Li He, Pan Hanqian, Li Yijian, Shang Shuaishuai, Huang Shihui, Cui Xili, Hu Jun, Liu Honglai
State Key Laboratory of Chemical Engineering, School of Chemistry and Molecular Engineering, East China University of Science and Technology 130 Meilong Road Shanghai 200237 China
Key Laboratory of Biomass Chemical Engineering of Ministry of Education, College of Chemical and Biological Engineering, Zhejiang University Hangzhou 310027 China
Chem Sci. 2023 Jul 17;14(31):8321-8326. doi: 10.1039/d3sc02622a. eCollection 2023 Aug 9.
A pain-point for material development is that computer-screened structures are usually difficult to realize in experiments. Herein, considering that linkages are crucial for building functional nanoporous polymers with diverse functionalities, we develop an efficient approach for constructing target-specific conjugated microporous polymers (CMPs) based on screening feasible polymerization pathways. Taking the deep removal of SO from a SO/CO mixture as the specific target, we precisely screen the linkages and fabricate different CMPs by manipulating the porosity and hydrophobicity. Based on the optimized Buchwald-Hartwig amination, the obtained CMPs can achieve SO/CO selectivity as high as 113 and a moderate of 30 kJ mol for feasible regeneration. Furthermore, the potential of CMPs for practical SO/CO separation is demonstrated through continued breakthrough tests. The SO binding sites are consistent with the screening results and proved by Fourier transform infrared spectroscopy and grand canonical Monte Carlo simulation, providing solid feasibility for synthesis realizability for future boosts of task-specific CMPs.
材料开发中的一个痛点是，通过计算机筛选的结构通常在实验中难以实现。在此，考虑到连接键对于构建具有多种功能的功能性纳米多孔聚合物至关重要，我们基于筛选可行的聚合途径，开发了一种构建目标特异性共轭微孔聚合物（CMP）的有效方法。以从SO/CO混合物中深度去除SO为特定目标，我们精确筛选连接键，并通过控制孔隙率和疏水性制备不同的CMP。基于优化的布赫瓦尔德-哈特维希胺化反应，所获得的CMP对SO/CO的选择性高达113，且再生能耗适中，为30 kJ/mol。此外，通过连续的突破测试证明了CMP在实际SO/CO分离中的潜力。SO结合位点与筛选结果一致，并通过傅里叶变换红外光谱和巨正则蒙特卡罗模拟得到证实，为未来特定任务CMP的合成可实现性提供了坚实的可行性依据。
