Applied Surface Science 368 (2016) 6368

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Applied Surface Science

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

Synthesis, surface and optical properties of Ag2 Cu(VO3 )4 and Cu(VO3 )2

vanadates
Xuebin Qiao a , Yingpeng Wan b , Yuze Li b , Lin Qin c , Hyo Jin Seo c,
a
Jiangsu Key Laboratory of Advanced Laser Materials and Devices, School of Physics and Electronic Engineering, Jiangsu Normal University, Xuzhou
221116, PR China
b
College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, PR China
c
Department of Physics and Interdisciplinary Program of Biomedical, Mechanical & Electrical Engineering, Pukyong National University, Busan 608-737,
Republic of Korea

a r t i c l e i n f o a b s t r a c t

Article history: Ag2 Cu(VO3 )4 and Cu(VO3 )2 were prepared via the solgel chemical synthesis. The phase formation was
Received 22 October 2015 conrmed by X-ray powder polycrystalline diffraction (XRD) measurements. The surface properties were
Received in revised form 20 January 2016 measured with the scanning electron microscope (SEM), energy dispersive spectra (EDS), transmission
Accepted 25 January 2016
electron microscopy (TEM), and nitrogen adsorptiondesorption isotherms. The optical properties and
Available online 28 January 2016
the band-gap structures were investigated. The vanadates have efcient optical absorption in the UV to
visible wavelength region with an indirect allowed transition. Ag2 Cu(VO3 )4 has smaller band gap (1.85 eV)
Keywords:
than that of Cu(VO3 )2 (2.03 eV). The narrowed band gap is due to the hybridization between the Ag-4d and
Inorganic compounds
Semiconductors
O-2p in the valence band. The photocatalysis was investigated by photodegradation of methylene blue
Catalytic properties (MB) solutions excited by the light with wavelength longer than 420 nm. Correspondingly Ag2 Cu(VO3 )4
Optical properties has more efcient photocatalytic activity on MB photodegradation than that of Cu(VO3 )2 . The photocat-
Electronic band structure alytic mechanisms were suggested according to the band positions and the trapping experiments.
Photocatalysis 2016 Elsevier B.V. All rights reserved.

1. Introduction
The advanced photocatalysts driven by visible light have
attracted continuous attention in potential applications such as
water splitting, environment pollution solution, and CO2 reduc-
tion etc. In recent years photocatalysts driven by visible-light have
been widely developed such as TiO2 [14], ZnO [5,6], g-C3 N4 [79],
BiVO4 [10], Ag3 VO4 [11], Ag2 O [12], and oxides nanocomposites
[13], etc. To develop semiconductors with narrow band gaps is one
of the major strategies established to design visible light-driven
photocatalysts.
Among the wide investigation, Ag-containing vanadates could
act as efcient photocatalysts because of the following character-
istics. Firstly, there are efcient optical absorption centers (VO4 3 )
groups in vanadates such as BiVO4 [14], InVO4 [15], SrBi3 VO8 [16],
etc., where photo-induced electrons can be easily induced by the
electron transition from oxygen (2p orbital) to V5+ (vacant 3d
orbital) ions [17]. This is important for its excellent photocatalytic
activity for photodegradation of dyes or depleting H2 O. Secondly,
Corresponding author. Tel.: +82 51 629 5568; fax: +82 51 6295549.
E-mail address: hjseo@pknu.ac.kr (H.J. Seo).
Ag+ is a special 4d transition metal ion with its electron congura-
tion in the ground state described by [Kr] 4d10 5s1 . The mixing of
Ag+ and O2 electronic states at the valence band maximum (VBM)
is a regarded to be one of the principles for lowing band energy of
semiconductors [18]. Kato et al. [19] have concluded that Ag+ ions in
a compound usually can led a valence band to a more negative posi-
tion than O 2p orbital at a more positive level, which is preferable for
water oxidation to form O2 . Usually Ag ions in lattices are important
to enhance the photocatalytic propertied [1921]. Consequently,
binary oxides of Ag and V have been studied as efcient photocata-
lysts, which show intense absorption bands of visible light due to
narrowed band-gap such as - and -AgVO3 [22], Ag4 V2 O7 [23],
Ag3 VO4 [24], Ag2 Sr(VO3 )4 [25].
In this work, Ag2 Cu(VO3 )4 vanadate was selected to develop a
potential photocatalyst, and the reference sample Cu(VO3 )2 was
also investigated as a comparison. The motivations are the fol-
lowing. Firstly, usually Cu2+ doping in a host could enhance the
Madelung energy and stabilize the silver-based oxides, which
are sensitive to photo-corrosion. Secondly, recently Li et al.
[25] reported the photocatalisis of Ag2 Sr(VO3 )4 and Sr(VO3 )2 .
Ag2 Sr(VO3 )4 has the lower O2 -evolution rates of Ag2 Sr(VO3 )4
(8.1 mol h1 ) than that of Sr(VO3 )2 (12 mol h1 ) [25]. This is due
to the bigger Sr2+ ions inserted into the lattices, which brings out the

