J O U R N A L O F C H E M I S T R Y Materials Hydrothermal synthesis and characterization of a new aluminium vanadium oxide hydroxide Al2(OH)3(VO4) Brigitte Pecquenard, Peter Y. Zavalij and M. Stanley Whittingham*† Chemistry Department and Material Research Center, State University of New York at Binghamton, Binghamton, NY 13902-6000, USA A new aluminium vanadium oxide hydroxide analog of the mineral augelite has been prepared by hydrothermal treatment of a 15152.65 aqueous solution of V2O5, Al(NO3)3·9H2O, and TMAOH at 200 °C for 5 days.X-Ray powder diVraction data show that this phase crystallizes with monoclinic symmetry with space group C2/m. The structure was solved by using direct methods and then full profile Rietveld refinement was carried out; it’s cell parameters are: a=13.5634(2) A ° , b=8.2267(2) A ° , c=5.31232(9) A ° and b=112.741(1)° in space group C2/m.The structure contains clusters of edge sharing AlO6 octahedra and AlO5 trigonal bipyramids. These clusters are joined together by VO4 tetrahedra. steps and 15 s per step. The TGA was obtained on a Perkin- Introduction Elmer model TGA 7, the FTIR on a Perkin-Elmer 1600 series, In a constant search for new compounds which could be used and the electron microprobe on a JEOL 8900.as cathodic materials for advanced lithium batteries, we focussed our research on new metastable vanadium oxides. Results and Discussion The structure of the oxide lattice and a possible addition of a second metal are critical to obtain lithium insertion and The resulting powder has a light brown color.The electron reversible reaction. Indeed, a recent study on a Fe0.11V2O5.16 microprobe picture (Fig. 1) shows that the morphology of this compound obtained by the sol–gel process has shown that the new compound is well formed spherical particles, with an presence of iron(III ) ions in the orthorhombic host lattice average diameter close to 70 mm. It seems that these particles induced a real improvement of its electrochemical properties result from a germination/growth process, with a nucleation compared to V2O5.1 The use of ‘chimie douce’ allows us to point at the center of each particle.The X-ray diVraction obtain new materials which are sometimes impossible to be pattern indicates the presence of sharp lines. Thermal graviformed by using solid state reactions at high temperature.metric analysis of the compound under nitrogen (Fig. 2) shows Among these, the hydrothermal approach under mild con- a total weight loss of about 13.1% appearing in one step ditions, using organic templates such as tetramethylammonium essentially due to loss of OH groups. From TGA and X-ray ion was found to be particularly adept at forming new data, the general formula of the compound was found to be structures.2–17 It is noticeable that the template is often Al2(OH)3(VO4), the tetramethylammonium not being incorretained in the structure, as for TMA0.17V2O5, TMAV3O7,18 porated in the structure. The infrared spectrum (Fig. 3) con- TMAV4O105,9 or TMAV8O20.19 Recently, a study achieved by firmed the absence of tetramethylammonium ion which is Zhang et al.17 indicate the possible synthesis of iron and zinc usually characterized by three bands at 945, 1386 and double vanadium oxides using TMA.Here we report the synthesis of a new aluminium vanadium oxide analog of the mineral augelite Al2(PO4)(OH)320 by using tetramethylammonium ion as a template. Experimental The title compound was prepared by hydrothermal treatment by mixing V2O5 and Al(NO3)3·9H2O powder from Johnson and Matthey with 25% tetramethylammonium hydroxide (TMAOH) aqueous solution from Alfa in a 15152.65 molar ratio.Typically, 5 g of V2O5, 10.3 g of Al(NO3)3·9H2O and 26.5 g of TMAOH were mixed together and the initial pH of the resulting solution was 3.21. Then, the solution was transferred to a 125 ml Teflon-lined autoclave (Parr bomb), sealed and reacted hydrothermally for 5 days at 200 °C.At shorter and longer reaction