International Journal of Photoenergy

Volume 2012 (2012), Article ID 520123, 10 pages

doi:10.1155/2012/520123

Research Article

Simultaneous Photocatalytic Reduction of Cr(VI) and Oxidation of Benzoic Acid in Aqueous N-F-Codoped TiO₂ Suspensions: Optimization and Modeling Using the Response Surface Methodology

Maria Antonopoulou, Aris Giannakas, and Ioannis Konstantinou

Department of Environmental and Natural Resources Management, University of Western Greece, 30100 Agrinio, Greece

Received 1 June 2012; Accepted 29 July 2012

Academic Editor: Manickavachagam Muruganandham

Copyright © 2012 Maria Antonopoulou et al. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

Abstract.

The simultaneous photocatalytic reduction of Cr(VI) and oxidation of benzoic acid (BA) in aqueous suspensions using N-F-codoped TiO₂ and simulated solar irradiation were investigated in the present study. Chemometric optimization tools such as response surface methodology (RSM) and experimental design were used to model and optimize selected operational parameters of the simultaneous photocatalytic reduction of Cr(VI) and oxidation of BA. RSM was developed by considering a central composite design with three input variables, that are, N-F-codoped TiO₂ mass, ratio of Cr/BA, and pH. The removal of Cr(VI) and BA in binary systems, containing both Cr(VI) and BA, showed a synergistic photocatalytic decontamination as BA significantly facilitated Cr(VI) reduction, whereas Cr(VI) accelerated also BA degradation. Due to the anionic-type adsorption onto TiO₂ and its acid-catalyzed photocatalytic reduction, the removal of Cr(VI) decreased with increasing pH, while the degradation of BA followed also the same trend. Under the optimum conditions (N-F-TiO₂) = 600 mg L⁻¹, ratio of Cr(VI)/BA = 5, pH = 4, the removal for both Cr and BA followed a pseudo first-order kinetic model. It was found that the selected variables have significant effect both on Cr(VI) removal and BA degradation efficiency. The results revealed the feasibility and the effectiveness of using N-F-codoped TiO₂ as photocatalyst for simultaneous decontamination of Cr(VI) and organic pollutants such as BA due to the appropriate oxidation and reduction ability of the photogenerated h⁺VB-e⁻CB pairs.

1. Introduction

The increasing level of global industrialization and urbanization has led to the transport and introduction of various contaminants in aquatic environment. The water pollution caused by organic pollutants and heavy metal ions represents an important ecological and health hazard and had gradually gained great scientific interest. Heavy metals enter aquatic environment through the discharge of treated or untreated industrial wastewater and municipal sewage, storm water runoff, acid mine drainage, and other diffuse sources [1]. On the other hand, a wide range of organic micropollutants are derived from a variety of agricultural, municipal, and industrial sources and pathways [2, 3]. Although, the co-existence of organic compounds and metal ions in wastewater is common [4], in conventional methods it is often indispensable to be treated separately, that means complicated process with the requirement of higher cost and more man power [5]. Hence, simultaneous decontamination of heavy metals and organic contaminants constitutes a very interesting and important aspect. In last decades, water pollution had resulted in the development of the so-called advanced oxidation processes (AOPs) as alternative to the conventional water and wastewater treatment methods. These enhanced processes aim to degrade the non biodegradable contaminants of water into harmless species [6]. Among AOPs, heterogeneous photocatalysis employing semiconductor solids has been applied with success for the oxidation of a variety of organic compounds [7] as well as for the removal/reduction of toxic metals from aqueous solutions [8–10]. Photocatalysis is a well-known and particularly promising method based on the activation of a semiconductor and utilizes the photogenerated positive holes and various oxygen radical species for the oxidation of organic compounds as well as the photogenerated electrons for the reduction of heavy metal ions [11]. Moreover, photoreduction of a metal ion is promoted significantly if it is accompanied by simultaneous oxidation of an organic compound able to act as ligand or as “sacrificial electron donor” [12], because of the enhanced charge separation of photo-induced hole/electron pairs by the simultaneous reduction/oxidation reactions [11].

The application of experimental design methodologies in the development of photocatalytic processes can result in improved remediation efficiency with the lesser number of experiments. Response surface methodology is a powerful and widely used mathematical method suitable for modeling and optimizing chemical reactions and or industrial processes [13].

