catalysts

Article
Highly Dispersed Ni Nanocatalysts Derived from
NiMnAl-Hydrotalcites as High-Performing Catalyst
for Low-Temperature Syngas Methanation
Bin Lu 1,2 , Jiahao Zhuang 1,2 , Jinping Du 1 , Fangna Gu 1,3, *, Guangwen Xu 4 , Ziyi Zhong 5 ,
Qing Liu 6 and Fabing Su 1,3,4, *
1 State Key Laboratory of Multiphase Complex Systems, Institute of Process Engineering,
Chinese Academy of Sciences, Beijing 100190, China; lubin162@mails.ucas.edu.cn (B.L.);
zhuangjiahao15@mails.ucas.ac.cn (J.Z.); djp0914@163.com (J.D.)
2 School of Chemical Engineering, University of Chinese Academy of Sciences, Beijing 100049, China
3 Zhongke Langfang Institute of Process Engineering, Fenghua Road No 1,
Langfang Economic & Technical Development Zone, Hebei 065001, China
4 Institute of Industrial Chemistry and Energy Technology, School of Chemical Engineering Shenyang
University of Chemical Technology, Shenyang, Liaoning 110142, China; gwxu@ipe.ac.cn
5 College of Engineering, Guangdong Technion Iarael Institute of Technology (GTIIT), 243 Daxue Road,
Shantou 515063, China; ziyi.zhong@gtiit.edu.cn
6 Key Laboratory of Low Carbon Energy and Chemical Engineering, College of Chemical and Environmental
Engineering, Shandong University of Science and Technology, Qingdao 266590, China; qliu@sdust.edu.cn
* Correspondence: fngu@ipe.ac.cn (F.G.); fbsu@ipe.ac.cn (F.S.); Tel.: +86-10-82544850 (F.S.);
Fax: +86-10-82544851 (F.G.)




Received: 15 February 2019; Accepted: 7 March 2019; Published: 19 March 2019


Abstract: Increasing the low-temperature performance of nickel-based catalysts in syngas

methanation is critical but very challenging, because at low temperatures there is high concentration
of CO on the catalyst surface, causing formation of nickel carbonyl with metallic Ni and further
catalyst deactivation. Herein, we have prepared highly dispersed Ni nanocatalysts by in situ reduction
of NiMnAl-layered double hydroxides (NiMnAl-LDHs) and applied them to syngas methanation.
The synthesized Ni nanocatalysts maintained the nanosheet structure of the LDHs, in which Ni
particles were decorated with MnOy species and embedded in the AlOx nanosheets. It was observed
that the Ni nanocatalysts exhibited markedly better low-temperature performance than commercial
catalysts in the syngas methanation. At 250 ◦ C, 3.0 MPa and a high weight hourly space velocity
(WHSV) of 30,000 mL·g−1 ·h−1 , both the CO conversion and the CH4 selectivity reached 100% over the
former, while those over the commercial catalyst were only 14% and 76%, respectively. Furthermore,
this NiMnAl catalyst exhibited strong anti-carbon and anti-sintering properties at high temperatures.
The enhanced low-temperature performance and high-temperature stability originated from the
promotion effect of MnOy and the embedding effect of AlOx in the catalyst.

Keywords: low-temperature methanation; nickel carbonyl; NiMnAl-LDHs; Ni nanocatalysts

1. Introduction
Over the last few decades, the preparation of synthetic natural gas (SNG) by coal gasification
has attracted worldwide attention, particularly in the coal-rich regions, because of the requirements
for efficient utilization of coal resources and for a secure supply of natural gas, which is a clean
fuel [1,2]. The main technology of producing SNG from syngas is CO methanation [3–5]. Until now,
all commercial methanation catalysts for SNG production have been Ni-based catalysts due to their

Catalysts 2019, 9, 282; doi:10.3390/catal9030282 www.mdpi.com/journal/catalysts

Catalysts 2019, 9, 282 2 of 15

high performance and low cost [6–18]. Nevertheless, the major weaknesses of nickel catalysts include
agglomeration of Ni nanoparticles, formation of carbon deposits at higher temperatures, and poor
activity at low temperatures (250 ◦ C) for the complete methanation of syngas [19–31]. The increase
in low temperature performance of the Ni catalysts in syngas methanation is critical. It is also very
challenging because the high concentration of CO on the catalyst surface may lead to the formation
of Ni(CO)4 and further catalyst deactivation. At present, research on low-temperature methanation
is mainly focused on hydrogen-rich systems and slurry-bed reactors [32–37], while that for syngas
(H2 /CO = 3/1) in fixed beds has rarely been reported.
Layered double hydroxides (LDHs) are widely used as catalysts or supports due to their unique
layered structure with distribution of M2+ (M = Mg, Co, Cu, Ni) and N3+ (N = Al, Fe, Co, Mn)
cations that are adjustable both in ratio and in type [38–43]. Ni-based hydrotalcites have been
used as precursors to obtain methanation catalysts via high temperature calcination followed by
reduction [13,44]. However, high temperature calcination would destroy the layered structure of
LDHs and reduce the specific surface area and pores volume, which leads to poor activity of the
obtained catalysts at low temperatures [45,46]. He et al. found that the Ni nanocatalysts prepared
via in situ reduction of NiAl-hydrotalcites with abundant surface defects showed excellent catalytic
performance in CO2 methanation [47]. Differing from CO2 methanation, the major challenge for low
temperature methanation of high concentration CO is a catalyst deactivation phenomenon due to
formation of Ni(CO)4 . In general, low temperature and high CO partial pressure favor formation of
Ni(CO)4 at equilibrium; thus, the inlet temperature of the feed gas should be above 300 ◦ C for SNG,
at which the catalyst can convert part of CO and maintain a low CO partial pressure so that Ni(CO)4
formation is negligible. In principle, the reaction can be operated smoothly at quite low temperatures
so that the catalyst can be active enough to maintain a low CO concentration on the catalyst surface.
Therefore, developing highly active catalysts for low-temperature CO methanation is possible but
quite challenging.
Herein, highly dispersed Ni nanocatalysts were obtained by in situ reduction of NiMnAl-LDHs
precursors and applied to CO methanation for the first time. The novel catalysts showed excellent
catalytic performance at low temperatures and high stability at high temperatures. According to
experimental results, the Ni nanocatalysts decorated with MnOy species and embedded in the AlOx
nanosheets have the application prospect for low temperature methanation.

2. Results and Discussion

2.1. Structure and Morphology of LDHs and Catalysts

The X-ray diffraction (XRD) results of the NiMnx Al10 -LDHs (x = 0, 0.5, 1, 2) are shown in Figure 1a
and the inset shows the displacement of the first diffraction peak. The diffraction peaks of all the
samples at 2θ = 11.6◦ –11.9◦ , 23.4◦ , 35.1◦ , 39.6◦ , 46.8◦ , 61.2◦ and 62.5◦ are corresponding to the (003),
(006), (009), (015), (018), (110), and (113) planes of typical hydrotalcites, respectively [41]. Table 1 shows
the lattice parameters of the NiMnx Al10 -LDHs. The lattice parameter “a” is related to the radius of
the cation [48]. Compared with NiAl-LDH, the values of "a" for NiMnAl-LDHs do not change after
adding Mn2+ , because the ionic radius of Ni and Mn (0.62 Å for Ni2+ , 0.66 Å for Mn2+ , respectively)
are relatively close, while the additive amount of Mn is low. When the Mn/Al molar ratios change
from 0:10 to 1:10, the lattice constant “c” gradually increases from 2.255 to 2.286 nm until “c” reaches
its maximum value, which is due to the difference in bond strength of Ni-O (372 kJ/mol) and Mn-O
(402 kJ/mol). When Ni is substituted by Mn, the bond strength of M-O (M-Metal cation) is increased,
resulting in the weakened interaction of the metal cations with the interlayer anions as well as the
water molecules, so that the interlayer spacing is increased. These results confirm that most of the
added Mn2+ entered the layered structure of the hydrotalcites and did not affect crystallinity of LDHs.
The XRD spectrums of the catalysts obtained from reducing LDHs directly are shown in Figure 1b.
In comparison to Figure 1a, it can be found that the characteristic peaks of LDHs disappeared after the
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FOR PEER REVIEW 3 3ofof15
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after the reduction, but some new diffraction peaks emerged at 2θ = 44.6°, 51.9°, 76.8°, attributing to
reduction, ◦ , 51.9◦ , 76.8◦ , attributing to (111), (200),
(111), (200),but some
(220) new diffraction
crystal planes of peaks emergedcube
face-centered at 2θ (fcc)
= 44.6Ni, respectively. Considering the low
(220) crystal
content planes
of added Mnof2+ face-centered cube
that is difficult (fcc) Ni,
to detect, werespectively.
mainly focus Considering the lowof
on the diffraction content
nickelof added
species.
2+
Mn weak that broad
is difficult to detect, we mainly
The diffraction peaks locatedfocus on the
at 37.1° anddiffraction of nickel species.
63.3° are attributing to the The
(111)weak
and broad
(220)
diffraction peaks located at 37.1 ◦ and 63.3◦ are attributing to the (111) and (220) crystal planes of NiO
crystal planes of NiO (fcc), respectively [41]. The sizes of Ni particles in these NiAl-C, NiMn0.5Al10-C,
(fcc), respectively
NiMn [41]. The sizes of Ni particles in these NiAl-C, NiMn 8.7
1Al10-C, and NiMn2Al10-C catalysts were calculated to be 9.0 ± 0.5,0.5
Al±100.5,
-C, NiMn 1 Aland
8.5 ± 0.5 10 -C,8.6
and±
NiMn Al -C catalysts were calculated to be 9.0 ± 0.5, 8.7 ± 0.5, 8.5 ± 0.5 and 8.6
0.5 nm, respectively. This indicates that the adding of Mn has only a slight influence on the size of
2 10 ± 0.5 nm, respectively.
ThisNiindicates
the particles.that the adding of Mn has only a slight influence on the size of the Ni particles.

