPD result.
Catalyst AH/ (AH+AL) Amount of H2 consumption (mmol/g) Desorbed CO2 (mmol/g)

Lower temperature Higher temperature Percentage of strong interaction

10 wt%Ni-TiO2 0.685 0.313 0.760 70.8 0.204

10 wt%Ni-Zr0.1Ti0.9O2 0.674 0.219 0.451 67.3 0.236
10 wt%Ni-Zr0.15Ti0.85O2 0.356 0.552 0.305 35.6 0.292
10 wt%Ni-Zr0.2Ti0.8O2 0.443 0.651 0.517 44.3 0.337

10Ni-10Zr

(a) (b)
Mean = 19.41 nm Mean = 20.17 nm
Mean = 12.48 nm Mean = 14.25 nm (c) (d)

Counts
Counts
Counts

Counts

0 20 40 60 80
0 5 10 15 20 25 30 35 40 0 10 20 30 40 50 60 70 Particle diameter (nm)
Particle diameter (nm) 0 10 20 30 40 50 Particle diameter (nm)
Particle diameter (nm)

Fig. 6. TEM images of reduced (a) 10 wt%Ni-TiO2, (b) 10 wt%Ni-Zr0.1Ti0.9O2, (c)10 wt%Ni- Zr0.15Ti0.85O2 and (d) 10 wt%Ni-Zr0.2Ti0.8O2 catalysts.

obtained by integrating of the peak area, were also taken into account
beside the shifting of the reduction temperature. The amount of H2
consumption of both two reduction temperatures were summarized in
Table 3. To more clarify on the amount of lower and higher binding
strength between NiO and TiO2 in all samples, the percentage of higher
binding strength (higher reduction peak in the range of 472–493 ◦ C)
were reported and compared. It can be seen that 10 wt%Ni-TiO2 and
10 wt%Ni-Zr0.1Ti0.9O2 exhibited higher fraction of higher binding
strength or strong interaction (70% and 67%, respectively). In contrast,
10 wt%Ni-Zr0.15Ti0.85O2 and 10 wt%Ni-Zr0.2Ti0.8O2 exhibited higher
fraction of lower binding strength or weak interaction (65% and 56%,
respectively). Since, the impregnated amount of Ni for all sample (with
and without Zr addition) were almost the same, therefore, different
fraction of weak and strong interaction of all catalysts should be caused
by Zr addition. These phenomena can indicate that Zr can tune or tailor
the metal (Ni)-support (TiO2) interaction and then also affect the cata­
lyst reducibility and NiO dispersion on the catalyst surface. Therefore, it
implied that the electronic state of Ni species must be tuned by the
addition of Zr. For this electronic state tuning phenomenon, X-ray ab­
sorption spectroscopy results were evidenced, which will be discussed
later.
To estimate the dispersion of Ni species on the catalyst’s surface, the Fig. 7. CO2-TPD profiles of 10 wt%Ni-ZrxTi1− xO2 (x = 0, 0.1, 0.15, and
ratio of peak area at higher temperature (AH) normalized by summation 0.2) catalysts.
of the peak area at lower (AL) and higher temperature (AH) was calcu­
lated [30] and expressed in Table 3. The results showed that 10 wt% were in agreement with the similar value of AH/(AH+AL) for both cat­
Ni-TiO2 catalyst exhibited the highest ratio, which indicated that NiO alysts which was calculated from H2-TPR results. The rest two catalysts
was highly dispersed on the catalyst surface. This ratio tended to reduce (10 wt%Ni-Zr0.15Ti0.85O2 and 10 wt%Ni-Zr0.2Ti0.8O2) showed low
upon increased Zr content, which indicated that lower NiO dispersion on dispersed Ni0 with larger particle size of reduced Ni species which also
the catalyst surface. This trend was correlated to the crystalline sizes of corresponded to XRD and H2-TPR results.
NiO obtained from the XRD results; i.e., a higher crystalline size of NiO The basicity and binding strength between CO2 molecule and the
with increased Zr loading. Larger crystalline size of NiO would result in catalyst was evaluated by CO2-TPD technique. In the CO2-TPD experi­
lower NiO surface area for activating the H2 molecule. ment, the surface of the catalyst was saturated by CO2, and then the
For more insight on the Ni species dispersion, transmission electron adsorbed CO2 was desorbed from the catalyst surface by increasing the
microscopy was used. Fig. 6 reveals the TEM images of 10 wt%Ni- temperature. Therefore, the amount of desorbed CO2 was proportional
ZrxTi1− xO2 (x = 0, 0.1, 0.15, and 0.2) catalysts which was reduced at to the amount of CO2 adsorption. Moreover, the binding strength be­
450 ◦ C for 90 min (pretreatment step in CO2 methanation activity test). tween CO2 and catalyst surface can be indicated by the desorption
It can be seen that all TEM images could be divided into two regions; temperature. The CO2-TPD profiles of 10 wt%Ni-ZrxTi1− xO2 (x = 0, 0.1,
dark and bright particles which corresponded to Ni0 and support area, 0.15, and 0.2) catalysts are shown in Fig. 7. It can be seen that the CO2-
respectively. The results showed that both 10 wt%Ni-TiO2 and 10 wt% TPD profiles exhibited three different regions: weak, medium, and
Ni-Zr0.1Ti0.9O2 exhibited similar dispersion of metallic Ni. These results strong regions. These regions were attributed to weak, medium, and

