Electronic Modulation in Cu Doped NiCo LDH/NiCo Heterostructure for Highly Efficient Overall Water Splitting

Abstract Layered double hydroxides (LDHs), promising bifunctional electrocatalysts for overall water splitting, are hindered by their poor conductivity and sluggish electrochemical reaction kinetics. Herein, a hierarchical Cu‐doped NiCo LDH/NiCo alloy heterostructure with rich oxygen vacancies by electronic modulation is tactfully designed. It extraordinarily effectively drives both the oxygen evolution reaction (151 mV@10 mA cm −2 ) and the hydrogen evolution reaction (73 mV@10 mA cm −2 ) in an alkaline medium. As bifunctional electrodes for overall water splitting, a low cell voltage of 1.51 V at 10 mA cm −2 and remarkable long‐term stability for 100 h are achieved. The experimental and theoretical results reveal that Cu doping and NiCo alloy recombination can improve the conductivity and reaction kinetics of NiCo LDH with surface charge redistribution and reduced Gibbs free energy barriers. This work provides a new inspiration for further design and construction of nonprecious metal‐based bifunctional electrocatalysts based on electronic structure modulation strategies.