J Mater Sci (2012) 47:2155–2161
DOI 10.1007/s10853-011-6016-4
Visible light-activated cadmium-doped ZnO nanostructured
photocatalyst for the treatment of methylene blue dye
Dongfang Zhang • Fanbin Zeng
Received: 25 May 2011 / Accepted: 30 September 2011 / Published online: 19 October 2011
 Springer Science+Business Media, LLC 2011
Abstract An attempt was made to prepare Cd-doped
ZnO photocatalyst for visible light assisted degradation of
a textile dye (methylene blue, MB) in aqueous solutions by
a traditional sol–gel process. The as-prepared nanoparticles
were characterized by X-ray diffraction, UV–vis diffuse
reflectance spectroscopy, and photoluminescence spectra
techniques. The results showed that the Cd-doped ZnO
possess the single-phase hexagonal wurtzite structure. The
photocatalytic activity of the nanoparticles under visible
light was investigated by measuring the photodegradation
of MB in aqueous dispersion. The effects of key operation
parameters such as initial dye concentration, catalyst
loading as well as initial pH value on the decoloriza-
tion extents were investigated. The results indicate that
the decolorization of the organic molecule followed a
pseudo-first-order kinetics according to the Langmuir–
Hinshelwood model. Under the optimum operation condi-
tions, approximately 85.0% dye removal was achieved
within 3.5 h.
Introduction
Textile industries produce large volume of colored dye
effluents. Among the different types of dyes used in textile
industries, 65–75% belongs to azo compounds. It is esti-
mated that approximately 12% of dyes are lost annually
during manufacturing and the processing operations. The
discharge of these colored dyes in the ecosystem without
treatment creates severe environmental pollution problems
D. Zhang (&)  F. Zeng
College of Science, Huazhong Agricultural University,
Wuhan 430070, People’s Republic of China
e-mail: zjzappletree@163.com
by releasing toxic and potential carcinogenic substances
into the aqueous phase and damaging to the aesthetic nat-
ure of the environment [1]. Therefore, various chemical
and physical processes such as precipitation, adsorption by
activated carbon, air stripping, coagulation, reverse osmo-
sis, and membrane ultrafiltration have been employed for
color removal from textile effluents [2–5]. Nonetheless, all
these treatments mentioned above have a major flaw of
simple transferring the pollutants from one phase to
another rather than destroying them, which consequently
leads to secondary pollution. Hence, it is necessary to
develop treatment methods that are more effective in
destructing dyes from wastewater [6].
Recently, there has been great interest in the utilization
of advanced oxidation processes (AOPs) for the complete
mineralization of dyes. AOPs are based on generation of
reactive species such as hydroxyl radicals that oxidizes a
broad range of organic pollutants rapidly and nonselec-
tively [7]. AOPs include photocatalysis systems such as
combination of semiconductors and light or oxidants.
Heterogeneous photocatalysis emerging as an important
destructive method for eliminating most of the organic
pollutants including reactive dyes during water treatment
has attracted considerable attention [8]. On this back-
ground, semiconductor photocatalysts have been widely
employed in the field of environmental protection owing to
its unique advantages in the decomposition of organic
pollutants into water, CO2, and mineral acids. The metal
oxide, ZnO, a wideband-gap semiconductor with a large
exciton binding energy of 60 meV at room temperature, is
rationally expected to be a promising candidate for heter-
ogeneous catalysis under solar light and optoelectronics
due to its long-term stability and biocompatibility [9, 10].
However, a vital problem, i.e., the large band gap energy
(3.3 eV), hampers its widespread practical applications.
123
2156
Thus, the photocatalytic activity of ZnO requires to be
further improved.
Up to now, many efforts have been paid to improve the
photocatalytic activity of semiconductor metal oxide, such
as semiconductor combination, transition metals doping,
and nobel metal deposition [11–13]. Among these tech-