(a) (b)
(003)

♦ ♦Ni
Intensity(a.u.)

(003) •NiO

Intensity(a.u.)
Intensity(a.u.)

♦
NiMn2Al10-C
• • ♦
(006) (009) 10 12 14 •
2θ
NiMn2Al10-LDH NiMn1Al10-C
NiMn1Al10-LDH NiMn0.5Al10-C
NiMn0.5Al10-LDH
NiAl-C
NiAl-LDH

20 40 60 80 40 60 80
2θ 2θ
Figure 1.
Figure XRD results
1. XRD results of
of LDHs
LDHs precursors
precursors (a) and NiMn
NiMnxAl10 catalysts (b).
10 catalysts (b). The
The inset
inset shows
shows the
the
displacement of the first diffraction peak (LDH-layered double hydroxide, C-catalyst).
displacement of the first diffraction peak (LDH-layered double hydroxide, C-catalyst).
Table 1. Lattice parameters of the LDHs.
Table 1. Lattice parameters of the LDHs.
LDHs d /nm d /nm d /nm d /nm a a = 2d /nm b c = (d + 2d + 3d )/nm
003 006
LDHs d003 /nm d006 /nm d009 009/nm d110
110/nm aa = 2d110
110/nm
003
bc = (d 006 009
003 + 2d006 + 3d009)/nm
NiAl-LDH 0.741 0.378 0.255 0.151 0.302 2.258
NiAl-LDH 0.741 0.378 0.255 0.151 0.302 2.258
NiMn0.5 Al10 -LDH 0.752 0.378 0.255 0.151 0.302 2.269
NiMn0.5Al10-LDH
NiMn1 Al10 -LDH 0.752
0.758 0.378
0.378 0.255
0.255 0.151
0.151 0.302
0.302 2.269
2.275
NiMn 1Al
NiMn Al-LDH
210 10 -LDH 0.758
0.752 0.378
0.378 0.255
0.255 0.151
0.151 0.302
0.302 2.275
2.269
NiMna2The
Al10average
-LDH distance
0.752of the metal
0.378cations0.255 0.151 b 0.302 2.269
in the hydrotalcite layer; Three times of the interlayer thickness.
a The average distance of the metal cations in the hydrotalcite layer; b Three times of the interlayer thickness.
The scanning electron microscope (SEM) images of NiMnx Al10 -LDHs before and after the
The scanning
reduction are shownelectron
in Figuremicroscope (SEM) images
2. The hydrothermally of NiMn
synthesized xAl10-LDHs before and after the
LDHs are composed of the connected
reduction are shown in Figure 2. The hydrothermally synthesized
nanosheets with relatively uniform size and smooth surface (Figure 2a–d). LDHs are
The composed
NiMn of the
x Al10 catalysts
connected nanosheets with relatively uniform size and smooth surface (Figure 2a–d). The NiMn
obtained after reduction maintain the flake-like morphology but with a rougher surface (Figure 2e–h). xAl10

catalysts
The SEM obtained after reduction
results demonstrate maintain
that the the flake-like
incorporation morphology
of Mn has no obviousbut with
effect on athe
rougher surface
morphology of
(Figure 2e–h). The SEM results demonstrate that the incorporation of Mn has no obvious effect
LDHs crystals, and the thin layered structure was still preserved after reduction, which is helpful on the
to
morphology of change
investigate the LDHs crystals, and the
of Ni particles thinand
before layered
after structure wasreaction.
methanation still preserved after reduction,
which is helpful to investigate the change of Ni particles before and after methanation reaction.
The physical properties of the catalysts were investigated by BET (Figure 3). As can be seen from
The physical properties of the catalysts were investigated by BET (Figure 3). As can be seen from
Figure 3a, all the catalysts exhibit IV type adsorption-desorption isotherms with type H3 hysteresis
Figure 3a, all the catalysts exhibit IV type adsorption-desorption isotherms with type H3 hysteresis
loops. The specific surface areas of the catalysts are similar (shown in Table 2). Nonetheless, the pore
loops. The specific surface areas of the catalysts are similar (shown in Table 2). Nonetheless, the pore
volume of NiMn0.5 Al10 -C and NiMn1 Al10 -C are relatively larger, which is possibly caused by the
volume of NiMn0.5Al10-C and NiMn1Al10-C are relatively larger, which is possibly caused by the
formation of macropores from the packing of nanosheets (Figure 3b).
formation of macropores from the packing of nanosheets (Figure 3b).
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Catalysts 2019, 9, x FOR PEER REVIEW 4 of 15

Figure
Figure2.2.
Figure 2.SEMSEM
SEM images
images
images ofLDHs
ofofthe
the the LDHs
LDHs precursors
precursors
precursors (a–d) (a–d)
(a–d) and
and theand
the the corresponding
corresponding
corresponding catalysts
after
catalysts after after
reduction
reduction
reduction
(e–h).
(e–h). (e–h).

(a)
(a) (b)
/g,STP))
cm /g,STP

NiAl10Mn
NiAl Mn-C-C NiAl10Mn -C
NiAl
10 22 10 2
3
3
absorbed((cm

dv/(dlogD)
dv/(dlogD)

NiAl10Mn1-C
NiAl 10 1
Volumeabsorbed

NiAl10Mn
NiAl Mn-C
-C
10 11
NiAl10Mn
NiAl Mn0.5-C
-C
10 0.5

NiAl Mn0.5-C
NiAl10Mn -C
10 0.5
Volume

NiAl-C NiAl-C
NiAl-C
NiAl-C

0.0 0.2
0.0 0.2 0.4
0.4 0.6
0.6 0.8
0.8 1.0
1.0 10 100
Relativepressure
pressure((p/p
p/p0)) 10 100
Relative 0
Pore size(nm)
Pore size(nm)
Figure 3. N2-adsorpotion/desoportion
-adsorpotion/desoportion isotherms (a)
isotherms(a) and
(a)and pore
andpore size
poresize distribution
distributionof
sizedistribution catalysts
catalysts(b).
Figure 3. N22-adsorpotion/desoportion isotherms ofofcatalysts (b).
(b).

Table 2. Physicochemical
Table2. Physicochemical property of catalysts.
catalysts.
Table 2. Physicochemical property of catalysts.
a Wt% ccV
Wt%a a± 0.1 ± 0.1 b Sb SBET Vpp H2 uptake
dd eDe (%)
Catalysts
Catalysts Wt% ± 0.1 b BET
S− BET c V p dHH22uptake
Uptake ee
De
De(%)
(%) ± 0.1
Catalysts Ni Ni
Al Al Mn Mn (m(m 2 ·g 1−1
2·g )) (cm3 ·3g−−11 )
(cm ·g ) (µmoL/g)
(μmoL/g) ± 0.1
Ni Al Mn (m ·g−1) 2 (cm3·g−1) (μmoL/g) ± 0.1
NiAl-CNiAl-C 61.7
NiAl-C 61.7 7.3
7.3 7.3 0 0
0 76
7676
0.2
0.2
534
534
10.210.2
61.7 0.2 534 10.2
NiMn0.5NiMn
Al10 -C 0.5Al10 -C
57.5 57.5 7.3 0.6
7.3 7.3 0.6 0.6 87
8787 0.5
0.5 559
559 11.411.4
NiMn 0.5Al10-C 57.5 0.5 559 11.4
NiMn1 AlNiMn
10 -C 1Al -C
57.8
10 57.8
7.7 7.7 1.7 1.7 6969 0.7
0.7 631
631 12.812.8
NiMn2NiMn
AlNiMn
1Al10-C
10 -C 2Al1057.9
-C
57.8
7.9
57.9
7.7 3.2 1.7
7.9 3.2 6669
66
0.7
0.2
0.2
631
550
550
12.8
11.211.2
2
a aDetermined NiMn Al -C
10 b 57.9 7.9 3.2 c 66 c 0.2 550 11.2
0
Determined byby ICP;
ICP;Calculated by BET
Calculated by equation; Determined
BET equation;
b by the volume
Determined by the of N2 adsorbed
volume of N2 at p/p = 0.97;
adsorbed at
Determined
ad
Calculated by ICP;
0 = 0.97;based on the Calculated
b
H2 -TPD data;by BET equation;
e Calculated c Determined by the volume of N2 adsorbed at
using the H2 -TPR and H2 -TPD results.
p/p d Calculated based on the H 2-TPD data; e Calculated using the H2-TPR and H2-TPD results.
p/p0 = 0.97; d Calculated based on the H2-TPD data; e Calculated using the H2-TPR and H2-TPD results.
Thereduction
The reductionbehaviors
behaviorsofofLDHs
LDHswerewere investigated
investigated by H22-TPR (Figure
(Figure 4a).
4a). All
Allthe
thesamples
sampleshavehave
The reduction behaviors of LDHs were investigated by H2◦-TPR (Figure 4a). All the samples have
twodistinct
two distinctreduction
reductionpeaks:
peaks: the
the first
first one located at 300–450
300–450 °C C is
is derived
derivedfrom
fromthe
thereduction
reductionofofNiNi
two distinct reduction peaks: the first one located at 300–450 °C is derived from the reduction of Ni
oxidespecies
oxide specieswith
with a weak
a weak interaction
interaction withwith the substrate,
the substrate, and
and the the second
second one at ◦450–700
one at 450–700 °C is
C is attributed
oxide species
attributed withreduction
to the a weak ofinteraction with thehaving
Ni oxide species, substrate, andinteraction
a strong the secondwithonetheat matrix.
450–700As°Ctheis
attributed to the reduction of Ni oxide species, having a strong interaction with the matrix. As the
Catalysts 2019, 9, 282 5 of 15

