Chemical Engineering Journal 454 (2023) 140079

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Chemical Engineering Journal

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

Improving the hydrogen evolution reaction activity of molybdenum-based

heterojunction nanocluster capsules via electronic modulation by
erbium–nitrogen–phosphorus ternary doping
Fang Tan a, 1, Yingtang Zhou b, 1, Hua Zhang a, 1, Pengliang Sun c, *, Hongyi Li d, *, Xijun Liu e,
Thomas Wågberg f, Guangzhi Hu a, f, *
a
School of Chemical Science and Technology, Institute for Ecological Research and Pollution Control of Plateau Lakes, School of Ecology and Environmental Science,
Yunnan University, Kunming 650504, China
b
National Engineering Research Center for Marine Aquaculture, Marine Science and Technology College, Zhejiang Ocean University, Zhoushan, China
c
School of Environmental Science and Engineering, Tongji University, Shanghai 200092, China
d
Guangzhou Panyu Polytechnic, Guangzhou 511483, China
e
MOE Key Laboratory of New Processing Technology for Non-ferrous Metals and Materials, Guangxi Key Laboratory of Processing for Non-ferrous Metals and Featured
Materials, Guangxi University, Nanning, Guangxi 530004, China
f
Department of Physics, Umeå University, S-901 87 Umeå, Sweden

A R T I C L E I N F O A B S T R A C T

Keywords: The realization of a hydrogen-based economy with robust hydrogen evolution reaction catalysts remains a
Hydrogen evolution reaction challenge. In this study, we prepared MoO2/Mo2N3 heterostructure nanoclusters co-doped with nitrogen,
Heterointerfaces phosphorus, and erbium for the first time. The introduction of the nitrogen and phosphorus atoms into the
Intrinsic activity
transition metal increases the d-electron density and contracts the d-band, which leads to a rearranged electronic
Rare earth element doping
Electrocatalysis
structure of the MoO2/Mo2N3 heterojunction. The coupling of the rare earth erbium dopant with the valence
band of the heterojunction leads to the redistribution of the electron density in the catalyst and promotes co­
valent interaction with the adsorbed intermediates, thereby optimizing the Gibbs free energy of intermediate
adsorption and improving the catalytic activity for the hydrogen evolution reaction. Not only is an efficient and
economical catalyst for electrolytic aquatic hydrogen production provided in this work, but a new synthesis
scheme is also proposed for the rational synthesis of homologous core–shell polymetallic nanostructures with
broad application prospects.

1. Introduction platinum and platinum-based materials are widely used as cathode

The considerable consumption of fossil fuels worldwide has led to
growing concerns regarding the energy crisis and environmental
pollution, warranting research on clean and renewable energy sources
[1,2]. As an ideal energy carrier, hydrogen has attracted significant in­
terest owing to its high energy density, environmental friendliness, and
renewability [3–5]. Electrochemical splitting of water driven by elec­
tricity generated by renewable energy sources (such as wind and solar
energy) is an important carbon–neutral method for producing green
hydrogen [6]. The catalytic activity of the cathodic hydrogen evolution
catalyst plays an important role in this process [7,8]. The precious metal
hydrogen evolution reaction (HER) catalysts to overcome the hysteresis
kinetics of water electrolysis [9,10]. However, the scarcity and high
price of such catalysts significantly hinder the large-scale industrial
production of hydrogen through water electrolysis [11]. Therefore,
developing high-performance HER catalysts with high efficiency, ample
abundance, and suitability in alkaline mediums is important for real­
izing large-scale green energy conversion and industrial hydrogen pro­
duction through water electrolysis.
Although many exciting achievements have been reported, electro­
catalysts with cell voltages close to the theoretical value of 1.23 V have
not yet been realized because of the combined effects of several factors,

* Corresponding authors at: School of Chemical Science and Technology, Institute for Ecological Research and Pollution Control of Plateau Lakes, School of Ecology
and Environmental Science, Yunnan University, Kunming 650504, China (G. Hu).
E-mail addresses: pengliangsun@tongji.edu.cn (P. Sun), lihy@gzpyp.edu.cn (H. Li), guangzhihu@ynu.edu.cn (G. Hu).
1
These authors contributed equally.