8
A. Makdee et al. Journal of Environmental Chemical Engineering 10 (2022) 107710

Fig. 8. (a) XANES Spectra of 10 wt%Ni-ZrxTi1− xO2 (x = 0, 0.1, 0.15, and 0.2) compared with Ni foil and NiO standards. (b) White line intensity comparison of NiO
standard and 10 wt%Ni-ZrxTi1− xO2 (x = 0, 0.1, 0.15, and 0.2).

strong basicity of the catalyst, which related to the strength of binding
between CO2 and catalyst surface with weak, medium, and strong
interaction, respectively. These three sites were found for 10 wt%Ni-
TiO2, and 10 wt%Ni-Zr0.1Ti0.9O2 catalysts while only two sites (weak
and medium) were found for 10 wt%Ni-Zr0.15Ti0.85O2 and 10 wt%Ni-
Zr0.2Ti0.8O2 catalysts. However, only adsorbed CO2 on weak and me­
dium basic sites are favor to involve in the CO2 methanation reaction
while the strong adsorbed CO2 on the catalysts cannot participate in the
reaction, since the reaction temperature was in the range of 100–500 ◦ C,
thus, the adsorbed CO2 in the strong region (over 550 ◦ C) should be
excluded [45]. Therefore, only those two former peaks (weak and me­
dium) were taken into account. The summation of desorbed CO2 amount
of weak and medium basic sites was calculated and presented in Table 2.
It can be seen that the CO2 adsorption of Zr-doped catalysts (10 wt%
Ni-ZrxTi1− xO2, x = 0.1, 0.15, and 0.2) was higher than that of
un-modified support (10 wt%Ni-TiO2) and the amount of CO2 uptake
was increased with further increased Zr content. This indicated that Zr
addition can increase the CO2 affinity on the catalyst surface which can
imply higher basicity of catalysts.
3.3. The role of modified catalyst on changes of electronic properties of
catalyst investigated by X-ray absorption spectroscopy
From the above results, the optimal Zr addition into the catalyst can
improve the CO2 conversion percentage and also shift the reaction to
occur at lower reaction temperature side. This is because the results
from H2-TPR indicated that the metal-support interaction was tuned
upon the incorporation of Zr into the TiO2-supported Ni catalyst, which
might be due to the changing of electronic state of Ni by Zr addition.
Therefore, in this section, X-ray absorption spectroscopy was used to
evidence the tailoring of those electronic perturbations. There are 2
experimental sets for conducting X-ray absorption spectroscopy with the
different aims as follows;.
1) Ex-situ X-ray absorption spectroscopy for investigating the electronic
state of Ni, Ti and Zr of freshly prepared catalysts.

