Dual action of non-metal doped C2N and Ti3C2T2 heterojunction enhances the catalytic activity of electrochemical simultaneous oxidation of hydrogen peroxide and peroxymonosulfate:A theoretical study

Yuxin Zhou; Yanru Huo; Yuhui Ma; Nuan Wen; Qingyuan Gu; Maoxia He

doi:10.1016/j.envres.2024.120698

Dual action of non-metal doped C₂N and Ti₃C₂T₂ heterojunction enhances the catalytic activity of electrochemical simultaneous oxidation of hydrogen peroxide and peroxymonosulfate:A theoretical study

Environ Res. 2024 Dec 24:267:120698. doi: 10.1016/j.envres.2024.120698. Online ahead of print.

Authors

Yuxin Zhou¹, Yanru Huo¹, Yuhui Ma¹, Nuan Wen¹, Qingyuan Gu¹, Maoxia He²

Affiliations

¹ Environment Research Institute, Shandong University, Qingdao, 266237, PR China.
² Environment Research Institute, Shandong University, Qingdao, 266237, PR China; School of Mining and Petroleum Engineering, Department of Civil and Environmental Engineering, University of Alberta, Edmonton, AB, T6G 1H9, Canada. Electronic address: hemaox@sdu.edu.cn.

PMID: 39725136
DOI: 10.1016/j.envres.2024.120698

Abstract

Electrochemical advanced oxidation processes (EAOPs) are energy-efficient methods for generating activated radicals like HO^• and SO₄^•-, which enable the degradation of difficult-to-mineralize chlorinated organic compounds. This study explored the catalytic activity and reaction mechanism of EAOPs under a dual strategy involving non-metal doped C₂N (X@C₂N (X = O, F, Si)) and a heterostructured build (X@C₂N/Ti₃C₂T₂) using first principles calculation. The non-metal doping and the heterojunction construction can make H₂O₂ and PMS spontaneously adsorb (E_ads < 0), with negative Gibbs free energy for their oxidation to HO^• and SO₄^•-, significantly enhancing catalytic activity. The catalytic activity of the X@C₂N catalysts was in the order of O@, F@, and Si@C₂N. The loading of Ti₃C₂T₂ improved the stability and activity of the material, while Ti₃C₂F₂ and Ti₃C₂O₂ proved superior as heterojunction carriers compared to Ti₃C₂(OH)₂. Notably, O@C₂N/Ti₃C₂F₂ is proved to be an appropriate catalyst for simultaneous hydrogen peroxide (ΔG_max = -0.90 eV) and peroxymonosulfate (ΔG_max = -0.99 eV) oxidation reactions, achieving non-selective generation of oxidants in electrochemistry. 2,4-D can be effectively degraded by surface-generated HO^• and SO₄^•-, with the reactivity of SO₄^•- towards 2,4-D greater than that of HO^•. This research highlights the potential of combining heteroatom doping with heterojunction catalyst formation to enhance EAOPs for environmental remediation.

Keywords: Electrochemical; First principles calculations; Hydrogen peroxide and peroxymonosulfate oxidation reaction; Non-metal doped C(2)N; Ti(3)C(2)T(2) MXene.