Journal of Crystal Growth 247 (2003) 419424

Synthesis and characterization of nanocrystalline niobates

Jun-Feng Liu, Xiao-Lin Li, Ya-Dong Li*
Department of Chemistry, Tsinghua University, Beijing 100084, Peoples Republic of China Received 13 September 2002; accepted 8 October 2002 Communicated by M. Schieber

Abstract Nanocrystalline potassium niobates (KNbO3, KNb3O8 and K4Nb6O17) of different morphologies were synthesized with the low-temperature hydrothermal method by adjusting the alkalinity of the reaction system. A possible formation mechanism of the nanocrystalline niobates was proposed based on the experimental results. All of the products were characterized with X-ray powder diffraction and transition electron microscopy. The Fourier transform (FT) infrared, FT-Raman and UVVIS properties of the niobates were studied. r 2002 Elsevier Science B.V. All rights reserved.
PACS: 61.46.+w; 61.82.Rx; 81.10.Dn Keywords: A1. Crystal morphology; A1. Low dimensional structures; A2. Hydrothermal crystal growth; B1. Niobates

1. Introduction With many size- and dimensionality-dependent physical properties, perovskite structure transition metal oxides such as niobium-based semiconductor materials are believed to have many promising applications. Recently, the investigations on the anisotropic perovskite nanocrystalline niobates with small dimensions have gained momentum [1,2]. KNbO3, KNb3O8 and K4Nb6O17 exhibit a variety of unique electronic and optical properties [35]. KNbO3 is a well-known ferroelectric material with high-electro-optic and nonlinear optical coefcients, and it has been studied for applica*Corresponding author. Tel.: +86-10-62772350; fax: +8610-62788765. E-mail address: ydli@mail.tsinghua.edu.cn (Y.-D. Li).

tions in optical waveguides, frequency doublers and holographic storage systems [6,7]. KNb3O8 and K4Nb6O17 have the unique layered structure and recently they have been at focus of researchers due to their distinctive photochemical and semiconductor properties, catalytic activity in the eld of water decomposition [8,9] and good properties as precursors for the synthesis of the novel composite nanostructures by the ionic exchange intercalation and exfoliation reactions [10]. Recently, we reported a solution route to synthesize polymorphous KNbO3 [11] and here we report a low-temperature hydrothermal method to prepare series of niobates: KNbO3 nanorods, KNb3O8 nanobundles and K4Nb6O17 nanoakes by further investigation was reported in contrast to the traditional high-temperature solid phase reaction of Nb2O5 and K2CO3 (Table 1) [12].

0022-0248/03/$ - see front matter r 2002 Elsevier Science B.V. All rights reserved. PII: S 0 0 2 2 - 0 2 4 8 ( 0 2 ) 0 2 0 1 5 - 8

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Table 1 By a novel low-temperature hydrothermal method, nanocrystalline KNbO3, KNb3O8 and K4Nb6O17 with different morphologies were successfully synthesized at a well-controlled condition
KNbO3 Nb2O5 + KOH
120-180C

Different alkali solution

K4Nb6O17 KNb3O8

The possible formation mechanism of those nanocrystalline niobates in solution was proposed. The as-synthesized niobates were characterized with XRD, TEM and the IR, Raman, and UVVIS properties were investigated.

half an hour. Then the mixed slurry was introduced into a Teon-lined stainless autoclave, and heated at 1801C for 4 days. The precipitates were ltered, rinsed with deionized water, and then annealed at 4501C for 2 h. KNb3O8: After the 0.5 g grinded Nb2O5 was added to the 40 ml 14 mol/l KOH solution, stirred for half an hour, the mixed slurry was sealed in a Teon-lined stainless autoclave at 1801C for 2 days. A clear solution was obtained by adding diluted HCl solution until the pH was between 5 and 6. Heated at 1801C for another 4 days, the typical precipitates were obtained, after being ltered, rinsed with deionized water and dried in vacuum at room temperature. 2.3. Characterization

As-synthesized products were characterized by Xray diffraction (XRD) and transmission electron microscopy (TEM). The infrared, Raman scattering and UVVIS spectroscopy were also reported. The study of the nanocrystalline niobates would provide valuable information.

2. Experimental procedure 2.1. Materials Analytical grade potassium hydroxide (KOH) and niobium oxide (Nb2O5) were used as raw materials. 2.2. Synthesis procedure Optimizing the reaction conditions, pure-phase KNbO3, KNb3O8 and K4Nb6O17 could be obtained. Typical synthesis processes are described below. KNbO3: 0.5 g grinded Nb2O5 was added to 40 ml 610 mol/l KOH solution, and stirred vigorously for half an hour. Then the mixed slurry was sealed in a Teon-lined stainless autoclave at 1201C for 7 days. The precipitates so produced were ltered, rinsed with deionized water, and then dried in vacuum at room temperature. K4Nb6O17: 0.5 g grinded Nb2O5 was dispersed to 10 ml 0.5 mol/l KOH solution after stirring for

