Porous silicon (Si) has a tetrahedral structure similar to that of sp-hybridized carbon atoms in a typical diamond structure, which affords it unique chemical and physical properties including an adjustable intrinsic bandgap, a high-speed carrier transfer efficiency. It has shown great potential in photocatalysis, rechargeable batteries, solar cells, detectors, and electrocatalysis. This review introduces various porous Si-supported electrocatalysts and analyzes the reasons why porous Si is used as a new carrier/active sites from the perspectives of its molecular structure, electronic properties, synthesis methods, etc. The electrochemical applications of porous Si-based electrocatalysts in energy conversion reactions such as hydrogen evolution reaction, oxygen evolution reaction, oxygen reduction reaction, and total water decomposition together with lithium-ion battery and supercapacitor in energy storage are summarized. The challenges and future research directions for porous Si are also discussed. This review aims to deepen the understanding of porous Si and promote the development and applications of this new type of Si material.
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