Solvent‐Free Hydrogenation of 5‐Hydroxymethylfurfural and Furfural to Furanyl Alcohols and their Self‐Condensation Polymers

Abstract 2,5‐Bis(hydroxymethyl)furan (BHMF) as well as furfuryl alcohol (FFA) are considered as highly valuable biomass‐derived alcohols resembling aromatic monomers in polymer synthesis. Herein, a series of cobaltic nitrogen‐doped carbon (Co−NC) catalysts calcinated at different temperatures were synthesized and tested for the solvent‐free hydrogenation of 5‐hydroxymethylfurfural (HMF) to prepare BHMF. It was found that the Co−NC catalyst calcinated at 600 °C (Co−NC‐600) exhibited a superior catalytic activity in the hydrogenation reaction mainly due to the doping of graphitic N, which probably facilitated the polarization of H 2 to afford H + and H − . Consequently, Co−NC‐600 offered a high BHMF/FFA yield greater than 90 % with a nearly complete conversion of HMF/furfural (FF) at the optimal conditions (80 °C, 4 h, and 5 MPa H 2 ). After the hydrogenation reaction, Co−NC catalyst was facilely recycled by magnetic separation, and the obtained BHMF/FFA was then successfully transformed into hypercrosslinked polymers with an excellent CO 2 /H 2 storage capacity comparable to aromatic hydroxymethyl polymers. Therefore, this is a novel and facile two‐step pathway for the conversion of biomass‐derived HMF/FF towards functional polymers from both industrial and environmental perspectives.