In the present study, the simultaneous photocatalytic reduction of Cr(VI) and oxidation of benzoic acid (BA) using N-F-codoped TiO₂ under simulated solar irradiation was studied. Cr(VI) and BA were selected as target compounds since they may be present in a great variety of industrial waste effluents and their simultaneous treatment will show both economical and technological profits. Benzoic acid, the simplest aromatic carboxylic acid, is a model compound representative of the aromatic content typically found in various industrial wastewaters. It also constitutes the parent molecule of various phenolic compounds which are usually low biodegradable and high ecotoxic and are commonly found in agro-industrial effluents [14]. BA is used to produce a broad range of organic chemicals [15]. Furthermore, it has a wide usage as preservative in the cosmetic, drug, and food industry because of its antibacterial and antifungal properties at a pH 4 or lower [16]. Among heavy metals, Cr(VI) is one of the most frequent and toxic contaminants in wastewaters arising from various industrial processes such as electroplating, pigment production, leather tanning, textile dying, wood preservation, as well as finishing of metals and plastics [17, 18]. Due to its carcinogenic and mutagenic properties as well as its high mobility, its concentration in drinking water has been regulated in many countries [17]. It is considered to be highly toxic to most of the living organisms when the Cr(VI) concentration level is higher than 0.05 mg  [19]. As a result, the removal of Cr(VI) or its reduction to less harmful and immobile Cr(III) is of great importance. Several studies have reported the simultaneous decontamination of Cr(VI) and organic contaminants such as carboxylic acids, phenols, phthalates, and dyes [11, 20–25]. However, in the above-mentioned researches commercial forms of (anatase, Degussa P25) were used. On the contrary, this study investigates the application of N-F-codoped , a photocatalyst with improved photo efficiency and visible light response compared to catalysts [26], for the simultaneous decontamination of organic pollutants and heavy metals. In addition, the assessment of the beneficial role of N-F-doping for the synergistic removal of Cr(VI) and organic pollutants in aqueous substrates has not been performed so far. The main objectives of this research were (a) to assess the simultaneous removal of an organic micropollutant, benzoic acid, and a toxic heavy metal Cr(VI); (b) to investigate the effect of three parameters (initial ratio Cr/Benzoic acid concentration, pH, catalyst concentration) on the total process efficiency; (c) to model and optimize the photocatalytic procedure by means of a central composite design and response surface methodology.

2. Experimental

2.1. Materials and Reagents

Benzoic acid was residue analysis grade, purchased from Sigma-Aldrich (USA), and Cr(VI) in the form of potassium dichromate was purchased from Fluka and used without further purification. N-F- (Ti : N,F molar ratio 1 : 1, named as TNF) was prepared based on a simple sol-gel impregnation method [26]. Titanium n-butoxide was used as inorganic precursor and ammonium fluoride as the source of N and F dopant atoms. X-ray diffraction analysis showed that the photocatalyst crystal phase is anatase with a crystallite size of 1.8 Å. A band-gap energy of 2.96 eV was determined using diffuse reflectance UV-Vis spectroscopy, while electron pair resonance revealed the presence of and photoactive centers. The point-of-zero charge (PZC) was determined at pH = 5.7 using the mass titration method [27]. All solvents used (acetonitrile, methanol and LC-grade water) were pesticide residue analysis grade from Merck (Darmstadt, Germany). HVLP 0.45 m filters were supplied by Millipore (Bedford, USA). Ultrapure water was obtained from a Millipore Waters Milli-Q water purification system.

2.2. Irradiation Procedure

Photocatalytic experiments were carried out in a Suntest XLS+ solar simulator (Atlas, Germany) equipped with a vapor xenon lamp (2.2 kW). The light source was jacked with special glass filters restricting the transmission of wavelengths below 290 nm. The temperature of the samples was maintained at 25°C using a tap water cooling circuit preventing any heating of the suspension. The irradiation intensity was measured by internal radiometer supplied by the manufacturer. Irradiation experiments were performed using a 250 mL Pyrex glass UV-reactor containing 250 mL of aqueous solutions at different pH. The pH of solutions was adjusted by or NaOH aqueous solutions. The solutions were mixed with the appropriate amount of catalyst and were magnetically stirred before and during the illumination. The suspensions were kept in the dark for 30 minutes, prior to illumination in order to reach adsorption equilibrium onto semiconductor surface. As the reaction progressed, aliquots of 5 ml were withdrawn from the reactor at specific time intervals for further analysis. In order to remove the N-F- particles the solution samples were filtered through a 0.45 m filter. Performance of the process was evaluated by analyzing the responses of Cr(VI) removal and BA degradation percentages after a fixed time of 30 min according to the equation:

where is the initial Cr(VI) or BA concentration and the concentration of Cr(VI) or BA after the photocatalytic treatment.

2.3. Kinetic Studies: Determination of Benzoic Acid and Cr(VI)

Benzoic acid concentrations were determined by a Dionex P680 HPLC equipped with a Dionex PDA-100 Photodiode Array Detector using a Discovery , (250 mm length × 4.6 mm ID: 5 m particle size) analytical column from Supelco (Bellefonte, PA, USA). The mobile phase was a mixture of LC-grade water (70%) at pH 3 (adjusted with formic acid) and acetonitrile (30%) with a flow rate of 1 ml/min. Column temperature was set at 40°C. The detection of BA was realized at 228 nm. The concentration of Cr(VI) was determined by the diphenylcarbazide colorimetric method [11] at a wavelength of 540 nm using a UV-Vis spectrophotometer (Hitachi, U-2000).

