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Structural, optical and photocatalytic properties of hafnium doped zinc

oxide nanophotocatalyst
M. Ahmada,b,n, E. Ahmeda, Z.L. Hongb, Z. Iqbala, N.R. Khalida,b, T. Abbasc, Imran Ahmada,
A.M. Elhissid, W. Ahmedd
a
Department of Physics, Bahauddin Zakariya University, Multan 60800, Pakistan
b
State Key Laboratory of Silicon Materials, Department of Materials Science & Engineering, Zhejiang University, Hangzhou 310027, China
c
Institute of Industrial Control System, Rawalpindi, Pakistan
d
Institute of Nanotechnology and Bioengineering, University of Lancashire, Preston PR1 2HE, United Kingdom
Received 5 February 2013; received in revised form 13 April 2013; accepted 15 April 2013

Abstract

A series of novel hafnium (Hf) doped ZnO nanophotocatalyst were synthesized using a simple sol–gel method with a doping content of up to
6 mol%. The structure, morphology and optical characteristics of the photocatalysts were characterized by XRD, SEM, TEM, FTIR, XPS, DRS
and PL spectroscopy. The successful synthesis and chemical composition of pure and doped ZnO photocatalysts were confirmed by XRD and
XPS. DRS confirmed that the spectral responses of the photocatalysts were shifted towards the visible light region and showed a reduction in
band gap energy from 3.26 to 3.17 eV. Fluorescence emission spectra indicated that doped ZnO samples possess better charge separation
capability than pure ZnO. The photocatalytic activity of Hf-doped ZnO was evaluated by the methylene blue (MB) degradation in aqueous
solution under sunlight irradiation. Parameters such as irradiation time and doping content were found effective on the photoactivity of pure ZnO
and Hf-doped ZnO. The photocatalysis experiments demonstrated that 2 mol% Hf-ZnO exhibited higher photocatalytic activity as compared to
ZnO, ZnO commercial and other hafnium doped ZnO photocatalysts and also revealed that MB was effectively degraded by more than 85%
within 120 min. The enhanced photoactivity might be attributed to effective charge separation and enhanced visible light absorption. It was
concluded that the presence of hafnium within ZnO lattice could enhance the photocatalytic oxidation over pure ZnO.
& 2013 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Keywords: A. Sol–gel; D. ZnO; Hf-doped ZnO; Methylene blue; Photocatalysts

1. Introduction biotechnology and environmental technology [5,6]. ZnO has

also been considered as a suitable alternate for TiO2 photo-
ZnO, a wide band compound semiconductor material is catalyst owing to its similar band gap, absence of toxicity, high
currently the subject of vigorous development and study chemical stability and lower cost. Moreover, it exhibits better
programs because of its potential applications in many areas performance in the degradation of organic dye molecules in
such as environmental pollution control, field emission dis- both acidic and basic media. The intrinsic defects of ZnO are
plays, photocatalysis, solar cell windows, gas sensors and advantageous to setting up catalytic systems, which are
pharmaceuticals [1–4]. ZnO is a biocompatible antibacterial expected to degrade the environmental pollutants [4]. The
compound that exhibits high mechanical, thermal and chemical main advantage of ZnO as compared with TiO2 is that it can
stability. Owing to its remarkable physical and chemical absorb larger fraction of the UV spectrum than TiO2 [7,8]. The
qualities, it can be used extensively in information technology, common scheme for the photocatalytic destruction of organic
pollutants encompasses the following three steps: (1) when the
n
energy (hν) of a photon is equal to or higher than the band gap
Corresponding author at: Department of Physics, Bahauddin Zakariya
University, Multan 60800, Pakistan. Tel.: +92 61 9210091; fax: +92 61 9210098.
(Eg) of the semiconductor, an electron is excited to conduction
E-mail addresses: mzkhm73@gmail.com, band (CB), with simultaneous generation of a hole in the
mzkhm@yahoo.com (M. Ahmad). valance band (VB); (2) then the photoexcited electrons and

