Vibrational Structure of Titanium Silicate Catalysts. A Spectroscopic and Theoretical Study

Abstract

A thorough analysis of the vibrational features of the titanium silicalite-1 (TS-1) catalyst is presented, based on quantitative IR measurements, Raman and resonant Raman experiments, quantitative XANES, and quantum chemical calculations on cluster and periodic models. The linear correlation of the intensity of the IR and Raman bands located at 960 and 1125 cm(-1) and the XANES peak at 4967 eV with the amount of tetrahedral Ti are quantitatively demonstrated. Raman and resonant Raman spectra of silicalite and TS-1 with variable Ti content are presented, showing main features at 960 and 1125 cm(-1) associated with titanium insertion into the zeolite framework. The enhancement of the intensity of the 1125 cm(-1) feature and the invariance of the 960 cm(-1) feature in UV-Raman experiments, are discussed in terms of resonant Raman selection rules. Quantum chemical calculations on cluster models Si[OSi(OH)(3)](4) and Ti[OSi(OH)(3)](4) at the B3LYP/6-31G(d) level of theory provide the basis for the assignment of the main vibrational contributions and for the understanding of Raman enhancement. The resonance-enhanced 1125 cm(-1) mode is unambiguously associated with a totally symmetric vibration of the TiO(4) tetrahedron, achieved through in-phase antisymmetric stretching of the four connected Ti-O-Si bridges. This vibration can also be described as a totally symmetric stretching of the four Si-O bonds pointing toward Ti. The resonance enhancement of this feature is explained in terms of the electronic structure of the Ti-containing moiety. Asymmetric stretching modes of TO(4) units show distinct behavior when (i) T is occupied by Si as in perfect silicalite, (ii) T is occupied by Ti as in TS-1, or (iii) the oxygen atom belongs to an OH group, such as in terminal tetrahedra of cluster models and in real defective zeolites. Asymmetric SiO(4) and TiO(4) stretching modes appear above and below 1000 cm(-1), respectively, when they are achieved through antisymmetric stretching of the T-O-Si bridges, and around 800 cm(-1) (in both SiO(4) and TiO(4)) when they involve symmetric stretching of the T-O-Si units. In purely siliceous models, the transparency gap between the main peaks at 800 and 1100 cm(-1) contains only vibrational features associated with terminal Si-OH groups, while in Ti-containing models it contains also the above-mentioned asymmetric TiO(4) modes, which in turn are strongly coupled with Si-OH stretching modes. Calculations on periodic models of silicalite and TS-1 free of OH groups using the QMPOT embedding method correctly reproduce the transparency gap of silicalite and the appearance of asymmetric TiO(4) vibrations at 960 cm(-1) in TS-1. Finally, we demonstrate, for the first time, that the distortion of the tetrahedral symmetry around Ti caused by water adsorption quenches the UV-Raman enhancement of the 1125 cm(-1) band.

Surface chromium single sites: open problems and recent advances

“…In some cases, the hosting matrix has crystalline character, and the position of the hosted centres is (consequently) well known. This is the case of the popular titanium silicalite (TS-1) catalyst where isolated titanium (Ti) centres occupy tetrahedral positions in substitution of silicon atoms in the mordenite framework inverted (MFI) structure (Ricchiardi et al 2001). In the presence of reactants, the Ti centres assume a more open structure, where the metal atoms display a full ability to bind substrates, and where bonds are broken and formed.…”

Identifying the isolated transition metal ions/oxides in molecular sieves and on oxide supports by UV resonance Raman spectroscopy

“…A thorough analysis of the vibrational features of the TS-1 catalyst was conducted by Ricchiardi et al [31] the TiO 4 tetrahedron, achieved through in-phase asymmetric stretching of the four connected Ti-O-Si bridges.…”

“…It is now possible to calculate the spectroscopic results by using theoretical calculations, such as Hartee-Fock, density functional theory, and molecular dynamics [31,[56][57][58][59].…”

Silica-supported Ti chloride tetrahydrofuranates, precursors of Ziegler–Natta catalysts

“…10,11,13,14 Amorphous silica was successively employed as a support also for Ti-based Ziegler-Natta catalysts for ethylene polymerization. 9,15,16 The simple combination of titanium 40 tetrachloride on silica yielded low-reactivity catalysts; however, the combination of a magnesium compound with a porous silica material, followed by reaction with titanium tetrachloride, resulted in a catalyst showing an enhanced reactivity and the excellent handling and polymer particle control characteristic of 45 Phillips' chromium catalysts. 9,15,16 In contrast to chromium-based catalysts, the role of silica surface chemistry in Ziegler-Natta catalysts is often overlooked.…”