https://doi.org/10.1016/j.cej.2022.140079
Received 14 August 2022; Received in revised form 20 October 2022; Accepted 25 October 2022
Available online 29 October 2022
1385-8947/© 2022 Elsevier B.V. All rights reserved.
F. Tan et al.
such as the low exposed active center densities and specific surface areas
and borehole conductance due to insufficient electron transport. To
improve catalytic efficiency, a new concept is required for designing a
catalyst in which the active centers are maximized and fast electron
transfer is ensured by tuning parameters such as the morphology, crystal
phase, defects, doping, van der waals interactions, and composition of
the catalyst [9,12]. Among all the non-noble-metal-based catalysts re­
ported to date, transition metal nitrides (TMNs) have attracted much
attention because of their unique metal-like physicochemical properties
and electronic structure [13]. The introduction of nitrogen atoms into
transition metals increases their d-electron density and contracts their d-
bands, which makes the electronic structures of TMNs near the Fermi
level similar to those of precious metals Pd and Pt [14]. Nitrogen plays a
positive role in improving the intrinsic and external properties of TMNs
because it can be used to improve their catalytic activity through
composition and phase control, interface engineering, and facet and
defect regulation [15]. In addition to having electrical conductivities
similar to those of metals, TMNs exhibit high corrosion resistance and
good electrocatalytic performance for splitting water into acidic and
alkaline solutions [16]. Therefore, the incorporation of nitrogen (N) into
the transition metal lattice of a catalyst can improve its activity by
increasing its conductivity, catalytic centers, and corrosion resistance in
alkaline and acidic solutions.
Rare earth elements, especially those in the La series, have attracted
extensive attention as electronic modulators in transition-metal-based
materials for energy conversion applications because of their unique
electronic structures due to their 4f orbitals [17,18]. Zhang et al. [19]
reported that Er-doped CoP ultrathin nanomeshes have excellent total
hydrolytic performance. Their density functional theory (DFT) results
showed that the electronic structure of CoP could be adjusted through Er
doping to improve its intrinsic catalytic performance. Ce-doped CoP
synthesized by Li et al. [20] exhibited high HER and oxygen evolution
reaction performance and can be used as an efficient splitting water
catalyst. This is helped by the fact that the introduction of Ce into CoP
can lead to electronic modulation of Co, thus reducing the energy barrier
of both to provide better activity. Chen et al. [21] reported that Ce-
doped CoMoP/MoP@C exhibited excellent bifunctional water electrol­
ysis catalytic performance under alkaline conditions. The addition of Ce
resulted in a redistribution of the electron density in the catalyst, which
changed its surface chemistry and valence state and thereby increased
its Gibbs free energy for intermediate adsorption and improved its cat­
alytic activity. The special electronic structures of rare earth species
cause the wave functions of their 4f and 5d orbitals to overlap and hy­
bridize when these species are used as electron modulators in transition-
metal-based active materials for electrocatalytic applications. This fa­
cilitates the coupling of the transition metal bands with the valence
bands of the rare earth species and the delocalization of the 4f electrons
in the latter. It also promotes covalent interactions with adsorbed in­
termediates, which is promising for modulating the electrocatalytic
properties of transition-metal-based materials [22]. Thus, rare earth
metal doping is a promising strategy for developing optimized multi­
functional electrocatalysts for hydrogen production through splitting
water.
Here, we demonstrate a new concept of simultaneous doping by
erbium (Er), nitrogen (N), and phosphorus (P) through a simple hy­
drothermal treatment and high-temperature carbonization process to
prepare Er-MoO2/Mo2N3@P, NC hollow nanocapsules. The strong
electronic interactions at the interface between MoO2 and Mo2N3 in the
Er-MoO2/Mo2N3 heterostructure allow smooth charge transfer within
the catalyst and provide active centers for the HER reaction. In addition,
the three-dimensional interconnected hollow nanosphere structure of
Er-MoO2/Mo2N3@P, NC significantly increases its active surface area,
exposes more active centers, promotes electrolyte penetration, and
mitigates gas leakage. The Mo nanostructures doped with P and N
exhibit high catalytic behavior because of their ability to transfer
charges from Mo to P and N, and the accelerated proton-coupled
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Chemical Engineering Journal 454 (2023) 140079
electron transfer process in the HER. These advantages result in Er-
MoO2/Mo2N3@P, NC achieving the highest electrochemical perfor­
mance among reported TMNs and excellent hydrogen evolution per­
formance superior to those of many previously reported TMNs. Not only
was a novel Mo-based catalyst prepared in an alkaline electrolyte
through a novel combination process in this study, but an in-depth un­
derstanding of how the stability and HER activity of a catalyst can be
improved by modulating its electronic structure is also provided.
2. Experimental section
2.1. Synthesis of Er-MoO2/Mo2N3@P, NC
Using SiO2 microspheres as hard templates, Er-MoO2/Mo2N3@P, NC
catalysts were prepared using a simple method as shown in Fig. 1a. SiO2
microspheres are first synthesized using a slightly modified Stöber
process. In a typical preparation process, silica microspheres (1.0 g) are
uniformly dispersed in a premixed solution of 30 mL ethanol and 70 mL
deionized water. Resorcinol, ethylenediamine (EDA), and formaldehyde
