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The preparation of titanium silicalite-1 (TS-1) containing Al (Al-TS-1) and its catalytic oxidation properties were investigated systematically. The features of Al-TS-1 were characterized using X-ray diffraction, ultraviolet-visible spectroscopy, inductively coupled plasma atomic emission spectroscopy, 27Al magic-angle spinning and 29Si magic-angle spinning nuclear magnetic resonance spectroscopies, and scanning electron microscopy. The results showed that incorporation of Al into the TS-1 framework influences the amount of framework Ti in Al-TS-1. However, when the Al/Si ratio is lower than 0.005, the amount of framework Ti in Al-TS-1 is hardly affected. Neither the Al centers nor the Ti centers in the Al-TS-1 framework influence the acidic catalytic and catalytic oxidation performance. Al in the Al-TS-1 framework suppressed desilication of silica species adjacent to framework Ti species in Al–TS-1 in a basic catalytic system, so Ti active sites in the Al–TS-1 framework could be protected.

A facile strategy is proposed to construct a highly active oxidation catalyst with optimally distributed titanium coordination states containing "TiO4" and "TiO6" species. The "TiO6" species in TS-1(+) shows a superior catalytic oxidation activity, which is 2-3 times that of "TiO4" species in TS-1.

A typical volcano-shaped curve has been found in heterogeneous catalytic systems containing titanosilicates for the first time. A new reactive intermediate with double H-bonds is proposed. Systematic results clearly evidence another H-bond formed between the high-electronegativity atom of the H-bond acceptor and the H(end) atom of Ti-Oα-Oβ-H(end).

Fluorine species were successfully implanted into a MWW-type titanosilicate via post-treatment, which generates the SiO3/2F units in the zeolite framework. The incorporated fluorine species significantly improved the catalytic performance in the epoxidation of alkenes as a result of enhancing the Lewis acid strength and the hydrophobicity of the zeolite.