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+1On+ (n = 2, 3, 4) - Université de Lille Accéder directement au contenu
Article Dans Une Revue ACS Omega Année : 2020

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+1On+ (n = 2, 3, 4)

Résumé

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.

Domaines

Catalyse

Dates et versions

hal-04442671 , version 1 (06-02-2024)

Identifiants

Citer

Rudy Thomas, Philippe Devaux, Murielle Rivenet, Natacha Henry, Francis Abraham. 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+1On+ (n = 2, 3, 4). ACS Omega, 2020, ACS Omega, 5, pp.21260-21270. ⟨10.1021/acsomega.0c03224⟩. ⟨hal-04442671⟩
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