Dataset Information

Enhancement of CO2 Uptake and Selectivity in a Metal-Organic Framework by the Incorporation of Thiophene Functionality.

ABSTRACT: The complex [Zn2(tdc)2dabco] (H2tdc = thiophene-2,5-dicarboxylic acid; dabco = 1,4-diazabicyclooctane) shows a remarkable increase in carbon dioxide (CO2) uptake and CO2/dinitrogen (N2) selectivity compared to the nonthiophene analogue [Zn2(bdc)2dabco] (H2bdc = benzene-1,4-dicarboxylic acid; terephthalic acid). CO2 adsorption at 1 bar for [Zn2(tdc)2dabco] is 67.4 cm3·g-1 (13.2 wt %) at 298 K and 153 cm3·g-1 (30.0 wt %) at 273 K. For [Zn2(bdc)2dabco], the equivalent values are 46 cm3·g-1 (9.0 wt %) and 122 cm3·g-1 (23.9 wt %), respectively. The isosteric heat of adsorption for CO2 in [Zn2(tdc)2dabco] at zero coverage is low (23.65 kJ·mol-1), ensuring facile regeneration of the porous material. Enhancement by the thiophene group on the separation of CO2/N2 gas mixtures has been confirmed by both ideal adsorbate solution theory calculations and dynamic breakthrough experiments. The preferred binding sites of adsorbed CO2 in [Zn2(tdc)2dabco] have been unambiguously determined by in situ single-crystal diffraction studies on CO2-loaded [Zn2(tdc)2dabco], 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 [Zn2(tdc)2dabco] 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.

SUBMITTER: Bolotov VA

PROVIDER: S-EPMC5951605 | biostudies-literature | 2018 May

REPOSITORIES: biostudies-literature

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Enhancement of CO2 Uptake and Selectivity in a Metal-Organic Framework by the Incorporation of Thiophene Functionality.

Bolotov Vsevolod A VA Kovalenko Konstantin A KA Samsonenko Denis G DG Han Xue X Zhang Xinran X Smith Gemma L GL McCormick Laura J LJ Teat Simon J SJ Yang Sihai S Lennox Matthew J MJ Henley Alice A Besley Elena E Fedin Vladimir P VP Dybtsev Danil N DN Schröder Martin M

Inorganic chemistry 20180423 9

The complex [Zn2(tdc)2dabco] (H2tdc = thiophene-2,5-dicarboxylic acid; dabco = 1,4-diazabicyclooctane) shows a remarkable increase in carbon dioxide (CO2) uptake and CO2/dinitrogen (N2) selectivity compared to the nonthiophene analogue [Zn2(bdc)2dabco] (H2bdc = benzene-1,4-dicarboxylic acid; terephthalic acid). CO2 adsorption at 1 bar for [Zn2(tdc)2dabco] is 67.4 cm ...[more]

PMID: 29683657

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Project description:Metal-organic frameworks (MOFs) have been an excellent platform for carbon dioxide reduction reactions (CO2RR). In this work, the feasibility of electrochemical reduction of CO2 to obtain C2-deep value-added products was investigated by the preparation of Mg-containing MOF-74 samples combined with transition metal cations (Ni2+, Co2+ and Zn2+). The prepared MOFs were used as electrocatalysts in CO2RR. Chronoamperometric analysis coupled to ATR-FTIR spectroscopy was employed to characterize the CO2 reduction products and subsequently via 1H NMR. Although an isostructural crystalline structure was observed in all synthesized MOFs, the pore diameter distribution was significantly affected due to the Mg coordination along with each transition metal nuclei with the organic ligand to form the MOF-74. Our results showed that Mg-containing MOF-74 electrocatalysts combined with Ni, Co and Zn ions successfully reduced CO2 to C2-deep products, while the monometallic Mg-MOF-74 showed only CO2 mineralization. An ester acetate, isopropyl alcohol, and formic acid were produced by Mg/Ni-MOF-74; isopropyl alcohol was provided by Mg/Co-MOF-74, and ethanol was generated by Mg/Zn-MOF-74. We observed that the change of the transition cation was a key factor in the selectivity of the obtained products, while the degree of Mg ions effectively incorporated into the MOF structure tuned the porosity and the electrocatalytic activity. Among them, Mg/Zn-MFOF-74 showed the highest Mg content loaded after synthesis and thus the most favorable electrocatalytic behavior towards CO2 reduction. Highlights • CO2-derived C2-deep reduction products were obtained by Mg-containing MOF-74 bimetallic electrocatalysts.• Mg-containing MOF-74 bimetallic electrocatalysts reduced CO2 to ester acetate, isopropanol, formic acid, and ethanol.• Mg/Zn-MOF-74 displayed the highest current density at a lower onset potential in CO2-saturated electrolyte.• The pore network could be tuned by the effective Mg content on a MOF-74 bimetallic sample.• Mg/Zn-MOF-74 showed the highest Mg content among all bimetallic electrocatalysts after the synthesis.

Dataset Information

Enhancement of CO2 Uptake and Selectivity in a Metal-Organic Framework by the Incorporation of Thiophene Functionality.

Publications

Enhancement of CO<sub>2</sub> Uptake and Selectivity in a Metal-Organic Framework by the Incorporation of Thiophene Functionality.

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