Enhancing Ni/Co Activity by Neighboring Pt Atoms in NiCoP/MXene Electrocatalyst for Alkaline Hydrogen Evolution.

Density functional theory (DFT) calculations demonstrate neighboring Pt atoms can enhance the metal activity of NiCoP for hydrogen evolution reaction (HER). However, it remains a great challenge to link Pt and NiCoP. Herein, we introduced curvature of bowl-like structure to construct Pt/NiCoP interface by adding a minimal 1 ‰-molar-ratio Pt. The as-prepared sample only requires an overpotential of 26.5 and 181.6 mV to accordingly achieve the current density of 10 and 500 mA cm-2 in 1 M KOH. The water dissociation energy barrier (Ea) has a ~43 % decrease compared with NiCoP counterpart. It also shows an ultrahigh stability with a small degradation rate of 10.6 µV h-1 at harsh conditions (500 mA cm-2 and 50 °C) after 3000 hrs. X-ray photoelectron spectroscopy (XPS), soft X-ray absorption spectroscopy (sXAS), and X-ray absorption fine structure (XAFS) verify the interface electron transfer lowers the valence state of Co/Ni and activates them. DFT calculations also confirm the catalytic transition step of NiCoP can change from Heyrovsky (2.71 eV) to Tafel step (0.51 eV) in the neighborhood of Pt, in accord with the result of the improved Hads at the interface disclosed by in situ electrochemical impedance spectroscopy (EIS) and scanning electrochemical microscopy (SECM) tests.

Tailored Heterojunction Active Sites for Oxygen Electrocatalyst Promotion in Zinc-Air Batteries.

Rechargeable zinc-air batteries (ZABs) are promising energy storage systems due to their low-cost and safety. However, the working principle of ZABs is based on oxygen evolution reaction (OER) and oxygen reduction reaction (ORR), which display sluggish kinetic and low stability. Herein, this work proposes a novel method to design a heterogeneous CoP/CoO electrocatalyst on mesopore nanobox carbon/carbon nanotube (CoP/CoO@MNC-CNT) that enriched active sites and synergistic effect. Moreover, the well-defined heterointerfaces could lower the energy barrier for intermediate species adsorption and promote OER and ORR electrochemical performances. The CoP/CoO@MNC-CNT electrocatalyst presents a high half-wave potential of 0.838 V for ORR and a small overpotential of 270 mV for OER. The ZABs-based CoP/CoO@MNC-CNT air-cathode shows an open-circuit voltage of 1.409 V, the long-term cycle life of 500 h with a small voltage difference change of 7.7%. Additionally, the flexible ZABs exhibit highly mechanical stability, demonstrating their application potential in wearable electronic devices.

Engineering Interfacial Built-in Electric Field in Polymetallic Phosphide Heterostructures for Superior Supercapacitors and Electrocatalytic Hydrogen Evolution.

Herein, a patterned rod-like CoP@NiCoP core-shell heterostructure is designed to consist of CoP nanowires cross-linked with NiCoP nanosheets in tight strings. The interfacial interaction within the heterojunction between the two components generates a built-in electric field that adjusts the interfacial charge state and create more active sites, accelerating the charge transfer and improving supercapacitor and electrocatalytic performance. The unique core-shell structure suppresses the volume expansion during charging and discharging, achieving excellent stability. As a result, CoP@NiCoP exhibits a high specific capacitance of 2.9 F cm-2 at a current density of 3 mA cm-2 and a high ion diffusion rate (Dion is 2.95 × 10-14  cm2  s-1 ) during charging/discharging. The assembled asymmetric supercapacitor CoP@NiCoP//AC exhibits a high energy density of 42.2 Wh kg-1 at a power density of 126.5 W kg-1 and excellent stability with a capacitance retention rate of 83.8% after 10 000 cycles. Furthermore, the modulated effect induced by the interfacial interaction also endows the self-supported electrode with excellent electrocatalytic HER performance with an overpotential of 71 mV at 10 mA cm-2 . This research may provide a new perspective on the generation of built-in electric field through the rational design of heterogeneous structures for improving the electrochemical and electrocatalytical performance.