(A) Powder X-ray diffraction: XRD patterns of all samples were measured on a Bruker D8advanced X-ray powder diffractometer with ( The operaCuKa radiation (l 1:5418 A). tion voltage and current were 40 kV and 40 mA, respectively. The 2y range used was from 1.51 to 701 in steps of 0.021 with a count time of 0.5 s. The samples were prepared from B0.5 g thoroughly washed and dried nanocrystal powder. (B) Transmission electron microscopy (TEM): The morphology investigations were performed on a Hitachi H-800 TEM, with a tungsten lament at an accelerating voltage of 200 kV. Samples were prepared by placing a drop of dilute alcohol dispersion of nanocrystals on the surface of a copper grid. (C) Fourier transform infrared (FT-IR) spectrum: The IR spectra were measured using KBr pellets made from a mixture of powder. IR shifts were recorded on a PerkinElmer spectrum GX FT-IR System with DTGS detector. (D) FT-Raman spectrum: Raman shifts were measured on a PerkinElmer spectrum GX NIR FT-Raman System with a 1064 nm laser. The Raman scattering was measured in a back-scattering geometry directly from the powder.

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(E) UVVIS diffuses reectance spectra. UVVIS diffuse reectance spectra were recorded with a Shimadzu UV-2100S spectrophotometer.
Intensity (a.u.)

111

a:KNbO3
110 220 001 002 221 112 311 022 222 400

3. Results and discussion Pure-phase KNbO3, KNb3O8 and K4Nb6O17 single nanocrystallines with the anisotropic morphology were obtained by controlling the synthetic condition strictly. Typical XRD patterns of the as-synthesized products of KNbO3, KNb3O8 and K4Nb6O17 are shown in Figs. 1(a)(c), with the main peaks readily indexed. In Fig. 1(a) all the reectance peaks were assigned to the orthorhombic KNbO3 ( phase, with lattice constants a 5:695 A, ( and c 3:974 A ( (JCPDS 32-0822). b 5:721 A, Fig. 1(b) was the orthorhombic structured ( KNb3O8 with lattice constants a 8:903 A, ( and c 3:799 A ( (JCPDS 75-2182) b 21:16 A, and Fig. 1(c) was the orthorhombic phase ( K4Nb6O17 with lattice constants a 7:86 A, ( and c 6:46 A ( (JCPDS 76-0977). b 33:21 A, The TEM image and the selected area electron diffraction (SAED) pattern of the products are provided in Figs. 2(a)(c). In Fig. 2(a), the single crystal rodlike KNbO3 with the length about several micrometers and diameters ranging from 50 to 100 nm could be seen. Unlike the usual nanorods, they all showed a regular rectangular section. TEM pattern of Fig. 2(b) showed the ber morphology of KNb3O8 nanocrystal. The KNb3O8 bers, which usually congregated to bundles, had the length of several microns and diameters of about less than 100 nm. Fig. 2(c) showed akes TEM image of K4Nb6O17 with an average size of about 150 nm. After a series of experiments, we found that the concentration of the KOH solution and the reaction temperature were the key factors that determined the nal products. Only when the KOH concentration was controlled between 6 and 10 mol/l, could pure-phase single crystal KNbO3 nanorods be obtained. The synthesis of single phase K4Nb6O17 3H2O succeeded by controlling the KOH concentration in the region of 0.51 mol/l. Since water would easily intercalate

20

30

40

50

60

70

(a)

2 (degree)

020

240

Intensity (a.u.)

b:KNb3O8
120 211 131

011 040 140 220

10

20

30

40

50

60

70

(b)

2 /degree

002 040

c: KN4b6 O17
Intensity (a.u.)
261

220 240

400

041 120 140

10

20

30

(c)

2 /degree

40

50

60

70

Fig. 1. XRD patterns of the typical products: (a) KNbO3, sample obtained at 1201C for 7 days, (b) KNb3O8, sample obtained at 1801C for 4 days, and (c) K4Nb6O17, sample obtained at 1801C for 4 days.

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Fig. 2. (a) TEM image of the rodlike nanocrystalline KNbO3. The inset is a typical SAED pattern. (b) TEM image of the bundles of KNb3O8. The inset image is the SAED pattern. (c) TEM image of the facets of K4Nb6O17. The inset image is the typical SAED pattern.

into the layer of K4Nb6O17, heat treatment was needed to obtain K4Nb6O17 nanocrystals. KNb3O8 could be synthesized by a relatively complicated procedure. Adopting 14 mol/l KOH solution and reacting in hydrothermal condition at 1801C for proper time, all of the solid dissolved to form a clear and colorless solution. After adjusting the solution pH to 56 and a secondary 4 day hydrothermal reaction, pure-phase single crystal KNb3O8 was obtained. Based on the experimental details, it was known that the pH value was the critical factor during the synthesis process of KNb3O8. As studied by us, when the pHo4, initial Nb2O5 formed again; and if the pH>7, it was very difcult to obtain pure-phase product of any composition. Only at proper pH, pure-phase nanocrystalline KNb3O8 could be obtained. According to the literature [13], the formation of the niobates in the solution phase could be expressed as follows: Strong alkaline : 3Nb2 O5 6OH 6NbO 3 3H2 O; 1

