Interfacial Engineering of Copper–Nickel Selenide Nanodendrites for Enhanced Overall Water Splitting in Alkali Condition (Small 33/2023)

Fabricating heterogeneous interfaces is an effective approach to improve the intrinsic activity of noble-metal-free catalysts for water splitting. Herein, 3D copper–nickel selenide (CuNi@NiSe) nanodendrites with abundant heterointerfaces are constructed by a precise multi-step wet chemistry method. Notably, CuNi@NiSe only needs 293 and 41 mV at 10 mA cm⁻² for oxygen evolution reaction (OER) and hydrogen evolution reaction (HER), respectively. Moreover, the assembled CuNi@NiSe system just requires 2.2 V at 1000 mA cm⁻² in anion exchange membrane (AEM) electrolyzer, which is 2.0 times better than Pt/C//IrO₂. Mechanism studies reveal Cu defects on the Cu_2−xSe surface boost the electron transfer between Cu atoms and Se atoms of Ni₃Se₄ via Cu_2−xSe/Ni₃Se₄ interface, largely lowering the reaction barrier of rate-determining step for HER. Besides, the intrinsic activity of Ni atoms for in situ generated NiOOH is largely enhanced during OER because of the electron-modulating effect of Se atoms at Ni₃Se₄/NiOOH interface. The unique 3D structure also promotes the mass transfer during catalysis process. This work emphasizes the essential role of interfacial engineering for practical water splitting.     

Phase Segregation in Cu0.5Ni0.5 Alloy Boosting Urea-Assisted Hydrogen Production in Alkaline Media

Coupling urea oxidation reaction (UOR) and hydrogen evolution reaction (HER) is promising for energy-efficient hydrogen production. However, developing cheap and highly active bifunctional electrocatalysts for overall urea electrolysis remains challenging. In this work, a metastable Cu_0.5Ni_0.5 alloy is synthesized by a one-step electrodeposition method. It only requires the potentials of 1.33 and −28 mV to obtain the current density of ±10 mA cm⁻² for UOR and HER, respectively. The metastable alloy is considered to be the main reason causing the above excellent performances. In the alkaline medium, the as-prepared Cu_0.5Ni_0.5 alloy exhibits good stability for HER; and conversely, NiOOH species can be rapidly formed during the UOR due to the phase segregation of Cu_0.5Ni_0.5 alloy. In particular, for the energy-saving hydrogen generation system coupled with HER and UOR, only 1.38 V of voltage is needed at 10 mA cm⁻²; and at 100 mA cm⁻², the voltage decreases by ≈305 mV compared with that of the routine water electrolysis system (HER || OER). Compared with some catalysts reported recently, the Cu_0.5Ni_0.5 catalyst owns superior electrocatalytic activity and durability. Furthermore, this work provides a simple, mild, and rapid method for designing highly active bifunctional electrocatalysts toward urea-supporting overall water splitting.     

Synergistic Coupling of Ni Nanoparticles with Ni3C Nanosheets for Highly Efficient Overall Water Splitting

Exploring earth‐abundant bifunctional electrocatalysts with high efficiency for water electrolysis is extremely demanding and challenging. Herein, density functional theory (DFT) predictions reveal that coupling Ni with Ni₃C can not only facilitate the oxygen evolution reaction (OER) kinetics, but also optimize the hydrogen adsorption and water adsorption energies. Experimentally, a facile strategy is designed to in situ fabricate Ni₃C nanosheets on carbon cloth (CC), and simultaneously couple with Ni nanoparticles, resulting in the formation of an integrated heterostructure catalyst (Ni–Ni₃C/CC). Benefiting from the superior intrinsic activity as well as the abundant active sites, the Ni–Ni₃C/CC electrode demonstrates excellent bifunctional electrocatalytic activities toward the OER and hydrogen evolution reaction (HER), which are superior to all the documented Ni₃C‐based electrocatalysts in alkaline electrolytes. Specifically, the Ni–Ni₃C/CC catalyst exhibits the low overpotentials of only 299 mV at the current density of 20 mA cm^?2 for the OER and 98 mV at 10 mA cm^?2 for the HER in 1 m KOH. Furthermore, the bifunctional Ni–Ni₃C/CC catalyst can propel water electrolysis with excellent activity and nearly 100% faradic efficiency. This work highlights an easy approach for designing and constructing advanced nickel carbide‐based catalysts with high activity based on the theoretical predictions.     

