Systematic Tuning and Multifunctionalization of Covalent Organic Polymers for Enhanced Carbon Capture

Abstract

Porous covalent polymers are attracting increasing interest in the fields of gas adsorption, gas separation, and catalysis due to their fertile synthetic polymer chemistry, large internal surface areas, and ultrahigh hydrothermal stabilities. While precisely manipulating the porosities of porous organic materials for targeted applications remains challenging, we show how a large degree of diversity can be achieved in covalent organic polymers by incorporating multiple functionalities into a single framework, as is done for crystalline porous materials. Here, we synthesized 17 novel porous covalent organic polymers (COPs) with finely tuned porosities, a wide range of Brunauer-Emmett-Teller (BET) specific surface areas of 430-3624 m(2) g(-1), and a broad range of pore volumes of 0.24-3.50 cm(3) g(-1), all achieved by tailoring the length and geometry of building blocks. Furthermore, we are the first to successfully incorporate more than three distinct functional groups into one phase for porous organic materials, which has been previously demonstrated in crystalline metal-organic frameworks (MOFs). COPs decorated with multiple functional groups in one phase can lead to enhanced properties that are not simply linear combinations of the pure component properties. For instance, in the dibromobenzene-lined frameworks, the bi- and multifunctionalized COPs exhibit selectivities for carbon dioxide over nitrogen twice as large as any of the singly functionalized COPs. These multifunctionalized frameworks also exhibit a lower parasitic energy cost for carbon capture at typical flue gas conditions than any of the singly functionalized frameworks. Despite the significant improvement, these frameworks do not yet outperform the current state-of-art technology for carbon capture. Nonetheless, the tuning strategy presented here opens up avenues for the design of novel catalysts, the synthesis of functional sensors from these materials, and the improvement in the performance of existing covalent organic polymers by multifunctionalization.

HiGee Strategy toward Rapid Mass Production of Porous Covalent Organic Polymers with Superior Methane Deliverable Capacity

“…As shown in Figure a (red points), the S BET of these products increases significantly from 2200 to 3068 m 2 g −1 as the residence time extends from 5 to 15 min. When the residence time further increases from 15 to 60 min, the S BET of these products is maintained at a similar level and is similar to the level in the results obtained in a conventional gravity environment with stirred solvothermal method. This indicates the reaction time via HiGee approach could be shortened by 40‐fold (15 vs 600 min) as compared with the traditional stirred solvothermal method.…”

Facile Carbonization of Microporous Organic Polymers into Hierarchically Porous Carbons Targeted for Effective CO2 Uptake at Low Pressures

“…[1][2][3] Recently, sorbents with large surface areas, high CO 2 capture capabilities and excellent regeneration abilities are abstracting more and more attention for the separation of CO 2 from N 2 in flue or natural gas. For this purpose, various porous solids including zeolites, 4 metal organic frameworks (MOFs), 5 porous 3 carbon 6 and microporous organic polymers (MOPs) [7][8][9] have been synthesized. They have also found to be of great potential for utilities in water treatment, 10 energy storage, 11 gas adsorption 12 and drug delivery.…”

Computational development of the nanoporous materials genome

“…One simply needs a single representative SBU to orient on all the nodes in a net, as the net inherently expresses the chirality in its nodes. It is worthy of note that this algorithm (or earlier versions of it) have been used to generate several hypothetical databases of porous materials with a record number of topologies 31,33,63,83,91 . While the sum of these structures consist of roughly 50 topologies, the RCSR contains a total of 2719 nets as of this writing, leaving a large amount of room for further structural diversity 70 .…”