Materials Research Bulletin 44 (2009) 654–659

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Materials Research Bulletin

journal homepage: www.elsevier.com/locate/matresbu

Phase formation of V2O5xNb2O5 compounds via gels and freeze-dried precursors

Hubert Langbein *, Tobias Mayer-Uhma
Department of Chemistry, Dresden University of Technology, Helmholtzstr. 10, D-01069 Dresden, Germany

A R T I C L E I N F O A B S T R A C T

Article history: An X-ray powder diffraction study of the phase formation in the system V2O5/Nb2O5 is performed. Freeze-
Received 8 November 2007 dried ammonium vanadate and ammonium oxalato niobate, alkoxide-derived xerogels and a mixture of
Received in revised form 13 May 2008 active oxides are used as precursors to compare the resulting phase composition. Thermal decomposition
Accepted 26 June 2008
of the freeze-dried precursor is monitored with DTA/TG and mass spectrometry. In the quasi-binary
Available online 6 July 2008
system V2O5–Nb2O5 metastable VNbO5, V4Nb18O55, VNb9O25 and solid solutions of V2O5 in TT-Nb2O5 as
also thermodynamically stable VNb9O25 exist. The thermal decomposition of freeze-dried vanadate–
Keywords:
oxalatoniobate solution allows the synthesis of all these phases in a relative simple manner. Structural
A. Oxides
B. Chemical synthesis
relationships between an intermediate phase and the product, or, in the case of solid-state reactions,
C. TGA between one of the starting oxide and the product, favour the desired reaction. Therefore, the structure of
C. X-ray diffraction a former phase influences or directs the structure of the product similar to a topotactic reaction.
D. Crystal structure ß 2008 Elsevier Ltd. All rights reserved.

1. Introduction synthesized for the first time in 1960 by a solid-state reaction [11]
and can also be synthesized at 1100 8C via chemical transport
Vanadium and niobium oxides have received much attention [12,13]. According to Trunov et al. the exact composition of this
in recent years because of their chemical and physical properties phase is V2Nb12O35 with a narrow homogeneity range [14]. But,
which are of special interest in catalysis [1–5] and electrochemical because of the high synthesis temperature of 1200 8C a vaporiza-
applications [6–8]. The reducibility of the mixed oxide systems tion of some V2O5 cannot be excluded. Yamaguchi et al. [15,16]
and, by this, the catalytic selectivity [2,3] and the electrochemical have synthesized metastable V4Nb18O55 and VNbO5 as well as
properties [6] are strongly influenced by the presence of the solid solutions of V2O5 (up to 10 mol%) in TT-Nb2O5 by thermal
hardly reducible niobium pentoxide. To get homogeneous and treatment of precipitated alkoxide hydrolysis products. Polte and
highly dispersed samples, unconventional preparation methods Langbein [17] obtained the same compounds by thermal
as sol–gel processes or coprecipitation are often used [2,9,10]. decomposition of precipitated and freeze-dried alkoxide hydro-
Because of the large structural flexibility and variety in modi- lysis products. Recently we have synthesized a new metastable
fications in the system V2O5–Nb2O5 different phases and phase VNb9O25 phase via a sol–gel process from alkoxides [18]. The new
mixtures are mostly formed by these unconventional preparation phase is structurally related to M-Nb2O5. Because of the high
processes. In this way, the large influence of the preparation content of alkyl groups in the precursor, carbon remains in the
method on the properties of the products is understandable and oxide up to a relatively high temperature and, possibly, it controls
for all applications the correct phase composition has to be the crystallization of the unexpected product. To reduce the
known. The latter requires an exact analysis of phase composition carbon content in the decomposition product, the freeze-drying
after synthesis and the knowledge of relationships between method can be used. This preparation was already applied in the
preparation conditions and phase composition of the resulting synthesis of ferrites and niobates [19,20], but hitherto not for
products. vanadates.
Four different phases are known in the system V2O5–Nb2O5: To enlighten further the relationships between preparation
VNb9O25 with a tetragonal block structure, the only known conditions and phase composition of the resulting products, we
thermodynamically stable phase in the system VxNb(2x)O5, was have investigated phase formation in the V2O5–Nb2O5 system after
thermal decomposition of freeze-dried precursors and sol–gel
products. Compared to these preparations, we have also investi-
* Corresponding author. Tel.: +49 351 46334366; fax: +49 351 46337287. gated the solid-state reaction with different Nb2O5 modifications
E-mail address: Hubert.Langbein@chemie.tu-dresden.de (H. Langbein). as starting compounds.