2.4. Experimental Design: Data Analysis

A central composite design was employed for the optimization of photocatalytic process in the present study. In order to evaluate the influence of operating parameters on the simultaneous photocatalytic efficiency of BA and Cr(VI), three main factors were chosen: catalyst concentration (mg ) , Cr(VI)/BA ratio , and pH . A total number of 17 experiments were determined by the expression: (8 factor points) +2*3 (6 axial points) central points, replications) = 17, as shown in Table 1. The three selected experimental parameters were optimized using RSM considering them as independent variables and % Cr(VI) removal and % BA degradation as response variables. The data set obtained from CCD was used for the optimization of the responses and RSM was used to fit the experimental data. A second order model was used to locate the optimum point and can be expressed as follows:

where is the response variable of degradation efficiency, is the constant term, represents the coefficients of the linear parameters, represents the variables, represents the coefficients of the quadratic parameters, represents the coefficients of the interaction parameters and is the random error [13]. Experimental data were analyzed using Design Expert V. 7.1.5 (Stat-Ease Inc. 2008, Mn, USA). Data were further estimated and evaluated by the analysis of variance (ANOVA). Correlation coefficients (, adj.) were used to evaluate the correlation between the experimental data and the predicted responses and thereby the goodness of the fit for the polynomial models. The statistical significance was also checked by the F value (Fisher variation ratio), probability value and adequate precision in the same program. The significance of each model term was evaluated based on value with 95% confidence level . Finally, three-dimensional response surface plots were developed in order to visualize the individual and the interaction effects of the independent variables on degradation efficiency.

Table 1: Central composite design matrix and experimental results for benzoic acid (BA) and Cr(VI) photocatalytic degradation.

Exper. no.
CTiO2-  

(mg L⁻¹)
Cr/BA

ratio-
pH-
(%) removal

Cr(VI)
(%) degradation

BA

1
200
5
10
32.36
2.5

2
600
15
4
55.22
49.47

3
400
1.59
7
100
17.5

4
400
18.41
7
36.41
32.78

5
600
5
10
54.95
5.1

6
600
5
4
100
36.61

7
400
10
1.95
58.9
47.84

8
400
10
7
45.96
9.49

9
200
5
4
76.16
23.07

10
200
15
10
4.58
6.56

11
400
10
12.05
4.85
2.79

12
200
15
4
24.06
30.34

13
400
10
7
45.57
8.18

14
63.64
10
7
18.85
2.7

15
736.36
10
7
65.82
17.24

16
400
10
7
47.44
8.66

17
600
15
10
32.92
12.08

3. Results and Discussion

3.1. Preliminary Experiments

Preliminary experiments were carried out, before the development of the experimental design, in order to evaluate the possible synergistic effect of the simultaneous photooxidation-photoreduction of the selected pollutants, Cr(VI) and BA. For this reason, experiments were conducted in single and binary systems at pH = 2, catalyst concentration 500 mg  and UV intensity 750 W . The initial concentrations used were 0.1 mM Cr(VI) and 0.01 mM BA. Figures 1 and 2 show the reduction of Cr(VI) and oxidation of BA under different conditions, respectively. The adsorbed percentages of Cr(VI) and BA in the binary system were 12.5% and 6%, respectively, while prolonged dark experiments in the presence of N-F- led to neither BA degradation nor metal reduction after 240 min. Direct photolysis in the single systems of Cr(VI) and BA resulted in low removals for both pollutants. Similarly, low removal was observed for both pollutants in the binary system under photolytic treatment, implying no severe interaction between Cr(VI) and BA under direct photolysis. As shown in Figures 1 and 2, in single systems the photocatalytic reduction of Cr(VI) was achieved after 150 min irradiation, whereas the photocatalytic oxidation of BA was much slower and almost complete degradation is accomplished after 240 min of irradiation time. On the other hand, the simultaneous photocatalytic treatment of Cr(VI) and BA in the binary system significantly enhanced the reduction/oxidation of substrates each other. In the binary system, the coupled oxidation of the BA consumes photo-generated holes and/or radicals efficiently, blocking the electron-hole recombination and thus, increasing the total efficiency. Moreover, the enhancement of the rates confirmed that Cr(VI) acted as an efficient scavenger of the photogenerated electrons. The results obtained, revealed not only the simultaneous decontamination of two pollutants but also the synergistic effect between the photocatalytic redox reactions.

Figure 1: Photocatalytic reduction of Cr(VI) in single and binary systems. ([Cr(VI)]₀ = 0.1 mM, [BA]₀ = 0.01 mM, pH = 2, N-F- = 500 mg ).

Figure 2: Photocatalytic degradation of benzoic acid in single and binary systems. ([Cr(VI)]₀ = 0.1 mM, [BA]₀ = 0.01 mM, pH = 2, N-F- = 500 mg ).

