Pore Network Percolation in Polymers of Intrinsic Microporosity Examined by Gaseous and Antimatter Probes

IF 5.2 1区 化学 Q1 POLYMER SCIENCE
Darin Sukalingum, Tianran Zhai, Marc H. Weber, Sohraab A. Khan, Thant H. Htut, Jeremy I. Feldblyum
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Abstract

Synthesis of polymers with tailored properties requires an understanding of the underlying phenomena leading to these properties. Polymers of intrinsic microporosity (PIMs) are non-network polymers with a substantial guest-accessible free volume. Their BET surface areas have been reported to be as high as 1000 m2/g, and their porosity has led to the demonstration of some of the best membrane-based gas separations to date. However, it has been challenging to predict porosity in PIMs a priori, in part due to an incomplete framework for understanding the origins of porosity in these materials. Here, porosity in several archetypal PIMs is examined through the lens of a percolation model, whereby porosity in oligomers follows behavior expected for nonpercolated and percolated networks. Positron-based Doppler broadening spectroscopy is used to examine buried pores in samples whose pores are inaccessible to typical (nonantimatter) guests and demonstrate that buried pores are present in PIMs with nonpercolated pore networks. Taken together, the findings are in agreement with the contention that network percolation plays a critical role in pore accessibility in PIMs.
用气体和反物质探针检测聚合物内禀微孔隙度的孔隙网络渗透
合成具有特定性质的聚合物需要了解导致这些性质的潜在现象。固有微孔聚合物(PIMs)是一种非网状聚合物,具有相当大的来宾可访问的自由体积。据报道,它们的BET表面积高达1000 m2/g,它们的孔隙率已经证明了迄今为止一些最好的膜基气体分离。然而,先验地预测PIMs的孔隙度一直具有挑战性,部分原因是对这些材料孔隙度起源的理解框架不完整。本文通过渗流模型考察了几种典型pim的孔隙度,其中低聚物的孔隙度遵循非渗流和渗流网络的预期行为。利用正电子多普勒增宽光谱分析了典型(非反物质)客体无法进入的样品中的埋藏孔隙,并证明了具有非渗透孔隙网络的pim中存在埋藏孔隙。综上所述,这些发现与网络渗透在pim的孔隙可达性中起关键作用的观点一致。
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来源期刊
Macromolecules
Macromolecules 工程技术-高分子科学
CiteScore
9.30
自引率
16.40%
发文量
942
审稿时长
2 months
期刊介绍: Macromolecules publishes original, fundamental, and impactful research on all aspects of polymer science. Topics of interest include synthesis (e.g., controlled polymerizations, polymerization catalysis, post polymerization modification, new monomer structures and polymer architectures, and polymerization mechanisms/kinetics analysis); phase behavior, thermodynamics, dynamic, and ordering/disordering phenomena (e.g., self-assembly, gelation, crystallization, solution/melt/solid-state characteristics); structure and properties (e.g., mechanical and rheological properties, surface/interfacial characteristics, electronic and transport properties); new state of the art characterization (e.g., spectroscopy, scattering, microscopy, rheology), simulation (e.g., Monte Carlo, molecular dynamics, multi-scale/coarse-grained modeling), and theoretical methods. Renewable/sustainable polymers, polymer networks, responsive polymers, electro-, magneto- and opto-active macromolecules, inorganic polymers, charge-transporting polymers (ion-containing, semiconducting, and conducting), nanostructured polymers, and polymer composites are also of interest. Typical papers published in Macromolecules showcase important and innovative concepts, experimental methods/observations, and theoretical/computational approaches that demonstrate a fundamental advance in the understanding of polymers.
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