Journal of Energy Chemistry 34 (2019) 111–160

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Journal of Energy Chemistry

journal homepage: www.elsevier.com/locate/jechem

Review

Recent progress on earth abundant electrocatalysts for hydrogen

evolution reaction (HER) in alkaline medium to achieve efficient water
splitting – A review
Jamesh Mohammed-Ibrahim a,b,c,d,∗, Xiaoming Sun a,∗
a
State Key Laboratory of Chemical Resource Engineering, College of Energy, Beijing Advanced Innovation Centre for Soft Matter Science and Engineering,
Beijing University of Chemical Technology, Beijing 100029, China
b
Department of Physics and Materials Science, City University of Hong Kong, Tat Chee Avenue, Kowloon, Hong Kong, China
c
Applied and Plasma Physics, School of Physics (A28), University of Sydney, Sydney, NSW 2006, Australia
d
CSIR-Central Electrochemical Research Institute-Chennai Unit, CSIR Madras Complex, Taramani, Chennai 600113, India

a r t i c l e i n f o a b s t r a c t

Article history: Developing earth-abundant-electrocatalysts for hydrogen evolution reaction is one of the promising ways
Received 19 June 2018 to achieve efficient water-splitting for hydrogen production (a clean chemical fuel). This paper reviews
Revised 3 September 2018
the activity, stability and durability for hydrogen evolution reaction in alkaline medium of different
Accepted 23 September 2018
types of recently reported potential electrocatalysts such as Ni, Co, NiCo, Fe, Cu, W, Mo, Se, Mn, Zn,
Available online 26 September 2018
V, and metal free based earth-abundant-electrocatalysts. Further, this paper reviews the strategies used
Keywords: to achieve the remarkably low overpotential (including η10 : ≤ 35 mV), high long term stability (includ-
HER electrocatalyst ing ≥ 100 h) and high durability (including ≥ 5000 cycles) of potential earth-abundant-electrocatalysts for
Electrochemical water splitting hydrogen evolution reaction in alkaline medium and those are better or well comparable with the
Earth abundant electrocatalyst state-of-the-art, noble, Pt/C electrocatalyst. Finally, this paper summarizes the efficient strategies such
Hydrogen energy as preparing porous structured materials, preparing nanostructured materials with superaerophobic sur-
face, preparing nanostructured materials, preparing carbon composites/integrating electrocatalysts with
carbon, preparing amorphous materials, preparing materials with oxygen vacancies/defects, preparing
metal chalcogenides, preparing bimetallic/multi-metallic materials, doping metals or heteroatoms, prepar-
ing electrocatalysts with core-shell structure, decorating electrocatalysts with amines, preparing homo-
junction/heterojunction structured materials, preparing hollow structured materials, and preparing boron-
rich surface to enhance the activity, stability, and durability for HER.
© 2018 Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published
by Elsevier B.V. and Science Press. All rights reserved.

Jamesh Mohammed-Ibrahim obtained dual Ph.D. from
the Department of Physics and Material Science, City
University of Hong Kong and School of Physics, The Uni-
versity of Sydney, in 2014. He is currently carrying-
out research at College of Energy, Beijing University of
Chemical Technology, China. His research interfaces with
material science and biological science, where these
prospective uses include energy and environmental sus-
tainability applications.
Xiaoming Sun obtained B.S. degree and Ph.D. in De-
partment of Chemistry, Tsinghua University, in 20 0 0 and
2005, respectively. After postdoctoral work at Stanford
University, he joined at Beijing University of Chemical
Technology in 2008, and he was received National Natu-
ral Science Funds for Distinguished Young Scholar in 2011.
His research focuses on separation and assembly of inor-
ganic nanostructures, synthesis and separation of carbon
nanomaterials and their composites, and structure control
and opto-/electro-property investigations of oxide nanoar-
rays, where these prospective uses include energy and en-
vironmental sustainability applications.

1. Introduction
∗
Corresponding author at: State Key Laboratory of Chemical Resource Engineer-
ing, College of Energy, Beijing Advanced Innovation Centre for Soft Matter Science
The depletion of fossil fuels and increasing energy demand
and Engineering, Beijing University of Chemical Technology, Beijing 10 0 029, China.
E-mail addresses: jmohammed2-c@my.cityu.edu.hk,
are essential challenging issues that cause the discovering of
mohammed@mail.buct.edu.cn (J. Mohammed-Ibrahim), sunxm@mail.buct.edu.cn (X. alternative earth abundant energies and efficient designing of
Sun). energy storage devices [1–12]. Therefore, sustainable-renewable

https://doi.org/10.1016/j.jechem.2018.09.016
2095-4956/© 2018 Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B.V. and Science Press. All rights reserved.
112 J. Mohammed-Ibrahim, X. Sun / Journal of Energy Chemistry 34 (2019) 111–160
energy resources such as solar energy, wave power, and wind en-
ergy can be used as alternative energy sources for energy demand
problems, whereas there is an important need to transform those
sustainable-renewable energy resources into ideal energy. Hence,
electrochemical water splitting is a promising technology for gen-
erating a clean chemical fuel (hydrogen), which transforms the re-
newable energy resources into ideal chemical energy (in the form
of H2 ) [3,7,13,14]. Electrochemical water splitting is composed of
hydrogen evolution reaction (HER) and oxygen evolution reaction
(OER) at the cathode and anode, respectively, whereas efficient wa-
ter splitting can be attained by using efficient electrocatalysts. Cur-
rently, the state of the art noble electrocatalysts such as Pt group
metals and Ru/Ir- based compounds for HER and OER, respectively,
are used as efficient electrocatalysts for water splitting with low
overpotential but their high cost and scarcity restrict their us-
age [15]. Hence, developing HER and OER electro-catalysts for wa-
ter splitting with efficient, stable, operating at low overpotential,
cheap, and earth-abundant is vitally important to attain cheap-
efficient hydrogen generation.
Developing the performance of the noble electrocatalysts is one
of the viable options to achieve efficient water splitting. Our group
[16] has designed superaerophobic pine shaped Pt nanoarray elec-
trocatalyst for HER, which exhibits much higher activity and sta-
bility than Pt flat in 0.5 M H2 SO4 . The micro/nanoporous architec-
ture of the superaerophobic Pt nanoarray electrode exhibits much
higher surface wettability (29.3° ± 2.5), lower bubble releasing size
(<50 μm) and lower bubble adhesive force (11.5 ± 1.2 μN) than that
of Pt flat, and that facilitates its gas release, which possibly en-
hances its activity and stability for HER. Besides, for OER in 0.5 M
H2 SO4 , IrOx /SrIrO3 [17] exhibits higher activity and stability than
IrOx and RuOx , where the IrOx /SrIrO3 was prepared by Sr leach-
ing from the surface of SrIrO3 during electrochemical testing. The
IrOx /SrIrO3 is composed of SrIrO3 , which is surrounded by IrOx as
surface layer, and that possibly enhances its activity and stability
for OER.
Improving the performance of earth-abundant electrocatalysts
is another viable option to achieve efficient and cheap water split-
ting. For HER, most of the earth-abundant electrocatalysts can
work well in acid medium as well as in alkaline medium, whereas,
for OER, most of the earth-abundant electrocatalysts can work
well only in alkaline medium but unstable in acid medium, while
electrochemical water splitting in acid medium requires acid in-
soluble, stable, expensive and scarce electrocatalysts [15]. Hence,
water electrolyzer system can be simplified by performing the
electrochemical water splitting in alkaline medium, where a cath-
ode (HER) and an anode (OER) can be simply immerse in a sin-
gle container containing alkaline electrolyte [3,18–23]. In alkaline
medium, water splitting can be performed using either earth-
abundant bifunctional electrocatalysts (where two same electro-
catalysts can be used for HER as well as OER) [3,19,21] or earth-
abundant electrocatalysts (where two different electrocatalysts can
be used for HER and OER) [24,25]. To attain efficient overall water
splitting in alkaline medium, developing efficient earth-abundant
electrocatalysts for HER (2H+ + 2e− → H2 ) and OER (4OH− ↔
2H2 O + O2 + 4e− ) [1] is essentially important, where HER is one
of the important part of the overall water splitting, which in-
volves the transport of two-electrons for the formation of a H2
molecule.
Recently, considerable efforts have been performed to attain
significantly low η on earth-abundant electrocatalysts for HER in
alkaline medium. For HER in 1.0 M KOH to achieve 10 mA cm−2 ,
NiMo1 M NaOH (η10 : − 10 mV) [26], Cux Ni4- x N (η10 : − 12 mV) [27],
NiMo (η10 : − 18 mV) [28], NiMo3 S4 /Ni3 S2 (η10 : − 23.4 mV) [29],
CdS-MoO3 /Ni3 S2 (η10 : − 30 mV) [30], Ni3 N–NiMoN (η10 : − 31 mV)
[31], Ni-(MoS2 -GO)1 M NaOH (η10 : − 33 mV) [32], and NiMo NS
(η10 : − 35 mV) [33] exhibit remarkably much low η, and those are
even higher or well comparable with the HER activity of Pt/C
[34] (η10 : − 33 mV). The activity for HER can be considerably en-
hanced by preparing nanoporous structured NiMo alloy. Our group
[26] has fabricated NiMo alloy with ultrahigh HER activity by sim-
ple electrodeposition method. It possesses nanoporous morphol-
ogy, while it is composed of crystalline Ni4 Mo, which can afford
abundant active sites and facilitate the release of gas, and that
possibly enhances its significantly much high activity for HER. The
NiMo alloy exhibits ultralow η of −10 mV at −10 mA cm−2 in
1.0 M NaOH, which is the lowest η among those ever reported
for non-noble-metal electrocatalysts [3], while it outperforms the
noble Pt/C at higher current density, which depicts its outstand-
ing HER activity. Preparing ultrathin nanostructured Ni4 Mo alloy
with superaerophobic surface can facilitate the release of gas and
afford abundant active sites, which can considerably enhance the
activity for HER. Our group [33] have designed ultrathin NiMo NS
(η10 : − 35 mV), which exhibits considerably much high HER activ-
ity. The NiMo NS possesses ultrathin nanosheet like morphology
with thickness of 2.0–2.1 nm, which corresponds to ≈ 10 atomic
layers of (001) crystalline lattice; it contains Ni and Mo, which are
uniformly distributed; it is composed of body-centered tetragonal-
phase of Ni4 Mo with (001) facet exposed; it contains Ni0 and
Mo0 ; it contains suitable surface electronic structure, which can
enhance the electron/mass transfer; it possesses superaerophobic
nanostructured surface, which facilitates the release of gas, and
that possibly enhance its considerably much high activity for HER.
The activity for HER can be enhanced by preparing copper − nickel
bimetallic nitrides. The Cux Ni4- x N (η10 : − 12 mV) [27] exhibits sub-
stantially much high HER activity. The Cux Ni4- x N is composed of
nanoparticles morphology, where Cu, Ni and N are uniformly dis-
tributed; it contains Cu4 N and Ni4 N phases; it contains Ni2+ , Ni0 ,
Cu2+ , and Cu0 , and that possibly enhance its significantly much
high activity for HER. Moreover, integrating nanostructured CdS,
MoO3 , and Ni3 S2 can provide high conductivity and electrochem-
ically active surface area, and that can enhance the HER activ-
ity. The CdS-MoO3 /Ni3 S2 (η10 : − 30 mV) [30] exhibits considerably
much high HER activity. The CdS-MoO3 /Ni3 S2 is composed of Ni3 S2
nanoarrays, which are covered by MoO3 nanosheets, which forms
a Ni3 S2 /MoO3 core/shell structure, where thin CdS is decorated on
Ni3 S2 /MoO3 ; it possesses conifer-like hierarchical nanoarray struc-
ture; it contains Cd, Ni, Mo, O and S, which are uniformly dis-
tributed; it contains Mo5+ and Mo6+ , where the presence of Mo5+
could be due to the existence of oxygen vacancies; it exhibits high
electrochemically active surface area (Cdl : 117.09 mF cm−2 ); it af-
fords high conductivity, and that possibly enhance its consider-
ably much high activity for HER. In addition to the unique ef-
fect offered by nano-structuring, synergistic effect arises from the
bimetallic or multi-metallic catalysts can also play a significant
role in improving the HER activity, while various researchers have
proved this phenomenon in 1.0 M KOH. Our group [21] has ob-
served that (Ni0.33 Fe0.67 )2 P NS (η of − 84 mV at − 10 mA cm−2 ) ex-
hibits higher HER activity than Ni2 P; Zhang et al. [35] have ob-
served that NiCo2 Px NW (η of − 58 mV at − 10 mA cm−2 ) exhibits
higher HER activity than NiPx and CoPx ; Sun et al. [36] have ob-
served that Ni58 Co42 (η of − 162 mV at − 10 mA cm−2 in 1 M NaOH)
exhibits higher HER activity than Ni and Co; Yu et al. [37] have
observed that Cu@NiFe LDH (η of − 116 mV at − 10 mA cm−2 ) ex-
hibits higher HER activity than NiFe LDH; Anis et al. [38] have ob-
served that oxides of NiW (η of − 60 mV at − 10 mA cm−2 in 0.1 M
KOH) exhibits higher HER activity than the NiO and WO3 ; Sun et
al. [39] have observed that Mo-Ni2 P NW (η of − 78 mV at − 10 mA
cm−2 ) exhibits higher HER activity than Ni2 P NW; Zhang et al.
[40] have observed that Mn-Ni2 P NS (η of − 103 mV at − 20 mA
cm−2 ) exhibits higher HER activity than Ni2 P; Lin et al. [41] have
observed that etched-NiZnP (η of − 50 mV at − 10 mA cm−2 ) ex-
hibits higher HER activity than NiP; Qu et al. [42] observed that V-
 J. Mohammed-Ibrahim, X. Sun / Journal of Energy Chemistry 34 (2019) 111–160
Ni3 S2 NW7000 cycles (η of − 68 mV at − 10 mA cm−2 ) exhibits higher
HER activity than Ni3 S2 NW.
In addition to achieving remarkably low η, attaining signifi-
cantly high long term stability and durability for HER electrocata-
lysts are vitally essential factors to achieve efficient water splitting,
which considerably reduce the cost for operation and maintenance
of the water electrolyzers [3,14,43]. However, achieving signifi-
cantly high long term stability and durability for earth-abundant
electrocatalysts for HER is not an easy task. Guo et al. [44] ob-
served that MoC/C exhibits slight decay at − 40 mA cm−2 after
50 0 0 cycles of CV, while Wu et al. [45] observed that Mo2 C/C
exhibits slight decay at − 80 mA cm−2 after 20 0 0 cycles of CV,
and Li et al. [46] observed that CoP and Ni2 P exhibit slight de-
cay after 10 0 0 cycles of CV, and those indicate their degrada-
tion upon pro-longed cycling for HER. The degradation upon cy-
cling could suggest the corrosion process of the electrocatalysts.
Although, corrosion stability is a part of the long-term stability of
the electrodes, whereas their corrosion behavior with and with-
out water-electrolysis could be different [3,47]. If the electrode is
stable in electrolyte, then it suggests its high corrosion stability
[48–50] but its corrosion products formation at various time in-
tervals can alter its corrosion stability [51,52]. Recently, remark-
able efforts have been performed to attain significantly high long
term stability on earth-abundant electrocatalysts for HER in alka-
line medium. Preparing porous ultrathin Co(OH)2 nanosheets on
N − doped CNTs can significantly enhance the stability for HER.
For HER in 1.0 M KOH, the Co(OH)2 @NCNTs [53] exhibits negligible
decay at − 10 mA cm−2 for 600 h, while its HER activity increases
during stability test (η10 decreases from − 170 mV to ∼− 115 mV),
which suggests that it gets activated during long-term HER,
and that indicates its substantially much high stability for HER.
The porous Co(OH)2 @NCNTs is composed of Co(OH)2 ultrathin
nanosheets, which are grown on the N − doped CNTs; it contains
C, Co, O and N, where N and C are uniformly distributed in the
region of NCNT, while Co and O are homogenously distributed on
the complete region, where the ultrathin porous structure can af-
ford abundant active sites and facilitate gas release, and that possi-
bly enhances its considerably much high stability for HER. Besides,
the stability for HER can be considerably enhanced by preparing
porous structured NiMo alloy. For HER in 1.0 M KOH, the NiMo
[28] exhibits significantly much high stability (reasonable stability
at η of − 200 mV for 300 h). The NiMo is composed of predominant
NiMo phase with tiny amount of Ni4 Mo phase, where Mo4+ and
Mo6+ are negligibly observed, which suggests the almost complete
reduction of oxides; it possesses porous structure, which can afford
abundant active sites and facilitate the release of gas, and that pos-
sibly enhances its substantially much high stability for HER. More-
over, N,P dual doping on etched stainless steel can enhance the
stability for HER. For HER in 1.0 M KOH, the NP-SS [54] exhibits sig-
nificantly much high stability (negligible decay at η of − 230 mV for
134.4 h). The NP-SS possesses nanosheet like structure; it is com-
posed of N, P dual doped SS, while it contains austenite, γ N , and
FeP phases; it contains pyridinic-N, where the nanosheet like mor-
phology with newly formed FeP phase along with N and P dual
doping can afford abundant active sites for HER, and that possibly
enhances its considerably much high stability for HER.
Recently, remarkable efforts have been performed to at-
tain significantly high durability on earth-abundant electro-
catalysts for HER in alkaline medium. Preparing Ni3 S2 with
nanorods@nanosheets homo-junction structure can enhance the
durability for HER. For HER in 1.0 M KOH, the Ni3 S2 [55] ex-
hibits negligible decay after 10,0 0 0 cycles of CV, which indi-
cates its substantially much high durability. The Ni3 S2 is com-
posed of crystalline Ni3 S2 ; it contains Ni2+ , and S2− ; it possesses
sulfur vacancy, which can alter electronic structure of the sur-
face; it exhibits high conductivity; it possesses nanorods, which
113
are further coated by nanosheets, which forms the Ni3 S2 with
nanorods@nanosheets homo-junction, which can afford abundant
active sites, reduce the transport of electron, and facilitate the gas
release, and that possibly enhances its considerably much high
durability for HER. Besides, the durability for HER can be en-
hanced by integrating NiFe LDH with defective graphene. For HER
in 1.0 M KOH, the NiFe LDH@def-Gr [56] exhibits negligible decay
at − 20 0 mA cm−2 after 80 0 0 cycles of CV, which indicates its sig-
nificantly much high durability. The NiFe LDH@def-Gr is composed
of NiFe LDH nanosheet, which are homogeneously distributed on
def-Gr, where the NiFe LDH exhibits single crystalline; it con-
tains Ni2+ , and Fe3+ ; it exhibits ID /IG ratio of 1.06, which suggests
the existence of the defects and disorders; it exhibits high defect
density (3.4 × 1012 cm−2 ), and that possibly enhances its remark-
ably much high durability for HER. Moreover, the durability for
HER can be enhanced by preparing Mott–Schottky electrocatalyst
(metal − semiconductor hybrid) encapsulated with carbon shell.
For HER in 1.0 M KOH, the NC/CuCo/CuCoOx [57] exhibits negligible
decay at − 50 0 mA cm−2 after 50 0 0 cycles of CV, which indicates
its remarkably much high durability. The NC/CuCo/CuCoOx pos-
sesses porous nanowire like morphology (Diameter: 20–50 nm); it
is composed of CuCo/CuCoOx (metal–semiconductor), which is en-
wrapped by the ∼5 nm thick N-doped carbon shell; it contains Cu0 ,
Cu+ , Co0 , Co2+ , Co3+ , C − C, C = O, C − N, pyridinic N, pyrrolic N,
and metal−oxygen bond with oxygen vacancies; it possesses high
surface area (83.7 m2 g−1 ), where the porous structure can afford
large active surface area with abundant active sites, while N-doped
carbon can enhance conductivity and afford continuous electron
transport for metal and semiconductor, and that possibly enhance
its considerably much high durability for HER. Thus, substantial
efforts have been recently performed to attain significantly much
high activity, stability, and durability for HER in alkaline medium
whereas reviews on recent progress on earth abundant electrocata-
lysts with remarkably much high performance have been rarely re-
ported. In this respect, the present paper reviews the activity, sta-
bility and durability for HER in alkaline medium of various kinds
of recently reported electrocatalysts such as Ni, Co, NiCo, Fe, Cu,
W, Mo, Se, Mn, Zn, V, and metal free based earth abundant elec-
trocatalysts. The present paper also reviews the strategies used to
attain the remarkably low-overpotential, high-long-term-stability
and high-durability of earth abundant electrocatalysts for HER in
alkaline medium and those are better or well comparable with the
activity and stability of noble, Pt/C electrocatalyst.
2. Earth abundant electrocatalysts for HER in alkaline
electrolyte
2.1. Ni based earth abundant electrocatalysts for HER
Nickel (Ni) is an earth-abundant first row transitional metal
with atomic number 28, and its abundance in Earth’s crust
is > 50 ppm [58], while it possesses high ductility and corrosion-
resistance. In alkaline environment, the Volmer step is the forma-
tion of adsorbed hydrogen atom and negatively charged hydroxide
anion by the reduction of a H2 O molecule, adsorbed on the elec-
trocatalyst surface (Volmer step: H2 O + e− → Hadsorbed + OH− ). Con-
sequently, there are two possible mechanisms: One is Tafel step,
where two adsorbed hydrogen atoms (generated by the Volmer
step) can be combined together to form a hydrogen molecule
that leaves the catalyst surface (Tafel step: Hadsorbed + Hadsorbed
→H2 ); Second is Heyrovsky step, where the adsorbed hydrogen
atom (generated by the Volmer step) is attacked by another H2 O
molecule to generate a H2 molecule and a hydroxide anion (Hey-
rovsky step: Hadsorbed + H2 O + e− → H2 + OH− ). Some researchers
proposed that the HER mechanisms on metallic Ni surfaces fol-
low Volmer-Tafel route whereas some other researchers proposed
114 J. Mohammed-Ibrahim, X. Sun / Journal of Energy Chemistry 34 (2019) 111–160
Fig. 1. Ni based electrocatalyst for HER (reproduced with permission): (a)
Schematic diagram depicts the fabrication of Ni-rGO, and (b) Gibbs free energy di-
agrams for HER calculated at the equilibrium potential for Ni-rGO, bulk Ni and rGO
[61] (Copyright 2017, Elsevier).
that the HER mechanisms on metallic Ni surfaces follow Volmer-
Heyrovsky step but the actual HER mechanisms on metallic Ni sur-
faces are still being debated [59].
Preparing nanostructured Ni can enhance the stability and ac-
tivity for HER. Abbas et al. [60] have observed that Ni exhibits
much high stability and activity for HER. The Ni was prepared by
hydrothermal treatment at 180 °C for 20 h. The Ni contains face-
centered cubic Ni phase; it possesses Ni nanoparticles with highly
branched structure, where the branched nanostructure can afford
abundant active sites, and that possibly enhances its much high
stability and activity for HER. For HER in 1.0 M NaOH, the Ni ex-
hibits high HER activity (η of − 202 mV at − 10 mA cm−2 ), and it
exhibits reasonable stability for 27.7777 h, which indicates its much
high stability.
The activity and stability for HER can be enhanced by preparing
nanostructured Ni-rGO composite by electrodeposition method
under supergravity field. Wang et al. [61] have observed that
Ni-rGO (rGO: reduced graphene oxide) exhibits significantly much
high activity and stability for HER. The Ni-rGO composite was
prepared on Ni foam by electrodeposition method under super-
gravity field (Fig. 1a). They observed that Ni-rGO prepared under
supergravity field exhibits higher HER activity than Ni-rGO pre-
pared under normal gravity field. They observed through density
functional theory (Fig. 1b) that Ni-rGO (GH∗ : 0.31 eV) exhibits
smaller adsorption free energy of H∗ than Ni (GH∗ : 0.73 eV)
and rGO (GH∗ : 2.22 eV). The Ni-rGO composite exhibits less
adsorption free energy of H∗ (GH∗ : 0.31 eV); it is composed
of Ni nanoparticles and rGO sheets, which are homogenously
loaded on Ni foam, where the Ni nanoparticles are well dis-
persed on rGO sheets, which can afford high surface area, good
electrical conductivity, and harmonious synergistic effect be-
tween rGO sheets and Ni particles, and that possibly enhances
its considerably much high activity and stability for HER. For
HER in 1.0 M NaOH, the Ni-rGO exhibits reasonable stability at
−250/−100 mA cm−2 for 40 h, which indicates its much high
stability, while it exhibits substantially much high HER activity
(η of − 36 mV at − 10 mA cm−2 ), which is nearly close to the HER
activity of Pt/C [34] (η10 : − 33 mV).
Preparing nanostructured Ni-rGO composite by electrodepo-
sition method under supergravity field can afford higher HER
activity than other Ni-carbon composites. Wang et al. [62] ob-
served that Ni-rGO exhibits much high activity and stability for
HER, while it was prepared on Cu foil by electrodeposition method
under supergravity field. They prepared three Ni-carbon compos-
ites by electrodeposition method under supergravity field, while
Ni-rGO exhibits higher HER activity than Ni-ONC and Ni-OCNT. The
Ni-rGO is composed of rGO sheets and Ni nanoparticles, which are
uniformly distributed, and that can provide high surface area and
it exhibits high conductivity, and that possibly enhances its much
high activity and stability for HER. For HER in 1.0 M NaOH, the
Ni-rGO exhibits much high HER activity (η of − 91 mV at − 10 mA
cm−2 ), while it exhibits reasonable stability at − 100 mA cm−2 for
5.5555 h.
The activity for HER can be enhanced by preparing nanos-
tructured Ni-rGO composite on the Ni pre-layer. Shervedani et al.
[63] have observed that Ni-Ni-rGO exhibits much high activity for
HER. The Ni-Ni-rGO was prepared by the following steps: At first,
Ni pre-layer was coated on copper substrate by electrodeposition
method; Finally, Ni-Ni-rGO was obtained by electroless-deposition.
The Ni-Ni-rGO is composed of hedgehog-like prickly nickel nanos-
tructures, which are covered by rGO, while the Ni possesses face-
centered cubic structure, where the synergistic effect between Ni
and rGO can enhance its much high activity for HER. For HER
in 0.1 M NaOH, the Ni-Ni-rGO exhibits much high HER activity (η
of − 57.5 mV at − 20 mA cm−2 ).
Preparing nanostructured Ni/C3 N4 composite by electrodepo-
sition method under supergravity field can enhance the stability
and activity for HER. Wang et al. [64] have observed that Ni/C3 N4
exhibits high stability and activity for HER. The Ni/C3 N4 composite
was prepared by electrodeposition method under supergravity
field, while C3 N4 was obtained by thermal decomposition of
melamine. The Ni/C3 N4 possesses coral-like morphology; it is
composed of C3 N4 , which is embedded in Ni matrix; it contains C
and N, which are uniformly distributed into Ni matrix; it contains
crystalline Ni, and that possibly enhances its high stability and
activity for HER. For HER in 1.0 M NaOH, the Ni/C3 N4 exhibits high
HER activity (η of − 222 mV at − 10 mA cm−2 ), and it exhibits neg-
ligible decay at − 100 mA cm−2 for 12 h, which indicates its high
stability.
The durability and activity for HER can be enhanced by prepar-
ing Ni3 S2 with nanorods@nanosheets homo-junction structure.
Tong et al. [55] have observed that Ni3 S2 exhibits substantially
much high durability and activity for HER. The Ni3 S2 was prepared
by hydrothermal treatment at 160 °C for 12 h. They observed
that Ni3 S2 nanorods@Ni3 S2 nanosheets homo-junction exhibits
higher HER activity than Ni3 S2 nanorods. The Ni3 S2 is composed
of crystalline Ni3 S2 ; it contains Ni2+ , and S2− ; it possesses sulfur
vacancy, which can alter electronic structure of the surface; it
exhibits high conductivity; it possesses nanorods, which are fur-
ther coated by nanosheets (Fig. 2), which forms the Ni3 S2 with
nanorods@nanosheets homo-junction, which can afford abundant
active sites, reduce the transport of electron, and facilitate the
gas release, and that possibly enhances its considerably much
high durability and activity for HER. For HER in 1.0 M KOH, the
Ni3 S2 exhibits negligible decay after 10,0 0 0 cycles of CV, which
indicates its substantially much high durability, while it exhibits
significantly much high HER activity (η of − 48.1 mV at − 10 mA
cm−2 ), and it exhibits reasonable stability at − 48 mV for 24 h,
which indicates its much high stability.
 J. Mohammed-Ibrahim, X. Sun / Journal of Energy Chemistry 34 (2019) 111–160
Fig. 2. Ni based electrocatalyst for HER (reproduced with permission): (a–c) SEM images of Ni3 S2 , (d) TEM image (Inset: HRTEM image) of Ni3 S2 , and (e, f) the corresponding
HRTEM images of the enlarged red frame portion obtained from (d) of Ni3 S2 [55] (Copyright 2018, American Chemical Society).
Preparing hollow Ni3 S2 microsphere with abundant protruding
edges can enhance the activity and stability for HER. Tian et al.
[65] have observed that Ni3 S2 exhibits much high activity and
stability for HER. The Ni3 S2 was prepared by hydrothermal sulfu-
rization of nickel foam at 200 °C for 24 h using polyoxometalate
and triblock copolymer pluronic as a hybrid soft template, where
sonication was used for the hybrid preparation. They observed that
Ni3 S2 prepared with sonication exhibits higher electrochemically
active surface area and HER activity than Ni3 S2 prepared without
sonication. The Ni3 S2 possesses hollow microsphere morphology
with abundant protruding edges, which can provide plenty of
active sites; it is composed of predominant crystalline Ni3 S2 with
minor Mo, which exists as Mo6+ ; it exhibits high conductivity and
electrochemically active surface area, and that possibly enhance
its much high activity and stability for HER. For HER in 1.0 M
KOH, the Ni3 S2 exhibits negligible decay at − 10 mA cm−2 after
10 0 0 cycles of CV, which indicates its high durability, while it
exhibits much high HER activity (η of − 77 mV at − 10 mA cm−2 ),
and it exhibits reasonable stability at η of − 120 mV for 25 h, which
indicates its much high stability.
The durability and activity for HER can be enhanced by prepar-
ing porous Ni3 S2 on nano-porous Cu. Yang et al. [66] have ob-
served that Ni3 S2 @Cuactivated exhibits much high durability and
activity for HER. The Ni3 S2 @Cuactivated was prepared by the fol-
lowing steps: At first, nano-porous Cu was obtained by electrode-
position of Zn on Cu followed by selective dissolution of Zn;
Then, Ni3 S2 @Cu was obtained by galvanic replacement reaction in
the Ethaline-based plating solution; Finally, Ni3 S2 @Cuactivated was
obtained by multi-step chronoamperometric measurements. The
Ni3 S2 @Cuactivated possesses porous surfaces with hierarchical ar-
chitectures (where the porosity increases upon activation process
(Fig. 3)); it contains Ni2+ and Ni3+ ; it has Ni3 S2 along with NiO,
where the porous structure can afford abundant active sites, and
that possibly enhances its much high durability and activity for
115
HER. For HER in 1.0 M KOH, the Ni3 S2 @Cuactivated exhibits negligible
decay at − 20 0 mA cm−2 after 20 0 0 cycles of CV, which indicates
its much high durability, while it exhibits much high HER activity
(η of − 60.8 mV at − 10 mA cm−2 ).
The activity for HER can be enhanced by integrating rGO with
Ni3 S2 . He et al. [67] have observed that Ni3 S2 -rGO exhibits signif-
icantly much high activity for HER. The Ni3 S2 -rGO was prepared
by hydrothermal treatment at 160 °C for 6 h. They observed that
Ni3 S2 -rGO exhibits higher HER activity than Ni3 S2 . The Ni3 S2 -rGO
possesses porous architecture; it is composed of ultrathin rhombo-
hedral Ni3 S2 nanosheets, which are homogeneously dispersed on
the rGO sheets; it contains Ni, S, and C, which are uniformly dis-
tributed, and that possibly enhances its considerably much high
activity for HER. For HER in 1.0 M KOH, the Ni3 S2 -rGO exhibits sub-
stantially much high HER activity (η of − 44 mV at − 10 mA cm−2 ).
Preparing nanostructured ultrathin metallic nickel can enhance
the stability and activity for HER. Ma et al. [68] have observed
that NiS2 activated exhibits much high stability and activity for HER.
The NiS2 activated was prepared by the following steps: At first,
NiS2 was obtained by heating Ni(OH)2 at 250 °C for 2 h; Finally,
NiS2 activated was activated by chronopotentiometry for ∼5 h. They
observed that NiS2 activated exhibits higher HER activity than bare
NiS2 and Ni(OH)2 . The NiS2 activated possesses ultrathin nanosheets
like morphology; it is composed of predominant Ni0 , which are en-
wrapped by a thin-layer of Ni(OH)2 , which can provide abundant
active sites, and that possibly enhances its much high stability and
activity for HER. For HER in 1.0 M KOH, the NiS2 activated exhibits
much high HER activity (η of − 67 mV at − 10 mA cm−2 ), while the
NiS2 exhibits negligible decay at − 20 mA cm−2 for 40 h, where the
overpotential decreases in the initial stage (for ∼3 h) due to activa-
tion, and remains stable in the subsequent stage, which indicates
its much high stability.
The stability and activity for HER can be enhanced by preparing
surface anion-rich NiS2 . Tian et al. [69] have observed that surface
116 J. Mohammed-Ibrahim, X. Sun / Journal of Energy Chemistry 34 (2019) 111–160

