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

hydrogen evolution reaction (HER) catalysts to overcome the hysteresis
The considerable consumption of fossil fuels worldwide has led to kinetics of water electrolysis [9,10]. However, the scarcity and high
growing concerns regarding the energy crisis and environmental price of such catalysts significantly hinder the large-scale industrial
pollution, warranting research on clean and renewable energy sources production of hydrogen through water electrolysis [11]. Therefore,
[1,2]. As an ideal energy carrier, hydrogen has attracted significant in­ developing high-performance HER catalysts with high efficiency, ample
terest owing to its high energy density, environmental friendliness, and abundance, and suitability in alkaline mediums is important for real­
renewability [3–5]. Electrochemical splitting of water driven by elec­ izing large-scale green energy conversion and industrial hydrogen pro­
tricity generated by renewable energy sources (such as wind and solar duction through water electrolysis.
energy) is an important carbon–neutral method for producing green Although many exciting achievements have been reported, electro­
hydrogen [6]. The catalytic activity of the cathodic hydrogen evolution catalysts with cell voltages close to the theoretical value of 1.23 V have
catalyst plays an important role in this process [7,8]. The precious metal 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: [email protected] (P. Sun), [email protected] (H. Li), [email protected] (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. Chemical Engineering Journal 454 (2023) 140079