Catalysts 2019, 9, x FOR PEER REVIEW 5 of 15

to the reduction of Ni oxide species, having a strong interaction with the matrix. As the molar ratio of
Mn/Alratio
molar changes from 0:10
of Mn/Al to 1:10,
changes fromthe0:10
firstto
reduction
1:10, thepeak first shifts to low
reduction peaktemperature
shifts to lowrange, indicating
temperature
that adding
range, a proper
indicating that amount
adding aofproper
Mn can improve
amount the reduction
of Mn can improve of nickel speciesof[12].
the reduction However,
nickel species with
[12].
However, with further increase of Mn/Al molar ratio to 2:10, the reduction temperature of is
further increase of Mn/Al molar ratio to 2:10, the reduction temperature of the catalyst theincreased
catalyst
again,
is because
increased of the
again, reinforced
because of theinteraction
reinforcedbetween
interaction nickle oxide nickle
between speciesoxideand the excess
species andofthe
Mnexcess
oxide
species
of [12]. species
Mn oxide Figure [12].
4b shows
Figurethe4bHshows
2 -TPDthecurves
H2-TPD of the NiMn
curves ofx Al catalysts.
the10NiMn Although MnOx is
xAl10 catalysts. Although

MnOx is capable of adsorbing hydrogen, the amount of Mn is much lower than in

capable of adsorbing hydrogen, the amount of Mn is much lower than that of Ni theofcatalyst,
that Ni in the so
we will mainly
so we willfocus on the
mainly Hon
focus 2 uptake of Ni. of
the H2 uptake InNi.
addition, there
In addition, is no
there H2Huptake
is no of Al2 O3 [11,24,28].
catalyst, 2 uptake of Al2O3 [11,24,28].
Therefore, the dispersion of Ni particles can be calculated from the H -TPD
Therefore, the dispersion of Ni particles can be calculated from the H2-TPD results. All catalysts
2 results. All catalysts
have have
only
only one H desorption peak at the temperature interval of 100–200 ◦ C, corresponding to desorption
2
one H2 desorption peak at the temperature interval of 100–200 °C, corresponding to desorption of H2
of highly
of H2 of highly
disperseddispersed Ni nanoparticles
Ni nanoparticles or Nior Ni nanoparticles
nanoparticles with with
manymany surfacesurface defects
defects [12],[12],
whichwhich
are
are benefit to the diffusion and dissociation of surface hydrogen [49]. Table
benefit to the diffusion and dissociation of surface hydrogen [49]. Table 2 lists the H22 adsorption 2 lists the H adsorption
amount on
amount on aa series
series of
of NiMn
NiMnxxAlAl10 (x = 0, 0.5, 1, 2) catalysts. Among them, NiMn Al 10 shows
10 (x = 0, 0.5, 1, 2) catalysts. Among them, NiMn11Al10
shows thethe
maximum H
maximum H22 uptake
uptake ofof 631
631 µmol/g
μmol/gcat and highest
catand highest Ni Ni distribution
distribution of 12.8 ±
of 12.8 0.1%, indicating
± 0.1%, indicating thatthat
incorporating an appropriate amount of Mn can significantly improve the
incorporating an appropriate amount of Mn can significantly improve the2 H2 adsorption capacity H adsorption capacity and
the dispersion
and the dispersionof Niofnanoparticles.
Ni nanoparticles.However, excessive
However, Mn will
excessive Mnoverlay
will overlayfractional the active
fractional site ofsite
the active Ni
particles and reduce the adsorption capacity for H 2 , which is very important
of Ni particles and reduce the adsorption capacity for H2, which is very important for the performance for the performance of
the catalyst.
of the catalyst.

(A) 404℃ 131℃ (B)

543℃
H2-TPR signal(a.u.)

H2-TPD signal(a.u.)

136℃
(d)
(d)
129℃
(c) (c)

(b) 121℃ (b)

(a) (a)

200 400 600 800 200 400 600 800

Temperature(℃) Temperature(℃)
Figure
Figure 4. (A) H22-TPR-TPR curves of the
the LDHs:
LDHs: (a)
(a) NiAl-LDH,
NiAl-LDH,(b) (b)NiMn
NiMn0.5 Al10
0.5Al 10-LDH, (c) NiMn
NiMn11Al10 10-LDH,
-LDH,
(d) NiMn22Al
(d) NiMn Al1010-LDH
-LDHandand(B)
(B)HH 2-TPD
2 -TPDresults
resultsofofthe
thecatalysts:
catalysts:(a) (a)
NiAl-C, (b) (b)
NiAl-C, NiMn 0.5Al
NiMn 10Al
0.5 -C,10(c)
-C,
(c) NiMn
NiMn 1 Al
1Al10 -C and
-C10and (d) NiMn
(d) NiMn Al10 -C.
2Al102-C.

The dispersion
The dispersion of of Ni
Ninanoparticles
nanoparticles was wasfurther
furtherinvestigated
investigatedby bytransmission
transmissionelectron
electronmicroscopy
microscopy
(TEM) (Figure 5). As can be seen from TEM images (Figure
(TEM) (Figure 5). As can be seen from TEM images (Figure 5a–d), the catalysts maintain the 5a–d), the catalysts maintain the
nanosheet morphology
nanosheet morphology of of the
the LDHs
LDHs precursors.
precursors. Additionally,
Additionally, Ni Ni nanoparticles
nanoparticles are are highly
highly dispersed
dispersed
and embedded
and embedded in in the
the AlO matrix. The
AlOxx matrix. The inserted
inserted histograms
histograms show show thethe size
size distributions
distributions of of the
the Ni
Ni
nanoparticles. The average diameters of Ni
nanoparticles. The average diameters of Ni in NiAl-C, NiMn in NiAl-C, NiMn Al
0.50.5Al -C, NiMn Al
1010-C, NiMn11Al10 -C and NiMn
10-C and NiMn22Al10Al -C
10-C

are 12.6 ±
are 12.6 ± 0.5, 12.3 ±±0.5,
0.5, 12.3 10.6 ±±0.5
0.5, 10.6 0.5and
and12.412.4±±0.5 0.5nmnm(based
(basedon onmeasurements
measurementsof of 150
150 particles),
particles),
respectively. These results are very close to those calculated from
respectively. These results are very close to those calculated from the XRD results. The latticesthe XRD results. The lattices
and
and distribution of Ni and Mn species on the substrate can be
distribution of Ni and Mn species on the substrate can be observed from the high resolutionobserved from the high resolution
transmission electron
transmission electron microscopy
microscopy(HRTEM) (HRTEM)images. images.The Thelattice
latticedistance
distance ofof 0.20,
0.20, 0.25
0.25 andand 0.21
0.21 nmnm is
is attributed to the (111) plane of Ni (fcc) particles, the (211) plane of Mn
attributed to the (111) plane of Ni (fcc) particles, the (211) plane of Mn33O4 4and the (420) plane of O and the (420) plane of
Mn22O
Mn O33, ,respectively.
respectively.The Thereason
reasonwhy whyMn Mnexists
existsininthe
the form
form of of oxides
oxides is is that
that the
the reduction
reduction order
order of of
MnOyy is
MnO is first
first from
from MnO
MnO2/Mn/Mn2O 2O toMn
3 3to Mn 3O
3O , andthen
4, 4and thentotoMnO,
MnO,and andthe thefinal
finalreduction
reductionto toelemental
elemental MnMn
requires a temperature higher than 800 °C [50]. The TEM image of NiAl-C demonstrates Ni particles
are fixed by the poorly crystallized AlOx shell (Figure 5e), and the AlOx is formed during the
reduction of the LDHs precursors [41]. For the Mn-added catalyst, Ni particles and the adjacent MnOy
Catalysts 2019, 9, 282 6 of 15

requires a temperature higher than 800 ◦ C [50]. The TEM image of NiAl-C demonstrates Ni particles
are fixed by the poorly crystallized AlOx shell (Figure 5e), and the AlOx is formed during the reduction
Catalysts 2019, 9, x FOR PEER REVIEW 6 of 15
of the LDHs precursors [41]. For the Mn-added catalyst, Ni particles and the adjacent MnOy are
collectively
are confined
collectively in the
confined matrix
in the of of
matrix AlO x (Figure
AlO 5e),
x (Figure 5e),which
whichisiscritical
criticalto
toimprove
improve the
the stability of
stability of
the catalyst. The XRD, SEM, and TEM results show that the Mn incorporated
the catalyst. The XRD, SEM, and TEM results show that the Mn incorporated LDHs maintains its LDHs maintains its
structural characteristics
structural characteristicsduring in situ
during reduction,
in situ which
reduction, is beneficial
which to preparation
is beneficial Ni-basedNi-based
to preparation catalysts
embedded in
catalysts embedded AlO matrix with high dispersion.
x in AlOx matrix with high dispersion.

Figure 5.
5. TEM
TEM pictures
pictures of ofthe
thecatalysts:
catalysts:(a–f)
(a–f)NiAl-C,
NiAl-C,NiMn
NiMn Al10-C,NiMn
Al10-C,
0.50.5 NiMn 1Al
1 Al -C, NiMn
1010-C, NiMn22Al
Al10
10-C,
-C,
NiAl-C and NiMn11Al
Al1010-C.
-C.The
Theinsets
insetsshow
showthe thesize
sizedistribution
distributionof ofNi
Ninanoparticles.
nanoparticles.

