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Embedded nano spin sensor for in situ probing of gas adsorption inside porous organic frameworks.

ABSTRACT: Spin-based sensors have attracted considerable attention owing to their high sensitivities. Herein, we developed a metallofullerene-based nano spin sensor to probe gas adsorption within porous organic frameworks. For this, spin-active metallofullerene, Sc₃C₂@C_80, was selected and embedded into a nanopore of a pyrene-based covalent organic framework (Py-COF). Electron paramagnetic resonance (EPR) spectroscopy recorded the EPR signals of Sc₃C₂@C₈₀ within Py-COF after adsorbing N₂, CO, CH₄, CO₂, C₃H₆, and C₃H₈. Results indicated that the regularly changing EPR signals of embedded Sc₃C₂@C₈₀ were associated with the gas adsorption performance of Py-COF. In contrast to traditional adsorption isotherm measurements, this implantable nano spin sensor could probe gas adsorption and desorption with in situ, real-time monitoring. The proposed nano spin sensor was also employed to probe the gas adsorption performance of a metal-organic framework (MOF-177), demonstrating its versatility. The nano spin sensor is thus applicable for quantum sensing and precision measurements.

SUBMITTER: Zhang J

PROVIDER: S-EPMC10427628 | biostudies-literature | 2023 Aug

REPOSITORIES: biostudies-literature

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Embedded nano spin sensor for in situ probing of gas adsorption inside porous organic frameworks.

Zhang Jie J Liu Linshan L Zheng Chaofeng C Li Wang W Wang Chunru C Wang Taishan T

Nature communications 20230815 1

Spin-based sensors have attracted considerable attention owing to their high sensitivities. Herein, we developed a metallofullerene-based nano spin sensor to probe gas adsorption within porous organic frameworks. For this, spin-active metallofullerene, Sc3C2@C80, was selected and embedded into a nanopore of a pyrene-based covalent organic framework (Py-COF). Electron paramagnetic resonance (EPR) spectroscopy recorded the EPR signals of Sc3C2 ...[more]

PMID: 37582960

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Project description:Framework materials at the molecular level, such as metal-organic frameworks (MOF), were recently found to exhibit exotic and counterintuitive micromechanical properties. Stimulated by host-guest interactions, these so-called soft porous crystals can display counterintuitive adsorption phenomena such as negative gas adsorption (NGA). NGA materials are bistable frameworks where the occurrence of a metastable overloaded state leads to pressure amplification upon a sudden framework contraction. How can we control activation barriers and energetics via functionalization of the molecular building blocks that dictate the frameworks' mechanical response? In this work we tune the elastic and inelastic properties of building blocks at the molecular level and analyze the mechanical response of the resulting frameworks. From a set of 11 frameworks, we demonstrate that widening of the backbone increases stiffness, while elongation of the building blocks results in a decrease in critical yield stress of buckling. We further functionalize the backbone by incorporation of sp3 hybridized carbon atoms to soften the molecular building blocks, or stiffen them with sp2 and sp carbons. Computational modeling shows how these modifications of the building blocks tune the activation barriers within the energy landscape of the guest-free bistable frameworks. Only frameworks with free energy barriers in the range of 800 to 1100 kJ mol-1 per unit cell, and moderate yield stress of 0.6 to 1.2 nN for single ligand buckling, exhibit adsorption-induced contraction and negative gas adsorption. Advanced experimental in situ methodologies give detailed insights into the structural transitions and the adsorption behavior. The new framework DUT-160 shows the highest magnitude of NGA ever observed for nitrogen adsorption at 77 K. Our computational and experimental analysis of the energetics and mechanical response functions of porous frameworks is an important step towards tuning activation barriers in dynamic framework materials and provides critical design principles for molecular building blocks leading to pressure amplifying materials.

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

Embedded nano spin sensor for in situ probing of gas adsorption inside porous organic frameworks.

Publications

Embedded nano spin sensor for in situ probing of gas adsorption inside porous organic frameworks.

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