Fast pyrolysis bio-oils possess unfavourable physicochemical properties and poor stability, due in large part to the presence of carboxylic acids, which hinders their use as biofuels. Catalytic esterification offers an atom and energy efficient route to upgrade pyrolysis bio-oils. Propyl sulfonic acid silicas are active for carboxylic acid esterification but suffer mass-transport limitations for bulky substrates. Macropore (200 nm) incorporation enhances the activity of mesoporous SBA-15 architectures (post-functionalised by hydrothermal saline promoted grafting) for the esterification of linear carboxylic acids, with the magnitude of turnover frequency (TOF) enhancement increasing with chain length from 5 % (C3) to 110 % (C12). Macroporous-mesoporous PrSO3H/SBA-15 also offers a two-fold TOF enhancement over its mesoporous analogue for the esterification of a real thermal fast pyrolysis bio-oil derived from woodchips. The total acid number was reduced by 57 %, with GCxGC-ToFMS evidencing ester and ether formation accompanying loss of acid, phenolic, aldehyde and ketone components.
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