Unraveling Valence Electron Number Dependent Excitonic Effects over M₁-N₃C₁ Sites in Single-Atom Catalysts

Abstract

Excitonic effects significantly influence the selective generation of reactive oxygen species and photothermal conversion efficiency in photocatalytic reactions; however, the intrinsic factors governing excitonic effects remain elusive. Herein, a series of single-atom catalysts with well-defined M 1 -N 3 C 1 (M = Mn, Fe, Co, and Ni) active sites are designed and synthesized to investigate the structure− activity relationship between photocatalytic materials and excitonic effects. Comprehensive characterization and theoretical calculations unveil that excitonic effects are positively correlated with the number of valence electrons in single metal atoms. The single Mn atom with 5.93 valence electrons exhibits the weakest excitonic effects, which dominate superoxide radical (O 2•− ) generation through charge transfer and enhance photothermal conversion efficiency. Conversely, the single Ni atom with 9.27 valence electrons exhibits the strongest excitonic effects, dominating singlet oxygen ( 1 O 2 ) generation via energy transfer while suppressing photothermal conversion efficiency. Based on the valence electron number dependent excitonic effects, a reaction environment with hyperthermia and abundant cytotoxic O 2•− is designed, achieving efficient and stable water disinfection. This work reveals single metal atom dependent excitonic effects and presents an atomic-level methodology for catalytic application targeted reaction environment tailoring.