Fig. 3. Ni based electrocatalyst for HER (reproduced with permission): (a) Schematic diagram depicts the structural changes from Ni3 S2 @Cu (pristine) to Ni3 S2 @Cu (activated
(5th)); (b-e) SEM images of (b) Ni3 S2 @Cu (pristine), (c) Ni3 S2 @Cu (activated (1st), (d) Ni3 S2 @Cu (activated (2nd)), and (e) Ni3 S2 @Cu (activated (5th)); (f-h) AFM images with
corresponding line scans of (f) Ni3 S2 @Cu (pristine), (g) Ni3 S2 @Cu (activated (1st)), and (h) Ni3 S2 @Cu (activated (5th)); (i–k) High resolution XPS spectra of (i) Ni 2p, (j) S 2p
and (k) Cu 2p obtained from Ni3 S2 @Cu (pristine) and Ni3 S2 @Cu (activated (5th) [66] (Copyright 2017, Elsevier).

anion-rich NiS2 hms (hms: hollow micro-sphere) exhibits high sta-
bility and activity for HER. The NiS2 hms was prepared from metal
organic framework (MOF) by microwave treatment at 160 °C for
30 min, while the MOF was obtained by hydrothermal treatment
at 150 °C for 24 h. They observed that surface anion-rich NiS2 hms
exhibits higher HER activity than NiS2 hms without surface anion-
rich. The NiS2 hms is composed of surface sulfate anion-rich cu-
bic pyrite NiS2 ; it possesses hollow micro-sphere morphology; it
contains Ni2+ , Ni3+ , and S2 2− , and that possibly enhances its high
stability and activity for HER. For HER in 1.0 M KOH, the NiS2 hms
exhibits high HER activity (η of − 219 mV at − 10 mA cm−2 ); it ex-
hibits reasonable stability at − 10 mA cm−2 for 19 h, which indi-
cates its high stability.
Preparing spherical structured Nix S can enhance the stability
and activity for HER. Fang et al. [70] have observed that Nix S ex-
hibits much high stability and activity for HER. The Nix S was pre-
pared by hydrothermal treatment at 180 °C for 48 h followed by
annealing at 300 °C for 2 h under N2 atmosphere. The Nix S con-
 J. Mohammed-Ibrahim, X. Sun / Journal of Energy Chemistry 34 (2019) 111–160
Fig. 4. Ni based electrocatalyst for HER (reproduced with permission): (a and b) SEM images, (c) TEM image (Inset: SAED pattern), and (d) HRTEM images of Ni5 P4 [71] (Copy-
right 2017, Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim).
tains NiS and Ni0.96 S phases; it contains Ni2+ , and S2− ; it possesses
spherical structure, and that possibly enhance its much high sta-
bility and activity for HER. For HER in 1.0 M KOH, the Nix S ex-
hibits negligible decay at − 10 mA cm−2 after 10 0 0 cycles of CV,
which indicates its high durability, while it exhibits high HER activ-
ity (η of − 113 mV at − 10 mA cm−2 ); it exhibits reasonable stability
at − 50 mA cm−2 for 25 h, which indicates its much high stability.
The activity and stability for HER can be enhanced by prepar-
ing nanostructured Ni5 P4 . Wang et al. [71] have observed that
Ni5 P4 exhibits considerably much high activity and stability for
HER. The Ni5 P4 was prepared on Ti foil by the following steps:
At first, Ni(OH)2 •0.75H2 O was obtained by hydrothermal treatment
at 95 °C for 20 h; Finally, Ni5 P4 was prepared by phosphoriza-
tion for 3 h at 370 °C under N2 atmosphere. They observed that
Ni5 P4 exhibits higher HER activity than Ni2 P and Ni(OH)2 •0.75H2 O.
The Ni5 P4 possesses flower-like micro-balls structure (Diameter:
12 μm) as shown in Fig. 4(a), where the micro-balls further possess
nano-plates like morphology (Fig. 4b), which can afford abundant
active sites; it contains hexagonal Ni5 P4 (Fig. 4); it contains Ni and
P, which are uniformly distributed; it exhibits high energy (001)
facet with surface energy of 1.590 J m−2 , which could facilitate the
inherent catalytic activity of each Ni site; it exhibits high conduc-
tivity, and that possibly enhances its significantly much high activ-
ity and stability for HER. For HER in 1.0 M KOH, the Ni5 P4 exhibits
negligible decay after 3600 cycles of CV, which indicates its much
high durability, while it exhibits substantially much high HER ac-
tivity (η of − 47 mV at − 10 mA cm−2 ).
Integrating Ni(OH)2 with Ni3 N can enhance the stability and ac-
tivity for HER. Gao et al. [72] have observed that Ni(OH)2 –Ni3 N ex-
hibits much high stability and activity for HER. The Ni(OH)2 –Ni3 N
was prepared by the following steps: At first, Ni(OH)2 was ob-
tained on Ti mesh by hydrothermal treatment at 120 °C for 6 h;
Then, Ni3 N was prepared by heating the Ni(OH)2 at 380 °C for
3 h under NH3 atmosphere; Finally, Ni(OH)2 –Ni3 N was obtained
by electro-deposition of Ni(OH)2 on Ni3 N. They observed that
Ni(OH)2 –Ni3 N nanosheet exhibits higher HER activity than Ni3 N
nanosheet, whereas Ni(OH)2 –Ni3 N possesses lower electrochemi-
cally active surface area than Ni3 N, where the synergistic activ-
ity between Ni(OH)2 and Ni3 N in Ni(OH)2 –Ni3 N enhanced its HER
117
activity. The Ni(OH)2 –Ni3 N possesses nanosheet like morphology
(Fig. 5c); it is composed of crystalline Ni3 N, which is covered
by ultrathin amorphous Ni(OH)2 layer with thickness of 2–3 nm
(Fig. 5e); it contains Ni, N, and O, which are uniformly distributed
(Fig. 5f), and that possibly enhances its much high stability and
activity for HER. For HER in 1.0 M KOH, the Ni(OH)2 –Ni3 N exhibits
negligible decay at − 100 mA cm−2 after 500 cycles of CV, which
indicates its much high durability, while it exhibits much high HER
activity (η of − 72 mV at − 20 mA cm−2 ); it exhibits negligible decay
at η of − 106 mV for 25 h, which indicates its much high stability.
Preparing nanostructured Ni − carbon composite with high Ni0
ratio can enhance the activity and stability for HER. Wang et al.
[73] have observed that NiOx @CNTs exhibits much high activity
and stability for HER. The NiOx @CNTs was prepared by annealing
the mixture of melamine/Ni(NO3 )2 •6H2 O at 600 °C for 1 h followed
by 700 °C for 2 h under N2 atmosphere. They prepared NiOx @CNTs
with different Ni0 ratios, while NiOx @CNTs with higher Ni0 ratio
exhibits higher HER activity. The NiOx @CNTs is composed of metal-
lic Ni (Ni0 ) nanoparticles, which are integrated with bamboo-like
carbon nanotubes (Fig. 6d), while it possesses a unique interface
between Ni and NiO (Fig. 6e), where the bulk Ni0 and the Ni0 on
the interface of Ni/NiO can facilitate HER activity; it contains N and
C, which are uniformly distributed; it contains graphitic carbon, Ni
and NiO phases; it exhibits C = C at 284.5 eV, C − C at 285.4 eV,
and C − N − C at ∼287.0 eV, where the N − doping in C can pre-
vent the agglomeration of metal particles, which could improve
the dispersion of metal particles; it possesses high structural de-
fects (ID /IG : 1.33), which could be due to the N − doping in C; it
exhibits high surface area (314 m2 g−1 ), and that possibly enhances
its much high activity and stability for HER. For HER in 1.0 M KOH,
the NiOx @CNTs exhibits much high HER activity (η of ∼− 79 mV
at − 10 mA cm−2 ), and it exhibits ∼90% retention for 10 h, which
indicates its much high stability.
2.2. Co based earth abundant electrocatalysts for HER
The activity for HER can be enhanced by preparing nanos-
tructured CoP. Guo et al. [74] have observed that CoP NS (NW:
Nanosheet) exhibits much high activity for HER. The CoP NS was
118 J. Mohammed-Ibrahim, X. Sun / Journal of Energy Chemistry 34 (2019) 111–160

Fig. 5. Ni based electrocatalyst for HER (reproduced with permission): (a) XRD pattern of the Ni(OH)2 –Ni3 N in comparison with Ni3 N, SEM images obtained from (b) Ni3 N
and (c) Ni(OH)2 –Ni3 N, HRTEM images of (d) Ni3 N and (e) Ni(OH)2 –Ni3 N, and (f) EDX elemental mapping images (Ni, N and O) of Ni(OH)2 –Ni3 N [72] (Copyright 2018, The
Royal Society of Chemistry).

prepared by the following steps: At first, α -Co(OH)2 was prepared
on Ni foam by electrodeposition; Finally, CoP NS was obtained
by heating α -Co(OH)2 with NaH2 PO2 at 300 °C under Ar atmo-
sphere. The CoP NS possesses nanosheet morphology; it contains
crystalline CoP; it contains defects, which can afford abundant ac-
tive sites and facilitate the gas release, and that possibly enhances
its much high activity for HER. For HER in 1.0 M KOH, the CoP NS
exhibits much high HER activity (η of − 86.6 mV at − 10 mA cm−2 ).
Moreover, Yan et al. [75] have observed that CoP NS exhibits much
high stability and activity for HER. The CoP NS was prepared by
the following steps: At first, CoF2 •4H2 O was prepared on carbon
cloth by hydrothermal treatment at 120 °C for 22 h; Finally, CoP
NS was obtained by phosphidation with NaH2 PO2 at 300 °C for
2 h under Ar atmosphere. The CoP NS is composed of crystalline
CoP with nanosheet morphology, and that possibly enhances its
much high stability and activity for HER. For HER in 1.0 M KOH, the
CoP NS exhibits 21 mV decay after 30 0 0 cycles of CV, which indi-
cates its high durability, while it exhibits much high HER activity
(η of − 90 mV at − 10 mA cm−2 ), and it exhibits reasonable stability
at η of − 106 mV for 50 h, which indicates its much high stability.
Preparing thin CoOx on nanostructured CoP can form CoP/CoOx
homojunction, and that enhances the activity and stability for HER.
Xu et al. [76] have observed that CoP NWs/CoOx exhibits signifi-
cantly much high activity and stability for HER. The CoP NWs/CoOx
was prepared by the following steps: At first, CoP NWs (Fig. 7a)
was prepared by hydrothermal treatment at 120 °C for 12 h fol-
lowed by subsequent phosphorization at 100 °C for 10 min and
then 320 °C for 2 h under Ar atmosphere; Finally, CoP NWs/CoOx
was obtained by oxygen plasma engraving treatment. They ob-
served that CoP NWs/CoOx exhibits higher HER activity than pris-
tine CoP NWs. The CoP NWs/CoOx possesses nanowire morphology;
it is composed of CoP, which is surrounded by thin CoOx layer (Di-
ameter: ∼3 nm) as shown in Fig. 7(b); it contains CoP/CoOx inter-
face, and that provide abundant active sites, and that possibly en-
hances its considerably much high activity and stability for HER.
For HER in 1.0 M KOH, the CoP NWs/CoOx exhibits negligible decay
at − 10 mA cm−2 after 50 0 0 cycles of CV, which indicates its much
high durability, while it exhibits substantially much high HER ac-
tivity (η of − 65 mV at − 10 mA cm−2 ), and it exhibits 93.7 % re-
tention at η of − 150 mV for 35 h, which indicates its much high
stability.
Integrating Co2 P with Co3 O4 can afford synergistic effect, which
can enhance the durability and activity for HER. Yao et al. [77] have
observed that Co2 P@Co3 O4 exhibits high durability and activity for
 J. Mohammed-Ibrahim, X. Sun / Journal of Energy Chemistry 34 (2019) 111–160
Fig. 6. Ni based electrocatalyst for HER (reproduced with permission): (a) TEM image of NiOx @CNTs (Inset: metal particle size distribution histogram), (b) TEM image of
NiOx @CNTs treated with acid, (c–e) HRTEM images of NiOx @CNTs (Inset in (d): Fast Fourier transform (FFT) images of Ni0 ) [73] (Copyright 2017, American Chemical Society).
HER. The Co2 P@Co3 O4 was prepared by the following steps: At
first, β -Co(OH)2 was obtained by refluxing at 95 °C for 5 h under
N2 atmosphere; Finally, Co2 P@Co3 O4 was prepared by phospha-
tization with NaH2 PO2 at 300 °C for 2.5 h under Ar atmosphere.
They observed that Co2 P@Co3 O4 exhibits higher electrochemically
active surface area and HER activity than Co(OH)2 and Co3 O4 . The
Co2 P@Co3 O4 contains Co2 P and Co3 O4 phases; it is composed of
Co2 P nanoparticles, which are homogenously anchored on Co3 O4
hexagonal platelets; it contains Co3+ and Co2+ ; it possesses high
electrochemically active surface area, where the synergistic effect
existed between the Co2 P and Co3 O4 can provide abundant active
sites, and that possibly enhances its high durability and activity
for HER. For HER in 1.0 M KOH, the Co2 P@Co3 O4 exhibits negligible
decay at − 60 mA cm−2 after 10 0 0 cycles of CV, which indicates its
high durability, while it exhibits high HER activity (η of − 159 mV
at − 10 mA cm−2 ), and it exhibits negligible decay at − 10 mA cm−2
for 8 h, which indicates its high stability.
The durability and activity for HER can be enhanced by inte-
grating nanostructured CoO@Co with N-doped carbon matrix. Liu
et al. [78] have observed that CoO@Co/N-rGO exhibits high durabil-
ity and activity for HER. The CoO@Co/N-rGO was prepared by the
following steps: At first, Co/GO was obtained by rapid microwave
polyol method; Finally, CoO@Co/N-rGO was prepared by heating
with melamine at 600 °C for 3 h under N2 atmosphere. They
observed that CoO@Co/N-rGO exhibits higher HER activity than
rGO, N-rGO, and CoO@Co/rGO. The CoO@Co/N-rGO is composed of
CoO@Co nanoparticles with core-shell structure, which are dis-
persed and anchored on N-doped reduced graphene oxide; it con-
tains metallic Co and CoO phases; it contains Co0 , Co2+ , pyridinic-
N, Co–N, pyrrolic-N, graphitic-N and oxidized-N, and that possibly
enhances its high durability and activity for HER. For HER in 0.1 M
KOH, the CoO@Co/N-rGO exhibits negligible decay at − 25 mA cm−2
after 10 0 0 cycles of CV, which indicates its high durability, while
it exhibits high HER activity (η of − 237 mV at − 10 mA cm−2 ).
Integrating CoP with CNTs can enhance the activity and dura-
bility for HER. Zhang et al. [79] have observed that CoP/CNTs ex-
119
hibits much high activity and durability for HER. For HER in 1.0 M
KOH, the CoP/CNTs exhibits very slight decay after 50 0 0 cycles of
CV, which indicates its high durability, while it exhibits much high
HER activity (η of − 76 mV at − 10 mA cm−2 ).
The durability and activity for HER can be enhanced by inte-
grating CoP with glucose derived carbon. Luo et al. [80] have ob-
served that CoP/C exhibits much high durability and activity for
HER. The CoP/C was prepared by hydrothermal treatment at 180 °C
for 10 h followed by phosphorization with (NH4 )2 HPO4 at 900 °C
for 2 h under H2 /Ar atmosphere. They observed that CoP/C exhibits
higher HER activity than Co3 O4 /C and Co2 P. The CoP/C is composed
of CoP nanoparticles, which are anchored on the microsphere car-
bon; it contains sp2 and sp3 graphitic carbon, which can afford
abundant active sites and facilitate conductivity, and that possibly
enhances its much high durability and activity for HER. For HER
in 1.0 M KOH, the CoP/C exhibits negligible decay at − 50 mA cm−2
after 30 0 0 cycles of CV, which indicates its much high durabil-
ity, while it exhibits high HER activity (η of − 163 mV at − 10 mA
cm−2 ), and it exhibits reasonable stability at η of − 163 mV, which
indicates its high stability.
Integrating CoP with N-doped carbon nanotube hollow polyhe-
dron can enhance the durability and activity for HER. Pan et al.
[81] have observed that CoP/NCNHP (NCNHP: N-doped carbon nan-
otube hollow polyhedron) exhibits high durability and activity for
HER. The CoP/NCNHP was prepared by the following steps: At first,
ZIF-8@ZIF-67 (Zeolitic imidazolate frameworks: ZIF) was obtained
from ZIF-8 by epitaxial growth; Then, Co/NCNHP was prepared by
pyrolysis of ZIF-8@ZIF-67 at 920 °C for 3 h under Ar atmosphere;
Later, Co3 O4 /NCNHP was obtained by oxidation of Co/NCNHP at
350 °C for 4 h in air; Finally, CoP/NCNHP was prepared by phos-
phorization of Co3 O4 /NCNHP with NaH2 PO2 at 300 °C for 2 h un-
der Ar atmosphere. They observed that CoP/NCNHP exhibits higher
HER activity than NCP, Co/NCP, Co/NCNHP and CoP/NCP. They ob-
served through density functional theory that the electron trans-
fer from NCNHP to CoP could facilitate the electronic states of Co
d-orbital around the Fermi level, and that can improve binding
120 J. Mohammed-Ibrahim, X. Sun / Journal of Energy Chemistry 34 (2019) 111–160
Fig. 7. Co based electrocatalyst for HER (reproduced with permission): (a) SEM im-
age of CoP NWs, and (b) HRTEM image of CoP NWs/CoOx [76] (Copyright 2018,
Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim).
strength with H, which can facilitate its electrochemical perfor-
mance. The CoP/NCNHP is composed of crystalline CoP nanoparti-
cles, which are anchored in N-doped carbon nanotube hollow poly-
hedron; it contains C, N, Co and P, which are uniformly distributed;
it contains graphitic N at 401.5 eV (39.65%), pyrrolic N at 400.1 eV
(44.52%) and pyridinic N at 398.8 eV (15.83%); it possesses micro-
pore and mesopore; it exhibits high surface area (86.5 m2 g−1 ),
where the synergistic effect between CoP and NCNHP can afford
abundant active sites, and that possibly enhances its high dura-
bility and activity for HER. For HER in 1.0 M KOH, the CoP/NCNHP
exhibits negligible decay at − 60 mA cm−2 after 10 0 0 cycles of CV,
which indicates its high durability, while it exhibits high HER activ-
ity (η of − 115 mV at − 10 mA cm−2 ); it exhibits reasonable stability
at η of − 120 mV for 20 h, which indicates its high stability.
The stability and activity for HER can be enhanced by integrat-
ing Co/CoP with hairy N-doped carbon hollow polyhedron. Hao et
al. [20] have observed that Co/CoP-hairy-NC exhibits high stability
and activity for HER. The Co/CoP-NC was prepared by heating ZIF-
67 with dicyandiamide at 700 °C for 2 h under Ar atmosphere fol-
lowed by phosphorization with sodium hypophosphite at 320 °C
for 2 h. They observed that Co/CoP-hairy-NC exhibits higher HER
activity than Co-hairy-NC and Co/CoP–NC. The Co/CoP-NC is com-
posed of Co/CoP particles, which are anchored on hairy N-doped
carbon hollow polyhedron; it contains Co and CoP phases; it con-
tains Co, P, C, and N; it contains pyridinic N, pyrrolic N, and graphic
N, which can afford abundant active sites and conductivity, and
that possibly enhances its high stability and activity for HER. For
HER in 1.0 M KOH, the Co/CoP-NC exhibits high HER activity (η
of − 180 mV at − 10 mA cm−2 ), and it exhibits reasonable stability
at − 10 mA cm−2 for 10 h, which indicates its high stability.
Integrating Co2 P quantum dots with N, P dual doped carbon can
enhance the durability and activity for HER. Zhang et al. [82] have
observed that Co2 P@NPC exhibits high durability and activity for
HER. The Co2 P@NPC was prepared by the following steps: At first,
a precursor was obtained by electro-deposition followed by im-
mersion in Co(NO3 )2 •6H2 O for 2 h at 40 °C; Finally, Co2 P@NPC was
prepared by calcination of the precursor at 800 °C for 2 h under H2
atmosphere. They observed that Co2 P@NPC exhibits higher HER ac-
tivity than NPC. The Co2 P@NPC is composed of orthorhombic Co2 P
quantum dots with ∼5 nm in size, which are anchored in the N,
P dual doped carbon; it possesses interconnected spherical parti-
cles structure (Diameters: 60 0–90 0 nm) with sub-nanospheres; it
contains N, C, Co and P, which are uniformly distributed; it con-
tains pyridinic N, pyrrolic N, graphitic N, C = C, C − N/C = N/C–P,
and O − C = O, and that possibly enhance its high durability and
activity for HER. For HER in 1.0 M KOH, the Co2 P@NPC exhibits
negligible decay at − 10 mA cm−2 after 10 0 0 cycles of CV, which
indicates its high durability, while it exhibits high HER activity (η
of − 129 mV at − 10 mA cm−2 ), and it exhibits reasonable stability
at η of − 190 mV for 5.5555 h.
Doping P with nanostructured Co3 O4 can enhance the dura-
bility and activity for HER. Wang et al. [83] have observed that
P8.6 –Co3 O4 NW (NW: nanowire) exhibits much high durability and
activity for HER. The P8.6 –Co3 O4 NW was prepared by the follow-
ing steps: At first, Co3 O4 was obtained by hydrothermal treatment
at 120 °C for 6 h; Finally, P8.6 –Co3 O4 NW was prepared by anneal-
ing Co3 O4 with NaH2 PO2 at 300 °C for 0.5 h. They observed that
P8.6 –Co3 O4 NW exhibits higher HER activity than pristine Co3 O4
NW. The P8.6 –Co3 O4 NW possesses nanowire morphology (Fig. 8c);
it is composed of P − doped crystalline Co3 O4 nanowire, which can
provide abundant active sites; it contains Co, P, and O, which are
uniformly distributed (Fig. 8); it contains Co2+ and Co3+ , and that
possibly enhances its much high durability and activity for HER.
For HER in 1.0 M KOH, the P8.6 –Co3 O4 NW exhibits negligible de-
cay at − 200 mA cm−2 after 1000 cycles of CV, which indicates its
much high durability, while it exhibits much high HER activity (η
of − 97 mV at − 10 mA cm−2 ), and it exhibits negligible decay at η
of − 140 mV for 20 h, which indicates its much high stability.
Filling P in the oxygen vacancies of Co3 O4 , can stabilize the va-
cancies by compensating the coordination number, and that can
enhances the stability and activity for HER. Xiao et al. [84] have
observed that P-Co3 O4 exhibits high stability and activity for HER.
The P-Co3 O4 was prepared by thermal coupled plasma modifica-
tion approach, where P was used to fill the oxygen vacancies in
Co3 O4 . They observed that P-Co3 O4 exhibits higher HER activity
than Co3 O4 with oxygen vacancies, while Co3 O4 with oxygen va-
cancies affords higher HER activity than pristine Co3 O4 . They ob-
served that P-Co3 O4 possesses more tetrahedral Co2+ (Td ) than oc-
tahedral Co3+ (Oh ), which could be due to the transfer of electrons
out of Co 3d states after filling P in the vacancy sites of Co3 O4 (Td :
Tetrahedral coordination by four oxygen atoms, Oh : Octahedral co-
ordination by six oxygen atoms), and the P-Co3 O4 is composed of
crystalline Co3 O4 , where the oxygen vacancies are filled by P; it
possesses nano-sheet morphology, and that possibly enhances its
high stability and activity for HER. For HER in 1.0 M KOH, the P-
Co3 O4 exhibits high HER activity (η of − 120 mV at − 10 mA cm−2 ),
and it exhibits reasonable stability at η of − 120 mV for 11.1111 h,
which indicates its high stability.
The stability and activity for HER can be significantly enhanced
by preparing porous ultrathin Co(OH)2 nanosheets on N − doped
CNTs. Guo et al. [53] have observed that Co(OH)2 @NCNTs ex-
hibits significantly much high stability and activity for HER. The
Co(OH)2 @NCNTs was prepared by electro-deposition of Co(OH)2
 J. Mohammed-Ibrahim, X. Sun / Journal of Energy Chemistry 34 (2019) 111–160
Fig. 8. Co based electrocatalyst for HER (reproduced with permission): (a) XRD pattern of P8.6 –Co3 O4 NW in comparison with Co3 O4 , (b, c) SEM image of (c) P8.6 –Co3 O4 NW
in comparison with (b) Co3 O4 (Inset: its higher magnification image), (d, e) TEM images of P8.6 –Co3 O4 NW, and (f) EDX mapping images of P8.6 –Co3 O4 NW [83] (Copyright
2018, American Chemical Society).
nanosheets on the NCNT in an aqueous solution. They observed
that Co(OH)2 @NCNTs exhibits higher HER activity than Co(OH)2
and NCNTs. The porous Co(OH)2 @NCNTs (Fig. 9) is composed of
Co(OH)2 ultrathin nanosheets, which are grown on the N − doped
CNTs (Fig. 9b); it contains C, Co, O and N, where N and C are
uniformly distributed in the region of NCNT, while Co and O are
homogenously distributed on the complete region, where the ul-
trathin porous structure can afford abundant active sites and fa-
cilitate gas release, and that possibly enhances its considerably
much high stability and activity for HER. For HER in 1.0 M KOH,
the Co(OH)2 @NCNTs exhibits high HER activity (η of − 170 mV
at − 10 mA cm−2 ), and it exhibits negligible decay at − 10 mA cm−2
for 600 h, while its HER activity increases during stability test (η10
decreases from − 170 mV to ∼− 115 mV), which suggests that it gets
activated during long-term HER, and that indicates its substantially
much high stability, which is much higher stability than the stabil-
ity of Pt/C [85] (79% retention at − 10 mA cm−2 after 24 h).
Preparing nanostructured crystalline cobalt carbide can enhance
the durability and activity for HER. Li et al. [86] have observed that
Co2 C exhibits much high durability and activity for HER. The Co2 C
was prepared by bromide-induced wet-chemistry route. The Co2 C
possesses nanoparticles morphology; it contains crystalline Co2 C,
and that possibly enhances its much high durability and activity
for HER. For HER in 0.1 M KOH, the Co2 C exhibits negligible decay
at − 10 mA cm−2 after 40 0 0 cycles of CV, which indicates its much
high durability, while it exhibits high HER activity (η of − 181 mV
at − 10 mA cm−2 ).
Designing nano-heterojunction and tuning electronic structure
at the interface can enhance the stability and activity for HER.
Zhu et al. [87] have observed that Co-Ni3 N exhibits much high
stability and activity for HER. The Co-Ni3 N was prepared by the
following steps: At first, NiCo2 O4 was obtained by hydrothermal
treatment at 120 °C for 5 h followed by annealing at 350 °C for
2 h in air; Finally, Co-Ni3 N was prepared by annealing at 250 °C
for 1 h under NH3 atmosphere. They observed that Co-Ni3 N ex-
hibits higher HER activity than Ni3 N. They observed through den-
sity functional theory that Co-Ni3 N possesses epitaxial interface,
while it exhibits efficient charge transfer across the Co/Ni3 N in-
terface, and the Co-Ni3 N possesses nano-rod morphology, which
121
are further composed of nanoparticles; it contains metallic Co and
Ni3 N phases, where a nano-confinement effect is reinforced at the
Co/Ni3 N interface; it contains Ni, Co, and N, which are uniformly
distributed; it shows slightly lower binding energy of Ni 2p in
Co-Ni3 N than that in Ni3 N, which could be due to the additional
charges in the Ni side, and that possibly enhances its much high
stability and activity for HER. For HER in 1.0 M KOH, the Co-Ni3 N
exhibits negligible decay for 24 h (negligible decay at − 10 mA cm−2
for 2 h, − 20 mA cm−2 for 2 h, − 30 mA cm−2 for 2 h, − 40 mA cm−2
for 2 h, − 50 mA cm−2 for 2 h followed by − 10 mA cm−2 for 14 h),
which indicates its much high stability, while it exhibits high HER
activity (η of − 194 mV at − 10 mA cm−2 ).
The stability and activity for HER can be enhanced by integrat-
ing Co9 S8 with heteroatoms doped carbon. Huang et al. [88] have
observed that Co9 S8 @NOSC exhibits high stability and activity for
HER. The Co9 S8 @NOSC was prepared by pyrolysis of S- and Co(II)-
containing polypyrrole solid precursors. The Co9 S8 @NOSC is com-
posed of cubic crystalline Co9 S8 nanoparticles, which are encapsu-
lated by N,O,S tri-doped C; it contains C = C − C, C − S, C − O/C − N,
C = O, pyridinic-N and quaternary-N, and the Co9 S8 @NOSC exhibits
ID /IG ratio of 0.82, which is lower than NOSC (0.87), which suggests
the higher degree of ordered carbon structure for Co9 S8 @NOSC
than NOSC, and that possibly enhances its high stability and activ-
ity for HER. For HER in 1.0 M KOH, the Co9 S8 @NOSC exhibits high
HER activity (η of − 320 mV at − 10 mA cm−2 ), and it exhibits rea-
sonable stability for 20 h, which indicates its high stability.
2.3. NiCo based earth abundant electrocatalysts for HER
Preparing nanostructured transition-bimetallic phosphides can
provide synergistic effect from bimetals, which can enhance the
durability and activity for HER. Zhang et al. [35] have observed
that NiCo2 Px NW (NW: nanowire) exhibits substantially much high
durability and activity for HER. The NiCo2 Px NW was prepared
by phosphorization of NiCo2 O4 nanowires with NaH2 PO2 •H2 O at
300 °C for 2 h under Ar atmosphere, while NiCo2 O4 nanowires
were obtained by hydrothermal treatment at 120 °C for 6 h fol-
lowed by calcination at 250 °C for 2 h in air. They observed that
NiCo2 Px NW exhibits higher HER activity than NiPx and CoPx . The
122 J. Mohammed-Ibrahim, X. Sun / Journal of Energy Chemistry 34 (2019) 111–160
Fig. 9. Co based electrocatalyst for HER (reproduced with permission): (a) SEM im-
age, and (b) TEM image of Co(OH)2 @NCNTs [53] (Copyright 2018, Elsevier).
Fig. 10. NiCo based electrocatalyst for HER (reproduced with permission): (a) XRD pattern of NiCo2 Px NW in comparison with NiPx , and CoPx , (b) SEM image (Inset: corre-
sponding higher magnification image), (c) elemental mapping (P, Co, and Ni), (d) EDX spectrum, (e) HRTEM image, and (f) the corresponding SAED pattern of the NiCo2 Px
NW [35] (Copyright 2017, Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim).
NiCo2 Px NW possesses nanowire morphology (Fig. 10b); it con-
tains hexagonal NiCoP and CoP phases; it contains Ni, Co, and P,
which are uniformly distributed (Fig. 10); it contains Ni2+ , Ni3+ ,
Co2+ , Co3+ , PO4 3− , and P3− , where the nanostructure can afford
abundant active sites, while the Ni and Co can provide syner-
gistic effect, and that possibly enhances its significantly much
high durability and activity for HER. For HER in 1.0 M KOH, the
NiCo2 Px NW exhibits negligible decay at − 250 mA cm−2 after 50 0 0
cycles of CV, which indicates its substantially much high dura-
bility, while it exhibits considerably much high HER activity (η
of − 58 mV at − 10 mA cm−2 ), and it exhibits negligible decay at η
of − 100 mV for 30 h, while it almost retains its morphology and
crystallographic structure, which indicates its much high stability.
Besides, Li et al. [46] have observed that urchin-like Ni0.5 Co0.5 P
exhibits much high activity and durability for HER. The urchin-
like Ni0.5 Co0.5 P was prepared by the following steps: At first,
NiCo(CO3 )(OH)2 was obtained by hydrothermal treatment at 120 °C
for 6 h; Then, Ni-Co oxide was obtained by calcination of
NiCo(CO3 )(OH)2 at 250 °C for 2 h in air; Finally, Ni0.5 Co0.5 P was
obtained by phosphorization of Ni-Co oxide with NaH2 PO2 •H2 O at
300 °C for 2 h under Ar atmosphere. The Ni0.5 Co0.5 P is crystalline;
it possesses porous urchin like morphology; it contains Ni, Co and
P, which are uniformly distributed, and that possibly enhance its
much high activity and durability for HER. For HER in 1.0 M KOH,
the Ni0.5 Co0.5 P exhibits negligible decay after 10 0 0 cycles of CV,
which indicates its high durability, while it exhibits much high HER
activity (η of − 87 mV at − 10 mA cm−2 ).
The durability and activity for HER can be enhanced by prepar-
ing nanostructured transition-bimetallic phosphides derived from
metal organic frameworks (MOFs). Yan et al. [89] have observed
that Co4 Ni1 P NTs (NTs: nano-tubes) exhibits considerably much
high durability and activity for HER. The Co4 Ni1 P NTs was pre-
pared by the following steps: At first, MOF-74-Cox Niy was obtained
by hydrothermal treatment at 110 °C for 24 h; Then, Cox Niy O/C
was obtained by calcination of MOF-74-Cox Niy at 350 °C for 2 h
in air; Finally, Co4 Ni1 P NTs was obtained by phosphorization of
Cox Niy O/C with NaH2 PO2 •H2 O at 300 °C for 2 h under N2 atmo-
 J. Mohammed-Ibrahim, X. Sun / Journal of Energy Chemistry 34 (2019) 111–160 123

