Facilely Tuning the First-Shell Coordination Microenvironment in Iron Single-Atom for Fenton-like Chemistry toward Highly Efficient Wastewater Purification

Precisely identifying the atomic structures in single-atom sites and establishing authentic structure–activity relationships for single-atom catalyst (SAC) coordination are significant challenges. Here, theoretical calculations first predicted the underlying catalytic activity of Fe–N x C 4– x sites with diverse first-shell coordination environments. Substituting N with C to coordinate with the central Fe atom induces an inferior Fenton-like catalytic efficiency. Then, Fe-SACs carrying three configurations (Fe–N 2 C 2, Fe–N 3 C 1, and Fe–N 4 ) fabricate facilely and demonstrate that optimized coordination environments of Fe–N x C 4– x significantly promote the Fenton-like catalytic activity. Specifically, the reaction rate constant increases from 0.064 to 0.318 min –1 as the coordination number of Fe–N increases from 2 to 4, slightly influencing the nonradical reaction mechanism dominated by 1 O 2 . In-depth theoretical calculations unveil that the modulated coordination environments of Fe-SACs from Fe–N 2 C 2 to Fe–N 4 optimize the d-band electronic structures and regulate the binding strength of peroxymonosulfate on Fe–N x C 4– x sites, resulting in a reduced energy barrier and enhanced Fenton-like catalytic activity. The catalytic stability and the actual hospital sewage treatment capacity also showed strong coordination dependency. This strategy of local coordination engineering offers a vivid example of modulating SACs with well-regulated coordination environments, ultimately maximizing their catalytic efficiency.