i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 4 ( 2 0 1 9 ) 2 8 0 6 5 e2 8 0 7 6

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Nickel based catalysts for methane dry reforming:

Effect of supports on catalytic activity and stability

Cristina Pizzolitto a, Eva Pupulin a, Federica Menegazzo a, Elena Ghedini a,

Alessandro Di Michele b, Maurizio Mattarelli b, Giuseppe Cruciani c,
Michela Signoretto a,*
a
CATMAT Lab, Department of Molecular Sciences and Nanosystems, Ca’ Foscari University Venice and INSTM RU
of Venice, Via Torino 155, I-30172, Venezia Mestre, Italy
b
Department of Physics and Geology, University of Perugia, Via Pascoli 1, I-06123, Perugia, Italy
c
Department of Physics and Earth Sciences, University of Ferrara, Via Saragat 1, I-44100, Ferrara, Italy

highlights graphical abstract

Nickel-based catalysts were

investigated for Methane dry
reforming (MDR).

Different supports (Ceria, zirconia,
alumina, silica, titania) were
studied.

Silica and zirconia present
moderated activity due to the poor
support stability.

Most promising results were ob-
tained with ceria and alumina-
based catalysts.

Alumina catalyst has proved to be
the most stable towards MDR.

article info abstract

Article history: Methane dry reforming (MDR) is a promising process for syngas production through the
Received 13 May 2019 valorisation of two of the main Greenhouse gases. Despite the high endothermicity, it
Received in revised form should be carried out at low temperature to directly use the syngas for Fischer-Tropsch
27 August 2019 reaction and oxygenated chemical production. The catalyst plays a key role in this pro-
Accepted 4 September 2019 cess as it must encourage syngas formation by limiting coke deactivation. This work
Available online 4 October 2019 focusses the attention on the effect of different supports in the activity and stability of
nickel-based catalysts. In particular, MDR has been studied at relatively low temperature,
Keywords: 500  C, to deeply investigate how the support influences the reaction pathway. Ceria, zir-
Ni catalysts conia, alumina, silica and titania were considered and the morphological and structural
Methane dry reforming features of the materials were analysed via N2-physisorption, AAS, TPR, XRD, CO2-TPD, and
Catalysts' deactivation SEM techniques. Moreover, by analysing the spent catalysts, it was possible to identify the
Support effect causes of catalysts deactivation. Titania based catalyst is not active for MDR, while silica

* Corresponding author.
E-mail address: miky@unive.it (M. Signoretto).
https://doi.org/10.1016/j.ijhydene.2019.09.050
0360-3199/© 2019 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
28066 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 4 ( 2 0 1 9 ) 2 8 0 6 5 e2 8 0 7 6

and zirconia present moderated activity due to the poor support stability. Most promising
results are obtained with ceria and alumina-based catalysts; for these materials, 70-h re-
action was carried out and alumina catalyst has proved to be the most stable towards MDR
at low reaction temperature with a stable H2 yield of 25% .
© 2019 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

Introduction CH4 ¼ C þ H2 DH0 ¼ 74.9 kJ/mol (5)

