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c Indian Academy of Sciences.
Abstract. Polyaniline (PANI) as a promising conducting polymer has been used to prepare polyaniline/TiO2
(PANI/TiO2 ) nanocomposite with core-shell structure as photocatalyst. Titanium dioxide (TiO2 ) nanoparticles with
an average crystal size of 21 nm were encapsulated by PANI via the in situ polymerization of aniline on the surface of
TiO2 nanoparticles. FT–IR, UV-Vis-NIR, XRD, SEM and TEM techniques were used to characterize the PANI/TiO2
core-shell nanocomposite. Photocatalytic activity of PANI/TiO2 nanocomposite was investigated under both UV and
visible light irradiations and compared with unmodified TiO2 nanoparticles. Results indicated deposition of PANI
on the surface of TiO2 nanoparticles which improved the photocatalytic activity of pristine TiO2 nanoparticles.
801
802 Ali Olad, Sepideh Behboudi and Ali Akbar Entezami
synthesis method has a great effect on the final properties of The mixture was allowed to polymerize under stirring for
PANI/TiO2 composite (Xu et al 2005; Shi et al 2009; Karim 5 h at room temperature. Reaction mixture was filtered under
et al 2009). Various methods such as ultrasonic irradiation, vacuum and washed with ethanol and water and then dried at
in situ polymerization, self assembly method, graft poly- 60 ◦ C for 24 h to obtain PANI emeraldine salt (ES) as a green
merization and UV curable polymerization methods have powder.
been used to prepare PANI/TiO2 composite systems (Li et al
2006; Kim et al 2009). In situ polymerization of ani-
line in the presence of TiO2 nanoparticles has been used 2.3 Instruments
commonly for preparation of PANI/TiO2 nanocomposites
(Xu et al 2005; Zhang et al 2005, 2006; Yavuz and Gok Fourier–transform infrared (FT–IR) spectra of HCl-doped
2007). In addition to TiO2 with established photocatalytic PANI and PANI/TiO2 nanocomposite were obtained by using
behaviour (Chen and Liu 2007), conjugated polymers were a Bruker Tensor 27 spectrometer. Morphology of samples
also used for photocatalysis (Muktha et al 2007). The pho- was observed on a Cam scan MV 2300 scanning elec-
tosensitizing effect of PANI on TiO2 has been reported. The tron microscope (SEM) and a Philips-CM10 transmission
application of a conducting polymer such as PANI expands electron microscope (TEM) with an accelerating voltage of
the photoactive region of TiO2 toward visible light irra- 100 kV. X-ray diffraction (XRD) patterns were taken on a
diation (Min et al 2007; Wang and Min 2007; Li et al Siemens D5000 X-ray diffractometer with a Cu Kα X-ray
2008a,b). Many efforts have been made to improve photo- radiation (λ = 0·154 nm). A Shimadzu UV-1700 Farma spec-
catalytic activity of the PANI/TiO2 system (Wang and Zeng trophotometer was used to record the UV-Vis-near IR spectra
2009a,b; Liao et al 2011). The application of PANI/TiO2 of samples and degradation measurement of MeO solutions.