Fig. 11. NiCo based electrocatalyst for HER (reproduced with permission): (a) TEM image, (b) powder XRD pattern, (c) N2 adsorption–desorption isotherm (Inset: correspond-
ing NLDFT pore diameter distribution), (d) HRTEM image, (e) EDS multilayered image, and (f) elemental mappings of Co4 Ni1 P NTs [89] (Copyright 2017, Wiley-VCH Verlag
GmbH & Co. KGaA, Weinheim).

sphere. They observed that Co4 Ni1 P NTs exhibits higher HER ac-
tivity than Ni − P and Co − P. The Co4 Ni1 P NTs contains hexago-
nal NiCoP and Co2 P phases; it possesses nanotube-like morphol-
ogy (Fig. 11a); it possesses high surface area (55.6 m2 g−1 ) with
porous structure; it contains Co, Ni, P, and C, which are homoge-
neously distributed (Fig. 11); it contains Niδ + , Ni2+ , Co2+ , phos-
phides, P3− , PO4 3− , C − C, C − O, and O = C − O, and that possibly
enhances its significantly much high durability and activity for
HER. For HER in 1.0 M KOH, the Co4 Ni1 P NTs exhibits negligible
decay at − 100 mA cm−2 after 3000 cycles of CV, which indicates
its substantially much high durability, while it exhibits high HER
activity (η of − 129 mV at − 10 mA cm−2 ), and it exhibits negligible
decay at η of − 129/ − 188 mV for 20 h, which indicates its much
high stability.
Preparing nanostructured Ni–Co mixed phosphides integrated
with N-doped carbon can enhance the durability and activity for
124 J. Mohammed-Ibrahim, X. Sun / Journal of Energy Chemistry 34 (2019) 111–160
HER. Han et al. [90] have observed that Ni2 P-NiCoP@NC exhibits
high durability and activity for HER. The Ni2 P-NiCoP@NC was pre-
pared by the following steps: At first, Ni-Co Prussian blue analogue
nanocubes was obtained by simple aging process at room temper-
ature for 24 h; Then, Ni-Co Prussian blue analogue nanocones was
prepared by facile ammonia-etching of nickel-cobalt Prussian blue
analogs nanocubes at room temperature; Finally, Ni2 P-NiCoP@NC
was obtained by phosphidation treatment of the above nanocones
at 350 °C for 2 h. The Ni2 P-NiCoP@NC possesses nanocone like
morphology; it is composed of Ni2 P-NiCoP nanoparticles, which
are enwrapped by N-doped carbon matrix; it contains C, Ni, Co,
and P, which are uniformly distributed, and that possibly enhances
its high durability and activity for HER. For HER in 1.0 M NaOH,
the Ni2 P-NiCoP@NC exhibits negligible decay at − 40 mA cm−2 af-
ter 10 0 0 cycles of CV, which indicates its high durability, while it
exhibits high HER activity (η of − 116 mV at − 10 mA cm−2 ).
The stability and activity for HER can be enhanced by prepar-
ing nanostructured nickel−cobalt nitride integrated with N-doped
carbon. Ray et al. [85] have observed that CoN/Ni3 N@NC exhibits
much high stability and activity for HER. The CoN/Ni3 N@NC was
prepared by the following steps: At first, polyaniline was deposited
on carbon cloth via polymerization of aniline; Then, mixed metal
hydroxides were coated via hydrothermal treatment at 120 °C for
12 h; Finally, CoN/Ni3 N@NC was obtained by heat treatment of the
above precursor at 700 °C for 2 h under Ar atmosphere. They ob-
served that CoN/Ni3 N@NC exhibits higher HER activity than CoN,
Ni3 N, and NC. The CoN/Ni3 N@NC possesses nanograss architecture,
where the nanograss is composed of stacked nanoparticles; it con-
tains cubic CoN, hexagonal Ni3 N, and N-doped carbon; it contains
Co0 , Co2+ , Co3+ , Ni0 , Ni+ , Ni2+ , C = C, C − N, C = N, metal − N, pyri-
dinic N, pyrrolic N, and quaternary N, and that possibly enhance
its much high stability and activity for HER. For HER in 1.0 M KOH,
the CoN/Ni3 N@NC exhibits negligible decay at − 10 mA cm−2 after
10 0 0 cycles of CV, which indicates its high durability, while it ex-
hibits much high HER activity (η of − 68 mV at − 10 mA cm−2 ), and
it exhibits 94 % retention at − 10 mA cm−2 for 24 h, which indicates
its much high stability.
Preparing mesoporous NiCo alloy can enhance the stability and
activity for HER. Sun et al. [36] have observed that Ni58 Co42 ex-
hibits high stability and activity for HER. The Ni58 Co42 was pre-
pared by reduction of metal ions in the presence of lyotropic liq-
uid crystals of non-ionic surfactants. They observed that Ni58 Co42
exhibits higher HER activity than Ni, Co, Ni72 Co28 , Ni51 Co49 , and
Ni18 Co82 . The Ni58 Co42 alloy possesses spherical particles mor-
phology with diameter ∼200 nm; it possesses highly ordered
mesostructures with mesopores (3–5 nm); it exhibits high surface
area (106 m2 g−1 ); it contains Ni0 , Ni2+ , Co0 , and Co2+ , and that
possibly enhance its high stability and activity for HER. For HER
in 1.0 M NaOH, the Ni58 Co42 exhibits very slight decay after 20 0 0
cycles of CV, while it exhibits high HER activity (η of − 162 mV
at − 10 mA cm−2 ), and it exhibits reasonable stability at − 10 mA
cm−2 for 25 h, which indicates its high stability.
The activity and stability for HER can be enhanced by prepar-
ing nanostructured Ni3 Co alloy integrated with carbon. Saha et al.
[91] have observed that Ni3 Co-G (G: Graphene) exhibits much high
activity and stability for HER. The Ni3 Co-G was prepared by the
following steps: At first, layered double hydroxide precursor was
obtained by co-precipitation method; Then, green precipitate was
obtained by refluxing for 5 h; Finally, Ni3 Co-G was obtained by cal-
cination at 500 °C for 5 h under H2 atmosphere. They observed
that Ni3 Co-G exhibits higher HER activity than Ni/Ni3 S2 , Co/Co9 S8
and Ni3 Co. The Ni3 Co-G is composed of Ni3 Co nanoparticles, which
are uniformly distributed on graphene sheet; it is crystalline, and
that possibly enhances it high activity and stability for HER. For
HER in 0.5 M KOH, the Ni3 Co-G exhibits much high HER activity
(η of − 95 mV at − 10 mA cm−2 ), and it exhibits reasonable stability
at − 10 mA cm−2 for 16 h, which indicates its high stability.
Preparing nanostructured NiCo2 O4 integrated with carbon can
enhance the stability and activity for HER. Deng et al. [92] have
observed that NiCo2 O4 @C exhibits much high stability and activity
for HER. The NiCo2 O4 @C was prepared by the following steps: At
first, NiCo precursor was obtained by hydrothermal treatment at
90 °C for 10 h; Finally, NiCo2 O4 @C was obtained by hydrothermal
treatment (at 180 °C for 8 h) followed by calcination (at 700 °C
under N2 atmosphere for 200 min) and then annealing (at 250
°C for 2 h in air). They observed that NiCo2 O4 @C exhibits higher
HER activity than NiCo2 O4 , Co3 O4 and NiO. The NiCo2 O4 @C pos-
sesses urchin-like peapoded morphology; it is composed of cubic
NiCo2 O4 nanoparticles, which are uniformly embedded in carbon
fiber; it contains Co2+ , Co3+ , Ni2+ and Ni3+ , where the porous
structure can afford abundant active sites and facilitate gas release,
and that possibly enhances its much high stability and activity for
HER. For HER in 1.0 M NaOH, the NiCo2 O4 @C exhibits high HER ac-
tivity (η of ∼− 109 mV at − 10 mA cm−2 ), and it exhibits ∼22 mV
decay at − 10 mA cm−2 for 30 h, which indicates its much high
stability.
Creating oxygen vacancies in the nanostructured cobalt–nickel
sulfide can enhance the stability and activity for HER. Yin et al.
[93] have observed that NiS2 /CoS2 –O NW (NW: nanowire) exhibits
much high stability and activity for HER. The NiS2 /CoS2 –O NW
was prepared by the following steps: At first, NiS2 /CoS2 NW was
prepared by calcination of NiCo2 O4 NW with sulfur at 300 °C for
2 h under nitrogen atmosphere; Finally, NiS2 /CoS2 –O NW was ob-
tained by leaching the sulfide from the surface of NiS2 /CoS2 NW
at 1.6 V in 1.0 M KOH for > 6 h. They observed that NiS2 /CoS2 –O
NW exhibits higher HER activity than NiS2 /CoS2 NW and NiCo2 O4
NW. The NiS2 /CoS2 –O NW possesses porous nanowire morphol-
ogy (Fig. 12) with pore volume of 0.064 cm3 g−1 and mesopores
with diameter of ∼4 nm; it contains cubic NiS2 (space group: Pa–
3), cubic CoS2 (space group: Pa–3), CoOx and NiO; it exhibits high
oxygen vacancies (Fig. 12c and d), and that possibly enhances its
much high stability and activity for HER. For HER in 1.0 M KOH,
the NiS2 /CoS2 –O NW exhibits high HER activity (η of − 174 mV
at − 10 mA cm−2 ), and it exhibits reasonable stability at − 10 mA
cm−2 for 70 h, which indicates its much high stability.
Preparing nanostructured nickel hydroxide − cobalt disulfide
can facilitate the adsorption of hydrogen intermediates, H2 gen-
eration, and water dissociation, and that can enhance the dura-
bility and activity for HER. Chen et al. [94] have observed that
Ni(OH)2 –CoS2 NW (NW: nanowire) exhibits much high durability
and activity for HER. The Ni(OH)2 –CoS2 NW was prepared by the
following steps: At first, Co(OH)F NW was obtained on carbon cloth
by hydrothermal treatment at 120 °C for 6 h; Then, CoS2 was pre-
pared by sulfidization of Co(OH)F at 400 °C for 1 h under Ar at-
mosphere; Finally, Ni(OH)2 –CoS2 NW was obtained by electrode-
position of Ni(OH)2 on CoS2 . They observed that Ni(OH)2 –CoS2
NW exhibits higher HER activity than Ni(OH)2 and CoS2 . The
Ni(OH)2 –CoS2 NW possesses nanowire morphology; it is composed
of crystalline CoS2 nanowire, which are covered by thin layer of
amorphous Ni(OH)2 ; it contains Co, S, Ni and O, which are uni-
formly distributed, and that possibly enhance its much high dura-
bility and activity for HER. They observed through density func-
tional theory that CoS2 enhances the adsorption of hydrogen inter-
mediates and H2 formation, while Ni(OH)2 functions as an impor-
tant role in dissociation of water to hydrogen intermediates. For
HER in 1.0 M KOH, the Ni(OH)2 –CoS2 NW exhibits negligible de-
cay at − 200 mA cm−2 after 1000 cycles of CV, which indicates its
much high durability, while it exhibits much high HER activity (η
of − 99 mV at − 20 mA cm−2 ), and it exhibits negligible decay at η
of − 98 mV for 30 h, which indicates its much high stability.
 J. Mohammed-Ibrahim, X. Sun / Journal of Energy Chemistry 34 (2019) 111–160
Fig. 12. NiCo based electrocatalyst for HER (reproduced with permission): (a, b) SEM images of (b) NiS2 /CoS2 –O NW in comparison with (a) NiS2 /CoS2 NW, (c) high-resolution
XPS spectra of the O 1s obtained from NiS2 /CoS2 –O NW and NiS2 /CoS2 NW, and (d) ESR spectra of NiS2 /CoS2 –O NW in comparison with NiS2 /CoS2 NW, and NiCo2 O4 NW
[93] (Copyright 2017, Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim).
2.4. Fe based earth abundant electrocatalysts for HER
Iron (Fe) is an earth-abundant first row transitional metal with
atomic number 26, while it is the 4th most common element in
the Earth’s crust (abundance: >3%) [58]. Considering Fe based elec-
trocatalyst is a promising choice for the development of cheap-
earth-abundant electrocatalyst because the price of Fe based ma-
terials such as stainless steel is 40 USD per square meter, which
is quite cheaper than the price of the commonly used materials
such as carbon cloth (≈875 USD for 1 m2 ) and nickel foam (≈ 100
USD for 1 m2 ) [54]. Hence, significant efforts have been made to
develop Fe based earth-abundant electrocatalysts for HER.
N, P dual doping on etched stainless steel can enhance the sta-
bility and activity for HER. Balogun et al. [54] have observed that
NP-SS (SS: Stainless steel) exhibits remarkably much high stabil-
ity and activity for HER. The NP-SS was prepared by annealing the
etched SS with NaH2 PO2 •H2 O at 400 °C for 2 h under NH3 atmo-
sphere (Fig. 13), while the etched SS was obtained by etching the
SS at 120 °C for 2 h in a solution, which contains 1 M of H3 PO4
and 1 M of LiCl•H2 O. The NP-SS possesses nanosheet like structure;
it is composed of N, P dual doped SS, while it contains austenite,
γ N , and FeP phases (Fig. 13b); it contains pyridinic-N, where the
nanosheet like morphology with newly formed FeP phase along
with N and P dual doping can afford abundant active sites for
HER, and that possibly enhances its considerably much high stabil-
ity and activity for HER. For HER in 1.0 M KOH, the NP-SS exhibits
significantly much high stability (negligible decay at η of − 230 mV
for 134.4 h), which is much higher stability than the stability of
Pt/C [85] (79% retention at − 10 mA cm−2 after 24 h), while it ex-
hibits high HER activity (η of − 230 mV at − 10 mA cm−2 ).
Incorporating Fe in nickel nitride can enhance the stability and
activity for HER. Liu et al. [95] have observed that Ni3 FeN ex-
hibits much high stability and activity for HER. The Ni3 FeN was
prepared on carbon cloth by thermal nitridation of NiFe-precursor
at 400 °C under NH3 atmosphere, while the NiFe-precursor was
obtained by electrodeposition method. They observed that Ni3 FeN
125
exhibits higher HER activity than Ni3 N and Fe2 N. The Ni3 FeN pos-
sesses 3D porous nanoframework, which contains interconnected
nanoparticles; it contains cubic Ni3 FeN phase; it contains Ni, Fe
and N, which are uniformly distributed; it contains Fe0 , Fe3+ , Ni0 ,
and Ni2+ , and that possibly enhances its much high stability and
activity for HER. For HER in 1.0 M KOH, the Ni3 FeN exhibits much
high HER activity (η of − 105 mV at − 10 mA cm−2 ), and it exhibits
negligible decay at η of − 180 mV for 20 h, which indicates its much
high stability.
Integrating Ni3 FeN with rGO can tune the electronic struc-
ture, which could diminish the Gibbs free energy for H adsorp-
tion, and that can enhance the activity and stability for HER.
Gu et al. [96] have observed that Ni3 FeN/rGO (rGO: Reduced
graphene oxide) exhibits much high stability and activity for HER.
The Ni3 FeN/rGO was prepared by nitrogenization of precursor of
(Ni,Fe)/r-GO alginate hydrogels at 700 °C under NH3 atmosphere
(Fig. 14), while the precursor was obtained by ion exchange pro-
cess. They observed that Ni3 FeN/rGO exhibits higher HER activity
than Ni3 Fe/rGO, Ni3 N/rGO, Fe2 N/rGO, and Ni3 FeN. The Ni3 FeN/rGO
is composed of Ni3 FeN nanoparticles (Diameter: 30–40 nm), which
are uniformly distributed on the rGO layers (Fig. 14b), where the
Ni3 FeN is encapsulated by thin graphitic carbon shell, which facil-
itates conductivity; it contains Ni3 FeN phase; it exhibits ID /IG ratio
of 0.94, which suggests the formation of high graphitic carbon; it
contains Ni0 , Ni2+ , Fe0 , Fe3+ , metal−N, pyrrolic N, and graphitic N;
it exhibits less (0.17 eV) Gibbs free energy for H adsorption (GH ∗ ),
and that possibly enhances its much high activity and stability
for HER. For HER in 1.0 M KOH, the Ni3 FeN/rGO exhibits negligi-
ble decay at − 10 mA cm−2 after 20 0 0 cycles of CV, which indi-
cates its high durability, while it exhibits much high HER activity
(η of − 94 mV at − 10 mA cm−2 ), and it exhibits negligible decay at
η of − 120 mV for 10 h, which indicates its high stability.
The durability and activity for HER can be enhanced by inte-
grating NiFe LDH with defective graphene. Jia et al. [56] have ob-
served that NiFe LDH@def-Gr (def-Gr: Defective graphene) exhibits
substantially much high durability and activity for HER. The NiFe
126 J. Mohammed-Ibrahim, X. Sun / Journal of Energy Chemistry 34 (2019) 111–160
Fig. 13. Fe based electrocatalyst for HER (reproduced with permission): (a) Schematic diagram depicts the fabrication of NP-SS, (b) XRD pattern of NP-SS in comparison
with N-SS, (c and d) high-resolution XPS spectra of the (c) Fe 2p and (d) P 2p obtained from NP-SS and N-SS [54] (Copyright 2017, Wiley-VCH Verlag GmbH & Co. KGaA,
Weinheim).
LDH@def-Gr was prepared by the following steps (Fig. 15): At first,
def-Gr was obtained by annealing N-doped graphene at 1150 °C for
2 h under N2 atmosphere, while the N-doped graphene was pre-
pared by annealing the monolayer graphene along with melamine
at 700 °C for 2 h under nitrogen atmosphere; Secondly, NiFe LDH
nanosheet was obtained by stirring NiFe LDH with formamide so-
lution under nitrogen atmosphere for 48 h, while NiFe LDH was
prepared by co-precipitation method; Finally, NiFe LDH@def-Gr was
obtained by electrostatic flocculation, where exfoliated positively
charged NiFe LDH nanosheet were heteroassembled with nega-
tively charged def-Gr. They observed that NiFe LDH@def-Gr exhibits
higher HER activity than NiFe LDH@NG, NiFe LDH@G, and NiFe
LDH. The NiFe LDH@def-Gr is composed of NiFe LDH nanosheet
(Fig. 15b), which are homogeneously distributed on def-Gr, where
the NiFe LDH exhibits single crystalline (inset of Fig. 15b); it con-
tains Ni2+ , and Fe3+ ; it exhibits ID /IG ratio of 1.06, which suggests
the existence of the defects and disorders; it exhibits high defect
density (3.4 × 1012 cm−2 ), and that possibly enhance its remarkably
much high durability and activity for HER. For HER in 1.0 M KOH,
the NiFe LDH@def-Gr exhibits negligible decay at − 200 mA cm−2
after 80 0 0 cycles of CV, which indicates its significantly much high
durability, while it exhibits considerably much high HER activity (η
of − 67 mV at − 10 mA cm−2 ), and it exhibits reasonable stability at
η of − 300 mV for 5.5555 h, which indicates its high stability.
The activity and stability for HER can be enhanced by preparing
nanostructured Fe doped Ni2 P. Our group [21] has observed that
(Ni0.33 Fe0.67 )2 P NS ((NS: Nanosheet) exhibits considerably much
high activity and stability for HER. The (Ni0.33 Fe0.67 )2 P NS was
prepared by phosphorization of NiFe precursor with NaH2 PO2 at
300 °C for 2 h under Ar atmosphere, while the NiFe precursor was
obtained by hydrothermal treatment at 120 °C for 12 h. They ob-
served that (Ni0.33 Fe0.67 )2 P NS exhibits higher HER activity than
Ni2 P. The (Ni0.33 Fe0.67 )2 P NS is composed of Fe doped crystalline
Ni2 P; it contains Fe2+ /Fe3+ ; it possesses nanosheet like morphol-
ogy (Fig. 16), which can afford abundant active sites and could
facilitate the evolution of gas, and that possibly enhances its re-
markably much high activity and stability for HER. For HER in 1.0 M
KOH, the (Ni0.33 Fe0.67 )2 P NS exhibits substantially much high HER
activity (η of − 84 mV at − 10 mA cm−2 ), while it exhibits 97.4% re-
tention at η of − 285 mV for 12 h, which indicates its much high
stability.
Preparing NiFe LDH heterostructure can afford strong elec-
tronic interactions at the interface, which can enhance the stabil-
ity and activity for HER. Zhang et al. [97] have observed that NiFe
LDH@NiCoP (LDH: Layered double hydroxide) exhibits substantially
much high stability and activity for HER. The NiFe LDH@NiCoP
was prepared by the following steps: At first, NiCoP NW was ob-
tained on Ni foam by hydrothermal treatment at 120 °C for 6 h
followed by phosphorization using NaH2 PO2 •H2 O at 300 °C for 2 h
under N2 atmosphere; Finally, NiFe LDH@NiCoP was prepared by
hydrothermal treatment at 120 °C for 10 h. They observed that NiFe
LDH@NiCoP exhibits higher HER activity and electrochemically ac-
tive surface area than NiFe LDH and NiCoP. The NiFe LDH@NiCoP
is composed of ultrathin NiFe LDH nanosheets, which are grown
on the surface of the NiCoP nanowires; it contains Ni, Co, P, and
Fe, which are uniformly distributed (Fig. 17); it exhibits (111) and
(012) planes for NiCoP and NiFe LDH, respectively, at the inter-
face with the lattice spacings of 0.22 and 0.23 nm, respectively
(Fig. 17g), which indicates its sophisticated inner structure; it con-
tains Ni-P, Ni-POx , Co-P, Co-POx , P3− , PO4 3− , whereas when com-
pared to the bare NiCoP, the peaks at Ni 2p3/2 , Co 2p3/2 , and P 2p
are shifted to lower binding energies (Fig. 17i-k) for NiFe LDH cou-
pled with NiCoP, which suggests the strong electronic interactions
at the NiFe LDH and NiCoP interface, and that possibly enhance its
considerably much high stability and activity for HER. For HER in
1.0 M KOH, NiFe LDH@NiCoP exhibits significantly much high sta-
 J. Mohammed-Ibrahim, X. Sun / Journal of Energy Chemistry 34 (2019) 111–160
Fig. 14. Fe based electrocatalyst for HER (reproduced with permission): (a) Schematic diagram depicts the fabrication of Ni3 FeN/rGO, and (b and c) TEM images of Ni3 FeN/rGO
[96] (Copyright 2018, American Chemical Society).
bility (Reasonable stability at − 10 mA cm−2 for 100 h), which is
much higher stability than the stability of Pt/C [85] (79% retention
at − 10 mA cm−2 after 24 h), while it exhibits high HER activity (η
of − 120 mV at − 10 mA cm−2 ).
The activity and stability for HER can be enhanced by preparing
Ni(OH)2 on Fe2 P. Zhang et al. [98] have observed that Ni(OH)2 -Fe2 P
exhibits much high activity and stability for HER. The Ni(OH)2 -Fe2 P
was prepared from Fe2 P by electrodeposition method, while Fe2 P
was obtained by phosphorization of FeOOH at 300 °C for 2 h under
Ar atmosphere, and FeOOH was obtained on Ti mesh by hydrother-
mal treatment at 100 °C for 4 h. They observed that Ni(OH)2 -Fe2 P
exhibits higher HER activity than Fe2 P. The Ni(OH)2 -Fe2 P is com-
posed of amorphous Ni(OH)2 , which are deposited on crystalline
Fe2 P; it possesses nanoarray structure; it contains Fe, Ni, P, and
O, which are uniformly distributed, and that possibly enhance its
much high activity and stability for HER. For HER in 1.0 M KOH,
the Ni(OH)2 -Fe2 P exhibits negligible decay after 500 cycles of CV,
which indicates its high durability, while it exhibits much high HER
activity (η of − 76 mV at − 10 mA cm−2 ), and it exhibits negligible
decay at η of 76 mV for 20 h, which indicates its much high stabil-
ity.
Preparing boron-rich surface can have appropriate binding en-
ergy for desorption and chemisorption of intermediates with hy-
drogen, which can enhance the activity and stability for HER. Li
et al. [23] have observed that FeB2 exhibits considerably high ac-
127
tivity and stability for HER. The FeB2 was prepared from Fe2 B in
aqueous solution, while Fe2 B was obtained from reduction of FeCl2
with LiBH4 by refluxing in tetrahydrofuran, where FeB2 and Fe2 B
are annealed at 600 °C for 2 h under Ar atmosphere. They observed
that FeB2 exhibits higher HER activity than Fe2 B. The FeB2 is com-
posed of hexagonal FeB2 phase; it possesses nanoparticle morphol-
ogy (Fig. 18d); it exhibit high surface area (51 m2 g−1 ); it con-
tains Fe and B, which are uniformly distributed (Fig. 18), where
the boron-rich surface acquires appropriate binding energy for des-
orption and chemisorption of intermediates with hydrogen, and
that possibly enhance its substantially high activity and stability
for HER. For HER in 1.0 M KOH, the FeB2 exhibits significantly high
HER activity (η of − 61 mV at − 10 mA cm−2 ), while it exhibits 97%
retention at η of − 100 mV for 24 h, which indicates its much high
stability.
The activity and stability for HER can be enhanced by preparing
nanostructured Co doped mixed metal oxides. Wu et al. [99] have
observed that Co6.25 Fe18.75 Ni75 Ox NS (NS: nanosheet) exhibits
much high activity and stability for HER. The Co6.25 Fe18.75 Ni75 Ox
NS was prepared by hydrothermal treatment at 120 °C for 6 h fol-
lowed by annealing at 350 °C for 2 h in air. The Co6.25 Fe18.75 Ni75 Ox
NS possesses nanosheet morphology; it is composed of NiFe2 O4
and NiO phases, which are doped with Co; it has Co, Fe, Ni and
O, which are uniformly distributed; it contains mesopores (Di-
ameter: 2 nm), where the mesoporous structure affords abundant
128 J. Mohammed-Ibrahim, X. Sun / Journal of Energy Chemistry 34 (2019) 111–160

Fig. 15. Fe based electrocatalyst for HER (reproduced with permission): (a) Schematic diagram depicts the fabrication of NiFe LDH@def-Gr, and (b) TEM image of NiFe
LDH@def-Gr (inset: corresponding selected area diffraction pattern) [56] (Copyright 2017, Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim).

