Superlattices and Microstructures 69 (2014) 194203

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Superlattices and Microstructures

journal homepage: www.elsevier.com/locate/superlattices

Preparation, characterization, and enhanced

visible-light photocatalytic activity of AgI/Bi2WO6
composite
Bingang Chen, Yongyong Deng, Hanxuan Tong, Jianhua Ma
College of Chemistry and Materials Engineering, Wenzhou University, Wenzhou, Zhejiang 325035, PR China

a r t i c l e

i n f o

Article history:
Received 9 January 2014
Accepted 29 January 2014
Available online 6 February 2014
Keywords:
Visible light
Photocatalyst
AgI/Bi2WO6
Heterojunction
Electronhole separation

a b s t r a c t
In this study, a series of AgI/Bi2WO6 heterojunction photocatalysts
were synthesized with depositionprecipitation method. The
photocatalysts were characterized by X-ray diffraction (XRD),
scanning electron microscopy (SEM), transmission electron
microscopy (TEM), energy-dispersive spectroscopy (EDS), UVvis
diffuse reectance spectroscopy (DRS). The photocatalysts exhibited enhanced photocatalytic activity on the RhB dye degradation
under visible-light irradiation. The 58.5% AgI/Bi2WO6 sample was
observed to have the highest photocatalytic degradation efciency.
Based on the calculated energy band positions, the mechanism of
enhanced photocatalytic activity was discussed.
2014 Elsevier Ltd. All rights reserved.

1. Introduction
With the industrial development of human society, environment problems are becoming more and
more serious. Since the discovery of photocatalytic splitting of water and photoinduced degradation of
organic compounds by TiO2 as a catalyst under UV light irradiation [1,2], various semiconductor
photocatalysts have been extensively developed to purify water and air. Sunlight contains 4%
ultraviolet light and 46% visible light, which can be used as excitation light source for semiconductor
photocatalyst [1,3]. However, this technique can hardly satisfy practical water treatment due to the
rapid recombination of the photoexcited carriers and limited efciency in visible light [4]. Therefore,
developing effective visible light-driven photocatalyst will be greatly benecial for environmental
Corresponding author. Tel.: +86 577 86669317; fax: +86 577 86689508.
E-mail address: mjh820@ustc.edu (J. Ma).
http://dx.doi.org/10.1016/j.spmi.2014.01.019
0749-6036/ 2014 Elsevier Ltd. All rights reserved.

B. Chen et al. / Superlattices and Microstructures 69 (2014) 194203

195

remediation. It is well known that the high performance of photocatalyst will mainly be greatly
depends on such characteristics as surface area, band gap, crystallinity, and quantum efciency
[57]. Pure semiconductor oxides usually exhibit low photocatalytic activity. In order to solve this
problem, great efforts have been made to improve the photocatalytic activity. Besides doping semiconductor oxides with metals or non-metals [810], fabrication of hetero-structured photocatalysts
with different carriers of different band gaps has turn out to be an effective approach [1113].
The interconnected heterojunction composite lead to low recombination ratio of photoexcited
electronhole pairs. Thus high photocatalytic activity can be achieved.
As a typical Aurivillius oxide, Bi2WO6 has been found to possess excellent intrinsic physical and
chemical properties, such as ferroelectric piezoelectricity behavior, and non-liner dielectric
susceptibility [1418]. Recently, many efforts have been made to synthesize Bi2WO6-semiconductor
nanocomposites (such as Bi2WO6/WO3 [19], Bi2WO6/Bi2O3 [20], Bi2WO6/BiOI and [21]) to effectively
decrease the recombination probability of electronhole pairs to enhance the photocatalytic activities.
The hybrid nanoparticles have shown novel catalytic properties compared to individual single
component materials. Silver halide (AgX:X = Cl, Br, and I) is an important photosensitive material
which is extensively used in photography. Under visible light, AgX absorbs a photon and generates
an electron and a positive hole. If the photographic process is inhibited, the generated electron and
hole can be used in the photocatalytic process [22]. Considering these great merits of Bi2WO6-based
complex photocatalysts and the limitations of AgX in photocatalytic system, the combination of
Bi2WO6 and AgI may be regarded as an ideal strategy to construct a stable and efcient heterojunction
photocatalyst.

