Cooperative CO2 adsorption mechanism in a perfluorinated CeIV-based metal organic framework
Margherita CavalloCesare AtzoriMatteo SignorileFerdinando CostantinoDiletta Morelli VenturiAthanasios KoutsianosKirill A. LomachenkoLucia CalucciFrancesca MartiniAndrea GiovanelliMarco GeppiValentina CrocellàMarco Taddei
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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 metal-organic framework based on CeIV and tetrafluoroterephthalate, dubbed F4_MIL-140A(Ce), displays a step-shaped CO2 adsorption isotherm, reaching saturation in conditions of temperature and pressure compatible with real life application in post-combustion carbon capture. 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 cooperative CO2 adsorption mechanism that involves concerted rotation of perfluorinated aromatic rings and interaction with open metal sites.Keywords:
Isothermal microcalorimetry
Saturation (graph theory)
Carbon fibers
The microcalorimetry is a method used for recording of the heat produced by a thermodinamic system in a scale of micronanojouls. One of the domains in which this method is used is the one called bacterial microcalorimetry, which studies the heat generated by the bacterial populations. The process of bacterial growth can be monitored in real time by the recording a graph of the generated power over time. The modern isothermal microcalorimeters allow the detection of a signal variation of only one microwatt. The estimated generated power of a bacteria is approximately 1-4pW thus only a small number of bacteria is necessary for the experiments. Recent studies in the field of bacterial microcalorimetry have demonstrated that, in standard conditions, this method can be reproductible and can be used to detect and characterize bacterial growth (through the study of the microcalorimetric growth curve particular to a bacterial species which is called a microcalorimetric fingerprint) and offers the new information in regards to bacterial metabolism. Also, microcalorimetry can offer information about bacterial interaction with different factors in the medium (for example, antibioticsubstances, in which case an antibiogram is obtained in 4-5 hours). In conclusion, we can say that microcalorimetry is a reproducible method, which offers an interesting perspective on bacterial characterization, with great scientific potential, and there are sufficient arguments to continue studies in this field.
Isothermal microcalorimetry
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