Regulating electronic structure of Fe single-atom site by S/N dual-coordination for efficient Fenton-like catalysis

The activity of single-atom catalysts in peroxymonosulfate activation process is bound up with the local electronic state of metal center. However, the large electronegativity of N atoms in Metal-N4 restricts the electron transfer between center metal atom and peroxymonosulfate. Herein, we constructed Fe-SN-C catalyst by incorporating S atom in the first coordination sphere of Fe single-atom site (Fe-S1N3) for Fenton-like catalysis. The Fe-SN-C with a low valent Fe is found to exhibit excellent catalytic activity for bisphenol A degradation, and the corresponding rate constant reaches 0.405 min−1, 11.9-fold higher than the original Fe-N-C. Besides, the Fe-SN-C/PMS system exhibits ideal catalytic stability under the effect of wide pH range and background substrates by the fast generation of high-valent Fe species. Experimental results and theoretical calculations reveal that the dual coordination of S and N atoms notably increases the local electron density of Fe atoms and electron filling in eg orbital, causing a d band center shifting close to the fermi level and thereby optimizes the activation energy for peroxymonosulfate decomposition via Fe 3d-O 2p orbital interaction. This work provides further development of promising SACs for the efficient activation of peroxymonosulfate based on direct regulation of the coordination environment of active center metal atoms. [Display omitted] •S/N dual-coordinated Fe-S1N3 site increases the local electron density on Fe atoms.•The Fe-S1N3 site with d band center close to the fermi level optimizes catalytic energy.•Fe-S1N3-C enhanced BPA degradation kinetic by 11.9-fold as compared to Fe-N4-C.•Stable catalytic activity of Fe-S1N3-C/PMS system in the change of pH and substrate.