See discussions, stats, and author profiles for this publication at: https://www.researchgate.

net/publication/260843507

SYNTHESIS OF SUBMICRON POWDERS OF ZnO AND ZnO-M n O m (M n O m = TiO

2 , V 2 O 5 ) BY SOL-GEL METHODS

Article · January 2009

CITATIONS READS

10 549

9 authors, including:

Yuliay Ivanova A. Staneva

Boreskov Institute of Catalysis University of Chemical Technology and Metallurgy
115 PUBLICATIONS   779 CITATIONS    62 PUBLICATIONS   1,255 CITATIONS   

SEE PROFILE SEE PROFILE

Maria Gancheva (Mancheva) Reneta Yordanova

Bulgarian Academy of Sciences Middlesex University, UK
39 PUBLICATIONS   463 CITATIONS    4 PUBLICATIONS   31 CITATIONS   

SEE PROFILE SEE PROFILE

Some of the authors of this publication are also working on these related projects:

"Photocatalytic activity of thin films with selectively photodeposited cocatalysts." Bulgarian National Science Fund (BNSF), Contract № KP-06-N59/11. View project

Synthesis, structure and luminescence properties of tungstate glasses containing Nb2O5 View project

All content following this page was uploaded by Nina V. Kaneva on 18 March 2014.

The user has requested enhancement of the downloaded file.

 Y. Dimitriev, Journal
Y. Ivanova, A. Staneva,
of the L. of
University Alexandrov, M. Mancheva,
Chemical Technology andR.Metallurgy,
Yordanova,44,
C. 3,
Dushkin, N. Kaneva, C. Iliev
2009, 235-242

SYNTHESIS OF SUBMICRON POWDERS

OF ZnO AND ZnO-MnOm (MnOm = TiO2, V2O5) BY SOL-GEL METHODS

Y. Dimitriev1, Y. Ivanova1, A. Staneva1, L. Alexandrov2,

M. Mancheva2, R. Yordanova2, C. Dushkin3, N. Kaneva3, C. Iliev4

1
University of Chemical Technology and Metallurgy Received 05 April 2009
8 Kl. Ohridsky, 1756 Sofia, Bulgaria Accepted 15 July 2009
E-mail: yanko@uctm.edu
2
Institute of General and Inorganic Chemistry,
Bulgarian Academy of Sciences, 1113 Sofia, Bulgaria
3
Laboratory of Nanoparticle Science and Technology,
Faculty of Chemistry, Kl. Ohridsky University of Sofia,
1 James Boucher blvd., 1164 Sofia, Bulgaria
4
Geological Institute, Bulgarian Academy of Sciences,
1113, Sofia, Bulgaria

ABSTRACT

The present study is based on experiments using Zn-nitrate and Zn-acetate as precursors along with several
variants of sol-gel technique which are widely popularized in the literature. The purpose is to check their applicability to
ZnO-TiO2 and ZnO-V2O5 binary mxtures as well as their photocatalytic activity towards model solutions. Comparative
analysis of different schemes of preparation of ZnO and binary mixtures with the participation of TiO2 and V2O5 show that
the production of powders for photocatalytic applications depends on many factors. It has been shown that the introduc-
tion of small amounts of TiO2 in presence of ethylene glycol leads to better results as compared to pure ZnO and a
combination of ZnO and V2O5.
Keywords: sol-gel methods, photocatalytic activity, Zn-nanoparticles, TiO2.

INTRODUCTION geous. Its properties, however, largely depend on the

The interest in studies of ZnO strongly increased
during the past years due to the electric, optic and mag-
netic properties of this compound as well as to its rela-
tively good chemical and thermal stability. Being char-
acterized by multifuntionality, ZnO found application
in various spheres already in the middle of 20th century.
Its photocatalytic activity is among the reasons for which
it is subjected to intense studies by physicists, chemists
and technologists as it is a material suitable for creating
a biologically pure environment. The methods of its
preparation are accessible and economically advanta-
morphology and dimensionality of its particles. Zinc
oxide has the unique ability fo form different
nanostructures from spheres, ribbons, pipes, sticks, tet-
rapods [1]. Regardless of the large number of investiga-
tions, the preparation of nanosized active particles es-
pecially by wet methods (which are more efficient and
preferred for large applications) is still a challenge to
scientists with respect to both obtaining reproducible
structures and constant physicochemical parameters.
There is no universal method for obtaining particles
with various geometry and properties . Thus, spherical
nanocrystals are prepared by spray pyrolysis and ther-