Drastic changes into the energy sector must be developed to

2CO ¼ C þ CO DH0 ¼ 172.4 kJ/mol (6)
observe the Paris Agreement stipulated in December 2015. The
aim of this pact, written below 195 countries, is to restrict the
CO2 þ 2H2 ¼ C þ 2H2O DH0 ¼ 90 kJ/mol (7)
increase of the average global temperature below 2  C above
pre-industrial levels [1]. In this contest, CO2 and CH4 are the
H2 þ CO ¼ H2O þ C DH0 ¼ 131.3 kJ/mol (8)
two main components that contribute to the Greenhouse
gases (GHGs) emissions, for 76% and 15.8% respectively [2].
Methane decomposition requires high reaction tempera-
Accordingly, capture, storage, and utilization of these gases
ture to occur, generally above 557  C, while the other re-
could be a proper solution to settle the problem [3]. For this
actions, being more exothermic, are developed mainly under
purpose, catalytic conversion of these gases into syngas,
700  C [7,8]. Wang et al. [9] reported that a temperature above
trough methane dry reforming (MDR, reaction 1), has attracted
850  C is required to achieve high conversion and to limit coke
much attention in recent years. Indeed, methane dry
deactivation. Nevertheless, the high-temperature condition
reforming combines the limitation of GHGs emission with the
involves a huge cost of heating and loss of energy efficiency. In
production of an important industrial resource [4].
fact, syngas is generally used in Fischer-Tropsch synthesis,
that works under 300  C. For this reason, this paper focuses
CH4 þ CO2 ¼ 2 CO þ 2H2 DH0 ¼ 247 kJ/mol (1) the attention on the evaluation of a catalyst able to work at the
low-temperature condition with high stability and activity. In
Syngas produced by this reaction has a H2/CO ratio close to
particular, supports for nickel-based catalysts have been
unit; this can be used to prepare acetic acid, dimethyl ether
studied. Nickel, indeed, is the most common non-noble metal
and oxo-alcohols. Moreover, by the addition of a Water Gas
used in reforming reaction; multiple reviews summarise the
Shift step, this ratio can be easily tuned to 2 and used in
effect of supports on nickel stability and activity for MDR but
Fischer-Tropsch and methanol synthesis. Nevertheless, the
all these works pay the attention to above 600  C reaction
applicability of this reaction at the industrial level is restricted
temperature [10e13]. Reducing reaction temperature should
due to the high endothermicity of the process. In comparison
be an important step to limit energy demand but also to
with methane steam reforming (MSR, reaction 2) and partial
reduce nickel sintering that is the main drawback of this
oxidation (PO, reaction 3), it requires a higher amount of en-
active phase. Therefore, ceria, zirconia, alumina, silica and
ergy to be activated due to the strong stability of CO2 molecule
titania [14e19] have been evaluated as support of nickel
(dissociation energy of COeO: 526 kJ/mol) [5].
catalyst. These materials are the most common supports in
catalysis and they own different properties such as surface
CH4 þ H2O ¼ 3H2 þ CO DH0 ¼ 206 kJ/mol (2)
area, acid-base features and redox ability. Moreover, they can
differently affect nickel's stability and reducibility. In this
CH4 þ ½ O2 ¼ 2H2 þ CO DH0 ¼ 36 kJ/mol (3)
work, all these properties have been evaluated via N2-phys-
isorption, TPR, XRD, CO2-TPD, and SEM techniques. Moreover,
In addition, the equilibrium of MDR process is controlled by
as reported by Jang et al. [10], carbon formation is not only
the simultaneous reaction of reverse water gas shift (RWGS,
connected with the operation condition, but it is strongly
reaction 4) that increases the conversion of CO2, decreasing
dependent on the type of catalyst. In fact, as reported by Seo
the H2 yield.
et al. [20], methane dry reforming reaction arise via two main
steps: decomposition of methane and CO2 dissociation. The
CO2 þ H2 ¼ CO þ H2O DH0 ¼ 36 kJ/mol (4)
first reaction takes place through the CH3 adsorption on the
top of Ni atom and it's generally favoured on the nickel step
For this reason, the catalyst has a strongly influence on
sites than on the nickel terraces. Therefore, small nickel
the efficiency of the process because it must activate re-
nanoparticles present more activity than the bigger one.
agents over the surface, limiting unwanted reactions.
Moreover, after the decomposition of CH4, carbon atoms are
Methane decomposition (reaction 5), CO disproportion (re-
left on the surface. To maintain high activity and stability of
action 6), hydrogenation of CO2 (reaction 7) and CO (reaction
the catalyst, oxidation of on carbon atoms is necessary and it
8) are the main reactions responsible for carbon formation
can happen by the interaction with atomic oxygen. The CO2
during MDR [6].
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 4 ( 2 0 1 9 ) 2 8 0 6 5 e2 8 0 7 6
dissociation is the main route for oxygen formation; it is re-
ported that high basicity properties of the catalyst can guar-
antee a proper CO2 dissociation. Therefore, support has
crucial importance in methane dry reforming reaction since it
must interact strongly with nickel phase guaranteeing a good
dispersion and preventing its sintering. Moreover, it must
have a good balance of acid-basic and redox properties to limit
coke formation. For all these reasons, a deep analysis of spent
catalysts was carried out via SEM and Raman spectroscopy to
correlate the catalysts deactivation with their features. For all
these reasons, considering how temperature conditions can
