Tailoring the Electronic Structure of Nickel With Ruthenium Nanocluster Arrays by Phosphorus Modification for Ampere-Level Hydrogen Production

Abstract

Proton exchange membrane water electrolysis (PEMWE) requires Pt-based hydrogen evolution reaction (HER) electrocatalysts, which makes current systems costly. Low-cost alternatives have struggled to meet the requirements of both electrocatalytic activity and durability at high-current density operations. Here, we developed phosphorus-modified nickel with ruthenium nanoclusters self-supported on carbon paper (P–NiRu/CP) as efficient HER electrocatalysts. By leveraging metal–organic framework precursors and optimizing the phosphidation process, a dynamic interface between Ru, Ni, and P exhibited optimized hydrogen adsorption/desorption energies and facilitated hydrogen mobility, promoting efficient Tafel recombination. The P–NiRu/CP exhibited an overpotential of 22 mV at 10 mA cm⁻² and a Tafel slope of 29 mV dec⁻¹, outperforming benchmark Pt/C. Computational studies revealed that the dynamic interface in P–NiRu/CP enhanced the electrocatalytic activity. When employed as the cathode in a PEMWE single cell (with commercial IrO₂ as the anode) operating with pure deionized water, P–NiRu/CP achieved 2.05 V at 3.0 A cm⁻² with stable operation over 500 h, highlighting P–NiRu/CP as a cost-effective, durable, and scalable electrocatalyst for sustainable hydrogen production.

Keywords

hydrogen evolution reaction / nickel–ruthenium nanosheets / phosphorus-modified / proton exchange membrane water electrolysis

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2025 The Author(s). SusMat published by Sichuan University and John Wiley & Sons Australia, Ltd.