Abstract Hydrogen energy stands out as a zero‐carbon emission and high‐density energy carrier, with the hydrogen evolution reaction being central to water electrolysis. The hydrogen‐bond network in the electrical double layer (EDL) significantly affects the reaction kinetics, yet the dynamic interactions between interfacial water, proton transfer pathways, and electrode structures remain elusive. Here, inspired by the natural proton regulation behavior of tannic acid (TA) in plant cells, a biomimetic strategy is proposed to reconstruct the hydrogen bond network in the EDL using TA‐modified Ni(OH) 2 . Experimental and theoretical studies demonstrate that TA establishes a robust hydrogen bond network and reduces the proton‐electron coupled transfer barrier through the Grotthuss mechanism. In situ surface‐enhanced infrared spectroscopy and molecular dynamics simulations reveal TA‐mediated reorganization of Ni coordination and stabilization of interfacial water molecules. The optimized Ni(OH) 2 ‐TA catalyst delivers 0.5 A cm −2 at 1.68 V in an anion exchange membrane electrolyzer, sustaining stable operation for 250 h (83% production efficiency@0.1 A cm −2 ). This work highlights organic ligand‐driven EDL hydrogen‐bond engineering as a universal strategy for high‐performance water electrolysis, bridging atomic‐level design with macroscopic performance.
Zhu et al. (2025) studied this question.