Regulating Electrochemical Kinetics of CoP by Incorporating Oxygen on Surface for High-Performance Li-S Batteries.

Lithium-sulfur (Li-S) batteries are widely studied because of their high theoretical specific capacity and environmental friendliness. However, the further development of Li-S batteries is hindered by the shuttle effect of lithium polysulfides (LiPSs) and the sluggish redox kinetics. Since the adsorption and catalytic conversion of LiPSs mainly occur on the surface of the electrocatalyst, regulating the surface structure of electrocatalysts is an advisable strategy to solve the obstacles in Li-S batteries. Herein, CoP nanoparticles with high oxygen content on surface embedded in hollow carbon nanocages (C/O-CoP) is employed to functionalize the separators and the effect of the surface oxygen content of CoP on the electrochemical performance is systematically explored. Increasing the oxygen content on CoP surface can enhance the chemical adsorption to lithium polysulfides and accelerate the redox conversions kinetics of polysulfides. The cell with C/O-CoP modified separator can achieve the capacity of 1033 mAh g-1 and maintain 749 mAh g-1 after 200 cycles at 2 C. Moreover, DFT calculations are used to reveal the enhancement mechanism of oxygen content on surface of CoP in Li-S chemistry. This work offers a new insight into developing high-performance Li-S batteries from the perspective of surface engineering.

Construction of Co2 P-Ni3 S2 /NF Heterogeneous Structural Hollow Nanowires as Bifunctional Electrocatalysts for Efficient Overall Water Splitting.

Designing efficient and stable transition metal-based catalysts for electrocatalytic water splitting is vital for the development of hydrogen production. Herein, a facile synthetic strategy is developed to fabricate transition metal-based heterogeneous structural Co2 P-Ni3 S2 hollow nanowires supported on nickel foam (Co2 P-Ni3 S2 /NF). Owing to the multiple active sites provided by transition metal compounds, large surface area of the unique hollow nanowire morphology, and the synergistic effect of Co2 P-Ni3 S2 heterostructure interfaces, Co2 P-Ni3 S2 /NF requires ultralow overpotentials of 110, 164 mV for HER and 331.7, 358.3 mV for OER at large current densities of 100, 500 mA cm-2 in alkaline medium, respectively. Importantly, the two-electrode electrolyzer assembled by Co2 P-Ni3 S2 /NF displays a cell voltage of 1.54 V at 10 mA cm-2 and operates stably over 24 h at 100 mA cm-2 , which performs better than reported transition metal-based bifunctional electrocatalysts. This work presents a successful fabrication of transition metal-based bifunctional HER/OER electrocatalysts at large-current density and brings new inspiration for developing applicable energy conversion materials.

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@RuSA -CoP). The obtained NC@RuSA -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 H2 SO4 , 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.

Synergistic Integration of Amorphous Cobalt Phosphide with a Conductive Channel for Highly Efficient Electrocatalytic Nitrate Reduction to Ammonia.

Electrocatalytic nitrate reduction to ammonia (NO3 RR) is regarded as a viable alternative reaction to "Haber Bosch" process. Nevertheless, it remains a major challenge to explore economical and efficient electrocatalysts that deliver high NH3 yield rates and Faraday efficiencies (FE). Here, it demonstrates the fabrication of a 3D core-shell structured Co-carbon nanofibers (CNF)/ZIF-CoP for NO3 RR application. Benefitting from the distinct electron transport property of Co-CNF and desirable mass transfer ability from amorphous CoP framework, the as-prepared Co-CNF/ZIF-CoP exhibits large NH3 FE (96.8 ± 3.4% at -0.1 V vs reversible hydrogen electrode (RHE)) and high yield rate (38.44 ± 0.65 mg cm-2 h-1 at -0.6 V vs RHE), which are better than Co-CNF/ZIF-crystal CoP. Density functional theory (DFT) calculations further reveal that amorphous CoP presents a lower energy barrier in the rate determination step of the protonation of *NO to produce *NOH intermediates compared with crystal CoP, resulting in a superior NO3 RR performance. Eventually, an aqueous galvanic Zn-NO3 - battery is assembled by using Co-CNF/ZIF-CoP as cathode material to achieve efficient production of NH3 whilst simultaneously supplying electrical power. This work offers a reliable strategy to construct amorphous metal phosphide framework on conducting CNF as efficient electrocatalyst and enriches its promising application for NO3 RR.

