Electrocatalysts For Alkaline Hydrogen Evolution Reaction Research Articles

Recent Development of Self‐Supported Alkaline Hydrogen Evolution Reaction Electrocatalysts for Industrial Electrolyzer

Hydrogen (H2) energy is presumed to be the most promising alternative to replacing traditional fossil fuels to achieve the global mission of carbon neutrality. Electrocatalytic water splitting driven by green electricity has been regarded as an ideal method for large‐scale green hydrogen production with a minimal CO2 footprint. However, most of the reported electrocatalysts still suffer from large overpotentials and severe activity degradation at high current density (>1000 mA cm−2). Therefore, a comprehensive review to summarize the representative alkaline hydrogen evolution reaction (HER) electrocatalysts with large current densities is essential to guide the fabrication of promising industrial electrocatalysts. In this review, starting from the fundamental of water electrolysis, the design principles to acquire alkaline electrocatalysts with large current density and high stability are elaborated. The critical factors for achieving high‐performance electrocatalysts to meet industrial H2 production are proposed. Additionally, the key processes for preparing self‐supported electrodes are clarified. Afterward, the recently advanced self‐supported transition metal‐based electrocatalysts with high current density for alkaline HER are systematically summarized. Finally, personal perspective on future opportunities and challenges is highlighted. It is hoped this review can guide the rational design of self‐supported high‐current density electrocatalysts for future commercial H2 production.

Ultra-Low Pt Doping and Pt-Ni Pair Sites in Amorphous/Crystalline Interfacial Electrocatalyst Enable Efficient Alkaline Hydrogen Evolution.

Noble metal doping can achieve an increase in mass activity (MA) without sacrificing catalysis efficiency and stability, so that alkaline hydrogen evolution reaction (HER) performance of the catalyst can be optimized to the maximum degree. However, its excessively large ionic radius makes it difficult to achieve either interstitial doping or substitutional doping under mild conditions. Herein, a hierarchical nanostructured electrocatalyst with enriched amorphous/crystalline interfaces for high-efficiency alkaline HER is reported, which is composed of amorphous/crystalline (Co, Ni)11 (HPO3 )8 (OH)6 homogeneous hierarchical structure with an ultra-low doped Pt (Pt-a/c-NiHPi). Benefiting from the structural flexibility of the amorphous component, extremely low Pt (0.21wt.%, totally 3.31µg Pt on 1 cm-2 NF) are stably doped on it via a simple two-phase hydrothermal method. The DFT calculations show that due to the strongly electron transfer between the crystalline/amorphous components at the interfaces, electrons finally concentrate toward Pt and Ni in the amorphous components, thus the electrocatalyst has near-optimal energy barriers and adsorption energy for H2 O* and H* . With the above benefits, the obtained catalyst exhibits an exceptionally high MA (39.1mA µg-1 Pt ) at 70mV, which is almost the highest level among the reported Pt-based electrocatalysts for alkaline HER.

Plasma Etching of Pyrite-Type Nickel Diselenide Nanosheets to Create Selenium Vacancies for Applications as Electrocatalysts for Hydrogen Evolution

Boosting the hydrogen evolution reaction (HER) process with highly efficient non-noble metal catalysts is crucial for hydrogen-powered fuel cells. Pyrite-type NiSe2 is one of the most promising HER catalysts due to its inexpensive cost and good conductivity, although its intrinsic activity is moderate. Using a plasma etching method on a carbon cloth substrate material, we created a large number of selenium vacancies on NiSe2 nanosheets (NiSe2-VSe/CC). With a low overpotential of 91 mV and a Tafel slope of 91 mV dec–1 at 10 mA cm–2, as well as a durability of 20 h at high current (100 mA cm–2), the NiSe2-VSe/CC demonstrates superior HER performance for its catalytic activity and long-term stability. Cross-validated by measurement analyses and density functional theory calculations, the introduction of vacancies reduces the resistivity of NiSe2 and optimizes its hydrogen adsorption energy (GH*) and water adsorption energy (GH2O*). Based on defect engineering, this study proposes an approach to designing improved electrocatalysts for alkaline HER.