0025-5408/$ – see front matter ß 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.materresbull.2008.06.023
 H. Langbein, T. Mayer-Uhma / Materials Research Bulletin 44 (2009) 654–659 655

2. Experimental

Aqueous solutions of doubly recrystallized NH4VO3 and

ammonium oxooxalatoniobate (HC Starck Berlin GmbH & Co.
KG) of appropriate compositions have been frozen with liquid
nitrogen. The frozen solid has been dried in the vacuum chamber of
an Alpha 2-4 freeze-drying apparatus (Christ) at a pressure of
0.018 mbar from 40 to 25 8C. The resulting fine powders have
been decomposed heating them with 2 8C/min to 350 8C (compo-
sitions V:Nb = 1:1 and 2:9) or 400 8C (1:9 or 0:1).
Xerogels have been obtained as described in [18] by a controlled
hydrolyzing of appropriate mixtures of alkoxides in presence of
oxalic acid, followed by drying the resulting gels under vacuum.
For the solid-state reactions, V2O5 and TT-Nb2O5 have been
milled together 0.5 h with acetone in a ball mill Pulverisette 5
(Fritsch). V2O5 has been synthesized from NH4VO3 in oxygen at
Fig. 2. Thermal analysis of ammonium oxo-oxalato-niobate. Heating rate: 10 K/
300 8C, TT-Nb2O5 was obtained by heating ammonium oxoox- min; atmosphere: air and argon.
alatoniobate 4 h at 575 8C. These solid-state precursors have a
larger surface area (6.7 and 21.4 m2/g) than the commercial
available products and should therefore react more quickly and dates [21,22]. The mass loss of the first endothermic step of about
homogeneously. All compositions were fired for 4 h on air, if not 15% correlates with the formation of NH4V3O8 (Dmcalc. = 14.58%).
specially described. The following exothermic step results in the formation of V2O5. The
Differential thermoanalysis (DTA) and thermogravimetric exothermic peak in the DTA curve with an onset temperature of
measurements (TG) have been performed using a Netzsch STA 335 8C indicates the beginning crystallization of V2O5. V2O5 melts
409 analyzer (Figs. 1, 4 and 5), or Netzsch STA 409 PC-Luxx endothermically at 665 8C.
analyzer (Figs. 2 and 3), capillary coupled with a quadrupol mass The ammonium oxooxalatoniobate produced by the HC
spectrometer QMG 420 (Balzers). Generally, for decompositions on Starck Berlin GmbH & Co. KG is a mixture of X3NbO(C2O4)3 and
air a heating rate of 10 K/min was used. In argon, the heating rate X2NbO(OH)(C2O4)2(H2O) with X = NH4+ or H+ wherein niobium is
was 5 K/min. X-ray powder diffraction patterns have been
collected by a Siemens D5000 X-ray diffractometer using Cu
Ka-radiation. Samples were radiated 1 h in the 2u region from 108
to 808. Surface area determinations have been done with a
Beckmann Coulter SA 3100. IR spectra were recorded with a BioRad
Excalibur FTS 3000.

3. Results and discussion

3.1. Thermal decomposition of freeze-dried products

To understand the decomposition of a mixture of precursor

components we first have to look at the decomposition of single
precursors. NH4VO3 decomposes in two clearly separated steps
(Fig. 1). The total mass loss of Dm = 22.4% agrees very well with the
release of (1NH3 + 1/2H2O) forming V2O5 (Dmcalc. = 22.27%).
According to the literature the decomposition proceeds in several
atmosphere-dependent steps with different intermediate vana-

