Yan Lin, Zihan Wang, Jiaye Li, Y. M. Liu, Pinxin Liu, Zichen Liu, Kun Hu, Xin Yang, Yue Zhou, Guoqiang Li, Chongzheng Sun, Zheng Chen, Bing Sun, Yuan Pan
Transition metal phosphides (TMPs) exhibit attracted application prospect as active electrocatalysts for the hydrogen evolution reaction (HER) through water electrolysis due to their compositional and structural advantages. Recent studies have shown that hydrogen production can be enhanced by modulating the microstructure of TMPs catalysts, but the understanding is incomplete, while rational design principles at the nanostructure or even atomic scale are still lacking. Here, the authors systematically summarize the existing research progress in modulating TMPs electrocatalysts from nanostructures to single atoms to enhance HER. The latest strategies to enhance the catalytic activity of TMPs are summarized. Then, the scaling effects in TMPs catalysts are discussed from the nanoscale and atomic scale, respectively, based on which rational design principles for improving the activity and stability of TMPs with single-atom catalysts are proposed. This review provides a theoretical reference for the design of high activity and high atom utilization catalysts for hydrogen production.