Advancing the Electrochemistry of the Hydrogen‐Evolution Reaction through Combining Experiment and Theory

TLDR

The electrocatalytic hydrogen‑evolution reaction (HER) is a central step in water splitting that has attracted extensive study, with many high‑performance electrocatalysts developed and significant advances in understanding its electrochemical nature. The study critically appraises both theoretical and experimental HER electrocatalyst research, emphasizing electronic structure, surface electrochemistry, and molecular design, and highlights the need to correlate calculations with measurements for atomic‑level understanding. The authors review HER electrocatalysts by integrating theoretical calculations and experimental measurements, focusing on electronic structure, surface electrochemistry, and molecular design.

Abstract

The electrocatalytic hydrogen-evolution reaction (HER), as the main step of water splitting and the cornerstone of exploring the mechanism of other multi-electron transfer electrochemical processes, is the subject of extensive studies. A large number of high-performance electrocatalysts have been developed for HER accompanied by recent significant advances in exploring its electrochemical nature. Herein we present a critical appraisal of both theoretical and experimental studies of HER electrocatalysts with special emphasis on the electronic structure, surface (electro)chemistry, and molecular design. It addresses the importance of correlating theoretical calculations and electrochemical measurements toward better understanding of HER electrocatalysis at the atomic level. Fundamental concepts in the computational quantum chemistry and its relation to experimental electrochemistry are also presented along with some featured examples.