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 ) 2 0 1 8 5 e2 0 1 9 3

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Protection and confinement effect of carbon on Co/

CoxOy nano-catalyst for efficient NaBH4 hydrolysis

Mingbin Li a, Shuyan Guan a, Lulu An a, Huanhuan Zhang a,

Yumei Chen a,*, Jianchao Shi a, Yanping Fan a, Baozhong Liu a,b,c,*
a
College of Chemistry and Chemical Engineering, Henan Polytechnic University, Jiaozuo 454000, China
b
State Collaborative Innovation Center of Coal Work Safety and Clean-efficiency Utilization, Jiaozuo 454000, China
c
Henan Key Laboratory of Coal Green Conversion, Henan Polytechnic University, Jiaozuo 454000, China

highlights graphical abstract

Co/CoxOy@C core-shell structure

immobilized in carbon substrate
was prepared by a facile
polymerization-pyrolysis method.

The optimal catalyst shows the
hydrogen generation rate of
4348.6 mL min1 g1Co.

The prepared Co/CoxOy@C shows
significantly enhanced stability
compared with pure Co/CoxOy
nanofilms for NaBH4 hydrolysis.

The protection and confinement
effect of carbon can stabilize the
active phase Co from the erosion
and migration.

article info abstract

Article history: The hydrolysis of sodium borohydride (NaBH4) over catalysts is a promising method to
Received 17 December 2021 produce hydrogen. Although Co-based catalysts exhibit high activity for NaBH4 hydrolysis,
Received in revised form they are still far from satisfying practical applications, especially their poor durability in
10 April 2022 alkaline media. Herein, a carbon shell structure was designed and synthesized to improve
Accepted 15 April 2022 the stability of the mixture of Co0 and CoxOy nanofilms (Co/CoxOy@C) during NaBH4 hy-
Available online 9 May 2022 drolysis via a facile polymerization-pyrolysis strategy with Co/CoxOy nanofilms as the
precursor. As a result, the Co/CoxOy@C catalyst can achieve a remarkable H2 generation
Keywords: rate of 4348.6 mL min1 gCo1 with a low activation energy of 43.6 kJ mol1, which is su-
Carbon coating perior to most previously reported catalysts. Moreover, the catalyst shows high stability
Confinement effect with an H2 generation-specific rate of 79% after five cycles. The excellent performance of
Co-based catalysts carbon substrate can well prevent the agglomeration of Co-based nanoparticle and
Hydrogen generation improve the corrosion resistance of the active Co to BO2 and OH. This work would widen
Sodium borohydride

