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JOURNAL OF MATERIALS SCIENCE & TECHNOLOGY · 2021 · IF 8.067

In situ coupled MoO3 with CoP/rGO to construct three-dimensional self-supported catalyst for highly efficient alkaline hydrogen evolution reaction

Zhuoran Hou,Di Yang,Yuntao Xin,Haoyu Huang,Xin Hu,Yuyang Guo,Siduo Wu,Liwen Hu

In order to solve the crisis of energy depletion and protect the beautiful natural environment, the development of efficient, cost-effective and stable hydrogen evolution reaction (HER) electrocatalyst has attracted great attention, but it is still an urgent challenge to fabricate an abundant and low cost electrocatalyst. In this article, a novel HER catalyst with heterogeneous structure interfaces was in situ synthesized by multi-step electrodeposition method, and the mechanism of the enhancement of its electrocatalytic activity was elucidated by the combination of density functional theory (DFT) calculation and multi-characterizations. The initial overpotential is only 83 mV and the Tafel slope is only 58.5 mV/dec, which is better than most of other reported CoP-based electrocatalyst. At the meantime, DFT calculations show that the incorporation of MoO 3 and rGO leads to electron redistribution among different components, which ensures efficient adsorption and activation of H 2 O molecules and hydrogen atoms. Therefore, this work will contribute to the understanding of the mechanisms associated with heterojunctions and provide guidance for the rational design of a hybrid catalyst.

CAS / MDL: 1310-58-3
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INTERNATIONAL JOURNAL OF HYDROGEN ENERGY · 2019 · IF 4.084

Porous coordination polymer-derived ultrasmall CoP encapsulated in nitrogen-doped carbon for efficient hydrogen evolution in both acidic and basic media

Shuai Liu,Anning Jiang,Zegao Wang,Mengxia Lin,Dan Xia,Qiang Li,Mingdong Dong

Exploiting high-efficient and stable non-precious metal-based electrocatalysts toward hydrogen evolution reaction (HER) is of enormous significance to address the shortage of global power source, but there remain major challenges. Here we present a facile and controllable strategy to synthesize a strongly coupled ultrasmall-cobalt phosphide/nitrogen-doped graphitic carbon (u-CoP@NC) hybrid structure via phosphorization from a porous coordination polymer (PCP) precursor. The PCP-derived u-CoP@NC exhibits remarkable activity and stability for HER, achieving a current density of 10 mA cm −2 with a low overpotential of 131 mV in acidic media and 111 mV in basic media. The corresponding Tafel slopes present in acidic and basic media are 62.7 and 70.3 mV dec −1 , respectively. Results reveal that the enhanced electrocatalytic performance of u-CoP@NC originates from the strongly coupled u-CoP nanoparticles and graphitic carbon layer, and the perfect dispersity of the active sites. This research opens up new avenues for designing earth-abundant metal-based electrocatalysts with high capability for water splitting applications.

CAS / MDL: 553-26-4
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Sustainable Energy & Fuels · 2017 ·Vol. 1 ·期 10 ·2172-2180 · IF 0

Diethylenetriamine-mediated self-assembly of three-dimensional hierarchical nanoporous CoP nanoflowers/pristine graphene interconnected networks as efficient electrocatalysts toward hydrogen evolution

