Highly Stable Nanoporous Sulfur‐Bridged Covalent Organic Polymers for Carbon Dioxide Removal

Abstract

Carbon dioxide capture and separation requires robust solids that can stand harsh environments where a hot mixture of gases is often found. Herein, the fi rst and comprehensive syntheses of porous sulfur-bridged covalent organic polymers (COPs) and their application for carbon dioxide capture in warm conditions and a wide range of pressures (0-200 bar) are reported. These COPs can store up to 3294 mg g − 1 of carbon dioxide at 318 K and 200 bar while being highly stable against heating up to 400 ° C. The carbon dioxide capacity of the COPs is also not hindered upon boiling in water for at least one week. Physisorptive binding is prevalent with isosteric heat of adsorptions around 24 kJ mol − 1 . M06-2X and RIMP2 calculations yield the same relative trend of binding energies, where, interestingly, the dimer of triazine and benzene play a cooperative role for a stronger binding of CO 2 (19.2 kJ mol − 1 ) as compared to a separate binding with triazine (13.3 kJ mol − 1 ) or benzene (11.8 kJ mol − 1 ).

Efficient CO 2 capture by triptycene-based microporous organic polymer with functionalized modification

“…Most TPPs are stable up to 300 C except for TPP-1-NH 2 which decomposes at about 180 C due to the decomposition of functionalization NH 2 group. It is worth mentioning that high thermal stability of these microporous TPPs are good enough for their potential applications in post combustion process and CO 2 scrubbing operation [36].…”

Knitting hypercrosslinked conjugated microporous polymers with external crosslinker

“…S8) showed that the polymer has an excellent thermalstability without thermal degradation up to 380 °C which is comparable to other porous organic polymers. [27][28][29] The porous properties of the samples were analyzed by N 2 sorption analysis at 77K.…”

Trends and challenges for microporous polymers

“…Synthetic protocols which can be used for the generation of microporous polymers are highly diverse and range from metalcatalyzed or -mediated (Sonogashira, 4,5 Suzuki, 6 Yamamoto, 7 Buchwald-Hartwig, 8 Eglinton, 9 Heck 10 ) to click-type reactions, 11 acid or base-catalyzed polycondensation reactions (formation of polyamides, 12 -imides, [13][14][15] -benzimidazoles, 16,17 -dioxanes, 18 -boroxines and boronate esters, 19 -imines 20 -aminals, 22 azo-bridged compounds [23][24][25] and many others [26][27][28][29] The great variety of synthesis conditions not only allows the usage of differentially functionalized monomers, but much more importantly to find appropriate reaction conditions tolerating any given functional group which is planned to be introduced into the network, i.e. synthesis can be carried out with high chemical orthogonality.…”