were then added to the solution every 5 min under stirring at a tem­
perature of 40 ◦ C. After 10 min, a certain amount of ethyl orthosilicate
(dispersed in 20 mL of ethanol) was added dropwise, and the solution
was kept warm and stirred for 14 h. Phosphomolybdic acid (H3[P
(Mo3O10)4]⋅xH2O) and Er(NO3)3⋅6H2O (Er: Mo = 0.091:0.909) were
then added and the solution was stirred for another 10 h. The sediment
was then separated by centrifugation and dried overnight at 60 ◦ C. The
product was then maintained at 500 ◦ C for 30 min under an argon at­
mosphere, followed by carbonization at 900 ◦ C for 3 h. Finally, 9.1
%-doped Er-MoO2/Mo2N3@P, NC catalyst was obtained by etching the
silica with a 5 wt% hydrofluoric acid solution. To investigate the effect
of the amount of Er rare earth element dopant on the catalyst perfor­
mance, the Er: Mo molar ratios were varied (4.8 %, 9.1 %, 16.7 %, and
23.1 %) and the resultant catalysts denoted as Erx-MoO2/Mo2N3@P, NC,
X = 4.8 %, 9.1 %, 16.7 %, and 23.1 %, respectively.
2.2. Theoretical calculation
Full computational methods are provided in the Supplemental
materials.
3. Results and discussion
3.1. Morphology and structure characterization
The electrochemical and structural stability of the Er-MoO2/
Mo2N3@P, NC heterostructures were determined experimentally.
Fig. 1a shows the detailed synthetic process of the Er-doped MoO2/
Mo2N3 heterojunction hollow nanocapsules. A layer of resorci­
nol–formaldehyde polymer was coated on the surface of silica (SiO2)
spheres using a one-pot polymerization method. EDA was used as a
catalyst for the polymerization reaction and ethyl orthosilicate hydro­
lysis [23] and as a nitrogen precursor for the in situ doping of N into the
carbon material [24]. Anionic clusters of phosphomolybdic acid and
rare earth erbium salts were then added and attached to the polymer
surface through electrostatic interactions. The formation of the metal
heterojunction nanoclusters was subsequently promoted by pyrolysis to
maximize metal utilization. Hollow nanocapsules with Er-MoO2/
Mo2N3@P, NC heterostructures were finally obtained by etching.
The nanostructures of the synthesized samples were characterized
using scanning electron microscopy (SEM) and scanning transmission
electron microscopy (STEM). The high-magnification SEM images
(Fig. 1b) and spherical aberration TEM images (Fig. 1c) show that the
synthesized Er-MoO2/Mo2N3@P, NC heterostructures are well-grown on
hollow carbon nanospheres with an average diameter of approximately
400 nm. The STEM images of the Er-MoO2/Mo2N3@P, NC catalysts
(Fig. 1d) show that the Er-MoO2/Mo2N3 nanoclusters with an average
F. Tan et al.
Fig. 1. Synthesis and characterization of Er-MoO2/Mo2N3@P, NC and its corresponding composites. (a) Schematic of the Er-MoO2/Mo2N3@P, NC synthesis
procedure. (b) Typical SEM image of Er-MoO2/Mo2N3@P, NC. (c) Typical TEM image of Er-MoO2/Mo2N3@P, NC. (d) HAADF-STEM image of Er-MoO2/Mo2N3@P,
NC. (e) HAADF-STEM image of MoO2/Mo2N3 in Er-MoO2/Mo2N3@P, NC (enlargement of the white dashed rectangle in (d)). The monodispersed MoO2/Mo2N3
clusters are denoted by red circles. (f) HAADF-STEM image of MoO2/Mo2N3 nanocrystals in Er-MoO2/Mo2N3@P, NC. (g) EDX elemental mapping of Er-MoO2/
Mo2N3@P, NC. Scale bars: 200 nm.
diameter of approximately 5 nm are uniformly anchored on the carbon
layer surface and provide abundant interfacial sites for electrocatalytic
reactions. The aberration-corrected high-angle annular dark-field scan­
ning electron microscopy (HAADF-STEM) image in Fig. 1f shows lattice
spacings of 0.240 nm and 0.343 nm corresponding to the interplanar
distances of the Mo2N3 (1 1 1) (PDF No. 89-3712) and MoO2 (1 1 0) faces
(PDF No. 78-1073), respectively. The corresponding intensity differ­
ences in the HAADF-STEM images confirm the formation of the MoO2/
Mo2N3 heterojunction nanocrystalline clusters. The electrical conduc­
tivity and stability are improved by the synergistic effect between the
clusters [8]. Isolated and scattered single clusters (the bright spots
denoted by the red circles in Fig. 1e) are visible on the entirety of the
support. The missing lattice stripes in Fig. 1e are defects (amorphiza­
tion) in the MoO2/Mo2N3 heterostructure, and the defects in the range of
the white dashed line should be the transformation defects of the metal
compound crystal from crystalline to amorphous. Such structural defects
may provide additional unsaturated active atoms, which modify the
electronic configuration, thereby promising to improve the catalytic
activity of the active centers [1]. Furthermore, the HAADF-STEM image
and corresponding energy-dispersive spectroscopy element mapping
images show that C, N, O, P, Mo, and Er are uniformly distributed
throughout the Er-doped MoO2/Mo2N3 heterojunction hollow carbon
spheres (Fig. 1g), which is consistent with the X-ray photoelectron
spectroscopy (XPS) results. The overlapping elemental signals confirm a
hierarchical structure consisting of Er-MoO2/Mo2N3 and heteroatom (N,
P)-doped carbon layers. More importantly, the clear interfaces resulting
from the mismatch between Mo2N3 and MoO2 provide abundant active
sites and defect-rich surface structures, as shown in Fig. 1f. Such het­
erointerfaces and defect-rich surfaces promote electrocatalysis by
inducing local electron delocalization [25].
The crystal structures and compositions of the obtained catalysts
were investigated using X-ray diffraction (XRD) and the results are
shown in Fig. 2a. In the XRD pattern of Er-MoO2/Mo2N3@P, NC, all the
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Chemical Engineering Journal 454 (2023) 140079
diffraction peaks match well with and are indexed to those of MoO2
(PDF #78-1073) and Mo2N3 (PDF #89-3712). In particular, there are no
diffraction peaks that indicate the presence of other substances such as
Er and P. This shows that Er and P were effectively doped into the Mo