such as the low exposed active center densities and specific surface areas electron transfer process in the HER. These advantages result in Er-
and borehole conductance due to insufficient electron transport. To MoO2/Mo2N3@P, NC achieving the highest electrochemical perfor­
improve catalytic efficiency, a new concept is required for designing a mance among reported TMNs and excellent hydrogen evolution per­
catalyst in which the active centers are maximized and fast electron formance superior to those of many previously reported TMNs. Not only
transfer is ensured by tuning parameters such as the morphology, crystal was a novel Mo-based catalyst prepared in an alkaline electrolyte
phase, defects, doping, van der waals interactions, and composition of through a novel combination process in this study, but an in-depth un­
the catalyst [9,12]. Among all the non-noble-metal-based catalysts re­ derstanding of how the stability and HER activity of a catalyst can be
ported to date, transition metal nitrides (TMNs) have attracted much improved by modulating its electronic structure is also provided.
attention because of their unique metal-like physicochemical properties
and electronic structure [13]. The introduction of nitrogen atoms into 2. Experimental section
transition metals increases their d-electron density and contracts their d-
bands, which makes the electronic structures of TMNs near the Fermi 2.1. Synthesis of Er-MoO2/Mo2N3@P, NC
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 Using SiO2 microspheres as hard templates, Er-MoO2/Mo2N3@P, NC
because it can be used to improve their catalytic activity through catalysts were prepared using a simple method as shown in Fig. 1a. SiO2
composition and phase control, interface engineering, and facet and microspheres are first synthesized using a slightly modified Stöber
defect regulation [15]. In addition to having electrical conductivities process. In a typical preparation process, silica microspheres (1.0 g) are
similar to those of metals, TMNs exhibit high corrosion resistance and uniformly dispersed in a premixed solution of 30 mL ethanol and 70 mL
good electrocatalytic performance for splitting water into acidic and deionized water. Resorcinol, ethylenediamine (EDA), and formaldehyde
alkaline solutions [16]. Therefore, the incorporation of nitrogen (N) into were then added to the solution every 5 min under stirring at a tem­
the transition metal lattice of a catalyst can improve its activity by perature of 40 ◦ C. After 10 min, a certain amount of ethyl orthosilicate
increasing its conductivity, catalytic centers, and corrosion resistance in (dispersed in 20 mL of ethanol) was added dropwise, and the solution
alkaline and acidic solutions. was kept warm and stirred for 14 h. Phosphomolybdic acid (H3[P
Rare earth elements, especially those in the La series, have attracted (Mo3O10)4]⋅xH2O) and Er(NO3)3⋅6H2O (Er: Mo = 0.091:0.909) were
extensive attention as electronic modulators in transition-metal-based then added and the solution was stirred for another 10 h. The sediment
materials for energy conversion applications because of their unique was then separated by centrifugation and dried overnight at 60 ◦ C. The
electronic structures due to their 4f orbitals [17,18]. Zhang et al. [19] product was then maintained at 500 ◦ C for 30 min under an argon at­
reported that Er-doped CoP ultrathin nanomeshes have excellent total mosphere, followed by carbonization at 900 ◦ C for 3 h. Finally, 9.1
hydrolytic performance. Their density functional theory (DFT) results %-doped Er-MoO2/Mo2N3@P, NC catalyst was obtained by etching the
showed that the electronic structure of CoP could be adjusted through Er silica with a 5 wt% hydrofluoric acid solution. To investigate the effect
doping to improve its intrinsic catalytic performance. Ce-doped CoP of the amount of Er rare earth element dopant on the catalyst perfor­
synthesized by Li et al. [20] exhibited high HER and oxygen evolution mance, the Er: Mo molar ratios were varied (4.8 %, 9.1 %, 16.7 %, and
reaction performance and can be used as an efficient splitting water 23.1 %) and the resultant catalysts denoted as Erx-MoO2/Mo2N3@P, NC,
catalyst. This is helped by the fact that the introduction of Ce into CoP X = 4.8 %, 9.1 %, 16.7 %, and 23.1 %, respectively.
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- 2.2. Theoretical calculation
doped CoMoP/MoP@C exhibited excellent bifunctional water electrol­
ysis catalytic performance under alkaline conditions. The addition of Ce Full computational methods are provided in the Supplemental
resulted in a redistribution of the electron density in the catalyst, which materials.
changed its surface chemistry and valence state and thereby increased
its Gibbs free energy for intermediate adsorption and improved its cat­ 3. Results and discussion
alytic activity. The special electronic structures of rare earth species
cause the wave functions of their 4f and 5d orbitals to overlap and hy­ 3.1. Morphology and structure characterization
bridize when these species are used as electron modulators in transition-
metal-based active materials for electrocatalytic applications. This fa­ The electrochemical and structural stability of the Er-MoO2/
cilitates the coupling of the transition metal bands with the valence Mo2N3@P, NC heterostructures were determined experimentally.
bands of the rare earth species and the delocalization of the 4f electrons Fig. 1a shows the detailed synthetic process of the Er-doped MoO2/
in the latter. It also promotes covalent interactions with adsorbed in­ Mo2N3 heterojunction hollow nanocapsules. A layer of resorci­
termediates, which is promising for modulating the electrocatalytic nol–formaldehyde polymer was coated on the surface of silica (SiO2)
properties of transition-metal-based materials [22]. Thus, rare earth spheres using a one-pot polymerization method. EDA was used as a
metal doping is a promising strategy for developing optimized multi­ catalyst for the polymerization reaction and ethyl orthosilicate hydro­
functional electrocatalysts for hydrogen production through splitting lysis [23] and as a nitrogen precursor for the in situ doping of N into the
water. carbon material [24]. Anionic clusters of phosphomolybdic acid and
Here, we demonstrate a new concept of simultaneous doping by rare earth erbium salts were then added and attached to the polymer
erbium (Er), nitrogen (N), and phosphorus (P) through a simple hy­ surface through electrostatic interactions. The formation of the metal
drothermal treatment and high-temperature carbonization process to heterojunction nanoclusters was subsequently promoted by pyrolysis to
prepare Er-MoO2/Mo2N3@P, NC hollow nanocapsules. The strong maximize metal utilization. Hollow nanocapsules with Er-MoO2/
electronic interactions at the interface between MoO2 and Mo2N3 in the Mo2N3@P, NC heterostructures were finally obtained by etching.
Er-MoO2/Mo2N3 heterostructure allow smooth charge transfer within The nanostructures of the synthesized samples were characterized
the catalyst and provide active centers for the HER reaction. In addition, using scanning electron microscopy (SEM) and scanning transmission
the three-dimensional interconnected hollow nanosphere structure of electron microscopy (STEM). The high-magnification SEM images
Er-MoO2/Mo2N3@P, NC significantly increases its active surface area, (Fig. 1b) and spherical aberration TEM images (Fig. 1c) show that the
exposes more active centers, promotes electrolyte penetration, and synthesized Er-MoO2/Mo2N3@P, NC heterostructures are well-grown on
mitigates gas leakage. The Mo nanostructures doped with P and N hollow carbon nanospheres with an average diameter of approximately
exhibit high catalytic behavior because of their ability to transfer 400 nm. The STEM images of the Er-MoO2/Mo2N3@P, NC catalysts
charges from Mo to P and N, and the accelerated proton-coupled (Fig. 1d) show that the Er-MoO2/Mo2N3 nanoclusters with an average

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F. Tan et al. Chemical Engineering Journal 454 (2023) 140079

