Probing the gold active sites in Au/TS-1 for gas-phase epoxidation of propylene in the presence of hydrogen and oxygen

Nano gold particles supported on titanium silicalite-1 catalysts (Au/TS-1) have shown high propylene oxide (PO) rate (∼160gPOh-1kgCat-1) at ∼200 °C and 1 atm for gas-phase epoxidation of propylene in the presence of hydrogen and oxygen. In this work, we address the issue of whether gold clusters inside TS-1 can be the active sites for the PO reaction. Coating TS-1 seeds with silicalite-1 produced a material (S-1/TS-1), which possessed a well-defined MFI structure, as shown by XRD and selected area electron diffraction, and Ti on the external surface could not be detected by XPS after addition of gold by deposition precipitation. The Au/S-1/TS-1 catalyst had at least 20 times higher PO rate (per gram of catalyst) at ∼200 °C compared to that of a Au/S-1 sample with similar gold loading at ∼0.05 wt%. Since neither Au nor Ti alone gives any significant PO activity, this is the first direct experimental evidence showing that gold clusters inside the TS-1 are active for the PO reaction at H2/C3H6/O2/N2 = 3.5/3.5/3.5/24.5 mL min−1 and a space velocity of 14,000mLh-1gCat-1. Furthermore, a much higher PO rate per gram of TS-1 for the Au/S-1/TS-1 catalyst (∼240gPOh-1kgTS-1-1) than expected for a Au/TS-1 with similar gold loading at ∼0.05 wt% and Si/Ti molar ratio from 65 to 100 (∼60–140gPOh-1kgTS-1-1) implies that Au clusters inside the TS-1 nanoporous channels can be the dominant active sites for the PO reaction.

Graphical abstractAu/S-1/TS-1 had at least 20 times higher PO rate at 200 °C (per gram of catalyst), compared to that of a Au/S-1 sample with similar gold loading at ∼0.05 wt%. Since neither Au nor Ti alone gives any significant PO activity, this is the first direct experimental evidence showing that the gold clusters inside the TS-1 are active for the PO reaction.Figure optionsDownload full-size imageDownload high-quality image (174 K)Download as PowerPoint slideHighlights► Silicalite-1-coated titanium silicalite-1 with no external Ti was synthesized. ► Au/S-1/TS-1 had 20 times higher PO rate (per gram catalyst) compared to Au/S-1. ► First direct evidence of PO activity of gold clusters inside the TS-1 nanopores.