期刊
INORGANIC CHEMISTRY
卷 57, 期 9, 页码 5074-5082出版社
AMER CHEMICAL SOC
DOI: 10.1021/acs.inorgchem.8b00138
关键词
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资金
- EPSRC
- ERC
- University of Manchester
- Russian Science Foundation [14-23-00013]
- Federal Agency for Scientific Organizations
- Russian Ministry of Science and Education [14.Z50.31.0006]
- DOE Office of Science User Facility [DE-AC02-05CH11231]
- Center for Gas Separations Relevant to Clean Energy Technologies, an Energy Frontier Research Center - U.S. Department of Energy, Office of Science, Basic Energy Sciences [DE-SC0001015]
- Russian Science Foundation [17-23-00006] Funding Source: Russian Science Foundation
- EPSRC [EP/I020942/1, EP/P001386/1, EP/I011870/2] Funding Source: UKRI
The complex [Zn-2(tdc)(2)dabco] (H(2)tdc = thiophene-2,5-dicarboxylic acid; dabco = 1,4-diazabicyclooctane) shows a remarkable increase in carbon dioxide (CO2) uptake and CO2/dinitrogen (N-2) selectivity compared to the nonthiophene analogue [Zn-2(bdc)(2)dabco] (H(2)bdc = benzene-1,4-dicarboxylic acid; terephthalic acid). CO2 adsorption at 1 bar for [Zn-2(tdc)(2)dabco] is 67.4 cm(3).g(-1) (13.2 wt %) at 298 K and 153 cm(3).g(-1) (30.0 wt %) at 273 K. For [Zn-2(bdc)(2)dabco], the equivalent values are 46 cm(3).g(-1) (9.0 wt %) and 122 cm(3).g(-1) (23.9 wt %), respectively. The isosteric heat of adsorption for CO2 in [Zn-2(tdc)(2)dabco] at zero coverage is low (23.65 kJmol(-1)), ensuring facile regeneration of the porous material. Enhancement by the thiophene group on the separation of CO2/N-2 gas mixtures has been confirmed by both ideal adsorbate solution theory calculations and dynamic breakthrough experiments. The preferred binding sites of adsorbed CO2 in [Zn-2(tdc)(2)dabco] have been unambiguously determined by in situ single-crystal diffraction studies on CO2-loaded [Zn-2(tdc)(2)dabco], coupled with quantum-chemical calculations. These studies unveil the role of the thiophene moieties in the specific CO2 binding via an induced dipole interaction between CO2 and the sulfur center, confirming that an enhanced CO2 capacity in [Zn-2(tdc)(2)dabco] is achieved without the presence of open metal sites. The experimental data and theoretical insight suggest a viable strategy for improvement of the adsorption properties of already known materials through the incorporation of sulfur-based heterocycles within their porous structures.
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