international journal of hydrogen energy xxx (xxxx) xxx

Available online at www.sciencedirect.com

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Influence of alloying on the catalytic performance

of NieAl catalyst prepared from hydrotalcite-like
compounds for methane decomposition

Chunsheng Wan, Zemin Shi, Min Huang, Jinhua Pan, Ruizhi Luo, Dalin Li*,
Lilong Jiang**
National Engineering Research Center of Chemical Fertilizer Catalyst, College of Chemical Engineering, Fuzhou
University, Xueyuan Road No.1, Quangang District, Quanzhou, Fujian, PR China

highlights

NieCo, NieFe, and NieCu alloy particles are composition-uniform.

Alloying Ni with Co, Fe, and Cu enhances the catalytic life and carbon yield.

The order of activity is NieCu >> NieFe > NieCo > Ni in terms of carbon yield.

NieCu alloying changes the carbon morphology giving CNFs as the main product.

NieCu alloy particles are aggregated into big particles (>60 nm) during the reaction.

article info abstract

Article history: Cobalt-, iron-, and copper-substituted nickel-aluminum hydrotalcite-like compounds

Received 11 August 2020 (Ni2.7Co0.3Al, Ni2.7Fe0.3Al, Ni2.7Cu0.3Al HTlcs) have been synthesized and used as precursors
Received in revised form to prepare NieCo, NieFe, and NieCu alloy catalysts for methane decomposition. The cat-
5 October 2020 alysts before and after reaction were characterized with various techniques including XRD,
Accepted 21 October 2020 H2-TPR, HAADF-STEM-EDX, SEM, TEM, and Raman. The characterization results indicate
Available online xxx that upon calcination HTlcs are transformed into a mixed oxide solid solution, where co-
balt, copper, and iron ions are incorporated into the nickel oxide, and the reduction
Keywords: treatment leads to composition-uniform alloy particles. In methane decomposition at
Catalytic methane decomposition 600  C, alloying Ni with Co, Fe, and especially Cu is found to enhance the catalytic life and
Hydrotalcite-like compounds carbon yield. The order of activity is Ni2.7Cu0.3Al >> Ni2.7Fe0.3Al > Ni2.7Co0.3Al > Ni3Al in
Nickel-copper alloy terms of carbon yield, highlighting that NieCu alloying is the most effective. Besides, Ni
Nickel-iron alloy eCu alloying remarkably changes the carbon morphology, giving carbon nanofibers as
Nickel-cobalt alloy the main product. TEM and STEM measurements suggest that NieCu alloy particles are
readily aggregated into big particles (>60 nm) under the reaction conditions, which may be
responsible for the significant effect of NieCu alloying.
© 2020 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

* Corresponding author.
** Corresponding author.
E-mail addresses: dalinli@fzu.edu.cn (D. Li), jll@fzu.edu.cn
(L. Jiang).
https://doi.org/10.1016/j.ijhydene.2020.10.186
0360-3199/© 2020 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

