X-ray absorption spectroscopy of Ti-containing molecular sieves ETS-10, aluminum-free Ti-β, and TS-1

Abstract

We report here the first structural characterization by Ti K-edge EXAFS and XANES of ETS-10 and aluminum-free Ti-β molecular sieves. A TS-1 sample was also studied for comparison. The near-edge spectrum of TS-1 revealed an intense pre-edge feature characteristic of Ti atoms in tetrahedral coordination. However, the pre-edge peak for ETS-10 was quite small and shifted in energy, which is consistent with the known octahedral structure surrounding Ti atoms in the material. Analysis of the EXAFS for ETS-10 revealed an average Ti-O interatomic distance of 2.00 +- 0.01 A which is longer than the Ti-O distance (1.95A) in anatase TiO2. For Ti-β, an intense pre-edge peak is present in the near-edge spectrum and the intensity, energy and width of this peak are the same as for TS-1. In addition, the average Ti-O interatomic distance in Ti-β and TS-1 was 1.80 +- 0.01 A, which is significantly shorter than the distance measured in ETS-10. The EXAFS and XANES results indicate that the Ti sites in aluminum-free Ti-β are structurally identical to the tetrahedral sites in TS-1. This conclusion is supported by the similarity of the UV absorption thresholds for the two samples. X-ray absorption spectra were also recorded with methanol or 2-propanol adsorbed on the Ti-β and TS-1 molecular sieves. Alcohol adsorption decreased the intensity and broadened the Ti pre-edge peak for both samples, demonstrating a local chemical interaction with the Ti sites. Methanol adsorption lengthened the average Ti-O bond to 1.83 ± 0.01 A. The similarity of the X-ray absorption spectra for aluminum-free Ti-β and TS-1 in the presence of alcohols suggests that the Ti sites in the two frameworks are chemically indistinguishable for vapor-phase adsorption of alcohols at low concentrations.