Fig. 3. Thermal analysis of ammonium oxo-oxalato-niobate and mass spectroscopic

characterization of the main gaseous decomposition products. Heating rate: 5 K/
Fig. 1. Thermal analysis of NH4VO3. Heating rate: 10 K/min; atmosphere: air. min; atmosphere: argon. (a) m/z = 18, 28, 44. (b) m/z = 17, 27, 44.
656 H. Langbein, T. Mayer-Uhma / Materials Research Bulletin 44 (2009) 654–659

sevenfold coordinated by oxygen [23,24]. According to our

chemical analysis, the approximate composition should be
[0.75(NH4)1.55yH1.45+y[NbO(C2O4)3] + 0.25H23y(NH4)3y[NbO(C2-
[NbO(C2O4)2(OH)(H2O)] + 3H2O] with y < 0.67 and a calculated
Mrel. = 435.8 g per formula unit. The result of the thermal analysis
of the oxooxalatoniobate is shown in Fig. 2. The decomposition
takes place in three endothermic main steps up to 300 8C. The
small mass loss at about 580 8C (air atmosphere) is caused by the
exothermic oxidation of traces of carbon formed by pyrolysis side
reactions or the Boudouard reaction (2CO ! C + CO2). In argon
atmosphere (pO2 < 103 bar), this oxidation process is not finished
till 900 8C. The total mass loss agrees well with the expected value
of 69.5%. To get further information concerning the decomposition,
the gaseous products were analysed by mass spectrometry. The
results are plotted in Fig. 3a and b. The decomposition starts with
the loss of crystal water between 100 and 140 8C (m/z = 18; 17). A Fig. 5. Thermal analysis and mass spectroscopic analysis of a freeze-dried mixture
theoretically calculated mass loss of 12.4% agrees well with the of NH4VO3 and ammonium oxo-oxalato-niobate in the molar ratio 1:1. Heating
experimental value of about 12%. The decomposition is continued rate: 5 K/min; atmosphere: argon.
in a second step with the release of mainly CO (m/z = 28), CO2 (m/
z = 44) and H2O. Obviously, the bisoxalato component of the (curve 4) and 1:9 (curve 3) beside the TG curves of the vanadate
mixture is decomposed at first. The release of small amounts of (curve 1) and oxooxalatoniobate (curve 2). Results of the mass
NH3 (m/z = 17) in this step cannot be excluded but, the relatively spectrometric analysis are shown in Fig. 5 for the 1:1 compound. In
higher intensity of the appropriate peak at about 250 8C compared the TG curves of the freeze-dried mixtures the clearly separated
to the intensities of the peaks for m/z = 17 at 120 and 160 8C (OH- steps of decomposition of the single components are no longer
fragment of H2O and/or NH3) illustrates the preferred release of observed. Additionally, the release of water starts already at 80 8C.
NH3 in the third main step. That means the ammonium cation This reflects not only the amorphous character of the freeze-dried
should be mainly connected with the trisoxalatoniobate anion. The product but also some interactions between the components. On
shoulder in the m/z = 17 peak at about 270 8C and a low intensity the other hand, the similar temperature position and width of the
peak of HCN (m/z = 27) at the same temperature demonstrate the mass spectroscopic CO2 peaks of the single niobate and the mixture
intermediate formation of some solid oxamide, H2N(CO)(CO)NH2, demonstrate the conservation of some individual characteristics of
