Applied Surface Science 462 (2018) 730–738

Contents lists available at ScienceDirect

Applied Surface Science

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

Full Length Article

Enhanced photocatalytic performance of ZnSe/PANI nanocomposites for T

degradation of organic and inorganic pollutants
Abbas Shirmardia, Mohd Asri Mat Teridib, H.R. Azimic, Wan Jeffrey Basirund,
⁎
Farid Jamali-Sheinie, Ramin Yousefic,
a
Department of Chemistry, Masjed-Soleiman Branch, Islamic Azad University (I.A.U), Masjed-Soleiman, Iran
b
Solar Cell Research Institute (SERI), Research Complex, Universiti Kebangsaan Malaysia, 43600 Bangi, Selangor, Malaysia
c
Department of Physics, Masjed-Soleiman Branch, Islamic Azad University (I.A.U), Masjed-Soleiman, Iran
d
Department of Chemistry, University of Malaya, Kuala Lumpur 50603, Malaysia
e
Advanced Surface Engineering and Nano Materials Research Center, Department of Physics, Ahvaz Branch, Islamic Azad University, Ahvaz, Iran

A R T I C LE I N FO A B S T R A C T

Keywords: Current work presents a study about the effect of polyaniline (PANI) as an organic semiconductor on the pho-
ZnSe/PANI nanocomposites tocatalytic performance of ZnSe nanoparticles (NPs). Pristine ZnSe NPs and ZnSe/PANI nanocomposites were
Type-II heterojunction synthesized by a simple and cost-effective co-precipitation method in the ambient conditions. X-ray diffraction
Optical properties (XRD), Raman, and Fourier-transform infrared spectroscopy (FTIR) results confirmed that, a heterojunction was
Photocatalytic performance
created by ZnSe NPs and PANI composite. High-resolution transmission electron microscopy (HRTEM) image
showed that the NPs were deposited by PANI completely and a core-shell structure was generated by ZnSe and
PANI. Photoluminescence (PL) spectroscopy results showed the optical properties of the pristine ZnSe NPs and
ZnSe/PANI nanocomposites were similar with lower defect emission intensity for the ZnSe/PANI nanocompo-
sites. However, the PL and UV–Vis results revealed that, the PANI caused a decrease in band-gap value of the
ZnSe/PANI nanocomposites in compared to the band-gap value of the pristine ZnSe NPs. In addition, X-ray
photoelectron spectroscopy (XPS) results indicated that, the PANI caused a shift in the valance band (VB) and
conduction band (CB) edges of ZnSe/PANI nanocomposites in compared with pristine ZnSe NPS. Finally, the
photocatalytic performance of the products for removing of methylene blue (MB) and chromate ions was ex-
amined under a visible-light source irradiation. An enhancement photocatalytic performance for ZnSe/PANI
nanocomposites in compared to the pristine ZnSe NPs was observed. Brunauer–Emmett–Teller (BET) results
indicated that textural properties of the nanocomposites were decreased by PANI. According to the optical
properties and band gap-value of the products a type-II heterojunction was created by band alignment of the
ZnSe and PANI and such heterojunction was the most important factor for the enhancement photocatalytic
performance of the ZnSe/PANI nanocomposites in compared to the photocatalytic activity of the pristine ZnSe
NPs.

1. Introduction commons photocatalytic materials have an important disadvantage and

Photocatalytic materials are important materials for purification of
the surface waters. In fact, photocatalytic process with semiconducting
nanostructures is the simplest and cost-effective process for removing
organic and inorganic pollutions from the surface waters. Therefore,
several semiconducting nanostructures such as ZnO, TiO2, CuO, AgX
(Br and Cl), and Ag2CO3 have been used as photocatalytic materials
during recent decades [1–6]. Among these nanostructures, ZnO and
TiO2 are two the most important photocatalytic materials due to their
stability during the photocatalytic process [7–11]. However, these two
it is their wide band-gap value. In fact, these materials cannot operate
as a photocatalytic material under a visible-light source irradiation due
to their wide band-gap that is in the ultraviolet region of the electro-
magnetic spectrum. Usually, using of doping materials in these nanos-
tructures is a common way to reduce the band-gap value of these wide
band-gap semiconductors and to create defect energy levels in the band
gap region that cause absorb the visible light photons [12,13]. How-
ever, these doping materials could be the source of secondary pollution.
Therefore, using the other semiconductors with the suitable band-gap
values, which are able to catch visible light photons, is the most

⁎
Corresponding author.
E-mail address: raminyousefi@iaumis.ac.ir (R. Yousefi).

