Photocatalytic Degradation of p-Nitrophenol in an
Annular Column Photoreactor and the
Intermediates
Masoumeh Heibati1, Elham Jalilnejad1, Farzaneh Vahabzadeh1,*
ABSTRACT: The photocatalytic degradation of p-nitrophenol using a
titanium dioxide suspension was studied in an annular column
photoreactor operating in batch recycle mode with an aerated reservoir
tank. The dependency of the process efficiency on the initial PNP
concentration was quantitatively defined using an exponential function.
The degradation rate was highest at pH 7-7.2. The appearance of p-
benzoquinone, p-hydroquinone, and phenol during the degradation
process was confirmed by high-performance liquid chromatography
analysis. The formation of similar intermediates during the microbial
degradation of PNP has been reported previously. The formation of
hydroxyl radicals is predominant in the PNP photodegradation route,
and fluctuations of the chemical oxygen demand may be indicative of the
appearance of unidentified and probably nonbiodegradable intermedi-
ates formed during photocatalysis. These compounds likely contribute to
the COD variations. Herein, the results of PNP removal via photocat-
alytic degradative reactions are discussed, and the intermediates are
compared to those observed in enzymatic reactions. Water Environ. Res.,
87, 437 (2015).
KEYWORDS: p-nitrophenol, annular column photoreactor, p-
benzoquinone, p-hydroquinone, phenol, intermediate formation.
doi:10.2175/106143015X14212658614234
Introduction
Industrial wastewaters are treated with many different
physical, chemical, and biological methods; and the target toxic
chemical(s) can thus be degraded in numerous ways. The high
energy consumption required for conventional chemical oxida-
tion methods in pollutant removal processes along with the
generation of less eco-friendly by-products during wastewater
treatments are considered as the major obstacles in applying
these techniques. The advanced oxidation process (AOP) of
semiconductor photocatalysis is based on the combined use of
ultraviolet (UV) light and a semiconductor. Although there are
fewer obstacles to using photocatalysis compared with other
chemical oxidation methods, more attention is needed to make
it an economically desirable process (Malato et al., 2009). For
instance, the cost effectiveness of AOPs that use artificial light
consumption has been measured as specific electric energy
utilization per unit mass of chemical oxygen demand (COD)
1
Chemical Engineering Department, Amirkabir University of
Technology (Tehran Polytechnic), 424 Hafez Ave., Tehran, Iran
* Corresponding author Tel.: þ98 21 64543161; Fax: þ98 21
66405847. E-mail address: far@aut.ac.ir
May 2015
removal (i.e., as a pollutant degradation index); but several other
factors such as reactor type, catalyst, and pre-/post-treatment
should also be considered if photocatalysis is used with solar or
UV lamps in combination with different oxidants and methods
(Mazzarino, 2001; Singh et al., 2011).
Titanium dioxide (TiO2) as a semiconductor material has
gained special interest mainly because its electronic structure
has an appropriate band gap that provides a filled valance band
(vb) and an empty conduction band (cb), which allow an
appropriate energetic separation that can go beyond the energy
content of a solar photon in the wavelength of 300–390 nm
(Malato et al., 2012). TiO2 in a test aqueous solution acts as a
sensitizer for UV light-induced redox reactions (Figure 1). The
þ
recombination of electrons and holes (e cb , h vb ) in photocatalysis
is a real practical issue, and the extent of this process inefficiency
can be reduced by applying several methods. For instance, by
adding other electron acceptors (e.g., chemical oxidants such as
H2O2) to the reaction mixture and increasing the number of
trapped electrons in the e/hþ pairs, the probability of e/hþ
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
TiO2 or injecting the holes of the vb of the TiO2 to the vb of CdS
increases the photocatalytic efficiency of pollutant degradation
as compared to the photocatalytic behavior by using TiO2 or
CdS separately (Malato et al., 2009).
The electrochemical generation of the Fenton reagent, also
known as the electro-Fenton process, is based on the
electrochemical concept that the reduction of dissolved O2
molecules to hydrogen peroxide occurs on the surface of a
carbonaceous cathode electrode and with TiO2 as the anode, and
then the electrons formed can be released into an external
circuit of an electrochemical cell; this process decreases the
extent of hole/electron recombinations, and the photocatalytic
efficiency is increased (Oturan et al., 2000; Lea and Adesoji 2001;
Vasudevan and Oturan, 2014). Alternatively, electrochemical
oxidation of pollutants at the anode surface is a direct process in
which TiO2 fabrication with the use of materials such as Cu2O
extends the light absorption capacity of the catalyst particles;
thus, the process efficiency is increased (Yang et al., 2010).
