Metal Phosphides Research Articles

Highly efficient oxygen carrier NiFeP (oxy) hydroxides nanoparticle embedded in N-doped porous carbon derived from bio-waste for bifunctional electrocatalysts

Developing cost-effective, readily available materials for efficient hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in water splitting is a crucial step toward enhancing the profitability and sustainability of energy conversion systems. This research introduces a novel synthesis method for NiFeP/NPC OHs from banana peel bio-waste, a method that could revolutionize the field of materials science and electrochemistry. The use of metallic phosphides, known for their excellent electrical conductivity and catalytic activity, as bifunctional catalysts, combined with the efficient synthesis of nanoporous carbons (NPC) from banana peel bio-waste (BPW), could pave the way for a new era of sustainable and cost-effective energy conversion. By chemically activating different porogens, such as nickel, iron, and phosphorus (NiFeP), to form (oxy) hydroxides (OHs), functional carbonaceous structures with a high density of pores and large specific surface areas can be achieved. The resulting materials, designated as NiFeP/NPC OHs, are characterized by their remarkable porosity, high conductivity, large surface area, and chemical stability. These properties make NiFeP/NPC OHs particularly suitable for electrocatalysis, where they exhibit outstanding activity in both HER and OER. The optimized NiFeP/NPC OHs material shows a very low overpotential of 93 mV for HER and 243 mV for OER at 10 mA cm⁻2 and high durability over 100 h. Moreover, the bifunctional NiFeP/NPC OHs electrode demonstrates exceptional catalytic activity and stability in alkaline solutions. This study not only highlights the innovative synthesis of NPC from BPW and the cost-effective fabrication of NiFeP/NPC OHs but also sparks curiosity about the potential of this novel synthesis method.

Three-dimensional porous structure CoP/N-doped carbon nanospheres as anode for enhanced lithium storage performance

Transition metal phosphides (TMPs) with high theoretical capacities and safe operating voltage are recognized as prospective anode materials for lithium-ion batteries (LIBs). While, the huge volume expansion and low conductivity of TMPs still restrict their applications. Engineering nanostructured composites consisting of TMPs and conductive carbon-based materials is of great importance to improve electrochemical performance. Herein, a novel and facile pyrolysis-oxidation-phosphidation approach is designed to fabricate porous nanospheres composing of CoP nanoparticles and N-doped carbon substrate. The abundant pores in CoP/N-C provide ample active sites for lithium storage and facilitate Li+ transport. The introduction of N-doped carbon substrate enhances the electrical conductivity, allowing CoP to maintain its structure during cycling. The CoP/N-C anode achieves remarkable cycle performance, maintaining an extremely stable cycle life over 2000 cycles at 5 A g−1. More importantly, the full cell consisting of CoP/N-C and LiFePO4 also exhibits a prominent cycling durability with a capacity retention of 96.5 % at 0.1 A g−1 after 150 cycles. This work proposes a simple and feasible structural engineering strategy, which can provide a new way for optimizing the electrochemical performance of conversion-type anode materials.

Boosting the potassium storage property of spongia-like copper phosphide anode via nano-in-micro construction

Metal phosphides (MPs) show great promise as anode material in potassium-ion batteries (PIBs) owing to their cost-effectiveness and high theoretical capacity. Despite that, MPs anode usually manifests inferior poor cyclability as a result of dramatic volume fluctuation during discharge–charge cycling. Herein, a scalable salt template-assisted spray-drying method is developed to fabricate the porous carbon microspheres wrapped CuP2 nanoparticles (p-CuP2/C) with a nano-in-micro structure. The combination of the CuP2 nanoparticles, large meso-porous carbon microspheres can simultaneously offer plenty of reactive sites, promote electrolyte penetration, and maintain structural integrity. Additionally, the proposed synthesis strategy is suit for the industrial manufacture. As an anode for PIBs, the p-CuP2/C anode presents a high reversible capacity (494 mAh/g at 0.05 A/g), excellent cycling stability (a capacity degradation rate of 0.04 % per cycle during 2000 cycles at 2 A/g), and superior rate capability (244 mAh/g at 2 A/g). More impressively, pairing with a potassium Prussian blue cathode, the potassium-ion coin cell shows an excellent cycling lifespan with 87.1 % capacity retention after 200 cycles at a current density of 0.1 A/g, the assembled pouch cell also maintains stable cycling at 0.3 A/g over 80 cycles. This research could offer a facile approach to develop other advanced anodes with industrial practicability for alkali ion batteries.

