草酸锆：Zr（OH）2（C2O4），（H11O5）2 [Zr2（C2O4）5（H2O）4]和MM'[Zr（C2O4）3]·xH2O，M和M'=铵，碱金属，和氢氧根离子H2n + 1O n +（n = 2、3、4）。,ACS Omega

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草酸锆：Zr（OH）2（C2O4），（H11O5）2 [Zr2（C2O4）5（H2O）4]和MM'[Zr（C2O4）3]·xH2O，M和M'=铵，碱金属，和氢氧根离子H2n + 1O n +（n = 2、3、4）。
ACS Omega ( IF 3.7 ) Pub Date : 2020-08-14 , DOI: 10.1021/acsomega.0c03224
Rudy Thomas ₁ , Philippe Devaux ₁ , Murielle Rivenet ₁ , Natacha Henry ₁ , Francis Abraham ₁

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通过沉淀获得二水合草酸锆锆Zr（OH）₂（C ₂ O ₄）（ZrOx）的结晶粉末，并根据粉末X射线数据确定结构。在（观察到的三维（3D）框架的ZrOx从氢氧化锆链的互连）结果¹_∞ [锆（OH）₂ ] ²⁺和锆草酸链¹_∞ [{的Zr（C ₂ Ò ₄）} ²⁺ ]。（H ₁₁ O ₅）₂ [Zr ₂（C ₂ O通过蒸发获得₄）₅（H ₂ O）₄ ]（H2Zr2O5）。该结构包含二聚阴离子[Zr ₂（C ₂ O ₄）₅（H ₂ O）₄ ] ^2–通过氢键连接到氢氧鎓离子（H ₁₁ O ₅）^+，从而形成3D超分子骨架。添加铵盐或碱式硝酸盐导致形成Na ₂ [Zr（C ₂ O ₄）₃ ]·2H ₂ O（Na2ZrOx3），M（H ₇ O ₃）[Zr（C ₂ O ₄）₃ ]·H ₂ O，M = K（KHZrOx3），M = NH ₄（NH4HZrOx3），M（H ₅ O ₂）_0.5（H ₉ O ₄）_0.5 [Zr（C ₂ O ₄）₃ ]，M ＝ Rb（RbHZrOx3），M ＝ Cs（CsHZrOx3）。对于五种化合物，该结构包含带¹_∞ [{的ZrOx ₃ } ^-2-由共享两个草酸酯的实体Zr（C ₂ O ₄）₄形成的] 。在（Na2ZrOx3），共享草酸盐是在顺式位置，并且链¹_∞ [Zr的牛]是阶梯状的与98.27（1）的Zr-Zr系的Zr角°。在其它化合物中，共享草酸盐是反式位置和链¹_∞ [Zr的牛]的波纹与Zr的Zr的Zr的在140.34（1）的范围内-141.07（1）°的角度。在化合物（MHZrOx3）中，对于M = K，NH ₄，（H ₅ O ），通过碱性或铵阳离子和氢氧鎓离子（H ₇ O ₃）⁺保证带之间的内聚。₂）⁺和（H ₉ O ₄）⁺对于M = Rb和Cs。在无碱锆草酸盐（热分解的ZrOx），（H2Zr2Ox5）和（NH4HZrOx3），所形成的无定形氧化锆是伴随着碳; 碳在约540°C氧化为二氧化碳的过程中，伴随着稳定的四方氧化锆的结晶。

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Zirconium Oxalates: Zr(OH)2(C2O4), (H11O5)2[Zr2(C2O4)5(H2O)4], and MM'[Zr(C2O4)3]·xH2O with M and M' = Ammonium, Alkali Metal, and Hydroxonium Ion H2n+1O n + (n = 2, 3, 4).

Crystallized powder of dihydroxide zirconium oxalate Zr(OH)₂(C₂O₄) (ZrOx) was obtained by precipitation and the structure determined from powder X-ray data. The three-dimensional (3D) framework observed in (ZrOx) results from the interconnection of zirconium hydroxide chains ¹_∞[Zr(OH)₂]²⁺ and zirconium oxalate chains ¹_∞[{Zr(C₂O₄)}²⁺]. Single crystals of (H₁₁O₅)₂[Zr₂(C₂O₄)₅(H₂O)₄] (H2Zr2O5) were obtained by evaporation. The structure contains dimeric anions [Zr₂(C₂O₄)₅(H₂O)₄]^2– connected through hydrogen bonds to hydroxonium ions (H₁₁O₅)⁺ to create a 3D supramolecular framework. The addition of ammonium or alkali nitrate led to the formation of single crystals of Na₂[Zr(C₂O₄)₃]·2H₂O (Na2ZrOx3), M(H₇O₃)[Zr(C₂O₄)₃]·H₂O, M = K (KHZrOx3), M = NH₄ (NH4HZrOx3), M(H₅O₂)_0.5(H₉O₄)_0.5[Zr(C₂O₄)₃], M = Rb (RbHZrOx3), and M = Cs (CsHZrOx3). For the five compounds, the structure contains ribbons ¹_∞[{ZrOx₃}^2–] formed by entities Zr(C₂O₄)₄ sharing two oxalates. In (Na2ZrOx3), the shared oxalates are in cis positions and the chain ¹_∞[Zr–Ox] is stepped with a Zr–Zr–Zr angle of 98.27(1)°. In the other compounds, the shared oxalates are in trans positions and the chains ¹_∞[Zr–Ox] are corrugated with Zr–Zr–Zr angles in the range 140.34(1)–141.07(1)°. In the compounds (MHZrOx3), the cohesion between the ribbons is ensured by the alkaline or ammonium cations and the hydroxonium ions (H₇O₃)⁺ for M = K, NH₄, (H₅O₂)⁺, and (H₉O₄)⁺ for M = Rb and Cs. During the thermal decomposition of the alkaline-free zirconium oxalates (ZrOx), (H2Zr2Ox5), and (NH4HZrOx3), the formed amorphous zirconia is accompanied by carbon; the oxidation of carbon at about 540 °C to carbon dioxide is concomitant with the crystallization of the stabilized tetragonal zirconia.

更新日期：2020-08-25

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