J Mater Sci: Mater Electron (2017) 28:5941–5952
DOI 10.1007/s10854-016-6268-5
New and highly efficient Ag doped ZnO visible nano photocatalyst
for removing of methylene blue
Roya Mohammadzadeh Kakhki1 · Reza Tayebee2,3,4 · Fatemeh Ahsani1 
Received: 1 November 2016 / Accepted: 19 December 2016 / Published online: 20 January 2017
© Springer Science+Business Media New York 2017
Abstract  Due to excellent properties, recently ZnO
nanomaterials are used as very efficient photocatalysts for
the photocatalytic degradation of toxic organic dyes and
chemicals under various light radiations. In this article we
used a new and simple method for synthesis of high effi-
cient ­AgxZn1−xO (x = 0, 0.3, 0.5, 1, 2, 4, 6) nano photocata-
lyst in visible region. The process is simple, cost-effective
and can be easily scaled-up. It was shown that the catalytic
behavior of ZnO that is synthesized with this method has
good efficiency about 63% for degradation of methylene
blue in visible-light illumination.With doping of a little
(0.5%) Ag the photocatalytic activity in the visible-light
range is notably improved with a maximum effeciency
of 98% degradation of methylene blue. In this work Ag
doped and oxygen vacancy defects on the surface of ZnO
nanoparticles benefit the separation of photogenerated elec-
tron–hole pairs, thus lead to enhancing the photocatalytic
activity. The properties of the nanoparticles were charac-
terized by the employments of UV–Vis spectroscopy (UV–
Vis), X-ray diffraction (XRD), Fourier transform infrared
spectroscopy(FT-IR),photoluminescence (PL), field emis-
sion scanning electron microscopy (FESEM) and scanning
energy dispersive X-ray spectroscopy (EDS).
* Roya Mohammadzadeh Kakhki
Romohammadzadeh@gonabad.ac.ir
1
Department of Chemistry, Faculty of Sciences, University
of Gonabad, Gonabad, Iran
2
Department of Chemistry, Faculty of Sciences, Hakim
Sabzevari University, Sabzevar, Iran
3
Department of Chemistry, Faculty of Sciences, Payam Noor
University, 19395‑4697 Tehran, Iran
4
Department of Chemistry, Faculty of Sciences, Payam Noor
University, Gonabad, Iran
1 Introduction
In recent years, there has been an increasing attention in
developing materials with nanostructures due to their inter-
esting applications in various fields [1–11]. It is clear that
the properties of nanoparticles depend on their size and
shape [12, 13].
The removal of hazardous materials such as toxic dyes
and organic residuals from waste water become very attrac-
tive over recent years [1, 14]. Methylene blue (MB) is one
of the organic dyes that is extensively used for the agri-
culture, cosmetic, paper-making, textile and pharmaceuti-
cal purposes [15]. Semiconductor photocatalysts are an
applicable field for removing various water contaminant
[16, 17]. Photocatalytic purification of organic contami-
nant from industrial wastewater by semiconducting oxides
shows great attention. It is due to their singular phys-
icochemical properties, allowing the‘‘green’’ removal of
organic residuals from waste water.Therefore the oxidation
of contaminants by photocatalysts under light illumination
provides an interesting way for purification of industrial
waste water.
Zinc oxide(ZnO) is one of the very interested and versa-
tile nano metal oxides and is used for various technological
operations [18, 19]. Zink oxide nanoparticles are effective
photocatalysts for degradation of toxic pollutants which
have unwanted effects on the life. It is found that the ZnO
nanomaterials have even better than T ­ iO2 for degradation
of organic dyes and some other compounds [20, 21].
Since, current applications are in a high need of visible-
light rather than ultraviolet light, the investigation in pho-
tocatalysis is mainly focused on the construction of high
efficient visible-light driven photocatalyst. Unfortunately,
inherent ZnO can only absorb UV light [22] due to its wide
band gap about 3.2 eV [23], which limits its photocatalytic
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performance for applications with visible light. For exam-
ple in a work a low degradation efficiency of 20.9% with
pure ZnO and 54.1% with Ag/ZnO for photodegradation of
2-chlorophenol was achieved in visible region [24].There-
fore it is interesting to develop ZnO photocatalysts with
high visible-light driven photoactivities.
The visible-light photocatalytic activity strongly depends
on the surface properties of metal oxide photocatalyst [25,
26]. The oxygen defects on the surface can act as charge
carrier traps where transfer the charges to the adsorbed
species. Also it prevent the photo generated electron/hole
­(e−/h+) recombination. Also bulk defects act as charge car-
rier traps where ­e−/h+ recombine during photocatalytic pro-
cess [27].
Moreover, there have been considerable interests in the
metal ion doped semiconductors as interesting materi-
als. It can facilitate interfacial charge-transfer reaction and
enhance their photocatalytic efficiency. Also it can modify
the absorption spectrum of the metal oxide nanoparticles
[28]. Among noble metals, Ag is stable and non-toxic
metal. Also it has the highest thermal and electrical con-
ductivity among all metals. Therefore it can act as a effec-
tive catalyst [29]. Surface plasmon resonance (SPR) prop-
erties of silver also can assist in visible light absorption and
subsequent electron–hole pair generation for degradation of
pollutants in water [30, 31].
Also incorporating silver in ZnO is an interesting area in
research for developing electronic applications. Moreover,
