Coordination Number Regulation of Molybdenum Single-Atom Nanozyme Peroxidase-like Specificity

By Ying Wang, Guangri Jia, X. Cui, Xiao Zhao, Qinghua Zhang, L. Gu, Lirong Zheng, L. Li, Qiong Wu, David J. Singh and 5 more. Chem, 2020

311 citations recorded by the source corpus.

Summary Nanozymes are promising alternatives to natural enzymes, but their use remains limited owing to poor specificity. Overcoming this and controlling the targeted enzyme-like performance of traditional nanozymes is extremely challenging due to the intrinsic structural complexity of these systems. We report theoretical design and experimental realization of a series of heterogeneous molybdenum single-atom nanozymes (named MoSA–Nx–C), wherein we find that the peroxidase-like specificity is well regulated by the coordination numbers of single Mo sites. The resulting MoSA–N3–C catalyst shows exclusive peroxidase-like behavior. It achieves this behavior via a homolytic pathway, whereas MoSA–N2–C and MoSA–N4–C catalysts have a different heterolytic pathway. The mechanism of this coordination-number-dependent enzymatic specificity is attributed to geometrical structure differences and orientation relationships of the frontier molecular orbitals toward these MoSA–Nx–C peroxidase mimics. This study demonstrates the rational design of peroxidase-specific nanozymes and precise regulation of their enzymatic properties.

Subfields: Electrical and Electronic Engineering, Materials Chemistry

View Paper: https://www.semanticscholar.org/paper/4acd3d60eed5378be8344faffb6d7ef175fe7a6d