Silicon‐Based Electrodes for Photoelectrochemical Redox Reactions

Abstract Photoelectrochemical (PEC) technology is one of the most promising methods for converting solar energy into valuable fuels and chemicals. Silicon (Si), a narrow band gap semiconductor with high carrier mobility, serves as a competitive material for photoelectrodes. This review outlines the research progress of Si‐based photoanodes and photocathodes in diverse economically beneficial PEC redox reactions, extending beyond water splitting to include alcohol oxidation, carbon dioxide reduction, ammonia synthesis, organic degradation, and more. To address the key barriers to achieving efficient PEC conversion – such as slow charge carrier dynamics, sluggish reaction kinetics, and the instability of Si‐based photoelectrodes – the mechanisms and implementation methods for fabricating efficient and stable Si‐based photoelectrodes are thoroughly discussed. Finally, the challenges faced in advancing the commercialization of Si‐based PEC solar energy conversion processes are explored.