Pillar[5]arene Based Conjugated Microporous Polymers for Propane/Methane Separation through Host–Guest Complexation

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• 作者：Siddulu Naidu Talapaneni ; Daeok Kim ; Gokhan Barin ; Onur Buyukcakir ; Sang Hyun Je ; Ali Coskun
• 刊名：Chemistry of Materials
• 出版年：2016
• 出版时间：June 28, 2016
• 年：2016
• 卷：28
• 期：12
• 页码：4460-4466
• 全文大小：464K
• 年卷期：0
• ISSN：1520-5002

文摘

We present an efficient strategy for the preparation of conjugated microporous polymers incorporating pillar[5]arenes (P5-CMPs) with surface areas up to 400 m² g^–1 via Pd-catalyzed Sonogashira–Hagihara cross-coupling reaction of triflate functionalized pillar[5]arene with 1,4-diethynylbenzene and 4,4′-diethynyl-1,1′-biphenyl linkers. In an effort to transfer intrinsic properties of pillar[5]arene, that is its ability to form strong host–guest complexes with linear hydrocarbons in solution, into the solid-state, we investigated the affinity of P5-CMPs toward propane gas. Unlike previously reported porous solids, which showed isosteric heats of adsorption (Q_st) for propane in the range of 32.9–36.9 kJ mol^–1 at zero coverage and increasing Q_st with rising loading due to intermolecular interactions between propane molecules, we observed very high Q_st values up to 53 kJ mol^–1 at zero coverage, which gradually decreased to ∼35 kJ mol^–1 with increasing loadings. This observation indicates strong supramolecular host–guest complexation between propane and pillar[5]arene via multiple C–H/π interactions, i.e., “macrocyclic effect” arising from the ideal size match of kinetic diameter of propane to the cavity of pillar[5]arene. This approach also allowed us to introduce thermodynamic selectivity for the separation of saturated hydrocarbons with low polarizability. High affinity of P5-CMPs for propane facilitated its efficient breakthrough separation from a simulated natural gas mixture (methane:propane, 9:1) at 298 K.