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CERAMICS
INTERNATIONAL
Ceramics International 39 (2013) 3007–3015
www.elsevier.com/locate/ceramint

Effect of fuel to oxidant molar ratio on the photocatalytic activity

of ZnO nanopowders
M. Ahmada,b,n, Zhanglian Honga,nn, E. Ahmedb, N.R. Khalida,b, A. Elhissic, W. Ahmadc
a
State Key Laboratory of Silicon Materials and Department of Materials Science and Engineering, Zhejiang University, Hangzhou 310027, PR China
b
Department of Physics, Bahauddin Zakariya University, Multan 60800, Pakistan
c
Institute of Nanotechnology and Bioengineering, University of Central Lancashire Preston PR1 2HE, UK
Received 28 June 2012; received in revised form 12 September 2012; accepted 21 September 2012
Available online 3 October 2012

Abstract

In this study, the effects of fuel to oxidant (F/O) molar ratio on the characteristics and photocatalytic activity of ZnO nano-powders
were investigated. A simple and inexpensive combustion process was utilized to synthesize the nano-powders. A range of analytical
techniques including X-ray diffraction (XRD), Scanning electron microscopy (SEM), Transmission electron microscopy (TEM), Fourier
transform infrared spectroscopy (FTIR), UV–vis diffuse reflectance spectroscopy (DRS) and Photoluminescence spectroscopy (PL) were
employed to characterize the nano-powders. XRD patterns showed that the synthesized powders have hexagonal wurtzite structure and
high crystallinity without any secondary phase. The calculated crystallite size was in the range of 35–29 nm which decreased by
increasing the F/O ratio. UV–vis diffuse reflectance spectroscopy showed a gradual shift of optical absorption spectra in the visible
region of light when F/O ratio was increased. PL spectroscopy confirmed that the prepared photocatalysts had better charge separation
capability as compared to the commercial ZnO. The photocatalytic activity of different samples was investigated by degradation of
methyl orange (MO) dye under UV and visible light irradiation. The results demonstrated that F/O ratio had a significant influence on
photocatalytic degradation of methyl orange compared to the commercially available ZnO and TiO2 powders. Moreover, the
photocatalysis of ZnO (F/O¼ 1.7) powder with particle size (31 nm) showed excellent performance for photodegradation of MO, which
suggests a balance among the recombination rate, surface hydroxyl groups and specific surface area.
& 2012 Elsevier Ltd and Techna Group S.r.l.. All rights reserved.

Keywords: Powders; ZnO; Optical properties; Photocatlysis

1. Introduction wastewater [3]. The photocatalytic process using nanos-

tructured semiconductors is one of the technologies used
Industrial wastewater contains various organic and for the destructive oxidation of organic compounds such
inorganic pollutants, which are generally toxic and resis- as dyes [4]. Among these semiconductors, TiO2 and ZnO
tant to destruction by biological methods of treatment. have extensively been studied in the field of photocatalysis
The conventional methods previously used for wastewater [5]. However ZnO has higher photocatalytic efficiency than
detoxification includes coagulation, flocculation, filtration, TiO2 due to its strong absorption of UV light from the
carbon adsorption process and treatment with ozone [1,2]. solar spectrum [6,7]. Moreover, ZnO is an efficient photo-
Unfortunately, these biological methods are ineffective due catalyst for waste-water detoxification because it produces
to high concentration and stability of organic dyes in the H2O2 more efficiently than any other photocatalysts [8].
Surface defects and interface properties of metal oxide
n
Corresponding author at: Department of Physics, Bahauddin Zakariya nanoparticles also play an important role in photocatalysis.
University, Multan 60800, Pakistan. Tel.: þ92 61 9210091; Nanoparticles with high specific surface area can provide
fax: þ 92 61 9210098.
nn surface states within the semiconductor band gap to enhance
Corresponding author. Tel./fax: þ 86 571 87951234.
E-mail addresses: [email protected] (M. Ahmad), the photocatalytic activity especially in the visible light region.
[email protected] (Z. Hong). It has been previously found that photocatalysis efficiency can