http://dx.doi.org/10.1016/j.apsusc.2016.01.221
0169-4332/ 2016 Elsevier B.V. All rights reserved.
64 X. Qiao et al. / Applied Surface Science 368 (2016) 6368

0.9 (a)

Ag2Cu(VO3)4
Intensity (a. u.)

0.6

0.3

0.0
10 20 30 40 50 60 70 80 90 100 110 120
Two theta (degree)

1.0
(b)
0.8
Intensity (a. u.)

0.6 Cu VO3 2

0.4

0.2

0.0
20 40 60 80 100 120

Two theta (degree)

Fig. 1. The experimental structural XRD patterns of Ag2 Cu(VO3 )4 (a) and Cu(VO3 )2 .

isolation of Ag+ ions inhibiting hybridization between Ag-d and O-

p. Compared with the bigger Sr ions (1.18 A, CN = 6) in Ag2 Cu(VO3 )4 ,
the smaller Cu2+ (0.73 A, CN = 6) could greatly reduce the inhibiting
effect for Ag dO p hybridization. Thirdly, according to the experi-
mental results available for the copper vanadate oxides, the lower
conduction band usually could be observed due to the mainly Cu-3d
wave functions in the conduction bands [26].
Ag2 Cu(VO3 )4 and Sr(VO3 )2 were developed by the Pechini
method. The phase formations were conrmed by XRD mea-
surements. The surfaces were characterized by morphologies,
elemental formation and BET measurements. The band energy
structure and photocatalytic abilities on degradation of methylene
blue (MB) dye were reported.
2. Experimental
The synthesis of Ag2 Cu(VO3 )4 and Cu(VO3 )2 powders were com-
pleted by the Pechini method. The starting materials are Cu(NO3 )2
(99.99%), AgNO3 (99.99%), and NH4 VO3 (99.99%). At rst, each of
the chemicals was dissolved in the citric acid solutions to realizing
the complexation of the Ag+ , Cu2+ and V5+ ions, respectively. The
solutions were promoted for 3 h at 90 C. Then the solutions were
mixed together keeping stirring for 25 h to get some yellow pre-
cursor gel. Then the gels were heated at 650 C for 5 h to burn off all
the organic contents. Finally the ne powders were obtained after
the elimination of organic components during the heating process.
XRD patterns were completed on a Rigaku D/Max diffractome-
ter operating at 40 kV, 30 mA with Cu K as an incident radiation.
The surface morphologies of the nanoparticles were conrmed by
scanning electron microscopy (SEM, Hitachi S-4800, Japan) and
Fig. 2. The typical SEM photos of Cu(VO3 )2 (a) and Ag2 Cu(VO3 )4 (b).
transmission electron microscopy (TEM, JEOL JEM-2100, Japan).
The N2 desorptionadsorption isotherm was performed at 77 K (liq-
uid nitrogen) by instrument of Nova 2000e (Quanta chrome Corp.).
The BrunauerEmmettTeller (BET) method was applied to deter-
mine the specic area. The sample was degassed at 150 C for 5 h
before this measurement.
The photocatalysis experiments were completed. The visible
light source of a 500 W Xe lamp was applied. UV light was moved
off by putting a cut-lter (420 nm). Air was input the reactor by a
pump with the ow rate at 500 mL min1 . For a photocatalysis test,
0.05 g of photocatalyst was dissolved in 300 mL of MB (10 mg L1 )
solution. The solutions were put in dark for 1 h to get adsorp-
tion/desorption equilibrium before the photocatalysis test. 5 mL
MB was taken to measure optical absorption at a time interval.
3. Results and discussion
3.1. Phase formation and surface characteristics
The phase formations of Ag2 Cu(VO3 )4 and Cu(VO3 )2 powders
were conrmed by XRD measurements. The experimental XRD
 X. Qiao et al. / Applied Surface Science 368 (2016) 6368
Fig. 3. TEM pictures (a, b), HRTEM images (c), the SAED pattern (d) of Ag2 Cu(VO3 )4 .
patterns are shown in Fig. 1. The patterns of Ag2 Cu(VO3 )4 and
Cu(VO3 )2 are in agreement with the standard PDF cards No: 49-
0031 and 45-1054, respectively. No impurity lines can be observed.
The structural framework of Ag2 Cu(VO3 )4 is composed of the dis-
torted VO tetrahedron with corner-sharing connection. The Ca2+
ions have an eightfold-coordination. The Ag+ ion has an octahe-
dral site. There is a hollow channel formed by four corner-shared
VO4 . Along b-axil there is a cation layer of octahedron (Ag-site).