235
 Journal of the University of Chemical Technology and Metallurgy, 44, 3, 2009

mal decomposition of zinc acetate [3, 4]. Precipitation popularized in the literature. The purpose is to check
from aqueous solutions results in prismatic and needle- their applicability to ZnO-TiO2 and ZnO-V2O5 binary
like particles [5, 6]. On the other hand, varying the kind mxtures as well as their photocatalytic activity towards
of precursor and the regime of thermal decomposition, model solutions.
it is also possible to obtain particles with different ge-
ometry {6-8]. Partly filled pipes have been synthesized EXPERIMENTAL
using block polymers. Sol-gel methods have found ap-
plication in the preparation of ZnO nanoparticles. Spe- Zn nitrate precursor. Three schemes were used
cial attention in this case is paid to the kind of solvent to prepare ZnOTiO2 mixtures. The first two schemes
with a view to achieving the desired particle geometry
[9,10]. The photocatalytic activity of pure powdery zinc
oxide has been investigated with respect to the decom-
position of phenol[1], methyl orange [12], methylene
blue [13], camphor and remazol red in water medium
[14-16]. There is an opinion with respect to the de-
composition of organic pollutants in water, that zinc
oxide nanoparticles exhibit better properties towards the
conventional ZnO and TiO2 available on the market [16].
The photocatalytic activity of mixed ZnO-TiO2 pow-
ders with respect to nitrophenol, formic and benzoic
acid is proved [17-19]. The study of the photocatalytic
activity of mixed systems of ZnO-WO3 and ZnO-V2O5
[20-22] is also of special interest since the addition of
transition element oxides which are also semiconduc-
tors, is expected to enhance the activity not only in the
ultraviolet but also in the visible region.
The present study is based on experiments us-
ing zinc nitrate and Zn acetate as precursors along with Fig. 1. Flow diagram for preparation of ZnO powder by Zn-
several variants of sol-gel technique which are widely nitrate and Ti-butoxide (sample 7A).

Fig. 2. Flow diagram for preparation of ZnO/TiO2 powder by Zn-nitrate and Ti-butoxide (sample 10).

236
 Y. Dimitriev, Y. Ivanova, A. Staneva, L. Alexandrov, M. Mancheva, R. Yordanova, C. Dushkin, N. Kaneva, C. Iliev

Fig. 3. Flow diagram for preparation of ZnO/TiO2 powder by Zn-nitrate and Ti-butoxide (sample 7B).

Fig. 4. Flow diagram for preparation of ZnO powder by Zn-acetate and propanol (sample 3A).

applied Zn(NO3)2.6H2O, CH3COOH and Ti-butoxide
Ti[O(CH2)3.CH3]4 (Figs. 1, 2) in different ratio (samples
7A and 10). The components were dissolved at room
temperature under intense stirring to achieve complete
dissolution and occurrence of hydrolysis processes. This
was followed by evaporation, drying and calcinations of
the samples at 400-420oC. In the third diagram (Fig. 3),
the Ti-butoxide content was reduced and ethylene glycol
was introduced instead of acetic acid (sample 7B). The
procedure of Chopali et al. [23] was followed in order
to obtain an initial homogeneous polymer solution.
Zn acetate precursor. According to the scheme
proposed (Fig. 4), evaporation and calcination of a solu-
tion with the participation of propanol and acetic acid
was applied (sample 3A). The next scheme (Fig. 5) is a
modification of the method proposed by Nondelaers et
al. [24] for preparation of ZnO nanoparticles. The re-
agents used were: Zn(CH3COO) 2.2H 2O, citric acid

237
 Journal of the University of Chemical Technology and Metallurgy, 44, 3, 2009

Fig. 5. Flow diagram for preparation of ZnO powder by Zn-acetate and amonium solution (25 %) (sample 4A).

Fig. 6. Flow diagram for preparation of ZnO/V2O5 powder by Zn-acetate and NH4VO3 (25 %) (sample 4B).

