Substantial Impact of Built‐in Electric Field and Electrode Potential on the Alkaline Hydrogen Evolution Reaction of Ru−CoP Urchin Arrays

Abstract Although great efforts on the delicate construction of a built‐in electric field (BIEF) to modify the electronic properties of active sites have been conducted, the substantial impact of BIEF coupled with electrode potential on the electrochemical reactions has not been clearly investigated. Herein, we designed an alkaline hydrogen evolution reaction (HER) catalyst composed of heterogeneous Ru−CoP urchin arrays on carbon cloth (Ru−CoP/CC) with a strong BIEF with the guidance of density functional theory (DFT) calculations. Impressively, despite its unsatisfactory activity at 10 mA cm −2 (overpotential of 44 mV), Ru−CoP/CC exhibited better activity (357 mV) than the benchmark Pt/C catalyst (505 mV) at 1 A cm −2 . Experimental and theoretical studies revealed that strong hydrogen adsorption on the interfacial Ru atoms created a high energy barrier for hydrogen desorption and spillover, resulting in unsatisfactory activity at low current densities. However, as the electrode potential became more negative (i.e., the current density increased), the barrier for hydrogen spillover from the interfacial Ru to the Co site, which had near‐zero hydrogen adsorption energy, significantly decreased, thus greatly accelerating the whole alkaline HER process. This explains why the activity of Ru−CoP is relatively susceptible to the electrode potential compared to Pt/C.