Sun Qi, Jin Yingyin, Aguila Briana, Meng Xiangju, Ma Shengqian, Xiao Feng-Shou
Key Laboratory of Applied Chemistry of Zhejiang Province and Department of Chemistry, Zhejiang University, Hangzhou, Zhejiang, 310028, P.R. China.
Department of Chemistry, University of South Florida, 4202 E. Fowler Avenue, Tampa, Florida, 33620, United States.
ChemSusChem. 2017 Mar 22;10(6):1160-1165. doi: 10.1002/cssc.201601350. Epub 2016 Dec 15.
Direct use of atmospheric CO as a C source to synthesize high-value chemicals through environmentally benign processes is of great interest, yet challenging. Porous heterogeneous catalysts that are capable of simultaneously capturing and converting CO are promising candidates for such applications. Herein, a family of organic ionic polymers with nanoporous structure, large surface area, strong affinity for CO , and very high density of catalytic active sites (halide ions) was synthesized through the free-radical polymerization of vinylfunctionalized quaternary phosphonium salts. The resultant porous ionic polymers (PIPs) exhibit excellent activities in the cycloaddition of epoxides with atmospheric CO , outperforming the corresponding soluble phosphonium salt analogues and ranking among the highest of known metal-free catalytic systems. The high CO uptake capacity of the PIPs facilitates the enrichment of CO molecules around the catalytic centers, thereby benefiting its conversion. We have demonstrated for the first time that atmospheric CO can be directly converted to cyclic carbonates at room temperature using a heterogeneous catalytic system under metal-solvent free conditions. Moreover, the catalysts proved to be robust and fully recyclable, demonstrating promising potential for practical utilization for the chemical fixation of CO . Our work thereby paves a way to the advance of PIPs as a new type of platform for capture and conversion of CO .
通过环境友好的过程直接利用大气中的一氧化碳作为碳源来合成高价值化学品备受关注，但也具有挑战性。能够同时捕获和转化一氧化碳的多孔多相催化剂是此类应用的有前途的候选者。在此，通过乙烯基官能化季鏻盐的自由基聚合合成了一类具有纳米多孔结构、大表面积、对一氧化碳有强亲和力且催化活性位点（卤离子）密度非常高的有机离子聚合物。所得的多孔离子聚合物（PIPs）在环氧化物与大气中的一氧化碳的环加成反应中表现出优异的活性，优于相应的可溶性鏻盐类似物，并且在已知的无金属催化体系中名列前茅。PIPs对一氧化碳的高吸附容量促进了一氧化碳分子在催化中心周围的富集，从而有利于其转化。我们首次证明，在无金属溶剂条件下，使用多相催化体系可在室温下将大气中的一氧化碳直接转化为环状碳酸酯。此外，这些催化剂被证明具有稳健性且可完全回收，在一氧化碳化学固定的实际应用中显示出有前途的潜力。我们的工作从而为将PIPs发展成为一种新型的一氧化碳捕获和转化平台铺平了道路。
