XEOL spectroscopy of lanthanides in aqueous solution

Abstract

As part of an ongoing study of the electronic interactions between solute and solvent molecules, a method for X-ray excited optical luminescence (XEOL) analysis of aqueous solutions was developed at the double-crystal monochromator beamline (DCM) of the Canadian Synchrotron Radiation Facility (CSRF). It was tested using a series of solutions containing lanthanide ions. The samples were contained in a sample holder for liquids with a 3 μm Mylar window separating them from the vacuum (≤3 × 10−6 torr, 1 torr = 133.3224 Pa) in the solid state absorption chamber of the DCM beamline. Terbium, samarium, and dysprosium have 4 intense and narrow luminescence peaks between 450 and 700 nm, well separated from the luminescence peak of the Mylar window between 300 and 425 nm. The intensity of the rare earth (RE3+) luminescence peaks was lower for the solutions than for solid RECl3·6H2O. In part, this was caused by the lower RE3+ concentration in the solutions than in the solid. In addition, the solvent (water) acts as a quencher. The disorder and the molecular motion in the solution increase the availability of nonradiative de-excitation pathways. A high concentration of SO42− in the solution enhanced the luminescence intensity, probably by inhibiting some nonradiative de-excitation pathways. This study has shown that it is in principle possible to investigate the luminescence of aqueous solutions with XEOL spectroscopy. Furthermore, it is possible to use this technique as a quantitative analytical tool for concentrated luminescent solutions and to study the shielding effects of anions in the solution that increase the luminescence intensity.