catalysts

Article
Highly-Dispersed Ni-NiO Nanoparticles Anchored
on an SiO2 Support for an Enhanced CO
Methanation Performance
Jiangwei Li 1,† , Panpan Li 1,† , Jiangbing Li 1 , Zhiqun Tian 2 and Feng Yu 1, *
1 Key Laboratory for Green Processing of Chemical Engineering of Xinjiang Bingtuan, School of Chemistry
and Chemical Engineering, Shihezi University, Shihezi 832003, China; jwlyshz@163.com (J.L.);
lppbjjt@163.com (P.L.); ljbin@shzu.edu.cn (J.L.)
2 Collaborative Innovation Center of Sustainable Energy Materials, Guangxi University, Nanning 530004,
China; tianzhiqun@gxu.edu.cn
* Correspondence: yufeng05@mails.ucas.ac.cn; Tel.: +86-993-205-7272; Fax: +86-993-205-7270
† These authors contributed equally to this work.




Received: 25 April 2019; Accepted: 3 June 2019; Published: 4 June 2019


Abstract: Highly-dispersed Ni-NiO nanoparticles was successfully anchored on an SiO2 support

via a one-pot synthesis and used as heterogeneous catalysts for CO methanation. The as-obtained
Ni-NiO/SiO2 catalyst possessed a high Ni content of 87.8 wt.% and exhibited a large specific surface
area of 71 m2 g−1 with a main pore diameter of 16.7 nm. Compared with an H2 -reduced Ni-NiO/SiO2
(i.e., Ni/SiO2 ) catalyst, the Ni-NiO/SiO2 displayed a superior CO methanation performance. At the
temperature of 350 ◦ C, the Ni-NiO/SiO2 showed a CO conversion of 97.1% and CH4 selectivity of
81.9%, which are much better values than those of Ni/SiO2 . After a 50-h stability test, the Ni-NiO/SiO2
catalyst still had an overwhelming stability retention of 97.2%, which was superior to the 72.8% value
of the Ni/SiO2 catalyst.

Keywords: Ni-NiO nanoparticles; nickel-based catalyst; CO methanation; syngas; synthetic natural gas

1. Introduction
Fossil fuels and their emissions cause environmental pollution. Therefore, the development of
environmentally friendly and sustainable energy is urgently required. The main component of natural
gas is methane (CH4 ), which is characterized by cleanliness, a high calorific value, and a high energy
efficiency. This is why it is considered to be an ideal energy source [1,2]. In recent years, the cost of
natural gas has increased because of an increase in its demand, and many countries have taken a series
of measures to deal with its tight supply. Other than this, synthetic natural gas (SNG) production by
methanation from coal or biomass synthesis gas is an effective method. In particular, the production of
synthetic gas by CO or CO2 methanation has been extensively studied [3–5].
The active components of methanation catalysts are mainly distributed throughout the group
VIIIB [6,7]. Among these metals, Ni-based catalysts exhibit excellent catalytic performances and better
CH4 selectivity, which make them usable in the industry [8,9]. CO methanation is performed on a
large scale and Ni-based catalysts are the most commonly used [10]. Lu et al. [11] and Wang et al. [12]
tested and compared the performances of methanation catalysts containing various metal components
and found that Ni-based catalysts have a good performance. Lakshmanan et al. [13] prepared Ni/SiO2
catalysts with different loadings and 55 wt.% Ni@SiO2 catalysts for CO methanation. It was found that
the core-shell Ni@SiO2 catalysts had a better performance. Yan et al. [14] prepared an Ni/SiO2 catalyst
and applied it to CO methanation, which exhibited superior activity and stability. Zhao et al. [15]
prepared an Ni/SiO2 catalyst by different solution impregnation methods for CO methanation research.

Catalysts 2019, 9, 506; doi:10.3390/catal9060506 www.mdpi.com/journal/catalysts

Catalysts 2019, 9, x FOR PEER REVIEW 2 of 12

prepared Ni/SiO2 catalysts with different loadings and 55 wt.% Ni@SiO2 catalysts for CO
methanation.
Catalysts It was found that the core-shell Ni@SiO2 catalysts had a better performance. Yan 2etofal.
2019, 9, 506 12
[14] prepared an Ni/SiO2 catalyst and applied it to CO methanation, which exhibited superior activity
and stability. Zhao et al. [15] prepared an Ni/SiO2 catalyst by different solution impregnation methods
The
for COresults showed that
methanation ammonia
research. impregnation
The results showedeffectively
that ammoniaimproved the activity
impregnation and enhanced
effectively improvedthe
high-temperature stability of the Ni/SiO
the activity and enhanced the high-temperature 2 catalyst.stability of the Ni/SiO2 catalyst.
It was reported that the morphology
It was reported that the morphology distribution distribution and particle size ofsize
and particle the of
COthemethanation catalyst
CO methanation
significantly affect the catalytic performance, so the catalysts with better
catalyst significantly affect the catalytic performance, so the catalysts with better dispersion and dispersion and smaller
particles exhibit significantly
smaller particles improvedimproved
exhibit significantly performances [16–18]. Some
performances [16–18].researchers have prepared
Some researchers have
Ni-based catalysts with higher dispersion and smaller particles for CO methanation;
prepared Ni-based catalysts with higher dispersion and smaller particles for CO methanation; these these measures
effectively effectively
measures prevent theprevent
sinteringtheof active components
sintering of activeand carbon deposition
components and carbon to improve the performance
deposition to improve
of the
the catalysts [19].
performance of the catalysts [19].
Here, we
Here, we report
reportaahighhighNiNicontent
content and andhigh-dispersion
high-dispersion nickel-based
nickel-basedcatalysts of Ni-NiO/SiO
catalysts 2 and2
of Ni-NiO/SiO
Ni/SiO
and Ni/SiO2 by a one-pot method for CO methanation.
2 by a one-pot method for CO methanation. The Ni-Ni/SiO
The Ni-Ni/SiO 2 catalysts had a metal dispersion
2 catalysts had a metal
that was 0.16% higher than the Ni/SiO catalysts of 0.05% and a
dispersion that was 0.16 % higher than the Ni/SiO2 catalysts of 0.05 % and a specific
2 specific surface area of surface g−1 that
71 m2 area of
was 2 −1
71 msuperior to the
2g-1 that was latter’s to
superior areatheoflatter’s
25 m garea . The two
of 25 m2catalysts were
g-1. The two subjected
catalysts to asubjected
were CO methanation
to a CO
performance
methanation test and a 50-htest
performance stability
and test at 350 ◦stability
a 50-hour C. It was test
noteworthy
at 350 °C.thatItthe
was catalyst of Ni-NiO/SiO
noteworthy that the2
exhibited exceptional stability and carbon deposition resistance, which may be
catalyst of Ni-NiO/SiO2 exhibited exceptional stability and carbon deposition resistance, which may due to its high dispersion.
The
be duehighto dispersibility of Ni-NiO
its high dispersion. catalysts
The high increasesoftheir
dispersibility activity,
Ni-NiO and higher
catalysts increasesNi their
loading provides
activity, and
more active
higher sites [20].
Ni loading provides more active sites [20].
2. Results and Discussion
2. Results and Discussion
Figure 1 shows the X-ray diffraction (XRD) pattern of the fresh catalyst before the reaction.
Figure 1 shows the X-ray diffraction (XRD) pattern of the fresh catalyst before the reaction. As
As observed in the figure, the Ni-NiO/SiO2 catalyst exhibited NiO diffraction peaks at 2θ = 37.2◦ and
observed in the figure, the Ni-NiO/SiO 2 catalyst exhibited NiO diffraction peaks at 2θ = 37.2° and 62.9°
62.9◦ (PDF-# NO. 47-1049). These peaks, which correspond to the (111) and (220) crystal faces of NiO,
(PDF-# NO. 47-1049). These peaks, which correspond to the (111) and (220) crystal faces of NiO, were
were relatively wide, indicating that it had a poor crystallinity. The Ni-NiO/SiO2 catalyst exhibited
relatively wide, indicating that it◦ had a poor crystallinity. The Ni-NiO/SiO2 catalyst exhibited an Ni
an Ni diffraction peak (2θ = 44.5 , PDF- # NO. 04-0850). The diffraction peaks of the Ni/SiO2 catalyst
diffraction◦ peak◦ (2θ = 44. 5°, PDF- # NO. 04-0850). The diffraction peaks of the Ni/SiO2 catalyst (2θ =
(2θ = 44.5 , 51.8 , and 76.4◦ , PDF-# NO. 04-0850) correspond to the (111), (200), and (220) crystal faces of
44. 5°, 51. 8°, and 76. 4°, PDF-# NO. 04-0850) correspond to the (111), (200), and (220) crystal faces of
Ni [21]. The diffraction peaks of the NiO/SiO catalyst (2θ = 37.2◦ , 43.3◦ , 62.9◦ , 75.4◦ , and 79.4◦ , PDF-#
Ni [21]. The diffraction peaks of the NiO/SiO22 catalyst (2θ = 37.2°, 43.3°, 62.9°, 75.4°, and 79.4°, PDF-#
NO. 47-1049) correspond to the (111), (200), (220), (311), and (222) crystal faces of NiO, respectively.
NO. 47-1049) correspond to the (111), (200), (220), (311), and (222) crystal faces of NiO, respectively.
The Ni diffraction peak for the Ni/SiO2 catalyst was sharp, indicating that it had a high crystallinity.
The Ni diffraction peak for the Ni/SiO2 catalyst was sharp, indicating that it had a high crystallinity.
Additionally, no other impurity peaks were observed, which shows that it had a higher purity. Because
Additionally, no other impurity peaks were observed, which shows that it had a higher purity.
the uncalcined Ni-NiO/SiO2 catalyst was amorphous and had a poor crystallinity, the NiO and Ni
Because the uncalcined Ni-NiO/SiO 2 catalyst was amorphous and had a poor crystallinity, the NiO
diffraction peaks were relatively wide and offset compared with those of the NiO/SiO2 catalyst and
and Ni diffraction peaks were relatively wide and offset compared with those of the NiO/SiO2 catalyst
Ni/SiO2 catalyst. NiO(200) and Ni(111) planes were chosen to calculate the mean size of NiO and Ni
and Ni/SiO 2 catalyst. NiO(200) and Ni(111) planes were chosen to calculate the mean size of NiO and
crystallites by Scherrer’s equation [22]. The crystal size of NiO particles was 16.5 nm more than the
Ni crystallites by Scherrer's equation [22]. The crystal size of NiO particles was 16.5 nm more than
catalysts NiO/SiO2 and the crystal size of Ni was 14.9 nm for the catalysts Ni/SiO2 .
the catalysts NiO/SiO 2 and the crystal size of Ni was 14.9 nm for the catalysts Ni/SiO2.