* Corresponding authors. College of Chemistry and Chemical Engineering, Henan Polytechnic University, Jiaozuo 454000, China.
E-mail addresses: chenyumei@hpu.edu.cn (Y. Chen), HPUliuking@163.com (B. Liu).
https://doi.org/10.1016/j.ijhydene.2022.04.139
0360-3199/© 2022 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
20186 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 ) 2 0 1 8 5 e2 0 1 9 3
the road for the preparation of nanoconfined catalysts, which has prospective application
potentials for H2 production from NaBH4 hydrolysis.
© 2022 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
Introduction
With the intensification of environmental pollution and the
energy crisis, hydrogen (H2) has considerable potential in
renewable energy systems as an alternative to fossil fuels due
to its relatively high energy density, nontoxicity, and non-
secondary pollution [1,2]. The key to the practical applica-
tion of hydrogen is efficient hydrogen production and safe
hydrogen storage [3,4]. Boron-based chemical hydrogen stor-
age materials, such as NaBH4, LiBH4, and NH3BH3, are poten-
tial hydrogen carriers due to their relatively high hydrogen
capacity and hydrogen generation under mild conditions [5,6].
Among them, NaBH4 has been considered as one of the most
promising candidates because of its high hydrogen density
(10.8 wt%), low price, nontoxicity, high purity of the obtained
hydrogen, and relatively high solubility in water and long-
term stability in solid and solution states [7e11]. High-
efficient catalysts play a key role in affecting the hydrogen
generation performance of NaBH4 hydrolysis.
Generally, noble metals, such as Ru, Pd, and Pt, are more
favorable for the chemical hydrolysis reaction of NaBH4
[12,13]. However, the outrageous price and low abundance
impede their large-scale practical application. The exploita-
tion of non-precious metal catalysts with high performance is
the main goal for NaBH4 hydrolysis [14]. The transition metals
or alloys (such as Fe, Co, and Ni) exhibit relatively evaluable
activity for NaBH4 hydrolysis due to their adjustable electronic
structure and bimetallic integration effect [15e17]. Co-based
catalysts, including Co3O4 [18], CoeB [19], CoO þ Co3O4/B
composition [20], Co/C [21], wz-CoO-NRs [22], Fe3O4@CeCo
core-shell [23], have been developed to catalyze hydrolysis of
NaBH4 [24,25]. For example, Zhang et al. [26] reported that the
presence of Na2SO4 and Na2S was beneficial for the in situ
transformation of Co3O4 into catalytically active CoeB alloys,
and then exhibited excellent hydrogen production perfor-
mances. Ding et al. [20] synthesized cobalt oxides with
different valence states supported on flower layered hydrox-
ide by hydrothermal crystallization, displaying a fast
hydrogen production rate. Kim et al. [22] developed wüsite
cobalt oxide nanorods with different sizes and high surface
activity growing along (002) direction by pyrolysis of cobalt
oleate and cobalt stearate, which exhibited outstanding per-
formance for the NaBH4 hydrolysis. Cobalt oxide-supported
multi-wall carbon nanotubes (Co/MWCNTs) catalysts were
synthesized through the impregnation method accompa-
nying with many numbers of surface Co2þ species and dis-
played excellent activity in catalytic hydrolysis of NaBH4 [27].
Therefore, the Co-based catalysts with different chemical
environments and structural control exhibit unique advan-
tages in hydrogen generation from NaBH4 hydrolysis. How-
ever, Co-based catalysts are not yet robust enough to suffer
from activity decay in long-term stability tests due to the
transformation of surface morphology, the aggregation of the
nanostructure, and the degeneration or overlap of active
species with the generation of NaBO2 and Co(OH)2 during
NaBH4 hydrolysis [28e32], which severely hinders their prac-
tical application. Therefore, it is necessary to explore effective
strategies to improve the stability of catalysts during NaBH4
hydrolysis.
Currently, a large number of nanomaterials (e.g., carbon-
based substrates [33e39], silica/titanium materials [40,41],
and metal and organic polymer [42e47]) have been used to
disperse and anchor Co-based materials because of their large
specific surface area and abundant pores structure, which can
expose more efficient active sites for prompting the Co-based
particles to form high dispersion and thus facilitate catalytic
activity. Furthermore, the immobilization effect prevents the
migration or detachment of active phases during the reaction
process. Among them, the carbon confinement effect as an
effective strategy to design active transition metal catalysts
has been reported and exhibited high chemical and thermal
stability under alkaline NaBH4 hydrolysis [48,49]. Therefore,
carbon nanomaterials, as substrates or shells, have high-
efficiency protective effects to stabilize the active species.
Herein, a carbon shell structure was designed and syn-
thesized to improve the stability of the mixture of Co0 and
CoxOy nanofilms (Co/CoxOy@C) during NaBH4 hydrolysis via a
facile polymerization-pyrolysis strategy with Co/CoxOy
nanofilms as the precursor, which were pre-synthesized
through the adsorption equilibrium leaded by ionic liquid/
water interface. The Co/CoxOy@C catalysts exhibited
outstanding stability for the production from NaBH4 hydro-
lysis than bare Co/CoxOy nanofilms. The experiments
confirmed that the carbon confinement effect on the Co/Cox-
Oy@C catalyst effectively prevented the Co-active phase from
being attacked by BO2 and OH and agglomerated. This work
offers an efficient pathway for improving the stability of non-
precious metal catalysts for hydrogen evolution reactions.
Experimental section
Synthesis of Co/CoxOy@C
The Co/CoxOy nanofilms were prepared by the procedures
described in our previous paper [50] (More details in Sup-
porting Information). First, Co/CoxOy nanofilms were coated
with dopamine hydrochloride and to form Co/CoxOy@PDA
precursor. Subsequently, Co/CoxOy nanoparticles coating on
carbon shell (Co/CoxOy@C) was obtained through high-
temperature pyrolysis of Co/CoxOy@PDA precursor. During
the pyrolysis process, the Co/CoxOy nanofilms were trans-
formed into nanoparticles and implanted into carbon
 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 ) 2 0 1 8 5 e2 0 1 9 3 20187

