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Effect of PH On Adsorption and Photocatalytic Degradation Efficiency of Different Catalysts On Removal of Methylene Blue
Effect of PH On Adsorption and Photocatalytic Degradation Efficiency of Different Catalysts On Removal of Methylene Blue
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A.F. ALKAIM1,*, A.M. ALJEBOREE1, N.A. ALRAZAQ1, S.J. BAQIR2, F.H. HUSSEIN2 and A.J. LILO2
1
Department of Chemistry, College of Science for Women, University of Babylon, Hilla, Iraq
2
Department of Chemistry, College of Science, University of Babylon, Hilla, Iraq
Received: 28 April 2014; Accepted: 8 July 2014; Published online: 1 December 2014; AJC-16378
The present study investigates the efficiency of adsorption and photodegradation catalyzed by TiO2, ZnO, CdS and Co3O4 on the removal
of methylene blue dye, in different pH values (4, 6, 9 and 11). The photocatalytic degradation of methylene blue dye in aqueous catalysts
TiO2, ZnO, CdS and Co3O4 suspension follows apparent after 0.5 h of photodegradation a first-order kinetics. The photodegradation
efficiency of methylene blue was fast in the present condition (pH 11, pH 6, pH 6 and pH 4) and slower in (pH 4, pH 11, pH 11 and pH
11) of ZnO, TiO2, CdS and Co3O4, respectively. The highest adsorption capacity as follow: TiO2 > ZnO ≈ CdS ≈ Co3O4, while the
photocatalytic activity: ZnO > TiO2 > CdS > Co3O4.
Keywords: pH, Adsorption, Photocatalytic degradation, Methylene blue, TiO2, ZnO, CdS and Co3O4.
INTRODUCTION whereas the electron in the conduction band reduces the oxygen
adsorbed on the photocatalyst. In the photocatalytic degra-
The textile dyes, with largest groups of organic com- dation of pollutants, when the reduction process of oxygen
pounds, are mainly dumped directly in the environment1,2. and the oxidation of pollutants do not advance simultaneously,
These dyes are toxic to microorganism, aquatic life and human there is an electron accumulation in the conduction band,
beings, by constituting a serious concern to the ecosystem3. thereby causing an increase in the rate of recombination13,14 of
Therefore, many efforts have been devoted to remove these e– and h+.
dyes from the waste water. Recently, the advanced oxidation In this work, methylene blue was selected for study. The
processes (AOPs) have drawn much attention in the wastewater main objective of this work is adsorption and photocatalytic
purification and other environment application4-7. Reactive degradation of methylene blue dye by four types of semi-
species based oxidation processes are usually performed as conductors (TiO2, ZnO, CdS, Co3O4) and examining the
effective photocatalytic medium through the photoexcitation influence of various pH values of solution on the adsorption
of the semiconductors through the solution pH8-11. In the photo- and photocatalytic efficiency.
catalytic oxidation process, organic pollutants are destroyed
in the presence of semiconductor photocatalysts (e.g., TiO2, EXPERIMENTAL
ZnO, CdS, Co3O4, WO3) an energetic light source and an Methylene blue used in this work was purchased from
oxidizing agent such as oxygen or air. To best of our aknowle- Sigma-Aldrich. The methylene blue was chosen in this study
dgement only photons with energies greater than the band- because of its known strong adsorption onto solids. Chemical
gap energy (∆E) can result in the excitation of valence band structure of methylene blue dye was shown in Fig. 1 and the
(VB) electrons which then promote the possible reactions with maximum wavelength of this dye is 663 nm.
organic pollutants12. The absorption of photons with energy All semiconductors (TiO2, ZnO, CdS and Co3O4) where
lower than ∆E or longer wavelengths usually causes energy supplied (Sigma-Aldrich) were used as purchased. Adjustment
dissipation in the form of heat. The illumination of the photo- of pH of the dye solutions prior to degradation was carried out
catalytic surface with sufficient energy, leads to the formation with NaOH or HNO3 from Merck. Distilled water was used in
of a positive hole (h+) in the valence band and an electron (e-) all experiments.
in the conduction band (CB). The positive hole oxidizes either Adsorption studies: Kinetic studies on the adsorption of
the pollutant directly or water to produce hydroxyl radical OH•, methylene blue dye by semiconductors (TiO2, ZnO, CdS and
8446 Alkaim et al. Asian J. Chem.
N
certain irradiation time of methylene blue versus irradiation
time assuming a first order reaction16:
CH 3
+ C0MB
N S N = e kt (3)
H 3C
Cl- CMB
CH 3 CH 3
(C0 – Ce ) V 12
qe = (1)
W 11
Qe (mg g )
–1
MB/MB0
and it is not controlled during the course of the reaction.