as a photocatalyst for the photodegradation of environmen-
tal pollutants has been investigated in literature (Li et al
2008a,b; Salem et al 2009). Liu and Guo (1991) used the 2.4 Evaluation of photocatalysis
hybrid of PANI and TiO2 for photocatalytic removal of phe-
nol from water. The synergetic effects of PANI and TiO2 The photocatalytic activity of pristine TiO2 and PANI/TiO2
in photocatalytic degradation of colourful water contami- nanocomposite was evaluated by determining the decolouri-
nants under visible light irradiation have been demonstrated zation efficiency and rate constant of MeO photodegrada-
(Zhang et al 2008; Wang et al 2010; Liao et al 2011). In tion. The aqueous solutions of MeO were used as model
this study, the PANI/TiO2 core-shell nanocomposite was pre- pollutant for investigation of the photocatalytic activity of
pared using in situ polymerization method and then photoca- samples. 0·01 g of pristine TiO2 or PANI/TiO2 photocatalysts
talytic degradation of methyl orange (MeO) in the presence was added to 50 ml of MeO aqueous solution (10 mg·L−1 )
of low amount of PANI/TiO2 nanocomposite as photocata- under magnetic stirring. The solid concentration in final sus-
lyst was investigated. pension was 200 mg·L−1 . The suspension was stirred in dark
condition at room temperature (25 ◦ C) for 30 min to achieve
adsorption equilibrium for MeO. Afterward, the suspension
2. Experimental was illuminated by a 50 W linear halogen lamp equipped
with UVA absorbent filter (λ > 400 nm) for 120 min. Sam-
2.1 Materials and reagents ples for monitoring of remaining MeO concentration in aque-
ous solution were drawn out by a syringe equipped with
Aniline monomer (Merck Company, Germany) was distilled
2·5 μm pore size filter at various time intervals of photocat-
two times under vacuum and stored below 4 ◦ C prior to
alytic degradation reaction. Concentration of remaining MeO
use. TiO2 nanoparticles (Degussa P25, average crystal size,
was obtained by measuring the absorbance of samples at
21 nm) were used to prepare PANI/TiO2 nanocomposite. All
λmax = 464 nm with a UV-Vis spectrophotometer. The deter-
other reagents including ammonium peroxodisulfate (APS,
mined absorption was converted to concentration through the
(NH4 )2 S2 O8 ), hydrochloric acid (HCl) and methyl orange
standard calibration curve (figure 1). Also figure 2 shows
(MeO), were purchased from Merck Company as analytical
UV-Vis absorption spectrum of MeO aqueous solution. In
grade and were used as received.
the next step, same experiments were repeated exactly with
30 W UV tube lamp (length, 41 cm, diameter, 2·5 cm).
2.2 Preparation of PANI/TiO2 core-shell nanocomposite The photocatalytic degradation efficiency was calculated
using (1).
PANI/TiO2 nanocomposite was prepared as follows: TiO2 C0 − Ct
nanoparticles (1 g) were dispersed in 190 ml of HCl aque- R% = × 100, (1)
ous solution (1·21 M) containing 0·3 ml aniline under C0
ultrasonic vibration to reduce the aggregation of TiO2 where R% is degradation efficiency of MeO, C0 the initial
nanoparticles. APS (0·863 g) was dissolved in 15 ml of HCl concentration of MeO in aqueous solution and Ct the con-
aqueous solution (1·21 M) and added drop wise into the centration of MeO in aqueous solution at different reaction
solution containing aniline monomer under constant stirring. time, t (Min et al 2007; Zhu et al 2010).
Photocatalytic activity of TiO2 /polyaniline 803
Figure 1. Calibration curve of MeO in λmax = 464 nm. Figure 3. FT–IR spectra of HCl-doped PANI (a) and PANI/TiO2
nanocomposite (b).
0·89λ
D= , (2)
β cos θ
TiOH + H+ ↔ TiOH+
2. (3)
Figure 8. UV-Vis-NIR spectra of pristine TiO2 nanoparticles (a) Figure 9. Degradation efficiency of MeO during 120 min illumi-
and PANI/TiO2 nanocomposite (b). nation under visible light using pristine TiO2 (a) and PANI/TiO2
nanocomposite (b) as photocatalyst.
MeO in the presence of pristine TiO2 and PANI/TiO2 et al 2010; Liao et al 2010) in figure 10. This model is
nanocomposite was obtained according to the procedure described by (4).
described § 2. Figure 9 shows photodegradation efficiency of
MeO in the presence of TiO2 and PANI/TiO2 nanocompo- − ln (Ct /C0 ) = kapp t, (4)
site photocatalysts under visible light irradiation against con- where kapp is the apparent rate constant, C0 the initial concen-
tact time. Figure 9 indicates photodegradation efficiency of tration of MeO and Ct the concentration of MeO at various
MeO in the presence of PANI/TiO2 nanocomposite as pho- contact times, t.
tocatalyst is significantly higher than pristine TiO2 nanopar- Half time of MeO photodegradation was calculated using
ticles. The kinetic plots for MeO degradation with pristine (5) which was derived from (4) by replacing Ct with C0 /2
TiO2 and PANI/TiO2 nanocomposite photocatalysts under (Dong et al 2010):
visible light illumination are shown by pseudo-first order
reaction (Li et al 2008a,b; Wang and Zeng 2009a; Wang t1/2 = ln 2/k = 0·6931/kapp , (5)
Photocatalytic activity of TiO2 /polyaniline 807
Figure 10. Kinetics plots for linear fitting of data obtained from Figure 11. Degradation efficiency of MeO during 120 min illu-
pseudo-first-order reaction model for MeO degradation under visi- mination under UV light using pristine TiO2 (a) and PANI/TiO2
ble light irradiation using pristine TiO2 (a) and PANI/TiO2 (b) as nanocomposite (b) as photocatalyst.
photocatalyst.
