A Series of Metal–Organic Frameworks for Selective CO₂ Capture and Catalytic Oxidative Carboxylation of Olefins

Abstract

Three new lanthanide-based metal–organic frameworks (Ln-MOFs), namely MOF-590, -591, and -592 constructed from a tetratopic linker, benzoimidephenanthroline tetracarboxylic acid (H4BIPA-TC), were synthesized under solvothermal conditions and fully characterized. All of the new MOFs exhibit three-dimensional frameworks, which adopt unprecedented topologies in MOF field. Gas adsorption measurements of MOF-591 and -592 revealed good adsorption of CO2 (low pressure, at room temperature) and moderate CO2 selectivity over N2 and CH4. Consequently, breakthrough experiments illustrated the separation of CO2 from binary mixture of CO2 and N2 with the use of MOF-592. Accordingly, MOF-592 revealed the selective CO2 capture effectively without any loss in performance after three cycles. Moreover, MOF-590, -591, and -592 showed to be catalytically active in the oxidative carboxylation of styrene and CO2 for a one-pot synthesis of styrene carbonate under mild conditions (1 atm CO2, 80 °C, and without solvent). Among the new materials, MOF-590 revealed a remarkable efficiency with exceptional conversion (96%), selectivity (95%), and yield (91%).

Oxidative carboxylation of olefins with CO2: environmentally benign access to five-membered cyclic carbonates

“…In 2018, Gándara and Nguyen designed and synthesized three new 3D lanthanide-based metal-organic frameworks, 34 Compared to other MOFs, MOF-590 was found to be more effective catalyst for the oxidative carboxylation of olens and CO 2 . Thus, in the presence of only 0.18 mol% of this MOF, 8 mol% of TBAB, and 1.9 equiv.…”

Cyclometalation of lanthanum(iii) based MOF for catalytic hydrogenation of carbon dioxide to formate

“…44 This was attributed to the framework exibility although other mechanisms were not ruled out. At 195 K, the amount of CO 2 uptake increases abruptly at low pressure range, with volumetric uptake more than doubling to 36.25 and 32.62 cm 3 40,[45][46][47] Catalysis NMR analysis of the digested MOFs before was carried out to conrm that no DMF molecules in the MOF catalysts and the formate product observed in our reaction was not from the DMF molecules. The conversion of CO 2 to formate using JMS-1a and Ru(II) @JMS-1a as catalysts was carried out as described in the experimental section.…”

Enthusiastic discussions on solid physic and material science at SPMS2019

“…Prof. Thang's center also synthesized a lot of MOF with the named VNU-number such as VNU-1, VNU-2, etc. and their application in energy, environment, catalysis, health care [10][11][12][13][14][15][16][17] . Dr. Phong D. Tran (University of Science and Technology of Hanoi, Vietnam) described the current state-of-the-art of the solar water splitting research.…”