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Instruments / Technical Area	Publication Details	Published	Actions
I19-Small Molecule Single Crystal Diffraction	Gas transport in mixed matrix membranes: Two methods for time lag determination Alessio Fuoco , Marcello Monteleone , Elisa Esposito , Rosaria Bruno , Jesus Ferrando-Soria , Emilio Pardo , Donatella Armentano , Johannes Carolus Jansen Computation 8(2), 28 DOI: 10.3390/computation8020028 Diamond Proposal Number(s): [18768] Open Access Show Abstract ▼ Abstract: The most widely used method to measure the transport properties of dense polymeric membranes is the time lag method in a constant volume/pressure increase instrument. Although simple and quick, this method provides only relatively superficial, averaged data of the permeability, diffusivity, and solubility of gas or vapor species in the membrane. The present manuscript discusses a more sophisticated computational method to determine the transport properties on the basis of a fit of the entire permeation curve, including the transient period. The traditional tangent method and the fitting procedure were compared for the transport of six light gases (H2, He, O2, N2, CH4, and CO2) and ethane and ethylene in mixed matrix membranes (MMM) based on Pebax®1657 and the metal–organic framework (MOF) CuII2(S,S)-hismox·5H2O. Deviations of the experimental data from the theoretical curve could be attributed to the particular MOF structure, with cavities of different sizes. The fitting procedure revealed two different effective diffusion coefficients for the same gas in the case of methane and ethylene, due to the unusual void morphology in the MOFs. The method was furthermore applied to mixed gas permeation in an innovative constant-pressure/variable-volume setup with continuous analysis of the permeate composition by an on-line mass-spectrometric residual gas analyzer. This method can provide the diffusion coefficient of individual gas species in a mixture, during mixed gas permeation experiments. Such information was previously inaccessible, and it will greatly enhance insight into the mixed gas transport in polymeric or mixed matrix membranes.	Apr 2020
I19-Small Molecule Single Crystal Diffraction	Efficient gas separation and transport mechanism in rare hemilabile metal-organic framework Marta Mon , Rosaria Bruno , Estefanía Tiburcio , Aida Grau-Atienza , Antonio Sepulveda-Escribano , Enrique V Ramos-Fernandez , Alessio Fuoco , Elisa Esposito , Marcello Monteleone , Johannes Carolus Jansen , Joan Cano , Jesus Ferrando-Soria , Donatella Armentano , Emilio Pardo Chemistry Of Materials DOI: 10.1021/acs.chemmater.9b01995 Diamond Proposal Number(s): [18768] Show Abstract ▼ Abstract: Understand/visualize the established interactions between gases and adsorbents is mandatory to implement better per-formant materials in adsorption/separation processes. Here we report the unique behavior of a rare example of a hemila-bile chiral three-dimensional metal-organic framework (MOF) with an unprecedented qtz-e-type topology, with formula CuII2(S,S)-hismox . 5H2O (1) (hismox = bis[(S)-histidine]oxalyl diamide). 1 exhibits a continuous and reversible breath-ing behavior, based on the hemilability of carboxylate groups from L-histidine. In-situ powder (PXRD) and single crystal X-ray diffraction (SCXRD) using synchrotron radiation allowed to unveil the crystal structures of 4 different host-guest adsorbates (Ar, N2, CO2 and C3H6@1), the rationalization of the breathing motion and unravel the mechanisms govern-ing the adsorption of these gases. Then, this information has been transferred to implement efficient separations of mix-tures of industrial and environmental relevance –CO2/N2, CO2/CH4 and C3H8/C3H6 using 1 in packed columns as the sta-tionary phase and dispersed in a mixed matrix membrane.	Jul 2019

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