MB/MB0
0.70 0.60
0.50
An important parameter in the photocatalytic reactions 0.60
pH 4
0.40
taking place on particulate surfaces is the pH of the solution, 0.50 pH 4
0.30
pH 6
pH 6 pH 9
since it dictates the surface charge properties of the photo- 0.40 pH 9 0.20 pH 11
pH 11 0.10
catalyst and size of aggregates it forms22. Hence, pH plays an 0.30
0 10 20 30 40 50 60 0.00
important role both in the characteristics of dyes and in the Irradiation time (min)
0 10 20 30 40 50 60
Irradiation time (min)
reaction mechanisms that can contribute to dye degradation, 1.00 1.00
namely, hydroxyl radical attack, direct oxidation by the positive Co3O 4 (c) (d)
0.98 0.90
hole and direct reduction by the electron in the conducting 0.96 0.80
band. In the presence of photcatalyst, it is presumed that the
MB/MB0
MB/MB0
0.94 0.70
photocatalytic processes are probably result from the electron- 0.92 0.60
hole pairs formed on the surface of the semiconductor by the pH 4 pH 4
0.90 0.50
irradiation of the UV-light23. Then the holes with the high pH 6
pH 9
pH 6
0.88 0.40 pH 9 CdS
oxidative potential either direct oxidize the reactive dye or pH 11 pH 11
0.86 0.30
react with the OH– to form hydroxyl radical. The total reaction 0 10 20 30 40 50 60 0 10 20 30 40 50 60
Irradiation time (min) Irradiation time (min)
between the photocatalyst and the reactive dye could be written
Fig. 3. Photocatalytic degradation of methylene blue in the presence of
as follows23. different pH of solution; (a) TiO2, (b) ZnO, (c) Co3O4 and (d) CdS
–
Semiconductor + hν → (semiconductor) eCB (
+ h +VB (4) ) Thus, the effect of pH on the photodegradation was versatile
h +VB •+
+ dye → dye (oxidation of the dye) (5) depending on the catalyst present in solution (TiO2, ZnO, CdS,
Or Co3O4). Low pH (pH 4) also favored the photodegradation of
methylene blue in the presence of CdS and Co3O4. While higher
h +VB + OH– → •OH (6) pH (pH 11) favourable of ZnO.
•
OH + dye → degradation of the dye (7) Comparison of different photocatalysis: In view of the
The point of zero charge (pzc) of the TiO2 (Degussa P25)24 advantages of different semiconductors in the heterogeneous
is at pH 6.8. Thus, the TiO2 surface is positively charged in photocatalysis, we tested the photocatalytic activity of four
acidic media (pH < 6.8), whereas it is negatively charged under different commercially available photocatalysis on the degra-
alkaline conditions (pH > 6.8). dation rate of methylene blue.
In the presence of TiO2 ( Fig. 3a), the photodegradation The degradation rates for the decomposition of the dye
was significantly enhanced at medium pH (pH = 6). The degra- with initial concentrations of 20 mg L-1 in the presence of
dation rate of some azo dyes increases with decrease in pH as different types of photocatalysis are shown in Fig. 4. The
reported elsewhere25. At pH < 6, a strong adsorption of the dye photocatalyst of ZnO and TiO2 was found to be more efficient
on the TiO2 particles is observed as a result of the electrostatic in degradation of the dye and other exhibits negligible catalytic
attraction of the positively charged TiO2 with the dye. At pH > activity compared to the other catalysts used in this study. by
6.8 as dye molecules are negatively charged in alkaline media, depending on zero point charge, The zero point charge is a
their adsorption is also expected to be affected by an increase condition where the surface charge of semiconductor is zero
in the density of TiO– groups on the semiconductor surface. or neutral that lies in the limited pH range, depending on the
Thus, due to coulombic repulsion the dyes are scarcely adsor- catalysts used29,30.
bed26. On the contrary, different optimal pHs (6-7) have been This phenomenon is attributed to the band gap energy of
observed for the photocatalytic degradation of other azo dyes catalyst, redox potentials and rates of these redox reactions.
and a decrease of degradation in both acidic and alkaline pH For desired reaction, the energy separation (band gap) between
was reported27. The inhibitory effect seems to be more pro- e– and h+ must be larger than the energy required and the redox
nounced in the alkaline range (pH 11). At high pH values the potentials of the e– and h+ (thus the position of conduction
hydroxyl radicals are rapidly scavenged and they do not have band and valence band) must be suitable for inducing redox
the opportunity to react with dyes. processes31. In addition, the rates of these redox reactions must
In the presence of ZnO ( Fig. 3b), the photodegradation be faster than or at least fast enough to compete with the e–
was significantly enhanced at high pH (pH = 11). While the and h+ recombination32.
lowest at low pH is due to the photodecomposition of ZnO Conclusion
to Zn2+ takes place in acidic and neutral solutions and that The pH-dependent surface charging of metal oxides and
efficient formation of hydroxyl radicals occurs in alkaline related materials remains an active field of research. Many
solution28. experimental studies were carried out for the materials whose
In the presence of Co3O4 (Fig. 3c), the photocatalytic surface charging behavior is already well known.
degradation efficiency slightly reduced at high pH (pH 11), In this study, adsorption and photocatalytic decolorization
similar trends were observed for CdS (Fig. 3d) when compared of an azo reactive textile dye, methylene blue dye, was investi-
to Co3O4. gated by the use of TiO2, ZnO, CdS and Co3O4 powder catalysts
8448 Alkaim et al. Asian J. Chem.
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