Media alkaline : 3Nb2 O5 4OH

Nb6 O4 17 2H2 O;

Slightly alkaline : 3Nb2 O5 2OH 2Nb3 O 8 H2 O: 3 All the experiment details, especially the synthesis of KNb3O8, implied that there exists an intermediate state during the reaction of Nb2O5 and KOH in the solution. Detailed procedures in the alkaline condition were presumed as follows: At room temperature, Nb2O5 does not react well with KOH, niobates could not be obtained. While in hydrothermal condition with temperature above 1201C, Nb2O5 could easily ionize, dissolve, and react with KOH. Supercial part of Nb2O5 particle rst hydroxylized and dissolved into the solution; then the dissolved proportion reacted further with Nb2O5 in different alkalinity and generated KNbO3, and K4Nb6O17, respectively. However, to obtain KNb3O8 by the procedure mentioned above was proved impossible because the required concentration of OH for the formation of

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877

c
214
912 844 889 778 595

c
275 538 586 641 842 950

Transmission (%)

b
999 954

Intensity (a.u.)

808 908 626 527

247 213 323 281 592 455 574 657 895

a
627

a
833

1200

1000

800

600

400

200

400

600

800

1000

wavenumber/cm-1

Raman shift (cm-1)

Fig. 3. FT-IR spectra of the samples: (a) KNbO3, (b) KNb3O8, and (c) K4Nb6O17.

Fig. 4. FT-Raman spectra of the samples: (a) KNbO3, (b) KNb3O8, and (c) K4Nb6O17.

KNb3O8 was too low to dissolve Nb2O5. Another synthesis route had to be adopted: rst dissolve Nb2O5 in strong alkali forming a clear solution and then add H+ to adjust the pH to satisfy the concentration of OH just as we did in the experiment. In addition to the KOH concentration, temperature and reaction time were also important factors that affected the morphology, dimension, and crystallinity of the products. KNbO3 could be obtained when the temperature was higher than 1201C, while KNb3O8 and K4Nb6O17 could only be obtained at temperature more than 1801C. On the basis of experimental facts, we found that generally lower temperature required longer reaction time, brought about better tropism of crystals and high slenderness ratio. Better crystallinity often needs comparatively longer reaction time. The IR spectra of as-synthesized KNbO3, KNb3O8 and K4Nb6O17 are represented in Fig. 3. As shown in curve (a), KNbO3 had a broad peak with the maximum at 627 cm1, which was coincident with the literature [14,15]. Figs. 3(b) and (c) were the IR spectrum of KNb3O8 and K4Nb6O17. The absorption bands of all the three niobates around 700 and 610/620 were believed to be the v3 mode in the corner-shared NbO6 octahedron, according to the reported IR spectra of niobate glass ceramics [14,15].

Raman scattering measurements were carried out at room temperature. The results are represented in Fig. 4. In curve (a), the three main peaks of KNbO3 Raman spectrum at about 281, 592 and 833 cm1 proved to be broader than in the literature [15,16]. The Raman spectra of KNb3O8 and K4Nb6O17 showed sharp and strong Raman bands around 877 cm1 in curve (b) for K4Nb6O17 and 950 cm1 in curve (c) for KNb3O8, both assigned to short NbO bonds, which stuck out into interlayers. Contrary to the literature values (880 cm1 for K4Nb6O17 and 955 cm1 for KNb3O8), the two sharp strong Raman bands of KNb3O8 and K4Nb6O17 had a little shift to lower wave number. UVVIS spectrums were provided in Fig. 5. It was obvious that almost all the UV light less than 300 nm was absorbed. The estimated band gaps of KNbO3, KNb3O8 and K4Nb6O17 were 3.57, 3.97 and 3.83 eV respectively, and these can be concluded from the corresponding curves a, b, c. The band gaps were larger than those of the bulk materials based on the literature [17].

4. Conclusion KNbO3 nanorods, KNb3O8 nanobers and K4Nb6O17 nanoakes were successfully synthesized by a novel low-temperature hydrothemal method. A possible formation mechanism of the nanocrystalline

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References
80 c:K4N6bO17 a:KNbO3
b:KNb3O8

60

40

20

0 200 300 400 500 600 700 800

wavelength (nm)

Fig. 5. UVVIS diffuses reectance spectra of the samples: (a) KNbO3, (b) KNb3O8, and (c) K4Nb6O17.

niobates was illustrated on the basis of the experimental result. The niobates products were characterized with X-ray powder diffraction and TEM. Their properties were investigated and the results conrmed that nanocrystalline niobates showed some difference in the IR, Raman and UVVIS spectra with corresponding materials obtained by the traditional high-temperature method.

Acknowledgements This work was supported by NSFC (20025102, 50028201, 20151001) and the state key project of fundamental research for nanomaterials and nanostructures.

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