Electronic Reconfiguration of Metal Rhenium Induced by Strong Metal–Support Interaction Enhancing the Hydrogen Evolution Reaction

Abstract Rhenium (Re), as a promising electrocatalyst with favorable abilities to adsorb/desorb the intermediate species (H*), is desirable for hydrogen evolution reaction (HER) in acidic solution, but the activity of Re remains a bottleneck in alkaline solution due to the weak ability to cleave the OH bonds of H 2 O as well as the lack of effective preparation strategies. Herein, an in situ phase separated strategy is developed to fabricate heterostructure rhenium/rhenium disulfide (Re/ReS 2 ) nanosheet arrays with the characteristics of rich micropore structure, an abundance of metal–support interfaces, interface enrichment of charge, and favorable d‐band level. As a result, the Re/ReS 2 heterostructures on 3D carbon cloth show a splendid catalytic performance toward the alkaline HER with an overpotential of 66 mV to achieve a current density of 10 mA cm −2 and a Tafel slope value of 45.23 mV dec −1 , as well as an overpotential of only 145 mV at 200 mA cm −2 . Experimental characterization combined with density functional theory calculations reveal that the excellent catalytic activity originates from the electronic reconfiguration of metal Re induced by strong Re/ReS 2 interface interaction.