https://doi.org/10.1016/j.apsusc.2018.06.252
Received 4 April 2018; Received in revised form 16 June 2018; Accepted 27 June 2018
Available online 28 June 2018
0169-4332/ © 2018 Elsevier B.V. All rights reserved.
A. Shirmardi et al. Applied Surface Science 462 (2018) 730–738

important factors to improve the photocatalytic process as a cost-ef- radiation), transmission electron microscopy (TEM, Hitachi H-7100),
fective way to remove pollutions from wastewaters. In addition, com- and Raman spectroscopy (Model: Almega ThermoNicolet Dispersive)
position of two type of 2D materials such as graphene and g-C3N4 sheets were used to check the crystal phase and morphology. Optical prop-
as photocatlytic materials is a new strategy to improve photocatalytic erties of the products such as photoluminescence (PL) and absorption
process under visible light irradtion [14]. regions were investigated by a Fluorescence spectrophotometer (Cary
Among different semiconductors with band-gap value in the visible Eclipse, Varian) with a Xenon flash lamp as an excitation source and
region of the electromagnetic spectrum, ZnSe is one of the best mate- UV–visible spectroscopy (Perkin-Elmer spectrometer). Elemental study
rials for the photocatalytic activity due to its unique properties such as of samples carried out by X-ray photoelectron spectroscopy (XPS)
its direct band-gap, suitable band-gap value (2.6 eV), and its en- (Multilab. ESCA 2000) in KOPTRI. The linear portion (P/
vironmentally friendly properties [15,16]. However, this semi- Po = 0.05–0.2) of the Brunauer–Emmett–Teller (BET) model by N2
conductor as a photocatalytic material has a big disadvantage and it is adsorption-desorption at liquid nitrogen temperature (77 K) was used
its instability during photocatalytic activity. In fact, this semiconductor for the calculation of specific surface area (BElSORP Mini (Microtrac
during photocatalytic activity reacts with pollution molecules and Bel Corp CO)). Pore diameter and pore volumes were calculated from
therefore it cannot be used for several times in photocatalytic activity. the desorption branch of the Barrett-Joyner-Halenda (BJH) model.
Consequently, it should be protected by another material that can be
participated in the photocatalytic process. Recently polyaniline (PANI) 2.3. Preparation of photocatalytic degradation samples
as a semiconductor polymer and semi-flexible rode polymer has been
used to improve the photocatalytic performance of several semi- The photocatalytic activity of the obtained powders was examined
conductors such as TiO2, ZnO, CdS, SnS, ZrO2, and Ag3PO4 [17–32]. In by degradation of MB dye solution under a visible-light source irra-
addition, the highest occupied molecular orbital (HOMU) and the diation. The MB dye conditions were similar to our recent work [34].
lowest unoccupied molecular orbital (LOMU) energy values of PANI The light source was an LED with 50 W powers and 4300 LM as a
can create type-II heterojunction with conduction band (CB) and va- visible-light source.
lence band (VB) value of the ZnSe. It is known, the type-II hetero-
junction is one the best semiconductor-semiconductor junctions for the 2.4. Electrical measurements
photocatalytic activity with high efficiency [33]. Furthermore, PANI
due to its flexibility properties can cover the ZnSe completely and A photoresponse cell was fabricated by samples to measure con-
creates a core-shell structure and causes protect of ZnSe against direct ductivity and photoresponse of the samples. TiO2 nanoparticles (NPs)
reaction with pollutions’ molecules. were deposited on Fluorine-doped tin oxide (FTO) substrates and they
Therefore, current work presents a study about the role of PANI to were used as a photoelectrode. Then, the powder samples were de-
improve the photocatalytic activity of ZnSe to remove organic pollution posited on the photoelectrode films by a drop-casting method. A com-
such as methylene blue (MB) and inorganic pollution such as Cr (VI). In merical KI/I (0.5 M of KI and 0.05 M I2) has been solved in ethylen
addition, the effects of PANI on the stability of ZnSe NPs after several glycol and applied as the electrolyte liquide to measure photocurrent
times photocatalytic activity was investigated. To the best of our intensity of the samples. The counter electrode was an Au coated FTO.
knowledge, the synthesis of ZnSe/PANI nanocomposites by the current The photocurrent test of the pristine ZnSe NPs and ZnSe/PANI nano-
method and photocatalytic performance of the products to remove or- composites were carried out under the same LED illumination that was
ganic and inorganic pollutants not been reported so far. used to examine photocatalytic activity. The photoresponse device was
fabricated according to FTO/samples/electrolyte/Au/FTO.
2. Experimental
3. Results and discussion
2.1. Materials and synthesis
Fig. 1 shows the XRD patterns of the products. These patterns in-
Detailed experimental conditions to synthesize ZnSe NPs were re-
dicate that the samples have zincblende structures (JCPDS 88-2345) for
ported in our previous work [34]. For the synthesis of ZnSe/PANI na-
the pristine ZnSe and ZnSe/PANI composites. In addition, the XRD
nocomposites, 25 mg of the synthesized ZnSe NPs were dissolved in
pattern of the pristine PANI composite is shown in Fig. 1. It can be seen;
portions of 100 ml double distilled deionized water then they were
the XRD pattern of the ZnSe/PANI indicates a heterostructure form that
sonicated for at least 1 h. 0.1 M aniline hydrochloride solution was
prepared by dissolving appropriate amounts of double distilled aniline
and hydrochloric acid in double distilled deionized water. A colorless
aqueous solution was obtained and it was stored in a refrigerator. 0.1 M
ammonium persulfate solution was prepared by dissolving appropriate
amounts of its salt in deionized water then it was also stored in the
refrigerator. Then, the ZnSe solutions were placed into the ice baths
over magnetic stirrer systems. Next 3 ml of the aniline hydrochloride
solution and 3 ml of ammonium persulfate solution were added to the
ZnSe solutions and then they stirred for at least 1 h, so that dark green
mixture containing ZnSe/PANI nanocomposites were obtained, which
were stored overnight. Then the mixtures were decanted for several
times using pure acetone. The decanting process was continued until
the decanted acetone got colorless; finally, aliquots of 5 ml of acetone
were added to them and sonicated for half an hour to obtain homo-
geneous composites. Next, the precipitates allowed to be dried at room
temperature.

