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ABSTRACT: The photocatalytic degradation of p-nitrophenol using a removal (i.e., as a pollutant degradation index); but several other
titanium dioxide suspension was studied in an annular column factors such as reactor type, catalyst, and pre-/post-treatment
photoreactor operating in batch recycle mode with an aerated reservoir should also be considered if photocatalysis is used with solar or
tank. The dependency of the process efficiency on the initial PNP
UV lamps in combination with different oxidants and methods
concentration was quantitatively defined using an exponential function.
(Mazzarino, 2001; Singh et al., 2011).
The degradation rate was highest at pH 7-7.2. The appearance of p-
benzoquinone, p-hydroquinone, and phenol during the degradation
Titanium dioxide (TiO2) as a semiconductor material has
process was confirmed by high-performance liquid chromatography gained special interest mainly because its electronic structure
analysis. The formation of similar intermediates during the microbial has an appropriate band gap that provides a filled valance band
degradation of PNP has been reported previously. The formation of (vb) and an empty conduction band (cb), which allow an
hydroxyl radicals is predominant in the PNP photodegradation route, appropriate energetic separation that can go beyond the energy
and fluctuations of the chemical oxygen demand may be indicative of the content of a solar photon in the wavelength of 300–390 nm
appearance of unidentified and probably nonbiodegradable intermedi- (Malato et al., 2012). TiO2 in a test aqueous solution acts as a
ates formed during photocatalysis. These compounds likely contribute to sensitizer for UV light-induced redox reactions (Figure 1). The
the COD variations. Herein, the results of PNP removal via photocat- þ
recombination of electrons and holes (e cb , h vb ) in photocatalysis
alytic degradative reactions are discussed, and the intermediates are
is a real practical issue, and the extent of this process inefficiency
compared to those observed in enzymatic reactions. Water Environ. Res.,
87, 437 (2015).
can be reduced by applying several methods. For instance, by
adding other electron acceptors (e.g., chemical oxidants such as
KEYWORDS: p-nitrophenol, annular column photoreactor, p- H2O2) to the reaction mixture and increasing the number of
benzoquinone, p-hydroquinone, phenol, intermediate formation.
trapped electrons in the e/hþ pairs, the probability of e/hþ
doi:10.2175/106143015X14212658614234 recombination decreases (Malato et al., 2009). Composite
(coupled) semiconductors also have provided satisfactory results
in inhibiting e/hþ recombination; for example, injecting
electrons from the cb of cadmium sulfide (CdS) into the cb of
Introduction TiO2 or injecting the holes of the vb of the TiO2 to the vb of CdS
Industrial wastewaters are treated with many different increases the photocatalytic efficiency of pollutant degradation
physical, chemical, and biological methods; and the target toxic as compared to the photocatalytic behavior by using TiO2 or
chemical(s) can thus be degraded in numerous ways. The high CdS separately (Malato et al., 2009).
energy consumption required for conventional chemical oxida- The electrochemical generation of the Fenton reagent, also
tion methods in pollutant removal processes along with the known as the electro-Fenton process, is based on the
generation of less eco-friendly by-products during wastewater electrochemical concept that the reduction of dissolved O2
treatments are considered as the major obstacles in applying molecules to hydrogen peroxide occurs on the surface of a
these techniques. The advanced oxidation process (AOP) of carbonaceous cathode electrode and with TiO2 as the anode, and
semiconductor photocatalysis is based on the combined use of then the electrons formed can be released into an external
ultraviolet (UV) light and a semiconductor. Although there are circuit of an electrochemical cell; this process decreases the
fewer obstacles to using photocatalysis compared with other extent of hole/electron recombinations, and the photocatalytic
chemical oxidation methods, more attention is needed to make efficiency is increased (Oturan et al., 2000; Lea and Adesoji 2001;
it an economically desirable process (Malato et al., 2009). For Vasudevan and Oturan, 2014). Alternatively, electrochemical
instance, the cost effectiveness of AOPs that use artificial light oxidation of pollutants at the anode surface is a direct process in
consumption has been measured as specific electric energy which TiO2 fabrication with the use of materials such as Cu2O
utilization per unit mass of chemical oxygen demand (COD) extends the light absorption capacity of the catalyst particles;
thus, the process efficiency is increased (Yang et al., 2010).
