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 ) 4 2 8 e4 4 2

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Synergistic effect of MgH2 doping with Ni and

carbon nanotubes on thermochemical CO2
recycling process for CH4-H2 mixtures production

Guillermina Amica a,*, Fabiana C. Gennari a,b,c

a
Consejo Nacional de Investigaciones Cientı́ficas y T
ecnicas (CONICET), Centro At
omico Bariloche (CNEA), Av.
Bustillo 9500, R8402AGP, S.C. de Bariloche, Rı́o Negro, Argentina
b
Comisi
on Nacional de Energı́a At
omica, Departamento Fisicoquı́mica de Materiales, Gerencia de Investigaci
on
Aplicada, Centro At
omico Bariloche, Av. Bustillo 9500, R8402AGP, S.C. de Bariloche, Rı́o Negro, Argentina
c
Universidad Nacional de Cuyo (Instituto Balseiro), Centro At
omico Bariloche (CNEA), Av. Bustillo 9500, R8402AGP,
S.C. de Bariloche, Rı́o Negro, Argentina

highlights graphical abstract

CO2 was transformed to CH4 by

thermochemical processes using
MgH2 as hydrogen source.

Ni and CNTs addition to MgH2 has
a synergetic effect on CH4 yield.

COx-free mixture of CH4:H2 were
produced from CO2 conversion at
350  C.

Ni-containing species are selective
catalysts that promote the Sabat-
ier reaction.

CNTs might act as hydride pro-
tection retarding its oxidation.

article info abstract

Article history: The synergistic effect of the nickel and carbon nanotubes addition on thermochemical
Received 10 August 2021 processes for CO2 recycling employing MgH2 as hydrogen source was demonstrated. By
Received in revised form reducing the metallic charge from 10wt.% Ni, replacing 5wt.% with CNTs, the amount of
13 September 2021 produced methane through thermal treatment at ~350e375  C under CO2 increased more
Accepted 1 October 2021 than 30%. A COx-free mixture of methane (70.9%) and hydrogen (29.1%) with a CH4 yield of
Available online 20 October 2021 79% was obtained by reaction at 350  C during 48 h. Ni-containing species act as selective
catalyst promoting the occurrence of the Sabatier reaction, which competes with the direct
Keywords: reduction of CO2 to generate CH4 via C as an intermediary. The role of CNTs is not catalytic
Hydrides but rather it could be related to the protection of the hydride. It is proposed that when
Carbon dioxide

