Wang Yaobin, Li Dong, Ge Xinlei, Yu Jianghua, Zhao Yunxia, Bu Yunfei
Jiangsu Collaborative Innovation Center of Atmospheric Environment and Equipment Technology (CICAEET), Jiangsu Key Laboratory of Atmospheric Environment Monitoring and Pollution Control (AEMPC), UNIST-NUIST Energy and Environment Jointed Lab, (UNNU), School of Environmental Science and Technology, Nanjing University of Information Science and Technology (NUIST), 219 Ningliu, Nanjing, 210044, P. R. China.
Adv Mater. 2024 Jul;36(27):e2402935. doi: 10.1002/adma.202402935. Epub 2024 Apr 23.
In the Fenton-like reaction, revealing the dynamic evolution of the active sites is crucial to achieve the activity improvement and stability of the catalyst. This study reports a perovskite oxide in which atomic (Co) in situ embedded exsolution occurs during the high-temperature phase transition. This unique anchoring strategy significantly improves the Co/Co cycling efficiency at the interface and inhibits metal leaching during peroxymonosulfate (PMS) activation. The Co@L-PBMC catalyst exhibits superior PMS activation ability and could achieve 99% degradation of tetracycline within 5 min. The combination of experimental characterization and density functional theory (DFT) calculations elucidates that the electron-deficient oxygen vacancy accepts an electron from the Co 3d-orbital, resulting in a significant electron delocalization of the Co site, thereby facilitating the adsorption of the *HSO/*OH intermediate onto the "metal-V bridge" structure. This work provides insights into the PMS activation mechanism at the atomic level, which will guide the rational design of next-generation catalysts for environmental remediation.
在类芬顿反应中,揭示活性位点的动态演变对于实现催化剂的活性提升和稳定性至关重要。本研究报道了一种钙钛矿氧化物,其中在高温相变过程中会发生原子(Co)的原位析出。这种独特的锚定策略显著提高了界面处Co/Co的循环效率,并抑制了过一硫酸盐(PMS)活化过程中的金属浸出。Co@L-PBMC催化剂表现出优异的PMS活化能力,能够在5分钟内实现99%的四环素降解。实验表征与密度泛函理论(DFT)计算相结合表明,缺电子的氧空位从Co 3d轨道接受一个电子,导致Co位点发生显著的电子离域,从而促进*HSO/*OH中间体吸附到“金属-空位桥”结构上。这项工作在原子水平上深入了解了PMS活化机制,将指导下一代环境修复催化剂的合理设计。