0272-8842/$ - see front matter & 2012 Elsevier Ltd and Techna Group S.r.l.. All rights reserved.
http://dx.doi.org/10.1016/j.ceramint.2012.09.079
3008 M. Ahmad et al. / Ceramics International 39 (2013) 3007–3015

be enhanced via optimizing of particle size of the ZnO

Directly mixing of glycine and zinc nitrate at room
photocatalyst [9,10]. However, preparation method and calci-
temperature in a desired molar ratio
nation temperature both strongly affect the properties of ZnO
photocatalyst. Many techniques have been developed to
synthesize nanocrystalline ZnO powders, including the co-
Stirring and heating at
precipitation method, sol–gel, intensive mechanical milling,
spray pyrolysis, solution coating and combustion synthesis etc. 90-100°C
[11–17]. Among these, the combustion synthesis appears to be Gel/ Precursor
the first choice for large scale economical production of
nanopowders [18]. Sousa et al. have investigated the synthesis Stirring and heating at
of pure and doped ZnO nanopowders by the combustion 180-200°C
method using urea as a fuel and a good control over the
compositions was observed [16]. Hwang and Wu have used Combustion
the combustion method with glycine as a fuel to prepare ZnO
nanopowders for their potential applications in electronic
devices such as varistor [17].
In this study, the effects of the fuel to oxidant molar
ratios on the properties of nanocrystalline ZnO photo-
catalysts were investigated using a single step chemical
combustion process of preparation. The photocatalytic
activity of the synthesized samples was studied by obser-
ving the degradation of the MO dye under ultraviolet (UV)
and visible light irradiation. Also the effects of particle size
on the optical properties and photocatalytic activity of Heat treatment at 500°C
nanocrystalline ZnO photocatalysts were evaluated. for 3h

2. Experimental

2.1. Catalysts preparation

Nanocrystalline ZnO photocatalysts were synthesized using Fig. 1. Flow chart for the synthesis of ZnO nanopowders.
a simple and inexpensive combustion method [17]. Zinc nitrate
(oxidant) and glycine (fuel) were used for the preparation of
ZnO nanopowders as elucidated in Fig. 1. The reagents were diffractometer with Ni-filtered Cu-Ka radiation source at
directly mixed at room temperature in the desired molar ratio. 40 kV and 36 mA. From the X-ray diffractograms, the
The nature of the fuel and its amount are important in average crystallite size was calculated using Scherer’s
combustion process for acquiring the transparent viscous gel formula. The surface morphology, particle size and com-
without any phase separation or precipitation. Since zinc positional analysis of photocatalysts were studied using a
nitrate is hygroscopic, the mixture easily absorbs moisture scanning electron microscope (SEM), Hitachi S-4800
from the surrounding environment, resulting in conversion of combined with EDX, transmission electron microscope
the material into transparent slurry. This slurry was dehy- (TEM), JEOL JEM 1200EX and high resolution transmis-
drated to form a gel by using a hot plate (90–100 1C). sion electron microscope (HRTEM) FEI TECNAI G2
Precursor/gel was further ignited by heating on the hot plate F20. The samples for SEM and TEM were prepared by
at  180–200 1C. During the combustion reaction, large dispersing the powders in ethanol via sonication and then
amounts of heat and non-toxic gases were explosively gener- dispersion was dropped on silicon coated glass slide and
ated, resulting in formation of dry and voluminous nanocrys- carbon coated copper grid respectively. UV–vis diffuse
talline ZnO powders. It was noted that the color of synthesized reflectance spectra (DRS) were measured in the range of
powders was changed from off-white to yellow, yellow to light 300–800 nm using a Hitachi U-4100 UV–vis-spectrometer
brown, light brown to brown and finally brown to black for equipped with an integrating sphere of 60 mm using BaSO4
F/O¼ 1.1, 1.4, 1.7, 2.1and 2.5 respectively. Finally, the as a standard. The PL emission spectra were recorded
prepared samples were calcined at 500 1C for 3 h in the using a Hitachi F-4500 fluorescence spectrophotometer.
furnace. The samples excitation was performed at 325 nm at room
temperature and the emission was scanned between 350
2.2. Catalyst characterization and 630 nm. Fourier transform infrared (FT-IR) spectra
were recorded at room temperature in 4000–400 cm  1
Powder X-ray diffraction (XRD) patterns for samples range using Nicolet Avatar 360 FT-IR with KBr pellet
were investigated using a Rigaku Dmax-IIIA X-ray method.
 M. Ahmad et al. / Ceramics International 39 (2013) 3007–3015 3009

