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

作者：Ling Li, Sujiao Cao, Zihe Wu, Ruiqian Guo, Lan Xie, Liyun Wang, Yuanjiao Tang, Qi Li, Xianglin Luo, Lang Ma, Chong Cheng, Li Qiu · 发表于：Advanced Materials · 年份：2022 · DOI：10.1002/adma.202108646 · 被引用次数：100 · 研究领域：Advanced Nanomaterials in Catalysis、Electrochemical sensors and biosensors、Electrochemical Analysis and Applications

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 V 2 O 5 , 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 H 2 O 2 . The VO x ‐AE exhibits a twofold V max and threefold turnover number than V 2 O 5 when catalyzing H 2 O 2 . 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.