during the decomposition of the ammonium oxotrisoxalatoniobate the components. The comparatively broad H2O peaks can be
component. The intermediate formation of some oxamide was also explained by the superimposition of different steps in the
observed during the decomposition of ammonium oxalate [25]. decomposition of the single components connected with a release
Oxamide is decomposed to NH3, CO2 and HCN. Logically, the of H2O. The full decomposition of the freeze-dried mixtures with
appropriate shoulders are also observed in the peaks of CO2 (m/ V:Nb = 1:1, 1:4.5 and 1:9 leads to single phases of VNbO5,
z = 44) and CO as a fragment of CO2 (m/z = 28). The final product at V4Nb18O55 and a solid solution of Nb2O5/V2O5 with TT-Nb2O5
300 8C is an amorphous, greyish Nb2O5. This niobia contains structure, respectively. Residing carbon will be burned out on air at
residual carbon, which generally can be found in Nb2O5 using 450, 560 and 580 8C. Regarding this temperatures, NH4VO3 has also
carbonaceous precursors. Beginning crystallization at 590 8C on air a promoting effect of the complete decomposition of the niobate
simultaneously burns out this contamination and a colorless component.
product with TT-Nb2O5 structure is obtained.
Fig. 4 shows the TG curves of freeze-dried ammonium 3.2. Phase formation of mixed oxides
vanadate/oxooxalatoniobate mixtures with ratios of V:Nb = 1:1
According to literature [17], metastable VNbO5 can be
synthesized between 400 and 700 8C, and V4Nb18O55 between
500 and 800 8C. Pure thermodynamically stable VNb9O25 forms at
1100 8C under oxygen. The latter can be seen in Fig. 6, where the
three above-mentioned preparation methods are compared. On
annealing different starting mixtures of a composition V:Nb = 1:9
at temperatures below 1100 8C, other phases than VNb9O25 in
different amounts appear, and the phase composition strongly
depends on the synthesis method: the thermal treatment of
reactive TT-Nb2O5/V2O5 mixtures at 700 8C results in a transfor-
mation of the low temperature TT-Nb2O5 into the T-form, which is
an ordered, defect free version of the pseudo hexagonal TT-
modification. Additionally, the peaks of V4Nb18O55 can be seen in
the diffraction pattern. At 800 8C M-Nb2O5 with an irregular block
structure or a solid solution of V2O5 in this phase is the main
product. The excess of V2O5 is mainly preserved as V4Nb18O55. At
900 8C crystallization of the well-known VNb9O25 begins. This
thermodynamically stable phase is the only existing phase after
annealing at 1100 8C (Fig. 6a). The thermal decomposition of
Fig. 4. Thermal analysis of NH4VO3 (curve 1), ammonium oxyoxalatoniobate (curve
2) and of freeze-dried mixtures of NH4VO3 and ammonium oxo-oxalato-niobate in
freeze-dried products between 550 and 650 8C forms pure solid
the molar ratios 1:9 (curve 3) and 1:1 (curve 4). Heating rate: 10 K/min, solutions of V2O5 in TT-Nb2O5. This solid solution changes into
atmosphere: air. V4Nb18O55 at 700 8C and, at 800 8C solid solutions with M-Nb2O5
 H. Langbein, T. Mayer-Uhma / Materials Research Bulletin 44 (2009) 654–659 657

