15213773, 0, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/anie.202215256 by Kyung Hee University Library, Wiley Online Library on [17/01/2023].
See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
Research Articles
Water Splitting
Amorphous Mo-doped NiS0.5Se0.5 Nanosheets@Crystalline NiS0.5Se0.5
Nanorods for High Current-density Electrocatalytic Water Splitting in
Neutral Media
Yang Wang, Xiaopeng Li, Zhong Huang, Haozhi Wang, Zelin Chen, Jinfeng Zhang,
Xuerong Zheng,* Yida Deng,* and Wenbin Hu
Abstract: It is vitally important to develop highly active,
robust and low-cost transition metal-based electrocata-
lysts for overall water splitting in neutral solution
especially at large current density. In this work,
amorphous Mo-doped NiS0.5Se0.5 nanosheets@crystalline
NiS0.5Se0.5 nanorods (Am Mo NiS0.5Se0.5) was synthe-
sized using a facil one-step strategy. In phosphate buffer
saline solution, the Am Mo NiS0.5Se0.5 shows tiny over-
potentials of 48 and 209 mV for hydrogen evolution
reaction (HER), 238 and 514 mV for oxygen evolution
reaction (OER) at 10 and 1000 mA cm 2, respectively.
Moreover, Am Mo NiS0.5Se0.5 delivers excellent stabil-
ity for at least 300 h without obvious degradation.
Theoretical calculations revealed that the Ni sites in the
defect-rich amorphous structure of Am Mo NiS0.5Se0.5
owns higher electron state density and strengthened the
binding energy of H2O, which will optimize H adsorp-
tion/desorption energy barriers and reduce the adsorp-
tion energy of OER determining step.
[*] Dr. Y. Wang, Dr. H. Wang, Dr. Z. Chen, Prof. X. Zheng, Prof. Y. Deng
State Key Laboratory of Marine Resource Utilization in South China
Sea, School of Materials Science and Engineering, Hainan Univer-
sity
Haikou 570228 (P. R. China)
E-mail: xrzh@tju.edu.cn
yida.deng@tju.edu.cn
Dr. J. Zhang, Prof. Y. Deng, Prof. W. Hu
School of Materials Science and Engineering, Tianjin Key Labo-
ratory of Composite and Functional Materials, and Key Laboratory
of Advanced Ceramics and Machining Technology of Ministry of
Education, Tianjin University
Tianjin 300072 (P. R. China)
Dr. Z. Huang
State Key Laboratory of Marine Resource Utilization in South China
Sea, College of Information and Communication Engineering,
Hainan University
Haikou 570228 (P. R. China)
Dr. X. Li
School of Materials Science and Engineering, Tianjin Key Labo-
ratory of Building Green Functional Materials, Tianjin Chengjian
University
Tianjin 300384 (China)
Angew. Chem. Int. Ed. 2023, e202215256 (1 of 11)
Angewandte
Chemie
www.angewandte.org
How to cite:
International Edition: doi.org/10.1002/anie.202215256
German Edition: doi.org/10.1002/ange.202215256
Introduction
Electrochemical water splitting has been considered as one
of the most promising technologies to obtain hydrogen (H2),
which is an ideal alternative to the ever-being-exhausted
conventional fossils. To date, Pt is the most widely used
catalysts for hydrogen evolution reaction (HER) and Ir-
based compounds are higly active electrocatalysts for oxygen
evolution reaction (OER). However, the scarcity, high cost
and poor stability limit their practical application in water
splitting.[1–3] In recent years, transition metal compounds
(TMCs), including cobalt (Co), nickel (Ni) and manganese
(Mn) -based electrocatalysts,[4–9] have been extensively
studied, owing to their abundance, low cost and environ-
mentally benignancy. Nevertheless, the electrocatalysts and
the water splitting devices in acidic and alkaline conditions
generally suffer from the corrosion issues, environmental
unfriendly and poor stability, which impedes their scalable
deployment for hydrogen generation systems.[10, 11] Develop-
ing neutral water splitting in systems is one of the most
promising tendencies for hydrogen production owing to its
non-pollution, low-cost, and easy for large-scale
application.[12, 13] However, it is still a great challenge for
rational designing highly efficient, low-cost and stable
bifunctional electrocatalysts in neutral solution for overall
water splitting. Moreover, to meet the requirement of
industrial water splitting, the electrocatalysts should keep
stable at high current densities of more than
500 mA cm 2.[14–16] These challenges have motivated the
development of highly efficient, durable, and cheap electro-
catalysts for high-current-density water splitting in neutral
solution.
Recent studies have primarily focused on enhancing
their intrinsic activity, including phase and interface engi-
neering, creating grain boundaries and regulating electronic
structures.[17–21] However, those researchers pay overwhelm-
ingly too much attention on crystalline materials and tend to
ignore their amorphous counterparts. Amorphous materials
are generally entities in which the arrangement of their
internal atoms is not periodic arranged but only bear the
local short-range order.[22–26] The inherent disorderliness of
amorphous materials can produce abundant “dangling
bonds” and defects in the loosely bonded atomistic free-
volume zones, which can rationally break the periodicity of
the crystal structures and thus can provide more active sites
and alter the electron distribution around the imperfections
© 2022 Wiley-VCH GmbH

