Two-Dimensional Transition Metal Phosphides As Cathode Additive in Robust Lithium-Sulfur Batteries.

The development of advanced cathode materials able to promote the sluggish redox kinetics of polysulfides is crucial to bringing lithium-sulfur batteries to the market. Herein, two electrode materials: namely, Zr2PS2 and Zr2PTe2, are identified through screening several hundred thousand compositions in the Inorganic Crystal Structure Database. First-principles calculations are performed on these two materials. These structures are similar to that of the classical MXenes. Concurrently, calculations show that Zr2PS2 and Zr2PTe2 possess high electrical conductivity, promote Li ion diffusion, and have excellent electrocatalytic activity for the Li-S reaction and particularly for the Li2S decomposition. Besides, the mechanisms behind the excellent predicted performance of Zr2PS2 and Zr2PTe2 are elucidated through electron localization function, charge density difference, and localized orbital locator. This work not only identifies two candidate sulfur cathode additives but may also serve as a reference for the identification of additional electrode materials in new generations of batteries, particularly in sulfur cathodes.

Multifunctional Catalytic Hierarchical Interfaces of Ni12 P5 -Ni2 P Porous Nanosheets Enabled Both Sulfides Reaction Promotion and Li-Dendrite Suppression for High-Performance Li-S Full Batteries.

The development of lithium-sulfur (Li-S) batteries is very promising and yet faces the issues of hindered polysulfides conversion and Li dendrite growth. Different from using different materials strategies to overcome these two types of problems, here multifunctional catalytic hierarchical interfaces of Ni12 P5 -Ni2 P porous nanosheets formed by Ni2 P partially in situ converted from Ni12 P5 are proposed. The unique electronic structure in the interface endows Ni12 P5 -Ni2 P effective electrocatalysis effect toward both sulfides' reduction and oxidation through reducing Gibbs free energies, indicating a bidirectional conversion acceleration. Importantly, Ni12 P5 -Ni2 P porous nanosheets with hierarchical interfaces also reduced the Li nucleation energy barrier, and a dendrite-free Li deposition is realized during the overall Li deposition and stripping steps. To this end, Ni12 P5 -Ni2 P decorated carbon nanotube/S cathode showing a high capacity of over 1500 mAh g-1 , and a high rate capability of 8 C. Moreover, the coin full cell delivered a high capacity of 1345 mAh g-1 at 0.2 C and the pouch full cell delivered a high capacity of 1114 mAh g-1 at 0.2 C with high electrochemical stability during 180° bending. This work inspires the exploration of hierarchical structures of 2D materials with catalytically active interfaces to improve the electrochemistry of Li-S full battery.

Copper Phosphide Nanostructures Covalently Modified Ti3 C2 Tx for Fast Lithium-Ion Storage by Enhanced Kinetics and Pesudocapacitance.

2D layer Ti3 C2 Tx material attracts enormous attention in lithium ion energy storage field owing to the unique surface chemistry properties, but the material still suffers from restacking issue and the restriction on capacity. Herein, copper phosphide (Cu3 P) nanostructures@Ti3 C2 Tx composites are prepared by the in situ generation of Cu-BDC precursor in the bulk material followed with phosphorization. The uniformly distributed copper phosphide nanostructures effectively expand the interlayer spacing promoting the structural stability, and achieves the effective connection with the bulk material accelerating the diffusion and migration of lithium ions. The electrochemical activity of Cu3 P also provides more lithium ion active sites for lithium storage. The X-ray photoelectron spectroscopy (XPS) analysis verifies that Ti─O─P bond with strong covalency allows the upper shift of maximum valence band and Fermi level, stimulating the charge transportation between Cu3 P and the bulk Ti3 C2 Tx for better electrode kinetics. 3Cu3 P@Ti3 C2 Tx exhibits excellent rate performance of 165.4 mAh g-1 at 3000 mA g-1 and the assembled 3Cu3 P@Ti3 C2 Tx //AC Lithium-ion hybrid capacitorsLIC exhibits superior energy density of 93.0 Wh kg-1 at the power density of 2367.3 W kg-1 . The results suggest that the interfacial modification of Ti3 C2 Tx with transition metal phosphides will be advantageous to its high energy density application in lithium-ion storage.