2. Material and methods

All reagents were of analytical purity. They were used without further purication. Bismuth nitrate
(Bi(NO3)3), bismuth tungstate (Na2WO42H2O), Rhodamine B (RhB), nitric acid (HNO3), silver nitrate
(AgNO3) and potassium iodide (KI) were purchased from Aladdin Chemical Reagents Co. and China
chemical Reagent Ltd. Deionized water and absolute ethyl alcohol were used in all experiments.
In a typical synthesis, 2.91 g Bi(NO3)35H2O and 0.99 g Na2WO42H2O were separately dissolved in
12 mL nitric acid solution (2 mL concentrated HNO3 and 10 mL distilled water) and 20 mL distilled
water. Then the Bi(NO3)3 solution was dropped into the Na2WO4 solution with constant magnetic
stirring for 30 min. The mixture was transferred to a 50 mL Teon-lined stainless steel autoclave
and the autoclave maintained at 200 C for 12 h. The resultant precipitate was washed with distilled
water (three times) and absolute ethanol (two times) to remove any ionic residual. Finally, the
obtained product was dried in oven at 80 C for 10 h.
AgI/Bi2WO6 was prepared by the depositionprecipitation method. The procedures are as follows:
0.5 g Bi2WO6 was added to 20 mL distilled water. The suspension was stirred for 3 h. 1 mmol AgNO3
was added to the suspension. Then 1 mmol KI was quickly added to the mixture with vigorous stirring.
Similar to this procedure, 2 mmol, 3 mmol, 4 mmol AgNO3 and KI were added to the Bi2WO6
suspension respectively. The prepared samples were denoted as 31.97% AgI/Bi2WO6, 48.45%
AgI/Bi2WO6, 58.5% AgI/Bi2WO6 and 65.3% AgI/Bi2WO6 respectively. These numbers refer to the AgI
weight ratios. For comparison, pure AgI sample was also prepared by a simple precipitation method
with AgNO3 and KI.
A 500 W Xe lamp with a 420 nm cutoff lter was used as the light source to provide visible-light
irradiation. The procedures were as follows: 0.1 g of the prepared photocatalyst was dispersed in a
50 mL RhB solution with concentration of 10 mg/L (pH = 7). Before irradiation, the suspensions was
magnetically stirring in the dark for 30 min to establish the absorptiondesorption equilibrium
between photocatalysts and RhB. At the given time intervals, 4 mL suspension was sampled,
centrifuged and analyzed by UVvis spectrophotometer. The initial and resultant solutions were
analyzed. The degradation efciency of RhB was calculated according to the initial and nal
absorbance of RhB in the solutions, according to the formula: g A0  At =A0  100%. Where g is
the photocatalytic efciency, A0 is the initial absorbance of RhB, At is the absorbance of RhB after
illumination(for time t).

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The crystal structures of the synthesized powers were determined by X-ray powder diffraction
(XRD) on a Bruker D8 diffractometer with CuKa radiation (k = 1.5418) in the range of 2h = 1090 .
The nanoparticle morphology was inspected by using a scanning electron microscope (Nova NanoSEM
200) and transmission electron microscope (JEOL JEM-2011). The UVvis spectra of prepared samples
were measured by using a UVvis spectrophotometer (UV 2501, Shimadzu).

