Impact of Macroporosity on the Transesterification of Triglycerides over MgO/SBA-15

Biofuels are critical drop-in replacement energy sources to support the decarbonisation of hard-to-abate sectors such as aviation and marine shipping. Transesterification of non-edible oils is a well-established route to biodiesel as a versatile liquid transport fuel, but is challenging to scale using existing homogeneous liquid base catalysts. In this work, we report the synthesis, characterisation, and application of silica-supported MgO solid base catalysts for triglyceride transesterification with methanol and highlight the impact of silica pore structure on performance. True liquid crystal templating enables the one-pot synthesis of mesoporous MgO/SBA-15 catalysts with variable Mg content, or hierarchical macroporous–mesoporous MgO/SBA-15 analogues through the addition of polystyrene nanospheres. Both MgO/SBA-15 families exhibit highly ordered pore networks; however, ~280 nm macropores stabilise Mg-O-Si interfacial species even at high Mg loading, in contrast to the mesoporous support that permits sintering of ~14 nm MgO nanocrystals. Hierarchical porous MgO/SBA-15 catalysts exhibit higher specific activity and conversion of tributyrin to methyl butyrate than their mesoporous analogues (3 mmol⋅h⁻¹⋅g⁻¹ versus 2 mmol⋅h⁻¹⋅g⁻¹ at 60 °C and 11 wt% Mg). The magnitude of this rate enhancement increases with triglyceride chain length, being approximately three-fold for trilaurin (C₁₂) transesterification at 90 °C, attributed to superior in-pore mass transport of bulky reactants through the hierarchical porous catalyst.