Fig. 1 e (a) Schematic diagram of the synthesis process of carbon coating. (b) XRD patterns and (c) H2 generation curves of Co/
CoxOy@C samples with the different mass of dopamine hydrochloride and the polymerization time of 12 h. (d) XRD patterns
and (e) H2 generation curves of Co/CoxOy@C samples with different polymerization times and the mass of dopamine
hydrochloride at 30 mg.

substrates derived from PDA under high-temperature con- Materials characterization

ditions [51,52]. Under the pyrolysis temperature of 500  C,
the Co/CoxOy nanofilms transform into Co/CoxOy nano-
particles and further be confined and wrapped with pyrol-
ysis carbon. In detail, Co/CoxOy nanofilms powder (40 mg)
and tris-HCl (48 mg) were dispersed in deionized water
(40 mL) by ultrasonic and stirring to form a uniform colloid
solution. Then, 30 mg of dopamine hydrochloride was
added to the colloid solution at 30  C. After the pH of the
solution was adjusted to 8.5 with KOH solution (0.1 M), it
was stirred for 12 h. Finally, the Co/CoxOy@C catalyst was
obtained by heat-treatment at 500  C for 2 h with a heating
rate of 2  C$min1 under Ar atmosphere. For comparison,
the control samples were also prepared by adjusting the
mass of dopamine hydrochloride (20, 40, 60, and 80 mg) and
stirring time (6, 9, and 18 h).
The samples were characterized by a X-ray diffractometer
(XRD, Rigaku, SmartLab, Cu-Ka radiation, l ¼ 1.5418
A) at a
scan rate of 5 $min1. Transmission electron microscope
(TEM, FEI Tecnai G2 F30 S-TWIN electron microscope) with
energy-dispersive X-ray spectroscopy (EDS) at an acceleration
voltage of 200 kV was applied to characterize the micro-
structure and morphology. Thermal gravimetric analysis
(TGA) was carried out on the STA 409 PC/PG (NETZSCH Ger-
many) with a heating rate of 10  C$min1. X-ray photoelectron
spectroscopy (XPS) was conducted to analyze the detailed
chemical compositions of the samples on a Thermofisher K-
alpha spectrometer. All XPS spectra were calibrated with the C
1s peak at a binding energy of 284.8 eV. The XPS data were
fitted using the software XPSPEAK41.
20188 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 ) 2 0 1 8 5 e2 0 1 9 3

Fig. 2 e (a) XRD patterns of CoxOy-nanofilms and Co/CoxOy@C. (b) TEM image of the CoxOy nanofilm. (c) TEM image and the
corresponding particle size distribution, (d) High-resolution TEM images, and (e) STEM image and the corresponding EDS
element mapping of Co/CoxOy@C.