Coupling highly reactive RuP2 with amorphous WP for boosting alkaline hydrogen evolution

Electrochemical water splitting stands out as an environmentally benign approach for generating green H2 through the harnessing of intermittent energy derived from renewable sources. However, the slow water dissociation kinetics hinders the commercialization for water-alkali electrolyzer. In this study, we synthesize a novel porous nanocomposite (RuP2/WP/PNC3-A) combined with RuP2 and amorphous WP by a facile and eco-friendly strategy. Detailed research results demonstrate that biomass-derived phytic acid not only promotes the formation of active metal phosphides, but also serves as a pore-forming agent to assist in the constructing a hierarchical porous structure, significantly enhancing the mass and electron transfer capability. Particularly noteworthy is that WP prevents the aggregation of RuP2. During the post-treatment process more protected RuP2 components are released and meanwhile leads to the conversion of WP from crystalline to amorphous. Benefitting from the applicable H adsorption ability of RuP2 and the enhanced H2O adsorption, dissociation capacity by amorphous WP, RuP2/WP/PNC3-A exhibits astonishing hydrogen evolution reaction (HER) performance, requiring an exceedingly low overpotential (only 24 mV) under 10 mA cm−2, featuring small Tafel slope (64.6 mV dec−1), and demonstrating excellent durability.

Recent progress in the synthesis and electrocatalytic application of MXene‐based metal phosphide composites

AbstractIn the domain of novel catalyst design and application, metal phosphides have attracted widespread interest due to their unique electronic structure and potential catalytic activity. Various types of supports that can effectively anchor metal phosphides have been reported, among which MXene have received significant attention due to their two‐dimensional (2D) structure, adjustable composition, and composite variability. This work mainly aims to elucidate the preparation of novel MXene carriers and their unique roles in loading metal phosphides and participating in catalytic reactions. We will clarify the preparation strategy of MXene, the interaction between metal phosphides and MXene carriers, to explain the stabilization of metal phosphide active sites and the rational adjustment of electronic structure. In addition, we will comprehensively summarize recent research progress of MXene‐based metal phosphide composites, with particular emphasis on advancements in the synergistic effect of heterostructures. Regarding applications, we review the utilization of MXene‐based metal phosphide composites in electrocatalysis, including hydrogen evolution reaction (HER), oxygen evolution reaction (OER), and oxygen reduction reaction (ORR). Finally, some fundamental challenges and prospects for the efficient electrocatalysis of MXene‐based metal phosphide composites are introduced.

Synergize Strong and Reactive Metal-Support Interactions to Construct Sub-2 nm Metal Phosphide Cluster for Enhanced Selective Hydrogenation Activities.

Strong metal-support interactions (SMSI) are crucial for stabilizing sub-2 nm metal sites, e.g. single atom (M1) or cluster (Mn). However, further optimizing sub-2 nm sites to break the activity-stability trade-off due to excessive interactions remains significant challenges. Accordingly, for the first time, we propose synergizing SMSI with reactive metal-support interactions (RMSI). Comprehensive characterization confirms that the SMSI stabilizes the metal and regulates the aggregation of Ni1 into Nin site within sub-2 nm. Meanwhile, RMSI modulates Nin through sufficiently activating P in the support and eventually generates sub-2 nm metal phosphide Ni2P cluster (Ni2Pn). The synergetic metal-support interactions triggered the adaptive coordination and electronic structure optimization of Ni2Pn, leading to the desired substrate adsorption-desorption kinetics. Consequently, the activity of Ni2Pn site greatly enhanced towards the selective hydrogenations of p-chloronitrobenzene and alkynyl alcohol. The formation rates of target products are up to 20.2 and 3.0 times greater than that of Ni1 and Nin site, respectively. This work may open a new direction for metal-support interactions and promote innovation and application of active sites below 2 nm.