Green fabrication of ultrafine N-MoxC/CoP hybrids for boosting electrocatalytic water reduction.

Developing non-noble-metal electrocatalysts for hydrogen evolution reactions with high activity and stability is the key issue in green hydrogen generation based on electrolytic water splitting. It has been recognized that the stacking of large CoP particles limits the intrinsic activity of as-synthesized CoP catalyst for hydrogen evolution reaction. In the present study, N-MoxC/CoP-0.5 with excellent electrocatalytic activity for hydrogen evolution reaction was prepared using N-MoxC as decoration. A reasonable overpotential of 106 mV (at 10 mA cm-2) and a Tafel slope of 59 mV dec-1in 1.0 M KOH solution was achieved with N-MoxC/CoP-0.5 electrocatalyst, which exhibits superior activity even after working for 37 h. Uniformly distributed ultrafine nanoclusters of the N-MoxC/CoP-0.5 hybrids could provide sufficient interfaces for enhanced charge transfer. The effective capacity of the hydrogen evolution reaction could be preserved in the complex, and the enlarged electrocatalytic surface area could be expected to offer more active sites for the reaction.

Oxygen-doped NiCoP derived from Ni-MOFs for high performance asymmetric supercapacitor.

Oxygen doping strategy is one of the most effective methods to improve the electrochemical properties of nickel-cobalt phosphide (NiCoP)-based capacitors by adjusting its inherent electronic structure. In this paper, O-doped NiCoP microspheres derived from porous nanostructured nickel metal-organic frameworks (Ni-MOFs) were constructed through solvothermal method followed by phosphorization treatment. The O-doping concentration has a siginificant influence on the rate performance and cycle stability. The optimized O-doped NiCoP electrode material shows a specific capacitance of 632.4 F-g-1at 1 A-g-1and a high retention rate of 56.9% at 20 A g-1. The corresponding NiCoP-based asymmetric supercapacitor exhibits a high energy density of 30.1 Wh kg-1when the power density is 800.9 W kg-1, and can still maintain 82.1% of the initial capacity after 10 000 cycles at 5 A g-1.

Chemiluminescence-assisted study on a peracetic acid-based advanced oxidation process activated with cobalt phosphide.

In recent years, the elimination of organic pollutants using advanced oxidation processes (AOPs) based on peracetic acid (PAA) has drawn increasing attention due to the high oxidative potential and low byproducts. However, to explore more efficient and stable PAA-based AOPs, there is still great room for study on the activation of PAA and degradation mechanism in the reaction process. In this study, a new PAA-based AOP activated by metal-organic framework-derived cobalt phosphide (CoP) and accompanied by chemiluminescence (CL) behaviour was explored. The CoP/PAA system could efficiently degrade 99.98% of RhB (20 mg L-1 ) within 5 min at pH 7 compared with the conventional Co3 O4 /PAA system (merely 17.29%), and the degradation process was matched well with the pseudo-first-order kinetic, and the kinetic constants was ~23.7 times higher than that of Co3 O4 (0.546 min-1 for CoP vs. 0.023 min-1 for Co3 O4 ). In the CoP/PAA/RhB process, the CL intensity was related to the concentration of 1 O2 , O2 •- and acetyl peroxyl radicals [CH3 C(O)OO• and CH3 C(O)O•]. Therefore, CL analysis, combined with quenching tests and electron paramagnetic resonance analysis, was used to study the degradation mechanism in detail, and 1 O2 was confirmed as the dominant contributor for the dye degradation.

Facile Electrochemical Synthesis of Bifunctional Needle-like Co-P Nanoarray for Efficient Overall Water Splitting.

