期刊
Environmental Science & Technology
标题
Single-Atom Fe-N4 Sites for Catalytic Ozonation to Selectively Induce a Nonradical Pathway toward Wastewater Purification
作者
Tengfei Ren, Mengxi Yin, Shuning Chen, Changpei Ouyang, Xia Huang, and Xiaoyuan Zhang
摘要
Nonradical oxidation has been determined to be a promising pathway for the degradation of organic pollutants in heterogeneous catalytic ozonation (HCO). However, the bottlenecks are the rational design of catalysts to selectively induce nonradicals and the interpretation of detailed nonradical generation mechanisms. Herein, we propose a new HCO process based on single-atom iron catalysts, in which Fe-N4 sites anchored on the carbon skeleton exhibited outstanding catalytic ozonation activity and stability for the degradation of oxalic acid (OA) and p-hydroxybenzoic acid (pHBA) as well as the advanced treatment of a landfill leachate secondary effluent. Unlike traditional radical oxidation, nonradical pathways based on surface-adsorbed atomic oxygen (*Oad) and singlet oxygen (1O2) were identified. A substrate-dependent behavior was also observed. OA was adsorbed on the catalyst surface and mainly degraded by *Oad, while pHBA was mostly removed by O3 and 1O2 in the bulk solution. Density functional theory calculations and molecular dynamics simulations revealed that one terminal oxygen atom of ozone preferred bonding with the central iron atom of Fe-N4, subsequently inducing the cleavage of the O–O bond near the catalyst surface to produce *Oad and 1O2. These findings highlight the structural design of an ozone catalyst and an atomic-level understanding of the nonradical HCO process.
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