Please cite this article as: Wan C et al., Influence of alloying on the catalytic performance of NieAl catalyst prepared from hydrotalcite-
like compounds for methane decomposition, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2020.10.186
2 international journal of hydrogen energy xxx (xxxx) xxx
Introduction
Catalytic methane decomposition (CMD) is an attractive
technology to produce hydrogen and carbon nanomaterials
[1e3]. Hydrogen is a clean energy source, which can be con-
verted into electricity via fuel cells with high efficiency and
less pollution. The hydrogen produced by CMD is COx-free,
which is greatly advantageous over the conventional steam
reforming of methane that usually produces large amounts of
carbon oxides. On the other hand, the carbon nanomaterials
produced by CMD such as carbon nanofibers (CNFs) and car-
bon nanotubes (CNTs), have promising application in many
fields due to their unique physical, chemical, optical, elec-
trical, and mechanical properties. Transition metals such as
nickel, cobalt, iron, and their combination ones are active for
methane decomposition [3e8], among which nickel-based
catalysts are the most widely investigated because of their
high activity at relatively low temperatures (e.g. 500  C) [3].
However, Ni catalysts are readily deactivated by the encap-
sulation of carbon on the Ni particle surface. Therefore,
various strategies have been developed to improve the cata-
lytic performance of Ni catalysts [9e19].
Among various preparation methods for Ni catalysts, using
hydrotalcite-like compounds (HTlcs) as precursor appears to be
a promising way to obtain a high-performance catalyst [20e33].
As well known, HTlcs are a class of anionic clay, which have a
layered structure composed of positively charged brucite-like
layers and negative anion interlayers [34]. The formula of
HTlcs can be described as [M2þ1exM3þx (OH)2][Ane]x/n$mH2O,
where M2þ and M3þ are the divalent and trivalent cations in the
brucite layers and Ane is the interlayer anion, respectively. A
variety of metal cations can be introduced into the HTlcs layers
and their chemical composition is tunable in a relatively wide
range (x ¼ 0.2e0.4). NieAl HTlcs (e.g. [Ni6Al2(OH)16]CO3$4H2O
also known as takovite) are one of representative HTlcs. Owing
to their high nickel contents, NieAl HTlcs can be a promising
catalyst precursor for methane decomposition. Upon thermal
treatment, NieAl HTlcs are transferred into homogeneous
mixed oxides (typically Ni(Al)O solid solution), which by
reduction generate small Ni metal crystallites. These HTlcs-
derived Ni catalysts are usually reported to show high activity
for methane decomposition. For example, Rivas et al. [20] re-
ported that the Ni1.8Al HTlcs catalyst was much more active
than NiAl2O4 and LaNiO3, where CH4 decomposition started at
temperature around 410  C, and Guo et al. [21] observed that the
Ni3Al HTlcs catalyst produced about 3.5 times of CNT yield
higher than the Ni/Al2O3 catalyst prepared by impregnation
method at a reaction temperature of 700  C. To optimize the
performance of the NieAl HTlcs catalyst, the influence of Ni/Al
ratio [21,23], calcination temperature [23,24], and dopants such
as rare earth metals (La, Pr, Nd, Gd, Sm) [25,26], Zn [27], and Cu
[28e33] have been investigated. Anjaneyulu et al. [25,26]
showed that the addition of La to Ni2Al HTlcs catalyst increased
the Ni metal surface area and as a result enhanced the catalytic
activity and the carbon and H2 yields at 550  C. Chen et al. [27]
studied the doping effect of ZnO to a Ni3Al HTlcs catalyst and
found that the doping of ZnO not only increased the carbon
growth rate, but also delayed the catalyst deactivation. They
suggested that the presence of ZnO may delay the occurrence of
Please cite this article as: Wan C et al., Influence of alloying on the catalytic performance of NieAl catalyst prepared from hydrotalcite-
like compounds for methane decomposition, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2020.10.186
quasi-liquid state of Ni particles and weaken their interaction
with carbon to postpone the formation of encapsulating carbon.
Li and co-workers [28e32] have investigated the Cu-doped Ni3Al
HTlcs catalysts for methane decompositioin. The influence of
Cu content on the carbon yield was examined and it was shown
that addition of a suitable amount of Cu (molar ratio
Ni:Cu:Al ¼ 75:2:23 [28] or 50:25:25 [30]) was favorable for the
carbon formation. Furthermore, they found that the
morphology of produced carbon was significantly changed by
Cu doping, where octopus- and bamboo-shaped carbons could
be formed depending on the catalyst composition, reaction
temperature, and presence of H2. For example, high purity
bamboo-shaped CNTs was obtained on the catalyst with
Ni:Cu:Al ¼ 75:15:10 at 730  C and 770  C in CH4eH2 (1:2) mixed
gas [31,32]. It was suggested that the formation of quasi-liquid
state of metal particles by doping Cu is important for the for-
mation of bamboo-shaped CNTs. Nonetheless, further charac-
terization on the metal particles was absent so that whether Ni
and Cu formed an alloy is unclear. Ashok et al. [33] also tested a
series of NieCueAl HTlcs catalysts with different Cu contents
for methane decomposition at 650  C, where higher H2 yied was
achieved at Ni:Cu:Al ¼ 60:25:15. However, the formation of
NieCu alloy and its influence on the carbon morphology is not
illustrated.
In this work, the effect of alloying nickel with cobalt, iron,
and copper on the structural and catalytic properties of the
NieAl HTlcs catalyst for methane decomposition has been
compared. The HTlcs precursors based on [Ni6Al2(OH)16]
CO3$4H2O, in which a part of nickel ions were substituted with
cobalt, iron, or copper ions, i.e., Ni2.7Co0.3Al, Ni2.7Fe0.3Al, and
Ni2.7Cu0.3Al HTlcs, were synthesized by co-precipitation
method, followed by calcination and reduction treatments.
The mixed metal oxides were reduced with H2 at 800  C in order
to completely reduce the metal species to form alloy particles.
The catalytic behavior of the alloy catalysts was tested in a
thermogravimeter, which is a simple way to in situ monitor the
carbon growth by methane decomposition. Various techniques
including powder X-ray diffraction (XRD), temperature-
programmed reduction (H2-TPR), scanning transmission elec-
tron microscopy (STEM)-energy dispersive X-ray spectroscopy
(EDX), scanning electron microscopy (SEM), transmission elec-
tronic microscopy (TEM), and Raman spectroscopy were applied
to characterize the catalysts before and after reaction in details.
Experimental
Catalyst preparation
Co-, Cu-, and Fe-substituted NieAl HTlcs were synthesized via
co-precipitation method [14]. Metal nitrates (Ni(NO3)2∙6H2O,
Co(NO3)2∙6H2O, Cu(NO3)2∙3H2O, Fe(NO3)3∙9H2O, and
Al(NO3)3∙9H2O) are used as metal precursors. At room tem-
perature, a solution containing the desired amounts of metal
nitrates was dropped into a stirred Na2CO3 solution; mean-
while, a NaOH solution (2 M) was added to adjust the solution
pH at 10 ± 0.5. The precipitate was filtered, washed with de-
ionized water, and dried at 100  C overnight. Subsequently,