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 diffraction peaks match well with and are indexed to those of MoO2
layer surface and provide abundant interfacial sites for electrocatalytic (PDF #78-1073) and Mo2N3 (PDF #89-3712). In particular, there are no
reactions. The aberration-corrected high-angle annular dark-field scan­ diffraction peaks that indicate the presence of other substances such as
ning electron microscopy (HAADF-STEM) image in Fig. 1f shows lattice Er and P. This shows that Er and P were effectively doped into the Mo
spacings of 0.240 nm and 0.343 nm corresponding to the interplanar structure without obvious impurities. The small amount of Er and P
distances of the Mo2N3 (1 1 1) (PDF No. 89-3712) and MoO2 (1 1 0) faces doped into the Mo structure resulted in a distortion of the crystal
(PDF No. 78-1073), respectively. The corresponding intensity differ­ structure relative to the structures in the MoO2 and Mo2N3 standard
ences in the HAADF-STEM images confirm the formation of the MoO2/ cards (some characteristic peaks, such as those at 25.95 and 43.41 ,
◦ ◦

Mo2N3 heterojunction nanocrystalline clusters. The electrical conduc­ were offset) [26]. This distortion is consistent with the formation of the
tivity and stability are improved by the synergistic effect between the lattice defects observed in the STEM images and increased the number of
clusters [8]. Isolated and scattered single clusters (the bright spots exposed electroactive sites. Furthermore, it also led to a modulation of
denoted by the red circles in Fig. 1e) are visible on the entirety of the the electronic structure of the d-band center on the strained surface of
support. The missing lattice stripes in Fig. 1e are defects (amorphiza­ the Mo layer, which improves the binding energy and reactivity to small
tion) in the MoO2/Mo2N3 heterostructure, and the defects in the range of adsorbed species and thereby promotes water electrolysis [5]. The
the white dashed line should be the transformation defects of the metal Raman spectra confirm the presence of graphitic carbon in the Er-MoO2/
compound crystal from crystalline to amorphous. Such structural defects Mo2N3@P, NC samples (Fig. 2b), which is consistent with the results of
may provide additional unsaturated active atoms, which modify the the XPS analysis. The Raman spectra of the Er-MoO2/Mo2N3@P, NC
electronic configuration, thereby promising to improve the catalytic catalyst exhibit two broad peaks at 1365 and 1584 cm− 1 corresponding
activity of the active centers [1]. Furthermore, the HAADF-STEM image to the D and G bands, respectively. The D band originates from the
and corresponding energy-dispersive spectroscopy element mapping hybridized sp3 orbitals of the carbon atoms in the defects and carbon
images show that C, N, O, P, Mo, and Er are uniformly distributed structure, while the G band originates from the sp2 orbitals of the hex­
throughout the Er-doped MoO2/Mo2N3 heterojunction hollow carbon agonally bonded carbon atoms in the graphite network [6]. The calcu­
spheres (Fig. 1g), which is consistent with the X-ray photoelectron lated ID/IG ratio of 0.939 indicates that the hybridized sp2 carbon
spectroscopy (XPS) results. The overlapping elemental signals confirm a orbitals significantly contribute to the porous carbon coating on the
hierarchical structure consisting of Er-MoO2/Mo2N3 and heteroatom (N, catalyst surface, which may effectively promote electron conduction
P)-doped carbon layers. More importantly, the clear interfaces resulting between the porous spheres and metal heterostructures.
from the mismatch between Mo2N3 and MoO2 provide abundant active N2 adsorption–desorption analysis was performed at 77.3 K to
sites and defect-rich surface structures, as shown in Fig. 1f. Such het­ determine the average pore size distribution (3.819 nm) and specific
erointerfaces and defect-rich surfaces promote electrocatalysis by surface area (596.87 m2/g) of Er-MoO2/Mo2N3@P, NC. The N2
inducing local electron delocalization [25]. adsorption–desorption results are summarized in Table S1 (Supple­
The crystal structures and compositions of the obtained catalysts mentary Material), and the curves are shown in Fig. 2c. According to the
were investigated using X-ray diffraction (XRD) and the results are IUPAC classification scheme, the isotherms of the Er-MoO2/Mo2N3@P,
shown in Fig. 2a. In the XRD pattern of Er-MoO2/Mo2N3@P, NC, all the NC catalyst are all type IV, indicating that the catalyst has a mesoporous

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F. Tan et al. Chemical Engineering Journal 454 (2023) 140079