niques, the modification transition metal has been proved
as an effective technique to improve the separation of
photo-induced electron–hole pairs and extend its photo-
response to visible region by modifying its surface struc-
ture, surface properties, and composition and so as to
improve its photocatalytic activity in visible/solar light.
Herein, our studies are focused on improving photo-
catalytic efficiencies of zinc oxide by cadmium ions for the
purpose of decomposing methylene blue (MB) dye. The
application of this type of metal promoter for enhancing the
efficiency of photocatalyst will help to solve environmental
problems by degradation of organic dye compounds. In
addition, the activity of cadmium incorporated inside
ZnO will also be examined. The textural, photophysical
and photochemical properties, and the crystalline structure
of the materials were studied using X-ray powder diffrac-
tion (XRD), UV–Vis diffuse reflectance spectroscopy
(DRS), and photoluminescence (PL) spectra techniques.
The reason for choosing MB (a blue cationic thiazine dye)
is due to its wider applications that include coloring paper,
temporary hair colorant, dyeing cottons, wools and coating
for paper stock and thus acute exposure to MB will cause
health problems such as increased heart rate, vomiting,
shock, Heinz body formation, cyanosis, and tissue necrosis
in humans [14].
Experimental section
Catalyst preparation
All the reagents were purchased from Shanghai Chemicals
Co. Ltd. with analytic grade and used as received without
further purification in our experiments. The typical prepa-
ration process of metal-ion-doped ZnO colloidal nanopar-
ticles was described in detail as follows: in the 300 mL
conical flask, zinc acetate dihydrate (Zn(Ac)22H2O,
0.1 mol/L), and lithium hydroxide monohydrate (Li(OH)
H2O, 0.14 mol/L) were dissolved in 300 mL ethanol sol-
vents under vigorous stirring at room temperature. To get a
transparent solution, the mixtures were dispersed by
ultrasonication for 20 min. After that, the conical flask was
put into the water tank with a constant temperature 70 C
and 6 mL distilled water was added into the conical flask.
To fabricate ZnO colloidal nanoparticles, the as-prepared
solution was agitated by a magnetic bead for 40 min at
70 C. During this process, the transparent solution became
123
J Mater Sci (2012) 47:2155–2161
milky white slowly, and then a calculated amount of
cadmium(II) acetate (0.08 g, 0.36 mmol) was added to the
above solution to get the dopant concentration in the value
of 1.2 at.%. Afterward, the conical flask was taken out
from the water bath and cooled to the room temperature.
There were some precipitates formed in the bottom of
conical flask. These precipitates were collected by centri-
fuge and dried at 70 C until the residual solvents were
evaporated. Finally, the obtained powders were calcinated
at 500 C for 2 h and used as photocatalysts. For com-
parison purposes, sample of pure ZnO nanoparticles was
also prepared by similar procedures.
Characterization of the catalyst
X-ray powder diffraction (XRD) data were recorded at
room temperature with an X-ray diffractometer (XRD-
6000, Shimadzu Corporation) using Cu Ka irradiation
(k = 0.15408 nm), operated at 40 kV and 100 mA, which
was used to establish the crystallographic information such
as structure properties, chemical composition, and phases.
The percentage of UV–Vis reflectance was measured by
DRS for the powder form of the catalysts using a scanning
UV–Vis–NIR spectrophotometer (Varian Cary 500) in
the region of 200–800 nm. The spectrophotometer was
equipped with an integrating sphere assembly and poly-
tetrafluoroethylene was used as a reflectance material. The
PL emission spectra of the samples were measured with a
Cary Eclipse spectrophotometer using the 300 nm line of a
Xe lamp as excitation source at room temperature.
Photocatalytic degradation procedure
The as-prepared materials were employed as photocatalysts
in the degradation aqueous MB, a model dye often inves-
tigated as representative of the category of azocompounds.
Artificial light photocatalytic activity tests were conducted
in a quartz photoreactor with a cylindrical configuration.