2.3. Measurement of photocatalytic activity 3. Results and discussion

The photocatalytic activity of ZnO powders were esti- Fig. 3 shows the XRD patterns of ZnO samples. All of
mated by monitoring the degradation of MO (Fig. 2a) as a the nanocrystalline ZnO powders synthesized for the range
model compound in a self-assembled apparatus with a of fuel to oxidant molar ratio (F/O ¼ 1.1–2.5) revealed
metal halogen lamp (HQIBT, 400 W/D, OSRAM, quite sharp X-ray diffraction peaks indicating crystallinity
Germany) as the radiation source. In the present investiga- of the samples. These XRD patterns clearly showed 10
tion, photocatalytic activities under visible as well as UV main peaks of hexagonal wurtzite structure of ZnO,
light were studied. The visible light (l Z 420 nm) used in namely, the planes (100), (002), (101), (102), (110), (103),
the present study was obtained by using a filter with cut-off (200), (112), (201) and (202), which all are in good
wavelength of 420 nm. The UV–visible spectrum of the dye agreement with JCPDS-05-0664 and literature findings
in aqueous medium is shown in Fig. 2(b). The peak at [19–21]. The lattice constant corresponding to the main
464 nm was used to monitor the photocatalytic degrada- peak of ZnO at 2y=36.31 were obtained by the following
tion of MO. For the photocatalytic experiment, 50 mg equation:
photocatalysts were suspended in MO aqueous solution

(50 mL) with a concentration of 10 mg/L in a beaker. The I=d 2 hkl ¼ 4=3 h2 þ hk þ k2 =a2 þ l 2 =c2
suspension was magnetically stirred for 30 min to reach the
adsorption/desorption equilibration without light expo- The average values of lattice constant calculated by using
sure. Following this, the photocatalytic reaction was the above equation are ‘‘a=3.2538 Å’’ and ‘‘c=5.2134 Å’’.
started by the exposure of the desired light. The tempera- These calculated values of lattice constants are in good
ture of the suspension was kept at about 20 1C by an agreement with standard data (a=3.249 Å and c=5.206 Å)
external cooling jacket with recycled water. After a setup [19]. The crystallite size was estimated using the full width at
exposure time, 3 mL suspension was sampled, centrifuged half maximum (FWHM) of high intensity peak (101) appear
and the supernatant was taken out for UV–vis absorption at 2y ¼ 36.31 using Scherer’s formula:
spectrum measurement (Hitachi U-4100 UV–vis spectro-
d ¼ kl=b cos y
meter). The intensity of the main absorption peak of the
MO dye was referred to as the measure of the residual dye
concentration.
O O---- ZnO

O
O
O
O O O
F/O=2.5 OO O

F/O=2.1
Intensity (a.u.)

0.7

0.6
F/O=1.7

0.5
Absorbance (a.u)

0.4
F/O=1.4
0.3

0.2

0.1 F/O=1.1

0.0

300 350 400 450 500 550 600 20 30 40 50 60 70 80

Wavelength (nm) 2θ (degree)

Fig. 2. (a) The structural and chemical formula of MO and (b) the Fig. 3. X-Ray diffraction patterns of ZnO nanopowders with different
UV–visible absorption spectrum of MO. F/O values.
3010 M. Ahmad et al. / Ceramics International 39 (2013) 3007–3015

where ‘‘d’’ is the crystallite size in nanometers, k ¼ 0.89 demonstrated clusters of very small and highly uniform
which is a constant, l is the wavelength of X-ray radiation nanocrystalline grains with a loose appearance. This porous
in nanometers, y is the Bragg angle in radians and b is the morphology observed is caused by the liberation of large
FWHM in radians. The results show that the particles amount of gases during the combustion reaction. It is also
obtained by the combustion process were nanocrystalline noted that lattice fringes of ZnO nanoparticles were sharper,
with size in the range of 35–29 nm (Fig. 4). indicating high crystallinity of the nanoparticles. The
Fig. 5(a,c,d) showed that the morphology of representative observed particle sizes and crystallinity are in good agreement
sample ZnO (F/O¼ 1.7) nanoparticles, examined under with XRD results. The chemical composition of ZnO (F/
SEM, TEM and HRTEM respectively. The images of ZnO O¼ 1.7) powders was examined by EDX measurements and
is shown in Fig. 5(b). The EDX analysis showed the weight
and atomic percentages of zinc and oxygen (Zn/O) in the
35
sample and values are presented in Table 2.
Fig. 6(a) shows the diffuse reflectance spectra of ZnO
34 samples measured in the 300–600 nm wavelength range.
Crystallite size (nm)

