School of Chemistry and Chemical Engineering, Shandong University, 250100, Jinan, China.
State Key Lab of Crystal Materials, Shandong University, 250100, Jinan, China.
Chemistry. 2018 Oct 1;24(55):14701-14706. doi: 10.1002/chem.201801267. Epub 2018 Sep 7.
Novel 17-nuclear Zr/Hf oxide clusters ({Zr } and {Hf }) are isolated from aqueous systems. In the clusters, Zr/Hf ions are connected through μ -O, μ -OH, and μ -OH linkages into a pinwheel core which is wrapped with SO , HCOO , and aqua ligands. Octahedral hexanuclear Zr/Hf oxide clusters ({Zr } and {Hf } ) are also isolated from the same hydrothermal system by decreasing the synthesis temperature. Structures, synthetic conditions, vibrational spectra, and ionic conductivity of the clusters are studied. Structural studies and synthesis inspection suggest that formation of {Zr } and {Zr } involves assembly of the same transferable building blocks, but the condensation degree and thermodynamic stability of the products increase with hydrothermal temperature. The role of {Zr } and {Zr } in the formation of ZrO nanocrystals are then discussed in the scenario of nonclassical nucleation theory. In addition, the Zr oxide clusters exhibit ionic conductivity owing to the mobility of protons. This study not only adds new members to the Zr/Hf oxide cluster family, but also establishes a connection from Zr ions to ZrO in the hydrothermal preparation of zirconium oxide nanomaterials.
从水相体系中分离出了新型的 17 核 Zr/Hf 氧化物簇（{Zr} 和 {Hf}）。在这些簇中，Zr/Hf 离子通过 μ-O、μ-OH 和 μ-OH 键连接成一个风车状核心，该核心被 SO42-、HCOO- 和水配体包裹。通过降低合成温度，也从相同的水热体系中分离出了八核六方 Zr/Hf 氧化物簇（{Zr} 和 {Hf}）。研究了这些簇的结构、合成条件、振动光谱和离子电导率。结构研究和合成检验表明，{Zr}和{Zr}的形成涉及相同可转移构建块的组装，但产物的缩合程度和热力学稳定性随水热温度的升高而增加。然后，在非经典成核理论的情景下，讨论了 {Zr}和{Zr}在 ZrO 纳米晶形成中的作用。此外，Zr 氧化物簇由于质子的迁移而表现出离子导电性。这项研究不仅为 Zr/Hf 氧化物簇家族增添了新成员，而且还建立了从 Zr 离子到水热制备氧化锆纳米材料中的 ZrO 的联系。
