Multiple Fluorine-Substituted Phosphate Germanium Fluorides and Their Thermal Stabilities.

Title Multiple Fluorine-Substituted Phosphate Germanium Fluorides and Their Thermal Stabilities.
Authors X. Huang; B. Liu; R.C. Zhuang; Y. Pan; J.X. Mi; Y.X. Huang
Journal Inorg Chem
DOI 10.1021/acs.inorgchem.6b02266

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.

Citation X. Huang; B. Liu; R.C. Zhuang; Y. Pan; J.X. Mi; Y.X. Huang.Multiple Fluorine-Substituted Phosphate Germanium Fluorides and Their Thermal Stabilities.. Inorg Chem. 2016;55(23):1237612382. doi:10.1021/acs.inorgchem.6b02266

Related Elements


See more Germanium products. Germanium (atomic symbol: Ge, atomic number: 32) is a Block P, Group 14, Period 4 element with an atomic weight of 72.63. Germanium Bohr ModelThe number of electrons in each of germanium's shells is 2, 8, 18, 4 and its electron configuration is [Ar] 3d10 4s2 4p2. The germanium atom has a radius of 122.5 pm and a Van der Waals radius of 211 pm. Germanium was first discovered by Clemens Winkler in 1886. In its elemental form, germanium is a brittle grayish white semi-metallic element. Germanium is too reactive to be found naturally on Earth in its native state. High Purity (99.999%) Germanium (Ge) MetalIt is commercially obtained from zinc ores and certain coals. It is also found in argyrodite and germanite. It is used extensively as a semiconductor in transitors, solar cells, and optical materials. Other applications include acting an alloying agent, as a phosphor in fluorescent lamps, and as a catalyst. The name Germanium originates from the Latin word "Germania" meaning "Germany."


Phosphorus Bohr ModelSee more Phosphorus products. Phosphorus (atomic symbol: P, atomic number: 15) is a Block P, Group 15, Period 3 element. The number of electrons in each of Phosphorus's shells is 2, 8, 5 and its electronic configuration is [Ne] 3s2 3p3. The phosphorus atom has a radius of and its Van der Waals radius is Phosphorus is a highly-reactive non-metallic element (sometimes considered a metalloid) with two primary allotropes, white phosphorus and red phosphorus its black flaky appearance is similar to graphitic carbon. Compound forms of phosphorus include phosphates and phosphides. Phosphorous was first recognized as an element by Hennig Brand in 1669 its name (phosphorus mirabilis, or "bearer of light") was inspired from the brilliant glow emitted by its distillation.


Fluorine is a Block P, Group 17, Period 2 element. Its electron configuration is [He]2s22p5. The fluorine atom has a covalent radius of 64 pm and its Van der Waals radius is 135 pm. In its elemental form, CAS 7782-41-4, fluorine gas has a pale yellow appearance. Fluorine was discovered by André-Marie Ampère in 1810. It was first isolated by Henri Moissan in 1886.

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