Design and synthesis of functional porous organic materials

Date
2020
Journal Title
Journal ISSN
Volume Title
Publisher
University of Delaware
Abstract
Attempts to modify porous aromatic frameworks (PAFs) via altering reagent composition, such as the addition of substituents to its precursor molecules, has largely shown to be ineffective. However, porous aromatic frameworks (PAFs) can be post-synthetically modified by relatively simple processes to create catalytically active analogous structures for tailored applications. Using previously published and novel methods, our group has post synthetically modify PAF-1with Brønsted acid functional groups. These modified PAFs were used as catalysts in hydroxyalkylation alkylation (HAA) reactions, commonly used in the synthesis of alkylfuran precursors to industrially relevant bio-lubricant base oils. Base oils are a vital commodity to the production of commercial lubricants. Here we seek to optimize a step in the synthetic route of bio lubricant precursors by creating a more efficient catalyst that can be used in combination with cheap starting materials found in biomass like sugars, alcohols, and agricultural waste. This allows for cost cutting in lubricant production while improving desirable characteristics in the end product lubricants utilizing them. ☐ As an alternative to PAFs, porous organic cages (POCs) can provide several benefits; mainly, their crystallinity and their compatibility with density modification strategies. An octahedral aldehyde and diamine-based imine cage, commonly referred to as CC3, has received a fair share of interest, becoming well known in POC based research into gas and small molecule storage and separations. While it excels at this application, its primary drawback is poor surface area when compared to other porous materials (MOFs, COFs, PAFs, etc.). Coupled with the moderately expensive starting materials required for synthesis, namely 1,3,5-triformylbenzene, there is much room for improvement in both synthetic process and molecular structure. The work outlined here describes a strategy to modify the packing arrangement and density of CC3 to explore optimization of density, to ultimately improve volumetric methane uptake in POCs. This was achieved through the synthesis of film phase POCs, and the effects of phase change on gas adsorption characteristics and density were investigated.
Description
Keywords
Metal-organic framework, Organic chemistry, Porous aromatic framework, Porous materials, Porous organic cage, Porous organic material
Citation