Figure 1.1. XRD

XRDpatterns
patterns
of of as-obtained
as-obtained Ni-NiO/SiO
Ni-NiO/SiO 2, NiO/SiO
2 , NiO/SiO 2, Ni/SiO
2 , and and Ni/SiO 2 catalysts
2 catalysts (Thepicture
(The inner inner
picture is the diffraction
is the diffraction SiO2 ).of SiO2).
peak of peak
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To study
To study thethe oxide
oxide state
state and
and surface
surface elemental
elemental composition,
composition, X-ray X-ray photoelectron
photoelectron spectroscopy
spectroscopy
(XPS) analysis
(XPS) analysis of of the
the Ni-NiO/SiO
Ni-NiO/SiO2 and and Ni/SiO
Ni/SiO2 catalysts was performed, and the results are shown in
2 2 catalysts was performed, and the results are shown in
Figure 2. Simultaneously, the peak value was
Figure 2. Simultaneously, the peak value was fitted by a Gaussian fitted by a Gaussian
componentcomponent to determine
to determine the
the valence
valence states of Ni, O, and Si in the sample. Figure 2a shows the survey
states of Ni, O, and Si in the sample. Figure 2a shows the survey peaks of the respective elements in peaks of the respective
elements
the catalystsin the catalysts Ni-NiO/SiO
Ni-NiO/SiO 2 and Ni/SiO2, and it is clear that there was almost no difference
2 and Ni/SiO2 , and it is clear that there was almost no difference between the
between the two catalysts. Figure
two catalysts. Figure 2b shows the valence 2b shows theofvalence
state state
Ni in the twoofcatalysts.
Ni in theThe twotypical
catalysts.
peaksTheof typical
the Ni
2p orbit range from 850 eV to 884 eV; both of the catalysts contain Ni 2p3/2 and Ni 2p1/2 orbits. and
peaks of the Ni 2p orbit range from 850 eV to 884 eV; both of the catalysts contain Ni 2p3/2 The NiNi
2p1/2 orbit
2p3/2 orbits. The
can be Ni 2p3/2into
divided orbitthree
can small
be divided
peaks:intofor three small
catalysts peaks: for ,catalysts
Ni-NiO/SiO Ni-NiO/SiO2, the 2+
2 the three peaks were Ni
three peaks were Ni 2+ at 856.6 eV, and satellite peaks of Ni 2p3/2 at 858.1 eV and 862.7 eV, respectively.
at 856.6 eV, and satellite peaks of Ni 2p3/2 at 858.1 eV and 862.7 eV, respectively. There are three peaks
There
at 856.6are
eV,three
858.9peaks
eV, andat 862.7
856.6eV eV,for858.9
Ni/SiO eV, and 862.7 eV for Ni/SiO2 catalysts. The Ni 2p1/2 orbit
2 catalysts. The Ni 2p1/2 orbit contains two characteristic
contains
peaks two
of Ni 2+characteristic
at 874.1 eV and peaks of Ni peak
a satellite
2+ at 874.1 eV and
at 880.2 eVafor
satellite peak at 880.2
both catalysts. TheeV for bothofcatalysts.
catalysts Ni/SiO2
The catalysts of Ni/SiO 2 contain
0 the characteristic Ni 0 peak at 853.1
contain the characteristic Ni peak at 853.1 eV, while no peak of Ni was observed in the 0 eV, while no peak of Ni0 was
Ni-NiO/SiO 2
observed ainpossible
catalysts, the Ni-NiO/SiO
reason for 2 catalysts, a possible reason for which may be that the Ni in the Ni-
which may be that the Ni in the Ni-NiO/SiO2 catalysts was relatively
NiO/SiO2 and
dispersed catalysts
couldwasnot berelatively
detecteddispersed
[9,23]. Figureand 2ccould
shows notthebecharacteristic
detected [9,23].
O 1sFigure
peak for 2cthe
shows the
catalyst,
characteristic O 1s peak for the catalyst, containing 531.4 eV, 532.4 eV,
containing 531.4 eV, 532.4 eV, and 533.2 eV peaks. The vibrational peaks at 531.4 eV and 532.4 eV were and 533.2 eV peaks. The
vibrational peaks
respectively lattice at 531.4 and
oxygen eV anddefect532.4 eV were
oxygen. The respectively
lattice oxygen lattice
peak oxygen andcatalyst
area of the defect Ni-NiO/SiO
oxygen. The
2
lattice oxygen peak area of the catalyst Ni-NiO/SiO 2 was larger than that of the catalyst Ni/SiO2,
was larger than that of the catalyst Ni/SiO2 , indicating that the catalyst Ni-NiO/SiO2 had more oxygen
indicating so
vacancies, that
thethe catalyst
catalyst hadNi-NiO/SiO 2 had more oxygen vacancies, so the catalyst had a better
a better catalytic performance. Figure 2d shows two fitted peaks at
binding energies of 102.6 eV and 103.5 eV for Si 2ppeaks
catalytic performance. Figure 2d shows two fitted in theat binding energies
high-resolution of 102.6 eV and 103.5 eV
spectrum.
for Si 2p in the high-resolution spectrum.