CuV2 O6 crystallizes in the triclinic layered structure (P1) [27],
which consists of innite chains in the [0 1 0]-direction formed by
the edge-shared CuO6 octahedra. V5+ ion has an oxidation state +5.
The typical SEM images of Ag2 Cu(VO3 )4 and Cu(VO3 )2 powders
are shown in Fig. 2, which have similar proles. There are many
short tetragonal columns with smooth surfaces. The samples show
the loosely aggregated particles, which can be easily separated from
each other by a slight stir when the particles were dispersed in
water solution. The size is not uniform with the estimated lengths
of 130 m, and widths of 13 m.
The TEM image of Ag2 Cu(VO3 )4 particles is shown in Fig. 3(a,
b), which has similar shapes to the SEM measurements. Evi-
dently, Ag2 Cu(VO3 )4 particles have uniform tetragonal slabs. The
high-resolution TEM (HRTEM) picture in Fig. 3(c) conrms the
single-crystalline nature of Ag2 Cu(VO3 )4 nanoparticles. As seen
in the inset of Fig. 3(c), some black dots could be observed in
the HRTEM measurements of some particles. The interplane dis-
tance displayed in the dots is about 0.23 nm, which is regarded
to (1 1 1) lattice space of metallic Ag. Actually small amount of Ag
by-product remnants on the surfaces usually cannot be avoidable
during the synthesis. The noble metals deposited on a photocat-
alyst enhance the capture of photo-induced electrons; decrease
the recombination of electronhole pairs. This benets the pho-
tocatalytic activity. Fig. 3(d) presents the measured selected area
electron diffraction (SAED), which exhibits the typical tetragonal
pattern for Ag2 Cu(VO3 )4 .
In addition, the elemental components in the lattices of
Ag2 Cu(VO3 )4 and Cu(VO3 )2 were examined by the typical EDS
65
measurement as displayed in Fig. 4. The signals indicate the
composition of Ag, V, Cu and O elements in the lattices. The exper-
imental ratio such as V/Ag and Cu/V are in agreement with the
theoretical values in the two chemical formula. Fig. 5 shows the typ-
ical measurements of N2 -adsorptiondesorption isotherm and the
corresponding pore-size distribution curves of Ag2 Cu(VO3 )4 and
Cu(VO3 )2 particles. BrunauerEmmettTeller (BET) results show
that Cu(VO3 )2 and Ag2 Cu(VO3 )4 have a specic surface area of
24.7 m2 g1 and 26.1 m2 g1 , respectively. In addition, there is a nar-
row pore size distribution for Cu(VO3 )2 and Ag2 Cu(VO3 )4 , which is
centered on around 3.2 nm and 3.5 nm (Fig. 5), respectively.
3.2. Optical absorption and band gap properties
The UVvis optical absorption spectra and the nature color of
Cu(VO3 )2 and Ag2 Cu(VO3 )4 powders were displayed in Fig. 6. The
absorption edges are about 600 nm indicating that both samples
can be driven by UV- and visible-light. It has been well docu-
mented that the optical absorption in visible wavelength region
of vanadates is induced by the CT transitions, i.e., an electron tran-
sition from O ligands to V inside of VO4 3 groups [17]. The energy
(wavelength) for the transition has been well conrmed, which
shows a dependence on the VO distance of [VO4 ]3 [28]. So far the
reported energy (wavelength) is in the UV- to near UV-wavelength
region, never extending to blue wavelength region [17]. Therefore
it is reasonable that the absorption in VO4 3 group (O2 V5+ )
in Cu(VO3 )2 and Ag2 Cu(VO3 )4 CT in should be limited in UV-near
UV region. According to the references in silver vanadtes [25], the
optical absorption in Cu(VO3 )2 and Ag2 Cu(VO3 )4 is attributed to
the mixed states from Ag, Cu and O at the valence band maximum
(VBM) due to the strong d-characteristics of Ag 4d states. This is one
of the principles for lowing the band energy of the semiconductors
[18].
As shown inset Fig. 6, Cu(VO3 )2 and Ag2 Cu(VO3 )4 are reddish
brown. This nature color is generated by the band-gap transitions.
The band gap (Eg ) is deduced from the formula h (h Eg )k .
66 X. Qiao et al. / Applied Surface Science 368 (2016) 6368

