Revealing the Intrinsic Peroxidase-Like Catalytic Mechanism of Heterogeneous Single-Atom Co–MoS(2)

The single-atom nanozyme is a new concept and has tremendous prospects to become a next-generation nanozyme. However, few studies have been carried out to elucidate the intrinsic mechanisms for both the single atoms and the supports in single-atom nanozymes. Herein, the heterogeneous single-atom Co–MoS(2) (SA Co–MoS(2)) is demonstrated to have excellent potential as a high-performance peroxidase mimic. Because of the well-defined structure of SA Co–MoS(2), its peroxidase-like mechanism is extensively interpreted through experimental and theoretical studies. Due to the different adsorption energies of substrates on different parts of SA Co–MoS(2) in the peroxidase-like reaction, SA Co favors electron transfer mechanisms, while MoS(2) relies on Fenton-like reactions. The different catalytic pathways provide an intrinsic understanding of the remarkable performance of SA Co–MoS(2). The present study not only develops a new kind of single-atom catalyst (SAC) as an elegant platform for understanding the enzyme-like activities of heterogeneous nanomaterials but also facilitates the novel application of SACs in biocatalysis. [Image: see text] ELECTRONIC SUPPLEMENTARY MATERIAL: The online version of this article (10.1007/s40820-019-0324-7) contains supplementary material, which is available to authorized users.