Separation and Purification Technology 151 (2015) 184–192

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Separation and Purification Technology

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

Detection of reactive oxygen species (ROS) and investigation of efficient

visible-light-responsive photocatalysis via nanoscale PbSe sensitized
TiO2
Lei Zhu a, Asghar Ali a, Ye Shu a, Kefayat Ullah a, Kwang-Youn Cho b, Won-Chun Oh a,⇑
a
Department of Advanced Materials Science & Engineering, Hanseo University, Seosan-si, Chungnam-do 356-706, Republic of Korea
b
Korea Institutes of Ceramic Engineering and Technology, Soho-ro, Jinju-Si, Gyeongsangnam-do, Republic of Korea

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

Article history: In this study, a novel visible-light-responsive PbSe–TiO2 nanocomposite photocatalysts were successfully
Received 13 January 2015 synthesized through a facile sonochemical-assisted method, and characterized by XRD, SEM–EDX, TEM,
Received in revised form 20 July 2015 and DRS to confirm its structure, morphology, composition, and optical property. In decolorization of rho-
Accepted 21 July 2015
damine B, a significant enhancement in the reaction rate was observed with PbSe–TiO2 composite, com-
Available online 21 July 2015
pared to the pure TiO2. The generation of reactive oxygen species was detected through the oxidation
reaction from 1,5-diphenyl carbazide (DPCI) to 1,5-diphenyl carbazone (DPCO). The high photocatalytic
Keywords:
activity can be attributed to the synergetic effect of PbSe nanoparticles and TiO2 by extending the spectral
TiO2
PbSe
response of TiO2 to visible region and also help to reduce the charge recombination. Finally, the possible
UV–vis mechanism for generation of reactive oxygen species under visible light irradiation was proposed as well.
Sonochemical Ó 2015 Elsevier B.V. All rights reserved.
Visible light photocatalytic
ROS

1. Introduction diodes [5], and infrared photodetectors [6] operating at lower cur-
rents and higher temperatures. Semiconductors have two unique
In most of the industrial wastewater treatment, adsorption by advantages: (1) their band gap can be modified by varying the size
activated carbon, advanced chemical oxidation, enhanced coagula- to tune the visible response; (2) they can utilize hot electrons to
tion and photochemical processes are commonly employed tech- generate multiple charge carriers with a single high energy photon
nologies for removal of refractory pollutants from industrial [7]. Various semiconductors, including ZnFe2O4 [8], PbS [9], Bi2S3
wastes. The advance of photochemical processes has made the [10], CdSe [11,12], and InP [13], have been investigated to sensitize
decomposition of synthesized refractory organics sustainable, TiO2 as a visible light absorber. However, there is no report on the
especially with the advent of semiconductor photocatalysts [1,2]. utilization of PbSe/TiO2 photocatalyst systems for environmental
Several semiconductors have been developed to exhibit photocat- purification under visible light irradiation. According to other’s
alytic behavior. The most commonly referenced semiconductors studies, PbSe is one kind of potential semiconductor to sensitize
for waste degradation are TiO2, ZnO, CdS, etc. [1]. TiO2 is of great TiO2 as a visible light absorber due to its excellent catalytic perfor-
interest mainly due to its unique properties, such as high photoac- mance. Manga et al. [14] reported high-performance broadband
tivity and size dependent optical properties [1]. However, TiO2 is a photodetector using solution-processible PbSe–TiO2–graphene
wide band gap semiconductor (band gap around 3.2 eV), which hybrids which act as light harvesting photoactive materials from
adsorbs light only in the UV region. To overcome this problem, var- the UV to IR regions of the electromagnetic spectrum. Néstor
ious materials, like dyes and metallic nanoparticles, have been et al. [15] reported sensitization of TiO2 with PbSe quantum dots
used as sensitizer to increase the photoactivity of TiO2 in the by SILAR: how mercaptophenol improves charge separation. It is
visible range. well known that the synthesis of nanomaterials with uniform size,
Compared with other materials, semiconductors have attracted shape and high crystallinity is one of the important challenging
considerable interest in the past two decades because of their appli- problems. There are various kinds of synthesis methods available
cations in single electron transistors [3], lasers [4], light emitting for the preparation of nanomaterials such as hydrothermal, micro-
wave synthesis, sol–gel, micro emulsion and the polyol technique.
⇑ Corresponding author. But each method has its own drawbacks such as long reaction time,
E-mail address: wc_oh@hanseo.ac.kr (W.-C. Oh). non-uniform shape and size, particle agglomeration and high cost