Electrochemical Deposition for Cultivating Nano- and Microstructured Electroactive Materials for Supercapacitors: Recent Developments and Future Perspectives.

The globe is currently dealing with serious issues related to the world economy and population expansion, which has led to a significant increase in the need for energy. One of the most promising energy devices for the next generation of energy technology is the supercapacitor (SC). Among the numerous nanostructured materials examined for SC electrodes, inorganic nanosheets are considered to be the most favorable electrode materials because of their excellent electrochemical performance due to their large surface area, very low layer thickness, and tunable diverse composition. Various inorganic nanosheets (NS) such as metal oxides, metal chalcogenides, metal hydroxides, and MXenes show substantial electrochemical activity. Herein, a comprehensive survey of inorganic NS arrays synthesized through the electrodeposition method is reported with the discussion on detailed growth mechanism and their application in the fabrication of SC electrodes/devices for powering flexible and wearable electronics appliances. To begin with, the first section will feature the various types of electrodeposition working mechanism, SC types and their working mechanisms, importance of nanosheet structure for SCs. This review gives a profound interpretation of supercapacitor electrode materials and their performances in different domains. Finally, a perspective on NS array through electrodeposition method applications in diverse fields is extensively examined.

A Metal-Organic Framework-Derived Strategy for Constructing Synergistic N-Doped Carbon-Encapsulated NiCoP@N-C-Based Anodes toward High-Efficient Lithium Storage.

Transition metal phosphides (TMPs) have been regarded as the prospective anodes for lithium-ion batteries (LIBs). However, their poor intrinsic conductivity and inevitable large volume variation result in sluggish redox kinetics and the collapse of electrode structure during cycling, which substantially hinders their practical use. Herein, an effective composite electrodes design strategy of "assembly and phosphorization" is proposed to construct synergistic N-doped carbon-encapsulated NiCoP@N-C-based composites, employing a metal-organic frameworks (MOFs) as sacrificial hosts. Serving as the anodes for LIBs, one representative P-NCP-NC-600 electrode exhibits high reversible capacity (858.5 mAh g-1, 120 cycles at 0.1 A g-1) and superior long-cycle stability (608.7 mAh g-1, 500 cycles at 1 A g-1). The impressive performances are credited to the synergistic effect between its unique composite structure, electronic properties and ideal composition, which achieve plentiful lithium storage sites and reinforce the structural architecture. By accompanying experimental investigations with theoretical calculations, a deep understanding in the lithium storage mechanism is achieved. Furthermore, it is revealed that a more ideal synergistic effect between NiCoP components and N-doped carbon frameworks is fundamentally responsible for the realization of superb lithium storage properties. This strategy proposes certain instructive significance toward designable high-performance TMP-based anodes for high-energy density LIBs.

Ginkgo Leaf-Derived Carbon Supports for the Immobilization of Iron/Iron Phosphide Nanospheres for Electrocatalytic Hydrogen Evolution.

Iron/iron phosphide nanospheres supported on ginkgo leaf-derived carbon (Fe&FeP@gl-C) are prepared using a post-phosphidation approach, with varying amounts of iron (Fe). The activity of the catalysts in the hydrogen evolution reaction (HER) outperforms iron/iron carbide nanospheres supported on ginkgo leaf-derived carbon (Fe&FexC@gl-C), due to enhanced work function, electron transfer, and Volmer processes. The d-band centers of Fe&FeP@gl-C-15 move away from the Fermi level, lowering the H2 desorption energy and accelerating the Heyrovsky reaction. Density functional theory (DFT) calculations reveal that the hydrogen-binding free energy |ΔGH*| value is close to zero for the Fe&FeP@gl-C-15 catalyst, showing a good balance between Volmer and Heyrovsky processes. The Fe&FeP@gl-C-15 catalyst shows excellent hydrogen evolution performance in 0.5 m H2SO4, driving a current density of 10 mA cm-2 at an overpotential of 92 mV. Notably, the Fe&FeP@gl-C-15 catalyst outperforms a 20 wt% Pt/C catalyst, with a smaller overpotential required to drive a higher current density above 375 mA cm-2.

BiVO4 Photoanodes Enhanced with Metal Phosphide Co-Catalysts: Relevant Properties to Boost Photoanode Performance.