3.2. RSM Modeling and Optimization for Cr(VI) Photocatalytic Removal

The design matrix and experimental results obtained for the Cr(VI) photocatalytic degradation are depicted in Table 1. The step-wise model fitting was employed in order to find the best model fitted. The quadratic model was selected to describe the relationship of operational parameters and photocatalytic removal based on lack-of-fit analysis and model summary statistics. The quadratic model obtained for the response of % Cr(VI) removal in terms of coded variables can be written as follows (4):

The model adequacy and significance were further checked by ANOVA and the results are shown in Table 2. The ANOVA of the second order quadratic polynomial model showed that the model was highly significant, as the F value for the model was 1841.56 and the corresponding value was 0.0001. This means that there was only a 0.01% chance for such model F value due to noise. The non significant lack of fit relative to the pure error also confirmed good predictability of the model. The experimental values plotted against the predicted responses for the degradation efficiency of Cr(VI) (Figure 3) showed good correlation indicating that the model explained the experimental range studied very well. The high model regression coefficient implied that 99.96% of the variations for % Cr(VI) removal were explained by the model. As well, adjusted correlation coefficient of 0.9990 was also very high to advocate for a high significance of the model. The adequacy of the model was also evaluated by the residuals. The normal probability plot of the residuals, shown in Figure 4, revealed that all the points approximate a straight line proving no severe indication of non normality and a good fit of the model. This was also supported by the low value of the coefficient of variation (CV = 1.84%). The significance of each term in the predictive model was evaluated by values using 5% significance level. Independent variables of the quadratic model, N-F-TiO₂ concentration , Cr(VI)/BA ratio , pH , the second order effect of them, as well as the interaction between Cr(VI)/BA ratio and pH were highly significant parameters (). Moreover, the interaction between N-F- concentration and Cr(VI)/BA ratio was significant at . On the contrary, Cr(VI) removal was not significantly affected by the interaction between N-F- concentration and pH . The effects of the three independent variables and their interaction on the removal of Cr(VI) were graphically represented by three-dimensional response surface plots by means of response surface methodology. The interaction effect of N-F- concentration and Cr(VI)/BA ratio is shown in Figure 5(a). As can be seen there was an increase in the removal percentage of Cr(VI) with an increase of N-F- concentration and a decrease of Cr(VI)/BA ratio. The removal percentage increased proportionally by the increase of N-F- dosage due to the increase of adsorption sites on the surface of catalyst as well as the generation of more electrons in the conduction band. An increase in the Cr (VI)/BA ratio by a consequently increase of initial Cr (VI) concentration led to a decreased removal. As initial Cr(VI) concentrations increased, more metal ions were adsorbed on the surface of the photocatalyst. Therefore, the photogenerated e- required for the removal of Cr(VI) also increased and hence, the available electrons were inadequate for pollutant removal at higher concentrations. Moreover, with the increase in the Cr(VI) concentration, less photons reach the photocatalyst surface (light screening effect), resulting in slower production of the photogenerated pair hole/electron. Consequently, the photocatalytic activity was decreased, since fewer available were available to reduce more metallic ions. Moreover, an increase in pH led to a decrease in the rate of Cr (VI) removal as illustrated in Figure 5(b). This can be attributed to the surface charge properties of the photocatalyst. Since, the point of zero charge of the NF- catalysts has been determined to be 5.7, the N-F- surface is negatively charged at pH 5.7, whereas is positively charged in more acidic conditions (pH 5.7). At pH values around 2.5 the predominant species of chromium are the negative charged and ions and at pH values around 6.5 Cr(VI) exists mainly as and [24]. As the pH of the solutions increased, the negatively charged sites of the catalyst increased, thus, the absorption of Cr(VI) anions was prevented due to electrostatic repulsion and consequently their reduction on N-F-TiO₂ surface. The adsorbed percentage of Cr(VI) at pH = 10, Cr(VI)/BA ratio = 5, and [TNF] = 600 mg  was found to be 5%. Conversely, as pH decreased, the electrostatic attraction between the positively charged surface and anionic Cr(VI) was enhanced, leading to increased removal. The adsorption percentage (%) of Cr(VI) at pH = 4 and using the same Cr(VI)/BA ratio and catalyst concentration increased to about 21%. An increase in the Cr(VI) photocatalytic reduction with decreasing pH values has been also reported elsewhere [28, 29].

Table 2: Analysis of variance (ANOVA) for % removal of Cr(VI).