Nickel–Cobalt Diselenide 3D Mesoporous Nanosheet Networks Supported on Ni Foam: An All‐pH Highly Efficient Integrated Electrocatalyst for Hydrogen Evolution

Novel 3D Ni_1?x Co_x Se₂ mesoporous nanosheet networks with tunable stoichiometry are successfully synthesized on Ni foam (Ni_1?x Co_x Se₂ MNSN/NF with x ranging from 0 to 0.35). The collective effects of special morphological design and electronic structure engineering enable the integrated electrocatalyst to have very high activity for hydrogen evolution reaction (HER) and excellent stability in a wide pH range. Ni_0.89Co_0.11Se₂ MNSN/NF is revealed to exhibit an overpotential (η₁₀) of 85 mV at ?10 mA cm^?2 in alkaline medium (pH 14) and η₁₀ of 52 mV in acidic solution (pH 0), which are the best among all selenide‐based electrocatalysts reported thus far. In particular, it is shown for the first time that the catalyst can work efficiently in neutral solution (pH 7) with a record η₁₀ of 82 mV for all noble metal‐free electrocatalysts ever reported. Based on theoretical calculations, it is further verified that the advanced all‐pH HER activity of Ni_0.89Co_0.11Se₂ is originated from the enhanced adsorption of both H⁺ and H₂O induced by the substitutional doping of cobalt at an optimal level. It is believed that the present work provides a valuable route for the design and synthesis of inexpensive and efficient all‐pH HER electrocatalysts.     

Construction of Nitrogen-Doped Biphasic Transition-Metal Sulfide Nanosheet Electrode for Energy-Efficient Hydrogen Production via Urea Electrolysis

Urea-assisted hybrid water splitting is a promising technology for hydrogen (H₂) production, but the lack of cost-effective electrocatalysts hinders its extensive application. Herein, it is reported that Nitrogen-doped Co₉S₈/Ni₃S₂ hybrid nanosheet arrays on nickel foam (N-Co₉S₈/Ni₃S₂/NF) can act as an active and robust bifunctional catalyst for both urea oxidation reaction (UOR) and hydrogen evolution reaction (HER), which could drive an ultrahigh current density of 400 mA cm⁻² at a low working potential of 1.47 V versus RHE for UOR, and gives a low overpotential of 111 mV to reach 10 mA cm⁻² toward HER. Further, a hybrid water electrolysis cell utilizing the synthesized N-Co₉S₈/Ni₃S₂/NF electrode as both the cathode and anode displays a low cell voltage of 1.40 V to reach 10 mA cm⁻², which can be powered by an AA battery with a nominal voltage of 1.5 V. The density functional theory (DFT) calculations decipher that N-doped heterointerfaces can synergistically optimize Gibbs free energy of hydrogen and urea, thus accelerating the catalytic kinetics of HER and UOR. This work significantly advances the development of the promising cobalt–nickel-based sulfide as a bifunctional electrocatalyst for energy-saving electrolytic H₂ production and urea-rich innocent wastewater treatment.     