Achieving highly performant photoanodes for oxygen evolution is key to developing photoelectrochemical devices for solar water splitting. In this work, BiVO4 photoanodes are enhanced with a series of core-shell structured bimetallic nickel-cobalt phosphides (MPs), and key insights into the role of co-catalysts are provided. The best BiVO4 /Ni1.5 Co0.5 P and BiVO4 /Ni0.5 Co1.5 P photoanodes achieve a 3.5-fold increase in photocurrent compared with bare BiVO4 . It is discovered that this enhanced performance arises from a synergy between work function, catalytic activity, and capacitive ability of the MPs. Distribution of relaxation times analysis reveals that the contact between the MPs, BiVO4 , and the electrolyte gives rise to three routes for hole injection into the electrolyte, all of which are significantly improved by the presence of a second metal cation in the co-catalyst. Kinetic studies demonstrate that the significantly improved interfacial charge injection is due to a lower charge-transfer resistance, enhanced oxygen-evolution reaction kinetics, and larger surface hole concentrations, providing deeper insights into the carrier dynamics in these photoanode/co-catalyst systems for their rational design.

Phosphide-Based Electrocatalysts for Urea Electrolysis: Recent Trends and Progress.

Electrolysis is a trend in producing hydrogen as a fuel for renewable energy development, and urea electrolysis is considered as one of the advanced electrolysis processes, where efficient materials still need to be explored. Notably, urea electrolysis came into existence to counter-part the electrode reactions in water electrolysis, which has hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). Among those reactions, OER is sluggish and limits water splitting. Hence, urea electrolysis emerged with urea oxidation reaction (UOR) and HER as their reactions to tackle the water electrolysis. Among the explored materials, noble-metal catalysts are efficient, but their cost and scarcity limit the scaling-up of the Urea electrolysis. Hence, current challenges must be addressed, and novel efficient electrocatalysts are to be implemented to commercialize urea electrolysis technology. Phosphides, as an efficient UOR electrocatalyst, have gained huge attention due to their exceptional lattice structure geometry. The phosphide group benefits the water molecule adsorption and water dissociation, and facilitates the oxyhydrate of the metal site. This review summarizes recent trends in phosphide-based electrocatalysts for urea electrolysis, discusses synthesis strategies and crystal structure relationship with catalytic activity, and presents the challenges of phosphide electrocatalysts in urea electrolysis.

Porous FeNi Prussian blue cubes derived carbon-based phosphides as superior sulfur hosts for high-performance lithium-sulfur batteries.

In contrast to lithium-ion batteries, lithium-sulfur batteries have higher theoretical energy density and lower cost, so they would become competitive in the practical application. However, the shuttle effect of polysulfides and slow oxidation-reduction kinetics can degrade their electrochemical performance and cycle life. In this work, we have first developed the porous FeNi Prussian blue cubes as precursors. The calcination in different atmospheres was employed to make precursors convert into common pyrolysis products or novel carbon-based phosphides, and sulfides, labeled as FeNiP/A-C, FeNiP/A-P, and FeNiP/A-S. When these products serve as host materials in the sulfur cathode, the electrochemical performance of lithium-sulfur batteries is in the order of S@FeNiP/A-P > S@FeNiP/A-S > S@FeNiP/A-C. Specifically, the initial discharge capacity of S@FeNiP/A-P can reach 679.1 mAh g-1at 1 C, and the capacity would maintain 594.6 mAh g-1after 300 cycles. That is because the combination of carbon-based porous structure and numerous well-dispersed Ni2P/Fe2P active sites contribute FeNiP/A-P to obtain larger lithium-ion diffusion, lower resistance, stronger chemisorption, and more excellent catalytic effect than other samples. This work may deliver that metal-organic framework-derived carbon-based phosphides are more suitable to serve as sulfur hosts than carbon-based sulfides or common pyrolysis products for enhancing Li-S batteries' performance.

Electrochemical Sensors Based on Transition Metal Materials for Phenolic Compound Detection.