http://dx.doi.org/10.1016/j.seppur.2015.07.052
1383-5866/Ó 2015 Elsevier B.V. All rights reserved.
 L. Zhu et al. / Separation and Purification Technology 151 (2015) 184–192 185

of the solvent medium. Recently, the sonochemical synthesis

became an imperative for the preparation of nanomaterials with
uniform size and shape with shorter reaction time. In sonochemical
synthesis, interaction occurs between energy and matter, where the
applied ultrasound incident on the liquid surface, there is a three
step process that takes place including the formation, growth and
finally implosive collapse of bubbles. This collapsing of bubbles pro-
duces an intense heat and high pressure within a very short time. In
this process, temperatures up to 5000 K and pressures greater than
20 MPa are created, and subsequently cooled at high cooling rates
of 1010 K/s [16]. These conditions are induced reactions such as oxi-
dation, reduction, hydrolysis, dissolution, and decomposition [17].
The high intensity shockwaves could be facilitating to prevent par-
ticle agglomeration and rapid crystal growth. Hence, considering
the advantage of using sonochemical method here we have adopted
the same for the synthesis of PbSe–TiO2 nanocomposite.
Subsequently, heat treatment was used to tune the morphology
of TiO2 particles. Finally the structural, morphological, visible light
photocatalysis properties of the prepared PbSe–TiO2 were Fig. 1. XRD patterns of pure PbSe, TiO2 nanoparticles and PbSe–TiO2 composite.

investigated.
dissolved in 30 mL distilled water and refluxed for 1 h to form
2. Experimental Na2SeSO3 solution in a particular situation. Meanwhile, 2 mM
PbCl2 was dissolved in 20 mL distilled water. NH4OH (4 mL) was
2.1. Materials added to the solution and the mixture was stirred till it dissolved
completely to form Pb(NH3)2+4 solution. Then 0.5 g TiO2 nanoparti-

Lead chloride (PbCl2), selenium metal powder and ammonium cles was added to the Pb(NH3)2+ 4 solution, followed by stirring for

hydroxide (NH4OH, 28%) were purchased from Dae Jung 2 h under ambient temperature for adsorption of Pb(NH3)2+ 4 on

Chemicals & Metal Co., Ltd, Korea. Anhydrous purified sodium sul- the surface of TiO2 nanoparticles. Finally, the Pb(NH3)2+
4 /TiO2 solu-

fite (Na2SO3, 95%) was purchased from Duksan Pharmaceutical Co., tion and a certain amount of Na2SeSO3 solution were mixed
Ltd, Korea. The titanium (IV) n-butoxide (TNB, C16H36O4Ti) as a together following by ultrasonicated for several hours. The sono-
titanium source for the preparation of TiO2 nanoparticles was pur- chemical synthesis time was adjusted to prepare different PbSe–
chased from Kanto Chemical Company (TOKYO, Japan). The Rh.B TiO2 nanocomposites. The obtained PbSe–TiO2 samples were
(C28H31ClN2O3, 99.99+%) was used as model pollutant which pur- labeled as PT1, PT2, and PT3, respectively. For comparison, another
chased from Duksan Pure Chemical Co., Ltd, Korea. All chemicals photocatalyst PbSe was prepared using similar procedure without
used without further purification and all experiments were carried adding TiO2.
out using distilled water.
2.3. Characterization
2.2. Synthesis of PbSe–TiO2 nanocomposite
The Brunauer–Emett–Teller (BET) surface area of PbSe–TiO2
TiO2 nanoparticles were prepared according to our previous composite was evaluated from the N2 adsorption isotherms at
work [18]. The detailed process is described as follows: firstly, 77 K using a BEL Sorp Analyzer (BEL). X-ray diffraction (XRD,
TiO2 precursors were prepared with the molar ratios of ethanol: Shimadz XD-D1) result was used to identify the phase with Cu
H2O: TNB = 35:15:4, finally the suspension was sonicated at room Ka radiation. Scanning electron microscopy (SEM, JSM-5600) was
temperature for 2 h using a Controllable Serial-Ultrasonic appara- used to observe the surface state and structure of PbSe–TiO2 com-
tus (Ultrasonic Processor, VCX 750, Korea). The final products were posite using an electron microscope. The element mapping over
filtered and washed repeatedly and then vacuum dried at 373 K. the desired region of PbSe–TiO2 composite was detected by an
The dried catalyst was ground in a ball mill and calcined at energy dispersive X-ray (EDX) analysis attached to SEM. UV–vis
773 K for 1 h to get TiO2 nanoparticles. diffuse reflectance spectra (DRS) were obtained using an UV–vis
For the synthesis of PbSe–TiO2 nanocomposites, the sodium spectrophotometer (Neosys-2000) by using BaSO4 as a reference
selenosulfite (Na2SeSO3) solution and Pb(NH3)2+ 4 solution was pre- and were converted from reflection to absorbance by the
pared. Na2SO3 (5 g) and selenium metal powder (0.5 g) were Kubelka–Munk method.