Fig. 9. (a) Ti K edge XANES spectra of anatase and rutile TiO2 standards, synthesized TiO2 and 10 wt%Ni-ZrxTi1− xO2 (x = 0 and 0.1) catalysts. (b) Comparison
between pre-edge of Ti K edge XANES spectra of TiO2 and 10 wt%Ni-Zr0.1Ti0.9O2 catalysts.

9
A. Makdee et al. Journal of Environmental Chemical Engineering 10 (2022) 107710

2) In-situ X-ray absorption spectroscopy for monitoring the electronic

state change of Ni during CO2 methanation reaction.

3.3.1. Ex-situ X-ray absorption spectroscopy for investigating the electronic

state of Ni, Ti and Zr of freshly prepared catalysts
Fig. 8(a) illustrates the normalized Ni K edge XANES spectra of 10 wt
%Ni-ZrxTi1− xO2 (x = 0, 0.1, 0.15, and 0.2) catalysts compared with NiO
(Ni2+) and Ni foil (Ni0) standards. It is seen that the Ni K edge XANES
spectra features of all prepared catalysts was similar to that of NiO
standard. The white line peak at 8350 eV was ascribed to the transition
from 1 s to unoccupied 4p state and the peak at 8366 eV was a signature
of six-fold coordinated nickel by oxygen [46,47]. In order to confirm the
electronic state of Ni species on the catalysts, comparison of all above
catalysts with NiO standard was constructed, as shown in Fig. 8(b). All
prepared catalysts exhibited the same absorption edge as NiO which
indicated that the oxidation state of Ni species on catalyst was 2+.
It can be noticed that the white line intensities of all modified cat­
alysts were different (clearly seen in inset) which can indicate the dif­
ference of the electron density within their d valence state. In the X-ray
absorption process, the corresponding core electron of probe atom
Fig. 10. Zr L3 edge XANES spectra of Zr foil and ZrO2 standards and 10 wt%Ni-
ZrxTi1− xO2 (x = 0.1, 0.15 and 0.2) catalysts.
absorbed an appropriate energy to its binding energy and was excited
into unoccupied valenced state. The absorption signal of those probe
atoms as a function of increasing incident photon energy is detected and
then the relationship between the absorption coefficient and photon
energy is constructed, which is called XAS spectrum. The different
electron density in unoccupied valence state can determine the feature
of XAS spectrum. According to exciting the core electron to low electron
density in unoccupied valence state, more electrons can be moved into

Fig. 11. Ni K edge XANES spectra during pretreatment and CO2 methanation conditions for (a) 10 wt%Ni-TiO2 and (b)10 wt%Ni-Zr0.1Ti0.9O2. (c) The Normalized
peak intensity at 8350 eV from Ni K edge XANES spectra as a function of pretreatment temperature for 10 wt%Ni-TiO2 and 10 wt%Ni-Zr0.1Ti0.9O2.

