“P‐Strengthening Strategy” of Nickel Single‐Atom Catalyst With Boosting Selective Generation of Nonradicals: Synergy of Metal Center and Substrate

Abstract Single‐atom catalysts (SACs) with atomically dispersed metal centers exhibit unparalleled atomic utilization efficiency in Fenton‐like Avenue. However, current strategies lack precise control over the introduction of active dopants to tailor the coordination environment (CE) of active sites, significantly restricting catalytic performance. Herein, to overcome the limited intrinsic activity of M‐N 4 ‐configured of SACs with symmetrically distributed charge on metal sites, “electron‐rich phosphorus (P)‐doping strategy” is conducted to modulate the second‐shell CE of Ni active center (Ni‐NCP 2 ), achieving ultra‐high Fenton‐like performance (over 98% tetracycline removal efficiency within 10 min). The phosphorus dopants, acting as nonmetallic coordination sites, not only enhance pollutant adsorption but also serve as PMS activation accelerators, circumventing the requirement for interfacial electron transfer between the catalyst and PMS. In situ characterizations and Density functional theory (DFT) calculations elucidates two key enhancement mechanisms: i) significantly improved PMS adsorption (adsorption energy: −3.42 eV of Ni‐N 4 P versus −1.89 eV of Ni‐N 4 ), and ii) reduced energy barriers for * O intermediates dimerization into adsorbed 1 O 2 (0.32 eV of Ni‐N 4 P versus 0.91 eV of Ni‐N 4 ). This work establishes an atomic‐level coordination engineering framework for SACs, enabling superior Fenton‐like activity with selective non‐radical pathway dominance, thereby advancing rational design principles for next‐generation environmental catalysts.