Ecofriendly Synthesis and Solar Photocatalytic Activity of S-Doped Zno
Ecofriendly Synthesis and Solar Photocatalytic Activity of S-Doped Zno
Ecofriendly Synthesis and Solar Photocatalytic Activity of S-Doped Zno
a r t i c l e i n f o a b s t r a c t
Article history: The S-doped ZnO was prepared by new ecofriendly method, which involves simple mechanochemical
Received 26 April 2010 synthesis followed by thermal decomposition of bisthiourea zinc oxalate (BTZO) powders. The BTZO was
Received in revised form 7 July 2010 characterized by FTIR and TG–DTA analysis while S-doped ZnO crystallite was characterized by XRD,
Accepted 8 July 2010
XPS, SEM, EDXS, and photoluminescence (PL) spectra. X-ray diffraction data suggest the single phase
Available online 15 July 2010
wurtzite structure for S-doped ZnO and the incorporation of sulfur expand the lattice constants of ZnO.
Room temperature PL spectra show more number of oxygen vacancies in S-doped ZnO as compare to
Keywords:
that of pure ZnO. Photocatalytic activity of S-doped ZnO was checked by means of solar photocatalytic
S-doped ZnO
XPS
degradation (PCD) of resorcinol, using a batch photoreactor. The PCD efficiency of S-doped ZnO was
Photoluminescence found to be 2 times greater than that of pure ZnO. The inherent relationship between PL intensity and
Photocatalysis photocatalytic activity of S-doped ZnO was discussed.
Resorcinol © 2010 Elsevier B.V. All rights reserved.
Sunlight
0304-3894/$ – see front matter © 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.jhazmat.2010.07.026
316 A.B. Patil et al. / Journal of Hazardous Materials 183 (2010) 315–323
2.2. Synthesis of S-doped zinc oxide intermediates were identified by HPLC and GC–MS analysis. HPLC
analysis was performed with a Shimadzu 20A instrument equipped
Sulfur-doped zinc oxide was prepared by a novel two-step pro- with C18 column. Acetonitrile/water (40:60) was used as mobile
cess. The first step is solution free mechanochemical synthesis of phase at a flow rate of 1 mL min−1 . The sample injection volume of
bisthiourea zinc oxalate (BTZO) powders and the second step is 10 L and UV wavelength of 254 nm were employed. GC–MS anal-
thermal decomposition of BTZO to form S-doped ZnO. In a typ- ysis was done with Shimadzu GCMS-QP5050 instrument equipped
ical synthesis, 219.5 mg of zinc acetate dihydrate and 151.2 mg with DB-5 capillary column and Quadrapole detector. Helium was
of oxalic acid were taken in agate mortar and mixture was hand used as a carrier gas. The GC injection volume of 2 L and the split
ground for 10 min at room temperature to obtain paste (semisolid) ratio of 25:30 were used.
of zinc oxalate dihydrate and acetic acid by-product (Scheme 1a). The reusability of the photocatalyst was evaluated by reclaiming
Then 152.2 mg of thiourea was added and hand grinding process the photocatalyst after PCD reaction in the batch mode, washing,
was continued for next 20 min. The thiourea coordinates with zinc drying in electric oven at 110 ◦ C and using it for resorcinol degra-
oxalate to form bisthiourea zinc oxalate complex (Scheme 1b). After dation under similar experimental conditions.
1 h, most of the acetic acid by-product goes off from the reaction
mixture and semisolid gradually turns into fine powder of BTZO.
