J Mater Sci: Mater Electron (2017) 28:18236–18243
DOI 10.1007/s10854-017-7772-y
Coinage metal (Ag, Cu) decorated ­BiFeO3 nanoparticles:
synthesis, characterization and their photocatalysis properties
Harsimranjit Kaur1 · Navjot1 · Alexandr Tovstolytkin2 · Gurmeet Singh Lotey1
Received: 5 June 2017 / Accepted: 19 August 2017 / Published online: 28 August 2017
© Springer Science+Business Media, LLC 2017
Abstract Plasmonic enhanced photocatalytic activity for
the degradation of industrial pollutants viz., Naphthol blue
black and Sudan-I dyes for bare and coinage metal (Ag,
Cu) decorated ­BiFeO3 nanoparticles have been presented.
­BiFeO3 nanoparticles have been synthesized by hydrother-
mal method and photo-deposition of the coinage metals (Ag,
Cu) done. The size of the synthesized nanoparticles and the
presence of metals on the surface of ­BiFeO3 have been tested
by the transmission electron microscopy and X-ray photo-
electron spectroscopy. Red-shift in the band gap of B­ iFeO3
has been observed with decoration of metals in the optical
spectra. Time resolved photoluminescence spectroscopy and
action spectra have been done to understand the dynamics
of the charge carriers and average relaxation time. The deg-
radation efficiency of the Ag decorated B ­ iFeO3 found to be
higher than that of the bare and Cu decorated. The mecha-
nism to understand the enhancement of photocatalytic activi-
ties has been presented.
1 Introduction
The speedy development of global industrialization, leads
to the exploitation of the natural resources such as water,
air, soil and results in environmental pollution that is get-
ting worse day by day [1]. Dyes are widely used in textile,
leather, rubber, paper, plastic, and cosmetic industries, and
* Gurmeet Singh Lotey
gslotey1986@gmail.com; gsloteyz@gmail.com
1
Nano Research Lab, Department of Physics, DAV
University, Jalandhar, Punjab 144012, India
2
Institute of Magnetism, 36b Vernadsky Blvd., Kyiv 03680,
Ukraine
13
Vol:.(1234567890)
this may leads to severe damage of ecological balance. After
the use of dyes, their heavy amount is discharged into the
water world-wide, every day. This is very alarming situation
and leading to very serious environmental problems viz.,
increase of toxicity, chemical oxygen demand, biochemical
oxygen demand, bad smell, and color in the water. There
are several non-destructive conventional water treatments
methods viz., adsorption, coagulation, flocculation, reverse
osmosis and ultrafiltration. These said methods just trans-
fer the contaminants from their one phase to other phase
and form secondary waste problems [2]. Azo dyes namely
naphthol blue black dye (NBB) [IUPAC name 4-amino-
5-hydroxy-3-[(4-nitrophenyl) azo]-6-(phenylazo)-2, 7-naph-
thalenedisulfonic acid disodium salt], and Sudan-I [IUPAC
name 1-(phenyldiazenyl) naphthalene-2-ol] are amongst
the prime colorants used in various industries [1]. The de-
colorization of these dyes releases the effluent of streams in
air, and results in air pollutions, whiles the treatment of their
liquid discharge, result in water pollution. The task to sort
out these problems is the main accountability of the indus-
tries in which these dyes are used. Therefore, it is an urgent
need of the hour to develop the highly efficient photocatalyst
to address above said concerns, and along with this to min-
eralize the water. Photo-catalytic degradation of above said
dyes, decolorizes them and offers the remedy for the puri-
fication of water and air pollution [3–5]. In the last decade,
a lot of reports on photo-degradation of various dyes using
­BiFeO3 nanoparticles viz., methylene blue [6], congo red [7,
8], rhodamine [1, 9–11], methyl orange [12–15] have been
presented. Also, there are several reports on use of oxide
for different applications [16, 17]. There is still requirement
to find efficient photocatalyst for the degradation of indus-
trial dyes such as NBB and Sudan-I. ­BiFeO3 being a direct
energy band-gap semiconductor ­(Eg 2.2–2.8 eV), exhibits
excellent properties such as chemical stability, high mobility,
J Mater Sci: Mater Electron (2017) 28:18236–18243 18237