structure without obvious impurities. The small amount of Er and P
doped into the Mo structure resulted in a distortion of the crystal
structure relative to the structures in the MoO2 and Mo2N3 standard
cards (some characteristic peaks, such as those at 25.95 and 43.41 ,
◦ ◦
were offset) [26]. This distortion is consistent with the formation of the
lattice defects observed in the STEM images and increased the number of
exposed electroactive sites. Furthermore, it also led to a modulation of
the electronic structure of the d-band center on the strained surface of
the Mo layer, which improves the binding energy and reactivity to small
adsorbed species and thereby promotes water electrolysis [5]. The
Raman spectra confirm the presence of graphitic carbon in the Er-MoO2/
Mo2N3@P, NC samples (Fig. 2b), which is consistent with the results of
the XPS analysis. The Raman spectra of the Er-MoO2/Mo2N3@P, NC
catalyst exhibit two broad peaks at 1365 and 1584 cm− 1 corresponding
to the D and G bands, respectively. The D band originates from the
hybridized sp3 orbitals of the carbon atoms in the defects and carbon
structure, while the G band originates from the sp2 orbitals of the hex­
agonally bonded carbon atoms in the graphite network [6]. The calcu­
lated ID/IG ratio of 0.939 indicates that the hybridized sp2 carbon
orbitals significantly contribute to the porous carbon coating on the
catalyst surface, which may effectively promote electron conduction
between the porous spheres and metal heterostructures.
N2 adsorption–desorption analysis was performed at 77.3 K to
determine the average pore size distribution (3.819 nm) and specific
surface area (596.87 m2/g) of Er-MoO2/Mo2N3@P, NC. The N2
adsorption–desorption results are summarized in Table S1 (Supple­
mentary Material), and the curves are shown in Fig. 2c. According to the
IUPAC classification scheme, the isotherms of the Er-MoO2/Mo2N3@P,
NC catalyst are all type IV, indicating that the catalyst has a mesoporous
F. Tan et al.
Fig. 2. Phases and surface chemical states of MoO2/Mo2N3@P, NC. (a) XRD spectra, (b) Raman spectra, (c) N2 adsorption–desorption isotherms, and (inset)
corresponding pore size distributions of the Er-MoO2/Mo2N3@P, NC samples. High-resolution (d) C 1 s, (e) N 1 s, (f) O 1 s, (g) P 2p, (h) Mo 3d, and (i) Er 4d XPS
spectra of Er-MoO2/Mo2N3@P, NC.
structure [6,27]. The isotherms exhibit a clear H4-type hysteresis loop
(P/P0 = 0.1–1.0), which may have resulted from the pore-forming effect
of the hard template, leading to the formation of mesopores and mac­
ropores interconnected with smaller surrounding pores [28]. The high
pore content in the catalyst indicated by these results leads to the
exposure of more active sites, thereby promising to improve the elec­
trocatalytic activity of the catalyst. The interconnected porous nature of
the outer carbon layer and the inner hollow space provides numerous
active sites that can be readily accessed by the electrolyte during the
HER.
X-ray photoelectron spectroscopy (XPS) analysis was performed to
determine the chemical states and composition of Er-MoO2/Mo2N3@P,
NC. In the high-resolution C1s spectrum (Fig. 2d), the dominant peak at
284.85 eV indicates that most of the species are graphitic carbon. C–N,
C–O, and C– – O bonds are also present in the C1s spectrum at 285.55,
286.67, and 288.56 eV, respectively. The weak C– – O bond strength in­
dicates that Er-MoO2/Mo2N3@P, NC contains a small amount of oxygen-
containing functional groups, including C–O bonds and carbonyl
groups. In addition, the C–N bond indicates some amount of nitrogen
doping in the carbon. As shown in Fig. 2e, the N1s spectrum is decon­
voluted and fitted to four peaks at 397.48, 399.09, 400.49, and 401.96
eV, which were assigned to Mo− N, pyridinic-N, pyrrolic-N, and
graphitic-N, respectively [6]. The peak at 397.48 eV in the N1s spectrum
can be attributed to the Mo− N coupling phase, which is the catalytic
center of the HER [29]. The formation of the Mo− N species indicates
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Chemical Engineering Journal 454 (2023) 140079
that N also tends to modify the surface of the Er-MoO2/Mo2N3 hetero­
junction nanoclusters. The broad O1s peak indicates the presence of
multiple oxygen chemical states (Fig. 2f). The O1s spectrum can be
divided into three components comprising the Mo-O (531.12 eV), C–O
(531.89 eV), and C– – O (532.73 eV) bonds. In addition, the deconvolu­
tion of the P2p spectrum reveals two peaks at 133.93 eV and 134.85 eV
attributed to the P–C and P–O species, respectively (Fig. 2g). There­
fore, through the double synergistic effect of Er-MoO2/Mo2N3 nano­
clusters and N, P co-doped carbon layer, carbon materials can be
induced to produce structural defects, increase the surface active sites of
electrolyte ion transport, and increase the electrical conductivity to
achieve excellent electrochemical behavior (Fig. 3d), which is expected
to improve the activity of HER. A new characteristic peak at 169.4 eV
(Fig. 2i) attributed to Er4d also indicates that Er was successfully doped
into MoO2/Mo2N3@P, NC and consistent with the results of the HAADF-
STEM image. Combined with the DFT analysis, the incorporation of Er
can modulate the electronic environment of MoO2/Mo2N3 and lead to
more unsaturated Moδ+, effectively increasing electrochemical active
sites and accelerating electron transfer, thereby increasing the electro­
catalytic intrinsic activity of the catalysts. Three pairs of characteristic
peaks can be observed in the high-resolution Mo3d spectrum (Fig. 2h).
The characteristic peaks at 228.81 eV and 232.03 eV are attributed to
the positively charged molybdenum species of Er-MoO2/Mo2N3@P, NC
(Moδ+ 3d5/2 and Moδ+ 3d3/2) (Moδ+, 0 < δ < 4), while the peaks at
229.72 eV and 232.87 eV are attributed to Mo4+ 3d5/2 and Mo4+ 3d3/2,
F. Tan et al. Chemical Engineering Journal 454 (2023) 140079

