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 7 ( 2 0 2 2 ) 5 3 3 7 e5 3 5 3

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A comparative study of Ni catalysts supported on

Al2O3, MgOeCaOeAl2O3 and La2O3eAl2O3 for the
dry reforming of ethane

Anastasios I. Tsiotsias a, Nikolaos D. Charisiou a,**, Victor Sebastian b,c,d,

Safa Gaber e,f, Steven J. Hinder g, Mark A. Baker g,
Kyriaki Polychronopoulou e,f, Maria A. Goula a,*
a
Laboratory of Alternative Fuels and Environmental Catalysis (LAFEC), Department of Chemical Engineering,
University of Western Macedonia, GR-50100, Greece
b
Department of Chemical Engineering and Environmental Technology, Universidad de Zaragoza, Campus Rı́o Ebro-
Edificio IþD, 50018, Zaragoza, Spain
c
Instituto de Nanociencia y Materiales de Aragon (INMA), Universidad de Zaragoza- CSIC, C/ Marı́a de Luna 3,
50018, Zaragoza, Spain
d
Networking Research Center on Bioengineering, Biomaterials and Nanomedicine, CIBERBBN, 28029, Madrid, Spain
e
Department of Mechanical Engineering, Khalifa University of Science and Technology, Abu Dhabi, P.O. Box 127788,
United Arab Emirates
f
Center for Catalysis and Separations, Khalifa University of Science and Technology, Abu Dhabi, P.O. Box 127788,
United Arab Emirates
g
The Surface Analysis Laboratory, Faculty of Engineering and Physical Sciences, University of Surrey, Guildford,
GU2 4DL, UK

highlights graphical abstract

 Ni catalysts on Al2O3 modified

with MgO/CaO and La2O3 for the
DER reaction.
 Modification of Al2O3 improves the
catalyst basicity and metal-
support interaction.
 Extensive ethane cracking into CH4
takes place during the first 3e4 h.
 Ni/LaeAl2O3 is the most active and
stable with H2 and CO yields
remaining constant.
 Modification of Al2O3 aids the coke
gasification and reduces catalyst
degradation.

* Corresponding author.
** Corresponding author. University of Western Macedonia Department of Chemical Engineering Laboratory of Alternative Fuels and
Environmental Catalysis Koila, Kozani, 50100, Greece.
E-mail addresses: ncharisiou@uowm.gr (N.D. Charisiou), mgoula@uowm.gr (M.A. Goula).
https://doi.org/10.1016/j.ijhydene.2021.11.194
0360-3199/© 2021 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
5338 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 7 ( 2 0 2 2 ) 5 3 3 7 e5 3 5 3

article info abstract

Article history: CO2 utilization through the activation of ethane, the second largest component of natural
Received 28 June 2021 and shale gas, to produce syngas, has garnered significant attention in recent years. This
Received in revised form work provides a comparative study of Ni catalysts supported on alumina, alumina modi-
23 November 2021 fied with CaO and MgO, as well as alumina modified with La2O3 for the reaction of dry
Accepted 25 November 2021 ethane reforming. The calcined, reduced and spent catalysts were characterized employing
Available online 18 December 2021 XRD, N2 physisorption, H2-TPR, CO2-TPD, TEM, XPS and TPO. The modification of the
alumina support with alkaline earth oxides (MgO and CaO) and lanthanide oxides (La2O3),
Keywords: as promoters, is found to improve the dispersion of Ni, enhance the catalyst's basicity and
CO2 utilization metal-support interaction, as well as influence the nature of carbon deposition. The Ni
Dry ethane reforming catalyst supported on modified alumina with La2O3 exhibits a relatively stable syngas yield
Ni catalysts during 8 h of operation, while H2 and CO yields decrease substantially for Ni/Al2O3.
Basic/lanthanide promoters © 2021 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
Modified alumina
Carbon deposition

aromatic hydrocarbons and syngas [26e29]. For syngas pro-

Introduction
The global effort to stave off the catastrophic effects of climate
change has propelled CO2 utilization at the forefront of in-
ternational research efforts [1]. A promising solution may be
provided by the use of light alkanes to activate stored CO2
towards the production of synthesis gas or syngas (i.e., H2/CO)
[2e6], which can then be used for the production of liquid
fuels via the Fischer-Tropsch synthesis [7e9]. The most
commonly used reactant (apart from CO2) for syngas pro-
duction is methane, due to its high natural abundance. It is
noted that CH4 is not only the largest component in natural
gas and shale gas (≈ 70e98%), but also in biogas (≈ 40e75%)
[10e12]. The reaction between methane and CO2 is commonly
known as dry methane reforming (DMR) (Eq. (1)) and, as it is
highly endothermic, it takes place at high temperatures
(650e850  C); the drawback is that this can cause severe car-
bon deposition and metal particle sintering on the catalysts
[13e17]. When biogas is used as a reactant mixture, then the
reaction can be also referred to as biogas dry reforming (BDR)
[18e21].
duction, the dry reforming reaction between ethane and CO2
(DER) (Eq. (2)) presents an advantage over the more common
dry methane reforming (DMR) as, due to its lower endo-
thermicity (per carbon atom converted), it requires milder
conditions for operation (around 100  C lower than DMR) [28].
DER: C2H6 þ 2CO2 / 4CO þ 3H2 (DrН ¼ þ 428 kJ/mol), (2)
Apart from the main reaction (i.e., ethane dry reforming),
other side-reactions can also take place, such as ethane
oxidative dehydrogenation that produces ethylene and CO
(CO2-ODH) (Eq. (3)) [30], and ethane cracking that produces
methane (Eqs. (4) and (5)) [28,30]. Through the CO2-ODH re-
action, a valuable product (i.e., ethylene) can be obtained and
later used in the production of polymers, whereas ethane
cracking leads to a product (i.e., methane) that is less valuable
than the reactant ethane [26,30].
C2H6 þ CO2 / C2H4 þ CO þ H2O (3)
C2H6 þ 2CO2 / CH4 þ 3CO þ H2O (4)

DMR: CH4 þ CO2 / 2CO þ 2H2 (DrН ¼ þ 247 kJ/mol) (1) C2H6 þ H2 / 2CH4 (5)

