Citation: Shiqing Zhang, Zihao Wang, Shaokai Ma, Zihang Cao, Fang Liu, Ying Li, Xuewen Xu, Yuanhui Ma, Yanming Xue, Chengchun Tang, Jun Zhang. Boosting alkaline hydrogen evolution kinetics in CoP via high-valence ion doping for anion exchange membrane electrolyzers[J]. Chinese Chemical Letters, ;2026, 37(10): 111785. doi: 10.1016/j.cclet.2025.111785 shu

Boosting alkaline hydrogen evolution kinetics in CoP via high-valence ion doping for anion exchange membrane electrolyzers

Shiqing Zhang ^{a, b} ,
Zihao Wang ^{a, b} ,
Shaokai Ma ^{a, b} ,
Zihang Cao ^{a, b} ,
Fang Liu ^{a, b} ,
Ying Li ^a ,
Xuewen Xu ^{a, b} ,
Yuanhui Ma ^{a, b} ,
Yanming Xue ^{a, b} ,
Chengchun Tang ^{a, b} ,
Jun Zhang ^{a, b, *,}

a.
School of Material Science and Engineering, Hebei University of Technology, Tianjin 300130, China
b.
Hebei Key Laboratory of Boron Nitride Micro and Nano Materials, Tianjin 300130, China

zhang.jun@hebut.edu.cn

Received Date: 18 June 2025
Revised Date: 7 August 2025
Accepted Date: 2 September 2025
Available Online: 2 September 2025

Figures(4)

Advancing low-cost and efficient electrocatalysts for the hydrogen evolution reaction (HER) in alkaline media is essential for sustainable hydrogen production, particularly in the context of anion exchange membrane (AEM) water electrolysis systems. Among various candidates, cobalt-based phosphides, particularly CoP, have drawn significant attention as cost-effective alternatives to platinum-based HER electrocatalysts due to their excellent catalytic performance. However, improving both water dissociation kinetics and hydrogen adsorption free energies remains a challenge. In this study, we introduce lead (Pb), a non-transition metal with higher electronegativity and a similar ionic radius to Co, to modify the electronic structure of CoP at both Co and P sites. Pb doping significantly optimizes both water dissociation and adsorption free energy in the alkaline HER process. The optimized Pb-CoP/CC electrocatalyst reduces the overpotential from 100 mV to 53 mV and achieves a Tafel slope of 57 mV/dec in alkaline electrolyte. Additionally, it exhibits excellent durability, maintaining stable performance for over 120 h. The improved HER performance of Pb-CoP/CC can be ascribed to the synergistic interactions between its components: accelerated water dissociation on Co sites, optimized hydrogen intermediate adsorption on P sites, and improved charge transfer abilities. These findings are supported by experimental data and DFT calculations. When used as the cathode in an AEM electrolyzer, Pb-CoP/CC achieves a current density of 500 mA/cm² at 1.95 V, demonstrating excellent stability. This work highlights the efficacy of metal ion doping with higher electronegativity in improving HER performance and establishes a versatile strategy for other non-precious metal-based transition metal compounds, paving the way for high-performance AEM electrolyzers.
- CoP,
- Electronic structure,
- Water dissociation,
- Adsorption free energy,
- AEM electrolyzer
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