0272-8842/$ - see front matter & 2013 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
http://dx.doi.org/10.1016/j.ceramint.2013.04.051

Please cite this article as: M. Ahmad, et al., Structural, optical and photocatalytic properties of hafnium doped zinc oxide nanophotocatalyst, Ceramics
International (2013), http://dx.doi.org/10.1016/j.ceramint.2013.04.051
2 M. Ahmad et al. / Ceramics International ] (]]]]) ]]]–]]]

holes can be trapped by the oxygen and surface hydroxyl, % of HfO2 were countered with appropriate amount of nitric
respectively, to ultimately produce the hydroxyl radicals acid to create hafnium nitrate then zinc acetate and hafnium
(dOH), which are known as the primary oxidizing species; nitrate were taken in a round bottom flask. This was followed
and (3) the hydroxyl radicals commonly mineralize the by gradual addition of ethanol to the solution under vigorous
adsorbed organic substances [9]. However, the photoexcited magnetic stirring. The resultant mixture was further stirred for
electrons and holes can also recombine to reduce photocata- 3 h at 80 1C and then kept at room temperature in air for 12 h
lytic efficiency of the semiconductor material [10]. Therefore, to form an aged homogeneous gel. Subsequently, the as-
suppression of the recombination of photogenerated electron– prepared gel was dried at 100 1C in an oven; gel was
hole pairs in the semiconductors is essential for improving porphyrized into powders and calcined at 500 1C in a furnace
their photocatalytic efficiency [11,12]. Doping of transition for 3 h. The ZnO doped with 1, 2, 3, 4 and 6 mol% of hafnium
metals, noble metals and non-metals is a very expedient way to were labeled as samples 1 mol% Hf-ZnO, 2 mol% Hf-ZnO,
improve the electron–hole separation in semiconductor sys- 3 mol% Hf-ZnO, 4 mol% Hf-ZnO and 6 mol% Hf-ZnO,
tems; many dopants such as La, Al, Sm, Ag and N have been respectively.
used [9,13–17] and showed better photocatalytic performance.
It is also accepted that the surface area and surface defects 2.2. Characterization
play an important role in photocatalytic activities of metal
oxide semiconductors, which could be accredited to the The XRD patterns were recorded using the Cu Kα radiation
variation of the surface area, surface defects and band gap (λ=1.5406 Å) of a Shimadzu XD-5A diffractometer. Typical
energy caused by the incorporation of dopant ions. It has been 2θ spectra were collected between 151 and 751. Diffuse
reported that the surface conditions of ZnO can be modified reflectance spectra were recorded on Hitachi U-4100 UV–vis
with the incorporation of dopant ions to enhance its photo- spectrophotometer in the wavelength range of 300–600 nm.
catalytic activity [13–16]. Doping is an effective and facile The nanopowders were pressed into pellets and BaSO4 was
method to modify the physical properties of the base materials used as a reference standard for correction of the instrumental
and this will also expand the applications of base materials [1]. background. The reflectance was converted to absorbance by
It has also been demonstrated that the structural and morpho- the Kubelka–Munk function: F(R)∝K/S=(1−R)2/2R, where K
logical characters such as particle size, shape, crystallinity, is the absorption coefficient, S is the scattering coefficient, and
photocatalytic activity and some relevant properties of ZnO R is the diffuse reflectance. The photoluminescence (PL)
can be significantly affected by the method used during its emission spectra were recorded using a HITACHI F-4500
synthesis [18]. Various approaches have been developed to Fluorescence spectrophotometer. The sample excitation was
prepare ZnO photocatalyst with special performance, which done at 325 nm at room temperature and the PL emission
mainly include template method, solution combustion, pre- spectra were collected in the range of 375–600 nm using Xe
cipitation, gas-phase reaction, hydrothermal synthesis and lamp as radiation source. These powders were also character-
microwave heating [19–21]. ized by using scanning electron microscope (SEM, HITACHI
In this study 0, 1, 2, 3, 4 and 6 mol% hafnium doped ZnO S-4800) and transmission electron microscope (TEM, JEOL
photocatalysts were synthesized by the sol–gel method. The JEM-1200EX). For IR measurements in the range 4000–
microstructure, morphology and optical properties of the 400 cm−1, a Nicolet Avatar 360 FTIR was used. X-ray
photocatalyst changes by hafnium doping were characterized photoelectron spectroscopy (XPS, Thermo-VG Scientific,
by X-ray diffraction (XRD), X-ray photoelectron spectroscopy ESCALAB 250, a monochromatic Al Kα X-ray source) was
(XPS), scanning electron microscopy (SEM), transmission used for elemental and chemical compositional analysis of the
electron microscopy (TEM), photoluminescence (PL) emission samples.
spectra, FT-IR and UV–vis diffuse reflectance spectra (DRS).
The photocatalytic activity of all the prepared photocatalysts 2.3. Photocatalytic activity measurement
under sunlight illumination was evaluated by the
degradation of MB. The photocatalytic activity of pure ZnO and Hf-doped ZnO
photocatalysts were studied by using MB degradation. Experiments
2. Experimental were performed under sunlight illumination in July 2011 in Multan
(Pakistan) and the light intensity was measured with an irradiat-
2.1. Synthesis of ZnO and Hf-doped ZnO nanoparticles ometer (FZ-A, Photoelectric Instrument Factory, Beijing). The
whole set-up was positioned in sunlight between 10am and 2pm.
All reagents were of analytical grade and were used without and the average intensity of sunlight during this period is about
further purification. The materials selected for this experimen- 1.263  105 lx unit. Experimental conditions are as follows: initial
tal work were zinc acetate [Zn(CH3COOH)2
2H2O], hafnium MB aqueous solution was 0.25 g/L; catalyst concentration was
oxide [HfO2], nitric acid [HNO3] and ethanol [C2H5OH]
25 mg/100 ml, taken in beaker covered with thin plastic sheet to
having 99.0% purity, supplied by Merck. Undoped ZnO and avoid evaporation of the dye solution under sunlight. The
Hf-doped ZnO were synthesized using a simple sol–gel suspension was magnetically stirred for 30 min to reach the
method. The undoped ZnO was prepared by using zinc acetate adsorption/desorption equilibrium without sunlight exposure. Fol-
and ethanol. For preparing Hf-doped ZnO, 1, 2, 3, 4, or 6 mol lowing this, the photocatalytic reaction was started by the exposure

