Selective oxidation of 5-HMF to DFF over alkali promoted Mn nanocomposite

Various compositions of Cs promoted Mn catalysts were synthesized and investigated for selective oxidation of 5HMF to DFF, among which Mn-Cs(80:20) was found to be most efficient giving 91 % conversion of 5-HMF and 99 % selectivity to DFF. Detail characterization like N2-sorption, BET surface area, TG-DTA, XRD, XPS, FE-SEM-EDX, TEM, HR-TEM, CO2-TPD, H2-TPR, O2-TPO, FTIR, Raman spectra and CH3OH-IR were done to establish structureactivity correlation. Enhanced surface area, porosity, thermal stability, dual morphologies were observed due to inclusion of Cs in Mn lattice domain which further enhanced the crystallinity, and oxygen diffusion on the surface. Mixed morphologies comprising nanoparticles (4-5 nm) and nanocubes (50-60 nm) were observed with enhanced redox potential and reduced work function due to weakening of Mn-O bonds. Significant increase in the basicity of catalyst, interfacial redox properties and lattice oxygen led to highly efficient oxidation of 5-HMF to DFF via Mars-van Krevelen mechanism at relatively milder conditions i.e. T = 90 degrees C and PO2= 200 psig. The catalyst was easily recyclable up to 7 times with minor loss in activity which was regenerated heat treatment protocol.

Automated summary

Various Cs promoted Mn catalysts were synthesized and investigated for selective oxidation of 5-HMF to DFF. Among them, Mn-Cs(80:20) showed the highest conversion of 5-HMF (91%) and selectivity to DFF (99%). The inclusion of Cs in the Mn lattice domain resulted in enhanced surface area, porosity, thermal stability, and dual morphologies, which further improved the crystallinity and oxygen diffusion on the surface. The catalyst exhibited a mixed morphology comprising nanoparticles and nanocubes, which weakened the Mn-O bonds, increased the redox potential, and reduced the work function.