Xiuling Fan,Xiaoyan Wang,Weiyong Yuan,Chang Ming Li

Highly active, durable, and low-cost hydrogen evolution reaction (HER) catalysts are critical for large-scale energy storage in the form of hydrogen through water splitting but their fabrication presents great challenges. Herein we report the synthesis of a novel 3D hierarchical nanoporous CoP nanoflowers/pristine graphene interconnected network structure via diethylenetriamine (DETA)-mediated self-assembly, in which DETA promoted the uniform dispersion of graphene and the nucleation of the CoP precursor on graphene, the seed aggregation facilitated the formation of nanoflowers and a 3D network, and the gas release during the low-temperature phosphidation produced nanopores inside the nanoflowers. This nanoarchitecture shows an onset potential of −0.014 V, an overpotential of 98.1 mV to achieve 10 mA cm−2, a Tafel slope of 40.9 mV dec−1, and an exchange current density of 0.119 mA cm−2. The onset overpotential, overpotential to achieve 10 mA cm−2, and Tafel slope are all among the lowest reported for non-noble metal hydrogen evolution reaction (HER) catalysts, and the exchange current density also compares favorably to those of most reported HER catalysts. In addition, the catalyst exhibits excellent durability with negligible loss in current density after 2000 cyclic voltammetry (CV) cycles (+0.01 to −0.17 V vs. the RHE, at a scan rate of 100 mV s−1) or 23.5 h of chronoamperometric measurement at an overpotential of 98.1 mV, and a high faradaic efficiency of close to 100%. This work not only creates a high-performance and inexpensive HER electrocatalyst by utilizing the great advantages of 3D hierarchically nanostructured networks, but also develops a facile and economical strategy for the self-assembly of hierarchical nanostructures and offers scientific insight into its mechanism.

CAS / MDL: 7681-53-0
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Nano Research · 2016 ·Vol. 10 ·期 2 ·595-604 · IF 8.893

Monolithically integrated CoP nanowire array: An on/off switch for effective on-demand hydrogen generation via hydrolysis of NaBH4 and NH3BH3

Cui Liang,Xu Yuanhong,Niu Li,Yang Wenrong,Liu Jingquan

The issues of hydrogen generation and storage have hindered the widespread use and commercialization of hydrogen fuel cell vehicles. It is thus highly attractive, but the design and development of highly active non-noble-metal catalysts for on-demand hydrogen release from alkaline NaBH 4 solution under mild conditions remains a key challenge. Herein, we describe the use of CoP nanowire array integrated on a Ti mesh (CoP NA/Ti) as a three-dimensional (3D) monolithic catalyst for efficient hydrolytic dehydrogenation of NaBH 4 in basic solutions. The CoP NA/Ti works as an on/off switch for on-demand hydrogen generation at a rate of 6,500 mL/(min·g) and a low activation energy of 41 kJ/mol. It is highly robust for repeated usage after recycling, without sacrificing catalytic performance. Remarkably, this catalyst also performs efficiently for the hydrolysis of NH 3 BH 3 .

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ACS Sustainable Chemistry & Engineering · 2024 · IF 7.1

Dual-Driven Interfaces of a CoP/CoO Cocatalyst on a Host Photocatalyst for Rapid Charge Transport in Solar-Driven H2 Evolution

Qiang Wang,Lina Kong,Jianping Xu,Baozeng Zhou,Xiaofan Liu,Ziyu Lin,Shaobo Shi,Xiaosong Zhang,Lan Li

The construction of efficient and nonprecious cocatalysts, along with the establishment of rapid interfacial charge migration pathways to host semiconductors, is a major process in enhancing photocatalytic water splitting performance and remains a formidable challenge. Herein, the composition of CoP/CoO cocatalysts on g-C3N4 is regulated through phosphating for efficient and stable H2 evolution. Comprehensive analyses reveal that the CoO nanocrystals, possessing a bandgap of 1.95 eV, are uniformly loaded onto g-C3N4 with a portion undergoing an in situ transformation to metallic CoP, thereby forming a well-defined interfacial energy level structure for carrier separation. Moreover, the CoP/CoO cocatalysts exhibited a lower hydrogen adsorption Gibbs free energy (ΔGH) than that of the mono CoP or CoO. The optimal CoP/CoO/g-C3N4 exhibits an attractive and stable rate of solar-driven H2 evolution at 0.86 mmol·g–1·h–1, surpassing the rates of CoO/g-C3N4 and Pt/g-C3N4 by 30 and 1.5 times, respectively. The dual-driven interfaces of CoP/CoO/g-C3N4 provide a 2-fold acceleration for directional carrier transfer, in conjunction with accelerated surface reaction kinetics, resulting in efficient and stable H2 evolution. This scalable strategy, focusing interfacial engineering for rapid carrier transfer, offers a novel perspective in the design of highly active cocatalysts to boost the photocatalytic application.

