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Electrostatic Design of the Nanoscale Internal Surfaces of Porous Covalent Organic Frameworks.

ABSTRACT: It is well established that the collective action of assemblies of dipoles determines the electronic structure of surfaces and interfaces. This raises the question, to what extent the controlled arrangement of polar units can be used to also tune the electronic properties of the inner surfaces of materials with nanoscale pores. In the present contribution, state-of-the-art density-functional theory calculations are used to show for the prototypical case of covalent organic frameworks (COFs) that this is indeed possible. Decorating pore walls with assemblies of polar entities bonded to the building blocks of the COF layers triggers a massive change of the electrostatic energy within the pores. This, inevitably, also changes the relative alignment between electronic states in the framework and in guest molecules and is expected to have significant impacts on charge separation in COF heterojunctions, on redox reactions in COFs-based electrodes, and on (photo)catalysis.

SUBMITTER: Zojer E

PROVIDER: S-EPMC10141416 | biostudies-literature | 2023 Apr

REPOSITORIES: biostudies-literature

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Electrostatic Design of the Nanoscale Internal Surfaces of Porous Covalent Organic Frameworks.

Zojer Egbert E

Nano letters 20230404 8

It is well established that the collective action of assemblies of dipoles determines the electronic structure of surfaces and interfaces. This raises the question, to what extent the controlled arrangement of polar units can be used to also tune the electronic properties of the inner surfaces of materials with nanoscale pores. In the present contribution, state-of-the-art density-functional theory calculations are used to show for the prototypical case of covalent organic frameworks (COFs) that ...[more]

PMID: 37014999

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Project description:Several synthetic methods have recently emerged to develop high-surface-area solid-state organic framework-based materials into free-flowing liquids with permanent porosity. The fluidity of these porous liquid (PL) materials provides them with advantages in certain storage and transport processes. However, most framework-based materials necessitate the use of cryogenic temperatures to store weakly bound gases such as H2, temperatures where PLs lose their fluidity. Covalent organic framework (COF)-based PLs that could reversibly form stable complexes with H2 near ambient temperatures would represent a promising development for gas storage and transport applications. We report here the development, characterization, and evaluation of a material with these remarkable characteristics based on Cu(I)-loaded COF colloids. Our synthetic strategy required tailoring conditions for growing robust coatings of poly(dimethylsiloxane)-methacrylate (PDMS-MA) around COF colloids using atom transfer radical polymerization (ATRP). We demonstrate exquisite control over the coating thickness on the colloidal COF, quantified by transmission electron microscopy and dynamic light scattering. The coated COF material was then suspended in a liquid polymer matrix to make a PL. CO2 isotherms confirmed that the coating preserved the general porosity of the COF in the free-flowing liquid, while CO sorption measurements using diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) confirmed the preservation of Cu(I) coordination sites. We then evaluated the gas sorption phenomenon in the Cu(I)-COF-based PLs using DRIFTS and temperature-programmed desorption measurements. In addition to confirming that H2 transport is possible at or near mild refrigeration temperatures with these materials, our observations indicate that H2 diffusion is significantly influenced by the glass-transition temperature of both the coating and the liquid matrix. The latter result underscores an additional potential advantage of PLs in tailoring gas diffusion and storage temperatures through the coating composition.

Dataset Information

Electrostatic Design of the Nanoscale Internal Surfaces of Porous Covalent Organic Frameworks.

Publications

Electrostatic Design of the Nanoscale Internal Surfaces of Porous Covalent Organic Frameworks.

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