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Title: Hydrothermal synthesis, structure and thermal stability of diamine templated layered uranyl-vanadates

Abstract

Six new layered uranyl vanadates (NH{sub 4}){sub 2}[(UO{sub 2}){sub 2}V{sub 2}O{sub 8}] (1), (H{sub 2}EN)[(UO{sub 2}){sub 2}V{sub 2}O{sub 8}] (2), (H{sub 2}DAP)[(UO{sub 2}){sub 2}V{sub 2}O{sub 8}] (3), (H{sub 2}PIP)[(UO{sub 2}){sub 2}(VO{sub 4}){sub 2}].0,8H{sub 2}O (4), (H{sub 2}DMPIP)[(UO{sub 2}){sub 2}V{sub 2}O{sub 8}] (5), (H{sub 2}DABCO)[(UO{sub 2}){sub 2}(VO{sub 4}){sub 2}] (6) were prepared from mild-hydrothermal reactions using 1,2-ethylenediamine (EN); 1,3-diaminopropane (DAP); piperazine (PIP); 1-methylpiperazine (MPIP); 1,4-diazabicyclo[2,2,2]octane (DABCO). The structures of 1, 4, 5 and 6 were solved using single-crystal X-ray diffraction data while the structural models of 2 and 3 were established from powder X-ray diffraction data. In compounds 1, 2, 3 and 5, the uranyl-vanadate layers are built from dimers of edge-shared UO{sub 7} pentagonal bipyramids and dimers of edge-shared VO{sub 5} square pyramids further connected through edge-sharing. In 1 and 3, the layers are identical to that occurring in the carnotite group of uranyl-vanadates. In 2 and 5, the V{sub 2}O{sub 8} dimers differ in orientation leading to a new type of layer. The layers of compound 4 and 6 are built from chains of edge-shared UO{sub 7} pentagonal bipyramids connected by VO{sub 4} tetrahedra and are of uranophane-type anion topology. For the six compounds, the ammonium or organoammonium cationmore » resides in the space between the inorganic layers. Crystallographic data: 1 monoclinic, space group P2{sub 1}/c with a=6.894(2), b=8.384(3), c=10.473(4) A and {beta}=106.066(5){sup o}, 2 monoclinic, space group P2{sub 1}/a with a=13.9816(6), b=8.6165(3), c=10.4237(3) A and {gamma}=93.125(3){sup o}, 3 orthorhombic, space group Pmcn with a=14.7363(8), b=8.6379(4) and c=10.4385(4) A, 4 monoclinic, space group C2/m with a=15.619(2), b=7.1802(8), c=6.9157(8) A and {beta}=101.500(2){sup o}, 5 monoclinic, space group P2{sub 1}/b with a=9.315(2), b=8.617(2), c=10.5246(2) A and {gamma}=114.776(2){sup o}, 6 monoclinic, space group C2/m with a=17.440(2), b=7.1904(9), c=6.8990(8) A and {beta}=98.196(2){sup o}. - Graphical abstract: The three types of layer in layered uranyl-vanadates using diamine as a structure-directing agent.« less

Authors:
 [1];  [2];  [2];  [2]
  1. Unite de Catalyse et de Chimie du Solide, Equipe Chimie du Solide, UCCS UMR CNRS 8181, USTL, ENSC-B.P. 90108, 59652 Villeneuve d'Ascq Cedex (France), E-mail: Murielle.rivenet@ensc-lille.fr
  2. Unite de Catalyse et de Chimie du Solide, Equipe Chimie du Solide, UCCS UMR CNRS 8181, USTL, ENSC-B.P. 90108, 59652 Villeneuve d'Ascq Cedex (France)
Publication Date:
OSTI Identifier:
21015702
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Solid State Chemistry; Journal Volume: 180; Journal Issue: 2; Other Information: DOI: 10.1016/j.jssc.2006.11.034; PII: S0022-4596(06)00629-3; Copyright (c) 2006 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ANIONS; CARNOTITE; CATIONS; CRYSTALLOGRAPHY; DIMERS; HYDROTHERMAL SYNTHESIS; LAYERS; MONOCLINIC LATTICES; MONOCRYSTALS; ORTHORHOMBIC LATTICES; PIPERAZINES; SPACE GROUPS; STRUCTURAL MODELS; URANIUM COMPOUNDS; URANOPHANE; VANADATES; X-RAY DIFFRACTION

Citation Formats

Rivenet, Murielle, Vigier, Nicolas, Roussel, Pascal, and Abraham, Francis. Hydrothermal synthesis, structure and thermal stability of diamine templated layered uranyl-vanadates. United States: N. p., 2007. Web. doi:10.1016/j.jssc.2006.11.034.