affect catalytic properties, especially for thermal and me-
chanical stability and redox ability, it was decided to carry out,
for the first time, MDR reaction at 500  C in order to evaluate
and compare the activity of the most common supports (ceria,
zirconia, alumina, silica and titania) at this low temperature
condition. It is important to point out the relevance of
decrease the reaction temperature since it can be an energetic
solution for the direct use of syngas produced by MDR.
Experimental
Supports preparation
Ceria support (denoted as Ce) was synthesized by precipita-
tion of an aqueous solution of (NH4)2Ce(NO3)6 (Sigma Aldrich)
using urea. The solution was maintained at 100  C for 6 h.
After that, the precipitate was washed in boiling deionized
water and dried at 110  C for 18 h. Calcination was performed
at 550  C under air flow (30 mL/min) for 4 h.
Zirconia support (denoted as Zr) was synthesized by pre-
cipitation of an aqueous solution of ZrOCl28H2O (Sigma
Aldrich) with NH3 at constant pH ¼ 8.5. The solution was aged
at 90  C for 20 h. The precipitate was washed and dried at
110  C for 18 h. Then zirconium hydroxide was calcined at
550  C in flowing air (30 mL/min) for 3 h.
A commercial g-alumina support (Condea) was used
(denoted as Al).
Silica based support, a ordered mesoporous SBA-15
(denoted as Si) was synthesized following the procedure re-
ported by Ghedini et al. [21]. For the preparation of SBA-15, 8 g
of Pluronic 123 were dissolved in an aqueous solution of HCl
(Sigma Aldrich), then the silica precursor (TEOS, Aldrich, pu-
rity 98%) was added dropwise. The system was aged at the
same temperature for 20 h, then at 100  C for 48 h in a her-
metically sealed vessel. The solid was extensively washed
with distilled water and dried at 60  C for 18 h. Calcination step
was performed at 500  C in flowing air (50 mL/min STP) for 6 h.
Titania support (denoted as Ti) was prepared by precipi-
tation of aqueous solution of TiOSO4 xH2SO4 xH2O (Aldrich)
with NaOH (9 M) at constant pH of 5.5. The precipitate was
aged at 60  C for 20 h, then repeatedly washed with distilled
water and finally dried at 110  C for 18 h. Calcination was
carried out at 550  C in flowing air (30 mL/min) for 4 h.
Catalyst preparation
Nickel was introduced on the calcined sample via incipient
wetness impregnation with a proper amount of Ni(NO3)2*6H2O
28067
(Sigma Aldrich) aqueous solution in order to obtain 10 wt% of
nickel on the material. After drying at 110  C for 18 h, calci-
nation was carried out at 550  C in flowing air (30 mL/min) for
4 h.
Samples are denoted as NiCe, NiZr, NiAl, NiSi and NiTi.
Characterizations
Specific surface areas and pore size distributions were evalu-
ated from N2 adsorption/desorption isotherms at 196  C
using a Tristal II Plus Micromeritics. Surface area was calcu-
lated using B.E.T. equation [22] while pore size distribution
was determined by the B.J.H. method [23], applied to the N2
desorption branch of the isotherm.
The metals amount was determined via atomic absorption
spectroscopy (AAS) using a Perkin-Elmer Analyst 100. Prior to
the analysis, each sample was disintegrated in aqua regia
under reflux for 5 h.
The Temperature Programme Reduction (TPR) measure-
ments were carried out by placing the catalyst in a quartz
reactor heating in a reductive mixture flow (5% H2/Ar 40 mL/
min) at a heating rate of 10  C/min from 25 to 800  C. H2
consumption was monitoring by a Gow-Mac TCD detector.
X-ray powder diffraction (XRD) analyses were carried out
by a Bruker D8 Advance diffractometer equipped with a Si(Li)
solid state detector (SOL-X) and a sealed tube providing Cu Ka
radiation. The quantitative phase analysis and crystal size
determination of the support and metal phases in the samples
were obtained by the Rietveld refinement method. The sam-
ples were reduced in H2 flow for 1 h at 550  C before the
analysis.
Temperature programmed desorption using CO2 as probe
molecule (CO2-TPD) was carried out in the same lab-made
equipment used for TPR. Samples were exposed to CO2 pul-
ses of 0.7 mL each to obtain over saturation of the samples.
After cleaning the surface with He flow (30 mL/min) for 0.5 h
at room temperature, samples were heated with a tempera-
ture rate of 10  C/min from 25  C to 800  C in He flow
(30 mL/min).
SEM images of fresh and used samples were obtained using
a Field Emission Gun Scanning Electron Microscopy LEO 1525,
after metallization with graphite. The images were acquired
by Inlens detector while elemental composition was deter-
mined using Bruker Quantax EDS.
Raman spectra were collected using a micro-Raman setup
equipped with a solid state laser operating at l ¼ 532 nm,
whose power was reduced to less than 10 mW to decrease the
thermal effects on the sample. The Raman setup consists of
iHR320 Triax Imaging Spectrometer (HORIBA Jobin Yvon)
coupled in an home-made configuration with a CM1 micro-
scope purchased from the JRS Scientific Instruments
(Switzerland). The microscope was equipped with a 20X long
working distance objective with a numerical aperture,
N.A. ¼ 0.42, providing a lateral resolution of about 2 mm. The
VV polarized Raman signal collected in back scattering
configuration was dispersed by a 600 grooves/mm grating and
acquired by a liquid nitrogen cooled CCD detector
(1024256pixels), allowing the simultaneous acquisition of
the Raman shift in the 100e3500 cm 1 spectral range with a
resolution of about 10 cm1. Before comparing the vibrational
28068 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 4 ( 2 0 1 9 ) 2 8 0 6 5 e2 8 0 7 6

