The Promotional Effect of Sulfates on TiO₂ Supported Pt‐WO_x Catalyst for Hydrogenolysis of Glycerol

Abstract

Pt-WO x based catalysts were widely investigated and showed high industrial application potential for glycerol hydrogenolysis. Further improving the catalytic activity and stability of the Pt-WO x based catalysts is important. Herein, we modified the TiO 2 supported Pt-WO x catalyst with sulfate doping and employed for the glycerol hydrogenolysis. The introduction of sulfates dramatically promoted the catalytic activity and stability of the Pt/W/Ti catalyst in glycerol hydrogenolysis. Sulfates-doped Pt/ WÀ S/Ti achieved 100 % conversion of glycerol, with 36 % selectivity to 1,3-PDO and 57 % selectivity to n-PO at 120°C and 4 MPa, while the conversion over Pt/W/Ti only reached 57 %. Moreover, Pt/WÀ S/Ti offered 22.5 times more glycerol conversion (90 %) than Pt/W/Ti (4 %) for the second run. The much higher activity of the Pt/WÀ S/Ti was ascribed to the better dispersion of Pt and WO x species and more Brønsted acid amount. The enhanced stability of Pt/WÀ S/Ti was attributed to its strong anti-leaching ability after sulfate doping.

Hydrogenolysis of glycerol over TiO2-supported Pt-WOx catalysts: Effects of the TiO2 crystal phase and WOx loading

“…To further explore the effect of WO x loading on the chemical state of Pt, we used CO as a probe molecule to characterize a series of catalysts with different W contents. As shown in Figure 3H, the peaks in the range of 2000-2,100 cm −1 are attributed to the linear adsorption of CO on the Pt site, and the peak at 1838 cm −1 is attributed to the bridge adsorption of CO on the metallic Pt unit (Xin et al, 2021) (Zhou et al, 2021) (Botao Qiao et al, 2011. The profiles recorded for Pt/A-Ti and Pt/2W/A-Ti reveal the presence of a shoulder peak at 2093 cm −1 , which is attributed to the linear adsorption of CO on the surface of the PtO x species.…”

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

“…Thus, the Pt-WO x -based catalysts are considered as promising catalysts for the synthesis of 1,3-PDO from glycerol hydrogenolysis. [13,25] However, the catalytic activity and 1,3-PDO selectivity on Pt-WO x -based catalysts cannot meet industrial applications.…”

“…Meanwhile, the valence states of W show little change and the structure of WO x species can remain relatively stable under reaction conditions. Thus, the Pt‐WO x ‐based catalysts are considered as promising catalysts for the synthesis of 1,3‐PDO from glycerol hydrogenolysis [13,25] . However, the catalytic activity and 1,3‐PDO selectivity on Pt‐WO x ‐based catalysts cannot meet industrial applications.…”

Selective Hydrogenolysis of Glycerol to 1,3-Propanediol over Supported Platinum-Tungsten Oxide Catalysts

“…In 2008, Kurosaka et al 19 found that Pt/WO3/ZrO2 catalyzed the glycerol hydrogenolysis to 1,3-PDO with a 24% yield at 170 °C and 8 MPa H2. Recent studies have reported the effects of different supports, WOx states and additives on the properties of the Pt-WOx-based catalysts 10,[20][21][22][23] . García-Fernández et al 24 characterized the Pt-WOx catalysts by in situ attenuated total reflection infrared spectroscopy, and proposed that the superior function of the WOx species for the formation of 1,3-PDO is attributed to their anchoring of the primary -OH groups of glycerol.…”

“…2− increased the surface negative charge and the Pt-WOx interaction, leading to a higher catalytic activity 22 . Similar promoting effect was also observed upon introduction of a small amount of Au into a Pt/WOx/Al2O3 catalyst, which increased the glycerol conversion from 66.3% to 77.5% while the 1,3-PDO selectivity remained unchanged (54.8% vs. 53.0%) at 180 °C and 5 MPa H2, as a result of the electron transfer from W to Au to weaken the Pt and WOx interaction 23 .…”