Photogenerated Carrier-assisted Electrocatalysis: Mechanistic Perspectives and Catalytic Advances

Abstract

Photogenerated carrier-assisted electrocatalysis (PCAE), an emerging strategy that couples light and electrical energy, offers a promising approach to improve catalytic efficiency and energy utilization. This comprehensive review systematically discusses the mechanistic fundamentals, system evolution, and recent advancements in PCAE. First of all, we clarify the distinctions between PCAE and conventional photo-assisted electrocatalysis processes, highlighting the role of photogenerated carriers in modulating local electron density and participating in redox pathways. Then, PCAE systems are classified into electron-assisted, hole-assisted, and electron-hole pair-assisted categories, with detailed mechanistic insights into their behavior in key electrocatalytic reactions including OER, HER, FAOR, CO2RR, NRR, and UOR. Second, we summarize advanced catalyst design strategies (such as morphological engineering, heterojunction/Schottky junction construction, active phase regulation and defect/doping optimization) that enhance charge separation and catalytic activity. Moreover, we explore the expanding applications of PCAE in water splitting, metal-air batteries and fuel cells. Compared to existing reviews, this work uniquely emphasizes charge carrier dynamics, interfacial transport and system-level challenges. Finally, future research directions are proposed, including carrier kinetics modulation, photostability improvement and intelligent PCAE system integration. This review aims to offer a structured theoretical foundation and strategic guidance for the continued development of PCAE technologies in energy conversion.