peaks, the background contribution due to luminescence,

Table 1 e Physical-chemical properties of nickel
particularly intense for NiZr, was modelled by a spline curve
supported samples (Surface area calculated via B.E.T.
and subtracted [24]. equation, Pore volume, Average pore diameter, Effective
amount of nickel determined via Atomic Adsorption,
Catalytic tests Nickel particle size calculated via Rietveld and NiO
particle size distribution calculated via EDX).
The catalytic tests were performed with a PID reference NiCe NiZr NiAl NiSi NiTi
reactor (Process Integral Development Eng&Tech) coupled to a 2
Surface Area (m /g) 94 53 150 342 30
gas-chromatograph (HP 6890) as reported in Scheme 1. Pore Volume (cm3/g) 0.15 0.17 0.32 0.49 0.06
Microactivity-Effi reactor is an automatic computerized high- Average pore 5.8 12.2 7.8 6.4 8.2
pressure catalytic reactor, which includes the valves and diameter (nm)
process layout inside a hot box to avoid possible condensation Effective Ni 8.5 8.3 7.5 10.0 8.0
of volatile products, while also preheating the reactants effi- amount (wt%)
Ni particle size (nm) 17 11 20
ciently. The catalyst, after calcination, is pelletized and
NiO particle size 13 ± 4 20 ± 4 17 ± 3 19 ± 3; 73 ± 12 17 ± 3
reduced into small pellets with an average size of 0.3e0.4 mm. distribution (nm)
The reactor is loaded with 150 mg of catalyst mixed with SiC
reaching 1 mL of catalytic bed. Reduction of the catalyst was
performed in situ under H2 flow (30 mL/min) for 1 h at 500  C. Indeed, in heterogeneous catalysts, high surface area, strong
After the reduction, catalytic surface was cleaned by flowing interaction between support and metals and active phase's
helium (180 mL/min) for 1 h. Catalytic tests were carried out at dispersion are important parameters that must be studied.
500  C for 18 and 70 h using CH4/CO2/He reagent mixture (5/5/ First, N2-physisorption was performed; B.E.T. specific surface
90) in a total flow of 200 mL/min. After the analysis, the area and pore size distribution are reported in Table 1 mean-
following data were calculated: while N2 adsorption-desorption isotherms and corresponding
BJH pore size distributions are presented in Fig. 1. All graphs
fH2 out
H2 Yield ð%Þ ¼ *100 (9) show type IV isotherms, according to IUPAC classification,
2 fCH4 in
although differences in surface area and pore volume are
clear. Silica based material (NiSi), which is a SBA-15, has, as
fH2out
H2 =CO ¼ (10) expected, the highest surface area value; this can be agreed
fCO out
with the previous samples prepared by with the same syn-
thetic approach [25]. Indeed, this catalyst presents an H1
Results and discussions hysteresis loop, characteristic of mesoporous material with
high specific surface area and narrow pore size distribution.
Preliminary characterizations Moreover, others present an H3 type hysteresis, typical of
materials that don't have a well-defined structure with wider
Preliminary characterizations were carried out to evaluate the pore size distribution, as its visible in Fig. 1 (lower part).
morphological and structural properties of the materials. Alumina and ceria supports guarantee a good surface area,

Scheme 1 e Lab set-up.