Fig. 6. X-ray powder diffraction patterns of vanadia/niobia mixtures after 4 h

annealing at different temperatures. V:Nb ratio = 1:9. Starting powders: (a) V2O5/
TT-Nb2O5; (b) freeze-dried product; (c) xerogel. V2O5 (*), TT-Nb2O5 ( ), T-Nb2O5
( ), M-Nb2O5 ( ), V4Nb18O55 (*), low-temperature VNb9O25 (&), high-
temperature VNb9O25 (&).

structure are formed. The crystallization of single-phase VNb9O25

requires an annealing temperature of 1100 8C (Fig. 6b). For all
preparation methods, peaks of the recently described low
temperature form of VNb9O25 [18] are visible, but only the sol–
gel method allows a nearly single-phase preparation between 800
Fig. 7. X-ray powder diffraction patterns of freeze-dried mixtures of NH4VO3 and
and 900 8C (Fig. 6c). Precursors of the low temperature form of ammonium oxo-oxalato-niobate in the molar ratios 2:9 after 4 h annealing at
VNb9O25 are solid solutions with TT-Nb2O5- and M-Nb2O5 different temperatures.
structure (600 and 700 8C, respectively). Perhaps, the irregular
block structure of M-Nb2O5 is a further necessary condition for the
intermediate formation of the low temperature form of VNb9O25 the low content of niobate-bound carbon in the precursor makes
(see below). Differently to the hitherto described phase formation, phase formation easier. Looking more precisely at the formation
on annealing a 1:9 mixture of V2O5 and H-Nb2O5 the thermo- process of VNbO5 from the freeze-dried precursor (Fig. 8), a slightly
dynamically stable VNb9O25 phase is already formed after 4 h at anomalous behaviour between 550 and 650 8C is observed. In the
900 8C in a well crystalline form. Although, this mixture should be XRD pattern of VNbO5, formed between 400 and 550 8C, no
the least reactive one, structural relationships between the block contaminations are visible, but after annealing at 600 8C some
structures of H-Nb2O5 and VNb9O25 favour the phase formation. V4Nb18O55 additionally has been formed. Unexpectedly, at 650 8C
Fig. 7 illustrates the phase formation of V4Nb18O55 on annealing after 4 h the composition no longer contains V4Nb18O55. Probably,
a freeze-dried precursor of the appropriate composition. The traces of molten V2O5 act as a solvent for the minor phase
crystallization begins at 550 8C and after annealing at 700 8C a well V4Nb18O55, and, according to Ostwald’s step rule [27], the least
crystalline single-phase product is formed. Above a temperature of stable phase VNbO5 crystallizes at first. Raising the temperature to
700 8C the decomposition of this metastable phase to VNb9O25 700 8C initiates the transformation to the next stable, but also only
takes place. Contrary to the formation of VNb9O25 from a metastable system (V4Nb18O55 + V2O5). On some further increase
stoichiometric 1:9 mixture (see Fig. 6), the thermodynamically of the annealing temperature to about 750 8C the transformation
stable phase is already formed at 850 8C as a well crystalline into the thermodynamically stable system (VNb9O25 + V2O5) takes
product. Obviously, the excess of molten V2O5 acts as a place. The occurrence and disappearance of V4Nb18O55 between
mineralizator. The V4Nb18O55 synthesis from a xerogel takes place 550 and 650 8C can also be observed in the IR spectra (right part of
in a similar way. On annealing V2O5/TT-Nb2O5 mixtures, the phase Fig. 8). The sharp absorption band at 1023 cm1, mainly observed
formation of V4Nb18O55 begins at 600 8C and is also finished after after annealing the sample at 600 8C, is characteristically for
4 h at about 700 8C. V4Nb18O55.
While the formation of V4Nb18O55 is independent of the nature The occurrence of VNbO5 as the main phase and its further
or homogeneity of the precursor, pure VNbO5 can preferred be transformation according to Ostwald’s step rule also can be
synthesized through a freeze-drying process. The sol–gel method observed on annealing 1:1 mixtures of V2O5 and TT-Nb2O5 and
and the solid-state process yield a mixture of VNbO5 and, V2O5 and B-Nb2O5 with a special heating regime above the melting
depending on temperature and annealing time, more or less temperature of V2O5, but not on annealing a 1:1 mixture of V2O5
V4Nb18O55 (and V2O5). The reaction of xerogel is in contrary to that and H-Nb2O5. A quick heat up and short annealing of the former
reported in the literature. Here, thermal treatment of opaque mixtures (20 min) at 680 8C (just above the melting temperature of
xerogels (600 8C, 6 h), obtained by gelation of a mixture of NbCl5 V2O5) results in the formation of VNbO5 as the main phase. On
and VO(i-C3H7)3 [8,26], or oxide hydrates, obtained by coprecipi- further annealing at 680–700 8C (4 h) V4Nb18O55 and the excess of
tation of alkoxide solutions with a large excess of H2O [16,17], V2O5 are formed. On raising the annealing temperature to 800 8C a
yields single-phase VNbO5. Probably, the high homogeneity and well crystalline VNb9O25 is formed beside the excess of V2O5.
658 H. Langbein, T. Mayer-Uhma / Materials Research Bulletin 44 (2009) 654–659

Fig. 8. X-ray powder diffraction patterns and IR spectra of freeze-dried mixtures of NH4VO3 and ammonium oxo-oxalato-niobate in the molar ratio 1:1 after 4 h annealing at
different temperatures. V4Nb18O55 (*). The asterisk indicates a device dependent spike.

