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<p>The fundamental understanding of activity differences between metal-rich transition metal phosphides in alkaline hydrogen evolution reaction (HER) remains limited. Here, Co<sub>2</sub>P and Ni<sub>2</sub>P nanoarrays grown on nickel foam (NF) were synthesized via hydrothermal and phosphidation methods. XRD, SEM, and XPS confirm phase-pure Co<sub>2</sub>P@NF (nanowires) and Ni<sub>2</sub>P@NF (nanosheet-assembled microspheres). In 1-M KOH, Co<sub>2</sub>P@NF exhibits a lower overpotential (78&#xa0;mV) than Ni<sub>2</sub>P@NF (80&#xa0;mV) at 10&#xa0;mA&#xa0;cm<sup>−2</sup>, with Tafel slopes of 67.30 and 69.61&#xa0;mV&#xa0;dec<sup>−1</sup>, indicating Heyrovsky-dominated kinetics. Co<sub>2</sub>P@NF also shows a larger electrochemical surface area (3.6&#xa0;cm<sup>2</sup>) and lower charge transfer resistance (1.2&#xa0;Ω). Density functional theory (DFT) reveals that Co<sub>2</sub>P has a higher density of states near the Fermi level and more optimal hydrogen adsorption free energy (−&#xa0;0.66&#xa0;eV vs. − 0.78&#xa0;eV for Ni<sub>2</sub>P), explaining its superior intrinsic activity. This study provides insights into designing efficient non-noble metal phosphide electrocatalysts.</p>

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Preparation and Electrocatalytic Performance Study of Metal-Rich Transition Metal Phosphides, Co2P and Ni2P

  • 期刊论文

  • 发表日期：

    2026年5月4日

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  • Xinxin Cui,
  • Bonian Jiang,
  • Jinjing Du,
  • Xiao Feng,
  • Haiyang Lin,
  • Ruitong Zhai,
  • Yu Zhou,
  • Yuxiang Yangxuan,
  • Qian Li,
  • Jun Zhu,
  • Bin Wang

摘要

The fundamental understanding of activity differences between metal-rich transition metal phosphides in alkaline hydrogen evolution reaction (HER) remains limited. Here, Co2P and Ni2P nanoarrays grown on nickel foam (NF) were synthesized via hydrothermal and phosphidation methods. XRD, SEM, and XPS confirm phase-pure Co2P@NF (nanowires) and Ni2P@NF (nanosheet-assembled microspheres). In 1-M KOH, Co2P@NF exhibits a lower overpotential (78 mV) than Ni2P@NF (80 mV) at 10 mA cm−2, with Tafel slopes of 67.30 and 69.61 mV dec−1, indicating Heyrovsky-dominated kinetics. Co2P@NF also shows a larger electrochemical surface area (3.6 cm2) and lower charge transfer resistance (1.2 Ω). Density functional theory (DFT) reveals that Co2P has a higher density of states near the Fermi level and more optimal hydrogen adsorption free energy (− 0.66 eV vs. − 0.78 eV for Ni2P), explaining its superior intrinsic activity. This study provides insights into designing efficient non-noble metal phosphide electrocatalysts.