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 that N also tends to modify the surface of the Er-MoO2/Mo2N3 hetero­
(P/P0 = 0.1–1.0), which may have resulted from the pore-forming effect junction nanoclusters. The broad O1s peak indicates the presence of
of the hard template, leading to the formation of mesopores and mac­ multiple oxygen chemical states (Fig. 2f). The O1s spectrum can be
ropores interconnected with smaller surrounding pores [28]. The high divided into three components comprising the Mo-O (531.12 eV), C–O
pore content in the catalyst indicated by these results leads to the (531.89 eV), and C– – O (532.73 eV) bonds. In addition, the deconvolu­
exposure of more active sites, thereby promising to improve the elec­ tion of the P2p spectrum reveals two peaks at 133.93 eV and 134.85 eV
trocatalytic activity of the catalyst. The interconnected porous nature of attributed to the P–C and P–O species, respectively (Fig. 2g). There­
the outer carbon layer and the inner hollow space provides numerous fore, through the double synergistic effect of Er-MoO2/Mo2N3 nano­
active sites that can be readily accessed by the electrolyte during the clusters and N, P co-doped carbon layer, carbon materials can be
HER. induced to produce structural defects, increase the surface active sites of
X-ray photoelectron spectroscopy (XPS) analysis was performed to electrolyte ion transport, and increase the electrical conductivity to
determine the chemical states and composition of Er-MoO2/Mo2N3@P, achieve excellent electrochemical behavior (Fig. 3d), which is expected
NC. In the high-resolution C1s spectrum (Fig. 2d), the dominant peak at to improve the activity of HER. A new characteristic peak at 169.4 eV
284.85 eV indicates that most of the species are graphitic carbon. C–N, (Fig. 2i) attributed to Er4d also indicates that Er was successfully doped
C–O, and C– – O bonds are also present in the C1s spectrum at 285.55, into MoO2/Mo2N3@P, NC and consistent with the results of the HAADF-
286.67, and 288.56 eV, respectively. The weak C– – O bond strength in­ STEM image. Combined with the DFT analysis, the incorporation of Er
dicates that Er-MoO2/Mo2N3@P, NC contains a small amount of oxygen- can modulate the electronic environment of MoO2/Mo2N3 and lead to
containing functional groups, including C–O bonds and carbonyl more unsaturated Moδ+, effectively increasing electrochemical active
groups. In addition, the C–N bond indicates some amount of nitrogen sites and accelerating electron transfer, thereby increasing the electro­
doping in the carbon. As shown in Fig. 2e, the N1s spectrum is decon­ catalytic intrinsic activity of the catalysts. Three pairs of characteristic
voluted and fitted to four peaks at 397.48, 399.09, 400.49, and 401.96 peaks can be observed in the high-resolution Mo3d spectrum (Fig. 2h).
eV, which were assigned to Mo− N, pyridinic-N, pyrrolic-N, and The characteristic peaks at 228.81 eV and 232.03 eV are attributed to
graphitic-N, respectively [6]. The peak at 397.48 eV in the N1s spectrum the positively charged molybdenum species of Er-MoO2/Mo2N3@P, NC
can be attributed to the Mo− N coupling phase, which is the catalytic (Moδ+ 3d5/2 and Moδ+ 3d3/2) (Moδ+, 0 < δ < 4), while the peaks at
center of the HER [29]. The formation of the Mo− N species indicates 229.72 eV and 232.87 eV are attributed to Mo4+ 3d5/2 and Mo4+ 3d3/2,

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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.

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F. Tan et al. Chemical Engineering Journal 454 (2023) 140079

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

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

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F. Tan et al. Chemical Engineering Journal 454 (2023) 140079