Energy dispersive
Energy dispersive spectroscopy
spectroscopy (EDS) (EDS) mapping
mapping was used to
was used to characterize
characterize the the spatial
spatial distribution
distribution
of individual
of individual elements
elements in in the
the catalyst
catalyst (Figure
(Figure 6). Fig. 6a
6). Fig. 6a shows
shows that that thethe signal
signal of of Ni Ni element
element is is strong
strong
in the central part of the particles, while the Al and O elements are mainly distributed around Ni
in the central part of the particles, while the Al and O elements are mainly distributed around Ni
particles. The distribution
particles. The distribution of of Mn
Mn element
element cannot
cannot be be clearly
clearly seen
seen in in Figure
Figure 6a 6a due
due to to the
the small
small amount
amount
of Mn
of Mn in in the
the catalyst.
catalyst. The The spatial
spatial distribution
distribution of of Ni
Ni and
and Mn Mn in in the
theNiMn
NiMn11Al Al10 -C catalyst
10-C catalyst is is shown
shown in in
Fig. 6b. MnO (Mn O or Mn O ) is also dispersed around the Ni particles;
Fig. 6b. MnOyy (Mn33O44or Mn22O3)3 is also dispersed around the Ni particles; thus, both the AlOxx and thus, both the AlO and
MnOyy have
MnO have aa certain
certain steric
steric hindrance
hindrance effecteffect onon the
the agglomeration
agglomeration of of the
the NiNi particles
particles to to increase
increase the the
stability of the catalysts. In addition, it can be seen from Fig. 6b that MnO
stability of the catalysts. In addition, it can be seen from Fig. 6b that MnOy is distributed around the y is distributed around the
Ni particles, which coincides exactly with the TEM
Ni particles, which coincides exactly with the TEM results (Figure 5f). results (Figure 5f).
The surface
The valence of
surface valence of the
the catalysts
catalysts derived
derived from from LDHs
LDHs precursors
precursors were were investigated
investigated by by XPS
XPS
(Figure 7). The Ni
(Figure 7). The Ni 2p3/2 2p spectrums are shown in Figure 7A. The surface of all
3/2 spectrums are shown in Figure 7A. The surface of all the catalysts is composed the catalysts is composed
of aa large 2+ (855.8 eV), and a little part of Ni0 (853.1 eV), which is probably due to the
of large portion
portion of of Ni
Ni2+ (855.8 eV), and a little part of Ni0 (853.1 eV), which is probably due to the
samples being exposed to air prior to
samples being exposed to air prior to testing
testing and and the
the surface
surface Ni Ni species
species being
being oxidized
oxidized [14,50]. After
[14,50]. After
adding Mn in the catalyst, the binding
adding Mn in the catalyst, the binding energy of Ni 2p3/2energy of Ni 2p shifts from 855.6 to 855.9
3/2 shifts from 855.6 to 855.9 eV, which can be eV, which can be
attributed to
attributed to the
the interaction
interaction between
betweenMnO MnOyyand andNi Ni[51].
[51].TheThespectrum
spectrum ofof Mn Mn 2p2p cancan
3/2 3/2 be broken
be broken up
4+
into three peaks with centers at 647.7, 642.9, and 637.8 eV, which are corresponding to the Mn , Mn3+,
up into three peaks with centers at 647.7, 642.9, and 637.8 eV, which are corresponding to the 4+ Mn
Mn Mn3+ and 2+
Mn species, respectively [12,51–53]. With the increase 4+ /Mn3+
and 2+ species, respectively [12,51–53]. With the increase of Mnofcontent,
Mn content, the Mn the Mn3+ atomic
4+/Mn

atomicinratios
ratios in the catalysts
the catalysts significantly
significantly increased increased
(Figure 7B (Figure 7B and
and Table 3). Table 3). O1sare
O1s spectra spectra
shownare in shown
Figure
in Figure 7C. All the catalysts are shown a broad peak that can be
7C. All the catalysts are shown a broad peak that can be fitted into two peaks by searching for thefitted into two peaks by searching
for the optimal
optimal combination combination
of Gaussian of Gaussian
bands. The bands. Thetwo
obtained obtained
peaks two center peaks
at 530.5 center eV and at 530.5
531.8eV eVandare
531.8 eV are attributed to lattice oxygen (O ) and surface adsorbed oxygen
attributed to lattice oxygen (OI) and surface adsorbed oxygen (OII), respectively [53,54]. The amounts
I (O II ), respectively [53,54].
of oxygen vacancies are positively correlated with the relative percentage of adsorbed oxygen species
[50,51]. The integrated area ratios of OII/(OII + OI) are listed in Table 3, indicating that the incorporated
Mn can significantly increase the oxygen vacancies in the catalyst.
Catalysts 2019, 9, 282 7 of 15

The amounts of oxygen vacancies are positively correlated with the relative percentage of adsorbed
oxygen species [50,51]. The integrated area ratios of OII /(OII + OI ) are listed in Table 3, indicating that
the incorporated Mn can significantly increase the oxygen vacancies in the catalyst.
Catalysts 2019,
Catalysts 2019, 9,
9, xx FOR
FOR PEER
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REVIEW 77 of
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15

Figure
Figure 6.
6. 6.
Figure TEM-EDSmapping
TEM-EDS
TEM-EDS mappingofof
mapping ofthe
theNiMn
the NiMn111Al
NiMn Al10 -C
10-C
10 catalyst:
-Ccatalyst: (a)
catalyst:(a) overlap
(a)overlap ofof
overlapof Ni, Al,
Ni,
Ni, Mn
Al,
Al, Mn and
Mn O,O,
and
and O, (b)(b)
(b) overlap
overlap
overlap
of
of of Ni
NiNi
andandMn.Mn. The
The scale
scale bar
bar isis 20
20 nm.
nm.
and Mn. The scale bar is 20 nm.

(A) (B)
2+ 3+
Ni2+
Ni Ni2p3/2
Ni2p Mn3+
Mn
3/2 4+
0+ Mn
Mn
4+ 2+
Mn2+
Mn
Ni0+
Ni Mn2p3/2
Mn2p
(d)
(d) 3/2

(d)
(d)
Intensity(a.u.)

Intensity(a.u.)
Intensity(a.u.)

Intensity(a.u.)

(c)
(c)
(c)
(c)
(b)
(b)
(b)
(b)
(a)
(a)

864 860 856 852 655 650 645 640 635

Binding Energy(eV) Binding Energy(eV)
OⅡ OⅠ
(C) OⅡ
OⅠ O1s
O1s

(d)
(d)
Intensity(a.u.)
Intensity(a.u.)

(c)
(c)

(b)
(b)

(a)
(a)

534 531 528

Binding Energy(eV)
Figure
Figure 7.
7. 7.
XPSXPS
XPS spectrasofof
spectras
spectras ofthe
thecatalysts:
the catalysts:(A)
catalysts: (A)Ni
(A) Ni 2p,
Ni 2p, (B)
2p, (B) Mn
Mn 2p,
Mn 2p, (C)
2p, (C) O
(C) O 1s.
O 1s. (a)
1s.(a) NiAl-C,
(a)NiAl-C, (b)
NiAl-C,(b) NiMn
(b)NiMn
NiMn Al1010-C,
0.5Al -C,-C,
Figure 0.5
0.5 Al 10
(C)
(C)(C) NiMn
NiMn
NiMn Al -C and (d) NiMn
1Al10-C and (d) NiMn2Al10-C.
1 10 2 Al 10 -C.
1 Al10 -C and (d) NiMn2 Al10 -C.
Catalysts 2019, 9, 282 8 of 15
Catalysts 2019, 9, x FOR PEER REVIEW 8 of 15

Table3.3.Surface
Table Surfacevalence
valenceof
ofcatalysts
catalystsdetermined
determinedby
byXPS.
XPS.

Mn
Mn2p 2/3position
2p2/3 Position (eV)(eV) 4+ /Mn
O 1s position (eV)
3+ 3+ O 1s Position (eV)
Catalysts
Catalysts Mn Mn 4+/Mn OIIⅡ/(O
OII /(O + OIII )+ OI)
MnMn
2+ 2+ Mn
Mn
3+
3+ Mn
Mn 4+4+
OI OⅠ OII OⅡ
NiAl-C - - - - 530.5 531.8 0.41
NiAl-C - - - - 530.5 531.8 0.41
NiMn 0.5Al 10-C
NiMn0.5 Al10 -C 637.8637.8 642.8
642.8 647.7
647.7 0.33
0.33 530.5
530.5 531.8531.8 0.49 0.49
NiMnNiMn1Al110-C10 -C 637.9
Al 637.9 642.9 642.9 647.6
647.6 0.59
0.59 530.5 531.8531.8
530.5 0.56 0.56
NiMn Al
NiMn2Al210-C10 -C 637.9
637.9 643.0
643.0 647.8
647.8 0.48
0.48 530.4
530.4 531.7531.7 0.50 0.50
Based on the above results, it is found that both MnOy and Ni particles are fixed by the AlOx
matrix,
Basedand onMnO y is distributed
the above results, it aroundis foundthe thatNiboth particles.
MnOy In andorder to further
Ni particles are elaborate
fixed by the the
microstructure
AlO x matrix, andof the
MnO catalyst,
y is we
distributed have drawn
around a schematic
the Ni diagram
particles. In of the
order structure
to further of the
elaborate catalyst
the
(Figure 8). During
microstructure of thethe reduction
catalyst, we have process,
drawn thea schematic
layered structurediagramof of LDHs is collapsed
the structure to form
of the catalyst
Ni(MnAl)O
(Figure x nanosheets,
8). During the reductionand the Ni clusters
process, the layereddecorated
structure withof MnO species
LDHsy is are to
collapsed formed, half-buried,
form Ni(MnAl)O x
and distributed
nanosheets, on Ni
and the theclusters
nanosheets. decorated In other
withwords,
MnOy speciesthe Ni particles
are formed,arehalf-buried,
decorated with MnOy and
and distributed
embedded
on on the AlO
the nanosheets. x matrix
In other words,[41].theThe Nisegregation
particles are effect of the with
decorated AlOx MnO
matrix prevents
y and embeddedthe sintering
on the
of Ni
AlO x particles
matrix during
[41]. The the methanation
segregation effectreaction,
of the thereby
AlO x increasing
matrix the
prevents service
the life
sintering of the
of Nicatalyst.
particles In
summary, the nickel-based catalyst synthesized by in situ reduction
during the methanation reaction, thereby increasing the service life of the catalyst. In summary, of LDHs has a unique structure,
which
the is important
nickel-based for enhancing
catalyst synthesized the bylowintemperature
situ reduction activity
of LDHsand has
higha temperature
unique structure, stability
which of the
is
catalyst. for enhancing the low temperature activity and high temperature stability of the catalyst.
important

Figure8.8.Schematic
Figure Schematicdiagram
diagramof
ofthe
thestructure
structureof
ofthe
thecatalyst.
catalyst.

