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首页> 外文期刊>Bulletin of the Chemical Society of Japan >Mixed-Valence Ammonium Trivanadate with a Tunnel Structure Prepared by Pyrolysis of Polyoxovanadate
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Mixed-Valence Ammonium Trivanadate with a Tunnel Structure Prepared by Pyrolysis of Polyoxovanadate

机译:聚氧钒酸盐热解制备的隧道结构混合价三钒酸铵

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摘要

The pyrolysis of a polyoxovanadate solid, (NH_4)_(12) [V_(18)O_(42)(H_2O)] centre dot nH_2O (n approx=11), at 300 deg C in an Ar + NH_3 atmosphere gave a mixed-valence vanadium oxide, (NH_4)_x V_3O_7 (x approx=0.6), isostructural with Cs_(0.37)V_3O_7. The crystal structure of (NH_4)_xV_3O_7 was refined by the Rietveld method (hexagonal, P6_3/m, a = 9.8436(60, c=3.6165(1) A, V= 303.47(3) A~3, Z=2). (NH_4)_x V_3O_7 comprises edge- and corner-sharing V~(IV/V)O_5 square-pyramids with an approximate ratio of V~(IV) : V~v approx=0.49 : 0.51, to form a columnar cavity along the c-axis, in which ammonium N atoms are hydrogen-bonded to apical O atoms of the V~(IV/V)O_5 square-pyramids. A reflux of the (NH_4)_xV_3O_7 powder in a 0.6 M LiOH/2-methoxyethanol solution brought about Li-insertion into the columnar cavity without any structural change in the {V_3O_7} framework.
机译:聚氧钒酸盐固体(NH_4)_(12)[V_(18)O_(42)(H_2O)]中心点nH_2O(n大约= 11)在Ar + NH_3气氛中在300摄氏度下热解价钒氧化物,(NH_4)_x V_3O_7(x大约= 0.6),具有Cs_(0.37)V_3O_7的等结构。 (NH_4)_xV_3O_7的晶体结构通过Rietveld方法精制(六角形,P6_3 / m,a = 9.8436(60,c = 3.6165(1)A,V = 303.47(3)A〜3,Z = 2)。 (NH_4)_x V_3O_7包括边和边角共享的V〜(IV / V)O_5方锥,其近似比为V〜(IV):V〜v约= 0.49:0.51,沿着该边形成柱状腔c轴,其中铵N原子氢键合至V〜(IV / V)O_5方锥的顶端O原子。(NH_4)_xV_3O_7粉末在0.6 M LiOH / 2-甲氧基乙醇溶液中的回流在{V_3O_7}框架中没有任何结构变化的情况下,将Li插入柱状腔中。

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