Tailoring d-band center of high-valent metal-oxo species for pollutant removal via complete polymerization

• Published in: Nature communications Vol. 15; no. 1; pp. 2327 - 11
• Main Authors: Liu, Hong-Zhi, Shu, Xiao-Xuan, Huang, Mingjie, Wu, Bing-Bing, Chen, Jie-Jie, Wang, Xi-Sheng, Li, Hui-Lin, Yu, Han-Qing
• Format: Journal Article
• Language: English
• Published: London Nature Publishing Group UK 14.03.2024; Nature Publishing Group; Nature Portfolio
• Subjects: 119/118; 140/133; 140/146; 147/135; 147/143; 639/638/169/896; 639/638/77/885; Copper; Humanities and Social Sciences; Metals; multidisciplinary; Oxidation; Pollutant removal; Pollutants; Polymerization; Resource recovery; Science; Science (multidisciplinary); Water purification
• ISSN: 2041-1723; 2041-1723
• DOI: 10.1038/s41467-024-46739-1

Polymerization-driven removal of pollutants in advanced oxidation processes (AOPs) offers a sustainable way for the simultaneous achievement of contamination abatement and resource recovery, supporting a low-carbon water purification approach. However, regulating such a process remains a great challenge due to the insufficient microscopic understanding of electronic structure-dependent reaction mechanisms. Herein, this work probes the origin of catalytic pollutant polymerization using a series of transition metal (Cu, Ni, Co, and Fe) single-atom catalysts and identifies the d -band center of active site as the key driver for polymerization transfer of pollutants. The high-valent metal-oxo species, produced via peroxymonosulfate activation, are found to trigger the pollutant removal via polymerization transfer. Phenoxyl radicals, identified by the innovative spin-trapping and quenching approaches, act as the key intermediate in the polymerization reactions. More importantly, the oxidation capacity of high-valent metal-oxo species can be facilely tuned by regulating their binding strength for peroxymonosulfate through d -band center modulation. A 100% polymerization transfer ratio is achieved by lowering the d -band center. This work presents a paradigm to dynamically modulate the electronic structure of high-valent metal-oxo species and optimize pollutant removal from wastewater via polymerization. Polymerization-driven removal of pollutants in advanced oxidation processes (AOPs) allows for sustainable contamination abatement and resource recovery. Here, authors achieved pollutant removal via complete polymerization by tailoring d -band center of high-valent metal-oxo species.