Source
Sum of

squares
df
Mean

square
value
value

Model
12510.88
9
1390.10
1841.56
<0.0001

-TiO₂ mg L⁻¹
2504.00
1
2504.00
3317.23
<0.0001

-Cr/BA ratio
4710.52
1
4710.52
6240.35
<0.0001

-pH
3593.50
1
3593.50
4760.57
<0.0001

21.35
1
21.35
28.29
0.0011

2.07
1
2.07
2.74
0.1416

276.95
1
267.95
366.89
<0.0001

22.49
1
22.49
29.79
0.0009

674.33
1
674.33
893.34
<0.0001

294.43
1
294.43
390.05
<0.0001

Residual
5.28
7
0.75

Lack of fit
3.34
5
0.67
0.69
0.6829

Pure error
1.95
2
0.97

Figure 3: Plot of predicted versus actual values for % Cr(VI) removal.

Figure 4: The normal probability (%) plot of the experimental results for % Cr(VI) removal.

(a)

(b)

Figure 5: 3D response surface plots for % Cr(VI) removal; (a) as a function of N-F- concentration and Cr (VI)/BA ratio; (b) as a function of pH and N-F- concentration.

3.3. RSM Modeling and Optimization for Benzoic Acid Photocatalytic Degradation

The experimental design matrix and experimental results obtained for the BA photocatalytic degradation are given in Table 1. Similarly to % Cr(VI) removal, a quadratic model was suggested as the most appropriate to approximate the % photocatalytic degradation of BA. The model can be written in terms of coded variables as follows:

ANOVA results of the suggested quadratic model (Table 3) and the comparison of actual versus predicted values (Figure 6) indicated that the model could adequately be used to describe the % benzoic acid degradation under the experimental range studied. The model value of 426.95 and value less than 0.0001 implied the high significance of the model. There was only a 0.01% chance that the “Model value” could occur due to noise. Moreover, lack of fit was shown to be not significant relative to the pure error, indicating good response to the model. The high model regression coefficient of 0.9982 implied that 99.82% of the variability can be revealed by the model and only 0.18% of residual variability remained. The of 0.9982 was in reasonable agreement with adjusted , indicating also good predictability of the model. A very high degree of precision and a good deal of reliability of the experimental values were indicated by the low value of the coefficient of variation (CV = 5.48%). As can be observed from the residual plot in Figure 7 the data were normally distributed denoting too a good fit of the model. Using 5% significance level, the independent variables of the quadratic model, N-F- concentration , Cr(VI)/BA ratio , pH , the second-order effects of Cr(VI)/BA ratio , and pH as well as the interaction between ratio N-F- concentration and pH were highly significant parameters due to . Moreover the interactions between N-F-TiO₂ concentration and Cr(VI)/BA ratio and between Cr(VI)/BA ratio and pH were significant at . On the contrary, the second-order effect of N-F- concentration was the only insignificant term ( value of 0.2284). Three-dimensional response surfaces computed for % BA degradation are depicted in Figure 8. As shown in Figures 8(a) and 8(b) the degradation percentage increased proportionally to N-F- concentration as expected, confirming the positive influence of the increased number of N-F- active sites/species (mainly holes and ) on the process kinetics. Several studies have indicated that photocatalytic degradation rate initially increased with catalyst loading and above a certain level of concentration, the reaction rate remains constant or even decreases and becomes independent of the catalyst concentration because of light scattering and screening effects as well as due to the tendency towards agglomeration at high solids concentration [30, 31]. However, this study was based on the use of moderate catalyst concentrations, where this limit was still far away, and thereby the degradation rate increased with NF-TiO₂ concentration within the selected range. From the response surface in Figure 8(b), it was clear that the BA degradation percentage decreased as the pH values increased from acidic to alkaline region. This is related to the ionization state of the surface of catalyst according to the determined PZC (5.7) as well as to that of the parent compound. The pKa of benzoic acid is 4.2 [32] thus, at a pH greater than this value the molecule bears a negative charge. As mentioned above, N-F- surface will be positively charged at pH values lower than 5.7 and negatively charged at higher ones. In consequence, as the pH increased from slightly acidic (5.7–6) to alkaline values, Columbic repulsion between the negative-charged surface of the catalysts and anionic form of BA was observed which led to decreased adsorption and consequently lower degradation. The adsorbed percentage of BA at pH = 10, Cr(VI)/BA ratio = 5, and [TNF] = 600 mg   was found to be only 0.5%. An increase in the degradation rate of BA was also observed with an increase in the Cr(VI)/BA ratio (Figure 8(a)). As the Cr(VI) concentration increased, the recombination of the photo-induced hole/electron pairs was strongly inhibited, as the electrons were scavenged by Cr(VI), enhancing the BA degradation. The numerical optimization of the software using desirability approach was employed to find the specific points that maximize the % removal for both pollutants. Based on the models, the optimum conditions for simultaneous removal of Cr(VI) and BA were found as follows: N-F- concentration = 600 mg , Cr(VI)/BA ratio = 5, and pH = 4.

Table 3: Analysis of variance (ANOVA) for % degradation of benzoic acid.