silver modification is effective for the fabrication of p- type
ZnO [32]. Naturally ZnO nanoparticle displays n- type con-
ductivity due to its native defects such as zinc interstitials
and oxygen vacancies. The modification of ZnO nanoma-
terial with silver, because of its exciting optical and elec-
tronic properties, has influenced on zinc oxid photocata-
lytic activity [33–35].
In this article, we present a novel synthesis method for
high efficient ZnO and Ag doped ZnO photocatalysts by
using simple and efficient modifiers. The photocatalytic
activities of Ag/ZnO nanoparticles were evaluated through
the degradations of methylene blue solutions by visible
light irradiation.To the best of our knowledge this is the
first report of application of ZnO and Ag–ZnO for degrada-
tion of methylene blue with highest efficiency photocatalyst
in visible region.
2 Experimental
2.1 Materials
Zinc chloride, silver nitrate and isoamyl alcohol were pur-
chased from Merck and used as received. The dye used for
the photocatalytic study (methylene blue) was purchased
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J Mater Sci: Mater Electron (2017) 28:5941–5952
from sigma and was of analytical reagent grade and used
without further purification. Double distilled water was
used in all the experiments.
2.2 Preparation of ZnO powders
In a typical experiment, 3.8 mmol of Zinc chloride was dis-
solved in 40 ml water. In other container Glycerol (0.25%),
fructose (2.5%) and L-Histidine (0.25%) were dissolved on
40  cc water-isoamylalcohol(1:1) mixture. Then this mix-
ture added to the zinc chloride solution.Under continuous
stirring at room-temperature NaOH solution was added by
drop-wise addition until pH reached to about 11. The stir-
ring of the solution was continued at 60̊ C for 8  h. After
completing the reaction, the solution was cooled to room-
temperature and finally white color precipitates were
obtained. The dried participate was calcined at 500 °C for
2 h to form ZnO nanoparticle powder.
For synthesis of Ag doped ZnO ­(AgxZn1−xO) various
mol% (x = 0.3, 0.5 ,1, 2, 4 and 6) of silver nitrate dissolved
in water were added to the zinc chloride solution with stir-
ring. The method is as described above.
2.3 Characterization
X-ray diffraction (XRD) patterns were recorded by a
Rigaku D-max C III, X-ray diffractometer using Ni-filtered
Cu K˛ radiation. Elemental analyses were obtained from
Carlo ERBA Model EA 1108 analyzer. Fourier transform
infrared (FT-IR) spectra were recorded on Shimadzu Var-
ian 4300 spectrophotometer in KBr pellets. Field emis-
sion scanning electron microscopy (FESEM) images were
obtained on HITACHI S-4160. The UV–Vis spectra of the
nanoparticles were taken on a Ultraviolet–visible (UV–Vis)
spectrometer (Model Photonix Ar). Room temperature
photoluminescence (PL) was studied on an F-4500 fluores-
cence spectrophotometer.
2.4 Evaluation of photocatalytic activity
The visible light photocatalytic activities of the A ­gx
­Zn1−xO, various mol% (x = 0, 0.3, 0.5, 1, 2, 4 and 6) nano-
composites were evaluated by the degradation of MB.
The photocatalytic procedure was conducted by addition
0.05 g of photocatalysts in a solution of ­10−5M methylene
blue. First it was stirred for 40 min in dark to reach adsorp-
tion–desorption equilibrium. After that the solution was
irradiated with a 60 W florescence lamp for up to 3 h. Dur-
ing the irradiation process the certain amount of samples
was taken outat interval of 0.5–1  h. Then samples were
analyzed by UV–Vis spectrophotometer.
J Mater Sci: Mater Electron (2017) 28:5941–5952 5943
3 Results and discussion
Pure ZnO and ­ AgxZn1−xO (0.3, 0.5, 1.0, 2.0, 4.0, and
6.0 wt%)nanoparticles were synthesized and examined for
visible degradation of MB.
3.1 Characterization
3.1.1 UV–Vis spectra
For study the optical properties of Pure ZnO and
­AgxZn1−xO, UV–Vis anaysis was performed (Fig. 1). Pure
ZnO nanoparticles gave a peak at 372  nm which is blue
shifted with respect to bulk value. Upon addition of the Ag
nanoparticle to the ZnO, an additional hump for silver is
observed at 420 nm due to localized surface Plasmon reso-
nance (LSPR) [36].
3.1.2 XRD analysis
In order to determination the crystallinity and the effect of
silver doping in the crystal phases of the ZnO, pure ZnO
and ­AgxZn1−xO powders were characterized by X-ray dif-
fraction (XRD) technique. Figure  2 exhibits the typical
XRD pattern. It can be seen that there were two sets of
strong diffraction peaks for the pure ZnO and A ­ gxZn1−xO,
which could be indexed to hexagonal wurtzite ZnO(JCPDS
No. 80-0075) indicating that the as-synthesized products
have high crystallinity.
As is shown in Fig.  2 two peak in the (111, 200)
direction of Ag nanoparticles, which was an important
Fig. 1  UV–Vis spectra of ZnO nanoparticles and Ag–ZnO nanocom-
posites
Fig. 2  XRD spectrum of a pureZnO and b 0.5%Ag/ZnO
property related to the enhanced photocatalytic activity of
­AgxZn1−xO sample.The intensity of these peaks is weak
because the amount of Ag is very small. According to some
previous reports, Ag can be incorporated in ZnO system
­ n2+or as an interstitial atom [37,
either as a substituent for Z
38]. If the silver is substituted for ­Zn2+, a corresponding
peak shift would be expected in the XRD. No such shift in
the peak positions was observed in Ag doped samples. This
indicates the existence of Ag particles in the grain bounda-
ries of ZnO crystallites rather than going into the lattice of
ZnO and an insignificant quantity may be going to the sub-