* Corresponding author.
E-mail address: guillerminaamica@gmail.com (G. Amica).
https://doi.org/10.1016/j.ijhydene.2021.10.007
0360-3199/© 2021 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
 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 ) 4 2 8 e4 4 2
Hydrogen-methane mixtures MgH2 is neighbored by graphitic planes, its oxidation due to direct contact with CO2 and/or
Carbon nanotubes the generated H2O could be impeded or retarded.
© 2021 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
Introduction
Human activities, in particular the massive use of fossil fuels,
are altering the climate system. According to the Intergov-
ernmental Panel on Climate Change (IPCC), sustained emis-
sions of greenhouse gases, where CO2 accounts for 86%, are
causing negative effects on the environment as there is a direct
relationship between the excessive emissions of greenhouse
gases and the increase in global temperature [1]. Therefore,
immediate actions are necessary to limit and reverse these
emissions and minimize any additional climate change.
Different scenarios are modeled to reduce CO2 concentration
and in all of them the development of technologies that allow
the capture, storage and/or conversion of CO2 play a crucial
role [2e4]. The CO2 transformation through catalytic processes
to products with added value (methane, methanol or other
fuels) is attractive both from an environmental and economic
point of view, since it can be considered an alternative to
employ a contaminant as a building block for fuels. Recently,
the Sabatier reaction through which carbon dioxide can be
combined with hydrogen at elevated temperatures and pres-
sures in the presence of a catalyst to produce methane and
water [5], has renewed relevance as an alternative for storing
the excess renewable energy produced during peak generation
periods and converting it into a grid compatible gas [6e11]. On
the one hand, there is a large methane gas distribution infra-
structure in many countries that allows its direct injection into
the existing gas network. On the other hand, considering mo-
bile devices, the difficulties related to intensive energy
requirement for ignition of a methane-powered vehicle can be
overcome by the use of Hythane, a mixture of hydrogen and
methane [12] as it was verified that, with the addition of
hydrogen, the fuel is easier to ignite with less energy input and
heat efficiency can be improved [13e16]. In order to reach an
acceptable rate and selectivity for the Sabatier process, the use
of appropriate catalysts is mandatory and its performance
depends on the nature of the catalyst, the structures of clusters
and the catalyst's support (oxides, zeolites, clays, mesoporous
materials) [17e23]. According to literature, the following order
of activity for various metals in CO2 methanation is revealed:
Ru > Rh > Ni > Fe > Co > Os > Pt > Ir > Mo > Pd > Ag > Au and the
following considering selectivity: Pd > Pt > Ir > Ni > Rh >
Co > Fe > Ru > Mo > Ag > Au [20]. Chemisorption of CO2 on
other transition metals such as iron, cobalt, nickel and copper
was proved to be spontaneous and due to their lower cost that
allows industrial application, they became widely explored.
The surface structure of the metal strongly alters the ther-
modynamic of the catalytic process, affecting both the acti-
vation and the reduction steps involved in CO2 hydrogenation
[18e20]. Co, Fe and Ni catalysts exhibit similar methanation
activity. However, cobalt is not suitable for industrial applica-
tions due to the high cost compared to Ni or Fe catalysts and Fe
429
catalysts are reported to have a reasonable activity but low
selectivity for CH4 [20]. Then, Ni-based catalysts supported on
Al2O3, SiO2, CeO2, ZrO2, CeeZrO2, zeolites or carbonaceous
materials have been deeply studied [17e27]. In particular, for
the purposes of this work, it is interesting to mention the
performance of Ni supported on Mg, MgO or carbon. Due to the
synergistic effect of Ni and Mg species, MgO was proved to be a
good support on which CO2 is strongly adsorbed [25]. Stable
and active Ni/MgO methanation catalyst, prepared by wet
impregnation, followed by calcination in air and reduction in
hydrogen, exhibited high CO2 conversion (~70%) and CH4
selectivity near thermodynamic equilibrium at moderate
temperatures (330  C) [28]. Moreover, magnesium modified Ni/
coconut shell carbon catalysts showed outstanding activity
and excellent stability, which performed the highest CO2
conversion (~90%) and CH4 selectivity (~99%) at 450  C [29]. In
addition, carbon nanotubes (CNTs)-supported catalysts dis-
played better catalytic activity than the Al2O3-supported cata-
lysts (74 and 47% CH4 yield at the initial stage, respectively).
The advantages were attributed to the large specific surface
areas of CNTs, which are conducive to the dispersion of nickel
species and to the high hydrogen storage capacity of CNTs that
promote the hydrogenation of CO2. However, its catalytic ac-
tivity decreased with the reaction proceeding due to the pro-
gressive sintering of nickel [30].
Recent studies have shown that CO2 can be reduced on the
surface of different types of hydrides through thermochemical
processes at moderate temperature and pressure [31e41]. This
allows the use of H2 stored safely in a solid matrix for the
transformation of CO2 into synthetic gas. Compared to mo-
lecular hydrogen, the negatively charged hydrogen atom of
metal hydrides has a stronger reducibility. It was demon-
strated that in a mixture of H2 and CO2, methane was markedly
formed on the metal hydride ZrCoHx during desorption and
not on the pristine intermetallic [42]. This is evidence that
atomic hydrogen on the surface of a metal with high hydrogen
solubility could facilitate the reduction of CO2 to CH4 [42]. Due
to their light weights and high capacities, alanates and boro-
hydrides have been studied for this application. Gassolid re-
action of CO2 with alanates (NaAlH4, LiAlH4) was proved to
occur in two distinct temperature regions (128e144  C and
145e250  C), yielding methane, hydrogen gas, and metal oxides
as the major products [31]. A recent study showed that me-
chanically activated alanates heated at 450  C for 48 h with CO2
exhibit high selectivity, fast kinetics and an interesting
methane yield of 44 and 52%, for the LiAlH4-CO2 and NaAlH4-
CO2 systems, respectively [32]. Reaction between different
metal borohydrides (BH3NH3, LiBH4, NaBH4 and KBH4) with COx
under different experimental conditions lead to a large quan-
tity of organic and inorganic compounds [43e45]. Among
them, the g-Mg(BH4)2 phase reacts with CO2 with rapid kinetics
at 30  C and 1 bar, mainly to produce formate and alkoxide-like
compounds [33] and KBH4 reacts with CO2 in solvent-free
430 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 ) 4 2 8 e4 4 2
conditions upon 500  C to generate potassium for-
mylhydroborates, hydrogen, methanol, carbon monoxide and
a small amount of methane [34]. Magnesium based-metal hy-
drides containing Ni or Fe can be considered suitable dual
conversion promoters and hydrogen sources for CO2 reduction
because the segregation of metallic nanoparticles increases
the catalytic activity of the system [35,36]. It was postulated
that the reaction rate of the CO2 hydrogenation process on the
surface of Mg2NiH4 is determined by the dissociative adsorp-
tion of CO2 molecules instead of the dissociation of H2 mole-
cules on the hydride [35]. Total conversion of CO2 was reached
after heating Mg2FeH6 and Mg2NiH4 under CO2 with a 4H2:CO2
molar ratio at 400  C during 5 and 10 h, respectively. For the
former, due to the catalytic action of Fe particles, the process
involves water-gas shift reaction followed by the methanation
of CO in the presence of steam [36]. For the later, in addition to
the catalytic reaction, the CO2 direct reduction has a substan-
tial contribution due the poisoning of Ni-based compounds by
CO during the early step of the reaction, hindering its further
catalytic action [36]. Methanation via-Mg2NiH4 synthesized by
in situ monitoring mechanical milling under hydrogen atmo-
sphere from a 2MgH2:Ni stoichiometric mixture [37] was
proved to be faster than via-Mg2NiH4 prepared by a two-step
procedure involving milling and sintering at high tempera-
ture [36]. This demonstrates that the complex hydride syn-
thesis method has big influence on the catalyst-support
interaction, affecting the methanation global mechanism [37].
Alkali metal hydrides (LiH and NaH) or alkaline-earth metal
hydrides (CaH2 and MgH2) in the absence of a catalyst have
shown their best performance for thermochemical CO2
reduction by heat treatment at 450  C for 48 h through a pro-
cess considering elemental carbon as an intermediate for the
formation of methane [38,39]. Moreover, it was demonstrated
that COx-free H2-mixed CH4 fuels can be obtained thought
thermochemical reaction between inorganic carbonates and
activated metal hydrides, as sources of CO2 and H2, with high
yields and selectivity. According to the experimental tuning,
CH4 content can range from 8.6% to 88.1% [40]. Our previous
investigation on the un-catalyzed reaction between MgH2 and
CO2, showed that a methane yield of 44.6% was obtained after
24 h of thermal treatment at 400  C employing a molar ratio
MgH2:CO2 of 2:1, through a methanation mechanism that
involved the direct reduction of CO2 and the generation of CH4
via C as an intermediary [41]. When either the temperature or
the reaction time was lowered, the yield values dropped
sharply due to partial reduction of CO2 to CO. Moreover, it was
proved that the presence of a catalyst and its nature allows the
methanation to follow another path of reaction, a mechanism
that responds to a Sabatier process. Through the incorporation
of an active catalyst, by heat treatment at 350  C for 48 h
considering a molar ratio MgH2:CO2 of 4:1, MgH2 doped with
10 wt% Co achieved a methane yield of 78% and the resulting
gas mixture was composed of CH4 (49.7%), CO2 (0.5%), CO