Source
Sum of

squares
df
Mean

square
value
value

Model
3908.5
9
434.28
426.95
<0.0001

-TiO₂ mg L⁻¹
311.69
1
311.69
306.43
<0.0001

-Cr/BA ratio
236.80
1
236.80
232.80
<0.0001

-pH
2616.02
1
2616.02
2571.86
<0.0001

9.05
1
9.05
8.90
0.0204

75.34
1
75.34
74.07
<0.0001

10.33
1
10.33
10.15
0.0153

1.77
1
1.77
1.74
0.2284

374.00
1
374.00
367.69
<0.0001

382.08
1
382.08
375.63
<0.0001

Residual
7.12
7
1.02

Lack of fit
6.24
5
1.25
2.84
0.2805

Pure error
0.88
2
0.44

Figure 6: Plot of predicted versus actual values for % BA degradation.

Figure 7: The normal prpbability (%) plot of the experimental results for % BA degradation.

(a)

(b)

Figure 8: 3D response surface plots for the % BA degradation; (a) as a function of N-F- concentration and Cr(VI)/BA ratio; (b) as a function of pH and N-F- concentration.

3.4. Model Validation and Confirmation—Evolution of Photocatalytic Reduction of Cr(VI) and Oxidation of Benzoic Acid under Optimized Conditions

To confirm the adequacy of the models for predicting the maximum simultaneous % removal Cr and % degradation of BA, verification experiments were conducted using the optimum conditions. The removal and degradation rates from the validation experiment are depicted in Figure 9. Under optimized conditions pseudo-first order kinetics were recorded for both the photocatalytic reduction of Cr(VI) and degradation of BA. Table 4 lists the values of apparent rate constants, , the correlation coefficients and the corresponding half-lives of Cr(VI) and BA. Half of Cr(VI) concentration was consumed within 7.22 min of irradiation under optimal conditions, while BA exhibited a much slower rate than the removal of Cr(VI). Complete Cr (VI) removal was achieved after 30 min of irradiation time. At the same time, the degradation of BA reached about 40%, and prolonged irradiation time was needed before complete degradation was achieved. As reported in the literature, the photocatalytic transformation products of BA using included salicylic acid, p-hydroxybenzoic acid, and 2,3- and/or 2,5-dihydroxybenzoic acid and phenol. The photocatalytic degradation pathway proceeds via attack on the aromatic moiety on several positions to produce hydroxy and dihydroxy derivatives, via decarboxylation (photo-Kolbe) reaction resulting from the direct attack of the carboxylic group by and finally ring opening to produce aliphatic acids [15, 32, 33]. The formation of such by-products reacts also with / resulting in a more prolonged time for the degradation of parent benzoic acid.

Table 4: Photocatalytic kinetic parameters (rate constants, half-lives, correlation coefficients) of Cr(VI) and BA under optimized conditions ([N-F-TiO₂]₀ = 600 mg L⁻¹, Cr/BA ratio = 5, pH = 4).

(min⁻¹)
(min)

Cr(VI)
0.0960
7.219
0.9929

BA
0.0109
63.578
0.9623

Figure 9: Kinetics of reduction of Cr(VI) and degradation of BA versus irradiation time under optimized conditions ([N-F TiO₂]₀ = 600 mg , Cr(VI)/BA ratio = 5, pH = 4).

According to previous findings [26] N-F-codoping of enhances the oxidative power of the but lessens the reduction ability of . This unveils the use of such photocatalytic materials to control the photocatalytic reactions of the redox pair species, and . Regarding the reduction process, the electrons of the N-F-, at states below the CB of , have weaker reduction ability, consequently they can reduce preferably strong oxidation agents such as Cr(VI) enhancing the target reduction reaction without the competence of other ineffective reactions for reduction, such as reduction. As far as the oxidation pathway, the enhancement in the oxidation power of the makes the oxidation of organic molecules and especially organic acids and water (for the production) more favourable and consequently enables the reduction reaction to occur more efficiently.

4. Conclusions

The simultaneous photocatalytic reduction of Cr(VI) and oxidation of benzoic acid in the presence of N-F-codoped was investigated focusing on the influence of parameters such as catalyst concentration, Cr(VI)/BA ratio, and pH on the photocatalytic efficiency that was optimized and modeled by response surface methodology (RSM). A considerable enhancement of the photocatalytic efficiency was observed for the binary system than in the single component systems, indicating a promoting synergistic effect. Also, it was noted that the three parameters tested had significant effect on the total efficiency. Under optimized conditions the removal for both Cr(VI) and BA followed pseudo-first order kinetic model. The results provide an efficient treatment method to remove organic and inorganic pollutants simultaneously in complex systems which presents special significance to water pollution control and remediation. Moreover, this study proves that RSM constitutes a powerful tool for optimizing the operational conditions of the simultaneous reduction of Cr (VI) and oxidation of benzoic acid by photocatalytic processes.

