Single-Atom Fe-N₄ Sites for Catalytic Ozonation to Selectively Induce a Nonradical Pathway toward Wastewater Purification

Citations Over TimeTop 1% of 2023 papers

Abstract

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 (*O_ad) and singlet oxygen (1O₂) were identified. A substrate-dependent behavior was also observed. OA was adsorbed on the catalyst surface and mainly degraded by *O_ad, 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 *O_ad and 1O₂. These findings highlight the structural design of an ozone catalyst and an atomic-level understanding of the nonradical HCO process.

Related Papers

• → Photodegradation of salicylic acid in aquatic environment: Effect of different forms of nitrogen(2012)29 cited
• → Photodegradation Des Pesticides a L'Etat Adsorbe: Photodegradation du Phenmediphame Photodegradation of Pesticides on Adsorbed Phases: Photodegradation of Phenmedipham(1995)4 cited
• → Photodegradation Des Pesticides a L'Etat Adsorbe: Photodegradation du Phenmediphame Photodegradation of Pesticides on Adsorbed Phases: Photodegradation of Phenmedipham(1995)1 cited
• The Photodegradation of Phenanthrene on Soil Surface Under UV Light(2009)
• Fe(III)-catalyzed ozonization of oxalic acid.(2004)