Weight % Atomic % Error %

(a) OK 14.31 36.58 10.27
VK 53.16 42.63 3.06
Cu K 32.52 20.78 5.25
Intensity (a. u.)

O Cu

Au V Cu
Cu

0 1 2 3 4 5 6 7 8 9 10 11 12 13

Weight % Atomic % Error %

400 (b) O-K 13.17 39.58 10.96

Ag-L 39.05 17.38 3.54

Ag
V V-K 37.33 35.19 3.60
300
Cu-K 10.42 7.83 5.45
Intensity (a. u.)

200
Ag
Cu
Ag
100
Au V
Cu
Cu
0
0 1 2 3 4 5 6 7 8 9 10 11 12 13
Energy (KeV)

Fig. 4. The typical EDS spectra of Cu(VO3 )2 (a) and Ag2 Cu(VO3 )4 (b). The table shows
the quanticational ratio of the elements.

15
280
Ds/Dd/m /g/nm

10
(a) Fig. 6. The UVvis optical absorption spectra of Cu(VO3 )2 (a) and Ag2 Cu(VO3 )4 (b);
240
2

inset shows the nature color and the calculation of band energy.
Volume adsorbed ml/g

200 5

160 Here is the optical absorbance,  is the frequency of the inci-

0
2 4 6 8 10 12 14 dent light, h (Planck constant) and k are constants. The transition
120
Pore diameter/nm nature is decided by the constant of k, which could possibly be direct
80 allowed, indirect allowed, direct forbidden and indirect forbidden
40
transitions when k = 1/2, 2, 3/2 or 3, respectively. The band gap (Eg )
of Cu(VO3 )2 and Ag2 Cu(VO3 )4 can be well taken at k = 2.
0 The linear portion is shown by extrapolating the curve to the
0.0 0.2 0.4 0.6 0.8 1.0
intercept of the x-axle. Inset in Fig. 6 displays the band gap tran-
Relative pressure P/P0 sitions for Cu(VO3 )2 and Ag2 Cu(VO3 )4 . The vanadates have the
20 indirect allowed characteristics with the lowest energy of 2.03 eV
and 1.85 eV for Cu(VO3 )2 and Ag2 Cu(VO3 )4 , respectively. In the
Ds/Dd/m /g/nm

160 15
(b) literatures the bandgap energies in some vanadate photocata-
Volume adsorbed ml/g