The development of low-cost and high-performance bifunctional electrocatalysts for overall water splitting is still challenging. Herein, we employed a facile electrodeposition method to prepare bifunctional cobalt phosphide for overall water splitting. The needle-like cobalt phosphide (Co-P-1) nanoarray is uniformly distributed on nickel foam. Co-P-1 exhibits excellent electrocatalytic activity for hydrogen evolution reaction (HER, 85 mV at 10 mA/cm2, 60 mV/dec) and oxygen evolution reaction (OER, 294 mV at 50 mA/cm2, 60 mV/dec). The cell-voltage of 1.60 V is found to achieve the current density of 10 mA/cm2 for overall water splitting in the two-electrode system, comparable to that of previously reported Pt/C/NF||RuO2/NF. The excellent electrocatalytic performance can be attributed to the needle-like structure with more active sites, accelerated charge transfer and evolved bubbles' release. This work can provide new approach to the development of a bifunctional electrocatalyst for overall water splitting.

In Situ Growth of CoP Nanosheet Arrays on Carbon Cloth as Binder-Free Electrode for High-Performance Flexible Lithium-Ion Batteries.

Cobalt phosphide (CoP) is considered as one of the most promising candidates for anode in lithium-ion batteries (LIBs) owing to its low-cost, abundant availability, and high theoretical capacity. However, problems of low conductivity, heavy aggregation, and volume change of CoP, hinder its practical applicability. In this study, a binder-free electrode is successfully prepared by growing CoP nanosheets arrays directly on a carbon cloth (CC) via a facile one-step electrodeposition followed by an in situ phosphorization strategy. The CoP@CC anode exhibits good interfacial bonding between the CoP and CC, which can improve the conductivity of the integrated electrode. More importantly, the 3D network structure composed of CoP nanosheets and CC provides sufficient space to alleviate the volume expansion of CoP and shorten the electron/ion transport paths. Moreover, the support of CC effectively prevents the agglomeration of CoP. Based on these advantages, when CoP@CC is paired with the NCM523 cathode, the full cell delivers a high discharge capacity 919.6 mAh g-1 (2.1 mAh cm-2 ) after 200 cycles at 0.5 A g-1 . The feasibility and safety of producing pouch cells are also explored, which show good flexibility and safety despite rigorous strikes (mechanical damage and severe deformations), implying a great potential for practical applications.

Ion/Electron Redistributed 3D Flexible Host for Achieving Highly Reversible Li Metal Batteries.

3D carbon frameworks are promising hosts to achieve highly reversible lithium (Li) metal anodes, whereas insufficient effects are attributed to their single electron conductivity causing local aggregating of electron/Li+ and uncontrollable Li dendrites. Herein, an ion/electron redistributed 3D flexible host is designed by lithiophilic carbon fiber cloth (CFC) modified with metal-organic framework (MOF)-derived porous carbon sheath with embedded CoP nanoparticles (CoP-C@CFC). Theory calculations demonstrate the strong binding energy and plenty of charge transfer from the reaction between CoP and Li atom are presented, which is beneficial to in situ construct a Li3 P@Co ion/electron conductive interface on every single CoP-C@CFC. Thanks to the high ionic conductive Li3 P and electron-conductive Co nanoparticles, the rapid dispersion of Li+ and obviously reduced local current density can be achieved simultaneously. Furthermore, in situ optical microscopy observations display obvious depression for volume expansion and Li dendrites. As expected, a miraculous average Coulombic efficiency (CE) of 99.96% over 1100 cycles at 3 mA cm-2 and a low overpotential of 11.5 mV with prolonged cycling of over 3200 h at 20% depth of discharge are successfully obtained. Consequently, the CoP-C@CFC-Li||LiFePO4 full cells maintain a capacity retention of 95.8% with high CE of 99.96% over 500 cycles at 2 C and excellent rate capability.

Effect of heat treatment on the morphology of carbon fibers doped with Co2p nanoparticles.