MoO2/Mo2N3@P, NC are calculated (Fig. 4f). The results show that surface chemistry and catalyst valency that optimize the Gibbs free
there is an obvious linear relationship between the H* adsorption energy energy for the intermediate adsorption and increase the catalytic ac­
and the d-band center, and the d-band interaction center on the Er- tivity. The changes in the inherent electronic structure of Mo that result
MoO2/Mo2N3@P, NC interface is the optimized OHBE and enhanced from the combined effects of Er doping and in situ double doping with N
HBE caused by charge transfer. It also illustrated that Er-MoO2/ and P reduce the kinetic energy barrier for the HER process. These
Mo2N3@P, NC exhibits the best hydrogen (H*) adsorption energy, which findings provide new insights for customizing the size of the active sites
can ensure the rapid occurrence of H* adsorption/desorption steps. At in the development of high-performance catalysts with active centers
the same time, the introduction of Er, N, and P is beneficial to improve formed from single clusters.
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 CRediT authorship contribution statement
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. Fang Tan: Conceptualization, Investigation, Visualization, Writing –
Electronic structures of Mo 3d orbitals in MoO2/Mo2N3, Er-MoO2/ original draft. Yingtang Zhou: Investigation, Data curation, Writing –
Mo2N3, and Er-MoO2/Mo2N3@P, NC (H adsorbed on Mo atom) were original draft. Hua Zhang: Investigation, Software, Writing – original
further analyzed by the projected density of states (PDOS) and charge draft. Pengliang Sun: Investigation, Resources, Visualization, Writing –
density distribution. It is found that the |ΔGH*| value and εd energy level review & editing. Hongyi Li: Resources, Investigation, Methodology.
value of MoO2/Mo2N3 are precisely modulated by introducing the Er Xijun Liu: Formal analysis, Methodology. Thomas Wågberg: Formal
atom. As shown in Fig. 4g, Er-MoO2/Mo2N3@P, NC exhibits a lower analysis, Methodology. Guangzhi Hu: Conceptualization, Project
εd energy level (-2.56 eV) of Mo 3d orbital compared to that of the administration, Supervision, Resources, Writing – review & editing.
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 Declaration of Competing Interest
[49], which is well consistent with the aforementioned description that
Er-MoO2/Mo2N3@P, NC (H adsorbed on Mo atom) possesses the lowest The authors declare that they have no known competing financial
|ΔGH*| value. These results suggest that Er, N, and P incorporation could interests or personal relationships that could have appeared to influence
effectively modulate the εd value of Mo 3d orbital, thus balancing the the work reported in this paper.
adsorption of H* and the desorption of H2. According to the Sabatier
principle [42], moderate adsorption and desorption energies of the in­ Data availability
termediates play a vital role in determining catalytic activities.
To elucidate the inherent relationship between the electronic struc­ Data will be made available on request.
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 Acknowledgments
termediates and worse charge was also evaluated. The relation between
Bader charge and the adsorption-free energy change of H* reveals that The authors acknowledge the financial support from the Double Tops
the Er-MoO2(1 1 0)/Mo2N3(1 1 1)@P, NC catalyst can promote the HER Joint Fund of the Yunnan Science and Technology Bureau and Yunnan
performance, matching well with their charge density difference results University (2019FY003025), Open Foundation of Guangxi Key Labora­
shown in Fig. S6 (Supplementary material), where the Er-MoO2(1 1 0)/ tory of Processing for Non-ferrous Metals and Featured Materials of