(<1000 ppm) and the rest of H2 [41]. The calculated methane
yield was not only considerably higher than the one previously
reported at 350  C (17%) but, interestingly, it was also higher
than that reported at 450  C (68%) for un-catalyzed MgH2 [39].
Then, the use of cobalt allowed lowering the operational
temperature without affecting the methane yield [41].
To the best of our knowledge, there are no other previous
investigations involving catalyzed-hydrides systems for CO2
conversion. Our current effort is orientated to the study of
hydrides-based systems that act as a source of hydrogen, which
in the presence of an active catalytic phase and under suitable
experimental conditions can generate significant amounts of
methane or CO2-free methane-hydrogen mixtures, through
processes with low operating temperature and fast reaction ki-
netics. The use of a solid matrix allows the safe storage of H2
produced from renewable energies. As hydride-forming mate-
rials can be employed to transform in-situ a polluting gaseous
waste into products with added value, through this approach,
the H2 cycle can be integrated into that of CO2. In this work we
analyze the feasibility of employing nickel-catalyzed MgH2 with
the incorporation of multi-walled carbon nanotubes for efficient
thermochemical CO2 conversion processes. Nickel and carbon
nanotubes synergy is demonstrated. The metal acts as an active
catalyst to promote the Sabatier process, whereas it was sug-
gested that CNTs protect the hydride from being oxidized by
preventing its direct contact with the CO2 and/or H2O. Through
reaction between Ni/CNTs edoped MgH2 and CO2 at 350  C
during 48 h, a gas phase free of CO2 or CO, composed of CH4
(70.9%) and H2 (29.1%) can be obtained, with a calculated a
methane yield of 79%.
Experimental
Material preparation
For the experiments, magnesium hydride (MgH2, 98%),
metallic nickel (Ni, 99.99%) and multi-walled carbon nano-
tubes (CNT, <95%) were purchased at Sigma-Aldrich. Due to
the high reactivity of the samples, they were handled in an
MBraun Unilab argon filled glove box, with oxygen and
moisture levels lower than 10 ppm. For all studies, high purity
argon (Linde, 99.999%) was used. Ball milling in a planetary
mill (Fritsch Pulverisette 6) was employed to prepare four
samples: (i) MgH2 and (ii) MgH2e10wt.% Ni, (iii) MgH2-5wt.%Ni-
5wt.%CNT and (iv) MgH2-5wt.%CNT. All samples were ball
milled for 5 h at 500 rpm with a ball to powder mass ratio of
53:1 using a sequence of 10 min milling and a 15 min pause.
Characterization of samples
The reaction between the samples and CO2 under different
experimental conditions was studied under static and dy-
namic conditions. Static measurements were performed in a
stainless steel reactor coupled to Sieverts volumetric equip-
ment that allows the selection of the pressure and tempera-
ture. A specific mass of each sample was introduced in the
reactor inside the glove box to avoid contamination with ox-
ygen or air humidity and then heated up with a ramp of 10  C
min1 to different temperatures (300, 350, 375 and 400  C)
under CO2 pressure during different reaction times (6, 12, 24
and 48 h). In all cases a molar ratio MgH2:CO2 of 4:1 was
considered. Under dynamic conditions, the samples were
heated at 5  C min1 up to 450  C in a continuous flow of CO2,
using a TG Analyzer (TG-HP50, TA Instruments). Additionally,
 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 ) 4 2 8 e4 4 2
the experiment was carried out using a flow of He to analyze
the decomposition of the sample in an inert atmosphere.
The composition of the gases after thermal treatment
under CO2 was studied through gas-phase FTIR analyses
(FTIR, PerkinElmer Spectrum 400 with an MCT detector) and
gas chromatography (GC, Agilent Technologies GC System
7820A). For the GC experiments 1 ml of the released gas was
taken using a syringe, which was injected into the GC equip-
ment. The molar amounts of gaseous CO2, CH4 and CO were
quantified using calibration curves. The methane yield was
calculated as the ratio between the produced CH4 moles and
the total CO2 moles at the beginning of the reaction. A nu-
merical example is available in the Supplementary Material
(see Methane yield calculation S1). For IR spectroscopy mea-
surements, the gases released were collected in a degassed
quartz optical cell with KBr windows and an optical length of
9 cm. The gas phase spectra at room temperature were taken
considering transmittance mode with a resolution of 0.5 cm1
and 10 scans. During each spectrum acquisition, part of the
optical path was in air atmosphere, so a baseline measure-
ment was required prior to each measurement. The structural
characterization of the solid samples was studied using X-ray
powder diffraction (XRPD, Bruker D8 Advance) and Fourier
transform infrared spectroscopy (FTIR, PerkinElmer Spectrum
400 with an MCT detector). An airtight holder (which has a
bump in the zone of 2q ¼ 15e25 ) was employed during the
XRPD data collection to prevent any reaction between the
samples and air. For IR spectroscopy measurements, the
samples were ground with dry KBr under a purified argon
atmosphere, pressed into pellets and placed in a specially
designed airtight cell. Solid state IR spectra were obtained in
the range of 4000e800 cm1 with a resolution of 4 cm1.
Morphological analysis of the samples was performed by
scanning electron microscopy (SEM, SEM-FIB, Zeiss, Cross-
beam 340), employing dispersed powders on carbon tape.
Elemental analyses of the materials were also performed by
energy-dispersive X-ray spectroscopy (EDXS) on the SEM.
Thermodynamic calculations
The equilibrium compositions for the Ni catalyzed MgH2eCO2
system as a function of temperature and total system pressure
were calculated using HSC Chemistry Windows [46]. The
program calculates the combination of the most stable species
and the phase composition to minimize the Gibbs free energy
of the system. The calculation was conducted based on the
gas phase containing CO, CH4, C2H6, CH3OH, H2O, H2, O2 and
CO2 and the solid phase containing MgCO3, MgO, Mg, MgH2,
Mg(OH)2, Ni, NiO, Ni (FCC), Ni(OH)2, Ni3C, Mg2Ni, MgNi2, C
(graphite) and C (amorphous).
Results
CO2 conversion employing Ni-doped MgH2 under static
conditions
A sample composed of magnesium hydride with 10wt.%
nickel was prepared through mechanical ball milling as
reactivity increase is expected with agglomerate and/or
431
crystallite size reduction. The chosen milling time (5 h) was
based on preliminary results, which indicated that during the
first 2 h only a reduction in particle size occurs without any
real mixing of the components [47]. Between 2 and 4 h Ni is
dispersed in the material, allowing Ni to be distributed on the
surface of the MgH2 or within its matrix, and thus can play its
role as a catalyst. After 4 h an effective mixing of the com-
ponents is produced accompanied by microstructure refine-
ment due to additional reduction of particle sizes [47]. For
these reasons and to minimize possible contamination with
Fe from the milling jar, a duration of 5 h was selected. SEM
images of the sample after ball milling shows agglomerate
size distribution between 5 and 50 mm (Fig. 1A). The sample
was characterized by its spongy shape, with some central
solid blocks and a large quantity of small agglomerates
adhering to its surface (Fig. 1B). Element mapping obtained by
EDXS indicated a homogeneous distribution of Ni (Fig. S2). To
investigate the conversion of CO2 in the presence of MgH2
with catalyst addition, the as-milled Ni-doped sample was
heated up to different temperatures in static conditions
under a CO2 atmosphere during a period of 24 h, considering a
molar relation MgH2:CO2 of 4:1 (see Table 1). Thought
elemental mapping it was verified that after the sample was
subjected to thermal treatment at 375  C under CO2 during
24 h, there was no migration or agglomeration of Ni (Fig. S3).
A wider size distribution with agglomerates of up to 200 mm
(Fig. 1C) and fewer exposed flat faces (Fig. 1D) were observed.
The gas-state products of the reaction between MgH2 and
CO2 were identified by FTIR (Fig. 2) and quantified by GC (Table
1). Clear H2 and CH4 chromatography peaks were detected at
all temperatures. A minor excess of CO2 and co-generation of
a minor percent of CO were also detected in some cases. A
direct relationship was observed between the operating tem-
perature and both the molar percentage and the yield of CH4.
As it can be observed in Table 1, when temperature was
reduced from 400 to 350  C, these values decreased from 50.2
to 35.2 and from 64.5 to 44.9, respectively. At this temperature
range, gaseous mixtures composed mainly of CH4 and H2 were
obtained and the remaining amount of CO2 in the gas
remained below 2%. However, when the temperature was
lowered, this mixture became enriched in H2. As the amount
of CO2 remained practically unchanged, the lower content of
CH4 suggests the formation of some other carbon-containing
species in the solid phase [41]. Moreover, thermal treatment
at 300  C was not enough to achieve a considerable rate of CO2
conversion. In this condition the gas phase was mainly
composed of unreacted CO2. The presence of CO was
confirmed by FTIR analyses at 300 and 350  C, unlike obser-
vations at higher temperatures. Regarding the operation time,
it was observed that at 350  C the increase from 24 to 48 h of
thermal treatment allowed a large growth in the amount of
methane in the gas phase, which raised from 35.2 to 67.7% and
in the methane yield from 44.9 to 74.2%. The difference cannot
be explained by the variation of CO2 in the gas phase, but
rather by the solid gas reaction of H2 with some component of
the solid phase. Gas-state FTIR was useful to identify the
presence of water in the gas phase in all the range of tem-
peratures (Fig. 2).
The evolution of the phases in the solid product due to the
interaction with CO2 was studied by XRPD (Fig. 3) and FTIR
432 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 ) 4 2 8 e4 4 2