10
 A. Makdee et al.
this band resulting in highly intense peak in the XAS spectra which is
seen by as a white line. Therefore, a comparison of the white line in­
tensities of probe atoms can indicate the electron density in the unoc­
cupied valence band. From Fig. 8(b), when comparing only NiO and
10 wt%Ni-TiO2, the Ni K edge white line intensity of the latter sample
was lower than that of the former sample. This indicated that the elec­
tron density in valence d state of Ni in 10 wt%Ni-TiO2 was higher than
that of NiO which is due to electron movement from Ti to Ni probe atom.
Moreover, when comparing only the modified catalysts, 10 wt%Ni-
ZrxTi1− xO2 (x = 0, 0.1, 0.15, and 0.2), the white line intensity of Ni K
edge was reduced upon increased Zr loading. This result implied that
some electron movement to valence d state of Ni also occurred and those
electrons would come from added Zr in the TiO2 lattice. Therefore, Zr
can perturb the electronic properties of Ni and this tuning phenomenon
can dominate the catalytic activity for CO2 methanation.
Fig. 9(a) displays normalized Ti K edge XANES spectra of TiO2 and
10 wt%Ni-ZrxTi1− xO2 (x = 0 and 0.1) catalysts compared with those of
anatase and rutile TiO2 standards. All prepared catalysts exhibited a
similar feature to the anatase TiO2 standard. Therefore, all catalysts
were in the anatase (Ti4+) phase which corresponded to the XRD results.
Confirmation of the incorporation of Zr into the TiO2 lattice can be
identified by the changing of the pre-edge of Ti K edge. The pre-edge of
Ti K edge XANES spectra exhibited three main peaks; A1, A2 and A3. A1
peak was ascribed to the transition from 1 s to 3d-t2 g state. A2 and A3
peaks were ascribed to the transition from 1 s to hybridized p-d (t2 g) and
p-d (eg), respectively [48,49]. The higher those peak intensities were
originated from the distortion of TiO6 symmetry by substituting of Zr4+
ion. Therefore, the higher the pre-edge peak intensity of 10 wt%
Ni-Zr0.1Ti0.9O2 than TiO2 as shown in Fig. 9(b) indicates the distortion of
the TiO2 lattice, which was caused by the incorporation of Zr4+ ion.
Normalized Zr L3 edge XANES spectra of 10 wt%Ni-ZrxTi1− xO2
(x = 0.1, 0.15, and 0.2) catalysts and standards (ZrO2 and Zr foil) are
shown in Fig. 10. It is seen that all modified catalysts exhibited the same
absorption edge as ZrO2 standard which indicated that the Zr probe in all
catalysts were in the Zr4+ state. It is noticed that the spectral feature of
all modified catalysts was different, which can indicate the different
environment around Zr ion. It has been reported that the Zr L3 edge
XANES spectral shape depended on the coordination number and the
symmetry around the Zr ion [50]. Normally, the Zr L3 edge XANES
spectrum exhibited two peaks labeled as A and B which were attributed
to the electron transition from 2p3/2 to 4d(t2 g) and 4d(eg), respectively.
The degree of difference between the energy level of t2 g and eg can
estimate the XANES spectral feature and can also indicate the coordi­
nation number around Zr ion. A larger difference between those two
energy levels would lead to a separation of A and B peaks which indi­
cated a lower coordination number around Zr ion. For 10 wt%Ni-Zr0.1
Ti0.9O2, the A and B peaks were clearly observed, which indicated that
the t2 g and eg energy levels were well separated. This indicated that
10 wt%Ni-Zr0.1Ti0.9O2 had the lowest coordination number around Zr
since it had the lowest amount of Zr4+ (10 mol%) incorporation into the
TiO2 lattice. In contrast, the A and B peaks of 10 wt%Ni-Zr0.15Ti0.85O2
were less separated and those peaks were almost merged for the 10 wt%
Ni-Zr0.2Ti0.8O2 sample. This indicated that a smaller difference of the
energy level between t2 g and eg occurred upon increased Zr content.
Therefore, it implied that higher coordination number with increased Zr
loading occurred, which was due to higher amount of substituted Zr4+
into the TiO2 lattice. However, comparing the white line intensity of the
Zr L3 edge to evidence the electron movement from Zr to Ni cannot be
used since the amount of Ni impregnated onto Zr-Ti support was almost
the same, but the loading amount of Zr was different; i.e.; the
electron-withdrawing effect by Ni was constant, but the Zr content was
increased.
3.3.2. In-situ X-ray absorption spectroscopy for monitoring the electronic
state change of Ni during CO2 methanation reaction
In this part, the change of Ni oxidation state during the CO2
