Catalytic Transfer Hydrogenation of 5‐Hydroxymethylfurfural with Primary Alcohols over Skeletal CuZnAl Catalysts

Catalytic transfer hydrogenation (CTH) with alcohols has been increasingly employed as effective tool for biomass upgrading, however, relying predominantly on secondary alcohols. Herein, for the first time skeletal CuZnAl catalysts were employed for the activation of a primary alcohol, ethanol, for the hydrogenation 5-hydroxymethylfurfual (HMF) to 2,5-bis(hydroxymethyl)furan (BHMF) under a mild condition. The catalysts were extensively characterized to reveal the structure characteristics and surface compositions. Over 90 % yield of BHMF were obtained over the optimal CuZnAl-0.5 catalyst at the reaction temperatures of 100-120 °C. Reaction kinetics indicated a competitive adsorption between HMF and ethanol on the catalyst surface, with the activation of ethanol being the rate-determining step (apparent activation energy Ea =70.9 kJ mol-1 ). Preliminary adsorption investigation using combined attenuated total reflectance infrared spectroscopy and density functional theory calculation proposed a η2 -(O,O)-aldehyde, furoxy perpendicular configuration of HMF on catalyst surface. The catalyst was further applied to the CTH of various aldehydes to the corresponding alcohols with high yields, demonstrating the broad applicability of the current system.