Zirconium–lignosulfonate polyphenolic polymer for highly efficient hydrogen transfer of biomass-derived oxygenates under mild conditions

Both value-added utilization of low-rank renewable feedstocks to prepare catalytic materials and selective transformation of bioderived aldehydes are very attractive topics. Herein, lignosulfonate, a waste by-product from the paper industry, was simply assembled with ZrCl4 under non-toxic hydrothermal conditions for scalable preparation of Zr-containing polyphenolic biopolymer catalysts (Zr LS). Systematic characterizations indicated that the strong coordination between Zr4+ and phenolic hydroxyl groups in lignosulfonate led to the formation of strong Lewis acid-base couple sites (Zr4+−O2−) and porous inorganic-organic framework structure (mesopores centered at 6.1 nm), while the inherent sulfonic groups in lignosulphonate could serve as Bronsted acidic sites. The cooperative role of these versatile acid−base sites in Zr LS afforded excellent catalytic performance for Meerwein-Ponndorf-Verley (MPV) reaction of a broad range of bioderived platform chemicals under mild conditions (80 °C), especially of furfural (FF) to furfuryl alcohol (FA), in quantitative yields (96%) with high FA formation rate of 9600 μmol g−1 h−1 and TOF of 4.37 h−1. Kinetic studies revealed that the activation energy of the MPV reduction of FF was as low as 52.25 kJ/mol, accounting for the high reaction rate. Isotopic labelling experiments demonstrated direct hydrogen transfer from the α-C of 2-PrOH to the α-C of FF on acid-base sites was the rate-determining step. Moreover, Zr LS showed good recyclability for at least seven reaction cycles.