and non-toxicity, which make it a good candidates to act as
excellent photocatalyst [18]. Also, it is well known multifer-
roic material exhibiting simultaneously ferroelectricity, and
magnetic ordering in a single phase [19–22]. Moreover, the
photocatalytic performance of semiconducting photocatalyst
may be largely improved by decorating them with coinage
metals viz., Au, Ag, Cu [9, 18, 21]. But Au is very expensive
metals, therefore the decoration using Ag and Cu paved to
be effective way to improve the photocatalytic properties.
In the present study, photodegradation of NBB and
Sudan-I dyes by coinage metal decorated B ­ iFeO3 nanopar-
ticles has been investigated.
2.2.1 Photocatalytic activity measurement
The dye and catalyst in concentrations of 10 mg/L and 1 g/L,
respectively have been dissolved in water and stirred for 1 h
in the dark for the adsorption of dye on catalyst and subse-
quently put in sunlight. The photocatalytic activity of cata-
lyst (BFO, Ag-BFO, and Cu-BFO) has been determined by
measuring the degradation of dyes NBB and Sudan-I in the
presence of sunlight at 25 °C, after each 10 min.
3 Results and discussion

3.1 Structural analysis
2 Materials and methods
Figure 1 displays the X-ray diffraction (XRD) patterns of
BFO, Cu-BFO and Ag-BFO nanoparticles. The observed
2.1 Synthesis
XRD peaks 22.55°, 32.01°, 32.26°, 39.69°, 39.72°, 45.84°,
51.55°, 51.65°, 57.19°, 57.28°, 66.70°, 67.18, 71.75°,
Hydrothermal method has been used for the synthesis of
75.95°, 80.64° are indexed to Miller indices (012), (104),
­BiFeO3 [8]. In the typical synthesis procedure, equimolar
(110), (006), (202), (024), (116), (122), (018), (300), (208),
amount of Fe(NO3)3·9H2O and Bi(NO3)3·5H2O has been
(220), (036), (312), (134), respectively. This indexing sug-
dissolved in water and then few drops of ­HNO3 added in it.
gests that the synthesized nanoparticles have rhombohedral
Afterwards, KOH solution of concentration 8 M has been in
structure (R3c) with hexagonal phase as per JCPDS file no.
it along with 3 g poly(ethylene glycol). The above said mix-
86–1518 [18–20]. Also, Fig. 1 shows that XRD patterns of
ture is then shifted to a stainless steel teflon-lined autoclave.
BFO nanoparticles exhibit an additional peak around 27.88°
The autoclave sealed tightly and put in oven at 200 °C for
marked by “*” corresponding to secondary impurities such
a 24 h, and then autoclave is allowed to cool down to room
as ­Bi2Fe4O9, ­Bi24Fe2O39 [19, 20]. No such peak has been
temperature naturally. The nanoparticles of B ­ iFeO3 have
observed in Ag-BFO and Cu-BFO, thereby confirming that
been collected by centrifugation. After the synthesis, the
the decoration of the metals on the surface of BFO results
synthesized nanoparticles have been washed several times
in suppressions of secondary impurities. Also, no peak
with distilled water and then dried at 60 °C. The dried nano-
corresponding to Ag and Cu metal have been detected in
particles have been grinded and used for the decoration with
the XRD patterns. This is precisely due to the very small
coinage metals. The decoration of metals viz., Cu and Ag
1% by weight on the surface of ­BiFeO3 has been done using
photo-deposition method [23]. The synthesized bare B ­ iFeO3,
Cu-decorated ­BiFeO3 and Ag-decorated B ­ iFeO3 nanoparti-
cles are named as BFO, Cu-BFO and Ag-BFO respectively,
for further references.