Table 1
The molecular structure and absorbance maximum (kmax) of organic dyes.

Organic dyes Molecular structure kmax

Rhodamine B (Rh.B) 554 nm
186 L. Zhu et al. / Separation and Purification Technology 151 (2015) 184–192

Fig. 2. SEM microphotograph of PbSe (a) and PbSe–TiO2 composite (b = PT1, c = PT2, d = PT3); EDX microanalysis (e) and element weight% (f) of PbSe and PT2 composite.

2.4. Photocatalytic performance of Rh.B pollutant. In an ordinary photocatalytic test performed at

room temperature, 0.05 g PbSe–TiO2 composite was added to
Photocatalytic activity of the PbSe–TiO2 composite was evalu- 50 mL of 2.0  105 mol/L Rh.B solution, which was hereafter con-
ated by the degradation of Rh.B solution under irradiation of visible sidered as the initial concentration (c0). The mixture was sonicated
light (8 W, k > 420 nm). Table 1 shows the structure and properties for 10 min and stirred for 30 min in the dark in order to reach
 L. Zhu et al. / Separation and Purification Technology 151 (2015) 184–192 187

(e)

Quantitative results
80

60
Weight%

40

20

0
Se Pb

(f)
Fig. 2 (continued)

Fig. 3. TEM microphotograph of PbSe (a) and PT2 (b) and HRTEM microphotograph of PT2 composite (c, d) with different resolution.
188 L. Zhu et al. / Separation and Purification Technology 151 (2015) 184–192