Mo2N3(1 1 1)@P, NC transferred 0.95 e to H*, higher than that in Er- Guangxi University (2022GXYSOF10), Double First Class University
MoO2(1 1 0)/Mo2N3(1 1 1) (0.89 e), and MoO2(1 1 0)/Mo2N3(1 1 1) Plan (C176220100042), Guangdong Colleges & Universities Charac­
(0.75 e). It clearly demonstrates that electron distribution on the surface teristic Innovation Project (2021KTSCX263), Guangdong Education &
of Er-MoO2(1 1 0)/Mo2N3(1 1 1)@P, NC is stronger than Er-MoO2(1 1 Scientific Research Project (2021GXJK535). T.W. acknowledges the
0)/Mo2N3(1 1 1) and MoO2(1 1 0)/Mo2N3(1 1 1), revealing excellent support from Vetenskapsrådet (2017-04862, and 2021-04629), Ener­
electronic mobility. In summary, the DFT calculation results prove that gimyndigheten (45419-1), and SSF-Agenda 2030-PUSH. The authors
introducing Er, P, and N to MoO2(1 1 0)/Mo2N3(1 1 1) reduces the en­ thank the Advanced Analysis and Measurement Center of Yunnan Uni­
ergy barrier of both H2O adsorption and hydrogen generation, regulates versity for the sample testing service.
the electronic microenvironment and improves electronic mobility.
Appendix A. Supplementary data
4. Conclusion
Supplementary data to this article can be found online at https://doi.
In summary, the present study is the first to successfully synthesize org/10.1016/j.cej.2022.140079.
efficient, durable, and low-cost MoO2/Mo2N3 heterojunction nano­
cluster catalysts co-doped with erbium, nitrogen, and phosphorus using References
a feasible method. The dispersed hollow porous spherical structure of Er-
MoO2/Mo2N3@P, NC formed by the MoO2/Mo2N3 heterojunction [1] J.N. Tiwari, S. Sultan, C.W. Myung, T. Yoon, N. Li, M. Ha, A.M. Harzandi, H.
J. Park, D.Y. Kim, S.S. Chandrasekaran, W.G. Lee, V. Vij, H. Kang, T.J. Shin, H.
nanoclusters hosts optimized intrinsic electronic interactions and pro­ S. Shin, G. Lee, Z. Lee, K.S. Kim, Multicomponent electrocatalyst with ultralow Pt
vides abundant electrocatalytic active centers and rapid diffusion paths loading and high hydrogen evolution activity, Nat. Energy 3 (2018) 773–782.
for the reactants and intermediates. Owing to the synergistic effect be­ [2] S. Chu, A. Majumdar, Opportunities and challenges for a sustainable energy future,
Nature 488 (2012) 294–303.
tween their composition and structure, the Er-MoO2/Mo2N3@P, NC [3] T.F. Jaramillo, K.P. Jorgensen, J. Bonde, J.H. Nielsen, S. Horch, I. Chorkendorff,
hollow nanocapsules achieved an outstanding HER performance in Identification of active edge sites for electrochemical H2 evolution from MoS2
alkaline electrolytes in which a current density of 10 mA cm− 2 was nanocatalysts, Science 317 (2007) 100–102.
[4] J. Mo, Y. Ko, Y.S. Yun, J. Huh, J. Cho, A carbonization/interfacial assembly-driven
driven by an overpotential of only 65.2 mV. This performance exceeds
electroplating approach for water-splitting textile electrodes with remarkably low
those of reported Mo-based catalysts doped with heteroatoms or rare overpotentials and high operational stability, Energy. Environ Sci (2022).
earth elements and is attributed to the adjustable structural/electronic [5] Q. Hu, K. Gao, X. Wang, H. Zheng, J. Cao, L. Mi, Q. Huo, H. Yang, J. Liu, C. He,
characteristics, which enhance the surface area and centers for elec­ Subnanometric Ru clusters with upshifted D band center improve performance for
alkaline hydrogen evolution reaction, Nat. Commun. 13 (2022) 1–10.
trocatalytic activity. The addition of the rare earth element Er results in [6] P. Sun, Y. Zhou, H. Li, H. Zhang, L. Feng, Q. Cao, S. Liu, T. Wågberg, G. Hu, Round-
a redistribution of the electron density, which leads to changes in its the-clock bifunctional honeycomb-like nitrogen-doped carbon-decorated Co2P/