Rivenet, Murielle, Vigier, Nicolas, Roussel, Pascal, & Abraham, Francis. Hydrothermal synthesis, structure and thermal stability of diamine templated layered uranyl-vanadates. United States. doi:10.1016/j.jssc.2006.11.034.
Rivenet, Murielle, Vigier, Nicolas, Roussel, Pascal, and Abraham, Francis. Thu . "Hydrothermal synthesis, structure and thermal stability of diamine templated layered uranyl-vanadates". United States. doi:10.1016/j.jssc.2006.11.034.
@article{osti_21015702,
title = {Hydrothermal synthesis, structure and thermal stability of diamine templated layered uranyl-vanadates},
author = {Rivenet, Murielle and Vigier, Nicolas and Roussel, Pascal and Abraham, Francis},
abstractNote = {Six new layered uranyl vanadates (NH{sub 4}){sub 2}[(UO{sub 2}){sub 2}V{sub 2}O{sub 8}] (1), (H{sub 2}EN)[(UO{sub 2}){sub 2}V{sub 2}O{sub 8}] (2), (H{sub 2}DAP)[(UO{sub 2}){sub 2}V{sub 2}O{sub 8}] (3), (H{sub 2}PIP)[(UO{sub 2}){sub 2}(VO{sub 4}){sub 2}].0,8H{sub 2}O (4), (H{sub 2}DMPIP)[(UO{sub 2}){sub 2}V{sub 2}O{sub 8}] (5), (H{sub 2}DABCO)[(UO{sub 2}){sub 2}(VO{sub 4}){sub 2}] (6) were prepared from mild-hydrothermal reactions using 1,2-ethylenediamine (EN); 1,3-diaminopropane (DAP); piperazine (PIP); 1-methylpiperazine (MPIP); 1,4-diazabicyclo[2,2,2]octane (DABCO). The structures of 1, 4, 5 and 6 were solved using single-crystal X-ray diffraction data while the structural models of 2 and 3 were established from powder X-ray diffraction data. In compounds 1, 2, 3 and 5, the uranyl-vanadate layers are built from dimers of edge-shared UO{sub 7} pentagonal bipyramids and dimers of edge-shared VO{sub 5} square pyramids further connected through edge-sharing. In 1 and 3, the layers are identical to that occurring in the carnotite group of uranyl-vanadates. In 2 and 5, the V{sub 2}O{sub 8} dimers differ in orientation leading to a new type of layer. The layers of compound 4 and 6 are built from chains of edge-shared UO{sub 7} pentagonal bipyramids connected by VO{sub 4} tetrahedra and are of uranophane-type anion topology. For the six compounds, the ammonium or organoammonium cation resides in the space between the inorganic layers. Crystallographic data: 1 monoclinic, space group P2{sub 1}/c with a=6.894(2), b=8.384(3), c=10.473(4) A and {beta}=106.066(5){sup o}, 2 monoclinic, space group P2{sub 1}/a with a=13.9816(6), b=8.6165(3), c=10.4237(3) A and {gamma}=93.125(3){sup o}, 3 orthorhombic, space group Pmcn with a=14.7363(8), b=8.6379(4) and c=10.4385(4) A, 4 monoclinic, space group C2/m with a=15.619(2), b=7.1802(8), c=6.9157(8) A and {beta}=101.500(2){sup o}, 5 monoclinic, space group P2{sub 1}/b with a=9.315(2), b=8.617(2), c=10.5246(2) A and {gamma}=114.776(2){sup o}, 6 monoclinic, space group C2/m with a=17.440(2), b=7.1904(9), c=6.8990(8) A and {beta}=98.196(2){sup o}. - Graphical abstract: The three types of layer in layered uranyl-vanadates using diamine as a structure-directing agent.},
doi = {10.1016/j.jssc.2006.11.034},
journal = {Journal of Solid State Chemistry},
number = 2,
volume = 180,
place = {United States},
year = {Thu Feb 15 00:00:00 EST 2007},
month = {Thu Feb 15 00:00:00 EST 2007}
}
  • The utilization of the hydrothermal technique in combination with cationic organic templates has been extensively used in the synthesis of zeolites and molecular sieves. Here, the authors report the hydrothermal synthesis and single-crystal structure of (H{sub 3}N(CH{sub 2}){sub 3}NH{sub 3})[V{sub 4}O{sub 10}], a layered mixed-valence vanadium oxide with organic ammonium cations between the layers. 21 refs., 4 figs.