Fig. 1 e SEM images of secondary electrons of the MgH2e10wt.% Ni sample as-milled (A and B) and after reaction with CO2 at
375  C during 24 h (C and D).

Table 1 e Gas-phase composition determined by GC analyses for as-milled MgH2-10wt.%Ni.

Temperature Reaction Molar percentage Molar percentage Molar percentage Molar CH4 yield
(ºC) time (h) of CH4 (%) of CO2 (%) of CO (%) percentage of H2 (%) (%)
400 24 50.2 0.8 <1000 ppm 49 64.5
375 24 45.5 1.9 <1000 ppm 52.6 57.5
350 24 35.2 0.4 1.2 63.2 44.9
350 48 67.7 1.2 <1000 ppm 31.1 74.2
300 24 2 89.6 0.6 7.8 1.7

(Fig. S4). Although the XRPD profile of the as-milled sample

Fig. 2 e Gas-state FTIR patterns for the as-milled MgH2-
10wt.%Ni sample after thermal treatment (24 h) under CO2
at different temperatures.
revealed low crystallinity after milling, the absence of impu-
rities was confirmed. The broad and weak diffraction peaks
showed that mechanical milling was effective in reducing the
particle size. As expected, the as-milled sample was mainly
composed of MgH2. Nickel peaks were also identified, veri-
fying that it remained in metallic state after milling. However,
weak diffraction peaks located at 2q ¼ 23.7 and 39.2 suggests
the incipient formation of Mg2NiH4 (cubic phase). No free Mg
was identified, which indicates that there was no decompo-
sition of the hydride. An orthorhombic metastable phase of
MgH2 (g-MgH2) was identified. Although this phase is formed
from the tetragonal phase (b-MgH2) at a pressure of 25 bar and
the milling was carried out at atmospheric pressure, the
impact of the balls on the wall can generate higher local
pressures that allows the generation of a minority amount of
the g phase [48]. The diffractograms obtained after heating
showed narrower peaks since high temperatures allow grain
growth and reduction of stresses and deformations present in
the crystalline network. After thermal treatment under CO2,
for all samples, Mg, MgO and unreacted MgH2 were identified.
 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 ) 4 2 8 e4 4 2
Fig. 3 e XRPD profiles of the as-milled MgH2e10wt.%Ni
sample and after thermal treatment under CO2 during 24 h
at different temperatures.
At 300  C the reflections corresponding to Mg2NiH4 became
very clear and metallic Ni was difficult to identify. At this
temperature the g phase was still detected. The weakly
identification of only the most intense reflection of Mg
(2q ¼ 36.6 ), suggests that dehydrogenation was poor, probably
due to passivation of the MgH2 surface with CO2. At higher
temperatures, the increase in the intensity of the Mg and MgO
peaks indicates that the hydrogen desorption progressed
much more than what happened at 300  C and, as expected,
the g-MgH2 was no longer observed [48]. Interestingly, partial
decomposition of Mg2NiH4 into Mg2NiH0.3 (hexagonal phase)
was detected. Solid-state FTIR (Fig. S4) showed the presence of
MgH2, whose stretching bands consist of various peaks with
the strongest one at 1246 cm1 and the bending band at
658 cm1, in all the samples. After heating under CO2, some
bands in the region 1700e1000 cm1 that could be related to
the presence of carbonates favored by the higher CO2 pressure
were detected. Although by XRPD no carbonates were identi-
fied in the bulk of the solid sample, the FTIR bands located at
1670, 1590, 1260 and 1130 cm1 could be attributed to the vi-
bration modes of superficial carbonate bidentate on MgO [49].
A weak band that is not associated with carbonates is
observed at 1150 cm1. It has been already demonstrated that
since many metal oxides and hydroxides adsorb CO2 readily at
room temperature, the oxidized surfaces allowed the gener-
ation of carbonate species on the top few layers [50].
CO2 conversion employing Ni and CNTs-doped MgH2 under
static conditions
As the main goal of this study is to achieve high CO2 conver-
sion rates under moderate conditions, the experimental
approach was oriented to the reduction of both the operating
temperature and the reaction time. A sample with double
doping was prepared, considering nickel and multi-walled
carbon nanotubes, in which each additive represented 5wt.%
of the total weight. This means a 5% decrease in the metallic
charge compared to the previous sample. It has been previ-
ously shown that the incorporation of CNTs into a doped
433
MgH2 matrix could improve the dispersion of a metallic phase
[51]. SEM images of the sample after ball milling showed
similar agglomerate sizes than the MgH2-10wt.%Ni sample,
without clear faces exposed (Figs. S5A and B) and element
mapping obtained by EDXS indicates a homogeneous distri-
bution of Ni (Fig. 4A).
To analyze the difference in reactivity of the samples, the
carbon dioxide absorption of the as-milled MgH2, MgH2-
e10wt.%Ni and MgH2e5wt.%Ni-5wt.%CNT was first studied
under dynamic conditions by thermogravimetry, under inert
and CO2 flux (Fig. 5). The response to heating under inert flow
of all samples displayed a one-step dehydrogenation reaction
with a big difference in the decomposition temperature. The
dehydrogenation temperature of MgH2 (330  C) was lowered
70  C by the addition of Ni and 80  C by the co-addition of Ni
and CNTs (estimated at 0.1% mass change). Under an inert gas
flow (Fig. 5A), the as-milled MgH2 released 7.3wt.% H2 at 400  C
(theoretical capacity of 7.6wt.% H2). With 10wt.% doping, the
measured capacity was ~6.2wt.% H2 (theoretical capacity
6.8wt.% H2). Fig. 5B shows that, for all samples, the constant
exposure to CO2 flux caused an increase in the mass from the
beginning of the heating and it was intensified at tempera-
tures higher than 350  C. In relation to temperature, the curves
were quite similar, with a small difference in the total mass
increase, ranging from 10 to 13wt.%. When the hydride is
exposed to a CO2 flux, its absorption retards the dehydroge-
nation by passivation or oxidation of the hydride surface and
H2 is released at higher temperatures with respect to an inert
gas flow.
Under static conditions and considering a molar relation
MgH2:CO2 of 4:1, the MgH2e5wt.%Ni-5wt.%CNT sample was
summited to different thermal treatments under CO2, varying
operational temperature and reaction time. The gas phase
compositions determined by GC are presented in Table 2. It
was verified that after thermal treatment, there was no
migration or agglomeration of nickel (Fig. 4B). Agglomerates of
up to 220 mm were observed (Figs. S5C and D).
FTIR analyses after thermal treatment during 24 h at
different temperatures and after thermal treatment at
400  C at different reaction times are shown in Figs. 6 and 7,
respectively. The obtained results are interesting and allow
several conclusions to be drawn. First, at 400  C, very similar
results were obtained after 12 and 24 h. Even though when
varying the duration of the thermal treatment a gas phase
richer in CH4 and poorer in CO2 and CO is expected, our
results indicate that at elevate temperatures, 12 h was
enough to obtain high molar percentage of methane (45.6%)
and an interesting methane yield (63.9%). However, when
performing a treatment of 6 h, a drop higher than 30% was
observed for both the molar percentage and methane yield
and the presence of higher hydrocarbons such as ethane or
propane (CxHy) can be suspected due to the weak absorption
peaks at 1470 and 2968 cm1 [38,41] (Fig. 7). This means that
even at high temperatures, the treatment time was crucial
to achieve desirable methane rates and high selectivity. At
350  C due to length treatment increase from 24 to 48 h, CH4
yield increased from 61.5 to 79%. Second, it was not possible
to decrease temperature below 350  C without collapsing
methane yield. Motivated by the good results at 350  C, the
reaction temperature was further decreased to 300  C.
434 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 ) 4 2 8 e4 4 2
Fig. 4 e SEM image of secondary electrons and Mg, Ni mapping of the MgH2-5wt.%Ni-5wt.CNT sample: as-milled (A) and
after thermal treatment under CO2 at 375  C during 24 h (B).
Fig. 5 e Thermogravimetric measurements of the MgH2,
MgH2e10wt.%Ni and MgH2e5wt%Ni-5 wt.%CNT samples
under CO2 (A) and He (B).
However poor results were obtained (CH4 yield 4.5%), most
of the CO2 remained unreacted and it was difficult to iden-
tify water in the gas phase. Third, although the results were
good for 24 h treatments in a CO2 atmosphere under static
conditions at 400 and 350  C, better results were obtained at
an intermediate temperature of 375  C, which allowed
obtaining a molar percentage of CH4 of 60.2% and a calcu-
lated CH4 yield of 74.5%.
XRPD analyses (Fig. 8) of the as-milled MgH2-5wt.%Ni-
5wt.%CNT sample revealed that there was no decomposition
of the hydride due to milling. The sample was mainly
composed of b-MgH2 with a small amount of g-MgH2 and
metallic nickel. Unlike what was observed for the Ni-doped
sample, no formation of Mg2NiH4 after milling was detected.
As expected, after thermal treatment under CO2, for all sam-
ples, Mg, MgO and unreacted MgH2 were identified. At 300  C
the reflections corresponding to Mg2NiH0.3 (hexagonal phase)
appeared, weak peaks could be assigned to Mg2NiH4 and
metallic Ni was no longer observed. At higher temperatures
the diffractograms were similar to those previously obtained.
The most important difference between both samples was
that during milling nickel did not react to form other com-
pounds, but remained in a metallic state. Moreover, at low
temperatures (300  C) there was already evidence of the
decomposition of Mg2NiH4 into Mg2NiH0.3. Only at 375  C the
relative intensity of the main peak corresponding to metallic
Mg is greater than that of the corresponding hydride. In order
to have a better clarity of the diffractogram, especially in the
region altered by an airtight holder (which has a bump at
2q ¼ 15-25 ), the sample subjected to a heating of 375  C for
24 h was additionally measured without using the holder
(Fig. S6). As the best results have been obtained under these
experimental conditions, it could be assumed that the dehy-
dration of the MgH2 was more effective and the amount that
remained has its surface well passivated, minimizing the risks
associated with the exposure of hydride to air. In this condi-
tion, the identification of the low angle peaks corresponding to
Mg2NiH0.3 and Mg2NiH4 at 375  C was clearer. Although the
 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 ) 4 2 8 e4 4 2 435

Table 2 e Gas-phase composition determined by GC analyses for as-milled MgH2-5wt.%Ni-5 wt.%CNT.