8
F. Tan et al. Chemical Engineering Journal 454 (2023) 140079

Mo2C-heterojunction electrocatalyst for direct water splitting with 18.1% STH oxygen evolution reactions, and full water splitting, Adv. Energy Mater. 9 (2019)
efficiency, Appl. Catal. B-Environ. 310 (2022), 121354. 1900624.
[7] S. Niu, Z. Yang, F. Qi, Y. Han, Z. Shi, Q. Qiu, X. Han, Y. Wang, X. Du, electrical [26] M. Li, Z. Zhao, W. Zhang, M. Luo, L. Tao, Y. Sun, Z. Xia, Y. Chao, K. Yin, Q. Zhang,
discharge induced bulk-to-nanoparticle transformation: nano high-entropy carbide L. Gu, W. Yang, Y. Yu, G. Lu, S. Guo, Sub-Monolayer YOx/MoOx on ultrathin Pt
as catalysts for hydrogen evolution reaction, Adv. Funct. Mater. (2022), 2203787. nanowires boosts alcohol oxidation electrocatalysis, Adv. Mater. 33 (2021)
[8] W. Yang, P. Cheng, Z. Li, Y. Lin, M. Li, J. Zi, H. Shi, G. Li, Z. Lian, H. Li, Tuning the e2103762.
cobalt-platinum alloy regulating single-atom platinum for highly efficient [27] H. Zhang, A. Aierke, Y. Zhou, Z. Ni, L. Feng, A. Chen, T. Wågberg, G. Hu, A high-
hydrogen evolution reaction, Adv. Funct. Mater. 2205920 (2022). performance transition-metal phosphide electrocatalyst for converting solar energy
[9] Z. Li, M. Hu, P. Wang, J. Liu, J. Yao, C. Li, Heterojunction catalyst in into hydrogen at 19.6% STH efficiency, Carbon Energy (2022).
electrocatalytic water splitting, Coordin. Chem. Rev. 439 (2021), 213953. [28] J. Ren, Y. Huang, H. Zhu, B. Zhang, H. Zhu, S. Shen, G. Tan, F. Wu, H. He, S. Lan,
[10] P. Wei, X. Li, Z. He, Z. Li, X. Zhang, X. Sun, Q. Li, H. Yang, J. Han, Y. Huang, X. Xia, Q. Liu, Recent progress on MOF-derived carbon materials for energy
Electron density modulation of MoP by rare earth metal as highly efficient storage, Carbon Energy 2 (2020) 176–202.
electrocatalysts for pH-universal hydrogen evolution reaction, Appl. Catal. B- [29] Y. Zhu, G. Chen, X. Xu, G. Yang, M. Liu, Z. Shao, Enhancing electrocatalytic activity
Environ. 299 (2021), 120657. for hydrogen evolution by strongly coupled molybdenum nitride@nitrogen-doped
[11] P. Babar, A. Lokhande, H.H. Shin, B. Pawar, M.G. Gang, S. Pawar, J.H. Kim, Cobalt carbon porous nano-octahedrons, ACS Catal. 7 (2017) 3540–3547.
Iron hydroxide as a precious metal-free bifunctional electrocatalyst for efficient [30] H. Song, Y. Li, L. Shang, Z. Tang, T. Zhang, S. Lu, Designed controllable nitrogen-
overall water splitting, Small 14 (2018) 1702568. doped carbon-dots-loaded MoP nanoparticles for boosting hydrogen evolution
[12] J. Zhang, Q. Zhang, X. Feng, Support and interface effects in water-splitting reaction in alkaline medium, Nano Energy 72 (2020), 104730.
electrocatalysts, Adv. Mater. 31 (2019) e1808167. [31] H. Yan, Y. Xie, Y. Jiao, A. Wu, C. Tian, X. Zhang, L. Wang, H. Fu, Holey reduced
[13] R. Jamil, R. Ali, S. Loomba, J. Xian, M. Yousaf, K. Khan, B. Shabbir, C. graphene oxide coupled with a Mo2N-Mo2C heterojunction for efficient hydrogen
F. McConville, A. Mahmood, N. Mahmood, The role of nitrogen in transition-metal evolution, Adv. Mater. 30 (2018) 1704156.
nitrides in electrochemical water splitting, Chem Catal. 1 (2021) 802–854. [32] X. Luo, P. Ji, P. Wang, R. Cheng, D. Chen, C. Lin, J. Zhang, J. He, Z. Shi, N. Li,
[14] S. Dutta, A. Indra, Y. Feng, H. Han, T. Song, Promoting electrocatalytic overall S. Xiao, S. Mu, Interface engineering of hierarchical branched Mo-doped Ni3S2/
water splitting with nanohybrid of transition metal nitride-oxynitride, Appl. Catal. NixPy hollow heterostructure nanorods for efficient overall water splitting, Adv.
B-Environ. 241 (2019) 521–527. Energy Mater. 10 (2020) 1903891.
[15] Q. Du, M. Arif Khan, J. Zhu, H. Zhao, J. Fang, D. Ye, J. Zhang, Interfacial [33] J.K. Norskov, F. Abild-Pedersen, F. Studt, T. Bligaard, Density functional theory in
engineering of two-dimensional MoN/MoO2 heterostructure nanosheets as a surface chemistry and catalysis, Proc. Natl. Acad. Sci. USA 108 (2011) 937–943.
bifunctional electrocatalyst for overall water splitting, Chem. Asian. J. 17 (2022) [34] Y. Fu, H.-Y. Yu, C. Jiang, T.-H. Zhang, R. Zhan, X. Li, J.-F. Li, J.-H. Tian, R. Yang,