CAS / MDL: 57-13-6
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JOURNAL OF COLLOID AND INTERFACE SCIENCE · 2024 · IF 9.4

Hollow CoP-FeP cubes decorating carbon nanotubes heterostructural electrocatalyst for enhancing the bidirectional conversion of polysulfides in advanced lithium-sulfur batteries

Fengjin Yi,Jiayu Wang,Weiliang Liu,Jinshui Yao,Mei Li,Chunsheng Li,Yan Sun,Jiaxi Cui,Manman Ren

The sluggish redox reaction kinetics and “shuttle effect” of lithium polysulfides (LPSs) impede the advancement of high-performance lithium-sulfur batteries (LSBs). Transition metal phosphides exhibit distinctive polarity, metallic properties, and tunable electron configuration , thereby demonstrating enhanced adsorption and electrocatalytic capabilities towards LPSs. Consequently, they are regarded as exceptional sulfur hosts for LSBs. Moreover, the introduction of a heterogeneous structure can enhance reaction kinetics and expedite the transport of electrons/ions. In this study, a composite of hollow CoP-FeP cubes with heterostructure modified carbon nanotube (CoFeP-CNTs) was fabricated and utilized as sulfur host in advanced LSBs. The presence of carbon nanotubes (CNTs) facilitates enhanced electron and Li + transport. Meanwhile, the active sites within the heterogeneous interface of CoP-FeP suppress the “shuttle effect” and enhance the conversion kinetics of LPSs. Therefore, the CoFeP-CNTs/S electrode exhibited exceptional cycling stability and demonstrated a capacity attenuation of merely 0.051 % per cycle over 600 cycles at 1C. This study presents a highly effective tactic for synthesizing dual-acting transition metal phosphides with heterostructure, which will play a pivotal role in advancing the development of efficient LSBs.

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SOLAR ENERGY MATERIALS AND SOLAR CELLS · 2024 · IF 6.3

High-efficiency acidic electrocatalytic hydrogen evolution enhanced by encapsulation of heterojunction CoP–MoP nanoparticles in a nitrogen-doped 3D nanocarbon framework

Dawei Zheng,Dekun Xv,Xingrui Lv,Wenbin Cao,Dong Liu

The development of low-cost, high-performance transition metal phosphide electrocatalysts is essential for producing hydrogen from renewable energy sources. Here, we report a N-doped three-dimensional nanocarbon framework encapsulating heterojunction CoP–MoP nanoparticles. Due to the synergistic effect between the bimetals, electron transfer is enhanced at multiple heterogeneous junctions, resulting in highly efficient acid electrocatalytic hydrogen evolution reaction (HER). Additionally, the introduction of N-doped carbon material not only improves the conductivity of the catalyst, but also effectively prevents the aggregation of transition metal phosphide nanoparticles, thus exposing more active sites. Notably, CoP–MoP/NC demonstrates HER catalytic activity comparable to 20% Pt/C in a 0.5 M H 2 SO 4 solution. Furthermore, it exhibits a significantly low overpotential and a small Tafel slope, measuring 105.2 mV and 79.7 mV dec −1 , respectively, at a current density of 10 mA cm −2 . And the catalyst also shows excellent long-term durability, further highlighting its potential as a high-performance HER electrocatalyst.

CAS / MDL: 10026-22-9
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DALTON TRANSACTIONS · 2025 · IF 3.3

Charge optimization induces reconstruction via compounding Ni(OH)2 and CoP: a novel route to construct electrocatalysts for overall water-splitting