Please cite this article as: M. Ahmad, et al., Structural, optical and photocatalytic properties of hafnium doped zinc oxide nanophotocatalyst, Ceramics
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 M. Ahmad et al. / Ceramics International ] (]]]]) ]]]–]]] 3

of sunlight. The temperature of the suspension was kept at about formula. The values of lattice parameters (a), (c) and (c/a)
20 1C by an external cooling jacket with recycled water. After a were calculated for undoped ZnO and Hf-doped ZnO photo-
setup exposure time, 5 ml suspension was sampled, centrifuged, catalysts, which were very close to result of wurtzite phase as
and the supernatant was taken out for UV–vis absorption reported previously [22,25]. Density plays a significant role in
measurement. The intensity of the main absorption peak analyzing physical properties of samples. The X-ray or
(660 nm) of the MB dye was referred to as the measure of the theoretical density Dx of the samples can be measured by
residual MB concentration. using the following equation: Dx=ZM/NAV. Where Z=2
(number of molecules per unit cell) [26], M is molecular
3. Results and discussion weight, NA is Avogadro's number (6.023  1023 mol−1) and V
is the volume of unit cell (√3/2 a2c). The changes in X-ray
X-ray diffraction patterns of undoped ZnO and Hf-doped density as a function of hafnium content is shown in Table 2.
ZnO photocatalysts with different hafnium doping concentra- The decreasing trend in X-ray density was due to the increase
tions are shown in Fig. 1. The patterns clearly showed peaks of in volume of hexagonal unit cell of ZnO.
wurtzite structure of ZnO, namely, the planes (100), (002),
(101), (102), (110), (103), (112), and (201) at 2θ values of ca.
32.031, 34.681, 36.491, 47.771, 56.761, 63.051, 68.111 and

(101)
69.341 respectively, which all are in good agreement with
JCPDS File no. 05-0664 and literature findings [22,23].