Acknowledgments

This research has been cofinanced by the European Union (European Social Fund, ESF) and Greek national funds through the Operational Program “Education and Lifelong Learning” of the National Strategic Reference Framework (NSRF)—Research Funding Program: Heracleitus II. Investing in knowledge society through the European Social Fund.

References

S. C. Hsu, H. L. Hsieh, C. P. Chen et al., “Tungsten and other heavy metal contamination in aquatic environments receiving wastewater from semiconductor manufacturing,” Journal of Hazardous Materials, vol. 189, no. 1-2, pp. 193–202, 2011.

J. J. Pignatello, B. G. Katz, and H. Li, “Sources, interactions, and ecological impacts of organic contaminants in water, soil, and sediment: an introduction to the special series,” Journal of Environmental Quality, vol. 39, no. 4, pp. 1133–1138, 2010.

M. Stuart, D. Lapworth, E. Crane, and A. Hart, “Review of risk from potential emerging contaminants in UK groundwater,” Science of the Total Environment, vol. 416, pp. 1–21, 2012.

R. Qiu, D. Zhang, Z. Diao et al., “Visible light induced photocatalytic reduction of Cr(VI) over polymer-sensitized TiO₂ and its synergism with phenol oxidation,” Water Research, vol. 46, no. 7, pp. 2299–2306, 2012.

X. Zhao, Q. Li, X. Zhang, H. Su, K. Lan, and A. Chen, “Simultaneous removal of metal ions and methyl orange by combined selective adsorption and photocatalysis,” Environmental Progress and Sustainable Energy, vol. 30, no. 4, pp. 567–575, 2011.

A. R. Khataee and M. B. Kasiri, “Artificial neural networks modeling of contaminated water treatment processes by homogeneous and heterogeneous nanocatalysis,” Journal of Molecular Catalysis A, vol. 331, no. 1-2, pp. 86–100, 2010.

I. K. Konstantinou and T. A. Albanis, “Photocatalytic transformation of pesticides in aqueous titanium dioxide suspensions using artificial and solar light: intermediates and degradation pathways,” Applied Catalysis B, vol. 42, no. 4, pp. 319–335, 2003.

T. Mishra, J. Hait, N. Aman, R. K. Jana, and S. Chakravarty, “Effect of UV and visible light on photocatalytic reduction of lead and cadmium over titania based binary oxide materials,” Journal of Colloid and Interface Science, vol. 316, no. 1, pp. 80–84, 2007.

M. I. Litter, “Treatment of chromium, mercury, lead, uranium, and arsenic in water by heterogeneous photocatalysis,” Advances in Chemical Engineering, vol. 36, pp. 37–67, 2009.

N. Aman, T. Mishra, J. Hait, and R. K. Jana, “Simultaneous photoreductive removal of copper (II) and selenium (IV) under visible light over spherical binary oxide photocatalyst,” Journal of Hazardous Materials, vol. 186, no. 1, pp. 360–366, 2011.

N. Wang, Y. Xu, L. Zhu, X. Shen, and H. Tang, “Reconsideration to the deactivation of TiO₂ catalyst during simultaneous photocatalytic reduction of Cr(VI) and oxidation of salicylic acid,” Journal of Photochemistry and Photobiology A, vol. 201, no. 2-3, pp. 121–127, 2009.

P. Banerjee, S. Chakrabarti, S. Maitra, and B. K. Dutta, “Zinc oxide nano-particles—sonochemical synthesis, characterization and application for photo-remediation of heavy metal,” Ultrasonics Sonochemistry, vol. 19, no. 1, pp. 85–93, 2012.

M. Antonopoulou, V. Papadopoulos, and I. Konstantinou, “Photocatalytic oxidation of treated municipal wastewaters for the removal of phenolic compounds: optimization and modeling using response surface methodology (RSM) and artificial neural networks (ANNs),” Journal of Chemical Technology & Biotechnology. In press

T. Velegraki and D. Mantzavinos, “Conversion of benzoic acid during TiO₂-mediated photocatalytic degradation in water,” Chemical Engineering Journal, vol. 140, no. 1–3, pp. 15–21, 2008.

A. A. Ajmera, S. B. Sawant, V. G. Pangarkar, and A. A. C. M. Beenackers, “Solar-assisted photocatalytic degradation of benzoic acid using titanium dioxide as a photocatalyst,” Chemical Engineering and Technology, vol. 25, no. 2, pp. 173–180, 2002.

E. I. Korotkova, O. A. Avramchik, T. M. Angelov, and Y. A. Karbainov, “Investigation of antioxidant activity and lipophilicity parameters of some preservatives,” Electrochimica Acta, vol. 51, no. 2, pp. 324–332, 2005.

N. Wang, L. Zhu, K. Deng, Y. She, Y. Yu, and H. Tang, “Visible light photocatalytic reduction of Cr(VI) on TiO₂ in situ modified with small molecular weight organic acids,” Applied Catalysis B, vol. 95, no. 3-4, pp. 400–407, 2010.