stitution Zn site.To study the effect of silver doping on the
crystal size, the mean crystal size was estimated from the
Debye–Scherrer equation. Crystalline size of ZnO and Ag
doped ZnO is 19.16 and 29.30 respectively.
3.1.3 Photoluminescence analysis
Photocatalytic activity is related with the recombination
rate of photo-excited electrons and holes. photolumines-
cence (PL) spectroscopy is a useful method for determina-
tion the efficiency of electron carrier generation, migration,
and transfer. PL spectra of ZnO and Ag/ZnO nanoparti-
cles recorded with an excitation wavelength of 325 nm are
shown in Fig. 3. As is shown in this Fig, an intense narrow
emission band in the ultraviolet range around 330  nm is
seen for all the samples. Generally, this emission is related
to the free excitonic recombination in ZnO. No change in
the position of this UV band has been observed on silver
doping, which could be due to the very small amount of Ag
in compare to the ZnO [39].
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5944
Fig. 3  PL spectra of ZnO and Ag doped ZnO
Also, there appeared another emission band in the vis-
ible region around 650 nm. This visible emission spectrum
in ZnO has been frequently assigned to defects and double
charged oxygen vacancy states ­(Vo++) in the nanostructures
[40].
As can be seen in the Fig.  3, in compare to pure ZnO
the intensity of visible emission increase for 0.5% silver
doping, and then decreases for higher Ag fractrions. This
behavior can be interpreted with considering the Ag doping
process in the nanoparticles.The ­Ag+ ions can be incorpo-
rated in to the ZnO phase in two different ways: substitut-
ing ­Zn+2 ions creating doubly ionized oxygen vacancies
or incorporating as interstitials ­Ag+ [41].It seems for low
doping concentrations e.g., 0.5%, A ­ g+ ions incorporated in
to the nanoparticles interstitially, lead to larger amount of
lattice defects. Presence of metallic Ag peaks in the XRD
patterns of the Ag doped samples supports this interprets.
As is reported in the literatures the peaks that appeared
around 483 nm related to band gap 2.56 eV, 528 nm related
to 2.35 eV, 583 nm related to 2.12 eV and 645 nm related to
1.92 eV [42, 43]. In this work ZnO show a peak at 650 nm
and this show the lowest band gap of ZnO nanoparticles
and therefore it can absorb the visible light with the highest
efficiency.
3.1.4 FT‑IR analysis
It is well known that the peaks appearing between 400
and 600  cm−1 are assigned to the metal–oxygen (M–O)
stretching mode [44] and as is reported in the literatures
peaks at around 437–455 cm−1 give the information about
Zn-O stretching vibration of crystalline hexagonal zinc
oxide [45]. As is shown in Fig. 4, the spectra of ZnO and
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J Mater Sci: Mater Electron (2017) 28:5941–5952
some of Ag-Doped ZnO nanostructures show a character-
istic band of ZnO at about 430  cm−1.The band at around
3300–3700 cm−1 is due to the O–H stretching of hydroxyl
group or absorbed water on nanoparticle surface. The silver
modified ZnO show no bands for silver, indicating there is
no chemical bonding between silver and ZnO.
The peak around 1500 is related to stretching modes of
vibrations in asymmetric and symmetric of C=O bonds and
bending vibrations of Zn(OH)2.Also some bands originated
from the presence of water moisture and carbon dioxide in
the air in the process of making nanoparticles. A peak was
observed at around 2350 cm−1 which is due to the absorp-
tion of atmospheric C ­ O2 on the surface of metal cations
[46].
3.1.5 SEM images
Information such as grain size and shape can be obtained
by FESEM analysis. Surface morphology of the pure ZnO
and silver doped ZnO nanoparticles is shown in Fig. 5. The
particle sizes were clearly of the order of nanometers (with
average size 75  nm) and it can be seen that the shape of
particles was quasi-spherical. Using silver doping, no sig-
nificant changes were observed in the size of nanoparticles.
The EDS spectra for ZnO and Ag doped ZnO are shown
in Fig.  6. As can be seen this analysis indicates the pres-
ence of only Zinc and Oxygen in pure ZnO and Zinc, oxy-
gen and silver in Ag doped ZnO. Therefore it show that
these nanoparticles are only made up of Zn,O and Zn,O
and Ag respectively, indicating the purity of the samples.
The EDS data are listed in Table 1, it is found from this
table that Zn:O ratio is non-stoichiometric, but it is in form
­ZnO1−x. Visible light absorptioncan be increased through
defects of the photocatalyst surface, that is well known as
“self-doping”. This phenomenon increases the range of
visible light absorption of the metal oxide [47–49]. Many
studies showed improvement in the photocatalytic perfor-
mance of nano particles by creating defects on the surface
of the metal oxide. Oxygen vacancies can enhance the pho-
tocatalytic oxidation of organic dyes [50, 51].
Surface disorders in Z ­ nO1−x nanostructures could cre-
ate some sites for photogenerated carriers and prevent them
from rapid recombination. This lead to increasing electron
transfer and photocatalytic reactions [52]. Therefore oxy-
gen defects can affect on the enhancement of photocatalytic
activity of ZnO nano structures.
3.2 Photocatalytic activity
The successful synthesis of ZnO nanoparticles offers an
opportunity to examine their photocatalytic activity. The
ZnO and Ag doped ZnO nanoparticles were selected for the
evaluation of photocatalytic activity with MB dye under the
J Mater Sci: Mater Electron (2017) 28:5941–5952 5945

