Abstract
The cross-coupling reaction of 1,3,5-triethynylbenzene with terephthaloyl chloride gives a novel ynone-linked porous organic polymer. Tethering alkyl amine species on the polymer induces chemisorption of CO2 as revealed by the studies of ex situ infrared spectroscopy. By tuning the amine loading content on the polymer, relatively high CO2 adsorption capacities, high CO2-over-N2 selectivity, and moderate isosteric heat (Qst) of adsorption of CO2 can be achieved. Such amine-modified polymers with balanced physisorption and chemisorption of CO2 are ideal sorbents for post-combustion capture of CO2 offering both high separation and high energy efficiencies.
Highlights
The long-term increasing CO2 emission from combustion of fossil fuels is widely considered as the main reason for the global climate change and associated environmental issues [1]
We attempted the cross-coupling of 1,3,5-triethynylbenzene with terephthaloyl chloride under Sonogashira conditions for the synthesis of y-porous organic polymers (POPs), which was catalyzed by bis(triphenylphosphine)palladium(II) dichloride and copper(I) iodide in the presence of trimethylamine as a base (Scheme 1a)
In order to graft amine species onto the polymer, the as-synthesized ynone-linked POP (y-POP) was treated by tris(2-aminoethyl)amine in a methanol solution (Scheme 1b)
Summary
The long-term increasing CO2 emission from combustion of fossil fuels is widely considered as the main reason for the global climate change and associated environmental issues [1]. The hydrophilicity of zeolites and the broad pore size distributions of activated carbons have significantly limited their performances in CO2 capture and separation Emerging porous materials such as metal−organic frameworks (MOFs) [15,16,17] and porous organic polymers (POPs) [18,19,20,21,22,23] are of great interest for CO2 capture because of their large surface areas and tunable pore sizes. The strong interactions, interpreted by the high isosteric heat (Qst) of adsorption (up to 80 kJ mol−1) [35,37], require high energy input to reactivate the sorbents in the process of temperature swing adsorption (TSA) or vacuum swing adsorption (VSA) [40] In this context, it would be great of interest to balance the trade-off between the separation efficiency and energy efficiency. We report a strategy to tune the amine density on a novel ynone-linked POP (y-POP) by the post-modification approach, which enables balancing of the effects of physisorption and chemisorption of CO2 and optimization of the CO2 adsorption capacity, CO2-over-N2 selectivity and heat of adsorption of CO2
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