Nitroaromatic phenolic derivatives are of industrial impor-
tance mainly because of their widespread use in the manufacture
of chemicals such as dyes, pigments, plastics, pharmaceuticals,
pesticides, and fungicidal agents (Morrison and Boyd, 1977). The
437
Heibati et al.
Figure 1—The TiO2/aqueous solution interface under UV
irradiation.
hydroxyl group of phenol is more acidic than that of an alkyl
alcohol due to resonance stabilization of the phenoxide anion
structure. Therefore, attachment of a nitro group on a
phenoxide ion results in the formation of an oxonium
intermediate that is even more stable than a phenoxide anion.
Because of these structural stabilization characteristics, the time
required for nitroaromatic oxidation and eventual degradation
in nature is long. The toxicity of these compounds has made the
issue of reducing nitroaromatics in nature more critical. Of note,
acidic aromatic compounds are effective uncouplers of oxidative
phosphorylation, and their lipophilic character can induce
perturbation of the cell membrane lipid bilayer (Schüürmann
et al., 1996). According to the United States Environmental
Protection Agency (USEPA) regulations, the PNP concentration
in natural waters should be less than 10 ng/L (Kim et al., 2001).
The popularity of biological treatments of organic pollutants
is due to the moderate operational conditions required in these
relatively low-cost techniques. The degradative ability of aerobic
microorganisms towards PNP, however, is low (Salehi et al.,
2009), and the production of nitroso compounds and hydrox-
ylamine with the use of anaerobic microorganisms has also
limited the application of PNP biodegradation under anaerobic
conditions (Marvin-Sikkema and Bont, 1994).
The importance of the formation of intermediates during
catalytic degradation of PNP (biological/nonbiological process-
es) has been well described in the literature (Kotronarou et al.,
1991; Johnson and Stanier 1971; Kulkarni and Chaudhari, 2007).
In these reactions, like other heterogeneous processes that occur
with solid catalysts, not all reactive molecules are available for
immediate conversion; thus, mass transfer limitations consider-
ably affect the reaction rate. For instance, self-inhibition (equally
known as substrate or product inhibition in microbial conver-
sions) occurs due to the formation of intermediates in catalysis,
likely due to intermediates occupying the catalyst particle active
sites. All of these events further limit the efficient transport of
substrate between the bulk liquid and the solid catalyst as well as
within the catalyst particles.
438
Figure 2—Experimental set-up: 1) annular column photoreactor;
2) 15W UV-A Lamp; 3) liquid jacketed tank containing test
solutions of PNP; 4) peristaltic pump; 5) air pump; 6) flow meter.
In the present work, the results of PNP photocatalytic
degradation by using a TiO2 suspension in an annular reactor
operating in batch recycle mode are reported. Some interme-
diates that formed during this photocatalytic reaction have
structural similarities to intermediates that form upon biological
degradation of PNP. To the best of our knowledge, there are no
previous reports described in the literature indicating these
similarities. Considering the roles of certain oxidoreductase
enzymes in plant cells, which respond to environmental stress
and injury by causing enzymatic browning of fruits and
vegetables, these results are particularly interesting (Eskin,
1990).
Materials and Methods
Chemicals. TiO2 nanoparticles (P-25) from Degussa (80%
anatase and 20% rutile, BET specific surface area of 50 6 15 m2/
g, and average primary particle size of 21 nm) were used as the
photocatalyst. PNP and other chemicals were of analytical grade
(Fluka, Buchs, Switzerland). All these chemicals were purchased
from local suppliers.
