Synthesis of Nanoceria with Varied Ratios of Ce(3+)/Ce(4+) Utilizing Soluble Borate Glass

Mixed-valence cerium oxide nanoparticles (nanoceria) have been investigated with pronounced interest due to a wide range of biomedical and industrial applications that arises from its remarkable redox catalytic properties. However, there is no understanding of how to control the formation of these two types of nanoceria to obtain Ce(3+)/Ce(4+) ratios required in various applications. In this work, using a soluble borate glass, nanoceria with specific ratios of Ce(3+)/Ce(4+) are created and extracted via controlled glass-melting parameters. Glass embedded with nanoceria as well as nanoceria extracted from the glass were studied via XANES and fitted with the Multivariate Curve Resolution (MCR) technique to calculate the ratio of Ce(3+)/Ce(4+). Results show that mixed-valence nanoceria with specific ratios are hermetically sealed within the glass for long durations. When the glass dissolves, the mixed-valence nanoceria are released, and the extracted nanoceria have unchanged Ce(3+)/Ce(4+) ratios. Furthermore, TEM investigation on released nanoceria show that the nanoceria consist of several different structures. Although nanocrystal structures of Ce(7)O(12), Ce(11)O(20), and Ce(2)O(3) contribute to the reduced state, a new quasi-stable phase of CeO1.66 has been observed as well.