Computational screening, synthesis and testing of metal?organic frameworks with a bithiazole linker for carbon dioxide capture and its green conversion into cyclic carbonates [electronic resource]
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| Format: | Government Document Electronic eBook |
| Language: | English |
| Published: |
Washington, D.C. : Oak Ridge, Tenn. :
United States. Department of Energy. Office of Science ; Distributed by the Office of Scientific and Technical Information, U.S. Department of Energy,
2019.
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| Abstract: | Computational crystal construction algorithms were used to create twelve metal?organic frameworks containing a newly synthesized [2,2'-bithiazole]-5,5'-dicarboxylic acid (H<sub>2</sub>TzTz) spacer and assorted transition metal nodes. Among the twelve structures, the zirconium-based MOF of general formula [Zr<sub>6</sub>O<sub>4</sub>(OH)<sub>4</sub>(TzTz)<sub>6</sub>] (1) was found to be the best candidate for carbon dioxide uptake, as judged from the results of the grand canonical Monte Carlo (GCMC) simulations of CO<sub>2</sub> adsorption isotherms. Guided by the simulation results, 1 was synthesized in the laboratory and thoroughly characterized. 1 is isoreticular to its bithiophene and bis(benzene) (UiO-67) analogues; it crystallizes in the cubic Pn$\bar{3}$ with combining macron] space group with fcu topology, and it features octahedral [Zr<sub>6</sub>] nodes connected by twelve carboxylate groups from six bridging TzTz<sup>2-</sup> spacers. It is a predominantly microporous material (micropore volume = 84% of the total pore volume), with a BET area of 840 m<sup>2</sup> g<sup>-1</sup> and a maximum CO<sub>2</sub> uptake at ambient pressure of 2.3 mmol g<sup>-1</sup> (10.0 wt%) or 1.7 mmol g<sup>-1</sup> (7.5 wt%) at 273 or 298 K, respectively. The CO<sub>2</sub> affinity (isosteric heat of adsorption Qst = 18.7 kJ mol<sup>-1</sup>; CO<sub>2</sub>/N<sub>2</sub> Henry selectivity = 10; CO<sub>2</sub>/N<sub>2</sub> IAST selectivity = 8.4) is similar to that of its bithiophene analogue. After partial removal of solvent (activation), 1 was tested as a heterogeneous catalyst in the reaction of CO<sub>2</sub> with epoxides bearing a ?CH<sub>2</sub>X pendant arm (X = Cl: epichlorohydrin; X = Br: epibromohydrin) to give the corresponding cyclic carbonates at T = 393 K and p<sub>CO<sub>2</sub></sub> = 1 bar under green (solvent- and co-catalyst-free) conditions. A good conversion of 74% and a turnover frequency of 12.3 mmol (cyclic carbonate) per mmol<sub>Zr</sub> per h have been recorded with epibromohydrin as a substrate. |
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| Item Description: | Published through Scitech Connect. 07/02/2019. "Journal ID: ISSN 2058-9689." "MSDEBG." Müller, Philipp ; Bucior, Benjamin ; Tuci, Giulia ; Luconi, Lapo ; Getzschmann, Jürgen ; Kaskel, Stefan ; Snurr, Randall Q. ; Giambastiani, Giuliano ; Rossin, Andrea ; Northwestern Univ., Evanston, IL (United States) |
| Physical Description: | Size: p. 1000-1013 : digital, PDF file. |