High-entropy alloys catalyzing polymeric transformation of water pollutants with remarkably improved electron utilization efficiency
Ziwei Yao, Yidi Chen, Xiaodan Wang, Kunsheng Hu, Shiying Ren, Jinqiang Zhang, Zhao Song, Nanqi Ren, Xiaoguang Duan
Abstract
High-entropy alloy nanoparticles (HEA-NPs) exhibit favorable properties in catalytic processes, as their multi-metallic sites ensure both high intrinsic activity and atomic efficiency. However, controlled synthesis of uniform multi-metallic ensembles at the atomic level remains challenging. This study successfully loads HEA-NPs onto a nitrogen-doped carbon carrier (HEAs) and pioneers the application in peroxymonosulfate (PMS) activation to drive Fenton-like oxidation. The HEAs-PMS system achieves ultrafast pollutant removal across a wide pH range with strong resistance to real-world water interferences. Furthermore, the nonradical HEAs-PMS system selectively transforms phenolics into high-molecular-weight products via a polymerization pathway. The unique non-mineralization regime remarkably reduces PMS consumption and achieves a high electron utilization efficiency of up to 213.4%. Further DFT calculations and experimental analysis reveal that Fe and Co in HEA-NPs act as the primary catalytic sites to complex with PMS for activation, while Ni, Cu, and Pd serve as charge mediators to facilitate electron transfer. The resulting PMS* complexes on HEAs possess a high redox potential, which drives spatially separated phenol oxidation on nitrogen-doped graphene support to form phenoxyl radicals, subsequently triggering the formation of high-molecule polymeric products via polymerization reactions. This study offers engineered HEAs catalysts for water treatment with low oxidant consumption and emissions.