Heterojunction-Mediated Co-Adjustment of Band Structure and Valence State for Achieving Selective Regulation of Semiconductor Nanozymes

Improving reaction selectivity is the next target for nanozymes to mimic natural enzymes. Currently, the majority of strategies in this field are exclusively applicable to metal-organic-based or organic-based nanozymes, while limited in regulating metal oxide-based semiconductor nanozymes. Herein, taking semiconductor Co3O4 as an example, a heterojunction strategy to precisely regulate nanozyme selectivity by simultaneously regulating three vital factors including band structure, metal valence state, and oxygen vacancy content is proposed. After introducing MnO2 to form Z-scheme heterojunctions with Co3O4 nanoparticles, the catalase (CAT)-like and peroxidase (POD)-like activities of Co3O4 can be precisely regulated since the introduction of MnO2 affects the position of the conduction bands, preserves Co in a higher oxidation state (Co3+), and increases oxygen vacancy content, enabling Co3O4-MnO2 exhibit improved CAT-like activity and reduced POD-like activity. This study proposes a strategy for improving reaction selectivity of Co3O4, which contributes to the development of metal oxide-based semiconductor nanozymes. It is introduced that MnO2 through a one-step formation of Z-scheme heterojunctions with Co3O4 while synergistically regulating three vital factors including band structure, metal valence state and oxygen vacancy content, resulting in improving the reaction selectivity with H2O2 as substrate. Based on efficient O2 production capacity, Co3O4-MnO2/MB nanoplatform within integrating diagnosis and therapy which combines photodynamic and photothermal therapy is developed. image