Enhanced Carbon Dioxide Adsorption on Post-Synthetically Modified Metal-Organic Frameworks

Abstract

Four MOFs functionalized with 1-Me, 1-Pr, 1-Ph, and 1-$PhCF_3$ were prepared through post-synthetic modifications of a metal-organic framework (MOF), UMCM-1-$NH_2$ (1) with acetic, butyric, benzoic, and 4-(trifluoromethyl)benzoic anhydrides, respectively. Methane adsorption measurements between 253 and 298 K at pressures up to 1 bar indicated that both 1-Ph and 1-$PhCF_3$ adsorbed more $CH_4$ than the parent MOF, 1. All the functionalized MOFs adsorbed more $CO_2$ than 1 under conditions similar to the $CH_4$ test. The introduction of functional groups promoted adsorption of both $CH_4$ and $CO_2$ despite significantly reducing Brunauer-Emmet-Teller (BET) surface area: 4170 (1), 3550 (1-Me), 2900 (1-Pr), 3680 (1-Ph), and 3520 $m^2/g$ (1-$PhCF_3$). Electron-withdrawing aromatic groups (1-Ph, 1-$PhCF_3$) more effectively enhanced $CO_2$ adsorption than electron-donating alkyl groups (1-Me, 1-Pr). In particular, 1-Ph adsorbed 23% more $CO_2$ at 298 K and 50% more at 253 K than 1.