Ultrafast Synthesis of Transition Metal Phosphides in Air via Pulsed Laser Shock.

Transition metal phosphide nanoparticles (TMP NPs) represent a promising class of nanomaterials in the field of energy; however, a universal, time-saving, energy-efficient, and scalable synthesis method is currently lacking. Here, a facile synthesis approach is first introduced using a pulsed laser shock (PLS) process mediated by metal-organic frameworks, free of any inert gas protection, enabling the synthesis of diverse TMP NPs. Additionally, through thermodynamic calculations and experimental validation, the phase selection and competition behavior between phosphorus and oxygen have been elucidated, dictated by the redox potential and electronegativity. The resulting composites exhibit a balanced performance and extended durability. When employed as electrocatalysts for overall water splitting, the as-constructed electrolyzer achieves a low cell voltage of 1.54 V at a current density of 10 mA cm-2. This laser method for phosphide synthesis provides clear guidelines and holds potential for the preparation of nanomaterials applicable in catalysis, energy storage, biosensors, and other fields.

Leaf-like Multiphase Metal Phosphides as Bifunctional Oxygen Electrocatalysts toward Rechargeable Zinc-Air Batteries.

Developing a bifunctional oxygen electrocatalyst is crucial to improve the reversibility and cycle life of a rechargeable zinc-air battery (RZAB). Here, transition metal phosphides (TMPs) with a leaf-like hierarchical structure and multiphase composition can be synthesized by the "alloying-dealloying-phosphating" strategy. The as-prepared P-NiCo(1:1) electrode takes advantage of its internal dense nanoholes and synergistic effects induced by NiCoP-containing polyphase to reveal multifunctional catalysis, such as OER and ORR. In combination of these advantages, P-NiCo(1:1) exhibits an extremely low OER overpotential of 220 mV at 10 mA cm-2, a higher half-wave potential of 0.79 V for ORR, and a smaller potential difference (ΔE) of 0.66 V. The liquid RZAB with P-NiCo(1:1) as a cathodic bifunctional catalyst delivers a higher open-circuit voltage (OCV), a larger power density of 175 mW cm-2, and longer cycling life for more than 180 h. Even when applied in solid-state flexible RZABs, the lightweight module could start high-power devices. With theoretical confirmation, the major phase NiCoP of P-NiCo(1:1) is helpful to increase the density of states, regulate the d-band center, and decrease the energy barrier to 2.13 eV, which are significantly superior to those of Co2P and Ni2P. It is believable that the synthetic strategy and activity-promoting mechanism acquired from this research can offer a guide to designing a promising rechargeable zinc-air battery system.

Recent progress in solar-driven CO2 reduction to multicarbon products.

Currently, most catalysts used for photoconverting carbon dioxide (CO2) typically produce C1 products. Achieving multicarbon (C2+) products, which are highly desirable due to their greater energy density and economic potential, still remains a significant challenge. This difficulty is primarily due to the kinetic hurdles associated with the C-C coupling step in the process. Given this, devising diverse strategies to accelerate C-C coupling for generating multicarbon products is requisite. Herein, we first give a classification of catalysts involved in the photoconversion of CO2 to C2+ fuels. We summarize metallic oxides, metallic sulfides, MXenes, and metal-organic frameworks as catalysts for CO2 photoreduction to C2+ products, attributing their efficacy to the inherent dual active sites facilitating C-C coupling. In addition, we survey covalent organic frameworks, carbon nitrides, metal phosphides, and graphene as cocatalysts for CO2 photoreduction to C2+ products, owing to the incorporated dual active sites that induce C-C coupling. In the end, we provide a brief conclusion and an outlook on designing new photocatalysts, understanding the catalytic mechanisms, and considering the practical application requirements for photoconverting CO2 into multicarbon products.

