The synthesis of chemicals from renewable, biomass-derived feedstocks has garnered significant attention in recent years, driven by the urgent need to reduce reliance on nonrenewable fossil resources and promote sustainable material development. Among various bio-based building blocks, 5-hydroxymethylfurfural (HMF), 2,5-furandicarboxylic acid (FDCA), and 2,5-diformylfuran (DFF) are particularly valuable platform molecules. These furanoid compounds, typically obtained through acid-catalyzed dehydration of carbohydrates, serve as precursors for a wide range of fine chemicals and high-performance polymers. The resulting furan-based polymers exhibit interesting chemical properties conferred by the furan moiety. They can be reversibly cross-linked with bis-maleimides via the Diels-Alder reaction, obtaining covalent adaptative networks with self-healing properties. This contribution focuses on DFF-based polyimines, synthesized through Schiff-base condensation between DFF and various diamine or polyamine spacers. The resulting polymers feature imine linkages (–C=N–) that are thermally robust and offer coordination sites for metal ions and particles. The lone pair on the imine nitrogen, in conjunction with the oxygen atoms on the furan ring, acts synergistically to chelate metal species, resulting in stable metal–polymer composites. These DFF-derived polyimines typically exhibit high thermal stability, insolubility in a wide range of organic solvents, and adjustable morphologies depending on the chosen amine monomer. Overall, DFF-derived polyimines represent a versatile class of entirely biosourced polymers that combine robust mechanical and thermal properties with functional sites for metal coordination. Such attributes make them highly suitable candidates for next-generation heterogeneous catalysts, especially in energy-related transformations. In this context, we present preliminary work on incorporating gold nanoparticles (AuNPs) as a catalytic species within DFF-polyimine matrices; these hybrid materials demonstrate promising activity in formic acid dehydrogenation (FAD), a process of considerable interest for hydrogen storage and release.
BIOSOURCED FURAN-DERIVED POLYIMINES AS SUPPORTS FOR METAL CATALYST FOR FORMIC ACID DEHYDROGENATION TO H2
Impemba Salvatore
;Crispino Valentina Agnese;Contento Irene;Grassi Alfonso;Buonerba Antonio.
2025
Abstract
The synthesis of chemicals from renewable, biomass-derived feedstocks has garnered significant attention in recent years, driven by the urgent need to reduce reliance on nonrenewable fossil resources and promote sustainable material development. Among various bio-based building blocks, 5-hydroxymethylfurfural (HMF), 2,5-furandicarboxylic acid (FDCA), and 2,5-diformylfuran (DFF) are particularly valuable platform molecules. These furanoid compounds, typically obtained through acid-catalyzed dehydration of carbohydrates, serve as precursors for a wide range of fine chemicals and high-performance polymers. The resulting furan-based polymers exhibit interesting chemical properties conferred by the furan moiety. They can be reversibly cross-linked with bis-maleimides via the Diels-Alder reaction, obtaining covalent adaptative networks with self-healing properties. This contribution focuses on DFF-based polyimines, synthesized through Schiff-base condensation between DFF and various diamine or polyamine spacers. The resulting polymers feature imine linkages (–C=N–) that are thermally robust and offer coordination sites for metal ions and particles. The lone pair on the imine nitrogen, in conjunction with the oxygen atoms on the furan ring, acts synergistically to chelate metal species, resulting in stable metal–polymer composites. These DFF-derived polyimines typically exhibit high thermal stability, insolubility in a wide range of organic solvents, and adjustable morphologies depending on the chosen amine monomer. Overall, DFF-derived polyimines represent a versatile class of entirely biosourced polymers that combine robust mechanical and thermal properties with functional sites for metal coordination. Such attributes make them highly suitable candidates for next-generation heterogeneous catalysts, especially in energy-related transformations. In this context, we present preliminary work on incorporating gold nanoparticles (AuNPs) as a catalytic species within DFF-polyimine matrices; these hybrid materials demonstrate promising activity in formic acid dehydrogenation (FAD), a process of considerable interest for hydrogen storage and release.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