Super-Hydrophilic Microporous Ni(OH)x/Ni3S2 Heterostructure Electrocatalyst for Large-Current-Density Hydrogen Evolution

Exploiting active and stable non-precious metal electrocatalysts for alkaline hydrogen evolution reaction (HER) at large current density plays a key role in realizing large-scale industrial hydrogen generation. Herein, a self-supported microporous Ni(OH)x/Ni₃S₂ heterostructure electrocatalyst on nickel foam (Ni(OH)x/Ni₃S₂/NF) that possesses super-hydrophilic property through an electrochemical process is rationally designed and fabricated. Benefiting from the super-hydrophilic property, microporous feature, and self-supported structure, the electrocatalyst exhibits an exceptional HER performance at large current density in 1.0 M KOH, only requiring low overpotential of 126, 193, and 238 mV to reach a current density of 100, 500, and 1000 mA cm⁻², respectively, and displaying a long-term durability up to 1000 h, which is among the state-of-the-art non-precious metal electrocatalysts. Combining hard X-rays absorption spectroscopy and first-principles calculation, it also reveals that the strong electronic coupling at the interface of the heterostructure facilitates the dissociation of H₂O molecular, accelerating the HER kinetics in alkaline electrolyte. This work sheds a light on developing advanced non-precious metal electrocatalysts for industrial hydrogen production by means of constructing a super-hydrophilic microporous heterostructure.     

3D Nitrogen‐Anion‐Decorated Nickel Sulfides for Highly Efficient Overall Water Splitting

Developing non‐noble‐metal electrocatalysts with high activity and low cost for both the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) is of paramount importance for improving the generation of H₂ fuel by electrocatalytic water‐splitting. This study puts forward a new N‐anion‐decorated Ni₃S₂ material synthesized by a simple one‐step calcination route, acting as a superior bifunctional electrocatalyst for the OER/HER for the first time. The introduction of N anions significantly modifies the morphology and electronic structure of Ni₃S₂, bringing high surface active sites exposure, enhanced electrical conductivity, optimal HER Gibbs free‐energy (ΔG_H*), and water adsorption energy change (ΔG_H2O*). Remarkably, the obtained N‐Ni₃S₂/NF 3D electrode exhibits extremely low overpotentials of 330 and 110 mV to reach a current density of 100 and 10 mA cm^?2 for the OER and HER in 1.0 m KOH, respectively. Moreover, an overall water‐splitting device comprising this electrode delivers a current density of 10 mA cm^?2 at a very low cell voltage of 1.48 V. Our finding introduces a new way to design advanced bifunctional catalysts for water splitting.     

Interfacial Engineering of Polycrystalline Pt5P2 Nanocrystals and Amorphous Nickel Phosphate Nanorods for Electrocatalytic Alkaline Hydrogen Evolution

Electrocatalytic hydrogen evolution reaction (HER) in alkaline media is important for hydrogen economy but suffers from sluggish reaction kinetics due to a large water dissociation energy barrier. Herein, Pt₅P₂ nanocrystals anchoring on amorphous nickel phosphate nanorods as a high-performance interfacial electrocatalyst system (Pt₅P₂ NCs/a-NiPi) for the alkaline HER are demonstrated. At the unique polycrystalline/amorphous interface with abundant defects, strong electronic interaction, and optimized intermediate adsorption strength, water dissociation is accelerated over abundant oxophilic Ni sites of amorphous NiPi, while hydride coupling is promoted on the adjacent electron-rich Pt sites of Pt₅P₂. Meanwhile, the ultra-small-sized Pt₅P₂ nanocrystals and amorphous NiPi nanorods maximize the density of interfacial active sites for the Volmer–Tafel reaction. Pt₅P₂ NCs/a-NiPi exhibits small overpotentials of merely 9 and 41 mV at −10 and −100 mA cm⁻² in 1 M KOH, respectively. Notably, Pt₅P₂ NCs/a-NiPi exhibits an unprecedentedly high mass activity (MA) of 14.9 mA µg_Pt⁻¹ at an overpotential of 70 mV, which is 80 times higher than that of Pt/C and represents the highest MA of reported Pt-based electrocatalysts for the alkaline HER. This work demonstrates a phosphorization and interfacing strategy for promoting Pt utilization and in-depth mechanistic insights for the alkaline HER.     

