Modification of Immobilized Titanium Dioxide Nanostructures by Argon Plasma for Photocatalytic Removal of Organic Dyes

The aim of this study was to modify surface properties of immobilized rutile TiO2 using Argon cold plasma treatment and to evaluate the performance of the catalyst in photocatalytic elimination of synthetic dyes in UV/TiO2/H2O2 process. The surface-modified TiO2 was characterized by XRD, EDX, SEM, UV-DRS and XPS analyses. Response surface methodology was adopted to achieve high catalyst efficiency by evaluating the effect of two main independent cold plasma treatment parameters (exposure time and pressure) on surface modification of the catalyst. The increase of the plasma operation pressure led to higher decolorization percentage, while the increase of plasma exposure time decreased the decolorization efficiency. RSM methodology predicted optimum plasma treatment conditions to be 0.78 Torr and 21 min of exposure time, which resulted in decolorization of 10 mg/L solution of the malachite green solution by 94.94% in 30 min. The plasma treatment decreased the oxygen to titanium ratio and caused oxygen vacancy on the surface of the catalyst, resulting in the superior performance of the plasma-treated catalyst. Pseudo first-order kinetic rate constant for the plasma-treated catalyst was 4.28 and 2.03 times higher than the rate constant for the non-treated photocatalyst in decolorization of aqueous solutions of malachite green and crystal violet, respectively.


Introduction
About 1-20% of total annually produced synthetic dyes are released into the effluents of the textile, paper, pharmaceutical, food, and plastic industries [1,2]. This causes considerable environmental pollution via production of hazardous byproducts through hydrolysis, oxidation and other chemical reactions [1,3,4]. Synthetic dyes such as malachite green oxalate (MG) and crystal violet (CV) are conditions to achieve the maximum photocatalytic performance. RSM is an efficient and widely used statistical-based method for multivariate analysis which has been employed to investigate the interaction between operational parameters and reduce the experimental workload in wastewater treatment [44,45]. interaction between operational parameters and reduce the experimental workload in wastewater treatment [44,45].  The results show that stable tetragonal rutile phase (JCPDS 00-004-0551) is the dominant crystal structure of the TiO2 nanoparticles. However, the peaks corresponding to anatase phase were not observed [46,47]. By the aid of the Scherer equation [48], crystal sizes were calculated as 54.04 and 58.73 nm for non-modified and plasma-treated catalyst, respectively.  interaction between operational parameters and reduce the experimental workload in wastewater treatment [44,45].  The results show that stable tetragonal rutile phase (JCPDS 00-004-0551) is the dominant crystal structure of the TiO2 nanoparticles. However, the peaks corresponding to anatase phase were not observed [46,47]. By the aid of the Scherer equation [48], crystal sizes were calculated as 54.04 and 58.73 nm for non-modified and plasma-treated catalyst, respectively.   However, the peaks corresponding to anatase phase were not observed [46,47]. By the aid of the Scherer equation [48], crystal sizes were calculated as 54.04 and 58.73 nm for non-modified and plasma-treated catalyst, respectively. interaction between operational parameters and reduce the experimental workload in wastewater treatment [44,45].  [46,47]. By the aid of the Scherer equation [48], crystal sizes were calculated as 54.04 and 58.73 nm for non-modified and plasma-treated catalyst, respectively.    Figure 2b-left revealed that entire surface of the treated sample is replete with valleys and cracks (Figure 2a-left). It has been reported that plasma modification was able to generate cracks and cavities on the surface of the catalyst. It is also important to note that plasma only affects upper monolayers of the surface [34,43,44].  Figure 2 shows SEM images of the rutile nano particles immobilized on glass plates before and after Ar plasma treatment. SEM images indicate that the surface of I-TiO2 sample is relatively flat (Figure 3(a)-right), while Ar plasma formed large cracks (Figure 2 (b)-right). Figure 2 (b)-left revealed that entire surface of the treated sample is replete with valleys and cracks (Figure 2(a)-left). It has been reported that plasma modification was able to generate cracks and cavities on the surface of the catalyst. It is also important to note that plasma only affects upper monolayers of the surface [34,43,44].