Hao Yin,Bingxian Wu,Xueyang Leng,Hong Gao,Jing Yao

Electrolytic water-splitting has the advantages of high efficiency, environmental friendliness, and sustainability. It is becoming a leading approach for producing hydrogen. In order to improve the efficiency of water-splitting, a bifunctional electrocatalyst with high performance is needed. Herein, we present a novel approach to construct a bifunctional electrocatalyst for overall water-splitting by compounding Ni(OH)2 and CoP. This combination induced charge optimization, thereby leading to surface reconstruction. The nanocomposite displayed outstanding catalytic performance, benefiting from its more reactive surface area, improved conductivity and enhanced electrocatalytic activity. The resulting Ni(OH)2/CoP electrocatalyst exhibited excellent catalytic performance, with low overpotentials of 266 mV at 50 mA cm−2 for the OER and 71 mV at −10 mA cm−2 for the HER, and required only 1.54 V to reach 10 mA cm−2 in an overall water-splitting device, overtaking most of the recently reported Co- and Ni-based catalysts. This innovative strategy offers new directions for the design of efficient electrocatalysts.

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Processes · 2026 ·Vol. 14 ·期 13 ·2173 · IF 3.4

Joule Heating-Assisted Synthesis of CoP-Loaded Carbons with Developed Porosity and Surface Phosphorous Functionality as Cathode Materials for Lithium–Sulfur Batteries

Zerui Bi,Xiaokai Zhou,Weiyue Feng,Fangang Zeng

Given the confining effect of porous carbon and strong surface polarity of transition metal phosphides, their composite would be a promising cathode candidate to solve the problems of lithium–sulfur batteries including volume expansion and the shuttling effect of polysulfides. Herein, cobalt phosphide (CoP)-loaded phosphorous (P)-containing carbonized bamboo (CoP/PCBs) composites were fabricated via the co-pyrolysis of phytic acid, waste bamboo and Co(NO3)2·6H2O via Joule heating at 600–1200 °C. Hydrogen radicals released from phytic acid enabled CoP/PCBs with developed porosity (438.1–812.4 m2/g). CoP nanoparticles coated with graphitic carbon were distributed uniformly on a porous matrix of PCBs. CoP/PCBs presented obviously enhanced adsorption capabilities for Li2S6, and 57.8–80.4 wt.% of sulfur was confined in CoP/PCBs/S cathodes. CoP/PCB heated at 1200 °C exhibited a high reversible capacity of 477.5 mAh/g after 500 cycles at a current density of 1 C with an average capacity decay rate of 0.045%. The specific capacity remained at 453.3 mAh/g after 300 cycles even under a high sulfur load of 4.0 mg/cm2. Conversion of sulfur/polysulfides during the electrochemical process could be promoted via the physical confinement of sulfur and chemical confinement of Li2S6. This work provided a valuable reference for the facile fabrication of lithium–sulfur cathodes and utilization of metal phosphides in advanced lithium–sulfur battery systems.

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SEPARATION AND PURIFICATION TECHNOLOGY · 2026 · IF 9.1

ZIF-67-derived CoP and MnCdS are used to construct a Schottky junction for highly efficient photocatalytic hydrogen and hydrogen peroxide production

Rongfeng Guan,Ze Liu,Changlei Huang,Jiacheng Liu,Changjian Zhou

Developing a bifunctional photocatalytic system that combines efficient hydrogen evolution and hydrogen peroxide generation is of great significance for achieving solar-driven water splitting and green oxidant synthesis. In this study, a cobalt phosphide (CoP) cocatalyst with metalloid conductivity and porous structure was prepared by phosphorizing ZIF-67, and then composited with MnCdS solid solution via a one-pot hydrothermal method, successfully constructing a MnCdS@ZIF/P (MCS@Z/P) Schottky junction photocatalyst with intimate interfacial contact. The Mn doping strategy effectively regulated the band structure of CdS, not only narrowing the bandgap from 2.27 eV to 2.17 eV but also shifting the valence band maximum upward, thereby significantly enhancing visible light absorption and hole oxidation potential. After contacting with high-work-function CoP, a strong built-in electric field is formed at the interface, efficient driving directional transfer of photogenerated electrons from MnCdS to CoP. Under visible light irradiation, the optimized MCS@10Z/P catalyst exhibits excellent photocatalytic activity for both H 2 evolution (42.33 mmol·g −1 ·h −1 ) and H 2 O 2 production (1951.09 μmol·g −1 ·h −1 in air) in two independent reaction systems. Mechanistic studies reveal that the introduction of CoP not only serves as an efficient electron transport medium, but also shifts the oxygen reduction pathway from an inefficient single-electron process to a highly efficient two-electron dominant pathway by optimizing the *OOH intermediate adsorption free energy. The Gibbs free energy(ΔG H ) of the optimal sample is reduced to 0.13 eV, which significantly reduces the reaction energy barrier. This work provides new insights into the design of efficient bifunctional Schottky junction photocatalysts based on MOF-derived materials.