2.2. Characterizations
Fig. 1. XRD patterns of the pristine ZnSe, pristine PANI composite, and ZnSe/
X-ray powder diffraction (XRD, Philips, X’pert, system using CuKα PANI nanocomposites.

731
A. Shirmardi et al.
is created by ZnSe and PANI because it includes two type patterns. In
addition, the full width at half maximum (FWHM) of the XRD peaks of
the ZnSe/PANI composites were increased in compared to the FWHM of
the XRD peaks of the pristine ZnSe. This increase could be due to the
matching of the main XRD peak of PANI with (1 1 1) peak of the ZnSe
sample.
TEM images of the pristine ZnSe and ZnSe/PANI composites are
shown in Fig. 2(a) and (b), respectively. As can be seen, the morphology
of the pristine ZnSe is NPs. Fig. 2(b) shows clearly a core-shell structure
for the ZnSe/PANI nanocomposites. The inset of Fig. 2(b) reveals how
PANI as a shell covers the ZnSe NP as a core. In addition, HRTEM image
of ZnSe NP indicates 0.33 nm interplanar distances that is in total
agreement with the ZnSe zincblend structure.
Fig. 3 shows FTIR spectra of the products. A comparative observa-
tion between the FTIR spectrum of the pristine ZnSe NPs and PANI
composite leads to understand that a heterostructure was created by
ZnSe and PANI. In fact, some peaks of the pristine PANI were also the
appeared in the ZnSe/PANI such as peaks at 3025, 2922, 1583, and
1506 cm−1 as well as ZnSe peak at 1403 cm−1. However, a little shift
was observed in the FTIR spectrum of ZnSe/PANI nanocomposites
compared to the FTIR spectra of the pristine ZnSe NPs and PANI
composite. Such shift could be due to an interaction between the ZnSe
NPs and PANI composite that was also observed in the XRD pattern of
the ZnSe/PANI nanocomposites.
The samples were also characterized by a Raman spectrometer to
compare vibration behavior of the pristine ZnSe NPs and ZnSe/PANI
nanocomposites and results are shown in Fig. 4. As shown, the Raman
spectrum of ZnSe NPs indicates a strong peaks at 500 cm−1 that belongs
to the E2(LO) mode of ZnSe structure [34]. Raman spectrum of ZnSe/
PANI nanocomposites also shows this peak with a weak intensity that
could be due to covering of the ZnSe NPs by PANI. In addition, Raman
spectrum of the ZnSe/PANI nanocomposites indicates two other peaks
that belonging to PANI structure. The band at 1105 cm−1 belongs to C-
H vibration of the semi-quinonoid rings (cation-radical segments) of the
PANI structure [35]. The peak at around 420 cm−1 also belongs to the
PANI structure and corresponds to out-of-plane ring-deformation of
PANI [35]. Therefore, Raman results also confirm that a heterostructure
was created by ZnSe NPs and PANI composites.
The PL spectra of the samples are shown in Fig. 5(a). As can be seen,
there are two peaks in two spectra from different regions of the visible
spectrum such as blue1 and green regions. According to our previous
study about ZnSe NPs, which were synthesized by a similar method,
these emissions are from different sources such as violet or blue emis-
sion that is belonged to the near-band-edge emission (NBE). However,
we used PL with laser source in our previous work and here the PL
source is a Xenon lamp. Therefore, the peak positions are not com-
pletely match with our previous work. As can be seen, NBE peak of the
ZnSe/PANI nanocomposites shows a red-shift in compared to the NBE
peak of the pristine ZnSe NPs. The green emission as defect emissions
belongs to Zn-vacancies. These defect sources present different loca-
lized energy levels within the band gap region and they are combined
with donor-acceptor pairs (DAPs). The addition of these intrinsic de-
fects, the other defects such surface trap states (STS) generate inter-
mediate level energy in band gap that is due to great surface/volume
ratio of the nanostructures [36]. In our previous study, we discussed
that the green emission is from STS and from conduction band (CB) to
singly negatively charged Zn-vacancies (VZn−) [34]. However, ac-
cording to the PL results, these defect emissions differ in intensity.
Consequently, efficient electron–hole separation is different in these
samples. As seen, the ZnSe/PANI nanocomposites have lower PL in-
tensity in compared with the pristine NPs. In fact, PANI enhances
1
The PL spectra of the samples are shown in Fig. 5(a). As can be seen, there
are two peaks in two spectra from different regions of the visible spectrum in
the 425-450 nm wavelength range and in the 485-495 nm wavelength range.
732
Applied Surface Science 462 (2018) 730–738
efficient electron–hole separation that could be due to its semi-
conducting behavior. Addition of the PL, absorption spectra of the
samples is shown in Fig. 5(b). It can be seen, the absorption peak of the
NPs was red-shifted by PANI. This shift could be due to heterostructure
behavior of two semiconductors and matching of Fermi level of the two
semiconductors. In fact, such results show that a type-II heterojunction
was created by the ZnSe and PANI as two semiconductors with different
band-gap value. The inset of Fig. 5(b) shows Tauc's plots of the samples
to estimate band gap value of the samples.
Fig. 6 shows the XPS spectra of the ZnSe/PANI nanocomposites and
PANI composite. C-1s peak (285 eV) was used to calibrate as a re-
ference. It can be observed that the spin-orbit splitting of 23 eV for Zn-
2p3/2 and Zn-2p1/2 (Fig. 6(a)) demonstrates that the Zn atoms are to-
tally bonded with Se in ZnSe phase. Fig. 6(b) reveals a Se-3d peak
around 55.5 eV. In addition, deconvolution results of the peak shows
two suborbital peaks that are belonged to Se-3d5/2/Se-3d3/2. Fig. 6(c)
shows N-1s of PANI shell. This peak was also deconvoluted to three
peaks. However, area ratios of the peaks in these samples are different
in compared to N-1s peak of the pristine PANI (Fig. 6(d)). In fact such
different feature of N-1s peak could be due to electron transfer between
PANI and the NPs. Furthermore, the XPS valence band spectra were also
measured to evaluate the valence band (VB) edge position of ZnSe/
PANI nanocomposites and pristine ZnSe NPs (Fig. 6(e) and (f), re-
spectively). The VB potential of ZnSe/PANI nanocomposites was esti-
mated to be 0.48 ± 0.05 eV, while, the pristine ZnSe NPs have the VB
potential at around 1.13 eV. In fact, PANI causes a shift in the VB edge
that could be affected the conduction band (CB) edge position. Ac-
