Hierarchical porous catalysts offer highly connected architectures for enhanced transport of bulky molecules and the sustainable manufacturing of bio-derived platform chemicals and fuels.

A family of faujasite (FAU) zeolites with different Si:Al ratio, and/or hierarchical porosity introduced via postsynthetic alkaline desilication treatment, have been evaluated as solid acid catalysts for esterification pretreatments of pyrolysis bio-oil components. Acetic acid esterification with aliphatic and aromatic alcohols including methanol, anisyl alcohol, benzyl alcohol, p-cresol and n-butanol was first selected as a model reaction to identify the optimum zeolite properties. Materials were fully characterised using N 2 porosimetry, ICP, XRD, XPS, FT-IR, pyridine adsorption, NH 3 TPD, In-situ ATR and inverse gas chromatography (IGC). IGC demonstrates that the surface polarity and hence hydrophobicity of FAU decreases with increased Si:Al ratio. Despite possessing a higher acid site loading and acetic acid adsorption capacity, high Al-content FAU possess weaker acidity than more siliceous catalysts. Esterification activity increases with acid strength and decreasing surface polarity following the order FAU30>FAU6>FAU2.6. The introduction of mesoporosity through synthesis of a hierarchical HFAU30 material further enhances esterification activity through improved acid site accessibility and hydrophobicity. Methanol was the most reactive alcohol for esterification, and evaluated with HFAU30 for the pretreatment of a real pyrolysis bio-oil, reducing the acid content by 76% under mild conditions.

Healthcare-associated infections and the rise of drug-resistant bacteria pose significant challenges to existing antibiotic therapies. Silver nanocomposites are a promising solution to the current crisis, however their therapeutic application requires improved understanding of underpinning structure-function relationships. A family of chemically and structurally modified mesoporous SBA-15 silicas were synthesized as porous host matrices to tune the physicochemical properties of silver nanoparticles. Physicochemical characterization by transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), X-ray absorption near-edge spectroscopy (XANES) and porosimetry demonstrate that functionalization by a titania monolayer and the incorporation of macroporosity both increase silver nanoparticle dispersion throughout the silica matrix, thereby promoting Ag2CO3 formation and the release of ionic silver in simulated tissue fluid. The Ag2CO3 concentration within functionalized porous architectures is a strong predictor for antibacterial efficacy against a broad spectrum of pathogens, including C. difficile and methicillin-resistant Staphylococcus aureus (MRSA).