Catalytic activity and reaction mechanisms of single-atom metals anchored on nitrogen-doped carbons for peroxymonosulfate activation

Abstract

Single-atom catalysts have attracted tremendous interests in peroxymonosulfate (PMS)-based advanced oxidation processes due to their maximum atom utilization and high reactivity, however the role of nitrogen-coordinated metal (MNx) sites with different metal centers remain blurred. Herein, a series of single-atom metals anchored on nitrogen-doped carbons (denoted as M-N/C, M = Fe, Co, Cu, and Mn) using zeolitic imidazolate frameworks as precursors are constructed for PMS activation. Their catalytic activity order follows Fe > Co > undoped N/C > Cu > Mn, especially the degradation rates of the eight model pollutants for Fe-N/C and Co-N/C are 2.5–22.4 and 1.5–19.5 times higher than those for undoped N/C, respectively. Moreover, the nature of catalytic metal center can govern the degradation behaviors in the coexisting water constituents. Experimental and theoretical results reveal that singlet oxygen (1O2) is the main oxidant responsible for pollutant degradation and its evolution path over FeN4 or CoN4 sites (PMS→OH*→*O→1O2) is elucidated, between which FeN4 with lower energy barrier is more conducive to 1O2 generation. This study can not only provide guidance for the development of highly active atomic M-N/C catalysts, but also lead to a better molecular-level understanding of PMS activation mechanism over MN4 sites.