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Issue 9, 2017
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Nanoparticulate Pt on mesoporous SBA-15 doped with extremely low amount of W as a highly selective catalyst for glycerol hydrogenolysis to 1,3-propanediol

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Abstract

It has been documented that W-modified Pt catalysts with relatively high tungsten contents are effective for the catalytic transformation of biodiesel-derived glycerol to 1,3-propanediol (1,3-PDO). Herein, we report a new finding that Pt/W–SBA-15 catalysts with extremely low W/Si atomic ratios (≤1/80) exhibit excellent catalytic performance in the hydrogenolysis of glycerol to 1,3-PDO. In particular, a Pt/W–SBA-15 catalyst with the W/Si ratio of as low as 1/640 (Pt/W–SBA-15(1/640)) gave rise to the highest 1,3-PDO selectivity of 70.8% at a high glycerol conversion of 86.8% and thus afforded the highest yield of 1,3-PDO of 61.5%. A combination of characterization techniques evidenced that tungsten was homogeneously incorporated into SBA-15 in the form of isolated tetragonal WO4 and only displayed Lewis acidity. The particle size of Pt evolved in a reverse volcanic curve with the W/Si ratio, with the smallest size being observed for Pt/W–SBA-15(1/640). Control experiments indicated strong synergy between Pt nanoparticles (NPs) and WO4 in the hydrogenolysis of glycerol. A probe reaction suggested that Brønsted acid sites were generated in situ on the Pt/W–SBA-15 catalysts in a H2 atmosphere by the reaction between WO4 and spillover H atoms from the Pt NPs. It is plausible that the hydrided WO4 functioned as a highly selective active centre in the hydrogenolysis of glycerol to 1,3-PDO, whereas the Pt NPs played the role of a reservoir of spillover H atoms. Thus, a good match between the isolated WO4 and the small Pt NPs was responsible for the superior catalytic performance of Pt/W–SBA-15(1/640).

Graphical abstract: Nanoparticulate Pt on mesoporous SBA-15 doped with extremely low amount of W as a highly selective catalyst for glycerol hydrogenolysis to 1,3-propanediol

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Publication details

The article was received on 26 Jan 2017, accepted on 04 Apr 2017 and first published on 04 Apr 2017


Article type: Paper
DOI: 10.1039/C7GC00317J
Citation: Green Chem., 2017,19, 2174-2183
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    Nanoparticulate Pt on mesoporous SBA-15 doped with extremely low amount of W as a highly selective catalyst for glycerol hydrogenolysis to 1,3-propanediol

    Y. Fan, S. Cheng, H. Wang, D. Ye, S. Xie, Y. Pei, H. Hu, W. Hua, Z. H. Li, M. Qiao and B. Zong, Green Chem., 2017, 19, 2174
    DOI: 10.1039/C7GC00317J

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