Tetrahedral Bonding Structure (Ni3-Se) Induced by Lattice-Distortion of Ni to Achieve High Catalytic Activity in Na–Se Battery

Fabrication of transition-metal catalytic materials is regarded as a promising strategy for developing high-performance sodium–selenium (Na–Se) batteries. However, more systematic explorations are further demanded to find out how their bonding interactions and electronic structures can affect the Na storage process. This study finds that lattice-distorted nickel (Ni) structure can form different bonding structures with Na₂Se₄, providing high activity to catalyze the electrochemical reactions in Na–Se batteries. Using this Ni structure to prepare electrode (Se@NiSe₂/Ni/CTs) can realize rapid charge transfer and high cycle stability of the battery. The electrode exhibits high storage performance of Na⁺; i.e., 345 mAh g⁻¹ at 1 C after 400 cycles, and 286.4 mAh g⁻¹ at 10 C in rate performance test. Further results reveal the existence of a regulated electronic structure with upshifts of the d-band center in the distorted Ni structure. This regulation changes the interaction between Ni and Na₂Se₄ to form a Ni₃–Se tetrahedral bonding structure. This bonding structure can provide higher adsorption energy of Ni to Na₂Se₄ to facilitate the redox reaction of Na₂Se₄ during the electrochemical process. This study can inspire the design of bonding structure with high performance in conversion-reaction-based batteries.     

Interstitial Hydrogen Atom to Boost Intrinsic Catalytic Activity of Tungsten Oxide for Hydrogen Evolution Reaction

Tungsten oxide (WO₃) is an appealing electrocatalyst for the hydrogen evolution reaction (HER) owing to its cost-effectiveness and structural adjustability. However, the WO₃ electrocatalyst displays undesirable intrinsic activity for the HER, which originates from the strong hydrogen adsorption energy. Herein, for effective defect engineering, a hydrogen atom inserted into the interstitial lattice site of tungsten oxide (H_0.23WO₃) is proposed to enhance the catalytic activity by adjusting the surface electronic structure and weakening the hydrogen adsorption energy. Experimentally, the H_0.23WO₃ electrocatalyst is successfully prepared on reduced graphene oxide. It exhibits significantly improved electrocatalytic activity for HER, with a low overpotential of 33 mV to drive a current density of 10 mA cm⁻² and ultra-long catalytic stability at high-throughput hydrogen output (200 000 s, 90 mA cm⁻²) in acidic media. Theoretically, density functional theory calculations indicate that strong interactions between interstitial hydrogen and lattice oxygen lower the electron density distributions of the d-orbitals of the active tungsten (W) centers to weaken the adsorption of hydrogen intermediates on W-sites, thereby sufficiently promoting fast desorption from the catalyst surface. This work enriches defect engineering to modulate the electron structure and provides a new pathway for the rational design of efficient catalysts for HER.     

Interface Modulation of MoS2/Metal Oxide Heterostructures for Efficient Hydrogen Evolution Electrocatalysis

Developing efficient earth‐abundant MoS₂ based hydrogen evolution reaction (HER) electrocatalysts is important but challenging due to the sluggish kinetics in alkaline media. Herein, a strategy to fabricate a high‐performance MoS₂ based HER electrocatalyst by modulating interface electronic structure via metal oxides is developed. All the heterostructure catalysts present significant improvement of HER electrocatalytic activities, demonstrating a positive role of metal oxides decoration in promoting the rate‐limited water dissociation step for the HER mechanism in alkaline media. The as‐obtained MoS₂/Ni₂O₃H catalyst exhibits a low overpotential of 84 mV at 10 mA cm^?2 and small charge‐transfer resistance of 1.5 Ω in 1 m KOH solution. The current density (217 mA cm^?2) at the overpotential of 200 mV is about 2 and 24 times higher than that of commercial Pt/C and bare MoS₂, respectively. Additionally, these MoS₂/metal oxides heterostructure catalysts show outstanding long‐term stability under a harsh chronopotentiometry test. Theoretical calculations reveal the varied sensitivity of 3d‐band in different transition oxides, in which Ni‐3d of Ni₂O₃H is evidently activated to achieve fast electron transfer for HER as the electron‐depletion center. Both electronic properties and energetic reaction trends confirm the high electroactivity of MoS₂/Ni₂O₃H in the adsorption and dissociation of H₂O for highly efficient HER in alkaline media.     

