Carbon Dioxide Capture Chemistry of Amino Acid Functionalized Metal-Organic Frameworks in Humid Flue Gas

Abstract

Metal-organic framework-808 has been functionalized with 11 amino acids (AA) to produce a series of MOF-808-AA structures. The adsorption of CO2 under flue gas conditions revealed that glycine- and DL-lysine-functionalized MOF-808 (MOF-808-Gly and -DL-Lys) have the highest uptake capacities. Enhanced CO2 capture performance in the presence of water was observed and studied using single-component sorption isotherms, CO2/H2O binary isotherm, and dynamic breakthrough measurements. The key to the favorable performance was uncovered by deciphering the mechanism of CO2 capture in the pores and attributed to the formation of bicarbonate as evidenced by 13C and 15N solid-state nuclear magnetic resonance spectroscopy studies. Based on these results, we examined the performance of MOF-808-Gly in simulated coal flue gas conditions and found that it is possible to capture and release CO2 by vacuum swing adsorption. MOF-808-Gly was cycled at least 80 times with full retention of performance. This study significantly advances our understanding of CO2 chemistry in MOFs by revealing how strongly bound amine moieties to the MOF backbone create the chemistry and environment within the pores, leading to the binding and release of CO2 under mild conditions without application of heat.

Modular Functionalization of Metal‐Organic Frameworks for Nitrogen Recovery from Fresh Urine**

“…[9,44] In order to introduce ammonium binding affinity to MOF-808 backbone, we selected a series of dicarboxylate compounds, namely oxalic acid (OA), malonic acid (MA), and succinic acid (SA), as anionic functional group. For each dicarboxylate compound, one carboxylate stitches strongly to the Zr 6 O 8 cluster via bidentate chelating, [45] whereas the other remains dangling inside the pore to serve as the ammonium adsorption sites (Scheme 3). Successful incorporation of MA and SA was confirmed and quantified with 1 H NMR spectra of the digested samples (Figure S6 and S7), whereas the incorporated OA was determined via colorimetric assay of the digested MOF-808-OA.…”