10 lysts were reported such as Mg3 V2 O8 (3.02 eV) [29], Zn3 V2 O8

120
5 (2.92 eV) [29], BiVO4 (2.262.43 eV) [30], and Sr(VO3 )2 (2.7 eV)
[25]. Compared with the references, the band gap of Cu(VO3 )2 and
0
80 2 4 6 8 10 Ag2 Cu(VO3 )4 are narrowed because of the introduction of Ag+ and
Pore diameter/nm Cu2+ in the lattices. As shown in inset Fig. 6, the two powder sam-
40 ples present yellowish red. The color is attributed to the band-gap
transitions in the lattices.
0 Recently Li et al. [25] reported that Ag2 SrV4 O12 and SrV2 O6
0.0 0.2 0.4 0.6 0.8 1.0 have the band gaps of 2.4 eV and 2.7 eV, respectively. In this work,
Relative pressure P/P0 the presence of Cu2+ in the lattices is benecial for the narrow
band gap due to the contribution of Cu2+ in the electronic com-
Fig. 5. The nitrogen adsorptiondesorption isotherms and pore-size distribution ponents. Consequently the optical absorption shifted toward the
curves (insert) of Cu(VO3 )2 (a) and Ag2 Cu(VO3 )4 (b). visible region thus to efciently utilize the solar energy. Compared