Figure 2. XPS spectrum of catalysts Ni-NiO/SiO2 and Ni/SiO2 : (a) survey, (b) Ni 2p, (c) O 1s, and (d) Si 2p.
Figure 2. XPS spectrum of catalysts Ni-NiO/SiO2 and Ni/SiO2: (a) survey, (b) Ni 2p, (c) O 1s, and (d)
Si 2p.
Figure 3 shows transmission electron microscopy (TEM) and high resolution TEM (HRTEM)
images of the Ni-NiO/SiO2 and Ni/SiO2 catalysts. Figure 3a shows a TEM image of Ni-NiO/SiO2
Figure 3 shows transmission electron microscopy (TEM) and high resolution TEM (HRTEM)
catalysts. It can be seen that the catalyst had a veil-like structure, which indicates better Ni dispersion.
images of the Ni-NiO/SiO2 and Ni/SiO2 catalysts. Figure 3a shows a TEM image of Ni-NiO/SiO2
As shown in Figure 3b, there were two lattice fringes of d = 0.241 and 0.203 nm in the catalysts of
catalysts. It can be seen that the catalyst had a veil-like structure, which indicates better Ni dispersion.
Ni-NiO/SiO2 , which correspond to the (111) plane of the NiO phase and the (111) plane of the Ni
As shown in Figure 3b, there were two lattice fringes of d = 0.241 and 0.203 nm in the catalysts of Ni-
NiO/SiO2, which correspond to the (111) plane of the NiO phase and the (111) plane of the Ni phase,
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Catalysts 2019, 9, x FOR PEER REVIEW 4 of 12

phase, respectively. The TEM image of Ni/SiO2 catalysts after calcination and reduction is shown in
respectively. The TEM image of Ni/SiO2 catalysts after calcination and reduction is shown in Figure
Figure 3c, and Figure 3d reveals the HRTEM figure of Ni/SiO2 catalysts, which contains a lattice fringe
3c, and Figure 3d reveals the HRTEM figure of Ni/SiO2 catalysts, which contains a lattice fringe of d
of d = 0.203 nm meeting the (111) crystal plane of Ni. Figure 3e–f shows the nitrogen adsorption and
= 0.203 nm meeting the (111) crystal plane of Ni. Figure 3e–f shows the nitrogen adsorption and
desorption curves and pore volume distributions of the two catalysts. Both catalysts exhibited type IV
desorption curves and pore volume distributions of the two catalysts. Both catalysts exhibited type
isothermal adsorption, suggesting that they were both mesoporous. Structural data for the catalyst
IV isothermal adsorption, suggesting that they were both mesoporous. Structural data for the catalyst
is shown in Table 1. The specific surface area of the Ni-NiO/SiO2 and Ni/SiO2 catalysts was 71 and
is shown in Table 1. The specific surface area of the Ni-NiO/SiO2 and Ni/SiO2 catalysts was 71 and 25
25 m2 g−1 , and the average pore diameter was 16.7 and 28.4 nm, respectively. The metal dispersion of
m2g−1, and the average pore diameter was 16.7 and 28.4 nm, respectively. The metal dispersion of the
the two catalysts was tested by hydrogen pulse adsorption. The dispersion of the Ni-NiO/SiO catalysts
two catalysts was tested by hydrogen pulse adsorption. The dispersion of the Ni-NiO/SiO22catalysts
was 0.16%, and the dispersion of the Ni/SiO2 catalysts was 0.05%, indicating that the Ni-NiO/SiO2
was 0.16 %, and the dispersion of the Ni/SiO2 catalysts was 0.05 %, indicating that the Ni-NiO/SiO2
catalysts exhibited better dispersion. The Brunauer–Emmett–Teller (BET) characterization results and
catalysts exhibited better dispersion. The Brunauer–Emmett–Teller (BET) characterization results and
the hydrogen pulse adsorption test results showed that the catalyst of Ni-NiO/SiO2 had a larger specific
the hydrogen pulse adsorption test results showed that the catalyst of Ni-NiO/SiO 2 had a larger
surface area and better dispersibility, and thus had a better performance.
specific surface area and better dispersibility, and thus had a better performance.

Figure 3. TEM and HRTEM images of (a,b) Ni-NiO/SiO2 and (c,d) Ni/SiO2 . (e) N2 adsorption–desorption
Figure 3. TEM and HRTEM images of (a, b) Ni-NiO/SiO 2 and (c, d) Ni/SiO2. (e) N2 adsorption–
isotherms and (f) pore size distribution for Ni-NiO/SiO2 and Ni/SiO2 , respectively.
desorption isotherms and (f) pore size distribution for Ni-NiO/SiO2 and Ni/SiO2, respectively.
Table 1. Specific surface area, pore size, and pore volume of the Ni-NiO/SiO2 and Ni/SiO2 catalysts.
Table 1. Specific surface area, pore size, and pore volume of the Ni-NiO/SiO2 and Ni/SiO2 catalysts.
Samples SBET (m2 g−1 ) a Pore Volume (cm3 g−1 ) b Pore Size (nm) b
Samples SBET(m2g-1) a Pore volume(cm3g-1) b Pore size(nm) b
Ni-NiO/SiO2 71 0.28 16.7
Ni/SiONi-NiO/SiO
2
2 71
25 0.28 0.16 16.7 28.4
a Obtained fromNi/SiO 2 b 25 0.16 28.4
the BET method. Obtained from the Barett-Joyer-Halenda (BJH) desorption average pore volume
Obtained
aand from the BET method. b Obtained from the Barett-Joyer-Halenda (BJH) desorption average
pore diameter.
pore volume and pore diameter.
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The reduction capacity of the catalyst surface is crucial for selective catalytic reduction.
The reduction
Therefore, we conducted capacity of the catalyst
a hydrogen surface is crucial for
temperature-programmed selective(Hcatalytic
reduction 2 -TPR) test reduction.
on the
Therefore, we conducted a hydrogen temperature-programmed reduction
catalyst, and the corresponding results are shown in Figure 4. The dispersion of the NiO peak position (H 2-TPR) test on the
catalyst,
and and the interaction
the mutual corresponding withresults are shown
the carrier were in Figure 4.The
assessed. Thereduction
dispersionpeak
of theofNiO
the peak position
Ni-NiO/SiO 2
and the mutual
catalysts ◦ C was the surface
at 152.0 interaction with the carrier
NiO, whilewere assessed. The
the reduction at 593.9 ◦ Cpeak
peakreduction was of
thetheNiO Ni-NiO/SiO
interacting2
catalysts
with at 152.0[24].
the carrier °C was Thethecatalysts
surface NiO, while the
of NiO/SiO reduction
2 showed peak at 593.9
reduction peaks°C atwas the◦ C
609.4 NiOand 765.1 ◦ C.
interacting
withdifference
The the carrierin [24].
theThe catalystspeak
reduction of NiO/SiO
positions2 showed
of the reduction
two catalystspeaks at 609.4
may °C and
be due 765.1
to the °C.NiO
high The
difference in the reduction peak positions of the two catalysts may be due
dispersion in the catalysts of Ni-NiO/SiO2 allowing some of the NiO to be reduced to Ni at a lowerto the high NiO dispersion
in the catalysts
temperature. of reduction
The Ni-NiO/SiO 2 allowing
peak some
of NiO/SiO of the NiO
2 catalysts to beto
shifted reduced
higher to Ni at a lower
temperatures, temperature.
indicating that
The reduction
NiO peak of NiO/SiO
interacts strongly with the2 catalysts shifted
SiO2 carrier. Theto higher
hydrogen temperatures,
consumption indicating
of the twothatcatalysts
NiO interacts
was
strongly with
calculated. Thethe SiO2 carrier.
hydrogen The hydrogen
consumption of theconsumption
Ni-NiO/SiO2 of andtheNiO/SiO
two catalysts waswas
2 catalysts calculated. The
44.3 cc and
hydrogen
86.6 cc. The consumption
difference inofhydrogen
the Ni-NiO/SiO 2 and NiO/SiO
consumption 2 catalysts
reflects the differencewasin44.3 cc and 86.6between
the interaction cc. The
difference
the SiO2 and in NiO.
hydrogenBoth consumption
catalysts had reflects the difference
two reduction peaks at indifferent
the interaction
positionsbetween the SiO2peak
and different and
NiO. Both catalysts had two reduction peaks at different positions and different
areas indicating different hydrogen consumption, corresponding to different reduction rates [25]. peak areas indicating
different
For hydrogen
the catalyst consumption,
of Ni-NiO/SiO 2 , thecorresponding
reduction rate of to the
different reduction
first reduction rates [25]. For
temperature wasthe3.6%,catalyst of
and the
Ni-NiO/SiO , the reduction rate of the first reduction temperature was 3.6
reduction rate of the second reduction temperature was 96.4%. The reduction rates were 98.8% and
2 %, and the reduction rate
of theofsecond
1.2% the NiO/ reduction temperature
SiO2 catalysts for the was
two 96.4 %. The
reduction reduction rates were 98.8 % and 1.2 % of the
temperatures.
NiO/ SiO2 catalysts for the two reduction temperatures.

