Challenges of and Insights into Acid-Catalyzed Transformations of Sugars

The selective transformation of hexose and pentose sugars to intermediate platform chemicals, such as furans, is an essential step in the conversion of cellulosic and hemicellulosic biomass to biofuels and biochemicals. Yet, many challenges in achieving commercially viable processes remain. In this feature article, we outline challenges that need to be overcome to enable these transformations. Then, we present the newly introduced acid-catalyzed isomerization of aldose sugars to ketose sugars via a class of solid Lewis acid catalysts (e.g., Sn-Beta, Ti-Beta). We elucidate mechanistic insights arising from subnanometer cooperativity and solvent effects that can be controlled to tune reaction pathways and selectivity and draw parallels between heterogeneous and homogeneous Lewis acid catalysts. Subsequently, we discuss fructose dehydration to 5-hydroxyl-methylfurfural (HMF) via homogeneous and heterogeneous Brønsted acid-catalyzed chemistry. We show how fundamental insights arising from the combination of kinetics, spectroscopy, and multiscale simulations rationalize the improved yield of HMF in water-organic cosolvents. The stability of heterogeneous Lewis acid catalysts under low pH enables tandem Brønsted and Lewis acid-catalyzed reactions in a single pot that overcomes equilibrium limitations and gives a high HMF yield starting from sugar raw materials. Additionally, we provide an overview of multicomponent adsorption of biomass derivatives from solution in microporous materials and discuss how structure-property relations can lead to superior micro- and micromesoporous carbon adsorbents for reactive adsorption toward high HMF yield. Finally, we provide an outlook for the field.