active sites, and that possibly enhances its much high stability and
activity for HER. For HER in 1.0 M KOH, the Co6.25 Fe18.75 Ni75 Ox NS
exhibits negligible decay at − 10 mA cm−2 after 10 0 0 cycles of CV,
which indicates its high durability, while it exhibits much high HER
activity (η of − 84 mV at − 10 mA cm−2 ), and it exhibits 9.7 mV de-
cay at − 20 mA cm−2 for 12 h, which indicates its high stability.
Preparing nanostructured Fe3 O4 and Co3 O4 with core-shell
structure can enhance the activity and stability for HER. Begum
et al. [100] observed that Fe-Co3 O4 /CNTs exhibits high activity
and stability for HER, while it was prepared by simple chem-
ical method. They observed that Fe-Co3 O4 /CNTs exhibits higher
HER activity than Co3 O4 and Co3 O4 /CNTs. The Fe-Co3 O4 /CNTs is
composed of Fe3 O4 nanoparticle surrounded by spinel structured
Co3 O4 with core-shell structure, which are grown on carbon nano-
tube; it possesses mesopores; it exhibits high surface area (373 m2
g−1 ), and that possibly enhance its much high activity and sta-
bility for HER. For HER in 1.0 M KOH, the Fe-Co3 O4 /CNTs exhibits
negligible decay at − 10 mA cm−2 after 10 0 0 cycles of CV, which
indicates its high durability, while it exhibits high HER activity
(η of − 120 mV at − 10 mA cm−2 ), and it exhibits reasonable stabil-
ity at η of − 140 mV for 20 h, which indicates its high stability.
The durability and activity for HER can be enhanced by prepar-
ing nanostructured NiFeOOH with Ni inner layer. Wu et al.
[101] have observed that Ni/NiFeOOH exhibits much high durabil-
ity and activity for HER. The Ni/NiFeOOH was prepared on Ni foam
by sequentially electrodepositing ZnO, Ni, and NiFeOOH followed
by ZnO template removal in NaOH. They observed that NiFeOOH
with Ni-rich inner layer exhibits higher HER activity than NiFeOOH
without Ni inner layer. The Ni/NiFeOOH is composed of NiFeOOH
nano-tubes with Ni-rich inner layer (Fig. 19), which are aligned
radially on Ni foam; it contains Ni, Fe, and O, which are uni-
formly distributed, while when compared to the NiFeOOH with-
out Ni inner layer, the peaks at Ni 2p and Fe 2p are shifted to
higher binding energies for NiFeOOH with Ni inner layer, which
suggests the strong electronic interactions at the NiFeOOH and Ni
inner layer interface, where the hierarchical structure can provide
abundant active sites and efficient electronic/ionic transport, and
that possibly enhances its much high durability and activity for
 J. Mohammed-Ibrahim, X. Sun / Journal of Energy Chemistry 34 (2019) 111–160
Fig. 16. Fe based electrocatalyst for HER (reproduced with permission): (a) SEM image, (b) TEM image, and (c) HRTEM image of (Ni0.33 Fe0.67 )2 P NS, and (d) high-resolution
XPS spectrum of the P 2p obtained from (Ni0.33 Fe0.67 )2 P NS [21] (Copyright 2017, Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim).
HER. For HER in 1.0 M KOH, the Ni/NiFeOOH exhibits negligible
decay at − 100 mA cm−2 after 10 0 0 cycles of CV, which indicates
its much high durability, while it exhibits high HER activity (η
of − 154 mV at − 10 mA cm−2 ), and it exhibits reasonable stability
at − 10 mA cm−2 for 12 h, which indicates its high stability.
2.5. Cu based earth abundant electrocatalysts for HER
Preparing nanostructured copper as core in the core-shell struc-
ture can enhance the stability and activity for HER. Yu et al.
[37] have observed that Cu@NiFe LDH (LDH: Layered double hy-
droxide) exhibits much high stability and activity for HER. The
Cu@NiFe LDH was prepared by the following steps: At first,
Cu(OH)2 NWs was obtained by chemical oxidation method; Then,
CuO NWs was prepared by calcination of Cu(OH)2 NWs at 180 °C
for 1 h, while Cu NWs was obtained by electro-reduction of CuO
NWs; Finally, Cu NWs@NiFe LDH was prepared by electrodeposit-
ing NiFe LDH on Cu NWs. They observed that Cu@NiFe LDH ex-
hibits higher HER activity than NiFe LDH. The Cu@NiFe LDH is
crystalline; it contains Ni2+ and Fe3+ ; it is composed of core-shell
structure (Fig. 20), where NiFe LDH NS are grown on Cu NWs (Fig.
20e and f), where the 3D core-shell nanostructures can afford large
surface area with abundant active sites, while the inner Cu NWs
can provide efficient electron transport to the outer NiFe LDH, and
the 3D structure could facilitate the release of gas, and that pos-
sibly enhance its much high stability and activity for HER. For
HER in 1.0 M KOH, the Cu@NiFe LDH exhibits high HER activity (η
of − 116 mV at − 10 mA cm−2 ), and it exhibits reasonable stability
at η of − 162 mV for 48 h, which indicates its much high stabil-
ity.
Tuning the thickness of the shell in the core–shell nanostruc-
ture can enhance the stability and activity for HER. Shen et al.
[102] have observed that NiCu@C exhibits much high stability and
activity for HER. The NiCu@C was prepared by the following steps:
At first, nickel–copper oxide was obtained by sol − gel process fol-
lowed by calcination for 5 h at 500 °C in air; Finally, NiCu@C was
129
prepared by a chemical vapor deposition, where methane was used
as a carbon source. They observed that NiCu@C exhibits higher
HER activity than NiCu, while NiCu@C (with single layered carbon
shell) exhibits higher HER activity than NiCu@2C (with two-layered
carbon shell), and the Ni43 Cu12 @C240 exhibits − 0.03 eV of Gibbs
free energy for H adsorption (GH ∗ ), which is close to 0 eV of ideal
GH ∗ , whereas Ni43 Cu12 @2C240 exhibits GH ∗ of 1.68 eV, which is
close to the GH ∗ value of 1.69 eV of bilayered graphene, which
suggests that the interaction of hydrogen with NiCu nanoparti-
cles is much higher when NiCu nanoparticles are enwrapped by a
single-layered graphene, which provides high HER activity whereas
the interaction of hydrogen with NiCu nanoparticles is much lower
when NiCu nanoparticles are enwrapped by two-layered carbon
shell, which shields the NiCu, and that affords less HER activ-
ity. The NiCu@C is composed of metallic NiCu alloy nanoparti-
cles, which are enwrapped by hexagonal carbon shells (Fig. 21a);
it exhibits nearly ideal GH ∗ (−0.03 eV) as shown in Fig. 21(b),
and that possibly enhances its much high stability and activity for
HER. For HER in 1.0 M KOH, the NiCu@C exhibits negligible de-
cay at − 100 mA cm−2 after 2000 cycles of CV, which indicates its
much high durability, while it exhibits much high HER activity (η
of − 74 mV at − 10 mA cm−2 ), and it exhibits reasonable stability at
η of − 150 mV for 10 h, which indicates its high stability.
The activity and stability for HER can be enhanced by prepar-
ing copper−nickel bimetallic nitrides. Ma et al. [27] have ob-
served that Cux Ni4- x N exhibits much high stability and activity for
HER. The Cux Ni4- x N was prepared by the following steps: At first,
Cu2 O@Ni(OH)2 was prepared on Ni foam by galvanic replacement-
mediated chemical precipitation method at 90 °C for 8 h; Fi-
nally, Cux Ni4- x N was obtained by calcination for 2 h at 380 °C
under NH3 atmosphere. The Cux Ni4- x N is composed of nanoparti-
cles morphology, where Cu, Ni and N are uniformly distributed;
it contains Cu4 N and Ni4 N phases; it contains Ni2+ , Ni0 , Cu2+ ,
and Cu0 (Fig. 22), and that possibly enhances its significantly
much high activity and stability for HER. For HER in 1.0 M KOH,
the Cux Ni4- x N exhibits substantially much high HER activity (η
130 J. Mohammed-Ibrahim, X. Sun / Journal of Energy Chemistry 34 (2019) 111–160

Fig. 17. Fe based electrocatalyst for HER (reproduced with permission): (a) XRD pattern of NiFe LDH@NiCoP in comparison with the bare Ni foam, NiCoP, and NiFe LDH,
(b) SEM image of the NiCoP nanowires (Inset: corresponding higher magnification image), (c) SEM image of the NiFe LDH@NiCoP nanowires (Inset: corresponding higher
magnification image), (d and e) TEM images of an NiCoP and NiFe LDH@NiCoP nanowire, respectively, (f) EDX mapping images of the NiFe LDH@NiCoP, (g) HRTEM image of
the NiFe LDH@NiCoP depicts the interface between nanowire and nanosheets, (h) SAED pattern of the interface of the NiFe LDH@NiCoP, (i–k) XPS spectra of the (i) Ni 2p3/2 ,
(j) Co 2p3/2 , and (k) P 2p obtained from NiFe LDH@NiCoP and NiCoP [97] (Copyright 2018, Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim).
 J. Mohammed-Ibrahim, X. Sun / Journal of Energy Chemistry 34 (2019) 111–160 131

Fig. 18. Fe based electrocatalyst for HER (reproduced with permission): (a) SEM, (b, c) EDX elemental mapping, (d) TEM image, (e) HRTEM image (Inset: corresponding SAED
pattern), (f) XRD pattern, and (g) N2 -sorption isotherm of FeB2 [23] (Copyright 2017, Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim).

of − 12 mV at − 10 mA cm−2 ), which is even higher HER activity
than Pt/C [34] (η10 : − 33 mV), and it exhibits reasonable stability
at − 20 mA cm−2 for 65 h, which indicates its much high stabil-
ity.
Preparing porous Cu − Co bimetallic nitride enwrapped with
carbon shell can enhance the durability and activity for HER. Zheng
et al. [103] have observed that NC@CuCo2 Nx exhibits much high
durability and activity for HER. The NC@CuCo2 Nx was prepared by
the following steps: At first, CuCo precursor nanosheet was ob-
tained on carbon fiber by hydrothermal treatment at 120 °C for
5 h; Finally, NC@CuCo2 Nx was prepared by immersing the above
precursor in 0.1 M of glucose for 24 h followed by calcination at
400 °C for 2 h under NH3 atmosphere. The NC@CuCo2 Nx possesses
porous nanosheet like morphology, where CuCo2 Nx (Co5.47 N and
Cu3 N phases) is enwrapped by N-doped carbon shell (Fig. 23),
where the porous structure can provide abundant active sites,
while the carbon shell can enhance its conductivity; it contains
C, N, O, Cu, and Co, which are uniformly distributed; it contains
disordered non-graphitic carbon, it possesses high surface area
(54.22 m2 g−1 ); it contains micro and mesopores; it contains Cu+ ,
Cu2+ , Co2+ , Co3+ , N − M, pyridinic N, pyrrolic N, and quaternary N
(Fig. 23c), and that possibly enhances its much high durability and
activity for HER. For HER in 1.0 M KOH, the NC@CuCo2 Nx exhibits
negligible decay at − 100 mA cm−2 after 2000 cycles of CV, which
indicates its much high durability, and it exhibits high HER activity
(η of − 105 mV at − 10 mA cm−2 ).
The stability and activity for HER can be enhanced by prepar-
ing Mott–Schottky electrocatalyst (metal−semiconductor hybrid)
132 J. Mohammed-Ibrahim, X. Sun / Journal of Energy Chemistry 34 (2019) 111–160

Fig. 19. Fe based electrocatalyst for HER (reproduced with permission): (a) Schematic diagram of Ni/NiFeOOH depicts the heterostructured nanotubes, which have been
radially aligned on the Ni foam, (b, c) SEM images and (d, e) TEM images of the nanotubes, inset of (d) depicts the corresponding SAED pattern, where the rings marked
with 1, 3, and 4 were from (10), (11), and (20) of LDH in-plane structure, while the one indicated with 2 could be attributed to (111) of Ni particles, (f) high-angle annular
dark field scanning TEM image with elemental line scanning at the wall edge portion, and (g-i) zoom-in TEM images for NiFeOOH, crystalline Ni, and the interface region
[101] (Copyright 2018, American Chemical Society).

encapsulated with carbon shell. Hou et al. [57] have observed
that NC/CuCo/CuCoOx exhibits substantially much high stability
and activity for HER. The NC/CuCo/CuCoOx was prepared by the
following steps: At first, CuCoO nanowire (semi conductor) was
obtained on Ni foam by hydrothermal treatment at 120 °C for
12 h followed by annealing at 400 °C for 1 h; Then, CuCo/CuCoOx
(metal–semiconductor heterojunction as Mott–Schottky electrocat-
alyst) was prepared by hydrogen-reduction treatment at 400 °C
under H2 /Ar atmosphere; Finally, NC/CuCo/CuCoOx was obtained
by immersing the above precursor in 0.15 M glucose/urea solution
followed by carbonization process at 400 °C. The NC/CuCo/CuCoOx
possesses porous nanowire like morphology (Diameter: 20–50 nm);
it is composed of CuCo/CuCoOx (metal–semiconductor), which are
enwrapped by the ∼5 nm thick N-doped carbon shell; it contains
Cu0 , Cu+ , Co0 , Co2+ , Co3+ , C − C, C = O, C − N, pyridinic N, pyrrolic
N, and metal − oxygen bond with oxygen vacancies (Fig. 24); it
possesses high surface area (83.7 m2 g−1 ), where the porous struc-
ture can afford large active surface area with abundant active
sites, while N-doped carbon can enhance conductivity and af-
ford continuous electron transport for metal and semiconductor,
and that possibly enhances its considerably much high stability
and activity for HER. For HER in 1.0 M KOH, the NC/CuCo/CuCoOx
exhibits negligible decay at − 500 mA cm−2 after 5000 cycles of
CV, which indicates its remarkably much high durability, while it
exhibits high HER activity (η of − 112 mV at − 10 mA cm−2 ), and
it exhibits substantially much high stability (negligible decay at
η of − 150 mV for 100 h), which is much higher stability than
the stability of Pt/C [85] (79% retention at − 10 mA cm−2 after
24 h).
2.6. W based earth abundant electrocatalysts for HER
Creating oxygen vacancies on the nanostructured electrocat-
alyst can improve the stability and activity for HER. Lv et al.
[104] have observed that WO3- x NS (NS: Nano sheet) exhibits sub-
stantially much high stability and activity for HER. The WO3- x
NS was synthesized by the following steps: At first, WO3 precur-
sor NS was prepared by hydrothermal treatment of Ni foam with
(NH4 )6 H2 W12 O40 •XH2 O solution at 105 °C for 3 h; Then, WO3 NS
was obtained by annealing the precursor in Ar for 2 h at 350 °C;
Finally, WO3- x NS was obtained by annealing the WO3 NS for 2 h
in Ar/H2 at 400 °C. They observed that WO3- x NS exhibits higher
HER activity than WO3 NS (Fig. 25b). The WO3- x NS exhibits W6+
state in oxides, while in addition, it also exhibits W5+ and W4+
state in oxides (Fig. 25a), which could be due to existence of oxy-
gen vacancies, and the oxygen vacancies can enhance the adsorp-
tion of surface species, and that enhances charge separation and
charge transfer, and the polycrystalline WO3- x NS is porous; it pos-
sesses nanosheet like morphology, which can facilitate active sites
interaction, and that possibly enhance its remarkably much high
stability and activity for HER. For HER in 1.0 M KOH, the WO3-x
NS exhibits negligible decay after 20 0 0 cycles of CV, which in-
dicates its much high durability, while it exhibits high HER ac-
tivity (η of − 175 mV at − 10 mA cm−2 ), and it exhibits negligible
potential decay at − 10 mA cm−2 for 105 h, which is significantly
much higher stability than the stability of Pt/C [85] (79% retention
at − 10 mA cm−2 after 24 h).
Preparing nanostructured tungsten nitride can enhance the
stability and activity for HER. Ren et al. [105] have observed
 J. Mohammed-Ibrahim, X. Sun / Journal of Energy Chemistry 34 (2019) 111–160 133

Fig. 20. Cu based electrocatalyst for HER (reproduced with permission): (a) lower and (c) higher magnification SEM images of Cu@NiFe LDH, (b) SEM image of Cu NWs, (d
and e) TEM images of Cu@NiFe LDH, (f) detailed TEM image of squared portion in (e), inset of (f) HRTEM image of Cu@NiFe LDH, (g) EDS line scan image and (h) DF-STEM
image of Cu@NiFe LDH with the corresponding elemental mapping [37] (Copyright 2017, The Royal Society of Chemistry).

that WN NW (NW: nanowire) exhibits much high stability and
activity for HER. The WN NW was prepared by the following steps:
At first, WOx NW was obtained by heating the WO3 powder with
carbon cloth for 5 min at 1050 °C; Finally, WN NW was obtained
by N2 plasma treatment of WOx NW. The WN NW contains hexag-
onal WN; it possesses nanowire like morphology (Fig. 26), where
W and N are uniformly distributed; it exhibits porous structure
(3.9877 m2 g−1 ), which could afford abundant active sites and fa-
cilitate electrolyte interaction, and that possibly enhance its much
high stability and activity for HER. For HER in 1.0 M KOH, the WN
NW exhibits negligible decay at − 10 mA cm−2 after 30 0 0 cycles
of CV, which indicates its much high durability, while it exhibits
high HER activity (η of − 130 mV at − 10 mA cm−2 ), and it exhibits
reasonable stability at − 20 mA cm−2 for > 40 h, which indicates its
much high stability.
The durability and activity for HER can be enhanced by prepar-
ing nanostructured tungsten phosphide. Wu et al. [106] have ob-
served that WP/W exhibits much high durability and activity for
HER. The WP/W was prepared by the following steps: At first WO3
nanorods were grown on W foil by spin-coating followed by direct
oxidation at 650 °C for 2 h.; Then, WP nanorods/W was obtained
by phosphorization of WO3 with NaH2 PO2 •H2 O at 800 °C for 1 h.
The WP/W contains orthorhombic WP; it possesses nanorods like
morphology, where W and P are homogenously distributed, and
that possibly enhance its much high durability and activity for
HER. For HER in 1.0 M KOH, the WP/W exhibits negligible de-
cay at − 100 mA cm−2 after 5000 cycles of CV, which indicates
its remarkably high durability, while it exhibits high HER activ-
ity (η of − 133 mV at − 10 mA cm−2 ); it exhibits reasonable stability
for > 35 h, which indicates its much high stability.
Preparing nickel tungsten oxide can enhance the activity for
HER. Anis et al. [38] have observed that oxides of NiW exhibits
much high activity for HER. The oxides of NiW with fibrous struc-
ture (Fig. 27) were prepared by electrospinning method using am-
monium metatungstate and nickel acetate as precursor solutions.
They observed that oxides of NiW exhibit higher HER activity than
the NiO and WO3 . They further observed that oxides of NiW com-
posite with 1:2 ratio of Ni and W exhibits higher HER activity than
the other composites (2:1, 1:1, 3:1 and 1:3 ratio of Ni and W),
while the oxides of NiW composites prepared using higher mo-
lar ratios of W (1:2 and 1:3 ratio of Ni and W) are composed of
WO3 and NiWO4 whereas the other composites (2:1, 1:1, and 3:1
ratio of Ni and W) are composed of NiO, WO3 , NiWO4 and W3 O9
(Fig. 27d). For HER in 0.1 M KOH, the NiW exhibits much high HER
activity (η of − 60 mV at − 10 mA cm−2 ), and it exhibits reasonable
stability at η of − 150 mV for 3 h.
134 J. Mohammed-Ibrahim, X. Sun / Journal of Energy Chemistry 34 (2019) 111–160
Fig. 21. Cu based electrocatalyst for HER (reproduced with permission): (a)
TEM image of NiCu@C, and (b) Gibbs free energy profiles of HER on NiCu@C
(Ni43 Cu12 @C240 ) in comparison with C240 , Ni43 Cu12 , and Ni43 Cu12 @2C [102] (Copy-
right 2018, Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim).
Preparing molybdenum carbide-tungsten carbide/graphene
composite can cause the redistribution of the valence electrons
of Mo and W elements, and that can enhance the stability and
activity for HER. Huo et al. [107] have observed that (Mo2 C)0.34 -
(WC)0.32 -QDs/NG (QDs: Quantum dots; G: Graphene) exhibits much
high stability and activity for HER. The (Mo2 C)0.34 -(WC)0.32 -QDs/NG
was prepared by nanocasting method, where KIT-6/graphene was
used as a template. They observed that (Mo2 C)0.34 -(WC)0.32 -
QDs/NG exhibits higher HER activity than Mo2 C-QDs/NG and
WC-QDs/NG. As shown in the Fig. 28, the (Mo2 C)0.34 -(WC)0.32 -
QDs/NG and Mo2 C-QDs/NG exhibit similar characteristic peaks for
Mo2 C in the Mo 3d region, while the (Mo2 C)0.34 -(WC)0.32 -QDs/NG
and WC-QDs/NG exhibit same characteristic peaks for WC in the
W 4f region, whereas the (Mo2 C)0.34 -(WC)0.32 -QDs/NG shows slight
positive shifts in compared with Mo2 C-QDs/NG and WC-QDs/NG,
which suggests the stronger electron donation from W and Mo to
C in (Mo2 C)0.34 -(WC)0.32 -QDs/NG, which can reduce the binding
energy for hydrogen in HER, and thereby facilitate the desorption
of Hads , and that possibly leads to (Mo2 C)0.34 -(WC)0.32 -QDs/NG
exhibits higher HER activity than Mo2 C-QDs/NG and WC-QDs/NG.
For HER in 1.0 M KOH, the (Mo2 C)0.34 -(WC)0.32 -QDs/NG exhibits
Fig. 22. Cu based electrocatalyst for HER (reproduced with permission): Auger
spectra of Cu LMM obtained from Cux Ni4- x N in comparison with before thermal
nitridation [27] (Copyright 2017, The Royal Society of Chemistry).
negligible decay at − 10 mA cm−2 after 30 0 0 cycles of CV, which
indicates its high durability, while it exhibits high HER activity (η
of − 93 mV at − 10 mA cm−2 ), and it exhibits reasonable stability at
η of − 90 mV for 25 h, which indicates its much high stability.
2.7. Mo based earth abundant electrocatalysts for HER
Creating structural defects and oxygen vacancies in α -MoO3 can
enhance the stability and activity for HER. Datta et al. [108] have
observed that α -MoO3- x exhibits much high stability and activity
for HER. The α -MoO3- x was prepared by liquid exfoliation method.
They observed that α -MoO3- x exhibits higher HER activity than
α -MoO3 . The α -MoO3- x possesses layered crystal arrangement of
orthorhombic α -MoO3 ; it shows nanosheet morphology; it con-
tains Mo5+ and Mo6+ , where the existence of Mo5+ is attributed
to the presence of oxygen vacancies; it possesses narrow bandgap
energy (∼2.9 eV), which suggests the existence of structural de-
fects, and that possibly enhances its much high stability and ac-
tivity for HER. For HER in 0.1 M KOH, the α -MoO3- x exhibits neg-
ligible decay at − 10 mA cm−2 after 10 0 0 cycles of CV, which in-
dicates its high durability, while it exhibits high HER activity (η
of − 142 mV at − 10 mA cm−2 ), and it exhibits reasonable stability
at η of − 140 mV for 4 h.
The durability and activity for HER can be enhanced by prepar-
ing nanostructured amorphous CoMoO4 . Zhao et al. [109] have ob-
served that CoMoO4 NW (NW: nanowire) exhibits much high dura-
bility and activity for HER. The CoMoO4 NW was prepared by the
following steps: At first, Co(OH)F was obtained on Ti by hydrother-
mal treatment at 120 °C for 6 h; Finally, CoMoO4 NW was pre-
pared by hydrothermal treatment of Co(OH)F at 130 °C for 6 h.
They observed that CoMoO4 NW exhibits higher electrochemically
active surface area, conductivity, and HER activity than Co(OH)F.
The CoMoO4 NW possesses nanowire morphology; it is amorphous,
which contains 1:0.91:3.79 atomic ratio of Co:Mo:O; it contains
Co, Mo and O, which are uniformly distributed; it contains Co2+
and Mo4+ ; it exhibits high electrochemically active surface area
and conductivity, which can afford abundant active sites and fa-
cilitate the gas release, and that possibly enhances its much high
durability and activity for HER. For HER in 1.0 M KOH, the CoMoO4
NW exhibits negligible decay at − 300 mA cm−2 after 1000 cycles
of CV, which indicates its much high durability, while it exhibits
 J. Mohammed-Ibrahim, X. Sun / Journal of Energy Chemistry 34 (2019) 111–160
Fig. 23. Cu based electrocatalyst for HER (reproduced with permission): (a) SEM
image, and (b) HRTEM image of NC@CuCo2 Nx , and (c) high-resolution XPS spectra
of N 1 s obtained from NC@CuCo2 Nx in comparison with CuCo2 Nx [103] (Copyright
2017, Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim).
much high HER activity (η of − 81 mV at − 10 mA cm−2 ), and it ex-
hibits negligible decay at η of − 184 mV for 20 h, which indicates
its much high stability.
Preparing nanostructured molybdenum carbide can enhance the
durability and activity for HER. Xiao et al. [110] have observed that
Mo2 C/C exhibits significantly much high durability and activity for
HER. The Mo2 C/C was prepared by the following steps: At first,
135
(NH4 )6 Mo7 O24 -loaded cotton textile was obtained by immersing a
piece of cotton textile in (NH4 )6 Mo7 O24 •4H2 O for 15 min followed
by drying at 60 °C for 2 h, where the cotton textile was obtained
from commercial T-shirt; Finally, Mo2 C/C was prepared by heating
the (NH4 )6 Mo7 O24 -loaded cotton textile at 900 °C for 5 h under
Ar atmosphere. The Mo2 C/C is composed of β -Mo2 C nanoparticles,
which are embedded on fiber cloth, which can afford abundant ac-
tive sites; it contains Mo and C, which are uniformly distributed; it
contains Mo2+ , which could be attributed to the Mo2 C (Fig. 29a),
while it also contains MoO3 and MoO2 due to the exposure to air;
it possesses hydrophilic surface (Fig. 29b), which can facilitate the
release of gas, and that possibly enhances its considerably much
high durability and activity for HER. For HER in 1.0 M KOH, the
Mo2 C/C exhibits negligible decay at − 70 mA cm−2 after 50 0 0 cy-
cles of CV, which indicates its substantially much high durability,
while it exhibits much high HER activity (η of − 71 mV at − 10 mA
cm−2 ), and it exhibits reasonable stability at η of − 100 mV for 50 h,
which indicates its much high stability.
The durability and activity for HER can be enhanced by prepar-
ing nanostructured Mo2 C embedded with BCN. Anjum et al.
[111] have observed that β -Mo2 C@BCN exhibits much high dura-
bility and activity for HER. The β -Mo2 C@BCN was prepared by the
following steps: At first, an organometallic complex of Mo cations
was obtained by heating the imidazole borate monomers at 130 °C
under nitrogen atmosphere in the solution containing glycerol and
dilute aqueous acetic acid; Finally, the Mo-complex was annealed
at 900 °C for 5 h under N2 atmosphere. The β -Mo2 C@BCN is com-
posed of Mo, B, N and C, which are uniformly distributed; it con-
tains Mo4+ , Mo6+ , pyridinic N, and pyrrolic N; it contains meso-
pores; it exhibits high surface area of 87.1 m2 g−1 ; it is composed
of hexagonal molybdenum carbide nanoparticles, which are en-
capsulated by BCN layers, where the BCN layer is comprised of
boron carbide and graphitic carbon, where BCN layer can func-
tion as electrophile, where B can coordinate with the lone elec-
tron pairs of oxygen atom of water molecule, which enhance the
wetting properties by affording easy release of protons, while BCN
layer can perform as nucleophile, which can tend to adsorb pro-
tons, and as a result, the BCN layer can not only enhance the elec-
trocatalytic activity but also prevent Mo2 C nanoparticles from cor-
rosion and agglomeration, and that possibly enhance its much high
durability and activity for HER. For HER in 1.0 M NaOH, the β -
Mo2 C@BCN exhibits negligible decay at − 50 mA cm−2 after 30 0 0
cycles of CV, which indicates its much high durability, while it ex-
hibits high HER activity (η of − 98 mV at − 10 mA cm−2 ) in 1.0 M
KOH.
Preparing nanostructured metallic Ni and Mo2 C embedded
with N-doped carbon can enhance the conductivity and surface-
wettability, and that can enhance the stability and activity for HER.
Zhang et al. [112] have observed that Ni/MoC2 @NC exhibits much
high stability and activity for HER. The Ni/MoC2 @NC was pre-
pared by the following steps: At first, precursor film was coated
on carbon cloth by dip coating under ultrasonic condition for
10 min followed by drying at 120 °C; Finally, Ni/MoC2 @NC was
obtained by annealing the precursor film for 2 h under Ar atmo-
sphere at 10 0 0 °C. They observed that Ni/MoC2 @NC exhibits higher
conductivity and HER activity than Ni@NC and MoC2 @NC. The
Ni/MoC2 @NC is composed of crystalline metallic Ni and γ -MoC2
nanoparticles, which are embedded on carbon cloth; it possesses
hydrophilic surface (contact angle: 8°), which could facilitate the
release of gas; it contains pyridinic N, graphitic N, Ni0 , Ni2+ , Mo2+ ,
Mo4+ , and Mo6+ , where Ni2+ , Mo4+ , and Mo6+ could be formed
due to the surface oxidation in air; it exhibits high conductivity,
and that possibly enhance its much high stability and activity for
HER. For HER in 1.0 M KOH, the Ni/MoC2 @NC exhibits high HER ac-
tivity (η of − 130 mV at − 10 mA cm−2 ), and it exhibits reasonable
stability for 60 h (at − 10 mA cm−2 for 20 h followed by − 30 mA
136 J. Mohammed-Ibrahim, X. Sun / Journal of Energy Chemistry 34 (2019) 111–160

Fig. 24. Cu based electrocatalyst for HER (reproduced with permission): (a-e) High-resolution XPS spectra of (a) Cu 2p, (b) Co 2p, (c) O 1 s, (d) C 1 s, and (e) N 1 s, and (f)
EPR spectra obtained from (iii) NC/CuCo/CuCoOx in comparison with (ii) CuCo/CuCoOx and (i) CuCoO [57] (Copyright 2018, Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim).

