Synthetic Control of the Pore Dimension and Surface Area in Conjugated Microporous Polymer and Copolymer Networks

Abstract

A series of rigid microporous poly(aryleneethynylene) (PAE) networks was synthesized by Sonogashira-Hagihara coupling chemistry. PAEs with apparent Brunauer-Emmet-Teller surface areas of more than 1000 m(2)/g were produced. The materials were found to have very good chemical and thermal stability and retention of microporosity under a variety of conditions. It was shown that physical properties such as micropore size, surface area, and hydrogen uptake could be controlled in a "quantized" fashion by varying the monomer strut length, as for metal-organic and covalent organic frameworks, even though the networks were amorphous in nature. For the first time, it was demonstrated that these properties can also be fine-tuned in a continuous manner via statistical copolymerization of monomer struts with differing lengths. This provides an unprecedented degree of direct synthetic control over micropore properties in an organic network.

Lithium Charge Storage Mechanisms of Cross-Linked Triazine Networks and Their Porous Carbon Derivatives

“…Triazine--containing materials with rigid linkers are known to create porous organic networks with high sur--face areas 22 which would allow for increased electrolyte access to the material and greater charge storage capabili--ties. The structures of these materials are not well--defined so it is important to understand how the structure and network change with increasing preparation temperature and ZnCl 2 equivalents.…”

Porous–Hybrid Polymers as Platforms for Heterogeneous Photochemical Catalysis

“…In our approach, we expanded the realm of previously utilized cross-coupling reactions of rigid and directional molecular building blocks (MBBs) 22,[33][34] into more intricate ruthenium-based, and cobaloxime-based brominated metal complexes. This new approach afforded extended porous solids containing the Ru-polypyridyl or cobaloxime functionalities as integral parts of the polymers' backbone.…”

Single Polymer Chain Surface Area as a Descriptor for Rapid Screening of Microporous Polymers for Gas Adsorption

“…It is widely accepted that the most challenging aspect is to create a reasonable simulation box that will capture the most important features of the porous material (Gelb 2009). While some researchers have used reverse Monte Carlo techniques to obtain a model description of a porous carbon using an experimental X-ray diffraction pattern (Pikunic et al 2003), some others have developed sophisticated algorithms to pack polymers in a simulation box and achieve the desired polymer density and porosity (Theodorou and Suter 1985;Trewin et al 2008). Another method to obtain model structures of amorphous or irregular materials is to follow selected synthesis steps in different simulations, such as a phase separation and sintering process Gelb and Gubbins 2008;Patti et al 2009).…”