adsorption – desorption equilibrium. The first sample was taken 1 lm. After introduced into TiO2, it can be clearly seen that the
out just before the light was turned on in order to determine the PbSe particles homogenously coated on the TiO2 particles with
dye concentration in solution after dark adsorption, which was smaller size comparing with pure PbSe sample, as showed in
henceforth considered as the initial concentration (cads). Samples Fig. 2b–d.
were then withdrawn regularly from the reactor by an order of Chemical composition analysis and element weight% of pre-
30 min, 60 min, 90 min, 120 min and 150 min, immediately cen- pared PbSe and PbSe–TiO2 composites was examined by EDX.
trifuged to separate any suspended solid. The clean transparent From Fig. 2((e) and (f)), we can see the main elements such as Ti,
solution was analyzed by using a UV–vis spectrophotometer O, Pb and Se are existed. It can be concluded that PbSe–TiO2 com-
(Optizen POP) at wavelength from 250 nm to 800 nm. posite with high purity has been successfully synthesized in this
study. According to former study, the small concentration of
2.5. Evaluation of reactive oxygen species dopant in TiO2 matrix can be prevented in formation of hole/
electron recombination centers and an increase of negative charge
Firstly, four 100 mL transparent volumetric flasks were marked capabilities.
with (a–d), respectively. Four 10.00 mL DPCI stock solutions For the obtaining of more detailed and higher magnification, the
(1.00  102 mol/L) were added into a–d correspondingly followed surface nanostructures and particle sizes of PbSe and PbSe–TiO2
by the addition of 50 mg PbSe–TiO2 samples in order of (1, 2, 3, 4) composites were studied by TEM and HRTEM analysis depicted
from a to d. All of the four solutions were diluted to 100 mL with in Fig. 3. TEM images revealed that, PT-2 sample displayed
double distilled water. The final DPCI concentration and PbSe– well-dispersed anatase TiO2 nanoparticles with average size
TiO2 amount were 1.00  103 mol/L and 1.00 g/L, respectively. around 15–20 nm since particle agglomeration was effectively
At first the experiment were performed without sample powder inhibited during introduction of PbSe nanoparticles. A few black
under the same condition and the DPCL solution were illuminated dots can be observed from these images correspond to the deposi-
by UV, Vis., Ultra, and under dark condition. After 120 min of irra- tion of PbSe nanoparticles with average size around 15–25 nm
diation, from each reactor 10 mL of solution were taken and having rectangular and square shape which were in accordance
extracted with benzene. In the second step all the extracted with the results reported by other studies with similar shape
solutions were diluted to 10 mL with benzene solution and their [21,22]. The presence of distinct juncture between two crystal
UV–Vis spectra were recorded by using a spectrometer. phases further confirmed the strong interaction between PbSe
and TiO2 in PbSe–TiO2.

3. Results and discussion

3.3. UV–vis diffuse reflectance spectroscopy
3.1. Structural analysis
Fig. 4 shows the UV–vis absorbance spectra and UV–vis diffuse
Fig. 1 shows the XRD patterns of pure TiO2, pure PbSe and pre- reflectance spectra of pure TiO2 and PT2 composite. A careful study
pared PbSe–TiO2 composite. The peaks marked by letters and sym- of both spectra shows the same absorbance peak at around
bols represent anatase structure of TiO2 and PbSe structure, 250 nm, indicating both pure TiO2 and PT2 composite has activity
respectively. The XRD diffraction peaks around 2h of 25.3°, 37.8°, at UV region. However, the pure TiO2 absorbs mainly the ultravio-
48.0°, 55° and 62.5° are the diffractions of (1 0 1), (0 0 4), (2 0 0), let light with absorption wavelength less than 400 nm, whereas
(2 0 1), and (2 0 4) planes of anatase TiO2 (JCPDS No. 21-1272) PT2 composite absorbs light at wavelength shorter than 618 nm.
[19] while (1 1 1), (2 2 0), (3 1 1), (2 2 2), (4 0 0), (3 3 1), (4 2 0) and After the introduction of PbSe, the absorption edge is shifted
(4 2 2) reflections that correspond to the clausthalite crystal phase toward the visible region (red shift). Pure TiO2 shows absorption
(JCPDS PDF: 00-065-0240) of lead selenide (PbSe), which were in only in the UV region due to the intrinsic band gap of TiO2. The
accordance with the results reported by Lee et al. with the lattice onset of the absorption spectrum of PT2 composite is shifted
parameters [20]. The diffractogram of prepared PbSe–TiO2 com- toward visible light. It is an emission peak from band edge free
posite suggests the presence of anatase structure TiO2 as well as excitation. The band gap energy of a semiconductor can be calcu-
single-phase cubic structure PbSe, and no peaks for impurities lated by the following formula:
are detected. The intensity variation of the diffraction PbSe peaks
1=2
ahv ¼ A hv  Eg
for the pure PbSe and prepared PbSe–TiO2 nanocomposites may
verify the suppression of the crystalline phases. The particles size where a, v, Eg, and A are the absorption coefficient, light frequency,
D was calculated by using the Scherrer formula, band gap, and a constant, respectively. Therefore, the band gap
D ¼ Kk=b cos HB ð1Þ energy (Eg) of PT2 composite can be estimated from a plot of
(ahv)1/2 versus photo energy (hv). The intercept of the tangent to
where b is the full width half maxima, K is a shape factor = 0.9, k is the X axis would give a good approximation of the band gap energy
the wavelength of incident X-ray. The average particle size fall in of the samples. The band gap of PT2 composite was found to be
the range of 10–50 nm, indicates the nano size of the PbSe particles 2.0 eV (Fig. 6 inset), which is smaller than the standard band gap
which was followed analysis by TEM and HRTEM. for TiO2 (3.25 eV) [1,6] showing a blue shift of 1.25 eV.