Hydroxyapatite-Derived Heterogeneous Ru-Ru2P Electrocatalyst and Environmentally-Friendly Membrane Electrode toward Efficient Alkaline Electrolyzer

Alkaline membrane water electrolysis is a promising production technology, and advanced electrocatalyst and membrane electrode design have always been the core technology. Herein, an ion-exchange method and an environmentally friendly in situ green phosphating strategy are successively employed to fabricate Ru-Ru₂P heterogeneous nanoparticles by using hydroxyapatite (HAP) as a phosphorus source, which is an exceptionally active electrocatalyst for hydrogen evolution reaction (HER). Density functional theory calculation results reveal that strong electronic redistribution occurs at the heterointerface of Ru-Ru₂P, which modulates the electronic structure to achieve an optimized hydrogen adsorption strength. The obtained Ru-Ru₂P possesses excellent HER performance (24 mV at 10 mA cm⁻²) and robust stability (1000 mA cm⁻² for 120 h) in alkaline media. Furthermore, an environmentally friendly membrane electrode with a sandwich structure is assembled by HAP nanowires as an alkaline membrane, Ru-Ru₂P as a cathodic catalyst, and NiFe-LDH as an anodic catalyst, respectively. The voltage of (−) Ru-Ru₂P || NiFe-LDH/CNTs (+) (1.53 V at 10 mA cm⁻²) is lower than that of (−) 20 wt% Pt/C || RuO₂ (+) (1.60 V at 10 mA cm⁻²) for overall water splitting. Overall, the studies not only design an efficient catalyst but also provide a new route to achieve a high-stability electrolyzer for industrial H₂ production.     

Nitrogen‐Doped CoP Electrocatalysts for Coupled Hydrogen Evolution and Sulfur Generation with Low Energy Consumption

Hydrogen production is the key step for the future hydrogen economy. As a promising H₂ production route, electrolysis of water suffers from high overpotentials and high energy consumption. This study proposes an N‐doped CoP as the novel and effective electrocatalyst for hydrogen evolution reaction (HER) and constructs a coupled system for simultaneous hydrogen and sulfur production. Nitrogen doping lowers the d‐band of CoP and weakens the H adsorption on the surface of CoP because of the strong electronegativity of nitrogen as compared to phosphorus. The H adsorption that is close to thermos‐neutral states enables the effective electrolysis of the HER. Only ?42 mV is required to drive a current density of ?10 mA cm^?2 for the HER. The oxygen evolution reaction in the anode is replaced by the oxidation reaction of Fe²⁺, which is regenerated by a coupled H₂S absorption reaction. The coupled system can significantly reduce the energy consumption of the HER and recover useful sulfur sources.     

Rational Synthesis of Core-Shell-Structured Nickel Sulfide-Based Nanostructures for Efficient Seawater Electrolysis

Versatile electrocatalysis at higher current densities for natural seawater splitting to produce hydrogen demands active and robust catalysts to overcome the severe chloride corrosion, competing chlorine evolution, and catalyst poisoning. Hereto, the core-shell-structured heterostructures composed of amorphous NiFe hydroxide layer capped Ni₃S₂ nanopyramids which are directly grown on nickel foam skeleton (NiS@LDH/NF) are rationally prepared to regulate cooperatively electronic structure and mass transport for boosting oxygen evolution reaction (OER) performance at larger current densities. The prepared NiS@LDH/NF delivers the anodic current density of 1000 mA cm⁻² at the overpotential of 341 mV in 1.0 m KOH seawater. The feasible surface reconstruction of Ni₃S₂-FeNi LDH interfaces improves the chemical stability and corrosion resistance, ensuring the robust electrocatalytic activity in seawater electrolytes for continuous and stable oxygen evolution without any hypochlorite production. Meanwhile, the designed Ni₃S₂ nanopyramids coated with FeNi₂P layer (NiS@FeNiP/NF) still exhibit the improved hydrogen evolution reaction (HER) activity in 1.0 m KOH seawater. Furthermore, the NiS@FeNiP/NF||NiS@LDH/NF pair requires cell voltage of 1.636 V to attain 100 mA cm⁻² with a 100% Faradaic efficiency, exhibiting tremendous potential for hydrogen production from seawater.     