Temperature Reaction Molar percentage Molar percentage Molar percentage Molar percentage CH4 yield
(ºC) time of CH4 (%) of CO2 (%) of CO (%) of H2 (%) (%)
400 24 49.5 1 <1000 ppm 49.5 62.1
400 12 45.6 1.8 <1000 ppm 52.6 63.9
400 6 32.9 7.3 <1000 ppm 59.8 39.5
375 24 60.2 1.8 <1000 ppm 38.0 74.5
350 24 47.2 1.1 0.1 51.6 61.5
350 48 70.9 e e 29.1 79
300 24 5.3 76 0.1 21.6 4.5

Fig. 8 e XRPD profiles of the as-milled MgH2e5wt.%Ni-

Fig. 6 e Gas-state FTIR patterns for the as-milled MgH2-
5wt.%CNT sample and after thermal treatment at different
5wt.%Ni-5wt.%CNT sample after thermal treatment under
temperatures under CO2.
CO2 during 24 h at different temperatures.

peaks were narrower when the interference from the dome
was absent, it was possible to identify correctly all the phases
safely employing the airtight holder without exposing the
solid sample to air. Moreover, solid-state FTIR analyses
(Fig. S7) showed that of the presence of MgH2 (bands located at
1246 and 658 cm1) could not be ruled out. Moreover, biden-
tate superficial carbonates on MgO were identified (1670, 1590,
1260 and 1130 cm1) [49]. As for the previous sample, a weak
band located at 1150 cm1 could not be assigned to carbon-
ates. In addition, the resulting solid phase of samples after
thermal treatments at 400  C under CO2 with different times
were analyzed (Fig. S8). XRPD spectra for 12 and 24 h were
similar. At this temperature there was no signal of Mg2NiH4
formation, not even at low reaction times. The pattern for 6 h
did not show different phases. The metallic magnesium main
peak located at 2q ¼ 36.62 was considerably higher than for
the other cases and the relative intensity of this peak with
respect to the magnesium hydride main peak located at
2q ¼ 27.9 was also higher.

Discussion

Results presented in Tables 1 and 2 indicate that the mole

Fig. 7 e Gas-state FTIR patterns for the as-milled MgH2-
5wt.%Ni-5wt.%CNT sample after thermal treatment under
CO2 at 400  C with different reaction times.
percent and yield of methane in the gas phase for both reac-
tion systems depended strongly on the reaction temperature
and time. The obtained methane yield and molar percentage
of CH4 and H2 are summarized in Figs. 9 and 10.
The methanation mechanism is a complex process which
depends on the grade of microstructural refinement provided
by mechanical activation, operating conditions and incorpo-
ration of an active catalyst which could allow reducing the
operational temperature. The catalyzed conversion of CO2 to
CH4 using hydrides as a source of hydrogen has not been
436 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 ) 4 2 8 e4 4 2
Fig. 9 e Molar fraction of CH4 and H2 (A, B) and methane yield (C) after reaction with CO2 during 24 h at different
temperatures for the MgH2-10wt.%Ni and MgH2-5wt.%Ni-5wt.%CNT samples.
widely studied [36,37,41]. In our previous work, by heat
treatment at 400  C for 24 h, the MgH2 system with 10% co-
balt achieved a methane yield of 60.9% and the resulting gas
mixture was composed of CH4 (38.2%), CO2 (0.8%), CO
(<1000 ppm) and the rest of H2 [41]. Under the same experi-
mental conditions, the nickel-doped MgH2 exhibited better
performance (methane yield of 64.5% and molar percentage
of CH4 of 50.2%). Even by heat treatment at 350  C for 24 h the
results were better (methane yield of 59.7% with Co and
61.5% with Ni). Moreover, it was proved that the length of the
heat treatment influences the performance of the system. At
350  C, when increasing the time from 24 to 48 h, the
methane yield rose to 74.2%. This value is similar to that
previously obtained with Co under the same conditions
(78%), but with a higher percentage of methane (67.7 vs
49.7%). This shows that the nature of the catalyst has an
important function. Theoretical studies have shown that
both Co and Ni show favorable thermodynamics and low CO2
decomposition barriers [17]. Cobalt is placed at the top of the
volcano curve which compares the activities of different
supported transition metals as a function of the reaction
energy for dissociative CO chemisorption but the diagram is
not useful when selectivity plays an important role [18]. In
this regard, our experimental results showed that metallic
nickel is useful to improve CO2 conversion processes using
hydrides and that its performance is as good than that of
cobalt or even slightly better in certain conditions. The
replacement of Co by Ni has advantages. On the one hand,
despite Co has a biologically necessary role as metal con-
stituent of vitamin B12, excessive exposure has been shown
to induce various adverse health effects. On the other hand,
Ni is cheaper and highly available. In addition, the use of a H2
storage material with a high Ni content, for example Mg2NiH4
solid matrix for reducing CO2, is not beneficial since the CO2
adsorption and disproportion of the surface that occurs
during its decomposition leads to the formation of MgH2,
MgNi2, MgO and carbonates and Ni-based compounds are
poisoned with CO during the early step of the reaction,
limiting the production of CH4 [36].
In this work, the performance of nickel-catalyzed MgH2
with the incorporation of CNTs has been analyzed. Previously
we have demonstrated that the simultaneous addition of
metal (in particular cobalt) and CNTs to MgH2 had a positive
effect on the hydrogen sorption properties compared to each
additive individually [51]. The improvements in the kinetics
were not attributed to CNTs but to metal. It was explained
that the presence of a transition metal allowed the dissocia-
tion of the H2 molecule at lower temperatures and when CNTs
are well distributed throughout the sample, they can play a
microstructural role that affects reaction kinetics [51]. Our TG
analyses (Fig. 5) showed that the dehydrogenation tempera-
ture of MgH2 (330  C) could be lowered 70  C or 80  C due to the
addition of Ni or Ni/CNTs, respectively. At low temperatures
(300  C) and also at high temperatures (400  C), the calculated
methane yield for the MgH2-10wt.%Ni and MgH2-5wt.%Ni-
5wt.%CNT samples after reaction with CO2 during 24 h did not
show great differences. In fact, this observation is positive,
since the reduction of the metallic charge, i.e. the amount of
nickel in the sample, did not cause a negative effect on the
performance of the reaction. This means that by replacing
5wt.% nickel with CNTs, a marginal improvement in methane
yield from 1.7 to 4.5% was obtained at 300  C and no
improvement was observed at 400  C (64.5 and 62.1%,
respectively). However, the differences were maximized at
 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 ) 4 2 8 e4 4 2
Fig. 10 e Molar percentage of CH4 after reaction with CO2 for the MgH2-10wt.%Ni and MgH2-5wt.%Ni-5wt.%CNT considering
different reaction times at (A) 400  C and (B) 350  C (CH4 yield is included).
intermediate temperatures. At 350 and 375  C the sample
with less metallic charge and with the addition of CNTs was
significantly better than the sample that only contained Ni:
the amount of methane in the gas phase increased 34% at
350  C and 32% at 375  C and the methane yield increased 37%
at 350  C and 29% at 375  C. With a thermal treatment of 24 h,