Electrochemical sensors have been recognized as crucial tools for monitoring comprehensive chemical information, especially in the detection of a significant class of molecules known as phenolic compounds. These compounds can be present in water as hazardous analytes and trace contaminants, as well as in living organisms where they regulate their metabolism. The sensitive detection of phenolic compounds requires highly efficient and cost-effective electrocatalysts to enable the development of high-performance sensors. Therefore, this review focuses on the development of advanced materials with excellent catalytic activity as alternative electrocatalysts to conventional ones, with a specific emphasis on transition metal-based electrocatalysts for the detection of phenolic compounds. This research is particularly relevant in diverse sectors such as water quality, food safety, and healthcare.

Highly Porous Carbon Flakes Derived from Cellulose and Nickel Phosphide Heterostructure towards Efficient Electrocatalysis of Oxygen Evolution Reaction.

This study delves into the pressing challenges of climate change and the escalating carbon dioxide (CO2) emissions by exploring hydrogen technology as a sustainable alternative. In particular, there is focus on nickel phosphide-based electrocatalysts, known for their promising performance in hydrogen evolution reactions (HERs) and oxygen evolution reactions (OERs). Therefore, here we have designed a facile strategy to deliver highly porous carbon flakes derived from cellulose fibers via carbonization at 850 °C, yielding highly porous structures and outstanding specific surface area (SSAcel_carb_850_act = 3164 m2/g) after activation. As-fabricated carbon was utilized as a support for Ni12P5 with an optimized mass ratio. Electrochemical testing revealed that the composite of Ni12P5 and carbon flakes with a ratio of 100:1, respectively, exhibited the most favorable kinetics for the oxygen evolution reaction (OER). Importantly, the durability tests of this sample demonstrated the most stable behavior and lowest potential change under high current density among the studied samples, making it a promising candidate in practical applications. Moreover, the analysis of electrocatalysts after an OER does not show any changes, indicating that the sample does not undergo undesired intermediate reactions and that unwanted products are not released, explaining its stable behavior. This provides a straightforward approach for creating a cellulose-derived composite with enhanced electroactivity and durability.

Phosphorus Modification of Iron: Mechanistic Insights into Ammonia Synthesis on Fe2P Catalyst.

Ammonia (NH3) is a critical chemical for fertilizer production and a potential future energy carrier within a sustainable hydrogen economy. The industrial Haber-Bosch process, though effective, operates under harsh conditions due to the high thermodynamic stability of the nitrogen molecule (N2). This motivates the search for alternative catalysts that facilitate ammonia synthesis at milder temperatures and pressures. Theoretical and experimental studies suggest that circumventing the trade-off between N-N activation and subsequent NHx hydrogenation, governed by the Brønsted-Evans-Polanyi (BEP) relationship, is key to achieving this goal. Recent studies indicate metal phosphides as promising catalyst materials. In this work, a comprehensive density functional theory (DFT) study comparing the mechanisms and potential reaction pathways for ammonia synthesis on Fe(110) and Fe2P(001) is presented. The results reveal substantial differences in the adsorption strengths of NHx intermediates, with Fe2P(001) exhibiting weaker binding compared to Fe(110). For N-N bond cleavage, multiple competing pathways become viable on Fe2P(001), including routes involving the pre-hydrogenation of adsorbed N2 (e.g., through *NNH*). Analysis of DFT-derived turnover rates as a function of hydrogen pressure (H2) highlights the increased importance of these hydrogenated intermediates on Fe2P(001) compared to Fe(110) where direct N2 dissociation dominates. These findings suggest that phosphorus incorporation modifies the ammonia synthesis mechanism, offering alternative pathways that may circumvent the limitations of traditional transition metal catalysts. This work provides theoretical insights for the rational design of Fe-based catalysts and motivates further exploration of phosphide-based materials for sustainable ammonia production.

Interfacial Chemistry and Catalysis of Inorganic Materials.

Heterogeneous catalysis is essential to most industrial chemical processes. To achieve a better sustainability of these processes we need highly efficient and highly selective catalysts that are based on earth-abundant materials rather than the more conventional noble metals. Here, we discuss the potential of inorganic materials as catalysts for chemical transformations focusing in particular on the promising transition metal phosphides and sulfides. We describe our recent and current efforts to understand the interfacial chemistry of these materials that governs catalysis, and to tune catalytic reactivity by controlled chemical modification of the material surfaces and by use of interfacial electric fields.

