How hydrothermal synthesis improves the preparation of (Zr,Ce)SiO 4 solid solutions
How hydrothermal synthesis improves the preparation of (Zr,Ce)SiO 4 solid solutions
复制标题
水热合成如何改进(Zr,Ce)SiO 4 固溶体的制备
DOI：
10.1039/d3dt01524f
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发表时间：
2023
影响因子：
4
通讯作者：
Guo, Xiaofeng
中科院分区：
文献类型：
--
作者：
Barral, Thomas;Estevenon, Paul;Chanteau, Yann;Kaczmarek, Thibault;Strzelecki, Andrew;Menut, Denis;Welcomme, Eleonore;Szenknect, Stéphanie;Moisy, Philippe;Guo, Xiaofeng
尽管ZrSiO4是锆石结构家族（空间群I41/amd）中最著名的化合物，但通过水热合成制备掺杂四价元素的纯且结晶良好的相的实验条件从未在文献中明确讨论过。为了回答这个问题，研究了ZrSiO4和(Zr,Ce)SiO4的制备实验条件，以合成结晶良好的纯相。使用软水热条件进行了多参数研究，变量包括反应物浓度、反应介质的初始 pH 值和水热处理的持续时间。纯ZrSiO4是通过在250℃、大酸度范围（1.0≤pH≤9.0）和CSi≈CZr≥0.2molL−1开始水热处理7天获得的。由于水热制备的锆石结构相既可以水合又可以羟基化，因此在加热到1000℃后也研究了其退火形式。基于这些结果，还研究了(Zr,Ce)SiO4固溶体的合成。获得纯相和结晶相的最佳水热条件如下：250°C、初始pH = 1、反应物浓度等于0.2 mol L−1 7天。这导致 Zr1−xCexSiO4 固溶体的 Ce 含量高达 40 mol%。使用多种方法对样品进行表征，包括实验室和同步加速器 PXRD、红外和拉曼光谱、SEM 和 TGA。此外，还发现这些相在空气中至少 1000 °C 的温度下是热稳定的。
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 CSi ≈ CZr ≥ 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 Zr1−xCexSiO4 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.