2.2 Characterization

The structural study has been carried out using an X-ray

diffractometer of PANalytical X’PertPRO MRD (Cu-Kα,
λ = 1.54060 Å). Determination of chemical compositions,
surrounding environment and oxidation states of elements
in BFO, Ag-BFO and Cu-BFO has been carried out by X-ray
photoelectron spectroscopy (XPS) measurement, using VG
MultiLab 2000, Thermo Electron Corp. transmission elec-
tron microscopy (TEM) has been carried out using Hitachi-
H7650 for morphological study. UV–visible spectra and
photo-catalytic studies have been performed using spec-
trometer UV-1800 Shimadzu. Fig. 1  XRD patterns for BFO, Ag-BFO and Cu-BFO

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concentration of these metal particles on the surface of BFO.
Williamson-Hall formula has been used to calculate the
crystallite size and strain in the synthesized nanoparticles
[24]. The crystallite size is found to be 12.69, 12.34 and
12.69 nm for BFO, Ag-BFO and Cu-BFO, respectively. The
value of the strain calculated for all the samples has been
found to be 0.0105 for all samples. The observed same value
of strain for all the samples indicate that the metals Ag and
Cu are present on the surface only and not become the part
of the crystal structure.
3.2 Morphological analysis
The presence of the deposited Ag and Cu nanoparticles on
the surface of B
­ iFeO3 has been tested by the TEM images as
shown in Fig. 2. It has been found that the average particle
sizes of BFO and Ag nanoparticles are 19 and 5 nm in Ag-
BFO respectively (Fig. 2a), while in those of BFO and Cu-
BFO are 16 and 5 nm (Fig. 2b). The size of the metal nano-
particles play a very important role in the photo-catalytic
activities of metal decorated semiconductor nanoparticles
[25, 26]. These results are further consistent with XRD study
as will be explained in Sect. 3.1.
3.3 Chemical composition analysis
XPS spectra for the synthesized nanoparticles of BFO, Ag-
BFO and Cu-BFO are shown in Fig. 3. The background cor-
rection using Shirley background subtraction with use of
non-linear least square fitting along with the mixed Gauss-
Lorentz function has been done to calculate the oxidation
state of Fe in all three samples, between the ranges from 705
to 735 eV as shown in Fig. 3a.
Figure 3a shows two peaks located around the 710.9 and
724.7 eV. These peaks are corresponding to the spin–orbit
doublet ­2p3/2 and ­2p1/2 of Fe, thereby approving the +3 oxi-
dation state of Fe. In addition to this, there is another peak
Fig. 2  TEM image for Ag-BFO
and Cu-BFO
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J Mater Sci: Mater Electron (2017) 28:18236–18243
around 781.7 eV, called the satellite peak, observed owing to
the shake-up process occurred during the measurement [27].
Figure 3b shows the enlarged view of the XPS spectrum
of Ag-BFO, revealing the photoemission peaks around 368
and 374 eV which correspond to the Ag 3­ d5/2 and Ag 3­ d3/2
respectively. This implies that Ag nanoparticles exhibit the
fcc structure in its metallic form on the surface of ­BiFeO3
[28].
Figure 3c shows the enlarged view of the XPS spectrum
of Cu-BFO nanoparticles. The two photoemission peaks
located around 934 and 954 eV consigned to the binding
energy of Cu 2­ p3/2 and Cu 2­ p1/2, respectively. This provides
evidence of the presence of the C ­ u2+ ions. In addition to this,
two peaks around 942 and 962 eV are corresponding to the
extra shake-up satellite peaks, thereby confirming the exist-
ence of unfilled Cu 3­ d9 orbitals. These may be due to the
+2 oxidation state of Cu [29]. Other than above mentioned
peaks, there is no extra peak observed in Fig. 3. Therefore,
it may be concluded that there is no additional impurities or
secondary phase in the synthesized nanoparticles.
3.4 Photochemical analysis
3.4.1 Optical analysis
Figure 4a displays UV–visible spectra of synthesized nano-
particles. It shows that the synthesized nanoparticles absorb
light in visible region of electromagnetic spectrum. This
illustrate that the synthesized nanoparticles can be used as
efficient visible-light catalyst. Figure 4b is Tauc’s graph used
to find energy band gap of the synthesized nanoparticles
using following relation:
( )n
𝛼h𝜈 = A h𝜈 − Eg 2
­ g stand for absorption coefficient,
where α, h, ν, A and E
Plank’s constant, frequency, absorbance and band gap
J Mater Sci: Mater Electron (2017) 28:18236–18243 18239