cording to the band-gap values that were obtained by Tauc’s plots and
following equation [37]:
ECB = EVB−Eg (1)
the ECB of the ZnSe/PANI nanocomposites and pristine ZnSe NPS is
−1.62 ± 0.05 eV and −1.67 ± 0.05 eV, respectively. Such shifts in
the CB and VB of the ZnSe/PANI nanocomposites in compared with CB
and VB of the pristine ZnSe NPs could affect photocatalytic activity of
the samples.
The obtained samples were used to remove MB dye under a visible-
light source irradiation. Fig. 7(a and b) shows the optical absorption
spectra of the MB aqueous solution by the pristine ZnSe NPs and ZnSe/
PANI nanocomposites after exposure to the visible light irradiation for
various time intervals. As can be seen, more than 50% of the MB dye is
degraded within the first 30-min by the ZnSe/PANI nanocomposites,
while, degradation of the MB by the pristine ZnSe NPs after 120 min is
around only 50%. In addition, Ct/C0 ratio, where C0 is the initial ab-
sorbance, Ct is the absorbance at a time t, for all samples have been
calculated and the results are shown in Fig. 7(c). As can be seen, the
degradation rate of the ZnSe/PANI is higher than the pristine ZnSe NPs
significantly. To demonstrate this point, the photocatalytic rate con-
stant for the MB degradation (k) was also determined for two samples
from the first-order plot using the following equation:
C0
ln = kt
Ct (2)
where k is the first-order rate constant. Fig. 7(d) presents the results of
this plot for two samples. As can be seen, the constant rate of the ZnSe/
PANI nanocomposites is 2.5 times bigger than the constant rate of the
pristine ZnSe NPs.
Photoconductivity behavior of the samples was examined under
visible light source and results are shown in Fig. 8. As it can be seen in
Fig. 8(a), the PANI causes decrease the resistance of the samples. In
addition, the residence of the samples decreases by illumination of the
samples through a visible light source. Furthermore, Fig. 8(b) indicates
photoresponse of the samples under ON and OFF the light source. As
can be observed, the intensity of photocurrent was increased by PANI.
Such enhancement of the photoresponse could be due to trapping of the
excited electrons in the heterostructure that were created by ZnSe and
A. Shirmardi et al.
Fig. 2. TEM image of (a) pristine ZnSe NPs and (b) ZnSe/PANI nanocomposites. The inset shows an HRTEM image of ZnSe/PANI nanocomposites.
Fig. 3. FTIR spectrum of the pristine ZnSe NPs, pristine PANI, and ZnSe/PANI
nanocomposites.
Fig. 4. Raman spectrum of (a) ZnSe NPs and (b) ZnSe/PANI nanocomposites.
PANI.
According to the band-gap value, XPS, and photoresponse results,
the photocatalytic process of the ZnSe/PANI nanocomposites can be
summarized according to the schematic that is shown in Fig. 9. This
schematic shows band alignment of the ZnSe and PANI that leads to
form type-II heterojunction structure. As can be seen, the PANI’s elec-
trons were excited by the visible-light photons energy and transferred
from the HUMO level to the LUMO level of the PANI. Then, the excited
electrons from LUMO level of the PANI were emigrated to the CB of the
733
Applied Surface Science 462 (2018) 730–738
ZnSe and caused reduction of the dye.
On the other hand, reminded holes in the HUMO of the PANI caused
oxidation of the dye. In fact, photon energies of the LED light cannot
excite more electrons of the ZnSe due to their lower energies in com-
pared to the band-gap value of the ZnSe, while, PANI’s electrons were
excited by the LED photons due to the small band-gap of the PANI.
Therefore, PANI plays as an enhanced factor for the photocatalytic
activity of the ZnSe.
It was reported that selenide based photocatalysts may have pho-
tocorrosive oxidation problem during the repeated photocatalytic pro-
cess that generates selenide ions [33]. Whilst, the photocatalytic ac-
tivity process should be stable and reusable for the industrial
application. Reusability test of the samples for degradation of the dye
pollutants under the visible-light irradiation condition was carried out
by a cyclic photocatalytic activity to degrade of MB dye. The photo-
catalytic materials were reused by centrifuging the MB and washing the
nanostructures after four times photocatalytic activity during 120 min.
The results of the reusability tests are shown in Fig. 10. The same results
were observed every time for the ZnSe/PANI nanocomposites, ap-
proximately, while, the reusability test result of the pristine ZnSe NPs
shows that, the pristine ZnSe NPs is not a stable photocatalytic material.
Moreover, the stability of the ZnSe/PANI nanocomposites and in-
stability of the pristine ZnSe NPs as photocatalytic materials were ex-
amined by the XRD characterization after four times of the photo-
catalytic activity according to the reusability test. The XRD patterns of
the samples after four times of the photocatalytic activity were com-
pared with the XRD patterns of the samples before of the photocatalytic
activity and the results are shown in Fig. 11. As can be seen, the XRD
pattern of the pristine ZnSe NPs was changed significantly after four
times photocatalytic activity. On the other hand, the XRD pattern of the
ZnSe/PANI nanocomposites after four times of the photocatalytic ac-
tivity is matched with the XRD pattern of this sample before of the
photocatalytic activity, approximately. In fact, the NPs were protected
by the PANI against the chemical reaction of the ZnSe with MB dye.
Meanwhile, the capability of the products to remove inorganic
pollution was also examined. Therefore, the obtained nanocomposites
were used to change Cr(VI) to Cr(III). Fig. 12 shows the optical ab-
sorption spectra of the K2Cr2O7 aqueous solution by the pristine ZnSe
NPs and ZnSe/PANI nanocomposites after exposure to the visible-light
irradiation for various time intervals. It can be seen that the intensity of
the absorption peak of K2Cr2O7 at 375 nm decreases by increasing of
the irradiation time, which indicates that the Cr(VI) ions are changed to
Cr(III) ions. As can be seen, this degradation is also higher for the ZnSe/
PANI nanocomposites in comparison to the pristine ZnSe NPs. A plau-
sible mechanism for the photocatalyst reduction of Cr(VI) over the
ZnSe/PANI nanocomposites under visible light irradiation can be
A. Shirmardi et al. Applied Surface Science 462 (2018) 730–738

