A new route for synthesizing VO2(B) nanoribbons and 1D vanadium-based nanostructures

doi:10.1016/j.materresbull.2007.06.048

Materials Research Bulletin

Volume 43, Issue 6, 3 June 2008, Pages 1384-1392

https://doi.org/10.1016/j.materresbull.2007.06.048 Get rights and content

Abstract

This paper demonstrated the large-scale fabrication of metastable single crystal VO₂(B) nanoribbons with a home-made vanadium (IV, V) compound as a precursor. The influence factors on the morphology and a primary formation mechanism were presumably studied. Furthermore, the capability fabricating other vanadium-based 1D nanostructures was also explored from the precursor.

Introduction

Over the past decade, one-dimensional (1D) nanostructured materials have received considerable attention [1], [2], [3], because of their different properties from corresponding bulk materials, their anisotropic structures, which provide an ideal model to study the effects of size and dimension, as well as their potential application as building blocks in nanodevices. By far, the syntheses and characterizations of a large number of 1D nanomaterials have been reported [4], [5], [6], [7], [8], including metals, oxides, hydrates, semiconductors, carbides, etc.

Hydrothermal synthesis is an effective method to fabricate 1D nanostructures not only because of its critical temperature and pressure but also the low-cost, large-scale and wide suitability for various materials. It is well known that reactant agents including precursors have significant effect on the reaction process and the formation of products. Felicitous choice of a precursor is feasible to obtain desired products [9], [10].

Vanadium oxides and derivative compounds have attracted special interest with respect to the applications in oxidation catalysis of hydrocarbons [11], cathode materials for reversible lithium batteries [12], sensor materials [13], intelligent coatings [14], etc.

The 1D nanostructured vanadium oxides show excellent electronic transport, sensitivity to organic gas, redox-active properties, due to high surface–volume ratio and homogenous structures along the longitudinal direction. Therefore, various methods to synthesize 1D nanostructured vanadium oxides, such as nanorods [15], nanotubes [16], nanobelts [17], [18], [19], nanowires [20], and nanoribbons [21], [22], have been reported. Nesper's group synthesized the representative VO_x nanotubes from various vanadium precursor and primary amines [15]. Recently Liu et al. [17] hydrothermally prepared single-crystal metastable VO₂(B) nanobelts using formic acid as a reductant, and studied the electronic transport through individual nanobelts. VO₂ nanosheets were synthesized starting from V₂O₄ particles in 10 M NaOH solution [23]. Among them, metastable VO₂(B) was especially interesting because of its layer structure and potential applications in lithium battery material [22], [24] and the capability of transformation to thermochromic VO₂ at high temperature [25].

In this paper, we reported a hydrothermal method to synthesize 1D single-crystalline metastable VO₂(B) nanoribbons on a large-scale from a mixed-valent vanadium precursor. The influence of reaction media, reductant PEG-600 on the morphology and the structure of products was studied. As a result, formation of 1D morphology mainly depended on the existence state of vanadium in an aqueous solution. Moreover, syntheses of other vanadium 1D nanostructures were also explored using this novel precursor. The precursor could be potentially utilized to fabricate other vanadium derivative compounds with 1D morphology.

Section snippets

Experimental

All chemicals were analytical grade and were used as received without further purification.

Synthesis of the precursor

During the preparation of the precursor, VO²⁺ ions with characteristic sapphire color were produced by reducing vanadium pentoxide with oxalic acid [26]. In the basic environment, VO²⁺ can be transformed to vanadium hydroxide and easily oxidized. The valence of vanadium in the as-synthesized precursor was about 4.76 determined by the redox titration [27], which indicates, V(IV) in the precursor was partly oxidized to V(V).

In order to get exactly centesimal content of vanadium in the precursor,

Conclusion

In summary, a hydrothermal method based on mixed-valent precursor has been developed to synthesize metastable VO₂(B) nanoribbons on a large scale. The resulting nanoribbons had uniform width in the range of 50–100 nm and length up to several micrometers, which provided an ideal model to study the fundamental properties of VO₂ nanoribbons. By experimental analysis, the existence state of vanadium in aqueous solution played an important role in the formation of nanoribbons. The novel precursor

Acknowledgements

This work was financially supported by the National Natural Scientific Foundation of China (20573126) and Chinese Academy of Sciences.

References (38)

Y.L. Wang et al.
Nano Lett.
(2003)
K.F. Zhang et al.
Mater. Res. Bull.
(2006)
L.F. Kong et al.
J. Solid State Chem.
(2004)
C.K. Chan et al.
Nano Lett.
(2007)
M.D. Wei et al.
J. Cryst. Growth
(2006)
J.S. Buchanan et al.
Appl. Catal.
(1985)
J. Kö hler et al.
Electrochim. Acta
(2000)
C. Burda et al.
Chem. Rev.
(2005)
H. Park et al.
Nano Lett.
(2006)
Z.L. Wang et al.
Science
(2006)

Z.-Y. Yuan et al.

Chem. Commun.

(2002)

X.Y. Song et al.

J. Phys. Chem. B

(2004)

Z.W. Pan et al.

Science

(2001)

N.J. Tang et al.

J. Phys. Chem. B

(2006)

H.S. Qian et al.

Cryst. Growth Des.

(2005)

O.P. Ferreira et al.

Cryst. Growth Des.

(2006)

N. Mizuno et al.

Chem. Mater.

(2001)

Y. Wang et al.

Chem. Mater.

(2006)

L. Biette et al.

Adv. Mater.

(2005)

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A new route for synthesizing VO2(B) nanoribbons and 1D vanadium-based nanostructures

Abstract

Introduction

Section snippets

Experimental

Synthesis of the precursor

Conclusion

Acknowledgements

Nano Lett.

Mater. Res. Bull.

J. Solid State Chem.

Nano Lett.

J. Cryst. Growth

Appl. Catal.

Electrochim. Acta

Chem. Rev.

Nano Lett.

Science

Chem. Commun.

J. Phys. Chem. B

Science

J. Phys. Chem. B

Cryst. Growth Des.

Cryst. Growth Des.

Chem. Mater.

Chem. Mater.

Adv. Mater.

A new route for synthesizing VO₂(B) nanoribbons and 1D vanadium-based nanostructures