Cooperative Boron and Vanadium Doping of Nickel Phosphides for Hydrogen Evolution in Alkaline and Anion Exchange Membrane Water/Seawater Electrolyzers

Developing low-cost and high-performance transition metal-based electrocatalysts is crucial for realizing sustainable hydrogen evolution reaction (HER) in alkaline media. Here, a cooperative boron and vanadium co-doped nickel phosphide electrode (B, V-Ni₂P) is developed to regulate the intrinsic electronic configuration of Ni₂P and promote HER processes. Experimental and theoretical results reveal that V dopants in B, V-Ni₂P greatly facilitate the dissociation of water, and the synergistic effect of B and V dopants promotes the subsequent desorption of the adsorbed hydrogen intermediates. Benefiting from the cooperativity of both dopants, the B, V-Ni₂P electrocatalyst requires a low overpotential of 148 mV to attain a current density of −100 mA cm⁻² with excellent durability. The B, V-Ni₂P is applied as the cathode in both alkaline water electrolyzers (AWEs) and anion exchange membrane water electrolyzers (AEMWEs). Remarkably, the AEMWE delivers a stable performance to achieve 500 and 1000 mA cm⁻² current densities at a cell voltage of 1.78 and 1.92 V, respectively. Furthermore, the developed AWEs and AEMWEs also demonstrate excellent performance for overall seawater electrolysis.     

自组装磷化镍纳米片阵列电极的电催化析氢性能研究

可持续发展的清洁氢能源是未来能源发展的方向之一,因而发展高效廉价的析氢材料变得尤为重要。本文首次通过水热和退火的方式制备出自组装磷化镍纳米片阵列结构,并通过SEM和XRD等技术表征这种结构的形貌和组成成分。与众多关于Ni-P纳米材料集中在酸性体系下的析氢电化学研究不同,本文首次通过在碱性条件下稳态极化曲线(LSV)、Tafel极化曲线、电流-时间曲线(i-t)以及交流阻抗曲线探究了其作为电解水析氢纳米电催化电极材料的电化学性能。该材料的电极具有特殊的纳米形貌结构和性质,使其具有更低的析氢反应电位、更大的析氢反应活性和较好的稳定性,具有替代贵金属作为水解析氢材料的潜力。     

Boosting Alkaline Hydrogen and Oxygen Evolution Kinetic Process of Tungsten Disulfide-Based Heterostructures by Multi-Site Engineering

Alkaline water electrolysis is an advanced technology for scalable H₂ production using surplus electricity from intermittent energy sources, but it remains challenging for non-noble electrocatalysts to split water into hydrogen and oxygen efficiently, especially for tungsten disulfide (WS₂)-based catalysts. Density functional theory calculations in combination with experimental study are used to establish a multi-site engineering strategy for developing robust WS₂-based hybrid electrocatalyst on mesoporous bimetallic nitride (Ni₃FeN) nanoarrays for bifunctional water splitting. This ingenious design endows the catalyst with numerous edge sites chemically bonded with the conductive scaffold, which are favorable for water dissociation and hydrogen adsorption. Benefiting from the synergistic advantages, the N-WS₂/Ni₃FeN hybrid exhibits exceptional bifunctional properties for hydrogen and oxygen evolution reactions (HER and OER) in base with excellent large-current durability, requiring 84 mV to afford 10 mA cm^?2 for HER, and 240 mV at 100 mA cm^?2 for OER, respectively. Assembling the catalytic materials as both the anode and cathode to construct an electrolyzer, it is actualized very good activities for overall water splitting with only 1.5 V to deliver 10 mA cm^?2, outperforming the IrO₂⁽⁺⁾//Pt^(?) coupled electrodes and many non-noble bifunctional electrocatalysts thus far. This work provides a promising avenue for designing WS₂-based heterogeneous electrocatalysts for water electrolysis.     

