Tang Xin, Ding Huiwei, Han Qiaofeng, Zhou Guolang, Ma Rongyao, Xue Zhipeng, Yan Shuolei, Zhang Lili, Yin Jingzhou, Ang Edison Huixiang
Key Laboratory for Soft Chemistry and Functional Materials of Ministry of Education, Nanjing University of Science and Technology, Nanjing 210094, China.
Jiangsu Key Laboratory for Chemistry of Low-Dimensional Materials, School of Chemistry and Chemical Engineering, Huaiyin Normal University, Huai'an 223001, China.
Mater Horiz. 2025 Jul 25. doi: 10.1039/d5mh01099c.
The efficiency of peroxymonosulfate (PMS) activation in advanced oxidation processes is often hindered by weak electronic interactions between the active sites and PMS molecules. To address this challenge, this study presents the synthesis of Fe-doped CeNiO (Fe-CNO) using a combined approach of Fe doping and a metal-organic framework (MOF)-derived strategy. The core innovation involves the introduction of Fe to induce electron-deficient B-site engineering, which strategically reconstructs the electronic structure of the original Ni sites, converting them into highly active, electron-deficient centers. Both experimental and theoretical investigations confirm that these modified centers exhibit reduced electron cloud density, thereby significantly strengthening their interaction with PMS. This enhancement facilitates an optimized electron transfer pathway, lowers the activation energy barrier for O-O bond cleavage, and promotes the generation of diverse reactive oxygen species (ROS). Concurrently, the MOF-derived architecture imparts a high specific surface area to Fe-CNO, and the increased density of active sites synergistically accelerates PMS activation. Fe-CNO achieved a TC degradation efficiency exceeding 90% within 60 minutes PMS activation, nearly three times higher than that of pristine CeNiO. Furthermore, it exhibited minimal metal leaching (<0.07 mg L), excellent pH tolerance (pH = 4-12), and strong cycling stability. This work provides an effective approach for designing novel, stable, and environmentally friendly catalysts and offers valuable insights into the use of CeNiO-based perovskites in AOPs.
过一硫酸盐（PMS）在高级氧化过程中的活化效率常常受到活性位点与PMS分子之间弱电子相互作用的阻碍。为应对这一挑战，本研究采用铁掺杂和金属有机框架（MOF）衍生策略相结合的方法合成了铁掺杂的CeNiO（Fe-CNO）。核心创新在于引入铁以诱导缺电子B位工程，该工程策略性地重构了原始镍位点的电子结构，将其转化为高活性的缺电子中心。实验和理论研究均证实，这些改性中心的电子云密度降低，从而显著增强了它们与PMS的相互作用。这种增强促进了优化的电子转移途径，降低了O-O键断裂的活化能垒，并促进了多种活性氧（ROS）的生成。同时，MOF衍生结构赋予Fe-CNO高比表面积，活性位点密度的增加协同加速了PMS的活化。Fe-CNO在PMS活化60分钟内实现了超过90%的TC降解效率，几乎是原始CeNiO的三倍。此外，它表现出极低的金属浸出（<0.07 mg L）、优异的pH耐受性（pH = 4-12）和强大的循环稳定性。这项工作为设计新型、稳定且环境友好的催化剂提供了一种有效方法，并为基于CeNiO的钙钛矿在AOPs中的应用提供了有价值的见解。
