Solvent-mediated Zr-based coordination polymer with tunable acid properties for the dehydration of fructose and catalytic transfer hydrogenation of 5-hydroxymethylfurfural

Abstract

In this work, a porous Zirconium based coordination polymer (Zr-ATMP) was facilely synthesized at room temperature with amino tris(methylene phosphonic acid) (ATMP) as ligand, and the surface acidic sites could be adjusted in different solvents. Specifically, the coordination polymer with equivalent content of Bronsted and Lewis acid sites was synthesized in aqueous system, showing high-efficiency catalytic activity for fructose dehydration to 5-hydroxymethylfurfural (HMF). In comparison, the coordination polymer containing an abundance of Lewis acid sites was synthesized in DMF solvent, which efficiently catalyzed the transfer hydrogenation of HMF. Compared to the catalysts preparation in organic solvents, the coordinatively unsaturated Zr4+ could be hydrated in water during catalyst preparation, resulting in the generation of additional Bronsted acid sites at the cost of Lewis acid sites. This contribution proposed a facile approach to prepare Zr-based coordination polymer with tunable acid properties for biomass valorization.