cm−2 for 20 h followed by − 50 mA cm−2 for 20 h), which indicates
its much high stability.
Integrating nanostructured MoP with CNTs can enhance the
conductivity, which can afford huge density of active sites with
high intrinsic activity, and that can enhance the stability and ac-
tivity for HER. Zhang et al. [113] have observed that MoP/CNTs
exhibits much high stability and activity for HER. The MoP/CNTs
was prepared by the following steps: At first, MoOx (OH)y /CNTs
intermediate was obtained by the reaction between MoCl5 and
NH4 HCO3 at room temperature in ethanol suspension of CNTs by
stirring for 5 h followed by centrifuging and lyophilization; Finally,
MoP/CNTs was obtained by phosphorization of MoOx (OH)y /CNTs
with NaH2 PO2 •H2 O at 700 °C for 1 h under N2 atmosphere. They
observed that MoP/CNTs exhibits higher conductivity and HER ac-
tivity than MoS2 /CNTs, MoNx /CNTs and MoOx /CNTs. The MoP/CNTs
is composed of crystalline MoP nanoparticles, which are uniformly
coated on CNTs; it exhibits high conductivity, and that possibly en-
hance its much high stability and activity for HER. For HER in 1.0 M
KOH, the MoP/CNTs exhibits 11 mV decay at − 10 mA cm−2 after
50 0 0 cycles of CV, which indicates its high durability, while it ex-
hibits much high HER activity (η of − 86 mV at − 10 mA cm−2 ), and
it exhibits 27 mV decay at − 10 mA cm−2 for 40 h, which indicates
its much high stability.
The activity and durability for HER can be enhanced by prepar-
ing hetero-atoms doped nanostructured molybdenum phosphide
integrated with carbon. Anjum et al. [114] have observed that SN-
MoP/G exhibits significantly much high activity and durability for
HER. The SN-MoP/G was prepared by (thio)urea-phosphate-assisted
strategy (Fig. 30). The SN-MoP/G is composed of S, N co-doped
hexagonal MoP with rod-shaped nanocrystallites, which are em-
bedded on graphene; it contains MoP, P-S, P-C, P-O and P-N/PON
(Fig. 30b); it contains -C-S/-C-SO, -C-SO2 , Mo-N, MoS2 , pyridinic-
N, pyrrolic-N, graphitic-N and –SCN; it contains Mo4+ , and Moδ +
(0 < δ ≤ 4), which can afford abundant active sites and high con-
ductivity, and that possibly enhance its considerably much high ac-
tivity and durability for HER. For HER in 1.0 M KOH, the SN-MoP/G
exhibits negligible decay at − 150 mA cm−2 after 20 0 0 cycles of CV,
which indicates its much high durability, while it exhibits remark-
 J. Mohammed-Ibrahim, X. Sun / Journal of Energy Chemistry 34 (2019) 111–160
Fig. 25. W based electrocatalyst for HER (reproduced with permission): (a) High-
resolution XPS spectra of W 4f obtained from WO3- x NS in comparison with its
precursors, and (b) polarization curves of WO3- x NS in comparison with WO3 and
Ni foam [104] (Copyright 2018, Elsevier).
ably much high HER activity (η of − 49 mV at − 10 mA cm−2 ); it ex-
hibits reasonable stability for 20 h, which indicates its much high
stability.
The durability and activity for HER can be enhanced by inte-
grating nanostructured MoP and Mo2 C with carbon matrix. Huang
et al. [34] have observed that N@MoPCx exhibits high durabil-
ity and activity for HER. The N@MoPCx was prepared by pyroly-
sis of the polyorganoimido-derivatized heteropolyoxometalates at
800 °C for 3 h under N2 atmosphere. The N@MoPCx possesses
nanosheet morphology, which contains MoP and Mo2 C nanocrys-
tals, while it also contains amorphous MoN, which is encapsu-
lated in a porous N, P-doped carbon matrix; it contains Mo0 , Mo3+ ,
Mo4+ , Mo6+ , graphitic carbon, C-P, C–N, pyridinic-N, graphitic-N,
N − Mo, P − Mo, P − C, and P − O; it is porous, while it exhibits high
surface area (154 m2 g−1 ), and that possibly enhance its high dura-
bility and activity for HER. For HER in 1.0 M KOH, the N@MoPCx ex-
hibits negligible decay after 10 0 0 cycles of CV, which indicates its
high durability, while it exhibits high HER activity (η of − 139 mV
at − 10 mA cm−2 ), and it exhibits reasonable stability at − 20 mA
cm−2 for > 40 h, which indicates its much high stability.
Preparing nanostructured Mo doped Ni2 P can enhance the
durability and activity for HER. Sun et al. [39] have observed that
Mo-Ni2 P NW (NW: nanowire) exhibits much high durability and
activity for HER. The Mo-Ni2 P NW was prepared by the following
137
steps: At first, NiMoO4 was obtained on Ni foam by hydrothermal
treatment at 160 °C for 6 h; Finally, Mo-Ni2 P NW was prepared by
topotactic phosphidation of NiMoO4 at 500 °C for 90 min under Ar
atmosphere. They observed that Mo-Ni2 P NW exhibits higher HER
activity than Ni2 P NW and NiMoO4 . The Mo-Ni2 P NW is composed
of Mo doped crystalline Ni2 P; it possesses nanowire morphology;
it contains Mo, Ni, and P, which are uniformly distributed, and the
atomic ratio of Mo, Ni, and P in Mo-Ni2 P NW are 0.43:1.57:1; it ex-
hibits high conductivity, where the synergistic effect between Mo
and Ni can afford abundant active sites, and that possibly enhance
its much high durability and activity for HER. For HER in 1.0 M
KOH, the Mo-Ni2 P NW exhibits negligible decay at − 50 mA cm−2
after 2500 cycles of CV, which indicates its much high durability,
while it exhibits much high HER activity (η of − 78 mV at − 10 mA
cm−2 ), and it exhibits reasonable stability at − 10 mA cm−2 for 24 h,
which indicates its much high stability.
The stability and activity for HER can be considerably enhanced
by preparing porous structured NiMo alloy. Hu et al. [28] have
observed that NiMo exhibits significantly much high stability and
activity for HER. The NiMo was prepared by the following steps
(Fig. 31a): At first, NiMoO4 nanofibers were obtained by hydrother-
mal treatment at 150 °C for 12 h; Finally, NiMo was prepared by re-
duction of NiMoO4 at 950 °C for 20 min under H2 /Ar atmosphere.
They observed that NiMo sample prepared at 950 °C exhibits
higher HER activity than NiMo sample prepared at 800 °C and
900 °C, where all the samples possesses porous structure while
NiMo-950 is almost completely reduced to NiMo phase with trace
amount of Ni4 Mo phase, whereas NiMo-800 and NiMo-900 are
only partially reduced with the existence of some oxide species.
The NiMo is composed of predominant NiMo phase with tiny
amount of Ni4 Mo phase, where Mo4+ and Mo6+ are negligibly ob-
served (Fig. 31b), which suggests the almost complete reduction
of oxides; it possesses porous structure, which can afford abun-
dant active sites and facilitate the release of gas, and that possibly
enhance its substantially much high stability and activity for HER.
For HER in 1.0 M KOH, the NiMo exhibits significantly much high
stability (reasonable stability at η of − 200 mV for 300 h, which is
much higher stability than the stability of Pt/C [85] (79% retention
at − 10 mA cm−2 after 24 h), and it exhibits substantially much high
HER activity (η of − 18 mV at − 10 mA cm−2 ), which is even higher
HER activity than Pt/C [34] (η10 : − 33 mV), and it exhibits negligible
decay at − 150 mA cm−2 after 20 0 0 cycles of CV, which indicates its
much high durability.
Preparing nanoporous structured NiMo alloy can considerably
enhance the activity and durability for HER. Our group [26] has
fabricated NiMo alloy with ultrahigh HER activity and robust
durability by simple electrodeposition method (Fig. 32a). It pos-
sesses nanoporous morphology, while it is comprised of crys-
talline Ni4 Mo, which can provide abundant active sites and facil-
itate the release of gas, and that possibly enhance its significantly
much high activity for HER. The NiMo alloy exhibits ultralow η
of − 10 mV at − 10 mA cm−2 in 1.0 M NaOH, which is the lowest
η among those ever reported for non-noble-metal electrocatalysts
[3], while it outperforms the noble Pt/C at higher current density
(Fig. 32b), which depicts its outstanding HER activity, and it ex-
hibits negligible decay after 10 0 0 cycles at higher current density
of − 100 mA cm−2 (Fig. 32b), which indicates its robust durability.
Preparing ultrathin nanostructured Ni4 Mo alloy with superaero-
phobic surface can facilitate the release of gas and afford abundant
active sites, which can considerably enhance the activity and dura-
bility for HER. Our group [33] has observed that ultrathin NiMo NS
(NS: nanosheet) exhibits significantly much high activity and dura-
bility for HER. The NiMo NS was prepared by the following steps:
At first, NiMoO4 NS was obtained by hydrothermal treatment at
120 °C for 8 h; Finally, NiMo NS was prepared by hydrothermal
treatment at 150 °C for 4 h, where in situ topotactic reduction of
138 J. Mohammed-Ibrahim, X. Sun / Journal of Energy Chemistry 34 (2019) 111–160
Fig. 26. W based electrocatalyst for HER (reproduced with permission): (a) lower and (b) higher magnification SEM images of WN NW, (c) SEM image of single nanowire of
WN NW and its corresponding elemental mapping of (d) N and (e) W [105] (Copyright 2017, The Royal Society of Chemistry).
NiMoO4 NS was occurred. They observed that NiMo NS exhibits
higher HER activity than NiMoO4 NS (Fig. 33a). They observed
that turnover frequency (TOF) of NiMo NS exhibits higher intrinsic
HER activity than Pt/C at η of about ≥ − 150 mV (Fig. 33b), which
could be due to the proper surface electronic structure and su-
peraerophobic nanostructured surface. They further observed that
the bubble adhesive force, and bubble releasing size (Fig. 33c-e)
of NiMo NS are ≈ 2 μN and < 95 μm, respectively, whereas the bub-
ble adhesive force, and bubble releasing size of Pt/C are ≈ 29 μN
and ∼364 μm, respectively, where the NiMo NS possesses super-
aerophobic nanostructured surface, which leads to rapid evolution
of H2 bubbles from the surface with smaller size and weaker adhe-
sive force, and that affords higher intrinsic HER activity for NiMo
NS. The NiMo NS possesses ultrathin nanosheet like morphology
with thickness of 2.0−2.1 nm, which corresponds to ≈10 atomic
layers of (001) crystalline lattice; it contains Ni and Mo, which are
uniformly distributed; it is composed of body-centered tetragonal-
phase of Ni4 Mo with (001) facet exposed; it contains Ni0 and
Mo0 ; it contains suitable surface electronic structure, which can
enhance the electron/mass transfer; it possesses superaerophobic
nanostructured surface, which facilitate the release of gas, and that
possibly enhance its considerably much high activity and durability
for HER. For HER in 1.0 M KOH, the NiMo NS exhibits substantially
much high HER activity (η of − 35 mV at − 10 mA cm−2 ), which is
nearly similar to the HER activity of Pt/C [34] (η10 : − 33 mV), while
it exhibits negligible decay at − 100 mA cm−2 after 10 0 0 cycles of
CV, which indicates its much high durability.
Decorating secondary amines with Ni4 Mo alloy can decrease
the charge transfer resistance and modulate the electronic struc-
tures of interfacial active sites, and that can enhance the stability
and activity for HER. Gao et al. [115] have observed that NiMo-EDA
(EDA: Ethylenediamine) exhibits considerably much high stability
and activity for HER. The NiMo-EDA was prepared using modified
precipitation method by the following steps: At first NiMo pre-
cursor was obtained by stirring at 300 °C; Then, NiMo nanopar-
ticles was prepared by reducing the precursor at 500 °C for 1 h
under H2 /Ar atmosphere; Finally, NiMo-EDA was obtained by stir-
ring. They observed that the decoration of primary amines such
as ethylamine and dodecylamine with NiMo exhibit lower HER ac-
tivity than bare NiMo because the decoration of primary amines
with NiMo increase the charge transfer resistance and decrease
the electrochemically active surface area, whereas the decoration
of secondary amine such as ethylenediamine, hexanediamine, and
dodecanediamine with NiMo exhibit higher HER activity than bare
NiMo (Fig. 34b), while NiMo-ethylenediamine exhibits highest HER
activity because the decoration of secondary amines with NiMo de-
crease the charge transfer resistance and increase the electrochem-
ically active surface area. The NiMo-EDA is composed of Ni4 Mo
phase, which are decorated by ethylenediamine (Fig. 34); it pos-
sesses aggregated nanoparticles morphology; it exhibits low charge
transfer resistance, high conductivity, and high electrochemically
active surface area, and they observed that the NiMo decorated
with EDA exhibits a downshift of ∼ 0.4 eV in the binding en-
ergies of both Ni 2p and Mo 3d, while after 10 h of HER, the
NiMo-EDA still retains the modulated oxidation states of NiMo by
the amine modifications, which suggests its preserved catalytic ef-
fect for long-term HER, and that possibly enhance its substan-
tially much high stability and activity for HER. For HER in 1.0 M
KOH, the NiMo-EDA exhibits much high HER activity (η of − 72 mV
at − 10 mA cm−2 ), while it exhibits significantly much high sta-
bility (reasonable stability at η of − 20 0 mV for 10 0 h), which is
much higher stability than the stability of Pt/C [85] (79% retention
at − 10 mA cm−2 after 24 h).
The durability and activity for HER can be enhanced by prepar-
ing nanostructured amorphous NiMoS4 . Wang et al. [116] have ob-
served that NiMoS4 exhibits much high durability and activity for
HER. The NiMoS4 was prepared by the following steps: At first,
Ni(OH)2 was obtained on Ti mesh by hydrothermal treatment at
120 °C for 6 h; Finally, NiMoS4 was prepared by hydrothermal
treatment of Ni(OH)2 at 160 °C for 9 h. They observed that NiMoS4
exhibits higher HER activity than Ni(OH)2 . The NiMoS4 is amor-
phous and it possesses nanosheet morphology; it contains Ni, Mo,
 J. Mohammed-Ibrahim, X. Sun / Journal of Energy Chemistry 34 (2019) 111–160 139

Fig. 27. W based electrocatalyst for HER (reproduced with permission): (a and b) TEM images of oxides of NiW, (c, d) XRD patterns of (c) standard samples, and (d) oxides
of NiW (along with other composites) [38] (Copyright 2017, Springer).

Fig. 28. W based electrocatalyst for HER (reproduced with permission): High-resolution XPS spectra of (a) Mo 3d, and (b) W 4f obtained from (Mo2 C)0.34 -(WC)0.32 -QDs/NG
in comparison with other samples [107] (Copyright 2017, The Royal Society of Chemistry).

and S, which are uniformly distributed, and the atomic ratio of Ni,
Mo, and S in NiMoS4 are 1:1:4; it contains Ni2+ , Mo4+ , S2− , and
S − Ni, and that possibly enhance its much high durability and ac-
tivity for HER. For HER in 0.1 M KOH, the NiMoS4 exhibits negli-
gible decay at − 50 mA cm−2 after 10 0 0 cycles of CV, which indi-
cates its much high durability, while it exhibits high HER activity
(η of − 138 mV at − 10 mA cm−2 ), and it exhibits reasonable stabil-
ity at η of − 220 mV for 50 h, which indicates its much high stabil-
ity.
Preparing nanostructured NiMo3 S4 /Ni3 S2 interface can enhance
the activity and stability for HER. Wu et al. [29] have observed that
NiMo3 S4 /Ni3 S2 exhibits significantly much high activity and sta-
bility for HER. The NiMo3 S4 /Ni3 S2 was prepared by the following
steps: At first, Ni(OH)2 was obtained on Ni foam by hydrothermal
treatment at 100 °C for 10 h; Finally, NiMo3 S4 /Ni3 S2 was prepared
by hydrothermal treatment of Ni(OH)2 at 200 °C for 12 h. They ob-
served that NiMo3 S4 /Ni3 S2 exhibits higher conductivity and HER
activity than Ni(OH)2 , MoS2 , and Ni3 S2 . The NiMo3 S4 /Ni3 S2 con-
140 J. Mohammed-Ibrahim, X. Sun / Journal of Energy Chemistry 34 (2019) 111–160
Fig. 29. Mo based electrocatalyst for HER (reproduced with permission): (a) High-
resolution XPS spectra of Mo 3d obtained from Mo2 C/C, and (b) pictures of water
droplet on the surface of bare carbon (left), and Mo2 C/C (right) [110] (Copyright
2017, American Chemical Society).
tains NiMo3 S4 and Ni3 S2 phases; it possesses flake like morphol-
ogy; it contains NiMo3 S4 /Ni3 S2 interface, and that possibly en-
hance its considerably much high activity and stability for HER.
For HER in 1.0 M KOH, the NiMo3 S4 /Ni3 S2 exhibits substantially
much high HER activity (η of − 23.4 mV at − 10 mA cm−2 ), which is
even higher HER activity than Pt/C [34] (η10 : − 33 mV), while it ex-
hibits reasonable stability at η of − 96 mV for 20 h, which indicates
its much high stability, and it exhibits negligible decay at − 10 mA
cm−2 after 10 0 0 cycles of CV, which indicates its high durability.
Integrating nanostructured CdS, MoO3 , and Ni3 S2 can pro-
vide high conductivity and electrochemically active surface area,
and that can enhance the activity and stability for HER. Lu
et al. [30] have observed that CdS-MoO3 /Ni3 S2 exhibits remark-
ably much high activity and stability for HER. The CdS-MoO3 /Ni3 S2
was prepared by the following steps: At first, MoO3 /Ni3 S2 was
obtained by microwave-assisted hydrothermal method at 220 °C
for 1 h; Finally, CdS-MoO3 /Ni3 S2 was prepared by electrochemi-
cal deposition. They observed that CdS-MoO3 /Ni3 S2 exhibits higher
HER activity than CdS, Ni3 S2 , CdS-Ni3 S2 , and MoO3 /Ni3 S2 . The
CdS-MoO3 /Ni3 S2 is composed of Ni3 S2 nanoarrays, which are cov-
ered by MoO3 nanosheets, which forms a Ni3 S2 /MoO3 core/shell
structure, where thin CdS is decorated on Ni3 S2 /MoO3 ; it pos-
sesses conifer-like hierarchical nanoarray structure; it contains Cd,
Ni, Mo, O and S, which are uniformly distributed; it contains
Fig. 30. Mo based electrocatalyst for HER (reproduced with permission): (a)
Schematic diagram depicts the synthesis of SN-MoP/G, and (b) high-resolution
XPS spectra of P 2p obtained from SN-MoP/G in comparison with other sample
[114] (Copyright 2017, American Chemical Society).
Mo5+ and Mo6+ , where the presence of Mo5+ could be due to
the existence of oxygen vacancies; it exhibits high electrochem-
ically active surface area (Cdl : 117.09 mF cm−2 ); it affords high
conductivity, and that possibly enhance its considerably much
high activity and stability for HER. For HER in 1.0 M KOH, the
CdS-MoO3 /Ni3 S2 exhibits substantially much high HER activity (η
of − 30 mV at − 10 mA cm−2 ), which is even higher HER activity
than Pt/C [34] (η10 : − 33 mV), and it exhibits reasonable stability
at η of − 30 mV for 24 h, which indicates its much high stability.
Integrating Ni with MoS2 -GO composite can enhance the con-
ductivity and electrochemically active surface area, and that can
enhance the activity and durability for HER. Yin et al. [32] have
observed that Ni-(MoS2 -GO) exhibits significantly much high ac-
tivity and durability for HER. The Ni-(MoS2 -GO) was prepared by
the following steps: At first, MoS2 was obtained by hydrother-
mal treatment at 220 °C for 24 h; Then MoS2 -GO was prepared
by stirring and ultra-sonication; Finally, Ni-(MoS2 -GO) composite
was obtained by electrodeposition under supergravity fields. The
Ni-(MoS2 -GO) is composed of nickel particles (∼50 nm), which are
homogenously distributed on the MoS2 /GO lamellae; it contains Ni,
Mo, S and C, which are uniformly distributed; it contains predomi-
nant Mo4+ with small amount of Mo6+ ; it contains C–C, C = C and
C–O bonds; it exhibits high electrochemically active surface area
 J. Mohammed-Ibrahim, X. Sun / Journal of Energy Chemistry 34 (2019) 111–160
Fig. 31. Mo based electrocatalyst for HER (reproduced with permission): (a)
Schematic diagram depicts the synthesis process of NiMo alloy, and (b) high-
resolution XPS spectra of Mo 3d obtained from NiMo alloy [28] (Copyright 2018,
MDPI).
(Cdl : 77 mF cm−2 ) and conductivity, and that possibly enhance
its considerably much high activity and durability for HER. For
HER in 1.0 M NaOH, the Ni-(MoS2 -GO) exhibits substantially much
high HER activity (η of − 33 mV at − 10 mA cm−2 ), which is simi-
lar to the HER activity of Pt/C [34] (η10 : − 33 mV), and it exhibits
10 mV decay at − 100 mA cm−2 after 3000 cycles of CV, which indi-
cates its much high durability, while it exhibits reasonable stability
at − 100 mA cm−2 for 20 h, which indicates its much high stability.
Integrating nanostructured NiOOH with MoS2 can afford syner-
getic effect, and that can enhance the stability and activity for HER.
Zhang et al. [117] have observed that 1T-MoS2 /Ni2+δ Oδ (OH)2−δ
exhibits much high stability and activity for HER. The 1T-
MoS2 /Ni2+δ Oδ (OH)2−δ was prepared by the following steps:
At first, metallic 1T-MoS2 was obtained by hydrothermal treatment
at 200 °C for 12 h; Finally, 1T-MoS2 /Ni2+δ Oδ (OH)2−δ was obtained
by chemical reaction between NH4 HCO3 and NiCl2 in 1T-MoS2
ethanol suspension, where in situ growth of Ni2+δ Oδ (OH)2−δ
was occurred on the surface of 1T-MoS2 . They observed that
1T-MoS2 /Ni2+δ Oδ (OH)2−δ exhibits higher HER activity than 1T-
MoS2 . The 1T-MoS2 /Ni2+δ Oδ (OH)2−δ is composed Ni2+δ Oδ (OH)2−δ
nanoparticles, which are anchored on the 2D 1T-MoS2 ultrathin
nanosheet (Fig. 35), where 1T-MoS2 is comprised of metallic
1T phase of the MoS2 while Ni2+δ Oδ (OH)2−δ is composed of
amorphous Ni(OH)2 and crystalline γ -NiOOH nanoparticles, and
the 1T-MoS2 /Ni2+δ Oδ (OH)2−δ contains Ni, Mo, S, and O, which
141
Fig. 32. Mo based electrocatalyst for HER (reproduced with permission): (a)
Schematic diagram depicts the fabrication of 3D nanoporous NiMo alloy on Cu
foam by electrodeposition technique, and (b) polarization curves recorded before
and after 10 0 0 cycles of CV of 3D nonoporous NiMo alloy in comparison with Pt/C
[26] (Copyright 2014, Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim).
are uniformly distributed, and they attributed a bifunctional
mechanism (Fig. 35e), where Ni2+δ Oδ (OH)2−δ nanoparticles with
suitable binding strength to H2 O and OHad enhances the adsorp-
tion/dissociation of H2 O, which affords protons to the nearby
active sites on 1T-MoS2 , where 1T-MoS2 involves the electron
transfer, adsorption/combination of intermediates of hydrogen
and desorption of hydrogen gas via a Heyrovsky step, and that
possibly enhance its much high stability and activity for HER. For
HER in 1.0 M KOH, the 1T-MoS2 /Ni2+δ Oδ (OH)2−δ exhibits negligible
decay at − 10 mA cm−2 after 50 0 0 cycles of CV, which indicates
its much high durability, while it exhibits much high HER activity
(η of − 73 mV at − 10 mA cm−2 ), and it exhibits 12 mV decay
at − 10 mA cm−2 for 30 h, which indicates its much high stability.
Preparing molybdenum-nickel bimetallic carbonitride can lower
the bonding strength between the adsorbed reactive intermediate
and the active site, and that can enhance the stability and ac-
tivity for HER. Wang et al. [118] have observed that MoNiNC ex-
hibits much high stability and activity for HER. The MoNiNC was
prepared by carbothermal ammonia reduction at 800 °C for 3 h
under NH3 atmosphere. They observed through DFT that alloy-
ing of Ni as well as introduction of N and C in MoNiNC can sig-
nificantly lower the bonding strength between the adsorbed re-
active intermediate and the active site, and the MoNiNC is com-
posed of crystalline Mo0.8 Ni0.2 N, which are intercalated with car-
bon; it is molybdenum-nickel bimetallic carbonitride; it possesses
porous structure; it contains Mo, Ni, N and C, which are uni-
formly distributed; it contains Mo2+ , Mo3+ , Mo6+ , and Mo−N, and
that possibly enhance its much high stability and activity for HER.
For HER in 0.1 M KOH, the MoNiNC exhibits high HER activity
(η of − 110 mV at − 10 mA cm−2 ), and it exhibits reasonable stabil-
ity at − 50 mA cm−2 for 24 h followed by − 100 mA cm−2 for 24 h,
which indicates its much high stability.
Preparing nanostructured Ni3 N–NiMoN can afford abundant ac-
tive sites and metallic characteristic, and that can enhance the
durability and activity for HER. Wu et al. [31] have observed that
142 J. Mohammed-Ibrahim, X. Sun / Journal of Energy Chemistry 34 (2019) 111–160

Fig. 33. Mo based electrocatalyst for HER (reproduced with permission): (a) Polarization curves of NiMo NS in comparison with Pt/C, NiMoO4 precursor, and Ni foam in 1 M
KOH, (b) turnover frequency of NiMo NS in comparison with Pt/C at various overpotential, (c) adhesive force measurements of gas bubbles on NiMo NS in comparison with
NiMoO4 , Pt/C, and Ni foam, and (d, e) digital images of bubble generation behavior during HER on NiMo NS and Pt/C, respectively (Scale bar: 500 μm) [33] (Copyright 2017,
Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim).

Ni3 N–NiMoN exhibits substantially much high durability and activ-
ity for HER. The Ni3 N–NiMoN was prepared by the following steps:
At first, Ni-Mo-O was obtained on carbon cloth by hydrothermal
treatment at 180 °C for 10 h; Finally, Ni3 N–NiMoN was prepared by
calcination of Ni-Mo-O at 350 °C for 2 h under N2 atmosphere fol-
lowed by nitridation at 500 °C for 2 h under NH3 atmosphere. They
observed that Ni3 N–NiMoN exhibits higher HER activity than Ni-
Mo-O. The Ni3 N–NiMoN exhibits interface between the (100) face
of Ni0.2 Mo0.8 N and (111) face of Ni3 N; it possesses nanosheet mor-
phology, which is further composed of nanoparticles, which can af-
ford abundant active sites; it contains Mo, Ni and N, which are
uniformly distributed; it contains Ni+ , Ni2+ , Mo+3 , Mo+4 , Mo+6 ,
N − Ni/Mo, and N − H; it exhibits high electrochemically active sur-
face area (Cdl : 241 mF cm−2 ); it exhibits very tiny (− 0.03 eV) Gibbs
free energy for H adsorption (GH ∗ ), which is almost close to the
optimal GH ∗ of 0 eV; it possesses lower water adsorption energy
(− 0.62 eV); it shows the continuous distribution of the density of
states near the Fermi level, which suggests its metallic charac-
teristic with high electrical conductivity, which can enhance the
fast electron transport, and that possibly enhance its considerably
much high durability and activity for HER. For HER in 1.0 M KOH,
the Ni3 N–NiMoN exhibits negligible decay at − 125 mA cm−2 af-
 J. Mohammed-Ibrahim, X. Sun / Journal of Energy Chemistry 34 (2019) 111–160
Fig. 34. Mo based electrocatalyst for HER (reproduced with permission): (a) FTIR
spectra of NiMo and NiMo-EDA nanoparticles, and (b) Schematic diagram depicts
the surface modification of NiMo nanoparticles with different amines [115] (Copy-
right 2018, American Chemical Society).
ter 50 0 0 cycles of CV, which indicates its significantly much high
durability, while it exhibits substantially much high HER activity
(η of − 31 mV at − 10 mA cm−2 ), which is even higher HER activity
than Pt/C [34] (η10 : − 33 mV), and it exhibits negligible decay for
20 h, which indicates its much high stability.
2.8. Se based earth abundant electrocatalysts for HER
The activity for HER can be enhanced by preparing nanostruc-
tured transition metal dichalcogenides. Ge et al. [119] observed
that NiSe2 NS (NS: Nanosheet) exhibits high activity for HER, and
it was prepared by anion-exchange reaction. The NiSe2 NS is com-
posed of pyrite-structure NiSe2 ; it possesses nanosheet like mor-
phology; it exhibits high conductivity, and that possibly enhance
its high activity for HER. For HER in 1.0 M KOH, the NiSe2 NS ex-
hibits high HER activity (η of − 164 mV at − 10 mA cm−2 ), while it
exhibits reasonable stability at − 10 mA cm−2 for 10 h.
Preparing peapod like composite can enhance the durabil-
ity and activity for HER. Fang et al. [120] have observed that
Co(S0.71 Se0.29 )2 /C exhibits much high durability and activity for
HER. The Co(S0.71 Se0.29 )2 /C was prepared by the following steps:
At first, Co(CO3 )0.5 (OH)0.11H2 O as precursor was prepared by
143
hydrothermal treatment at 170 °C for 16 h; Then, Co@Carbon
nanocomposite was obtained by hydrothermal treatment of the
above precursor at 180 °C for 6 h followed by calcination at 700 °C
for 200 min under Ar/H2 atmosphere; Finally, Co(S0.71 Se0.29 )2 /C
was prepared by sulfuration/selenylation at 450 °C for 1 h under Ar
atmosphere. They observed that Co(S0.71 Se0.29 )2 /C exhibits higher
HER activity than CoSe2 and CoS2 (Fig. 36b). The Co(S0.71 Se0.29 )2 /C
is composed of Co(S0.71 Se0.29 )2 nanoparticles, which are aligned
in the carbon fibers; it possesses porous peapod like morphology
(Fig. 36a), where the porous structure can afford abundant ac-
tivity sites; it exhibits high surface area (244.774 m2 g−1 ); it
contains graphitized carbon; it contains Co, S, Se, and C, which
are uniformly distributed, and that possibly enhance its much
high durability and activity for HER. For HER in 1.0 M KOH, the
Co(S0.71 Se0.29 )2 /C exhibits negligible decay at − 100 mA cm−2 after
10 0 0 cycles of CV, which indicates its much high durability, while
it exhibits high HER activity (η of − 122 mV at − 10 mA cm−2 ), and
it exhibits negligible decay at − 10 mA cm−2 for 20 h, which indi-
cates its much high stability.
The stability and activity for HER can be enhanced by prepar-
ing defect-rich nanostructured chalcogenides. Hu et al. [121] have
observed that Se-(NiCo)Sx /(OH)x exhibits much high stability and
activity for HER. The Se-(NiCo)Sx /(OH)x was prepared on Ni foam
by Se-induced hydrothermal treatment at 150 °C for 3 h. They
observed that Se-(NiCo)Sx /(OH)x exhibits high HER activity than
(NiCo)S/OH and (NiCo)OH (Fig. 37b). The Se-(NiCo)Sx /(OH)x pos-
sesses nanosheet like morphology with abundant edge sites (Fig.
37a); it contains disorders and defects; it contains Ni, Co, O, S,
and Se, which are uniformly distributed; it contains (NiCo)0.85 Se
and (NiCo)4 S3 phases, and that possibly enhance its much high
stability and activity for HER. For HER in 1.0 M KOH, the Se-
(NiCo)Sx /(OH)x exhibits negligible decay for 80 h (Fig. 37c), which
indicates its much high stability, while it exhibits high HER activity
(η of − 103 mV at − 10 mA cm−2 ).
Preparing Mo and S co-doped NiSe can enhance the activity
for HER. Zhang et al. [122] have observed that Mo-S-NiSe ex-
hibits much high activity for HER, and it was prepared by hy-
drothermal treatment at 160 °C for 12 h. The Mo-S-NiSe is com-
posed of Mo and S, which are co-doped in NiSe; it possesses
nanosheet morphology; it contains Ni2+ , Mo4+ , S2 2− , and S2− , and
that possibly enhance its much high activity for HER. For HER
in 1.0 M KOH, the Mo-S-NiSe exhibits much high HER activity (η
of − 88 mV at − 10 mA cm−2 ), while it exhibits reasonable stability
at η of − 108 mV for 12 h, which indicates its high stability, and it
exhibits negligible decay at − 10 mA cm−2 after 10 0 0 cycles of CV.
Preparing nanostructured MoSe2 /NiSe hybrid can enhance its
electrochemical surface area and that improve its HER activity.
Wang et al. [123] have observed that MoSe2 @Ni0.85 Se NW (NW:
nanowire) exhibits high activity for HER, and it was prepared
by hydrothermal selenization of NiMoO4 at 160 °C for 6 h, while
NiMoO4 was obtained by hydrothermal treatment at 120 °C for
10 h. They observed that MoSe2 @Ni0.85 Se NW exhibits high HER
activity than NiMoO4 NW. The MoSe2 @Ni0.85 Se NW possesses
nanowire morphology, which further contains nanosheets; it con-
tains Ni0.85 Se and MoSe2 phases; it possesses high electrochemical
surface area (Cdl : 193.185 mF cm−2 ), and that possibly enhance its
high activity for HER. For HER in 1.0 M KOH, the MoSe2 @Ni0.85 Se
NW exhibits reasonable stability at η of − 124.5 mV for 20 h, which
indicates its high stability, while it exhibits high HER activity
(η of − 117 mV at − 10 mA cm−2 ), and it exhibits negligible decay
at − 10 mA cm−2 after 10 0 0 cycles of CV.
The stability and activity for HER can be enhanced by preparing
nanostructured mixed metal selenides from metal-organic frame-
work (MOF). Xu et al. [124] have observed that NiSe2 /Fe3 Se4 /C
exhibits high stability and activity for HER. The NiSe2 /Fe3 Se4 /C
was prepared by selenylation of Ni/Fe MOF using Se powder at
144 J. Mohammed-Ibrahim, X. Sun / Journal of Energy Chemistry 34 (2019) 111–160

Fig. 35. Mo based electrocatalyst for HER (reproduced with permission): (a and b) TEM images of 1T-MoS2 /Ni2+δ Oδ (OH)2−δ , (c) high-resolution TEM image of marked area in
(a), (d) magnified TEM image of the marked area in (c), and (e) schematic diagram depicts the HER mechanism of 1T-MoS2 /Ni2+δ Oδ (OH)2−δ [117] (Copyright 2017, Wiley-VCH
Verlag GmbH & Co. KGaA, Weinheim).