Fig. 3. HER electrocatalytic performance of Er-MoO2/Mo2N3@P, NC and the related electrocatalysts in 1.0 M KOH. (a) Polarization curves of Er-MoO2/
Mo2N3@P, NC and the related catalysts. (b) Tafel plots of Er-MoO2/Mo2N3@P, NC, MoO2/Mo2N3@P, NC, Er-MoO2, and Pt/C were obtained from the corresponding
polarization curves. (c) Comparison of the overpotentials required to achieve current densities of − 10, − 50, and − 200 mA cm− 2 for the various catalysts. d)
Electrochemical impedance spectroscopy of the different electrodes at 1.55 V versus RHE. Inset: Equivalent circuit used for data analyses. (e) Double-layer
capacitance. (f) Chronopotentiometry curve of Er-MoO2/Mo2N3@P, NC at a constant potential for 20 h and the corresponding linear sweep voltammetry (LSV)
polarization curves before and after 20 h of steady-state operation (inset). (g) Schematic of the HER reaction mechanism under alkaline conditions. h) Comparison of
the overpotential (j = 10 mA cm− 2) values of Er-MoO2/Mo2N3@P, NC, and the other reported noble-metal electrocatalysts in 1.0 M KOH.

5
F. Tan et al.
respectively. The other two high-intensity peaks at 233.5 eV and 236.02
eV are attributed to Mo6+ 3d5/2 and Mo6+ 3d3/2, respectively, which
resulted from the surface oxidation of the molybdenum species (MoO2
and MoO3) [30]. Moreover, due to the difference in electronegativities
between Er (1.24) and Mo (2.16), the proportion of Mo6+ increases
significantly after Er doping, which leads to a shift in the electron den­
sity from Er to Mo. Furthermore, the Mo3d peaks from Er-MoO2/
Mo2N3@P, NC are 0.3 eV more negative than those from MoO2/
Mo2N3@P, NC, respectively. This may be suggestive of the electron
transfer from Er to Mo, which may arise due to differences in their
electronegativities. Combined with the former analysis, the incorpora­
tion of Er can modulate the electronic environment of MoO2/Mo2N3 and
lead to more unsaturated Moδ+, effectively increasing electrochemical
active sites and accelerating electron transfer, the increased electron
density of the Mo species can modulate the electronic states of the
catalyst and promote hydrogen adsorption, thereby improving its
intrinsic catalytic activity [31].
3.2. Electrochemical HER performance
To evaluate the electrocatalytic performance of the Er-MoO2/
Mo2N3@P, NC heterointerface, a three-electrode device was assembled
to investigate the HER of the synthesized catalyst in 1.0 M KOH elec­
trolyte saturated with nitrogen. All potentials were recorded relative to
the RHE with 90 % iR compensation. Fig. 3a and Fig. S1 (Supplementary
Material) show the HER properties of the samples through their polar­
ization curves. As expected, the Er-MoO2/Mo2N3@P, NC heterogeneous
interfacial catalyst shows a higher catalytic activity compared to the
other electrocatalysts. The overpotential (η) of only 65.2 mV required to
reach a current density of 10 mA cm− 2 is lower than those of MoO2/
Mo2N3@P, NC (η 10 = 80.1 mV) and MoO2 (η 10 = 124.1 mV) and
comparable to that of commercial Pt/C. Er-MoO2/Mo2N3@P, NC out­
performs Pt/C when the current density increases beyond 40 mA cm− 2.
The catalytic activity for the HER is affected by the amount of doping:
The overpotential of Er4.8%-MoO2/Mo2N3@P, NC is 137 mV, and that of
Er16.7%-MoO2/Mo2N3@P, NC is 120 mV, and that of Er23.7%-MoO2/
Mo2N3@P, NC is 154 mV. These results confirm that the introduction of
the 9.1 % Er dopant into the MoO2/Mo2N3 nanostructures can reduce
the series resistance, and increase the active centers and conductivity of
the electrode. However, a further increase in the doping concentration
increases the resistance and greatly reduces the number of active sites
because of the more complicated distortion of the crystal lattice. These
results demonstrate the advantages of Er doping for enhancing the HER
performance of MoO2/Mo2N3. It should be stressed that Er-MoO2/
Mo2N3@P, NC achieved an outstanding HER efficiency close to that of
Pt/C. This efficiency is attributed to the 3D porous structure of the
capsules, which provided abundant active sites for the H* adsorption
and continuous conductive channels that accelerated electron transport.
It is noteworthy that few reported Mo-based catalysts have achieved
such high HER activity, which is comparable to even those of transition
metal sulfide and phosphide catalysts in alkaline media (Fig. 3h and
Table S2 Supplementary material). In general, combined with XPS and
DFT calculations, it is confirmed that rare earth metal doping can adjust
the electron density around Mo and N atoms, thus adjusting the elec­
tronic state of Mo2N3, optimizing the adsorption of Gibbs free energy to
hydrogen, and improving the inherent HER activity. The high HER ac­
tivity of Er-MoO2/Mo2N3@P, NC may be due to the synergistic catalytic
effects of the high-conductivity heterogeneous interfaces between
Mo2N3 and MoO2. In addition, the catalytic reaction kinetics and