approximately 26.4 is attributed to the (002) lattice facet of

Results and discussion
Fig. 1a illustrates the synthesis process of the Co/CoxOy@C.
The crystal structures and the catalytic performance for
NaBH4 hydrolysis of Co/CoxOy@C samples prepared with
different dopamine hydrochloride mass and polymerization
time are shown in XRD patterns and VH2-t curves, respectively
(Fig. 1bee). As shown in Fig. 1b, the XRD patterns of Co/Cox-
Oy@C show the characteristic diffraction peaks at 44.2 , 51.5 ,
and 75.9 , which correspond to the (111), (200), and (220) lattice
facets of Co0 (JCPDS Card No. 15e0806). The peak at
carbon (JCPDS No. 41e1487) and its intensity is relatively
enhanced along with the additional content of dopamine hy-
drochloride, demonstrating the increasing degree of pyrolytic
carbon (Fig. 1b). The corresponding VH2-t curves display the
significant variation in catalytic activity for NaBH4 hydrolysis
(Fig. 1c). Excessive carbon coating has no distinct optimistic
effect on the NaBH4 hydrolysis from the above relevant
experimental results and the Co/CoxOy@C prepared using
30 mg dopamine hydrochloride exhibits the optimal perfor-
mance during the H2 generation reaction. Moreover, the
XRD peaks of Co/CoxOy@C obtained by different
 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 ) 2 0 1 8 5 e2 0 1 9 3
polymerization times are similar (Fig. 1d). Notably, Co/CoxOy
nanoparticles tend to aggregate into larger particle sizes due
to inadequate dopamine polymerization. The corresponding
NaBH4 hydrolysis measurement shows that the Co/CoxOy@C
prepared with the dopamine polymerization time of 12 h ex-
hibits prominent activity. The characterizations given below
are based on the optimized Co/CoxOy@C catalysts.
The Co/CoxOy nanofilms and Co/CoxOy@C samples were
measured by XRD (Fig. 2a). The XRD patterns of Co/CoxOy
nanofilms show the characteristic diffraction peaks of hex-
agonal closed-packed crystalline structure, in which the
typical diffraction peaks at about 41.7 , 44.8 , 47.6 , and 75.9
are according to the (100), (002), (101) and (110) lattice facets of
Co (JCPDS Card No. 05e0727). The XRD peaks at 36.4 and 61.5
are corresponded to (111) and (220) lattice planes of CoO
(JCPDS Card No. 43e1004). After the polymerization-pyrolysis,
the XRD peak at approximately 26.4 is attributed to carbon
(002) lattice facet (JCPDS Card No. 41e1487), which shows the
presence of pyrolytic carbon. The peaks of CoO in Co/CoxOy@C
cannot be detected, which may be related to the reduction of
the CoO phase by carbon during high-temperature pyrolysis
[53,54].
Fig. 2b displays a typical TEM image of CoxOy nanofilm with
a few folds, which were prepared on the immiscible ionic
liquid (IL)/water interface. The TEM image of Co/CoxOy@C and
Fig. 3 e XPS characterization of Co/CoxOy@C: (a) XPS survey. High-resolution XPS spectrum of (b) Co 2p3/2, (c) C 1s and (d) O
1s.
20189
the corresponding particle distribution display that the Co/
CoxOy nanoparticles were formed with an average particle of
about 10 nm (Fig. 2c). From the HRTEM images of Co/CoxOy@C
(Fig. 2d), the lattice spacing values of 0.207 nm and 0.201 nm
are matching to the metallic Co (d(111)) and Co (d(002)) phase
[55]. The marked grey substrate is assigned to pyrolytic carbon
and as support for Co/CoxOy nanoparticles. The magnified
HRTEM images of Co/CoxOy@C nanoparticles exhibit obvious
amorphous carbon marked with a yellow line. Fig. 2e presents
the elemental mapping of C, O, and Co of Co/CoxOy@C. The
results of element mapping manifest Co/CoxOy@C core-shell
nanostructure. Co and C elements exhibit that each Co
nanoparticle was enveloped by carbon layers (Fig. 2e), in
which the confinement effect can effectively prevent the Co
nanoparticles from being corroded and agglomerated in harsh
solutions and thus enhance the hydrolysis performances of
NaBH4.
The surface chemical states of Co/CoxOy@C were elucidated
by XPS measurement. The XPS survey spectra indicate that Co/
CoxOy@C is mainly composed of elemental C, O, and Co, and
the characteristic binding energies of C 1s, O 1s, and Co 2p are
located at 283.7, 531.0, and 780.8 eV, respectively (Fig. 3a). The
peaks at 778.10, 780.78 and 783.45 eV are ascribed to Co0, Co3þ
and Co2þ of the Co 2p3/2 (Fig. 3b), respectively [56], and the peak
at 786.57 eV is corresponded to the satellite peak. Summarily,
20190 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 ) 2 0 1 8 5 e2 0 1 9 3