Self-assembled NiMn2O4 shell on nanoporous Ni(Mn) core for boosting alkaline hydrogen production

Alkaline hydrogen evolution reaction (HER) is more sluggish than that in acidic media because of the additional energy required for water dissociation. Herein, we report a scalable strategy (alloying-dealloying) to synthesize self-assembled shell-core porous configuration as active and cost-effective electrocatalyst for alkaline HER. Benefiting from the dual function of oxygen vacancies (OV) defects on NiMn2O4 shell and large specific surface area provided by Mn-doped nanoporous Ni core, the resultant OV-NMO/np-Ni30(Mn) electrode achieves a lower overpotential of 130 mV at 10 mA cm−2, a higher exchange current density of 0.5011 mA cm−2 and long-term operational durability in hostile basic environment. Density functional theory (DFT) calculations reveal that appropriate concentration of OV in NiMn2O4 could decreases the energy barrier of Volmer step from 1.59 eV to 1.49 eV, suggesting OV serves as a hot-spot for the dissociation of water molecules during alkali-HER. This work paves a novel approach to fabricate robust shell-core porous structure with abundant defects, dopants and active sites that are favorable for efficient and inexpensive alkaline hydrogen production.

NiCoP/CoP sponge-like structure grown on stainless steel mesh as a high-performance electrocatalyst for hydrogen evolution reaction

The stainless steel mesh (SSM) has received remarkable attention for hydrogen and oxygen evolution reactions. It was demonstrated that the SSM exhibits admirable performance towards oxygen evolution reaction (OER) electrocatalysis, while its catalytic activity for hydrogen evolution reaction (HER) remains quite low. This obstructs the utilization of SSM-based catalysts for sustainable complete water electrolysis. In this study, a facile hydrothermal route followed by a phosphorization process was adopted to transform commercially available SSM materials into high-performance and stable electrocatalysts for alkaline HER. We report an interconnected NiCoP-CoP sponge-like structure on SSM substrate without polymer binder. Benefiting from the 3D construction with high exposed surface area, close contact between electroactive species and conductive surface, and facilitated infiltration of electrolyte, the as-prepared NiCoP@SSM electrocatalyst brought an improved catalytic activity for HER, required a low overpotential of 138 mV to derive a current density of 10 mAcm−2 in 1.0 M KOH aqueous solution. The high performance of the NiCoP@SSM catalyst has also unveiled fast reaction kinetics (presents a small Tafel slope of 74 mV/dec), a relatively large electrochemical active surface area (ECSA), and small charge transfer resistance. Furthermore, the NiCoP@SSM electrode also presented excellent stability during long-term measurements, making it one of the most encouraging HER electrodes to date. This research study paves the way for the development of HER-active electrocatalysts made from SSMs that are commercially available, low-cost, and highly active.

High-valence metal doped Co2FeAl alloy as efficient noble-metal-free electrocatalyst for alkaline hydrogen evolution reaction

Most efficient electrochemical hydrogen evolution reaction (HER) catalysts in alkaline solutions are based on precious metals, whose rarity and high cost are severely limiting their large-scale applications. In this work, we synthesized Mo-doped and W-doped Co2FeAl alloys by a simple coprecipitation method. The HER in alkaline solution is promoted through the synergistic effect of thermal annealing and doping of high-valence metal atoms. Thermal annealing could optimize the surface morphology and improve the crystallinity. In the meantime, the doping of high-valence metal atoms could further regulate the crystal structure and electronic structure of alloys. Therefore, annealing temperatures and doping concentrations have a marked impact on the catalytic performance. In particular, when the Mo doping concentration is 27 at% and the annealing temperature is 750 ℃, the synthesized Co2FeAlMo1.5 (750 ℃) alloy electrocatalyst exhibits the superior HER performance in alkaline media. It displays a low overpotential of only 71 mV at 10 mA cm−2 and a Tafel slope of 110 mV dec−1. An excellent stability is also demonstrated that the electrocatalyst can work stably for 20 h and the overpotential is only shifted by 2 mV after 1000 cycles. A series of characterization tests indicate that the crystal structure and electronic structure of Co2FeAlMo1.5 (750 ℃) are optimized, which can improve the catalytic activity and promote alkaline HER. This work provides a new strategy for improving the catalytic performance of non-noble metal electrocatalysts for alkaline HER.