Fig. 3  XPS spectra for a BFO,

b Ag-BFO and c Cu-BFO

Fig. 4  a UV–visible spectra

and b band gap calculation
using Tauc’s relations of BFO,
Ag-BFO and Cu-BFO

respectively [30]. The value of n is taken as 1 because
­BiFeO3 is a direct band semiconductor. The band gap has
been calculated by extrapolating graph to abscissa. The band
gap of BFO, Ag-BFO and Cu-BFO has been found to be
2.82, 2.40 and 2.14 eV respectively. It has been observed
that the deposition of metals results in the decrease of band
gap ­BiFeO3. The decrease in band gap indicates red shift in
the absorption edge. This could be attributed to localized
surface plasmon resonance absorption of metallic silver and
copper on the ­BiFeO3 surface [9, 18, 21].
3.4.2 Action spectra
The standard procedure has been followed to measure the
action spectra [21]. The action spectra of synthesized pho-
tocatalysts are shown in Fig. 5. It clearly reveals that in

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Fig. 5  Action spectra for BFO, Ag-BFO and Cu-BFO
visible range of spectrum, Ag-BFO and Cu-BFO exhibit
high quantum efficiency as compared to BFO. The observed
high quantum efficiency for Ag-BFO and Cu-BFO can be
ascribed to the generation of localized surface plasmon reso-
nance in the metal nanoparticles of Ag and Cu, which this
may lead to enhancement of their photocatalytic activities.
3.4.3 Time resolved photoluminescence spectra
The electron transfer from metal nanoparticles to semicon-
ductor nanoparticles and vice-versa along with the dynamics
of the charge recombination can be well understood with
Fig. 6  Time resolved photo-
luminescence decay curves for
BFO, Cu-BFO and Ag-BFO
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J Mater Sci: Mater Electron (2017) 28:18236–18243
time resolved photoluminescence spectroscopy (TRL). Fig-
ure 6, shows the dynamics of the charge carriers measured
by exciting the samples with the help of nitrogen pulse laser
and corresponding decay curves are obtained. The average
life time has been found to be 9, 13 and 16 ns for BFO, Cu-
BFO and Ag-BFO respectively. This is mainly associated
with the band edge of the lifetime as well as the trappings/
defects states. It has been found that the relaxation time of
electron–hole pairs increases as it move from bare BFO to
Cu-BF, Ag-BFO samples. The large value of the relaxation
time has been observed for Ag metal and this confirmed that
it exhibiting maximum electron capturing as well as storage
capacity and acting like better electron reservoir as compare
to Cu-BFO and BFO [31]. This is because of the fact that the
presence of metal nanoparticles always promotes the non-
radiative recombination.
3.4.4 Photocatalysis
In order to evaluate the photocatalytic activity of synthe-
sized photocatalyst BFO, Ag-BFO and Cu-BFO, the photo-
degradation of NBB and Sudan-I dyes has been carried out
with aqueous suspension of dyes with photocatalyst under
solar light irradiation. The time course curves between the
extent of degradation (C/C0) versus time has been shown in
Fig. 7, here C is the absorbance of substrate solution at each
interval of time of irradiation and C ­ 0 is the absorbance of
the initial concentration. It is clear from the Fig. 7 that 90%
of the NBB and Sudan-I dyes photodegraded with Ag-BFO
catalyst, while 40 and 62% with Cu-BFO and there is very
J Mater Sci: Mater Electron (2017) 28:18236–18243
Fig. 7  Time course graph for the photocatalytic degradation of a Sudan-I and b NBB dye
small variation with BFO in 40 and 50 min, respectively.
This is revealing that photodegradation efficiency of Ag-
BFO is highest amongst the synthesized catalyst. Also, the
time taken for the photodegradation of NBB dye is less than
that of Sudan-I. This can be well illustrated with the help of
schematic energy diagram as shown in Fig. 8. It is instituting
the proposed mechanism involving the various processes in
the photocatalysis of Ag-BFO and Cu-BFO. The enhanced