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Journal of Environmental Chemical Engineering 10 (2022) 107710
methanation reaction was monitored by time-resolved X-ray absorption
spectroscopy (TRXAS). In the in-situ XAS experiment, the procedure was
similar to the catalytic activity test. The sample was firstly pretreated
under H2 atmosphere at 450 ◦ C for 90 min to reduce NiO to metallic Ni
active species. After the pretreatment step, the system was cooled down
under H2 flow to 100 ◦ C and then the CO2 methanation reaction was
started by switching to the mixed feed gas (CO2:H2 with ratio of 1:4)
over the sample and then the Ni K edge XANES spectra were collected.
After that, the reaction temperature was increased for each 50 ◦ C and
the XANES spectra were collected until the reaction temperature
reached 500 ◦ C. Fig. 11(a) and 11(b) illustrate the Ni K edge XANES
spectra during the pretreatment step and CO2 methanation reaction for
10 wt%Ni-TiO2 and 10 wt%Ni-Zr0.1Ti0.9O2 catalysts, respectively. These
two catalysts exhibited a similar changing of XANES spectra during the
two steps (pretreatment and CO2 methanation reaction). For the pre­
treatment step, the oxidation state of Ni was changed from Ni2+ to Ni0
with increased temperature from 50 to 450 ◦ C and held at 450 ◦ C for
90 min. During the pretreatment step, Ni2+ in both catalysts were
completely reduced to Ni0. However, the starting reduction temperature
of both catalysts was different, which can point to the strength of the
metal-support interaction. To evidence the strength of the Ni species
with the catalysts surface, the plotting of normalized peak intensity at
8350 eV (white line peak of Ni2+) as a function of temperature was
constructed, as shown in Fig. 11(c). The normalized peak intensity can
be calculated from the difference of peak intensity at 8350 eV between
the initial state and that of each temperature divided by that of the initial
state. Therefore, an increase of normalized peak intensity indicated that
Ni2+ was more rapidly reduced to Ni0. The difference in starting
reduction temperature was due to different binding strength between Ni
and support. According to the results from H2-TPR, the Ni species of
10 wt%Ni-Zr0.1Ti0.9O2 exhibited higher binding strength to the support
than Ni of the 10 wt%Ni-TiO2 sample, which is evidenced by shifting the
reduction temperature of Ni2+ to higher temperature side. It can be seen
that the starting reduction temperature of 10 wt%Ni-TiO2 was observed
at lower temperature than that of the 10 wt%Ni Zr0.1Ti0.9O2. This indi­
cated that Ni2+ in the 10 wt%Ni-TiO2 catalyst was more easily reduced
than that of the 10 wt%Ni-Zr0.1Ti0.9O2 catalyst. Although 10 wt%Ni-
TiO2 was more easily reduced, however, Ni2+ in both prepared catalysts
was completely reduced to Ni0 after finishing the pretreatment step.
Therefore, a few differences in the starting reduction temperature did
not affect the CO2 methanation activity of both catalysts since the initial
Ni species for the CO2 methanation reaction was in the same species
(Ni0). Furthermore, under CO2 methanation conditions, the oxidation
state of Ni for both catalysts remained unchanged from the initial state
(Ni0).
3.4. The role of Zr addition on properties and catalytic activity of the
catalyst
From the results of CO2 methanation catalytic activity, the catalytic
performance of bare TiO2 was much enhanced by impregnation of Ni,
which was due to the existence of the active site for dissociative
adsorption of H2 molecules. CO2 methanation catalytic activity was
further increased upon doping of Zr4+ into TiO2 support. Since the bare
TiO2 and zirconia-titania mixed oxide supports were firstly synthesized
and then the same amount of Ni was impregnated onto those supports,
increased CO2 methanation catalytic activity of Ni-impregnated zirco­
nia-titania mixed oxide support resulted from Zr4+ addition. From all of
the above characterization techniques, the role of Zr doping on catalysts
properties which also affected their catalytic activity were summarized
as follows;.
i) the incorporation of Zr4+ ion into the TiO2 lattice improved the
physical properties of the catalysts. The added Zr incorporated
into TiO2 lattice to form a solid solution structure which resulted
in a reduction of TiO2 crystalline size. This was because the
A. Makdee et al.
Fig. 12. Dispersion of Ni species (expressed as ratio of AH/(AH+AL)) and des­
orbed CO2 of all modified catalysts as a function of Zr content.
addition of Zr could inhibit TiO2 crystal growth, leading to sur­
face area enhancement when compared with unmodified support