Finally, dark yellow colored S-doped ZnO was obtained by calcina- 2.4. Photocatalytic degradation experiments
tion of BTZO at 600 ◦ C. Same procedure is repeated, without adding
thiourea to obtain zinc oxalate (ZO) and pure ZnO for comparison. The PCD efficiency of S-doped zinc oxide was investigated by
means of solar photocatalytic degradation of resorcinol a model
endocrine disruptor. All PCD experiments were carried out in dupli-
2.3. Equipments
cate and at an ambient temperature, without external supply of
oxygen. Pure resorcinol (Merck, 99%) was dissolved in double dis-
The BTZO was characterized by FTIR (Shimadzu FTIR-8400 spec-
tilled water to obtain desired concentration solutions. In all PCD
trometer equipped with KBr beam splitter) and thermogravimetry
experiments, 100 mL resorcinol solution (150 ppm) was taken in
(Shimadzu TG–DTG-60H). While, S-doped ZnO crystallite were
batch photocatalytic reactor vessel and optimum amount of photo-
characterized by X-ray diffractometer (D-8 Advance Brkur AXS),
catalyst was added and mixture was agitated in an ultrasonic bath
energy dispersive X-ray spectra (EDXS) attached to scanning elec-
for 5 min to obtain uniform suspension. Initial pH of suspension
tron micrograph (SEM JEOL JSM-6360A) and photoluminescence
was recorded and whole setup was then placed in sunlight with
(PL) spectra (Shimadzu, RF-5301PC). X-ray photoelectron spectra
constant stirring for specific period of time between 9:00 a.m. to
(XPS) of S-doped ZnO were recorded with a V. G. Microtech (UK)
5:00 p.m. during the months of December to March. After the spe-
unit ESCA 3000 spectrometer equipped with Mg K␣ X-ray source
cific sunlight irradiation time PCD reaction was stopped and whole
(h = 1253.6 eV) and a hemispherical electron analyzer. The X-ray
suspension was centrifuged at a speed of 3000 rpm for 5 min (Remi,
source was operated at 150 W. The residual pressure in the ion-
India) and then filtered through a 0.45 m polytetrafluro ethylene
pumped analysis chamber was maintained below 1.0 × 10−9 Torr
(PTFE) filter. The filtrate was directly used for absorbance and COD
during data acquisition. The C 1s peak at a binding energy 284.6 eV
measurement. While, some part of filtrate was acidified with dil.
was taken as an internal standard. The accuracy of BE values
H2 SO4 and extracted with ethyl acetate. The resulting sample was
was within ±0.2 eV. The photocatalytic reactions were carried
then dried under vacuum and used for GC–MS analysis.
out at ambient temperature under the irradiation of sunlight in
The extent of degradation of resorcinol was also studied under
batch photoreactor. The details of setup of photoreactor were
similar experimental conditions in the dark as a control experi-
already explained elsewhere [16]. The initial pH of suspension
ment.
was recorded with the help of pH meter (EUTECH-pH510). The
extent of photocatalytic degradation (PCD) at an interval of 1 h sun-
light irradiation was primarily checked by means of decrease in 3. Results and discussion
absorbance on UV–vis spectrophotometer (UV-1601, Shimadzu).
Complete mineralization of resorcinol was confirmed by chemical 3.1. Characterization of BTZO complex
oxygen demand (COD) reduction method. The COD determination
tests were performed according to standard dichromate method Fig. 1 shows the FTIR spectrum of BTZO and ZO synthesized by
[17] using COD digester (SPECTRALAB 2015M). The photocatalytic mechanochemical method. The FTIR frequencies and assignment
degradation (PCD) efficiency was calculated from the following of bands of ZO and BTZO in the region 4000–400 cm−1 are summa-
expression (1): rized in Table 1. The high frequency N–H absorption bands in the
CODi − CODt region 3400–3100 cm−1 of the BTZO spectrum were not shifted to
= × 100 (1) a lower frequency upon formation of metal thiourea complex, indi-
CODi
cating that nitrogen to zinc bonds are absent and that the bonding
where is the photocatalytic degradation efficiency, CODi is the ini- must be between sulfur and zinc atoms [19]. There is distinct band
tial chemical oxygen demand, CODt is the chemical oxygen demand at 2705 cm−1 in BTZO which corresponds to symmetric stretching
at time t. The intensity of sunlight was periodically checked by modes of NH2 groups of thiourea. Similar observation was reported
ferrioxalate actinometry [18]. The average photon flux calculated by Dhumane et al. [20] for Zn [CS(NH2 )2 ]2 Cl2 complex, stating that
for sunlight was found to be 1.7 × 10−7 Einstein s−1 cm−2 . The PCD there is bonding between sulfur and zinc.
A.B. Patil et al. / Journal of Hazardous Materials 183 (2010) 315–323 317
Table 1
Infrared spectral data of BTZO and ZO.