V. Prigione, M. Zerlottin, D. Refosco, V. Tigini, A. Anastasi, and G. C. Varese, “Chromium removal from a real tanning effluent by autochthonous and allochthonous fungi,” Bioresource Technology, vol. 100, no. 11, pp. 2770–2776, 2009.

A. Pandikumar and R. Ramaraj, “Titanium dioxide-gold nanocomposite materials embedded in silicate sol-gel film catalyst for simultaneous photodegradation of hexavalent chromium and methylene blue,” Journal of Hazardous Materials, vol. 203-204, pp. 244–250, 2012.

B. Sun, E. P. Reddy, and P. G. Smirniotis, “Visible light Cr(VI) reduction and organic chemical oxidation by TiO₂ photocatalysis,” Environmental Science and Technology, vol. 39, no. 16, pp. 6251–6259, 2005.

X. R. Xu, H. B. Li, and J. D. Gu, “Photocatalytic reduction of hexavalent chromium and degradation of di-N-Butyl phthalate in aqueous TiO₂ suspensions under ultraviolet light irradiation,” Environmental Technology, vol. 28, no. 9, pp. 1055–1061, 2007.

G. Colón, M. C. Hidalgo, and J. A. Navío, “Photocatalytic deactivation of commercial TiO₂ samples during simultaneous photoreduction of Cr(VI) and photooxidation of salicylic acid,” Journal of Photochemistry and Photobiology A, vol. 138, no. 1, pp. 79–85, 2001.

S. G. Schrank, H. J. José, and R. F. P. M. Moreira, “Simultaneous photocatalytic Cr(VI) reduction and dye oxidation in a TiO₂ slurry reactor,” Journal of Photochemistry and Photobiology A, vol. 147, no. 1, pp. 71–76, 2002.

T. Papadam, N. P. Xekoukoulotakis, I. Poulios, and D. Mantzavinos, “Photocatalytic transformation of acid orange 20 and Cr(VI) in aqueous TiO₂ suspensions,” Journal of Photochemistry and Photobiology A, vol. 186, no. 2-3, pp. 308–315, 2007.

H. Kyung, J. Lee, and W. Choi, “Simultaneous and synergistic conversion of dyes and heavy metal ions in aqueous TiO₂ suspensions under visible-light illumination,” Environmental Science and Technology, vol. 39, no. 7, pp. 2376–2382, 2005.

Q. Wang, C. Chen, W. Ma, H. Zhu, and J. Zhao, “Pivotal role of fluorine in tuning band structure and visible-light photocatalytic activity of nitrogen-doped TiO₂,” Chemistry—A European Journal, vol. 15, no. 19, pp. 4765–4769, 2009.

K. Bourikas, J. Vakros, C. Kordulis, and A. Lycourghiotis, “Potentiometric mass titrations: experimental and theoretical establishment of a new technique for determining the point of zero charge (PZC) of metal (hydr)oxides,” Journal of Physical Chemistry B, vol. 107, no. 35, pp. 9441–9451, 2003.

L. B. Khalil, W. E. Mourad, and M. W. Rophael, “Photocatalytic reduction of environmental pollutant Cr(VI) over some semiconductors under UV/visible light illumination,” Applied Catalysis B, vol. 17, no. 3, pp. 267–273, 1998.

Y. Ku and I. L. Jung, “Photocatalytic reduction of Cr(VI) in aqueous solutions by UV irradiation with the presence of titanium dioxide,” Water Research, vol. 35, no. 1, pp. 135–142, 2001.

I. K. Konstantinou and T. A. Albanis, “TiO₂-assisted photocatalytic degradation of azo dyes in aqueous solution: kinetic and mechanistic investigations: a review,” Applied Catalysis B, vol. 49, no. 1, pp. 1–14, 2004.

V. A. Sakkas, P. Calza, A. D. Vlachou, C. Medana, C. Minero, and T. Albanis, “Photocatalytic transformation of flufenacet over TiO₂ aqueous suspensions: Identification of intermediates and the mechanism involved,” Applied Catalysis B, vol. 110, pp. 238–250, 2011.

V. G. Gandhi, M. K. Mishra, M. S. Rao, A. Kumar, P. A. Joshi, and D. O. Shah, “Comparative study on nano-crystalline titanium dioxide catalyzed photocatalytic degradation of aromatic carboxylic acids in aqueous medium,” Journal of Industrial and Engineering Chemistry, vol. 17, no. 2, pp. 331–339, 2011.

A. Assabane, Y. Ait Ichou, H. Tahiri, C. Guillard, and J. M. Herrmann, “Photocatalytic degradation of polycarboxylic benzoic acids in UV-irradiated aqueous suspensions of titania. Identification of intermediates and reaction pathway of the photomineralization of trimellitic acid (1,2,4-benzene tricarboxylic acid),” Applied Catalysis B, vol. 24, no. 2, pp. 71–87, 2000.