In situ Raman spectroscopic study towards the growth and excellent HER catalysis of Ni/Ni(OH)2 heterostructure

Abstract

Abstract The electrochemical water splitting to produce H2 in high efficiency with earth-abundant-metal catalysts remains a challenge. Here, we describe a simple “cyclic voltammetry\xa0+\xa0ageing” protocol at room temperature to activate Ni electrode (AC-Ni/NF) for hydrogen evolution reaction (HER), by which Ni/Ni(OH)2 heterostructure is formed at the surface. In situ Raman spectroscopy reveals the gradual growth of Ni/Ni(OH)2 heterostructure during the first 30\xa0min of the aging treatment and combined with polarization measurements, it suggests a positive relation between the Ni/Ni(OH)2 amount and HER performance of the electrode. The obtained AC-Ni/NF catalyst, with plentiful Ni–Ni(OH)2 interfaces, exhibits remarkable performance towards HER, with the low overpotential of only 30\xa0mV at a H2-evolving current density of 10\xa0mA/cm2 and 153\xa0mV at 100\xa0mA/cm2, as well as a small Tafel slope of 46.8 mV/dec in 1\xa0M KOH electrolyte at ambient temperature. The excellent HER performance of the AC-Ni/NF could be maintained for at least 24\xa0h without obvious decay. Ex situ experiments and in situ electrochemical-Raman spectroscopy along with density functional theory (DFT) calculations reveal that Ni/Ni(OH)2 heterostructure, although partially reduced, can still persist during HER catalysis and it is the Ni–Ni(OH)2 interface reducing the energy barrier of H∗ adsorption thus promoting the HER performance.