  • Four scandium phosphate-based structures have been prepared hydrothermally in the presence of the primary diamines ethylenediamine and diaminobutane and the primary amine cyclohexylamine and characterised by single crystal and powder X-ray diffraction, {sup 31}P and {sup 45}Sc solid-state MAS NMR and chemical analysis. Charge balancing protons in the structures are located using bond valence sum calculations and postulated hydrogen bonding networks. Compound 1, [(H{sub 3}NC{sub 2}H{sub 4}NH{sub 3}){sub 3}][Sc{sub 3}(OH){sub 2}(PO{sub 4}){sub 2}(HPO{sub 4}){sub 3}(H{sub 2}PO{sub 4})], P1-bar , a=5.4334(6), b=8.5731(9), c=16.3022(18)A, {alpha}=79.732(4), {beta}=83.544(4), {gamma}=80.891(5){sup o}, Z=2, is built up of scandium phosphate ribbons, based on trimers of ScO{sub 6}more » octahedra linked by OH groups. These trimers are joined through phosphate groups bound through three oxygens, and are decorated by phosphate groups linked by a single oxygen atom. The ribbons are arranged parallel to the a-axis and linked one to another by fully protonated ethylenediammonium ions. Compounds 2, [(H{sub 3}NC{sub 4}H{sub 8}NH{sub 3}){sub 3}][(Sc(OH{sub 2})){sub 6}Sc{sub 2}(HPO{sub 4}){sub 12}(PO{sub 4}){sub 2}], P3-bar , a=13.8724(3), c=9.4351(11)A, Z=1, and 3, [(H{sub 3}NC{sub 4}H{sub 8}NH{sub 3}){sub 2}(H{sub 3}O)][Sc{sub 5}F{sub 4}(HPO{sub 4}){sub 8}], C2/m, a=12.8538(4), b=14.9106(4), c=10.1906(3)A, {beta}=101.17(9){sup o}, Z=2, were prepared using diaminobutane as the organic template in the absence and presence, respectively, of fluoride ions in the gel. Compound 2 has a pillared layered structure, in which ScO{sub 6} octahedra are linked by three vertices of hydrogenphosphate groups into sheets and the sheets pillared by ScO{sub 6} octahedra to give a three-dimensionally connected framework isostructural with a previously reported iron(III) hydrogenphosphate. The protonated diaminobutane molecules occupy cavities between the layers. Compound 3 has a layered structure in which isolated ScO{sub 6} octahedra and tetrameric arrangements of ScO{sub 4}F{sub 2} octahedra, the latter linked in squares through fluoride ions, are connected by phosphate tetrahedra that share two or three oxygens with scandium atoms. In this structure, the protonated diaminobutane molecules connect the layers, the -NH{sub 3}{sup +} groups fitting into recesses in the layers. Compound 4, [(C{sub 6}H{sub 11}NH{sub 3})][ScF(HPO{sub 4})(H{sub 2}PO{sub 4})], Pbca, a=7.650(3), b=12.867(5), c=26.339(11)A, Z=8, the first scandium phosphate to be prepared with a monoamine, is also a layered solid. In this case, the layers contain single chains of ScO{sub 4}F{sub 2} octahedra which share fluoride ions in trans positions. Phosphate tetrahedra bridge across scandiums via two of their four oxygens, both within the same chain and also to neighbouring chains to make up the layer. The protonated amine groups of the cyclohexylamine molecules achieve close contact with phosphates of the layer, while the cyclohexyl moieties, which are in the chair configuration, project into the interlayer space.« less
  • Two new fluoro-vanadyl-hydrogenarsenate compounds templated by ethylenediamine and piperazine with formula, (C{sub 2}N{sub 2}H{sub 10}){sub 0.5}[(VO)(HAsO{sub 4})F] (1) and (C{sub 4}N{sub 2}H{sub 12}){sub 0.5}[(VO)(HAsO{sub 4})F] (2), respectively, have been synthesized by using mild hydrothermal conditions under autogenous pressure. The crystal structures have been solved from single-crystal X-ray diffraction data. The phases crystallize in the P2{sub 1}/c monoclinic space group with the unit-cell parameters a=7.8634(4) A, b=7.7658(4) A, c=10.4195(6) A, {beta}=101.524(5){sup o} for compound (1) and a=6.301(1) A, b=10.244(1) A, c=10.248(1) A and {beta}=95.225(1){sup o} for compound (2). These phases exhibit a layered inorganic framework. In both cases, the structure ismore » built from secondary building units (SBU) which are formed by [V{sub 2}O{sub 8}F{sub 2}] edge-shared dimeric vanadyl octahedra, connected