In-Situ Synchrotron Radiation Study of Formation and Growth of Crystalline CexZr1−xO₂ Nanoparticles Synthesized in Supercritical Water

In situ synchrotron powder X-ray diffraction (PXRD) measurements have been conducted to follow the nucleation and growth of crystalline Ce x Zr 1− x O 2 nanoparticles synthesized in supercritical water with a full substitution variation ( x = 0, 0.2, 0.5, 0.8, and 1.0). Direction-dependent growth curves are determined and described using reaction kinetic models. A distinct change in growth kinetics is observed with increasing cerium content. For x = 0.8 and 1.0 (high cerium content), the growth is initially limited by the surface reaction kinetics; however, at a size of ∼6 nm, the growth changes and becomes limited by the diffusion of monomers toward the surface. For x = 0 and 0.2, the opposite behavior is observed with the growth initially being limited by diffusion (up to ∼3.5 nm) and later by the surface reaction kinetics. Thus, although a continuous solid solution can be obtained for the ceria−zirconia system, the growth of ceria and zirconia nanoparticles is fundamentally different under supercritical water conditions. For comparison, ex situ synthesis has also been performed using an in-house supercritical flow reactor. The resulting samples were analyzed using PXRD, small-angle X-ray scattering (SAXS), and transmission electron microscopy (TEM). The nanoparticles with x = 0, 0.2, and 0.5 have very low polydispersities. The sizes range from 4 nm to 7 nm, and the particles exhibit a reversibly pH-dependent agglomeration.