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Solubility of Nanocrystalline Cerium Dioxide: Experimental Data and Thermodynamic Modeling

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journal contribution
posted on 12.09.2016, 00:00 by Tatiana V. Plakhova, Anna Yu. Romanchuk, Sergey N. Yakunin, Thomas Dumas, Selvan Demir, Shuao Wang, Stefan G. Minasian, David K. Shuh, Tolek Tyliszczak, Andrey A. Shiryaev, Alexander V. Egorov, Vladimir K. Ivanov, Stepan N. Kalmykov
Ultrafine 5 nm ceria isotropic nanoparticles were prepared using the rapid chemical precipitation approach from cerium­(III) nitrate and ammonium hydroxide aqueous solutions. The as-prepared nanoparticles were shown to contain predominantly Ce­(IV) species. The solubility of nanocrystalline CeO2 at several pH values was determined using ICP-MS and radioactive tracer methods. Phase composition of the ceria samples remained unchanged upon partial dissolution, while the shape of the particles changed dramatically, yielding nanorods under neutral pH conditions. According to X-ray absorption spectroscopy investigation of the supernatant, Ce­(III) was the main cerium species in solution at pH < 4. Based on the results obtained, a reductive dissolution model was used for data interpretation. According to this model, the solubility product for ceria nanoparticles was determined to be log Ksp = −59.3 ± 0.3 in 0.01 M NaClO4. Taken together, our results show that the pH dependence of ceria anti- and pro-oxidant activity can be related to the dissolution of CeO2 in aqueous media.