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Structure and luminescence of extraframework TiCl62− in Cs+-containing zeolite LTA

  • Gi Beom Park
  • Joon Young Kim
  • Hong Joo Kim
  • Nam Ho Heo
  • Karl Seff
Article
  • 18 Downloads

Abstract

Octahedral TiCl62− ions were introduced into zeolite LTA at extraframework positions by allowing TiCl4(g) to react with dehydrated Cs,Na-A. The structure of the product, Ti,Cl,Cs,Na-A, was determined by single-crystal crystallographic technique in the space group \(Pm\bar {3}m\) (a = 12.228(1) Å) and refined to the error index R1 = 0.046. Its composition was confirmed by energy-dispersive X-ray analysis. Octahedral TiCl62− ions center 8% of the large cavities. The TiCl62− ion is stabilized by eight surrounding Cs+ ions to form a Cs8TiCl66+ cluster. Each of these Cl ions bonds further to an 8-ring Cs+ ion. These 8-ring Cs+ ions bridge between TiCl62− ions of adjacent unit cells to form a Cs11TiCl69+ continuum in the surface volume of the crystal. The X-ray induced luminescence spectrum of the product is a broad band from 360 to 700 nm, peaking at 475 nm. The emission is red-shifted and less intense than those of M,Cl,Cs,Na-A, M = Zr and Hf, but appears to occur by the same self-trapped exciton (STE) mechanism.

Keywords

Crystal structure Luminescence Zeolite A Vapor-phase reaction Extraframework Ti4+ TiCl62− 

Notes

Acknowledgements

We gratefully acknowledge the Photon Factory (PF), High Energy Accelerator Research Organization, KEK, Tsukuba, Japan for the use of their synchrotron, diffractometer, and computing facilities. The color CCD images were taken at the Pohang Accelerator Laboratory (PAL), Pohang, Korea. This work was supported by a National Research Foundation of Korea (NRF) Grant No. NRF-2017R1E1A1A01074837 funded by the Korean government (MSTI).

Supplementary material

10934_2018_708_MOESM1_ESM.docx (122 kb)
Supplementary material 1 (DOCX 122 KB)

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Copyright information

© Springer Science+Business Media, LLC, part of Springer Nature 2018

Authors and Affiliations

  1. 1.Laboratory of Structural Chemistry, Department of Applied Chemistry, College of EngineeringKyungpook National UniversityDaeguSouth Korea
  2. 2.Department of Physics, College of Natural ScienceKyungpook National UniversityDaeguSouth Korea
  3. 3.Department of ChemistryUniversity of HawaiiHonoluluUSA

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