However, besides methane, other light hydrocarbons can
also be used for syngas production, such as ethane (C2H6),
propane (C3H8) and, butane (C4H10) [2,3]. Among these, ethane
is an attractive choice, since it constitutes the second largest
component in natural and shale gas [3,22]. Although the
composition of these reserves can vary, in general, the ethane
content in shale gas is higher than that of conventional nat-
ural gas reserves. For example, ethane content in US shale gas
reserves can reach as high as 35% [23], while conventional
natural gas typically contains around 6% ethane [24]. The
increased exploitation of shale gas fields in the past decade
has increased the supply of ethane and other natural gas liq-
uids (NGLs) [23,25], which can then be isolated and utilized for
the production of value-added products such as ethylene,
The DER reaction has mostly been studied in recent times,
due to the shale gas boom occurring in the last decade.
Because of that, one may find only a handful of works dedi-
cated to this reaction, the majority of which have been pro-
duced by Chen and his co-workers [3,22,28e39]. Myint et al.
[28] used CeO2-supported monometallic and bimetallic cat-
alysts and showed that Ni-, Co- and Pt-containing catalysts
exhibited high selectivity for CO (reforming), while C2H4
selectivity (dehydrogenation) was higher for Fe/CeO2 and
NiFe/CeO2, compared to the other catalysts tested. Yan et al.
[3] studied the mechanism and kinetics of the DER reaction
over NiPt/CeO2 catalysts. They showed that NiPt bimetallic
catalysts can be superior to the monometallic Ni ones, with
the Pt-dominated bimetallic surface reducing the surface O
 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 7 ( 2 0 2 2 ) 5 3 3 7 e5 3 5 3
binding strength, as well as the stability of deposited carbon.
The NiPt bimetallic and Ni monometallic catalysts were
found to be selective for the scission of CeC bonds in ethane,
whereas Ni-FeOx interfacial sites on Fe-rich NiFe/CeO2
bimetallic catalysts could selectively cleave the CeH bonds
instead to produce ethylene [36]. Xie et al. [35] highlighted the
significance of the type of support in the DER reaction using
NiPt bimetallic catalysts. More specifically, a reducible sup-
port such as CeO2 was shown to be more suitable for the DER
reaction, compared to irreducible supports, such as Al2O3
and SiO2. It was proposed, that DER followed a mono-
functional (single site) mechanism over NiPt catalysts sup-
ported on irreducible supports (e.g. SiO2), where C2H6 and
CO2 were activated over the same sites, whereas a bi-
functional (double site) mechanism was followed over NiPt/
CeO2 with C2H6 and CO2 being activated on separate active
sites. Furthermore, perovskite oxides such as LaFe0$9Ni0$1O3
have been also reported as active and stable catalysts for DER
[22]. Exsolved Ni nanoparticles with a strong metal-support
interaction, formed on the perovskite surface, provided su-
perior stability and coking resistance compared to Ni/La2O3
prepared via a mere impregnation step. In an attempt to
simulate a shale gas feed, Liu et al. [29] employed a CH4:C2-
H6:CO2 mixture with a ratio of 4:1:6. They modified the
alumina support in Ni/Al2O3 with Ce and observed that Ce
could promote the activation of CH4, C2H6 and CO2 mole-
cules, as well as increase the catalyst stability via an intricate
Ni/CeOx interaction. A redox cycle between Ni0/Ni2þ/Ni3þ and
Ce4þ/Ce3þ could also promote the gasification of deposited
carbon. Lastly, Al-Mamoori et al. [38] impregnated Ni on
Al2O3 that was previously modified with NaeMg, KeMg,
NaeCa and KeCa double salts, which greatly promoted the
support basicity. They tested the materials on a combined
CO2 capture and utilization process using ethane. During this
process, CO2 was captured in a first step by the basic cata-
lysts, whereas ethane was flowed in the reactor in a subse-
quent step to convert the captured CO2 into syngas.
Ni catalysts are widely employed in reforming reactions
due to their high activity, while they are also preferred over
precious metal catalysts due to their low cost [13,40e42].
However, extensive coke formation over Ni nanoparticles can
cause severe catalyst deactivation [43]. The support plays a
major role in determining the catalyst activity and coking
propensity. In general, basic supports mitigate coke deposi-
tion, whereas acidic supports favor coke accumulation
[43e46]. Furthermore, the metal dispersion and the strength
of the metal support-interaction can also determine the
amount of deposited carbon. For example, Ni nanoparticles
exsolved from perovskites that retain a strong interaction
with their underlying perovskite support have been found to
be highly resistant towards coke deposition, whereas
impregnated Ni nanoparticles are quite more prone to coking
[22,47]. Alumina-based supports generally attract great inter-
est in heterogeneous catalysis due to their high surface area,
as well as mechanical and chemical resistance under severe
reaction conditions [48]. However, the acidic sites on alumina
can favor the formation of carbon deposits on the supported
Ni nanoparticles [49]. To overcome this problem, research has
focused on the introduction of basic promoters (such as Mg
and Ca), as well as lanthanide ones (such as La and Ce) in order
5339
to promote carbon gasification and increase the catalyst sta-
bility [43,45]. This approach has successfully led to the crea-
tion of more active and stable Ni catalysts used in reactions
such as dry methane reforming, glycerol steam reforming and
CO2 methanation [50e53].
In previous works by our group, we have shown that, in
agreement with the literature, modification of the Al2O3 sup-
port in Ni catalysts with MgO, CaO, La2O3 and CeO2 can be
employed to increase the activity, stability, as well as coking
resistance during the biogas dry reforming (BDR) reaction
[50,54]. More specifically, MgO and CaO increased the inter-
action with Ni and also promoted the support basicity, thus
mitigating the Al2O3 acidic sites [50]. On the other hand, La2O3
and CeO2 phases on alumina participate in redox reactions
that promote the gasification of deposited carbon [54]. Car-
rying out an extensive study on the carbon deposition on Ni/
Al2O3 and Ni/La2O3eAl2O3 [18] we reported that the crystal-
linity of the deposited carbon was higher for the Ni/Al2O3
catalyst, while the introduction of La2O3 not only reduced the
amount of deposited carbon, but also altered its nature, as it
led to the deposition of less graphitic carbon. It was thus
deduced that highly dispersed La2O3 phase could promote the
gasification of carbon deposits, which was attributed to the
increased CO2 adsorption on the surface basic sites. We have
also reported that Ni catalysts supported on commercially
available MgOeCaOeAl2O3 (Mg,CaeAl2O3) and La2O3eAl2O3
(LaeAl2O3) materials exhibited improved dispersion of the
active species, increased population of surface basic sites and
enhanced metal-support interaction [51,52].
Based on such promising characteristics, we decided to use
the aforementioned Ni catalysts i.e., Ni/Mg,CaeAl2O3 and Ni/
LaeAl2O3 to perform a comparative study for the dry ethane
reforming (DER) reaction. Catalytic performance was investi-
gated in terms of: (i) C2H6 and CO2 conversion, (ii) CO, C2H4 and
CH4 selectivity, (iii) H2 and CO yield, as well as the (iv) H2/CO
ratio. The stability of the catalysts was also assessed at a low
reaction temperature of 600  C. A short summary of the pre-
viously reported XRD, N2 physisorption, H2-TPR, CO2-TPD,
NH3-TPD, XPS and TEM results obtained over the calcined and/
or their reduced samples is provided herein to isolate the most
important physicochemical and structural characteristics and
their effect on catalytic performance. The extent of carbon
deposition on the catalytic surface was assessed via XRD, TPO,
XPS and TEM. To the best of our knowledge, this is the first
time that Al2O3-supported monometallic Ni catalysts have
been studied in the DER reaction, even though the Ni/Al2O3
system is generally considered as a benchmark in heteroge-
neous catalysis.
Experimental part
Catalyst preparation and characterization
The synthesis procedure followed for the catalysts used
herein has been extensively described in Refs. [51,52]. Briefly,
the supported Ni catalysts were prepared by impregnating the
three alumina-based supports, i.e., (i) Al2O3, (ii) Mg,CaeAl2O3,
and (ii) LaeAl2O3, with aqueous solutions of Ni(NO3)2$6H2O,
targeting a Ni loading of 8 wt%. The resulting slurries were
evaporated via a rotary evaporator at 75  C for 5 h and dried at
120  C overnight, before being calcined at 800  C for 4 h. These
5340 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 7 ( 2 0 2 2 ) 5 3 3 7 e5 3 5 3

