Reducibility and Adsorbate Interactions of Ti in Titanosilicate Molecular Sieve TS-1

Abstract

Electron spin resonance (ESR) and electron spin echo modulation (ESEM) spectroscopy are used to study reducibility and adsorbate interaction of Ti in titanosilicate TS-1 molecular sieve. Various reduction methods were used to reduce Ti(IV) in TS-1 to Ti(III) which was then monitored by ESR. When TS-1, after dehydration and oxygen treatment at high temperature followed by evacuation (activation), is γ-irradiated at 77 K; an ESR signal withg‖=1.970 andg⊥=1.906 is observed for isolated Ti(III) centers. Radiation induced defect centers known as V centers are also observed after γ-irradiation. When activated TS-1 is treated with CO or H2at 673 K, an axial ESR signal withg⊥=1.968 andg‖=1.933 is observed which is suggested to be Ti(III)(CO)nand Ti(III)(H2)ncomplexes. When activated TS-1 is exposed to D2O at room temperature and subsequently γ-irradiated at 77 K, a new ESR signal withg=1.924 is observed. This species is identified as Ti(III)-(OD)1from2D ESEM data. Adsorption of CH3OD on activated TS-1 produces a new Ti(III) species withg=1.931. This species is identified as Ti(III)-(CH3OD)1from2D ESEM data. Adsorption of C2D4on activated TS-1 produces a new Ti(III) species withg⊥=1.968 andg‖=1.910. This species is identified as Ti(III)-(C2D4)1from2D ESEM data. Possible coordination geometries of the various Ti(III)-adsorbate complexes are discussed.