Figure 4. H
Figure 4. H22 -TPR
-TPR patterns
patterns of
of Ni-NiO/SiO
Ni-NiO/SiO22 and
and Ni/SiO
Ni/SiO22...

Figure ◦ C–550 ◦ C, where the test conditions

Figure 55 shows
shows aa catalyst
catalyst performance
performancechart chartinin the
the range
range 250
250 °C–550 °C, where the test conditions
−1 −1
were
were 0.1
0. 1MPa
MPaand andthe thespace
spacevelocity
velocitywaswas19,19,500 mL·g−1·h·h−1.. As
500mL·g As is
is shown
shown in in Figure
Figure 5a,
5a, the
the CO
CO
conversion of the Ni-NiO/SiO 2 and Ni/SiO 2 catalysts increased with the reaction
conversion of the Ni-NiO/SiO2 and Ni/SiO2 catalysts increased with the reaction temperature in the temperature in the
range ◦ C–300 ◦ C and remained mainly stable in the range 300 ◦ C–400 ◦ C. The main reason for the
range 250
250 °C–300 °C and remained mainly stable in the range 300 °C–400 °C. The main reason for the
decrease ◦ C was the fact that the high temperature made the catalyst
decrease in catalyst performance
in catalyst performanceafterafter 400
400 °C was the fact that the high temperature made the catalyst
agglomerate
agglomerate and and caused
caused carbon
carbon deposition
deposition during
during the
the reaction.
reaction. These
These two
two phenomena
phenomena werewere the
the main
main
reasons for the catalyst deactivation during CO methanation. The CO conversion
reasons for the catalyst deactivation during CO methanation. The CO conversion of the Ni-NiO/SiO22 of the Ni-NiO/SiO
and
and Ni/SiO
Ni/ SiO 2 2catalysts
catalystswaswas97.1%
97.1 % andand88.7%, which werewere
88.7 %，which the highest at 350at◦350
the highest C. The
°C. corresponding CH4
The corresponding
selectivity of the two catalysts was 81.9% and 75.3%, respectively. The turnover frequency
CH4 selectivity of the two catalysts was 81.9 % and 75.3 %, respectively. The turnover frequency (TOF) (TOF) of the
Ni-NiO/SiO catalysts was 2.3 s −1 , while that of Ni/SiO catalysts was 7.1 s−1 at 350 ◦ C. Compared
2
of the Ni-NiO/SiO 2 catalysts was 2.3 s−1, while that of Ni/SiO 2 2 catalysts was 7.1 s−1 at 350 °C. Compared
with
with Ni-NiO/SiO2 and Ni/SiO2 catalysts, the performance and
Ni-NiO/SiO 2 and Ni/SiO 2 catalysts, the performance and stability
stability of
of NiO/SiO
NiO/SiO22 catalysts
catalysts were
were
poor. Therefore, only Ni-NiO/SiO 2 and Ni/SiO 2 catalysts were systematically
poor. Therefore, only Ni-NiO/SiO2 and Ni/SiO2 catalysts were systematically studied. studied.
Catalysts 2019, 9, 506 6 of 12
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Figure 5. (a) CO conversion

conversion and
and(b)
(b)CH
CH44 selectivity
selectivity of
ofas-obtained
as-obtainedNi-NiO/SiO
Ni-NiO/SiO2 ,2,NiO/SiO
NiO/SiO2 ,2,and
andNi/SiO
Ni/SiO2 .2.
Figure 5. (a) CO conversion and (b) CH4 selectivity of as-obtained Ni-NiO/SiO2, NiO/SiO2, and Ni/SiO2.
In
In order
order toto study
study thethe structure
structure of of the
the catalyst
catalyst after
after the
the activity
activity test,
test, the
the two
two catalysts
catalysts were
were
In order to
characterized. The study the structure
two catalysts
catalysts after of the catalyst after the activity test, the-550twoandcatalysts
Ni/SiO2were
characterized. The two after the
the activity
activity test
test were
were named
named Ni-NiO/SiO
Ni-NiO/SiO22-550 and Ni/SiO -550,
-550,
characterized.
respectively. TheXRD
The twopattern
catalysts of after
the the activity
catalyst after test
the were
250 named◦ C
◦ C–550 Ni-NiO/SiO
activity 2-550 and Ni/SiO2-550,
test is shown in Figure 6.
respectively. The XRD pattern of the catalyst after the 250 °C–550 °C activity test is shown in Figure
respectively. The XRD pattern of the catalyst after the 250 °C–550 °C activity test is shown in Figure
at=2θ44.5
The two catalysts hadhad
Ni Nidiffraction peaks at 2θ ◦ ◦
, 51.851.8°,
, andand ◦
76.476.4°
(PDF-# NO.NO. 44-0850), andand
the
6. The two catalysts diffraction peaks = 44.5°, (PDF-# 44-0850),
6. Thediffraction
three two catalysts
peakshad Ni diffraction
correspond to thepeaks at(200),
(111), 2θ = 44.5°,
and 51.8°,
(220) and 76.4°
phases of (PDF-#
Ni, NO. 44-0850),
respectively. Comparedand
the three diffraction peaks correspond to the (111), (200), and (220) phases of Ni, respectively.
the three
with the XRD diffraction
pattern ofpeaks correspondcatalyst,
thepattern
pre-reaction to the the
(111), (200),
twocatalyst,
catalystsandhad
(220) phases of peak
a Ccatalysts
diffraction Ni, respectively.
2θ = 26.6◦
Compared with the XRD of the pre-reaction the two had a Catdiffraction
Compared
(PDF-# with the XRD pattern of the pre-reaction catalyst, the two catalysts had a C diffraction
peak atNO. 2θ =26-1076), indicating
26.6° (PDF-# that thereindicating
NO. 26-1076), was C formation
that therein the
wascatalyst after the
C formation inreaction, which
the catalyst could
after the
peak
be an atimportant
2θ = 26.6°cause
(PDF-# of NO. 26-1076),
catalyst indicatingThe
inactivation. thatCthere
peak was
for C formation
Ni/SiO -550 in the catalyst
catalysts was after the
stronger
reaction, which could be an important cause of catalyst inactivation. 2The C peak for Ni/SiO2-550
reaction,
than that which could be -550,
for Ni-NiO/SiO an important
indicating cause of catalyst
that carbon inactivation.
deposition Thesevere.
C peakThis for showed
Ni/SiO2-550
catalysts was stronger than 2 that for Ni-NiO/SiO 2-550, indicatingwas thatmore
carbon deposition that
was more
catalysts
Ni-NiO/SiO was-550
stronger
could than
improvethat the
for resistance
Ni-NiO/SiO 2-550, indicating that carbon deposition was more
to improve
carbon deposition [26]. to carbon deposition [26].
severe. This2showed that Ni-NiO/SiO 2-550 could the resistance
severe. This showed that Ni-NiO/SiO2-550 could improve the resistance to carbon deposition [26].