mechanisms of the HER electrocatalysts were investigated through their
Tafel slopes [25]. As shown in Fig. 3b, the Tafel slope of Er-MoO2/
Mo2N3@P, NC (23.4 mV/dec) is approximately 17 mV/dec smaller than
that of the benchmark Pt/C (40.4 mV/dec) and significantly smaller
than those of MoO2/Mo2N3@P, NC (25.6 mV/dec) and MoO2 (42.9 mV/
dec). These results demonstrate the improved hydrogen adsorption and
water dissociation processes in Er-MoO2/Mo2N3@P, NC. In addition, the
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Chemical Engineering Journal 454 (2023) 140079
Tafel slope of Er-MoO2/Mo2N3@P, NC falls within the range of the
theoretical values for the Volmer–Heyrovsky mechanism. This suggests
that the HER kinetics are described by the Volmer–Heyrovsky mecha­
nism and the Volmer reaction (Mcat + H2O + e− → McatHad + OH− ) is the
rate-determining step (Fig. 3g) [32]. The OH− produced by the H2O
splitting may be favorably chemisorbed on the interfaces of Er-MoO2/
Mo2N3@P, NC, which have a moderate electrostatic affinity. According
to the Sabatier principle, moderate adsorption/desorption of the reac­
tion intermediate is required for the highest catalyst effectiveness [33].
The coupling of Mo2N3 and MoO2 changes the metal–hydrogen bond
energy to a value favorable for the desorption and release of the
hydrogen atoms absorbed at the active sites. Therefore, the MoO2/
Mo2N3 heterogeneous interface provides a promising active site for the
adsorption and release of hydrogen atoms.
Electrochemical impedance spectroscopy (EIS) measurements were
performed at − 0.1 V vs RHE in 1.0 M KOH to study the kinetic activities
of the as-obtained catalysts. Fig. 3d shows that the charge transfer
resistance of the Er-MoO2/Mo2N3@P, NC (Rct = 38.7 Ω) is significantly
lower than that of the MoO2/Mo2N3@P, NC (Rct = 116.3 Ω) and MoO2
(Rct = 165.2 Ω). This indicates that the former has a higher electrical
conductivity and charge transfer rate, further confirming that Er doping
and heterojunction construction can promote electron transfer and
result in different arrangements of the energy bands in different phases.
This leads to a charge transfer at the interface, which modulates the
surface electrons of the heterostructures and thereby enhances the cat­
alytic activity for water reduction. To better understand the effect of
doping on the active centers, we studied the electrochemical active
surface area (ECSA) of the Er-MoO2/Mo2N3@P, NC samples. It is well
known that the ECSA of a sample is directly proportional to its elec­
trochemical double-layer capacitance Cdl [34] as described by the
equation ECSA = Cdl/Cs, where Cs is the specific capacitance of a flat
surface and has a typical value of 0.040 mF cm− 2 in 1.0 M NaOH [35].
The linear relationship between the ECSA and Cdl can be calculated from
the cyclic voltammogram [36,37]. Cdl is related to the double-layer
charging current (Ic) and scan rate (ν) by Cdl = Ic/ν. The data from the
CV curves recorded at the scan rates of 20, 40, 60, 80, 100, and 120 mV
s− 1 (Fig. S2 Supplementary material) were used to generate the graph of
the current density plotted against the scan rate in Fig. 3e. A good linear
relationship is observed between the two quantities. The larger Cdl value
of 40.59 mF cm− 2 for the Er-MoO2/Mo2N3@P, NC sample compared to
that of the MoO2 sample (11.31 mF cm− 2) implies that the former has a
larger ECSA and more catalytic active centers. The Er doping improved
the HER catalytic activity of the catalyst by effectively increasing its
electrochemically active surface area and creating more active sites.
Surprisingly, the chronopotentiometry results (Fig. 3f) show that the
overpotential required for Er-MoO2/Mo2N3@P, NC at 10 mA cm− 2
decayed by only 3 % over 20 consecutive hours of testing under alkaline
conditions. The almost complete overlap between the initial polariza­
tion curve of the catalyst and the curve after 20 h of steady-state oper­
ation indicates the excellent durability of the catalyst (Fig. 3f,
illustration). The STEM images in Fig. S3 (Supplementary material)
show that the heterojunction hollow capsule structure of Er-MoO2/
Mo2N3@P, NC was well preserved after the HER test, which proves that
the catalyst is highly stable for the HER.
3.3. Theoretical calculation analysis
To unveil the catalytic mechanism for the superior HER performance
of MoO2/Mo2N3 co-doped with nitrogen, phosphorus, and erbium het­
erojunction nanocluster, density functional theory (DFT) calculations
were employed (Fig. 4a). According to the XRD and STEM data, models
of MoO2(1 1 0)/Mo2N3(1 1 1), Er-MoO2(1 1 0)/Mo2N3(1 1 1), and Er-
MoO2(1 1 0)/Mo2N3(1 1 1)@P, NC were established, respectively
(Fig. 4h and Fig. S4 Supplementary material).
H2O adsorption is key to three main stages is involved in the HER
pathway of alkaline media [38]. The H2O adsorption energies (ΔGH2O)
F. Tan et al. Chemical Engineering Journal 454 (2023) 140079