Table 1. Apparent rate constants (kapp ), linear regression co- Both PANI and TiO2 nanoparticles absorb photons at
efficients, half time of MeO photodegradation from a plot of their interface under irradiation. Since the CB of TiO2 and
−ln (Ct /C0 ) = kapp t and degradation efficiency (%) of MeO after lowest unoccupied molecular orbital (LUMO) of PANI are
120 min illumination under visible light. well matched for the charge transfer, the electrons gene-
rated by PANI π → π ∗ transition under visible light illu-
Degradation mination can be injected into the CB of TiO2 and the elec-
Photocatalyst efficiency (%) R2 kapp (min−1 ) t1/2 (min) trons in the VB of TiO2 are delivered to PANI layer (Wang
and Min 2007). While under UV light illumination pho-
Neat TiO2 32·5 0·993 0·0023 301·35
PANI/TiO2 49·9 0·985 0·0037 187·32
togenerated holes in the VB of TiO2 can be transferred
directly to highest unoccupied molecular orbital (HOMO)
of PANI, as the VB of TiO2 matches well with the HOMO
of PANI (Zhang et al 2008). Subsequently the photogene-
The determined pseudo-first-order rate constants (kapp ), li- rated electron–hole pairs in the PANI/TiO2 photocatalyst
near regression coefficients (R 2 ), degradation efficiency and interface can be transferred to the surface, which reacts
half time of MeO photodegradation after 120 min illumina- directly with adsorbed MeO molecules on the surface of
tion are presented in table 1. From table 1, it can be seen that PANI/TiO2 nanocomposite or indirectly decompose MeO
the deposition of PANI shell on the surface of TiO2 nanopar- through the production of OH· radicals (Salem et al 2009).
ticles improves apparent rate constant and half time of MeO Therefore, charge separation enhancement in PANI/TiO2
degradation compared to pristine nano-TiO2 photocatalyst. nanocomposite interface causes improvement of photocat-
Figure 11 shows photodegradation efficiency of MeO against alytic activity of PANI/TiO2 nanocomposite under both
contact time with TiO2 and PANI/TiO2 photocatalysts under UV and visible light illuminations. Enhancement of charge
UV irradiation. Figure 11 indicates degradation efficiency of separation in the PANI/TiO2 nanocomposite is achieved,
MeO in the presence of PANI/TiO2 nanocomposite which is because PANI is an efficient electron donor and good hole
higher than pristine TiO2 nanoparticles. The kinetic plots of transporter. These features of PANI lead to the effective
MeO degradation with PANI/TiO2 and pristine TiO2 photo- separation of photogenerated electron–holes at the inter-
catalysts under UV light illumination are shown in figure 12. face of PANI and TiO2 in the nanocomposite (Zhang
Also apparent rate constants, regression coefficients, degra- et al 2008; Wang et al 2010). Although in this particular
dation efficiency and half time of MeO photodegradation molar ratio of TiO2 /PANI (3·79) which was used to pre-
under UV illumination are tabulated in table 2. One of the pare PANI/TiO2 nanocomposite, improvement of PANI/TiO2
possible reasons for the improvement of PANI/TiO2 photo- photocatalytic activity under UV light illumination is neg-
catalytic activity under both UV and visible light illumina- ligible compared to pristine TiO2 nanoparticles while, pho-
tions is the reduced aggregation state of TiO2 nanoparticles tocatalytic activity of the same composition of PANI/TiO2
in PANI/TiO2 nanocomposite. This leads to the higher spe- under visible light irradiation is considerably higher than
cific surface area and higher interaction between PANI/TiO2 pristine TiO2 nanoparticles. Also, the obtained regression
photocatalyst and dye aqueous solution compared to pris- coefficients suggest the kinetics equation of MeO pho-
tine TiO2 nanoparticles (Li et al 2008a,b). Therefore, adsorp- todegradation under both UV and visible light illumina-
tion of dye molecules on the nanocomposite is higher than tions well concisely follow the pseudo-first order reaction
pristine TiO2 nanoparticles. kinetics.
808 Ali Olad, Sepideh Behboudi and Ali Akbar Entezami
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