Homo- and heterobimetallic niobiumv and tantalumv peroxo-tartrate complexes and their use as molecular precursors for Nb-Ta mixed oxides

被引:59
作者
Bayot, D
Tinant, B
Devillers, M
机构
[1] Catholic Univ Louvain, Unite Chim Mat Inorgan & Organ, B-1348 Louvain, Belgium
[2] Catholic Univ Louvain, Unite Chim Struct & Mecan React, B-1348 Louvain, Belgium
关键词
D O I
10.1021/ic0484250
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
New water-soluble bimetallic peroxo-tartrato complexes of niobium(V) and/or tantalum(V) have been prepared, characterized from the structural and spectroscopic point of view, and used as molecular precursors for Nb-Ta mixed oxides. Two new homometallic complexes, (gu)(5)[Nb-2(O-2)(4)(tart)(Htart)].4H(2)O (1a) and (gu)(6)[Ta-2(O-2)(4)(tart)(2)].4H(2)O (2a), and the corresponding heterometallic complex, (gu)(5)[NbTa(O-2)(4)(tart)(Htart)].4H(2)O (3), have been obtained. The crystal structures of the homometallic compounds, (gu)(5)[Nb-2(O-2)(4)(tart)(Htart)].6H(2)O.1H(2)O(2) (1b) and (gu)(6)[Ta-2(O-2)(4)(tart)(2)].6H(2)O (2b), have been determined, showing, for both cases, two 8-fold-coordinated metal atoms, each surrounded by oxygen atoms belonging to two bidentate peroxides, two monodentate carboxylato, and two alkoxo groups from both bridging tartrato ligands. The coordination polyhedron around each metal atom is a dodecahedron. The thermal treatment of complexes la, 2a, and 3 in air at 700 or 800 degreesC, depending of the Ta content, provided Nb2O5, Ta2O5, and the solid solution TaNbO5, respectively. The thermal treatment of a 1:1 Nb/Ta molar ratio mixture of la and 2a has also been studied. BET and SEM measurements have been carried out and reveal these oxides possess relatively high specific surface areas and display a porous character. Comparison between the use of homo- and heterometallic precursors is discussed.
引用
收藏
页码:1554 / 1562
页数:9
相关论文
共 39 条
[1]   MVO(5) (M=Nb, Ta) mixed oxides: Sol-gel synthesis, structural and thermal characterization and electrochemical Li+ insertion [J].
Amarilla, JM ;
Casal, B ;
RuizHitzky, E .
JOURNAL OF MATERIALS CHEMISTRY, 1996, 6 (06) :1005-1011
[2]   VIBRATIONAL SPECTROSCOPIC STUDY OF FERROELECTRIC SBNBO4, ANTIFERROELECTRIC BINBO4, AND THEIR SOLID-SOLUTIONS [J].
AYYUB, P ;
MULTANI, MS ;
PALKAR, VR ;
VIJAYARAGHAVAN, R .
PHYSICAL REVIEW B, 1986, 34 (11) :8137-8140
[3]   Spectroscopic and structural characterizations of novel water-soluble tetraperoxo and diperoxo[polyaminocarboxylato bis(N-oxido)]tantalate(V) complexes [J].
Bayot, D ;
Tinant, B ;
Devillers, M .
INORGANIC CHEMISTRY, 2004, 43 (19) :5999-6005
[4]   Water-soluble niobium peroxo complexes as precursors for the preparation of Nb-based oxide catalysts [J].
Bayot, D ;
Tinant, B ;
Devillers, M .
CATALYSIS TODAY, 2003, 78 (1-4) :439-447
[5]  
Bayot D, 2003, EUR J INORG CHEM, P737
[6]   Nb-Ta, Nb-Ta-V, and Nb-Ta-Bi oxides prepared from molecular precursors based on EDTA [J].
Bayot, DA ;
Devillers, MM .
CHEMISTRY OF MATERIALS, 2004, 16 (25) :5401-5407
[7]   Chemical routes to oxides: alkoxide vs. alkoxide-acetate routes: synthesis, characterization, reactivity and polycondensation of MNb2(OAc)(2)(OPri)(10) (M = Mg, Cd, Pb) species [J].
Boulmaaz, S ;
Papiernik, R ;
HubertPfalzgraf, LG ;
Septe, B ;
Vaissermann, J .
JOURNAL OF MATERIALS CHEMISTRY, 1997, 7 (10) :2053-2061
[8]   EMPIRICAL PARAMETERS FOR CALCULATING CATION-OXYGEN BOND VALENCES [J].
BROWN, ID ;
WU, KK .
ACTA CRYSTALLOGRAPHICA SECTION B-STRUCTURAL SCIENCE, 1976, 32 (JUL15) :1957-1959
[9]   Low temperature synthesis of lithium niobate powders based on water-soluble niobium malato complexes [J].
Camargo, ER ;
Kakihana, M .
SOLID STATE IONICS, 2002, 151 (1-4) :413-418
[10]   Synthesis and characterization of two new niobium(V) diperoxo complexes containing 8-quinolinolate as the ligand [J].
de Oliveira, V ;
San Gil, RAD ;
Lachter, ER .
POLYHEDRON, 2001, 20 (20) :2647-2649