Arrayed metal phosphide heterostructure by Fe doping for robust overall water splitting

Transition metal phosphides (TMPs) show promise in water electrolysis due to their electronic structures, which activate hydrogen/oxygen reaction intermediates. However, TMPs face limitations in catalytic efficiency due to insufficient active sites, poor conductivity, and multiple intermediate steps in water electrolysis. Here, we synthesize a highly efficient bifunctional self-supported electrocatalyst, which consists of an N-doped carbon shell anchored on Fe-doped CoP/Co2P arrays on nickel foam (NC@Fe-CoxP/NF) using hydrothermal and phosphorization techniques. Experimental and theoretical results indicate that the modified morphology, with increased active site density and a tunable electronic structure induced by Fe doping in the CoP/Co2P heterostructure, leads to superior water electrolysis performance. The resulting NC@Fe0.1-CoP/Co2P/NF catalyst exhibits overpotentials of 122 mV for the hydrogen evolution reaction (HER) and 270 mV for the oxygen evolution reaction (OER) at 100 mA cm−2. Furthermore, using NC@Fe0.1-CoP/Co2P/NF as both the cathode and anode in an alkaline electrolyzer enables the cell system to achieve 100 mA cm−2 at a voltage of 1.70 V, while maintaining long-term catalytic durability. This work may pave the way for designing self-supported, highly efficient electrocatalysts for practical water electrolysis applications.

Preparation of hollow CoFe Prussian blue analogues and their derived CoP-FeP nanoboxes as efficient electrocatalysts as oxygen evolution reactions

Reasonably designing and constructing transition metal based compounds with controllable composition and structure is a promising option for obtaining economically efficient oxygen evolution reaction (OER) electrocatalysts. This paper presents a one-pot self-templated epitaxial growth, phase transition and self-dissolution strategy for constructing hollow nanoboxes/solid nanocubes of CoFe bimetallic Prussian blue analogues (PBAs). The CoFe mixed phosphide with a porous hollow nanoboxes structure obtained after subsequent phosphating heat treatment exhibite enhanced OER electrocatalytic activity in alkaline media, exhibiting a low overpotential of 230 mV and a Tafel slope of 35.5 dec−1 at 10 mA cm−2, as well as excellent stability for 48 h. The excellent OER activity of CoP-FeP nanoboxes (CoP-FeP NBs) can be attributed to the combination effect between their composition and structure. Structurally, the exquisite porous hollow nanoboxes structure greatly expands the surface area, reduces ion diffusion pathways, and reduces charge transfer resistance. Compositionally, the inner transition metal phosphide exhibits good conductivity and undergoes surface reconstruction during OER, forming high valence Co(Fe)OOH active substances in situ. The strong interface coupling effect of CoOOH/FeOOH optimizes the electronic structure. This work presents a facile and efficient strategy for the construction of PBAs hollow structural materials and the exploitation of low-cost and efficient electrocatalysts.

Reasonable design of PBA-derived interfacial modified ternary compounds and hollow structure materials in high-performance asymmetric supercapacitors

Prussian blue analogues (PBA), common metal-organic frameworks (MOFs), are typically binary metal compounds. In this study, chromium was incorporated during the preparation of nickel‑cobalt PBA, resulting in the adjustment of the micro-morphology of PBA and the synthesis of small-sized PBA (sPBA) electrode materials with diameters ranging from 20 to 30 nm. These materials underwent various interfacial modifications to yield ternary metal phosphide (sPBA-P) and hollow nanostructures (sPBA-C). Additionally, by integrating graphene oxide (GO) as the growth substrate, successful preparation of GO@sPBA-P and GO@sPBA-C electrode materials was achieved. Significantly, these materials showcase outstanding electrochemical properties and interesting interfacial reactions when employed as cathode and anode components. Through a comprehensive series of characterization analyses, the electrochemical properties and reaction mechanisms of these materials were thoroughly investigated. Ultimately, an asymmetric supercapacitor (ASC) was assembled using the synthesized GO@sPBA-P and GO@sPBA-C to explore the material's potential in energy materials applications.