 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 4 ( 2 0 1 9 ) 2 8 0 6 5 e2 8 0 7 6
Fig. 1 e N2 physisorption isotherms (upper part) and BJH
pore size distributions (lower part) for all the catalysts.
around 100 m2/g. On the other hand, the values of surface area
for titania and zirconia are quite low. The effective amount of
nickel was also determined via atomic adsorption analysis
and the results are reported in Table 1. As can be seen, NiCe,
NiZr, NiAl and NiTi present lower amount of nickel in com-
parison with the nominal amount (10 wt%).
TPR analysis were carried out to identify NiO reduction
temperature and the interactions between NiO and supports.
Indeed, nickel has only one possible reduction stage, from
Ni2þ to Ni0. Thus, different peaks in TPR analysis are associ-
ated with different interactions between support and active
phase [26]. As can be seen in TPR spectrums of all materials,
two nickel species are visible (Fig. 2). NiCe catalyst presents
two defined reduction peaks, at 250  C and 350  C associated
with nickel that weakly and strongly interacts with the sup-
port, respectively [27]. The behaviour of NiZr, NiSi and NiTi is
quite similar to ceria, despite the peaks appear at higher
temperature. So, for all these catalysts, it is possible to affirm
the existence of two reduced species which were weakly and
strongly interacted with the support. In fact, the higher is the
reduction temperature of nickel species, the stronger is the
interaction with the support. However, the four mentioned
catalysts are different in the relative area of the two peaks.
Regarding NiCe and NiZr, the low-temperature peak is more
moderate than the one at high temperature; on the contrary,
for NiSi and NiTi, the low temperature reduction peak is more
intense than the high temperature one. This suggests that for
28069
Fig. 2 e TPR profile of the catalysts.
NiCe and NiZr, more NiO species have strong interaction with
the support while for NiSi and NiTi, there are lower interacting
species. For NiAl, it is quite difficult to identify a peak. In fact, a
broad peak starting from 300  C is visible. As reported by Ma
et al. [28], this behaviour can be assigned to well-dispersed
NiO species. Moreover, Ron-jun et al. reported that this
broad peak can be related to the formation of NiAl2O4 spinel
due to the strong interaction of NiO and Al2O3 [29,30]. The
importance of TPR analysis is also associated with the reac-
tion temperature. In this work, catalytic tests were conducted
at 500  C. As can be seen in the TPR profiles, it is possible to
affirm that, in the reaction conditions, all nickel species
should be reduced except for a small amount of NiTi. As a
matter of fact, NiTi catalyst has two reduction peaks at 410  C
and 635  C. The latter is associated with nickel that strongly
interacts with TiO2. Nevertheless, there is a lower intensive
peak which could be assigned to the small amount of unre-
duced nickel species.
To further understand this fact, XRD analysis was per-
formed on the reduced samples to prove the efficiency of H2
reduction treatment performed before the reaction. Moreover,
X-Ray diffraction measurements allow getting information
regarding support and metal's crystal phase. Fig. 3 shows X-
Ray diffraction pattern for all the catalysts and the nickel
particle size determined via Rietveld analysis are reported in
the Table 1.
For NiSi, NiZr, and NiCe samples (Fig. 3), the occurrence of
nickel metal is clearly detectable from its most intense peaks
at 2q z 44,5 and 51,8 , associated respectively with (111) and
(200) Miller indexes of fcc nickel. However, no peak is detected
at about 2q z 43,5 related to the NiO (200) phase (bunsenite).
In conclusion, H2 reduction treatment at 500  C of NiSi, NiZr,
and NiCe samples allows to reduce all nickel oxide to in nickel
metal making the active phase for the reaction. Regarding
NiCe catalyst, ceria peaks are visible at 2q z 28,5 33,1 47,5
56,3 59,1 and 69,4 ; these are respectively associated to the
(111), (200), (220), (311), (222) and (400) of the fluorite type cubic
phase. Concerning NiZr, both monoclinic and tetragonal
phases are present; peaks of m-ZrO2 are at 2q z 24,3 28
28070 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 4 ( 2 0 1 9 ) 2 8 0 6 5 e2 8 0 7 6
