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Abstract Utilizing plasmon‐generated hot carriers to drive chemical reactions has emerged as a popular topic in solar photocatalysis. However, a complete description of the underlying mechanism of hot‐carrier transfer in photochemical processes remains elusive, particularly for those involving hot holes. Photoelectrochemistry enables to localize hot holes on photoanodes and hot electrons on photocathodes and thus offers an approach to separately explore the hole‐transfer dynamics and electron‐transfer dynamics. This review summarizes a comprehensive understanding of both hot‐hole and hot‐electron transfers from photoelectrochemical studies on plasmonic electrodes. Additionally, working principles and applications of spectroelectrochemistry are discussed for plasmonic materials. It is concluded that photoelectrochemistry provides a powerful toolbox to gain mechanistic insights into plasmonic photocatalysis. 

Abstract Plasmon‐mediated carrier transfer (PMCT) at metal–semiconductor heterojunctions has been extensively exploited to drive photochemical reactions, offering intriguing opportunities for solar photocatalysis. However, to date, most studies have been conducted using noble metals. Inexpensive materials capable of generating and transferring hot carriers for photocatalysis via PMCT have been rarely explored. Here, we demonstrate that the plasmon excitation of nickel induces the transfer of both hot electrons and holes from Ni to TiO₂in a rationally designed Ni–TiO₂heterostructure. Furthermore, it is discovered that the transferred hot electrons either occupy oxygen vacancies (V_O) or produce Ti³⁺on TiO₂, while the transferred hot holes are located on surface oxygens at TiO₂. Moreover, the transferred hot electrons are identified to play a primary role in driving the degradation of methylene blue (MB). Taken together, our results validate Ni as a promising low‐cost plasmonic material for prompting visible‐light photochemical reactions. 

Plasmonic nanostructures possess broadly tunable optical properties with catalytically active surfaces. They offer new opportunities for achieving efficient solar-to-chemical energy conversion. Plasmonic metal–semiconductor heterostructures have attracted heightened interest due to their capability of generating energetic hot electrons that can be collected to facilitate chemical reactions. In this article, we present a detailed survey of recent examples of plasmonic metal–semiconductor heterostructures for hot-electron-driven photochemistry, including plasmonic metal–oxide, plasmonic metal–two-dimensional materials, and plasmonic metal–metal–organic frameworks. We conclude with a discussion on the remaining challenges in the field and an outlook regarding future opportunities for designing high-performance plasmonic metal–semiconductor heterostructures for photochemistry.