Microporous 2D indium metal–organic frameworks for selective CO₂ capture and their application in the catalytic CO₂-cycloaddition of epoxides

Abstract

Four new 2D indium metal-organic frameworks (MOFs) (Me2NH2)[In(SBA)2] (1), (Me2NH2)[In(SBA)(BDC)] (2), (Me2NH2)[In(SBA)(BDC-NH2)] (3), and (NH4)3[In3Cl2(BPDC)5] (4), (H2SBA = 4,4'-sulfonyldibenzoic acid; H2BDC = 1,4-benzenedicarboxylic acid; H2BDC-NH2 = 2-amino-1,4-benzenedicarboxylic acid; H2BPDC = 4,4'-biphenyldicarboxylic acid) have been synthesized under solvothermal reaction conditions for compounds 1 to 3 and the DES (deep eutectic solvent) reaction has been attempted for compound 4. The structure of these MOFs has been determined by using single crystal X-ray diffraction study and all of theses four 2D monolayer framework with porous properties. The N2 gas sorption measurements indicated that Brunauer-Emmer-Teller (BET) and Langmuir surface areas of compound 1 are 207 and 301 m2 g-1, respectively, which is probably the first one having substantial gas uptake properties in the entire 2D In-MOF family to date. Furthermore, these new indium MOFs on the addition of n-Bu4NBr were active for the cycloaddition of CO2 and propylene oxide, generating propylene carbonates in high conversions under mild conditions. Particularly, the most active MOF 4 was found to efficiently couple CO2 with a series of terminal epoxides to give the corresponding cyclic organic carbonates with high selectivities.

2D-enabled membranes: materials and beyond

“…MOFs are frequently used as a filler for fabrication of a mixed matrix membrane due to the partial organic nature of its framework-affinity toward a polymeric matrix is higher than other purely inorganic materials. Two dimensional (MOF nanosheets) MOFs have been also reported to show favorable applications in catalysis [66,67], gas storage and separations [68,69], and chemical sensors [70,71]. MOF nanosheets are prepared in two different ways: 1) Bottom-up synthesis (c.f., arresting crystallization) [72], 2) Top-down synthesis (c.f., exfoliation of layered MOF crystals) [73,74] (Fig.…”

2D Metal–Organic Frameworks as Multifunctional Materials in Heterogeneous Catalysis and Electro/Photocatalysis

“…In another precedent, four 2D In MOFs, namely, (Me 2 NH 2 )[In(SBA) 2 ], (Me 2 NH 2 )[In(SBA)(BDC)], (Me 2 NH 2 )[In(SBA)(BDC‐NH 2 )], and (NH 4 ) 3 [In 3 Cl 2 (BPDC) 5 ] ( Figure ) (H 2 SBA:4,4′‐sulfonyldibenzoic acid; H 2 BDC‐NH 2 : 2‐amino‐1,4‐benzenedicarboxylic acid; H 2 BPDC: 4,4′‐biphenyldicarboxylic acid), were prepared under solvothermal reaction conditions . The powder XRD patterns of these 2D MOFs showed coincident diffraction patterns with their respective patterns simulated for their ideal structure, thus implying the phase purity of the bulk sample.…”

“…d) Thickness of the interpenetrated 2D framework structure of (NH 4 ) 3 [In 3 Cl 2 (BPDC) 5 ]. a–d) Reproduced with permission . Copyright 2018, Royal Society of Chemistry.…”

Three new V‐shape dicarboxylate coordination polymers: syntheses, crystal structures and properties

“…[16][17][18] Through literature research, we found that 4,4'-dicarboxybiphenyl sulfone (H 2 SDBA) as a Vshaped dicarboxylate ligand is an good candidate and has been widely employed as the organic building block for the construction of novel coordination frameworks independently or in combination with N-donor auxiliary ligands. [19][20][21][22][23] (2) and [Cu(SDBA) 0.5 (μ 2 -OH)] n (3) (H 2 SDBA=4,4'-dicarboxybiphenyl sulfone, im = imidazole, DMA = N,N'-dimethylacetamide). The structures of CPs 1-3 have been described, and the luminescent properties of 1-2, gas adsorption properties of 2 a (solvent-free form of 2) and photocatalytic property of 3 have also been investigated.…”

“…Among the reported CPs, polydentate organic carboxylic acid ligands have been proven to be one of the most effective organic building blocks to bind metal ions into well‐defined crystalline functional materials, [13–15] and lots of CPs with high thermal stabilities and promising functional properties have been synthesized by using the polycarboxylate ligands [16–18] . Through literature research, we found that 4,4’‐dicarboxybiphenyl sulfone (H 2 SDBA) as a V‐shaped dicarboxylate ligand is an good candidate and has been widely employed as the organic building block for the construction of novel coordination frameworks independently or in combination with N‐donor auxiliary ligands [19–23] . The characteristics of H 2 SDBA is the appropriate angle and spacer length between two coordination carboxylate groups.…”