Facile Tuning Non-radical/Radical Oxidation by Nitrogen Doping on Fe-S Doped Carbonaceous Catalysts for Peroxymonosulfate Activation

In this paper, iron-sulfur-nitrogen co-doped carbonaceous materials (Fe@SxNyC) was prepared by doping N during the preparation of iron-sulfur co-doped carbonaceous material (Fe@SC), which was used to activate PMS and effectively modulate the radical and non-radical oxidation pathways in the catalytic system to achieve efficient degradation of sulfamerazine (SMR). N doping introduced multiple N sites (graphitic N, pyridinic N and pyrrolic N) in the Fe@SxNyC while promoting the generation of thiophene sulfur of the pristine active sites. Meanwhile, N doping introduced more defects in Fe@S4NC and thus exhibited better catalytic activity than Fe@SC, promoting the decomposition of PMS with a maximum k value (0.1721 min-1). Notably, the involvement of nitrogen shifted the cooperative oxidation reaction from a non-radical (1O2) to a radical-dominated (SO4·–) oxidation pathway with more oxidative intensity, resulting in deeper mineralization of organic pollutants. Moreover, compared with Fe@SC/PMS system, the radical-dominated Fe@S4NC/PMS system had better cycling stability, and the efficiency of SMR degradation could still reach 85% after 4 cycles. The prepared Fe@S4NC catalytic ceramic membrane exhibited stable water flux and exceptional catalytic activity, demonstrating that Fe@S4NC had good potential for practical applications. This work elucidated the improvement of the catalytic mechanism of iron-carbon based materials by doping with various heteroatoms and provided a theoretical basis to design Fenton-like heterogeneous catalysts suitable for different water matrix.