Enhancement of Ethane Selectivity in Ethane-Ethylene Mixtures by Perfluoro Groups in Zr-Based Metal-Organic Frameworks

authors	Pires, J; Fernandes, J; Dedecker, K; Gomes, JRB; Perez-Sanchez, G; Nouar, F; Serre, C; Pinto, ML
nationality	International
journal	ACS APPLIED MATERIALS & INTERFACES
author keywords	gas separation; metal-organic frameworks; ethane/ethylene separation; gas adsorption; simulation
keywords	TOTAL-ENERGY CALCULATIONS; ADSORPTIVE SEPARATION; MOLECULAR-DYNAMICS; FORCE-FIELD; MOFS; UIO-66(ZR); IRMOF-8; OLEFIN; CLAYS; ZIF-7
abstract	A series of zirconium dicarboxylate-based metal-organic frameworks (Zr MOFs) of the UiO-66 (tetrahedral and octahedral cages) or MIL-140 (triangular channels) structure type were investigated for the separation of ethane/ethylene mixtures. The adsorption, investigated both experimentally and computationally, revealed that the size and type of pores have a more pronounced effect on the selectivity than the aromaticity of the linker. The increase in pore size when changing from benzene to naphthalene (NDC) dicarboxylate ligand makes UiO-NDC less selective (1.3-1.4) than UiO-66 (1.75-1.9) within the pressure range (100-1000 kPa), while the three-dimensional (3D) pores of the UiOs favor the adsorption of ethane due to the interactions between ethane with more spacers than in the case of the 1D channels of MIL-140s. The impact of the functionalization revealed a very interesting increase of selectivity when two perfluoro groups are present on the aromatic ring (UiO-66-2CF(3)) (value of 2.5 up to 1000 kPa). Indeed, UiO-66-2CF3 revealed a unique combination of selectivity and working capacity at high pressures. This is due to a complex adsorption mechanism involving a different distribution of the guest molecules in the different cages associated with changes in the ligand/perfluoro orientation when the pressure increases, favoring the ethane adsorption at high pressures.
publisher	AMER CHEMICAL SOC
issn	1944-8244
isbn	1944-8252
year published	2019
volume	11
issue	30
beginning page	27410
ending page	27421
digital object identifier (doi)	10.1021/acsami.9b07115
web of science category	Nanoscience & Nanotechnology; Materials Science, Multidisciplinary
subject category	Science & Technology - Other Topics; Materials Science
unique article identifier	WOS:000479020300093