the dry sample was calcined in air at 500  C for 5 h. Finally, the
calcined sample was reduced with H2 at 800  C for 0.5 h. The
 international journal of hydrogen energy xxx (xxxx) xxx
prepared catalysts are described as Ni2.7Co0.3Al, Ni2.7Fe0.3Al,
and Ni2.7Cu0.3Al, where the molar ratios of (Ni þ M)/Al and M/
(Ni þ M) (M ¼ Co, Fe, Cu) are 3 and 0.1, respectively. For
comparison, a monometallic Ni3Al catalyst was prepared by
the same procedure.
Catalyst characterization
The crystalline structure of the samples including the as-
synthesized and after calcination and reduction treatments
was measured by XRD on a PANalytical X’PertPro diffractometer
using monochromatized Co Ka radiation (l ¼ 0.1789 nm) at 40 kV
and 40 mA. The textural property of the calcined samples was
analyzed by N2 physical adsorption at liquid nitrogen temper-
ature (196  C) on Micromeritics ASAP 2020 equipment. The
reducibility of the calcined samples was tested by H2-TPR on
Micrometrics AutoChem 2920. The H2-TPR profiles were ob-
tained by heating the calcined sample (100 mg) from ambient
temperature to 900  C (10  C min1) in 10% H2/Ar (30 mL min1),
during which the consumption of H2 was recorded with a
thermal conductivity detector. The alloy particles on the
reduced catalysts were analyzed by HAADF-STEM-EDX on JEOL
JEM-2100F microscope at an accelerating voltage of 200 kV. The
morphology of the prepared samples and the carbon produced
by methane decomposition was investigated with SEM on a
Hitachi S4800 microscope operating at 5.0 kV. TEM was further
applied to determine the microstructure of the produced car-
bon, which was conducted on a JEM-2100 (JEOL) microscope at
an accelerating voltage of 200 kV. Raman spectroscopy was used
to analyze the graphitization degree of carbon, which was car-
ried out on Renishaw inVia Reflex Raman spectrometer using Ar
ion laser (532 nm) as the excitation source.
Catalytic reaction
Catalytic methane decomposition was conducted in a Syn-
chronous Thermal Analyzer (Setsys Evolution, Setram,
France). Prior to the test, the calcined sample was reduced
with H2 at 800  C for 0.5 h in a fixed bed quartz reactor and
then 1 mg of the reduced catalyst was loaded into the TG
sample holder and purged with N2 flow. When the tempera-
ture was raised to 600  C in N2 flow, the feed gas (pure
methane 5 mL min1) was added. The carbon growth was
continuously measured through the weight change of the
sample by the TG recording system. The reaction was stopped
when the catalyst was completely deactivated, while it was
extended to 300 min for the Ni2.7Cu0.3Al catalyst because of its
longer catalytic life. The final carbon yield and catalytic life-
time were determined from the TG curve and the H2 yield was
estimated from the carbon yield according to the stoichiom-
etry of the reaction, and the carbon growth rate was calculated
from the first derivative of the TG curve (DTG).
Results and discussion
Catalyst characterizations
The XRD patterns of the as-synthesized precursors with var-
iable metal cations are presented in Fig. 1A. All of the
Please cite this article as: Wan C et al., Influence of alloying on the catalytic performance of NieAl catalyst prepared from hydrotalcite-
like compounds for methane decomposition, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2020.10.186
3
diffraction peaks correspond well with a crystalline HTlcs
phase with rhombohedral 3R symmetry (JCPDS 00-014-0191).
It is noted that the intensities of the basal diffraction peaks
increase to a certain degree especially for the cobalt- and
copper-doped samples, signifying enhanced crystallinity. Ac-
cording to the layered structure of HTlcs, the diffraction peak
at 2q ¼ 13 is ascribed to the (003) basal plane, whose d spacing
is equal to the thickness of one brucite sheet and one inter-
layer, from which the unit cell parameter c can be calculated
(c ¼ 3d003). On the other hand, the in-plane diffraction peak at
2q ¼ 72 is indexed to the (110) plane, whose d spacing in-
dicates the average cation-cation distance in the brucite sheet,
from which the unit cell parameter a can be calculated
(a ¼ 2d110). As listed in Table 1, the parameter an increases by
the presence of cobalt and copper and decreases slightly by
the presence of iron. Since the ionic radius of Ni2þ (0.069 nm) is
smaller than those of Co2þ (0.074 nm) and Cu2þ (0.073 nm) and
larger than that of Fe3þ (0.065 nm) [35], the change of param-
eter a follows the Vegard’s law, verifying that Co2þ, Cu2þ, and
Fe3þ are incorporated into the HTlcs lattice, similar to those
reported in our previous work [36e38]. Fig. 1B shows the XRD
patterns of the samples calcined at 500  C. The diffraction
peaks at 2q ¼ 43.6 , 50.9 , 75.0 , 91.0, and 96.3 are character-
istic of cubic NiO. These diffraction peaks are broad, which
has been widely attributed to the formation of aluminum-
substituted nickel oxide, i.e., Ni(Al)O solid solution [39].
Other metal oxides such as Co3O4, CoAl2O4, Fe2O3, CuO, or
CuAl2O4 are not identified by XRD. One possible explanation is
that these metal cations are incorporated into the NiO lattice
to form a solid solution. For this, the lattice parameters of the
oxides are calculated and given in Table 1 for a reference.
There is no distinct change in the lattice parameter by the
presence of Co2þ, Fe3þ, and Cu2þ, probably due to their low
content and small difference in ionic radius with Ni2þ. Despite
of this, their incorporation into Ni(Al)O solid solution is in part
corroborated by H2-TPR measurement (see below). Table 1 lists
the BET specific surface area of the calcined samples
measured by N2 physical adsorption. The presence of cobalt
and iron leads to a decrease of surface area, whereas it is
increased slightly by the presence of copper. Anyway, all
samples show a relatively high surface area (132e171 m2 g1),
and this can be related to the low crystallinity of the mixed
oxide solid solution. In this work, the calcined samples were
reduced at 800  C with H2 to obtain active metal catalysts. The
XRD results of the reduced catalysts are displayed in Fig. 1C.
The diffraction peaks of the NiO-like phase are basically dis-
appeared and three strong peaks at about 2q ¼ 52.1 , 61.0 , and
91.8 appear, which can be indexed to the (111), (200), and (220)
reflections of fcc Ni metal in the case of Ni3Al. According to the
XRD data base, fcc Co metal shows three main peaks at
2q ¼ 51.8 , 60.6 , and 91.1 (JCPDS 15e0806), and bcc a-Fe metal
displays the (110) and (200) peaks at 2q ¼ 52.4 and 77.2 (JCPDS
6e0696), whereas fcc Cu metal gives the peaks at 2q ¼ 50.7 ,
59.3 , and 88.8 (JCPDS 4e0836). Apparently, no peaks due to
metallic Co, Fe, and Cu are observed in the XRD patterns
presented. This may imply that Co, Fe, and Cu are well alloyed
with Ni. From the (220) and (111) peaks, the lattice parameter
and average crystal size of the metallic phase are calculated.
As listed in Table 1, the lattice parameter of Ni metal increases
slightly by the addition of Co, Fe, and Cu, indicative of the
4 international journal of hydrogen energy xxx (xxxx) xxx

