The importance of water-tolerance in sustainable fuel production Lee Durndell 1 and Vannia dos Santos Durndell 1 , Mark A. Isaacs 2,3 , Adam F. Lee 4* and Karen Wilson 5* 1 School of Geography, Earth and Environmental Sciences, Plymouth University, Plymouth, PL4 8AA, UK, 2 Department of Chemistry, University College London, London, WC1E 6BT, UK, 3 HarwellXPS, Research Complex at Harwell, Rutherford Appleton Laboratory, Didcot, Oxfordshire, OX11 0DE, UK, 4 Centre for Catalysis and Clean Energy, School of Environment and Science, Griffith University, QLD 4222, Australia, 5 Centre for Advanced Materials and Industrial Chemistry (CAMIC), RMIT University, Melbourne VIC 3000, Australia. Catalyst hydrophobicity is an oft-neglected property despite its significance in aqueous phase reactions and those wherein water is a by-product, such as condensation and esterification. Selective incorporation of organic moieties, such as phenyl groups, into the framework of well-established mesoporous SBA-15 silica imparts facile (and tuneable) changes in support surface hydrophobicity and solid acidity, while preserving the textural properties of the parent silica. In this work, we report the successful synthesis of WO x /ZrO x impregnated periodic mesoporous organosilicas (PMOs) of varying organic framework content, through the stepwise substitution of bis(triethoxysilyl)benzene (BTSB) for tetraethyl orthosilicate (TEOS), followed by tungsten and zirconium co-grafting.The resulting catalysts exhibit excellent turnover frequencies (TOFs) for the esterification of C 3 –C 16 carboxylic acids in a variety of alcohols (in batch and flow); and in the acetalisation of furfural to sustainable aviation fuel (SAF) precursors. The superior activity and stability (water tolerance up to 50 mol%) of WO x /ZrO x /PMO versus WO x /ZrO x /SBA-15 is attributed to the displacement of water from in-pore active sites, mitigating reverse hydrolysis reactions. Such hydrophobic, solid acid catalysts are anticipated to find widespread application in aqueous phase synthesis, particularly of biorefinery output streams. References 1. dos Santos-Durndell, V.C., Durndell, L.J., Isaacs, M.A., Lee, A.F. and Wilson, K., 2023. WOx/ZrOx functionalised periodic mesoporous organosilicas as water-tolerant catalysts for carboxylic acid esterification. Sustainable Energy & Fuels, 7(7), pp.1677-1686. 2. Manayil, J.C., dos Santos, V.C., Jentoft, F.C., Granollers Mesa, M., Lee, A.F. and Wilson, K., 2017. Octyl Co ‐ grafted PrSO 3 H/SBA ‐ 15: Tunable Hydrophobic Solid Acid Catalysts for Acetic Acid Esterification. ChemCatChem, 9(12), pp.2231- 2238. 3. Morales, G., Paniagua, M., de la Flor, D., Sanz, M., Leo, P., López-Aguado, C., Hernando, H., Orr, S.A., Wilson, K., Lee, A.F. and Melero, J.A., 2023. Aldol condensation of furfural and methyl isobutyl ketone over Zr-MOF-808/silica hybrid catalysts. Fuel, 339, p.127465.
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