3. Results and discussion

XRD pattern of Bi2WO6 was shown in Fig. 1a. A series of characteristic peaks at different d-spacing
are observed. They are in according with the standard Bi2WO6 (JCPDS card No. 39-0256). The renement gives the cell constants (a = 5.4552 , b = 16.4474 and c = 5.4468 ), which are consistent with
the value reported in the literature (a = 5.457 , b = 16.435 and c = 5.438 ) (JCPDS card No. 390256). From the renement results, we can conclude that there are no impurities in our product.
The XRD patterns of Bi2WO6 powders with different AgI amount are shown in Fig. 1. For comparison,
the XRD patterns for Bi2WO6 are also given. As shown in Fig. 1a, The diffraction peaks of Bi2WO6 are
clearly observed. We can see diffraction peaks ((1 0 0), (0 0 2), (1 0 1), (1 1 0), (1 0 3) and (1 1 2)) of AgI
appear when AgI content is 1 mmol. When the amount of AgI increases from 1 mmol to 4 mmol,
the intensity of diffraction peak of AgI improves remarkably while the intensity of diffraction peak
of Bi2WO6 decreases remarkably.
Fig. 2 shows the SEM images of AgI, Bi2WO6 and 58.5% AgI/Bi2WO6 composites. Fig. 2a shows typical SEM images of Bi2WO6 sample annealed at 200 C for 12 h. It looks like a ower. It can be seen that
the sample consists of particles with an average diameter of 3.64.3. The particles exhibit slightly
agglomerated morphology due to the ultrane nature of the sample. However, the morphology of pure
AgI was quite different from the pure Bi2WO6. As shown in Fig. 2b, the obtained AgI particles exhibit
cubic morphology with the edge length of 1355. Fig. 2c and d shows the SEM images of 58.5% AgI/
Bi2WO6 composites. In Fig. 2c and d, the ower-like particles can be attributed to Bi2WO6 (according
to Fig. 2a), while the small particles can be attributed to AgI (according to Fig. 2b). There were many
nanoparticles with small size on the surface. It can be clearly seen that small hetero particles were distributed uniformly on the surface of the Bi2WO6 particles. It can be inferred from Fig. 2d that the AgI
particle is smaller than pure AgI particle with sizes of 40100 nm, deposited over the surface of

100 002

101
100

002

Intensity/a.u.

101
002

100

112
103

110

002

25

112

103

100 101

110

(e)

(d)

(c)

(b)

(a)

35

112

103

30

110

112
103

101

20

Bi WO

110

40

45

50

55

60

65

70

75

80

2-Theta/degree
Fig. 1. XRD patterns of AgI/Bi2WO6 catalysts prepared with different AgI amounts: (a) 0, (b) 31.97%, (c) 48.45%, (d) 58.5%, and
(e) 65.3%.

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197

Fig. 2. SEM images of (a) pure Bi2WO6 and (b) pure AgI, (c and d) 58.5% AgI/Bi2WO6.

Bi2WO6. The EDS spectrum in Fig. 3 further demonstrates that the AgI/Bi2WO6 composites is composed
of Bi, O, W, Ag, I, which proves that AgI existed in the AgI/Bi2WO6 heterojunction. Fig. 4a and b shows
the TEM images of typical composite hetero-structure. Fig. 4a and b clearly exhibits that small particles disperse over the edge of large Bi2WO6 particles. They form a kind of composite with a heterojunction structure. The TEM analysis further conrmed the coexistence of AgI and Bi2WO6 in the samples.
Fig. 5a shows UVvis diffuse reection spectra of Bi2WO6, AgI, and 48.45% AgI/Bi2WO6 composites.
For pure Bi2WO6, the absorption spectrum display absorption bands in the range of 360460 nm. It can
be seen that the AgI display strong absorption bands in the range of 370440 nm in Fig. 5a. It indicates
that the prepared samples can absorb visible light. These results indicated that AgI/Bi2WO6
composites have potential ability for photocatalytic decomposition of organic contaminants under visible-light irradiation. The band gaps of the AgI and Bi2WO6 samples can be estimated by using the
KubelkaMunk function (shown in Fig. 5b and c): The band gap of AgI was found to be 2.81 eV, which
is consistent with the value reported in the literature (2.80 eV) [23]. The band gap of Bi2WO6 was estimated to be 2.78 eV, which is consistent with the value reported in the literature (2.77 eV) [24]. Fig. 5a
shows UVvis diffuse reectance spectrum of 48.45% AgI/Bi2WO6. Compared with pure AgI (shown in
Fig. 5a), it can be seen that the absorption wavelength range of the 48.45% AgI/Bi2WO6 is substantially
extended toward visible light and the ability of light absorption is enhanced. The absorption edge
exhibits a slight shift towards shorter wavelengths for the 48.45% AgI/Bi2WO6, revealing the good contract between Bi2WO6 and AgI crystallites as a consequence of the two-phase dispersion produced by
depositionprecipitation method. Since the absorption wavelength range is signicantly extended

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Fig. 3. The EDS spectrum of as prepared 58.5% AgI/Bi2WO6 sample.