2.2. Catalytic Activity

2.2. Catalytic Activity
Generally, high pressure is used in the synthesis of SNG in the industry [14]. For the purpose
Generally, high pressure is used in the synthesis of SNG in the industry [14]. For the purpose of
of studying the low temperature activity of the catalysts for CO methanation under the industrial
studying the low temperature activity of the catalysts for CO methanation under the industrial
reaction conditions, the performance test was executed at 3.0 MPa and a WHSV of 30,000 mL·g−1 ·−1h−1−1
reaction conditions, the performance test was executed at 3.0 MPa and a WHSV of 30000 mL·g ·h
(Figure 9). For NiAl-C, the CO conversion and CH4 yield at 250 ◦ C is 62% and 59%, respectively. After
(Figure 9). For NiAl-C, the CO conversion and CH4 yield at 250 °C is 62% and 59%, respectively. After
adding Mn in the catalyst, the performances of NiMnx Al10 -C are significantly improved (shown in
adding Mn in the catalyst, the performances of NiMnxAl10-C are significantly improved (shown in
Figure 9a–b). Among them, NiMn1 Al10 -C exhibits the highest performance at low temperature, and
Figure 9a–b). Among them, NiMn1Al10-C exhibits the highest performance at low temperature, and
both CO conversion and selectivity of CH4 achieve 100% at 250 ◦ C, owning to the high scatter of Ni
both CO conversion and selectivity of CH4 achieve 100% at 250 °C, owning to the high scatter of Ni
nanoparticles and H2 uptake (Table 2), and appearance of a number of oxygen vacancies in the catalyst
nanoparticles and H2 uptake (Table 2), and appearance of a number of oxygen vacancies in the
(Table 3). However, the conversion of CO on commercial catalyst (Ni-35.3 wt%) is only 14% at the
catalyst (Table 3). However, the conversion of CO on commercial catalyst (Ni-35.3 wt%) is only 14%
same reaction condition. To the best of our knowledge, there is no reported Ni-based catalyst that
at the same reaction condition. To the best of our knowledge, there is no reported Ni-based catalyst
can achieve 100% conversion of CO at such low temperatures and high pressure of CO with feed gas
that can achieve 100% conversion of CO at such low temperatures and high pressure of CO with feed
H2 :CO of 3:1 [16,24,26], at which the conventional nickel-based catalysts are susceptible to inactivation
gas H2:CO of 3:1 [16,24,26], at which the conventional nickel-based catalysts are susceptible to
owing to the formation of Ni(CO)4 . In this work, the synthesized NiMnx Al10 -C can convert most of the
inactivation owing to the formation of Ni(CO)4. In this work, the synthesized NiMnxAl10-C can
CO even at low temperatures, so that the CO concentration on the surface of the catalysts is very low,
convert most of the CO even at low temperatures, so that the CO concentration on the surface of the
which can avoid the formation of nickel carbonyl. Therefore, the NiMnx Al10 -C catalyst is promising in
catalysts is very low, which can avoid the formation of nickel carbonyl. Therefore, the NiMnxAl10-C
industrial applications of low temperature methanation.
catalyst is promising in industrial applications of low temperature methanation.
Catalysts 2019, 9, 282 9 of 15
Catalysts 2019, 9, x FOR PEER REVIEW 9 of 15

100 100

80 (a) (b)

CH4 selectivity(%)
CO convertion(%) 80 3.0 MPa
3.0 MPa -1 -1
-1 -1 30000 mL g h
60 30000 mL g h
NiAl-C 60 NiAl-C
40 NiMn0.5Al10-C NiMn0.5Al10-C
NiMn1Al10-C NiMn1Al10-C
NiMn2Al10-C 40 NiMn2Al10-C
20
Commercial-C Commercial-C

0 20
250 300 350 400 450 500 250 300 350 400 450 500
Temperature(℃) Temperature(℃)
100

80 (c)
3.0 MPa
CH4 yield(%)

-1 -1
60 30000 mL g h
NiAl-C
40 NiMn0.5Al10-C
NiMn1Al10-C
NiMn2Al10-C
20
Commercial-C

0
250 300 350 400 450 500
Temperature(℃)
Figure
Figure9.9.Catalytic
Catalyticactivity
activityof
ofthe
thecatalysts
catalystsfor
forCO
COmethanation:
methanation:(a)
(a)CO
COconversion,
conversion,(b)
(b)CH
CH4 4selectivity,
selectivity,
(c) CH44yield.
(c) CH yield.

The durability
The durability test is indispensable
indispensablefor forfurther
furtherinvestigation
investigationofofthe thelow
lowtemperature
temperature performance
performance of
the catalysts (Figure 10a). The conversion of CO of the Commercial-C decreased
of the catalysts (Figure 10a). The conversion of CO of the Commercial-C decreased from 36% to 24% from 36% to 24% after
23 h of
after 23reaction at a low
h of reaction at temperature. The amount
a low temperature. of Ni of the
The amount fresh
of Ni of and
the used
fresh catalysts
and usedarecatalysts
determined are
by ICP; we found
determined by ICP; that
wethefoundamount
that of
theNi decreased
amount of Ni from 35.3 wt%
decreased fromto 28.4 wt% to
35.3 wt%, 28.4 wt%,
which is a result
which ofisthe
a
formation of a Ni(CO) . However, the performance
result of the formation 4of a Ni(CO)4. However, the performance of of the NiMn Al
1 the -C did not decrease, which
10 NiMn1Al10-C did not decrease, was
attributed
which was to the fact that
attributed to thethe added
fact Mnadded
that the increased Mn the H2 uptake
increased the H and the number
2 uptake and theofnumber
oxygenof vacancies
oxygen
(Figures 4b
vacancies and 7C).
(Figure 4b Although
and FigureCommercial-C
7C). Althoughhas poor low temperature
Commercial-C has poor low activity, its high temperature
temperature activity, its
stability
high is good [9].
temperature Furthermore,
stability is good [9].a good methanation
Furthermore, a goodcatalyst should show
methanation high
catalyst performance
should show high at
low temperatures
performance at low andtemperatures
strong resistance andagainst
strongsintering
resistance andagainst
coking at high temperatures.
sintering and cokingTherefore,
at high
the stability of NiMn Al -C was evaluated at 500 ◦ C and 3.0 MPa with different space velocities.
temperatures. Therefore, 1 10the stability of NiMn1Al10-C was evaluated at 500 °C and 3.0 MPa with
The NiMn
different 1 Al10
space -C is very
velocities. The stable
NiMn at1Al
a 10high
-C is temperature
very stable atwith a high different spacewith
temperature velocities:
differentthe CO
space
conversionthe
velocities: maintains at 100%maintains
CO conversion for 180 h,atand 100%the for
selectivity of CH
180 h, and the4 is slightly reduced
selectivity of CH4 iswhen the
slightly
space velocity is increased from 30,000 mL · g −1 ·h−1 to 60,000 −1mL−1·g−1 ·h−1 (Figure−1 10b). Compared
reduced when the space velocity is increased from 30000 mL·g ·h to 60000 mL·g ·h (Figure 10b). −1

with the supported

Compared with the nickel-based
supported catalyst, the NiMn
nickel-based X Al10 -C
catalyst, catalyst
the NiMnhas high
XAl10 low-temperature
-C catalyst has highactivity
low-
and strong anti-sintering
temperature activity and strong performance [15,17,35,37].
anti-sintering The high
performance stability of The
[15,17,35,37]. the NiMn Al10 -C at
high 1stability ofhigh
the
temperatures
NiMn 1Al10-C atishigh
attributed to the confinement
temperatures is attributed effect
to the of AlOx and MnO
confinement effectyof( Figures
AlOx and 5fMnO
and 6), which
y ( Figure

prevents
5f the sintering
and Figure 6), whichofprevents
Ni particles during the
the sintering of reaction.
Ni particles during the reaction.
Catalysts 2019, 9, 282 10 of 15
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15

(a)
(a) (b)
(b)
100
100 100
100
convertion(%)
COconvertion(%) 0.1 MPa
0.1 MPa
30000 ml
ml g
g-1 h
h-1 60000
-1 -1 -1 -1
280 ℃
280 ℃ 30000 60000 ml
ml g
g-1 h
h-1
75
75 30000 ml g
30000 ml
-1 -1
g-1 h
h-1 75
75 3.0 MPa
MPa
3.0

(%)
500

(%)
500 ℃ ℃
NiAl10Mn
NiAl Mn1-C
-C NiMn Al10-C
-C
NiMn1Al
50
50
10 1
50
50
1 10
Commercial-C
Commercial-C CO conversion
conversion
CO
CO

CH4 selectivity
CH selectivity
4
25
25 25
25
0
0 5
5 10 15
10 15 20
20 25
25 0
0 50
50 100
100 150
150
Time/h
Time/h Time (h)
Time (h)
Figure 10.
Figure 10. Low
Low temperature
Low temperature (a) and
temperature (a) and high
high temperature
temperature (b)
(b) lifetime
lifetime tests
tests of
of the
the catalysts.
catalysts.