3.2. Surface characteristics of the samples 3.4. Catalytic activity studies and generation of ROS

SEM with EDX analysis provides information on the morphol- Two steps are involved in the photocatalytic decomposition of
ogy and chemical composition of the prepared samples. The SEM dyes: the adsorption of dye molecules and photodegradation. To
technique is used to inspect the topographies of specimens at very evaluate the adsorption ability of the as-prepared composite cata-
high magnifications using a piece of equipment called a scanning lysts, the reactor was placed on the magnetic churn dasher, stirring
electron microscope. Fig. 2 shows the SEM microphotograph (a– for 30 min in the darkness box to establish an adsorption–desorp-
d), EDX microanalysis (e) and element weight% (f) of PbSe and tion equilibrium. From the result shown in Fig. 5, the level of Rh.B
PbSe–TiO2 composite. Fig. 2a exhibits irregular nanoparticles of adsorption by PbSe–TiO2 was higher than that of the TiO2 powder.
truncated octahedron structures with an average diameter of This can be attributed to the larger surface area of the PbSe–TiO2
 L. Zhu et al. / Separation and Purification Technology 151 (2015) 184–192 189

Fig. 4. UV–vis diffuse reflectance spectra of pure TiO2, PT2 composite. The inset shows the variation of (ahv)2 versus photon energy (hv) for PT2 composite.

Table 2
Visible light photocatalytic degradation rate (kapp) constants and BET surface areas of
pure TiO2, PbSe and PbSe–TiO2.

Samples BET (m2/g) kapp (min1)

Pure TiO2 11.59 7.24  105
PbSe 27.84 4.53  105
PT1 48.62 1.86  104
PT2 69.37 5.16  104
PT3 72.15 4.68  104

Fig. 5. UV/Vis spectra of Rh.B concentration against the as-prepared samples after
adsorption–desorption equilibrium.

catalysts shown in Table 2, which correlates to a strong adsorption

ability. Fig. 6 shows the time series of Rh.B degradation using PT2
catalyst under visible light irradiation.
The photocatalytic degradation of Rh.B containing different
photocatalysts under visible light obeys pseudo-first-order kinetics
with respect to the concentration of Rh.B:
dc=dt ¼ kapp c

Integrating this equation (with the restriction of c = c0 at t = 0, with Fig. 6. UV/Vis spectra of Rh.B concentration against the PT2 sample for adsorption
c0 being the initial concentration in the bulk solution after dark and degradation.
adsorption and t the reaction time) will lead to the following
expected relation:
in Fig. 7 and also summarized in Table 1. The Rh.B degradation rate
 lnðct =c0 Þ ¼ kapp t
constant for PT2 composites reaches 5.16  104 min1 under visi-
where ct and c0 are the reactant concentrations at times t = t and ble light, which are much higher than the corresponding values for
t = 0, respectively, and kapp and t are the apparent reaction rate con- pure PbSe and TiO2. The above results suggest that the PbSe–TiO2
stant and time, respectively. According to this equation, a plot of composites are much more effective photocatalysts than any
ln(ct/c0) versus t will yield a slope of kapp. The results are displayed other composites. The excellent photocatalytic activity could be
190 L. Zhu et al. / Separation and Purification Technology 151 (2015) 184–192

Fig. 7. Apparent first order kinetics of Rh.B degradation over pure TiO2, PbSe and Fig. 9. UV–vis spectra of DPCO extract liquors (a), and of the liquors in the presence
PbSe–TiO2 photocatalysts under visible light irradiation. of PT2 composites photocatalyst under visible light irradiation 60 min (b), 90 min
(c) and 120 min (d).