(10 wt%Ni-TiO2). However, the TiO2 crystalline size increased
with further increased Zr content, which was probably due to an
excessive Zr addition decreased the amount of phase boundary.
Furthermore, the surface area also increased with increased Zr
content, which was possibly due to higher interparticle cavities
formation. In the case of NiO, the larger crystalline size was ob­
tained with increased Zr loading. It is noticed that the impreg­
nated Ni for all catalysts were an almost constant amount, but
their crystalline size was different, which indicated that NiO
would also exist in a different active area. This implied that Zr can
alter the Ni species property such as its binding strength with the
support which can be evidenced by, the H2-TPR results.
ii) the incorporation of Zr4+ into TiO2 lattice facilitated the
adsorption ability of H2 and CO2 by tuning the interaction be­
tween NiO-support and increasing the catalyst basicity, respec­
tively. According to the H2-TPR results, the reduction
temperature of NiO was shifted toward higher temperature upon
the addition of Zr. This indicated that higher binding strength
between NiO and TiO2 support existed when Zr was incorporated
into the TiO2 lattice. An appropriate binding strength between
them would promote the highest Ni dispersion on the catalyst
surface, which can facilitate the adsorption and dissociation of H2
molecules to involve in the reaction pathway. Therefore, tuning
the interaction between metal and support was one of the main
effects for dominating the catalytic activity. This point can be
described by the results from XAS experiment in the next sub­
section. Another one important effect of Zr addition was to in­
crease the catalyst basicity. From the CO2-TPD results, doping of
Zr led to an increase of CO2 adsorption amount, which indicated
higher basicity upon the addition of Zr. Chen and co-workers [51]
reported a DFT study of the basic property of TiO2 and ZrO2 by
adsorption of CO2. They found that ZrO2 was more reactive to­
ward CO2 than TiO2 or it can be proposed that ZrO2 has more
basicity than TiO2. From all of the above results, it can be
concluded that the co-addition of Zr into the TiO2 lattice to form a
mixed oxide support can improve the surface properties of the
catalysts which can promote the H2 and CO2 adsorption. Fig. 12
illustrates the Ni dispersion (expressed as ratio of AH/(AH+AL))
and the amount of desorbed CO2 which directly related to the
adsorption amount of H2 and CO2 on the catalyst surface,
respectively, as a function of Zr content. A lower area of active Ni
species on the catalyst surface resulted in a lowering of dissoci­
ated H atoms to involve the hydrogenation reaction. Likewise,
higher CO2 adsorption amount can competitively adsorb and
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Journal of Environmental Chemical Engineering 10 (2022) 107710
Fig. 13. Temperature-dependent CO conversion of 10 wt%Ni-TiO2 and 10 wt%
Ni-Zr0.1Ti0.9O2 catalysts for CO methanation (CO:H2 = 1:4).
inhibit H2 adsorption on the catalyst surface. Therefore, optimal
H2 and CO2 adsorption ability on the surface of 10 wt%
Ni-Zr0.1Ti0.9O2 catalyst would lead to its highest catalytic
activity.
iii) From the above discussion, it can be concluded that the role of Zr
addition was to tune the interaction between NiO and TiO2 sup­
port and resulting in improving the catalyst properties which can
promote the CO2 methanation reaction rate. This tuning phe­
nomenon was caused by the electronic property changing of Ni
species when Zr was doped into TiO2. Upon the addition of Zr into
the TiO2 support which is then impregnated by Ni, electrons from
Zr were transferred to Ni. This was due to higher electronega­
tivity of Ni (1.91) than that of Zr (1.33). From the electron
movement phenomena, Ni had a high electron density in valence
d state, which was beneficial to the activation of CO molecules. It
is known that the CO2 methanation reaction mechanism can
proceed via CO intermediate, which originated from dissociation
of CO2 on the catalyst surface. To elucidate that CO was probably
occurred as an intermediate for this reaction, CO methanation
catalytic activity of two catalysts (with and without Zr addition)
was examined as shown in Fig. 13. For CO methanation, CO
molecule was directly adsorbed on catalyst surface and then
further associated with adsorbed H atom into various interme­
diate and then finally converted to CH4. Therefore, we used this
reaction to indirect support that Zr addition can promote the
