Switching Lead for Tin in PbHfO 3 : Noncubic Structure of SnHfO 3 **
Switching Lead for Tin in PbHfO 3 : Noncubic Structure of SnHfO 3 **
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PbHfO 3 中锡的开关引线：SnHfO 3 的非立方结构 **
DOI：
10.1002/anie.202312130
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发表时间：
2023
期刊：
影响因子：
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通讯作者：
Maggard, Paul A.
中科院分区：
文献类型：
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作者：
Gabilondo, Eric A.;Newell, Ryan J.;Broughton, Rachel;Koldemir, Aylin;Pöttgen, Rainer;Jones, Jacob L.;Maggard, Paul A.
由于许多国家的立法，从商业化的钙钛矿型氧化物基压电陶瓷中去除铅已经成为最近材料研究的一个主要课题。在这方面，锡(II)-钙钛矿氧化物由于其大的自发电极化和等电子性质取代了铅(II)离子而引起了人们的兴趣。然而，由于它们的高亚稳性，它们还没有被认为是可合成的。其中，钙钛矿型PbHfO_3空间群PbHfO_3在30 0 °C的低温下与SnClF反应，得到了第一次完全的锡(II)取代铅(II)，即SnHfO_3。通过X射线、电子衍射、元素分析和~(119)Sn穆斯堡尔谱证实，在这种拓扑定向转变过程中，Pbam对称性保持了较高的纯度和结晶度。原位衍射表明，SnHfO_3也具有可逆的相变，并且在≈130-200 °C之间具有潜在的极性。因此，这种所谓的“脱铅”被认为是一种非常有用的策略，可以完全去除钙钛矿型氧化物基压电陶瓷中的铅，并为极性和反极性锡(II)氧化物材料的新探索打开了大门。
The removal of lead from commercialized perovskite‐oxide‐based piezoceramics has been a recent major topic in materials research owing to legislation in many countries. In this regard, Sn(II)‐perovskite oxides have garnered keen interest due to their predicted large spontaneous electric polarizations and isoelectronic nature for substitution of Pb(II) cations. However, they have not been considered synthesizable owing to their high metastability. Herein, the perovskite lead hafnate, i.e., PbHfO3in space groupPbam, is shown to react with SnClF at a low temperature of 300 °C, and resulting in the first complete Sn(II)‐for‐Pb(II) substitution, i.e. SnHfO3. During this topotactic transformation, a high purity and crystallinity is conserved withPbamsymmetry, as confirmed by X‐ray and electron diffraction, elemental analysis, and119Sn Mössbauer spectroscopy. In situ diffraction shows SnHfO3also possesses reversible phase transformations and is potentially polar between ≈130–200 °C. This so‐called ‘de‐leadification’ is thus shown to represent a highly useful strategy to fully remove lead from perovskite‐oxide‐based piezoceramics and opening the door to new explorations of polar and antipolar Sn(II)‐oxide materials.