450 °C for 1 h, while Ni/Fe MOF was obtained by hydrothermal
treatment at 100 °C for 12 h. They observed that NiSe2 /Fe3 Se4 /C
exhibits higher HER activity than Ni/Fe@C and Ni/Fe − OH. The
NiSe2 /Fe3 Se4 /C possesses nanorod like morphology; it contains
NiSe2 and Fe3 Se4 phases; it contains Fe2+ and Fe3+ ; it contains
graphitized carbon, and that possibly enhance its high stability and
activity for HER. For HER in 1.0 M KOH, the NiSe2 /Fe3 Se4 /C ex-
hibits negligible decay at η of − 160 mV for 20 h, which indicates
its high stability, while it exhibits high HER activity (η of − 160 mV
at − 10 mA cm−2 ).
2.9. Mn/Zn/V/metal free based earth abundant electrocatalysts for
HER
Creating defects in MnO2 can enhance the stability and ac-
tivity for HER. Zhao et al. [125] observed that δ -MnO2 NS (NS:
Nanosheet) exhibits high stability and activity for HER, and it was
prepared by hydrothermal treatment at 180 °C for 3 h. The δ -MnO2
NS possesses nanosheet morphology; it contains δ -MnO2 phase,
while it contains Mn3+ , and Mn4+ ; it exhibits defects, where the
defects and oxygen vacancies could form the Mn3+ active sites,
which can afford half-metallicity, and that possibly enhance its
high stability and activity for HER. For HER in 1.0 M KOH, the δ -
MnO2 NS exhibits reasonable stability at η of − 196 mV for 10 h,
which indicates its high stability, while it exhibits high HER ac-
tivity (η of − 196 mV at − 10 mA cm−2 ).
Preparing nanostructured Mn doped Ni2 P can enhance the sta-
bility and activity for HER. Zhang et al. [40] have observed that
Mn-Ni2 P NS exhibits much high stability and activity for HER. The
Mn-Ni2 P NS was prepared from MnNi-hydroxide precursor by low
temperature phosphidation reaction at 300 °C for 2 h, while the
hydroxide precursor was prepared by hydrothermal treatment at
90 °C for 6 h. They observed that Mn-Ni2 P NS exhibits higher elec-
trochemical surface area (Fig. 38) and HER activity than Ni2 P. The
Mn-Ni2 P NS possesses porous nanosheet morphology; it is com-
posed of Mn doped cubic Ni2 P; it contains Mn, Ni, and P, which are
uniformly distributed; it contains Mn2+ and Ni2+ , and that possi-
bly enhance its much high stability and activity for HER. For HER
 J. Mohammed-Ibrahim, X. Sun / Journal of Energy Chemistry 34 (2019) 111–160 145

Fig. 36. Se based electrocatalyst for HER (reproduced with permission): (a) SEM
image, and (b) polarization curve of Co(S0.71 Se0.29 )2 /C [120] (Copyright 2017, Wiley-
VCH Verlag GmbH & Co. KGaA, Weinheim).

in 1.0 M KOH, the Mn-Ni2 P NS exhibits negligible decay after 500

cycles of CV, which indicates its high durability, while it exhibits
high HER activity (η of − 103 mV at − 20 mA cm−2 ), and it exhibits
reasonable stability at η of − 140 mV for 25 h, which indicates its
much high stability.
The activity and stability for HER can be enhanced by prepar-
ing NiZnP with Ni(OH)2 and tiny amount of Zn. Lin et al. [41] have
observed that etched-NiZnP exhibits substantially much high activ-
ity and stability for HER. The etched-NiZnP on Ni foam was pre-
pared by electroless plating at 40 °C for 2 h followed by H2 SO4
etching for 5 min. They observed that etched-NiZnP exhibits higher
HER activity than NiP (Fig. 39b), while the NiZnP prepared by
Fig. 37. Se based electrocatalyst for HER (reproduced with permission): (a)
H2 SO4 etching affords higher HER activity than NiZnP prepared by HRTEM image, (b) polarization curve, and (c) chronoamperometric curve of Se-
NaOH etching. The etched-NiZnP possesses rimose like morphol- (NiCo)Sx /(OH)x [121] (Copyright 2018, Wiley-VCH Verlag GmbH & Co. KGaA, Wein-
ogy; it is composed of Ni83 Zn3 P13 ; it contains metallic Ni, Ni(OH)2 heim).
(Fig. 39a), NiPx , ZnPx , P, POx , Zn and ZnO, where the Ni(OH)2 is
formed instead of NiO after H2 SO4 etching, and that possibly en-
hance its considerably much high activity and stability for HER. For possesses hollow, polyhedral morphology; it contains Co, Zn and S,
HER in 1.0 M KOH, the etched-NiZnP exhibits reasonable stability which are uniformly distributed; it exhibits high surface area (85.5
at η of − 100 mV after 24 h, which indicates its much high stability, m2 g−1 ), and that possibly enhance its much high stability and ac-
while it exhibits remarkably much high HER activity (η of − 50 mV tivity for HER. For HER in 1.0 M KOH, the Zn-Co-S exhibits negli-
at − 10 mA cm−2 ). gible decay after 10 0 0 cycles of CV, which indicates its high dura-
Adding Zn to Co-S can enhance the stability and activity for bility, while it exhibits high HER activity (η of − 176 mV at − 10 mA
HER. Zhang et al. [126] have observed that Zn-Co-S exhibits cm−2 ), and it exhibits 91.7% retention for 10 h, which indicates its
high stability and activity for HER. The Zn-Co-S was prepared by high stability.
solvent-based sulfidation at room temperature followed by ther- Doping V in Ni3 S2 can enhance the durability and activity
mal annealing at 300 °C for 2 h. They observed that Zn-Co-S ex- for HER. Qu et al. [42] observed that V-Ni3 S2 NW7000 cycles ex-
hibits high HER activity than Co-S. The Zn-Co-S is amorphous; it hibits much high durability and activity for HER, while it was
146 J. Mohammed-Ibrahim, X. Sun / Journal of Energy Chemistry 34 (2019) 111–160

Fig. 38. Mn based electrocatalyst for HER (reproduced with permission): The ca-
pacitive current densities of Mn-Ni2 P NS in comparison with Ni2 P at − 0.41 V under
different scan rates [40] (Copyright 2017, The Royal Society of Chemistry).

prepared by hydrothermal treatment at 160 °C for 24 h. They ob-

served that V-Ni3 S2 NW7000 cycles exhibits higher HER activity than
Ni3 S2 NW. The V-Ni3 S2 NW7000 cycles possesses nanowire morphol-
ogy (Fig. 40a); it is composed of V doped crystalline Ni3 S2 , and
that possibly enhance its much high durability and activity for
HER. For HER in 1.0 M KOH, the V-Ni3 S2 NW7000 cycles exhibits
much high HER activity (η of − 68 mV at − 10 mA cm−2 ), and it ex-
hibits negligible decay after 20 0 0 cycles of CV (Fig. 40b), while af-
ter durability test (V-Ni3 S2 NW9000 cycles ), it also exhibits negligi-
ble decay at − 20 mA cm−2 for 12 h, which indicates its much high
durability and stability, respectively.
Doping V can vary the electronic structure of pyrite NiS2
from semiconductor to metallic property, which can enhance its
stability and activity for HER. Liu et al. [127] have observed that
V-NiS2 exhibits high stability and activity for HER. The V-NiS2
was prepared by sulfidation of NiV LDHs at 40 0 °C for 20 0 min Fig. 39. Zn based electrocatalyst for HER (reproduced with permission): (a) High-
under H2 /Ar atmosphere, while the NiV LDHs was obtained by resolution XPS spectra of Ni 2p obtained from etched-NiZnP, and (b) polarization
hydrothermal treatment at 120 °C for 12 h. They observed that curves of etched-NiZnP in comparison with Pt/C, Ni foam, and NiP in 1 M KOH
[41] (Copyright 2017, Elsevier).
V-NiS2 exhibits higher HER activity than NiS2 . The V-NiS2 is
composed of V doped pyrite NiS2 ; it contains Ni, V and S, which
cates its much high durability, while it exhibits high HER activity
are uniformly distributed; it contains V4+ and Ni2+ , and the V
(η of − 380 mV at − 10 mA cm−2 ).
doping shifts the band gap from 0.41 eV to 0 eV, while its electrical
resistivity increases with increase in temperature, which suggests
the V doping alters the electronic structure of pyrite NiS2 from 2.10. Comparison of η for earth abundant electrocatalysts for HER
semi conductor property to metallic nature, and that possibly
enhance its high stability and activity for HER. For HER in 1.0 M Comparison of overpotential to achieve − 10 mA cm−2 (η10 ) of
KOH, the V-NiS2 exhibits reasonable stability at − 10 mA cm−2 for various kinds of reported earth abundant electrocatalysts with Pt/C
20 h, which indicates its high stability, while it exhibits high HER for HER in 1.0 M KOH alkaline electrolyte are presented in Table
activity (η of − 110 mV at − 10 mA cm−2 ). 1 [20,21,23,27–42,44–46,53–57,60–139]. For HER in 1.0 M KOH, Ni
Doping of S with N-doped C lowers the Gibbs free energy for based earth abundant electrocatalysts such as Ni-rGO1M NaOH
H adsorption, which can enhance its durability and activity for (η10 : − 36 mV) [61], Ni3 S2 -rGO (η10 : − 44 mV) [67], Ni5 P4
HER. Qu et al. [128] have observed that NS-C exhibits much high (η10 : − 47 mV) [71], Ni3 S2 (η10 : − 48.1 mV) [55], Ni-Ni-rGO0.1 M NaOH
durability and activity for HER. The NS-C (Fig. 41a) was prepared (η20 : − 57.5 mV) [63], Ni3 S2 @Cuactivated (η10 : − 60.8 mV) [66],
by carbonization of S-Graphene at 400 °C for 2 h under N2 at- NiS2 activated (η10 : − 67 mV) [68], Ni(OH)2 –Ni3 N (η20 : − 72 mV)
mosphere followed by heating at 800 °C for 3 h. They observed [72], Ni3 S2 (η10 : − 77 mV) [65], and NiOx @CNTs NiOx @CNTs (η10 :
that NS-C exhibits higher HER activity than NP-C, N–C, and NB- ∼− 79 mV) [73], exhibit substantially much high HER activity, and
C, while their HER activity are in the following order: NS-C > NP- those are even higher or well comparable with the HER activity
C > N–C > NB-C. The NS-C shows ID /IG ratios of 1.15; it possesses of Pt/C [34] (η10 : − 33 mV). Preparing nanostructured Ni-rGO com-
sheet like morphology with wrinkle, while it exhibits abundant lat- posite by electrodeposition method under supergravity field can
tice structures of graphene sheets (Fig. 41); it contains 5.8 atomic% enhance the activity for HER. The Ni-rGO1M NaOH (η10 : − 36 mV)
of S, and 3.7 atomic% of N, and the co-doping of S to N–C de- [61] exhibits considerably much high HER activity. The Ni-rGO
creases the Gibbs free energy for H adsorption (GH ∗ ) from 0.81 eV composite exhibits less adsorption free energy of H∗ (GH∗ :
to 0.23 eV, and that possibly enhance its much high durability and 0.31 eV); it is composed of Ni nanoparticles and rGO sheets, which
activity for HER. For HER in 1.0 M KOH, the NS-C exhibits negligi- are homogenously loaded on Ni foam, where the Ni nanoparticles
ble decay at − 100 mA cm−2 after 10 0 0 cycles of CV, which indi- are well dispersed on rGO sheets, which can afford high surface
 J. Mohammed-Ibrahim, X. Sun / Journal of Energy Chemistry 34 (2019) 111–160 147

Table 1. Comparison of overpotential to achieve − 10 mA cm−2 of various kinds of reported earth abundant electrocatalysts with Pt/C for hydrogen evolution reaction (HER)
in 1.0 M KOH alkaline electrolyte.

Section 1 Section 2 Section 3

HER electrocatalysts η10 (mV) Ref. HER electrocatalysts η10 (mV) Ref. HER electrocatalysts η10 (mV) Ref.
∗
Pt/C −33 [34] CoMoO4 NW −81 [109] Mo2 C/C NS −125 [45]
NiMo1M NaOH −10 [26] P-Mo2 C@NC −83 [131] Co2 P@NPC −129 [82]
Cux Ni4- x N −12 [27] Mo2 C/C–N0.1 M KOH −84 [132] Co4 Ni1 P NTs −129 [89]
NiMo −18 [28] Co6.25 Fe18.75 Ni75 Ox NS −84 [99] WN NW −130 [105]
NiMo3 S4 /Ni3 S2 −23.4 [29] (Ni0.33 Fe0.67 )2 P NS −84 [21] Ni/MoC2 @NC −130 [112]
CdS-MoO3 /Ni3 S2 −30 [30] MoP/CNTs −86 [113] Mo1 N1 C2 0.1 M KOH −132 [133]
Ni3 N–NiMoN −31 [31] CoP NS −86.6 [74] Mo-NiCo0.1 M KOH −132.3 [134]
Ni-(MoS2 -GO)1 M NaOH −33 [32] Ni0.5 Co0.5 P −87 [46] WP/W −133 [106]
NiMo NS −35 [33] Mo-S-NiSe −88 [122] NiMoS4 0.1 M KOH −138 [116]
Ni-rGO1M NaOH −36 [61] CoP NS −90 [75] dr-MoN −139 [135]
Ni3 S2 -rGO −44 [67] Ni-rGO1M NaOH −91 [62] N@MoPCx −139 [34]
Ni5 P4 −47 [71] MoS2 /NiS/MoO3 −91 [136] Mo2 C −139 [137]
Ni3 S2 −48.1 [55] (Mo2 C)0.34 -(WC)0.32 -QDs/NG −93 [107] α -MoO3- x 0.1 M KOH −142 [108]
SN-MoP/G −49 [114] Ni3 FeN/rGO −94 [96] Ni/NiFeOOH −154 [101]
etched-NiZnP −50 [41] Ni3 Co-G0.5 M KOH −95 [91] Co2 P@Co3 O4 −159 [77]
Ni-Ni-rGO0.1 M NaOH −57.5a [63] Mo2 C–C −96 [44] NiSe2 /Fe3 Se4 /C −160 [124]
NiCo2 Px NW −58 [35] P8.6 –Co3 O4 NW −97 [83] Ni58 Co42 1M NaOH −162 [36]
NiW0.1 M KOH −60 [38] β -Mo2 C@BCN −98 [111] CoP/C −163 [80]
Ni3 S2 @Cuactivated −60.8 [66] Ni(OH)2 –CoS2 NW −99c [94] NiSe2 NS −164 [119]
FeB2 −61 [23] Mn-Ni2 P NS −103d [40] MoS2 /Co3 O4 −170 [138]
CoP NWs/CoOx −65 [76] Se-(NiCo)Sx /(OH)x −103 [121] Co(OH)2 @NCNTs −170 [53]
NiS2 activated −67 [68] Ni3 FeN −105 [95] NiS2 /CoS2 –O NW −174 [93]
Co9 S8 –NC@MoS2 −67 [129] NC@CuCo2 Nx −105 [103] WO3- x NS −175 [104]
NiFe LDH@def-Gr ∼− 67 [56] NiCo2 O4 @C1M NaOH ∼− 109 [92] Zn-Co-S −176 [126]
V-Ni3 S2 NW7000 cycles −68 [42] N-Mo2 C nb −110 [139] Co/CoP–NC −180 [20]
CoN/Ni3 N@NC −68 [85] MoNiNC0.1 M KOH −110 [118] Co2 C0.1 M KOH −181 [86]
Mo2 C–NP-rGO −71 [130] V-NiS2 −110 [127] Co-Ni3 N −194 [87]
Mo2 C/C −71 [110] NC/CuCo/CuCoOx −112 [57] δ -MnO2 NS −196 [125]
NiMo-EDA −72 [115] Nix S −113 [70] Ni1M NaOH −202 [60]
Ni(OH)2 –Ni3 N −72b [72] CoP/NCNHP −115 [81] NiS2 hms −219 [69]
1T-MoS2 /Ni2+δ Oδ (OH)2−δ −73 [117] Ni2 P-NiCoP@NC1M NaOH −116 [90] Ni/C3 N4 1M NaOH −222 [64]
NiCu@C −74 [102] Cu@NiFe LDH −116 [37] NP-SS −230 [54]
Ni(OH)2 -Fe2 P −76 [98] MoSe2 @Ni0.85 Se NW −117 [123] CoO@Co/N-rGO0.1 M KOH −237 [78]
CoP/CNTs −76 [79] NiFe LDH@NiCoP −120 [97] Co9 S8 @NOSC −320 [88]
Ni3 S2 −77 [65] Fe-Co3 O4 /CNTs −120 [100] NS-C −380 [128]
Mo-Ni2 P NW −78 [39] P-Co3 O4 −120 [84]
NiOx @CNTs ∼− 79 [73] Co(S0.71 Se0.29 )2 /C −122 [120]

HER test performed in 0.1/1 M NaOH/0.1/0.5 M KOH is indicated on the electrocatalyst name. η10 = Overpotential for HER to achieve − 10 mA cm−2 in 1 M KOH; ∗ = Non-
earth-abundant HER electrocatalyst; − 57.5a : − 57.5 mV at − 20 mA cm−2 ; − 72b : − 72 mV at − 20 mA cm−2 ; − 99c : − 99 mV at − 20 mA cm−2 ; − 103d : − 103 mV at − 20 mA
cm−2 ; NWs: Nanowires; rGO: reduced graphene oxide; EDA: Ethylenediamine; NS: Nanosheet; dr: Defect rich; nb: Nano-belt; NW: Nano-wire; hms: hollow microspheres;
QDs: Quantum Dots; G: Graphene; CNTs: Carbon Nano-Tubes; NCNHP: N-doped carbon nanotube hollow polyhedron; LDH: Layered Double Hydroxide; def-Gr: defective
graphene; NTs: Nanotubes; SS: Stainless steel.

area, good electrical conductivity, and harmonious synergistic
effect between rGO sheets and Ni particles, and that possibly en-
hance its considerably much high activity for HER. The activity for
HER can be enhanced by preparing nanostructured Ni-rGO com-
posite on the Ni pre-layer. The Ni-Ni-rGO0.1 M NaOH (η20 : − 57.5 mV)
[63] exhibits much high HER activity. The Ni-Ni-rGO is composed
of hedgehog-like prickly nickel nanostructures, which are covered
by rGO, while the Ni possesses face-centered cubic structure,
where the synergistic effect between Ni and rGO can enhance its
much high activity for HER.
Preparing Ni3 S2 with nanorods@nanosheets homo-junction
structure can enhance the activity for HER. The Ni3 S2
(η10 : − 48.1 mV) [55] exhibits much high HER activity. The Ni3 S2 is
composed of crystalline Ni3 S2 ; it contains Ni2+ , and S2− ; it pos-
sesses sulfur vacancy, which can alter electronic structure of the
surface; it exhibits high conductivity; it possesses nanorods, which
are further coated by nanosheets, which forms the Ni3 S2 with
nanorods@nanosheets homo-junction, which can afford abundant
active sites, reduce the transport of electron, and facilitate the
gas release, and that possibly enhance its much high activity for
HER. The activity for HER can be enhanced by preparing hollow
Ni3 S2 microsphere with abundant protruding edges. The Ni3 S2
(η10 : − 77 mV) [65] exhibits much high HER activity. The Ni3 S2
possesses hollow microsphere morphology with abundant protrud-
ing edges, which can provide plenty of active sites; it is composed
of predominant crystalline Ni3 S2 with minor Mo, which exists as
Mo6+ ; it exhibits high conductivity and electrochemically active
surface area, and that possibly enhance its much high activity for
HER. Preparing porous Ni3 S2 on nano-porous Cu can enhance the
activity for HER. The Ni3 S2 @Cuactivated (η10 : − 60.8 mV) [66] ex-
hibits much high HER activity. The Ni3 S2 @Cuactivated possesses
porous surfaces with hierarchical architectures (where the porosity
increases upon activation process); it contains Ni2+ and Ni3+ ; it
has Ni3 S2 along with NiO, where the porous structure can afford
abundant active sites, and that possibly enhance its much high ac-
tivity for HER. The activity for HER can be enhanced by integrating
rGO with Ni3 S2 . The Ni3 S2 -rGO (η10 : − 44 mV) [67] exhibits much
high HER activity. The Ni3 S2 -rGO possesses porous architecture; it
is composed of ultrathin rhombohedral Ni3 S2 nanosheets, which
are homogeneously dispersed on the rGO sheets; it contains Ni, S,
and C, which are uniformly distributed, and that possibly enhances
its considerably much high activity for HER. The activity for HER
can be enhanced by preparing nanostructured ultrathin metallic
nickel. The NiS2 activated (η10 : − 67 mV) [68] exhibits much high HER
activity. The NiS2 activated possesses ultrathin nanosheets like mor-
phology; it is composed of predominant Ni0 , which are enwrapped
by a thin-layer of Ni(OH)2 , which can provide abundant active
sites, and that possibly enhances its much high activity for HER.
148 J. Mohammed-Ibrahim, X. Sun / Journal of Energy Chemistry 34 (2019) 111–160
Fig. 40. V based electrocatalyst for HER (reproduced with permission): (a) SEM im-
age of V-Ni3 S2 NW7000 cycles , and (b) polarization curves of V-Ni3 S2 NW7000 cycles be-
fore and after 20 0 0 cycles of CV [42] (Copyright 2017, American Chemical Society).
Preparing nanostructured Ni5 P4 can enhance the activity for
HER. The Ni5 P4 (η10 : − 47 mV) [71] exhibits much high HER activ-
ity. The Ni5 P4 possesses flower-like micro-balls structure (Diam-
eter: 12 μm), where the micro-balls are further possesses nano-
plates like morphology, which can afford abundant active sites;
it contains hexagonal Ni5 P4 ; it contains Ni and P, which are uni-
formly distributed; it exhibits high energy (001) facet with surface
energy of 1.590 J m−2 , which could facilitate the inherent catalytic
activity of each Ni site; it exhibits high conductivity, and that pos-
sibly enhance its significantly much high activity for HER. Inte-
grating Ni(OH)2 with Ni3 N can enhance the activity for HER. The
Ni(OH)2 –Ni3 N (η20 : − 72 mV) [72] exhibits much high HER activity.
The Ni(OH)2 –Ni3 N possesses nanosheet like morphology; it is com-
posed of crystalline Ni3 N, which is covered by ultrathin amorphous
Ni(OH)2 layer with thickness of 2–3 nm; it contains Ni, N, and
O, which are uniformly distributed, and that possibly enhance its
much high activity for HER. The activity for HER can be enhanced
by preparing nanostructured Ni − carbon composite with high Ni0
ratio. The NiOx @CNTs NiOx @CNTs (η10 : ∼− 79 mV) [73] exhibits
much high HER activity. The NiOx @CNTs is composed of metallic Ni
(Ni0 ) nanoparticles, which are integrated with bamboo-like carbon
nanotubes, while it possesses a unique interface between Ni and
NiO, where the bulk Ni0 and the Ni0 on the interface of Ni/NiO
can facilitate HER activity; it contains N and C, which are uni-
formly distributed; it contains graphitic carbon, Ni and NiO phases;
it exhibits C = C at 284.5 eV, C − C at 285.4 eV, and C − N − C at
∼287.0 eV, where the N − doping in C can prevent the agglomer-
ation of metal particles, which could improve the dispersion of
metal particles; it possesses high structural defects (ID /IG : 1.33),
which could be due to the N−doping in C; it exhibits high sur-
face area (314 m2 g−1 ), and that possibly enhance its much high
activity for HER.
Preparing thin CoOx on nanostructured CoP can form CoP/CoOx
homojunction, and that enhances the activity for HER. The CoP
NWs/CoOx (η10 : − 65 mV) [76] exhibits much high HER activity. The
CoP NWs/CoOx possesses nanowire morphology; it is composed of
CoP, which is surrounded by thin CoOx layer (Diameter: 3 nm);
it contains CoP/CoOx interface, and that provides abundant active
sites, and that possibly enhances its much high activity for HER.
The activity for HER can be enhanced by integrating CoP with
CNTs. The CoP/CNTs (η10 : − 76 mV) [79] exhibits much high HER
activity.
Preparing nanostructured transition-bimetallic phosphides can
provide synergistic effect from bimetals, which can enhance the
activity for HER. The NiCo2 Px NW (η10 : − 58 mV) [35] exhibits
much high HER activity. The NiCo2 Px NW possesses nanowire mor-
phology; it contains hexagonal NiCoP and CoP phases; it contains
Ni, Co, and P, which are uniformly distributed; it contains Ni2+ ,
Ni3+ , Co2+ , Co3+ , PO4 3− , and P3− , where the nanostructure can af-
ford abundant active sites, while the Ni and Co can provide syn-
ergistic effect, and that possibly enhance its much high activity for
HER. The activity for HER can be enhanced by preparing nanostruc-
tured nickel − cobalt nitride integrated with N-doped carbon. The
CoN/Ni3 N@NC (η10 : − 68 mV) [85] exhibits much high HER activ-
ity. The CoN/Ni3 N@NC possesses nanograss architecture, where the
nanograss is composed of stacked nanoparticles; it contains cubic
CoN, hexagonal Ni3 N, and N-doped carbon; it contains Co0 , Co2+ ,
Co3+ , Ni0 , Ni+ , Ni2+ , C = C, C − N, C = N, metal − N, pyridinic N,
pyrrolic N, and quaternary N, and that possibly enhance its much
high activity for HER.
Integrating NiFe LDH with defective graphene can enhance the
activity for HER. The NiFe LDH@def-Gr (η10 : ∼− 67 mV) [56] ex-
hibits much high HER activity. The NiFe LDH@def-Gr is composed
of NiFe LDH nanosheet, which are homogeneously distributed on
def-Gr, where the NiFe LDH exhibits single crystalline; it con-
tains Ni2+ , and Fe3+ ; it exhibits ID /IG ratio of 1.06, which suggests
the existence of the defects and disorders; it exhibits high de-
fect density (3.4 × 1012 cm−2 ), and that possibly enhance its much
high activity for HER. Preparing Ni(OH)2 on Fe2 P can enhance
the activity for HER. The Ni(OH)2 -Fe2 P (η10 : − 76 mV) [98] exhibits
much high HER activity. The Ni(OH)2 -Fe2 P is composed of amor-
phous Ni(OH)2 , which is deposited on crystalline Fe2 P; it possesses
nanoarray structure; it contains Fe, Ni, P, and O, which are uni-
formly distributed, and that possibly enhance its much high ac-
tivity for HER. Preparing boron-rich surface can have appropriate
binding energy for desorption and chemisorption of intermediates
with hydrogen, which can enhance the activity for HER. The FeB2
(η10 : − 61 mV) [23] exhibits much high HER activity. The FeB2 is
composed of hexagonal FeB2 phase; it possesses nanoparticle mor-
phology; it exhibits high surface area (51 m2 g−1 ); it contains
Fe and B, which are uniformly distributed, where the boron-rich
surface acquires appropriate binding energy for desorption and
chemisorption of intermediates with hydrogen, and that possibly
enhance its high activity for HER.
Tuning the thickness of the shell in the core–shell nanostruc-
ture can enhance the activity for HER. The NiCu@C (η10 : − 74 mV)
[102] exhibits much high HER activity. The NiCu@C is composed of
metallic NiCu alloy nanoparticles, which are enwrapped by hexag-
onal carbon shells; it exhibits nearly ideal GH ∗ (− 0.03 eV), and
that possibly enhances its much high activity for HER. The activ-
ity for HER can be enhanced by preparing copper − nickel bimetal-
lic nitrides. The Cux Ni4- x N (η10 : − 12 mV) [27] exhibits substantially
much high HER activity, which is even higher HER activity than
 J. Mohammed-Ibrahim, X. Sun / Journal of Energy Chemistry 34 (2019) 111–160 149

Fig. 41. Metal free based electrocatalyst for HER (reproduced with permission): (a) Schematic diagram illustrates the fabrication of NS-C along with N–C, N,B-C, and N,P-C,
where R-SH represents 2-mercaptoethanol (In doped graphene models. green: C; pink: B; blue: N; red: O; yellow: S; purple: P), (b) TEM image of NS-C, and (c) magnified
TEM image of NS-C [128] (Copyright 2017, American Chemical Society).