Photoreactor Configuration and PNP Degradation Exper-
iments. The experiments were carried out in an annular
photoreactor in batch recycle mode with an aerated liquid
reservoir tank situated externally to the photoreactor. The
photoreactor was made of two concentric columns at a distance
of 7 mm from each other in which the inner and outer tubes
were made of quartz and Pyrex glass, respectively (Figure 2). The
light source consisted of one UV lamp (Philips Actinic BL 15W)
emitting UV-A radiation (350–400 nm), and the lamp was
placed in the space within the inner quartz tube. PNP at the
defined initial concentrations (10, 20, 30, and 40 mg/L) was
dissolved in distilled water, and the photocatalytic activity of the
suspended TiO2 in the photoreactor was determined by
monitoring the PNP concentration changes. The pH value of
each test solution was adjusted with H2SO4 and KOH, as
needed, before the solution was transferred to the photoreactor
Water Environment Research, Volume 87, Number 5

Figure 3—Dependency of photocatalytic degradation of PNP on
TiO2 concentration (PNP concentration: 10 mg/L; pH of the
reaction mixture: 4.960.21).
(in the annulus space between the two concentric tubes) and
exposed to UV light. The test solution was stirred continuously
in the dark in the liquid jacketed tank. The batch-wise
experiments in the photoreactor were performed while the test
liquid was circulated using a peristaltic pump (Heidolph 5201) at
a flow rate of 145 ml/min, in which 600 ml of test solution was
circulated between the 300-ml-capacity photoreactor and the
liquid jacketed reservoir tank. The system’s temperature was also
controlled through this liquid jacketed tank. Aeration of the test
solution was done by bubbling air into the reaction vessel by
using a perforated line in the photoreactor as well as a sparger in
the reservoir tank.
Analytical Methods. PNP was measured spectrophotometri-
cally (Jasco V-550 UV/Vis Spectrophotometer). At regular time
intervals, an appropriate aliquot was withdrawn from the test
system; and after centrifugation at 8000 rpm for 15 min
(Heraeus Biofuge Stratos, DJB Labcare Ltd., Newport Pagnell,
England), the amount of PNP was measured by reading the
absorption maximum at 400 nm after the addition of 5 ml of 0.1
N NaOH to 1 ml of supernatant, followed by the development of
the yellow color after the test solution stood for 5 min at
ambient temperature (Chandekar and Ingle, 1990). The alter-
ation of PNP concentration during the photodegradation
process was also determined through COD measurements,
which were performed spectrophotometerically (at 445 nm)
using the COD cells containing specific reagents and following
the instructions provided by the supplier (COD Cell Test –
Merck Spectroquant). High-performance liquid chromatogra-
phy (HPLC) analysis was also used to identify the intermediates
by comparing the retention times and UV-visible spectra (280
nm) with those of external standards (HPLC: Knauer, Germany,
equipped with a C18 column and a UV-visible detector). The
eluent used was a mixture of acetonitrile and water (75:25) at a
flow rate of 0.8 ml/min.
Results and Discussion
Effect of TiO2 Concentration. Based on the type and
concentration of test pollutant, a wide range of TiO2 concen-
trations have been used in different photocatalysis experiments
reported in the literature. The optimum amount of TiO2 is the
concentration in which all the exposed TiO2 surfaces are
efficiently illuminated by UV light, thus facilitating the
formation of reactive species through oxidative/reductive
reactions that are responsible for the oxidative attack on
pollutant molecules in aqueous media either under the influence
of O2 or directly reacting with the pollutant molecules adsorbed
May 2015
Heibati et al.
Figure 4—Effect of the initial PNP concentration on the
photocatalytic degradation (TiO2 concentration: 2 g/L; pH of the
reduction mixture: 7–7.2).
on the catalyst surfaces (Figure 1). In the present study, by
varying the amount of TiO2 from 0.5 to 3 g/L, the effect of TiO2
loading on the PNP photodegradation reaction was determined
in the test photoreactor. The initial pH of the test solutions
prepared with 10 mg/L PNP was 4.960.2. Figure 3 shows that
the PNP removal increased by increasing the amount of
photocatalyst up to 2 g/L, and the PNP removal decreased at
photocatalyst concentrations above 2 g/L. At high concentra-
tions of photocatalyst, TiO2 may aggregate, thus decreasing the
interfacial area between the reaction mixture and the photocat-
alyst surface. By decreasing the number of active sites on the
photocatalyst surface, the effectiveness of TiO2 to generate
reactive species becomes limited. Increasing the opacity and
decreasing the light reflection capacity of TiO2 at high catalyst
concentrations also decreases the photocatalytic efficiency (San
et al., 2002).