samples are denoted as “calcined” catalysts. Their “reduced” Velocity (WHSV) was kept constant at 15,000 ml g1 h1. In
counterparts were prepared after activation for 1 h at 800  C addition, catalyst activation was always carried out in-situ at
with a pure H2 flow. 800  C for 1 h under flow of pure H2 (reduced catalysts) prior to
Detailed information regarding the characterization of the the commencement of any experimental work.
samples prior to the catalytic experiments (i.e., calcined and Three different experimental protocols were used. For the
reduced samples) has been already reported in Refs. [51,52]. In evaluation of the catalytic activity (protocol #1), the total flow
short, Inductively Coupled Plasma Atomic Emission Spectros- rate was set at 60 ml min1 and consisted of a gas mixture of
copy (ICP-AES), performed on a PerkinElmer instrument (Op- C2H6, CO2 and Ar. The molar ratio between C2H6 and CO2 was
tima 4300 Dual View model) was used for the determination of set at 1:2, according to the reaction stoichiometry, while Ar
the total Ni loading (wt.%). N2 adsorption/desorption at 78 K took up 50% of the total feed gas volume and served as an
was recorded manometrically up to 1 bar employing the 3Flex internal standard, accounting for volume expansion during
(Micromeritics) accelerated surface area and porosimetry the reaction. Following reduction, the temperature was low-
analyzer. X-ray Diffraction (XRD) was conducted to investigate ered to 400  C under Ar flow. The reaction mixture was then
the crystalline structure of the supports and final catalysts introduced in the reactor and the temperature was increased
using a ThermoAl diffractometer (40 kV, 30 mA, Cu Ka radia- stepwise up to 750  C, remaining for 30 min at each temper-
tion, l ¼ 0.154178 nm). Temperature Programmed Reduction ature to ensure steady-state operation. For the time-on-
with H2 (H2-TPR), as well as CO2 Temperature Programmed stream experiments (protocol #2) a similar to protocol#1 pro-
Desorption (CO2-TPD), for the investigation of reducibility, cedure was followed, with the only difference concerning a
basicity and acidity of the catalytic materials were conducted final attained temperature of 600  C, at which the catalysts
using an Autochem 2920 (Micromeritics). Transmission Elec- were maintained for continuous operation at reaction condi-
tron Microscopy (TEM) studies were performed using a 200 kV tions up to 8 h. Finally, in protocol #3, the molar ratio between
G2 20 S-Twin Tecnai microscope equipped with a LaB6 electron C2H6 and CO2 was set at 1:1, in agreement with other literature
source fitted with a “SuperTwin®” objective lens that allows a works [22,35]. The total flow rate was 40 ml min1 and the
point-to-point resolution of 0.24 nm. Energy Dispersive X-ray catalyst mass was lowered accordingly, in order to keep the
Spectroscopy (EDS) analysis and High Angle Annular Dark same WHSV.
Field Scanning Transmission Electron Microscopy (STEM- The gaseous products of the reaction were analyzed via on-
HAADF) were carried out using a Tecnai G2-F30 Field Emission line gas chromatography in an Agilent GC-systems-7890A,
Gun microscope with a super-twin lens and 0.2 nm point-to- with He as carrier gas, and two columns in parallel, Agilent
point resolution, as well as 0.1 nm line resolution operated at J&W HP Plot-Q (19095-Q04, 30 m length, 0.530 mm I.D.) and
a voltage of 300 kV. X-ray photoelectron spectroscopy (XPS) Agilent J&WHP-Molesieve (19095P-MSO, 30 m length,
analyses on the reduced Ni/Al2O3 and Ni/Mg,CaeAl2O3 0.530 mm I.D.), equipped with TCD and FID detectors. The
described in Ref. [52] was carried out on a ThermoFisher Sci- conversions for ethane and carbon dioxide, the yields for
entific Instruments K-Alpha þ spectrometer. XPS spectra were hydrogen, carbon monoxide, ethylene and methane, as well
collected using a monochromated Al Ka X-ray source as the selectivities (ethane basis) for ethylene (dehydrogena-
(hv ¼ 1486.6 eV). XPS analysis of the reduced Ni/LaeAl2O3 was tion), methane (cracking) and carbon monoxide (reforming),
performed with the same method. together with the H2/CO molar ratio were determined ac-
For the purposes of the work reported herein, the spent cording to the following equations (Eqs. (6)e(15)):
catalytic materials after the dry ethane reforming (DER) re-
FC2 H6; in  FC2 H6; out
action were characterized using TEM, XPS (the same in- XC2 H6 ¼  100 (6)
FC2 H6; in
struments and methodologies mentioned above were used),
XRD and Temperature Programmed Oxidation (TPO). Suc-
cinctly, XRD was carried out on a Rigaku MiniFlex II powder FCO2; in  FCO2; out
XCO2 ¼  100 (7)
diffraction system equipped with Cu-Ka1 radiation at 30 kV FCO2; in
and 20 mA, following the procedure reported in Ref. [55]. TPO
experiments were carried out using an Autochem 2920 FH2; out
YH2 ¼  100 (8)
(Micromeritics) unit and a 20% O2/He gas atmosphere. Addi- 3  FC2 H6; in
tional information regarding the instruments/methodology
for the latter technique can be found in Ref. [56]. FCO;out
YCO ¼  100 (9)
ð2  FC2 H6; in þ FCO2; in Þ
Catalytic performance studies
FC2 H4; out
Y C2 H 4 ¼  100 (10)
To test the catalytic performance, experiments were per- FC2 H6; in
formed in a fixed bed stainless-steel reactor (9 mm I.D.) and at
atmospheric pressure. The experimental set up used also FCH4; out
utilized a pre-heater before the reactor. Both the reactor and YCH4 ¼  100 (11)
2  FC2 H6; in
the pre-heater were placed into electrical ovens and were
regulated with programmed-temperature controllers. The YC2 H4
thermocouples used were of K-type. Irrespective of the S C2 H 4 ¼  100 (12)
XC2 H6
experimental protocol followed, the Weight Hourly Space
 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 7 ( 2 0 2 2 ) 5 3 3 7 e5 3 5 3
YCH4
SCH4 ¼  100
XC2 H6
SCO ¼ 100  SCH4  SC2 H4