(100)
(002)
Moreover, all Hf doped samples showed no extra peaks due

(110)
to hafnium, zinc hafnium or any other oxide phase, indicating

(103)

(112)
(102)

(201)
that the as-synthesized samples are of single phase [24]. A
slight shift of peaks toward lower 2θ values was noted after Hf
doping in all XRD patterns. The lattice parameters of Hf-doped
ZnO were calculated, and were found to be slightly larger than
those of undoped ZnO. This increase in lattice parameters
might be attributed to the larger ionic radius of Hf4+ (0.78 Å)
Intensity (a.u.)

compared to that of Zn2+ (0.74 Å) [24]. The length of both

lattice parameters “a,c” was increased with increasing Hf
doping. The expansion of the lattice constants and the slight
shift of XRD peaks with Hf doping confirmed that the hafnium
was doped into the ZnO structure [22]. The average crystallite
size (d) estimated from full-width at half-maxima of the (101)
peak of the wurtzite ZnO by using the Scherrer formula
(d¼ kλ/β cos θ) showed an approximate value of 17 to 14 nm
(Table 1). The crystallite size of the ZnO nanopowders was
decreased for doping content of 2 mol% and then increased for
the doping of 3, 4, and 6 mol%.
Particle size and morphology of the selective photocatalysts
were investigated using SEM and TEM (Fig. 2). SEM images
showed surface and grain morphology of ZnO powders while
10 15 20 25 30 35 40 45 50 55 60 65 70 75
TEM images showed the size of particles and the manner of
particle distribution in the samples. The TEM images clearly 2θ (degree)
showed that the particles were homogeneous and their size was Fig. 1. XRD patterns of (a) ZnO (b) 1 mol% Hf-ZnO (c) 2 mol% Hf-ZnO (d)
approximately the same as that calculated by the Scherrer 3 mol% Hf-ZnO (e) 4 mol% Hf-ZnO and (f) 6 mol% Hf-ZnO.

Table 1
Values of crystallite size, and lattice parameters “a”, “c”, “c/a” ratio for ZnO, 1 mol% Hf-ZnO, 2 mol% Hf-ZnO, 3 mol% Hf-ZnO, 4 mol% Hf-ZnO and 6 mol%
Hf-ZnO photocatalysts.

Samples Crystallite size (nm) Lattice parameter “a” [Å] Lattice parameter Ratio “c/a”
“c” [Å]

ZnO 17 3.22 5.18 1.60

1 mol% Hf-ZnO 15 3.23 5.23 1.62
2 mol% Hf-ZnO 14 3.24 5.26 1.62
3 mol% Hf-ZnO 15 3.25 5.27 1.62
4 mol% Hf-ZnO 15 3.25 5.28 1.62
6 mol% Hf-ZnO 16 3.27 5.29 1.62

Please cite this article as: M. Ahmad, et al., Structural, optical and photocatalytic properties of hafnium doped zinc oxide nanophotocatalyst, Ceramics
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Fig. 2. SEM images of (a) ZnO (b) 2 mol% Hf-ZnO at lower magnification (c) ZnO (d) 2 mol% Hf-ZnO at higher magnification and TEM images of (c) ZnO and
(d) 2 mol% Hf-ZnO photocatalysts.

Table 2
X-ray density, volume and band gap of ZnO, 1 mol% Hf-ZnO, 2 mol% Hf-ZnO, 3 mol% Hf-ZnO, 4 mol% Hf-ZnO and 6 mol% Hf-ZnO photocatalysts.