Fig. 4  FT-IR of a ZnO, b 0.5% Ag, c 2% Ag, d 6% Ag doped ZnO

Fig. 5  The FESEM morpholo-

gies of a undoped, b 0.5% Ag
doped ZnO nanoparticles

Fig. 6  EDS of a undoped, b 0.5% Ag doped ZnO nanoparticles

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Table 1  EDS results for ZnO and 0.5% Ag–ZnO nanomaterials Secondly, noble metal nanoparticles on ZnO exhibit local-
EDS ZnO Ag/ZnO ized surface Plasmon resonance (LSPR) absorption of light
which can have significant impact on semiconductor pho-
Element %Weight %Atomic %Weight %Atomic tocatalysis. The LSPR wavelength of noble metal nanopar-
Oxygen 13.58 39.10 12.88 37.80 ticles can be tuned from near UV to the visible region by
Zink 86.42 60.90 85.91 61.68 controlling their size, shape, inter-particle spacing and sur-
Silver 1.21 0.52 rounding medium [54]. In case of ZnO modified with noble
metal nanoparticles, LSPR absorption can lead to enhanced
utilization of UV–visible light as compared to pure ZnO
[55, 56].
In the case of metal modification in nanoparticles, a par-
ticular concentration of metal modifier can tune the photo-
physical properties. From the study, it can be seen that the
addition of silver enhances the photocatalytic degradation
of the dye up to 0.5  mol% with degradation efficiency of
98% in 180  min and above this concentration there isn’t
significant effect on the photocatalytic activity. There-
fore we select 0.5% Ag as the best composition for further
investigation.
Two comparative spectra for degradation MB with pure
ZnO and 0.5% Ag doped ZnO are shown in Fig. 8.

3.2.1 Factors to the catalyst activity

Fig. 7  Degradation of methylene blue with pure ZnO and Ag-doped
ZnO
illumination of visible light. In order to study the effect of
the visible light on the degradation of MB dye, ZnO and
Ag (mol% = 0.3, 0.5, 1, 2, 4, 6) doped ZnO were examined.
As can be seen from Fig. 7 with pure ZnO degradation effi-
ciency is about 63% and with doping of Ag in to ZnO nan-
oparticle the degradation efficiency is improved. Surface
modification of ZnO nanostructures with Ag nanoparticles
improves the photocatalytic efficiency, since the Ag–ZnO
system has two distinct features. Firstly, Ag–ZnO contacts
result in a Schottky junction, which creates an internal
electric field close to the interface causing the photogen-
erated electrons and holes to move in different directions,
which results in a decrease of their recombination rate [53].
3.2.1.1  Effect of calcination temperature  In this research
of the effect of temperature of calcination on photocatalytic
activity of ZnO nanoparticle was investigated. We have
demonstrated that the direct calcination of ZnO at moderate
temperature provides an effective route for easy, cost-effec-
tive and large-scale production of ZnO photo catalyst. The
synthesis is simple, high-yield and no special equipment is
required.To reveal the effect of calcination temperature on
the photocatalytic properties of ZnO, photocatalytic degra-
dation of methylene blue under visible light irradiation was
examined. It can be seen that the photocatalytic degrada-
tion efficiency of MB increases gradually with an increase
in the calcination temperature from 300 °C up to 600 °C.
However, as can be seen from Fig. 9 there isn’t significant
difference between them. It is believed that in the present

Fig. 8  Degradation of MB with a pureZnO and b 0.5% Ag–ZnO

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J Mater Sci: Mater Electron (2017) 28:5941–5952 5947

Fig. 9  Effect of calcination temperature on photocatalytic activity of ZnO nanoparticle