FH2; out
H2 CO ¼
FCO;out
Finally, the carbon balance was calculated via Eq. (16), and
was found to close at z98% for all catalysts, at the final
measurement, for the time-on-stream experiments (protocol
#2):
2FC2 H6; out þFCO2; out þ2FC2 H4; out þFCH4; out þFCO;out
Carbon balanceð%Þ¼
2FC2 H6; in þFCO2; in
100
Results and discussion
Overview of the characteristics of the calcined and reduced
catalysts
As mentioned above, this section provides only a summary of
the main physicochemical properties of the catalysts used
herein; detailed information can be found in Refs. [51,52].
Briefly, the desired Ni content (Table S1), i.e., around 8 wt%,
was largely achieved for all calcined catalysts.
The isotherms of all three reduced catalysts are type IV(a)
(Fig. S1), i.e., typical of mesoporous materials with various
amounts of macropores [57]. Their specific surface areas (SSA)
are similar, i.e., 136 m2/g for the Ni/Al2O3, 126 m2/g for the Ni/
Mg,CaeAl2O3 and 123 m2/g for the Ni/LaeAl2O3 (Table S1),
while their hysteresis loops could be classified as type H2(b)
due to pore blocking upon desorption [57]. The pore size dis-
tribution profiles (PSD) of the catalysts show that mesopores
(2e50 nm) mostly contribute to the total porosity, with a small
contribution from macropores (>50 nm), especially in Ni/
LaeAl2O3.
The XRD patterns of the Al2O3, Mg,CaeAl2O3 and LaeAl2O3
supports and the corresponding calcined and reduced catalysts
are depicted in Fig. S2. All supports exhibit reflections charac-
teristic of g-Al2O3. All calcined catalysts present additional re-
flections of a secondary spinel-type NiAl2O4 (nickel aluminate)
phase. The occurrence of this spinel-type ternary oxide phase
can be attributed to a solid-state reaction between the NiO and
Al2O3 binary oxides, with a percentage of Ni2þ ions diffusing
into the lattice of g-Al2O3 during the high temperature calci-
nation (800  C), instead of forming NiO surface oxides [58,59].
Regarding the reduced catalysts, additional weak and broad
reflections corresponding to metallic Ni0 can be observed,
which indicate the presence of small and highly dispersed
metallic Ni nanoparticles [58]. The strongest (111) reflection of
the metallic Ni phase overlaps to a high degree with the re-
flections from alumina, thus it is not possible to use this peak
for the calculation of the nickel crystallite size.
H2-TPR profiles are comparatively depicted in Fig. S3. For
the Ni/Al2O3 catalyst, a small reduction peak at low temper-
5341
atures (300e400  C) is indicative of NiO phases in weak
interaction with Al2O3. High temperature reduction peaks in
(13)
all three catalysts are attributed to the reduction of the
formed spinel-phase NiAl2O4, and/or the reduction of NiO
(14) interacting strongly with the support [51,60]. One can also
observe that the high-temperature reduction peaks are
considerably shifted towards higher temperatures for the Ni
(15) catalysts supported on modified alumina (Ni/Mg,CaeAl2O3
and Ni/LaeAl2O3). This can be either due to the different na-
ture of the NiAl2O4 spinel phases, since Ni2þ ions can be
hosted in tetrahedral and octahedral sites of Al2O3, with spi-
nels hosting Ni2þ in the octahedral sites being more reducible,
or due to the possible formation of other mixed phases that
are harder to reduce, such as spinel-like Mg(Al,Ni)Ox and
Ca(Al,Ni)Ox in Ni/Mg,CaeAl2O3 or perovskite-type LaAl1-
xNixO3 in Ni/LaeAl2O3 [61e64]. In any case, the occurrence
of these reduction peaks at higher temperatures is indicative
(16)
of a stronger metal-support interaction between metallic Ni
and the corresponding support in Ni/Mg,CaeAl2O3 and Ni/
LaeAl2O3, compared to Ni/Al2O3 [65].
CO2-TPD profiles for the reduced catalysts were carried out
in order to assess the catalysts’ basicity and their propensity
for CO2 activation; these are depicted in Fig. S4. Succinctly, low
strength basic sites (peaks up to 200  C) can be assigned to
surface eOH groups, medium strength (peaks between 200
and 400  C) to Lewis acid-base pairs and strong basic sites
(peaks over 400  C) to O2 species at low coordination envi-
ronment [52,66]. By comparing the three Ni catalysts, it can be
concluded that Ni/Al2O3 presents fewer and weaker basic
sites, followed by Ni/Mg,CaeAl2O3 that presents more basic
sites of moderate and high strength. Meanwhile, the Ni/
LaeAl2O3 catalyst appears to have the highest population of
basic sites, with many of them being of moderate and high
strength, probably due to the high dispersion of the La2O3
phase that can effectively bind CO2 molecules [66,67]. It has
also been suggested, that medium strength basic sites play a
vital role by enhancing CO2 activation in reactions where CO2
acts as a reactant molecule [67]. On the other hand, NH3-TPD
profiles (not shown herein) indicate that MgO, CaO, as well as
La2O3 phases induce a redistribution and partial neutraliza-
tion of the acidic sites in alumina [51,52].
STEM-HAADF images and particle size distribution histo-
grams for the reduced Ni/Al2O3, Ni/Mg,CaeAl2O3 and Ni/
LaeAl2O3 are depicted in Fig. S5. In short, the metallic Ni
particles in all three catalysts appear to be spherical and with
a relatively uniform distribution throughout their supports.
Size distribution analysis through TEM images for the three
reduced catalysts was also performed. The average Ni particle
size was calculated at 14.4 (±4.5) nm for Ni/Al2O3, 6.7 (±1.9) nm
for Ni/Mg,CaeAl2O3 and 10.3 (±2.2) nm for Ni/LaeAl2O3 (Table
S1). Thus, Ni catalysts supported on modified alumina pre-
sented a smaller Ni particle size on average, compared to Ni/
Al2O3, meaning that Ni dispersion was enhanced upon
modification of Al2O3 with basic and lanthanide promoters
(MgO and CaO, as well as La2O3).
XPS spectra of the reduced Ni/Al2O3 and Ni/Mg,CaeAl2O3
catalysts have been previously presented in Ref. [52], while the
spectra obtained for the reduced Ni/LaeAl2O3 can be found in
Fig. S6. Additionally, the elemental surface concentrations for
5342 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 7 ( 2 0 2 2 ) 5 3 3 7 e5 3 5 3

all three reduced catalysts can be found in Table S2. In short,
regarding the Ni 2p spectra, all catalysts exhibit a low binding
energy shoulder (z853.0 eV) due to surface metallic Ni, while a
more intense peak at z 856.5e857.1 eV can be attributed to
NiAl2O4 (phase detected via XRD), with possibly also some NiO
[52]. The fact that XPS was not conducted in-situ results in re-
oxidation and formation of hydroxide species from air expo-
sure. However, this is expected to have affected all catalysts in
a similar manner. Despite the fact that in the case of Ni/
LaeAl2O3 there is an overlap between the Ni 2p region and the
La 3d3/2 peak [18], it appears that, in all likelihood, the metallic
Ni0 phase in this catalyst is more pronounced compared to the
other two catalysts (Ref. [52]), as evidenced by the intensity of
the shoulder peak at z 853.0 eV. Finally, peak fitting of the O1s
peak reveals the presence of two oxygen species, i.e., lattice
oxygen and surface hydroxides.
Evaluation of the catalytic performance
Effect of reaction temperature on catalytic performance
The influence of the reaction temperature on ethane (XC2 H6 )
and carbon dioxide ðXCO2 Þ conversions, as well as on the se-
lectivities (ethane basis) for carbon monoxide ðSCO Þ and
methane ðSCH4 Þ is depicted in Fig. 1. The evolution of the H2, CO
and CH4 yields, as well as the H2/CO ratio with temperature
can be found in Fig. S7. Since no ethylene was produced over
the entire temperature range, ethylene selectivity ðSC2 H4 Þ was
not included in the presented figures. The absence of ethylene
could be explained by the fact that either some C2H4 is initially
produced via the ethane oxidative dehydrogenation (CO2-
ODH) reaction, which is then further converted into syngas
and methane [30,68], or that no C2H4 is produced altogether,
since the scission of the CeC bond is known to occur prefer-
entially over the CeH bond scission over the surface of
metallic Ni [34].
A notable feature in all three catalysts, is that CH4 selec-
tivity is high for temperatures lower than 600  C (Fig. 1d),
while it remains steady in the temperature range of
600e750  C, at about 6%. This feature is very prominent in the
unmodified Ni/Al2O3 catalyst, less pronounced in Ni/
Mg,CaeAl2O3 and quite less prominent in Ni/LaeAl2O3. For the
first two catalysts, a spike in C2H6 conversion (Fig. 1a) is also
observed in this low-temperature range (500e550  C), while
the conversion of CO2 steadily increases with reaction tem-
perature in all three catalysts (Fig. 1b). At first glance, CH4
production through the ethane cracking side-reaction appears
to preferentially take place at lower temperatures, and that it
consumes additional C2H6 without the participation of CO2. At
higher temperatures, CO selectivity (Fig. 1c) through reform-
ing appears to increase again and CH4 production decreases.
The possible mechanism for this CH4 production will be dis-
cussed at a later part. At the higher temperature range
(600e750  C), it is also clear that the Ni catalysts supported on
modified alumina with MgO and CaO or La2O3 present a su-
perior catalytic performance over the unmodified Ni/Al2O3
catalyst in terms of C2H6 and CO2 conversion.