1.0 to conduction band (CB). Simultaneity, the electron–hole pairs

1st run 2st run 3st run 4st run
form on the surface or in the inner of PbSe–TiO2 samples. The elec-
trons and holes react with the molecular oxygen (O2) dissolved in
0.8
aqueous solution and water molecules (H2O) absorbed on the sur-
face of PbSe–TiO2, respectively, producing the superoxygen radical
0.6
anions (O  
2 ) and hydroxyl radicals ( OH). These OH can oxidize
C/C0

1,5-diphenyl carbazide (DPCI) into 1,5-diphenyl carbazone

(DPCO). The DPCO can be extracted by the solvent of benzene
0.4 and show an absorbance at 560 nm wavelength. Sequentially, the
produce and output of OH can be easily detected. According to d-
ifferent irradiation time, the DPCO solution exhibits different
0.2
absorbance and shows an obvious increase compared with the
corresponding ones without any irradiation [24].
0.0
It was generally thought that the photocatalytic performance
0 90 180 270 360 depends on phase structure, the absorbance and the adsorption
Time (min) capacity of photocatalyst [25]. In our experiments, the enhanced
activity is probably attributed to the improved optical absorption
Fig. 8. Cycling runs about degradation of Rh.B with sample PT2 under visible light and the heterostructure which favors the separation of photo-
(VL) irradiation.
introduced electrons/holes pairs in photosensitizer-titanium
dioxide photocatalysts [26]. Meanwhile, due to the large surface
attributed to the synergetic effects of high charge mobility and the area of as-prepared composite photocatalyst, more dye molecules
red shift in the absorption edge of the PbSe–TiO2 composites. can be adsorbed onto the photocatalyst surface, which increase
To demonstrate the stability, cyclic performance of the PT2 the photocatalytic reaction site [27]. The scheme of degradation
photocatalyst, consecutive photocatalytic Rh.B degradation reac- Rh.B and ROS generation on the interface of PbSe and TiO2
tions were conducted under visible light irradiation. As shown in particles under visible light irradiation is shown in Fig. 10. Under
Fig. 8, PT2 did not exhibit any significant loss of photocatalytic irradiation by visible lamp, the generated electrons in PbSe and
activity after four runs of Rh.B degradation. These results indicate holes in TiO2 are then immigrated to the conduction band (CB) of
that the PT2 photocatalyst has high stability and is not photocor- TiO2 and the valence band (VB) of PbSe, respectively (correspond-
roded during photocatalytic oxidation of Rh.B. TiO2 modification ing to Eqs. (2) and (3), respectively). This transfer process is
with semiconductor not only improves the photocatalytic thermodynamically favorable because of CB and VB of PbSe lie
performance but also achieve the long-term stability of PbSe above that of TiO2. Meanwhile, the generated electrons probably
nanocrystals [11,23]. This result is significant from a practical react with dissolved oxygen molecules and produce oxygen perox-
+
viewpoint, as the enhanced photocatalytic activity and stability ide radical O2 (Eqs. (4) and (5)), the positive charged hole (h ) may

will lead to more cost-effective operation. These results further react with the OH derived from H2O to form hydroxyl radical OH
confirm that PbSe–TiO2 nanocomposite can be used as catalytic (Eqs. (6) and (7)). It is well known that the O 
2 and OH are power-

materials in environmental purification process or in waste water ful oxidizing agent capable of degrading most pollutants [28]. The
treatment in future. dye molecule then can be photodegraded by oxygen peroxide
Fig. 9 is the UV–vis spectra of DPCO extract liquors in the radical O 
2 and hydroxyl radical OH to CO2, H2O or other mineral-

presence of PbSe–TiO2 composite under ultrasonic irradiation. ization (Eq. (8)).