Figure 6.
Figure 6. XRD
XRD patterns
patterns of
of the
the Ni-NiO/SiO
Ni-NiO/SiO2-550
-550 and
and Ni/SiO
Ni/SiO2-550
-550 catalysts.
catalysts.
Figure 6. XRD patterns of the Ni-NiO/SiO22-550 and Ni/SiO22-550 catalysts.

TEM and and HRTEM

HRTEMimages imagesofofthethe catalysts after
catalysts the the
after activity test are
activity test shown in Figure
are shown 7. From
in Figure 7.
TEM and HRTEM images of the catalysts after the activity test are shown in Figure 7. From
Figures
From 7a and
Figure c,ititisisclear
7a,c, clearthat
thatboth
both
ofofthethe catalysts
catalysts generated
generated a large
a large number
number of carbon
of carbon nanotubes
nanotubes after
Figures 7a and c, it is clear that both of the catalysts generated a large number of carbon nanotubes
after
the the reaction,
reaction, whichwhich is a critical
is a critical factor
factor of of catalyst
catalyst deactivation.
deactivation. The HRTEM The HRTEM
images in images
Figurein Figure
7b,d 7b
clearly
after the reaction, which is a critical factor of catalyst deactivation. The HRTEM images in Figure 7b
and d the
show clearly show
lattice the lattice
fringes on thefringes on the two
two catalysts. catalysts.
Each catalystEach
hadcatalyst had fringes
two lattice two lattice = 0.335ofand
of dfringes d=
and d clearly show the lattice fringes on the two catalysts. Each catalyst had two lattice fringes of d =
0.335 nm,
0.203 and which
0.203 nm, which correspond
correspond to the (006) to the (006)
crystal planecrystal plane
of C and (111)ofcrystal
C and plane
(111) crystal plane of Ni.
of Ni. Furthermore,
0.335 and 0.203 nm, which correspond to the (006) crystal plane of C and (111) crystal plane of Ni.
Furthermore,
Ni/SiO Ni/SiO2-550
2 -550 produced more produced more carbon
carbon nanotubes thannanotubes
Ni-NiO/SiO than Ni-NiO/SiO
2 -550, indicating 2-550,
moreindicating more
serious carbon
Furthermore, Ni/SiO2-550 produced more carbon nanotubes than Ni-NiO/SiO2-550, indicating more
serious carbon
deposition, deposition,
which which was
was consistent withconsistent with
the results of the results of the XRD
XRD analysis. Fromanalysis.
FigureFrom
7a,c, Figs.
we can7a
serious carbon deposition, which was consistent with the results of the XRD analysis. From Figs. 7a
and c, we can see that the Ni particles in Ni/SiO2-550 were larger than those in Ni-NiO/SiO2-550,
and c, we can see that the Ni particles in Ni/SiO2-550 were larger than those in Ni-NiO/SiO2-550,
suggesting that agglomeration occurred during the reaction, leading to catalyst deactivation.
suggesting that agglomeration occurred during the reaction, leading to catalyst deactivation.
Catalysts 2019, 9, 506 7 of 12

see that2019,
Catalysts the 9,Nix FOR
particles in Ni/SiO2 -550 were larger than those in Ni-NiO/SiO2 -550, suggesting
PEER REVIEW that
7 of 12
agglomeration occurred during the reaction, leading to catalyst deactivation.

Figure 7. TEM
Figure and HRTEM
7. TEM images
and HRTEM of (aof
images and b) Ni-NiO/SiO
(a,b) Ni-NiO/SiO22-550 and (c,d)
(c and d) Ni/SiO
Ni/SiO 2-550.
2 -550.

In the process
process of
of CO
COmethanation,
methanation,carbon
carbonformation
formationand anddeposition
deposition is is one
one ofof
thethe main
main causes
causes of
of catalyst deactivation. Thermal gravimetric analysis (TGA) is
catalyst deactivation. Thermal gravimetric analysis (TGA) is a common means a common means for characterizing
carbon deposition in catalysts
catalysts [27]. Therefore, the
[27]. Therefore, the thermogravimetric
thermogravimetric method method was employed to
analyze the catalyst
catalyst after
afterthe
thereaction.
reaction.The
Theresults
resultsofofthe
thestudy
studyare areshown
shown inin Figure
Figure 8. 8.
TheThe catalysts
catalysts of
of Ni-NiO/SiO and Ni/SiO showed weight gain in the range of 420 to 500 ◦ C and 420 to 530 ◦ C,
Ni-NiO/SiO2 and 2 Ni/SiO2 showed
2 weight gain in the range of 420 to 500 °C and 420 to 530 °C,
respectively,
respectively, possibly
possibly due
due to the oxidation of Ni nanoparticles to NiO. By comparing the weight loss
of the two catalysts, it was found
found that
that the
the carbon
carbon content
content ofof the
the Ni-NiO/SiO
Ni-NiO/SiO22catalyst
catalystwas
was15.86
15.86%,
%,
while the Ni/SiO2 catalyst’s
catalyst’s carbon
carbon content
content was
was 18.74
18.74%.%. The removal temperatures of carbon in the
two catalysts were different; ◦ C and Ni/SiO ◦ C.
different; the
thecatalyst
catalystof
ofNi-NiO/SiO
Ni-NiO/SiO22was was500–790
500-790 °C 530–690 °C.
Ni/SiO22 was 530-690
They were mainly
mainly deactivating
deactivating carbon species deriving
deriving from CH CH44 decomposition, which cannot be
removed until a high temperature. [24,28]. The weight weight of the Ni/SiO2 catalysts
catalysts was increased
increased after
690 ◦°C,
C, possibly because the unreacted Ni was exposed and oxidized after carbon deposition was
removed. Combined
Combined withwith XRD
XRD and and TEM characterization
characterization results,
results, it
it was found that the catalysts of
Ni-NiO/SiO2 had a better carbon deposition resistance and activity. activity.
To test the catalyst stability, the two catalysts were tested at 350 ◦ C for 50 h, and the results are
shown in Figure 9, which indicates the change in the CO conversion of the two catalysts within 50 h.
The CO conversion of Ni-NiO/SiO2 catalysts decreased from 97.8% to 97.2%, while that of Ni/SiO2
catalysts decreased from 78.9% to 72.8%. The inside figure shows the change in the CH4 selectivity of
the catalyst. It was clear that the CH4 selectivity of the two catalysts remained mainly constant within
50 h at 350 ◦ C. The test results showed that the catalytic performance and stability of Ni-NiO/SiO2
catalysts were better than those of Ni/SiO2 .
Figure 10 shows the XRD pattern of the catalyst after 50-h testing at 350 ◦ C. The two catalysts
after the stability test were named Ni-NiO/SiO2 -350 and Ni/SiO2 -350, respectively. Both catalysts
showed Ni diffraction peaks at 2θ = 44.5◦ , 51.8◦ , and 76.3◦ (PDF-# NO. 04-0850). However, their peak
intensities were significantly different. The XRD peaks of Ni of Ni-NiO/SiO2 -350 were more intense
than those of Ni/SiO2 -350. The grain size of Ni in the catalyst after the stability test was calculated by

Figure 8. TG images of used catalysts of Ni-NiO/SiO2-550 and Ni/SiO2-550.