The absorption spectra from reflectance data were

33 obtained by application of the Kubelka–Munk algorithm
and are shown in Fig. 6(b). The absorption spectra of ZnO
32 powders synthesized with different fuel to oxidant molar

31 Table 1
Detail of crystallite size and band gap for different
F/O values.
30
F/O molar ratio Crystallite size Band gap
29
1.1 35 3.263
1.4 33 3.260
1.0 1.2 1.4 1.6 1.8 2.0 2.2 2.4 2.6 1.7 31 3.257
Fuel to oxidant molar ratio 2.1 30 3.251
2.5 29 3.248
Fig. 4. Plot of crystallite size as a function of F/O molar ratio.

Fig. 5. (a) SEM image, (b) EDX spectra, (c) TEM image and (d) HRTEM image of the ZnO (F/O¼1.7).
 M. Ahmad et al. / Ceramics International 39 (2013) 3007–3015 3011

ratios shifted to visible light region. This type of modifica- where A is the absorption constant. The plots of (ahu)2
tion in optical properties can be attributed to charge versus hu from the spectral data of Fig. 6(b) are presented
transfer from O2  to Zn2 þ responsible for the band-gap in Fig. 6(c). By extrapolating the linear portion of the
[22]. Band gap energy can be estimated from the absorp- curve to zero absorbance, the direct band gap energy
tion spectra. Semiconductors are classified to be direct or values of the ZnO powders can be estimated. Table 1
indirect according to the lowest allowed electronic transi- shows the band gap energy values of different photocata-
tion. Direct band semiconductors are characterized by the lysts. The band gap energy values decrease due to the
minimum of the lowest conduction band position in decrease in particle size of ZnO powders. [23–25]. It can
k-space directly under the maximum of the highest valance also be seen that the slope of UV–vis absorption spectra of
band. The relation between absorption coefficient (a) and ZnO powders was steeper for the sample having smaller
incident photon energy (hu) for allowed direct transitions particle size of 29 nm. A sharp UV–vis absorption curve
can be presented as (steep slope) indicates a high degree of crystallinity [23].

The photoluminescence emission spectra is advanta-
ðahuÞ2 ¼ A huEg geous for investigation of the effectiveness of charge carrier
trapping, imigration, transfer and in understanding the
Table 2 fate of electron–hole pairs in semiconductor nanoparticles
Weight and atomic percentage of zinc and [26]. To study the effect of fuel to oxidant molar ratio on
oxygen (Zn/O) in ZnO (F/O¼ 1.7).
the photoluminescence of ZnO powders, the room tem-
Element Weight% Atomic% perature photoluminescence measurements were carried
out at the excitation wavelength of 325 nm. The PL spectra
O 20.31 50.53 of different ZnO photocatalysts are shown in Fig. 6(d).
Zn 79.69 49.47
A strong UV emission at 385 nm and several relatively
Total 100 100
weak visible emissions in the range of 400–590 nm were

100

80
Diffuse Reflectance

Absorbance

60

F/O=2.5
F/O=1.1 F/O=2.1
40 F/O=1.4 F/O=1.7
F/O=1.7 F/O=1.4
F/O=2.1 F/O=1.1
20 F/O=2.5

0
300 350 400 450 500 550 600 350 360 370 380 390 400 410 420 430
Wavelength (nm) Wavelength (nm)

F/O=1.1
F/O=1.4
PL Intensity (a.u.)

F/O=1.7
(αhν)2(a.u.)