ZnO system, ­Ag2O is the stable phase at 300 °C and as the
temperature increases, A­ g2O decomposes to metallic silver
[37]. Therefore we select 500 °C as the optimum calcination
temperature.
In this experiment with using 0.5% Ag–ZnO nanocom-
posite as the best photocatalyst calcined at 500 C we exam-
ined the effect of concentration of MB, amount of catalyst
and pH for degradation of MB.
3.2.1.2 Effect of  concentration  In the experiment, the
effects of MB concentration is shown in Fig. 10.The effect
of dye concentration from 0.5 × 10−5 to 5 × 10−5 mol/L was
investigated. The results show with increase the concentra-
tion of MB, the photocatalytic activity slightly decreased.
This phenomenon was closely related to the radical genera-
tion on the catalyst surface and probability of subsequent
radical reaction with dye molecules [57]. When MB con-
centration increased, the probability of reaction between
MB increased, which led to an improvement of degradation
efficiency. However, the equilibrium adsorption of dye at
the active sites on the catalyst surface also increased with
the increasing of the dye concentration. It decreased the for-
mation rate of ­O2 and ­OH− sites, which were necessary for
high degradation efficiency as principal oxidants [58, 59].
Further, according to the Beer–Lambert law, the path length
of photons entering the solution decreased with the increas-
ing of the initial dye concentration, which led to a lower
photon adsorption on catalyst particles as well as lower pho-
tocatalytic efficiency.
3.2.1.3  Effect of amount of catalyst  The amount of cata-
lyst was another effective factor on the degradation of MB.
Therefore, experiments with various amount of catalyst
were conducted. The corresponding result was presented
in Fig. 11. It revealed that the photo degradation efficiency
increased with the increasing of nanophotocatalyst amount
from 0.05 to 0.1 g and then decreased. The highest degrada-
tion efficiency of MB was 98% corresponding to 0.05 and

Fig. 10  Effect of MB concentration on photocatalytic degradation efficiency of 0.5%Ag–ZnO

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Fig. 11  Effect of amount of catalyst on photocatalytic degradation efficiency of 0.5%Ag–ZnO
0.1 g/L Ag–ZnO. This result was related to the availability
of active sites on the catalyst surface and the penetration
of light into the suspension. The total active surface area
increased with the increasing of the amount of catalyst [60].
However, the excess dosage of Ag–ZnO heterostructure
may lead to an increased light scattering effect [61], which
decreased the light penetration.
3.2.1.4  Effect of pH  One of the most important parameter
that influences the photocatalytic degradation of dye is pH.
This is due to the effect of pH on the surface-charge-prop-
erties of the photocatalyst and the influences on the ionic
species in the solution. Therefore, the effects of pH were
investigated on the photocatalytic activity of Ag doped ZnO.
In order to study the effect of pH value on the degra-
dation activity, several experiments were conducted at sta-
ble dye concentration (1 × 10−5mol/L) and catalyst dosage
(0.05  g/L). NaOH and HCl solutions were used to adjust
Fig. 12  Effect of amount of pH of MB on photocatalytic degradation efficiency of 0.5% Ag–ZnO
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J Mater Sci: Mater Electron (2017) 28:5941–5952
the pH value. The corresponding results were shown in
Fig.  12. It can be found that the degradation efficiency
increases with the increase of pH. The low initial photocat-
alytic efficiency at the acidic pH value is due to the dissolu-
tion of ZnO by ­H+. Therefore, the degradation efficiency
increase with the increasing of pH value, this can be attrib-
ute to the decrease of ­H+ and gradually increasing amount
of .OH in the catalyst surface, which is of great importance
to the degradation of MB [62].
3.3 Kinetic study for degradation of dye
The photocatalytic activity study of ZnO and Ag doped
ZnO nanocomposites was performed by investigating the
kinetics of degradation of aqueous MB dye solutions under
visible light. The adsorption equilibrium was established in
all the cases by keeping the samples in dye solution in dark
for 40 min.
J Mater Sci: Mater Electron (2017) 28:5941–5952 5949
The degradation rate for the decomposition of dyes
was calculated using a simplified Langmuir–Hinshel-
wood model, which follows a pseudofirst-order reaction
rate [63, 64]:
( )
ln C0 ∕Ct = kt
where ­C0 and ­Ct are initial concentration and concentra-
tions at particular irradiation time of the dye in the aqueous
solution and k is the pseudo-first order rate constant.
For each experiment, the rate constant (k) of all the
dye derivatives was calculated from the plot of -lnC/Co
versus the irradiation time.
As can be seen from Fig.  13, the rate constant of Ag
doped ZnO show higher activity (in terms of rate con-
stant) compared to pure ZnO (0.005 min−1) under visible
light.
The enhanced activity of Ag/ZnO is due to the Ag
loading. The SPR effect of Ag increases the absorp-
tion spectrum of ZnO in the higher wavelength side and
reduces the charge carrier recombination and enhances
the visible-light driven photocatalytic efficiency.
Fig. 13  lnC/Co versus time plot
to determine the rate of constant
Fig. 14  Schematic diagram of
the proposed mechanism for the
degradation of MB by the Ag–
ZnO heterostructures
3.4 Mechanism of enhancement of photocatalytic
activity by silver
The deposition of noble metals on semiconductor nanopar-
ticles is an effective way for improving the photocatalytic.
The metal modifier can indirectly influence the interfacial
charge transfer processes. As a noble metal, silver can act
as electron scavenger and store them effectively. Certainly,
a primary understanding of photo induced interactions as
well as the interfacial charge transfer processes in metal-
modified semiconductors is important to explain the exact
role of metal in semiconductor photocatalysis.
The possible catalytic mechanism of Ag–ZnO was
shown in Fig.  14. During the catalytic process, firstly, the
electron of valence band(VB) in ZnO will be forced to the
conduction band(CB) and generate the same number of
valence band holes. Meanwhile, owing to the lower Fermi
level(Ag–ZnO) compared with the conduction band energy
of ZnO, photoexcited electrons will be eagerly transferred
from ZnO to Ag nanoparticles under the potential energy.
This leads to the accumulation of the photogenerated
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5950 J Mater Sci: Mater Electron (2017) 28:5941–5952

