Multiple Fluorine-Substituted Phosphate Germanium Fluorides and Their Thermal Stabilities

详细信息    查看全文

• 作者：Xia Huang ; Biao Liu ; Rong-Chuan Zhuang ; Yuanming Pan ; Jin-Xiao Mi ; Ya-Xi Huang
• 刊名：Inorganic Chemistry
• 出版年：2016
• 出版时间：December 5, 2016
• 年：2016
• 卷：55
• 期：23
• 页码：12376-12382
• 全文大小：500K
• ISSN：1520-510X

文摘

Anhydrous compounds are crucially important for many technological applications, such as achieving high performance in lithium/sodium cells, but are often challenging to synthesize under hydrothermal conditions. Herein we report that a modified solvo-/hydro-fluorothermal method with fluoride-rich and water-deficient condition is highly effective for synthesizing anhydrous compounds by the replacement of hydroxyl groups and water molecules with fluorine. Two anhydrous phosphate germanium fluorides, namely, Na₃[GeF₄(PO₄)] and K₄[Ge₂F₉(PO₄)], with chainlike structures involving multiple fluorine substitutions, were synthesized using the modified solvo-/hydro-fluorothermal method. The crystal structure of Na₃[GeF₄(PO₄)] is constructed by the common single chains _∞¹{[GeF₄(PO₄)]^3–} built from alternating GeO₂F₄ octahedra and PO₄ tetrahedra. For K₄[Ge₂F₉(PO₄)], it takes the same single chain in Na₃[GeF₄(PO₄)] as the backbone but has additional flanking GeOF₅ octahedra via an O-corner of the PO₄ groups, resulting in a dendrite zigzag single chain _∞¹{[Ge₂F₉(PO₄)]^4–}. The multiple fluorine substitutions in these compounds not only force them to adopt the low-dimensional structures because of the “tailor effect” but also improve their thermal stabilities. The thermal behavior of Na₃[GeF₄(PO₄)] was investigated by an in situ powder X-ray diffraction experiment from room temperature to 700 °C. The modified solvo-/hydro-fluorothermal method is also shown to be effective in producing the most germanium-rich compounds in the germanophosphate system.