Fig. 1 e Catalytic performance for Ni/Al2O3, Ni/Mg,CaeAl2O3 and Ni/LaeAl2O3 catalysts as a function of reaction temperature.
(a) C2H6 Conversion, (b) CO2 Conversion, (c) CO Selectivity (Reforming), and (d) CH4 Selectivity (Cracking). Reaction conditions:
Experimental Protocol #1. The dotted lines represent thermodynamic equilibrium calculations using Aspen Plus for ratio
C2H6:CO2 ¼ 1:2 and total pressure of 1 atm.
 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 7 ( 2 0 2 2 ) 5 3 3 7 e5 3 5 3
Table S3 shows the values for C2H6 and CO2 conversions
during a blank test. No thermal conversion of the reactants
C2H6 and CO2 is observed up to 600  C. From 650  C to 750  C
C2H6 and CO2 conversions gradually increase, with C2H6 con-
version being higher than CO2 conversion, because the direct
dehydrogenation of ethane to ethylene is favored at high
temperatures, even in the absence of catalyst [69]. For further
time-on-stream experiments, the temperature of 600  C was
chosen similarly to other works [22,28,35], in order to avoid the
contribution of the thermal conversions of the two reactants
and to examine the effects of the promoter phases on carbon
deposition, which is known to be favored at lower tempera-
tures [13,18].
Effect of reaction time on catalytic performance
The catalytic stability was evaluated via 8 h time-on-stream
experiments on the three Ni catalysts. The influence of the
reaction time on ethane (XC2 H6 ) and carbon dioxide ðXCO2 Þ
conversions, on the selectivities (ethane-basis) for the carbon
products carbon monoxide ðSCO Þ and methane ðSCH4 Þ, on the
yields for hydrogen (YH2 ), carbon monoxide (YCO ) and methane
(YCH4 ), as well as on the H2/CO ratio during the stability tests is
depicted in Fig. 2. Similarly to the activity experiments dis-
cussed above, ethylene was not produced and thus, ethylene
selectivity was not included. An apparent feature is the rapid
decrease in C2H6 conversion from an initially very high value
of over 90% to around 20e50% after 8 h, depending on the
catalyst used (Fig. 2a). The selectivity for CH4 (cracking) also
greatly decreases in all three catalysts during this timeframe,
with a concomitant increase in CO selectivity (reforming),
reaching a final steady-state value of around 4e6% after 8 h of
operation (Fig. 2c and d). Interestingly, CO2 conversion does
not appear to correlate with these changes (Fig. 2b). CO2 con-
version drops only slightly for the Ni catalysts supported on
La2O3-modified alumina and alumina modified with MgO and
CaO, but decreases by a great amount for the Ni/Al2O3 catalyst.
It can also be observed that the values for H2 and CO yield
remain quite stable for the Ni/LaeAl2O3 catalyst, drop slightly
for the Ni/Mg,CaeAl2O3 catalyst and drop considerably for the
Ni/Al2O3 catalyst, while CH4 yield drops drastically for all
catalysts during the first 3e4 h (Fig. 2eeg). Furthermore, the
values for H2 and CO yield are the highest for Ni/LaeAl2O3,
followed by Ni/Mg,CaeAl2O3, while Ni/Al2O3 has the lowest H2
and CO yields. The H2/CO ratio remains relatively stable for
the first two catalysts and drops only for the Ni/Al2O3 one
(Fig. 2h).
Regarding the drop in C2H6 conversion in all three cata-
lysts, it appears to at least partially correlate with the drop in
CH4 selectivity and CH4 yield, without affecting much the CO2
conversion and syngas yield (H2 and CO). This could mean that
some sites that are active for the splitting of CeC bonds in
ethane, deactivate over time, with reforming reactivity how-
ever being retained. Nevertheless, the end-effect is that C2H6
conversion is gradually stabilized over the duration of the 8 h
time-on-stream, along with the yield for the side-product CH4.
Looking back at the activity experiments, a similar phenom-
enon could also occur during the duration of the experiments,
with the drop in CH4 selectivity being rather a result of
increasing time spent on reactant stream, rather than
increasing temperature.
5343
The possible pathways for CH4 production are summarized
by Eqs. (4) and (5) and Eqs. (17) and (18). Eq. (4) refers to C2H6
cracking via the participation of CO2 [28,30]. Eq. (5) refers to the
direct splitting of the CeC bond in ethane to form methane, in
the presence of H2 produced from reforming [69,70]. Eq. (17)
refers to the methanation of reactant CO2 by produced H2
and Eq. (18) refers to the methanation of produced CO [7,71].
CO2 þ 4H2 / CH4 þ 2H2O (17)
CO þ 3H2 / CH4 þ H2O (18)
Considering the correlation between CH4 yield and C2H6
conversion, as well as the lack of correlation between CH4
yield and CO2 conversion, Eq. (5), namely ethane cracking
without the participation of CO2, is indicated as the most
probable pathway. The proposed mechanism would proceed
via an initial splitting of the CeC bond in gaseous ethane
(C2H6(g)) over the Ni surface, to yield surface adsorbed CH3(ads)
species on the Ni active sites, via ethane dissociation (Eq. (19)).
Then, part of the adsorbed H(ads) species (from reforming)
would be consumed to rehydrogenate the CH3(ads) species into
gaseous methane (CH4(g)) (Eq. (20)) [69,70].
C2H6(g) / C2H6(ads) / 2CH3(ads) (19)
CH3(ads) þ H(ads) / CH4(ads) / CH4(g) (20)
Literature reports on the dry reforming of methane (DMR)
and biogas dry reforming (BDR) highlight major activity losses
for Ni/Al2O3-type catalysts, as well as the extensive partici-
pation of the methane decomposition side-reaction, that
leads to coke formation [14,18,72,73]. This catalyst deactiva-
tion appears to be much more severe at lower operating
temperatures (600e700  C), since coke formation is typically
favored at this temperature range [14,18,74]. It is also known
that the methane decomposition reaction towards carbon and
dihydrogen takes place over supported Ni catalysts at this
temperature range [75e77]. The possible re-hydrogenation of
some of these carbon deposits during the DMR reaction would
not be easily detectable, since CH4 produced from the re-
hydrogenation would be the same gas as the reactant used.
However, the gasification of deposited coke in the form of CH4
using hydrogen as the gasifying agent, as a means for catalyst
regeneration, has been reported in a previous work [78].
In analogy to the DMR reaction, similar catalysts tested for
ethane dry reforming are expected to show a deactivation
behavior at low temperatures, due to coke formation [22],
induced via the decomposition of the reactant ethane to
atomic carbon and dihydrogen. Previous works have already
reported the occurrence of the ethane decomposition reaction
to carbon and dihydrogen over Ni catalysts [79e81]. Severe
and rapid catalyst deactivation takes place after a short time
due to extensive carbon accumulation, while CH4 formation
as a side-product has also been reported in all three cases.
Interestingly, Shen et al. [81] reported that a stabilization of
CH4 yield, along with H2 yield, occurs at 650  C after the initial
rapid deactivation phenomenon. A mechanism for CH4 for-
mation has also been reported by the authors of these works
[79e81]. In our case, for the DER reaction, the drop in CH4 yield
5344 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 7 ( 2 0 2 2 ) 5 3 3 7 e5 3 5 3

