Zhou Lu-Lu, Xu Hengyue, Sheng Yi-Han, Wang Wei-Kang, Xu Juan
Shanghai Organic Solid Wastes Biotransformation Engineering Technical Research Center, Shanghai Key Lab for Urban Ecological Processes and Eco-Restoration, School of Ecological and Environmental Sciences, East China Normal University, Shanghai 200241, China.
Department of Chemistry, Tsinghua University, Beijing 100084, China.
J Hazard Mater. 2025 Mar 5;485:136826. doi: 10.1016/j.jhazmat.2024.136826. Epub 2024 Dec 12.
Persulfates-based advanced oxidation processes are highly efficient in degrading refractory organic contaminants in wastewater. However, their practical application is often limited by the extensive consumption of catalysts and oxidants. Therefore, constructing catalysts with abundant and efficient reaction interfaces is essential for improving the efficiency of persulfate activation. In this work, we develop a novel MnCoO spinel with highly exposed surface active sites by etching Mn-based precursors with Co ions. This process forms sufficient interface Co-O-Mn bonds, which effectively activate peroxymonosulfate (PMS) for bisphenol A (BPA) degradation. A clear structure-activity relationship is observed between the Co/Mn content ratio and the BPA degradation rate in the MnCoO/PMS system. Notably, MnCoO demonstrates superior PMS activation efficiency, achieving 100 % degradation of 10 mg/L BPA within 2 minutes with 0.05 g/L catalyst and 0.05 g/L persulfate usage. Experimental analyses combined with theoretical calculations identify the interface Co-O-Mn as the active site, which plays a crucial role in accelerating PMS molecule adsorption and O-O bond activation. Additionally, the spatially adjacent Co-O-Mn sites promote redox cycling for efficient interface electron transfer during the PMS activation process. Furthermore, Zebrafish toxicity studies revealed a considerable reduction in the toxicity of the BPA treatment residue in the MnCoO/PMS system. Overall, this work presents a novel strategy for constructing spatially adjacent redox sites in dual-metal spinel materials, offering valuable insights into reducing chemical input and advancing persulfate-based environmental remediation technology.
基于过硫酸盐的高级氧化工艺在降解废水中的难降解有机污染物方面具有很高的效率。然而,它们的实际应用常常受到催化剂和氧化剂大量消耗的限制。因此,构建具有丰富且高效反应界面的催化剂对于提高过硫酸盐活化效率至关重要。在这项工作中,我们通过用钴离子蚀刻锰基前驱体来开发一种具有高度暴露表面活性位点的新型锰钴尖晶石。这个过程形成了足够的界面Co-O-Mn键,有效地活化过一硫酸盐(PMS)以降解双酚A(BPA)。在MnCoO/PMS体系中,观察到Co/Mn含量比与BPA降解速率之间存在明确的构效关系。值得注意的是,MnCoO表现出卓越的PMS活化效率,在使用0.05 g/L催化剂和0.05 g/L过硫酸盐的情况下,能在2分钟内实现10 mg/L BPA的100%降解。结合理论计算的实验分析确定界面Co-O-Mn为活性位点,其在加速PMS分子吸附和O-O键活化方面起着关键作用。此外,空间相邻的Co-O-Mn位点促进氧化还原循环,以便在PMS活化过程中进行高效的界面电子转移。此外,斑马鱼毒性研究表明,MnCoO/PMS体系中BPA处理残余物的毒性显著降低。总体而言,这项工作提出了一种在双金属尖晶石材料中构建空间相邻氧化还原位点的新策略,为减少化学投入和推进基于过硫酸盐的环境修复技术提供了有价值的见解。