Expedited Synthesis of Metal Phosphides Maximizes Dispersion, Air Stability, and Catalytic Performance in Selective Hydrogenation.

Metal phosphides have been hailed as potential replacements for scarce noble metal catalysts in many aspects of the hydrogen economy from hydrogen evolution to selective hydrogenation reactions. But the need for dangerous and costly phosphorus precursors, limited support dispersion, and low stability of the metal phosphide surface toward oxidation substantially lower the appeal and performance of metal phosphides in catalysis. We show here that a 1-step procedure that relies on safe and cheap precursors can furnish an air-stable Ni2P/Al2O3 catalyst containing 3.2 nm nanoparticles. Ni2P/Al2O3 1-step is kinetically competitive with the palladium-based Lindlar catalyst in selective hydrogenation catalysis, and a loading corresponding to 4 ppm Ni was sufficient to convert 0.1 mol alkyne. The 1-step synthetic procedure alters the surface ligand speciation of Ni2P/Al2O3, which protects the nanoparticle surface from oxidation, and ensures that 85 % of the initial catalytic activity was retained after the catalyst was stored under air for 1.5 years. Preparation of Ni2P on a variety of supports (silica, TiO2, SBA-15, ZrO2, C and HAP) as well as Co2P/Al2O3, Co2P/TiO2 and bimetallic NiCoP/TiO2 demonstrates the generality with which supported metal phosphides can be accessed in a safe and straightforward fashion with small sizes and high dispersion.

Transition Metal Phosphide Nanoarchitectonics for Versatile Organic Catalysis.

Transition metal phosphides (TMP) posses unique physiochemical, geometrical, and electronic properties, which can be exploited for different catalytic applications, such as photocatalysis, electrocatalysis, organic catalysis, etc. Among others, the use of TMP for organic catalysis is less explored and still facing many complex challenges, which necessitate the development of sustainable catalytic reaction protocols demonstrating high selectivity and yield of the desired molecules of high significance. In this regard, the controlled synthesis of TMP-based catalysts and thorough investigations of underlying reaction mechanisms can provide deeper insights toward practical achievement of desired applications. This review aims at providing a comprehensive analysis on the recent advancements in the synthetic strategies for the tailored and tunable engineering of structural, geometrical, and electronic properties of TMP. In addition, their unprecedented catalytic potential toward different organic transformation reactions is succinctly summarized and critically analyzed. Finally, a rational perspective on future opportunities and challenges in the emerging field of organic catalysis is provided. On the account of the recent achievements accomplished in organic synthesis using TMP, it is highly anticipated that the use of TMP combined with advanced innovative technologies and methodologies can pave the way toward large scale realization of organic catalysis.

Ammonia Electrosynthesis with a Stable Metal-Free 2D Silicon Phosphide Catalyst.

Metal-free 2D phosphorus-based materials are emerging catalysts for ammonia (NH3 ) production through a sustainable electrochemical nitrogen reduction reaction route under ambient conditions. However, their efficiency and stability remain challenging due to the surface oxidization. Herein, a stable phosphorus-based electrocatalyst, silicon phosphide (SiP), is explored. Density functional theory calculations certify that the N2 activation can be realized on the zigzag Si sites with a dimeric end-on coordinated mode. Such sites also allow the subsequent protonation process via the alternating associative mechanism. As the proof-of-concept demonstration, both the crystalline and amorphous SiP nanosheets (denoted as C-SiP NSs and A-SiP NSs, respectively) are obtained through ultrasonic exfoliation processes, but only the crystalline one enables effective and stable electrocatalytic nitrogen reduction reaction, in terms of an NH3 yield rate of 16.12 µg h-1  mgcat. -1 and a Faradaic efficiency of 22.48% at -0.3 V versus reversible hydrogen electrode. The resistance to oxidization plays the decisive role in guaranteeing the NH3 electrosynthesis activity for C-SiP NSs. This surface stability endows C-SiP NSs with the capability to serve as appealing electrocatalysts for nitrogen reduction reactions and other promising applications.

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-Ni2 P) is developed to regulate the intrinsic electronic configuration of Ni2 P and promote HER processes. Experimental and theoretical results reveal that V dopants in B, V-Ni2 P 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-Ni2 P electrocatalyst requires a low overpotential of 148 mV to attain a current density of -100 mA cm-2  with excellent durability. The B, V-Ni2 P 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.

