Promoting the Effect of Au on the Selective Hydrogenolysis of Glycerol to 1,3-Propanediol over the Pt/WO_x/Al₂O₃ Catalyst

Abstract

The selective hydrogenolysis of glycerol to 1,3propanediol (1,3-PDO) is an important yet challenging reaction because it requires the selective cleavage of the sterically hindered secondary C−O bond of glycerol. In this work, we have developed a new catalyst, 0.1Au-2Pt/7.5W/Al, which affords both high glycerol conversion (77.5%) and 1,3-PDO selectivity (54.8%), which are significantly higher than the Au-free counterpart. HAADF-STEM reveals that the structure of 0.1Au-2Pt/7.5W/Al is characterized with ∼2 nm Pt NPs decorated with Au-WO x at the periphery, where the Au additive exists most likely as single atoms. Chemisorption and XPS show that the electron transfer from W to Au can help to weaken the strong metal support interaction (SMSI) between Pt and WO x , and thus greatly enlarges the exposed Pt surface and increases the H-spillover capacity. The 2-butanol dehydration in H 2 reveals that the H-spillover capacity is proportional to the number of Bronsted acid sites, which, in conjunction with the only water desorption in H 2 -TPD results, strongly suggests that the active sites for breaking the secondary C−O bond of glycerol should be Bronsted acid sites generated by the H-spillover at the interface between Pt and WO x , and the modification by the Au additive increases the number of interfacial sites, and thus enhances the 1,3-PDO yield.

Supported MoOx and WOx Solid Acids for Biomass Valorization: Interplay of Coordination Chemistry, Acidity, and Catalysis

“…167 Improved catalytic results were found in glycerol hydrogenolysis (77.5% conversion) to 1,3-PDO (54.8% selectivity) when Au (0.1 wt %) was added to the 2Pt/7.5W/Al 2 O 3 catalyst. 168 In this catalyst structure, Au is dispersed as single atoms and Pt NPs (∼2 nm) are decorated with Au−WO x at the periphery. The improved H-spillover at the interface between Pt and WO x generates Brønsted acid sites, which cleave the secondary C−O bond of glycerol, giving excellent results from the glycerol hydrogenolysis reaction (Figure 14).…”

“…Improved catalytic results were found in glycerol hydrogenolysis (77.5% conversion) to 1,3-PDO (54.8% selectivity) when Au (0.1 wt %) was added to the 2Pt/7.5W/Al 2 O 3 catalyst . In this catalyst structure, Au is dispersed as single atoms and Pt NPs (∼2 nm) are decorated with Au–WO x at the periphery.…”

“…Proposed mechanism of glycerol hydrogenolysis over the 0.1Au-2Pt/7.5W/Al catalyst. Reproduced from ref . Copyright 2021 American Chemical Society.…”

Insight into the Influence of WOx‐Support Interaction over Pt/W/SiZr Catalysts on 1,3‐Propanediol Synthesis from Glycerol

“…Table S4 compares 1.3-PDO STY in the present study with the reported Pt-WO x -based catalysts in literature. [27][28]51,[57][58][59][60][61][62][63][64][65][66] In order to describe the catalytic performance more intuitively, the relationship between 1,3-PDO STY and glycerol conversion is plotted in Figure 6. Under low glycerol conversion, initial 1,3-PDO STY on Pt/W/SiZr-70 reaches…”

Controlled Metal–Support Interactions in Au/CeO2–Mg(OH)2 Catalysts Activating the Direct Oxidative Esterification of Methacrolein with Methanol to Methyl Methacrylate

“…Conversely, with a given metal oxide support, variation of the metal nanoparticles can also change the catalytic behavior [15][16][17]. In general, SMSIs change the surface characteristics of the main metal nanoparticles and the metal oxide supports, such that the electronic properties of the catalyst surface can be changed [18][19][20]. This unique effect results in changes to the interaction of the catalyst surface with the approaching reactant molecules and their adsorption geometries, the formation of intermediate species and transition states, and finally the thermodynamics and kinetics of product formation [14,15].…”