Co oxides are the main ingredients on the Co/CoxOy surface
from the above XPS results. The spectra of C 1s can be decon-
voluted into three peaks at 284.80 eV (CeC), 285.50 eV (CeO),
and 288.5 eV(C]O/O]CeO) (Fig. 3c). The typical CeC peak is
attributed to the sp3-hybridized carbon atoms in the amor-
phous carbon film formed through PDA pyrolysis, which is
consistent with the TEM results. The high-resolution spectra
for O 1s show four individual peaks of Co]O (529.18 eV), CoeO
(530.45 eV), eOH (531.18 eV), and H2O (532.11 eV) (Fig. 3d). The
above results confirm that the heterogeneous composition of
Co/CoxOy was designed successfully.
The catalytic activity of Co/CoxOy@C for NaBH4 hydrolysis
was evaluated. The fresh Co/CoxOy@C catalyst can release the
100% H2 in less than 5 min in the first hydrolysis experiment at
30  C and the H2 generation-specific rate reaches
4348.6 mL min1 gCo1 (Fig. 4a and b). Illustratively, the recy-
clability experiments of the Co/CoxOy@C catalyst exhibit
excellent stability for NaBH4 hydrolysis, and the H2 generation-
specific rate maintains 79% catalytic activity even after five
cycles (Fig. 4a and b). However, Co/CoxOy nanofilms show poor
stability and cannot completely hydrolyze NaBH4 within 20 min
in the second cycle (Fig. 4a). These results demonstrate a
markedly enhanced durability of the Co/CoxOy@C, which is due
to the protection and confinement effect of carbon on Co/
CoxOy. The effect of NaBH4 concentration on the hydrogen
generation rate was examined, and the result is shown in
Fig. S3. It reveals that no obvious change is observed in the
hydrogen generation rate with the increase of NaBH4
concentration, indicating that the concentration of NaBH4 has
little effect on the hydrolysis of NaBH4. Fig. S4 shows the plot of
hydrogen generation rate versus NaOH concentration in the
presence of Co/CoxOy@C at 30  C. According to the results, the
most economical and effective NaOH concentration was 1.25 M.
The catalytic reaction at different temperatures
(30  Ce45  C) was investigated to investigate the reaction ki-
netics (Fig. 4c and d). Along with increasing the reaction
temperatures, the H2 generation rates correspondingly in-
crease from 4348.6 to 9495.9 mL min1 gCo1. This phenome-
non is ascribed to the enhanced transmission of reactants as
the temperature increases. According to the Arrhenius equa-
tion, the Arrhenius plot of lnk vs the reciprocal absolute
temperature (1/T) was obtained as a straight line. The Arrhe-
nius activation energy (Ea) of Co/CoxOy@C is 43.6 kJ mol1. The
Ea value is lower or equivalent to those of the reported liter-
ature [8,57], indicating a higher intrinsic activity of the Co/
CoxOy@C. We have prepared the comparison table to confirm
the novelty and superiority of our work and the comparison
table of the hydrogen generation from NaBH4 hydrolysis be-
tween this work and other cobalt-based catalysts in the
literature is shown in Table 1. It can indicate the better cata-
lytic activity of these Co-based catalysts. The follow-up
improvement work will further optimize synthesis condi-
tions to improve the catalytic activity and reduce the activa-
tion energy.
The catalytic and carbon-stabilized mechanism is proposed
in Fig. 5. In the process of NaBH4 hydrolysis, excessive OH

Fig. 4 e (a) H2 generation curves of NaBH4 hydrolysis catalyzed by Co/CoxOy and Co/CoxOy@C catalysts. (b) The
corresponding H2 generation rates under different cycles and H2 conversion catalyzed by Co/CoxOy@C catalysts. (c) H2
production curves catalyzed by Co/CoxOy@C catalysts under different temperatures, and (d) the corresponding H2 generation
rates and the corresponding Arrhenius plot.
 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 ) 2 0 1 8 5 e2 0 1 9 3 20191