times second phases were formed, the compositions of which have not yet been determined. The resulting light brown powder was filtered, washed with distilled water and dried in air. The pH of the solution after reaction was 6.32, higher than that of the initial mixture.X-Ray powder diVraction was performed using Cu-Ka radiation (l=1.5418 A° ) on a Scintag XDS2000 h–h diVractometer. The data were collected from 17° 2h to 90° 2h with 0.03° 2h Fig. 1 Electron microprobe picture of Al2(OH)3(VO4) †E-mail: stanwhit@binghamton.edu J. Mater. Chem., 1998, 8(5), 1255–1258 1255Fig. 2 Thermal gravimetric analysis of Al2(OH)3(VO4) under nitrogen Fig. 4 Calculated X-ray diVraction pattern resulting from final Rietveld refinement (thin line), experimental data (dotted line) and a diVerence plot (on the bottom) Table 1 Crystallographic data for Al2(OH)3(VO4) compound Al2(OH)3(VO4) crystal system monoclinic space group C2/m (no. 12) a/A ° 13.5634(2) b/A ° 8.2267(2) c/A ° 5.31232(9) b/° 112.741(1) cell volume, V/A° 3 546.68(3) calculated density, Dc/g cm-3 2.672 absorption coeYcient, m/cm-1 191.7 radiation, l(Cu-Ka)/A ° 1.54178 diVractometer Scintag XDS2000 Fig. 3 Infrared spectrum of Al2(OH)3(VO4) indexing method Ito software CSD mode of refinement full profile 1492 cm-1.21 All the bands are observed in the range 2h (max) 90° 450–1050 cm-1 which correspond to the MMO bonds domain number of refined parameters 29 (21 atomic) (M being a metallic atom).The precise assignment of IR peaks number of reflections 87 R(I) 0.062 is however not obvious. Only characteristic frequency ranges R(prof ) 0.086 are known for ‘condensed’ and ‘isolated’ AlMO octahedra and Rw (prof ) 0.105 tetrahedra.22 Peak positions are really dependent on the structure. After thermal treatment under air, the compound is decomposed into V2O5 and AlVO4.The powder diVraction Table 2 Atomic coordinates and thermal parameters for pattern was indexed with a monoclinic symmetry and the Al2(OH)3(VO4) space group C2/m using the Ito method from the CSD Software.23 The cell parameters of this new compound are: atom x/a y/b z/c Uiso/A° N a=13.5634(2) A ° , b=8.2267(2) A ° , c=5.31232(9) A ° and b= Al(1) 0 0.1911(5) 0.5 0.78(1) 4 112.741(1)°.Integrated intensities of 87 peaks were used in Al(2) 0.1824(3) 0 0.4637(8) 1.01(1) 4 direct methods to solve the structure. The powder X-ray V 0.3510(2) 0 0.1210(5) 0.88(6) 4 diVraction patterns of the observed and calculated data after O(1) 0.2463(7) 0 0.229(2) 1.438 4 Rietveld refinement are shown in Fig. 4. The final refinement O(2) 0.2962(6) 0 -0.242(2) 1.438 4 was achieved by using the CSD program and the results are O(3) 0.4234(5) 0.1672(7) 0.233(1) 1.438 8 O(4)* 0.9171(6) 0 0.295(1) 1.438 4 collected in Table 1.This gave R(F2)=0.062 and R(profile)= O(5)* 0.1065(5) 0.1788(6) 0.358(1) 1.438 8 0.086. The calculated density of this new compound is 2.672 g cm-3. The atomic positions, the selected interatomic aO(4) and O(5) are bonded to hydrogen.distances and the bond angles are given in Tables 2 and 3. The structure of this new aluminium vanadium hydroxide contains two types of polyhedra around aluminium (Fig. 5). of a continuous network. The projection of the structure along the b-axis (Fig. 7) shows that the groups of aluminium Al(1) belongs to an octahedron with four OH groups and 2 O atoms.The cation–anion distances in the polyhedron vary polyhedra are concentrated in layers parallel to the 00l plane, and separated by d(001). It also highlights the existence of from 1.821 A ° to 1.995 A ° with an average value of 1.896 A ° . The other aluminium, Al(2), is surrounded by five neighbors: two tunnels which contain hydrogen from the OH groups. The structure is very close to that described for the mineral O atoms and 1 OH group located in the basal plane and the other two OH groups quasi-perpendicular to this plane.The augelite Al2(OH)3(PO4). The cell parameters for the augelite structure are a=13.124 A ° , b=7.988 A ° , c=5.066 A ° and cation–anion distances in this trigonal bipyramid vary from 1.721 A ° to 2.193 A ° with an average value of 1.84 A ° . 