P-Band Intermediate States Mediate Electron Transfer at Confined Nanoscale

In this Perspective, mainly based on the model of structural water molecules (SWs) as bright color emitters, we briefly summarize the development and theoretical elaboration of P-band intermediate state (PBIS) theory as well as its application in several typical catalytic redox reactions. In addition, with a simple equation (2∫ψ²_σ1' + ∫ψ²_σ2 + ∫ψ²_π = 1), we clearly define how the interface states correlate with the three basic parameters of heterogeneous catalysis (conversion, selectivity, and stability), and what is the dynamic nature of catalytic active sites. Overall, the proposal of SW-dominated PBIS theory establishes an internal physical connection between the decay kinetics of excited electrons and the catalytic reaction kinetics and provides new insights into the physical origin of photoluminescence emission of low-dimensional quantum nanodots and the physical nature of nanoconfinement and nanoconfined catalysis.