Fig. 2 e Catalytic performance for Ni/Al2O3, Ni/Mg,CaeAl2O3 and Ni/LaeAl2O3 catalysts as a function of reaction time. (a) C2H6
Conversion, (b) CO2 Conversion, (c) CO Selectivity (Reforming) and (d) CH4 Selectivity (Cracking), (e) H2 Yield, (f) CO Yield (g)
CH4 Yield and (h) H2/CO Ratio. Reaction conditions: Experimental Protocol #2. The dotted lines represent thermodynamic
equilibrium calculations using Aspen Plus for ratio C2H6:CO2 ¼ 1:2, total pressure of 1 atm and temperature of 600  C.
 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 7 ( 2 0 2 2 ) 5 3 3 7 e5 3 5 3
during the first 3e4 h spent on the reactant stream can also be
attributed to coke formation around the Ni nanoparticles. In a
similar fashion to the previously discussed works regarding
ethane decomposition [79,81], the exposed metallic Ni surface
required for H2 splitting, that leads to carbon rehydrogenation
and CH4 formation, would drastically diminish after some
time due to encapsulation of the Ni nanoparticles with carbon,
as hydrogen competes with ethane for chemisorption over the
metallic Ni surface sites [75,79,81,82].
Regarding the variation in the H2/CO ratio, according to the
DER reaction stoichiometry in Eq. (2), the nominal H2/CO ratio
should be 3/4 or 0.75. For the three catalysts tested, this ratio is
lower than the theoretical value (0.50, 0.55 and 0.59 for Ni/
Al2O3, Ni/Mg,CaeAl2O3 and Ni/LaeAl2O3 respectively, after 8 h
time-on-stream, Fig. 2h). This could be explained by the fact
that some of the produced H2 gets consumed by side-
reactions, such as ethane cracking (Eq. (5)) [69,70] and
reverse water-gas shift (Eq. (21)) [22,83]. Reverse-water gas
shift could also account for the relatively higher final values
for CO2 conversion, compared to C2H6 conversion.
CO2 þ H2 / CO þ H2O
A comparison between the three catalysts regarding the
steady-state yields (after 8 h of operation) for the reaction
products (H2 and CO) is given in Fig. 3. Similarly, the steady-
state conversions and selectivities for all three catalysts are
summarized in Table 1. In short, it can be concluded that
modification of the Al2O3 support with basic promoters, such
as alkaline earth (MgO and CaO) and lanthanide (La2O3) ones,
led to increased catalytic performance and stability in terms
of H2 and CO yields. This could be traced back to the more
beneficial physicochemical characteristics of the Ni catalysts
supported on modified alumina, namely to the higher Ni
dispersion and support alkalinity, as well as to the stronger
metal-support interaction [18,35,50,84]. La2O3 in particular,
has been shown to provide the highest population of Lewis-
basic sites (CO2-TPD, Fig. S4), and can potentially also supply
some more labile oxygen species that can further aid the in-
situ gasification of carbon [14]. It has already been reported
Fig. 3 e Comparison between the three catalysts regarding
the steady-state H2 and CO yields at 600  C (after 8 h of
operation). Reaction conditions: Experimental Protocol #2.
5345
Table 1 e Steady-state values (after 8 h of operation) and
initial values in parenthesis regarding reactant
conversions and product selectivities of the three
catalysts. Reaction conditions: Experimental Protocol #2.
Catalyst name Conversion (%) Selectivity
(ethane-basis) (%)
C2H6 CO2 CO CH4 C2H4
Ni/Al2O3 19 (92) 29 (53) 94 (56) 6 (44) 0 (0)
Ni/Mg,CaeAl2O3 35 (99) 40 (52) 95 (58) 5 (42) 0 (0)
Ni/LaeAl2O3 43 (93) 48 (55) 94 (55) 6 (45) 0 (0)
elsewhere, that La2O3 acts as a very efficient promoter when
dispersed over alumina in multiple catalytic applications,
such as methane dry reforming, glycerol dry/steam reforming
and CO2 methanation [51,54,85,86].
Effect of the C2H6:CO2 ratio on the catalytic performance
A similar 8 h time-on-stream experiment at 600  C was per-
formed on the best-performing catalyst (i.e., Ni/LaeAl2O3) at a
(21) different C2H6:CO2 feed molar ratio, namely 1:1 (with 50%
dilution with Ar), in order to assess the effect of the C2H6:CO2
feed molar ratio on the catalytic performance. The total flow
rate was reduced to 40 ml min1 and the catalyst mass was
lowered accordingly to keep the WHSV at 15000 ml gcat1 h1
(protocol #3). This was considered necessary, since most of
the works in the literature, especially those concerning the
CO2-assisted oxidative dehydrogenation of ethane (CO2-ODH)
reaction [28,30], but also the DER reaction [22,35], employ a
C2H6:CO2 molar ratio of 1:1. According to the Le Chatelier
principle in Eq. (2) [87], by decreasing the amount of CO2 in
relation to C2H6, a lower conversion of C2H6 and H2 yield would
be expected.
As shown in Fig. 4, the catalytic performance regarding
C2H6 conversion is greatly impeded using the 1:1 C2H6:CO2
feed molar ratio, while CO2 conversion remains roughly
similar. Furthermore, H2 yield drops greatly during the reac-
tion, reaching to about half the amount when compared to the
Ni/LaeAl2O3 catalyst tested at a molar ratio of 1:2, while the
CO yield is also diminished. CH4 yield and CH4 selectivity
follow the same trends for both C2H6:CO2 feed molar ratios
used. The evolution of the CO (reforming) and CH4 (cracking)
selectivity, the H2, CO and CH4 yield, as well as the H2/CO ratio
with time can be found in Fig. S8. The results regarding the
steady-state (after 8 h of operation) conversions and selec-
tivities for Ni/LaeAl2O3 when using different C2H6:CO2 feed
molar ratios are summarized in Table 2. Thus, the use of a
C2H6:CO2 feed molar of 1:2 rather than 1:1 clearly results in a
better catalytic performance, as well as a better utilization of
the two reactants, i.e., C2H6 and CO2.
Comparison of the catalytic performance with other studies
Table 3 provides a comparison between the catalytic perfor-
mance for dry ethane reforming (DER) of our best-performing
catalyst (Ni/LaeAl2O3) with other literature works. As already
mentioned in the introduction part, the majority of the works
concerning the DER reaction have been produced by Chen and
his co-workers [3,22,28,29,31e39]. Ni, Pt and NiPt alloy-based
catalysts have been reported to be the most active for the
5346 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 7 ( 2 0 2 2 ) 5 3 3 7 e5 3 5 3

Fig. 4 e Catalytic performance for the Ni/LaeAl2O3 catalyst operated at a C2H6:CO2 ratio of 1:2 and 1:1 as a function of
reaction time. (a) C2H6 Conversion and (b) CO2 Conversion. Reaction conditions: Experimental Protocols #2 and #3.

DER reaction, while disfavoring the ethane oxidative dehy-
drogenation pathway [28]. CeO2 has been used as a support in
most of these cases, owning to its unique redox properties
that can alter the reaction mechanism and aid the gasification
of coke [3,35], whereas perovskite oxide supported catalysts
have also been utilized [22,39]. However, Al2O3-based supports
can usually offer a much higher surface area, which generally
favors a better dispersion of the active metal phase [48].
From the results presented herein, and by taking into ac-
count different important parameters such as metal loading
and weight hourly space velocity, it appears that the Ni/
LaeAl2O3 catalyst can be considered as highly active for the
dry ethane reforming reaction. The most favorable physico-
chemical characteristics that contribute to its high catalytic
activity can be considered to be its high surface area, high Ni
dispersion, as well as the increased support basicity, which
Table 2 e Steady-state values (after 8 h of operation) and
initial values in parenthesis regarding reactant
conversions and product selectivities at different
C2H6:CO2 molar ratios for the Ni/LaeAl2O3 catalyst.
Reaction conditions: Experimental Protocols #2 and #3.
C2H6:CO2 Conversion (%) Selectivity
molar ratio (ethane-basis) (%)
C2H6 CO2 CO CH4
1:1 27 (84) 50 (56) 95 (53) 5 (47)
1:2 43 (93) 48 (55) 94 (55) 6 (45)
arises from the modification of the Al2O3 support with
moderately basic La2O3. The modification with La2O3 has
indeed been shown to result in an increased catalyst stability,
with the yields for the desirable reaction products, i.e., H2 and
CO, remaining relatively constant, as evidenced by the results
obtained from the corresponding time-on-stream experiment
(Fig. 2).
Spent catalysts characterization
To get an understanding of the causes of deactivation, the
spent catalysts obtained under experimental protocol #2 (i.e.,
T ¼ 600  C, C2H6/CO2 ¼ 1/2) were examined using XRD, TPO,
XPS and TEM. The XRD patterns of the spent Ni/Al2O3, Ni/
Mg,CaeAl2O3 and Ni/LaeAl2O3 catalysts, presented in Fig. 5,
show that the most prominent crystalline phases are g-Al2O3,
metallic Ni and crystalline carbon (2q z 26.3 ). As discussed
previously, the metallic nickel crystallite size cannot be reli-
ably determined via the strongest (111) Ni0 reflection, since it
overlaps with reflections from g-Al2O3. Regarding the carbon
reflection ((002) reflection of graphite), it can be attributed to
the orientation of the aromatic ring carbon reticulated layers
in 3D arrangement [88]. According to Qiu et al. [88], the average
stacking height (Lc) of crystalline graphite-type materials can
be calculated via the broadening of the (002) reflection and
C2H4 higher Lc values correspond to a better orientation of the ar-
omatic layer slice. The average Lc values in the spent samples
0 (0)
0 (0) were calculated at 4.5 nm for Ni/Al2O3, 4.9 nm for Ni/