Research Articles
to improve catalytic activity.[27–29] For example, Xin et al.
prepared amorphous RuTe2 porous nanorods for water
splitting in acid solution.[30] Density functional theory (DFT)
calculations demonstrated that high amorphization degree
of amorphous RuTe2 lead to the local short-range disorder,
inducing the system to be the meta-stable state, thus
facilitating the HER and OER activities. Besides, amor-
phous materials own strong corrosion resistance in both
alkaline and acidic conditions due to their unique structure,
providing new insights into the study of highly stable
catalysts.[30–32] For example, Zhang et al. synthesized amor-
phous lithium-incorporated palladium phosphosulfide nano-
dots (Li-PPS NDs) by electrochemical lithiated layered
Pd3P2S8 crystal.[33] Interestingly, this amorphization process
can activate the electrochemical inert Pd3P2S8, thereby
significantly enhancing its HER activity. The obtained
amorphous Li-PPS NDs also possess excellent stability
under the acidic condition that no obvious current density
decay occured after 10 000 potential cycles. More impor-
tantly, owing to the isotropic and flexible properties,
amorphous materials can provide multiple pathways for ion
migration without changing the lattice structure, which is
benefit for designing optimal heterostructures to facilitate
charge and mass transfer kinetics. Thus, designing amor-
phous electrocatalysts or amorphous/crystalline composites
is therefore an attractive strategy for developing highly
active and stable electrocatalysts for water splitting in
neutral condition. However, the reports for designing
amorphous based electrocatalysts for water splitting in
neutral condition are still rare and the underlying mecha-
nism has not yet been clearly illustrated.
In this context, amorphous Mo-doped NiS0.5Se0.5 nano-
sheets@crystalline NiS0.5Se0.5 nanorods (Am Mo NiS0.5Se0.5)
with high density of unsaturated active sites was synthesized
by a simple hydrothermal method. The obtained
Am Mo NiS0.5Se0.5 exhibited outstanding bifunctional
(HER/OER) catalytic activity in neutral condition, in which
a current density of 1000 mA cm 2 can be achieved at 209
and 514 mV for the HER and OER overpotentials reach,
respectively. Experimental results demonstrated that, com-
paring with crystalline structure, Am Mo NiS0.5Se0.5 owns
more active sites, and the amorphous structure changes the
local electronic structure of active sites and thus enhances
their intrinsic activity. Additionally, DFT calculations dem-
onstrated that amorphous structure strengthened the water
molecule binding energy, optimized H adsorption/desorp-
tion energy and reduced the adsorption energy of OER
determining step. These results revealed the possible origin
of high activity of Am Mo NiS0.5Se0.5 towards HER and
OER processes. This work yields an efficient bifunctional
electrocatalyst toward both the HER and OER in neutral
environment, markedly outperforming current reported
HER/OER catalysts elsewhere.
Results and Discussion
The preparation of Am Mo NiS0.5Se0.5 on Ni foam (NF)
was realized by the one-pot hydrothermal method with
Angew. Chem. Int. Ed. 2023, e202215256 (2 of 11)
15213773, 0, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/anie.202215256 by Kyung Hee University Library, Wiley Online Library on [17/01/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
Angewandte
Chemie
regulating hydrazine hydrate and sodium borohydride
reducing agents (see the Supporting Information for details).
Detailed characterizations of the Am Mo NiS0.5Se0.5 are
presented in Figure 1. The transmission electron microscopy
(TEM) image (Figure 1a) shows that ultrathin nanosheets
were uniformly wrapped on the nanorods. The cross-section
of TEM images further confirmed the formation of nano-
sheets@nanorods structure (Figure S1). This wrapped nano-
sheet structure facilitated the suspension and immersion of
the nanosheets in the electrolyte solution, which was favour
of exposing more active sites and electron transport during
the catalytic process. Moreover, this wrapped nanosheet
structure owns better dispersibility and structural stability
comparing with 2D nanosheets. From the high-resolution
TEM (HRTEM) (Figure 1b,c), no clear long-range ordered
atomic arrangements can be observed in the ultrathin
nanosheets and the atoms present a random distribution
without remarkable periodicity. The selected-area electron
diffraction (SAED) pattern reveals a set of diffuse rings
(Figure 1d), confirming the existence of amorphous struc-
ture, which is consistent with HRTEM results. The struc-
tural model of Am Mo NiS0.5Se0.5 with an amorphous
feature can be described as shown in Figure 1e, where the
Ni, Mo, and S/Se atoms exhibit a random arrangement with
isotropic, short-range order in atomistic free-volume zones.
While for the nanorods, lattice fringe of 0.20 nm can be
observed (Figure 1f), which is assigned to the (102) crystal
plane of crystalline NiS0.5Se0.5.[34] The SAED pattern (inset
of Figure 1f) shows obvious diffraction spots arranged in
order, revealing the high crystalline of NiS0.5Se0.5 nanorods.
In addition, the X-ray diffraction (XRD) patterns of
Am Mo NiS0.5Se0.5 composite is in agreement with the
hexagonal standard values NiSe (JCPDS No. 02-0892) and
NiS (JCPDS No. 02-1280) (Figure S2). The diffraction peaks
of Am Mo NiS0.5Se0.5 between NiSe and NiS demonstrates
their mixing at the atomic level, which was accordance with
our previous work.[34] Notably, without discernible peaks of
impurities, indicating the doping state of Mo element in the
sample. Scanning transmission electron microscopy-energy-
dispersive X-ray spectroscopy (STEM-EDS) element map-
pings manifest that the Ni, Mo, S, and Se are distributed
uniformly throughout the whole sample (Figure 1g). The
cross-section of EDS element mappings reveals that Mo is
mainly distributed on the nanosheets (Figure S1), demon-
strating Mo was doping in the NiS0.5Se0.5 nanosheets, but not
in the nanorods. The specific concentrations of Mo and Ni
in the catalyst were determined using inductively coupled
plasma-atomic emission spectrometry (ICP-AES), EDS and
X-ray photoelectron spectroscopy (XPS). The atomic ratio
of Mo to Ni is 4.0: 96.0 from the ICP-AES results, which is
similar with the EDS result (3.7: 96.3) (Table S1). While
from XPS result, the atomic ratio of Mo to Ni is 5.9: 94.1,
which is higher than those of EDS and ICP-AES, confirming
the Mo was doping only in amorphous NiS0.5Se0.5 nano-
sheets. In a word, the forming of Am Mo NiS0.5Se0.5
composites not only possessed large surface area and inter-
face-synergistic-effect, but also provided sufficient space to
avoid possible structural deformation, which showed ex-
© 2022 Wiley-VCH GmbH
 15213773, 0, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/anie.202215256 by Kyung Hee University Library, Wiley Online Library on [17/01/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
Angewandte
Research Articles Chemie

Figure 1. a) TEM image, b), c) HRTEM images, d) SAED pattern, e) structural model of nanosheets; f) HRTEM image of nanorods of
Am Mo NiS0.5Se0.5, the inset of f is the corresponding SAED pattern; g) STEM EDS elemental mappings of Am Mo NiS0.5Se0.5.

cellent electrocatalytic HER and OER activities and
stabillity.[35–39]
To further investigate the role of the reducing agents for
synthesizing amorphous Am Mo NiS0.5Se0.5 nanosheets, the
influence of different reducing agents towards the micro-
structure of the products were systematically investigated.
When both the sodium borohydride and hydrazine hydrate
were added as reducing agents in the hydrothermal process,
the amorphous nanosheets can be obtained (Figure S2a,b).
However, when adding only one reducing agent, either
sodium borohydride or hydrazine hydrate, only crystalline
but not amorphous nanosheets was obtained (Figure S2c–f).
We predict that the formation of amorphous nanosheets
should benefiting from the following factors: (1) the (NH4)
in ammonium fluoride would react with cationic precorsors
and forming big complex of Ni[(NH4) ]2;[40, 41] (2) The mixed
hydrazine hydrate and sodium borohydride are strong
reductants which can dissolve Se powder into Se2 , ensuring
Se2 and S2 possess similar reaction kinetics for reacting
with Ni[(NH4) ]2 and thus forming NiS0.5Se0.5;[42–48] (3) the
big molecules of Ni[(NH4) ]2 as capping agents can prolong
the reaction time and slow down the reaction kinetics and