Ni-NiO/SiO2 and Ni/SiO2 showed weight gain in the range of 420 to 500 °C and 420 to 530 °C,
respectively, possibly due to the oxidation of Ni nanoparticles to NiO. By comparing the weight loss
of the two catalysts, it was found that the carbon content of the Ni-NiO/SiO2 catalyst was 15.86 %,
while the Ni/SiO2 catalyst’s carbon content was 18.74 %. The removal temperatures of carbon in the
two catalysts were different; the catalyst of Ni-NiO/SiO2 was 500-790 °C and Ni/SiO2 was 530-690 °C.
Catalysts 2019, 9, 506 8 of 12
They were mainly deactivating carbon species deriving from CH4 decomposition, which cannot
Catalysts 2019, 9, x FOR PEER REVIEW
be
8 of 12
removed until a high temperature. [24,28]. The weight of the Ni/SiO2 catalysts was increased after
690 °C,
To possibly
Scherrer’s formula.
test because
the catalyst the unreacted
The grain sizes
stability, theoftwoNi was
Ni(111) exposed
of the
catalysts andNi-NiO/SiO
catalysts
were testedoxidized
at 350 °Cafter
2 and
for carbon
50 h, anddeposition
Ni/SiO were
2the 16.3was
results nm
are
removed.
shown in Figure 9, which indicates the change in the CO conversion of the two catalysts within 50 of
and 20.0 Combined
nm, with
respectively. XRD and TEM characterization results, it was found that the catalysts h.
Ni-NiO/SiO 2 had a better
The CO conversion carbon deposition
of Ni-NiO/SiO 2 catalystsresistance
decreasedandfromactivity.
97.8 % to 97.2 %, while that of Ni/SiO2
catalysts decreased from 78.9 % to 72.8 %. The inside figure shows the change in the CH4 selectivity
of the catalyst. It was clear that the CH4 selectivity of the two catalysts remained mainly constant
within 50 h at 350 °C. The test results showed that the catalytic performance and stability of Ni-
NiO/SiO2 catalysts were better than those of Ni/SiO2.

Catalysts 2019, 9, x FOR PEER REVIEW 8 of 12

To test the catalyst stability, the two catalysts were tested at 350 °C for 50 h, and the results are
shown in Figure 9, which indicates the change in the CO conversion of the two catalysts within 50 h.
The CO conversion of Ni-NiO/SiO2 catalysts decreased from 97.8 % to 97.2 %, while that of Ni/SiO2
catalysts decreased from 78.9 % to 72.8 %. The inside figure shows the change in the CH4 selectivity
of the catalyst. It was clear that the CH4 selectivity of the two catalysts remained mainly constant
within 50 h at 350 °C. The test results showed that the catalytic performance and stability of Ni-
NiO/SiO2 catalysts
Figurewere
Figure 8. TGbetter
8. TG images
imagesthan
of thosecatalysts
of used
used of Ni/SiOof
catalysts of2. Ni-NiO/SiO
Ni-NiO/SiO2-550
-550 and
and Ni/SiO
Ni/SiO2-550.
-550.
2 2

Figure 9. CO conversion and CH4 selectivity (inside) of Ni-NiO/SiO2 and Ni/SiO2 catalysts.

Figure 10 shows the XRD pattern of the catalyst after 50-h testing at 350 °C. The two catalysts
after the stability test were named Ni-NiO/SiO2-350 and Ni/SiO2-350, respectively. Both catalysts
showed Ni diffraction peaks at 2θ = 44.5°, 51.8°, and 76.3° (PDF-# NO. 04-0850). However, their peak
intensities were significantly different. The XRD peaks of Ni of Ni-NiO/SiO2-350 were more intense
than those of Ni/SiO2-350. The grain size of Ni in the catalyst after the stability test was calculated by
Scherrer's formula. The grain sizes of Ni(111) of the catalysts Ni-NiO/SiO2 and Ni/SiO2 were 16.3 nm
and 20.0 nm, respectively.
Figure
Figure 9. CO9. conversion
CO conversion
andand
CHCH 4 selectivity (inside)
4 selectivity (inside) of
ofNi-NiO/SiO2 and
Ni-NiO/SiO Ni/SiO
2 and 2 catalysts.
Ni/SiO 2 catalysts.

Figure 10 shows the XRD pattern of the catalyst after 50-h testing at 350 °C. The two catalysts
after the stability test were named Ni-NiO/SiO2-350 and Ni/SiO2-350, respectively. Both catalysts
showed Ni diffraction peaks at 2θ = 44.5°, 51.8°, and 76.3° (PDF-# NO. 04-0850). However, their peak
intensities were significantly different. The XRD peaks of Ni of Ni-NiO/SiO2-350 were more intense
than those of Ni/SiO2-350. The grain size of Ni in the catalyst after the stability test was calculated by
Scherrer's formula. The grain sizes of Ni(111) of the catalysts Ni-NiO/SiO2 and Ni/SiO2 were 16.3 nm
and 20.0 nm, respectively.

Figure 10.
Figure 10. XRD patterns
patterns of
of catalysts
catalysts Ni-NiO/SiO
Ni-NiO/SiO22-350 and Ni/SiO
Ni/SiO22-350.
Catalysts 2019, 9, 506 9 of 12
Catalysts 2019, 9, x FOR PEER REVIEW 9 of 12

TEMandandHRTEM
HRTEMfigures figuresofof ◦ are shown in Figure 11.
TEM thethe catalyst
catalyst after
after 50 h50testing
h testing
at 350at °C
350areCshown in Figure 11. From
From Figure
Figures 11a 11a,c,
and c, it isitclear that after
is clear that the 50-hthe
after reaction, Ni-NiO/SiO
50-h reaction, 2 -350 maintained
Ni-NiO/SiO its veil morphology,
2-350 maintained its veil
regardless of regardless
morphology, slight agglomeration. However, Ni/SiO
of slight agglomeration. 2 -350 showed
However, Ni/SiO2significant
-350 showed agglomeration.
significant
Figure 11b,d show
agglomeration. HRTEM
Figs. 11b andimages d of Ni-NiO/SiO
show HRTEM 2 -350 and Ni/SiO
images 2 -350, respectively.
of Ni-NiO/SiO 2-350 andCrystal
Ni/SiOlattices
2-350,
of C and Ni can be clearly seen in both pictures. After comparing these results
respectively. Crystal lattices of C and Ni can be clearly seen in both pictures. After comparing with the XRD results
these
before the reaction, it was found that a small quantity of C was formed on the catalyst
results with the XRD results before the reaction, it was found that a small quantity of C was formed surface after the
50-h reaction.
on the catalyst surface after the 50-h reaction.