Transition Metal Phosphides: The Rising Star of Lithium-Sulfur Battery Cathode Host.

Lithium-sulfur batteries (LSBs) with ultra-high energy density (2600 W h kg-1 ) and readily available raw materials are emerging as a potential alternative device with low cost for lithium-ion batteries. However, the insulation of sulfur and the unavoidable shuttle effect leads to slow reaction kinetics of LSBs, which in turn cause various roadblocks including poor rate capability, inferior cycling stability, and low coulombic efficiency. The most effective way to solve the issues mentioned above is to rationally design and control the synthesis of the cathode host for LSBs. Transition metal phosphides (TMPs) with good electrical conductivity and dual adsorption-conversion capabilities for polysulfide (PS) are regarded as promising cathode hosts for new-generation LSBs. In this review, the main obstacles to commercializing the LSBs and the development processes of their cathode host are first elaborated. Then, the sulfur fixation principles, and synthesis methods of the TMPs are briefly summarized and the recent progress of TMPs in LSBs is reviewed in detail. Finally, a perspective on the future research directions of LSBs is provided.

Establishing Transition Metal Phosphides as Effective Sulfur Hosts in Lithium-Sulfur Batteries through the Triple Effect of "Confinement-Adsorption-Catalysis".

Structurally optimized transition metal phosphides are identified as a promising avenue for the commercialization of lithium-sulfur (Li-S) batteries. In this study, a CoP nanoparticle-doped hollow ordered mesoporous carbon sphere (CoP-OMCS) is developed as a S host with a "Confinement-Adsorption-Catalysis" triple effect for Li-S batteries. The Li-S batteries with CoP-OMCS/S cathode demonstrate excellent performance, delivering a discharge capacity of 1148 mAh g-1 at 0.5 C and good cycling stability with a low long-cycle capacity decay rate of 0.059% per cycle. Even at a high current density of 2 C after 200 cycles, a high specific discharge capacity of 524 mAh g-1 is maintained. Moreover, a reversible areal capacity of 6.56 mAh cm-2 is achieved after 100 cycles at 0.2 C, despite a high S loading of 6.8 mg cm-2 . Density functional theory (DFT) calculations show that CoP exhibits enhanced adsorption capacity for sulfur-containing substances. Additionally, the optimized electronic structure of CoP significantly reduces the energy barrier during the conversion of Li2 S4 (L) to Li2 S2 (S). In summary, this work provides a promising approach to optimize transition metal phosphide materials structurally and design cathodes for Li-S batteries.

Nickel Phosphonate MOF Derived N-Doped Carbon-Coated Phosphorus-Vacancies-Rich Ni2 P Particles as Efficient Bifunctional Oxygen Electrocatalyst.

The design of non-noble metal bifunctional electrocatalysts with outstanding performance and remarkable stability for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) is one of the most essential issues to the realization of rechargeable zinc-air battery, and transition metal phosphides (TMPs) have emerged as robust candidates for oxygen electrocatalysts. Herein, N-doped carbon-coated phosphorus-vacancies-rich Ni2 P particles (Vp -Ni2 P@NC) is proposed via simple carbonization and following Ar plasma treatment from a single nickel phosphonate metal-organic framework (MOF) without extra phosphine and nitrogen sources. The facile and rapid plasma treatment can achieve phosphorus vacancies which could modulate the electronic structure to enhance the inherent active and electrical conductivity. Meanwhile, the pyridine-N and graphitized-N produced during calcination also could provide more active sites and increase the electrical conductivity. The resultant Vp -Ni2 P@NC catalyst shows excellent bifunctional electrocatalytic activity (OER/ORR) based on synergistic effect of introducing P vacancies into Ni2 P and N-doped carbon. Vp -Ni2 P@NC catalyst shows more advantageous ΔE value (0.70 V) compared to Pt/C+RuO2 (0.73 V) and most reported catalysts. Additionally, the zinc-air bbatterie (ZAB) employing Vp -Ni2 P@NC as air cathode shows excellent performance. The maximum power density of 203.48 mW cm-2 , the cycling stability of more than 150 h at 10 mA cm-2 .