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 (CoÀ NC) catalysts calcinated at different temperatures were synthesized and tested for the solvent-free hydrogenation of 5hydroxymethylfurfural (HMF) to prepare BHMF. It was found that the CoÀ NC catalyst calcinated at 600 °C (CoÀ 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 À .Consequently, CoÀ 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, CoÀ 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.

Biobased 2,5-Bis(hydroxymethyl)furan as a Versatile Building Block for Sustainable Polymeric Materials

“…Schematic representation of BHMF conversion to a hyper-cross-linked polymer (HCP). Reproduced with permission from ref . Copyright 2022 Wiley-VCH GmbH.…”

“…Recently, Wang et al used a cobaltic nitrogen-doped carbon catalyst for the production of BHMF from HMF in high conversion and yield, 99.3% and 91.5%, respectively. 69 Subsequently, BHMF was used for the production of a porous hyper-cross-linked polymer (HCP) (Figure 7), meant for CO 2 /H 2 storage. This was achieved via a Friedel−Crafts alkylation reaction using ferric chloride as the catalyst and 1,2dichloroethane as the solvent.…”

A unique air-assisted DMSO oxidation pathway for the highly efficient synthesis of 2,5-diformylfuran from 5-hydroxymethylfurfural/fructose

“…This implied that the calcination temperature has an important impact on the formation of defects over CoNC as confirmed by previous works. 43,44…”

Recent advances in catalytic synthesis of 2,5-furandimethanol from 5-hydroxymethylfurfural and carbohydrates

“…For example, an 89% yield of MFA was obtained after increasing the temperature and H 2 pressure to 100 °C and 30 bar, respectively. Wang et al (Wang et al 2022c ) reported the solvent-free synthesis of FDM from HMF over cobaltic nitrogen-doped carbon (Co–NC) catalysts, and a desirable FDM yield of 91.5% was afforded at 90 °C in the presence of 50 bar H 2 . The doped graphitic N might facilitate the polarization of H 2 to form H + and H – , which promoted the hydrogenation of HMF.…”