The XRD results of the fresh fresh and

and used
used NiMn Al10
NiMn111Al -C are
10-C are shown
shown in in Figure
Figure 11a, and both of them
The XRD results of the fresh and used ◦
NiMn ◦
10-C are shown in Figure 11a, and both of them
◦
the characteristic peaks
display the peaks at 2θ
2θ === 44.6
44.6°,, 51.9°,
51.9 , 76.8°,
51.9°, 76.8 , attributing
attributing to (111), (200), (220) planes of Ni
display characteristic peaks at 2θ 44.6°, 76.8°, attributing to (111), (200), (220) planes of Ni
(fcc), respectively.
respectively. Additionally,
Additionally, the
the peak
peak intensities
intensities of Ni for the used catalyst almost do not change
(fcc), respectively. Additionally, the peak intensities of Ni for the used catalyst almost do not change
compared with that of the fresh one. The The average
average diameters
diameters of of Ni
Ni particles
particles inin the fresh and used
compared with that of the fresh one. The average diameters of Ni particles in the fresh and used
catalysts are 8.5 ±0.50.5and 8.3 ±±0.5
and 8.3 0.5nm,nm,respectively,
respectively,indicating
indicatingtherethere was
was nono agglomeration
agglomeration of the Ni
catalysts are 8.5 ±± 0.5 and 8.3 ± 0.5 nm, respectively, indicating there was no agglomeration of the Ni
particles
particles after
after the
thehigh
hightemperature
temperaturestability
stabilitytest.
test.The
Theresult
resultproves
provesthat the
that NiMn
the NiMn1 Al
1Al -C-Ccatalyst
1010 catalysthas
hasa
particles after the high temperature stability test. The result proves that the NiMn 1Al10-C catalyst has
high stability at high temperatures, which was due to the confinement of the AlO substrate (Figure 5).
aa high
high stability
stability at
at high
high temperatures,
temperatures, whichwhich was was due
due to
to the
the confinement
confinement of of the
the AlO
AlO substrate (Figure
x xx substrate (Figure
The carbon
5). The
The carbondeposit
depositamount
amount was investigated
was investigated by by
thermogravimetric
thermogravimetric (TG) (Figure
(TG) 11b).
(Figure The
11b). weights
The weightsof
5). carbon deposit amount was investigated by thermogravimetric (TG) (Figure 11b).
◦ C is associated with the oxidation of the reduced Ni
The weights
fresh and
of fresh
fresh and used
and used catalysts
used catalysts increased
catalysts increased
increased atat 200–400
at 200–400
200–400 °C °C is
is associated
associated withwith the
the oxidation
oxidation of of the
the reduced Ni
of
particles. TheThe superposition
superposition of of both
both TG curves indicates
indicates that there were almost no carbon deposits
particles. The superposition of both TG curves indicates that there were almost no carbon deposits
implying that NiMn1Al10
formed, implying -C possesses
-C possesses excellent
excellent anti-coking
anti-coking properties
properties due
due to the high H H222
formed, that NiMn1Al1010-C possesses excellent anti-coking properties due to the high H
adsorption and catalyst containing a larger number of oxygen vacancies (Tables 2 and 3). By By contrast,
contrast,
adsorption and catalyst containing a larger number of oxygen vacancies (Tables 2 and 3). By contrast,
with the nickel-based
nickel-based catalyst
catalyst synthesized
synthesizedby by traditional
traditionalmeansmeans[9–11,15,21],
[9–11,15,21],thetheNiMn
NiMn111AlAl10
10-C catalyst
with the nickel-based catalyst synthesized by traditional means [9–11,15,21], the NiMn Al 10-C catalyst
exhibits much higher stability due to greatly improved resistance to coking and sintering. The carbon
exhibits much higher stability due to greatly improved resistance to coking and sintering. The carbon
deposit amount
deposit amount was was further
further investigated
investigated by by Raman spectra (Figure 11c). No
Raman spectra (Figure 11c). No No peak
peak of carbon was
peak of carbon was
observed, indicating that there was no carbon deposit on on the
the used
used catalyst
catalyst surface.
surface.
observed, indicating that there was no carbon deposit on the used catalyst surface.

(a)
(a) ♦ (b)
(b) (c)
(c)
♦ ♦Ni
♦Ni 105
105
(a.u.)
Intensity(a.u.)

♦
Intensity(a.u.)
Intensity(a.u.)

♦
Weigth(%)

♦
Weigth(%)

♦ NiMn Al10-C-fresh
NiMn11Al10 -C-fresh
NiMn Al10-C-fresh
Intensity

NiMn11Al10 -C-fresh NiMn Al10-C-fresh

NiMn11Al10-C-fresh
NiMn Al10-C-used
NiMn11Al10 -C-used
90
90 NiMn Al10-C-used
NiMn Al10-C-used NiMn11Al10 -C-used
NiMn11Al10 -C-used

20 40 60 80 200 400
400 600
600 800
800 0
0 1000 2000
1000 2000 3000
3000 4000
4000
20 40 60 80 200 -1
2θ(degree)
2θ(degree) Temperature(°C)
Temperature(°C) Raman shift (cm-1 )
Raman shift (cm )
Figure 11.
Figure
Figure 11. XRD
11. XRD (a),
XRD (a), TG
(a), TG (b)
TG (b) and
(b) and Raman
and Raman spectrum (c)
Raman spectrum
spectrum (c) of
(c)of the
ofthe catalysts.
thecatalysts.
catalysts.

3. Materials
3. Materials and
and Methods
Methods

3.1. Chemicals
3.1. Chemicals
3.1. Chemicals
Aluminum nitrate
Aluminum nitrate nonahydrate
nonahydrate (Al(NO ·9H22O),
(Al(NO333)))333·9H
·9H O), urea
urea (CO(NH
(CO(NH22))22),), Nickel
Nickel (II)
(II) nitrate
nitrate
Aluminum nitrate nonahydrate (Al(NO 2O), urea (CO(NH2)2), Nickel (II) nitrate
hexahydrate
hexahydrate (Ni(NO
(Ni(NO ) · 6H
33)22·6H2O)2 O) and
and manganese
manganese nitrate
nitrate (Mn(NO
(Mn(NO ) · 4H
33)22·4H2O)
2 O) were
were purchased
purchased from
from
hexahydrate (Ni(NO3)2·6H2O) and manganese nitrate (Mn(NO3)2·4H2O) were purchased from
Sinopharm Chemical Reagent Co. Ltd., Shanghai, China. All reagents were
Sinopharm Chemical Reagent Co. Ltd., Shanghai, China. All reagents were of analytical grade and of analytical grade and
used without
used without further
further purification.
purification.
Catalysts 2019, 9, 282 11 of 15

Sinopharm Chemical Reagent Co. Ltd., Shanghai, China. All reagents were of analytical grade
and used without further purification.

3.2. Catalysts Preparation

The NiAl hydrotalcite was prepared by hydrothermal method. First, 1.5 mmol of Ni(NO3 )2 ·6H2 O,
0.5 mmol of Al(NO3 )3 ·9H2 O and 10 mmol of CO(NH2 )2 were dissolved in 70 mL of deionized
water. Then the solution was transferred into an autoclave for a hydrothermal treatment at 120 ◦ C
for 12 h. Subsequently, the product was centrifuged and washed with deionized water. The collected
product was subsequently dried at 80 ◦ C for 15 h, which was named NiAl-LDH. The synthesis
of the NiMnAl ternary hydrotalcites is similar to the above process, except that a certain amount
of Mn(NO3 )2 ·4H2 O was added. The synthesized NiMnAl ternary hydrotalcites with the molar
ratios of Mn/Al (Mn:Al = 0.5:10, 1:10, 2:10) are denoted as NiMn0.5 Al10 -LDH, NiMn1 Al10 -LDH,
and NiMn2 Al10 -LDH, respectively. After reduction in hydrogen at 600 ◦ C for 2 h (10 ◦ C/min), the
methanation catalysts are marked as NiAl-C (C stands for the catalyst), NiMn0.5 Al10 -C, NiMn1 Al10 -C,
and NiMn2 Al10 -C accordingly. The commercial catalyst (Ni-35.3 wt%) was purchased from LiaoNing
HaiTai SCI-TECH Development CO., Ltd., Fushun, China. For comparison with the commercial
catalyst, nickel content of the NiMnAl catalysts was diluted to 35 wt% with α-Al2 O3 (commercial
γ-Al2 O3 (GongYi HuaYu, Zhengzhou, China) calcined at 1200 ◦ C in air for 6 h), and the α-Al2 O3 is
inactive for CO methanation.

3.3. Catalysts Characterization

The X-ray diffraction (XRD) characterization was carried out on Cu-Ka radiation with a rate
of 10◦ min−1 (40 kV, 40 mA). N2 adsorption/desorption isotherms and the specific surface area
and pore size distributions of the samples were tested on the Quantachrome NOVA 3200e (FL, USA).
The morphology and microscopic feature of the samples were detected by scanning electron microscope
(SEM) (JSM-7001F, INCA X-MAX, Tokyo, Japan, 15 kV) and transmission electron microscopy
(TEM) (JEM-2010F, JEOL, Tokyo, Japan). Hydrogen temperature programmed reduction (H2 -TPR)
and Hydrogen temperature programmed desorption (H2 -TPD) were obtained from Quantachrome
automated chemisorption analyzer. In a typical experiment of H2 -TPR, the hydrotalcite precursor
(30 mg) was sealed in the quartz U-tube reactor and purged in a He flow for 2 h at 150 ◦ C (10 ◦ C/min),
and then reduced by injecting H2 and Ar (10% H2 /Ar) at a given temperature. In a typical experiment
of H2 -TPD, the hydrotalcite precursor (100 mg) firstly in situ reduced with pure H2 , then cooled down
in the N2 atmosphere, and subsequently switched to Ar flow purging for 1.5 h to remove the physically
adsorbed H2 on the surface of the catalysts. The H2 adsorption amounts of the catalysts were measured
at a heating rate of 10 ◦ C/min. The dispersion of Ni nanoparticles was calculated from the data of
H2 -TPD, and the calculation details can be found in our previous work [9]. The elements amount
of the catalysts were obtained from Optima 7000 DV inductively coupled plasma optical emission
spectrometer (ICP, MA, USA). The surface chemical compositions of the catalysts were measured by
X-ray photoelectron spectroscopy (XPS) on an Esca Lab 250Xi with a monochromatic Al Kα radiation.
The carbon deposits on the surface of the used catalyst were determined by thermogravimetric analyzer
(TG/DTA 6300, Seiko Instruments, Tokyo, Japan) and Raman Spectrometer (Renishaw RM 2000, laser
wavelength = 532 nm, London, UK).

