Products Cited in Publications Worldwide Unlocking enhanced gas capture via core scrambling of porous-organic cages

Unlocking enhanced gas capture via core scrambling of porous-organic cages

Root, Harrison D; Hurlock, Matthew J; Bays, Nathan R; Addison, Brianna M; Rimsza, Jessica M

DOI:

Abstract

The demand for low-cost, low-energy, and highly selective gas capture and separations is an ongoing driver of porous material development. Porous liquids have been identified as a promising gas separation material by creating permanent porosity in inorganic solvents through inclusion of nanoporous materials that sterically exclude solvent from their internal porosity. Among the nanoporous materials that can be used to form porous liquids, porous-organic cages (POCs) have been one of the most popular due to the inherent tunability of POCs. “Scrambled” POCs with varying functionalities on the POC vertices have been developed and incorporated into porous liquid compositions, increasing their gas adsorption capacity. An unexplored avenue to tailor the properties of porous liquids is through scrambling the functionality of the core of the POC. Therefore, we have synthesized a new POC, a CC3-OH derivative with scrambled hydroxides on the core and evaluated the impact on the CO2 uptake capacity in silicon oil-based porous liquids. Core scrambling of the POC resulted in a twofold increase CO2 adsorption capacity in the porous liquid, an emergent property that is a dramatic increase beyond a linear combination of the gas adsorption capacity of the neat solvent and the POC. Density functional theory modeling of the CC3 POC and its hydroxide-based derivatives identified that free rotation of the linker hydroxide allowed for forced interaction between the CO2 molecule and the hydroxide in the pore window. Solvation of the POC may release scrambled core hydroxides from intramolecular bonding with a neighboring imine, allowing for increased gas uptake in the porous liquid over the neat POC. These results identify a key structural relationship of POCs that enables emergent properties in porous liquids and can guide future development of liquid phase gas capture and separation materials for environmental and industrial applications.

Keywords

Porous liquids ; Gas capture ; Gas separation ; Porous organic cages

Purchased from AmBeed

(1S,2S)-Cyclohexane-1,2-diamine

A147123321436-03-398% 99%ee

(1S,2S)-Cyclohexane-1,2-diamine

30.0/5g

Detail
1,3,5-Benzenetricarbaldehyde

A3725283163-76-696%

1,3,5-Benzenetricarbaldehyde

23.0/1g

Detail

A95493881502-74-195%

2-Hydroxybenzene-1,3,5-tricarbaldehyde

549.0/25g

Detail