The catalytic performance of a series of 1 wt % Pd/C catalysts prepared by the sol-immobilization method has been studied in the liquid-phase hydrogenation of furfural. The temperature range studied was 25–75 °C, keeping the H2 pressure constant at 5 bar. The effect of the catalyst preparation using different capping agents containing oxygen or nitrogen groups was assessed. Polyvinyl alcohol (PVA), polyvinylpyrrolidone (PVP), and poly (diallyldimethylammonium chloride) (PDDA) were chosen. The catalysts were characterized by ultraviolet-visible spectroscopy (UV-Vis), Fourier transform infrared spectroscopy (FTIR), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS). The characterization data suggest that the different capping agents affected the initial activity of the catalysts by adjusting the available Pd surface sites, without producing a significant change in the Pd particle size. The different activity of the three catalysts followed the trend: PdPVA/C > PdPDDA/C > PdPVP/C. In terms of selectivity to furfuryl alcohol, the opposite trend has been observed: PdPVP/C > PdPDDA/C > PdPVA/C. The different reactivity has been ascribed to the different shielding effect of the three ligands used; they influence the adsorption of the reactant on Pd active sites.
The effect of support, stabilizing agent, and Pd nanoparticles (NPs) size was studied for sodium muconate and t,t-muconic acid hydrogenation to bio-adipic acid. Three different activated carbons (AC) were used (Norit, KB, and G60) and carbon morphology did not affect the substrate conversion, but it greatly influenced the adipic acid yield. 1% Pd/KB Darco catalyst, which has the highest surface area and Pd surface exposure, and the smallest NPs size displayed the highest activity. Furthermore, the effect of the amount of the protective agent was studied varying metal/protective agent weight ratios in the range of 1/0.00–1/1.20, using KB as the chosen support. For sodium muconate reduction 1% Pd/KB_1.2 catalyst gave the best results in terms of activity (0.73 s−1), conversion, and adipic acid yield (94.8%), while for t,t-muconic acid hydrogenation the best activity result (0.85 s−1) was obtained with 1% Pd/KB_0.0 catalyst. Correlating the results obtained from XPS and TEM analyses with catalytic results, we found that the amount of PVA (polyvinyl alcohol) influences mean Pd NPs size, Pd(0)/Pd(II) ratio, and Pd surface exposure. Pd(0)/Pd(II) ratio and Pd NPs size affected adipic acid yield and activity during sodium muconate hydrogenation, respectively, while adipic acid yield was related by exposed Pd amount during t,t-muconic acid hydrogenation. The synthesized catalysts showed higher activity than commercial 5% Pd/AC.
27 April 2017 in Environmental Science and Pollution Research