Spatial Coordination Structure-Driven Enzyme-Like Selectivity in Single-Atom Nanozymes.

Single-atom nanozymes (SAzymes) are nanomaterials that rely on atomic-level active sites to efficiently express catalytic functions like natural enzymes. With their outstanding robustness and exceptional atomic utilization, they are among the most competitive nanozymes used to overcome the inherent shortcomings of natural enzymes. However, SAzymes lack the precise structural complexity of natural enzymes and therefore do not exhibit the same level of catalytic selectivity-a major barrier to fully replacing natural enzymes. Previous studies have primarily focused on summarizing the methods and rules for improving the enzyme-like activity of SAzymes, while comparatively little attention has been given to their catalytic selectivity. Herein, this work reviews recent progress in enhancing the enzyme-like catalytic selectivity of SAzymes through the rational design of their spatial coordination structures. It emphasizes the structure-activity relationships of various attributes of these coordination structures in promoting selective catalytic behavior, the strategic design of coordination structures for target enzyme-like reactions, and effective synthesis methods for integrating these structures onto supports. In addition, the development prospects and current challenges in exploring SAzyme coordination structures are analyzed to provide new inspiration constructing next generation, highly selective SAzymes.