Abstract

Hydrogen evolution and oxidation reactions (HER/HOR) are the most fundamental reactions in electrocatalysis. Despite the practical significance, the mechanisms of HER/HOR in aqueous solutions are still elusive. Various theories have been proposed to rationalize the pH effect, cation effect, and structure effect of HER/HOR but none of them can explain all observations. In this review, we discuss four schools of thought for the HER/HOR, focusing on the strengths and shortcomings of each hypothesis and highlighting the magnitude of electrochemical interface structure in hydrogen electrocatalysis.