Fig. 5. (a) PL spectra of the pristine ZnSe NPs and ZnSe/PANI nanocomposites. (b) Absorbance spectra of the pristine ZnSe NPs, pristine PANI, and ZnSe/PANI
nanocomposites. The inset shows Tauc’s plots of the pristine PANI, ZnSe NPs, and ZnSe/PANI nanocomposites.

Fig. 6. XPS spectrum of (a) Z-2p and (b) Se-3d of ZnSe/PANI nanocomposites. XPS spectrum of N-1s orbital of (c) ZnSe/PANI nanocomposites and (d) pristine PANI
composite. The XPS valance band edge spectrum of (e) ZnSe/PANI nanocomposites and (f) pristine ZnSe NPs.

734
A. Shirmardi et al. Applied Surface Science 462 (2018) 730–738

Fig. 7. UV–vis absorbance of the MB for

different time intervals during photo-
catalytic degradation of MB under a visible-
light source irradiation using (a) pristine
ZnSe NPs, (b) ZnSe/PANI nanocomposites.
(c) Comparative results of C/C0 for the dif-
ferent time interval during photocatalytic
degradation of MB by the pristine ZnSe NPs
and ZnSe/PANI nanocomposites. (d) Kinetic
study of photocatalytic MB degradation
using the pristine ZnSe NPs and ZnSe/PANI
nanocomposites.

Fig. 8. (a) I-V measurement of the pristine ZnSe NPs and ZnSe/PANI nanocomposites under dark and visible light illumination. (b) Photocurrent results of the
samples under visible light chopper.

H2O + h+ → %OH + H+ (5)

% −
Cr 3+
+ 2 h + OH → Cr
+ 6+
+ OH (6)

For more understanding about the effects of PANI on the photo-

catalytic performance of the ZnSe nanostructures, the pristine ZnSe NPs
and ZnSe/PANI nanocomposites were characterized by N2 adsorption-
desorption measurements. N2 adsorption-desorption isotherms of these
samples show different types of hysteresis loops. In fact, the pristine
ZnSe NPs indicates type IV characteristics with H1 type (pore with cy-
lindrical shape) of hysteresis loop according to Fig. 13(a) [19]. On the
other hand, the ZnSe/PANI nanocomposites, which had nanorods
Fig. 9. Schematic of dye degradation by ZnSe/PANI nanocomposites under the
morphology, reveal the H2 type (pore with slits shape) of hysteresis
visible-light irradiation.
loop (Fig. 13(a)). Actually, these samples include mesoporous due to
hysteresis loop shape of adsorption-desorption isotherms curves [28].
summarized according to the following reactions: However, pore shapes of the samples are different. Fig. 13(b) shows
pore size distribution of the samples that are drawn according to the
ZnSe/PANI + hv → ZnSe/PANI(h+ + e−) (3)
BJH method. It can be seen different pore size distribution for two
Cr2O72− + 14H+ + 6e− → 2Cr3+ + 7H2O (4) samples that could be due to different morphology. Surface area was