activation of CO on catalyst surface. Higher CH4 production
implied that CO was favor to adsorb on catalyst surface and then
convert to product [52]. The results in Fig. 13 illustrated that
catalyst with Zr addition (10 wt%Ni-Zr0.10Ti0.90O2) had much
higher CO conversion than catalyst without Zr addition (10 wt%
Ni-TiO2). Therefore, it can be expected that CO molecule was
favor to adsorb on catalyst surface and also favor to convert to
CH4 on the former catalyst. From above results, it can be seen that
Zr addition played the role on activating of adsorbed CO molecule
on catalyst surface. From above XAS results, the electron move­
ment from Zr to Ni led to higher electron density in its valence
d state, or Ni acts as an electron rich site. After CO intermediate,
which originated from CO2 dissociation, was adsorbed on Ni
electron rich site, the electron in d state of Ni was donated to π*
antibonding of CO molecule. Upon the donation of electrons from
the Ni electron rich site, the bonding between carbon and oxygen
of the CO molecule was weakened and then the CO molecule was
easily dissociated to carbon and oxygen. The dissociated carbon
A. Makdee et al.
Fig. 14. Proposed the effect of Zr addition on enhancing CH4 selectivity over Ni-TiO2 for CO2 methanation.
atom was then further reacted with nearby H atom by hydroge­
nation reaction to form CH4. Oxygen atoms also reacted with H
atoms to produce H2O. Therefore, the role of Zr addition was to
activate the CO intermediate leading to further involvement in
hydrogenation reaction to form CH4 by a lowering of the C-O
bonding dissociation barrier. Therefore, facilitating the dissoci­
ation of CO molecule not only sped up the rate of reaction but also
improved the selectivity to CH4 production, since undesired CO
product vanished. The above discussion on the role of Zr addition
on enhancing CO2 methanation catalytic activity was expressed
by a proposed schematic in Fig. 14. However, high loading of Zr
resulted in lowering of CO2 methanation catalytic activity and
CH4 selectivity. This was caused by a larger amount of electron
movement to Ni and leading to a favoring of CO adsorption on
this electron rich site. Therefore, higher CO adsorption amount
on Ni would lead to inhibiting of the reactant adsorption on the
catalyst surface, thus suppressing the catalytic activity.
4. Conclusion
TiO2 and 10 wt%Ni-ZrxTi1− xO2 (x = 0, 0.1, 0.15, and 0.2) catalysts
were prepared, characterized by several techniques, and tested for their
catalytic activity for the CO2 methanation reaction. The 10 wt%Ni-
Zr0.1Ti0.9O2 catalyst exhibited excellent CO2 methanation catalytic ac­
tivity with great stability at 350 ◦ C for 50 h. The role of Zr addition in
the TiO2 lattice on the enhancement of the catalytic activity for CO2
methanation reaction was tuning the interaction between NiO and TiO2
support. This effect can result in an optimal metal-support interaction
and high active site dispersion which can facilitate the adsorption of H2
molecules. Meanwhile, Zr addition can also improve the catalyst ba­
sicity, which also increases the CO2 adsorption amount; thus, an
appropriate amount of H2 and CO2 adsorption can promote the CO2
methanation catalytic activity. The tuning of electronic property resul­
ted from electron movement from Zr to Ni valence d state. After CO
intermediate, which originated from CO2 dissociation, was adsorbed on
Ni electron rich site, the bonding between carbon and oxygen atom of
the CO molecule was then weakened and easily dissociated to carbon
and oxygen to hydrogenate with nearby H atom to form products.
13
Journal of Environmental Chemical Engineering 10 (2022) 107710
CRediT authorship contribution statement
Ammarika Makdee: Investigation, Writing – original draft. Pinit
Kidkhunthod: Methodology. Yingyot Poo-arporn: Methodology.
Kingkaew Chayakul Chanapattharapol: Conceptualization, Writing –
review & editing.
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.
Acknowledgements
The authors would like to thank the Department of Chemistry, Fac­
ulty of Science, Khon Kaen University for providing research facilities.
Thanks to the Synchrotron Light Research Institute (Public Organiza­
tion) for XAS analysis and generous beamtime. The financial support
from the Science Achievement Scholarship of Thailand (SAST) and
Materials Chemistry Research Center, Department of Chemistry, Faculty
of Science, Khon Kaen University are gratefully acknowledged.
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