Recent Advances in Photoelectrochemical Applications of Silicon Materials for Solar‐to‐Chemicals Conversion

Abstract Photoelectrochemical (PEC) technology for the conversion of solar energy into chemicals requires cost‐effective photoelectrodes to efficiently and stably drive anodic and/or cathodic half‐reactions to complete the overall reactions for storing solar energy in chemical bonds. The shared properties among semiconducting photoelectrodes and photovoltaic (PV) materials are light absorption, charge separation, and charge transfer. Earth‐abundant silicon materials have been widely applied in the PV industry, and have demonstrated their efficiency as alternative photoabsorbers for photoelectrodes. Many efforts have been made to fabricate silicon photoelectrodes with enhanced performance, and significant progress has been achieved in recent years. Herein, recent developments in crystalline and thin‐film silicon‐based photoelectrodes (including amorphous, microcrystalline, and nanocrystalline silicon) immersed in aqueous solution for PEC hydrogen production from water splitting are summarized, as well as applications in PEC CO 2 reduction and PEC regeneration of discharged species in redox flow batteries. Silicon is an ideal material for the cost‐effective production of solar chemicals through PEC methods.