Angew. Chem. Int. Ed. 2023, e202215256 (3 of 11) © 2022 Wiley-VCH GmbH

Research Articles
thus forming amorphous nanosheets.[43, 44] Thus, the intro-
duction of hydrazine hydrate, sodium borohydride and
ammonium fluoride result in the formation of
Am Mo NiS0.5Se0.5 composites.
To study the influence of amorphous/crystalline struc-
ture for catalytic performance, we synthesized well crystal-
lineed Mo NiS0.5Se0.5 nanosheets@crystalline NiS0.5Se0.5
nanorods (Cr Mo NiS0.5Se0.5) to compare with
Am Mo NiS0.5Se0.5. The Cr Mo NiS0.5Se0.5 (Figure 2) was
obtained by controlled hydrothermal process and thermal
treatments. XRD pattern shows no big change of peaks for
Cr Mo NiS0.5Se0.5 and Am Mo NiS0.5Se0.5, except the en-
hanced peak intensity (Figure S3), indicating the higher
crystallinity of Cr Mo NiS0.5Se0.5 than Am Mo NiS0.5Se0.5.
From the TEM images of Cr Mo NiS0.5Se0.5 (Figure 2a), the
morphology of Am Mo NiS0.5Se0.5 is mainly maintained.
Figure 2. a) TEM image, b) HRTEM image of Cr Mo NiS0.5Se0.5 nanosheets, the inset of b is the corresponding SAED pattern, c) structural model
of nanosheets; d) HRTEM image of nanorods, the inset of d is the corresponding SAED pattern.
Angew. Chem. Int. Ed. 2023, e202215256 (4 of 11)
15213773, 0, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/anie.202215256 by Kyung Hee University Library, Wiley Online Library on [17/01/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
Angewandte
Chemie
Meanwhile, regularly long-range order atoms can be
observed in the HRTEM image of Cr Mo NiS0.5Se0.5 nano-
sheets and the interplanar spacing is 0.27 nm, corresponding
to the (101) plane of NiS0.5Se0.5(Figure 2b). SAED pattern
also shows a set of distinct rings made of diffraction spots
(inset in Figure 2b), being ascribed to the (102) and (101)
planes. The structural model of Cr Mo NiS0.5Se0.5 nano-
sheets can be described as shown in Figure 2c, presenting a
long-range orthorhombic structure. For the
Cr Mo NiS0.5Se0.5 nanorods, the lattice spacing remains
0.20 nm corresponding to the (102) plane of NiS0.5Se0.5
(Figure 2d). As seen from the SAED pattern, a similar set
of distinct rings composed of diffraction spots with
Cr Mo NiS0.5Se0.5 nanorods (inset of Figure 2d) were ob-
served, being assigned to the (102) and (101) planes. From
the cross-section of EDS element mappings of
© 2022 Wiley-VCH GmbH

Research Articles
Cr Mo NiS0.5Se0.5 (Figure S4), the Mo element was also
mainly distributed on the nanosheets, not on the nanorods.
ICP-AES and EDS results demonstrated that the atomic
ratio of Mo to Ni was similar, from XPS results, the atomic
ratio of Mo to Ni was higher than those of ICP-AES and
EDS (Table S1). It means that the morphology and
composition of Cr Mo NiS0.5Se0.5 are well maintained,
reflecting that the controlled hydrothermal process and
thermal treatments could only influence the crystallinity of
nanosheets, but neither the morphology nor the composi-
tion.
As shown in Figure 3a, the peaks located at 232.5 and
229 eV in Am Mo NiS0.5Se0.5 are ascribed to Mo4 +.[49] The
other two peaks at 233.7 and 235.8 eV are assigned to Mo6 +,
which might be attributed to surface oxidation or unsatu-
rated sulfur ligands (MoS42 ) on the sample.[50] There is an
additional peak at 226.1 eV, which is related to Mo S
ligand.[51] It can be seen that comparing with highly
crystalline sample, the Mo4 + peaks of Am Mo NiS0.5Se0.5
exhibit an obvious positive shift of � 0.3 eV, indicating the
decrease of electrons around Mo atoms in amorphous
structure. In the case of Ni 2p (Figure 3b), a negative shift of
� 0.3 eV in the binding energy of Am Mo NiS0.5Se0.5
compared with Cr Mo NiS0.5Se0.5 can be observed, implying
the accumulation of electrons around Ni atoms in the
Am Mo NiS0.5Se0.5.[52–54] These changes indicate that the
electron distribution of Am Mo NiS0.5Se0.5 changes, thus
influences the local electronic structure of the metal
atoms.[55, 56] X-ray absorption spectroscopy (XAS) was
performed to investigate the electronic and local structure of
samples (Figure 3c,d). The obtained X-ray absorption near
edge structure (XANES) spectra for Ni K-edge in both
Am Mo NiS0.5Se0.5 and Cr Mo NiS0.5Se0.5 show similar
Figure 3. XPS patterns of a) Mo 3d, b) Ni 2p; c) Ni K-edge XANES spectra, d) the corresponding FT curves of Am Mo NiS0.5Se0.5,
Cr Mo NiS0.5Se0.5; e) Positron lifetime spectra and f) ESR spectra of Am Mo NiS0.5Se0.5, Cr Mo NiS0.5Se0.5.
Angew. Chem. Int. Ed. 2023, e202215256 (5 of 11)
15213773, 0, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/anie.202215256 by Kyung Hee University Library, Wiley Online Library on [17/01/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
Angewandte
Chemie
shape, indicating their similar coordination
environment.[33, 57, 58] The significantly decreased white line
intensity of Am Mo NiS0.5Se0.5 comparing with of
Cr Mo NiS0.5Se0.5 indicates that the lower valence state of
Ni atoms in Am Mo NiS0.5Se0.5,[59–61] and this is consistent
with the XPS results. As shown in the Fourier transforms of
the extended X-ray absorption fine structure (EXAFS) for
Ni K-edge in Cr Mo NiS0.5Se0.5, the peaks centred at 1.82
and 2.12 Å correspond to the nearest Ni S and Ni Se
coordination. Similar peaks ascribed to the Ni S and Ni Se
coordination in the Am Mo NiS0.5Se0.5 can also be ob-
served. Comparing with Cr Mo NiS0.5Se0.5, the peak inten-
sity of Ni S and Ni Se for Am Mo NiS0.5Se0.5 decreases,
which implies the increased amorphization and decreased
crystallinity states for Am Mo NiS0.5Se0.5.[62–64] Positron
annihilation spectroscopy (PAS) were then performed to
study the defects in the samples (Figure 3e and Table S2).
According to the lifetime parameters, the
Am Mo NiS0.5Se0.5 exhibits a prolonged lifetime (τ1) than
Cr Mo NiS0.5Se0.5, mainly due to higher density of defects.
To certify this conjecture, electron spin resonance (ESR)
was also carried out to probe the unpaired electrons which
generated by defects (Figure 3f). A pair of sharp peaks can
be clearly seen for Am Mo NiS0.5Se0.5 comparing with
Cr Mo NiS0.5Se0.5, suggesting a higher density of S/Se
vacancies in the Am Mo NiS0.5Se0.5.[65, 66]
A neutral-effective electrocatalyst is urgently desired
due to its environmental benignity and safety. The electro-
catalytic HER activity of Am Mo NiS0.5Se0.5 was investi-
gated in 1.0 M PBS solution, comaring with
Cr Mo NiS0.5Se0.5, Pt/C, and NF. As shown in Figure 4a, the
overpotentials at 10 mA cm 2 for Am Mo NiS0.5Se0.5 was
only 48 mV, outperforming that of Cr Mo NiS0.5Se0.5. For
© 2022 Wiley-VCH GmbH

