Heteroatom Lewis acid zeolites: synthesis, characterization and application in the conversion of biomass-derived oxygenates

Heteroatom (such as Ti, Sn, Zr, and Hf) zeolites that contain Lewis acid site (LAS) centers with tetrahedral coordination confined in micropores with various topologies are able to catalyze reactions distinct from those catalyzed by Br & oslash;nsted acid sites (BASs). In particular, these LAS centers are able to coordinate with two oxygen atoms of one or two oxygenated molecules on a single LAS simultaneously, which are suitable for the conversion of biomass-derived oxygenates via unique reaction pathways, and have been widely explored in the conversion of biomass-derived oxygenates to value-added products. In this review, methods of conventional hydrothermal synthesis, improved direct synthesis (such as interzeolite transformation and dry gel conversion) and post-synthesis (such as solid-state ion change, structural reconstruction and grafting) are compared. Next, approaches for the qualification and quantification of the location (framework or extra-framework), fine structure (closed or open), and acidity of heteroatom centers are summarized. Thereafter, we present the applications of Lewis acid zeolites in the conversion of platform oxygenates of hexoses, furan derivatives and acid derivatives via reactions of isomerization, Meerwein-Ponndorf-Verley reduction, oxidation, and ketonization. Notably, the integration of multiple steps into a one-pot cascade reaction for the conversion of oxygenates (for example, glucose to 5-hydroxymethylfurfural and furfural to gamma-valerolactone) mediated by the synergy of LASs and BASs or metal sites is also discussed. Finally, the opportunities and challenges in the low-cost synthesis and large-scale application of Lewis acid zeolites for the green and sustainable synthesis of chemicals are proposed. This review summarizes recent advances in the synthesis, characterization and application of heteroatom (Ti, Zr, Sn, and Hf) Lewis acid zeolites in the conversion of biomass-derived oxygenates.