the best results for sample MgH2-5wt.%Ni-5wt.%CNT were
obtained at 375  C. Under these conditions, the gas phase was
mainly composed of CH4 (60.2%) and H2 (38.0%) with small
amount of CO2 (1.8%) and traces of CO and a methane yield of
74.5% was calculated. Considering long reaction times (48 h)
at 350  C, CH4 yield rose to 79%. The performance improve-
ment observed with the increase in treatment time from 24 to
48 h at 350  C for the Ni and CNTs-doped sample was weaker
than that observed for the sample catalyzed only with Ni. It is
worth mentioning that after 24 h treatment, the best CH4
yields for the Co [41] or Ni doped-MgH2 have been obtained at
400  C and resulted to be 60.9% and 64.5%, respectively, and
that after 48 h treatment at 350  C these samples have shown
a methane yield of 78% and 74.2%, respectively. Then, the
above presented results indicate that the co-addition of CNTs
allows obtaining better conversion rates, especially at shorter
reaction time. Interestingly, when comparing values for 24 h
treatment, for the Ni and CNT-doped MgH2, there seems to
exist an optimal operating temperature (Fig. 9). As the
Sabatier reaction is exothermic and is disadvantaged with
increasing temperature, this behavior is expected for a reac-
tion that undergoes this catalyzed mechanism. As for the
MgH2-10wt.%Ni sample a linear relationship between the
temperature and methane yield was observed, it would seem
that in that case it was not possible to reduce the activation
energy enough to observe an optimum point in the range of
temperatures studied.
437
Theoretical calculations based on Gibbs free energy mini-
mization method for the MgH2-Ni system with CO2 (4:0.1:1) at
400, 375 and 350  C were performed. Carbon nanotubes were
not considered as an active phase. The possible reactivity of
CNTs was tested with a synthetic mixture of 4H2:1CO2 through
heat treatment during 24 h at 375  C. GC analyses indicated
that after exposure to the gas mixture, the resulting gas phase
was mainly H2 (76.3%) and CO2 (22.0%), with very small
amount of CH4 (1.0%) and CO (0.7%) (Fig. S9). Gas analyses of
the synthetic mixture under the same conditions showed the
generation of CO (0.6%) and CH4 (0.1%). The difference in CH4
content in the gas phase after heating may be due to the
presence of iron particles coming from the milling jar or,
although being purified, to a very small amount of metallic
nanoparticles from which the nanotubes were grown. This
observation indicates that the addition of CNTs does not affect
the thermodynamics as it can be considered as an inert specie
for the system. Our simulations show that the gas phase is
expected to be a mixture of H2 and CH4 with no residual CO2 or
CO formation (Fig. 11A). Water is not expected since as this
method allows predicting the phases in the chemical equi-
librium, it considers the direct reduction and not the Sabatier
route with catalysis. At a given total pressure of the system, as
the temperature increases, the amount of methane decreases.
Then, from a thermodynamic point of view, low temperatures
are required to obtain high CH4 yields because if the temper-
ature rises the proportion of H2 in the gas phase grows.
However, experimentally, poor conversion is obtained at low
temperature due to kinetic restrictions. Regarding the solid
phase at 375  C, Mg, MgO, unreacted MgH2, Mg2Ni and carbon
deposition is expected (Fig. 11B). It is interesting to observe
that at this temperature the hydride phase remains without
totally decomposing.
438 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 ) 4 2 8 e4 4 2
Fig. 11 e Equilibrium composition (mol%) as a function of the total pressure of the system considering the mixture
4MgH2:0.1Ni:1CO2 for the (A) gas phase at 350, 375 and 400  C and the (B) solid phase at 375  C.
To further study the role of the carbon nanotubes, some
extra measurements under the same experimental conditions
were included. In addition to the two samples previously
analyzed (MgH2-10wt.%Ni and MgH2-5wt.%Ni-5wt.%CNT), as-
milled MgH2 without any additives and MgH2 only with 5wt.%
of carbon tubes without Ni were analyzed. Table 3 compares
the compositions of the gas phase and the calculated CH4 yield
for the four mentioned samples after heat treatment under
CO2 at 375  C for 24 h and Fig. 12 shows the FTIR gas phase
analysis. This temperature was chosen because it allows a
high conversion rate for the catalyzed sample at moderate
reaction times.
Gas analysis by FTIR showed interesting aspects. On the
one hand, the samples that did not contain metallic catalyst,
either MgH2 alone or with CNT, did not present the bands
corresponding to water vapor. The presence of water proves
that the methanation process takes place through the
Sabatier reaction (Reaction 2) with Ni-containing species as
active catalysts (metallic Ni, Mg2NiH4 and Mg2NiH0.3) after
the MgH2 decomposition (Reaction 1). The contribution of
direct reduction of CO2 to produce carbonaceous deposits in
the solid phase (Reaction 3) and the generation of CH4 via C
as an intermediary could not be discarded (Reaction 4).
Either, they might be considered simultaneous and comple-
mentary process. Moreover, in the absence of Ni higher hy-
drocarbons such as ethane or propane (CxHy) due to the weak
absorption peaks at 1470 and 2968 cm1 [38,41] were identi-
fied. Then, when Ni is available, the methanation process
goes via water and its role is also related to selectivity. As CO
formation was observed only at short reaction times or low
temperatures (Figs. 2 and 6), for longer reaction times it is
consumed through reaction with H2 to generate more CH4
(Reactions 5 and 6).
MgH2(s) / Mg(s) þ H2(g) (1)
CO2(g) þ 4H2(g) / CH4(g) þ 2H2O(g) (2)
2MgH2(s) þ CO2(g) / 2MgO(s) þ 2H2(g) þ C(s) (3)
C(s) þ 2H2 (g) / CH4(g) (4)
Mg(s) þ CO2(g) / MgO(s) þ CO(g) (5)
CO(g) þ 3H2(g) / CH4(g) þ H2O(g) (6)
It was previously proved that carbon nanotubes are prac-
tically unreactive when exposed to a gas mixture of H2 and
CO2 at moderate temperatures (Fig. S9). This observation
suggests that CNTs do not play a catalytic role. Previously, we
proved that they can produce an open structure with diffusion
channels that facilitate the hydrogen desorption inside MgH2
grains and along the grain boundaries [51]. These observations
for the behavior of the materials in the desorption/absorption
of hydrogen are important to understand the improvements
that can be achieved on CO2 conversion processes since for
our study, the metal hydride acts as source of H2 for the
methanation. The addition of CNTs not only allowed reducing
the metallic charge of nickel by 5wt.% without affecting the
yields of CH4, but also the existence of a synergy due to the
double doping was proved. Although the MgH2-5wt.%CNT and
MgH2-10wt.%Ni samples reacted with CO2 through different
reaction pathways (direct reduction and Sabatier, respec-
tively), after 24 h at 375  C similar methane contents (46.8 and
45.5%) and yields (56.9 and 57.5%) were obtained (Table 3).
When Ni and CNTs were used simultaneously, the gas phase
 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 ) 4 2 8 e4 4 2 439