Fig. 3. XRD pattern of S-doped ZnO obtained by calcination of bisthiourea zinc oxalate, (a) commercial ZnS; bisthiourea zinc oxalate calcined at (b) 450 ◦ C; (c) 500 ◦ C; (d)
550 ◦ C; (e) 600 ◦ C (S-doped ZnO) and (f) zinc oxalate calcined at 600 ◦ C (pure ZnO).
Fig. 4. XPS whole scanning spectrum (a); fine spectra of Zn 2p3/2 , Zn 2p1/2 (b); O 1s (c); and S 2p1/2 (d) of S-doped ZnO.
A.B. Patil et al. / Journal of Hazardous Materials 183 (2010) 315–323 319
COD of resorcinol and results are illustrated in Fig. 8. The 150 ppm 3.3.2. Effect of photocatalyst loading
resorcinol was completely mineralized by using 250 mg/100 mL of The blank experiments were carried out without photocatalyst
S-doped ZnO and it shows approximately double PCD efficiency to examine the extent of resorcinol ‘photolyzed’ in the absence of
than that of pure ZnO. However after 150 ppm, PCD efficiency photocatalyst. No detectable PCD of resorcinol was evidenced in
was found to be inversely affected by concentration of resorci- aqueous solution in the absence of photocatalyst. When 150 ppm
nol. As the concentration of resorcinol increases, the photons get resorcinol containing photocatalyst was irradiated with sunlight,
interrupted before they can reach the photocatalyst surface hence PCD of resorcinol was observed. Fig. 9 shows degradation profile
absorption of photons by the photocatalyst decreases and con- of 150 ppm resorcinol under loadings of photocatalyst from 100
sequently the PCD was reduced. The PCD efficiency of S-doped to 350 mg/100 mL. The PCD efficiency was gradually increased up
ZnO was found to be greater than that of pure ZnO. This could to 250 mg/100 mL and then it was decreased. At lower photocata-
be correlated with more number of oxygen vacancies in S-doped lyst loading level than the optimum amount, photonic absorption
ZnO than that of pure ZnO as seen in PL spectra of these materi- controls the efficiency of PCD due to limited surface area of photo-
als (Fig. 7a and b). During the process of photocatalytic reaction, catalyst. The increase in the amount of photocatalyst also increased
oxygen vacancies and defects become centers to capture photo- the number of active sites on the photocatalyst surface, which
induced electrons, as a result the recombination of photo-induced in turn increased the number of hydroxyl, and superoxide radi-
electrons and holes can be effectively inhibited. Moreover, oxygen cals. Therefore efficiency of PCD increased linearly with increase
vacancies also promote the adsorption of O2 which is converted in photocatalyst loading up to 250 mg. It is interesting to note that
into superoxide radicals (• O2 − ) by interacting with photo-induced for every photocatalyst loading the PCD efficiency of S-doped ZnO
electron (Scheme 2a–c). These • O2 − radicals are active to promote was found to be approximately 2 times greater than that of pure
the oxidation of organic substances by forming other radicals such ZnO. This is due to fact that the S doping into the ZnO introduces
as • OH, HO2 • (Scheme 2d–f). Thus, oxygen vacancies and defects are nonradiative relaxation pathway as well as increases surface to vol-
in favor of photocatalytic reactions and larger the content of oxygen ume ratio in ZnO that enhances visible light absorption. The same
vacancy or defect, higher is the photocatalytic activity. This shows observation was reported by Foreman et al. [23]. The S doping
that S-doped ZnO is effective photocatalyst in solar light as com- also interfere with the crystallization of ZnO and helps to absorb
pare to pure ZnO. The 150 ppm resorcinol was selected as optimum more photons and transport of the photogenerated charge carri-
concentration for the study of other parameters. ers which improves PCD efficiency of S-doped ZnO. Above 250 mg
A.B. Patil et al. / Journal of Hazardous Materials 183 (2010) 315–323 321
4. Reuse of photocatalyst
tions of 150 ppm were completely mineralized over S-doped ZnO. It The reuse of S-doped ZnO was separately studied, by keeping
is observed that with increase in irradiation time, the absorbance of all other parameters constant. During this study, after sunlight
resorcinol at 274 nm (max ) was found to decrease and it becomes irradiation for 7 h, photoreaction mixture was centrifuged and fil-
nearly zero after 7 h irradiation of sunlight (Fig. 12a–i). Thus 7 h tered. Filtrate was used for COD determination and residue was
irradiation time was selected for the study of other parameters. washed several times with double distilled water in ultrasonic
Fig. 13 shows a plot of ln (CODi /CODt ) versus irradiation time for bath followed by filtration and drying at 110 ◦ C in an electric oven.