ABSTRACT: Carbon fibers (CFs) decorated by Co2P nanoparticles and carbon nanotubes were prepared via needle-less electrospinning technique. Formation of catalytically active Co2P nanoparticles and growth of carbon nanotubes were monitored in open and closed sintering environment at different sintering exposure times. Higher porosity, important in the catalytic reaction for easier penetration of electrolyte into the CFs, was achieved by mixing two immiscible polymers with natrium dodecyl sulfate and subsequent heat treatment process. Structure and morphology of the prepared modified carbon fibers were characterized by XRD, SEM and TEM. The time of heat exposure at the sintering temperature of 1200 °C and closure of the sintering space showed distinct effect on the growth and shape of carbon nanotubes. SEM and Raman spectroscopy revealed that closure of the system led to the formation of carbon nanotubes with smaller diameters and less structural disorder. Comparing of as-prepared CFs revealed that CFs with Co2P sintered in the closed system exhibited the best electrocatalytic activity for hydrogen evolution reaction due to lower overpotential and smaller Tafel slope in acidic solution.

Urchin-Type Architecture Assembled by Cobalt Phosphide Nanorods Encapsulated in Graphene Framework as an Advanced Anode for Alkali Metal Ion Batteries.

Urchin-type cobalt phosphide microparticles assembled by nanorod were encapsulated in a graphene framework membrane (CoP@GF), and used as a binder-free electrode for alkali metal ion batteries. Electrochemical measurements indicate that this membrane exhibits enhanced reversible lithium, sodium, and potassium storage capabilities. Moreover, the energy storage properties of CoP@GF electrodes in alkali metal ion batteries display an order of Li>Na>K. DFT calculations on adsorption energy of CoP surfaces for Li, Na, and K indicated that CoP surfaces were more favorable to transfer electrons to Li atoms than Na and K, and the surface reactivity can be ordered as Li-CoP>Na-CoP>K-CoP; thus, CoP@GF exhibits better storage capacity for lithium. This work provides experimental and theoretical basis for understanding the electrochemical performance of cobalt phosphide-based membranes for alkali metal ion batteries.

Nano-dendrite structured cobalt phosphide based hybrid supercapacitor with high energy storage and cycling stability.

The supercapacitors possessing high energy storage and long serving period have strategic significance to solve the energy crisis issues. Herein, fluffy nano-dendrite structured cobalt phosphide (CoP) is grown on carbon cloth through simple hydrothermal and electrodeposition treatments (CoP/C-HE). Benefit from its excellent electrical conductivity and special structure, CoP/C-HE manifests a high specific capacity of 461.4 C g-1at 1 A g-1. Meanwhile, the capacity retention remains 92.8% over 10 000 cycles at 5 A g-1, proving the superior cycling stability. The phase conversion of Co2P during the activation process also contributes to the improved performance. The assembled two-electrode asymmetric supercapacitor demonstrates excellent performance in terms of energy density (42.4 W h kg-1at a power density of 800.0 W kg-1) and cycling stability (86.3% retention over 5000 cycles at 5 A g-1), which is superior to many reported cobalt-based supercapacitors. Our work promotes the potential of transition metal phosphides for the applications in supercapacitors.

Nanostructure Engineering of Metal-Organic Derived Frameworks: Cobalt Phosphide Embedded in Carbon Nanotubes as an Efficient ORR Catalyst.

Heteroatom doping is considered an efficient strategy when tuning the electronic and structural modulation of catalysts to achieve improved performance towards renewable energy applications. Herein, we synthesized a series of carbon-based hierarchical nanostructures through the controlled pyrolysis of Co-MOF (metal organic framework) precursors followed by in situ phosphidation. Two kinds of catalysts were prepared: metal nanoparticles embedded in carbon nanotubes, and metal nanoparticles dispersed on the carbon surface. The results proved that the metal nanoparticles embedded in carbon nanotubes exhibit enhanced ORR electrocatalytic performance, owed to the enriched catalytic sites and the mass transfer facilitating channels provided by the hierarchical porous structure of the carbon nanotubes. Furthermore, the phosphidation of the metal nanoparticles embedded in carbon nanotubes (P-Co-CNTs) increases the surface area and porosity, resulting in faster electron transfer, greater conductivity, and lower charge transfer resistance towards ORR pathways. The P-Co-CNT catalyst shows a half-wave potential of 0.887 V, a Tafel slope of 67 mV dec-1, and robust stability, which are comparatively better than the precious metal catalyst (Pt/C). Conclusively, this study delivers a novel path for designing multiple crystal phases with improved catalytic performance for energy devices.