Figure 11. TEM and HRTEM images of the catalysts Ni-NiO/SiO -350 (a,b) and Ni/SiO2 -350 (c,d).
Figure 11. TEM and HRTEM images of the catalysts Ni-NiO/SiO22-350 (a and b) and Ni/SiO 2-350 (c

and d).
3. Materials and Methods

3. Materials
3.1. andofMethods
Preparation the Catalysts
The catalysts were prepared as follows. A total of 56 mL ethanol and 24 mL deionized water were
3.1. Preparation of the Catalysts
put in a three-necked flask and mixed well at 30 ◦ C. Then, Ni(NO3 )2 ·6H2 O (1.5 g) was added to the
The and
solution catalysts were
stirred prepared
it until as follows.
completely A total
dissolved. of 56
After themL ethanol
nickel and
nitrate 24completely
was mL deionized water
dissolved,
were put in a three-necked flask and mixed well at 30 °C. Then, Ni(NO ) ·6H
a small amount of TEOS (0.5 mL) was used as a silicon precursor for synthesizing silica [13]. TEOS was
3 2 2 O (1.5 g) was added to
the
addedsolution
dropwiseandtostirred it until
the reaction completely
vessel dissolved.
and stirring After the
was continued fornickel nitrate was
two minutes. Then,completely
an NaBH4
dissolved,
solution (0.4 a small amount
g of NaBH 4 of TEOS
dissolved (0.5
in 5 mL)
mL was
of used
water) as
was a silicon
quickly precursor
added. The for synthesizing
reaction was silica
stopped
[13]. TEOS was added dropwise to the reaction vessel and stirring was continued
after stirring for 1 h. After the reaction was completed, the solution was centrifuged and dried at for two minutes.
80 ◦ C an
Then, forNaBH solution
10 h. 4The (0.4 gcatalyst
obtained of NaBH was4 dissolved in 5 mL of water)
named Ni-NiO/SiO 2 . Some was
of quickly added.
this catalyst was The reaction
calcined in
was
air at 550 ◦ C after
stopped for 4 stirring for 1h. NiO/SiO
h and named After the2 ,reaction
whereaswas somecompleted,
NiO/SiO2the solution
was reduced was 500 ◦ C in anand
atcentrifuged H2
dried at 80 °C
atmosphere forfor
2 h 10h. The obtained
and named Ni/SiO2catalyst was named
. The theoretical loadNi-NiO/SiO
of Ni in the2.catalyst
Some of of this catalyst2 was
Ni-NiO/SiO was
calcined
69.5 wt.%, in while
air at 550 °C for 4h and
the inductive named
coupled NiO/SiO
plasma (ICP) 2, whereas some NiO/SiO
characterization was reduced
results 2showed at load
that the 500 °C of
in an H atmosphere for 2h and named Ni/SiO .The theoretical
Ni was 87.8 wt.%, which may be due to the incomplete hydrolysis of TEOS.
2 2 load of Ni in the catalyst of Ni-
NiO/SiO2 was 69.5 wt.%, while the inductive coupled plasma (ICP) characterization results showed
3.2. the
that Catalyst
load Characterization
of Ni was 87.8 wt.%, which may be due to the incomplete hydrolysis of TEOS.
X-ray diffractometry was carried out to determine the crystallographic properties of the materials,
3.2. Catalyst Characterization
and XRD patterns were obtained with a BrukerD8 Advance X-ray diffractometer (Bruker Biosciences
Corporation, Billerica, MA,
X-ray diffractometry wasUSA) usingout
carried Cu to
K radiation
determineinthe 2θ range 0–90◦ . properties
thecrystallographic XPS experiments
of the
used a Thermo
materials, ESCALAB
and XRD patterns250XIelectron
were obtained spectrometer from Kratos
with a BrukerD8 AdvanceAnalytical with Mg Kα (Bruker
X-ray diffractometer (20 mA,
12 kV) radiation
Biosciences (Escalab 250Xi,
Corporation, Thermo
Billerica, MA, Fisher
USA) Scientific,
using Cu Waltham, MA,inUSA).
K radiation H2range
the 2θ -TPR experiments
0–90°. XPS
experiments used a Thermo ESCALAB 250XIelectron spectrometer from Kratos Analytical with Mg
Kα (20 mA, 12 kV) radiation (Escalab 250Xi, Thermo Fisher Scientific, Waltham, MA, USA). H2-TPR
Catalysts 2019, 9, 506 10 of 12

were conducted to determine the reducibility of the NiO oxides by the Micromeritics TPx system
(Micromeritics ASAP 2720, Micromeritics Instrument Ltd., Norcross, GA, USA) from 20 ◦ C to 900 ◦ C
at the heat up speed of 10 ◦ C/min using a 10 vol% H2 /Ar flow at 45 mL/min and maintaining
the sample at 900 ◦ C for 20 min. TEM and HRTEM images were obtained using a Tecnai G2 F20
S-TWIN(200KV)(Hillsboro, OR, USA). The BET specific surface area and BJH pore structure of the
catalysts were evaluated using a Micromeritics ASAP 2020 BET apparatus (Micromeritics Instrument
Ltd., Norcross, GA, USA). TGA was conducted on TG-DSC analysis system (STA 449 F3 Jupiter,
Germany). ICP was used to detect the content of elements in a sample, and the sample is analyzed by
inductively coupled plasma optical emission spectrometer (Agilent ICPOES730, America).

3.3. Activity Measurement

The catalytic performance was evaluated by a fixed-bed reactor e. The catalyst of Ni-NiO/SiO2
(0.2 g) was heated to 250 ◦ C in N2 atmosphere, and the synthesis gas (H2 /CO = 3, the CO concentration is
23.0% mol/mol, WHSV = 19, 500 mL·g−1 ·h−1 , P = 0.1 MPa) was then introduced for testing. The catalyst
of Ni/SiO2 (0.2 g) was reduced in an H2 atmosphere for 2 h at 500 ◦ C in the reactor and then cooled to
250 ◦ C in an N2 atmosphere. After that, synthesis gas was introduced into the reactor. The performances
of the two catalysts were tested from 250 ◦ C to 550 ◦ C, and the effluent gas was analyzed by online gas
chromatography (GC-2014C, SHIMADZU, Kyoto, Japan).

4. Conclusions
The catalysts of Ni-NiO/SiO2 and Ni/SiO2 were successfully prepared through co-precipitation
with TEOS as the silicon source and Ni(NO3 )2 ·6H2 O as the nickel source. The methanation performances
of the two catalysts were tested and the results showed that Ni-NiO/SiO2 catalysts exhibited a good
catalytic performance. The CO conversion of the Ni-NiO/SiO2 catalysts reached 97.1% at 350 ◦ C,
while that of Ni/SiO2 was 88.7%. The CH4 selectivity of the two catalysts was 81.9% and 75.3% at
350 ◦ C, respectively. The fresh and used catalysts were characterized through a variety of testing
techniques, demonstrating that Ni-NiO/SiO2 catalysts had a better dispersion, catalytic performance,
and carbon deposition resistance. After testing the two catalysts at 350 ◦ C for 50 h, it was found that
the Ni-NiO/SiO2 catalyst was more stable than Ni/SiO2 . Although the performance of the catalysts was
very good, we can conduct more in-depth research to further improve the performance of the catalysts.

Author Contributions: F.Y. designed and administered the experiments. J.L. (Jiangwei Li) and P.L. performed
experiments. Z.T. and J.L. (Jiangbing Li) collected and analyzed data. All authors discussed the data and wrote
the manuscript.
Acknowledgments: The work was supported by the International Science and Technology Cooperation Project
of Shihezi Univeristy (No. GJHZ201804), and the International Science and Technology Cooperation Project of
Bingtuan (No. 2018BC002).
Conflicts of Interest: The authors declare no conflicts of interests.

