Spin Cooperated Catalytic Activities in Mn-N4 based Single-atom Nanozyme: Mechanisms and a Brief Charge-spin Model

Although developing artificial enzymes has made great progress, there is still a gap between artificial enzymes and natural enzymes in catalytic performance. Designing and constructing efficient artificial biocatalysts is extremely desirable because of their high stability, low cost and easy storage. Here, we report a synthesized amino-functionalized graphene quantum dots-based manganese single atom catalyst (SAC) Mn-N4, which exhibits POD-, CAT, SOD-like activities, especially the superior SOD-like activity. Recent studies have reported Mn-based SAzymes, however, the multi-enzyme mimicking catalytic mechanisms for Mn-N4 are not comprehensive and in-depth enough. Therefore, we combine density functional theory (DFT) calculations and machine learning (ML) to validate the performance of the multi-enzyme mimicking activities. The DFT simulations show that Mn-N4 owns a highly effective SOD in the "one-side adsorption" with a very low energy barrier of 0.077 eV, which can be attributed to variation of the preferred spin states of Mn-O2.- system and its "spin flip-collection lock" in the SOD-like catalytic procedure. Furthermore, spin related charge distributions on Mn-N4 configurations by machine learning (ML) analysis suggest that the pattern of spin and natural charge/valence electron distribution will exhibit similarity in the structures of multiple intermediate steps of multi-enzyme mimicking activities. This work not only puts forward the catalytic mechanisms of Mn-N4 SAzymes, but also provides essential guidance for future design of highly performance artificial enzymes.