Effect of Initial PNP Concentration. The effect of the initial
pollutant concentration on the extent of organic compound
removal is the most studied subject in wastewater treatment by
oxidative catalysis. Formation of the active species in the
presence of the catalyst, movement of these species and their
location in a particular position on the catalyst surface, and
finally participation of the species in the reaction of interest are
the key steps in a catalytic process (biological or nonbiological).
In this study, the photocatalytic degradation of PNP in aqueous
solution occurred via first-order kinetics:
Ct ¼ C0 expðkd tÞ ð1Þ
where C0 and Ct are the pollutant (PNP) concentrations (mg/L)
at time zero and at time ‘t’ during the process, respectively, and
kd is the PNP degradation rate constant (min1) .The variation in
the degradation rate as a function of the initial concentration of
PNP over the range of 10–40 mg/L is shown in Figure 4. The
acidic pH of the test solution initially at 4.9–5.2 was adjusted to
neutral pH (7–7.2), and there was almost no PNP degradation in
the absence of UV light at room temperature. The effect of the
photocatalytic degradation rate on the initial concentration of
the test pollutant (PNP) can be explained in terms of PNP
þ
adsorption on the catalyst surface (generated e cb and hvb ), where
competition occurred between the adsorbed organic pollutant
and the hydroxyl radical produced at the catalyst active sites.
Mass transfer limitations as a result of the competitions were
noticeable at this stage of the heterogeneous reaction, i .e., low kd
values corresponded to high initial PNP concentrations, as
439
Heibati et al.

Figure 6—COD values for the photocatalytic degradation of PNP

Figure 5—Plot of the degradation rate constant kd against the
(initial PNP concentration: 20 mg/L, TiO2: 2 g/L; pH of the
reciprocal of the initial PNP concentration.
reaction mixture: 4.9–5.2).

shown by the plot of the rate constant versus 1/C0 (correlation

despite a constant effluent COD (Hernandez et al., 2012).
coefficient for the fitted line ¼ 0.943; Figure 5). Photodegrada-
Furthermore, a study on the oxidative degradation of olive oil mill
tion of PNP also occurred in aqueous solution, and nonsignif-
wastewater using the Fenton reagent also showed that although the
icant mass transfer effects may have occurred in the test solution
phenol content decreased by 90%, the COD did not decrease
with a low initial PNP concentration (high kd values corre-
beyond 60% (Ahmadi et al., 2005).
sponded to high ratios of 1/C0) (Yang et al., 2010).
Effect of pH. By analyzing four different initial pH values (3,
The appearance of intermediates also is a major concern during
5, 7, and 9) for the test solutions (without changing or checking
the degradation of a refractory pollutant because they may possess
them during the test processes), the influence of the solution’s
a higher toxicity than the original organic compound. Table 1
pH on the efficiency of PNP photocatalytic degradation was
shows that at the initial stage of photocatalysis, there was a faster
determined. Variation of the reaction rate constant as a function
degradation in terms of the COD removal (50% reduction within
of the initial pH of the reaction mixture, with an initial PNP
1.5 h). Then the rate of COD removal decreased considerably. After
concentration of 20 mg/L, is shown in Figure 7; the highest
6 h, the decrease was only 90%; and this slow COD removal
degradation rate constant was at pH 7–7.2. This figure (inset)
continued for the next 1.5 h, decreasing by only 5%. The same trend
also shows that the solution pH remained constant during the
was seen for the other initial PNP concentrations (Table 1). Figure 6
degradation process, although the decrease of the system pH
shows the trend of COD changes as a function of the irradiation
from the initial pH of 9 was relatively considerable. In addition,
time. The COD fluctuations may be due to resistance of the
the decrease in the kd value with an increase of the initial pH
intermediates to photo-oxidation, thus leading to an increase of
above 7.5 was noticeable (Figure 7). The main steps of
intermediate concentrations and further limiting the COD
photocatalytic processes occur on the catalyst surface. Consid-
removal. Similar findings have been reported elsewhere. For
ering the acid-base chemistry of the TiO2surface (equations
example, the maximum amount of intermediates formed from the
below) and the pH point of zero charge of this photocatalyst (pH
photocatalytic degradation of o-nitrophenol when there was a 50%
6.6–6.8), the predominant forms of TiO2 in acidic and alkaline
reduction of the total organic carbon (TOC), and a slow decrease in 
solutions are TiOHþ 2 and TiO , respectively. The neutral state of
the TOC content was observed thereafter (Wang et al., 1998). In
the TiO2 surface is TiOH (Wang et al., 1998; Zhu at al., 2013):
addition, during catalytic wet air oxidation of high-strength PNP
wastewater, an increase in the intermediate concentration was seen, TiOH þ Hþ ’ TiOHþ
2

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

440 Water Environment Research, Volume 87, Number 5


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
the photocatalytic degradation rate is the likely result. Because of
the low concentration of nitrophenoxide anions in acidic
solutions, the reaction between this anion and TiOHþ 2 (the
preferred form of TiO2 in acidic solution) is not favored and the
slow rate of PNP degradation at pH 3.7–7 is a reasonable result
in the present study (Figure 7). In addition, agglomeration of
TiO2 particles under acidic conditions reduces the efficient
response of TiO2 to photo-absorption (i.e., decreasing trend of
þ
e
cb and h vb generation), thus decreasing the degradation rate of
PNP at low pH values.