Table 3 e C2H6 and CO2 conversion, CO and H2 yield, CO selectivity, as well as temperature, WHSV and C2H6:CO2 feed ratio
during the dry ethane reforming (DER) reaction in the presence of different catalysts reported in the literature.
Catalyst Temp. (oC) Conversion (%) Selectivity (%) Yield (%) WHSV C2H6: CO2 Ref.
(ml gcat1 h1)
C2H6 CO2 CO (Reforming) CO H2
Ni/LaeAl2O3 600 43 48 94 49 40 15,000 1:2 This work
Pt/CeO2 600 10 28 98 e e 24,000 1:1 [33]
PtCo/CeO2 600 26 47 99 e e 24,000 1:1 [33]
Ni/CeO2 600 13 21 94 e e 24,000 1:1 [28]
Ni/CeO2 600 9 15 z100 e e 240,000 1:2 [3]
PtNi/CeO2 600 28 36 99 e e 240,000 1:2 [3]
PtNi/CeO2 600 23 53 93 21 e 24,000 1:1 [35]
LaFe0$9Ni0$1O3 600 21 50 98 21 20 24,000 1:1 [22]
HT-2-R (Rh-doped SrTiO3) 550 13 19 99 13 e 120,000 1:2 [39]
 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 7 ( 2 0 2 2 ) 5 3 3 7 e5 3 5 3
Fig. 5 e X-ray diffractograms of the spent catalysts after
DER reaction at 600  C for 8 h (Results obtained for samples
tested under Experimental Protocol #2).
Mg,CaeAl2O3 and 4.7 nm for Ni/LaeAl2O3, which do not differ
very much from each other. However, other types of non-
crystalline carbon cannot be detected via XRD and thus,
further characterization techniques were employed.
Fig. 6 presents the temperature programmed oxidation
(TPO) profiles obtained over all spent catalysts tested herein.
Different types of carbon have been reported to accumulate on
Ni catalysts during reforming reactions, such as amorphous
and crystalline carbon structures [14,18,89]. It is also known
that not all kinds of carbon contribute equally to the loss of
Fig. 6 e TPO profiles of the spent catalysts after DER
reaction at 600  C for 8 h and amount of carbon combusted
from the spent samples expressed in mmol of carbon per
catalyst gram (inset) (Results obtained for samples tested
under Experimental Protocol #2).
5347
catalytic activity. In general, the peaks up to 250  C correspond
to amorphous carbon weakly adsorbed on the surface of
metallic Ni nanoparticles. Peaks from 250 to 500/550  C can
also be attributed to amorphous carbon, which is however
more strongly bound at the catalyst surface. TPO peaks at
temperatures between 500/550e600/650  C can be attributed
to the combustion of carbon nanofibers (CNFs) and carbon
nanotubes (CNTs), while highly crystalline carbon structures,
such as multi-walled carbon nanotubes (MWCNTs) combust
at temperatures over 600/650  C [14,18,51,52]. When exam-
ining the spent catalysts, it appears that the deposited carbon
is mostly amorphous, however the coke on the spent Ni/
Mg,CaeAl2O3 and Ni/LaeAl2O3 catalysts is combusted at lower
temperatures compared to the spent Ni/Al2O3. A possible
explanation for this behavior, is that the higher population of
basic sites provided by the alkaline earth (MgO and CaO) and
lanthanide (La2O3) dispersed promoter phases can aid the
gasification of weakly adsorbed and amorphous carbon spe-
cies at lower temperatures [18,52]. The fact that Ni/
Mg,CaeAl2O3 and Ni/LaeAl2O3 catalysts contain rather more
alkaline sites of moderate and high strength, compared to Ni/
Al2O3, has also been demonstrated via the CO2-TPD profiles
(Fig. S4).
The amount of carbon combusted during the TPO experi-
ments was also calculated (expressed in mmol of carbon per
catalyst gram) and was found at 6.29 mmol/g for Ni/Al2O3,
5.91 mmol/g for Ni/Mg,CaeAl2O3 and 4.81 mmol/g for Ni/
LaeAl2O3. These values reflect the trend regarding the activity
and time-on-stream stability observed for these catalysts
(Fig. 2), i.e., Ni/LaeAl2O3 was found to be the most active and
stable and Ni/Al2O3 the least active and stable. Therefore, it is
further confirmed that highly dispersed alkaline oxide phases
of moderate and high strength over the support act to disturb
the process of coke formation, by leading to lower carbon
deposition (quantity) that is of different nature (quality), i.e.,
higher fraction of amorphous carbon deposits.
TEM images of the spent Ni/Al2O3, Ni/Mg,CaeAl2O3 and Ni/
LaeAl2O3 catalysts are presented in Fig. 7. Deposited carbon is
quite apparent in all of the spent catalysts, with its observed
forms being amorphous carbon, as well as carbon allotrope
structures in the shape of filamentous carbon i.e., multi-wall
carbon nanotubes (MWCNTs), and/or carbon nanofibers
(CNFs) [18]. Fig. 8 provides a more detailed overview of the
carbon structures, where Ni nanoparticles are indicated by red
circles. The formation of carbon filaments appears to differ in
the three catalysts. The typical tip-growth mechanism [47] that
detaches the Ni nanoparticles from their support is quite
prevalent in the spent Ni/Al2O3 catalyst, with Ni nanoparticles
acting as seeds for the carbon nanotube growth, leaving
MWCNTs with either attached or detached nanoparticles. On
the Ni catalysts supported on modified alumina, a larger pro-
portion of Ni nanoparticles appear to be attached to their
respective supports, suggesting that carbon could also grow on
top of the nanoparticles, with the carbon tubes appearing to be
less continuous. This behavior could also be attributed to the
presence of a higher population of alkaline sites (CO2-TPD,
Fig. S4), as well as to the stronger metal-support interaction (H2-
TPR, Fig. S3) observed for the Ni/Mg,CaeAl2O3 and Ni/LaeAl2O3
catalysts. From the Ni nanoparticle size histograms presented
in Fig. 7, it appears that sintering did not occur in any of the
5348 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 7 ( 2 0 2 2 ) 5 3 3 7 e5 3 5 3

Fig. 7 e TEM images and particle size histograms of the spent (a) Ni/Al2O3, (b) Ni/Mg,CaeAl2O3 and (c) Ni/LaeAl2O3 catalysts
after DER reaction at 600  C for 8 h (Results obtained for samples tested under Experimental Protocol #2).

