Synthesis of Hierarchical Titanium‐Rich Titanium Silicalite‐1 Zeolites and the Highly Efficient Catalytic Performance for Hydroxylation of Phenol.

Improving the framework titanium (Ti) of titanium silicalite‐1 (TS‐1) zeolites and creating inter‐crystalline mesoporosity are two ways to enhance the catalytic properties of TS‐1 for hydroxylation of phenol. Most researches only used one of the ways. In this study, we successfully synthesized of hierarchical Titanium‐Rich (Ti‐rich) TS‐1. Ti‐rich TS‐1 was synthesized in the presence of ammonium carbonate ((NH4)2CO3). The framework Ti content of TS‐1 zeolites synthesized by different content of (NH4)2CO3 was studied by X‐ray fluorescence (XRF), Fourier transform infrared spectra (FTIR) and ultraviolet visible spectra, the framework Ti content was significantly increased by using (NH4)2CO3 as crystallization‐mediating agent. The synthesized samples were evaluated in hydroxylation of phenol. When the molar ratio of ammonium carbonate and tetraethyl orthosilicate in the synthesis gel was 0.2, the molar ratio of Si/Ti reached 34.43 and the Ti‐rich TS‐1 shows the optimum catalytic activity in hydroxylation of phenol. The post‐modification with aqueous solution of tetrapropylammonium hydroxide (TPAOH) was used to further improve the diffusion property. Compared with the parent TS‐1, the secondary pore volume was all increased. The developed hierarchical Ti‐rich TS‐1 zeolites were also assessed in hydroxylation of phenol. It was confirmed that hierarchical Ti‐rich titanium silicalite‐1 zeolites can improve the catalytic activity in phenol conversion considerably. Here, we have synthesized the hierarchical Titanium‐Rich TS‐1 zeolites using (NH4)2CO3 as a crystallization‐mediating agent and TPAOH as mesoporous structure direction. The phenol conversion, dihydroxybenzene selectivity and H2O2 efficiency were all increased compared to the conversional TS‐1 zeolites [ABSTRACT FROM AUTHOR]