F/O=2.5 F/O=2.1
F/O=1.7 F/O=2.5
F/O=2.1
F/O=1.4
F/O=1.1

3.15 3.18 3.21 3.24 3.27 3.30 3.33 390 420 450 480 510 540 570 600
hν (eV) Wavelength (nm)

Fig. 6. Diffuse reflectance spectra (a) UV–vis absorption spectra (b) the (ahu)2 versus hu curves for band gap determination (c) and photoluminescence
spectra (d) of ZnO powders with different F/O values.
3012 M. Ahmad et al. / Ceramics International 39 (2013) 3007–3015

observed. The UV emission is attributed to free excitonic are present in all ZnO powders with the hydroxylated
emission near the band edge and the visible emissions may surfaces [29]. The bands at  2920 and  2850 cm  1
be due to the transition from various kinds of defect states correspond to C–H stretching [30]. Another IR peak at
[27,28]. It was observed that the positions of the peaks  1385 cm  1 results from OH– absorption of hydrogen-
were almost similar, while PL intensities were quite related defects [29]. As the F/O ratio increases, the
different among these samples. It is known that the PL intensity of all IR peaks except the one at  440 cm  1
emission is caused by the recombination of excited elec- becomes weaker step by step [21]. In addition, a strong
trons and holes, and the lower PL intensity may indicate absorption band corresponding to the stretching and
the lower recombination rate of electrons and holes under vibrational modes of metal–oxygen bands (Zn–O) was
light irradiation. The PL intensity of ZnO (F/O=1.1) is also observed for each powder sample at  440 cm  1
highest among all the samples, indicating the highest [21,31]. The shape of the IR spectrum of ZnO particles is
recombination of electrons and holes. The emission inten- generally influenced by particle size, morphology, the
sities were significantly weakened with the increase in F/O degree of particles aggregation and the crystal structure
ratio, implying that the recombination of charge carriers of the ZnO polymorph [32].
was effectively suppressed. Among all the samples the The photocatlytic activities of ZnO powders were stu-
lowest intensity was observed for ZnO (F/O=2.5). This died by photodegradation of MO as model dye under UV
indicates that the charge carriers were separated more as well as visible light. A blank experiment study of MO
effectively. degradation without catalyst under the same condition was
The FT-IR spectra for the ZnO powders were obtained also observed. The results indicate that the mere photolysis
at the room temperature as shown in Fig. 7. A few distinct can be ignored as the corresponding degradation is about
bands were observed in the high wave number region, at 0.3% after illumination for 2 h. The photocatalytic per-
 3440,  2920,  2850,  1640, and  1385 cm  1. The formances for MO degradation by the ZnO catalysts are
peaks at 3440 and 1640 cm  1 imply that the basic hydroxyl shown as plots of C/C0(%) versus t (min) in Fig. 8. About
groups of chemisorbed and/or physisorbed H2O molecules 8% of the MO was adsorbed for ZnO (having F/O of 1.7)
upon stirring for 30 min in the dark and it increased to
60 some extent in comparison to other ZnO powders. Photo-
tcatalytic degradation of MO follows roughly the pseudo-
40
CO2
first-order reaction kinetics for low dye concentrations
20

ln C0 =C ¼ kapp t
0 F/O=2.5
where kapp is the apparent constant, used as the basic
60 kinetic parameter for different photocatalysts. C0 is the
initial concentration of MO in aqueous solution and C is
40
the residual concentration of MO at time t. The apparent
constant values could be deduced from the linear fitting of
F/O=2.1
ln(C0/C) versus irradiation time. The initial degradation
rate (r0 ¼ kappC0) of 10 mgL  1 MO with different catalysts
Transmittance %

60
was studied and the results are presented in Fig. 9. The
degradation rate of MO is in the order; ZnO (F/
40 O ¼ 1.7) 4 ZnO (F/O ¼ 2.1) 4 ZnO (F/O ¼ 2.5) 4 ZnO (F/
F/O=1.7 O ¼ 1.4) 4 ZnO (F/O ¼ 1.1). The degradation rate under
60
UV and visible light for ZnO (F/O ¼ 1.7) catalyst was
found superior to commercially available P-25 and ZnO
(Fig. 9).
40 The dependence of percentage conversion of MO
F/O=1.4
decomposition on the particle size of ZnO powders after
time ‘t’ is shown in Fig. 10. The percentages of MO
degradation after 1 h increased from 78% to 100% under
40
C=O O-H UV and from 2% to 25% under visible light when the
C-H particle size of ZnO powders decreased from 35 to 31 nm.
20 O-H
For the smaller particle sizes (30–29 nm) of ZnO powders,
0 Zn-O F/O=1.1 the percentages of MO degradation gradually decreased
from 100% to 97% under UV and from 25% to 11%
0 500 1000 1500 2000 2500 3000 3500 4000 4500
under visible light. Therefore, 31 nm ( for ZnO F/O ¼ 1.7)
Wavenumber (cm-1)
is an optimum particle size of ZnO for maximum photo-
Fig. 7. FT-IR spectra of ZnO powders with different F/O values. catalytic activity of the catalyst.
 M. Ahmad et al. / Ceramics International 39 (2013) 3007–3015 3013