Differently to this phase sequence, on annealing a 1:1 mixture of with different block sizes and block connections [28]. On annealing
V2O5 and H-Nb2O5 the stable form of VNb9O25 is already formed the M-(Nb, V)2O5 phase in air atmosphere a rearrangement of the
after 4 h at 700 8C without the intermediate occurrence of the irregular block structure takes place in which the already existing
other V2O5–xNb2O5 mixed oxides. This corresponds with the and dominant 3  4 blocks act as crystallization centers. This
likewise lower synthesis temperature of VNb9O25 from a 1:9 process results in the formation of the low temperature form of
mixture of V2O5 and H-Nb2O5 and cannot be explained by the VNb9O25 with a regular 3  4  1 block structure.
mineralizing influence of the V2O5 melt alone. The H-Nb2O5 structure consists of 3  4  1 and 3  5  1
ReO3-type blocks of NbO6 octahedra, which are joined by sharing
4. Conclusion edges and with tetrahedrally coordinated niobium atoms ordered
at the junctions of every four blocks [29]. The parallel arrangement
It can be concluded from the results discussed above that the in direction of the short edges of both kinds of blocks (three
phase formation and phase composition in the system V2O5–Nb2O5 octahedra wide) is similar to the arrangement of the of 3  3  1
strongly depends on the kind of starting powders, the reaction blocks in the stable form of VNb9O25 [30]. This structural
temperature and reaction time. Only the thermal decomposition of relationship between H-Nb2O5 and the product allows an easier
freeze-dried vanadate–oxalatoniobate solutions of appropriate nucleation step during the reaction with the molten vanadia than
composition allows the synthesis of all the known phases in a that for reactions without such a relationship. In other words, the
relative simple manner. Independently of the kind of the starting structure of the starting material influences or directs the structure
powder, the thermal treatment of samples in the investigated of the product similar to a topotactic reaction.
composition range above a temperature of 1000 8C results in the VNbO5 has an open structure with only corner sharing NbO6
formation of thermodynamically stable VNb9O25 and an excess of octahedra and VO4 tetrahedra [8]. There is no structural relation-
V2O5. The formation of the other phases at lower temperature is ship between this structure and any Nb2O5 structure. The
controlled kinetically and each compound requires a special crystallization of single-phase VNbO5 only takes place between
temperature–time regime. about 500 and 650 8C from a highly pure and homogeneous
As shown in Fig. 6, the thermal treatment of different precursors amorphous precursor. Obviously, the latter condition is fulfilled in
with a V:Nb ratio of 1:9 at about 600 8C results in solid solutions case of the freeze-dried precursor, but also in case of oxide
with the structure of TT-Nb2O5. Further reactions strongly depend hydrates obtained by coprecipitation of alkoxide solutions with a
on the precursor. In the case of the xerogel precursor a nearly large excess of H2O [16,17]. Contrary to this, homogeneous gels,
single-phase M-Nb2O5 structure is formed at 700 8C which is obtained by a controlled hydrolysis process with small amounts of
transformed to a new low temperature form of VNb9O25 at 800 and water, are no suitable precursors for single-phase VNbO5. Despite a
900 8C. The thermodynamically stable VNb9O25 is formed only V:Nb ratio of 1:1, the thermal treatment of such RO-groups
above a temperature of 1000 8C. Contrary to this, the reaction of H- containing gels results in the crystallization of V4Nb18O55 beside
Nb2O5 with V2O5 produces the stable form already at 900 8C, and VNbO5. Carbon impurities likely favour the crystallization of the
with the mineralizing influence of a V2O5 excess even at 700 8C. former phase similar to the crystallization of TT- and M-Nb2O5
This refers to a strong influence of the structure of a starting or from samples with a lower content of vanadia.
intermediate phase on the kinetics of phase formation and Single-phase V4Nb18O55 can be produced from different reactive
transformation. We have already shown [18] that the intermediate precursors of appropriate composition between about 500 and
formation of the M-Nb2O5 structure, induced by the internal 700 8C. It’s decomposition above 700 8C results in the formation of
reducing conditions in the xerogel precursor (unburned carbon), is the thermodynamically stable phase VNb9O25 beside an excess of
a necessary condition for the formation of low temperature V2O5 (see above). On annealing solid-state mixtures of V2O5 and TT-
VNb9O25. M-Nb2O5 is characterized by an irregular block structure Nb2O5 with a V:Nb ratio 2:9, independently of the composition,
 H. Langbein, T. Mayer-Uhma / Materials Research Bulletin 44 (2009) 654–659 659

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