A mixture of 1000 mL of aqueous MB (10 mg/L = 3.0 9
10-5 M) and 25 mg of Cd-doped ZnO powder was stirred
for 30 min in a quartz beaker in the dark (without light
exposure) to establish an equilibrium for the adsorption of
MB dye and dissolved oxygen on the surface of nano-
crystalline ZnO. Photocatalytic reactions were carried out
in an opened reactor under visible light irradiation using a
500 W halogen tungsten lamp equipped with a 400 nm
cutoff glass filter. The distance between the light and the
suspension was 10 cm. During the irradiation experiments,
5 mL aliquots were withdrawn from the suspension at
given intervals and immediately centrifuged at 3000 r/min
for 10 min to remove solids. The concentration of MB after
illumination was monitored at 668 nm using a Shimadzu
2101 spectrophotometer. The decolorization efficiency was
J Mater Sci (2012) 47:2155–2161
determined by the formula: decolorization = (C0 - C)/C0,
where C0 and C represent the initial and residual concen-
trations, respectively, of MB dye.
Results and discussion
XRD analysis
Figure 1 shows the XRD patterns of the pure and Cd-doped
ZnO samples. The XRD analysis reveals that samples
exhibit single-phase hexagonal wurtzite structure, which is
identified by comparing the spectra with the JCPDS file #
75-0576. The average crystallite size of nano-sized ZnO
was estimated from its XRD patterns using the Scherrer’s
equation, which relates the crystallite size to the broaden-
ing of the peak. The calculated crystallite size is about
20 nm. It was observed that cadmium ion doping appre-
ciably influences the ZnO crystallinity. The intensity of the
diffraction peak increases and Cd-doped ZnO samples
showed better crystallinity when compared to undoped
ZnO. The differences between doped and undoped ZnO
could also arise from the fact that sol–gel processing is
very sensitive to all kind of additives, i.e., the addition of
the cadmium-containing species could change the mor-
phology and thus the properties of the obtained ZnO par-
ticles. It is reported that in the case of metal oxides there is
critical value of dispersion capacity, at values lower than
which the oxide might become highly dispersed on the
support without the formation of a separate crystalline
phase. Therefore, the absence of any impurity-related
peaks or characteristic peaks corresponding to Cd species
indicate that transition metal ion was highly dispersed on
: Wurtzite ZnO (NO: 75-0576)
Intensity (a. u.)
Cd-doped ZnO
Pure ZnO
36 48 60 72
Cu Kα 2θ (degree)
Fig. 1 XRD patterns of the as-prepared samples: pure ZnO and
1.2 at.% Cd-doped ZnO
2157
the surface of ZnO catalyst or it was successfully doped
into the ZnO structure and the metal ion doping is below
the dispersion capacity, e.g., the amount of Cd is quite low
and therefore difficult to see by XRD, or Cd species may
precipitate separately in an amorphous fashion, etc.
UV–Vis diffuse reflectance spectra
Figure 2 shows UV–Vis diffuse reflectance spectra of pure
ZnO and Cd-doped ZnO with different V contents. It is
known that the band gap of n-ZnO is about 3.2 eV, it can
be excited by photons with wavelengths below 387 nm.
From Fig. 2, it can be seen that the curve of pure ZnO
powder has no clear absorption in the visible range,
because its absorption edge near 390 nm. However, the
absorption wavelength range of Cd-doped ZnO catalysts
red shift about 30–70 nm, compared to the pure ZnO cat-
alyst, and their absorption intensity also increases. Because
of the absorption wavelength range red shift of about
30–70 nm and absorption intensity increases, the formation
rate of electron–hole pairs on the catalyst surface will
increase greatly, resulting in the catalyst exhibiting higher
photocatalytic efficiency. The reason for the absorption
wavelength range red shift of the Cd-doped ZnO could
probably be attributed to the formation of defect energy
level between the valence and the conduction bands in the
ZnO band structure.
Fluorescence emission spectra
Photocatalysts generate electrons and holes after being
activated by light, and recombination of some electrons
and holes can release energy in the form of fluorescence
Absorbance (a. u.)
Pure ZnO
