Experimental and DFT Study of Metal-Free Catalyst for Selective Oxidation of Biomass-Derived Molecule (HMF).

Catalytic conversion of biomass or biomass-derived intermediate to value-added chemicals is important for both biomass waste management and production of industrially important chemicals. Oxidation of 5-hydroximethyl furfural (HMF) is considered one of the most important biomass conversion processes, which resulted in many value-added products such as 2,5-diformylfuran (DFF), 2,5-furandicarboxylic acid (FDCA), 5-hydroxymethyl-2-furancarboxylic acid (HMFCA), and 5-formyl-2-furancarboxylic acid (FFCA). In this study, the three morphologies of CdS catalyst (nanorod, nanosheet, and nanosphere) with two different crystalline structures are synthesized and characterized by SEM, TEM, and XRD analysis. The oxidation of HMF to FFCA is performed using the synthesized catalysts in the presence of different solvents and oxidizing agents. We find that CdS nanorod provides the selective oxidation of HMF to FFCA in the presence of dimethyl sulfoxide solvent and -butyl hydrogen peroxide oxidizing agent. The density functional theory (DFT) simulations are carried out to explain the catalytic activity of the CdS catalyst for oxidation of HMF to FFCA. The DFT simulations show that CdS is an excellent catalyst for binding HMF on the CdS surface. Our findings provide the way of effective oxidation of biomass into value-added products using the cheap CdS catalyst.