Fig. 1 e XRD patterns of the samples: (A) as-synthesized, (B) after calcination, and (C) after reduction; (a) Ni3Al, (b)
Ni2.7Co0.3Al, (c) Ni2.7Fe0.3Al, and (d) Ni2.7Cu0.3Al. Crystalline phases: (C) hydrotalcite, (-) NiO-based solid solution, and (A) Ni
metal or alloy.

Table 1 e Physicochemical property of the prepared catalysts.

Samples BET surface areaa (m2 Lattice Lattice parameter of oxidec Lattice parameter of metald Crystal size of metale
g1
cat) parameter (nm) (nm) (nm)
of HTlcs
(nm)b
a c
Ni3Al 160 0.3025 2.3107 0.4159 0.3525 10.7
Ni2.7Co0.3Al 150 0.3042 2.3291 0.4156 0.3526 8.7
Ni2.7Fe0.3Al 132 0.3022 2.3107 0.4163 0.3532 9.5
Ni2.7Cu0.3Al 171 0.3044 2.3198 0.4158 0.3529 9.6
a
Measured by N2 physical adsorption on the calcined samples.
b
Calculated by a ¼ 2d110 and c ¼ 3d003 (Fig. 1A).
c
Estimated from the NiO(200) peak at 2q ¼ 75 (Fig. 1B).
d
Estimated from the Ni(220) peak at 2q ¼ 91.8 (Fig. 1C).
e
Calculated from the FWHM of the Ni(111) peak at 2q ¼ 52 by the Scherrer equation (Fig. 1C).

formation of alloys [37,40,41]. Besides, the average crystal size
of Ni metal decreases to some degree by alloying, in accor-
dance with the results obtained on the alloy catalysts derived
from the MgeAl based HTlcs [37,41].
The SEM images of the as-synthesized precursors and
those after calcination and reduction are provided in Supple-
mentary materials. All of the synthesized precursors display
the plate-like morphology characteristic of HTlcs (Fig. S1);
after calcination, the plate-like morphology basically disap-
pears, and agglomerates of particles are observed (Fig. S2);
similar agglomerates of particles are observed on the reduced
samples, too (Fig. S3). Upon heating HTlcs up to 500  C, HTlcs
gradually loss the interlayer water, hydroxyl groups, and
interlayer anions (e.g. CO2 3 ); this process results in the
destruction of the layered structure of HTlcs, giving mixed
metal oxides as the product. From the SEM images, there is no
distinct change in the morphology by the presence of cobalt,
iron, and copper.
Fig. 2 shows the H2-TPR profiles of the calcined samples
and the integrated peak areas are given in Table S1. The Ni3Al
calcined sample shows a H2 consumption peak in the range of
350e850  C with the peak maximum at about 650  C, corre-
sponding to the reduction of Ni2þ species in Ni(Al)O. The
reduction temperature for Ni(Al)O is much higher than that
for pure NiO (300e500  C with the maximum at about 425  C
[42]), attributable to the strong interaction of nickel with
aluminum. For the Ni2.7Co0.3Al calcined sample, the H2-TPR
profile displays a large reduction peak at 685  C together with a
small peak at about 280  C. Judging from the reduction tem-
perature, the low-temperature peak is probably due to CoO or
Co3O4. Typically, bulk CoO shows a reduction peak at
300e500  C (Fig. S4), and Co3O4 shows a two-step reduction at
200e500  C [43]. Firstly, the formation of CoO can be excluded
since it is easily oxidized to Co3O4 by calcination in air. Sec-
ondly, if the cobalt species all exist as Co3O4, its peak area
should be 12.9% of the total area (see Supplementary mate-
rials). Nonetheless, the area of the low-temperature peak is
calculated to be only 2.6% of the total area (Table S1). Thus,
this possibility can also be excluded. On the other hand, the
area of the high-temperature peak is close to that of Ni3Al
(Table S1). Hence, the high-temperature peak should be due to
the co-reduction of nickel and cobalt species. Since the

Please cite this article as: Wan C et al., Influence of alloying on the catalytic performance of NieAl catalyst prepared from hydrotalcite-
like compounds for methane decomposition, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2020.10.186
 international journal of hydrogen energy xxx (xxxx) xxx 5

Fig. 2 e H2-TPR profiles of the calcined samples: (a) Ni3Al, (b) Ni2.7Co0.3Al, (c) Ni2.7Fe0.3Al, and (d) Ni2.7Cu0.3Al.

formation of CoO, Co3O4, and CoAl2O4 is excluded by XRD and
H2-TPR measurements, we consider that most of the cobalt
species are incorporated into the NiO lattice forming Ni(Co,Al)
O solid solution. By the way, our previous study [36] shows
that calcination of CoeAl HTlcs leads to Co(Co,Al)2O4 spinel
and the reduction of Co(Co,Al)2O4 occurs in two steps
including from Co(Co,Al)2O4 to Co(Al)O solid solution and from
Co(Al)O to metallic Co. Especially, the reduction of Co(Al)O
starts from ~450 to 500  C with the maximum at ~660e750  C
depending on the Co/Al molar ratio (1e6). The reduction
behavior of Co(Al)O is similar to that of Ni(Al)O. This allows us
to infer that the nickel and cobalt species in Ni(Co,Al)O may be
simultaneously reduced to their metallic state. Based on these
considerations, the high-temperature peak is assigned to the
co-reduction of Ni2þ and Co2þ in Ni(Co,Al)O, whereas the low-
temperature peak is attributed to the reduction of surface
Co2þ and/or Co3þ species arising from the oxidation of Co2þ
during calcination. For the Ni2.7Fe0.3Al calcined sample, the
H2-TPR profile displays a large reduction peak at 630  C and a
small peak at 310  C. The integrated result of the peak area is
similar to the case of Ni2.7Co0.3Al (Table S1), and the formation
of FeO and a-Fe2O3 may be excluded, although the latter
shows one or two-step reduction at 250e600  C [8,44]. It is
deduced that the high-temperature peak is due to the co-
reduction of Ni2þ and Fe3þ in Ni(Fe,Al)O, and the low-
temperature one is probably due to the reduction of surface
Fe3þ species. As for the Ni2.7Cu0.3Al calcined sample, one
sharp peak at 180e250  C with the maximum at 215  C and a
broad peak at 280e800  C are presented, which can be
assigned to the reduction of Cu2þ and Ni2þ species in Ni(Cu,Al)
O, respectively [33]. This assignment is corroborated by the
area ratio of the low-temperature peak to the high-
temperature one (10.4:89.6 Table S1) being consistent with
the Cu/Ni molar ratio in the calcined sample. Interestingly,
although Cu2þ and Ni2þ are reduced with a large temperature
difference, uniform NieCu alloy can still be formed (see
below). It is also noted that the nickel reduction temperature
for Ni(Cu,Al)O is much lower than that of Ni(Al)O, indicating
that nickel reduction is promoted by the presence of copper.
This is similar to the result obtained on CuFe2O4 and may be
explained as due to the spillover-hydrogen from reduced Cu
metal [45].
Fig. 3 shows the HAADF-STEM-EDX results of the Ni2.7-
Co0.3Al, Ni2.7Fe0.3Al, and Ni2.7Cu0.3Al reduced catalysts. It is
somewhat difficult to measure the particle size appropriately
due to overlapping of particles (white-colored spots), but on
the whole most of the particles are below 25 nm. EDX-spot
scan analysis was applied to determine the bulk composi-
tion of several individual particles. As shown in the inserted
numbers, the molar ratios of Ni to Co, Fe, and Cu are similar to
each other and to the catalyst composition, suggesting that
the alloy particles have uniform composition. Furthermore,
EDX-line scan analysis reveals that the alloy components are
evenly distributed across the whole particle, suggesting that
no phase separation occurs. These results highlight the great
advantage of using HTlcs to prepare alloy catalysts over