Table 3 e Gas-phase composition determined by GC analyses for as-milled MgH2, as-milled MgH2-10wt.%Ni, as-milled
MgH2-5wt.%CNT and as-milled MgH2-5wt.%Ni-5wt.%CNT after thermal treatment at 375  C for 24 h.
Sample Molar percentage Molar percentage Molar percentage Molar percentage CH4 yield
of CH4 (%) of CO2 (%) of CO (%) of H2 (%) (%)
MgH2 21.3 4.3 6.5 67.9 28.6
MgH2-5wt.% CNT 46.8 2 0.1 51.1 56.9
MgH2-10 wt% Ni 45.5 1.9 <1000 ppm 52.6 57.5
MgH2-5% wt.Ni-5wt.% CNT 60.3 1.8 <1000 ppm 38 74.5

Fig. 12 e Gas-state FTIR patterns analyses for as-milled MgH2, MgH2-10wt.%Ni, MgH2-5wt.%CNT and MgH2-5wt%Ni-5wt%
CNT after thermal treatment at 375  C for 24 h.

Fig. 13 e Relative intensities of the phases of Mg/MgO and Mg/(Mg þ MgO þ MgH2) at different temperatures for samples
MgH2-10wt.%Ni and MgH2-5wt.%Ni-5wt.%CNT.
440 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 ) 4 2 8 e4 4 2
was richer in methane (60.3%) and the CH4 yield grew to 74.5%.
The Ni crystallite size calculation for the MgH2-10wt.%Ni and
MgH2-5wt.%Ni-5wt.%CNT samples after mechanical milling
applying the Scherrer method from X-ray diffraction patterns
was useful to verify that co-addition of CNTs did not modify
the size of the initial active catalytic phase, which is approx-
imately 30 nm. This allows ruling out that the performance
improvements were due to the catalytic phase size variation.
Since CO2 is easily adsorbed on the surface of MgH2, in the
absence of carbon nanotubes, it can be easily oxidized to MgO.
This discourages the occurrence of the Sabatier reaction that
requires H2 from the hydride and the obtained CH4 yield is
lower. If the main peak relative intensities (i.e., integrated
intensity) of the phases with magnesium (MgO, Mg and MgH2)
are compared in the XRD diffractograms after reaction at
375  C, it can be observed that for the sample MgH2-5wt.%Ni-
5wt.%CNT the relations Mg/MgO and Mg/(Mg þ MgO þ MgH2)
are higher than for the sample MgH2-10wt.%Ni (see Fig. 13).
Same trend is obtained at 350 and 400  C. Considering the
MgH2 and MgH2-5wt.% CNT solid samples after reaction at
375  C, the later displayed a bigger proportion of metallic Mg
(Fig. S10). These observations suggest that regardless of the
reaction path followed, the role of CNT may be to function as a
protector of magnesium hydride, preventing or retarding its
oxidation. It was previously proved that crystallites of MgH2
are neighbored by graphitic planes with open and inter-
connected structure [51]. It could be hypothesized that carbon
nanotubes can surround the grain boundaries inside the hy-
dride particles and this can hinder MgH2 from being oxidized
by preventing its direct contact with the CO2 and/or H2O that
is produced by methanation through the Sabatier reaction.
Moreover, for the process to occur via Sabatier reaction, it is
necessary to have an active catalytic species (in this case
nickel) capable of dissociating the H2 and the CO2 adhered to
the surface of the hydride in the vicinity of the H activated
form. These observations can justify the observed synergistic
effect of the two additives.
Conclusions
In this work the performance of nickel-catalyzed MgH2 with
the incorporation of carbon nanotubes has been analyzed,
seeking to achieve high CO2 conversion rates under moderate
conditions, with reduced operating temperature and reaction
time. When metallic Ni is available, the methanation process
takes place through the Sabatier reaction with Ni-containing
species as active catalysts (metallic Ni, Mg2NiH4 and
Mg2NiH0.3), capable of dissociating the H2 and the CO2 adhered
to the surface of the hydride, without formation of higher hy-
drocarbons such as ethane or propane. The contribution of
direct reduction of CO2 to produce carbonaceous deposits in
the solid phase and the generation of CH4 via C as an inter-
mediary can be considered as a simultaneous and comple-
mentary process. In addition to its lower cost and not being
associated with health problems due to exposure, Ni was
proved to be as good or even better than Co as catalyst. The
addition of CNTs allowed reducing the metallic charge without
affecting the yields of CH4. Instead, the existence of a synergy
between dopants was observed. At intermediate temperatures
(~350-375  C) the MgH2-5wt.%Ni-5wt.%CNT sample was
significantly better than the sample that only contained Ni: the
amount of methane in the gas phase and the methane yield
increased more than 30%. Its incorporation did not modify the
initial size of the nickel crystallites, nor did it have a catalytic
role as it was proved that they do not interact with a gas
mixture of H2 and CO2 at moderate temperatures. It is postu-
lated that the role of CNTs could be related to the protection of
the magnesium hydride. While MgH2 crystallites are neigh-
bored by graphitic planes with open and interconnected
structure, its oxidation due to direct contact with CO2 and/or
the generated H2O could be impeded or retarded, promoting
the occurrence of the Sabatier reaction. Through reaction be-
tween Ni/CNTs doped MgH2 and CO2 at 350  C during 48 h, a gas
phase free of CO2 or CO, composed of CH4 (70.9%) and H2 (29.1%)
was obtained, with a calculated a methane yield of 79%. Then,
this investigation provides a thermochemical method for CO2
recycling to synthesize COx-free mixture of methane and
hydrogen employing a well-known metal hydride (MgH2) as
hydrogen source, doped with a cheap and high available cat-
alytic phase (Ni) and carbon nanotubes.
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
The work was supported by CONICET (Consejo Nacional de

