A Kinetic Isotope Effect in the Formation of Lanthanide Phosphate Nanocrystals
Gal Schwartz, Uri Hananel, Liat Avram, Amir Goldbourt, Gil Markovich
Abstract
Mechanisms of nucleation and growth of crystals are still attracting a great deal of interest, in particular with recent advances in experimental techniques aimed at studying such phenomena. Studies of kinetic isotope effects in various reactions have been useful for elucidating reaction mechanisms, and it is believed that the same may apply for crystal formation kinetics. In this work, we present a kinetic study of the formation of europium-doped terbium phosphate nanocrystals under acidic conditions, including a strong H/D isotope effect. The nanocrystal growth process could be quantitatively followed through monitoring of the europium luminescence intensity. Hence, such lanthanide-based nanocrystals may serve as unique model systems for studying crystal nucleation and growth mechanisms. By combining the luminescence and NMR kinetics data, we conclude that the observed delayed nucleation occurs due to initial formation of pre-nucleation clusters or polymers of the lanthanide and phosphate ions, which undergo a phase transformation to crystal nuclei and further grow by cluster attachment. A scaling behavior observed on comparison of the H2O and D2O-based pre-nucleation and nanocrystal growth kinetics led us to conclude that both pre-nucleation and nanocrystal growth processes are of similar chemical nature.