Table 2  Comparation of this work with pervious Ag/ZnO visible photocatalysts

ZnO Ag–ZnO
pH rate constant MB degradation %Doped of Ag rate constant MB degradation Time of degradation Ref
efficiency% efficiency%

11 1.37 × 10− 3 48% 2% 5.47 × 10− 3 92 8 h [65]

– 0.085× 4.9 10% 3.666× ~ 90 90 min [66]
10− 4 10− 4
– – 31.3 3 – 97 5h [67]
– 0.0026 25 1 0.014 80 100 min [68]
7 0.005 63 0.5 0.017 98 120 min This work

electrons in Ag nanoparticles, as well as the migration of
photogenerated holes to the surface of ZnO, which greatly
promotes the separation of photogenerated electrons and
holes. In such a photocatalytic process, the separation and
recombination of photoinduced charge carriers are compet-
itive pathways and photocatalytic activity is effective when
recombination between them is prevented.
Afterwards, as a receptor, photoelectron will adsorb ­O2
and turn to superoxide anion (·O−2), the obtained ·O−2 and
photogenerated holes would finally turn to a strong oxidiz-
ing agent (·OH). It can effectively degrade the organic dye
to ­CO2 and H ­ 2O, which will greatly improve the photocata-
lytic efficiency. The possible photocatalytic reaction can be
expressed as follows:
Zno+hv(vis) → ZnO(e- CB +h+ VB )
e− CB + O → ⋅ O− 2
Ag+ + e− CB → Ag
h+ VB + OH− → ⋅ OH
O− 2 + 2H+ → 2 ⋅ OH
OH + MB → Degradation products
In overall since today a few researches has been made on
ZnO and Ag doped ZnO nanophotocatalyst for degradation
of organic dyes in visible light irradiation. In Table  2 we
compare this new ZnO and Ag-doped ZnO with the previ-
ous reports. As can be seen from this Table, pure ZnO has
the highest efficiency in compare with previous works. Also
with the minimum amount of Ag (0.5%) doped in ZnO the
best efficiency for degradation of MB was obtained.
4 Conclusion
In this work efficient ZnO and Ag doped ZnO based visi-
ble-light photocatalysts developed by using a new method.
Our method would be important for application of ZnO
photocatalytic materials due to its advantage of its simplic-
ity; low cost, high production and excellent performance of
the resulting products. Various mol% of highly active sil-
ver-modified and unmodified ZnO photocatalysts were pre-
pared. The structural and optical properties of the resultant
materials were characterized by UV–Vis, XRD, PL, FTIR,
FESEM and EDS.
Photocatalytic activity of all samples was determined by
analyzing the degradation of methylene blue in the pres-
ence of the pure ZnO and Ag doped ZnO nanopartices.
Silver modification caused the material to show significant
improvement in the photocatalytic activity. 0.5  mol% sil-
ver was considered as the optimum concentration. Also the
effect of initial MB concentration, the amount of catalyst
(1) and the pH of solution on photo degradation of MB was
investigated.
(2) The mechanism of photocatalytic activity was studied
and it was found that the presence of silver facilitates the
(3) interfacial charge transfer processes. This results show that
silver has a significant role to play in the trapping of elec-
(4) trons in these materials. Moreover oxygen defects play a
key role in enhancing the photocatalytic efficiency. There-
(5) fore these materials applications could be extend to the
development of a photocatalyst which is applicable in vis-
(6) ible region.
References
1. R. Mohammadzadeh Kakhki, F. Ahsani, N. Mir, J. Mater. Sci.
(2016). doi:10.1007/s10854-016-5279-6
2. R. Mohammadzadeh Kakhki, Arab. J. Chem. (2014).
doi:10.1016/j.arabjc.2014.11.058
3. R. Mohammadzadeh Kakhki, J. Incl. Phenom. Macrocycl. Chem.
82, 301–310 (2015)
4. R. Mohammadzadeh Kakhki, M. Rakhshanipour, Arab. J. Chem.
(2015). doi:10.1016/j.arabjc.2015.07.012
5. G. Rounaghi, R. Mohammadzadeh Kakhki, H. Azizi-toupkanloo,
Mater. Sci. Eng. C, 32, 172 (2012)
6. R. Mohammadzadeh Kakhki, Russ. J. Electrochem. 49(5), 458–
465 (2013)