Please cite this article as: Wan C et al., Influence of alloying on the catalytic performance of NieAl catalyst prepared from hydrotalcite-
like compounds for methane decomposition, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2020.10.186
6 international journal of hydrogen energy xxx (xxxx) xxx

(a-1
Ni/Co = 9.2
• Ni/Co = 8.8 •

•
Ni/Co = 8.1

b-1 Ni/Fe = 9.1

•

• Ni/Fe = 9.5
•
Ni/Fe = 9.8

c-1
Ni/Cu = 9.8
•
• Ni/Cu = 10.6

• Ni/Cu = 9.5

Fig. 3 e HAADF-STEM-EDX analysis of the reduced catalysts: (a) Ni2.7Co0.3Al, (b) Ni2.7Fe0.3Al, and (c) Ni2.7Cu0.3Al. The inserted
values are the molar ratios of Ni to Co, Fe, or Cu in alloy particles.

conventional impregnation method. The latter usually causes
large particles, composition-inhomogeneity, and multiple
alloy phases [40,46]. In HTlcs, all of the metal cations including
nickel, cobalt, iron, copper as well as aluminum are homo-
geneously distributed in the brucite sheet, and upon calcina-
tion this homogeneous dispersion state is well maintained via
the formation of mixed oxide solid solution. We believe that
the homogeneous distribution of the metal cations in the
HTlcs precursors and in the mixed oxide solid solution is
favorable to generate composition-uniform alloy particles.
Catalytic methane decomposition
Fig. 4a shows the in situ TG profiles for methane decomposi-
tion at 600  C over the four catalysts. In general, the catalyst
weight initially increases with time on stream as a result of
carbon accumulation and it finally approaches a constant
value, signifying the stop of carbon growth, i.e., the catalyst is
completely deactivated. From the in situ TG profile, the carbon
growth rate can be calculated (the first derivative of the TG
curve). Fig. 4b shows the change of carbon growth rate with
time on stream. All curves present an initial increase in the
reaction rate and pass through a maximum, after that they
continuously decline. The initial carbon growth rate is com-
parable for the four catalysts, and the maximum growth rate
is 0.42, 0.41, 0.40, and 0.35 mg-C g1 1
cat min , respectively. This
indicates that the maximum growth rate is affected by NieCu
alloying to a larger extent than by alloying Ni with Co and Fe.
On the other hand, the carbon growth rate decreases with
increasing time-on-stream and the degree to which the rate

Please cite this article as: Wan C et al., Influence of alloying on the catalytic performance of NieAl catalyst prepared from hydrotalcite-
like compounds for methane decomposition, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2020.10.186
 international journal of hydrogen energy xxx (xxxx) xxx 7

Fig. 4 e (a) In situ TG profiles, (b) carbon growth rates, (c) carbon yields, and (d) H2 yields for methane decomposition at 600  C
over the Ni3Al, Ni2.7Co0.3Al, Ni2.7Fe0.3Al, and Ni2.7Cu0.3Al catalysts.

