文献类型：期刊文献

英文题名：Dual-active-site engineering of urea-based ionic polymer towards enhanced synergistic catalytic performance of carbon dioxide fixation

作者：Wan, Ya-Li Chen, Ying Wang, Hu Lei, Yi-Zhu Wen, Li-Li Zhong, Shenglai

第一作者：Wan, Ya-Li;万亚荔

通信作者：Lei, YZ[1];Wen, LL[2]

机构：[1]Liupanshui Normal Univ, Sch Chem & Mat Engn, Guizhou Prov Key Lab Coal Clean Utilizat, Liupanshui 553004, Guizhou, Peoples R China;[2]Guizhou Inst Technol, Sch Chem Engn, Guiyang 550025, Peoples R China;[3]Cent China Normal Univ, Coll Chem, Wuhan 430079, Peoples R China;[4]Nanjing Tech Univ, State Key Lab Mat Oriented Chem Engn, Nanjing 211816, Peoples R China

第一机构：Liupanshui Normal Univ, Sch Chem & Mat Engn, Guizhou Prov Key Lab Coal Clean Utilizat, Liupanshui 553004, Guizhou, Peoples R China

通信机构：corresponding author), Liupanshui Normal Univ, Sch Chem & Mat Engn, Guizhou Prov Key Lab Coal Clean Utilizat, Liupanshui 553004, Guizhou, Peoples R China;corresponding author), Cent China Normal Univ, Coll Chem, Wuhan 430079, Peoples R China.

年份：2025

卷号：366

外文期刊名：SEPARATION AND PURIFICATION TECHNOLOGY

收录：;EI(收录号：20251418165149);WOS:【SCI-EXPANDED(收录号:WOS:001460769700001)】；

基金：The National Natural Science Foundation of China (Grant Nos. 22162017 and 22171097) , the Foundation of Guizhou Institute of Technology (Grant No. 2024XSXM002) , the Natural Science Foundation of Guizhou Province (Grant No. Qiankehejichu-ZK [2024] zhong-dian090) , the Program for High-level Innovative Talents in Guizhou Province (Grant No. GCC [2023] 049) , the State Key Laboratory of Materials-Oriented Chemical Engineering (Grant No. KL-MCE-22B01) , the Natural Science Foundation of Liupanshui (Grant No. 52020-2023-0-2-9) , and the Foundation of Liupanshui Normal University (LPSSY2023KJZDPY01) , have kindly provided financial support for this research project.

语种：英文

外文关键词：Bifunctional catalyst; Dual-active sites; Synergistic catalysis; Carbon dioxide; Cyclic carbonate

摘要：Bifunctional catalysts featuring synergistic hydrogen-bond donor (HBD) and halogen anion nucleophile functionalities hold substantial promise for the catalytic conversion of carbon dioxide (CO2). However, the rational design of such solid catalysts at the molecular level is yet to be comprehensively elucidated. In this proof-of-concept study, we synthesized a series of porous ionic polymers (PIPs). These PIPs integrate urea groups and pyridinium bromide as cooperative moieties to promote the conversion of CO2 with epoxides. Through meticulous adjustment of the chemical structure of urea-based monomers, we were able to regulate the relative spatial positioning between neighboring urea and pyridinium salt units within the PIPs. Experimental results revealed that the spatial arrangement of these partners within PIPs not only influences the spatial distance between dual-active sites, but also affects the HBD ability of the urea groups, which subsequently impacts catalytic performance. The optimal catalyst, UPIP-1, distinguished by the placement of the urea group in the ortho-position of the pyridinium salts, showcased the highest HBD ability and the closest dual-active-site distance, resulting in the highest catalytic activity. Specifically, the activity of UPIP-1 was 2.1-fold higher than that of PIPs with the longest dual-site distance and 2.4-fold higher than that of PIPs lacking HBD functionalities. Moreover, UPIP-1 displayed exceptional catalytic performance, broad substrate tolerance, high stability, and recyclability under mild conditions. As a highly effective solid catalyst, UPIP-1 also efficiently catalyzed the cycloaddition reaction, achieving a remarkable yield of 94.3 % under simulated flue gas conditions (15 % CO2 and 85 % N2). This study elucidates the molecular-level correlation between spatial arrangement of cooperative sites and catalytic performance in urea-based bifunctional systems, thereby offering a valuable reference for the rational design of high-efficiency bifunctional catalysts for CO2 conversion.