Fabrication of Hollow CoP/TiOx Heterostructures for Enhanced Oxygen Evolution Reaction.

Transition-metal phosphides have flourished as promising candidates for oxygen evolution reaction (OER) electrocatalysts. Herein, it is demonstrated that the electrocatalytic OER performance of CoP can be greatly improved by constructing a hybrid CoP/TiOx heterostructure. The CoP/TiOx heterostructure is fabricated using metal-organic framework nanocrystals as templates, which leads to unique hollow structures and uniformly distributed CoP nanoparticles on TiOx . The strong interactions between CoP and TiOx in the CoP/TiOx heterostructure and the conductive nature of TiOx with Ti3+ sites endow the CoP-TiOx hybrid material with high OER activity comparable to the state-of-the-art IrO2 or RuO2 OER electrocatalysts. In combination with theoretical calculations, this work reveals that the formation of CoP/TiOx heterostructure can generate a pathway for facile electron transport and optimize the water adsorption energy, thus promoting the OER electrocatalysis.

An Efficient Cobalt Phosphide Electrocatalyst Derived from Cobalt Phosphonate Complex for All-pH Hydrogen Evolution Reaction and Overall Water Splitting in Alkaline Solution.

The development of low-cost and highly efficient electrocatalysts via an eco-friendly synthetic method is of great significance for future renewable energy storage and conversion systems. Herein, cobalt phosphides confined in porous P-doped carbon materials (Co-P@PC) are fabricated by calcinating the cobalt-phosphonate complex formed between 1-hydroxyethylidenediphosphonic acid and Co(NO3 )2 in alkaline solution. The P-containing ligand in the complex acts as the carbon source as well as in situ phosphorizing agent for the formation of cobalt phosphides and doping P element into carbon material upon calcination. The Co-P@PC exhibits high activity for all-pH hydrogen evolution reaction (overpotentials of 72, 85, and 76 mV in acidic, neutral, and alkaline solutions at the current density of 10 mA cm-2 ) and oxygen evolution reaction in alkaline solution (an overpotential of 280 mV at the current density of 10 mA cm-2 ). The alkaline electrolyzer assembled from the Co-P@PC electrodes delivers the current density of 10 mA cm-2 at the voltage of 1.60 V with a durability of 60 h. The excellent activity and long-term stability of the Co-P@PC derives from the synergistic effect between the active cobalt phosphides and the porous P-doped carbon matrix.

3D Architectures of Cox P Using Silk Fibroin Scaffolds: An Active and Stable Electrocatalyst for Hydrogen Generation in Acidic and Alkaline Media.

Developing nonprecious, highly active, and stable catalysts is essential for efficient electrocatalytic hydrogen evolution reaction in water splitting. In this study, the facile synthesis of a 3D flower-like Cox P/carbon architecture is proposed composed of an assembly of nanosheets interconnected by silk fibroin that acts as 3D scaffolds and a carbon source. This unique 3D architecture coupled with a carbon matrix enhances catalytic activity by exposing more active sites and increasing charge transport. The flower-like Cox P/carbon can facilitate a lower overpotential, Tafel slope, charge transfer resistance, and a higher electrochemically active surface than carbon-free and silk-free Cox P. The nanostructured architecture exhibits excellent catalytic performance with low overpotentials of 109 and 121 mV at 10 mA cm-2 and Tafel slopes of 55 and 62 mV dec-1 in acidic and alkaline media, respectively. Furthermore, it minimally degrades the overpotential and current density after long-term stability tests 10 000 cyclic voltammetry cycles and a chronoamperometric test over 40 h, respectively, in acidic media, which confirms the high durability and stability of the flower-like Cox P/carbon.