0.8
Intensity (a. u.)
0.6
0.4
0.2
400 480 560 640 720
Wavelength (nm)
Fig. 7. The UV/vis optical absorption of MB-Ag2 Cu(VO3 )4 solutions irradiated by
under visible light.
with Cu(VO3 )2 , Ag2 Cu(VO3 )4 possesses more narrowed band gap
due to the hybridization Ag+ ions with O components.
3.3. Photocatalytic activity and stability
The photocatalytic activities of Cu(VO3 )2 and Ag2 Cu(VO3 )4 were
tested by the MB photodegradation under the irradiation of the vis-
ible light with wavelength longer than 420 nm. The photocatalytic
degradation was recorded by the UV-visible absorption spectra
after the visible light illumination for different time periods. As
an example, the MB absorption with the existence of Ag2 Cu(VO3 )4
decreased with the increase of the irradiation shown in Fig. 7. The
optical absorption is getting weak and no new absorption peaks
were detected indicating no reaction intermediates in the process.
The degradation effects of the MB are shown in Fig. 8. The pho-
todegradation rate by Ag2 Cu(VO3 )4 can reach about 95% on visible
light irradiation. It could be been that Ag2 Cu(VO3 )4 has more active
photocatalytic ability to the visible light than Cu(VO3 )2 sample.
By referring the results in the references [25,26], the band struc-
tures of Cu(VO3 )2 and Ag2 Cu(VO3 )4 are shown in Fig. 9. Benko
and Koffyberg [26] have investigated the detailed band structure of
Cu(VO3 )2 . It has a typical indirect allowed transition with the con-
duction band formed by metal-3d wave functions; however, the
electrochemical experiments and the calculations conrmed that
the contribution of Cu-3d atomic wave functions to the valence-
band wave functions of vanadates is rather small. According to
the similar reports in silver vanadates [2225], the band structure
of Ag2 Cu(VO3 )4 was displayed in Fig. 9(b). The conduction band
1.0
Background
0.8 dark
C/C0
0.6
Cu VO3
0.4
Ag2Cu VO3
0.2 4 that the photo-reaction was dementedly driven by the OH radi-
0.0
0 50 100 150
Time ( min )
Fig. 8. The photodegradation effects of MB solutions by Cu(VO3 )2 and Ag2 Cu(VO3 )4 .
X. Qiao et al. / Applied Surface Science 368 (2016) 6368 67
0
30 min
60 min
120 min
180 min
210 min
240 min
800 880
Fig. 9. The suggested band components and positions of Cu(VO3 )2 (a) and
Ag2 Cu(VO3 )4 (b).
consists of the V/Cu 3d empty orbitals. While, similar to the com-
mon silver vanadates, the valence band of Ag2 Cu(VO3 )4 is the
mixture of both Ag 4d- and O 2p orbitals.
Theoretically, the positions for valence band and conduction
band are determined by the equations (1) and (2) [31]:
EVB = X E e + 0.5Eg (1)
ECB = X E e + 0.5Eg (2)
Here Eg is energy of the band gap, X is the absolute electronegativity
of a semiconductor (geometric mean of the absolute electronega-
tivity of the constituent atoms). Ee is the energy of free electrons
on the hydrogen scale (4.5 eV vs SHE). Here the experimental Eg is
1.85 eV for Ag2 Cu(VO3 )4 and 2.03 for Cu(VO3 )2 . The corresponding
VB and CB levels of Cu(VO3 )2 are calculated to be 2.376 and 0.345 eV
vs SHE, respectively. And the VB and CB levels in Ag2 Cu(VO3 )4 are
2.364 and 0.514 eV vs SHE, respectively.
Fig. 9 displayed the band components and positions of Cu(VO3 )2
and Ag2 Cu(VO3 )4 . The two vanadates show similar results, i.e., the
photocatalyst cannot convert the electrons into the reactive super-
oxide anions. However, the valence band maximum potential of
the vanadates indicates the creation of the hydroxyl radicals is
allowed. It could be suggested that the hydroxyl radicals could act
as the active species in the photo-decomposition of the organic
dyes. Similar to the reported results in Ag2 Sr(VO3 )4 [25], Cu(VO3 )2
and Ag2 Cu(VO3 )4 cannot split water into H2 , however, it is possible
to generate O2 in the photocatalysis process.
To detect active species in photocatalysis, the trapping exper-
iments were conducted. In this experiment, the three scavengers
(10 mmol/L) of the tertbutyl alcohol (TBA), ammonium oxalate (AO)
and benzoquinone (BQ) were added in the photocatalysis, which
are known to trap hydroxyl radical ( OH), hole (h+ ) and superox-
ide radical (O2 ), respectively [32,33]. As shown in Fig. 10, the
2
photodegradation on the MB solutions was greatly lower after
adding the TBA additive in the solutions. This experiment shows
cals, i.e., the active species of the hydroxyl radicals were created
by visible light irradiation in the photocatalytic process. The mech-
200 250 anism for the photodegradation was recommended. The excitons
could be initially created by the light excitation as shown in Eq.
(3). The photo-generated holes subsequently nish the formation
of the oxidize OH (Eq. (4)) and OH active species (Eq. (5)). It is
68 X. Qiao et al. / Applied Surface Science 368 (2016) 6368
1.0
0.8 sample+TBA
0.6
C/C0
sample+AO
0.4 sample+BQ
0.2
Ag2Cu VO3 4
0.0
0 25 50 75 100 125 150 175 200 225 250
Time ( min )
Fig. 10. The trapping photodegradation experiments by Ag2 Cu(VO3 )4 with the addi-
tions of different scavengers under visible light irradiation.
well-known that the radicals have strong oxidability, which nish
the MB photodegradation (Eq. (6)).
Ag2 Cu(VO3 )4 + h Ag2 Cu(VO3 )4 (h+ ) + Ag2 Cu(VO3 )4 (e ) (3)
+
H2 O H + OH (4)
+
h + OH OH (5)
OH + MB photodegraded products (6)
4. Conclusions
In summary, vanadates Ag2 Cu(VO3 )4 and Cu(VO3 )2 were pre-
pared by the solgel synthesis. The crystals could develop into
regular tetragonal prism with the lengths of 130 m and widths
of 13 m. Cu(VO3 )2 and Ag2 Cu(VO3 )4 have a specic surface area
of 24.7 m2 g1 and 26.1 m2 g1 , respectively. The vanadates display
typical indirect allowed transitions with band energy of 2.03 eV and
1.85 eV, respectively. Ag2 Cu(VO3 )4 has conduction band of the V/Cu
3d empty orbitals and the valence band with the mixture of both
Ag 3d- and O 2p orbitals. As expected, Ag2 Cu(VO3 )4 has more ef-
cient photocatalytic activity on MB photodegradation. The energy
positions for band gap indicate that the two vanadates can con-
vert photo-generated holes into the reactive OH radicals for MB
photodegradation. This was conrmed by the trapped experiments.
Acknowledgments
This work was supported by Basic Science Research Pro-
gram through the National Research Foundation of Korea (NRF)
funded by the Ministry of Science, ICT & Future Planning (NRF-
2013RA1A2009154), by National Natural Science Foundation of
China (No. 61405081) and the Priority Academic Program Devel-
opment of Jiangsu Higher Education Institutions (PAPD), China.
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