3.4. Catalytic Performance Measurement

The methanation measurements are similar to what we have reported previously [11]. The CO
methanation reaction was performed in a fixed bed reactor at 3.0 MPa, and the reaction data were
recorded in the temperature interval of 250–500 ◦ C; the spacing is 20 ◦ C or 50 ◦ C. In each case,
the catalyst (200 mg) admixed with 5 g of quartz sand, then heated to the reaction temperature (250 ◦ C)
in a H2 atmosphere, and finally switched to syngas (H2 :CO:N2 = 3:1:1) for methanation reaction.
The mixed gas after the methanation reaction was first cooled down and then analyzed on line by
Catalysts 2019, 9, 282 12 of 15

Micro Gas chromatography (3000A; Agilent Technologies, CA, USA). The amount of H2 , N2 , CH4 , and
CO in the outlet gases were analyzed by a thermal conductivity detector (TCD, CA, USA) connected to
a molecular sieve column. The amount of CO2 , C2 H4 and C2 H6 in the outlet gases were detected by
TCD connected to a Plot Q column (CA, USA). The stability of the catalyst is investigated at 3.0 MPa
and 500 ◦ C.

4. Conclusions
In summary, to enhance the low-temperature performance of the Ni catalysts for syngas
methanation, the highly dispersed Ni nanocatalysts are successfully prepared by in situ reduction of
NiMnAl-LDHs precursors, and Ni particles decorated with the promoter of MnOy are confined in the
matrix of AlOx . The synthesized NiMnAl catalysts exhibit higher properties than the NiAl catalyst
since the addition of Mn increases dispersion of Ni particles and H2 uptake. The NiMn1 Al10 exhibits
the best performance at low temperatures and the greatest resistance to sintering and coking due to
the highest dispersion of Ni and the steric hindrance of AlOx and MnOy against aggregation of the Ni
particles. This work demonstrates how to enhance the performance of the Ni catalysts in methanation
by carefully adding promoter MnOy and by embedding the fine Ni particles on the AlOx nanosheets.

Author Contributions: Conceptualization, B.L., F.G. and F.S.; methodology, B.L. and F.G.; validation, B.L., J.Z.,
J.D., F.G., G.X., Z.Z., Q.L. and F.S.; investigation, B.L. and F.G.; resources, F.G. and F.S.; writing—original draft
preparation, B.L., J.Z., J.D., F.G. and F.S.; writing—review and editing, B.L., F.G., G.X., Z.Z., Q.L. and F.S.;
supervision, F.G. and F.S.; funding acquisition, F.G. and F.S.
Funding: This research was funded by National Key R&D Program of China (2018YFB0604501) and the National
Natural Science Foundation of China (21776286).
Conflicts of Interest: There are no conflicts of interest to declare.

References
1. Razzaq, R.; Li, C.; Zhang, S. Coke oven gas: Availability, properties, purification, and utilization in China.
Fuel 2013, 113, 287–299. [CrossRef]
2. Zhang, J.; Xin, Z.; Meng, X.; Tao, M. Synthesis, characterization and properties of anti-sintering nickel
incorporated MCM-41 methanation catalysts. Fuel 2013, 109, 693–701. [CrossRef]
3. Höhlein, B.; Menzer, R.; Range, J. High Temperature Methanation in the Long-distance Nuclear energy
transport system. Appl. Catal. 1981, 1, 125–139. [CrossRef]
4. Höhlein, B.; Niessen, J.; Schiebahn, H.J.R.; Vorwerk, M. Methane from synthesis gas and operation of
high-temperature methanation. Nucl. Eng. Des. 1984, 78, 241–250. [CrossRef]
5. Nguyen, T.T.M.; Wissing, L.; Skjøth-Rasmussen, M.S. High temperature methanation: Catalyst considerations.
Catal. Today 2013, 215, 233–238. [CrossRef]
6. Ma, S.; Tan, Y.; Han, Y. Methanation of syngas over coral reef-like Ni/Al2 O3 catalysts. J. Nat. Gas. Chem.
2011, 20, 435–440. [CrossRef]
7. Zhang, M.; Yu, F.; Li, J.; Chen, K.; Yao, Y.; Li, P.; Zhu, M.; Shi, Y.; Wang, Q.; Guo, X. High CO Methanation
Performance of Two-Dimensional Ni/MgAl Layered Double Oxide with Enhanced Oxygen Vacancies via
Flash Nanoprecipitation. Catalysts 2018, 8, 363. [CrossRef]
8. Hu, D.; Gao, J.; Ping, Y.; Jia, L.; Gunawan, P.; Zhong, Z.; Xu, G.; Gu, F.; Su, F. Enhanced Investigation of CO
Methanation over Ni/Al2 O3 Catalysts for Synthetic Natural Gas Production. Ind. Eng. Chem. Res. 2012, 51,
4875–4886. [CrossRef]
9. 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]
10. Liu, Q.; Gu, F.; Zhong, Z.; Xu, G.; Su, F. Anti-sintering ZrO2 -modified Ni/α-Al2 O3 catalyst for CO
methanation. RSC Adv. 2016, 6, 20979–20986. [CrossRef]
11. Liu, Q.; Gao, J.; Gu, F.; Lu, X.; Liu, Y.; Li, H.; Zhong, Z.; Liu, B.; Xu, G.; Su, F. One-pot synthesis of ordered
mesoporous Ni–V–Al catalysts for CO methanation. J. Catal. 2015, 326, 127–138. [CrossRef]
Catalysts 2019, 9, 282 13 of 15

12. Lu, X.; Gu, F.; Liu, Q.; Gao, J.; Jia, L.; Xu, G.; Zhong, Z.; Su, F. Ni-MnOx Catalysts Supported on
Al2 O3 -Modified Si Waste with Outstanding CO Methanation Catalytic Performance. Ind. Eng. Chem. Res.
2015, 54, 12516–12524. [CrossRef]
13. Tang, H.; Li, S.; Gong, D.; Guan, Y.; Liu, Y. Bimetallic Ni-Fe catalysts derived from layered double hydroxides
for CO methanation from syngas. Front. Chem. Sci. Eng. 2017, 11, 613–623. [CrossRef]
14. Gao, J.; Jia, C.; Li, J.; Gu, F.; Xu, G.; Zhong, Z.; Su, F. Nickel Catalysts Supported on Barium Hexaaluminate
for Enhanced CO Methanation. Ind. Eng. Chem. Res. 2012, 51, 10345–10353. [CrossRef]
15. Gao, J.; Jia, C.; Zhang, M.; Gu, F.; Xu, G.; Zhong, Z.; Su, F. Template preparation of high-surface-area barium
hexaaluminate as nickel catalyst support for improved CO methanation. RSC Adv. 2013, 3, 18156. [CrossRef]
16. Jia, C.; Gao, J.; Li, J.; Gu, F.; Xu, G.; Zhong, Z.; Su, F. Nickel catalysts supported on calcium titanate for
enhanced CO methanation. Catal. Sci. Technol. 2013, 3, 490–499. [CrossRef]
17. Jin, G.; Gu, F.; Liu, Q.; Wang, X.; Jia, L.; Xu, G.; Zhong, Z.; Su, F. Highly stable Ni/SiC catalyst modified by
Al2 O3 for CO methanation reaction. RSC Adv. 2016, 6, 9631–9639. [CrossRef]
18. Sun, J.; Feng, Q.; Liu, Q.; Ji, S.; Fang, Y.; Peng, X.; Wang, Z.-J. An Al2 O3 -Coated SiC-Supported Ni Catalyst
with Enhanced Activity and Improved Stability for Production of Synthetic Natural Gas. Ind. Eng. Chem. Res.
2018, 57, 14899–14909. [CrossRef]
19. Wang, X.; Liu, Q.; Jiang, J.-X.; Jin, G.; Li, H.; Gu, F.; Xu, G.; Zhong, Z.; Su, F. SiO2 -stabilized Ni/t-ZrO2 catalysts
with ordered mesopores: One-pot synthesis and their superior catalytic performance in CO methanation.
Catal. Sci. Technol. 2016, 6, 3529–3543. [CrossRef]
20. Jiang, Y.; Huang, T.; Dong, L.; Su, T.; Li, B.; Luo, X.; Xie, X.; Qin, Z.; Xu, C.; Ji, H. Mn Modified Ni/Bsentonite
for CO2 Methanation. Catalysts 2018, 8, 646. [CrossRef]
21. Feng, F.; Song, G.; Xiao, J.; Shen, L.; Pisupati, S.V. Carbon deposition on Ni-based catalyst with TiO2 as
additive during the syngas methanation process in a fluidized bed reactor. Fuel 2019, 235, 85–91. [CrossRef]
22. Dai, X.; Liang, J.; Ma, D.; Zhang, X.; Zhao, H.; Zhao, B.; Guo, Z.; Kleitz, F.; Qiao, S. Large-pore mesoporous
RuNi-doped TiO2 –Al2 O3 nanocomposites for highly efficient selective CO methanation in hydrogen-rich
reformate gases. Appl. Catal. B-Environ. 2015, 165, 752–762. [CrossRef]
23. Mebrahtu, C.; Krebs, F.; Perathoner, S.; Abate, S.; Centi, G.; Palkovits, R. Hydrotalcite based Ni-Fe/(Mg,
Al)Ox catalysts for CO2 methanation-tailoring Fe content for improved CO dissociation, basicity, and particle
size. Catal. Sci. Technol. 2018, 8, 1016–1027. [CrossRef]
24. Liu, Q.; Gu, F.; Gao, J.; Li, H.; Xu, G.; Su, F. Coking-resistant Ni-ZrO2 /Al2 O3 catalyst for CO methanation.
J. Energy. Chem. 2014, 23, 761–770. [CrossRef]
25. Zeng, Y.; Ma, H.; Zhang, H.; Ying, W.; Fang, D. Ni-Ce-Al composite oxide catalysts synthesized by solution
combustion method: Enhanced catalytic activity for CO methanation. Fuel 2015, 162, 16–22. [CrossRef]
26. Zhao, A.; Ying, W.; Zhang, H.; Ma, H.; Fang, D. Ni-Al2 O3 catalysts prepared by solution combustion method
for syngas methanation. Catal. Commun. 2012, 17, 34–38. [CrossRef]
27. Bian, L.; Zhang, L.; Zhu, Z.; Li, Z. Methanation of carbon oxides on Ni/Ce/SBA-15 pretreated with dielectric
barrier discharge plasma. Mol. Catal. 2018, 446, 131–139. [CrossRef]
28. Liu, Q.; Zhong, Z.; Gu, F.; Wang, X.; Lu, X.; Li, H.; Xu, G.; Su, F. CO methanation on ordered mesoporous
Ni-Cr-Al catalysts: Effects of the catalyst structure and Cr promoter on the catalytic properties. J. Catal. 2016,
337, 221–232. [CrossRef]
29. Liu, Q.; Qiao, Y.; Tian, Y.; Gu, F.; Zhong, Z.; Su, F. Ordered Mesoporous Ni-Fe-Al Catalysts for CO Methanation
with Enhanced Activity and Resistance to Deactivation. Ind. Eng. Chem. Res. 2017, 56, 9809–9820. [CrossRef]
30. Xu, L.; Lian, X.; Chen, M.; Cui, Y.; Wang, F.; Li, W.; Huang, B. CO2 methanation over Co-Ni bimetal-doped
ordered mesoporous Al2 O3 catalysts with enhanced low-temperature activities. Int. J. Hydrog. Energy 2018,
43, 17172–17184. [CrossRef]
31. Liu, Q.; Wang, S.; Zhao, G.; Yang, H.; Yuan, M.; An, X.; Zhou, H.; Qiao, Y.; Tian, Y. CO2 methanation over
ordered mesoporous NiRu-doped CaO-Al2 O3 nanocomposites with enhanced catalytic performance. Int. J.
Hydrog. Energy 2018, 43, 239–250. [CrossRef]
32. Hayashi, K.; Miyao, T.; Tabira, Y.; Higashiyama, K. Low-temperature Selective CO Methanation over
Unsupported Nickel Catalyst Covered by Silica Thin Layer. J. Jpn. Petrol. Inst. 2016, 59, 65–71. [CrossRef]
33. Feng, X.; Dong, C.; Ping, D.; Geng, J.; Zhang, J.; Dong, X. Zr-Modified SBA-15 Supported Ni Catalysts
with Excellent Catalytic Performance of CO Selective Methanation in H2 -Rich Fuels. Catal. Lett. 2018, 148,
2967–2973. [CrossRef]
Catalysts 2019, 9, 282 14 of 15

