Structure control using bioderived solvents in electrochemical metal-organic framework synthesis Stephen Worrall 1 , Meha Bhindi 1 , Liam Massengo 1,2 , James Hammerton 1 , Matthew J. Derry 1 1 Aston Institute of Materials Research, Aston University, Birmingham, B4 7ET, UK 2 Polytech - Materials Department, Université de Montpellier, Montpellier, 34095, France Electrochemical synthesis of metal-organic frameworks (MOFs) has proven to possess many environmental advantages over traditional synthesis methods such as reduced energy use and shorter reaction times. However, the use of toxic, fossil fuel derived solvents such as N,N -dimethylformamide (DMF) presents a challenge to the environmental credentials of this method that has yet to be dealt with. Here we investigate bioderived solvents, CyreneTM and γ-valerolactone (GVL), as an alternative for the synthesis of a range of MOFs via the anodic deposition method. The obtained MOF materials are characterized using X-ray diffraction (XRD) and scanning electron microscopy (SEM) to confirm their identities and morphologies and for comparison with MOFs synthesized using the traditional DMF-based solvent systems. When using Cyrene TM and GVL solvents, crystalline MOF materials were obtained of comparable quality to those afforded using DMF. However in several cases, using Cyrene TM or GVL led to the formation of less stable, higher porosity MOF structures than those obtained using DMF, indicating that the larger bio solvent molecules may also play a templating role during the synthesis. This study successfully demonstrates the combination of the environmental advantages of electrochemical synthesis and bio solvents for MOF synthesis and suggests a novel and facile method for controlling the structures of the final MOF products. References 1. Xie, S.; Monnens, W.; Wan, K.; Zhang, W.; Guo, W.; Xu, M.; Vankelecom, I.; Zhang, X.; Fransaer, J. Cathodic Electrodeposition of MOF Films Using Hydrogen Peroxide. Chem. Int. Ed. 2021, 60(47), pp. 24950-24957 2. Butova, V.V.; Soltadov, M.A.; Guda, A.A.; Lomachenko, K.A.; Lamberti, C. Metal-organic frameworks: structure, properties, methods of synthesis and characterization. Chem. Rev. 2016, 85(280), pp. 287
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