PCD of resorcinol over S-doped ZnO and bare ZnO. The linearity of Recovered S-doped ZnO was then reused for new PCD batch, with-
kinetic curves reveals that the photocatalytic degradation of resor- out any further treatment such as heating in any kind of furnace.
cinol follows apparent first order reaction kinetics. The apparent Activity of recycled S-doped ZnO was found to retain even after fifth
rate constants of PCD of resorcinol over S-doped ZnO are greater photodegradation experiment.
(2.51 × 10−1 h−1 ) than that over pure ZnO (8.09 × 10−2 h−1 ). Thus,
the photocatalytic activity of S-doped ZnO determined in terms of 5. Conclusions
the rate constant was found to be higher than that of bare ZnO.
In present study S-doped ZnO was synthesized by ecofriendly
mechanochemical method. When bisthiourea zinc oxalate was cal-
cined at 600 ◦ C it forms S-doped ZnO, as confirmed by XRD, XPS,
SEM, EDXS, and PL studies. The incorporation of S into ZnO was
supported by broadening and lower Bragg angle shift (by 0.18◦ ) in
XRD pattern of S-doped ZnO as compare to that of pure ZnO. The XPS
of S-doped ZnO shows the peaks positioned at 162 eV and 163 eV
which are assigned to S 2p3/2 and S 2p1/2 electronic states respec-
tively. The green emission band in room temperature PL spectra
of S-doped ZnO was found to be 1.5 times stronger than that of
pure ZnO which suggest that the large number of oxygen vacancies
exist in S-doped ZnO. The oxygen vacancies and defects are in favor
of photocatalytic reactions. The complete PCD of 150 ppm resorci-
nol was achieved over 250 mg/100 mL loading of S-doped ZnO at
its natural pH within 7 h irradiation of sunlight. The rate constants
of PCD of resorcinol over S-doped ZnO are greater (2.51 × 10−1 h−1 )
than that over pure ZnO (8.09 × 10−2 h−1 ). Hence, the solar PCD effi-
ciency of S-doped ZnO was found to be 2 times greater than that
of pure ZnO. Activity of recycled S-doped ZnO was found to retain
even after fifth PCD experiment.
References
[2] S.K. Pardeshi, A.B. Patil, A simple route for photocatalytic degradation of phenol [14] P. Zhou, X. Yu, L. Yang, Z. Tao, Simple air oxidation synthesis and
in aqueous zinc oxide suspension using solar energy, Solar Energy 82 (2008) optical properties of S-doped ZnO microspheres, Mater. Lett. 61 (2007)
700–705. 3870–3872.
[3] K. Chiang, T.M. Lim, L. Tsen, C.C. Lee, Photocatalytic degradation and miner- [15] Q.W. Zhang, J. Wang, S. Yin, T. Sato, F. Saito, Synthesis of a visible-light active
alization of bisphenol A by TiO2 and platinized TiO2 , Appl. Catal. A: Gen. 261 TiO2−x Sx photocatalyst by means of mechanochemical doping, J. Am. Ceram.
(2004) 225–237. Soc. 87 (6) (2004) 1161–1163.
[4] H. Lachheb, E. Puzenat, A. Houas, M. Ksibi, E. Elaloui, C. Guillard, J.M. Herrmann, [16] S.K. Pardeshi, A.B. Patil, Solar photocatalytic degradation of resorcinol a model
Photocatalytic degradation of various types of dyes (Alizarin S, Crocein Orange endocrine disrupter in water using zinc oxide, J. Hazard. Mater. 163 (2009)
G, Methyl Red, Congo Red, Methylene Blue) in water by UV-irradiated titania, 403–409.