Research Articles
Figure 4. a) HER polarization curves, b) Tafel plots of Am Mo NiS0.5Se0.5, Cr Mo NiS0.5Se0.5, NF, and 20 % commercial Pt/C; c) Comparison of
overpotential (@ 100 mA cm 2) and Tafel slope for various reported HER catalysts in neutral medium; d) Linear fitting of the capacitive current
densities vs the scan rates, e) TOF of Am Mo NiS0.5Se0.5 and Cr Mo NiS0.5Se0.5; f) The polarization curves were recorded before and after
20 000 CV cycles for Am Mo NiS0.5Se0.5, the inset is the long-term durability of Am Mo NiS0.5Se0.5 and 20 % commercial Pt/C.
practical applications, the high-current-density performance
of catalysts is vitally important. At high current density of
300 and 1000 mA cm 2, the Am Mo NiS0.5Se0.5 shows an
overpotential of 133 and 209 mV, much lower than commer-
cial Pt/C (153 and 447 mV) and Cr Mo NiS0.5Se0.5 (205 and
295 mV). NF shows negligible HER activity in 1.0 M PBS,
which means that the measured activity is mostly ascribed to
the Am Mo NiS0.5Se0.5 rather than the NF substrate. The
Tafel slope of Am Mo NiS0.5Se0.5 (52 mV dec 1) was ap-
proaching to that of Pt/C (36 mV dec 1) and lower than
those of Cr Mo NiS0.5Se0.5 (71 mV dec 1) and NF
(177 mV dec 1) (Figure 4b), indicating Am Mo NiS0.5Se0.5
possesses superior catalytic kinetics. Moreover, the electro-
catalytic activities of state-of-the-art HER catalysts in recent
literatures at neutral-solution are summarized in Figure 4c
and Table S3. It can be seen that Am Mo NiS0.5Se0.5 owns
favorable HER activity comparing with previously reported
electrocatalysts. The excellent HER activity for
Am Mo NiS0.5Se0.5 in neutral-solution can be mainly attrib-
uted to the formation of amorphous structure which lead to
more vacancy and higher electronic density of states. Mean-
while, the Rct for Am Mo NiS0.5Se0.5 is 0.8 Ω, which is much
lower than that of Cr Mo NiS0.5Se0.5 (1.7 Ω) (Figure S5),
implying the enhanced electronic conductivity of the
amorphous structure, which promoting the electrocatalytic
process of HER/OER.[30, 67] The electrochemical double-
layer capacitance (Cdl) of Am Mo NiS0.5Se0.5 and
Cr Mo NiS0.5Se0.5 catalysts were measured (Figure 4d and
Figure S6a,b). It can be seen that Am Mo NiS0.5Se0.5 owns
higher electrochemical surface area (ECSA)
(117.65 mF cm 2) than Cr Mo NiS0.5Se0.5 (91.81 mF cm 2),
which should be attributed to the more defects in
Angew. Chem. Int. Ed. 2023, e202215256 (6 of 11)
15213773, 0, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/anie.202215256 by Kyung Hee University Library, Wiley Online Library on [17/01/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
Angewandte
Chemie
Am Mo NiS0.5Se0.5. The linear scan voltammogram results
after normalized by ECSA values show that
Am Mo NiS0.5Se0.5 owns better intrinsic HER activity than
that of Cr Mo NiS0.5Se0.5 (Figure S6c). The turnover fre-
quency (TOF) of Am Mo NiS0.5Se0.5 can reach 0.482 s 1 at
100 mVRHE, which is also much higher than those of
Cr Mo NiS0.5Se0.5 (0.141 s 1) (Figure 4e). The higher intrin-
sic activity of Am Mo NiS0.5Se0.5 might be ascribed to the
altered electronic density of states. The stability was another
vital factor for the future application of electrocatalysts.
Significantly, the high HER stability of Am Mo NiS0.5Se0.5
was confirmed by chronoamperometry and the LSV results
at 1st and 20 000th cycles (Figure 4f). Excitingly, no obvious
activity degradation of Am Mo NiS0.5Se0.5 can be detected
at 10 mA cm 2 after 300 h (the inset of Figure 4f), which was
much better than that of Pt/C. In addition, the XPS and
TEM results after HER process (Figures S7 and S8)
indicated that the Am Mo NiS0.5Se0.5 remained the original
morphology and composition. This excellent stability might
be attributed to theunique morphology and amorphous
structure.
Besides HER, the as-prepared Am Mo NiS0.5Se0.5 also
exhibits remarkable OER performance in 1.0 M PBS
solution as shown in Figure 5a. The Am Mo NiS0.5Se0.5
requires only an overpotential of 238 mV to delivers a
current density of 10 mA cm 2, which is much lower than
those of commercial IrO2 (365 mV), Cr Mo NiS0.5Se0.5
(329 mV), NF (434 mV) and most of the reported transition
metal compound electrocatalysts (Table S4). Especially,
Am Mo NiS0.5Se0.5 shows a much lower overpotential
(514 mV) at a high current density (1000 mA cm 2) than
those of commercial IrO2 and Cr Mo NiS0.5Se0.5. The
© 2022 Wiley-VCH GmbH