Carbon onions coated Ni/NiO nanoparticles as catalysts for alkaline hydrogen evolution reaction

High-performance carbon onions coated Ni/NiO nanoparticles (CNN NPs) acting as electrocatalysts in alkaline hydrogen evolution reaction (HER) is synthesized base on a self-assembly process combined with a calcination process. By systematically regulating the surface composition, we find that controlling the kinetic steps in HER by regulating the ratio of Ni/NiO can significantly promote alkaline HER activity, and CNN-500 with a Ni/NiO ratio of 1.31 display an overpotential of 127 mV (vs. RHE) at a current density of 10 mA cm−2 for HER in 1 M KOH electrolyte. The ratio of Ni and NiO active catalytic components are adjustable via controlling the calcination process, which play an important role in alkaline HER performance. Due to the synergistic effect between Ni, NiO and C, the CNN-500 shows superior intrinsic catalytic activity than that of currently reported HER electrocatalysts. This work provides a facile and useful strategy to get high-performance alkaline HER electrocatalysts for hydrogen energy source.

Ru anchored on Mo@MoOx nanowires as self‐supported electrocatalysts for efficient hydrogen production in alkaline media

AbstractRu‐based materials are expected to be a promising alternative to commercial Pt/C for electrocatalytic hydrogen evolution reaction (HER), but they still suffer from large overpotential and low mass activity in alkaline medium. Here, we reported Ru (∼0.24 wt%) anchored on the Mo@MoOx nanowires (Ru−Mo@MoOx) as an efficient alkaline HER electrocatalyst. The Ru−Mo@MoOx nanowires exhibit a considerably low overpotential of only 16 mV at 10 mA cm−2 and a Tafel slope of ∼30 mV dec−1 in a 1 M KOH aqueous solution, which outperform those for commercial Pt/C and most reported Ru‐based electrocatalysts. Electrochemical and structural investigations reveal that Mo@MoOx support can modulate electronic structure of Ru active sites, leading to the optimizations of adsorption and dissociation for H2O. Meanwhile the improved electron and mass transfer also contribute to the HER performance. The water electrolyzer using Ru−Mo@MoOx as the cathode afford a stable voltage of ∼1.47 V to deliver 10 mA cm−2.

Competitive Adsorption: Reducing the Poisoning Effect of Adsorbed Hydroxyl on Ru Single-Atom Site with SnO2 for Efficient Hydrogen Evolution.

Ruthenium (Ru) has been theoretically considered a viable alkaline hydrogen evolution reaction electrocatalyst due to its fast water dissociation kinetics. However, its strong affinity to the adsorbed hydroxyl (OHad ) blocks the active sites, resulting in unsatisfactory performance during the practical HER process. Here, we first reported a competitive adsorption strategy for the construction of SnO2 nanoparticles doped with Ru single-atoms supported on carbon (Ru SAs-SnO2 /C) via atomic galvanic replacement. SnO2 was introduced to regulate the strong interaction between Ru and OHad by the competitive adsorption of OHad between Ru and SnO2 , which alleviated the poisoning of Ru sites. As a consequence, the Ru SAs-SnO2 /C exhibited a low overpotential at 10 mA cm-2 (10 mV) and a low Tafel slope of 25 mV dec-1 . This approach provides a new avenue to modulate the adsorption strength of active sites and intermediates, which paves the way for the development of highly active electrocatalysts.

Competitive Adsorption: Reducing the Poisoning Effect of Adsorbed Hydroxyl on Ru Single‐Atom Site with SnO2for Efficient Hydrogen Evolution

AbstractRuthenium (Ru) has been theoretically considered a viable alkaline hydrogen evolution reaction electrocatalyst due to its fast water dissociation kinetics. However, its strong affinity to the adsorbed hydroxyl (OHad) blocks the active sites, resulting in unsatisfactory performance during the practical HER process. Here, we first reported a competitive adsorption strategy for the construction of SnO2nanoparticles doped with Ru single‐atoms supported on carbon (Ru SAs‐SnO2/C) via atomic galvanic replacement. SnO2was introduced to regulate the strong interaction between Ru and OHadby the competitive adsorption of OHadbetween Ru and SnO2, which alleviated the poisoning of Ru sites. As a consequence, the Ru SAs‐SnO2/C exhibited a low overpotential at 10 mA cm−2(10 mV) and a low Tafel slope of 25 mV dec−1. This approach provides a new avenue to modulate the adsorption strength of active sites and intermediates, which paves the way for the development of highly active electrocatalysts.

Positively Charged Pt-Based Nanoreactor for Efficient and Stable Hydrogen Evolution.