Fig. 8 e TEM images of the spent (a) Ni/Al2O3, (b) Ni/Mg,CaeAl2O3 and (c) Ni/LaeAl2O3 catalysts, after DER reaction at 600  C
for 8 h (Results obtained for samples tested under Experimental Protocol #2), showing the carbon allotrope structures. Ni
nanoparticles are indicated by red circles. (For interpretation of the references to color in this figure legend, the reader is
referred to the Web version of this article.)

materials tested herein, at least to a substantial effect. A formed carbon filaments [46]. Therefore, the largest contributor
possible explanation for the fact that Ni nanoparticles are to the catalyst degradation is not the sintering of the metallic Ni
smaller in the spent Ni/Al2O3, compared to the reduced one, is nanoparticles, but rather the formation of filamentous carbon
the melting and confinement of the nanoparticles by the structures, which especially in the case of Ni/Al2O3, appear to
 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 7 ( 2 0 2 2 ) 5 3 3 7 e5 3 5 3 5349

completely detach the Ni nanoparticles and sever their inter-
action with the Al2O3 support.
XPS analyses of the spent catalysts were also conducted.
Table S5 contains the peak binding energies and elemental
surface concentrations. All three spent catalysts present a
similar and very high surface carbon content (85.2e86.9 at.%),
which is slightly higher for Ni/Al2O3, compared to the other
two catalysts. This very high surface carbon content arises
from the extensive deposition of coke [18,46] during the DER
reaction at 600  C. As a consequence, the surface concentra-
tions of all the other elements appear particularly low
(0.2e0.3 at.% for Ni, 2.8e4.4% for Al and 8.9e11.6% for O). The
oxygen surface content appears to be lower for spent Ni/Al2O3
and higher for spent Ni/Mg,CaeAl2O3. The higher oxygen sur-
face content for the latter catalyst could potentially contribute
to the easing of coke combustion, as evidenced by TPO (Fig. 6).
Fig. 9aec presents the Ni 2p region of the XPS spectra of the
spent catalysts (the La 3d region is also presented for spent Ni/
LaeAl2O3). The spent catalysts contain two main types of Ni,
i.e., metallic Ni0 (low energy peak at z 853.0 eV) and Ni2þ
incorporated into the Al2O3 lattice in the form of NiAl2O4 (high
energy peak at z 856.5e857.1 eV), with the presence of some
NiO (z854.5 eV) also being possible [18,46,52]. As mentioned
previously, the ex-situ XPS characterization is expected to
result in catalyst re-oxidation to some extent, though in this
case, the presence of metallic Ni in all three spent catalysts is
quite apparent. A higher percentage of metallic Ni (as
observed via the relative intensities of the peaks attributed to
Ni0 and NiAl2O4) appears to be present in the spent Ni cata-
lysts supported on modified alumina (with MgO/CaO and
La2O3). It should also be noted again, that the Ni 2p region
overlaps with the La 3d3/2 peak for the Ni/LaeAl2O3 catalyst

Fig. 9 e XPS peaks (aec) Ni 2p (and La 3d in (c)); (d) O1s; (e) C 1s; (f) derivative of the XPS excited C KLL Auger spectrum, for the
spent Ni/Al2O3, Ni/Mg,CaeAl2O3 and Ni/LaeAl2O3 catalysts after DER reaction at 600  C for 8 h (Results obtained for samples
tested under Experimental Protocol #2).
5350 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 7 ( 2 0 2 2 ) 5 3 3 7 e5 3 5 3
[18]. Nevertheless, the Ni 2p peak shape in this case is similar
to that of the other two samples.
The O1s spectra are presented in Fig. 9d and two different
oxygen species, i.e., lattice oxygen and surface hydroxides, can
be observed, similar to the reduced catalysts [52]. However,
peak fitting indicates that a much higher percentage of surface
hydroxyl species are present in the spent Ni/Mg,CaeAl2O3.
Regarding the intense peaks observed at the C 1s region
(Fig. 9e), their shape and binding energy indicates the carbon to
be sp2 hybridized [18]. The sp2/sp3 ratio is also reflected in the
D-parameter obtained from the differentiated X-ray excited C
Auger KLL peak (Fig. 9f) [46]. The D-parameter is calculated
from the binding energy difference between the most positive
and the most negative points in the differentiated spectrum.
The D-parameter values were found to be 20.0 eV for the spent
Ni/Al2O3 and Ni/LaeAl2O3 catalysts and 20.8 eV for the spent
Ni/Mg,CaeAl2O3. These values are typical of sp2 hybridized
graphitic carbon (z90% sp2 hybridization) [18,46,90].
It is known, that different reaction conditions can lead to
the formation of different types of carbon. Previously, it has
been shown that the dry reforming of biogas (i.e., methane dry
reforming) at low operating temperatures (e.g., 600  C) can
induce severe catalyst degradation, as it favors extensive
deposition of carbon [14,18]. This is also confirmed by the
study presented herein. Based on the study reported by
Damaskinos et al. [91], which traced the origin of coke on
spent catalysts after DMR on the methane decomposition
side-reaction over the Ni metallic surface, we could assume
that the origin of the deposited carbon lies in the decompo-
sition (i.e. cracking) of ethane, since ethane is thermody-
namically less stable than methane and thus its dissociation
over the Ni active sites would be more favored [79,81].
Summarizing, from the analysis of carbon deposits on the
different catalysts tested herein, it appears that the incorpo-
ration of basic alkaline earth (MgO and CaO) and lanthanide
(La2O3) promoter phases on the support disturbs the typical
tip-growth carbon formation mechanism, thus maintaining
the metal-support interaction and favoring the gasification of
coke at lower temperatures. On the other hand, tip-growth
carbon formation on Ni/Al2O3, that contains alkaline sites of
lower strength and demonstrates a relatively weaker metal-
support interaction, uplifts and encapsulates the active Ni
particles, resulting in a severe catalyst degradation.
Conclusions
A comparative investigation of the catalytic performance of Ni
catalysts supported on Al2O3, MgO- and CaO-modified Al2O3,
as well as La2O3-modified Al2O3 during the dry ethane
reforming reaction was performed. It was shown, that the
modification of the alumina support with alkaline earths and
lanthanides could promote the dispersion of the Ni active
phase, enhance the metal-support interaction and increase
the catalyst's basicity and thus propensity for CO2 activation.
The Ni catalysts supported on modified Al2O3 were superior to
the Ni/Al2O3 benchmark, as they provided a higher catalytic
stability in terms of C2H6 and CO2 conversion at 600  C, as well
as a constant and high yield for the two syngas components,
namely CO and H2. Characterization of the spent catalysts also
revealed that carbon deposited over Ni/Al2O3 appeared to be
more pronounced and followed the tip-growth mechanism,
that severed the metal-support interaction and was harder to
combust, whereas the gasification of deposited carbon pro-
ceeded easier on the Ni catalysts supported on alumina that
contained dispersed phases of alkaline metal oxides. In gen-
eral, our best-performing Ni/LaeAl2O3 catalyst, which
exhibited a high population of alkaline sites and a strong
metal-support interaction, is quite promising for the dry
ethane reforming reaction, as its catalytic performance com-
pares favorably with other studied catalysts in the literature.
Declaration of competing interest
The authors declare that they have no known competing
financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
Acknowledgements
MAG and NDC gratefully acknowledge that this research has
been co-financed by the European Union and Greek national
funds under the call “Greece e China Call for Proposals for
Joint RT&D Projects” (Project code: T7DKI-00388). KP ac-
knowledges the support from Khalifa University through the
grant RC2-2018-024.
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.ijhydene.2021.11.194.
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