6533b7d9fe1ef96bd126d751

RESEARCH PRODUCT

Selective photocatalytic oxidation of 5-hydroxymethylfurfural to 2,5-furandicarboxaldehyde by polymeric carbon nitride-hydrogen peroxide adduct

Leonardo PalmisanoEva DíazSalvador OrdóñezGiuseppe MarcìJosé R. GarcíaOlena KhainakovaMarina IlkaevaElisa I. García-lópezIgor KrivtsovIgor Krivtsov

subject

HeptazineCarbon nitridechemistry.chemical_element02 engineering and technology010402 general chemistryPhotochemistry01 natural sciencesPeroxideCatalysisCatalysiCatalysisAdductchemistry.chemical_compoundPhotocatalysiPhysical and Theoretical ChemistryHydrogen peroxideCarbon nitride5-Hydroxymethylfurfural021001 nanoscience & nanotechnologySelective photo-oxidation0104 chemical scienceschemistry25-FurandicarboxaldehydePhotocatalysisSettore CHIM/07 - Fondamenti Chimici Delle Tecnologie0210 nano-technologyCarbon

description

Abstract Polymeric carbon nitride-hydrogen peroxide adduct (PCN-H2O2) has been prepared, thoroughly characterised and its application for selective photocatalytic conversion of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxaldehyde (FDC) in aqueous suspension has been studied. The PCN-H2O2 adduct is stable in aqueous suspension under UV and solar irradiation up to 100 °C. It is also stable up to 200 °C if heated in air, while at temperatures close to 300 °C its decomposition takes place. Based on the obtained characterisation data it has been proposed that H2O2 attaches to the non-polymerised carbon nitride species and to the heptazine nitrogen atoms, thus producing strong hydrogen bonding within the PCN-H2O2 adduct. The blockage of the surface amino-groups in PCN-H2O2 by H2O2 hinders the interaction of HMF with these sites, which are responsible for unselective substrate conversion. PCN-H2O2, although being less active, possesses a superior selectivity in natural solar light assisted oxidation of HMF to FDC reaching 80% with respect to its thermally etched PCN counterpart, which gives rise to a 40–50% selectivity. We believe that the exceptional performance of the applied photocatalyst in the selective photocatalytic conversion of HMF to a high added value FDC in a green solvent under natural illumination makes a significant contribution to the development of environmentally friendly technologies for biomass valorisation.

https://doi.org/10.1016/j.jcat.2018.01.012