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.
Metal nanocrystals (NCs), particularly for plasmonic metal NCs with specific morphology and size, can strongly interact with ultraviolet-visible or even near-infrared photons to generate energetic charge carriers, localized heating, and electric field enhancement. These unique properties offer a promising opportunity for maneuvering solar-to-chemical energy conversion through different mechanisms. As distinct from previous works, in this review, recent advances of various characterization techniques in probing and monitoring the photophysical/photochemical processes, as well as the reaction mechanisms of plasmon-mediated photoredox catalysis are thoroughly summarized. Understanding how to distinguish and track these reaction mechanisms would furnish basic guidelines to design next-generation photocatalysts for plasmon-enhanced catalysis.
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