Samples X-ray density “Dx” [g/cm3] Volume [(Å)3] Band gap (eV)

ZnO 5.82 46.51 3.26

1 mol% Hf-ZnO 5.68 47.25 3.24
2 mol% Hf-ZnO 5.64 47.22 3.23
3 mol% Hf-ZnO 5.62 48.29 3.21
4 mol% Hf-ZnO 5.60 48.30 3.19
6 mol% Hf-ZnO 5.57 48.98 3.17

For the FT-IR analysis, KBr pellets were prepared for pure and to identify the adsorbed impurities at the surface of ZnO
and hafnium doped ZnO photocatalysts. The IR measurements photocatalyst. Fig. 3 exhibited the FTIR spectra of undoped
were carried out in the range of 4000–400 cm−1 in order to ZnO and 2 mol% Hf-ZnO samples. In IR spectra of undoped
verify the preparation of nanocrystalline ZnO photocatalyst ZnO and 2 mol% Hf-ZnO samples, the strong peaks at 3450,

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1642 cm−1 originated from surface adsorbed water and hydro- 2 mol% Hf-ZnO photocatalyst. The survey spectrum (Fig. 4)
xyl groups. The weak absorption bands located at  2920, indicated that the sample was composed of Zn, O and Hf, and
2350, 1429 and 1051 cm−1 were related to C–H mode, no peaks of other elements were observed. The two peaks
atmospheric CO2, OH bending vibration of C–OH and C–O detected at the energy positions of 1010–1050 eV correspond to
stretching vibration respectively. In both IR spectra, the the Zn 2p3/2 and Zn 2p1/2 orbitals. The high-resolution scan of
significant absorption band in the region 430–450 cm−1 was
assigned to the characteristic absorption band of ZnO.
X-ray photoelectron spectroscopy (XPS) measurements were
carried out to determine the chemical states of elements in the

6mol% Hf-ZnO

Absorbance
Transmittance (a.u.)

4mol% Hf-ZnO
(b) 3mol% Hf-ZnO
2mol% Hf-ZnO
1mol% Hf-ZnO
1051 1429 (a) ZnO
2350
1642
2920

450 3450

500 1000 1500 2000 2500 3000 3500 4000 300 350 400 450 500 550 600
Wavenumber (cm-1) Wavelength (nm)
Fig. 3. FTIR spectra of (a) ZnO and and (b) 2 mol% Hf-ZnO photocatalysts. Fig. 5. UV–vis absorption spectra of ZnO and Hf-doped ZnO photocatalysts.

1022.8 eV
Zn 2p3/2

Zn 2p
Zn 2p1/2
Zn LMM
O KLL

O KLL

1045.9 eV
Intensity (a.u.)

Intensity (a.u.)
O 1s
Zn LMM

Zn KLL
Zn LMM
C 1s

Hf 4F
Zn 3p
Zn 3s
Zn 3d

0 200 400 600 800 1000 1200 1010 1020 1030 1040 1050 1060
Binding energy (eV) Binding energy (eV)

532.8 eV O 1s Hf 4f
16.0 eV

18.0 eV
Intensity (a.u.)
Intensity (a.u.)

Gaussian fitting

Experimental data

525 528 531 534 537 540 14 15 16 17 18 19

Binding energy (eV) Binding energy (eV)

Fig. 4. XPS survey spectra and high resolution spectra of Zn 2p, O 1s and Hf 4f region for 2 mol% Hf-ZnO photocatalyst.

Please cite this article as: M. Ahmad, et al., Structural, optical and photocatalytic properties of hafnium doped zinc oxide nanophotocatalyst, Ceramics
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6 M. Ahmad et al. / Ceramics International ] (]]]]) ]]]–]]]

ZnO
6mol% Hf-ZnO
4mol% Hf-ZnO
3mol% Hf-ZnO
1mol% Hf-ZnO

PL Intensity (a.u.)
2mol% Hf-ZnO

375 400 425 450 475 500 525 550 575 600
Wavelength (nm)

Fig. 7. Photoluminescence spectra of ZnO and Hf-doped ZnO photocatalysts.

