Molecular‐level Manipulation of Interface Charge Transfer on Plasmonic Metal/MOF Heterostructures

Abstract Plasmon‐excited hot carriers have drawn great attention for driving various chemical reactions, but the short lifetimes of hot carriers seriously restrict the performance of plasmonic photocatalysis. Constructing plasmonic metal/metal‐organic framework (MOF) heterostructures has been proved as an effective strategy to extend the lifetimes of hot carriers. Due to the high molecular tunability of MOFs, the MOF substrate in plasmonic metal/MOF heterostructures is able to capture hot electrons on the conduction band of MOF and hot holes on its valence band, and thus offers an ideal platform to separately study the detailed mechanism of hot electron and hole transfer processes. This review focuses on a molecular‐level understanding of both hot‐electron and hot‐hole transfer at plasmonic metal/MOF interfaces. The enhanced stability and photocatalytic performance by introducing MOF substrates are discussed for plasmonic metal/MOF heterostructures. Additionally, typical characterization technologies are also proposed as powerful tools for tracking hot carrier transfer process.