Pt/C [34] (η10 : − 33 mV). The Cux Ni4- x N is composed of nanopar-
ticles morphology, where Cu, Ni and N are uniformly distributed;
it contains Cu4 N and Ni4 N phases; it contains Ni2+ , Ni0 , Cu2+ , and
Cu0 , and that possibly enhances its significantly much high activity
for HER.
Preparing nickel tungsten oxide can enhance the activity for
HER. The oxides of NiW0.1 M KOH (η10 : − 60 mV) [38] exhibit much
high HER activity than the NiO and WO3 . Oxides of NiW compos-
ite with 1:2 ratio of Ni and W exhibits higher HER activity than the
other composites (2:1, 1:1, 3:1 and 1:3 ratio of Ni and W), while
the oxides of NiW composites prepared using higher molar ratios
of W (1:2 and 1:3 ratio of Ni and W) are composed of WO3 and
NiWO4 whereas the other composites (2:1, 1:1, and 3:1 ratio of Ni
and W) are composed of NiO, WO3 , NiWO4 and W3 O9 .
For HER in 1.0 M KOH, Mo based earth abundant elec-
trocatalysts such as NiMo1M NaOH (η10 : − 10 mV) [26], NiMo
(η10 : − 18 mV) [28], NiMo3 S4 /Ni3 S2 (η10 : − 23.4 mV) [29], CdS-
MoO3 /Ni3 S2 (η10 : − 30 mV) [30], Ni3 N–NiMoN (η10 : − 31 mV)
[31], Ni-(MoS2 -GO)1 M NaOH (η10 : − 33 mV) [32], and NiMo NS
(η10 : − 35 mV) [33] exhibit substantially much high HER ac-
tivity, and those are higher or well comparable with the HER
activity of Pt/C [34] (η10 : − 33 mV). Moreover, Mo based earth
abundant electrocatalysts such as SN-MoP/G (η10 : − 49 mV)
[114], Co9 S8 –NC@MoS2 (η10 : − 67 mV) [129], Mo2 C–NP-rGO
(η10 : − 71 mV) [130], Mo2 C/C (η10 : − 71 mV) [110], NiMo-EDA
(η10 : − 72 mV) [115], 1T-MoS2 /Ni2+δ Oδ (OH)2−δ (η10 : − 73 mV) [117],
and Mo-Ni2 P NW (η10 : − 78 mV) [39] exhibit much high HER
activity, while those are even lesser than − 100 mV. The activity for
HER can be enhanced by preparing nanostructured molybdenum
carbide. The Mo2 C/C (η10 : − 71 mV) [110] exhibits much high HER
activity. The Mo2 C/C is composed of β -Mo2 C nanoparticles, which
are embedded on fiber cloth, which can afford abundant active
sites; it contains Mo and C, which are uniformly distributed; it
contains Mo2+ , which could be attributed to the Mo2 C, while
it also contains MoO3 and MoO2 due to the exposure to air; it
possesses hydrophilic surface, which can facilitate the release
of gas, and that possibly enhance its much high activity for
HER.
Preparing hetero-atoms doped nanostructured molybdenum
phosphide integrated with carbon can enhance the activity for
HER. The SN-MoP/G (η10 : − 49 mV) [114] exhibits much high HER
activity. The SN-MoP/G is composed of S, N co-doped hexagonal
MoP with rod-shaped nanocrystallites, which are embedded on
graphene; it contains MoP, P-S, P-C, P-O and P-N/PON; it contains
-C-S/-C-SO, -C-SO2 , Mo-N, MoS2 , pyridinic-N, pyrrolic-N, graphitic-
N and –SCN; it contains Mo4+ , and Moδ + (0 < δ ≤ 4), which can af-
ford abundant active sites and high conductivity, and that possi-
bly enhances its much high activity for HER. The activity for HER
can be enhanced by preparing nanostructured Mo doped Ni2 P. The
Mo-Ni2 P NW (η10 : − 78 mV) [39] exhibits much high HER activity.
150 J. Mohammed-Ibrahim, X. Sun / Journal of Energy Chemistry 34 (2019) 111–160
The Mo-Ni2 P NW is composed of Mo doped crystalline Ni2 P; it
possesses nanowire morphology; it contains Mo, Ni, and P, which
are uniformly distributed, and the atomic ratio of Mo, Ni, and P in
Mo-Ni2 P NW are 0.43:1.57:1; it exhibits high conductivity, where
the synergistic effect between Mo and Ni can afford abundant ac-
tive sites, and that possibly enhances its much high activity for
HER.
Preparing nanoporous structured NiMo alloy can considerably
enhance the activity for HER. Our group [26] has fabricated NiMo
alloy with ultrahigh HER activity (η of − 10 mV at − 10 mA cm−2 in
1.0 M NaOH), which is the lowest η among those ever reported for
non-noble-metal electrocatalysts [3], while it outperforms the no-
ble Pt/C at higher current density, which depicts its outstanding
HER activity. The NiMo alloy possesses nanoporous morphology,
while it is composed of crystalline Ni4 Mo, which can afford abun-
dant active sites and facilitate the release of gas, and that possi-
bly enhance its significantly much high activity for HER. Moreover,
the NiMo (η10 : − 18 mV) [28] exhibits significantly much high HER
activity. The NiMo is composed of predominant NiMo phase with
tiny amount of Ni4 Mo phase, where Mo4+ and Mo6+ are negli-
gibly observed, which suggests the almost complete reduction of
oxides; it possesses porous structure, which can afford abundant
active sites and facilitate the release of gas, and that possibly en-
hance its substantially much high activity for HER. Preparing ul-
trathin nanostructured Ni4 Mo alloy with superaerophobic surface
can facilitate the release of gas, which can considerably enhance
the activity for HER. Our group [33] has fabricated ultrathin NiMo
NS (η10 : − 35 mV), which exhibits considerably much high HER ac-
tivity. The NiMo NS possesses ultrathin nanosheet like morphology
with thickness of 2.0 − 2.1 nm, which corresponds to ≈ 10 atomic
layers of (001) crystalline lattice; it contains Ni and Mo, which are
uniformly distributed; it is composed of body-centered tetragonal-
phase of Ni4 Mo with (001) facet exposed; it contains Ni0 and Mo0 ;
it contains suitable surface electronic structure, which can enhance
the electron/mass transfer; it possesses superaerophobic nanos-
tructured surface, which facilitate the release of gas, and that pos-
sibly enhance its considerably much high activity for HER. Deco-
rating secondary amines with Ni4 Mo alloy can decrease the charge
transfer resistance and modulate the electronic structures of inter-
facial active sites, and that can enhance the activity for HER. The
NiMo-EDA (η10 : − 72 mV) [115] exhibits much high HER activity.
The NiMo-EDA is composed of Ni4 Mo phase, which is decorated by
ethylenediamine; it possesses aggregated nanoparticles morphol-
ogy; it exhibits low charge transfer resistance, high conductivity,
and high electrochemically active surface area, and they observed
that the NiMo decorated with EDA exhibits a downshift of ∼ 0.4 eV
in the binding energies of both Ni 2p and Mo 3d, while after 10 h
of HER, the NiMo-EDA still retains the modulated oxidation states
of NiMo by the amine modifications, which suggests its preserved
catalytic effect for long-term HER, and that possibly enhances its
much high activity for HER.
The activity for HER can be enhanced by preparing
nanostructured NiMo3 S4 /Ni3 S2 interface. The NiMo3 S4 /Ni3 S2
(η10 : − 23.4 mV) [29] exhibits substantially much high HER activity.
The NiMo3 S4 /Ni3 S2 contains NiMo3 S4 and Ni3 S2 phases; it pos-
sesses flake like morphology; it contains NiMo3 S4 /Ni3 S2 interface,
and that possibly enhances its considerably much high activity
for HER. Integrating nanostructured CdS, MoO3 , and Ni3 S2 can
provide high conductivity and electrochemically active surface
area, and that can enhance the HER activity. The CdS-MoO3 /Ni3 S2
(η10 : − 30 mV) [30] exhibits considerably much high HER activity.
The CdS-MoO3 /Ni3 S2 is composed of Ni3 S2 nanoarrays, which
are covered by MoO3 nanosheets, which forms a Ni3 S2 /MoO3
core/shell structure, where thin CdS is decorated on Ni3 S2 /MoO3 ;
it possesses conifer-like hierarchical nanoarray structure; it con-
tains Cd, Ni, Mo, O and S, which are uniformly distributed; it
contains Mo5+ and Mo6+ , where the presence of Mo5+ could be
due to the existence of oxygen vacancies; it exhibits high elec-
trochemically active surface area (Cdl : 117.09 mF cm−2 ); it affords
high conductivity, and that possibly enhances its considerably
much high activity for HER. Integrating Ni with MoS2 -GO com-
posite can enhance the conductivity and electrochemically active
surface area, and that can enhance the activity and durability for
HER. The Ni-(MoS2 -GO)1 M NaOH (η10 : − 33 mV) [32] exhibits sig-
nificantly much high HER activity. The Ni-(MoS2 -GO) is composed
of nickel particles (∼50 nm), which are homogenously distributed
on the MoS2 /GO lamellae; it contains Ni, Mo, S and C, which are
uniformly distributed; it contains predominant Mo4+ with small
amount of Mo6+ ; it contains C–C, C = C and C–O bonds; it exhibits
high electrochemically active surface area (Cdl : 77 mF cm−2 ) and
conductivity, and that possibly enhance its considerably much
high activity for HER.
Integrating nanostructured NiOOH with MoS2 can afford syn-
ergetic effect, and that can enhance the activity for HER.
The 1T-MoS2 /Ni2+δ Oδ (OH)2−δ (η10 : − 73 mV) [117] exhibits much
high HER activity. The 1T-MoS2 /Ni2+δ Oδ (OH)2−δ is composed
Ni2+δ Oδ (OH)2−δ nanoparticles, which are anchored on the 2D 1T-
MoS2 ultrathin nanosheet, where 1T-MoS2 is comprised of metal-
lic 1T phase of the MoS2 while Ni2+δ Oδ (OH)2−δ is composed of
amorphous Ni(OH)2 and crystalline γ -NiOOH nanoparticles, and
the 1T-MoS2 /Ni2+δ Oδ (OH)2−δ contains Ni, Mo, S, and O, which are
uniformly distributed, and they attributed a bifunctional mecha-
nism, where Ni2+δ Oδ (OH)2−δ nanoparticles with suitable binding
strength to H2 O and OHad enhances the adsorption/dissociation
of H2 O, which affords protons to the nearby active sites on
1T-MoS2 , where 1T-MoS2 involves the electron transfer, adsorp-
tion/combination of intermediates of hydrogen and desorption of
hydrogen gas via a Heyrovsky step, and that possibly enhance its
much high activity for HER.
Preparing nanostructured Ni3 N–NiMoN can afford abundant ac-
tive sites and metallic characteristic, and that can enhance the ac-
tivity for HER. The Ni3 N–NiMoN (η10 : − 31 mV) [31] exhibits con-
siderably much high HER activity. The Ni3 N–NiMoN exhibits in-
terface between the (100) face of Ni0.2 Mo0.8 N and (111) face of
Ni3 N; it possesses nanosheet morphology, which is further com-
posed of nanoparticles, which can afford abundant active sites; it
contains Mo, Ni and N, which are uniformly distributed; it contains
Ni+ , Ni2+ , Mo+3 , Mo+4 , Mo+6 , N − Ni/Mo, and N − H; it exhibits
high electrochemically active surface area (Cdl : 241 mF cm−2 ); it
exhibits very tiny (−0.03 eV) Gibbs free energy for H adsorption
(GH ∗ ), which is almost close to the optimal GH ∗ of 0 eV; it pos-
sesses lower water adsorption energy (−0.62 eV); it shows the con-
tinuous distribution of the density of states near the Fermi level,
which suggests its metallic characteristic with high electrical con-
ductivity, which can enhance the fast electron transport, and that
possibly enhance its considerably much high activity for HER.
The activity for HER can be enhanced by preparing Mo and S
co-doped NiSe. The Mo-S-NiSe (η10 : − 88 mV) [122] exhibits much
high HER activity. The Mo-S-NiSe is composed of Mo and S, which
are co-doped in NiSe; it possesses nanosheet morphology; it con-
tains Ni2+ , Mo4+ , S2 2− , and S2− , and that possibly enhance its
much high activity for HER.
Preparing nanostructured Mn doped Ni2 P can enhance the ac-
tivity for HER. The Mn-Ni2 P NS (η20 : − 103 mV) [40] exhibits much
high HER activity. The Mn-Ni2 P NS possesses porous nanosheet
morphology; it is composed of Mn doped cubic Ni2 P; it contains
Mn, Ni, and P, which are uniformly distributed; it contains Mn2+
and Ni2+ , and that possibly enhances its much high activity for
HER.
The activity for HER can be enhanced by preparing NiZnP with
Ni(OH)2 and tiny amount of Zn. The etched-NiZnP (η10 : − 50 mV)
[41] exhibits much high HER activity. The etched-NiZnP possesses
 J. Mohammed-Ibrahim, X. Sun / Journal of Energy Chemistry 34 (2019) 111–160 151

Table 2. Comparison of long term stability (Part 1: 24 h to 600 h of duration) of various kinds of reported earth abundant electrocatalysts with Pt/C for hydrogen evolution
reaction (HER) in 1.0 M KOH alkaline electrolyte.

HER electrocatalysts ChrAmp ChrPot Dur (h) Remark after stability test Ref.
∗
Pt/C1 M NaOH YES NA ∼10 ∼50% R [60]
∗
Pt/C NA YES 24 79% R at − 10 mA cm−2 [85]
Co(OH)2 @NCNTs NA YES 600 NDa at − 10 mA cm−2 [53]
NiMo YES NA 300 RS at η of − 200 mV [28]
NP-SS YES NA 134.4 ND at η of − 230 mV [54]
WO3- x NS NA YES 105 ND at − 10 mA cm−2 [104]
NiMo-EDA YES NA 100 RS at η of − 200 mV [115]
NC/CuCo/CuCoOx YES NA 100 ND at η of − 150 mV [57]
NiFe LDH@NiCoP NA YES 100 RS at − 10 mA cm−2 [97]
Se-(NiCo)Sx /(OH)x YES NA 80 ND [121]
NiS2 /CoS2 –O NW NA YES 70 RS at − 10 mA cm−2 [93]
Cux Ni4- x N NA YES 65 RS at − 20 mA cm−2 [27]
Ni/MoC2 @NC NA YES 60 RS at − 10/ − 30/ − 50 mA cm−2 [112]
NiMoS4 0.1 M KOH YES NA 50 RS at η of − 220 mV [116]
Mo2 C/C YES NA 50 RS at η of − 100 mV [110]
CoP NS YES NA 50 RS at η of − 106 mV [75]
MoNiNC0.1 M KOH NA YES 48 RS at − 50/ − 100 mA cm−2 [118]
Cu@NiFe LDH YES NA 48 RS at η of − 162 mV [37]
WN NW NA YES ∼41.5 RS at − 20 mA cm−2 [105]
NiS2 NA YES 40 ND at − 20 mA cm−2 [68]
Ni-rGO1M NaOH NA YES 40 RS at − 250/ − 100 mA cm−2 [61]
MoP/CNTs NA YES 40 27 mV decay at − 10 mA cm−2 [113]
WP/W NA YES ∼37 RS [106]
CoP NWs/CoOx YES NA 35 93.7% R at η of − 150 mV [76]
1T-MoS2 /Ni2+δ Oδ (OH)2−δ NA YES 30 12 mV decay at − 10 mA cm−2 [117]
Ni(OH)2 –CoS2 NW YES NA 30 ND at η of − 98 mV [94]
NiCo2 Px NW YES NA 30 ND at η of − 100 mV [35]
NiCo2 O4 @C1 M NaOH NA YES 30 ∼22 mV decay at − 10 mA cm−2 [92]
Ni1M NaOH YES NA 27.7777 RS [60]
Ni(OH)2 –Ni3 N YES NA 25 ND at η of − 106 mV [72]
Ni3 S2 YES NA 25 RS at η of − 120 mV [65]
Mn-Ni2 P NS YES NA 25 RS at η of − 140 mV [40]
(Mo2 C)0.34 -(WC)0.32 -QDs/NG YES NA 25 RS at η of − 90 mV [107]
Nix S NA YES 25 RS at − 50 mA cm−2 [70]
Ni58 Co42 1 M NaOH NA YES 25 RS at − 10 mA cm−2 [36]
CoN/Ni3 N@NC NA YES 24 94% R at − 10 mA cm−2 [85]
CdS-MoO3 /Ni3 S2 YES NA 24 RS at η of − 30 mV [30]
Ni3 S2 YES NA 24 RS at − 48 mV [55]
Mo2 C/C–N0.1 M KOH YES NA 24 ND [132]
Mo-Ni2 P NW NA YES 24 RS at − 10 mA cm−2 [39]
etched-NiZnP YES NA 24 RS at η of − 100 mV [41]
Co-Ni3 N NA YES 24 ND at − 10/ − 20/ − 30/ − 40/ − 50 mA cm−2 [87]
FeB2 YES NA 24 97% R at η of − 100 mV [23]

HER test performed in 1 M NaOH/0.1 M KOH is indicated on the electrocatalyst name. Chr Amp = Chronoamperometry; Chr Pot = Chronopotentiometry; Dur = duration
for stability test; ∗ = Non-earth-abundant electrocatalyst for HER and its corresponding stability retention calculated from the graph; NA = Not Applicable; R = Retention;
ND: Negligible decay; RS = Reasonable stability; NWs: Nanowires; rGO: reduced graphene oxide; EDA: Ethylenediamine; NS: Nanosheet; dr: Defect rich; nb: Nano-belt;
NW: Nano-wire; hms: hollow microspheres; QDs: Quantum Dots; G: Graphene; CNTs: Carbon Nano-Tubes; NCNHP: N-doped carbon nanotube hollow polyhedron; LDH:
Layered Double Hydroxide; NDa at 10 mA cm−2 : Negligible decay at 10 mA cm−2 , while the HER activity further improved after 600 h that is η10 decreased from − 170 mV
to ∼− 115 mV; def-Gr: defective graphene; NTs: Nanotubes; SS: Stainless steel.

rimose like morphology; it is composed of Ni83 Zn3 P13 ; it contains
metallic Ni, Ni(OH)2 , NiPx , ZnPx , P, POx , Zn and ZnO, where the
Ni(OH)2 is formed instead of NiO after H2 SO4 etching, and that
possibly enhance its much high activity for HER.
Doping V in Ni3 S2 can enhance the activity for HER. The V-
Ni3 S2 NW7000 cycles (η10 : − 68 mV) [42] exhibits much high HER ac-
tivity. The V-Ni3 S2 NW7000 cycles possesses nanowire morphology;
it is composed of V doped crystalline Ni3 S2 , and that possibly en-
hances its much high activity for HER.
2.11. Stability of earth abundant electrocatalysts for HER
Comparison of long term stability of various kinds of reported
earth abundant electrocatalysts with Pt/C for HER in 1.0 M KOH
alkaline electrolyte are presented in Table 2 (Part 1: 24 h to
600 h of duration), and Table 3 (Part 2: 2.7777 h to 20 h of du-
ration) [20,21,23,27–32,35–42,45,53–57,60–62,64,65,68–70,72,73,
75–77,80–85,87–89,91–102,104–110,112–127,129–133,135–139]. For
HER in 1.0 M KOH, earth abundant electrocatalysts such as
Co(OH)2 @NCNTs (600 h) [53], NiMo (300 h) [28], NP-SS (134.4 h)
[54], NiFe LDH@NiCoP (100 h) [97], WO3- x NS (105 h) [104], NiMo-
EDA (100 h) [115], NC/CuCo/CuCoOx (100 h) [57], Se-(NiCo)Sx /(OH)x
(80 h) [121], NiS2 /CoS2 –O NW (70 h) [93], and Ni-rGO1M NaOH (40 h)
[61] exhibit substantially much high stability for HER, and those
are much higher stability than the stability of Pt/C [85] (79%
retention at − 10 mA cm−2 after 24 h).
Preparing porous ultrathin Co(OH)2 nanosheets on N − doped
CNTs can significantly enhance the stability for HER. For HER
in 1.0 M KOH, the Co(OH)2 @NCNTs [53] exhibits negligible de-
cay at − 10 mA cm−2 for 600 h (Fig. 42a), while its HER activ-
ity increases during stability test (η10 decreases from − 170 mV to
∼− 115 mV), which suggests that it gets activated during long-term
HER, and that indicates its substantially much high stability for
HER. The porous Co(OH)2 @NCNTs is composed of Co(OH)2 ultra-
thin nanosheets, which are grown on the N−doped CNTs; it con-
tains C, Co, O and N, where N and C are uniformly distributed
in the region of NCNT, while Co and O are homogenously dis-
tributed on the complete region, where the ultrathin porous struc-
152 J. Mohammed-Ibrahim, X. Sun / Journal of Energy Chemistry 34 (2019) 111–160

Table 3. Comparison of long term stability (Part 2: 2.7777 h to 20 h of duration) of various kinds of reported earth abundant electrocatalysts with Pt/C for hydrogen
evolution reaction (HER) in 1.0 M KOH alkaline electrolyte.

HER electrocatalysts ChrAmp ChrPot Dur (h) Remark after stability test Ref.
∗
Pt/C1 M NaOH YES NA ∼10 ∼50% R [60]
∗
Pt/C NA YES 24 79% R at − 10 mA cm−2 [85]
Mo2 C–NP-rGO YES NA 20 88.6% R at η of − 80 mV [130]
Ni(OH)2 -Fe2 P YES NA 20 ND at η of 76 mV [98]
NiMo3 S4 /Ni3 S2 YES NA 20 RS at η of − 96 mV [29]
Mo2 C/C NS YES NA 20 RS at η of − 130 mV [45]
dr-MoN YES NA 20 RS at η of − 150 mV [135]
CoMoO4 NW YES NA 20 ND at η of − 184 mV [109]
Ni-(MoS2 -GO)1 M NaOH NA YES 20 RS at − 100 mA cm−2 [32]
MoSe2 @Ni0.85 Se NW YES NA 20 RS at η of − 124.5 mV [123]
SN-MoP/G YES NA 20 RS [114]
MoS2 /NiS/MoO3 YES NA 20 RS at η of − 106 mV [136]
CoP/NCNHP YES NA 20 RS at η of − 120 mV [81]
Ni3 FeN YES NA 20 ND at η of − 180 mV [95]
Ni3 N–NiMoN YES NA 20 ND [31]
V-NiS2 NA YES 20 RS at − 10 mA cm−2 [127]
P8.6 –Co3 O4 NW YES NA 20 ND at η of − 140 mV [83]
Fe-Co3 O4 /CNTs YES NA 20 RS at η of − 140 mV [100]
NiSe2 /Fe3 Se4 /C YES NA 20 ND at η of − 160 mV [124]
Co4 Ni1 P NTs YES NA 20 ND at η of − 129/ − 188 mV [89]
Co(S0.71 Se0.29 )2 /C NA YES 20 ND at − 10 mA cm−2 [120]
Co9 S8 @NOSC YES NA 20 RS [88]
NiS2 hms NA YES 19 RS at − 10 mA cm−2 [69]
Ni3 Co-G0.5 M KOH NA YES 16 RS at − 10 mA cm−2 [91]
P-Mo2 C@NC YES NA 12 RS at − 190 mV [131]
Mo-S-NiSe YES NA 12 RS at η of − 108 mV [122]
Co9 S8 –NC@MoS2 YES NA 12 RS at η of − 67 mV [129]
Ni/C3 N4 1M NaOH NA YES 12 ND at − 100 mA cm−2 [64]
V-Ni3 S2 NW9000 cycles NA YES 12 ND at − 20 mA cm−2 [42]
Co6.25 Fe18.75 Ni75 Ox NS NA YES 12 9.7 mV decay at − 20 mA cm−2 [99]
Ni/NiFeOOH NA YES 12 RS at − 10 mA cm-2 [101]
(Ni0.33 Fe0.67 )2 P NS YES NA 12 97.4% R at η of − 285 mV [21]
P-Co3 O4 YES NA 11.1111 RS at η of − 120 mV [84]
Mo2 C YES NA 11 RS at η of − 140 mV [137]
Zn-Co-S YES NA 10 91.7% R [126]
Mo1 N1 C2 0.1 M KOH NA YES 10 RS at − 10 mA cm−2 [133]
NiCu@C YES NA 10 RS at η of − 150 mV [102]
CoP/C YES NA 10 RS at η of − 163 mV [80]
NiSe2 NS NA YES 10 RS at − 10 mA cm−2 [119]
NiOx @CNTs YES NA 10 ∼90 R [73]
Ni3 FeN/rGO YES NA 10 ND at η of − 120 mV [96]
Co/CoP-NC NA YES 10 RS at − 10 mA cm−2 [20]
δ -MnO2 NS YES NA 10 RS at η of − 196 mV [125]
Co2 P@Co3 O4 NA YES 8 ND at − 10 mA cm−2 [77]
Co2 P@NPC YES NA 5.5555 RS at η of − 190 mV [82]
Ni-rGO1M NaOH NA YES 5.5555 RS at − 100 mA cm−2 [62]
NiFe LDH@def-Gr YES NA 5.5555 RS at η of − 300 mV [56]
α -MoO3- x 0.1 M KOH YES NA 4 RS at η of − 140 mV [108]
MoS2 /Co3 O4 YES NA 4 RS at η of − 170 mV [138]
NiW0.1 M KOH YES NA 3 RS at η of − 150 mV [38]
N-Mo2 C nb YES NA 2.7777 73% R at η of − 130 mV [139]

HER test performed in 1 M NaOH/0.1/0.5 M KOH is indicated on the electrocatalyst name. Chr Amp = Chronoamperometry; Chr Pot = Chronopotentiometry; Dur = duration
for stability test; ∗ = Non-earth-abundant electrocatalyst for HER and its corresponding stability retention calculated from the graph; NA = Not applicable; R = Retention;
ND: Negligible decay; RS = Reasonable stability; NWs: Nanowires; rGO: reduced graphene oxide; EDA: Ethylenediamine; NS: Nanosheet; dr: Defect rich; nb: Nano-belt; NW:
Nano-wire; hms: hollow microspheres; QDs: Quantum dots; G: Graphene; CNTs: Carbon nano-tubes; NCNHP: N-doped carbon nanotube hollow polyhedron; LDH: Layered
Double Hydroxide; NDa at 10 mA cm−2 : def-Gr: defective graphene; NTs: Nanotubes.

ture can afford abundant active sites and facilitate gas release,
and that possibly enhance its considerably much high stability for
HER.
The stability for HER can be considerably enhanced by prepar-
ing porous structured NiMo alloy. For HER in 1.0 M KOH, the NiMo
[28] the NiMo exhibits significantly much high stability (reason-
able stability at η of − 200 mV for 300 h). The NiMo is composed of
predominant NiMo phase with tiny amount of Ni4 Mo phase, where
Mo4+ and Mo6+ are negligibly observed, which suggests the almost
complete reduction of oxides; it possesses porous structure, which
can afford abundant active sites and facilitate the release of gas,
and that possibly enhance its substantially much high stability for
HER.
N,P dual doping on etched stainless steel can enhance the sta-
bility for HER. For HER in 1.0 M KOH, the NP-SS [54] exhibits sig-
nificantly much high stability (negligible decay at η of − 230 mV for
134.4 h as shown in Fig. 42b). The NP-SS possesses nanosheet like
structure; it is composed of N, P dual doped SS, while it contains
austenite, γ N , and FeP phases; it contains pyridinic-N, where the
nanosheet like morphology with newly formed FeP phase along
with N and P dual doping can afford abundant active sites for HER,
and that possibly enhances its considerably much high stability for
HER.
Preparing NiFe LDH heterostructure can afford strong electronic
interactions at the interface, which can enhance the stability for
HER. For HER in 1.0 M KOH, NiFe LDH@NiCoP [97] exhibits signif-
 J. Mohammed-Ibrahim, X. Sun / Journal of Energy Chemistry 34 (2019) 111–160 153

icantly much high stability (Reasonable stability at − 10 mA cm−2

for 100 h). The NiFe LDH@NiCoP is composed of ultrathin NiFe
LDH nanosheets, which are grown on the surface of the NiCoP
nanowires; it contains Ni, Co, P, and Fe, which are uniformly dis-
tributed; it exhibits (111) and (012) planes for NiCoP and NiFe LDH,
respectively, at the interface with the lattice spacings of 0.22 and
0.23 nm, respectively, which indicates its sophisticated inner struc-
ture; it contains Ni-P, Ni-POx , Co-P, Co-POx , P3− , PO4 3− , whereas
when compared to the bare NiCoP, the peaks at Ni 2p3/2 , Co 2p3/2 ,
and P 2p are shifted to lower binding energies for NiFe LDH cou-
pled with NiCoP, which suggests the strong electronic interactions
at the NiFe LDH and NiCoP interface, and that possibly enhances
its considerably much high stability for HER.
Creating oxygen vacancies on the nanostructured electrocata-
lyst can improve the stability for HER. For HER in 1.0 M KOH, the
WO3- x NS [104] exhibits negligible potential decay at − 10 mA cm−2
for 105 h (Fig. 42c), which is considerably much high stability for
HER. The WO3- x NS exhibits W6+ state in oxides, while in addition,
it also exhibits W5+ and W4+ state in oxides, which could be due
to existence of oxygen vacancies, and the oxygen vacancies can en-
hance the adsorption of surface species, and that enhances charge
separation and charge transfer, and the polycrystalline WO3-x NS is
porous; it possesses nanosheet like morphology, which can facili-
tate active sites interaction, and that possibly enhances its remark-
ably much high stability for HER.
Decorating secondary amines with Ni4 Mo alloy can decrease
the charge transfer resistance and modulate the electronic struc-
tures of interfacial active sites, and that can enhance the stability
for HER. For HER in 1.0 M KOH, the NiMo-EDA [115] exhibits signif-
icantly much high stability (reasonable stability at η of − 200 mV
for 100 h). The NiMo-EDA is composed of Ni4 Mo phase, which are
decorated by ethylenediamine; it possesses aggregated nanoparti-
cles morphology; it exhibits low charge transfer resistance, high
conductivity, and high electrochemically active surface area, and
they observed that the NiMo decorated with EDA exhibits a down-
shift of ∼ 0.4 eV in the binding energies of both Ni 2p and
Mo 3d, while after 10 h of HER, the NiMo-EDA still retains the
modulated oxidation states of NiMo by the amine modifications,
which suggests its preserved catalytic effect for long-term HER,
and that possibly enhances its substantially much high stability for
HER.
The stability for HER can be enhanced by preparing Mott–
Schottky electrocatalyst (metal − semiconductor hybrid) en-
capsulated with carbon shell. For HER in 1.0 M KOH, the
NC/CuCo/CuCoOx [57] exhibits substantially much high stabil-
ity (negligible decay at η of − 150 mV for 100 h as shown in
Fig. 43a). The NC/CuCo/CuCoOx possesses porous nanowire like
morphology (Diameter: 20-50 nm); it is composed of CuCo/CuCoOx
(metal–semiconductor), which are enwrapped by the ∼5 nm thick
N-doped carbon shell, it contains Cu0 , Cu+ , Co0 , Co2+ , Co3+ , C − C,
C = O, C − N, pyridinic N, pyrrolic N, and metal − oxygen bond with
oxygen vacancies; it possesses high surface area (83.7 m2 g−1 ),
where the porous structure can afford large active surface area
with abundant active sites, while N-doped carbon can enhance Fig. 42. Long term stability for HER in 1 M KOH (Reproduced with permis-
conductivity and afford continuous electron transport for metal sion): (a) Chronopotentiometric curves of Co(OH)2 @NCNTs at − 10 mA cm−2 for
and semiconductor, and that possibly enhances its considerably 600 h [53] (Copyright 2018, Elsevier), (b) chronoamperometric curve of NP-SS at η
much high stability for HER. of − 230 mV for 134.4 h [54] (Copyright 2017, Wiley-VCH Verlag GmbH & Co. KGaA,
Weinheim), and (c) chronopotentiometric curve of WO3- x NS at − 10 mA cm−2 for
Preparing defect-rich nanostructured chalcogenides can en- 105 h [104] (Copyright 2018, Elsevier).
hance the stability for HER. For HER in 1.0 M KOH, the Se-
(NiCo)Sx /(OH)x [121] exhibits negligible decay for 80 h, which is
considerably much high stability for HER. The Se-(NiCo)Sx /(OH)x
possesses nanosheet like morphology with abundant edge sites; Creating oxygen vacancies in the nanostructured cobalt–nickel
it contains disorders and defects; it contains Ni, Co, O, S, and sulfide can enhance the stability for HER. For HER in 1.0 M KOH,
Se, which are uniformly distributed; it contains (NiCo)0.85 Se and the NiS2 /CoS2 –O NW [93] exhibits reasonable stability at − 10 mA
(NiCo)4 S3 phases, and that possibly enhances its much high stabil- cm−2 for 70 h, which is substantially much high stability for HER.
ity for HER. The NiS2 /CoS2 –O NW possesses porous nanowire morphology with
154 J. Mohammed-Ibrahim, X. Sun / Journal of Energy Chemistry 34 (2019) 111–160
Fig. 43. Long term stability for HER in 1 M KOH (Reproduced with permission):
(a) Chronoamperometric curve of NC/CuCo/CuCoOx at η of − 150 mV for 100 h
[57] (Copyright 2018, Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim). Durability
for HER in 1 M KOH (Reproduced with permission): Inset of (a) polarization curve
of NC/CuCo/CuCoOx before and after 50 0 0 cycles of CV [57] (Copyright 2018, Wiley-
VCH Verlag GmbH & Co. KGaA, Weinheim), (b) polarization curve of Ni3 S2 before
and after 10,0 0 0 cycles of CV [55] (Copyright 2018, American Chemical Society),
and (c) polarization curve of NiFe LDH@def-Gr before and after 8,0 0 0 cycles of CV
[56] (Copyright 2017, Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim).
pore volume of 0.064 cm3 g−1 and mesopores with diameter of
∼4 nm; it contains cubic NiS2 (space group: Pa–3), cubic CoS2
(space group: Pa–3), CoOx and NiO; it exhibits high oxygen va-
cancies, and that possibly enhances its much high stability for
HER.
The stability for HER can be enhanced by preparing nanostruc-
tured Ni-rGO composite by electrodeposition method under su-
pergravity field. For HER in 1.0 M NaOH, the Ni-rGO [61] exhibits
reasonable stability at − 250/ − 100 mA cm−2 for 40 h, which is sig-
nificantly much high stability for HER. The Ni-rGO composite ex-
hibits less adsorption free energy of H∗ (GH∗ : 0.31 eV); it is com-
posed of Ni nanoparticles and rGO sheets, which are homogenously
loaded on Ni foam, where the Ni nanoparticles are well dispersed
on rGO sheets, which can afford high surface area, good electri-
cal conductivity, and harmonious synergistic effect between rGO
sheets and Ni particles, and that possibly enhances its considerably
much high stability for HER.
Preparing nanostructured Mn doped Ni2 P can enhance the sta-
bility for HER. For HER in 1.0 M KOH, the Mn-Ni2 P NS [40] exhibits
reasonable stability at η of − 140 mV for 25 h, which indicates its
much high stability. The Mn-Ni2 P NS possesses porous nanosheet
morphology; it is composed of Mn doped cubic Ni2 P; it contains
Mn, Ni, and P, which are uniformly distributed; it contains Mn2+
and Ni2+ , and that possibly enhance its much high stability for
HER.
The stability for HER can be enhanced by preparing NiZnP
with Ni(OH)2 and tiny amount of Zn. For HER in 1.0 M KOH, the
etched-NiZnP [41] exhibits reasonable stability at η of − 100 mV af-
ter 24 h, which indicates its much high stability. The etched-NiZnP
possesses rimose like morphology; it is composed of Ni83 Zn3 P13 ;
it contains metallic Ni, Ni(OH)2 , NiPx , ZnPx , P, POx , Zn and ZnO,
where the Ni(OH)2 is formed instead of NiO after H2 SO4 etching,
and that possibly enhance its much high stability for HER.
Doping V can vary the electronic structure of pyrite NiS2 from
semiconductor to metallic property, which can enhance its stability
for HER. For HER in 1.0 M KOH, the V-NiS2 [127] exhibits reason-
able stability at − 10 mA cm−2 for 20 h, which indicates its much
high stability. The V-NiS2 is composed of V doped pyrite NiS2 ;
it contains Ni, V and S, which are uniformly distributed; it con-
tains V4+ and Ni2+ , and the V doping shifts the band gap from
0.41 eV to 0 eV, while its electrical resistivity increases with in-
crease in temperature, which suggests the V doping alters the elec-
tronic structure of pyrite NiS2 from semi conductor property to
metallic nature, and that possibly enhance its high stability for
HER.
2.12. Durability of earth abundant electrocatalysts for HER
Durability of various kinds of reported earth abun-
dant electrocatalysts for HER in 1.0 M KOH alkaline elec-
trolyte are presented in Table 4 (Part 1: 20 0 0-10,0 0 0 cy-
cles) and Table 5 (Part 2: 50 0-10 0 0 cycles) [28,29,31–
36,39,40,42,44–46,55–57,65,66,70-72,75-83,85,86,89,90,94,96,98–
111,113,114,116,117,120,122,123,126,128,129,132,133,135–139]. Prepar-
ing Ni3 S2 with nanorods@nanosheets homo-junction structure can
enhance the durability for HER. For HER in 1.0 M KOH, the Ni3 S2
[55] exhibits negligible decay after 10,0 0 0 cycles of CV (Fig. 43b),
which indicates its substantially much high durability. The Ni3 S2
is composed of crystalline Ni3 S2 ; it contains Ni2+ , and S2− ; it pos-
sesses sulfur vacancy, which can alter electronic structure of the
surface; it exhibits high conductivity; it possesses nanorods, which
are further coated by nanosheets, which forms the Ni3 S2 with
nanorods@nanosheets homo-junction, which can afford abundant
active sites, reduce the transport of electron, and facilitate the gas
release, and that possibly enhances its considerably much high
durability for HER.
 J. Mohammed-Ibrahim, X. Sun / Journal of Energy Chemistry 34 (2019) 111–160 155

Table 4. Durability of various kinds of reported earth abundant electrocatalysts for hydrogen evolution reaction (HER) in 1.0 M KOH alkaline electrolyte (Part 1: 20 0 0-10,0 0 0
cycles).