Table 1 e Comparison of different Co catalysts for hydrogen generation from NaBH4 hydrolysis.
Catalyst Hydrogen production rate Temp. ( C) Ea (kJ mol1) Ref.
1 1
Co/AC 530 mL min gcat 25 44.1 58
Co/g-Al2O3 220 mL min1 gmetal1 30 32.63 59
P(SPM)-Co 1690 mL min1 gmetal1 30 44.3 60
Co-B-TiO2 1017 mL min1 gmetal1 30 e 61
Co-Mo-B-3 4200 mL min1 gmetal1 30 43.7 62
CoOx-GCNFs 2696 mL min1 gmetal1 30 28.3 63
Co-Cr-B/CeO2 9182 mL min1 gmetal1 30 35.52 64
Co(0)-HAP 5000 mL min-1 gmetal1 25 53 ± 2 65
Co/Fe3O4@C-5 1403 mL min1 gcat1 25 49.2 66
Co/CoxOy@C 4348.6 mL min1 gmetal1 30 43.6 This work

4348.6 mL min1 gCo1 at 30  C. Experimental data and corre-

sponding characterization confirmed that the excellent
durability and enhanced activity are due to the protection and
confinement effect of carbon on the Co/CoxOy nano-catalyst.
This work is anticipated to stimulate the design of high-
performance catalysts for hydrogen generation in borohy-
dride hydrolysis. It is envisaged that the as-proposed poly-
merization-pyrolysis strategy could be broadly applied to
design other transition metal catalysts for H2 generation from
chemical hydrides.

Authorship contributions

Fig. 5 e The catalytic and carbon-stabilized mechanism of
Co/CoxOy@C catalyst.
covers the catalytic sites and reacts with active Co phases,
issuing in the partial deactivation of the catalysts except for the
deactivation effect of BO2 hydrolysate [28,67]. The XRD
pattern of the fresh Co/CoxOy@C catalyst and that used after
five cycles for NaBH4 hydrolysis are given in Fig. S1. Two
characteristic peaks of Co(OH)2 appear in the XRD pattern of
used Co/CoxOy@C and this may be one of the main reasons for
decreasing the active Co components [34,68]. Although the
corrosion from the reaction solution and by-products cannot
be completely avoided, the confinement effect of carbon on Co/
CoxOy particles in Co/CoxOy@C catalyst can prevent conglom-
eration of Co active phase and restraint the reaction between
excessive OH and Co-based core, further protecting the Co
active phase from the erosion of BO2 [32,69]. In conclusion, the
protection and confinement effect of carbon on Co/CoxOy@C
immensely promoted their catalytic activity and durability.
Conclusions
In conclusion, Co/CoxOy@C core-shell structure was rationally
constructed through a simple polymerization-pyrolysis
strategy and presents excellent stability during NaBH4 hy-
drolysis. Illustratively, Co/CoxOy@C convey markedly
enhanced stability compared with pure Co/CoxOy nanofilms,
which retain 79% of the premier catalytic activity even after
five cycles of hydrolysis experiments. Additionally, prepared
Co/CoxOy@C also exhibits superior activity in the hydrolysis
of NaBH4 with an H2 generation-specific rate value of
Mingbin Li: Investigation, Data curation, Formal analysis,
Writing e original draft. Shuyan Guan: Data curation, Formal
analysis. Lulu An: Investigation, Data curation. Huanhuan
Zhang: Writing-review& editing. Yumei Chen*: Conceptuali-
zation, Writing-review& editing, Supervision. Jianchao Shi:
Conceptualization, Supervision. Yanping Fan: Conceptuali-
zation, Supervision. Baozhong Liu*: Conceptualization,
Writing-review& editing, Supervision.
Declaration of competing interest
The authors declare that they have no know competing for
financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
Acknowledgements
This research is financially supported by the National Natural
Science Foundation of China (52071135，51871090, U1804135,
and 51671080), Plan for Scientific Innovation Talent of Henan
Province (194200510019), Key Project of Educational Commis-
sion of Henan Province (19A150025) and the Fundamental
Research Funds for the Universities of Henan Province
(NSFRF200402).
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.ijhydene.2022.04.139.
20192 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 ) 2 0 1 8 5 e2 0 1 9 3

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