Hierarchical TS-1 has attracted enormous attention from both academia and industry due to its remarkable catalytic performance in epoxidation reactions. However, sustainable synthesis of hierarchical-nanosized TS-1 without mesoporogens is still challenging. In this work, we report a facile and mesoporogen-free strategy to simultaneously manipulate pore structure and particle size of TS-1 employing the concentrated system. Taking advantage of the suspended nuclei in the concentrated system as confirmed by the DLS-PSD and atomic force microscopy, the novel TS-1 is demonstrated to have higher Ti concentration on surface, higher surface area (539 m 2 /g), abundant mesopores, and reduced crystal size (ca. 150 nm). Moreover, this Au−Ti bifunctional catalyst shows a good PO formation rate with enhanced catalytic stability due to the hierarchical structure. This strategy opens a novel way for the green synthesis of hierarchical-nanosized TS-1 and facilitates industrial development of the Au/TS-1 catalyst for propene epoxidation.

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The traditional deposition–precipitation (DP) method is common but not universal in manipulating Au nanoparticles’ spatial locations in propene epoxidation catalysts, especially for hierarchical hydrophilic TS-1 supports. Directional loading of Au nanoparticles to hierarchical hydrophilic TS-1 pores is challenging because the strong hydrophilicity of the hierarchical TS-1 zeolite would make Au nanoparticles loaded by the DP method tend to be deposited on the hydrophilic support surface, thus blocking the pore mouths and leading to deactivation. Therefore, manipulating Au nanoparticles’ spatial locations on hierarchical hydrophilic TS-1 supports is of great significance to enhance the catalytic performance but is a bottleneck problem. In this work, taking hierarchical hydrophilic HTS-1 supports as an example, we propose a new modified isometric impregnation (NIMG) method to manipulate the spatial location of Au nanoparticles. Moreover, the Au spatial location inside HTS-1 pores is quantitatively reflected by introducing the V na parameter. Combined with the N2 physisorption, high-angle annular dark-field scanning transmission electron microscopy, inductively coupled plasma, and X-ray photoelectron spectroscopy, it is found that the Au nanoparticles loaded by the NIMG method tend to be uniformly distributed inside the pores of HTS-1 due to the capillary effect. As expected, the Au/HTS-1­(NIMG) catalyst (with the Au nanoparticles inside the pores) exhibits a much higher propylene oxide (PO) formation rate, PO selectivity, and H2 efficiency than the Au/HTS-1­(DP) catalyst (with the Au nanoparticles on the outer surface). This is possibly because loading Au nanoparticles inside the pores is conducive to the transfer of H2O2 from Au to the nearby abundant Ti active sites, thus weakening the decomposition of H2O2 to H2O, avoiding the ring-opening side reactions, and promoting propene epoxidation into PO. This work sheds new light for controlling the spatial location of Au in hierarchically structured hydrophilic catalysts for direct propene epoxidation.

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Rational regulation of the local environment of Ti-sites in TS-1 harbors tremendous industrial and scientific significance to epoxidation reactions. Herein, we report a facile and environment-friendly strategy to boost catalytic selectivity by covering the Tisites on an external surface of TS-1 (ITS-1) without sacrificing activity of internal Ti sites. By a quantitative analysis of d 3 -acetonitrile and quinoline-DRIFTS, 1 H MAS NMR and XPS, it is found that the percentage of external Ti-sites decreased from 11% to 6% after depositing surface silica islands. This successfully inhibits ringopening reaction of 1,2-epoxyhexane on catalyst surface, as demonstrated by slower kinetic decomposition rate of 1,2-epoxyhexane. Compared with conventional TS-1 catalyst, selectivity of 1,2-epoxyhexane over ITS-1 catalyst significantly increased from 83.5% to 98.5% while maintaining high 1-hexene conversion. Furthermore, overmuch surface silica coverage only leads to extremely low conversion (2%) due to inhibition of mass transfer. This work paves the way for rational construction of Ti-containing catalysts for 1-hexene epoxidation.