Cd-doped ZnO
312 364 416 468 520 572
Wavelength (nm)
Fig. 2 UV–Vis diffuse reflectance spectrum of pure and Cd-doped
ZnO nanoparticles
123
2158
emission [15]. Lower fluorescence emission intensity
implies lower electron–hole recombination rate. Using an
ultraviolet light with a 300 nm wavelength as the excitation
source, the fluorescence emission spectra of as-prepared
ZnO nanoparticles are shown in Fig. 3. It can be seen that
pure ZnO powder has emission peaks at around 390 nm
(3.2 eV), showing direct band gap characteristics. It is clear
that the relative intensity of the emission spectra of Cd-
doped ZnO is the lowest, suggesting a low recombination
rate of electrons and holes. Pure ZnO has the greatest
relative intensity of emission spectra, which means that
electrons and holes in pure ZnO are easy to recombine.
Therefore, doping ZnO with cadmium ion is helpful to
inhibit the recombination of electrons and holes and to
improve the photocatalytic efficiency.
Photocatalytic efficiency on the degradation of MB
In order to evaluate the effect of Cd2?-doping on the
photocatalytic properties of the as-prepared photocatalysts,
the decomposition of MB aqueous solution under visible
light illumination was carried out and compared with that
of the pure ZnO sample (as shown in Fig. 4). It is widely
accepted that, upon excitation, a conduction-band electron
and a valence-band hole separate, and hole initiates an
oxidative reaction, while the electron initiates a reductive
reaction. Organic compounds such as MB are believed to
be destroyed via direct oxidation by the trapped holes or
being attacked by hydroxyl groups. As displayed in Fig. 4,
the photocatalytic activity of ZnO catalyst can be enhanced
by doping a suitable content of cadmium when the Cd(II)
content is 1.2 at.%. Overall, a large amount of MB can
be decomposed by Cd-doped catalysts under visible
Emission intensity (a. u.)
Pure ZnO
Cd-doped ZnO
315 350 385 420 455 490 525
Wavelength (nm)
Fig. 3 Fluorescence spectra of the pure and Cd-doped ZnO nano-
particles with the excitation wavelength of 300 nm
123
J Mater Sci (2012) 47:2155–2161
105
Dark
90
75
MB, C /C0*100
Light on
60 Pure ZnO
Cd-doped ZnO
45
30
-30 0 30 60 90 120 150 180
Irradiation time / min
Fig. 4 The photocatalytic activity of the as-prepared ZnO samples by
evaluating the residual concentration ratio of MB solution under
visible light illumination
irradiation. The Cd-doped sample exhibits a good visible-
light-driven activity and nearly 55% MB is degraded in
200 min, which means that Cd2?-doping enhance the
photocatalytic activity of ZnO remarkably. In addition, the
influence of electronic configuration of the dopant on
photocatalytic activity cannot be ignored also. Cadmium in
?2 oxidation state has a stable fulfilled electronic config-
uration of 4d10. If Cd2? is assumed to trap electron, its
stable completely empty electronic configuration is dis-
tributed. The trapped electron may thus be readily trans-
ferred to oxygen molecule to form a superoxide radical
anion, while Cd? can also trap valence band hole to
restrain its stable electronic configuration. Alternatively if
Cd2? ion is assumed to behave as a hole trap, its stable
fulfilled electronic configuration is distributed again. Thus,
the trapped hole can be easily transferred to hydroxyl anion
adsorbed on the surface forming hydroxyl radical or it can
also be transferred to adsorbed dye molecule to form a dye
radical. In summary, doping an appropriate amount of
cadmium can effectively enhance the separation rates of
photo-induced charge carriers of ZnO, and this is respon-
sible for the enhancement of the photocatalytic efficiency.
Effect of catalyst loading
The amount of catalyst loading is one of the important
parameters for the degradation studies from economical
point of view. For the sake of avoiding the use of excess
catalyst it is needed to determine the optimum loading for
560
efficient removal of MB dye. The effect of catalyst loading
on the removal efficiency of the dye was explored and the
results are shown in Fig. 5. As can be seen, when the con-
centration of the catalyst increases from 0.02 to 0.06 g/L,
J Mater Sci (2012) 47:2155–2161 2159