C(OH)(COOH)(CH2COOH)2 and 25 % ammonia solu-
tion (sample 4A). The aqueous solution of Zn-acetate
was mixed with citric acid which, being a complex form-
ing factor, prevents precipitation and helps the coordina-
tion of metal ions. The ammonia solution maintains a
constant pH of 8.5 to the complete deprotonation of the
acid. Additional introduction of NH4VO3 led to the
preparation of binary ZnO/V2O5 composition (Fig. 6).
Drying and calcination proceeded stepwise, maintain-
ing a maximum temperature of 420oC (sample 4B). The
last combination studied was again ZnO/TiO2 mixture
(Fig. 7) using Zn- acetate, Ti-butoxide and ethylene
glycol as a precursor (sample 11).
The phase formation processes were followed
by Bruker D8 Advance X-ray phase analysis. The main
short range order structural units of the submicron pow-

238
 Y. Dimitriev, Y. Ivanova, A. Staneva, L. Alexandrov, M. Mancheva, R. Yordanova, C. Dushkin, N. Kaneva, C. Iliev

Fig. 7. Flow diagram for preparation of ZnO/TiO2 powder by Zn-acetate and Ti-butoxide and etylene glycol (sample 11).

ders were determined by IR spectroscopy (Nicolet 320

FTIR spectrometer). The structure of calcined samples
at 420oC was observed by scanning electron micros-
copy (JEOL, JEM-200, CX). The photocatalytic activ-
ity of the powders was studied using model solutions of
malachite green after subjecting it to UV-radiation. The
decomposition degree was determined by a Jenway 400
spectrophotometer.

RESULTS AND DISCUSSION

Phase and structure analysis

Fig. 8 shows the X-ray patterns of TiO2 contain-
ing samples. With increasing TiO2 content, peaks char-
acteristic to Zn2TiO4 are visible in addition to ZnO.
Besides, a weak amorphous halo appears (sample 7A).
When the TiO2 content decreases, the only phase ob-
served is ZnO (sample 7B, 10). It is worth noting that
the sample containing small amounts of TiO2 and
ethylene glycol in the initial solution has the finest crys-
talline structure (sample 10). The calculated particle
dimensions are of the order of 5-7 nm. The powders
obtained from acetates (samples3A, 4A, 4B and 11) ex-
hibit the peaks of ZnO (Fig. 9). According to calcula-
tions made by the Scherrer method the powder dimen-
sions in this case are 190 - 200 nm. All IR- spectra of
the calcined samples show characteristic bands at
420, 480 cm-1 which can be ascribed to the vibrations Fig. 8. X-ray diffraction paterns of: a) sample 7A; b) sample
of ZnO6 polyhedra (Figs. 10 and 11). The presence of 7B; c) sample 10.

239
 Journal of the University of Chemical Technology and Metallurgy, 44, 3, 2009
Fig. 9. X-ray diffraction paterns of: a) sample 3A; b) sample
4A; c) sample 4B; d) sample 11.
two peaks at 400-530 cm-1 can be attributed to the dif-
ferent geometry of the crystals (a transition from spheri-
cal to prismatic microstructure) [3].
According to SEM, during the calcination all
samples are characterized by a trend to aggregation.
Typical examples are shown in Fig. 12. Sample 7A shows
formation of hexagonal flat crystallites whereas in
240
Fig. 10. IR-spectra of: a) sample 7A; b) sample 7B; c)
sample 10.
sample 10 there are aggregates with a pronounced re-
lief surface.
Photocatalytic activity
Figs. 13 and 14 show he results from photocata-
lytic experiments for all the samples investigated. The pho-
tocatalytic reaction takes place in a shorter time with
samples 4A (obtained according to the scheme in Fig. 5)
and 10 (obtained as shown in Fig.2). However,
samples7B and 3A show the highest degree of mala-
chite green decomposition during the first 30 minutes,
which is probably due to the fact that these samples
have a higher aggregation degree and during the reac-
tion the active sites on the particle surfaces are con-
sumed. Thus, a short additional mechanical activation
with a view to improving the material may lead to a
higher photocatalytic activity.
 Y. Dimitriev, Y. Ivanova, A. Staneva, L. Alexandrov, M. Mancheva, R. Yordanova, C. Dushkin, N. Kaneva, C. Iliev

a)

b)

c)

Fig. 11. IR-spectra of: a) sample 3A; b) sample 4A; c) Fig. 12. SEM micrographs of: a) sample 7A; b) sample 7B;
sample 4B; d) sample 11. c) sample 10.