0.8
100
ZnO
90 Photocatalysis 0.7 (F/O=1.7)

80 Adsorption ZnO
0.6
(F/O=2.1) ZnO
70
P-25 TiO2 ZnO (F/O=2.5)

r0(mg.L-1.min-1)
0.5
60 (F/O=1.4)
C/Co(%)

50 0.4 ZnO(c)

40 ZnO (com.) ZnO

0.3 (F/O=1.1)
P25 TiO2
30
F/O=1.1 0.2
20 F/O=1.4
F/O=1.7 0.1
10
F/O=2.1
0 F/O=2.5 0.0
1 2 3 4 5 6 7
-30 0 30 60 90
0.08
Irradiation time (min)

100 Photocatalysis 0.07

0.06

90
Adsorption
r0(mg.L-1.min-1)

0.05

0.04 ZnO
80
C/Co(%)

(F/O=1.7) ZnO
0.03 P-25 TiO2 (F/O=2.1)
ZnO (c)
ZnO
70 P25 TiO2
0.02 ZnO(c) ZnO (F/O=2.5)
F/O=1.1 (F/O=1.4)
ZnO
F/O=1.4 0.01
60
(F/O=1.1)
F/O=1.7
F/O=2.1 0.00
F/O=2.5 1 2 3 4 5 6 7
50
Fig. 9. The initial degradation rate of MO in the presence of various
-30 0 30 60 90 120
catalysts under (a) UV light and (b) visible light irradiation.
Irradiation time (min)

Fig. 8. Time profiles of C/Co for various catalysts under (a) UV light and
(b) visible light irradiation. electron recombines with the hole in valence band. As
such, photoluminescence (PL) can successfully be
employed to monitor low intensity signals corresponding
In general, photocatalysis can be considered to be to lower recombination rates [35]. According to PL results,
dominated by the following linked mechanisms, namely ZnO photocatalyst with lower F/O ratio should exhibit
recombination of electron-hole pair and surface catalytic lower photocatalytic activity and must increase with
effects [33]. Surface hydroxyl groups contribute in the increasing F/O ratio. However, it was noted that the
photocatalytic process in a number of ways. They trap photocatalytic activity initially increased with a maximum
photoexcited electrons and create OH radicals. They can at F/O ¼ 1.7 and then decreased for higher molar ratios.
also act as active sites for the pollutants [34]. Recombina- On the other hand, surface hydroxyl groups were
tion is a major limitation in semiconductor photocatalysis decreased with increasing F/O ratio; herein the photoca-
as it decreases the overall quantum efficiency of the talyst with the lowest molar ratio (ZnO F/O ¼ 1.1) should
photocatalyst due to high recombination rate of photo- show best photocatalytic activity [34]. The specific surface
induced electron–hole pair at the surface of the catalyst area also plays a vital role during photocatalysis, because
[35]. When recombination occurs, the excited electron large surface area will result in an increase in the number
returns to the valence band without reacting with adsorbed of active sites existing for degradation reactions. Accord-
species [36]. Radiation may be emanated when an excited ing to results, the photocatalyst with moderate molar ratio
3014 M. Ahmad et al. / Ceramics International 39 (2013) 3007–3015

105 photo degradation of MO dye under UV and visible light

irradiation.
100
Percentage degradation of MO

Acknowledgments

95 This work was supported partially by the State Key

Laboratory of Silicon Materials (SKL2009-14) at Zhejiang
University. The authors also thank the Higher Education
90
Commission of Pakistan for IRSIP scholarship.

85 References

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