100 100

90
90
80
Decolorization ratio (%)

80

Degradation ratio (%)

70
70
60 30 mg/L
10 mg/L
50 60
20 mg/L
40 0.02 g/L 50
0.04 g/L
30
0.06 g/L 40
20
30
10

0 20
0 30 60 90 120 150 180 210 0 35 70 105 140 175
Reaction time / min
Irradiation time / min
Fig. 6 Effect of various dye concentrations on the degradation ratio
Fig. 5 Effect of catalyst loading on the decolorization rate of reactive
of MB. Experimental conditions: [catalyst] = 0.04 g/L and pH 6.0
MB dye. Experimental conditions: [MB] = 10 mg/L and pH 6.0

the removal ratio of dye increases from 61 to 70% after
200 min reaction, which is attributed to the increase in the
number of active sites and more active sites will provide
more chances to receive both light and guest molecules.
The reasons for decrease in color removal at high catalyst
concentration may lead to the aggregation of catalyst par-
ticles, which consequently causes a decrease in the number
of surface active sites and reduces the catalytic efficiency.
Moreover, high catalyst concentration increases in opacity
of the suspension and light scattering, and thus results in
decrease in the passage of irradiation light through the
catalyst. In this study, the optimum amount of catalyst
loading is determined to be 0.04 g/L for the degradation of
MB dye. Therefore, 0.04 g/L was used as the catalyst
dosage for the photodegradation reactions.
Effect of initial concentration of MB
The effect of initial dye concentration on the photocatalytic
efficiency has been explored by varying the initial dye
concentration from 10 to 30 mg/L with catalyst loading of
0.04 g/L, as is shown in Fig. 6. It can be seen that the
degradation ratio decreases with the increase in the dye
concentration. The possible explanation for this phenom-
enon is that the amount of dye adsorbed on the catalyst
surface increases with the increase of dye concentration,
but the intensity of light and irradiation time are constant,
so the path length of incident photons entering the solution
decreases and consequently the OH• radicals formed on the
surface of ZnO decreases and thus results in the decrease of
removal efficiency.
In most of the photocatalytic studies, mechanistic stud-
ies over the irradiated ZnO surface usually only involve a
single constituent model organic compound and the
influence of the initial concentration of the solution on the
photodegradation rate of the dye molecules can be descri-
bed by pseudo-first-order kinetic, which is rationalized in
terms of the Langmuit–Hinshelwood model, modified to
accommodate reactions occurring at a solid–liquid inter-
face. As the L–H model is a surface-area dependent, the
rate dependence on substrate concentration is given by the
following equation:
dC kr KC
r¼ ¼ kr h ¼ ð1Þ
dt 1 þ KC
where the photocatalytic reaction rate (r) is proportional to
the fraction of surface coverage by the organic substrate
(h), kr is the reaction rate constant, C is the concentration of
organic species, and K is the Langmuir absorption constant.
While the initial concentration of organic species is low (in
mM) in this study, an apparent first-order rate constant
(Eq. 2) could be expressed where k0 (min-1) = krK:
dC
r¼ ¼ kr KC ¼ k0 C ð2Þ
dt
Rearranging and integration of the above equation yields
the typical pseudo-first-order model as in Eq. 3:
C ¼ C0 ek0 t ð3Þ
The apparent rate constant (k0) has been chosen as the
basic kinetic parameter for the different photocatalysts,
since it enables one to determine a photocatalytic activity
independent of the previous adsorption period in the dark
and the concentration of MB remaining in the solution.
Therefore, the apparent rate constant will mainly serve as a
comparison and description for the photocatalytic reaction
rate in the reactor system. The apparent first-order kinetic
(Eq. 3) is used to fit experimental data (Fig. 6) as follows:

123
2160
1.6
1.4
1.2
Linear fitting
1.0
Ln (C0 / C)
0.8
0.6
0.4
0.2
0.0
0 35 70 105 140 175
Reaction time / min
Fig. 7 Representation of Langmuir–Hinshelwood equation. Experi-
mental conditions: [catalyst] = 0.04 g/L, [MB] = 10 mg/L and pH
6.0
lnðC0 =CÞ ¼ kr Kt ¼ k0 t
where C is the concentration of MB remaining in the
solution at irradiation time of t, and C0 is the initial con-
centration at t = 0. The variations in ln(C0/C) as a function
of irradiation time are given in Fig. 7 and the calculated k0
data according from the straight line were 0.008 min-1.
Effect of initial pH
An important parameter in the photocatalytic reaction
occurring on the particulate surface is the pH of the solu-
tion, since it determines the surface charge properties of the
catalyst and size of aggregates it forms. Therefore, the
influence of pH on the decolorization of MB dye was
investigated with pH ranging from 2.0 to 12.0. The result
showed that the best efficiency for the decolorization of the
dye is in weak acidic environment (i.e., pH 5.0). It is
obvious that pH significantly influences the efficiency of
the degradation process which correlates with the genera-
tion of positive holes, the surface coverage and the
absorption behavior. According to the DLVO theory, the
surface charge property of nanoparticles depends sensi-
tively on its iso-electronic point (IEP, defined as the pH at
which the net proton charge of the particles equals zero).
When pH is lower or higher than its IEP, the surface charge
of the particles will be positive or negative, respectively.
The farther the pH from the IEP, the better the particles
will be dispersed because the electrostatic interactions
between the semiconductor’s surface, which lead to a
higher surface coverage, otherwise the nanoparticles will
tend to aggregate. For synthesized ZnO nanoparticles,
123
J Mater Sci (2012) 47:2155–2161
qualitative IEP can be obtained to be *6.0 by prediction
[16]. When the pH is lower than its IEP, the surface of the
catalyst is positively charged. A positively charged surface
favors the generation of positive holes which are consid-
ered to be the active center of the reaction; hence, the
excellent generation of holes in turn leads to an effective
removal of MB dye. Nonetheless, MB dye is positively
charged in aqueous medium. A much lower pH than its IEP
will result in the surface charge repulsion between the
catalyst surface and the MB molecules, which would make
the MB molecules access to the catalyst a diffusion-con-
trolled process hence smaller removal efficiency. When the
pH is much closer to the IEP, the particle aggregate in
serious due to the lack of repulsion force, which results in
the smallest surface coverage and hence the lowest deg-
radation efficiency. When the pH is higher than its IEP,
although the negative surface charge will hinder the crea-
tion of holes, the MB molecules can be predominantly
located at the adsorbent sites generating a highly concen-
trated environment around the catalyst and relatively high
degradation efficiency. Clearly, with a pH closer to the IEP
ð4Þ of the catalyst, the surface coverage will be the dominant
factor in the degradation process. With the pH farther from
the IEP, the degradation efficiency depends on the com-
petition between the adsorption capacity of the target
molecules and the creation of positive holes.
Conclusions
Nanoparticles of ZnO photocatalyst were prepared by
modified sol–gel method and they were doped with
transition metal ion Cd2?. The photocatalytic activities of
these catalysts were tested under visible light for MB
degradation. It was found that Cd-doped ZnO photocat-
alyst showed superior performance than the pure ZnO,
which probably due to the completely empty stable
electronic configuration (d10) of Cd2? which shallowly
traps the charge carriers and detraps the same to surface
adsorbed species thereby accelerating the interfacial
charge transfer process. Moreover, the Cd-doped ZnO
nanoparticles showed a stronger absorption of visible
light and lower intensity of PL emission than the pure
ZnO. For degradation 10 mg/L of reactive MB dye (as
representative concentration in wastewater), the most
suitable operation parameters are: catalyst concentration
0.04 g/L, pH 5.0. Under the above conditions, approxi-
mately 80% color removal is achieved within 200 min.
The results also indicate that the Cd-doped ZnO powder
is a very interesting and a promising photocatalytic
material and has good potential for application to water
purification.
J Mater Sci (2012) 47:2155–2161 2161

References 8. Fox MA, Dulay MT (1993) Chem Rev 93:341

9. Srikant V, Clarke DR (1998) J Appl Phys 83:5447
1. Neppolian B, Choi HC, Sakthivel S, Arabindoo B, Murugesan V 10. Polarz S, Orlov AV, Schuth F, Lu AH (2007) Chem Eur J 13:592
(2002) J Hazard Mater 89:303 11. Henglein A (1989) Chem Rev 89:1861
2. Gupta GS, Prasad G, Singh VN (1990) Water Res 24:45 12. Ekambaram S, Likubo Y, Kudo A (2007) J Alloys Compd
3. Rozzi A, Antonelli M, Arcari M (1999) Water Sci Technol 433:237
40:409 13. Zhou G, Deng J (2007) Mater Sci Semicond Process 10:90
4. Xu L, Li W, Lu S, Wang Z, Zhu Q, Ling Y (2002) Desalination 14. Karakitsou KE, Verykios XE (1993) J Phys Chem 97:1184
149:199 15. Li FB, Li XZ (2002) Appl Catal A 228:15
5. Mo J, Hwang JE, Jegal J, Kim J (2007) Dyes Pigments 72:240 16. Pan R, Liew K, Xu L, Gao Y, Zhou J, Zhou H (2007) Colloid
6. Zhang DF, Zeng FB (2010) Appl Surf Sci 257:867 Surf A 305:17
7. Saien J, Soleymani AR (2007) J Hazard Mater 144:506

123