Research Articles
Figure 5. a) OER polarization curves of Am Mo NiS0.5Se0.5, Cr Mo NiS0.5Se0.5, NF, and commercial IrO2; b) The comparison of specific current
density for Am Mo NiS0.5Se0.5, Cr Mo NiS0.5Se0.5, and commercial IrO2 at 1.6 V versus RHE; c) Tafel plots of Am Mo NiS0.5Se0.5,
Cr Mo NiS0.5Se0.5, NF, and commercial IrO2; d) Normalized LSV basing on ECSA, e) TOF of the Am Mo NiS0.5Se0.5 and Cr Mo NiS0.5Se0.5; f) The
polarization curves were recorded before and after 20 000 CV cycles for Am Mo NiS0.5Se0.5, the inset is the long-term durability of
Am Mo NiS0.5Se0.5 and commercial IrO2.
specific activity is another evaluation indicator of OER
performance (Figure 5b). Compared with Cr Mo NiS0.5Se0.5
and IrO2, the specific activity of Am Mo NiS0.5Se0.5 showed
22 and 5 times of Cr Mo NiS0.5Se0.5 and IrO2, respectively.
In addition, Am Mo NiS0.5Se0.5 also possesses a lower Tafel
slope of 48 mV dec 1 as compared with 69 mV dec 1 for
Cr Mo NiS0.5Se0.5 and 92 mV dec 1 for IrO2 (Figure 5c),
indicating better OER kinetics of Am Mo NiS0.5Se0.5.
Electrochemical impedance spectroscopy (EIS) analyses
were further investigated in Figure S9. Apparently,
Am Mo NiS0.5Se0.5 owns faster charge transfer than
Cr Mo NiS0.5Se0.5. To evaluate the intrinsic OER activity,
the normalized LSV based on ECSA was investigated and
results reveal that Am Mo NiS0.5Se0.5 owns higher intrinsic
OER activity than Cr Mo NiS0.5Se0.5 (Figure 5d). The TOF
of Am Mo NiS0.5Se0.5 can reach 0.202 s 1 at 1.7 VRHE, which
is much higher than those of Cr Mo NiS0.5Se0.5 (0.054 s 1)
and IrO2 (0.015 s 1) (Figure 5e). The above mentioned
aspects manifest that the Am Mo NiS0.5Se0.5 is a promising
candidate for OER at neutral solution. This excellent OER
activity of Am Mo NiS0.5Se0.5 can be attributed to the
abundant defects of amorphous structure and the altered
electronic structure, which owns more active sites and higher
intrinsic activity. Moreover, the high OER stability of
Am Mo NiS0.5Se0.5 in 1.0 M PBS solution was confirmed by
chronoamperometry and CV cycles (Figure 5f).
Am Mo NiS0.5Se0.5 was demonstrated as a robust electro-
catalyst with small degradation of activity after 300 h and
20 000 cycles of continuous reaction. XPS spectra of
Am Mo NiS0.5Se0.5 after the OER stability test demon-
strated that there is no evident change in chemical
Angew. Chem. Int. Ed. 2023, e202215256 (7 of 11)
15213773, 0, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/anie.202215256 by Kyung Hee University Library, Wiley Online Library on [17/01/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
Angewandte
Chemie
composition (Figure S10), except partial oxidation of Ni3 +.
Moreover, the TEM image of Am Mo NiS0.5Se0.5 after the
OER stability test reveals that the heterostructure is well
preserved after continuous operation 300 h (Figure S11).
The excellent HER and OER durability of
Am Mo NiS0.5Se0.5 may benefit from the amorphous nano-
sheets wrapped nanorods structure.
According to it’s excellent HER and OER activities of
Am Mo NiS0.5Se0.5 (Figure 6a), it is expected to further
investigate full-cell water splitting toward industrial applica-
tions. As such, overall watersplitting performance was
assessed by using the Am Mo NiS0.5Se0.5 and
Cr Mo NiS0.5Se0.5 electrode as both the anode and cathode
materials. The potential polarization curves of synthesized
samples and Pt/C j j IrO2 water electrolyzer in 1.0 M PBS
solution are shown in Figure 6b. Remarkably, the overall-
water-splitting performance of Am Mo NiS0.5Se0.5 (1.52 V)
is superior to the Cr Mo NiS0.5Se0.5 (1.66 V) and Pt/C j j
IrO2 (1.64 V) at 10 mA cm 2. At room temperature, this
electrolyzer (Am Mo NiS0.5Se0.5) requires only a cell volt-
age of 1.98 V to reach the current density of 1000 mA cm 2
for water-splitting, much lower than those of
Cr Mo NiS0.5Se0.5 and Pt/C j j IrO2. The electrocatalytic
performances of state-of-the-art water splitting catalysts in
recent literatures are presented in Figure 6c and Table S5. It
can be seen that Am Mo NiS0.5Se0.5 owns better electro-
catalytic activities for water splitting compared with most
previously reported catalysts. Meanwhile, the amount of
evolved H2 and O2 match well with those calculated volume
ratio (Figure S12), implying a nearly 100 % Faradaic effi-
ciency of Am Mo NiS0.5Se0.5 for water splitting. In addition,
© 2022 Wiley-VCH GmbH
 15213773, 0, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/anie.202215256 by Kyung Hee University Library, Wiley Online Library on [17/01/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
Angewandte
Research Articles Chemie

Figure 6. a) The required potentials to achieve HER and OER at a current density of 10 mA cm 2; b) Polarization curves for overall water splitting
with the Am Mo NiS0.5Se0.5 electrode as both the anode and cathode (The benchmark electrodes of Cr Mo NiS0.5Se0.5 and IrO2(+) j j Pt/C( ) are
tested for comparison.); c) Comparison of overpotential (@ 10 mA cm 2) for our work and various previous reported catalysts in neutral medium;
d) The polarization curves of Am Mo NiS0.5Se0.5 recorded before and after 20 000 CV cycles. The inset is the chronopotentiometry curves of
Am Mo NiS0.5Se0.5 and IrO2(+) j j Pt/C( ) at a constant current density of 10 mA cm 2 tested in a two-electrode configuration.

the excellent stability of Am Mo NiS0.5Se0.5 measured at
10 mA cm 2 for 300 h can be seen in the inset of Figure 6d,
which is much better than that of Pt/C j j IrO2. And the slight
degradation of 20 000 CV cycles also confirms its excellent
stability (Figure 6d).
In order to investigate the intrinsic activity of amorphous
samples, DFT calculations were carried out to evaluate the
water splitting process of Am Mo NiS0.5Se0.5 system and
Cr Mo NiS0.5Se0.5. The Am Mo NiS0.5Se0.5 and
Cr Mo NiS0.5Se0.5 model were built as shown in Figure S13–
S16. The theoretical derivation of band structures is plotted
to further shows the difference in electronic contribution of
the amorphous and crystalline structures for
Cr Mo NiS0.5Se0.5 in boosting the catalysis. Notably, the
crystalline structure reveals an obvious indirect band gap of
0.4 eV (Figure 7a), which proves the energy barriers for d-d
and d-p transitions. For comparison, the Am Mo NiS0.5Se0.5
owns electron-rich feature crossing without any energy gap
(Figure 7b), facilitating the facile d-d electron transition for
achieving superior performance. Moreover, the forbidden p-
d electron transition in the crystalline structure has been
loosen by the amorphous structure. Therefore, these results
demonstrate that such different electron transfer causes the
contrast selectivity of water splitting process.[30] The pro-
jected densities of states (PDOS) for Am Mo NiS0.5Se0.5
and Cr Mo NiS0.5Se0.5 were calculated as illustrated in
Figure 7c. Compared to Cr Mo NiS0.5Se0.5, the d orbital of
Ni-site for Am Mo NiS0.5Se0.5 is shifted upward, reflecting
the facilitated electron transport ability and improved
chemical activity.[68] Then, we evaluated the adsorption
energies of H2O (ΔEH2 O ) on the surface of
Am Mo NiS0.5Se0.5 and Cr Mo NiS0.5Se0.5 (Figure 7d),
which is a prerequisite step in the following H2 evolution. As
a result, the Am Mo NiS0.5Se0.5 owns a much lower ΔEH2 O
than Cr Mo NiS0.5Se0.5, indicating that the amorphous
structure facilitates the Volmer step (H2O + e !Had +
OH ).[69, 70] Additionally, the calculated adsorption free
energies of HER and OER processes are shown in Fig-
ure 7e,f and Figure S13–16. Figure 7e shows a ΔGH (hydro-
gen adsorption free energy) of 0.13 eV for
Am Mo NiS0.5Se0.5 at Ni sites and a ΔGH of 0.22 eV for
Am Mo NiS0.5Se0.5 at Mo sites, which are lower than those