Positively charged Pt can work as the active center for hydrogen evolution reaction (HER) but the corresponding design of state‐of‐the‐art electrocatalysts at high current densities has never been realized. Here the application of positively charged Pt in an effective Fe‐PtNiPO nanoreactor for highly efficient and stable HER is demonstrated. Synchrotron radiation X‐ray absorption spectroscopy confirms the formation of internal positively charged Pt and the in situ experiments reveal the quick charge transfer in the nanoreactor. Ni‐based materials around Pt are used to tune the electronic structure and promote the water dissociation to form locally enriched H+, while a porous Fe shell can both prevent the loss of active material and allow the efficient material transport. All the beneficial compositions work together to form an effective nanoreactor for HER. As a result, the Fe‐PtNiPO nanoreactor shows a low overpotential of 19 mV to achieve 10 mA cm−2 and exhibits a high mass activity of 10.93 A mgPt −1 (at 100 mV). Most importantly, it only needs an ultra‐low overpotential of 193 mV to achieve a high current density of 1000 mA cm−2 with an excellent stability over 300 h, which represents one of the best electrocatalysts for alkaline HER and might be used for large‐scale industrial application in the future.

Tailoring Binding Abilities By Incorporating Oxophilic Transition Metals on 3D Nanostructured Ni Arrays for Accelerated Alkaline Hydrogen Evolution Reaction

Developing efficient and inexpensive electrocatalysts for the hydrogen evolution reaction (HER) in alkaline water electrolysis plays a key role for renewable hydrogen energy technology. The slow reaction kinetics of HER in alkaline solutions, however, has hampered advances in high-performance hydrogen production. Herein, we investigated the trends in HER activity with respect to the binding energies of Ni-based thin film catalysts by incorporating a series of oxophilic transition metal atoms. It was found that the doping of oxophilic atoms enables the modulation of binding abilities of hydrogen and hydroxyl ions on the Ni surfaces, leading to the first establishment of a volcano relation between OH-binding energies and alkaline HER activities. In particular, Cr-incorporated Ni catalyst shows optimized OH-binding as well as H-binding energies for facilitating water dissociation and improving HER activity in alkaline media. Further enhancement of catalytic performance was achieved by introducing an array of three-dimensional (3D) Ni nanohelixes (NHs) that provide abundant surface active sites and effective channels for charge transfer and mass transport. The Cr dopants incorporated into the Ni NHs accelerate the dissociative adsorption process of water, resulting in remarkably enhanced catalytic activities in alkaline medium. Our approach can provide a rational design strategy and experimental methodology toward efficient bimetallic electrocatalysts for alkaline HER using earth-abundant elements.

One-step synthesis of Co2P/N-P co-doped porous carbon composites derived from soybean derivatives as acidic and alkaline HER electrocatalysts

Developing inexpensive and efficient electrocatalysts for hydrogen evolution reaction (HER) in both acidic and alkaline mediums is of great significance to the hydrogen energy industry. Hereby, we prepared a mixture of precursors with homogeneous composition by using the chelating ability of soybean protein isolate (C and N source) and phytic acid (dopant and phosphating agent) with cobalt ions, and achieved one-step synthesis and construction of Co2P/N–P co-doped porous carbon composite by carbonization at 800 °C. The as-synthesized Co2P/NPPC-800 electrocatalyst exhibits low HER overpotentials of 121 and 125 mV at 10 mA cm−2 in 0.5 M H2SO4 and 1.0 M KOH, which are close to those of the commercial Pt/C catalyst. Additionally, the NPPC substrate surrounding the Co2P could diminish the corrosion during the HER, and Co2P/NPPC-800 displays good stability and durability. Furthermore, this work offers a convenient synthesis strategy for phosphide/doped porous carbon composites in other electrochemical energy technologies.

Synergic Reaction Kinetics over Adjacent Ruthenium Sites for Superb Hydrogen Generation in Alkaline Media.

Ruthenium (Ru)-based electrocatalysts as platinum (Pt) alternatives in catalyzing hydrogen evolution reaction (HER) are promising. However, achieving efficient reaction processes on Ru catalysts is still a challenge, especially in alkaline media. Here, the well-dispersed Ru nanoparticles with adjacent Ru single atoms on carbon substrate (Ru1,n -NC) is demonstrated to be a superb electrocatalyst for alkaline HER. The obtained Ru1,n -NC exhibits ultralow overpotential (14.8mV) and high turnover frequency (1.25H2 s-1 at -0.025V vs reversible hydrogen electrode), much better than the commercial 40 wt.% Pt/C. The analyses reveal that Ru nanoparticles and single sites can promote each other to deliver electrons to the carbon substrate. Eventually, the electronic regulations bring accelerated water dissociation and reduced energy barriers of hydroxide/hydrogen desorption on adjacent Ru sites, then an optimized reaction kinetics for Ru1,n -NC is obtained to achieve superb hydrogen generation in alkaline media. This work provides a new insight into the catalyst design in simultaneous optimizations of the elementary steps to obtain ideal HER performance in alkaline media.

