Directing the Structural Features of N<sub>2</sub>-Phobic Nanoporous Covalent Organic Polymers for CO<sub>2</sub>Capture and Separation
作者:Hasmukh A. Patel、Sang Hyun Je、Joonho Park、Yousung Jung、Ali Coskun、Cafer T. Yavuz
DOI:10.1002/chem.201303493
日期:2014.1.13
synthesized through a catalyst‐free direct coupling of aromatic nitro and amine compounds under basic conditions. The azo‐COPs formed 3D nanoporous networks and exhibited surface areas up to 729.6 m2 g−1, with a CO2‐uptake capacity as high as 2.55 mmol g−1 at 273 K and 1 bar. Azo‐COPs showed remarkable CO2/N2 selectivities (95.6–165.2) at 298 K and 1 bar. Unlike any other porous material, CO2/N2 selectivities
在碱性条件下,通过无催化剂的芳族硝基和胺化合物的直接偶联,合成了一系列偶氮桥键共价有机聚合物(azo-COPs)。偶氮-COPs形成3D纳米多孔网络,其表面积高达729.6 m 2 g -1,在273 K和1 bar下的CO 2吸收能力高达2.55 mmol g -1。Azo- COPs在298 K和1 bar下显示出显着的CO 2 / N 2选择性(95.6–165.2)。与其他任何多孔材料不同,偶氮-COPs的CO 2 / N 2选择性随温度升高而增加。发现偶氮-COPs对N 2的亲和力低于预期气体,因此使框架相对而言“ N 2恐惧的”。我们的理论模拟表明,这种异常行为的起源与N 2气体分子与偶氮基团相互作用时的更大熵损失有关。还证明了稠合芳环对偶氮-COPs中CO 2 / N 2选择性的影响。增大π表面积会增加框架的CO 2亲和性,从而使我们在323 K和1 bar下达到307.7的CO