Fig. 3 e XRD pattern of reduced nickel supported catalysts.
31,55 34,2 40,8 44,9 45,5 49,4 54,0 55,4 while those of t-
ZrO2 are at 2q z 30,2 35,5 and 50,3 . As far as NiSi sample,
mesoporous SBA-15 silica does not exhibit any peak in the
XRD pattern of Fig. 3 due to the amorphous nature of the pore
walls. The mesopore order has been checked by low angle
XRD, the relevant pattern is provided in supporting informa-
tion (Fig. S1).
Samples NiTi and NiAl show a different behaviour in which
the nickel metal phase is absent or below the XRD detection
limit whereas it only occurs in oxide forms. The NiTi sample
contains both the rutile and anatase TiO2 polymorphs while Ni
occurs in bunsenite (NiO) and in the ilmenite-type phase
NiTiO3 [31]. Sample NiAl exhibits broad peaks associated to
the poor crystalline g -Al2O3 phase which might mask some
minor occurrence of metal nickel. On the other hand, NiO
peaks are clearly visible. As suggested by Ron-jun et al., The
possible formation of a spinel phase NiAl2O4 has been checked
by adding the NiAl2O4 crystal structure model in the Rietveld
refinement. The profile fit does not support the occurrence of a
NiAl2O4 spinel phase. However, considering that the structure
of g-Al2O3 can be described as a cubic defect spinel type in
which the oxygen atoms are arranged in a cubic close packing
and Al atoms occupy the octahedral and tetrahedral sites, it
cannot be ruled out that some Al3þ ions in the tetrahedral site
of g-Al2O3 was replaced by Ni2þ ions.
SEM analysis of fresh catalysts after calcination were car-
ried out to understand the morphological feature of the ma-
terials and the Images are reported in Fig. 4. For all the
catalysts, a homogeneous distribution of NiO is visible while
for NiTi sample, the agglomeration of NiO nanoparticles is
evident. Furthermore, The NiO particle size was calculated
and reported in Table 1. It is also perceived that NiSi has a
double distribution of NiO nanoparticles, 19 ± 3 and 73 ± 12 nm
respectively.
CO2-TPD technique was carried out to evaluate surface
basicity of the materials and to study the capacity of adsorp-
tion of one of the MDR reagent. Fig. 5 presents the CO2-TPD
profile and Table 2 reports the number of basic sites, calcu-
lated by the integration of the desorption peaks. Wierzberg
et al. [32] divide the desorption curves into three different
regions, associated respectively with weak (50e250  C), me-
dium (300e600  C) and strong (600e800  C) basic sites. For
NiCe, NiZr, and NiSi, three clear regions are visible; in partic-
ular, for NiCe the number of weak sites is the highest among
the samples. Regarding NiAl, the second and last region are
merged and indistinguishable. This gives high basicity to the
system; indeed, as reported in Table 2, it's the most basic one.
Finally, for NiTi sample, only small pronounced peaks of weak
and medium basic sites are visible, making it the least basic
sample.
Catalytic tests
As previously stated, MDR is a promising process for syngas
production due to its possible combination with acetic acid,
dimethyl ether, and oxo-alcohols production and Fischer-
Tropsch synthesis. It has been reported that conducting
MDR at low reaction temperatures could help to develop an
energetically advantageous system [33]. For this reason, cat-
alytic tests were conducted at 500  C for 18 h. The activity and
stability of the catalysts in terms of hydrogen yield and carbon
monoxide yield are presented in Fig. 6. The materials can be
divided into three different groups: completely not active
catalyst such as NiTi, materials that can be deactivated in time
such as NiZr and NiSi and the most active and stable catalysts
such as NiCe and NiAl. As was mentioned, NiTi doesn't show
any kind of activity which is related to having the lowest CO2
adsorption property and lowest surface area. Moreover, as
analysed by XRD, it seems that the reduction step doesn't
allow to reduce NiO in its active form due to the incorporation
of part of the nickel inside the titania lattice. Moreover, SEM
image shows high amount of agglomerated nickel. Therefore,
no further investigation was carried out for NiTi catalyst. NiZr
and NiSi present quite similar behavior. They have a moderate
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 4 ( 2 0 1 9 ) 2 8 0 6 5 e2 8 0 7 6 28071