greatly toward visible region, the formation rate of electronhole pairs on the photocatalyst surface is
also substantially increased, resulting in higher photocatalytic activity.
Using RhB dye as a contaminant, the photocatalytic activity of the AgI, Bi2WO6 and AgI/Bi2WO6
composites were tested. The result was shown in Fig. 6a. It can be seen that photocatalytic activity
of all AgI/Bi2WO6 heterojunction photocatalysts is higher than that of AgI and Bi2WO6, which indicated that RhB could be degraded more efciently by AgI/Bi2WO6 composites than AgI but also
Bi2WO6. It was interesting that the 58.5% AgI/Bi2WO6 heterojunction exhibited the highest photocatalytic degradation efciency. The photocatalytic activity of AgI/Bi2WO6 composites increased with the
increasing AgI content. But the photocatalytic activity decreased at the higher AgI content (>58.5%
AgI). This probably derived from excessive trapping sites caused by the increased AgI amount in the
AgI/Bi2WO6 composite which facilitated the recombination of photoinduced carriers. So it suggested
that the optimal AgI content in AgI/Bi2WO6 composite is 3 mmol.
Fig. 6b shows the variation of absorption of RhB versus irradiation time on the 58.5% AgI/Bi2WO6
composite and the shift of maximum absorption peak. It can be seen in Fig. 6b that the characteristic
absorption band of RhB at 554 nm signicantly decreased. The wavelength of maximum absorption of
RhB had a signicantly offset. The maximum absorption peak gradually shifted from 554 nm to
497 nm. According to the reports, this blue shift of absorption wavelength can be interpreted by
the incomplete mineralization of RhB during the light-irradiation.
Photoluminescence (PL) emission spectra mainly result from the recombination of free carriers.
Therefore, the PL emission spectrum is a useful technique to survey the separation efciency of the
photogenerated charge carriers in a semiconductor. In general, the lower the PL intensity, the lower
the recombination rate of photogenerated electronhole pairs. The photocatalytic activity of semiconductor photocatalysts is higher. Fig. 7 presents the comparison of PL spectra (excited at 295 nm) of
Bi2WO6, AgI, 31.97% AgI/Bi2WO6, 48.45% AgI/Bi2WO6, 58.5% AgI/Bi2WO6 and 65.3% AgI/Bi2WO6 at
room temperature. It can be seen that 58.5% AgI/Bi2WO6 has the lowest relative PL intensity suggesting that it has lowest recombination rate of electron and hole pairs, which results in highest photocatalytic activity [25]. It is in accordance with the photocatalytic experiment.

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199

(a)

(b)
AgI

Fig. 4. (a) TEM image of 58.5% AgI/Bi2WO6 and (b) HRTEM image of 58.5% AgI/Bi2WO6.

It is known that the photocatalytic activity of photocatalyst mainly depends on whether the electronhole pairs can be separated effectively [2630]. Photocatalytic reaction is effective only when the
photoexcited electron/holes can be captured. If there are no appropriate trapping centers for electron
or holes, they will recombine and annihilate each other, giving off heat inside or on the semiconductor
surface. In order to increase the photocatalytic activity of the photocatalyst, two important ways
should be taken into consideration. One is to increase the separation efciency of the photoexcited
electronhole pairs and the other is to increase the amount of the photocatalytic active species
[31]. When loading AgI over Bi2WO6 particle, a number of micro-heterojunction photocatalyst AgI/
Bi2WO6 will be formed. The migration direction of the photogenerated charge carrier depends on
the band edge positions of the two semiconductors. The band edge positions of conduction band
and valance band of semiconductor can be determined with a simple approach [32]. The conduction
band (CB) and valance band (VB) potentials of the two semiconductors at the point of zero charge can
be predicated by the following empirical equation: ECB X  Ec  1=2Eg where X is the absolute electronegativity of the semiconductor, expressed as the geometric mean of the absolute electronegativity
of the constituent atoms, which is dened as the arithmetic mean of the atomic electron afnity and
the rst ionization energy. Ec is the energy of free electrons on the hydrogen scale (4.5 eV). Eg is the
band gap of the semiconductor. EVB can be determined by EVB = ECB + Eg. The X values for AgI and
Bi2WO6 are 5.49 eV and 6.4 eV, respectively. The calculated CB and VB edge potentials of AgI and
Bi2WO6 are shown in Table 1.
The photocatalytic property of the photocatalyst is mainly related to its corresponding band structure. As we can see from Fig. 8, ECB of Bi2WO6 is located at 0.5 eV, which is more positive than the CB