Fig. 4. DFT calculation. (a) Schematic diagram of adsorption configuration of HER on Er-MoO2/Mo2N3@P, NC heterojunction catalyst. (b) Calculated adsorption
free energy of water on different configures on MoO2(1 1 0)/Mo2N3(1 1 1), Er-MoO2(1 1 0)/Mo2N3(1 1 1), and Er-MoO2(1 1 0)/Mo2N3(1 1 1)@P, NC surfaces. (c)
Calculated the hydrogen adsorption energy (ΔGH*) on different atom sites of Er-MoO2(1 1 0)/Mo2N3(1 1 1)@P, NC. (d, e) Calculated free energies of H* (HBE) and
OH* (OHBE) on MoO2, Mo2N3, MoO2/Mo2N3, Er-MoO2, Er-MoO2/Mo2N3,and Er-MoO2/Mo2N3@P, NC. (f) Relationship between d band center values and ΔGH* over
various models. (g) Mo 3d orbitals and corresponding εd value of the MoO2/Mo2N3, Er-MoO2/Mo2N3, and Er-MoO2/Mo2N3@P, NC. (h) Top and side views of
optimized structures of Er-MoO2/Mo2N3@P, NC.

on different configurations (top site, bridge site, and hollow site) of
MoO2(1 1 0)/Mo2N3(1 1 1), Er-MoO2(1 1 0)/Mo2N3(1 1 1) and Er-
MoO2(1 1 0)/Mo2N3(1 1 1)@P, NC catalysts are calculated (Fig. 4b). The
results show that all of the bridge sites on MoO2(1 1 0)/Mo2N3 (1 1 1),
Er-MoO2(1 1 0)/Mo2N3(1 1 1), and Er-MoO2(1 1 0)/Mo2N3(1 1 1)@P,
NC catalysts are favorable for H2O adsorption to be − 0.82, − 0.95, and
− 1.07 eV, respectively, indicating Er-MoO2/Mo2N3@P, NC with more
negative ΔEH2O value displays effective H2O adsorption for subsequent
hydrogen evolution than other two catalysts.
The hydrogen (H*) adsorption free energy (ΔGH*) is also regarded as
a key descriptor in determining HER activity [39]. The ΔGH* values
varied from − 0.452 eV on MoO2(1 1 0) to − 0.117 eV on Er-MoO2(1 1
0)/Mo2N3(1 1 1)@P, NC via Mo2N3(1 1 1) (− 0.364 eV) and Er-MoO2(1
1 0)/Mo2N3(1 1 1) (− 0.185 eV) (Fig. S5), indicating very small ΔGH*
value with Er-MoO2(1 1 0)/Mo2N3(1 1 1)@P, NC supports its superior
HER performance. It is ascribed to co-doped with nitrogen, phosphorus,
and erbium to MoO2(1 1 0)/Mo2N3(1 1 1) boosting HER performance.
To gain an in-depth understanding of the origins of active site behavior,
the hydrogen species on different atoms sites of Er-MoO2(1 1 0)/
Mo2N3(1 1 1)@P, NC was investigated (Fig. 4c), Mo2 in close proximity
to the optimum ΔGH* with a zero value implies high-activity HER
catalysis. Interestingly, hydrogen species preferred to adsorb on Er-
adjacent Mo sites Er-MoO2(1 1 0)/Mo2N3(1 1 1)@P, NC catalyst.
According to previous reports, the active center with the lowest free
energy, that is, the most stable adsorption center, can be determined as
the best adsorption site for OH* or H* species on the catalyst [40]. The
binding energy of hydrogen (HBE), is treated as the key prerequisite for
HER catalysts to achieve excellent performance during H2 evolution in
Fig. 4d. Compared with the highest HBE value of − 0.43 eV for the
MoO2(1 1 0) nanoparticle, the Er-MoO2(1 1 0)/Mo2N3(1 1 1)@P, NC
exhibited the weakest hydrogen binding with a value of − 0.17 eV,
implying the powerful regulation of hydrogen adsorption with nitrogen,
phosphorus, and erbium loading. In addition, hydroxyl species also
affect the HER process in an alkaline solution [41]. Therefore, the
binding energy of hydroxyl species (OHBE) was also investigated
(Fig. 4e). Relative to MoO2(1 1 0) nanoparticle, Er-MoO2(1 1 0)/
Mo2N3(1 1 1)@P, NC structures exhibited enhanced hydroxyl adsorp­
tion with increased OHBE absolute values, which is consistent with the
Tafel plot analysis. In order to further elucidate the origin of the
improved HER activity of MoO2(1 1 0)/Mo2N3(1 1 1) after introducing
Er, P, N and C, the d band, charge difference distribution and Bader
charge were also calculated to deeply investigate the changes of the
electronic structure of the catalyst. It is worth noting that the d-band
centers on the Mo sites of MoO2/Mo2N3, Er-MoO2/Mo2N3, and Er-