Fig. 4 e SEM images of fresh catalysts at 50.00Kx (left) and 250.00 KX (right) and NiO particle size distribution.

activity at the beginning of the reaction since hydrogen yield is
15% for NiSi and 14% for NiZr. Moreover, they are gradually
deactivated and reach the hydrogen yield of 4% and 5% after
18 h, respectively. However, NiCe and NiAl catalysts are the
most active catalysts. for NiCe, 28% of hydrogen yield is
registered in the first hours, getting to 22% after 18 h of reac-
tion. On the contrary, NiAl remains stable during 18 h reaction
with constantly 20% of hydrogen yield. For all the samples, CO
yield values are higher than H2 yield values nevertheless, the
CO and H2 trends are comparable.
Another important parameter that must be evaluated to
understand the grade of deactivation of the catalysts is H2/CO
ratio. As reported in the introduction part, one is the sto-
chiometric ratio of MDR; nevertheless, different reactions
such as reverse water gas shift, CO disproportion and CH4
decomposition can be involved. Fig. 7 reports the H2/CO trends
on time of steam for all the catalysts.
As it is visible, H2/CO ratio is lower than 1 for all the sam-
ples. This fact is ascribed to the reaction temperature. Water
gas shift, in fact, is an exothermic reaction thus it is favoured
at low temperature. Therefore, it can compete with methane
dry reforming at 500  C, consuming CO and decreasing H2/CO
ratio. At the same time, at the beginning of reaction, NiCe
catalyst presents a value next to the unit that gradually
28072 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 4 ( 2 0 1 9 ) 2 8 0 6 5 e2 8 0 7 6
Fig. 5 e CO2-TPD profiles of nickel supported catalysts.
decreases to 0,6 during 18 h. This fact gives a clear indication
to of how reaction pathway changes during the time of
stream. The same trend is observed for NiZr catalyst. For NiSi,
small changes is are observed, from 0,7 to 0,4 meanwhile only
for NiAl catalyst, a constant ratio is preserved.
Characterisation of used catalysts
SEM, EDX and Raman spectroscopy were carried out on the
used samples to understand the reasons of catalytic behav-
iour. SEM images of used catalysts are reported in the left
section of Fig. 8 and EDX images and Carbon mapping of the
same materials are presented in the right section of Fig. 8. As
can be seen, NiTi has a completely free surface, with no car-
bon formation. This can be agreed with catalytic test, in which
no hydrogen production was obtained. However, the second
group of catalysts were gradually deactivated during the time.
SEM images of NiZr and NiSi after 18 h of reaction are
completely different in cooperation with the first group. NiZr
Table 2 e Distribution of basic sites for nickel supported catalysts.
Weak basic sites (mmol/g) Medium basic sites (mmol/g)
NiCe 102 88
NiZr 8 74
NiAl 8 132
NiSi 10 89
NiTi 28 48
Fig. 6 e H2 yield (section a) and CO yield (section b) evolution for 18 h of reaction at 500  C for all the reduced catalysts.
Fig. 7 e H2/CO evolution for 18 h at 500  C for NiCe, NiZr,
NiAl and NiSi.
has a partially free surface whereas NiSi's surface is
completely covered by carbon nanotubes. The same trend is
visible for the third group. NiCe and NiAl have a completely
different effect in terms of carbon formation. NiAl is covered
by nanotubes meanwhile for NiCe, sporadic whisker carbons
are present.
Raman spectra of used catalysts are reported in Fig. 9
which confirms this trend. At frequency below 1000 cm1 all
the spectra show the peaks related to the oxide supports while
the peaks related to the carbon deposits are in the frequency
range of 1350e2900 cm1. D, G, 2D and CH stretching peaks
appear at about 1350 cm1, 1580 cm1, 2700 cm1 and
2900 cm1, respectively [34]. These contributions are pre-
sented in all the samples with similar shapes, apart from NiTi
sample where the broad asymmetric peak at 1500 cm1 in-
dicates that the deposit has an amorphous nature. In the
others, the relative intensity of the different bands can give
further information on the catalytic process. In particular, it is
evident that the intensity of the carbon peaks is much higher
in the spectra of Si and Al based catalysts which is in agree-
ment with the SEM images. Moreover, for these catalysts, it is
Strong basic sites (mmol/g) Total basicity (mmol/g)
51 242
50 133
91 231
96 196
27 103
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 4 ( 2 0 1 9 ) 2 8 0 6 5 e2 8 0 7 6 28073

