Structural analysis of interpenetrated methyl-modified MOF-5 and its gas-adsorption properties

Abstract

The first example of an interpenetrated methyl-modified MOF-5 with the formula Zn4O(DMBDC)3(DMF)2, where DMBDC2− is 2,5-dimethylbenzene-1,4-dicarboxylate and DMF is N,N-dimethylformamide (henceforth denoted as Me2MOF-5-int), namely, poly[tris(μ4-2,5-dimethylbenzene-1,4-dicarboxylato)bis(N,N-dimethylformamide)-μ4-oxido-tetrazinc(II)], [Zn4(C10H8O4)3O(C3H7NO)2] n , has been obtained from a solvothermal synthesis of 2,5-dimethylbenzene-1,4-dicarboxylic acid and Zn(NO3)2·6H2O in DMF. A systematic study revealed that the choice of solvent is of critical importance for the synthesis of phase-pure Me2MOF-5-int, which was thoroughly characterized by single-crystal and powder X-ray diffraction (PXRD), as well as by gas-adsorption analyses. The Brunauer–Emmett–Teller surface area of Me2MOF-5-int (660 m2 g−1), determined by N2 adsorption, is much lower than that of nonpenetrated Me2MOF-5 (2420 m2 g−1). However, Me2MOF-5-int displays an H2 uptake capacity of 1.26 wt% at 77 K and 1.0 bar, which is comparable to that of non-interpenetrated Me2MOF-5 (1.51 wt%).

Advancing stroke therapy: the potential of MOF-based nanozymes in biomedical applications

“…In instances where metal-ligand bonds exhibit exceptional strength, modulators are used to prevent the rapid precipitation of amorphous material. Modulators, such as benzoic acid, acetic acid, or hydrochloric acid, establish dynamic bonds with the metal precursor, competing with the linkers for metal coordination sites (Sugamata et al, 2020;Mao et al, 2022). They play a crucial role in the synthesis of Zr-MOFs, which contain robust Zr (IV)−O bonds.…”

Zn‐Based Metal–Organic Frameworks Using Triptycene Hexacarboxylate Ligands: Synthesis, Structure, and Gas‐Sorption Properties

“…Especially the functionalization of MOFs with CH 3 , NH 2 , NO 2 , Cl, Br,CO 2 H, OCH 3 , or SO 3 H functional groups enhances their adsorption performances for various gases (mainly H 2 , CO 2 , and CH 4 ) [29–35] . In this context, we have already reported alkyl‐functionalized MOF‐5, which exhibits an enhanced H 2 ‐uptake capacity and CO 2 /N 2 selectivity compared to its parent MOF‐5 [36,37] . Furthermore, MOFs with smaller pore size exhibit enhanced gas‐adsorption capacity.…”

“…[29][30][31][32][33][34][35] In this context, we have already reported alkylfunctionalized MOF-5, which exhibits an enhanced H 2 -uptake capacity and CO 2 /N 2 selectivity compared to its parent MOF-5. [36,37] Furthermore, MOFs with smaller pore size exhibit enhanced gas-adsorption capacity. For example, UiO-66 (pore volume: 0.45 cm 3 g À 1 ; CO 2 -uptake volume: 1.67 mmol g À 1 ) exhibits a smaller pore volume than isomorphic UiO-67 (pore volume: 1.10 cm 3 g À 1 ; CO 2 -uptake volume: 1.02 mmol g À 1 ) but enhanced CO 2 adsorption.…”

Gas Adsorption in R2‐MOF‐5 Difunctionalized with Alkyl Groups

“…[27] Recently, we have reported the controlled synthesis of non-interpenetrated and interpenetrated methyl-modified MOF-5 derivatives, which exhibit different pore structures. [28] These compounds were prepared via a hydrothermal synthesis using 2,5-dimethyl-1,4benzenedicarboxylic acid and Zn(NO 3 ) 2 • 6H 2 O, in which the choice of solvent (N,N-dimethylformamide or N,N-diethylformamide) is of critical importance. Our results suggest that the suppression of framework interpenetration and control over the pore architecture is not only the result of simple steric criteria regarding the ligand but may be governed by other mechanisms such as solvent templating.…”

“…MOF-5 and Me 2 -MOF-5 were synthesized via a previously reported solvothermal reaction between Zn(NO 3 ) 2 • 6H 2 O and terephthalic acid in N,Ndimethylformamide (DMF) or N,N-diethylformamide (DEF). [28] The chosen synthetic route to the difunctionalized R 2 -MOF-5 (R = Et, Pr, or Bu) is similar to that of MOF-5. Colorless microcrystalline powders were obtained following slow cooling of the reaction mixtures to room temperature, and their structures were subsequently analyzed using powder X-ray diffraction (PXRD) analysis, Fourier-transform infrared (FT-IR) spectroscopy, thermogravimetric analysis (Figure S4), and gasadsorption analysis.…”