Appearance of Some Aromatic Intermediates. Figure 8
shows the mechanisms possibly involved in the photocatalytic
degradation of PNP. The hydroxyl radical, having a strong
electrophilic character, attacks the benzene ring at the carbon
atom with the highest electron density (the two ortho positions
with respect to the hydroxyl functional group; benzoquinune
radical); next, the hydroxylation reaction affords the formation
of 4-nitrocatechol (San et al., 2002). This intermediate was not
detected in the present study. As a result of the hydroxyl radical
attack on PNP, production of benzoquinone and hydroquinone
are also possible; and these conversions may proceed through
benzoquinone radical formation (Figure 8, ‘A’) (Kotronarou et al.
1991; Shaoqing et al., 2010).
Hydroxylation of aromatic rings of molecules such as phenol
and PNP as the primary enzymatic oxidation step in the
microbial biodegradation of aromatic compounds has been well
May 2015
Heibati et al.
demonstrated in the literature (Johnson and Stanier, 1971; Spain
et al., 1979; Spain and Gibson, 1991; Kitagawa et al., 2004). With
reference to the biochemistry of food spoilage, the initiation of
enzymatic browning in many fruits and vegetables is due to the
activity of certain oxidoreductase enzymes, such as monophenol
monooxygenase, which incorporate one oxygen atom with the
production of benzoquinone products (e.g., p-Bnq and p-Hyq).
The result of these catalytic reactions is the formation of deep-
colored polymeric pigments in the later stage of the enzymatic
browning process (Eskin, 1990).
Conclusions
An annular column photoreactor operating in batch recycle
mode with an aerated reservoir tank was satisfactorily used in the
photocatalytic degradation of PNP using a TiO2 suspension. By
applying the exponential equation, the degradation process was
mathematically quantified. The kinetics and mass transfer
resistances both are operative in the catalytic processes. High
initial concentrations of PNP, which corresponded to low kd
values, may be indicative of mass transfer effects. In addition, the
extent of these limitations was low when the photodegradation of
PNP in the aqueous reaction mixture was followed (higher rate
constant values were observed at lower initial concentrations of
PNP). The detection of p-benzoquinone, p-hydroquinone, and
phenol in the reaction mixture was also reported in this study.
Similarities exist between these intermediates and those reported
in the literature upon microbial degradation of PNP as well as by
441
Heibati et al.
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
combined treatments of photocatalysis and microbial oxidation
appears to be fairly feasible for the degradation of high
concentrations of PNP. In the present study, the variation of the
reaction rate constant as a function of the initial pH of the
reaction mixture also was discussed. The decrease of the kd with
an increase of the initial pH above 7.5 could be related to the
unfavorable interaction between the phenoxide anion and TiO.
Because of the low concentration of the nitrophenoxide anion in
acidic solutions, the probability of the reaction between this anion
and TiOHþ 2 is decreased. By changing and modifying the TiO2
catalyst surface and considering the concepts of electrochemistry,
it is also possible to improve photoabsorption and the
photocatalytic degradation of PNP.
Acknowledgment
The third author deeply appreciates the sincere assistance
provided by PhD student Alireza Monazzami in this department
for completion of this manuscript.
Submitted for publication June 11, 2013; accepted for
publication July 23, 2014.
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