Single-Step Hydrogenolysis of Furfural to 1,2-Pentanediol Using a Bifunctional Rh/OMS-2 Catalyst

Abstract

Hydrogenolysis of biomass-derived furfural (FFA) to 1,2-pentanediol (1,2-PeD) was investigated using a bifunctional catalyst with basic and metallic sites, which was synthesized by the hydrothermal method. The synthesized catalyst consisting of rhodium (Rh) supported on an octahedral molecular sieve (OMS-2) of different loadings, such as 0.5, 1, and 1.5% w/w, was studied, and 1% (w/w) loading gave the best results. This 1% w/w Rh/OMS-2 catalyst showed excellent catalytic activity and selectivity for the hydrogenolysis reaction because of better dispersion of rhodium, later revealed by characterization. Furthermore, 1% Rh/OMS-2 catalyst was well characterized in virgin and reused states using various techniques such as Fourier-transform infrared spectroscopy, NH3-temperature-programmed desorption (TPD), CO2-TPD, temperature-programmed reduction, H2 pulse chemisorption, scanning electron microscopy, high-resolution transmission electron microscopy, X-ray diffraction, Brunauer–Emmett–Teller surface area, X-ray photoelectron spectroscopy, Raman spectroscopy, and differential scanning calorimetry–thermogravimetry analysis. The catalyst showed a higher surface area of 72 m2/g and the average size of the highly dispersed Rh metal of ∼2 nm. The studies were performed in a batch reactor; the catalyst offered almost 100% conversion of FFA with 87% selectivity to 1,2-PeD at 160 °C and 30 atm hydrogen pressure in 8 h. The reaction mechanism and kinetic model have been developed using a dual-site Langmuir–Hinshelwood–Hougen–Watson mechanism. The activation energies were 12.3 and 27.6 kcal/mol, correspondingly. The catalyst was found to be active, selective, and reusable.