Angew. Chem. Int. Ed. 2023, e202215256 (8 of 11) © 2022 Wiley-VCH GmbH

Research Articles
Figure 7. The band structure of the a) Cr Mo NiS0.5Se0.5 and b) Am Mo NiS0.5Se0.5; c) DOS of Am Mo NiS0.5Se0.5 and Cr Mo NiS0.5Se0.5; d) The
calculated adsorption free energy of water on Am Mo NiS0.5Se0.5 and Cr Mo NiS0.5Se0.5. Calculated free energy diagram of the e) HER and f) OER
on Am Mo NiS0.5Se0.5 and Cr Mo NiS0.5Se0.5.
of Ni sites (ΔGH = 0.3 eV) and Mo sites (ΔGH = 0.59 eV)
in Cr Mo NiS0.5Se0.5. Those results demonstrate that Ni
sites are the active sites during HER process in
Am Mo NiS0.5Se0.5, and the proceeding of adsorption of H
on Am Mo NiS0.5Se0.5 is easier than on Cr Mo NiS0.5Se0.5.
For the various OER intermediates (*OH, *O, *OOH, and
O2) formation steps, the free-energy in the potential rate-
determining-step of Ni sites for Am Mo NiS0.5Se0.5 (ΔGH =
1.67 eV) is much lower than that of Cr Mo NiS0.5Se0.5
(ΔGH = 1.86 eV) as shown in Figure 7f, which is consistent
with the experimental OER results.
Conclusion
In summary, an Am Mo NiS0.5Se0.5 was synthesized by
hydrothermal method with utilizing reductive agent. The
Am Mo NiS0.5Se0.5 exhibit outstanding catalytic activities
and excellent stability toward HER and OER at the neutral
solution. It only needs overpotentials of 209 and 514 mV for
HER and OER at 1000 mA cm 2, respectively. The out-
standing catalytic activity is due to its amorphous structure
with high density of unsaturated sites, altered the local
electronic structure of the metal atom and the reduced of
binding energy of hydrogen and oxygen intermediates in the
HER and OER process. Overall, this work provides a highly
active and stable TMCs material for HER and OER by
designing and synthesizing amorphous phase, which will
promote the future application of overall water splitting in
the neutral environment.
Angew. Chem. Int. Ed. 2023, e202215256 (9 of 11)
15213773, 0, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/anie.202215256 by Kyung Hee University Library, Wiley Online Library on [17/01/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
Angewandte
Chemie
Acknowledgements
This work is partially supported by the grants from the
National Natural Science Foundation of China (Grant Nos.
52177220 and 52231008) and Key research and development
program of Hainan province (ZDYF2022GXJS006).
Conflict of Interest
The authors declare no conflict of interest.
Data Availability Statement
Research data are not shared.
Keywords: Amorphous · Crystalline · High-Current-Density ·
Neutral Environment · Water Splitting
[1] Q. Lu, H. Wu, X. Zheng, Y. Cao, J. Li, Y. Wang, H. Wang, C.
Zhi, Y. Deng, X. Han, W. Hu, Adv. Energy Mater. 2022, 12,
2202215.
[2] H. Li, S. Chen, X. Jia, B. Xu, H. Lin, H. Yang, L. Song, X.
Wang, Nat. Commun. 2017, 8, 15377.
[3] Y. Wang, X. Li, M. Zhang, J. Zhang, Z. Chen, X. Zheng, Z.
Tian, N. Zhao, X. Han, K. Zaghib, Y. Wang, Y. Deng, W. Hu,
Adv. Mater. 2022, 34, 2107053.
[4] Q. Lin, D. Guo, L. Zhou, L. Yang, H. Jin, J. Li, G. Fang, X.
Chen, S. Wang, ACS Nano 2022, 16, 15460–15470.
[5] X. Zheng, X. Han, Y. Cao, Y. Zhang, D. Nordlund, J. Wang, S.
Chou, H. Liu, L. Li, C. Zhong, Y. Deng, W. Hu, Adv. Mater.
2020, 32, 2000607.
© 2022 Wiley-VCH GmbH

