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Updated: Aug 6, 2026

Controlled Photoredox Ring-Opening Polymerization of O-Carboxyanhydrides Mediated by Ni/Zn Complexes
Published on: November 21, 2017
Synergetic Relay of Phenoxyl-Radical-Mediated Oligomerization and Aromatic-Ring-Opening Processes for Organic
Xiaoru Huang1, Jiangzhi Zi1, Jiaxing Li1
1Institute of Photochemistry and Photofunctional Materials, School of Materials and Chemistry, University of Shanghai for Science and Technology, Shanghai, China.
Abstract:
Efficient removal of recalcitrant aromatic compounds in organic wastewater is hindered by ambiguous reaction pathways in conventional single-process polymerization or ring-opening mineralization. Herein, we report a synergistic relay strategy that integrates phenoxyl-radical-mediated oligomerization and aromatic-ring-opening pathways for the highly efficient treatment of organic wastewater. This approach couples an initial high-valence iron-oxo species (HVIO)-driven oligomerization via formal hydrogen atom transfer at one site with a subsequent singlet oxygen (1O2)-mediated ring-opening reaction at an adjacent site, enabled by a dual-single-atom Fe1Cu1/TiO2 photocatalyst. Under solar-light irradiation, photoinduced electrons are transferred to peroxymonosulfate (PMS) at the Fe1 site, which acts as a critical activator to generate HVIO for oligomerization-based removal. Simultaneously, holes oxidize PMS at the Cu1 site to produce 1O2, leading to efficient aromatic-ring-opening. This sequential strategy achieved nearly 72% chemical oxygen demand removal with 23% carbon recovery into separable polymer products within 10 min for the phenol and ultimately reached complete removal with a rate constant of 1.21 min-1, significantly surpassing most reported values. Moreover, the system exhibited excellent stability and long-term activity in a custom-designed photo-filter reactor, highlighting its practical potential. By coupling oligomerization and mineralization, this work provides a groundbreaking and versatile platform for treating complex organic wastewater.
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