e202200035. NiCo alloy nanoparticles decorated on N-doped carbon nanofibers as highly active
[16] P. Zhou, X. Lv, D. Xing, F. Ma, Y. Liu, Z. Wang, P. Wang, Z. Zheng, Y. Dai, B. Huang, and durable oxygen electrocatalyst, Adv. Funct. Mater. 28 (2018) 1705094.
High-efficient electrocatalytic overall water splitting over vanadium doped [35] J. Li, J. Li, J. Ren, H. Hong, D. Liu, L. Liu, D. Wang, Electric-field-treated Ni/Co3O4
hexagonal Ni0.2Mo0.8N, Appl. Catal. B-Environ. 263 (2020), 118330. film as high-performance bifunctional electrocatalysts for efficient overall water
[17] Z. Zeng, Y. Xu, Z. Zhang, Z. Gao, M. Luo, Z. Yin, C. Zhang, J. Xu, B. Huang, F. Luo, splitting, Nano-micro Lett. 14 (2022) 148.
Y. Du, C. Yan, Rare-earth-containing perovskite nanomaterials: design, synthesis, [36] J. Xie, X. Zhang, H. Zhang, J. Zhang, S. Li, R. Wang, B. Pan, Y. Xie, Intralayered
properties and applications, Chem. Soc. Rev. 49 (2020) 1109–1143. ostwald ripening to ultrathin nanomesh catalyst with robust oxygen-evolving
[18] S. Shit, S. Bolar, N.C. Murmu, T. Kuila, Minimal lanthanum-doping triggered performance, Adv. Mater. 29 (2017) 1604765.
enhancement in bifunctional water splitting activity of molybdenum oxide/sulfide [37] J. Bao, X. Zhang, B. Fan, J. Zhang, M. Zhou, W. Yang, X. Hu, H. Wang, B. Pan,
heterostructure through structural evolution, Chem. Eng. J. 428 (2022), 131131. Y. Xie, Ultrathin spinel-structured nanosheets rich in oxygen deficiencies for
[19] G. Zhang, B. Wang, J. Bi, D. Fang, S. Yang, Constructing ultrathin CoP nanomeshes enhanced electrocatalytic water oxidation, Angew. Chem. Int. Ed. Engl. 54 (2015)
by Er-doping for highly efficient bifunctional electrocatalysts for overall water 7399–7404.
splitting, J. Mater. Chem. A 7 (2019) 5769–5778. [38] Y. Zhou, R. Abazari, J. Chen, M. Tahir, A. Kumar, R.R. Ikreedeegh, E. Rani,
[20] J. Li, S. Zou, X. Liu, Y. Lu, D. Dong, Electronically modulated CoP by Ce doping as a H. Singh, A.M. Kirillov, Bimetallic metal–organic frameworks and MOF-derived
highly efficient electrocatalyst for water splitting, ACS Sustain. Chem. Eng. 8 composites: recent progress on electro- and photoelectrocatalytic applications,
(2020) 10009–10016. Coordin. Chem. Rev. 451 (2022).
[21] T. Chen, Y. Fu, W. Liao, Y. Zhang, M. Qian, H. Dai, X. Tong, Q. Yang, Fabrication of [39] J. Chen, R. Abazari, K.A. Adegoke, N.W. Maxakato, O.S. Bello, M. Tahir,
cerium-doped CoMoP/MoP@C heterogeneous nanorods with high performance for S. Tasleem, S. Sanati, A.M. Kirillov, Y. Zhou, Metal–organic frameworks and
overall water splitting, Energy Fuel 35 (2021) 14169–14176. derived materials as photocatalysts for water splitting and carbon dioxide
[22] X. Wang, Y. Tang, J.-M. Lee, G. Fu, Recent advances in rare-earth-based materials reduction, Coordin. Chem. Rev. 469 (2022).
for electrocatalysis, Chem. Catal. 2 (2022) 967–1008. [40] Z. Ni, C. Luo, B. Cheng, P. Kuang, Y. Li, J. Yu, Construction of hierarchical and self-
[23] L. Wang, F. Liu, A. Pal, Y. Ning, Z. Wang, B. Zhao, R. Bradley, W. Wu, Ultra-small supported NiFe-Pt3Ir electrode for hydrogen production with industrial current
Fe3O4 nanoparticles encapsulated in hollow porous carbon nanocapsules for high- density, Appl. Catal. B-Environ. 321 (2023).
performance supercapacitors, Carbon 179 (2021) 327–336. [41] L. Su, Y. Zhao, Y. Jin, Z. Liu, H. Cui, W. Luo, Identifying the Role of hydroxyl
[24] L. Wang, F. Liu, Y. Ning, R. Bradley, C. Yang, K.T. Yong, B. Zhao, W. Wu, binding energy in a non-monotonous behavior of Pd-Pd4S for hydrogen oxidation
Biocompatible mesoporous hollow carbon nanocapsules for high-performance reaction, Adv. Funct. Mater. 32 (2022).
supercapacitors, Sci. Rep. 10 (2020) 4306. [42] J. Yan, L. Kong, Y. Ji, J. White, Y. Li, J. Zhang, P. An, S. Liu, S.T. Lee, T. Ma, Single
[25] S. Sultan, J.N. Tiwari, A.N. Singh, S. Zhumagali, M. Ha, C.W. Myung, P. Thangavel, atom tungsten doped ultrathin alpha-Ni(OH)2 for enhanced electrocatalytic water
K.S. Kim, Single atoms and clusters based nanomaterials for hydrogen evolution, oxidation, Nat. Commun. 10 (2019) 2149.