Fig. 8 e SEM (left) and EDX (right) analysis of spent catalysts.

also possible to observe the significant contribution of the CH

vibration, potentially associated with the residual hydrocar-
bon compounds. The high intensity of the D band with respect
the G band (ID/IG > 1, for all the samples with the exception of
NiTi) indicates that the deposits is mainly in the form of
nanocarbon or highly defective multi walled carbon nano-
tubes [35].

Discussion

As previously reported, NiTi catalyst, prepared in this way,

Fig. 9 e Room temperature Raman spectra of used catalysts
upon 532 nm excitation.
does not present any kind of activity for methane dry
reforming reaction. This behaviour can be ascribed to several
factors such as the low surface area and the irregular disper-
sion of Ni nanoparticles. Indeed, as was seen in the SEM im-
ages, nickel oxide agglomeration is visible. Moreover, in
accordance with XRD technique, a part of nickel is incorpo-
rated inside titania's lattice so it is inactive for the reaction.
28074 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 4 ( 2 0 1 9 ) 2 8 0 6 5 e2 8 0 7 6
Considering the activity of other catalysts, it is possible to
divide the materials into two groups, NiSieNiZr and
NiAleNiCe, respectively. Nevertheless, it cannot be consid-
ered the same if the attention is paid to selectivity. In this
contest, it is useful to look at H2/CO ratio, reported in Fig. 7. For
NiSi and NiAl, the ratio remains almost constant during the
measurement whereas for NiCe and NiZr there is a gradual
drop of the ratio, indicating a progressive increase of CO and
decrease of H2. Therefore, the reaction pathway involved for
the catalysts is different. According to CO2-TPD, NiSi and NiAl
are the catalysts with the stronger basic sites. As reported by
Das et al. [36], excessive surface basicity lead to the catalyst
deactivation by carbon formation. In fact, excess amount of
CO, generated by CO2 dissociation, can favour Boudouard re-
action (reaction 6) generating filamentous carbon. For these
catalysts, indeed, a huge amount of filamentous coke is visible
by SEM and Raman spectroscopy of used catalysts. Moreover,
as was demonstrated in Fig. 7, the continuous consume of CO
allows to keep the H2/CO ratio constant. At the same time,
NiAl catalyst maintains a stable catalytic activity over time,
indicating that filamentous coke does not cause deactivation.
As was previously reported, whisker carbon leaves the surface
free for reagent access. In the case of NiSi, the strong surface
carbon coating is also accompanied by a collapse of the sup-
port structure as it is visible from SEM image of used NiSi. The
limited stability of the SBA-15 has not allowed to maintain a
Fig. 10 e H2 yield evolution for 70 h of reaction at 500  C for
NiCe and NiAl reduced catalysts.
Fig. 11 e SEM image of used NiCe catalyst after 70 h of reaction.
stable activity in time. These data agree with literature results.
Zhang et al. carried out catalytic test at 750  C using NiO
deposited over SiO2 demonstrating that the initial high ac-
tivity is due to the large surface area and the high metal
dispersion [37]; as highlighted in current work, this material
gradually deactivated due to the low metal-support interac-
tion and the small support stability. Considering NiZr and
NiCe catalysts, small number of nanotubes are formed during
the reaction. Despite the activity of NiCe is constant in time,
NiZr is gradually deactivated during the 18 h of reaction.
Nevertheless, deactivation of the catalyst is not connected
with carbon coke deposition. As it is obvious in the SEM image
of used sample in Fig. 8, sintering of nickel nanoparticle over
zirconia support is the main reason of catalyst deactivation.
As reported by Rezaei et al., introduction of promoters such as
CeO2, La2O3 and K2O is needed to improve the metal-support
interaction and as consequence the activity of NieZrO2 ma-
terial [38].
After determining the stability of all catalysts during18 h,
70-h reaction tests were carried out for NiCe and NiAl as the
most active and stable catalysts. The hydrogen yield trend
along the 70 h of reaction is presented in Fig. 10. Despite NiAl
catalyst presents a lower activity at the beginning of reaction
than NiCe, it is stable for all the time of stream. On the
contrary, NiCe was gradually deactivated during the first 30 h
of reaction and levelled out at 10% hydrogen yield. SEM
analysis of used NiCe catalyst after 70 h reaction was carried
out and the images are reported in Fig. 11. In comparisomon
with the SEM of the same used catalyst after 18 h of reaction,
the formation of carbon nanotubes is evident which explain
the decrease in hydrogen yield after the first hours of
reaction.
In conclusion, NiAl seems the most stable catalyst among
the studied materials. For this catalyst, the interactions be-
tween metal and support are strong, as demonstrated by XRD
and H2-TPR analysis. As was reported by Shang et al. [39], the
formation of strong interactions between nickel and alumina
makes the catalyst not so active as the metal form but at the
same time, they preserve nickel surface from sintering and
cause a good dispersion of the active phase. This can be
agreed with the results reported in Fig. 10; indeed, NiAl ac-
tivity is not so high as NiCe but it is constant during 70 h of
reaction.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 4 ( 2 0 1 9 ) 2 8 0 6 5 e2 8 0 7 6
Conclusions
Support has a strong effect on the activity and stability of
the nickel-based catalyst. In particular, it plays a key role in
the two main causes of deactivation: sintering and carbon
poisoning. Ceria, zirconia, alumina, SBA-15 and titania
were analysed and compared at low reaction temperature
for the first time. Titania based catalyst didn't show any
activity for MDR due to the low surface area and the
irregular dispersion of Ni nanoparticles, as demonstrated
by SEM analysis. In the case of SBA-15, despite the initial
activity, the collapse of the structure and the presence of a
strong basic site had caused the formation of carbon
nanotubes that deactivate the catalyst. Zirconia based
catalyst, as well, deactivated in time but in this case, nickel
sintering was the cause; therefore, limited stability of zir-
conia material had brought to catalyst's deactivation. On
the contrary, ceria and alumina catalysts remain stable for
the 18 h of reaction; analysing the spent catalyst via SEM
and Raman spectroscopy, two different behaviours were
observed. NiCe was completely free from carbon deposits
due to its strong redox ability meanwhile, NiAl was covered
by carbon nanotubes. Nevertheless, conducting the reac-
tion for 70 h, NiAl remained stable while NiCe gradually
deactivated during the firsts 30 h, reaching than a plateau of
10% of hydrogen yield. Concluding, despite the lower initial
activity of NiAl than NiCe, NiAl was demonstrated to be the
most stable catalyst. This effect relates to the strong
interaction between nickel and alumina that makes the
catalyst not so active as the metallic form, but it allows to
keep strong stability in time. This study allows to compare,
for the first time, the most traditional nickel supported
catalysts at low reaction temperature in order to increase
the efficiency of MDR process, making the syngas applica-
tion more economically advantageous. Therefore, it de-
termines how, among the studied catalysts, nickel alumina
supported material is the most stable one, even at low
temperatures.
Author contributions
Catalytic tests and Atomic Adsorption analyses, E.P.; XRD
Analysis, G.C.; SEM analysis, A.D.M.; Raman analysis, M. M.;
Physisorption and Temperature Programmed Reduction, E.G.;
Synthesis of samples, C.P., Writing-Review & Editing F.M.;
Supervision, M.S.
Funding
This research was funded by MIUR-Italy (PRIN2015).
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.ijhydene.2019.09.050.
28075
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