Fig. 13. Photocatalytic activities of: a) sample 7A; b) sample Fig. 14. Photocatalytic activities of: a) sample 3A; b) sample
7B; c) sample 10. 4A; c) sample 4B; d) sample 11.

241
 Journal of the University of Chemical Technology and Metallurgy, 44, 3, 2009
CONCLUSIONS
Comparative analysis of different schemes of
preparation of ZnO and binary mixtures with its par-
ticipation shows that the production of powders for
photocatalytic applications depends on many factors.
Of importance are: the main precursor, the concentra-
tion and type of the solvents, the time of thermal treat-
ment. All these factors are to be taken into account in
each separate case. The experiments performed showed
that an important problem with sol-gel methods is the
trend to aggregation of the particles. It has been shown
that the introduction of small amounts of TiO2 in pres-
ence of ethylene glycol leads to better results as com-
pared to pure ZnO and a combination of ZnO and V2O5.
Acknowledgements
This study was supported by the Ministry of Educa-
tion and Science within contract TK-X-1702/07.
REFFERENCES
1. Z. L. Wang, Mater. Today, 2004, 26.
2. D. Li, H. Haneda, Chemosphere, 51, 2003, 129.
3. M. Andres-Verges, M. Martinez-Gallego, J. Mater.
Sci., 27, 1992, 375.
4. S. Haile, D. Jonson, G. Wiesemen, H. Bowen, J. Amer.
Ceram. Soc., 72, 1989, 227.
5. N. Audebrand, J. Auffredic, D. Louer, Chem. Mater.,
10, 1998, 2450.
6. R. B. Petrson, C. L. Fields, B. A. Gregg, Langmuir,
20, 2004, 5114.
7. J. Hu, Q. Li, X. Meng, C. Lee, S. Lee, Chem. Mater.,
15, 2003, 305.
242
View publication stats
8. Q. Huang, L. Gao, J. Am. Ceram. Soc., 88, 2005,
1403.
9. Q. Li, V. Kumar, Y. Li, H. Zhang, T. Marks, R. Chang,
Chem. Mater., 17, 2005, 1001.
10. M. Height, L. Madler, S. Pratsinis, Chem. Mater.,
18, 2006, 572.
11. C. Wang, X. Wang, Bo-Qing Xu, J. Zhao, B. Mai,
Ping’an Peng, G. Sheng, J. Fu, J. Photochem. Pho-
tobiology A Chem., 168, 2004, 47.
12.Y. Jang, C. Simer, T. Ohm, Mater. Res. Bull., 41, 2006,
67.
13. C. Sirtori, P. K. Altvater, A. M. de Freitas, P. G. Peralta-
Zamora, J. Hazardous Mater., 129, 2006, 110.
14. Akyol, H. C. Yatmaz, M. Bayramoglu, Appl. Catal.
B Environmental, 54, 2004, 19.
15. N. Daneshvar, D. Salari, A. Khataee, Appl. Catal. B
Environmental, 162, 2004, 317.
16. C. Hariharan, Appl. Catal., A 304, 2006, 55.
17. C. Marci, V. Augugliaro, M. L. Lopez-Munoz, C.
Martin, L. Palmisano, V. Rives, M. Schiavello, R. J.
D. Tilley, A. M. Venezia, J. Phys. Chem., B 105,
2001, 1033.
18. M. Mrowetz, E. Selli, J. Photochem. Photobiology
A Chem., 180, 2006, 15.
19. B. Pal, M. Sharon, Mater. Chem. Phys. 76 (2002) 82.
20 D. Li, H. Haneda, J. Photochem. Photobiology A
Chem., 160, 2003, 203.
21. D. Li, H. Heneda, N. Ohashi, S. Hishita, Y.
Yoshikawa, Catal.Today, 93-95, 2004, 895.
22. C. Ge, C. Xie, D. Zeng, S. Cai, J. Amer. Ceram.
Soc., 90, 2007, 3263.
23. U. Chopali, B. P. Corman, J. Amer. Ceram. Soc.,
90, 2007, 443.
24. D. Mondelaers, Mater. Res. Bull., 37, 2002, 901.