1
Chemical Engineering Department, Amirkabir University of Nitroaromatic phenolic derivatives are of industrial impor-
Technology (Tehran Polytechnic), 424 Hafez Ave., Tehran, Iran tance mainly because of their widespread use in the manufacture
* Corresponding author Tel.: þ98 21 64543161; Fax: þ98 21 of chemicals such as dyes, pigments, plastics, pharmaceuticals,
66405847. E-mail address: far@aut.ac.ir pesticides, and fungicidal agents (Morrison and Boyd, 1977). The
Table 1—Time to reach 50%, 90%, and 95% PNP removal as a TiOH þ OH TiO þ H2 O
function of the initial concentration of PNP (according to the
defined conditions provided in the present work to study the The pKa values of nitrophenols are 7.15–8.28, and the
photocatalytic degradation of PNP). dissociated forms are predominant at pH values above and
below the pka values (Wang et al., 1998). The presence of the
Removal (%) negative charge on the phenoxide anion at basic pH decreases
the chance of adsorption of this anion on the catalyst surface
50% 90% 95%
having TiO. Considering the ionization state of water as the
PNP concentration (mg/L) Time (min) aqueous medium in photocatalytic degradation processes, the
probability of hydroxyl radical formation increases as the result
10 92 315 412 of the reaction between hþvb and hydroxyl ions. However, there is
20 149 484 629
also competition between hydroxyl anions and nitrophenoxide
30 189 624 812
40 359 1206 1571
ions (a higher proportion of the anionic form of nitrophenoxide
than its nonionized form at an alkaline pH) for the generated
Figure 7—Plot of the rate constant kd as a function of the initial pH during PNP photodegradation (initial PNP concentration: 20 mg/L;
TiO2: 2 g/L).
active species of hþ
vb on the TiO2 surface; therefore, a decrease in demonstrated in the literature (Johnson and Stanier, 1971; Spain
the photocatalytic degradation rate is the likely result. Because of et al., 1979; Spain and Gibson, 1991; Kitagawa et al., 2004). With
the low concentration of nitrophenoxide anions in acidic reference to the biochemistry of food spoilage, the initiation of
solutions, the reaction between this anion and TiOHþ 2 (the enzymatic browning in many fruits and vegetables is due to the
preferred form of TiO2 in acidic solution) is not favored and the activity of certain oxidoreductase enzymes, such as monophenol
slow rate of PNP degradation at pH 3.7–7 is a reasonable result monooxygenase, which incorporate one oxygen atom with the
in the present study (Figure 7). In addition, agglomeration of production of benzoquinone products (e.g., p-Bnq and p-Hyq).
TiO2 particles under acidic conditions reduces the efficient The result of these catalytic reactions is the formation of deep-
response of TiO2 to photo-absorption (i.e., decreasing trend of colored polymeric pigments in the later stage of the enzymatic
þ
e
cb and h vb generation), thus decreasing the degradation rate of browning process (Eskin, 1990).
PNP at low pH values.
Appearance of Some Aromatic Intermediates. Figure 8 Conclusions
shows the mechanisms possibly involved in the photocatalytic An annular column photoreactor operating in batch recycle
degradation of PNP. The hydroxyl radical, having a strong mode with an aerated reservoir tank was satisfactorily used in the
electrophilic character, attacks the benzene ring at the carbon photocatalytic degradation of PNP using a TiO2 suspension. By
atom with the highest electron density (the two ortho positions applying the exponential equation, the degradation process was
with respect to the hydroxyl functional group; benzoquinune mathematically quantified. The kinetics and mass transfer
radical); next, the hydroxylation reaction affords the formation resistances both are operative in the catalytic processes. High
of 4-nitrocatechol (San et al., 2002). This intermediate was not initial concentrations of PNP, which corresponded to low kd
detected in the present study. As a result of the hydroxyl radical values, may be indicative of mass transfer effects. In addition, the
attack on PNP, production of benzoquinone and hydroquinone extent of these limitations was low when the photodegradation of
are also possible; and these conversions may proceed through PNP in the aqueous reaction mixture was followed (higher rate
benzoquinone radical formation (Figure 8, ‘A’) (Kotronarou et al. constant values were observed at lower initial concentrations of
1991; Shaoqing et al., 2010). PNP). The detection of p-benzoquinone, p-hydroquinone, and
Hydroxylation of aromatic rings of molecules such as phenol phenol in the reaction mixture was also reported in this study.