HER electrocatalysts Cycles of CV Remark after durability test Ref.

Ni3 S2 10 0 0 0 Negligible decay [55]

NiFe LDH@def-Gr 80 0 0 Negligible decay at − 200 mA cm−2 [56]
1T-MoS2 /Ni2+δ Oδ (OH)2−δ 50 0 0 Negligible decay at − 10 mA cm−2 [117]
CoP NWs/CoOx 50 0 0 Negligible decay at 10 mA cm−2 [76]
WP/W 50 0 0 Negligible decay at 100 mA cm−2 [106]
Mo2 C/C 50 0 0 Negligible decay at − 70 mA cm−2 [110]
NiCo2 Px NW 50 0 0 Negligible decay at − 250 mA cm−2 [35]
Mo2 C–C 50 0 0 17 mV decay [44]
MoP/CNTs 50 0 0 11 mV decay at − 10 mA cm−2 [113]
NC/CuCo/CuCoOx 50 0 0 Negligible decay at − 500 mA cm−2 [57]
Ni3 N–NiMoN 50 0 0 Negligible decay at − 125 mA cm−2 [31]
CoP/CNTs 50 0 0 Very slight decay [79]
Co2 C0.1 M KOH 40 0 0 Negligible decay at − 10 mA cm−2 [86]
Ni5 P4 3600 Negligible decay [71]
Mo2 C/C–N0.1 M KOH 30 0 0 Negligible decay [132]
CoP/C 30 0 0 Negligible decay at − 50 mA cm−2 [80]
WN NW 30 0 0 Negligible decay at − 10 mA cm−2 [105]
(Mo2 C)0.34 -(WC)0.32 -QDs/NG 30 0 0 Negligible decay at − 10 mA cm−2 [107]
β -Mo2 C@BCN1 M NaOH 30 0 0 Negligible decay at − 50 mA cm−2 [111]
CoP NS 30 0 0 21 mV decay [75]
Co4 Ni1 P NTs 30 0 0 Negligible decay at − 100 mA cm−2 [89]
Mo-Ni2 P NW 2500 Negligible decay at − 50 mA cm−2 [39]
Mo2 C/C NS 20 0 0 Slight decay at − 10 mA cm−2 [45]
dr-MoN 20 0 0 Negligible decay [135]
NiMo 20 0 0 Negligible decay at − 150 mA cm−2 [28]
NiCu@C 20 0 0 Negligible decay − 100 mA cm−2 [102]
WO3-x NS 20 0 0 Negligible decay [104]
Co9 S8 –NC@MoS2 20 0 0 Negligible decay at − 10 mA cm−2 [129]
Ni-(MoS2 -GO)1 M NaOH 20 0 0 10 mV decay at − 100 mA cm−2 [32]
MoS2 /Co3 O4 20 0 0 Negligible decay at − 10 mA cm−2 [138]
Ni3 S2 @Cuactivated 20 0 0 Negligible decay at − 200 mA cm−2 [66]
SN-MoP/G 20 0 0 Negligible decay at − 150 mA cm−2 [114]
Ni58 Co42 1 M NaOH 20 0 0 Very slight decay [36]
V-Ni3 S2 NW7000 cycles 20 0 0 Negligible decay [42]
Ni3 FeN/rGO 20 0 0 Negligible decay at − 10 mA cm−2 [96]
NC@CuCo2 Nx 20 0 0 Negligible decay at − 100 mA cm−2 [103]

HER test performed in 1 M NaOH/0.1 M KOH is indicated on the electrocatalyst name. CV = Cyclic voltammetry; NWs: Nanowires; rGO: NS: Nanosheet; dr: Defect rich;
nb: Nano-belt; NW: Nano-wire; QDs: Quantum dots; G: Graphene; CNTs: Carbon Nano-Tubes; NCNHP: N-doped carbon nanotube hollow polyhedron; def-Gr: defective
graphene; LDH: Layered Double Hydroxide; NTs: Nanotubes.

Doping P with nanostructured Co3 O4 can enhance the durabil-
ity for HER. For HER in 1.0 M KOH, the P8.6 –Co3 O4 NW [83] ex-
hibits negligible decay at − 200 mA cm−2 after 1000 cycles of CV,
which indicates its much high durability. The P8.6 –Co3 O4 NW pos-
sesses nanowire morphology; it is composed of P − doped crys-
talline Co3 O4 nanowire, which can provide abundant active sites; it
contains Co, P, and O, which are uniformly distributed; it contains
Co2+ and Co3+ , and that possibly enhances its much high durabil-
ity for HER.
Preparing nanostructured transition-bimetallic phosphides can
provide synergistic effect from bimetals, which can enhance the
durability for HER. For HER in 1.0 M KOH, the NiCo2 Px NW [35] ex-
hibits negligible decay at − 250 mA cm−2 after 50 0 0 cycles of CV,
which indicates its substantially much high durability. The NiCo2 Px
NW possesses nanowire morphology; it contains hexagonal NiCoP
and CoP phases; it contains Ni, Co, and P, which are uniformly dis-
tributed; it contains Ni2+ , Ni3+ , Co2+ , Co3+ , PO4 3− , and P3− , where
the nanostructure can afford abundant active sites, while the Ni
and Co can provide synergistic effect, and that possibly enhance
its significantly much high durability for HER.
The durability for HER can be enhanced by integrating NiFe
LDH with defective graphene. For HER in 1.0 M KOH, the NiFe
LDH@def-Gr [56] exhibits negligible decay at − 200 mA cm−2 af-
ter 80 0 0 cycles of CV (Fig. 43c), which indicates its significantly
much high durability. The NiFe LDH@def-Gr is composed of NiFe
LDH nanosheet, which are homogeneously distributed on def-Gr,
where the NiFe LDH exhibits single crystalline; it contains Ni2+ ,
and Fe3+ ; it exhibits ID /IG ratio of 1.06, which suggests the exis-
tence of the defects and disorders; it exhibits high defect density
(3.4 × 1012 cm−2 ), and that possibly enhances its remarkably much
high durability for HER.
The durability for HER can be enhanced by preparing
Mott–Schottky electrocatalyst (metal − semiconductor hybrid) en-
capsulated with carbon shell. For HER in 1.0 M KOH, the
NC/CuCo/CuCoOx [57] exhibits negligible decay at − 500 mA cm−2
after 50 0 0 cycles of CV (Fig. 43a), which indicates its remark-
ably much high durability. The NC/CuCo/CuCoOx possesses porous
nanowire like morphology (Diameter: 20–50 nm); it is composed
of CuCo/CuCoOx (metal–semiconductor), which are enwrapped by
the ∼5 nm thick N-doped carbon shell, it contains Cu0 , Cu+ ,
Co0 , Co2+ , Co3+ , C − C, C = O, C − N, pyridinic N, pyrrolic N, and
metal − oxygen bond with oxygen vacancies; it possesses high sur-
face area (83.7 m2 g−1 ), where the porous structure can afford
large active surface area with abundant active sites, while N-doped
carbon can enhance conductivity and afford continuous electron
transport for metal and semiconductor, and that possibly enhances
its considerably much high durability for HER.
Preparing nanostructured tungsten phosphide can enhance the
durability for HER. For HER in 1.0 M KOH, the WP/W [106] exhibits
negligible decay at − 100 mA cm−2 after 5000 cycles of CV, which
indicates its remarkably high durability. The WP/W contains or-
thorhombic WP; it possesses nanorods like morphology, where W
and P are homogenously distributed, and that possibly enhances
its much high durability for HER.
156 J. Mohammed-Ibrahim, X. Sun / Journal of Energy Chemistry 34 (2019) 111–160

Table 5. Durability of various kinds of reported earth abundant electrocatalysts for hydrogen evolution reaction (HER) in 1.0 M KOH alkaline electrolyte (Part 2: 50 0-10 0 0
cycles).

HER electrocatalysts Cycles of CV Remark after durability test Ref.

NiMo1 M NaOH 10 0 0 Negligible decay at − 100 mA cm−2 [26]

Co2 P@NPC 10 0 0 Negligible decay at − 10 mA cm−2 [82]
Zn-Co-S 10 0 0 Negligible decay [126]
NiMo3 S4 /Ni3 S2 10 0 0 Negligible decay at − 10 mA cm−2 [29]
Mo1 N1 C2 0.1 M KOH 10 0 0 Negligible decay [133]
α -MoO3- x 0.1 M KOH 10 0 0 Negligible decay at − 10 mA cm−2 [108]
Ni3 S2 10 0 0 Negligible decay at − 10 mA cm−2 [65]
N@MoPCx 10 0 0 Negligible decay [34]
N-Mo2 C nb 10 0 0 Negligible decay [139]
Ni(OH)2 –CoS2 NW 10 0 0 Negligible decay at − 200 mA cm−2 [94]
CoMoO4 NW 10 0 0 Negligible decay at − 300 mA cm−2 [109]
NiMo NS 10 0 0 Negligible decay at − 100 mA cm−2 [33]
Mo-S-NiSe 10 0 0 Negligible decay at − 10 mA cm−2 [122]
Mo2 C 10 0 0 Negligible decay at − 10 mA cm−2 [137]
Ni0.5 Co0.5 P 10 0 0 Negligible decay [46]
NiMoS4 0.1 M KOH 10 0 0 Negligible decay [116]
Ni2 P-NiCoP@NC1 M NaOH 10 0 0 Negligible decay at − 40 mA cm−2 [90]
NS-C 10 0 0 ND at − 100 mA cm−2 [128]
MoSe2 @Ni0.85 Se NW 10 0 0 Negligible decay at − 10 mA cm−2 [123]
Nix S 10 0 0 Negligible decay at − 10 mA cm−2 [70]
CoO@Co/N-rGO0.1 M KOH 10 0 0 Negligible decay at − 25 mA cm−2 [78]
MoS2 /NiS/MoO3 10 0 0 Slight decay [136]
Co2 P@Co3 O4 10 0 0 Negligible decay at − 60 mA cm−2 [77]
Co6.25 Fe18.75 Ni75 Ox NS 10 0 0 Negligible decay at − 10 mA cm−2 [99]
CoP/NCNHP 10 0 0 Negligible decay at − 60 mA cm−2 [81]
CoN/Ni3 N@NC 10 0 0 Negligible decay at − 10 mA cm−2 [85]
Ni/NiFeOOH 10 0 0 Negligible decay at − 100 mA cm−2 [101]
P8.6 –Co3 O4 NW 10 0 0 Negligible decay at − 200 mA cm−2 [83]
Fe-Co3 O4 /CNTs 10 0 0 Negligible decay at − 10 mA cm−2 [100]
Co(S0.71 Se0.29 )2 /C 10 0 0 Negligible decay at − 100 mA cm−2 [120]
Ni(OH)2 -Fe2 P 500 Negligible decay [98]
Ni(OH)2 –Ni3 N 500 Negligible decay at − 100 mA cm−2 [72]
Mn-Ni2 P NS 500 Negligible decay [40]

HER tests performed in 1 M NaOH/0.1/ M KOH are indicated on the electrocatalyst name. CV = Cyclic voltammetry; NWs: Nanowires; rGO: NS: Nanosheet; dr: Defect rich;
nb: Nano-belt; NW: Nano-wire; QDs: Quantum dots; G: Graphene; CNTs: Carbon Nano-Tubes; NCNHP: N-doped carbon nanotube hollow polyhedron; def-Gr: defective
graphene; LDH: Layered Double Hydroxide; NTs: Nanotubes.

Preparing nanostructured Ni3 N–NiMoN can afford abundant
active sites and metallic characteristic, and that can enhance
the durability for HER. For HER in 1.0 M KOH, the Ni3 N–NiMoN
[31] exhibits negligible decay at − 125 mA cm−2 after 50 0 0 cy-
cles of CV, which indicates its significantly much high durabil-
ity. The Ni3 N–NiMoN exhibits interface between the (100) face of
Ni0.2 Mo0.8 N and (111) face of Ni3 N; it possesses nanosheet mor-
phology, which is further composed of nanoparticles, which can
afford abundant active sites; it contains Mo, Ni and N, which are
uniformly distributed; it contains Ni+ , Ni2+ , Mo+3 , Mo+4 , Mo+6 ,
N − Ni/Mo, and N − H; it exhibits high electrochemically active sur-
face area (Cdl : 241 mF cm−2 ); it exhibits very tiny (− 0.03 eV) Gibbs
free energy for H adsorption (GH ∗ ), which is almost close to the
optimal GH ∗ of 0 eV; it possesses lower water adsorption energy
(− 0.62 eV); it shows the continuous distribution of the density of
states near the Fermi level, which suggests its metallic charac-
teristic with high electrical conductivity, which can enhance the
fast electron transport, and that possibly enhance its considerably
much high durability for HER.
The durability for HER can be enhanced by preparing pea-
pod like composite. For HER in 1.0 M KOH, the Co(S0.71 Se0.29 )2 /C
[120] exhibits negligible decay at − 100 mA cm−2 after 10 0 0
cycles of CV, which indicates its much high durability. The
Co(S0.71 Se0.29 )2 /C is composed of Co(S0.71 Se0.29 )2 nanoparticles,
which are aligned in the carbon fibers; it possesses porous pea-
pod like morphology, where the porous structure can afford abun-
dant activity sites; it exhibits high surface area (244.774 m2 g−1 ); it
contains graphitized carbon; it contains Co, S, Se, and C, which are
uniformly distributed, and that possibly enhances its much high
durability for HER.
Preparing nanostructured Mn doped Ni2 P can enhance the
durability for HER. For HER in 1.0 M KOH, the Mn-Ni2 P NS [40] ex-
hibits negligible decay after 500 cycles of CV, which indicates its
high durability. The Mn-Ni2 P NS possesses porous nanosheet mor-
phology; it is composed of Mn doped cubic Ni2 P; it contains Mn,
Ni, and P, which are uniformly distributed; it contains Mn2+ and
Ni2+ , and that possibly enhances its much high durability for HER.
Adding Zn to Co-S can enhance the durability for HER. For HER
in 1.0 M KOH, the Zn-Co-S [126] exhibits negligible decay after
10 0 0 cycles of CV, which indicates its high durability. The Zn-Co-S
is amorphous; it possesses hollow, polyhedral morphology; it con-
tains Co, Zn and S, which are uniformly distributed; it exhibits high
surface area (85.5 m2 g−1 ), and that possibly enhances its much
high durability for HER.
Doping V in Ni3 S2 can enhance the durability for HER. For HER
in 1.0 M KOH, the V-Ni3 S2 NW7000 cycles [42] exhibits negligible de-
cay after 20 0 0 cycles of CV, which indicates its much high durabil-
ity. The V-Ni3 S2 NW7000 cycles possesses nanowire morphology; it is
composed of V doped crystalline Ni3 S2 , and that possibly enhances
its much high durability for HER.
Co-doping of S to N–C lowers the Gibbs free energy for H ad-
sorption, which can enhance its durability for HER. For HER in
1.0 M KOH, the NS-C [128] exhibits negligible decay at − 100 mA
cm−2 after 10 0 0 cycles of CV, which indicates its much high dura-
bility. The NS-C shows ID /IG ratios of 1.15; it possesses sheet like
morphology with wrinkle, while it exhibits abundant lattice struc-
tures of graphene sheets; it contains 5.8 atomic % of S, and 3.7
atomic % of N, and the co-doping of S to N–C decreases the Gibbs
free energy for H adsorption (GH ∗ ) from 0.81 eV to 0.23 eV, and
that possibly enhances its much high durability for HER.
 J. Mohammed-Ibrahim, X. Sun / Journal of Energy Chemistry 34 (2019) 111–160
2.13. Possible reason for high stability and durability
The stability and durability for HER can be substantially en-
hanced by preparing nanostructured electrocatalyst. For HER in
1.0 M KOH, the Co(OH)2 ultrathin nanosheets on the N − doped
CNTs [53] exhibits negligible decay at − 10 mA cm−2 for 600 h,
while the porous structured NiMo alloy [28] exhibits reasonable
stability at η of − 200 mV for 300 h, and the N,P dual doped on
etched stainless steel with nanosheet like structure [54] exhibits
negligible decay at η of − 230 mV for 134.4 h. Moreover, for HER
in 1.0 M KOH, the Ni3 S2 with nanorods@nanosheets homo-junction
structure [55] exhibits negligible decay after 10,0 0 0 cycles of CV,
while the NiFe LDH nanosheet on defective graphene [56] exhibits
negligible decay at − 200 mA cm−2 after 8000 cycles of CV, and the
NC/CuCo/CuCoOx with porous nanowire like morphology [57] ex-
hibits negligible decay at − 50 0 mA cm−2 after 50 0 0 cycles of CV,
and the nanoporous structured NiMo alloy [26] exhibits negligi-
ble decay after 10 0 0 cycles at higher current density of − 100 mA
cm−2 , while the NiMo alloy outperforms the noble Pt/C at higher
current density in 1 M NaOH. Our group demonstrated that prepar-
ing nanostructured electrocatalyst with superaerophobic surface
facilitate the evolution of gas, which enhance the activity and sta-
bility of the electrocatalyst [16,21,33,140]. Preparing nanostructured
electrode can afford superaerophobic surface, which can provide
a discontinuous three-phase (solid, liquid, and gas) contact line
(TPCL), while the gas bubbles undergo a very low contact area with
the solid electrode, and that can lead to much low adhesive force
to the surface, and that can accelerate the gas evolution [141,142].
Zhang et al. [33] have observed that turnover frequency (TOF) of
ultrathin NiMo NS exhibits higher intrinsic HER activity than Pt/C
at η of about ≥ − 150 mV (Fig. 33b) in 1.0 M KOH, while it exhibits
negligible decay at − 100 mA cm−2 after 10 0 0 cycles of CV, which
indicates its much high durability. They further observed that the
bubble adhesive force, and bubble releasing size (Fig. 33c–e) of
NiMo NS are ≈ 2 μN and < 95 μm, respectively, whereas the bubble
adhesive force, and bubble releasing size of Pt/C are ≈ 29 μN and
∼364 μm, respectively, where the NiMo NS possesses superaero-
phobic nanostructured surface, which leads to rapid evolution of
H2 bubbles from the surface with smaller size and weaker adhesive
force, and that could afford higher intrinsic HER activity and dura-
bility for NiMo NS. Preparing superaerophobic nanostructured sur-
face not only improves the stability of the earth-abundant electro-
catalyst in alkaline medium but also improves the stability of the
electrocatalyst in acid medium. Lu et al. [140] have observed that
nanostructured MoS2 affords higher HER activity and stability than
flat MoS2 in 0.5 M H2 SO4 , while it outperforms the noble Pt/C at
higher current density. They further observed that the contact an-
gle, bubble releasing size, and bubble adhesive force of nanostruc-
tured MoS2 are 52.3°± 2.2, < 100 μm, and 10.8 ± 1.7 μN respectively
while the contact angle, bubble releasing size, and bubble adhe-
sive force of flat MoS2 are 77.1°± 3.4, > 400 μm, and 124.8 ± 6.1 μN,
respectively, where the nanostructured MoS2 possesses superaero-
phobic nanostructured surface, which leads to rapid evolution of
H2 bubbles from the surface with smaller size and weaker adhesive
force, and that could afford higher intrinsic HER activity and stabil-
ity for nanostructured MoS2 . Preparing superaerophobic nanostruc-
tured surface not only enhances the stability of the earth-abundant
electrocatalyst but also enhances the stability of the noble, state-
of-art catalyst such as Pt. Li et al. [16] have observed that pine
shaped Pt nanoarray provides much higher HER activity and sta-
bility than Pt flat in 0.5 M H2 SO4 . They further observed that the
contact angle, bubble releasing size, and bubble adhesive force of
Pt nanoarray are 29.3°± 2.5, <50 μm, and 11.5 ± 1.2 μN, respectively
while the contact angle, bubble releasing size, and bubble adhesive
force of Pt flat are 81.4°± 2.4, ∼500 μm, and 145.6 ± 2.1 μN, respec-
tively, where the Pt nanoarray possesses superaerophobic nanos-
tructured surface, which leads to rapid evolution of H2 bubbles
157
from the surface with smaller size and weaker adhesive force, and
that could afford higher intrinsic HER activity and stability for Pt
nanoarray.
Conventional earth-abundant electrodes and noble electrodes
have been used in commercial water electrolysers, which are de-
veloped by Norsk Hydro, De Nora S.A.P, Electrolyzer Corp. Ltd.,
Teledyne Energy systems, and General Electric [14]. The activ-
ity, stability and durability for HER in alkaline medium of dif-
ferent types of recently reported electrocatalysts such as Ni, Co,
NiCo, Fe, Cu, W, Mo, Se, Mn, Zn, V, and metal free based earth-
abundant-electrocatalysts have been reviewed in this paper. The
strategies used to achieve the remarkably low overpotential (in-
cluding η10 : ≤ 35 mV), high long term stability (including ≥ 100 h)
and high durability (including ≥ 50 0 0 cycles) of earth-abundant-
electrocatalysts for HER in alkaline medium have been reviewed
in this paper, and those are better or well comparable with the
state-of-the-art, noble, Pt/C electrocatalyst. The noble metal Pt is
considered as a kinetically most active species for HER because
it lie at the apex of volcano curve [143], whereas a considerably
lower exchange current density and catalytic activity have been
observed on Pt/C in alkaline environment compared to those in
acidic environment [59,144], while the stability and activity of the
Pt catalyst have been significantly improved by using suitable strat-
egy [16]. Thus, we should impartially evaluate the performance
of earth-abundant-electrocatalysts. The scientific and engineering
knowledge gained on HER electrocatalysts afford conceivable de-
velopment for practical application in near future.
3. Conclusions
The activity, stability and durability for HER in alkaline medium
of different types of recently reported electrocatalysts such as Ni,
Co, NiCo, Fe, Cu, W, Mo, Se, Mn, Zn, V, and metal free based earth-
abundant-electrocatalysts have been reviewed in this paper. The
strategies used to achieve the remarkably low overpotential (in-
cluding η10 : ≤ 35 mV), high long term stability (including ≥ 100 h)
and high durability (including ≥ 50 0 0 cycles) of earth-abundant-
electrocatalysts for HER in alkaline medium have been reviewed
in this paper, and those are better or well comparable with the
state-of-the-art, noble, Pt/C electrocatalyst.
The strategies such as preparing porous structured materials,
preparing nanostructured materials with superaerophobic surface,
preparing nanostructured materials, preparing carbon compos-
ites/integrating electrocatalysts with carbon, preparing amorphous
materials, preparing materials with oxygen vacancies/defects,
preparing metal chalcogenides, preparing bimetallic/multi-metallic
materials, doping metals or heteroatoms, preparing electrocata-
lysts with core-shell structure, decorating electrocatalysts with
amines, preparing homo-junction/heterojunction structured mate-
rials, preparing hollow structured materials, and preparing boron-
rich surface are the efficient approach to enhance the activity, sta-
bility, and durability for HER.
The activity, stability and durability for HER have been
enhanced by preparing porous structured materials such as
nanoporous Ni4 Mo alloy, porous Ni3 S2 on nano-porous Cu, and
mesoporous NiCo alloy. Preparing nanostructured materials with
superaerophobic surface such as ultrathin nanostructured Ni4 Mo
alloy with superaerophobic surface facilitated the release of gas,
which enhanced the activity and durability for HER.
The activity, stability and durability for HER have been en-
hanced by preparing nanostructured materials such as nanostruc-
tured Ni, nanostructured ultrathin metallic nickel, nanostructured
Ni5 P4 , nanostructured CoP, nanostructured tungsten nitride, nanos-
tructured tungsten phosphide, P filled in the oxygen vacancies of
Co3 O4 nanosheet, and nanostructured Ni(OH)2 –Ni3 N.
158 J. Mohammed-Ibrahim, X. Sun / Journal of Energy Chemistry 34 (2019) 111–160
Preparing carbon composites/integrating electrocatalysts
with carbon such as nanostructured molybdenum carbide,
molybdenum-nickel bimetallic carbonitride, Ni/C3 N4 compos-
ite, nanostructured crystalline cobalt carbide, Ni-rGO composite,
rGO integrated with Ni3 S2 , Ni-rGO composite on the Ni pre-layer,
peapod like Co(S0.71 Se0.29 )2 /C composite, nanostructured CoO@Co
integrated with N-doped carbon matrix, CoP integrated with CNTs,
CoP integrated with glucose derived carbon, CoP integrated with
N-doped carbon nanotube hollow polyhedron, Co/CoP integrated
with hairy N-doped carbon hollow polyhedron, Co2 P quantum
dots integrated with N, P dual doped carbon, porous ultrathin
Co(OH)2 nanosheets on N−doped CNTs, Co9 S8 integrated with het-
eroatoms doped carbon, nanostructured Ni–Co mixed phosphides
integrated with N-doped carbon, nanostructured nickel−cobalt
nitride integrated with N-doped carbon, nanostructured Ni3 Co
alloy integrated with carbon, nanostructured NiCo2 O4 integrated
with carbon, NiFe LDH integrated with defective graphene, nanos-
tructured Mo2 C embedded with BCN, metallic Ni and Mo2 C
embedded with N-doped carbon, nanostructured MoP integrated
with CNTs, hetero-atoms doped nanostructured molybdenum
phosphide integrated with carbon, nanostructured MoP and Mo2 C
integrated with carbon matrix, nanostructured electrocatalysts
with CdS, MoO3 , and Ni3 S2 , and Ni integrated with MoS2 -GO com-
posite, molybdenum carbide-tungsten carbide/graphene composite,
nanostructured Ni − carbon composite with high Ni0 ratio, S doped
with N-doped C, and Ni3 FeN integrated with rGO enhanced the
activity, stability, and durability for HER.
The activity, stability and durability for HER have been en-
hanced by preparing amorphous materials such as nanostructured
amorphous CoMoO4 , and nanostructured amorphous NiMoS4 .
Preparing materials with oxygen vacancies/defects such as and
oxygen vacancies created in the nanostructured cobalt–nickel sul-
fide, oxygen vacancies created on the nanostructured W based
electrocatalyst, structural defects and oxygen vacancies created
in α -MoO3 , defect-rich nanostructured chalcogenides, and defects
created in MnO2 enhanced the activity, stability, and durability for
HER.
The activity, stability and durability for HER have been en-
hanced by preparing metal chalcogenides such as nanostructured
transition metal dichalcogenides, nanostructured MoSe2 /NiSe hy-
brid, and nanostructured mixed metal selenides from MOF.
Preparing bimetallic/multi-metallic materials such as nanos-
tructured transition-bimetallic phosphides, nanostructured
transition-bimetallic phosphides derived from MOFs, nanos-
tructured nickel hydroxide − cobalt disulfide, NiFe LDH/NiCoP,
Ni(OH)2 on Fe2 P, nanostructured NiFeOOH with Ni inner layer,
copper − nickel bimetallic nitrides, nickel tungsten oxide, nanos-
tructured NiMo3 S4 /Ni3 S2 , nanostructured NiOOH integrated with
MoS2 , nanostructured Ni3 N–NiMoN, and NiZnP with Ni(OH)2
along with tiny amount of Zn enhanced the activity, stability, and
durability for HER.
Doping metals or heteroatoms such as P doped with nanos-
tructured Co3 O4 , N,P dual doped on etched stainless steel, Fe in-
corporated in nickel nitride, nanostructured Fe doped Ni2 P, nanos-
tructured Co doped mixed metal oxides, nanostructured Mo doped
Ni2 P, Mo and S co-doped NiSe, nanostructured Mn doped Ni2 P, V
doped in Ni3 S2 , V doped pyrite NiS2 , and Zn added to Co-S en-
hanced the activity, stability, and durability for HER.
The activity, stability and durability for HER have been en-
hanced by preparing electrocatalysts with core-shell structure such
as nanostructured Fe3 O4 and Co3 O4 with core-shell structure, thin
CoOx on nanostructured CoP, nanostructured copper as core in the
core-shell structure, core–shell nanostructure with optimized shell
thickness, Cu − Co bimetallic nitride enwrapped with carbon shell,
and Mott–Schottky electrocatalyst (metal − semiconductor hybrid)
encapsulated with carbon shell.
Decorating electrocatalysts with amines such as secondary
amines decorated with Ni4 Mo alloy decreased the charge transfer
resistance and modulated the electronic structures of interfacial ac-
tive sites, and that enhanced the stability and activity for HER.
Preparing homo-junction/heterojunction structured materials
such as Ni3 S2 with nanorods@nanosheets homo-junction structure,
and nano-heterojunction with tuned electronic structure at the
Co/Ni3 N interface enhanced the activity, stability, and durability for
HER. The activity, stability and durability for HER have been en-
hanced by preparing hollow structured materials such as hollow
Ni3 S2 microsphere with abundant protruding edges, and surface
anion-rich NiS2 hollow micro-sphere. Preparing boron-rich surface
such as FeB2 with appropriate binding energy for desorption and
chemisorption of intermediates with hydrogen enhanced the activ-
ity and stability for HER.
Acknowledgments
This work was supported by the National Natural Science Foun-
dation of China, the Innovative Research Team in the University,
the Program for Changjiang Scholars, the Fundamental Research
Funds for the Central Universities, and the longterm subsidy mech-
anism from the Ministry of Finance and the Ministry of Educa-
tion of People’s Republic of China (PRC). The author (M.I.J) thanks
the Science and Engineering Research Board (SERB), Department
of Science and Technology, Government of India (Reference No.
PDF/2017/0 0 0 015).
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