Simultaneous Coproduction of Xylonic Acid and Xylitol: Leveraging <i>In Situ</i> Hydrogen Generation and Utilization from Xylose

Pentose oxidation and reduction, processes yielding value-added sugar-derived acids and alcohols, typically involve separate procedures necessitating distinct reaction conditions. In this study, a novel one-pot reaction for the concurrent production of xylonic acid and xylitol from xylose is proposed. This reaction was executed at ambient temperature in the presence of a base, eliminating the need for external gases, by leveraging Pt-supported catalysts. Initial experiments using commercially available metal-supported carbon catalysts validated the superior activity of Pt. However, a notable decline in recycling performance was observed in Pt/C, which is attributed to the sintering of Pt nanoparticles. In contrast, the synthesized Pt-supported ZrO₂ catalysts exhibited enhanced recycling performance because of the strong metal-support interaction between Pt and the ZrO₂ support. Furthermore, mechanistic insights and density functional theory calculations show that product desorption involves a significantly higher energy barrier compared to substrate adsorption and hydrogenation, highlighting an efficient transfer hydrogenation mechanism leading to equivalent yields of both xylonic acid and xylitol. This study introduces a promising approach for the simultaneous production of sugar-derived acids and alcohols, with implications for sustainable catalysis and process optimization.