Rapid Synthesis of Diesel Precursors from Biomass‐Derived Furanics Over Aluminum‐Doped Mesoporous Silica Sphere Catalysts

The condensation of biomass-derived molecules has been increasingly utilized as a sustainable strategy for the preparation of high-carbon precursors for high-density fuels, thus stimulating the demand for more efficient catalysts. This study concerns the synthesis of an aluminum-doped mesoporous silica sphere (Al-MSS) catalyst for the conversion of biobased furfural and 2-methylfuran into a C15 diesel precursor through a hydroxyalkylation/alkylation (HAA) reaction. A series of Al-MSS catalysts with different Si/Al ratios and calcination temperatures is prepared and extensively characterized, among which Al-MSS20-450 (Si/Al=20 : 1, calcined at 450 °C) exhibits unprecedentedly high reaction efficiency in catalyzing HAA reaction, offering a 94 % product yield at 140 °C in 20 min. The catalyst also gives high product yields across a broad temperature range from 80 °C to 140 °C with varied reaction time. Reaction kinetics reveal that both competitive substrate adsorption and temperature-dependent system viscosity affect the reaction efficiencies. Correlations between the catalytic activity and surface acid sites disclose that moderate and strong acid sites are primarily responsible for catalysis. Brønsted and Lewis acid sites are found by poisoning assays to work synergistically to catalyze the reaction, with the former being the primary sites. Finally, the catalyst displays good recycling performance, which further highlights its potential for industrial application.