13
J Mater Sci: Mater Electron (2017) 28:5941–5952 5951
7. R. Mohammadzadeh Kakhki, Russ. J. Appl. Chem. 89(3),
480–488 (2016)
8. R. Tayebee, K. Savoji, M K. Razi, B. Malek, RSC Adv. 6,
55319–55326 (2016)
9. F. Javadi, R. Tayebee, Microporous Mesoporous Mater. 231,
100–109 (2016)
10. R. Tayebee, M.M. Amini, N. Abdollahi, A. Aliakbari, S.
Rabiei, H. Ramshini, Appl. Catal. A 468, 75–87 (2013)
11. R. Tayebee, M.M Amini, H. Rostamian, A. Aliakbari. Dalton
Trans. 43, 1550–1563 (2014)
12. J.J. Shiang, A.V. Kadavanich, R.K. Grubbs, A.P. Alivisatos, J.
Phys. Chem. 99, 17417 (1995)
13. S. Ahmadi, Z.L. Wang, T.C. Green, A. Henglein, M.A.
Elsayed, Science 272, 1924 (1996)
14. R.M. Kakhki, M. Nejati-Yazdinejad, F. Kakeh, Arab. J. Chem.
(2013). doi:10.1016/j.arabjc.2013.09.020
15. K. Rastogi, J.N. Sahu, B.C. Meikap, M.N. Biswas, J. Hazard.
Mater. 158, 531–540 (2008)
16. J. Nishio, M. Tokumura, H.T. Znad, Y. Kawase, J. Hazard.
Mater. 138, 106–115 (2006)
17. R. van Grieken, Ind. Eng. Chem. Res. 46, 7605–7610 (2007)
18. M. Farbod, M. Khademalrasool, Powder Technol. 214, 344
(2011)
19. I. El Saliby, Y. Okour, H.K. Shon, J. Kandasamy, W.E. Lee,
J.-H. Kim, J. Ind. Eng. Chem. 18, 1033 (2012)
20. A. Shafaei, M. M. Nikazar, M. Arami Desalination 252, 8–16
(2010)
21. J. Xie, Y. Li, W. Zhao, L. Bian, Y. Wei, Powder Technol. 207,
140–144 (2011)
22. T. Bak, J. Nowotny, M. Rekas, C. Sorrell, Int. J. Hydr. Energy
27, 991–1022 (2002)
23. M. Miyauchi, A. Nakajima, T. Watanabe, K. Hashimoto,
Chem. Mater. 14, 2812–2816 (2002)
24. J. Rashid, M.A. Barakat, N. Salah, S.S. Habib, RSC Adv.
(2014). doi:10.1039/C4RA12990C
25. E. Grabowska, J.W. Sobczak, M. Gazda, A. Zaleska, Appl.
Catal. B 117, 351–359 (2012)
26. X. Chen, L. Liu, Y.Y. Peter, S.S. Mao, Science 331, 746–750
(2011)
27. X. Bai, L. Wang, R. Zong, Y. Lv, Y. Sun, Y. Zhu, Langmuir
29, 3097–3105 (2013)
28. M.E. Hilo, A.A. Dakhel, A.Y. Ali-Mohamed, J. Magn. Magn.
Mater. 321, 2279–2283 (2009)
29. M. Rycenga, C.M. Cobley, J. Zeng, W.Y. Li, C.H. Moran, Q.
Zhang, D. Qin, Y.N. Xia, Controlling the synthesis and assem-
bly of silver nanostructures forplasmonic applications. Chem.
Rev. 111, 3669–3712 (2011)
30. P. Christopher, H. Xin, S. Linic. Nat. Chem 3, 1–6 (2011)
31. W. Hou, Z. Liu, P. Pavaskar, W.H. Hung, S.B. Cronin, J. Catal.
277, 149–153 (2011)
32. H.E. Chao, Y.U. Yun, H.U. Xiangfang, A. Larbot J. Eur.
Ceram. Soc. 23, 1457 (2003)
33. H.S. Kang, B.D. Ahn, J.H. Kim, G.H. Kim, S.H. Lim, H.W.
Chang, Lee, S. Y. Appl. Phys. Lett. 88, 202108 (2006)
34. P. Pathak, M.J. Meziani, L. Castillo, Y.P. Sun, Green Chem. 7,
667 (2005)
35. E. Stathatos, T. Petrova, P. Lianos, Langmuir 17, 5025 (2001)
36. A. Pal, S. Shah, S. Devi, Microwave-assisted synthesis of sil-
ver nanoparticles using ethanol as a reducing agent. Mater.
Chem. Phys. 114, 530–532 (2009)
37. J. Fan, R. Freer, J. Appl. Phys. 77, 9 (1995)
38. D.J. Blinks, R.W. Grimes, J. Am. Ceram. Soc. 76, 2370 (1993)
39. L. Irimpan, V.P.N. Nampoori, P. Radhakrishnan, Spectral and
nonlinear optical characteristics of nanocomposites of ZnO–
Ag. Chem. Phys. Lett. 455, 265–269 (2008)
40. J.D. Ye, S.L. Gu, F. Qin, S.M. Zhu, S.M. Liu, X. Zhou, W. Liu,
L.Q. Hu, R. Zhang, Y. Shi, Y.D. Zheng, Correlation between
green luminescence and morphology evolution of ZnO films,
Appl. Phys. A 81, 759–762 (2005)
41. S.T. Kuo, W.H. Tuan, J. Shieh, S.F. Wang, J. Eur. Ceram. Soc.
27, 4521 (2007)
42. Z. Fu, B. Lin, G. Liao, Z. Wu, J. Cryst. Growth 93, 316 (2008)
43. L. Dai, X.L. Chen, W.J. Wang, T. Zhou, B.Q. Hu, J. Phys.:
