Dataset Information

Cooperative CO₂ adsorption mechanism in a perfluorinated Ce^IV-based metal organic framework.

ABSTRACT: Adsorbents able to uptake large amounts of gases within a narrow range of pressure, i.e., phase-change adsorbents, are emerging as highly interesting systems to achieve excellent gas separation performances with little energy input for regeneration. A recently discovered phase-change metal-organic framework (MOF) adsorbent is F4_MIL-140A(Ce), based on Ce^IV and tetrafluoroterephthalate. This MOF displays a non-hysteretic step-shaped CO₂ adsorption isotherm, reaching saturation in conditions of temperature and pressure compatible with real life application in post-combustion carbon capture, biogas upgrading and acetylene purification. Such peculiar behaviour is responsible for the exceptional CO₂/N₂ selectivity and reverse CO₂/C₂H₂ selectivity of F4_MIL-140A(Ce). Here, we combine data obtained from a wide pool of characterisation techniques - namely gas sorption analysis, in situ infrared spectroscopy, in situ powder X-ray diffraction, in situ X-ray absorption spectroscopy, multinuclear solid state nuclear magnetic resonance spectroscopy and adsorption microcalorimetry - with periodic density functional theory simulations to provide evidence for the existence of a unique cooperative CO₂ adsorption mechanism in F4_MIL-140A(Ce). Such mechanism involves the concerted rotation of perfluorinated aromatic rings when a threshold partial pressure of CO₂ is reached, opening the gate towards an adsorption site where CO₂ interacts with both open metal sites and the fluorine atoms of the linker.

SUBMITTER: Cavallo M

PROVIDER: S-EPMC10012411 | biostudies-literature | 2023 Mar

REPOSITORIES: biostudies-literature

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Publications

Cooperative CO2 adsorption mechanism in a perfluorinated CeIV-based metal organic framework.

Cavallo Margherita M Atzori Cesare C Signorile Matteo M Costantino Ferdinando F Venturi Diletta Morelli DM Koutsianos Athanasios A Lomachenko Kirill A KA Calucci Lucia L Martini Francesca F Giovanelli Andrea A Geppi Marco M Crocellà Valentina V Taddei Marco M

Journal of materials chemistry. A 20230214 11

Adsorbents able to uptake large amounts of gases within a narrow range of pressure, i.e., phase-change adsorbents, are emerging as highly interesting systems to achieve excellent gas separation performances with little energy input for regeneration. A recently discovered phase-change metal-organic framework (MOF) adsorbent is F4_MIL-140A(Ce), based on CeIV and tetrafluoroterephthalate. This MOF displays a non-hysteretic step-shaped CO2 adsorption isotherm, reaching s ...[more]

PMID: 36936468

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Project description:Carbon capture and sequestration is a key element of global initiatives to minimize anthropogenic greenhouse gas emissions. Although many investigations of new candidate CO2 capture materials focus on equilibrium adsorption properties, it is also critical to consider adsorption/desorption kinetics when evaluating adsorbent performance. Diamine-appended variants of the metal-organic framework Mg2(dobpdc) (dobpdc4- = 4,4'-dioxidobiphenyl-3,3'-dicarboxylate) are promising materials for CO2 capture because of their cooperative chemisorption mechanism and associated step-shaped equilibrium isotherms, which enable large working capacities to be accessed with small temperature swings. However, the adsorption/desorption kinetics of these unique materials remain understudied. More generally, despite the necessity of kinetics characterization to advance adsorbents toward commercial separations, detailed kinetic studies of metal-organic framework-based gas separations remain rare. Here, we systematically investigate the CO2 adsorption kinetics of diamine-appended Mg2(dobpdc) variants using a thermogravimetric analysis (TGA) assay. In particular, we examine the effects of diamine structure, temperature, and partial pressure on CO2 adsorption and desorption kinetics. Importantly, most diamine-appended Mg2(dobpdc) variants exhibit an induction period prior to reaching the maximum rate of CO2 adsorption, which we attribute to their unique cooperative chemisorption mechanism. In addition, these materials exhibit inverse Arrhenius behavior, displaying faster adsorption kinetics and shorter induction periods at lower temperatures. Using the Avrami model for nucleation and growth kinetics, we determine rate constants for CO2 adsorption and quantitatively compare rate constants among different diamine-appended variants. Overall, these results provide guidelines for optimizing adsorbent design to facilitate CO2 capture from diverse target streams and highlight kinetic phenomena relevant for other materials in which cooperative chemisorption mechanisms are operative.

Dataset Information

Cooperative CO₂ adsorption mechanism in a perfluorinated Ce^IV-based metal organic framework.

Publications

Cooperative CO<sub>2</sub> adsorption mechanism in a perfluorinated Ce<sup>IV</sup>-based metal organic framework.

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