Ma Lei, Jin Chu-Jia, Niu Huai-Yuan, Dong Zheng-Tao, Sui Long, Wu Qian, Peng Yan-Rong, Wang Jia-Jia, Niu Cheng-Gang
College of Environmental Science and Engineering, Key Laboratory of Environmental Biology and Pollution Control, Ministry of Education, Hunan University, Changsha 410082, China.
State Key Laboratory of Chemo/Biosensing and Chemometrics, College of Chemistry and Chemical Engineering, Hunan University, Changsha 410082, China.
J Hazard Mater. 2025 Aug 15;494:138615. doi: 10.1016/j.jhazmat.2025.138615. Epub 2025 May 18.
Ruddlesden-Popper (R-P) perovskites have emerged as superior candidates for peroxymonosulfate-based advanced oxidation processes (PMS-AOPs) due to their tunable electronic configurations and enhanced electron transfer kinetics. Although metal doping has been extensively studied as the most common catalyst modification strategy in PMS activation processes, systematic identification of the dominant metal species in doped systems remains lacked. In this work, copper-doped R-P perovskite (LaSrNiCuO, LSNC) was employed to investigate the influence of B-site ion electronic environment evolution on reactive oxygen species (ROS) generation during PMS activation, with the dominant metal species being determined through combined density functional theory (DFT) calculations and characterization. LSNC demonstrated exceptional activation performance, achieving 94 % levofloxacin (LVFX) removal within 30 min (k = 0.0853 min), significantly surpassing undoped LaSrNiO (LSNO). Cu doping induced anisotropic lattice strain through synergistic Jahn-Teller distortion and B-site dual-metal redox cycling, thereby enhancing oxygen vacancies (OVs) density and enabling dual radical (•OH/•O⁻) and non-radical (O/electron transfer process (ETP)) pathways. DFT calculations revealed that Cumediated downshift of Ni 3d band center (-0.266 eV) optimized PMS adsorption energy (-4.218 eV), confirming Ni's predominant role in this system. LC-MS/DFT analyses identified piperazine cleavage and quinolone oxidation as primary LVFX degradation pathways, with toxicity reduction verified by T.E.S.T. This work provides guidance for designing robust perovskite catalysts in advanced water remediation applications.
由于其可调的电子构型和增强的电子转移动力学，Ruddlesden-Popper（R-P）钙钛矿已成为基于过一硫酸盐的高级氧化过程（PMS-AOPs）的优质候选材料。尽管金属掺杂作为PMS活化过程中最常见的催化剂改性策略已得到广泛研究，但在掺杂体系中仍缺乏对主要金属物种的系统鉴定。在这项工作中，采用铜掺杂的R-P钙钛矿（LaSrNiCuO，LSNC）来研究B位离子电子环境演变对PMS活化过程中活性氧（ROS）生成的影响，并通过结合密度泛函理论（DFT）计算和表征来确定主要金属物种。LSNC表现出优异的活化性能，在30分钟内实现了94%的左氧氟沙星（LVFX）去除率（k = 0.0853 min），显著超过未掺杂的LaSrNiO（LSNO）。铜掺杂通过协同的 Jahn-Teller 畸变和 B 位双金属氧化还原循环诱导各向异性晶格应变，从而提高氧空位（OVs）密度，并实现双自由基（•OH/•O⁻）和非自由基（O/电子转移过程（ETP））途径。DFT计算表明，Cu介导的Ni 3d带中心下移（-0.266 eV）优化了PMS吸附能（-4.218 eV），证实了Ni在该体系中的主导作用。LC-MS/DFT分析确定哌嗪裂解和喹诺酮氧化为LVFX的主要降解途径，毒性降低通过T.E.S.T.验证。这项工作为在先进的水修复应用中设计稳健的钙钛矿催化剂提供了指导。
