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Cooperative CO 2 adsorption mechanism in a perfluorinated Ce IV -based metal organic framework
Adsorbents able to uptake large amounts of gases within a narrow range of pressure, , 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 frame...
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Published in: | Journal of materials chemistry. A, Materials for energy and sustainability Materials for energy and sustainability, 2023-03, Vol.11 (11), p.5568-5583 |
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Main Authors: | , , , , , , , , , , , , |
Format: | Article |
Language: | English |
Citations: | Items that this one cites Items that cite this one |
Online Access: | Get full text |
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Summary: | Adsorbents able to uptake large amounts of gases within a narrow range of pressure,
, 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
and tetrafluoroterephthalate. This MOF displays a non-hysteretic step-shaped CO
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 CO
/N
selectivity and reverse CO
/C
H
selectivity of F4_MIL-140A(Ce). Here, we combine data obtained from a wide pool of characterisation techniques - namely gas sorption analysis,
infrared spectroscopy,
powder X-ray diffraction,
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 CO
adsorption mechanism in F4_MIL-140A(Ce). Such mechanism involves the concerted rotation of perfluorinated aromatic rings when a threshold partial pressure of CO
is reached, opening the gate towards an adsorption site where CO
interacts with both open metal sites and the fluorine atoms of the linker. |
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ISSN: | 2050-7488 2050-7496 |
DOI: | 10.1039/D2TA09746J |