Dataset Information

Molecular Insights into Carbon Dioxide Sorption in Hydrazone-Based Covalent Organic Frameworks with Tertiary Amine Moieties.

ABSTRACT: Tailorable sorption properties at the molecular level are key for efficient carbon capture and storage and a hallmark of covalent organic frameworks (COFs). Although amine functional groups are known to facilitate CO2 uptake, atomistic insights into CO2 sorption by COFs modified with amine-bearing functional groups are scarce. Herein, we present a detailed study of the interactions of carbon dioxide and water with two isostructural hydrazone-linked COFs with different polarities based on the 2,5-diethoxyterephthalohydrazide linker. Varying amounts of tertiary amines were introduced in the COF backbones by means of a copolymerization approach using 2,5-bis(2-(dimethylamino)ethoxy)terephthalohydrazide in different amounts ranging from 25 to 100% substitution of the original DETH linker. The interactions of the frameworks with CO2 and H2O were comprehensively studied by means of sorption analysis, solid-state NMR spectroscopy, and quantum-chemical calculations. We show that the addition of the tertiary amine linker increases the overall CO2 sorption capacity normalized by the surface area and of the heat of adsorption, whereas surface areas and pore size diameters decrease. The formation of ammonium bicarbonate species in the COF pores is shown to occur, revealing the contributing role of water for CO2 uptake by amine-modified porous frameworks.

SUBMITTER: Gottschling K

PROVIDER: S-EPMC6438324 | biostudies-literature | 2019 Mar

REPOSITORIES: biostudies-literature

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Publications

Molecular Insights into Carbon Dioxide Sorption in Hydrazone-Based Covalent Organic Frameworks with Tertiary Amine Moieties.

Gottschling Kerstin K Stegbauer Linus L Savasci Gökcen G Prisco Nathan A NA Berkson Zachariah J ZJ Ochsenfeld Christian C Chmelka Bradley F BF Lotsch Bettina V BV

Chemistry of materials : a publication of the American Chemical Society 20190213 6

Tailorable sorption properties at the molecular level are key for efficient carbon capture and storage and a hallmark of covalent organic frameworks (COFs). Although amine functional groups are known to facilitate CO<sub>2</sub> uptake, atomistic insights into CO<sub>2</sub> sorption by COFs modified with amine-bearing functional groups are scarce. Herein, we present a detailed study of the interactions of carbon dioxide and water with two isostructural hydrazone-linked COFs with different polar ...[more]

PMID: 30930535

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Project description:Covalent organic frameworks (COFs) are an emerging material family having several potential applications. Their porous framework and redox-active centers enable gas/ion adsorption, allowing them to function as safe, cheap, and tunable electrode materials in next-generation batteries, as well as CO2 adsorption materials for carbon-capture applications. Herein, we develop four polyimide COFs by combining aromatic triamines with aromatic dianhydrides and provide detailed structural and electrochemical characterization. Through density functional theory (DFT) calculations and powder X-ray diffraction, we achieve a detailed structural characterization, where DFT calculations reveal that the imide bonds prefer to form at an angle with one another, breaking the 2D symmetry, which shrinks the pore width and elongates the pore walls. The eclipsed perpendicular stacking is preferable, while sliding of the COF sheets is energetically accessible in a relatively flat energy landscape with a few metastable regions. We investigate the potential use of these COFs in CO2 adsorption and electrochemical applications. The adsorption and electrochemical properties are related to the structural and chemical characteristics of each COF, giving new insights for advanced material designs. For CO2 adsorption specifically, the two best performing COFs originated from the same triamine building block, which-in combination with force-field calculations-revealed unexpected structure-property relationships. Specific geometries provide a useful framework for Na-ion intercalation with retainable capacities and stable cycle life at a relatively high working potential (>1.5 V vs Na/Na+). Although this capacity is low compared to conventional inorganic Li-ion materials, we show as a proof of principle that these COFs are especially promising for sustainable, safe, and stable Na-aqueous batteries due to the combination of their working potentials and their insoluble nature in water.

Dataset Information

Molecular Insights into Carbon Dioxide Sorption in Hydrazone-Based Covalent Organic Frameworks with Tertiary Amine Moieties.

Publications

Molecular Insights into Carbon Dioxide Sorption in Hydrazone-Based Covalent Organic Frameworks with Tertiary Amine Moieties.

Similar Datasets

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