Smart
materials that both sorb and announce the presence of radioactive
isotopes such as 201Tl and 137Cs are needed
for human safety in environmental catastrophies. This study reports
progress toward zeolite-based self-luminous sensors for radioactive
isotopes. Hf4+ was introduced into zeolite A by treating
Tl-A and Cs,Na-A with HfCl4(g) under anhydrous
conditions. The crystal structures of the products, Hf,Cl,Tl-A and
Hf,Cl,Cs,Na-A, were determined by single-crystal crystallography using
synchrotron X-radiation, with compositional confirmation by SEM-EDX
analysis. Their luminescence properties upon X-ray, UV, and proton
beam irradiation were studied. In Hf,Cl,Tl-A, some Hf4+ ions are 3-coordinate with three framework oxygen atoms of 6-rings;
octahedral HfCl6
2– ions are at the very
centers of 7% of the large cavities within Tl14HfCl6
12+ clusters. HfCl6
2– ions are also seen in Hf,Cl,Cs,Na-A; they similarly occupy 7% of
the large cavities and are members of a Cs11HfCl6
9+ continuum. The X-ray-induced luminescence spectra of
Hf,Cl,Tl-A and Hf,Cl,Cs,Na-A, and that of Hf,Cl,Tl-A induced by UV,
are all broad bands from 300 to 720 nm, peaking near 400 nm. By comparisons
with the corresponding spectra of Zr,Cl,Tl-A, Zr,Cl,Cs,Na-A, Cs2HfCl6, and Cs2ZrCl6, several
luminescence mechanisms are proposed. These zeolite-based materials
can be expected to emit light (be self-luminous) as radioactive isotopes
exchange into them.