2 Al(1) b=112.25°.20 The substitution of phosphorus by vanadium induces an increase of the cell parameters along the three and 2 Al(2) are bound together, sharing OH–OH edges. These aluminium clusters are connected to vanadium tetrahedra by directions. The array of the diVerent polyhedra is similar, but the anion–cation distances in some polyhedra are slightly sharing an oxygen apex (Fig. 6), which induces the existence 1256 J. Mater. Chem., 1998, 8(5), 1255–1258Table 3 Selected interatomic distances and bond angles for Al2(OH)3(VO4) VO4 tetrahedron VMO(1) 1.73(1) VMO(2) 1.778(8) VMO(3) 1.661(6) (×2) O(1)MVMO(2) 108.0(4) O(1)MVMO(3) 109.3(3) (×2) O(2)MVMO(3) 109.2(3) (×2) O(3)MVMO(3) 111.8(3) Al(1) octahedron Al(1)MO(3) 1.821(6) (×2) Al(1)MO(4) 1.995(6) (×2) Al(1)MO(5) 1.873(7) (×2) O(3)MAl(1)MO(3) 100.4(3) O(3)MAl(1)MO(4) 92.7(3) (×2) O(3)MAl(1)MO(5) 91.0(3) (×2) O(3)MAl(1)MO(4) 164.3(3) (×2) O(3)MAl(1)MO(5) 93.0(3) (×2) O(4)MAl(1)MO(5) 95.5(3) (×2) Fig. 6 Projection of the structure of Al2(OH)3(VO4) along the c-axis. O(5)MAl(1)MO(5) 173.8(3) Al(1), Al(2) and vanadium respectively occupy dark grey octahedra, medium grey trigonal pyramids and light grey tetrahedra.Al(2) trigonal bipyramid Al(2)MO(1) 1.770(1) Al(2)MO(2) 1.721(9) Al(2)MO(4) 2.193(9) Al(2)MO(5) 1.758(6) (×2) O(1)MAl(2)MO(2) 97.3(4) O(1)MAl(2)MO(5) 99.3(4) (×2) O(2)MAl(2)MO(4) 90.4(3) O(4)MAl(2)MO(5) 76.7(3) (×2) O(5)MAl(2)MO(5) 113.6(3) O(1)MAl(2)MO(4) 172.3(4) O(2)MAl(2)MO(5) 119.9(4) (×2) Fig. 7 Projection of the structure of Al2(OH)3(VO4) along the b-axis kinetic control which may exhibit new structures and properties.A new aluminium vanadium oxide hydroxide Al2(OH)3(VO4) analog of the mineral augelite has been synthesized hydrothermally and structurally characterized. This was Fig. 5 Representation of an aluminium polyhedral group connected achieved by mixing vanadium pentoxide, aluminium nitrate to a vanadium tetrahedron with the atom-labelling scheme.The and tetramethylammonium hydroxide. The last, used as a aluminium polyhedral group is composed of two Al(1) octahedra and template, is not retained in the structure after reaction. This two Al(2) trigonal pyramids bound together by sharing OH–OH edges. three dimensional structure is built up of clusters of aluminium octahedra and trigonal pyramids sharing edges.These clusters are connected together by vanadium tetrahedra. The structure diVerent. The Al(1) octahedron is quite similar with cation–anion distances which range from 1.826 A ° to 1.983 A ° of the mineral augelite Al2(OH)3(PO4), which is very similar, exhibits smaller cell parameters because of the shorter tetra- and average 1.891 A ° . The Al(2) trigonal bipyramid is less distorted in the augelite structure.In this case, the cation–anion hedral PMO bonds. Furthermore, this new compound as well as the mineral augelite is one of the few compounds to contain distances range from 1.750 A ° to 2.054 A ° and average 1.833 A ° which correspond to four short bonds, longer than in our aluminium in a trigonal pyramidal environment. A study by 27Al fast MAS NMR spectroscopy is now in progress.compound, and a long bond, which is shorter than in our compound. The average distance in the phosphate tetrahedron There are numerous aluminium phosphate hydroxide structures, but Al2(OH)3(VO4) is the first related vanadate. There is 1.519 A ° compared with 1.706 A ° for the vanadate, which induces a bigger unit cell, 546.7 A ° 3 for the vanadate and is just one other report of an aluminium vanadate hydroxide, but it is hydrated with the formula Al6V10(OH)12O28·29H2O, 491.5 A ° 3 for the phosphate.which indicates a decavanadate cluster.24 Conclusion This work was partially supported by the National Science Foundation through grant DMR-9422667. 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