Pt nanoclusters anchored on ordered macroporous nitrogen-doped carbon for accelerated water dissociation toward superior alkaline hydrogen production

Developing effective electrocatalysts with reduced Pt content for fast hydrogen evolution reaction (HER) kinetics toward efficient and stable hydrogen production in alkaline media is highly desirable but rather challenging. Herein, Pt nanoclusters (∼1.6 nm) uniformly anchored on ordered macroporous nitrogen-doped carbon support (Pt-30/NCM) with only 3.39 wt% Pt loading is rationally constructed via a polystyrene spheres (PS) template method followed by an impregnating method as a highly enhanced electrocatalyst for alkaline HER. Benefiting from the enhanced mass and charge transport via the ordered macroporous carbon structure as well as the strong metal-support interaction between Pt nanoclusters and nitrogen-doped carbon framework, Pt-30/NCM exhibits superior intrinsic activity and operation stability compared to the solid counterpart without ordered macropores (Pt-30/NCS), even affording a more than 10 times higher mass activity and much better operation stability after 3000 cycles than those of commercial 20 wt% Pt/C. The density functional theory (DFT) calculations reveal that the strong coupling between Pt nanoclusters and nitrogen-doped carbon support can induce favorable charge transfer for accelerated water dissociation as well as desirable d-band center position for suitable adsorption and desorption of alkaline HER intermediates, thus contributing to remarkably improved kinetics of hydrogen production.

In-situ formed Cu-doped RuS2 hollow polyhedrons integrated with simultaneously heterostructure engineering with metallic Ru for boosting hydrogen evolution in alkaline media

Promoting hydrogen evolution reaction (HER) in alkaline media is currently vital to practicing the sustainable development of hydrogen economy. As an emerging candidate, pyrite-structured ruthenium disulfide (RuS2) is a promising electrocatalyst for alkaline HER. Nevertheless, much less efforts have been devoted to RuS2, thus whose intrinsic properties still remain to be improved via promoting the water dissociation and hydrogen adsorption processes. Herein, we report the facile synthesis of Cu-doped RuS2 hollow polyhedrons coupled with metallic Ru from bimetallic MOF of RuCu-BTC to boost alkaline hydrogen evolution. In which, in-situ Cu doping integrated with simultaneous heterostructure engineering with metallic Ru are achieved for RuS2. Benefitting from modified electronic structure, heterogeneous interfaces and 3D hollow polyhedral morphology, the Cu-doped RuS2/Ru heterostructure exhibits admirable electrocatalytic activity with small overpotential of 169 mV at a high current density of 200 mA cm−2 in 1 M KOH, superior to that of commercial Pt/C. Density functional theory calculations indicate that the incorporation of Cu heteroatoms can not only decrease the energy barrier for water dissociation of RuS2 but also optimize its hydrogen adsorption. Simultaneously, the construction of heterointerfaces between RuS2 and metallic Ru demonstrates further improved conductivity, increased active sites and enhanced specific activity. This work discloses an innovative strategy for the simultaneous implementation of heteroatom doping and heterostructure engineering on RuS2 to collaboratively promote the HER electrocatalytic performance.

Orbital engineering of C3N monolayer to design efficient synergistic sites electrocatalyst for boosting alkaline hydrogen evolution

Alkaline water electrolyzer (AWE) is one of the promising technologies for hydrogen production at the industrial level. However, energetic inefficiency and low current density impede the development of AWE. Compared with acidic conditions, the Volmer step in alkaline hydrogen evolution reaction (HER) involves extra water dissociation, whose barrier is one of the most vital reasons for the sluggish kinetics of alkaline HER. Herein, choosing C3N monolayer as an ideal theoretical model, we design several empty orbitals through intentional metal doping, and further construct synergistic sites on the C3N monolayer to accelerate both water dissociation and hydrogen adsorption for alkaline HER. The as-designed Be-doped and Cr-doped C3N monolayers exhibit rather low theoretical overpotential of 0.476 eV and 0.216 eV for alkaline HER, respectively, which are even lower than Pt (111) surface. Moreover, by comparing the water dissociation behaviors on metal-doped C3N monolayer, we find that the empty orbitals with suitable orientation and energy level are useful for promoting the water dissociation process, indicating that we can use orbital engineering strategy to regulate the adsorption strength between adsorbate and surface site. Consequently, it is reasonable to suggest that our orbital engineering strategy would significantly benefit the design of highly efficient alkaline HER electrocatalysts.

