How hydrothermal synthesis improves the synthesis of (Zr,Ce)SiO4 solid solutions

Abstract

Although ZrSiO₄ is the most well-known compound in the zircon-structured family (space group I4₁/amd), the experimental conditions for preparing pure and well-crystallized phases that are doped with a tetravalent element via hydrothermal synthesis have never been clearly discussed in the literature. With the aim to answer this question, the experimental conditions of the preparation of ZrSiO₄ and (Zr,Ce)SiO₄ were investigated in order to synthesize well-crystallized and pure phases. A multiparametric study has been carried out using soft hydrothermal conditions with variables including reactant concentration, initial pH of the reactive medium, and duration of the hydrothermal treatment. Pure ZrSiO₄ was obtained through hydrothermal treatment for 7 days at 250 °C, within a large acidity range (1.0 ≤ pH ≤ 9.0) and starting from C_Si ≈ C_Zr ≥ 0.2 mol L⁻¹. As hydrothermally prepared zircon structured phases can be both hydrated and hydroxylated, its annealed form was also studied after heating to 1000 °C. Based on these results, the synthesis of (Zr,Ce)SiO₄ solid solutions was also investigated. The optimal hydrothermal conditions to acquire pure and crystallized phases were as follows: 7 days at 250 °C with initial pH = 1 and concentration of the reactants equal to 0.2 mol L⁻¹. This led to Zr_1−xCe_xSiO₄ solid solutions with the incorporated Ce content up to 40 mol%. Samples were characterized using multiple methods, including laboratory and synchrotron PXRD, IR and Raman spectroscopies, SEM, and TGA. Moreover, it was found that these phases were thermally stable in air up to at least 1000 °C.