文献类型：期刊文献

英文题名：Sulfur Conversion to Donor-Acceptor Ladder Polymer Networks through Mechanochemical Nucleophilic Aromatic Substitution for Efficient CO2 Photoreduction

作者：Yang, Na[1];Zhou, Zi-Jian[3,4];Zhu, Xiang[1];Wu, Jiwei[1];Zhang, Yifan[5];Wang, Tao[6];Wu, Xin-Ping[3,4];Tian, Chengcheng[2];Jiang, Xia[1];Dai, Sheng[6]

机构：[1]Sichuan Univ, Sch Carbon Neutral Future Technol, Chengdu 610065, Peoples R China;[2]East China Univ Sci & Technol, Sch Resources & Environm Engn, Shanghai 200237, Peoples R China;[3]East China Univ Sci & Technol, Ctr Computat Chem, Sch Chem & Mol Engn, State Key Lab Green Chem Engn & Ind Catalysis, Shanghai 200237, Peoples R China;[4]East China Univ Sci & Technol, Res Inst Ind Catalysis, Sch Chem & Mol Engn, Shanghai 200237, Peoples R China;[5]Shanghai Univ, Sch Environm & Chem Engn, Shanghai 200444, Peoples R China;[6]Chem Sci Div, Oak Ridge Natl Lab, Oak Ridge, TN 37831 USA

年份：2025

卷号：64

期号：20

外文期刊名：ANGEWANDTE CHEMIE-INTERNATIONAL EDITION

收录：;EI(收录号：20250817892628);WOS:【SCI-EXPANDED(收录号:WOS:001420879900001)】；

基金：X.Z. thanks the financial support from "the Fundamental Research Funds for the Central Universities", Sichuan Science and Technology Program (2025YFHZ0177), and National Natural Science Foundation of China (22078349 and 22005319). C.T. was supported by Shanghai Science and Technology Innovation Plan (22DZ1208600), the Innovation Program of Shanghai Municipal Education Commission (2023ZKZD41), and National Natural Science Foundation of China (52170109). X.-P.W. appreciates the support from National Natural Science Foundation of China (52394271 and 52394273). Y.Z. thanks the support from National Natural Science Foundation of China (22302119). S.D. and T.W. were supported by the Division of Chemical Sciences, Geosciences, and Biosciences, Office of Basic Energy Sciences, US Department of Energy.

语种：英文

外文关键词：sulfur conversion; mechanochemical nucleophilic aromatic substitution; ladder polymer networks; CO2 photoreduction; donor-acceptor molecular junctions

摘要：The development of synthetic methods capable of converting elemental sulfur into conjugated porous sulfur-rich polymers remains a great challenge, although direct utilization of this readily available feedstock can significantly enrich its uses and circumvent environmental problems during sulfur storage. We report herein mechanochemical (MC) nucleophilic aromatic substitution (SNAr) that enables sulfur conversion into thianthrene-bridged porous ladder polymer networks with dense donor-acceptor (D-A) molecular junctions. We demonstrate that the key lies in the generation of bent thianthrene units through a solid-state ball-milling condensation reaction between 1,2-dihaloarenes and elemental sulfur. We also show that the assembling of D-A structural motifs into porous networks affords efficient visible-light-driven photocatalytic reduction of carbon dioxide (CO2) with water (H2O) vapor, in the absence of any additional photosensitizer, sacrificial agents or cocatalysts. Exceptional photoinduced charge separation along with boosted exciton dissociation results in a high-performance of carbon monoxide (CO) production rate of 306.1 mu mol g(-1) h(-1) with near 100 % CO selectivity, which is accompanied by H2O oxidation to O-2, as confirmed by both experimental and theoretical results. We anticipate this novel MC SNAr approach will advance processing techniques for direct sulfur utilization and facilitate new possibilities for the synthesis of D-A ladder polymer networks with promising potential in photocatalysis.