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Asymmetric Fe-N3C coordination in Fe single-atom sites boosts electrochemical activation of H2O2 for efficient •OH
Shiyan Sun1, Peike Cao1, Shuo Chen1
1Key Laboratory of Industrial Ecology and Environmental Engineering (Ministry of Education, China), School of Environmental Science and Technology, Dalian University of Technology, Dalian, 116024, , PR China.
Abstract:
Heterogeneous electro-Fenton process enables efficient mineralization of organic contaminants by highly oxidative hydroxyl radicals (•OH) generated from electrochemical activation of H2O2 (EAH). Compared with iron nanoparticles, single-atom catalysts (SACs) with isolated Fe-N4 sites offer higher metal utilization, improved structural stability, and enhanced catalytic performance in the EAH process. However, symmetric Fe-N4 sites exhibit suboptimal intermediate adsorption, which limits further enhancement of •OH generation. Herein, atomically dispersed asymmetric Fe-N3C sites were engineered on carbon nanoflowers (FeN3C@CNFs), which exhibit higher •OH generation and more efficient contaminant removal than carbon nanoflowers featuring Fe-N4 sites. Density functional theory (DFT) calculations revealed that the asymmetric Fe-N3C coordination facilitates H2O2 adsorption and O-O bond cleavage, thereby lowering the energy barrier for •OH formation. The FeN3C@CNFs-catalyzed system exhibited effective treatment performance toward actual pharmaceutical wastewater, reducing TOC from 94.0 to 34.1 mg L-1 and COD from 265.9 to 81.3 mg L-1, meeting the discharge standard of water pollutants for pharmaceutical industry chemical synthesis products category (GB 21,904-2008, China) and further confirming the pivotal role of •OH-driven oxidation. This work highlights the critical role of atomic coordination in boosting •OH electro-generation for wastewater treatment.
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