decreases is strongly dependent on the catalysts. A rapid
decrease in the carbon growth rate is observed on Ni3Al, fol-
lowed by Ni2.7Co0.3Al and Ni2.7Fe0.3Al, whereas it is signifi-
cantly slowed down on Ni2.7Cu0.3Al. After 300 min of reaction,
Ni2.7Cu0.3Al still displays a carbon growth rate of 0.08 mg-C
mg1 1
cat min . From the carbon growth rates at the maximum
and zero (at the end of test for Ni2.7Cu0.3Al), the average
deactivation rate is estimated to be 15.9  103, 8.8  103,
6.9  103, and 0.9  103 mg-C mg1 1
cat min , respectively. It
is apparent that NieCu alloying effectively inhibits the rapid
deactivation of catalyst. From the in situ TG profiles, the total
catalytic lifetimes are determined to be 40, 62, and 78, and
>300 min, and the final yields of carbon produced at the end of
test are 11.5, 20.0, 24.1, and 66.3 mg-C mg1 cat for the Ni3Al,
Ni2.7Co0.3Al, Ni2.7Fe0.3Al, and Ni2.7Cu0.3Al catalysts, respec-
tively. This result reveals that alloying Ni with 10 at% Co, Fe,
and Cu enhances the catalytic lifetime and carbon yield and
NieCu alloying is the most effective.
To examine the morphology of carbon produced on the
catalysts, SEM and TEM measurements were performed.
Some typical SEM and TEM images are presented in Figs. 5 and
6, respectively. From the SEM images, the carbon morphology
is similar for Ni3Al, Ni2.7Co0.3Al, and Ni2.7Fe0.3Al catalysts.
There are many carbon filaments, whose diameters are basi-
cally below 50 nm, and at the tip of the carbon filaments are
the metal particles. The TEM images further indicate that the
carbon filaments are carbon nanotubes (CNTs). From the TEM
images, the CNT diameters were measured, which are
distributed in a relatively narrow range of 10e50 nm
(Fig. 7aec). It is also noted that the metal particles are pre-
sented in several states. For example, some of them are
located at the tip of CNTs and presented as pear-shaped or
elongated (Figs. 6a-2; a-3; b-2; c-2), whereas some of them are
presented as small fragments and included in the cavities of
CNTs (Figs. 6a-2; b-3; c-3). Both the metal particles and the
metal fragments are severely covered with carbon layers (Figs.
6a-4; b-4; c-4). As a result, they are no more active for methane
decomposition, and this should be responsible for the catalyst
deactivation. On the other hand, a different morphology of
carbon is observed on Ni2.7Cu0.3Al. Both the SEM and TEM
images clearly reveal the formation of rough filaments and
this type of carbon filaments is mainly due to carbon nano-
fibers (CNFs) as indicated from Figs. 6(d-1; d-2). Besides, the
diameters of CNFs are distributed in a wide range (Fig. 7d); the
largest one is about 180 nm and those above 50 nm account for
approximately 61%. At the tip of such CNFs, big metal particles
(130e180 nm) can also be observed. It is worth noting that
there are no dense carbon layers on the surface of the big
metal particles (Figs. 6d-4), suggesting that they are still active
for methane decomposition. This may explain the TG result
that carbon continues to grow on this catalyst even at the end
of test. By the way, it is occasionally observed the presence of
CNTs (Fig. S5). In this case, the diameters of CNTs and metal
particles are similar to those of the other catalysts.

Please cite this article as: Wan C et al., Influence of alloying on the catalytic performance of NieAl catalyst prepared from hydrotalcite-
like compounds for methane decomposition, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2020.10.186
8 international journal of hydrogen energy xxx (xxxx) xxx

Fig. 5 e SEM images of the used catalysts: (a) Ni3Al, (b) Ni2.7Co0.3Al, (c) Ni2.7Fe0.3Al, and (d) Ni2.7Cu0.3Al.

Raman spectroscopy was further applied to investigate the
influence of alloying on the carbon graphitization degree. The
obtained spectra are shown in Fig. 8. In all cases, there are two
strong bands at about 1350 and 1595 cm1 together with a
small shoulder peak at 1605 cm1. The former can be assigned
to the structural disorder/defects of graphite (D band), and the
latter can be ascribed to the in-plane carbon-carbon stretching
vibration of graphite layer (G band), where carbon atoms are
bonded in the hexagonal lattice with a sp2 hybrid mode, while
the shoulder peak (D0 band) is related to the imperfect graphite
or disordered carbons [47,48]. Generally, the intensity ratio of D
band to G band (ID/IG) is related to the graphitization degree,
i.e., the higher the ID/IG ratio is, the lower the graphitization
degree is. By curve fitting of the three bands using Lorentzian
function [48,49], the ID/IG ratio is calculated and given in Fig. 8.
Notably, the ID/IG ratio is affected by alloying, which decreases
from 1.72 for Ni3Al to 1.66 for Ni2.7Co0.3Al and 1.43 for Ni2.7-
Fe0.3Al, respectively, indicating that the graphitization degree
is increased by alloying Ni with Co and Fe. On the contrary, the
ID/IG ratio increases markedly to 2.21 for Ni2.7Cu0.3Al, suggest-
ing that NieCu alloying decreases the graphitization degree.
The influence of alloying of Ni with Co, Fe, and Cu on the
carbon graphitization degree is in general agreement with
those reported in Refs. [16,50,51]. As shown in the TEM images
(Fig. 6), CNTs are formed on the Ni3Al, Ni2.7Co0.3Al, and Ni2.7-
Fe0.3Al catalysts, while CNFs are formed on the Ni2.7Cu0.3Al
catalyst. Thus, the decrease of carbon graphitization degree by
NieCu alloying is attributable to the formation of CNFs,
because the graphitization degree of CNFs is lower than that of
CNTs. On the other hand, the increase of carbon graphitization
degree by NieCo alloying and NieFe alloying may be explained
as due to the change of graphitic arrangement by the formation
of hollow nanofilaments close to the nanotube structure [52].
To get more information about the state of metal particles
after reaction, HAADF-STEM measurement was done. Fig. 9
shows some typical HAADF-STEM images as well as the
particle-size distributions. For the Ni3Al, Ni2.7Co0.3Al, and
Ni2.7Fe0.3Al used catalysts, most of the metal particles are
below 60 nm. As for the Ni2.7Cu0.3Al used catalyst, in addition to
the metal particles <60 nm, some particles above 100 nm are
presented. This observation is somewhat similar to that of
carbon-diameter distribution (Fig. 7). As well known, the size of
metal particle determines the diameter of carbon filament
formed on it, i.e., the diameters of metal particle and carbon
filament are similar. Nonetheless, the comparison between
Figs. 7 and 9 indicates that the size distribution of metal par-
ticles is shifted to small-size region as compared to the carbon
diameter distribution. This difference can be explained by that
the metal particles were broken down to small fragments (e.g.
Figs. 6b-3; c-3). The average particle size (Sauter mean diam-
P 3
eter) was calculated according to the equation: d ¼ nidi /
P 2
nidi , in which di means the diameter of particle and ni is the
number of the particles with diameter of di. As shown in Fig. 9,
the metal size after reaction (23.6e121.4 nm) is much larger
than the size (8.7e10.7 nm) determined by XRD on the freshly
reduced catalyst, indicative of the sintering of metal particles
during the reaction. In particular, the Ni2.7Cu0.3Al used catalyst
shows the largest metal size, about 4e5 times that of the other

