Lu Sen, Li Xuechuan, Zhang Guan, Wang Shaobin
State Key Laboratory of Urban Water Resource and Environment, School of Ecology and Environment, Harbin Institute of Technology, Shenzhen (HITSZ), Shenzhen, 518055, China.
School of Chemical Engineering, The University of Adelaide, Adelaide, SA, 5005, Australia.
Nat Commun. 2025 May 10;16(1):4346. doi: 10.1038/s41467-025-59722-1.
Electro-oxidation is a promising green technology for decentralized wastewater purification. However, its efficacy is primarily constrained by the selectivity and efficiency of hydroxyl radical (•OH) generation through one-electron water oxidation. In this study, we elucidate the mechanism of electronic metal-support interactions (EMSI) of Ni single-atoms on antimony-doped tin oxide anode (Ni/ATO) to enhance •OH production and overall water treatment efficiency. We experimentally and theoretically investigate both the structural evolution process and micro-interface mechanisms associated with the EMSI effects induced by Ni single-atoms. The optimized electronic structures in the interfacial catalysts under EMSI conditions and the co-catalytic role of Ni single-atoms synergistically facilitate selective and efficient •OH generation, resulting in over a fivefold increase in its steady-state concentration and tenfold enhancement in pseudo-first-order rate constant of sulfamethoxazole degradation compared to those on bare ATO. With the EMSI, rapid electron transfer channels were established for a marked enhancement in the adsorption, conversion, and dissociation of interfacial HO molecules. Notably, it is revealed that Ni single-atoms serve as co-catalytic sites, exhibiting a "H-pulling effect" that is crucial for •OH generation. The Ni/ATO anode demonstrates great efficiency in degrading various refractory organic pollutants, and effectively treats real pharmaceutical wastewater with low energy consumption. Furthermore, it presents remarkable stability and adaptability, while maintaining a minimal environmental footprint during wastewater treatment processes. This work addresses the theoretical gaps between EMSI effects and co-catalysis in electro-oxidation systems, while providing a robust technological solution for wastewater purification.
电氧化是一种很有前景的用于分散式废水净化的绿色技术。然而，其功效主要受限于通过单电子水氧化产生羟基自由基（•OH）的选择性和效率。在本研究中，我们阐明了镍单原子在锑掺杂氧化锡阳极（Ni/ATO）上的电子金属-载体相互作用（EMSI）机制，以提高•OH的产生量和整体水处理效率。我们通过实验和理论研究了与镍单原子诱导的EMSI效应相关的结构演变过程和微界面机制。在EMSI条件下，界面催化剂中优化的电子结构以及镍单原子的共催化作用协同促进了选择性和高效的•OH生成，与裸ATO相比，其稳态浓度增加了五倍以上，磺胺甲恶唑降解的准一级速率常数提高了十倍。通过EMSI，建立了快速电子转移通道，显著增强了界面HO分子的吸附、转化和解离。值得注意的是，研究发现镍单原子作为共催化位点，表现出对•OH生成至关重要的“氢提取效应”。Ni/ATO阳极在降解各种难降解有机污染物方面表现出很高的效率，并且能以低能耗有效处理实际制药废水。此外，它还具有出色的稳定性和适应性，同时在废水处理过程中保持最小的环境足迹。这项工作填补了电氧化系统中EMSI效应和共催化之间的理论空白，同时为废水净化提供了一种强大的技术解决方案。
