The “4 + 1” strategy fabrication of iron single-atom catalysts with selective high-valent iron-oxo species generation

Single-atom catalysts (SACs) with atomic dispersion active sites have exhibited huge potentials in peroxymonosulfate (PMS)-based Fenton-like chemistry in water purification. However, four-N coordination metal (MN ₄ ) moieties often suffer from such problems as low selectivity and narrow workable pH. How to construct SACs in a controllable strategy with optimized electronic structures is of great challenge. Herein, an innovative strategy (i.e., the “4 + 1” fabrication) was devised to precisely modulate the first-shell coordinated microenvironment of FeN ₄ SAC using an additional N (SA-FeN ₅ ). This leads to almost 100% selective formation of high-valent iron-oxo [Fe(IV)═O] (steady-state concentration: 2.00 × 10 ⁻⁸ M) in the SA-FeN ₅ /PMS system. In-depth theoretical calculations unveil that FeN ₅ configuration optimizes the electron distribution of monatomic Fe sites, which thus fosters PMS adsorption and reduces the energy barrier for Fe(IV)═O generation. SA-FeN ₅ was then attached to polyvinylidene difluoride membrane for a continuous flow device, showing long-term abatement of the microcontaminant. This work furnishes a general strategy for effective PMS activation and selective high-valent metal-oxo species generation by high N-coordination number regulation in SACs, which would provide guidance in the rational design of superior environmental catalysts for water purification.