photocatalytic activity Ag-BFO and Cu-BFO than BFO can
be explained due to following reason:
• Formation of Schottky barriers Fig. 8 reflects the pos-
sible electronic transitions at metal/semiconductor inter-
face in the vicinity of the Fermi level of the synthesized
photocatalyst due to the charge equilibration, before and
after the contact with one another under the irradiation
Fig. 8  Schematic diagram
representing various electronic
transitions in Fermi level for
bare and metal (Ag, Cu) deco-
rated BFO nanoparticles
18241
of sun light. Bismuth ferrite is n-type semiconductor,
therefore Fermi level of it lies just below the conduction
band (CB), as shown in Fig. 8. The Fermi levels of metal
nanoparticles are lower than that of BFO. As the metal
and semiconductor are placed in contact, electrons in the
n-type semiconductor can lower their energy by travers-
ing the junction. As the electrons leave the semiconduc-
tor, a positive charge, due to the ionized donor atoms,
stays behind called hole. This charge creates a negative
field and lowers the band edges of the semiconductor.
Electrons flow into the metal until equilibrium is reached
between the diffusion of electrons from the semiconduc-
tor into the metal. There is shifting of Fermi level of
exited metal nanoparticles near the conduction band of
the ­BiFeO3 nanoparticles, because of increase in electron
accumulation at the Fermi level of metals, and this is in
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well agreement with Wood et al. [32]. This would inhibit
the recombination
) rate of photogenerated electron–hole
pair h+VB + e−CB and increase the light harvesting proper-
(
ties [33]. The various reactions involed in the degrada-
tion of dyes are illustrated below:
BiFeO3 + h𝜈 (photon) → BiFeO3 h+VB + e−CB
( )
h+VB + H2 O or OH− → OH⋅
2e−CB + O2 + 2H+ → H2 O2
H2 O2 + e−CB → OH− + OH⋅
The hydroxyl radicals produced during the chemical
reaction reacts with pollutants, i.e., dyes—NBB and
Sudan-I and dissociates them into the simpler form
viz., carbon dioxide and water and these are environ-
ment friendly [34].
• Size of deposited metal nanoparticles The photocatalytic
properties of metal decorated semiconductor nanopar-
ticles is dependent on the size of metal nanoparticles.
Basically, the photocatalytic process involves the photo-
induced electron-transfer process. The capability of metal
nanoparticles to accept electrons from excited semicon-
ducting nanoparticles is size-dependent, and occurs if
and only if, the size of the deposited metal nanoparticle
is ≤5 nm [25, 26]. In present case the size of the Cu and
Ag decorated nanoparticles is 5 nm, thereby their photo-
catalytic properties are superior to BFO. But, however,
in Lu et al. [9] size of the decorated Ag metals nanopar-
ticles is bigger, i.e., 20–50 nm and show less efficiency
to degraded methyl orange dye.
• Electron reservoirs It has been found that the modifi-
cation of semiconductor nanostructures by the decora-
tion of coinage metals such Au, Ag, Cu enhances their
photo-catalytic performance [4, 35, 36]. The decora-
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J Mater Sci: Mater Electron (2017) 28:18236–18243
tion of coinage metals behave like electron reservoirs.
These internment the photo-generated electrons and
leave behind the holes on the photocatalyst surface,
thus, they could inhibit the recombination of photogen-
erated electron–hole pairs and enhance the photocata-
lytic activity [4, 35, 36].
• Localized surface plasmon resonance In addition, the
localized surface plasmon resonance (LSPR) effect
observed in the action spectra and UV–visible spectra,
Figs. 5 and 6 also play an important role and influence
the photocatalytic activity. Among modified noble met-
als, Ag is one of the most suitable for industrial appli-
cations because of its low cost and easy preparation
[37].
• Lower quantum yield The action spectrum is suggesting
