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Continuous negative-to-positive tuning of thermal expansion achieved by controlled gas sorption in porous coordination frameworks.

ABSTRACT: Control of the thermomechanical properties of functional materials is of great fundamental and technological significance, with the achievement of zero or negative thermal expansion behavior being a key goal for various applications. A dynamic, reversible mode of control is demonstrated for the first time in two Prussian blue derivative frameworks whose coefficients of thermal expansion are tuned continuously from negative to positive values by varying the concentration of adsorbed CO₂. A simple empirical model that captures site-specific guest contributions to the framework expansion is derived, and displays excellent agreement with the observed lattice behaviour.

SUBMITTER: Auckett JE

PROVIDER: S-EPMC6242975 | biostudies-literature | 2018 Nov

REPOSITORIES: biostudies-literature

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Continuous negative-to-positive tuning of thermal expansion achieved by controlled gas sorption in porous coordination frameworks.

Auckett Josie E JE Barkhordarian Arnold A AA Ogilvie Stephen H SH Duyker Samuel G SG Chevreau Hubert H Peterson Vanessa K VK Kepert Cameron J CJ

Nature communications 20181119 1

Control of the thermomechanical properties of functional materials is of great fundamental and technological significance, with the achievement of zero or negative thermal expansion behavior being a key goal for various applications. A dynamic, reversible mode of control is demonstrated for the first time in two Prussian blue derivative frameworks whose coefficients of thermal expansion are tuned continuously from negative to positive values by varying the concentration of adsorbed CO<sub>2</sub ...[more]

PMID: 30451823

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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

Continuous negative-to-positive tuning of thermal expansion achieved by controlled gas sorption in porous coordination frameworks.

Publications

Continuous negative-to-positive tuning of thermal expansion achieved by controlled gas sorption in porous coordination frameworks.

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