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Strong CO2Chemisorption in a Metal–Organic Framework with Proximate Zn–OH Groups
- Source :
- Inorganic Chemistry; 20220101, Issue: Preprints
- Publication Year :
- 2022
-
Abstract
- A novel Zn benzotriazolate metal–organic framework (MOF), [Zn9(OAc)6(bbtm)6] (1, bbtm2–= bis(benzotriazolyl)methanone, OAc–= acetate), has been synthesized and structurally characterized using micro-crystal electron diffraction. The framework contains 12-connected nonanuclear Zn clusters with Zn–OAc groups separated by short intercluster Zn···Zn distances of 6.06 Å. Postsynthetic OAc–/OH–ligand exchange followed by thermal activation generates 1a-OH, which adsorbs CO2at very low pressures (1.37 mmol/g at 2.5 mbar) and requires an unusually high desorption temperature (>160 °C). Diffuse reflectance IR Fourier transform spectroscopy (DRIFTS) and density functional theory (DFT) calculations have been used to interrogate the CO2binding mechanism in 1a-OH. The formation of unsymmetric bridging carbonate ligands within the Zn···Zn pockets accompanied by strong hydrogen bonding of the carbonate with a neighboring zinc aqua ligand explains the remarkably strong CO2affinity of 1a-OH.
Details
- Language :
- English
- ISSN :
- 00201669 and 1520510X
- Issue :
- Preprints
- Database :
- Supplemental Index
- Journal :
- Inorganic Chemistry
- Publication Type :
- Periodical
- Accession number :
- ejs61118766
- Full Text :
- https://doi.org/10.1021/acs.inorgchem.2c03212