cnicas), ANPCyT (Agencia
Investigaciones Cientı́ficas y Te

n Cientı́fica y Tecnolo
gica) and CNEA
Nacional de Promocio

n Nacional de Energı́a Ato
mica). The authors also
(Comisio
thank Bernardo Pentke (Departamento Fisicoquı́mica de
Materiales) for the SEM micrographs and Pierre Arneodo Lar-
ochette (Departamento Fisicoquıı́mica de Materiales) for TG
measurements.
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.ijhydene.2021.10.007.
references
[1] IPCC. Climate Change 2014: mitigation of climate Change.
Cambridge University Press; 2015.
[2] Leung D, Caramanna G, Maroto-Valer M. An overview of
current status of carbon dioxide capture and storage
technologies. Renew Sustain Energy Rev 2014;39:426.
[3] Bui C, Adjiman A, Bardow Anthony E, Boston A, Brown S,
Fennell P. Carbon capture and storage (CCS): the way
forward. Energy Environ Sci 2018;11:1062e176.
[4] Khan MHA, Daiyan R, Neal P, Haque N, MacGill I, Amal R. A
framework for assessing economics of blue hydrogen
 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 ) 4 2 8 e4 4 2
production from steam methane reforming using carbon
capture storage & utilization. Int J Hydrogen Energy
2021;46:22685e706.
[5] Sabatier P, Senderens JB. New synthesis of methane. Acad Sci
Paris 1902;134:514e6.
[6] Vogt C, Monai M, Kramer GJ, Weckhuysen BM. The
renaissance of the Sabatier reaction and its applications on
Earth and in space. Nat Catal 2019;2:188e97.
[7] Iaquaniello G, Setinib S, Salladini A, De Falco M. CO2
valorization through direct methanation of flue gas and
renewable hydrogen: a technical and economic assessment.
Int J of Hydrogen Energy 2018;43:17069e81.
[8] Go€ tz M, Lefebvre J, Mo € rs F, Koch AMD, Graf F, Bajohr S,
Reimert R, Kolb T. Renewable Power-to-Gas: a
technological and economic review. Renew Energy
2016;85:1371e90.
[9] Schaaf T, Grünig J, Roman Schuster M, Rothenfluh T,
Orth A. Methanation of CO2 - storage of renewable energy
in a gas distribution system. J Energy Sustain Soc
2014;4:2e14.
[10] Ro€ nsch S, Schneider J, Matthischke S, Schlüter M, Go € tz M,
Lefebvre J, Prabhakaran P, Bajohr S. Review on methanation -
from fundamentals to current projects. Fuel
2016;166:276e96.
[11] Gutie
rrez-Martı́n F, Rodrı́quez-Anto
n LM. Power-to-SNG
technologies by hydrogenation of CO2 and biomass
resources: a comparative chemical engineering process
analysis. Int J Hydrogen Energy 2019;44:12544e53.
[12] Vincenzo M, Jacopo D. Burning behaviour of high-pressure
CH4-H2-air mixtures. Energies 2013;6:97e116.
[13] Ilbas M, Crayford AP, Yılmaza I, Bowen PJ, Syred N. Laminar-
burning velocities of hydrogeneair and
hydrogenemethaneeair mixtures: an experimental study.
Int J Hydrogen Energy 2006;31:1768e79.
[14] Orhan Akansu S, Kahraman N, Çeper B. Experimental study
on a spark ignition engine fueled by methaneehydrogen
mixtures. Int J Hydrogen Energy 2007;32:4279e84.
[15] Klell M, Eichlseder H, Sartory M. Mixtures of hydrogen and
methane in the internal combustion engine -synergies,
potential and regulations. Int J Hydrogen Energy
2012;37:11531e40.
[16] € Galata S, Karago
Sandalci T, Is‚ın O, _ Effect of
€ z Y, Güler I.
hythane enrichment on performance, emission and
combustion characteristics of an ci engine. Int J Hydrogen
Energy 2019;44:3208e20.
[17] Lui C, Cundari TR, Wilson AK. CO2 reduction on transition
metal (Fe, Co, Ni and Cu) surfaces: in comparison with
heterogeneous catalysis. J Phys Chem C 2012;116:5681e8.
[18] Frontera P, Macario A, Ferraro M, Antonucci PL. Supported
catalysts for CO2 methanation: a review. Catalysts
2017;7e35:59.
[19] Li W, Wang H, Jiang X, Zhu J, Liu A, Guo X, Song C. A short
review of recent advances in CO2 hydrogenation to
hydrocarbons over heterogeneous catalysts. RSC Adv
2018;8:7651e69.
[20] Younas M, Kong LL, Bashir MJK, Nadeem H, Shehzad A,
Sethupathi S. Recent advancements, fundamental
challenges, and opportunities in catalytic methanation of
CO2. Energy Fuels 2016;30:8815e31.
[21] Fumihiko K, Toshiaki Y, Yuji A, Takehisa M, Hideyuki T,
Koichi M, Yoshinobu F, Koji K. Effect of Ni content on CO2
methanation performance with tubular-structured Ni-YSZ
catalysts and optimization of catalytic activity for
temperature management in the reactor. Int J Hydrogen
Energy 2020;45:12911e20.
441
[22] Varun Y, Sreedhar I, Singh SA. Highly stable M/NiO-MgO
(M¼Co, Cu and Fe) catalysts towards CO2 methanation. Int J
Hydrogen Energy 2020;45:28716e31.
[23] Jin L, Xie T, Ma B, Li Y, Hu H. Preparation of carbon-Ni/MgO-
Al2O3 composite catalysts for CO2 reforming of methane. Int J
Hydrogen Energy 2017;42:5047e55.
[24] De S, Zhang J, Luque R, Yan N. Ni-based bimetallic
heterogeneous catalysts for energy and environmental
applications. Energy Environ Sci 2016;9:3314e47.
[25] Tada S, Shimizu T, Kameyama H, Haneda T, Kikuchi R. Ni/
CeO2 catalysts with high CO2 methanation activity and high
CH4 selectivity at low temperatures. Int J Hydrogen Energy
2012;37:5527e31.
[26] Guo M, Lu G. The effect of impregnation strategy on
structural characters and CO2 methanation properties over
MgO modified Ni/SiO2 catalysts. Catal Commun
2014;54(55e60).
[27] Renda S, Ricca A, Palma V. Study of the effect of noble metal
promotion in Ni-based catalyst for the Sabatier reaction. Int J
of Hydrogen Energy 2021;46:12117e27.
[28] Baldauf-Sommerbauera G, Luxa S, Anisera W, Bitschnaub B,
Letofsky-Papstc I, Siebenhofera M. Steady-state and
controlled heating rate methanation of CO2 on Ni/MgO in a
bench-scale fixed bed tubular reactor. J CO2 Util 2018;23:1e9.
[29] Li X, Wang Y, Zhang G, Sun W, Bai Y, Zheng L, Han X, Wu L.
Influence of Mg-promoted Ni-based catalyst supported on
coconut shell carbon for CO2 methanation. Chem Sel
2019;4:838e45.
[30] Feng Y, Yang W, Chen S, Chu W. Cerium promoted nano
nickel catalysts Ni-Ce/CNTs and Ni-Ce/Al2O3 for CO2
methanation. Integrated Ferroelectrics Int J: Int J
2014;151(1):116e25.
[31] Hugelshofer CL, Borgschulte A, Callini E, Matam SK, Gehrig J,
Hogand D, Züttel A. Gasesolid reaction of carbon dioxide
with alanates. JPhysChemC 2014;118:15940e5.
[32] Zhao J, Teng Y-L, Dong B-X. Thermal reduction of CO2 with
activated alkali metal aluminum hydrides for selective
methanation. Energy Fuels 2020;34:11210e8.
[33] Vitillo JG, Groppo E, Gil Bardajı́ E, Baricco M, Bordiga S. Fast
carbon dioxide recycling by reaction with g-Mg(BH4)2. Phys
Chem Chem Phys 2014;16:22482.
[34] Picasso CV, Safin DA, Dovgaliuk I, Devred F, Debecker D,
Li HW, Filinchuk Y. Reduction of CO2 with KBH4 in solvent-
free conditions. Int J Hydrogen Energy 2016;41:14377e86.
[35] Kato S, Borgschulte A, Ferri D, Bielmann M, Crivello J-C,
Wiedenmann D, Parlinska-Wojtan M, Rossbach P, Lu Y,
Remhof A, Züttel A. CO2 hydrogenation on a metal hydride
surface. Phys Chem Chem Phys 2012;14:5518e26.
[36] Grasso ML, Puszkiel J, Ferna
ndez Albanesi L, Dornheim M,
Pistidda C, Gennari FC. CO2 reutilization for methane
production via catalytic process promoted by hydrides. Phys
Chem Chem Phys 2019;21:19825e34.
[37] Grasso ML, Puszkiel J, Gennari FC, Santoru A, Dornheim M,
Pistidda C. CO2 reactivity with Mg2NiH4 synthesized by in
situ monitoring mechanical milling. Phys Chem Chem Phys
2020;22:1944e52.
[38] Dong B-X, Wang LZ, Song L, Zhao J, Teng YL.
Thermochemical reduction of carbon dioxide with alkali
metal hydrides, producing methane and hydrogen fuels at
moderate temperature. Energy Fuels 2016;30:6620e5.
[39] Zhao J, Wei Y-F, Cai Y-L, Wang L-Z, Xie J, Teng Y-L, Zhu W,
Shen M, Dong B-X. Highly selective and efficient reduction of
CO2 to methane by activated alkaline earth metal hydrides
without a catalyst. ACS Sustainable Chem Eng
2019;7:4831e41.
442 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 ) 4 2 8 e4 4 2
[40] Zhang S, Chen H-Q, Kan X-T, Tai Y-L, Liu W-L, Dong B-X,
Teng Y-L. Storage and in-situ preparation of H2-mixed CH4
fuel by thermochemical reduction of inorganic carbonates
with activated metal hydrides. Fuel 2021;292.
[41] Amica G, Rozas Azcona S, Aparicio S, Gennari FC. Catalysis
effect on CO2 methanation using MgH2 as a portable
hydrogen medium. Phys Chem Chem Phys 2020;22:14720e30.
[42] Kato S, Kumar Matam S, Kerger P, Bernard L, Battaglia C,
Vogel D, Rohwerder M, Züttel A. The origin of the catalytic
activity of a metal hydride on CO2 reduction. Angew Chem
2016;128:6132e6.
[43] Burr JG, Weldon G, Brown WG, Heller HE. The reduction of
carbon dioxide to formic acid. Am Chem Soc
1950;72:2560e2.
[44] Gribble GW, Nutaitis CF. Sodium borohydride in carboxylic
acid media. A review of the synthetic utility of
acyloxyborohydrides. Org Prep Proced Int: New J Org Synth
1985;17:317e84.
[45] Gamba N, Puszkiel JA, Larochette PA, Gennari FC. Dual
application of Ti-catalyzed Li-RHC composite for H 2
purification and CO methanation. Int J Hydrogen Energy
2020;45:19493e504.
[46] Outokumpu HSC. Chemistry for windows, version 6.1.
Finland: Outokumpu Research Oy; 2009.
[47] Cova F, Arneodo Larochette P, Gennari FC. Hydrogen sorption
in MgH2-based composites: the role of Ni and LiBH4
additives. Int J of Hydrogen Energy 2012;37:15210e9.
[48] Gennari FC, Castro F, Urretavizcaya G. Hydrogen desorption
behavior from magnesium hydrides synthesized by reactive
mechanical alloying. J Alloys Compd 2001;321:46e53.
[49] Du H, Williams CT, Ebner AD, Ritter A. In situ FTIR
spectroscopic analysis of carbonate transformations during
adsorption and desorption of CO2 in K-promoted HTlc. Chem
Mater 2010;22:3519.
[50] Selvam P. Evidence for the formation of surface carbonates
on some hydrogen storage intermetallic compounds: an XPS
study. Int J Hydrogen Energy 1990;15:133e7.
[51] Vero
n M, Troiani H, Gennari FC. Synergetic effect of Co and
carbon nanotubes on MgH2 sorption properties. Carbon
2011;49:2413e23.