School of Resources and Environmental Engineering, Hefei University of Technology, Hefei 230009, People's Republic of China; Key Laboratory on Nanominerals and Pollution Control of Higher Education Institutes, Hefei University of Technology, Hefei 230009, People's Republic of China.
CAS Key Laboratory of Urban Pollutant Conversion, Department of Environmental Science and Engineering, University of Science & Technology of China, Hefei 230026, People's Republic of China.
Sci Total Environ. 2022 Dec 1;850:158055. doi: 10.1016/j.scitotenv.2022.158055. Epub 2022 Aug 13.
Bimetallic catalysts are often used for peroxymonosulfate (PMS) activation in recent years due to the synergistic effects between two different metal species. However, the synergy between Zn and other transition metal in PMS activation are rarely studied because of the ease of evaporation of Zn species at high temperature. In this work, a Co/Zn co-doped carbonaceous catalyst derived from ZIF-67@ZIF-8 (Z67@8D) was prepared successfully by the core-shell replacement strategy, and used to activate PMS for sulfamethoxazole (SMX) degradation. Due to the co-existence of Co/Zn species (e.g., Co/Zn-N site), Z67@8D showed a much higher catalytic activity than that of Z8D, Z67D, and several commercial oxides. Importantly, the CoZn synergy was deeply revealed by combining experiments and density functional theory (DFT) calculations, in which Zn could adjust the electron distribution of Co, reducing the PMS adsorption energy and thus enhancing PMS decomposition and singlet oxygen (O) formation. Moreover, formed ZnO and graphitic structure of Z67@8D could also promote the catalytic activity. In addition, the good stability and reusability, universal applicability, and high environmental robustness of Z67@8D were demonstrated. Our findings may provide a new insight into the Zn-based bimetallic catalysts for PMS activation and pollutant degradation.
近年来,双金属催化剂由于两种不同金属物种之间的协同作用,常用于过一硫酸盐(PMS)的活化。然而,由于 Zn 物种在高温下易蒸发,因此很少研究 Zn 与 PMS 活化中的其他过渡金属之间的协同作用。在这项工作中,通过核壳取代策略成功制备了一种由 ZIF-67@ZIF-8(Z67@8D)衍生的 Co/Zn 共掺杂碳质催化剂,并用于活化 PMS 降解磺胺甲恶唑(SMX)。由于 Co/Zn 物种(例如,Co/Zn-N 位)的共存,Z67@8D 表现出比 Z8D、Z67D 和几种商业氧化物更高的催化活性。重要的是,通过实验和密度泛函理论(DFT)计算相结合,深入揭示了 CoZn 协同作用,其中 Zn 可以调整 Co 的电子分布,降低 PMS 的吸附能,从而增强 PMS 的分解和单线态氧(O)的形成。此外,Z67@8D 中形成的 ZnO 和石墨结构也可以促进催化活性。此外,还证明了 Z67@8D 具有良好的稳定性和可重复使用性、普遍适用性和高环境稳健性。我们的发现可能为基于 Zn 的双金属催化剂用于 PMS 活化和污染物降解提供新的见解。