Fig. 6. Plots of (αhυ)2 versus photon energy (hυ) of ZnO and Hf-doped ZnO
photocatalysts.
399 nm is attributed to the near band-edge emission of ZnO.
Other peaks observed at 422 nm can be ascribed to divalent zinc
Zn 2p showed the exact peak location of Zn 2p3/2 at 1022.8 eV vacancy and 469 nm to intrinsic defects such as interstitial zinc
and of Zn 2p1/2 at 1045.9 eV [27]. In O 1s core level spectrum, and oxygen [32,33]. The small peak observed at 443 nm
the single peak observed at 532.8 eV can be attributed to corresponds to the transition of electrons from shallow donor
chemisorbed oxygen caused by the surface hydroxyl [9]. levels of oxygen vacancies to the valence band and the peak at
Finally, in Hf 4f core level spectrum, two peaks at binding 463 nm is assigned to electronic transition from shallow donor
energies 16.0 eV and 18.0 eV confirmed the presence of Hf in levels of zinc interstitial to the valence band [34]. All these peaks
the doped sample [28]. were observed for undoped as well as for Hf-doped ZnO. It is
UV–vis spectroscopy study was conducted on all the photo- seen that the positions of the peaks are similar, while their
catalysts to observe the changes in optical properties as a intensities are quite different. It is known that the PL emission is a
function of material composition. The UV–vis diffuse absorp- result of the recombination of excited electrons and holes, the
tion spectra of undoped and doped ZnO photocatalysts with lower PL intensity may indicate the lower recombination rate of
different hafnium contents are shown in Fig. 5. The band edge electrons and holes under light irradiation. It is renowned that the
for the undoped ZnO sample appeared at 378 nm while the band photoluminescence of ZnO is sensitive to the defects in the
edges of the Hf-doped ZnO samples were shifted toward longer material [35,36]. The PL intensity of ZnO was highest among all
wavelength regions along with stronger absorption intensities the samples, demonstrating the higher recombination of electrons
for the higher hafnium concentration samples. Typically, the and holes. The emission intensities were significantly weakened
light absorption edge extended to 388, 391, 396, 401 and with hafnium doping, which implies that the recombination of
408 nm as hafnium was incorporated into ZnO matrix with 1, 2, charge carriers was effectively suppressed. Among all the
3, 4 and 6 mol% respectively. The absorbance coefficient (α) samples the lowest intensity was observed for the 2 mol%
was calculated from the raw absorbance data to obtain the Hf-ZnO sample, suggesting that the charge carriers were sepa-
optical band gap (Eg). The band gap values were thus rated more effectively due to the effect of hafnium doping.
determined by the extrapolation of the linear portion of the However, 3, 4 and 6 mol% Hf-ZnO exhibited significant
(αhν)2 curve versus the photon energy hν (Table 2). With increases in PL emission intensities compared to that of 2 mol
increasing the hafnium content from 0.0 to 6.0 mol%, the band % Hf-ZnO. This may be due to the fact that the excess
gap energies decreased continuously from 3.26 to 3.17 eV introduction of Hf4+ in to ZnO lattice also acts as the
(Fig. 6). The slight decrease of band gap was possibly due to recombination center, which is detrimental to the photocatalytic
the doping which might have caused band edge bending [29]. activity.
The red shift of the band gap edge with incorporation of Hf into The photocatalytic degradation of highly concentrated MB
ZnO has also been reported [30] and interpreted to be due to the aqueous solution (250 mg/l) using very small amount of pure
sp–d exchange interactions between the band electrons and the and doped ZnO photocatalysts (25 mg/100 ml) under sunlight
localized d electrons of the Hf4+ ions substituting Zn ions [31]. irradiation are shown in Fig. 8. Phototcatalytic degradation of
Fig. 7 shows the photoluminscence emission spectra of ZnO MB follows roughly the pseudo-first-order reaction kinetics for
and Hf-doped ZnO photocatalysts. Photoluminescence spectra low dye concentrations [37]:
exhibited five main emission peaks at about 399, 422, 443, 453
and 469 nm with excitation at 325 nm. A broad peak around lnðC o =CÞ ¼ k app t