1,5-diphenyl carbazide (DPCI) can be oxidized by oxidizing þ
PbSe þ hv ! PbSeðh Þ þ PbSeðe Þ ð2Þ
substances into 1,5-diphenyl carbazone (DPCO). Under ultrasonic
irradiation, some electrons are transited from valence band (VB) þ þ
PbSeðh ; e Þ—TiO2 ! PbSeðh Þ—TiO2 ðe Þ ð3Þ
 L. Zhu et al. / Separation and Purification Technology 151 (2015) 184–192 191

Fig. 10. The scheme of degradation Rh.B and ROS generation on the interface of PbSe and TiO2 particles under visible light irradiation.

e þ O2 ! O
2 ð4Þ [6] Z. Ye, J.C. Campbell, Z. Chen, E.T. Kim, A. Madhukar, InAs quantum dot infrared
photodetectors with In0.15Ga0.85As strain-relief cap layers, J. Appl. Phys. 92
(2002) 7462–7468.
TiO2 ðe Þ þ O2 ! TiO2 þ O
2 ð5Þ [7] L.M. Peter, D.J. Riley, E.J. Tull, K.G.U. Wijayantha, Photosensitization of
nanocrystalline TiO2 by self-assembled layers of CdS quantum dots, Chem.
þ Commun. Cambridge (2002) 1030–1031.
h þ OH ! OH ð6Þ [8] Y. Hou, X.Y. Li, Q.D. Zhao, X. Quan, G.H. Chen, Electrochemical method for
synthesis of a ZnFe2O4/TiO2 composite nanotube array modified electrode
þ with enhanced photoelectrochemical activity, Adv. Funct. Mater. 20 (2010)
h þ H2 O ! OH þ Hþ ð7Þ 2165–2174.
[9] A.J. Nozik, Quantum dot solar cells, Phys. E-Amsterdam 14 (2002) 115–120.
O  [10] R. Schaller, V.I. Klimov, High efficiency carrier multiplication in PbSe
2 or OH þ dye ! degradation products ð8Þ
nanocrystals: implications for solar energy conversion, Phys. Rev. Lett. 92
(2004) 186601–186604.
[11] H.H. Yang, W.G. Fan, A. Vaneski, A.S. Susha, W.Y. Teoh, A.L. Rogach,
4. Conclusions Heterojunction engineering of CdTe and CdSe quantum dots on TiO2
nanotube arrays: intricate effects of size-dependency and interfacial
contact on photoconversion efficiencies, Adv. Funct. Mater. 22 (2012) 2821–
In this study, we present the synthesis and characterization of 2829.
PbSe–TiO2 composites through a facile sonochemical method. [12] I. Robel, V. Subramanian, M. Kuno, P.V. Kamat, Harvesting light energy with
The results showed that PbSe–TiO2 composites are able to exhibit CdSe nanocrystals molecularly linked to mesoscopic TiO2 films, J. Am. Chem.
Soc. 128 (2006) 2385–2389.
high surface area, excellent structure, and great electrical and opti- [13] R. Plass, S. Pelet, J. Krueger, M. Gratzel, Quantum dot sensitization of
cal properties. The PbSe–TiO2 composites showed an intense organic–inorganic hybrid solar cells, J. Phys. Chem. B 106 (2002)
absorption and a red-shifted absorption onset compared to pure 7578–7583.
[14] K.K. Manga, J.Z. Wang, M. Lin, J. Zhang, M. Nesladek, V. Nalla, W. Ji, K.P. Loh,
TiO2 and PbSe. The excellent visible light photocatalytic activities High-performance broadband photodetector using solution-processible
of PbSe–TiO2 for the degradation of Rh.B were higher than that of PbSe–TiO2–Graphene Hybrids, Adv. Mater. 24 (2012) 1697–1702.
pure TiO2. The quantities of generated hydroxyl radicals can be [15] G. Néstor, L.V. Teresa, L. Thierry, A.H. Saif, G. Roberto, Sensitization of TiO2 with
PbSe quantum dots by silar: how mercaptophenol improves charge separation,
analyzed by DPCI degradation and it is proved that under visible J. Phys. Chem. Lett. 3 (2012) 3367–3372.
light irradiation it can generate more electron–hole pairs. It is [16] K.S. Suslick, S.B. Choe, A.A. Cichowlas, M.W. Grinstaff, Sonochemical synthesis
expected that this work would offer some valuable references for of amorphous iron, Nature 353 (1991) 414–416.