Please cite this article as: Wan C et al., Influence of alloying on the catalytic performance of NieAl catalyst prepared from hydrotalcite-
like compounds for methane decomposition, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2020.10.186
 international journal of hydrogen energy xxx (xxxx) xxx 9

a-1 a-2 a-3 a-4

b-1 b-2 b-3 b-4

c-1 c-2 c-3 c-4

d-1 d-2 d-3 d-4

500 nm

Fig. 6 e TEM images of carbon formed by CH4 decomposition over the catalysts: (a) Ni3Al, (b) Ni2.7Co0.3Al, (c) Ni2.7Fe0.3Al, and
(d) Ni2.7Cu0.3Al.

used catalysts. It is thus concluded that NieCu alloy particles
are aggregated into bigger particles than Ni metal and NieCo
and NieFe alloy particles under the reaction conditions.
From the results presented above, it is evident that the
influence of NieCu alloying is more pronounced than those of
NieCo alloying and NieFe alloying; NieCu alloying not only
significantly enhances the catalytic lifetime and carbon yield,
but also remarkably changes the carbon morphology. In terms
of carbon yield, the catalysts can be ranked in the order of
Ni2.7Cu0.3Al >> Ni2.7Fe0.3Al > Ni2.7Co0.3Al > Ni3Al. There have
been several studies investigating CMD over the Ni catalysts
modified with cobalt, iron, and copper. For example, Torres
et al. [52] used fusion method to prepare bimetallic NieCo/
Al2O3, NieCu/Al2O3, and NieFe/Al2O3 catalysts (molar ratio Ni/
Al ¼ 4; Co/Ni ¼ Cu/Ni ¼ Fe/Ni ¼ 0.08). The catalytic result of
CMD at 650  C in a fixed bed reactor showed that Cu addition
had a positive effect on the catalytic stability and carbon yield,
while Co and Fe addition presented a negative one. According
to the carbon yield, the catalysts could be ranked in the order
of NieCu/Al2O3 >> Ni/Al2O3 > NieCo/Al2O3 ~ NieFe/Al2O3.
Besides, the NieCu/Al2O3 catalyst produced wide carbon
nanofibers with diameters of 150e600 nm; in contrast, there
was no significant difference in the carbon morphology for the
NieCo/Al2O3, NieFe/Al2O3, and Ni/Al2O3 catalysts, all of which
produced narrow carbon nanofilaments with a tube-like
structure, similar to our result. In another study, Wang et al.
[16] examined the effect of additives (5 wt% Cu, Mn, Pd, Co, Zn,
Fe, Mg) on the catalytic activity and stability of 60 wt% Ni/
Al2O3, where the catalysts were prepared by co-impregnation
method and tested for CMD at 650  C in a fixed-bed reactor. It
was shown that the addition of Fe, Co, and especially Cu
enhanced the catalytic activity and stability. During 250 min
of test, the carbon yield on the catalysts was NieCu/Al2-
O3 >> NieCo/Al2O3 > Ni/Al2O3 > NieFe/Al2O3. Furthermore,
Raman spectra indicated that the carbon graphitization de-
gree was increased by the addition of Co and Fe and decreased
by the addition of Cu, in accordance with our result. Although
there are some differences in the influence of NieCo alloying
and NieFe alloying, these reports confirm the significant effect
of NieCu alloying observed in this work.

Please cite this article as: Wan C et al., Influence of alloying on the catalytic performance of NieAl catalyst prepared from hydrotalcite-
like compounds for methane decomposition, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2020.10.186
10 international journal of hydrogen energy xxx (xxxx) xxx

Fig. 7 e Diameter distributions of carbon filaments formed on (a) Ni3Al, (b) Ni2.7Co0.3Al, (c) Ni2.7Fe0.3Al, and (d) Ni2.7Cu0.3Al.

The significant effect of NieCu alloying on the CMD reac-
tion is likely associated with the structural change of metal
particles during reaction. There have been many reports on
Fig. 8 e Raman spectra of carbon formed by CH4
decomposition: (a) Ni3Al, (b) Ni2.7Co0.3Al, (c) Ni2.7Fe0.3Al,
and (d) Ni2.7Cu0.3Al.
the aggregation of metal particles under the reaction condi-
tions of methane decomposition [53,54]. For example, Tak-
enaka et al. [53] investigated the structural change of Ni
species on a Ni/SiO2 catalyst during methane decomposition
by means of XRD and XANES/EXAFS. They showed that Ni
metal particles were aggregated at a very early period of
methane decomposition. After the initial aggregation, the
structure of Ni metal did not change appreciably when the
catalyst was active for decomposing methane. They suggested
that the aggregation of Ni metal particles occurred by contact
of methane with the Ni/SiO2 catalyst. Similar phenomenon is
expected to occur on the hydrotalcite-derived catalysts. As
indicated from the TEM and HAADF-STEM measurements, the
aggregation of metal particles occurs to a much higher extent
on Ni2.7Cu0.3Al than on Ni3Al, Ni2.7Co0.3Al, and Ni2.7Fe0.3Al.
This means that NieCu alloy tends to aggregate into big par-
ticles than Ni metal and NieCo and NieFe alloys. One possible
explanation for this is due to the difference of melting point/
Tammann temperature between Ni, Co, Fe, and Cu. The order
of melting point is Fe (1537  C) > Co (1495  C) > Ni
(1455  C) >> Cu (1084  C), and the melting point of NieCu alloy
was reported to be between those of Ni and Cu [55]. That is to
say, NieCu alloying decreases the melting point of Ni metal.
Tammann temperature (minimum temperature for solid-
state mobility) is expected to follow a similar trend. Gener-
ally, Tammann temperature is about 0.5 times the melting
point (in degree Kelvin). Tammann temperature of Ni is 691  C
[56], while Tammann temperature of Cu is estimated to be
405  C [57], which is much lower than the reaction