Excellent thermoelectric performance in alkali metal phosphides M3P (M = Na and K) with phonon-glass electron-crystal like behaviour.

Identifying ideal thermoelectric materials presents a formidable challenge due to the intricate coupling relationship between thermal conductivity and power factor. Here, based on first-principles calculations, along with self-consistent phonon theory and the Boltzmann transport equation, we theoretically investigate the thermoelectric properties of alkali metal phosphides M3P (M = Na and K). The evident 'avoided crossing' phenomenon indicates the phonon glass behavior of M3P (M = Na and K). Due to the strong lattice anharmonicity induced by alkali metal elements, accounting for quartic anharmonic corrections, the lattice thermal conductivities of Na3P and K3P at room temperature are merely 0.25 and 0.12 W m-1 K-1, respectively. Furthermore, the high degeneracy and 'pudding-mold-type' band structure lead to high p-type PF in M3P (M = Na and K). At 300 K, the p-type power factors (PF) of Na3P and K3P can reach 3.90 and 0.80 mW mK-2, respectively. The combination of ultralow κL and high PF leads to excellent thermoelectric figure of merit (ZT) values of 1.70 (3.38) and 1.18 (2.13) for p-type Na3P and K3P under optimal doping concentration at 300 K (500 K), respectively, surpassing traditional thermoelectric materials. These findings demonstrate that M3P (M = Na and K) exhibits behavior similar to phonon-glass electron crystals, thereby indicating a direction for the search for high-performance thermoelectric materials.

Plasma-Constructed Co2P-Ni2P Heterointerface for Electro‑Upcycling of Polyethylene Terephthalate Plastic to Co-Produce Hydrogen and Formate.

Integrating electrochemical upcycling of polyethylene-terephthalate (PET) and the hydrogen evolution reaction (HER) is an energy-saving approach for electrolytic hydrogen (H2) production, along with the coproduction of formate. Herein, a novel and rapid strategy of cold plasma phosphating is employed to synthesize Co2P-Ni2P heterointerface decorated on carbon cloth (Co2P-Ni2P/CC) to catalyze H2 generation and reform PET. Notably, the obtained Co2P-Ni2P/CC exhibits eminent ethylene glycol oxidation reaction (EGOR) and HER activities, effectuating low potentials of merely 1.300 and -0.112V versus RHE at 100mAcm-2 for the EGOR and HER, respectively, also attaining an ultralow cell bias of 1.300V at 10mAcm-2 for EG oxidation assisted-water splitting. DFT and characterization results validate that the as-formed built-in electric fields in the Co2P-Ni2P heterointerface can accelerate electrons transfer and deepen structural self-reconstruction, thereby boosting effectively water dissociation and ethylene glycol (EG) dehydrogenation. Impressively, coupling HER with PET-derived EG-to-formate in a flow-cell electrolyzer assembled with Co2P-Ni2P/CC pair achieves an intriguing formate Faradaic efficiency of 90.6% and an extraordinary stable operation of over 70h at 100mAcm-2. The work exemplifies a facile and effective strategy for synthesizing metal phosphides electrocatalysts with extraordinary performance toward H2 generation of water splitting and recycling of PET.

