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

• Published in: Angewandte Chemie International Edition Vol. 54; no. 1; pp. 52 - 65
• Main Authors: Zheng, Yao, Jiao, Yan, Jaroniec, Mietek, Qiao, Shi Zhang
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 02.01.2015; WILEY‐VCH Verlag; Wiley Subscription Services, Inc
• Edition: International ed. in English
• Subjects: Appraisals; Correlation; density-functional theory; Electrocatalysis; Electrocatalysts; Electrochemistry; Electron transfer; Electronic structure; Hydrogen; Hydrogen evolution reactions; hydrogen-evolution reaction; Mathematical analysis; mechanistic studies; Molecular structure; Quantum chemistry; Theory; Water splitting; density-functional theory; mechanistic studies; hydrogen-evolution reaction; electrocatalysis
• ISSN: 1433-7851; 1521-3773; 1521-3773
• DOI: 10.1002/anie.201407031

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. All for HER: A large number of high‐performance electrocatalysts for the hydrogen‐evolution reaction (HER) have been developed. Computational chemistry can direct the molecular design of these catalysts, and electrochemical experiments can be used to verify theoretical predictions.