and PNP as the primary enzymatic oxidation step in the Similarities exist between these intermediates and those reported
microbial biodegradation of aromatic compounds has been well in the literature upon microbial degradation of PNP as well as by
Figure 8—PNP degradation pathways via oxidative routes that are likely to be active during the photocatalytic process, according to the
findings obtained in the present study (a). HPLC chromatograms of the intermediates formed during the photocatalysis of PNP aqueous
solution are also shown (b). Benzoquinone radical is shown (A).
ultrasonic irradiation of PNP in aqueous solution. Thus, the use of Oil Processing Wastewater Using Fenton’s Peroxidation, J. Hazard.
combined treatments of photocatalysis and microbial oxidation Mater., 123, 187–195(2005).
appears to be fairly feasible for the degradation of high Chandekar, C. J.; Ingle, A. O. (1990) Degradation of p-Nitrophenol by
Pseudomonas sp. Strain PC Isolated from Sewage, J. Ind. Poll. Cont.,
concentrations of PNP. In the present study, the variation of the
6, 11–17.
reaction rate constant as a function of the initial pH of the Eskin, N. A. M. (1990) Biochemistry of Foods (2nd Ed.) Academic Press
reaction mixture also was discussed. The decrease of the kd with Inc. ISBN:0-12-242351-8.
an increase of the initial pH above 7.5 could be related to the Hernandez, M. M.; Carrera, J.; Ojeda, M. E. S.; Besson, M.; Descorme, C.
unfavorable interaction between the phenoxide anion and TiO. (2012) Catalytic Wet Air Oxidation of a High Strength p-
Because of the low concentration of the nitrophenoxide anion in Nitrophenol Wastewater Over Ru and Pt Catalyst: Influence of
acidic solutions, the probability of the reaction between this anion the Reaction Conditions on Biodegradability Enhancement. Appl.
Catal. B: Environ.,123–124, 141–150
and TiOHþ 2 is decreased. By changing and modifying the TiO2
Johnson, B. F.; Stanier, R. Y. (1971) Dissimilation of Aromatic
catalyst surface and considering the concepts of electrochemistry,
Compounds by Alcaligenes eutrophus, J. Bacteriol., 107, 468–475.
it is also possible to improve photoabsorption and the Kim, I. S.; Lee, H.; Trevors, J. T. (2001) Effects of 2,2 0 ,5,5 0 -
photocatalytic degradation of PNP. Tetrachlorobiphenyl and Biphenyl on Cell Membranes of Ralstonia
eutropha H850, FEMS Microbiol. Lett., 200, 17–24.
Acknowledgment Kitagawa, W.; Kimura, N.; Kamagata, Y. (2004) A Novel p-Nitrophenol
The third author deeply appreciates the sincere assistance Degradation Gene Cluster from a Gram-positive Bacterium,
provided by PhD student Alireza Monazzami in this department Rhodococcusopacus SAO101, J. Bacteriol., 186, 4894–4902.
Kotronarou, A.; Mills, G.; Hoffmann, M. R. (1991) Ultrasonic Irradiation
for completion of this manuscript.
of p-Nitrophenol in Aqueous Solution. J. Phys. Chem., 95 (9), 3630–
Submitted for publication June 11, 2013; accepted for 3638.
publication July 23, 2014. Kulkarni, M.; Chaudhari, A. (2007) Microbial Remediation of Nitro-
Aromatic Compounds: An Overview. Environ. Manage., 85, 496–
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