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100
90

(a)

80
70

R%

60
Bi 2 WO 6

50

48.45% AgI/Bi 2 WO6

40

AgI

30
20
10
0
380

400

420

440

460

480

500

520

540

Wavelength (nm)

(Ahv) (eV)

(b)

Eg=2.78eV
Bi2 WO6

2.7

2.8

2.9

3.0

3.1

3.2

3.3

hv (eV)

(Ahv) (eV)

(c)

AgI

2.60

Eg=2.81ev

2.65

2.70

2.75

2.80

2.85

2.90

hv/eV
Fig. 5. UVvis diffuse reectance spectra of photocatalysts (a) estimated band gap of Bi2WO6 and AgI by KubelkaMunk
function (b and c).

potential of AgI 0.43 eV. EVB of AgI is located at 2.38 eV, which is negative than the VB potential of
Bi2WO6 (3.28 eV). According to our estimated Eg values of AgI and Bi2WO6, the schematic energy band
diagram of the composite can be depicted in Fig. 8. When the combination is put under near UV-light
irradiation, both semiconductors are excited. On the one hand, the CB electrons (AgI) easily ow into
the CB edge of Bi2WO6 through the interface because the CB edge of AgI is higher than that of Bi2WO6,
thereby, preventing the formation of silver atoms by the combination of the photogenerated electrons
and the interstitial sliver ion. One the other hand, because the VB edge level of the Bi2WO6 is lower
than that of AgI, holes in the VB edge of Bi2WO6 will transfer to that of AgI by the control of interface.
In such a way, the AgI/Bi2WO6 composites enable the AgI to be stable under irradiation. Additionally,
we can observe that AgI and Bi2WO6 have matching band potentials, which can decrease the
recombination of electrons and holes. It supports the experimental result that AgI/Bi2WO6 composites
exhibited much higher photocatalytic performance than the single AgI or Bi2WO6.

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1.0

(a)

0.9

Bi 2WO6
31.97% AgI/Bi 2 WO 6
48.45% AgI/Bi 2 WO 6
58.5% AgI/Bi2 WO 6
65.3% AgI/Bi2 WO 6
AgI

0.8

A/A 0

0.7
0.6
0.5
0.4
0.3
0.2
0.1
0

Irradiation time (h)

1.0
0.9

(b)
0h

0.8

1h
Absorbance

0.7

2h

0.6

3h

0.5

4h

0.4
0.3

58.5% AgI/Bi 2 WO6

0.2
0.1
0.0
300

400

500

600

Wavelength (nm)
Fig. 6. (a) Effect of AgI content in the heterojunction catalysts on the degradation of RhB and (b) temporal UVvis absorption
spectra changes during photocatalytic degradation of RhB by 58.5% AgI/Bi2WO6 under visible light irradiation.

AgI
Bi2WO6
31.97% AgI/Bi2WO6
48.45% AgI/Bi2WO6

Intensity

58.5% AgI/Bi2WO6

400

65.3% AgI/Bi2WO6

425

450

475

500

525

550

Wavelength (nm)
Fig. 7. PL spectrum of Bi2WO6, AgI and AgI/Bi2WO6 sample with different AgI content.

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Table 1
Absolute electronegativity, estimated band gap, energy levels of calculated conduction band edge, and valence band at the point of
zero charge for Bi2WO6 and AgI.
Semiconductor

Absolute electronegativity (X)

Calculated conduction
band edge (eV)

Calculated valance
band edge (eV)

Estimated energy band

gap, Eg (eV)

Bi2WO6
AgI

6.4
5.49

0.5
0.43

3.28
2.38

2.78
2.81

Fig. 8. Schematic diagram of separation process of photoexcited electronhole.

4. conclusion
The heterojunctions AgI/Bi2WO6 synthesized by depositionprecipitation method show better photocatalytic activity than single Bi2WO6 or AgI. The obvious increment in the photocatalytic experiment
as AgI is combined over the Bi2WO6 is mainly ascribed to the smooth charge transfer between the two
materials and the consequent electronhole separation in two materials. The best photocatalytic
activity occurs when the weight proportion of AgIBi2WO6 is 58.5%. As the formation of heterojunction,
the photogenerated electronhole pairs are separated due to the band matching of the heterostructures. The photocatalytic activity is improved greatly.
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