Condens. Matter 15, 2221 _2003_
44. M. Srivastava, A.K. Ojha, S. Chaubey, P.K. Sharma, A.C. Pan-
dey, J. Alloys Compd. 494, 275–284 (2010)
45. R. Saleh, L. Munisa, W. Beyer, Infrared absorption in a-SiC:H
alloy prepared by d.c. sputtering. Thin Solid Films 426, 117–
123 (2003)
46. C. K. Ghosh, S. R. Popuri, T. U. Mahesh, K. K. Chattopad-
hyay, Preparation of nanocrystalline CuAlO2 through sol–gel
route. J. Sol–Gel Sci. Technol. 52, 75–81 (2009)
47. X. Zhang, J. Qin, Y. Xue, P. Yu, B. Zhang, L. Wang, R. Liu,
Effect of aspect ratio and surface defects on the photocatalytic
activity of ZnOnanorods. Sci. Rep. 4, 4596 (2014)
48. T.L Thompson, J.T. Yates Jr T ­ iO2-based photocatalysis: sur-
face defects, oxygen and charge transfer. Top. Catal. 35, 197–
210 (2005)
49. Liu, S.; Li, C.; Yu, J.; Xiang, Q. Improved visible-light photo-
catalytic activity of porous carbon self-doped ZnOnanosheet-
assembled flowers. Cryst. Eng. Comm. 13, 2533–2541 (2011)
50. D. Chen, Z. Wang, T. Ren, H. Ding, W. Yao, R. Zong, Y. Zhu,
Influence of defects on the photocatalytic activity of ZnO. J.
Phys. Chem. C 118, 15300–15307 (2014)
51. J. Fang, H. Fan, Y. Ma, Z. Wang, Q. Chang, Surface defects
control for ZnOnanorods synthesized by quenching and their
anti-recombination in photocatalysis. Appl. Surf. Sci. 332,
47–54 (2015)
52. J. Wang, P. Liu, X. Fu, Z. Li, W. Han, X. Wang, 670 Relation-
ship between oxygen defects and the photocatalytic property
671 of ZnO nanocrystals in nafion membranes. Langmuir, 25,
1218–1223 (2009)
53. Q. Deng, X. Duan, D.H.L. Ng, H. Tang, Y. Yang, M. Kong, Z.
Wu, W. Cai, G. Wang ACS Appl. Mater. Interfaces 4, 6030–
6037 (2012). doi:10.1021/am301682g
54. K.L. Kelly, E. Coronado, L.L. Zhao, G.C. Schatz, J. Phys.
Chem. B 107, 668–677 (2003). doi:10.1021/jp026731y
55. Y.K. Mishra, V.S.K. Chakravadhanula,, V. Hrkac, S.
Jebril, D.C. Agarwal, S. Mohapatra, D.K. Avasthi, L.
Kienle, R. Adelung, J. Appl. Phys. 112, 064308 (2012).
doi:10.1063/1.4752469
56. I. Thomann, B.A. Pinaud, Z. Chen, B.M. Clemens, T.F. Jara-
millo, M.L. Brongersma, Nano Lett. 11, 3440–3446 (2011).
doi:10.1021/nl201908s
57. B. Subash, B. Krishnakumar, M. Swaminathan, M. Shanthi,
Langmuir 29, 939 (2013)
58. D. Y. Fang, C. L. Li, N. Wang, P. Li, P. Yao, Crys. Res. Technol.
48, 265 (2013)
59. L. C. Zhang, Y. F. Ruan, Y. L. Liu, Y. Zhai, Crys. Res. Technol.
48, 996 (2013)
60. B. Krishnakumar, B. Subash, M. Swaminathan, Sep. Purif. Tech-
nol. 85, 35 (2012)
61. R. Velmurugan, K. Selvam, B. Krishnakumar, M. Swaminathan,
Sep. Purif. Technol. 80, 119 (2011)
62. Y.F. Tu, Q.M. Fu, X.J. Niu, J.P. Sang, Z.J. Tan, G. Zheng, X.W.
Zou, Crys. Res. Technol. 48, 138 (2013).
63. Y. Peng, S. Qin, W.S. Wangb, A.W. Xu, Fabrication of porous
Cd-doped ZnOnanorods with enhanced photocatalytic activity
and stability. Cryst. Eng. Comm. 15, 6518–6525 (2013)
64. M. Ahmada, E. Ahmed, Y. Zhang, N.R. Khalid, J. Xu, M.
Ullah, Z. Hong, Preparation of highly efficient Al-doped
13

5952 J Mater Sci: Mater Electron (2017) 28:5941–5952

ZnOphotocatalyst by combustion synthesis, Current. Appl. Phys.
13, 697–704 (2013)
65. T.J. Whang, M.T. Hsieh, H.H Chen, Appl. Surf. Sci. 258, 2796–
2801 (2012)
6 6. R. Saravanana, M.M. Khan, V.K. Gupta, E. Mosquera, F. Gracia,
V. Narayanan, A. Stephen, J. Colloid Interface Sci. 452, 126–133
(2015)
67. S.A. Ansari, M.M. Khan, J. Lee, M.H. Cho J. Ind. Eng. Chem.
doi:10.1016/j.jiec.2013.08.006
68. B.M. Rajbongshi, A. Ramchiary, B.M. Jha, S. K. Sam-
darshi, J. Mater. Sci. 25, 2969–2973 (2014). doi:10.1007/
s10854-014-1968-1

13