735
A. Shirmardi et al.
Fig. 10. Reusability test of the ZnSe NPs and ZnSe/PANI nanocomposites cat-
alyst for the photodegradation of MB.
Fig. 11. Comparative between XRD patterns before and after four times the photocatalytic activity of (a) ZnSe NPs and (b) ZnSe/PANI nanocomposites.
Fig. 12. UV–vis absorbance of K2Cr2O7 for different time intervals during photocatalytic degradation of MB under a visible-light source irradiation using (a) ZnSe
NPs, (b) ZnSe/PANI nanocomposites.
calculated by N2 adsorption-desorption curves, while, mean pore dia-
meter and pore volumes were calculated from the desorption branch
according to the BET model, which these data are summarized in
Table 1.
As can be seen, the textural parameters such as surface area, mean
pore diameter, and pore volume of the samples are different, sig-
nificantly. According to the Table 1 results, the surface area and mean
pore diameter of the ZnSe/PANI nanocomposites are smaller than those
736
Applied Surface Science 462 (2018) 730–738
of the pristine ZnSe NPs, which could be due to the morphology of the
PANI that were covered in ZnSe/PANI nanocomposites. In fact, the
PANI has caused the pores of the nanoparticles to be filled and due to
the same reason pore volume of the ZnSe/PANI nanocomposites is
smaller than those of the pristine NPs. According to Table 1 results,
textural properties of the NPs were decreased by PANI, while the
photocatalytic performance was improved by PANI. In fact, pore
structure of porous is not responsible for the enhancement photo-
catalytic performance of the ZnSe/PANI and it is type-II heterojunction
structure of ZnSe and PANI that increases photocatalytic activity of the
ZnSe/PANI nanocomposites.
4. Conclusion
The effects of PANI on the photocatalytic performance of ZnSe NPs
under a visible-light source irradiation were investigated. The XRD,
Raman, and FTIR results indicated that a heterostructure of ZnSe and
PANI was formed. Optical characterization showed the PANI caused
decrease band-gap in compared to the band-gap of the pristine ZnSe
NPs. XPS results indicated that, PANI caused a shift in CB and VB po-
sitions. In addition, the optical and XPS results indicated that, a type-II
heterojunction was created by the PANI and ZnSe NPs. Electrical
measurements revealed that, resistance and photoresponse of the
samples were decreased and increased, respectively by PANI.
Comparison of the BET results of the pristine ZnSe NPs and ZnSe/PANI
revealed the PANI caused decrease textural properties of the ZnSe/PANI
nanocomposites. Therefore, type-II heterojunction structure of the ZnSe
and PANI was the most important factor for enhanced photocatalytic
performance of the ZnSe/PANI nanocomposites because caused de-
crease recombination process of electron-hole pairs. The obtained
A. Shirmardi et al.
Fig. 13. N2 adsorption–desorption isotherm (a) and the pore size distribution of the samples with Zn/Se ratio of 1:1, 1:0.6, and 1:1.4 (b).
Table 1
Textural Properties of the samples.
Sample Surface area (m2/ Mean pore diameter Pore volume (cm3/
g) (nm) g)
ZnSe 44.36 5.45 9.85
ZnSe/PANI 19.16 21.68 4.40
results of this research showed that, PANI could be the best material to
protect metal-selenide nanostructures, which were used as photo-
catalytic materials. In addition, if the second semiconductor, which was
chosen PANI, has a suitable band-gap value, then it can create a type-II
heterojunction with PANI that is the best heterojunction for the pho-
tocatalytic activity.
Acknowledgment
R. Yousefi and F. Jamali-Sheini gratefully acknowledge Islamic
Azad University (I.A.U), Masjed-Soleiman and Ahvaz Branches, re-
spectively, for partial supporting of this research. M.A.M. Teridi ac-
knowledges UKM for obtaining a research grant with name and number
of “Dana Impak Perdana (DIP-2016-003) of Universiti Kebangsaan
Malaysia (UKM)”.
References
[1] R. Yousefi, F. Jamali-Sheini, M. Cheraghizade, S. Khosravi-Gandomani, A. Sáaedi,
N.M. Huang, W.J. Basirun, M. Azarang, Enhanced visible light photocatalytic ac-