Integration of vanadium diphosphide with 2D cobalt phosphide architected as an extensible redox active positrode for alkaline supercapacitor

Metal phosphides in the form of rationally constructed two-dimensional (2D) nanosheets hold significant promise as versatile materials for energy storage applications. This study introduces a novel hybrid supercapacitor electrode, composed of a binder-free vanadium phosphide integrated cobalt phosphide (VP@CP) on a nickel foam substrate. The fabrication process involves the hydrothermal growth of Co2(OH)2BDC (BDC- 1,4-benzenedicarboxylate) nanosheets on a Ni-foam substrate (CMF-Ni), followed by the deposition of VO2 on CMF nanosheets (VO@CMF-Ni) using chronoamperometry and phosphorization of the VO@CMF-Ni to yield VP@CP-Ni nanosheets. Particularly, the density functional theory (DFT) results show that the VP2 integrated Co2P sample provides metallic behavior and low adsorption energy of OH− ions, resulting in improved electrochemical redox process. These bimetallic phosphides exhibit outstanding properties, including enhanced pathways for rapid ion transport and storage, increased electronic conductivity, and expanded electroactive regions facilitating the faradaic charge storage process. Due to the presence of vanadium and cobalt coupled sites, the fabricated VP@CP-Ni electrode was able to attain a maximum areal capacity (CAR) of 971 mA h cm−2 at 6 mA cm−2. Additionally, the fabricated hybrid device (HDC) exhibits an impressive specific energy (SE) of 30.9 Wh kg−1 at a specific power (SP) of 1344 W kg−1, and excellent cyclic durability. These remarkable results stimulate the exploration of such possible 2D VP@CP-Ni nanosheets with promising charge storage electrode capabilities to develop a future era of energy storage devices.

Bimetallic MoFe phosphide catalysts for the hydrogen evolution reaction

In this work, highly efficient and stable (bi)metallic phosphides were prepared by a facile, flexible, and controllable sol-gel method followed by sintering. This novel approach allowed to avoid complicated and dangerous phosporization using, e.g. red phosphorus. The doping of the MoP catalysts with Fe was used to further boost their catalytic performance. Monometallic MoP and Mo3P, as well as bimetallic MoFeP were tested in both acidic and alkaline environments and showed remarkable results. The incorporation of Fe enabled the creation of a scalable and cost-effective catalyst for the hydrogen evolution reaction due to the synergy between Fe and Mo in the bimetallic phosphides. Using MoFeP for catalysing the hydrogen evolution reaction, overpotentials of only -132 mV (in an acidic medium) and -142 mV (in an alkaline medium) were needed to reach current density of -10 mA.cm−2, indicating the possibility of use this catalyst in a large pH range. Its high catalytic activity was maintained even at current density of -100 mA.cm−2 as documented by overpotentials of -202 mV and -246 mV in acid and alkaline environment, respectively. This, along with excellent stability and durability confirms its promising potential for incorporation into industrially relevant applications. The experimental data were confirmed by computational (DFT) results, showcasing that incorporation of Fe caused an increase in the number of active sites with Gibbs adsorption energy close to zero.

Oxygen-doped FeP on Ti Foil with Ti3O Interlayer for Efficient and Durable Electrolysis.

Thedevelopment of electrocatalysts withlow cost, high efficiency, and long-term durability is crucial for advancing green hydrogen production.Transition metal phosphides (TMPs) have been proved to be efficient electrocatalyst, while the improvement in the performance and durability of the TMPs remains a big challenge.Employing atmospheric pressure chemical vapor deposition (APCVD) and phosphorization, FeP/Ti electrodes are fabricated featuring controllable oxygen ingredients (O-FeP/Ti). This manipulation of oxygen content fine-tunes the electronic structure of the catalyst, resulting in improved surface reaction kinetics and catalytic activity.The optimized O-FeP-400/Ti exhibits outstanding HER activity with overpotentials of 142 and 159 mV at -10 mA cm-2in 0.5 M H2SO4and 1 M KOH, respectively.Notably, the obtained O-FeP/Ti cathode also displays remarkable durability of up to 200 h in acidic electrolyte withsurface topographyremaining intact.For the first time, the low-valence titanium oxide (Ti3O) interlayeris identified in the composite electrode and ascribed for the superior connection between Ti substrate and the surface O-FeP catalyst, as supported by experimental resultsand density functional theory (DFT) analysis.This work has expanded the potential applicationsof transition metal phosphides (TMPs) as a cost-effective, highly efficient and durable catalyst for water splitting.