by the vertices to two hydrogenarsenate tetrahedra. The repetition of this SBU unit originates sheets along the [1 0 0] direction. The ethylenediammonium and piperazinium cations are located inside the interlayer space. The limit of thermal stability for compounds (1) and (2) is, approximately, 250 and 230 deg. C, respectively. Near this temperature, both phases loose their organic cations and the fluoride anions. The diffuse reflectance spectra confirm the presence of vanadyl ions, in which the vanadium(IV) cations have a d{sup 1} electronic configuration in a slightly distorted octahedral environment. ESR spectra of both phases are isotropic with mean g-values of 1.93 and 1.96 for ethylendiamine and piperazine phases, respectively. Magnetic measurements for (1) and (2) indicate the existence of antiferromagnetic exchange couplings. - Graphical abstract: Polyhedral view of the layered crystal structure of (C{sub 2}H{sub 10}N{sub 2}){sub 0.5} [(VO)(HAsO{sub 4})F].« less
  • A new family of three-dimensional (3D) uranyl vanadates (C{sub 3}N{sub 2}H{sub 12}){l_brace}[(UO{sub 2})(H{sub 2}O)][(UO{sub 2})(VO{sub 4})]{sub 4}{r_brace}.1H{sub 2}O (C3UV), (C{sub 4}N{sub 2}H{sub 14}){l_brace}[(UO{sub 2})(H{sub 2}O)][(UO{sub 2})(VO{sub 4})]{sub 4}{r_brace}.2H{sub 2}O (C4UV), (C{sub 5}N{sub 2}H{sub 16}) {l_brace}[(UO{sub 2})(H{sub 2}O)][(UO{sub 2})(VO{sub 4})]{sub 4}{r_brace} (C5UV), (C{sub 6}N{sub 2}H{sub 20}) {l_brace}[(UO{sub 2})(H{sub 2}O)][(UO{sub 2})(VO{sub 4})]{sub 4}{r_brace} (C6UV) and (C{sub 7}N{sub 2}H{sub 22}) {l_brace}[(UO{sub 2})(H{sub 2}O)][(UO{sub 2})(VO{sub 4})]{sub 4}{r_brace} (C7UV) was prepared from mild-hydrothermal reactions using 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane and 1,7-diaminoheptane as structure directing agents. The five compounds are orthorhombic, space group Cmc2{sub 1}, with a{approx}15.6, b{approx}14.1, c{approx}13.6 A. The structures were solved using single-crystalmore » X-ray diffraction data. The compounds contain the same three-dimensional inorganic framework built from uranyl-vanadate layers of uranophane-type anion topology pillared by [UO{sub 6}(H{sub 2}O)] pentagonal bipyramids. The doubly protonated diamines reside in the cavities created by the inorganic framework and are linked to the inorganic framework through hydrogen bonds involving one nitrogen atom. The structure is compared with that of uranyl-phosphates and uranyl-arsenates containing alkaline metals. The use of alkaline metals for the synthesis of uranyl-vanadates leads to carnotite-type compounds. - Graphical abstract: The (C{sub 6}N{sub 2}H{sub 20}){l_brace}[(UO{sub 2})(H{sub 2}O)][(UO{sub 2})(VO{sub 4})]{sub 4}{r_brace} compound: projection in the (1 0 0) and in the (0 0 1) planes showing the amine position.« less
  • The hydrothermal treatment of uranyl nitrate and 1,4-benzenebisphosphonic acid with a variety of aliphatic amines (tetramethylammonium hydroxide, tetraethylammonium hydroxide, and diethyldimethylammonium hydroxide) and small quantities of hydrofluoric acid at 200 °C results in the crystallization of a series of layered uranyl diphosphonate compounds, [(CH 3) 4N][(UO 2) 3(O 3PC 6H 4PO 3H) 2F(H 2O)]·0.5H 2O (Me 4Ubbp), [(CH 3CH 2) 4N](UO 2)[C 6H 4(PO 3H)(PO 3H 1.5)] 2(H 2O) (Et 4Ubbp), and [(CH 3CH 2) 2N(CH 3) 2][(UO 2) 3(O 3PC 6H 4PO 3H) 2F(H 2O)] (Et 2Me 2Ubbp). All these new compounds have layered structures, but the structures ofmore » Me 4Ubbp and Et 2Me 2Ubbp are similar in that they both contain UO 6F and UO 7 pentagonal bipyramids within dimers that are bridged by the phosphonate into a three-dimensional structure. The structure of Et 4Ubbp contains a single crystallographically unique UO 7 unit. The edge-sharing pentagonal bipyramids are linked into chains formulated as (UO 2)[C 6H 4(PO 3H)(PO 3H 1.5)] 2(H 2O) 1-. The voids in these structures are filled with the organic templates so that the overall charge balance is maintained. Intense fluorescence was observed from these compounds at room temperature.« less