tivity of Sr-doped ZnO nanoparticles, Mater. Sci. Semicond. Process. 32 (2015)
152–159.
[2] H. Donga, G. Chen, J. Sun, C. Li, Y. Yu, D. Chen, A novel high-efficiency visible-light
sensitive Ag2CO3 photocatalyst with universal photodegradation performances:
simple synthesis, reaction mechanism and first-principles study, Appl. Catal., B.
134–135 (2013) 46–54.
[3] K. Nakataa, A. Fujishim, TiO2 photocatalysis: design and applications, J.
Photochem. Photobiol.C. 13 (2012) 169–189.
[4] Z. Liu, C. Zhou, Improved photocatalytic activity of nano CuO-incorporated TiO2
granules prepared by spray drying, Pro. Nat. Sci-Mater. 25 (2015) 334–341.
[5] F. Chen, W. An, L. Liu, Y. Liang, W. Cui, Highly efficient removal of bisphenol A by a
three-dimensional graphene hydrogel-AgBr@rGO exhibiting adsorption/photo-
catalysis synergy, Appl. Catal. B. 217 (2017) 65–80.
[6] Y. Liang, S. Lin, L. Liu, J. Hu, W. Cui, Oil-in-water self-assembled Ag@AgCl QDs
sensitized Bi2WO6: enhanced photocatalytic degradation under visible light irra-
diation, Appl. Catal. B. 164 (2015) 192–203.
[7] R. Yousefi, J. Beheshtian, S.M. Seyedeh-Talebi, H.R. Azimi, F. Jamali-Sheini,
Experimental and theoretical study of enhanced photocatalytic activity of Mg-
doped ZnO NPs and ZnO/rGO nanocomposites, Chem. Asian J. 13 (2018) 194–203.
[8] Q. Zhu, Y. Peng, L. Lin, C.-M. Fan, G.-Q. Gao, R.-X. Wang, A.-W. Xu, Stable blue
TiO2-x nanoparticles for efficient visible light photocatalysts, J. Mater. Chem. A. 2
(2014) 4429–4437.
[9] Y. Li, W. Cui, L. Liu, R. Zong, W. Yao, Y. Liang, Y. Zhu, Removal of Cr(VI)by3DTiO2-
graphene hydrogel via adsorption enriched with photocatalytic reduction, Appl.
Catal. B. 199 (2016) 412–423.
[10] Y. Zhang, W. Cui, W. An, L. Liu, Y. Liang, Y. Zhu, Combination of photoelec-
trocatalysis and adsorption for removal of bisphenol A over TiO2-graphene hydrogel
with 3D network structure, Appl. Catal. B. 221 (2018) 36–46.
737
Applied Surface Science 462 (2018) 730–738
[11] H. Wang, Y. Liang, L. Liu, J. Hu, W. Cui, Highly ordered TiO2 nanotube arrays
wrapped with g-C3N4 nanoparticles for efficient charge separation and increased
photoelectrocatalytic degradation of phenol, J. Hazar. Mater. 344 (2018) 369–380.
[12] M. Samadi, M. Zirak, A. Naseri, E. Khorashadizade, A.Z. Moshfegh, Recent progress
on doped ZnO nanostructures for visible-light photocatalysis, Thin Solid Films 605
(2016) 2–19.
[13] R. Yousefi, H.R. Azimi, M.R. Mahmoudian, M. Cheraghizade, Highly enhanced
photocatalytic performance of Zn(1–x)MgxO/rGO nanostars under sunlight irradia-
tion synthesized by one-pot refluxing method, Adv. Powder. Tech. 29 (2018) 78–85.
[14] X. Wang, Y. Liang, W. An, J. Hu, Y. Zhu, W. Cui, Removal of chromium (VI) by a
self-regenerating and metal free g-C3N4/graphene hydrogel system via the synergy
of adsorption and photo-catalysis under visible light, Appl. Catal. B. 219 (2017)
53–62.
[15] Q. Zhang, H. Li, Y. Ma, T. Zhai, ZnSe nanostructures: synthesis, properties and
applications, Prog. Mater. Sci. 83 (2016) 472–535.
[16] P. Chen, T.-Y. Xiao, H.-H. Li, J.-J. Yang, Z. Wang, H.-B. Yao, S.-H. Yu, Nitrogen-
doped graphene/ZnSe nanocomposites: hydrothermal synthesis and their enhanced
electrochemical and photocatalytic activities, ACS Nano 6 (2012) 712–719.
[17] W. Cui, J. He, H. Wang, J. Hu, L. Liu, Y. Liang, Polyaniline hybridization promotes
photo-electro-catalytic removal of organic contaminants over 3D network structure
of rGH-PANI/TiO2 hydrogel, Appl. Catal. B. 232 (2018) 232–245.
[18] L. Liu, L. Ding, Y. Liu, W. An, S. Lin, Y. Liang, W. Cui, A stable Ag3PO4@PANI core@
shell hybrid: enrichment photocatalytic degradation with π−π conjugation, Appl.
Catal. B. 201 (2017) 92–104.
[19] C. Yang, W. Dong, G. Cui, Y. Zhao, X. Shi, X. Xia, B. Tang, W. Wang, Enhanced
photocatalytic activity of PANI/TiO2 due to their photosensitization-synergetic ef-
fect, Electrochim. Acta. 247 (2017) 486–495.
[20] F. Chen, W. An, Y. Li, Y. Liang, W. Cui, Fabricating 3D porous PANI/TiO2–graphene
hydrogel for the enhanced UV-light photocatalytic degradation of BPA, Appl. Surf.
Sci. 427 (2018) 123–132.