34. Meng, F.; Song, Y.; Li, X.; Cheng, Y.; Li, Z. Catalytic methanation performance in a low-temperature slurry-bed
reactor over Ni-ZrO2 catalyst: effect of the preparation method. J. Sol-Gel. Sci. Technol. 2016, 80, 759–768.
[CrossRef]
35. Cui, D.; Liu, J.; Yu, J.; Su, F.; Xu, G. Attrition-resistant Ni-Mg/SiO2 -Al2 O3 catalysts with different silica
sources for fluidized bed syngas methanation. Int J Hydrog. Energy 2017, 42, 4987–4997. [CrossRef]
36. Meng, F.; Li, Z.; Ji, F.; Li, M. Effect of ZrO2 on catalyst structure and catalytic methanation performance over
Ni-based catalyst in slurry-bed reactor. Int. J. Hydrog. Energy 2015, 40, 8833–8843. [CrossRef]
37. Liu, C.; Zhou, J.; Ma, H.; Qian, W.; Zhang, H.; Ying, W. Antisintering and High-Activity Ni Catalyst
Supported on Mesoporous Silica Incorporated by Ce/Zr for CO Methanation. Ind. Eng. Chem. Res. 2018, 57,
14406–14416. [CrossRef]
38. Chen, G.; Gao, R.; Zhao, Y.; Li, Z.; Waterhouse, G.I.N.; Shi, R.; Zhao, J.; Zhang, M.; Shang, L.; Sheng, G.;
et al. Alumina-Supported CoFe Alloy Catalysts Derived from Layered-Double-Hydroxide Nanosheets for
Efficient Photothermal CO2 Hydrogenation to Hydrocarbons. Adv. Mater. 2018, 30. [CrossRef]
39. Chen, G.; Wang, T.; Zhang, J.; Liu, P.; Sun, H.; Zhuang, X.; Chen, M.; Feng, X. Accelerated Hydrogen
Evolution Kinetics on NiFe-Layered Double Hydroxide Electrocatalysts by Tailoring Water Dissociation
Active Sites. Adv. Mater. 2018, 30. [CrossRef]
40. Li, P.; Zhu, M.; Tian, Z.; Han, Y.; Zhang, Y.; Zhou, T.; Kang, L.; Dan, J.; Guo, X.; Yu, F.; et al. Two-Dimensional
Layered Double Hydroxide Derived from Vermiculite Waste Water Supported Highly Dispersed Ni
Nanoparticles for CO Methanation. Catalysts 2017, 7, 79. [CrossRef]
41. Fan, Q.; Li, X.; Yang, Z.; Han, J.; Xu, S.; Zhang, F. Double-Confined Nickel Nanocatalyst Derived from
Layered Double Hydroxide Precursor: Atomic Scale Insight into Microstructure Evolution. Chem. Mater.
2016, 28, 6296–6304. [CrossRef]
42. Chen, H.; He, S.; Cao, X.; Zhang, S.; Xu, M.; Pu, M.; Su, D.; Wei, M.; Evans, D.G.; Duan, X.
Ru-Cluster-Modified Ni Surface Defects toward Selective Bond Breaking between C-O and C-C. Chem. Mater.
2016, 28, 4751–4761. [CrossRef]
43. Li, C.; Chen, Y.; Zhang, S.; Xu, S.; Zhou, J.; Wang, F.; Wei, M.; Evans, D.G.; Duan, X. Ni-In Intermetallic
Nanocrystals as Efficient Catalysts toward Unsaturated Aldehydes Hydrogenation. Chem. Mater. 2013, 25,
3888–3896. [CrossRef]
44. Li, Z.; Bian, L.; Zhu, Q.; Wang, W. Ni-based catalyst derived from Ni/Mg/Al hydrotalcite–like compounds
and its activity in the methanation of carbon monoxide. Kinet. Catal. 2014, 55, 217–223. [CrossRef]
45. Kim, W.Y.; Lee, Y.H.; Park, H.; Choi, Y.H.; Lee, M.H.; Lee, J.S. Coke tolerance of Ni/Al2 O3 nanosheet catalyst
for dry reforming of methane. Catal. Sci. Technol. 2016, 6, 2060–2064. [CrossRef]
46. He, S.; Li, C.; Chen, H.; Su, D.; Zhang, B.; Cao, X.; Wang, B.; Wei, M.; Evans, D.G.; Duan, X. A Surface
Defect-Promoted Ni Nanocatalyst with Simultaneously Enhanced Activity and Stability. Chem. Mater. 2013,
25, 1040–1046. [CrossRef]
47. Mitchell, R.W.; Lloyd, D.C.; van de Water, L.G.A.; Ellis, P.R.; Metcalfe, K.A.; Sibbald, C.; Davies, L.H.;
Enache, D.I.; Kelly, G.J.; Boyes, E.D.; et al. Effect of Pretreatment Method on the Nanostructure and
Performance of Supported Co Catalysts in Fischer-Tropsch Synthesis. ACS Catal. 2018, 8, 8816–8829. [CrossRef]
48. Li, F.; Liu, J.; Evans, D.G.; Duan, X. Stoichiometric synthesis of pure MFe2 O4 (M = Mg, Co and Ni) spinel
ferrites from tailored layered double hydroxide (hydrotalcite–like) precursors. Chem. Mater. 2004, 16,
1597–1602. [CrossRef]
49. Liu, J.; Li, C.; Wang, F.; He, S.; Chen, H.; Zhao, Y.; Wei, M.; Evans, D.G.; Duan, X. Enhanced low-temperature
activity of CO2 methanation over highly-dispersed Ni/TiO2 catalyst. Catal. Sci. Technol. 2013, 3, 2627–2633.
[CrossRef]
50. Grosvenor, A.P.; Biesinger, M.C.; Smart, R.S.C.; McIntyre, N.S. New interpretations of XPS spectra of nickel
metal and oxides. Surf. Sci. 2006, 600, 1771–1779. [CrossRef]
51. Zhang, Y.; Qin, Z.; Wang, G.; Zhu, H.; Dong, M.; Li, S.; Wu, Z.; Li, Z.; Wu, Z.; Zhang, J.; et al. Catalytic
performance of MnOx -NiO composite oxide in lean methane combustion at low temperature. Appl. Catal.
B-Enriron. 2013, 129, 172–181. [CrossRef]
52. Biesinger, M.C.; Payne, B.P.; Grosvenor, A.P.; Lau, L.W.M.; Gerson, A.R.; Smart, R.S.C. Resolving surface
chemical states in XPS analysis of first row transition metals, oxides and hydroxides: Cr, Mn, Fe, Co and Ni.
Appl. Surf. Sci. 2011, 257, 2717–2730. [CrossRef]
Catalysts 2019, 9, 282 15 of 15

53. Mo, S.; Li, S.; Li, W.; Li, J.; Chen, J.; Chen, Y. Excellent low temperature performance for total benzene
oxidation over mesoporous CoMnAl composited oxides from hydrotalcites. J. Mater. Chem. A 2016, 4,
8113–8122. [CrossRef]
54. Hernández, W.Y.; Centeno, M.A.; Ivanova, S.; Eloy, P.; Gaigneaux, E.M.; Odriozola, J.A. Cu-modified
cryptomelane oxide as active catalyst for CO oxidation reactions. Appl. Catal. B 2012, 123–124, 27–35.
[CrossRef]

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