Sun Pengliang, Zheng Xiong, Zhang Qingran, Wu Yang, Long Min, Wang Zhiwei, Zheng Guanghong, Chen Yinguang
State Key Laboratory of Water Pollution Control and Green Resource Recycling, School of Environmental Science and Engineering, Tongji University, 1239 Siping Road, Shanghai 200092, PR China; Department of Materials Science & Engineering, National University of Singapore, Singapore 117575, Singapore.
State Key Laboratory of Water Pollution Control and Green Resource Recycling, School of Environmental Science and Engineering, Tongji University, 1239 Siping Road, Shanghai 200092, PR China; Key Laboratory of Yangtze River Water Environment, School of Environmental Science and Engineering, Tongji University, Shanghai 200092, PR China; Shanghai Institute of Pollution Control and Ecological Security, Shanghai 200092, PR China.
Water Res. 2025 Dec 1;287(Pt B):124511. doi: 10.1016/j.watres.2025.124511. Epub 2025 Aug 29.
A precise modulation of heterogeneous catalysts in structural and surface properties promises the development of more sustainable advanced oxidation water purification technologies. However, the poor catalyst stability due to covering of surface-active sites by oxidation intermediates remains a key bottleneck to their practical applications. Herein we propose a simple defect-induced in-situ single-atom anchoring strategy to overcome this challenge by creating unique asymmetric active-sites on the catalyst surface. The single-atom-anchored asymmetric coordination sulfide (Ce-CoS) offers a highly active surface rich in sulfur vacancy defects, displaying excellent affinity for peroxymonosulfate (PMS) binding and charge transfer capabilities, along with a strong pollutant adsorption capacity, and initiates synergistic free radical and non-radical reactions, achieving nearly complete degradation of recalcitrant pollutants within 15 min, thereby alleviating the catalyst passivation by oxidation intermediate accumulation. Theoretical calculations unveil that the optimized configuration enhances the strength of the asymmetric Ce-S-Co sites by adjusting the E orbital, consequently reducing the energy barrier for the pivotal *O intermediate responsible for active oxygen species generation. This work provides a broader perspective for regulating the electronic structure of the single-sites at the atomic level and precisely designing efficient Fenton-like catalysts to alleviate water pollution dilemmas.
对多相催化剂的结构和表面性质进行精确调控，有望开发出更具可持续性的高级氧化水净化技术。然而，由于氧化中间体覆盖表面活性位点而导致的催化剂稳定性较差，仍然是其实际应用的关键瓶颈。在此，我们提出一种简单的缺陷诱导原位单原子锚定策略，通过在催化剂表面创建独特的不对称活性位点来克服这一挑战。单原子锚定的不对称配位硫化物（Ce-CoS）提供了一个富含硫空位缺陷的高活性表面，对过一硫酸盐（PMS）结合和电荷转移能力表现出优异的亲和力，同时具有很强的污染物吸附能力，并引发协同自由基和非自由基反应，在15分钟内实现难降解污染物的几乎完全降解，从而减轻氧化中间体积累导致的催化剂钝化。理论计算表明，优化后的构型通过调整E轨道增强了不对称Ce-S-Co位点的强度，从而降低了负责活性氧物种生成的关键*O中间体的能垒。这项工作为在原子水平上调控单位点的电子结构和精确设计高效类芬顿催化剂以缓解水污染困境提供了更广阔的视角。