[21] M. Radoičić, G. Ćirić-Marjanović, V. Spasojević, P. Ahrenkiel, M. Mitrić,
T. Novaković, Z. Šaponjića, Superior photocatalytic properties of carbonized PANI/
TiO2 nanocomposites, Appl. Catal. B. 213 (2017) 155–166.
[22] F. Jamali-Sheini, R. Yousefi, N.A. Bakr, M. Cheraghizade, M. Sookhakian,
N.M. Huang, Highly effecient photo-degradation of methyl blue and band gap shift
of SnS nanoparticles under different sonication frequencies, Mater. Sci. Semicond.
Process. 32 (2015) 172–178.
[23] S. Kalikeri, N. Kamath, D. Jayant Gadgil, V. Shetty Kodialbail, Visible light-induced
photocatalytic degradation of Reactive Blue-19 over highly efficient polyaniline-
TiO2 nanocomposite: a comparative study with solar and UV photocatalysis,
Environ. Sci. Pollut. Res. 25 (2018) 3731–3744.
[24] S. Gunti, T. Alamro, M. McCrory, M.K. Ram, The use of conducting polymer to
stabilize the nanostructured photocatalyst for water remediation, J. Environ. Chem.
Eng. 5 (2017) 5547–5555.
[25] Y. Deng, L. Tang, G. Zeng, H. Dong, M. Yan, J. Wang, W. Hu, J. Wang, Y. Zhou,
J. Tang, Enhanced visible light photocatalytic performance of polyaniline modified
mesoporous single crystal TiO2 microsphere, Appl. Surf. Sci. 387 (2016) 882–893.
[26] N. Guo, Y. Liang, S. Lan, L. Liu, J. Zhang, G. Ji, S. Gan, Microscale hierarchical
three-dimensional flowerlike TiO2/PANI composite: synthesis, characterization,
and its remarkable photocatalytic activity on organic dyes under UV-light and
sunlight irradiation, J. Phys. Chem. C 118 (2014) 18343–18355.
[27] S. Sharma, S. Singh, N. Khare, Enhanced photosensitization of zinc oxide nanorods
using polyaniline for efficient photocatalytic and photoelectrochemical water
splitting, Int. J. Hydrogen Energy 41 (2016) 21088–21098.
[28] K. Pandiselvi, H. Fang, X. Huang, J. Wang, X. Xu, T. Li, Constructing a novel carbon
nitride/polyaniline/ZnO ternary heterostructure with enhanced photocatalytic
performance using exfoliated carbon nitride nanosheets as supports, J. Hazar.
Mater. 314 (2016) 67–77.
[29] C. Wang, L. Wang, J. Jin, J. Liu, Y. Li, M. Wu, L. Chen, B. Wang, X. Yang, B.-L. Su,
Probing effective photocorrosion inhibition and highly improved photocatalytic
hydrogen production on monodisperse PANI@CdS core-shell nanospheres, Appl.
Catal. B. 188 (2016) 351–359.
[30] S. Sharma, S. Singh, N. Khare, Synthesis of polyaniline/CdS (nanoflowers and na-
norods) nanocomposites: a comparative study towards enhanced photocatalytic
activity for degradation of organic dye, Colloid. Polym. Sci. 294 (2016) 917–926.
A. Shirmardi et al.
[31] M.V. Carevi, N.D. Abazovi, M.N. Mitri, G. Ciri c-Marjanovi, M.D. Mojovi,
S.P. Ahrenkiel, M.I. Comor, Properties of Zirconia/Polyaniline hybrid nano-
composites and their application as photocatalysts for degradation of model pol-
lutants, Mater. Chem. Phys. 205 (2018) 130–137.
[32] L. Liu, L. Ding, Y. Liu, W. An, S. Lin, Y. Liang, W. Cui, A stable Ag3PO4@PANI core@
shell hybrid: enrichment photocatalytic degradation with-conjugation, Appl. Catal.
B. 201 (2017) 92–104.
[33] S. Wang, J.-H. Yun, B. Luo, T. Butburee, P. Peerakiatkhajohn, S. Thaweesak,
M. Xiao, L. Wang, Recent progress on visible light responsive heterojunctions for
photocatalytic applications, J. Mater. Sci. Tech. 33 (2017) 1–22.
[34] R. Yousefi, H.R. Azimi, M.R. Mahmoudian, Wan Jeffrey Basirun, The effects of
738
Applied Surface Science 462 (2018) 730–738
defect emissions on enhancement photocatalytic performance of ZnSe QDs and
ZnSe/rGO nanocomposites, Appl. Surf. Sci. 435 (2018) 886–893.
[35] M. Trchová, Z. Morávková, M. Bláha, J. Stejskal, Raman spectroscopy of polyaniline
and oligoaniline thin films, Electrochim. Acta. 122 (2014) 28–38.
[36] L. Hu, H. Wu, L. Du, H. Ge, X. Chen, N. Dai, The effect of annealing and photo-
activation on the optical transitions of band–band and surface trap states of col-
loidal quantum dots in PMMA, Nanotechnology 22 (2011) 125202.
[37] J.R. Waldrop, R.W. Grant, Measurement of AlN/GaN (0001) heterojunction band
offsets by x-ray photoemission spectroscopy, Appl. Phys. Lett. 68 (1996)
2879–2881.