Research Articles
[6] Z. Gu, Y. Zhang, X. Wei, Z. Duan, L. Ren, J. Ji, Adv. Sci.
2022, 38, 3469–3479.
[7] X. Zheng, Y. Cao, Z. Wu, W. Ding, T. Xue, J. Wang, Z. Chen,
X. Han, Y. Deng, W. Hu, Adv. Energy Mater. 2022, 12,
2103275.
[8] C. Lin, J. Li, X. Li, S. Yang, W. Luo, Y. Zhang, S. Kim, D.
Kim, S. S. Shinde, Y. Li, Z. Liu, Z. Jiang, J. Lee, Nat. Catal.
2021, 4, 1012–1023.
[9] H. Liu, J. Cheng, W. He, Y. Li, J. Mao, X. Zheng, C. Chen, C.
Cui, Q. Hao, Appl. Catal. B 2022, 304, 120935.
[10] X. Zhang, X. Yu, L. Zhang, F. Zhou, Y. Liang, R. Wang, Adv.
Funct. Mater. 2018, 28, 1706523.
[11] L. Zhang, L. Han, H. Liu, X. Liu, J. Luo, Angew. Chem. Int.
Ed. 2017, 56, 13694–13698.
[12] Q. Lu, H. Wu, X. Zheng, Y. Chen, A. L. Rogach, X. Han, Y.
Deng, W. Hu, Adv. Sci. 2021, 8, 2101438.
[13] G. Valenti, A. Boni, M. Melchionna, M. Cargnello, L. Nasi, G.
Bertoni, R. J. Gorte, M. Marcaccio, S. Rapino, M. Bonchio, P.
Fornasiero, M. Prato, F. Paolucci, Nat. Commun. 2016, 7,
13549.
[14] Y. Luo, L. Tang, U. Khan, Q. Yu, H. Cheng, X. Zou, B. Liu,
Nat. Commun. 2019, 10, 269.
[15] L. A. King, M. A. Hubert, C. Capuano, J. Manco, N. Danilovic,
E. Valle, T. R. Hellstern, K. Ayers, T. F. Jaramillo, Nat.
Nanotechnol. 2019, 14, 1071–1075.
[16] J. Yang, A. R. Mohmad, Y. Wang, R. Fullon, X. Song, F.
Zhao, I. Bozkurt, M. Augustin, E. J. G. Santos, H. S. Shin, W.
Zhang, D. Voiry, H. Y. Jeong, M. Chhowalla, Nat. Mater. 2019,
18, 1309–1315.
[17] Y. Zheng, X. Zhou, Y. Jiao, M. Jaroniec, S. Qiao, J. Am.
Chem. Soc. 2019, 141, 7646–7659.
[18] J. Shan, C. Guo, J. Shan, C. Guo, Y. Zhu, S. Chen, L. Song, M.
Jaroniec, Chem 2019, 5, 445–459.
[19] P. Wang, X. Zhang, J. Zhang, S. Wan, S. Guo, G. Lu, J. Yao,
X. Huang, Nat. Commun. 2017, 8, 14580.
[20] Q. Lu, A. Wang, Y. Gong, W. Hao, H. Cheng, J. Chen, B. Li,
N. Yang, W. Niu, J. Wang, Y. Yu, X. Zhang, Y. Chen, Z. Fan,
X. Wu, J. Chen, J. Luo, S. Li, L. Gu, H. Zhang, Nat. Chem.
2018, 10, 456–461.
[21] J. Wang, Y. Ji, Q. Shao, R. Yin, J. Guo, Y. Li, X. Huang, Nano
Energy 2019, 59, 138–145.
[22] H. Han, H. Choi, S. Mhin, Y. Hong, Energy Environ. Sci. 2019,
12, 2443–2454.
[23] J. S. Kim, I. Park, E. Jeong, K. Jin, W. M. Seong, G. Yoon, H.
Kim, B. Kim, K. T. Nam, K. Kang, Adv. Mater. 2017, 29,
1606893.
[24] D. Merki, S. Fierro, H. Vrubel, X. Hu, Chem. Sci. 2011, 2,
1262–1267.
[25] S. Hu, M. R. Shaner, J. A. Beardslee, M. Lichterman, B. S.
Brunschwig, N. S. Lewis, Science 2014, 344, 1005–1009.
[26] G. Chen, Y. Zhu, H. M. Chen, Z. Hu, S. Hung, N. Ma, J. Dai,
H. Lin, C. Chen, W. Zhou, Z. Shao, Adv. Mater. 2019, 31,
1900883.
[27] J. Marie, V. Nsanzimana, Y. Peng, Y. Y. Xu, L. Thia, C. Wang,
B. Y. Xia, X. Wang, Adv. Energy Mater. 2018, 8, 1701475.
[28] J. Sun, D. Yang, S. Lowe, L. Zhang, Y. Wang, S. Zhao, Adv.
Mater. 2018, 30, 1801495.
[29] N. Yang, H. Cheng, X. Liu, Q. Yun, Y. Chen, B. Li, B. Chen,
Z. Zhang, X. Chen, Q. Lu, J. Huang, Y. Huang, Y. Zong, Adv.
Mater. 2018, 30, 1803234.
[30] J. Wang, L. Han, B. Huang, Q. Shao, H. L. Xin, X. Huang,
Nat. Commun. 2019, 10, 5692.
[31] J. Zhang, Y. Hu, D. Liu, Y. Yu, B. Zhang, Adv. Sci. 2017, 4,
1600343.
[32] M. Fang, D. Han, W. Xu, Y. Shen, Y. Lu, P. Cao, S. Han, W.
Xu, D. Zhu, W. Liu, J. C. Ho, Adv. Energy Mater. 2020, 10,
2001059.
Angew. Chem. Int. Ed. 2023, e202215256 (10 of 11)
15213773, 0, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/anie.202215256 by Kyung Hee University Library, Wiley Online Library on [17/01/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
Angewandte
Chemie
[33] X. Zhang, Z. Luo, P. Yu, Y. Cai, Y. Du, D. Wu, S. Gao, C.
Tan, Z. Li, M. Ren, T. Osipowicz, S. Chen, Z. Jiang, J. Li, Y.
Huang, J. Yang, Y. Chen, C. Y. Ang, Y. Zhao, P. Wang, L.
Song, X. Wu, Z. Liu, A. Borgna, H. Zhang, Nat. Catal. 2018, 1,
460–468.
[34] X. Zheng, X. Han, Y. Zhang, J. Wang, C. Zhong, Y. Deng, W.
Hu, Nanoscale 2019, 11, 5646.
[35] Y. Wang, X. Li, M. Zhang, Y. Zhou, D. Rao, C. Zhong, J.
Zhang, X. Han, W. Hu, Y. Zhang, K. Zaghib, Y. Wang, Y.
Deng, Adv. Mater. 2020, 32, 2000231.
[36] P. Zhai, Y. Zhang, Y. Wu, J. Gao, B. Zhang, S. Cao, Y. Zhang,
Z. Li, L. Sun, J. Hou, Nat. Commun. 2020, 11, 5462.
[37] J. Diao, Y. Qiu, S. Liu, W. Wang, K. Chen, H. Li, W. Yuan, Y.
Qu, X. Guo, Adv. Mater. 2020, 32, 1905679.
[38] X. Yu, G. Chen, Y. Wang, J. Liu, K. Pei, Y. Zhao, W. You, L.
Wang, J. Zhang, L. Xing, J. Ding, G. Ding, M. Wang, R. Che,
Nano Res. 2020, 13, 437–446.
[39] Y. Jia, L. Zhang, G. Gao, H. Chen, B. Wang, J. Zhou, M. T.
Soo, M. Hong, X. Yan, G. Qian, J. Zou, A. Du, X. Yao, Adv.
Mater. 2017, 29, 1700017.
[40] X. Wu, X. Han, X. Ma, W. Zhang, Y. Deng, C. Zhong, W. Hu,
ACS Appl. Mater. Interfaces 2017, 9, 12574–12583.
[41] X. Chen, D. Chen, X. Guo, R. Wang, H. Zhang, ACS Appl.
Mater. Interfaces 2017, 9, 18774–18781.
[42] X. Zheng, Y. Zhang, H. Liu, D. Fu, J. Chen, J. Wang, C.
Zhong, Y. Deng, X. Han, W. Hu, Small 2018, 14, 1803666.
[43] R. Xu, R. Wu, Y. M. Shi, J. F. Zhang, B. Zhang, Nano Energy
2016, 24, 103–110.
[44] E. Kamali-Heidari, Z. L. Xu, M. H. Sohi, A. Ataie, J. K. Kim,
Electrochim. Acta 2018, 271, 507–518.
[45] D. Nicholls, M. Rowley, R. Swindells, J. Chem. Soc. A 1966,
950–952.
[46] J. W. Park, E. H. Chae, S. H. Kim, J. H. Lee, J. W. Kim, S. M.
Yoon, J. Y. Choi, Mater. Chem. Phys. 2006, 97, 371–378.
[47] Z. G. Wu, M. Munoz, O. Montero, Adv. Powder Technol.
2010, 21, 165–168.
[48] Y. Cao, X. Zheng, H. Zhang, J. Zhang, X. Han, C. Zhong, W.
Hu, Y. Deng, J. Power Sources 2019, 437, 226893.
[49] Q. Xu, Y. Liu, H. Jiang, Y. Hu, H. Liu, C. Li, Adv. Energy
Mater. 2019, 9, 1802553.
[50] B. Zhang, J. Li, Q. Song, X. Xu, W. Hou, H. Liu, Inorg. Chem.
2021, 60, 2604–2613.
[51] H. Xu, Y. Liao, Z. Gao, Y. Qing, Y. Wu, L. Xia, J. Mater.
Chem. A 2021, 9, 3418–3426.
[52] L. Lv, Z. Yang, K. Chen, C. Wang, Y. Xiong, Adv. Energy
Mater. 2019, 9, 1803358.
[53] J. Zhang, J. Liu, L. Xi, Y. Yu, N. Chen, W. Wang, K. M. Lange,
B. Zhang, J. Zhang, J. Liu, L. Xi, Y. Yu, N. Chen, S. Sun, W.
Wang, J. Am. Chem. Soc. 2018, 140, 3876–3879.
[54] M. Asnavandi, Y. Yin, Y. Li, C. Sun, C. Zhao, ACS Energy
Lett. 2018, 3, 1515–1520.
[55] Z. Qiu, C. W. Tai, T. Edvinsson, G. A. Niklasson, Energy
Environ. Sci. 2019, 12, 572–581.
[56] P. Li, M. Wang, X. Duan, L. Zheng, X. Cheng, Y. Zhang, Y.
Kuang, Y. Li, Q. Ma, Z. Feng, W. Liu, X. Sun, Nat. Commun.
2019, 10, 1711.
[57] F. Boscherini, Synchrotron Radiat. 2015, 14, 485–498.
[58] Z. Sun, Q. Liu, T. Yao, W. Yan, S. Wei, Sci. China Mater. 2015,
58, 313–341.
[59] K. Jiang, B. Liu, M. Luo, S. Ning, M. Peng, Y. Zhao, Y. R. Lu,
T. S. Chan, F. M. F. de Groot, Y. Tan, Nat. Commun. 2019, 10,
1743.
[60] C. Meng, T. Ling, T. Y. Ma, H. Wang, Z. Hu, Y. Zhou, J. Mao,
X. W. Du, M. Jaroniec, S. Z. Qiao, Adv. Mater. 2017, 29,
1604607.
© 2022 Wiley-VCH GmbH

