Single-atom Fe-N4 sites on crumpled N-C-MoS2 nanospheres for peroxymonosulfate activation and FeIV=O generation

作者：Yu Yin, Wenning Li, Xuan Li, Yantao Wang, Qinxin Wang, Abdul Hannan Asif, Sheng Cui, Xiaoguang Duan, Shaobin Wang, Hongqi Sun · 发表于：Chemical Engineering Journal · 年份：2025 · DOI：10.1016/j.cej.2025.165664 · 被引用次数：9 · 研究领域：Advanced oxidation water treatment、Advanced Photocatalysis Techniques、Catalytic Processes in Materials Science

Efficient heterogeneous iron-based catalysts have demonstrated great potential for advanced oxidation processes (AOPs). In this study, enhancement of peroxymonosulfate (PMS)-based pollutant elimination was achieved through two approaches: maximizing exposed Fe sites and producing high-valent iron-oxo (Fe IV =O) species. To this end, crumpled nanospheres of molybdenum disulfide ( cn MoS 2 ) were fabricated, followed by the coating of nitrogen/carbon species to accommodate single-atom Fe N 4 sites. The resulting catalysts of Fe-N-C- cn MoS 2 were employed for degradation of 2,4,6-trichlorophenol (TCP) and other pollutants via PMS activation. The optimum 0.7Fe-N-C- cn MoS 2 /PMS system achieved 100 % TCP removal within only 5 min, along with good resistance to environmental disturbances. The Fe N 4 single sites and cn MoS 2 substrate worked synergistically for efficient catalysis, with the former playing a predominant role. Classical quenching and EPR experiments demonstrated that reactive radicals of • OH, SO 4 • − and O 2 • − were generated in the 0.7Fe-N-C- cn MoS 2 /PMS system. However, these were not the key driving forces in the decontamination processes. Further exploration demonstrated that the dominant reactive species for TCP degradation were Fe IV O, rather than traditionally recognized radicals. DFT calculations revealed that Fe-N 4 -C and MoS 2 in the catalyst cooperatively expedited the PMS adsorption and binding, thus facilitated the Fe IV O generation.