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A New Anilato-based Series of 3D MOFs for Environmental Quality
1 , 1 , 1 , 1 , 2 , 2 , 1 , 3 , * 1
1  Department of Chemical and Geological Sciences, University of Cagliari, Highway 554, Crossroads for Sestu, I-09042 Monserrato, CA, Italy
2  Dipartimento di Chimica, Centro NIS, Unità di Ricerca INSTM, Università di Torino, Via G. Quarello 15, I-10135 and Via P. Giuria 7, Torino I-10125, Italy
3  Department of Science and High Technology, University of Insubria, Via Valleggio 11, 22100 Como, Italy
Academic Editor: Federico Bella

Abstract:

Capturing CO2 from the atmosphere represents a key challenge, since CO2 has been recognized as the primary anthropogenic greenhouse contributor to the increase in Earth’s average temperature. Their high porosity, tunable pore size and large surface area make Metal-Organic Frameworks (MOFs) promising candidates to uptake and separate CO2 from gaseous mixtures. In 2021, some of us synthesized, via hydrothermal approach, a new microporous MOF, formulated as [Co(trz2An)]n·2.5H2O (CAMOF-1), by combining 3, 6-N-ditriazolyl-2,5-dihydroxy-1,4-benzoquinone, as organic linker, with a CoII metal node in a 1:1 stoichiometric ratio. This MOF showed a favourable balance of high selectivity, high adsorption capacity, and high regenerability, thus being a promising candidate for CO2 gas separation processes. We report herein the synthesis, crystal structure and performance studies of three new microporous MOFs obtained by combining trz2An with CuII, ZnII and FeII metal nodes, formulated as [Cu(trz2An)].nH2O (CAMOF-2), Zn(Trz2An).3H2O (CAMOF-3) and Fe(Trz2An). 3H2O (CAMOF-4). CAMOF-2-4 show a 3D robust structure, with a pore size of 3.46 Å for CAMOF-2 and 3,89 Å for CAMOF-3,4, consistent with the kinetic radius of CO2 and absorption capacity of 2 molecules of CO2 / unit formula as confirmed by pore analysis data. Static and Dynamic Adsorption Measurements revealed i) remarkable carbon dioxide uptake, ii) high selectivity in CO2:N2 gas mixtures, iii) easy regeneration in mild conditions. Furthermore, i) preliminary CO2 electroreduction studies showed a good capability of CAMOF-2 to convert carbon dioxide into ethylene and ii) adsorption test removal, performed on CAMOF-3 and CAMOF-4, revealed a good performance inremoving CdII, at different pH ranges and concentrations. In conclusion, trz2An is a strategic organic linker, which combined with different transition metal ions, gave rise to a novel thermal stable, robust, microporous 3D MOFs family employing for environmental quality.

Keywords: Metal-Organic Frmeworks; porous materials; CO2 uptake; CO2 reduction; Cd(II) removal
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