Selective adsorption of CO2 in TAMOF-1 for the separation of CO2/CH4 gas mixtures

Additional raw data files for manuscript "Selective adsorption of CO2 in TAMOF-1 for the separation of CO2/CH4 gas mixtures" by 

Santiago Capelo-Avilés,†a,b Mabel de Fez-Febré,†‡a,b Salvador R. G. Balestra,§c Juanjo Cabezas-Giménez,∆a,b Anton Vidal-Ferran,d,e Jesús González-Cobos,¶a Vanesa Lillo,a Oscar Fabelo,f Eduardo C. Escudero-Adán,a Larry R. Falvello,g José B. Parra,h Paolo Rumori,i Gemma Turnes-Palomino,i Carlos Palomino-Cabello,i Stefano Giancola,*j Sofia Calero*k and Jose Ramon Galan-Mascaros*a,d

abstract: TAMOF-1 is a robust, highly porous metal–organic framework built from Cu2+ centers linked by a L-histidine derivative. Thanks to its high porosity and homochirality, TAMOF-1 has shown interesting molecular recognition properties, being able to resolve racemic mixtures of small organic molecules in liquid solution. Now, we have discovered that TAMOF-1 also offers outstanding performance as solid adsorbent for CO2 physisorption, offering record CO2 adsorption capacity (> 3 mmol g–1) with excellent CO2/CH4 selectivity (> 50). We have identify the key interactions of CO2 within the TAMOF-1 framework by a combination of structural (neutron diffraction), spectroscopic and theoretical analyses which conclude a dual-site adsorption mechanism with the majority of adsorbed CO2 molecules occupying the empty voids in the TAMOF-1 channels without strong, directional supramolecular interactions. This dominant very weak binding opens the unique possibility of low energy regeneration process for convenient CO2 purification, since it can be recovered at very high purity in just ione step at ambient, mild conditions. These features identify TAMOF-1 as a viable solid-state adsorbent for the realization of low-cost biogas upgrading.

a.Institute of Chemical Research of Catalonia (ICIQ-CERCA), The Barcelona Institut of Science and Technology (BIST), Av. Països Catalans 16, Tarragona E-43007, Spain.

b.Departament de Química Física i Inorgànica, Universitat Rovira i Virgili, Marcel.lí Domingo s/n, Tarragona E-43007, Spain.

c. Centro de Nanociencia y Tecnologías Sostenibles (CNATS), Departamento de Sistemas Físicos, Químicos y Naturales, Universidad Pablo de Olavide, Ctra. Utrera km 1, ES-41013 Sevilla, Spain.

d.ICREA, Passeig Lluís Companys, 23, Barcelona E-08010, Spain.

e. Department of Inorganic and Organic Chemistry and the Institute of Nanoscience and Nanotechnology (IN2UB), Universitat de Barcelona (UB), 08028 Barcelona, Spain.

f. Institut Laue-Langevin, 71 Avenue des Martyrs, 38000, Grenoble, France.

g.Instituto de Nanociencia y Materiales de Aragón (INMA) and Departamento de Química Inorgánica, CSIC-Universidad de Zaragoza, Zaragoza 50009, Spain

h.Instituto de Ciencia y Tecnología del Carbono, INCAR-CSIC, Francisco Pintado Fe 26, 33011, Oviedo, Spain.

i.  Departamento de Química, Universidad de las Islas Baleares, Cra. de Valldemossa km 7.5, 07122, Palma de Mallorca, Spain.

j.  Orchestra Scientific S.L. Av. Països Catalans 16, Tarragona E-43007, Spain.

k. Materials Simulation and Modelling, Department of Applied Physics, Eindhoven University of Technology, 5600 MB Eindhoven, The Netherlands.

† These authors contributed equally to this work.

‡ Present address: Arcamo Controls, S. A. Juan Esplandiú 15, 28007 Madrid, Spain.

§ Present address: Área de Física Teórica, Departamento de Física Atómica, Molecular y Nuclear, Universidad de Sevilla, Av. Reina Mercedes s/n, Seville, Spain.

∆ Present address: Hipra Scientific, S.L.U., Av. La Selva 135, 17170 Amer, Spain.

¶ Present address: Institut de Recherches sur la Catalyse et l’Environnement de Lyon, UMR 5256, CNRS, Université Claude Bernard Lyon 1, 2 Avenue A. Einstein, 69626 Villeurbanne, France.