Research Articles
[61] B. J. Hwang, S. M. Senthil Kumar, C. H. Chen, Monalisa,
M. Y. Cheng, D. G. Liu, J. F. Lee, J. Phys. Chem. C 2007, 111,
15267–15276.
[62] A. I. Frenkel, C. W. Hills, R. G. Nuzzo, J. Phys. Chem. B 2001,
105, 12689–12703.
[63] V. V. Srabionyan, A. L. Bugaev, V. V. Pryadchenko, L. A.
Avakyan, J. A. Van Bokhoven, L. A. Bugaev, J. Phys. Chem.
Solids 2014, 75, 470–476.
[64] H. Cheng, N. Yang, G. Liu, Y. Ge, J. Huang, Q. Yun, Y. Du,
C. Sun, B. Chen, J. Liu, H. Zhang, Adv. Mater. 2020, 32,
1902964.
[65] A. Chang, C. Zhang, Y. Yu, Y. Yu, B. Zhang, ACS Appl.
Mater. Interfaces 2018, 10, 41861–41865.
[66] Y. Liu, Y. Chen, Y. Tian, T. Sakthivel, H. Liu, S. Guo, H.
Zeng, Z. Dai, Adv. Mater. 2022, 34, 2203615.
Angew. Chem. Int. Ed. 2023, e202215256 (11 of 11)
15213773, 0, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/anie.202215256 by Kyung Hee University Library, Wiley Online Library on [17/01/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
Angewandte
Chemie
[67] S. Jiao, Z. Yao, M. Li, C. Mu, H. Liang, Y. Zeng, H. Huang,
Nanoscale 2019, 11, 18894–18899.
[68] H. Zhang, T. Wang, A. Sumboja, W. Zang, J. Xie, D. Gao, S. J.
Pennycook, Z. Liu, C. Guan, J. Wang, Adv. Funct. Mater. 2018,
28, 1804846.
[69] D. Strmcnik, M. Uchimura, C. Wang, R. Subbaraman, N.
Danilovic, D. Van Der Vliet, A. P. Paulikas, V. R. Stamen-
kovic, N. M. Markovic, Nat. Chem. 2013, 5, 300–306.
[70] T. Cheng, L. Wang, B. V. Merinov, W. A. Goddard, J. Am.
Chem. Soc. 2018, 140, 7787–7790.
Manuscript received: October 17, 2022
Accepted manuscript online: December 3, 2022
Version of record online: ■■■, ■■■■
© 2022 Wiley-VCH GmbH
 15213773, 0, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/anie.202215256 by Kyung Hee University Library, Wiley Online Library on [17/01/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
Angewandte
Research Articles Chemie

Research Articles
Water Splitting Am Mo NiS0.5Se0.5 nanocomposites
were synthesized by a simple one-step
Y. Wang, X. Li, Z. Huang, H. Wang, Z. Chen, strategy. The catalysts display efficient
J. Zhang, X. Zheng,* Y. Deng,* and stable bifunctional electrocatalytic
W. Hu e202215256 performance for HER and OER, as well
as for water splitting in neutral solution.
Amorphous Mo-doped NiS0.5Se0.5 Nano- The amorphous structure abundant un-
sheets@Crystalline NiS0.5Se0.5 Nanorods for saturated sites altered the local elec-
High Current-density Electrocatalytic Water tronic structure of metallic sites and
Splitting in Neutral Media optimized the energy barrier for the rate-
determining step (O* to OOH*).

Angew. Chem. Int. Ed. 2023, e202215256 © 2022 Wiley-VCH GmbH