Appl. Catal. B: Environ. 39 (2002) 75–90. [17] J.T. Bellaire, G.A. Parr-Smith, Standard Methods for the Examination of Water
[5] P. Qu, J. Zhao, T. Shen, H. Hidaka, TiO2 -assisted photodegradation of dyes: a and Wastewater, seventeenth ed., Am. Public Health Association, Washington,
study of two competitive primary processes in the degradation of RB in an DC, 1985.
aqueous TiO2 colloidal solution, J. Mol. Catal. A: Chem. 129 (1998) 257–268. [18] C.G. Hatchard, C.A. Parker, A new sensitive chemical actinometer. II. Potassium
[6] S.K. Pardeshi, A.B. Patil, Effect of morphology and crystallite size on solar pho- ferrioxalate as a standard chemical actinometer, Proc. R. Soc. London A235
tocatalytic activity of zinc oxide synthesized by solution free mechanochemical (1956) 518.
method, J. Mol. Catal. A: Chem. 308 (2009) 32–40. [19] K. Nakamoto, Infrared and Raman Spectra of Inorganic and Coordination Com-
[7] F. Peng, H. Wang, H. Yu, S. Chen, Preparation of aluminum foil-supported nano- pounds, fourth ed., J. Wiley and Sons, New York, 1986, p. 269.
sized ZnO thin films and its photocatalytic degradation to phenol under visible [20] N.R. Dhumane, S.S. Hussaini, V.V. Nawarkhele, M.D. Shirsat, Dielectric studies of
light irradiation, Mater. Res. Bull. 41 (2006) 2123–2129. metal complexes of thiourea crystals for electro-optic modulation, Cryst. Res.
[8] J. Lu, Q. Zhang, J. Wang, F. Saito, M. Uchida, Synthesis of N-doped ZnO by grinding Technol. 41 (9) (2006) 897–901.
and subsequent heating ZnO–urea mixture, Powder Technol. 162 (2006) 33–37. [21] S. Wang, Q. Gao, J. Wang, Thermodynamic analysis of decomposition of thiourea
[9] L.C. Chen, Y.J. Tu, Y.S. W, R.S. Kan, C.M. Huang, Characterization and photore- and thiourea oxides, J. Phys. Chem. B 109 (2005) 17281–17289.
activity of N-, S-, and C-doped ZnO under UV and visible light illumination, J, [22] J. Liqiang, Q. Yichun, W. Baiqi, L. Shudan, J. Baojiang, Y. Libin, F. Wei, F. Hong-
Photochem. Photobiol. A: Chem. 199 (2008) 170–178. gang, S. Jiazhong, Review of photoluminescence performance of nano-sized
[10] G. Shen, J.H. Cho, J.K. Yoo, G.C. Yi, C.J. Lee, Synthesis and optical properties of semiconductor materials and its relationships with photocatalytic activity, Sol.
S-doped ZnO nanostructures: nanonails and nanowires, J. Phys. Chem. B 109 Energy Mater. Sol. Cells 90 (2006) 1773–1787.
(2005) 5491–5496. [23] J.V. Foreman, J. Li, H. Peng, S. Choi, H.O. Everitt, J. Liu, Time-resolved
[11] T. Ohno, M. Akiyoshi, T. Umebaysshi, K. Asai, T. Mitsui, M. Matsumura, Prepa- investigation of bright visible wavelength luminescence from sulfur-
ration of S-doped TiO2 photocatalysts and their photocatalytic activities under doped ZnO nanowires and micropowders, Nano Letters 6 (2006)
visible light, Appl. Catal. A: Gen. 265 (2004) 115–121. 1126–1130.
[12] G. Shen, J.H. Cho, S.I. Jung, C.J. Lee, Synthesis and characterization of S-doped [24] M.A. Behnajady, N. Modirshahla, R. Hamzavi, Kinetic study on photocatalytic
ZnO nanowires produced by a simple solution-conversion process, Chem. Phys. degradation of C.I. acid yellow 23 by ZnO photocatalyst, J. Hazard. Mater. 133
Lett. 401 (2005) 529–533. (2006) 226–232.
[13] X.H. Wang, S. Liu, P. Chang, Y. Tang, Influence of S incorporation on the lumi- [25] M. Muruganandham, M. Swaminathan, Solar photocatalytic degradation of a
nescence property of ZnO nanowires by electrochemical deposition, Phys. Lett. reactive azo dye in TiO2 -suspension, Sol. Energy Mater. Sol. Cells 81 (2004)
A 372 (2008) 2900–2903. 439–457.