The selective ring-opening of cellulose-derived furanic molecules is a promising pathway for the production of industrially relevant linear oxygenates, such as 1,6-hexanediol. 2,5-Dimethylfuran (DMF) is employed as a model compound in a combined experimental and computational investigation to provide insights into the metal-catalyzed ring-opening. Ring-opening to 2-hexanol and 2-hexanone and ring-saturation to 2,5-dimethyltetrahydrofuran (DMTHF) are identified as two main parallel pathways. DFT calculations and microkinetic modeling indicate that DMF adsorbs on Ru in an open-ring configuration, which is potentially a common surface intermediate that leads to both ring-opening and ring-saturation products. Although the activation barriers for the two pathways are comparable, the formation of DMTHF is more thermodynamically favorable. In addition, steric interactions with co-adsorbed 2-propoxyl, derived from the solvent, and the oxophilic nature of Ru play key roles to determine the product distribution: the former favors less bulky, that is, ring-closed, intermediates, and the latter retards O-H bond formation. Finally, we show that the hydrodeoxygenation of oxygenated furanics, such as 5-methylfurfural and (5-methyl-2-furyl)methanol, on Ru occurs preferentially at oxygen-containing side groups to form DMF, followed by either ring-opening or ring-saturation.
Low-loading Pt supported on TiC powder catalysts were synthesized by an impregnation method. After the Pt(NH 3 ) 4 (NO 3 ) 2 precursor was impregnated onto the TiC support, different pretreatment atmospheres were used to study the influence on Pt dispersion, surface composition, and catalytic activity towards oxygen reduction reaction (ORR). Direct reduction of the Pt precursor in hydrogen led to small Pt particles with an average size of ~2.2 nm and superior ORR activity at low overpotential compared to commercial Pt/C. However, calcination of the Pt precursor in air resulted in larger Pt particles with an average size of ~6.7 nm and lower ORR specific activity. The decrease in ORR activity was primarily attributed to the surface oxidation of the TiC support during calcination. X-ray photoelectron spectroscopy (XPS) and Xray diffraction (XRD) confirmed that the TiC powder was oxidized when the catalyst was calcined in air. The finding reported here demonstrates the importance of pretreatment atmosphere for synthesizing Pt-modified transition metal carbides as highly active electrocatalysts.
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