Theory-guided unraveling of the mechanism underlying Cu1.0/Mn1.0-ZnO with dual reaction centers for enhanced peroxymonosulfate activation

• Published in: Environmental research Vol. 247; p. 118258
• Main Authors: Wang, Kaixuan, Li, Haibo, Qin, Xiaofei, Ma, Ting, Zhu, Lin, Zhang, Chenxi, Yu, Wei, Zhou, Xulun
• Format: Journal Article
• Language: English
• Published: Elsevier Inc 15.04.2024
• Subjects: Dual reaction centers; PMS activation; Rapid electron transfer; Theory-guided; Theory-guided; PMS activation; Dual reaction centers; Rapid electron transfer
• ISSN: 0013-9351; 1096-0953
• DOI: 10.1016/j.envres.2024.118258

Developing efficient catalytic systems for water contamination removal is a topic of great interest. However, the use of heterogeneous catalysts faces challenges due to insufficient active sites and electron cycling. In this study, results from first-principles calculations demonstrate that dual reaction centers (DRCs) are produced around the Cu and Mn sites in Cu1.0/Mn1.0-ZnO due to the electronegativity difference. Experimental results reveal the material with DRCs greatly enhances electron transfer efficiency and significantly impacts the oxidation and reduction of peroxymonosulfate (PMS). In addition, the self-consistent potential correction (SCPC) method was introduced to correct the energy and charge of charged periodic systems simulating a catalytic process, resulting in more precise catalytic results. Specifically, the material exhibits a preference for adsorbing negatively charged PMS anions at electron-deficient Mn sites, facilitating PMS oxidation for the generation of 1O2, and PMS reduction around the electron-rich Cu for the formation of •OH and SO4•−. The major reactive oxygen species is 1O2, showcasing effective performance in various degradation systems. Overall, our work provides novel insights into the persulfate-based heterogeneous catalytic oxidation process, paving the way for the development of high-performance catalytic systems for water purification. [Display omitted] •Cu1.0/Mn1.0-ZnO exhibits high electron transfer rate and multi-active sites.•Theoretical calculations revealed the catalytic reaction's microscopic mechanism.•The degradation pathway of Rh–B was unveiled and an assessment was made of its toxicity.•The energy and charge of the charged system were corrected using the SCPC method.