References
1. Lucchini, M.A.; Testino, A.; Kambolis, A.; Proff, C.; Ludwig, C. Sintering and coking resistant core–shell
microporous silica–nickel nanoparticles for co methanation: Towards advanced catalysts production.
Appl. Catal. B Environ. 2016, 182, 94–101. [CrossRef]
2. Le, T.A.; Kim, T.W.; Lee, S.H.; Park, E.D. Effects of Na content in Na/Ni/SiO2 and Na/Ni/CeO2 catalysts for
CO and CO2 methanation. Catal. Today 2018, 303, 159–167. [CrossRef]
3. Li, H.; Wang, L.; Dai, Y.; Pu, Z.; Lao, Z.; Chen, Y.; Wang, M.; Zheng, X.; Zhu, J.; Zhang, W.; et al. Synergetic
interaction between neighbouring platinum monomers in CO2 hydrogenation. Nat. Nanotechnol. 2018, 13, 411–417.
[CrossRef] [PubMed]
4. Fukuhara, C.; Hayakawa, K.; Suzuki, Y.; Kawasaki, W.; Watanabe, R. A novel nickel-based structured catalyst
for CO2 methanation: A honeycomb-type Ni/CeO2 catalyst to transform greenhouse gas into useful resources.
Appl. Catal. A Gen. 2017, 532, 12–18. [CrossRef]
Catalysts 2019, 9, 506 11 of 12

5. Li, P.; Yu, F.; Altaf, N.; Zhu, M.; Li, J.; Dai, B.; Wang, Q. Two-Dimensional Layered Double Hydroxides for
Reactions of Methanation and Methane Reforming in C1 Chemistry. Materials 2018, 11, 221. [CrossRef]
[PubMed]
6. Cai, W.-J.; Qian, L.-P.; Yue, B.; He, H.-Y. Rh doping effect on coking resistance of Ni/SBA-15 catalysts in dry
reforming of methane. Chin. Chem. Lett. 2014, 25, 1411–1415. [CrossRef]
7. Liu, Q.H.; Dong, X.F.; Lin, W.M. Highly selective CO methanation over amorphous Ni–Ru–B/ZrO2 catalyst.
Chin. Chem. Lett. 2009, 20, 889–892. [CrossRef]
8. Song, Q.; Altaf, N.; Zhu, M.; Li, J.; Ren, X.; Dan, J.; Dai, B.; Louis, B.; Wang, Q.; Yu, F. Enhanced low-temperature
catalytic carbon monoxide methanation performance via vermiculite-derived silicon carbide supported
nickel nanoparticles. Sustain. Energy Fuels 2019, 3, 965–974. [CrossRef]
9. Li, P.; Wen, B.; Yu, F.; Zhu, M.; Guo, X.; Han, Y.; Kang, L.; Huang, X.; Dan, J.; Ouyang, F.; et al. High efficient
nickel/vermiculite catalyst prepared via microwave irradiation-assisted synthesis for carbon monoxide
methanation. Fuel 2016, 171, 263–269. [CrossRef]
10. Pan, Q.; Peng, J.; Wang, S.; Wang, S. In situ FTIR spectroscopic study of the CO2 methanation mechanism on
Ni/Ce0.5 Zr0.5 O2 . Catal. Sci. Technol. 2014, 4, 502–509. [CrossRef]
11. Lu, H.; Yang, X.; Gao, G.; Wang, J.; Han, C.; Liang, X.; Li, C.; Li, Y.; Zhang, W.; Chen, X. Metal (Fe, Co, Ce or
La) doped nickel catalyst supported on ZrO2 modified mesoporous clays for CO and CO2 methanation. Fuel
2016, 183, 335–344. [CrossRef]
12. Wang, X.; Hong, Y.; Shi, H.; Szanyi, J. Kinetic modeling and transient DRIFTS–MS studies of CO2 methanation
over Ru/Al2 O3 catalysts. J. Catal. 2016, 343, 185–195. [CrossRef]
13. Lakshmanan, P.; Kim, M.S.; Park, E.D. A highly loaded Ni@SiO2 core–shell catalyst for CO methanation.
Appl. Catal. A Gen. 2016, 513, 98–105. [CrossRef]
14. Yan, X.; Liu, Y.; Zhao, B.; Wang, Z.; Wang, Y.; Liu, C.-J. Methanation over Ni/SiO2 : Effect of the catalyst
preparation methodologies. Int. J. Hydrogen Energy 2013, 38, 2283–2291. [CrossRef]
15. Zhao, B.; Chen, Z.; Yan, X.; Ma, X.; Hao, Q. CO Methanation over Ni/SiO2 Catalyst Prepared by Ammonia
Impregnation and Plasma Decomposition. Top. Catal. 2017, 60, 879–889. [CrossRef]
16. Zhang, J.; Bai, Y.; Zhang, Q.; Wang, X.; Zhang, T.; Tan, Y.; Han, Y. Low-temperature methanation of syngas in
slurry phase over Zr-doped Ni/γ-Al2 O3 catalysts prepared using different methods. Fuel 2014, 132, 211–218.
[CrossRef]
17. Shinde, V.M.; Madras, G. CO methanation toward the production of synthetic natural gas over highly active
Ni/TiO2 catalyst. AIChE J. 2014, 60, 1027–1035. [CrossRef]
18. Zhang, M.; Li, P.; Zhu, M.; Tian, Z.; Dan, J.; Li, J.; Dai, B.; Yu, F. Ultralow-weight loading Ni catalyst supported
on two-dimensional vermiculite for carbon monoxide methanation. Chin. J. Chem. Eng. 2018, 26, 1873–1878.
[CrossRef]
19. Li, P.; Zhu, M.; Dan, J.; Kang, L.; Lai, L.; Cai, X.; Zhang, J.; Yu, F.; Tian, Z.; Dai, B. Two-dimensional porous SiO2
nanomesh supported high dispersed Ni nanoparticles for CO methanation. Chem. Eng. J. 2017, 326, 774–780.
[CrossRef]
20. Zhang, M.; Li, P.; Tian, Z.; Zhu, M.; Wang, F.; Li, J.; Dai, B.; Yu, F.; Qiu, H.; Gao, H. Clarification of Active Sites
at Interfaces between Silica Support and Nickel Active Components for Carbon Monoxide Methanation.
Catalysts 2018, 8, 293. [CrossRef]
21. Zhang, S.; Gai, S.; He, F.; Dai, Y.; Gao, P.; Li, L.; Chen, Y.; Yang, P. Uniform Ni/SiO2 @Au magnetic hollow
microspheres: Rational design and excellent catalytic performance in 4-nitrophenol reduction. Nanoscale
2014, 6, 7025–7032. [CrossRef] [PubMed]
22. Lv, Y.; Xin, Z.; Meng, X.; Tao, M.; Bian, Z. Ni based catalyst supported on KIT-6 silica for CO methanation:
Confinement effect of three dimensional channel on NiO and Ni particles. Microporous Mesoporous Mater.
2018, 262, 89–97. [CrossRef]
23. Li, Z.; Mo, L.; Kathiraser, Y.; Kawi, S. Yolk–Satellite–Shell Structured Ni–Yolk@Ni@SiO2 Nanocomposite:
Superb Catalyst toward Methane CO2 Reforming Reaction. ACS Catal. 2014, 4, 1526–1536. [CrossRef]
24. Guo, C.; Wu, Y.; Qin, H.; Zhang, J. CO methanation over ZrO2 /Al2 O3 supported Ni catalysts: A comprehensive
study. Fuel Process. Technol. 2014, 124, 61–69. [CrossRef]
25. Ren, J.; Li, H.; Jin, Y.; Zhu, J.; Liu, S.; Lin, J.; Li, Z. Silica/titania composite-supported Ni catalysts for CO
methanation: Effects of Ti species on the activity, anti-sintering, and anti-coking properties. Appl. Catal. B
Environ. 2017, 201, 561–572. [CrossRef]
Catalysts 2019, 9, 506 12 of 12

26. Zhang, C.; Yue, H.; Huang, Z.; Li, S.; Wu, G.; Ma, X.; Gong, J. Hydrogen Production via Steam Reforming
of Ethanol on Phyllosilicate-Derived Ni/SiO2 : Enhanced Metal–Support Interaction and Catalytic Stability.
ACS Sustain. Chem. Eng. 2012, 1, 161–173. [CrossRef]
27. Liu, Q.; Gao, J.; Zhang, M.; Li, H.; Gu, F.; Xu, G.; Zhong, Z.; Su, F. Highly active and stable Ni/γ-Al2 O3
catalysts selectively deposited with CeO2 for CO methanation. RSC Adv. 2014, 4, 16094–16103. [CrossRef]
28. Bian, L.; Wang, W.; Xia, R.; Li, Z. Ni-based catalyst derived from Ni/Al hydrotalcite-like compounds by the
urea hydrolysis method for CO methanation. RSC Adv. 2016, 6, 677–686. [CrossRef]

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