Facilitating Pt−WO_x Species Interaction for Efficient Glycerol Hydrogenolysis to 1,3‐Propanediol

Abstract

Designing efficient catalysts for glycerol hydrogenolysis to 1,3‐propanediol (1,3‐PDO), which involves the selective cleavage of the secondary C−O bond, is a challenging task. Current Pt−WOx‐based catalysts often provide low atom efficiency of W and Pt toward 1,3‐PDO production due to undesired catalyst structures. Herein, we fabricate the highly‐dispersed substantially uniform WOx species on inert α‐Al2O3 support by simple high‐temperature heat‐treatment, and the amount of Pt−WOx interface active sites could be adjusted by Pt loading, showing an excellent catalytic performance in glycerol hydrogenolysis at high concentration of glycerol, especially the unprecedented W efficiency (76 g1,3‐PDOgW−1 h−1) toward 1,3‐PDO. The high catalytic efficiency is attributed to the strong interaction between the isolated WO4 species and platinum, which could in‐situ generate the Brønsted acid sites during the reaction as evidenced by IR analysis with NH3 adsorption.

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

“…+ on Brønsted acid sites, while that at 1600 cm À 1 is assigned to adsorbed NH 3 on Lewis acid sites. [27,[53][54][55] Brønsted and Lewis acid sites coexist on four Pt/W/SiZr-T catalysts before the introduction of H 2 , in agreement with Py-IR results. However, after the introduction of H 2 , Brønsted acid sites on four catalysts remarkably increased with the decrease of Lewis acid sites, indicating the transformation of acid sites from Lewis acid to Brønsted acid.…”

“…This strong interaction between WO x species and support on Pt/W/SiZr‐0 and Pt/W/SiZr‐70 is further identified by the higher surface W 5+ /(W 5+ +W 6+ ) ratio on these two catalysts (Figure S5 and Table S2). According to the present literature, inert supports are usually chosen to study the interaction between Pt and WO x species [27–29] . Thus, even though WO x species are highly dispersed on the surface of support, the weak interaction between WO x species and support is not helpful for the catalytic performance.…”

“…According to the present literature, inert supports are usually chosen to study the interaction between Pt and WO x species. [27][28][29] Thus, even though WO x species are highly dispersed on the surface of support, the weak interaction between WO x species and support is not helpful for the catalytic performance. However, in the present work, the strong interaction between WO x species and support due to ZrÀ OÀ W bands creates a new interface site, which is helpful for 1,3-PDO formation.…”

“…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…”

“…To improve the catalytic performance of Pt-WO x -based catalysts, significant efforts have been devoted to studying the interaction between Pt and WO x species as well as the influence of WO x domain size for glycerol hydrogenolysis reaction. To study the former influencing factor, bulk Pt-WO x catalysts [26] or supported Pt-WO x catalysts with inert support [27][28][29] are usually chosen. For example, Wang et al [26] employed a bulk Pt-WO x catalyst without additional support to study the interaction between Pt and WO x species on glycerol hydrogenolysis.…”