Unlocking the catalytic activities of 2H-phase Mo-based compounds via topological conversion reaction

Although 2H molybdenum disulfide (MoS₂) layers are highly desirable for hydrogen evolution reaction (HER) owing to their high chemical stabilities and low cost, the inert basal plane and semiconducting nature severely hinder their practical applications. Here, the catalytic activities of 2H phase molybdenum-based compounds are unlocked via topological conversion reaction from Mo₂GeC MAX phase to accordion-like molybdenum phosphosulphide. During the conversion reaction, phosphorus atoms can be implanted into the sandwich-like S-Mo-S planes and gradually substitute sulfur atoms, which are beneficial to optimize the electronic configuration and facilitate to absorb water molecules, unlocking the inert basal planes of 2H phase molybdenum-based compounds. The accordion-like molybdenum phosphosulphide exhibits high hydrogen production rates up to 288 mmol g⁻¹ h⁻¹ cm⁻² at a high loading of 3 mg cm⁻² and ultralong durability up to 35,000 cycles, satisfying the practical application for HER.     

NiSe‐Ni0.85Se Heterostructure Nanoflake Arrays on Carbon Paper as Efficient Electrocatalysts for Overall Water Splitting

Fabricating cost‐effective, bifunctional electrocatalysts for both the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in basic media is critical for renewable energy generation. Here, NiSe/CP, Ni_0.85Se/CP, and NiSe‐Ni_0.85Se/CP heterostructure catalysts with different phase constitutions are successfully prepared through in situ selenylation of a NiO nanoflake array oriented on carbon paper (CP) by tuning the original Ni/Se molar ratio of the raw materials. The relationship between the crystal phase component and electrocatalytic activity is systematically studied. Benefiting from the synergetic effect of the intrinsic metallic state, facile charge transport, abundant catalytic active sites, and multiple electrolyte transmission paths, the optimized NiSe‐Ni_0.85Se/CP exhibits a remarkably higher catalytic activity for both the HER and OER than single‐phase NiSe/CP and Ni_0.85Se/CP. A current density of 10 mA cm⁻² at 1.62 V and a high stability can be obtained by using NiSe‐Ni_0.85Se/CP as both the cathode and anode for overall water splitting under alkaline conditions. Density functional theory calculations confirm that H and OH⁻ can be more easily adsorbed on NiSe‐Ni_0.85Se than on NiSe and Ni_0.85Se. This study paves the way for enhancing the overall water splitting performance of nickel selenides by fabricating heterophase junctions using nickel selenides with different phases.     

Optimizing the Electronic Structure of Atomically Dispersed Ru Sites with CoP for Highly Efficient Hydrogen Evolution in both Alkaline and Acidic Media

Developing efficient and stable electrocatalysts for hydrogen evolution reaction (HER) over a wide pH range and industrial large-scale hydrogen production is critical and challenging. Here, a tailoring strategy is developed to fabricate an outstanding HER catalyst in both acidic and alkaline electrolytes containing high-density atomically dispersed Ru sites anchored in the CoP nanoparticles supported on carbon spheres (NC@Ru_SA-CoP). The obtained NC@Ru_SA-CoP catalyst exhibits excellent HER performance with overpotentials of only 15 and 13 mV at 10 mA cm⁻² in 1 m KOH and 0.5 m H₂SO₄, respectively. The experimental results and theoretical calculations indicate that the strong interaction between the Ru site and the CoP can effectively optimize the electronic structure of Ru sites to reduce the hydrogen binding energy and the water dissociation energy barrier. The constructed alkaline anion exchange membrane water electrolyze (AAEMWE) demonstrates remarkable durability and an industrial-level current density of 1560 mA cm⁻² at 1.8 V. This strategy provides a new perspective on the design of Ru-based electrocatalysts with suitable intermediate adsorption strengths and paves the way for the development of highly active electrocatalysts for industrial-scale hydrogen production.