Modulating Electron Transfer in Vanadium‐Based Artificial Enzymes for Enhanced ROS‐Catalysis and Disinfection

Abstract Nanomaterials‐based artificial enzymes (AEs) have flourished for more than a decade. However, it is still challenging to further enhance their biocatalytic performances due to the limited strategies to tune the electronic structures of active centers. Here, a new path is reported for the de novo design of the d electrons of active centers by modulating the electron transfer in vanadium‐based AEs (VO_x‐AE) via a unique Zn–O–V bridge for efficient reactive oxygen species (ROS)‐catalysis. Benefiting from the electron transfer from Zn to V, the V site in VO_x‐AE exhibits a lower valence state than that in V₂O₅, which results in charge‐filled V‐d_yz orbital near the Fermi level to interfere with the formation of sigma bonds between the V‐ and O‐p_z orbitals in H₂O₂. The VO_x‐AE exhibits a twofold V_max and threefold turnover number than V₂O₅ when catalyzing H₂O₂. Meanwhile, the VO_x‐AE shows enhanced catalytic eradication of drug‐resistant bacteria and achieves comparable wound‐treatment indexes to vancomycin. This modulating charge‐filling of d electrons provides a new direction for the de novo design of nanomaterials‐based AEs and deepens the understanding of ROS‐catalysis.