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

• Published in: Chem Vol. 7; no. 2; pp. 436 - 449
• Main Authors: Wang, Ying, Jia, Guangri, Cui, Xiaoqiang, Zhao, Xiao, Zhang, Qinghua, Gu, Lin, Zheng, Lirong, Li, Lu Hua, Wu, Qiong, Singh, David J., Matsumura, Daiju, Tsuji, Takuya, Cui, Yi-Tao, Zhao, Jingxiang, Zheng, Weitao
• Format: Journal Article
• Language: English
• Published: Elsevier Inc 11.02.2021
• Subjects: biocatalysis; coordination environment; MoSA–N3–C catalyst; peroxidase-like specificity; single-atom nanozyme; single-atom nanozyme; coordination environment; SDG3: Good health and well-being; peroxidase-like specificity; MoSA–N3–C catalyst; biocatalysis
• DOI: 10.1016/j.chempr.2020.10.023
• ISSN: 2451-9294

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. [Display omitted] •A class of MoSA–Nx–C nanozymes are designed and implemented•The peroxidase-like specificity is regulated by Mo–Nx coordination numbers•MoSA–N3–C single-atom nanozyme has superior and exclusive peroxidase-like activity•The mechanism of coordination-number-dependent POD-like specificity is elucidated Nanozymes, which are nanomaterials with enzyme-like characteristics, combine the advantages of nanomaterials and biocatalysts. Although the stability and durability of these nanozymes are comparable to those of natural enzymes, unsatisfactory specificity still limits their wide application as alternatives to natural enzymes. Controlling the targeted enzyme-like performance of traditional nanozymes is extremely challenging owing to the intrinsic structural complexity of nanomaterials. Here, we report the theoretical design and experimental realization of a series of heterogeneous molybdenum single-atom nanozymes. Their peroxidase-like specificity is well regulated by the coordination numbers of single Mo sites. A MoSA–N3–C single-atom nanozyme with superior and specific peroxidase-like activity is demonstrated. This work unravels the structure-selectivity relationships and provides an effective strategy for the rational design of targeted nanozymes. Nanozymes are promising alternatives to natural enzymes, but their use remains limited owing to poor specificity. In this context, a clear relationship between the peroxidase-like specificity and configurations of molybdenum single-atom nanozymes (MoSA–Nx–C) is established through the regulation of Mo–Nx coordination numbers at the atomic level. The resulting MoSA–N3–C nanozyme has superior and exclusive peroxidase-like activity. This work provides a strategy for the rational design and realization of selective single-atom nanozymes.