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Adsorption Photocatalysis (ro ¼ 3.75 min−1) was found to be higher than that of undoped
1.0 ZnO (ro ¼ 1.53 min−1) and commercial ZnO (ro ¼ 1.47 min−1).
It was found that pure ZnO had little ability to degrade MB
0.9 under sunlight irradiation and all the Hf-doped ZnO photo-
catalysts exhibited higher photocatalytic activity than that of
0.8 pure ZnO under sunlight. The order of photocatalytic activity
of Hf-doped ZnO after 120 min was as follows: 2 mol% Hf-
0.7 ZnO 4 1 mol% Hf-ZnO 4 3 mol% Hf-ZnO 4 4 mol% Hf-
ZnO 4 6 mol% Hf-ZnO 4ZnO 4 ZnO commercial, which
0.6 advocated that Hf doping has enhanced the photocatalytic
C/Co

activity of ZnO. 2 mol% Hf-doped ZnO photocatalyst showed

0.5 the highest photocatalytic degradation efficiency; with the MB
concentration reduction by 85% in 120 min (Fig. 8). Firstly,
0.4 the enhanced photocatalytic activity of hafnium doped ZnO
MB catalyst might be attributed to extended light absorption in the
0.3 ZnO (Com) visible-light region due to Hf doping. Secondly, the presence
ZnO of Hf into ZnO favors the transfer of photogenerated electrons
1 mol % Hf-ZnO to Hf and then Hf acts as a reservoir for these electrons,
0.2
2 mol % Hf-ZnO
thereby promoting an interfacial charge-transfer process and
3 mol % Hf-ZnO
0.1 4 mol % Hf-ZnO
hence the rate of degradation of MB was significantly
6 mol % Hf-ZnO increased. This can be attributed to suppressed recombination
0.0 of photogenerated electron–hole pairs due to presence of
0 30 60 90 120 hafnium in the ZnO photocatalyst.
Irradiation time (min)
Fig. 8. Time profiles of C/Co for various photocatalysts under sunlight 4. Conclusions
irradiation.
Pure ZnO and Hafnium doped ZnO photocatalysts were
synthesized using a facile sol–gel method. It was found that all
the doped samples had stronger light absorption in visible light
Degradation Rate (100 mg/L.min)

range when compared with the pure ZnO. The doped ZnO
4
photocatalysts showed enhanced photocatalytic activity than
3.5
pure ZnO under sunlight irradiation for MB degradation. The
3
2 mol% Hf-doped ZnO photocatalyst demonstrated the highest
2.5
photocatalytic degradation efficiency which was about 85% in
2 120 min. All these results indicated that doped ZnO is a
1.5 potential candidate for the practical application in photocata-
1 lytic degradation of organic contaminant.
0.5
0
1 2 3 4 5 6 7 8 Acknowledgements
Photocatalyst
The author M. Ahmad thanks the Higher Education Com-
Fig. 9. The initial degradation rate ro (mg l−1 min−1) of photocatalysts in
methylene blue aqueous solution; (1) MB (2) ZnO commercial (3) ZnO (4)
mission of Pakistan for financial support and also gratefully
1 mol% Hf-ZnO (5) 2 mol% Hf-ZnO, (6) 3 mol% Hf-ZnO (7) 4 mol% Hf-ZnO acknowledged the support of State Key Laboratory of Silicon
and (8) 6 mol% Hf-ZnO photocatalysts under sunlight irradiation. Materials, Department of Materials Science and Engineering,
Zhejiang University, China.

where kapp is the apparent constant, used as the basic kinetic

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International (2013), http://dx.doi.org/10.1016/j.ceramint.2013.04.051
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Please cite this article as: M. Ahmad, et al., Structural, optical and photocatalytic properties of hafnium doped zinc oxide nanophotocatalyst, Ceramics
International (2013), http://dx.doi.org/10.1016/j.ceramint.2013.04.051