Nanoscale mixed metal frameworks for photocatalysis Allan Niidu , Tanel Mõistlik, Moonika Ferschel, Anastassia Raag Tallinn University of Technology Virumaa college, Järveküla tee 75, Kohtla-Järve, 32303, Estonia Cerium containing metal-organic frameworks (MOFs) are known photo-catalysts, although there thermal stability is lower than that of purely zirconium-based MOFs. Therefore easy and reliable access to the mixed metal frameworks is desirable. To that end a sustainable synthesis method was developed entailing the combination of liquid assisted grinding (LAG) and accelerated aging. In the first stage a modulator (acetic acid, trifluoroacetic acid or formc acid) was mixed in a planetary mill with ligand (terephthalic acid and its derivatives) and metal salts (cerium ammonium nitrate and zirconyl chloride) prior to the heating at 120 o C for 24 h. Thus formed MOFs were characterised by X-Ray powder diffraction, ATR-FTIR, nitrogen adsorption, thermogravimetric analysis and scanning electron microscopy. Ce to Zr ratio was determined by MP-AES. Photocatalytic activity was assessed in oxidative desulphurisation reactions of thiophenic compounds. References 1. Wu, X.-P.; Gagliardi, L.; Truhlar, D. G. Cerium Metal–Organic Framework for Photocatalysis. J. Am. Chem. Soc. 2018 , 140 (25), 7904–7912. https://doi.org/10.1021/jacs.8b03613. 2. Campanelli, M.; Del Giacco, T.; De Angelis, F.; Mosconi, E.; Taddei, M.; Marmottini, F.; D’Amato, R.; Costantino, F. Solvent- Free Synthetic Route for Cerium(IV) Metal–Organic Frameworks with UiO-66 Architecture and Their Photocatalytic Applications. ACS Appl. Mater. Interfaces 2019 , 11 (48), 45031–45037. https://doi.org/10.1021/acsami.9b13730. 3. Lomachenko, K. A.; Jacobsen, J.; Bugaev, A. L.; Atzori, C.; Bonino, F.; Bordiga, S.; Stock, N.; Lamberti, C. Exact Stoichiometry of CexZr6–x Cornerstones in Mixed-Metal UiO-66 Metal–Organic Frameworks Revealed by Extended X-Ray Absorption Fine Structure Spectroscopy. J. Am. Chem. Soc. 2018 , 140 (50), 17379–17383. https://doi.org/10.1021/ jacs.8b10343. 4. Lammert, M.; Glißmann, C.; Stock, N. Tuning the Stability of Bimetallic Ce(Iv)/Zr(Iv)-Based MOFs with UiO-66 and MOF-808 Structures. Dalton Trans. 2017 , 46 (8), 2425–2429. https://doi.org/10.1039/C7DT00259A.
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