LAUSR

The ability of metal nanocrystals (NCs) to maneuver light, trap charge carriers, and enrich reactive sites for photoredox reactions has received considerable attention for constructing metal‐semiconductor heterostructures (MSHs) toward solar‐to‐chemical production. In this review, the comprehensive and fundamental understanding of the structure‐property‐catalysis interplays of MSHs is mainly described. The fundamentals, including basic concepts, and critical insights of MSH‐mediated photoredox catalysis, are first demonstrated. Particular focus is placed on the state‐of‐the‐art technological advances in monitoring the key photophysical/photochemical processes associated with MSH‐mediated photoredox catalysis, followed by highlighting the design parameters for high‐performance MSHs. Then, the applications of MSHs for solar energy conversion, especially for some emerging reaction types are discussed. This review is concluded by casting a perspective on the challenges as well as the opportunities for further promoting this burgeoning field.