[17] Y. Cuicui, Y. Min, L. Chunxia, Z. Cuimiao, Y. Piaoping, L. Jun, Spindle-like
the study of the reaction mechanism of visible light photocatalytic
lanthanide orthovanadate nanoparticles: facile synthesis by ultrasonic
degradation to promote their applications in the environmental irradiation, characterization, and luminescent properties, Cryst. Growth Des.
treatments and energy exploitations. 9 (2009) 783–791.
[18] L. Zhu, G. Trisha, C.Y. Park, Z.D. Meng, W.C. Oh, Enhanced sonocatalytic
degradation of rhodamine B by graphene–TiO2 composites synthesized by an
References ultrasonic-assisted method, Chin. J. Catal. 33 (2012) 1276–1283.
[19] W.C. Oh, Review of carbon based titania photocatalysts, J. Photocatal. Sci. 1
[1] A.L. Linsebigler, G. Lu, J.T. Yates, Photocatalysis on TiO2 surfaces: principles, (2010) 29–34.
mechanisms, and selected results, Chem. Rev. 95 (1995) 735–758. [20] M.A. Mahdy, I.A. Mahdy, E.A. Mahmoud, Structural and optical properties of
[2] M. Wang, J. Ioccozia, L. Sun, C. Lin, Z. Lin, Inorganic-modified semiconductor PbSe nanostructure thin films prepared by inert gas condensation, Physica E
TiO2 nanotube arrays for photocatalysis, Energy Environ. Sci. 7 (2014) 2182– 59 (2014) 117–123.
2202. [21] C.G. Li, T.Y. Bai, F.F. Li, L. Wang, X.F. Wu, L. Yuan, Z. Shi, S.H. Feng, Growth
[3] K. Kawasaki, D. Yamazaki, A. Kinoshita, H. Hirayama, K. Tsutsui, Y. Aoyagi, GaN orientation, shape evolution of monodisperse PbSe nanocrystals and their use
quantum-dot formation by self-assembling droplet epitaxy and application to in optoelectronic devices, CrystEngComm 15 (2013) 597–603.
single-electron transistors, Appl. Phys. Lett. 79 (2001) 2243–2248. [22] H.B. Li, D. Chen, L.L. Li, F.Q. Tang, L. Zhang, J. Ren, Size- and shape-controlled
[4] T.R. Nielsen, P. Gartner, F. Jahnke, Many-body theory of carrier capture and synthesis of PbSe and PbS nanocrystals via a facile method, CrystEngComm 12
relaxation in semiconductor quantum-dot lasers, Phys. Rev. B 69 (2004) (2010) 1127–1133.
235314–235319. [23] S.S. Qian, C.S. Wang, W.J. Liu, Y.H. Zhu, W.J. Yao, X.H. Lu, An enhanced
[5] J.M. Lupton, I.D.W. Samuel, R. Beavington, P.L. Burn, H. Bässler, Nanoengineering CdS/TiO2 photocatalyst with high stability and activity: effect of mesoporous
of organic semiconductors for light-emitting diodes: control of charge transport, substrate and bifunctional linking molecule, J. Mater. Chem. 21 (2011)
Mater. Lett. 74 (2012) 104–106. 4945–4952.
192 L. Zhu et al. / Separation and Purification Technology 151 (2015) 184–192

[24] Z.D. Meng, T. Ghosh, L. Zhu, J.G. Choi, C.Y. Park, W.C. Oh, Synthesis of fullerene [27] U.G. Akpan, B.H. Hameed, Parameters affecting the photocatalytic degradation
modified with Ag2S with high photocatalytic activity under visible light, J. of dyes using TiO2-based photocatalysts: a review, J. Hazard. Mater. 170 (2009)
Mater. Chem. 22 (2012) 16127–16135. 520–529.
[25] D. Jiang, Y. Xu, D. Wu, Y.h. Sun, Visible-light responsive dye-modified TiO2 [28] M.A. Rauf, M.A. Meetani, S. Hisaindee, An overview on the photocatalytic
photocatalyst, J. Solid State Chem. 181 (2008) 593–602. degradation of azo dyes in the presence of TiO2 doped with selective transition
[26] W.K. Ho, J.C. Yu, Sonochemical synthesis and visible light photocatalytic metals, Desalination 276 (2011) 13–27.
behavior of CdSe and CdSe/TiO2 nanoparticles, J. Mol. Catal. A: Chem. 247
(2006) 268–274.