Synergistic Effect of P and Co Dual Doping Endows CuNi with High–Performance Hydrogen Evolution Reaction

Abstract The rational design of highly active and durable non‐noble electrocatalysts for hydrogen evolution reaction (HER) is significantly important but technically challenging. Herein, a phosphor and cobalt dual doped copper–nickel alloy (P, Co–CuNi) electrocatalyst with high–efficient HER performance is prepared by one‐step electrodeposition method and reported for the first time. As a result, P, Co–CuNi only requires an ultralow overpotential of 56 mV to drive the current density of 10 mA cm −2 , with remarkable stability for over 360 h, surpassing most previously reported transition metal‐based materials. It is discovered that the P doping can simultaneously increase the electrical conductivity and enhance the corrosion resistance, while the introduction of Co can precisely modulate the sub‐nanosheets morphology to expose more accessible active sites. Moreover, XPS, UPS, and DFT calculations reveal that the synergistic effect of different dopants can achieve the most optimal electronic structure around Cu and Ni, causing a down‐shifted d‐band center, which reduces the hydrogen desorption free energy of the rate‐determining step (H 2 O + e − + H* → H 2 + OH − ) and consequently enhances the intrinsic activity. This work provides a new cognition toward the development of excellent activity and stability HER electrocatalysts and spurs future study for other NiCu‐based alloy materials.