Computational insights into the deoxygenation reaction of biomass-derived phenolic compounds over Ni2P (001) catalysts

This research sets the scene for understanding the interaction of phenolic molecules (i.e., phenol, o-cresol, m-cresol, and p-cresol) with Ni2P catalyst surface and how their hydrodeoxygenation reaction progresses over the surface. The hydrodeoxygenation process is responsible for removing the oxygen content from the pyrolysis oil compounds, particularly through direct deoxygenation route. Ni2P, which is one of the most common transition metal phosphides, serves as a candidate surface of this study. Two main investigations were carried out including the optimization of (1) adsorption configuration of the phenolic compounds and the (2) net charge distribution between the surface and the adsorbate. According to the adsorption energy studies, the horizontal configuration of the o-cresol molecule on the Ni2P(001) hollow site presented the most optimized and stable configuration with the least negative adsorption energy (−0.26 eV), resulting in the most negative net charge density at −0.286 |e|, as determined by the Bader charge analysis. Upon adsorption on Ni2P(001) surface, o-cresol undergoes significant charge redistribution, where the oxygen atom (-OH group) exhibits a net charge of −1.3443 |e|, indicating electron transfer to the surface. The catalytic pathway proceeded with deoxygenation followed by ring hydrogenation to produce toluene (C7H8), such that C–O bond dissociation has a reaction energy of −0.715 eV, while C–H bond formation step had a reaction energy of 0.011 eV.

Boosting hydrogen adsorption via manipulating interfacial electronic structure of NiPx for enhanced alkaline seawater electrolysis

The development of transition metal phosphides (TMPs) electrocatalysts with appropriate binding strength towards intermediates and resistant to chlorine in alkaline seawater electrocatalysis remains a formidable challenge. Herein, an approach for manipulating electron redistribution in Ni2P/Ni5P4 treated by Co cationic doping engineering (denoted as Act-Co-NiPx) is proposed, exhibiting excellent catalytic activities and stability toward HER in alkaline seawater solution. First-principles calculations demonstrate that the Co doping can effectively adjust the electron redistribution of Ni2P/Ni5P4, resulting in a reduction in the hydrogen adsorption free energy for HER and an acceleration in the interfacial charge transfer. Furthermore, the enhanced Cl- adsorption energy avoids the toxicity of Cl- to the active sites in alkaline seawater splitting. Consequently, the resulting Act-Co-NiPx catalyst demonstrates remarkable HER performance with low overpotentials of 77 and 97 mV at a current density of 10 mA cm−2 in both 1.0 M KOH and 1.0 M KOH+Seasalt electrolytes. Furthermore, the seasalt electrolyzer assembled from Act-Co-NiPx achieves the low cell voltage of 1.63 V at 10 mA cm−2. This work demonstrates a feasible method for designing cost-effective and stable catalysts with excellent selectivity via regulating the electronic structure of TMPs for seawater electrolysis.

Performance of cobalt doped two dimensional black phosphorus (Co-2D BP) for bifunctional hydrolysis in alkaline solution

The present study contributes to the exploration of transition metal phosphides with specific composition and structure to enhance electrocatalytic ability. Cobalt doped two dimensional black phosphorus (Co-2D BP) with layered structure exhibits excellent electrocatalytic activity for hydrogen evolution reaction (HER) in alkaline solutions, and demonstrates an overpotential of 86.42 mv at a current density of 10 mA cm−2, requiring only 140.29 mv, 198 mv, and 238.89 mv to reach 20, 50, and 100 mA cm−2 respectively. The catalytic performance was stable even after 10 h using in alkaline electrolytes, demonstrating good chemical stability. Co-2D BP can also improve the catalytic performance for oxygen evolution reaction (OER). This study provides a novel strategy for the design of multifunctional 2D BP-based catalytic materials for hydrolysis.