Please cite this article as: Wan C et al., Influence of alloying on the catalytic performance of NieAl catalyst prepared from hydrotalcite-
like compounds for methane decomposition, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2020.10.186
 international journal of hydrogen energy xxx (xxxx) xxx
a b
100 nm 100 nm
Fig. 9 e HAADF-STEM images and particle-size distributions of the used catalysts: (a) Ni3Al, (b) Ni2.7Co0.3Al, (c) Ni2.7Fe0.3Al,
and (d) Ni2.7Cu0.3Al.
temperature (600  C) adopted in this work. Therefore, Cu has a
higher mobility than Ni at 600  C. Higher mobility can also be
expected for NieCu alloy as compared to Ni metal. Thus, it is
reasonable to deduce that NieCu alloy is readily aggregated
into big particles under the present reaction conditions. As
can be expected, the formation of big particles would affect
the CH4 activation and carbon growth. Firstly, big particles are
less active for CH4 activation than small particles. For
methane decomposition and reforming reactions, CH4 disso-
ciation on metal surface is considered as the rate-determining
step and structure-sensitive [3]. Small particles have more
coordination-unsaturated sites (e.g. kinks, steps) and are
more active for CH4 dissociation than big particles [58,59].
Besides, they have more surface active sites than the big ones
when the metal loading is the same. As a result, small parti-
cles are favored for CH4 activation and show higher carbon
growth rate. This is consistent with the DTG result that the
maximum carbon growth rate for Ni2.7Cu0.3Al is lower than
the other catalysts. Secondly, big particles may be favorable
for bulk diffusion of carbon. Takenaka et al. [48] consider that
CNTs are formed by the diffusion of carbon atoms on the
surface of Ni metal particles (surface diffusion), whereas CNFs
are formed by the diffusion of carbon atoms through the Ni
metal particles (bulk diffusion). Accordingly, carbon growth
may proceed via surface diffusion on the Ni3Al, Ni2.7Co0.3Al,
and Ni2.7Fe0.3Al catalysts and via bulk diffusion on the Ni2.7-
Cu0.3Al catalyst. We think that big NieCu alloy particles have
higher driving force for carbon diffusion (higher carbon con-
centration gradient in the particle), thus carbon atoms on the
metal surface can readily diffuse through the metal particle
forming CNFs at the other side of the particle. Thirdly, big
particles are benefited to long catalytic life. Studies indicate
that there exists some optimal size of Ni particles for long
catalytic life [48,54,60]. Takenaka et al. [48] reported that Ni/
Please cite this article as: Wan C et al., Influence of alloying on the catalytic performance of NieAl catalyst prepared from hydrotalcite-
like compounds for methane decomposition, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2020.10.186
11
c d
100 nm 100 nm
SiO2 with Ni metal particles of 60e100 nm showed the longest
lifetime for methane decomposition at 500  C. Similar result is
obtained on the Ni2.7Cu0.3Al catalyst, where particles between
60 and 180 nm are formed and the longest catalytic life is
achieved. From the TEM measurement, there is no observa-
tion of dense carbon layers on the big particles so that they
should be still active for methane decomposition, demon-
strating that these big particles have longer catalytic life.
Generally, catalytic life (or deactivation rate) is determined by
the ratio of carbon formation rate to its diffusion rate. Big
particles have lower CH4 dissociation rate and higher carbon
bulk-diffusion rate; this is favorable for carbon growth, lead-
ing to longer catalytic life. In addition to the size effect, other
effect induced by NieCu alloying such as enhancements in
hydrogen mobility, carbon solubility, and carbon diffusion
rate may also play a role [28,61]. To better understanding the
great effect of NieCu alloying on the catalytic activity, stabil-
ity, and carbon morphology, further studies are underway in
our laboratory.
Conclusions
Nickel-cobalt, nickel-iron, and nickel-copper alloy catalysts
have been prepared from hydrotalcite-like compounds
(HTlcs). Upon calcination at 500  C, the HTlcs precursors are
transformed into a mixed oxide solid solution, where cobalt,
iron, copper as well as aluminum ions are all incorporated into
the nickel oxide. After reduction at 800  C, the mixed oxide
solid solution is completely reduced to form alloy nano-
particles with mean crystal size of 8.7e9.6 nm. HAADF-STEM-
EDX reveals that the alloy particles are composition-uniform.
This should be attributed to the homogeneous distribution of
the metal cations during the catalyst preparation. In methane
12 international journal of hydrogen energy xxx (xxxx) xxx
decomposition at 600  C, all of the alloy catalysts show higher
carbon yield and longer catalytic life than the Ni counterpart.
Especially, the carbon yield on the NieCu catalyst is more than
5 times that on the Ni catalyst. In terms of carbon yield, the
activity order is Ni2.7Cu0.3Al >> Ni2.7Fe0.3Al > Ni2.7Co0.3Al > Ni3-
Al. Alloying Ni with Co and Fe has no significant affect on the
carbon morphology, where carbon nanotubes are formed. In
contrast, the carbon morphology is remarkably changed by
NieCu alloying, which gives carbon nanofibers as the main
product. TEM and STEM reveals that NieCu alloy particles are
aggregated into big particles (60e180 nm) under the reaction
conditions, and this may account for the significant effect of
NieCu alloying.
Declaration of competing interest
We declare that there are no known competing financial in-
terests or personal relationships that could have appeared to
influence the work reported in this paper.
Acknowledgement
The authors acknowledge financial supports from NSFC
(21576052 & 21878051) and Program of New Century Excellent
Talents in University, Fujian Province, China.
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.ijhydene.2020.10.186.
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Please cite this article as: Wan C et al., Influence of alloying on the catalytic performance of NieAl catalyst prepared from hydrotalcite-
like compounds for methane decomposition, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2020.10.186