that the quantum efficiency of the Ag-BFO is highest
amongst the synthesized photocatalyst. Further, it is
clear from the photo catalytic properties (Fig. 7) that
the degradation of dyes is higher in Ag-BFO than Cu-
BFO and BFO. Therefore, it can be hypothesized that
photo-generated electrons having high energy are local-
ized and actively participate in degradation of organic
compounds. These electrons are highly reactive, and
possess higher quantum yield.
• Red-shift in band gap The observed red-shift in the
band-gap of Ag-BFO and Cu-BFO compare to BFO
leads to increase in the scattering of light and this pro-
cess is size-dependent, i.e., depends upon the size of
on metal nanoparticles [21, 30]. Hence, it can be drawn
that when sun light falls on the suspension solution of
photocatalyst and dyes, then metal nanoparticles (Ag
and Cu) acts like pool of electrons and this impedes the
recombination of electrons and holes. The scavenging
nature of metal nanoparticles increases the rate of the
photoreaction and hence photodegradation [21].
• High volume to surface ratio of atoms The synthesized
photocatalyst are of nanosized as confirms from Fig. 2
and have high volume to surface ratios of atoms. It is
well known fact that rate of reaction is directly propor-
tional to the surface area. Therefore, higher the surface
area higher will be rate of photo-degradation of dyes.
J Mater Sci: Mater Electron (2017) 28:18236–18243
Other than above said facts, the Fig. 7 suggest that the
high numbers of electrons are being injected in Ag-BFO
nanoparticles than Cu-BFO and BFO, thereby resulting in
the higher photocatalytic activity under visible light. Also,
the effect of quantum-confinement cannot be ignored for
the improvement in the photocatalytic properties of the
synthesized photocatalyst.
4 Conclusions
Bare and coinage metal (Ag, Cu) decorated ­BiFeO3 nano-
particles has been synthesized. The photocatalytic activi-
ties of these synthesized nanoparticles for the degradation
industrial dyes viz., NBB and Sudan-I have been explored.
Synthesized ­BiFeO3 nanoparticles exhibit rhombohedral
structure (R3c) and have hexagonal phase. TEM confirmed
that 5 nm Ag nanoparticles have been decorated on the sur-
face of 19 nm BFO, while 5 nm of Cu nanoparticles on
decorated on the surface of 16 nm BFO in Ag-BFO and
Cu-BFO respectively. This further corroborated with XPS
investigation. UV–visible spectra revealed that the band gap
of synthesized BFO, Ag-BFO and Cu-BFO nanoparticles
is 2.82, 2.40 and 2.14 eV, respectively, clearly demonstrat-
ing the red-shift upon decoration of metal nanoparticles.
The action spectra establish the high quantum efficiency for
Ag-BFO as compare to Cu-BFO and BFO due to genera-
tion of localized surface plasmon resonance. The average
life time calculated from time-resolved photoluminescence
spectroscopy has been found to be 9, 13 and 16 ns, respec-
tively for BFO, Cu-BFO and Ag-BFO. Photo degradation
study established that 90% of the NBB and Sudan-I dyes
photodegraded with Ag-BFO catalyst, while 40% and 62%
with Cu-BFO and there is very small variation with BFO
in 40 and 50 min, respectively. This is revealing that pho-
todegradation efficiency of Ag-BFO is highest amongst the
synthesized catalyst. Hence, it can be drawn from this study
that the synthesized photocatalyst are proposed to be highly
efficient for the degradation of NBB and Sudan-I dyes.
Acknowledgements Dr. G. S. Lotey gratefully acknowledges the
Department of Science and Technology (DST), Government of India,
for providing funding, to carry out this research work under Indo-
Ukraine International project via their sanction letter no. INT/UKR/P-
17/2015 dated 14 August 2015. The work is partly supported by the
Ministry of Education and Science of Ukraine through Indo-Ukraine
International project “Spectroscopy study of multifunctional multifer-
roics materials” (protocol MES of Ukraine from 09.09.2015).
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