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CHINESE JOURNAL OF CATALYSIS · 2023 · IF 16.5

Surface-enriched ultrafine Pt nanoparticles coupled with defective CoP as efficient trifunctional electrocatalyst for overall water splitting and flexible Zn-air battery

Zexing Wu,Yuxiao Gao,Zixuan Wang,Weiping Xiao,Xinping Wang,Bin Li,Zhenjiang Li,Xiaobin Liu,Tianyi Ma,Lei Wang

Developing multifunctional electrocatalysts toward energy-related reactions could reduce the cost and improve the utilization efficiency of raw materials. Herein, defective CoP decorated with ultrafine Pt nanoparticles (Pt/d-CoP/NPC) with multifunctional electrocatalytic performances is prepared via facile pyrolysis and following chemical reduction process. The as-synthesized Pt/d-CoP/NPC owns high half-wave potential of 0.82 V for oxygen reduction reaction with excellent stability in 0.1 mol/L KOH. Density functional theory calculations demonstrate that the adsorption energy of *OO at Pt/d-CoP/NPC is stronger compared to Pt, yielding higher catalytic activity for ORR. Moreover, the resultant electrocatalyst possesses excellent catalytic activities with low overpotentials toward hydrogen evolution reaction (33 mV in 1 mol/L KOH, 6 mV in 0.5 mol/L H 2 SO 4 and 70 mV in 1 mol/L PBS) and oxygen evolution reaction (320 mV) at 10 mA/cm 2 . Water-splitting and rechargeable Zn-air batteries assembled with the as-synthesized Pt/d-CoP/NPC as electrodes exhibit outstanding activity and long-range stability. Remarkably, sustainable energies and homemade Zn-air battery can efficiently drive the Pt/d-CoP/NPC electrolyzer with sumless hydrogen bubbles generated, verifying the potential applications for renewable energy storage.

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Materials Chemistry Frontiers · 2023 ·Vol. 7 ·期 13 ·2628-2636 · IF 7

Electron-transfer enhancement of urchin-like CoP–Ce2(CO3)2O/NF as an ultra-stable bifunctional catalyst for efficient overall water splitting

Lixia Wang,Meilin Huang,Mingcheng Gao,Tayirjan Taylor Isimjan,Xiulin Yang

Effective control of strong electron interaction at heterogeneous interfaces is crucial for the creation of highly efficient and stable bifunctional catalysts for water splitting. In this work, we synthesized an urchin-like CoP–Ce2(CO3)2O catalyst on nickel foam (CoP–Ce2(CO3)2O/NF) via a facile hydrothermal and gas-phase phosphating process, which enhances active site exposure and improves catalytic reaction kinetics. Spectroscopy analysis reveals that the enhanced performance is due to the charge transfer between CoP and Ce2(CO3)2O and the unique urchin-like structure of the hybrid catalyst. The CoP–Ce2(CO3)2O/NF catalyst showed excellent hydrogen/oxygen evolution reaction (HER/OER) performance (η10 = 85.2 and 205.5 mV) and robust long-term stability in 1.0 M KOH. Additionally, the CoP–Ce2(CO3)2O/NF(+)||CoP–Ce2(CO3)2O/NF(−) electrolyzer required only a low cell voltage of 1.82 V to produce 100 mA cm−2 for overall water splitting, outperforming most previous catalysts. This work presents a strategy for interfacial engineering to improve the activity of bifunctional heterojunction electrocatalysts for overall water splitting.

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