p‐Xylene is a major commodity chemical used for the production of polyethylene terephthalate, a polymer with applications in polyester fibers, films, and bottles. The Diels–Alder cycloaddition of 2,5‐dimethylfuran and ethylene and the subsequent dehydration of the cycloadduct intermediate is an attractive reaction pathway to produce renewable p‐xylene from biomass feedstocks. However, the highest yields reported previously do not exceed 75 %. We report that P‐containing zeolite Beta is an active, stable, and selective catalyst for this reaction with an unprecedented p‐xylene yield of 97 %. It can catalyze the dehydration reaction selectively from the furan‐ethylene cycloadduct to p‐xylene without the production of alkylated and oligomerized products. This behavior is distinct from that of Al‐containing zeolites and other solid phosphoric acid catalysts and establishes a commercially attractive process for renewable p‐xylene production.

Renewable jet-fuel-range alkanes are synthesized by hydrodeoxygenation of lignocellulose-derived high-carbon furylmethanes over ReO -modified Ir/SiO catalysts under mild reaction conditions. Ir-ReO /SiO with a Re/Ir molar ratio of 2:1 exhibits the best performance, achieving a combined alkanes yield of 82-99 % from C -C furylmethanes. The catalyst can be regenerated in three consecutive cycles with only about 12 % loss in the combined alkanes yield. Mechanistically, the furan moieties of furylmethanes undergo simultaneous ring saturation and ring opening to form a mixture of complex oxygenates consisting of saturated furan rings, mono-keto groups, and mono-hydroxy groups. Then, these oxygenates undergo a cascade of hydrogenolysis reactions to alkanes. The high activity of Ir-ReO /SiO arises from a synergy between Ir and ReO , whereby the acidic sites of partially reduced ReO activate the C-O bonds of the saturated furans and alcoholic groups while the Ir sites are responsible for hydrogenation with H .

Solvent selection is a pressing challenge in developing efficient and selective liquid phase catalytic processes, as predictive understanding of the solvent effect remains lacking. In this work, an attenuated total reflection infrared spectroscopy technique is developed to quantitatively measure adsorption isotherms on porous materials in solvent and decouple the thermodynamic contributions of van der Waals interactions within zeolite pore walls from those of pore-phase proton transfer. While both the pore diameter and the solvent identity dramatically impact the confinement (adsorption) step, the solvent identity plays a dominant role in proton-transfer. Combined computational and experimental investigations show increasingly favorable pore-phase proton transfer to pyridine in the order: water < acetonitrile < 1,4dioxane. Equilibrium methods unaffected by mass transfer limitations are outlined for quantitatively estimating fundamental thermodynamic values using statistical thermodynamics.