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.

Heterogenized Molecular Rhodium Phosphine Catalyst within Metal-Organic Framework for Ethylene Hydroformylation

“…MOF-808 has been discovered by Yaghi and co-workers 43 and further pioneered in different applications. [44][45][46][47] MOF-808 is built around Zr6O4(OH)6 inorganic nodes connected by 1,3,5-benzenetricarboxylate (BTC) organic linkers to form a network of one-dimensional channels with pore size of 1.8 nm. 43 Although MOF-808 does not possess any direct functional groups, the possible installation of functional organic species at the secondary building unit by formate linker exchange has made it an attractive platform for molecular catalyst heterogenization.…”

Nanocage-Based Tb3+-Organic Framework for Efficiently Catalyzing the Cycloaddition Reaction of CO2 with Epoxides and Knoevenagel Condensation

“…Due to the fact that NUC-58a has good structure stability, strong CO 2 adsorption capacity, a rich pore structure, and a high density of coexisting Lewis acidic and basic sites, the catalytic performance of NUC-58a for the cycloaddition reaction was investigated. First, a series of control experiments were finished by using styrene oxide as the model substrate to obtain optimum reaction conditions, and all the products were analyzed by 1 H NMR spectroscopy and GC−MS spectrometry. As shown in Table S3, the reaction with 0.10 mol % NUC-58a as a catalyst at room temperature proceeded slowly (entry 1).…”

A novel copper metal–organic framework catalyst for the highly efficient conversion of CO2 with propargylic amines

“…To alleviate the abovementioned environmental problems, a lot of work on the capture, storage and utilization of carbon dioxide has been carried out. [1][2][3][4][5] Strategies for converting carbon dioxide into high value-added chemicals using clean and renewable solar energy is a very promising pathway to address energy and environmental issues. [6][7][8][9][10][11] Among the environmentally friendly and atom economical reactions, the carboxyl cyclization of propargylic amines with CO 2 to generate 2-oxazolidinones has a wide range of potential applications in synthetic and medicinal chemistry.…”

“…(TSP) was synthesized according to the previously reported procedure. 1 H NMR data were collected on a Varian DLG400 MHz spectrometer at ambient temperature. Peak frequencies were referenced versus an internal standard (TMS) for 1 H NMR.…”

“…Fig.4(a) IR spectra of Cu-TSP impregnated with propargylic amine (Cu-TSP@4a, red); free Cu-TSP (black); free propargylic amine (4a, blue); (b)1 H NMR spectra of the crystals of TSP, 4a, Cu-TSP, and Cu-TSP@4a (digested in DMSO-d 6 ); and (c) catalytic traces of cyclization performed under optimal conditions with the catalyst Cu-TSP filtered after 4 h. (d) Recycling experiments at each run.…”