7
F. Tan et al.
MoO2/Mo2N3@P, NC are calculated (Fig. 4f). The results show that
there is an obvious linear relationship between the H* adsorption energy
and the d-band center, and the d-band interaction center on the Er-
MoO2/Mo2N3@P, NC interface is the optimized OHBE and enhanced
HBE caused by charge transfer. It also illustrated that Er-MoO2/
Mo2N3@P, NC exhibits the best hydrogen (H*) adsorption energy, which
can ensure the rapid occurrence of H* adsorption/desorption steps. At
the same time, the introduction of Er, N, and P is beneficial to improve
the d-band center of MoO2/Mo2N3, thus synergistically enhancing the
activity of HER. In addition, the the d-band center of Mo on Er-MoO2(1
1 0)/Mo2N3(1 1 1)@P, NC shifted to Fermi level (Fig. 4g), corresponding
to boost catalyst performance on Er-MoO2(1 1 0)/Mo2N3(1 1 1)@P, NC.
Electronic structures of Mo 3d orbitals in MoO2/Mo2N3, Er-MoO2/
Mo2N3, and Er-MoO2/Mo2N3@P, NC (H adsorbed on Mo atom) were
further analyzed by the projected density of states (PDOS) and charge
density distribution. It is found that the |ΔGH*| value and εd energy level
value of MoO2/Mo2N3 are precisely modulated by introducing the Er
atom. As shown in Fig. 4g, Er-MoO2/Mo2N3@P, NC exhibits a lower
εd energy level (-2.56 eV) of Mo 3d orbital compared to that of the
MoO2/Mo2N3 (-2.14 eV) while a positively shifted εd energy level of Mo
3d orbital in comparison with that of the Er-MoO2/Mo2N3 (-2.32 eV).
The deeper the Mo 3d orbital εd value is, the less |ΔGH*| value it has
[49], which is well consistent with the aforementioned description that
Er-MoO2/Mo2N3@P, NC (H adsorbed on Mo atom) possesses the lowest
|ΔGH*| value. These results suggest that Er, N, and P incorporation could
effectively modulate the εd value of Mo 3d orbital, thus balancing the
adsorption of H* and the desorption of H2. According to the Sabatier
principle [42], moderate adsorption and desorption energies of the in­
termediates play a vital role in determining catalytic activities.
To elucidate the inherent relationship between the electronic struc­
ture and the enhanced electrocatalytic HER performance of Er-MoO2(1
1 0)/Mo2N3(1 1 1)@P, NC, the adsorption-free energy of the HER in­
termediates and worse charge was also evaluated. The relation between
Bader charge and the adsorption-free energy change of H* reveals that
the Er-MoO2(1 1 0)/Mo2N3(1 1 1)@P, NC catalyst can promote the HER
performance, matching well with their charge density difference results
shown in Fig. S6 (Supplementary material), where the Er-MoO2(1 1 0)/
Mo2N3(1 1 1)@P, NC transferred 0.95 e to H*, higher than that in Er-
MoO2(1 1 0)/Mo2N3(1 1 1) (0.89 e), and MoO2(1 1 0)/Mo2N3(1 1 1)
(0.75 e). It clearly demonstrates that electron distribution on the surface
of Er-MoO2(1 1 0)/Mo2N3(1 1 1)@P, NC is stronger than Er-MoO2(1 1
0)/Mo2N3(1 1 1) and MoO2(1 1 0)/Mo2N3(1 1 1), revealing excellent
electronic mobility. In summary, the DFT calculation results prove that
introducing Er, P, and N to MoO2(1 1 0)/Mo2N3(1 1 1) reduces the en­
ergy barrier of both H2O adsorption and hydrogen generation, regulates
the electronic microenvironment and improves electronic mobility.
4. Conclusion
In summary, the present study is the first to successfully synthesize
efficient, durable, and low-cost MoO2/Mo2N3 heterojunction nano­
cluster catalysts co-doped with erbium, nitrogen, and phosphorus using
a feasible method. The dispersed hollow porous spherical structure of Er-
MoO2/Mo2N3@P, NC formed by the MoO2/Mo2N3 heterojunction
nanoclusters hosts optimized intrinsic electronic interactions and pro­
vides abundant electrocatalytic active centers and rapid diffusion paths
for the reactants and intermediates. Owing to the synergistic effect be­
tween their composition and structure, the Er-MoO2/Mo2N3@P, NC
hollow nanocapsules achieved an outstanding HER performance in
alkaline electrolytes in which a current density of 10 mA cm− 2 was
driven by an overpotential of only 65.2 mV. This performance exceeds
those of reported Mo-based catalysts doped with heteroatoms or rare
earth elements and is attributed to the adjustable structural/electronic
characteristics, which enhance the surface area and centers for elec­
trocatalytic activity. The addition of the rare earth element Er results in
a redistribution of the electron density, which leads to changes in its
8
Chemical Engineering Journal 454 (2023) 140079
surface chemistry and catalyst valency that optimize the Gibbs free
energy for the intermediate adsorption and increase the catalytic ac­
tivity. The changes in the inherent electronic structure of Mo that result
from the combined effects of Er doping and in situ double doping with N
and P reduce the kinetic energy barrier for the HER process. These
findings provide new insights for customizing the size of the active sites
in the development of high-performance catalysts with active centers
formed from single clusters.
CRediT authorship contribution statement
Fang Tan: Conceptualization, Investigation, Visualization, Writing –
original draft. Yingtang Zhou: Investigation, Data curation, Writing –
original draft. Hua Zhang: Investigation, Software, Writing – original
draft. Pengliang Sun: Investigation, Resources, Visualization, Writing –
review & editing. Hongyi Li: Resources, Investigation, Methodology.
Xijun Liu: Formal analysis, Methodology. Thomas Wågberg: Formal
analysis, Methodology. Guangzhi Hu: Conceptualization, Project
administration, Supervision, Resources, Writing – review & editing.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Data availability
Data will be made available on request.
Acknowledgments
The authors acknowledge the financial support from the Double Tops
Joint Fund of the Yunnan Science and Technology Bureau and Yunnan
University (2019FY003025), Open Foundation of Guangxi Key Labora­
tory of Processing for Non-ferrous Metals and Featured Materials of
Guangxi University (2022GXYSOF10), Double First Class University
Plan (C176220100042), Guangdong Colleges & Universities Charac­
teristic Innovation Project (2021KTSCX263), Guangdong Education &
Scientific Research Project (2021GXJK535). T.W. acknowledges the
support from Vetenskapsrådet (2017-04862, and 2021-04629), Ener­
gimyndigheten (45419-1), and SSF-Agenda 2030-PUSH. The authors
thank the Advanced Analysis and Measurement Center of Yunnan Uni­
versity for the sample testing service.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.cej.2022.140079.
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