Review of the Hydrogen Evolution Reaction—A Basic Approach

An increasing emphasis on energy storage has resulted in a surge of R&D efforts into producing catalyst materials for the hydrogen evolution reaction (HER) with emphasis on decreasing the usage of platinum group metals (PGMs). Alkaline water electrolysis holds promise for satisfying future energy storage demands, however the intrinsic potential of this technology is impeded by sluggish reaction kinetics. Here, we summarize the latest efforts within alkaline HER electrocatalyst design, where these efforts are divided between three catalyst design strategies inspired by the three prevailing theories describing the pH-dependence of the HER activity. Modifying the electronic structure of a host through codoping and creating specific sites for hydrogen/hydroxide adsorption stand out as promising strategies. However, with the vast amount of possible combinations, emphasis on screening parameters is important. The authors predict that creating a codoped catalyst using the first strategy by screening materials based on their hydrogen, hydroxide and water binding energies, and utilizing the second and third strategies as optimization parameters might yield both active and stable HER catalyst materials. This strategy has the potential to greatly advance the current status of alkaline water electrolysis as an energy storage option.

Three-dimensional ZnCo/MoS2–Co3S4/NF heterostructure supported on nickel foam as highly efficient catalyst for hydrogen evolution reaction

Exploring inexpensive and earth-abundant electrocatalysts for hydrogen evolution reactions is crucial in electrochemical sustainable chemistry field. In this work, a high-efficiency and inexpensive non-noble metal catalysts as alternatives to hydrogen evolution reaction (HER) was designed by one-step hydrothermal and two-step electrodeposition method. The as-prepared catalyst is composed of the synergistic MoS2–Co3S4 layer decorated by ZnCo layered double hydroxides (ZnCo-LDH), which forms a multi-layer heterostructure (ZnCo/MoS2–Co3S4/NF). The synthesized ZnCo/MoS2–Co3S4/NF exhibits a small overpotential of 31 mV and a low Tafel plot of 53.13 mV dec−1 at a current density of 10 mA cm−2, which is close to the HER performance of the overpotential (26 mV) of Pt/C/NF. The synthesized ZnCo/MoS2–Co3S4/NF also has good stability in alkaline solution. The excellent electrochemical performance of ZnCo/MoS2–Co3S4/NF electrode originates from its abundant active sites and good electronic conductivity brought by the multilayer heterostructure. This work provides a simple and feasible way to design alkaline HER electrocatalysts by growing heterostructures on macroscopic substrates.

Uniform W-NiCoP microneedles by molten salt decomposition as bifunctional electrocatalyst for alkaline water splitting

Transition metal phosphides (TMPs) owing to the unique Pt-like electron structure have been used as electrocatalysts for hydrogen evolution reaction (HER). Facile metal doping especially high valence metal is an effective strategy but a big challenge for improving HER performances of TMPs. Herein, a simple and mild molten salt decomposition followed by phosphorization method is adopted to obtain W-NiCoP microneedles uniformly distributed on nickel foam (W-NiCoP/NF) with multisite for alkaline HER. The prepared NiCo/NF as precursor assisted by molten salt method can provide the homogenous dispersion and uniform needles arrays, which are also helpful for the interaction with W elements. Notably, W doping could effectively regulate the electronic structure of NiCoP, contributing to enriched electrocatalytic active sites and accelerated Volmer step. As a result, the optimized W-NiCoP/NF only requires 113.7 mV and 295.1 mV to reach 100 mA cm−2 for alkaline HER and oxygen evolution reaction (OER), even outperforming Pt/C and RuO2. The electrocatalyst remains stable after 5000 cycling stability. Therefore, this work based on molten salt decomposition may provide insights for the simple synthesis of efficient bifunctional electrocatalysts for alkaline HER and OER.