Characterizing of the Catalysts
where α is the optical absorption coefficient, hυ (h = Planck's constant and υ = frequency) is the photon energy, B is constant, is the optical band gap energy (eV) and n is ½ for direct band gap semiconductors. In order to obtain the optical band gap energy of the samples, (αhv) 2 was plotted versus hv (Figure 3(b)) and Eg was calculated. Optical band gap energy for Ar plasma and non-treated samples were found as 2.94 and 2.97 eV, respectively. Although plasma treatment slightly decreased  Figure 3a shows UV-vis diffuse reflectance spectra of I-TiO 2 and Ar-TiO 2 samples. Optical band gap energy of the samples can be obtained by the Tauc equation [49] (Equation (1)): where α is the optical absorption coefficient, hυ (h = Planck's constant and υ = frequency) is the photon energy, B is constant, E g is the optical band gap energy (eV) and n is 1 ⁄2 for direct band gap semiconductors. In order to obtain the optical band gap energy of the samples, (αhv) 2 was plotted versus hv ( Figure 3b) and E g was calculated. Optical band gap energy for Ar plasma and non-treated samples were found as 2.94 and 2.97 eV, respectively. Although plasma treatment slightly decreased the band gap energy, difference between the band gap energies is not significant for the rutile phase, which already possess a narrow band gap (~3 eV) [33,50]. the band gap energy, difference between the band gap energies is not significant for the rutile phase, which already possess a narrow band gap (~3 eV) [33,50]. EDX spectra of the TiO2 nanoparticles immobilized on glass plates were collected to investigate the bulk elemental composition of the Ar-TiO2 and I-TiO2 samples. It can be seen in Figure 4 that plasma treatment slightly reduced atomic percentage of oxygen in the favor of titanium. Also, as it was expected, plasma treatment did not have a significant effect on the bulk structure. It has been EDX spectra of the TiO 2 nanoparticles immobilized on glass plates were collected to investigate the bulk elemental composition of the Ar-TiO 2 and I-TiO 2 samples. It can be seen in Figure 4 that plasma treatment slightly reduced atomic percentage of oxygen in the favor of titanium. Also, as it was expected, plasma treatment did not have a significant effect on the bulk structure. It has been reported that cold plasma treatment only modified a few monolayers of the surface, without altering the bulk properties [38,39]. reported that cold plasma treatment only modified a few monolayers of the surface, without altering the bulk properties [38,39]. XPS analysis was performed to further examine the effect of non-thermal Ar plasma on rutile TiO2 nanoparticles. Figure 5 shows XPS spectra of non-immobilized treated and non-treated TiO2 nanoparticles. Sharp peaks of C1s, Ti2p and O1s appeared the in the wide-scan spectra for both samples ( Figure 5(a)). High resolution XPS (HR-XPS) spectra of Ti2p are depicted in Figure 5(b). The two broad peaks shown in the spectrum of the unmodified sample at 464.09 and 458.38 eV are attributed to Ti2p1/2 and Ti2p3/2, respectively. After Ar plasma treatment, atomic percentages of Ti 3+ and Ti 2+ increased by 91.62 and 49.51%, respectively (increasing from 3.82% to 7.32% for Ti 3+ and from 1.03% to 1.54% for Ti 2+ ); while, atomic percentage was reduced by 4.4% for tetravalent Ti 4+ , which is in agreement with the results observed by Bharti et al. [51]. Therefore, oxidation state of Ti decreased after the plasma treatment. HR-XPS spectra of O1s are presented in Figure 5(c). Deconvolution of the O1s peak revealed the presence of lattice and non-lattice/surface OH oxygen at 529.71 and 531.65 eV, respectively. Contribution of the non-lattice/surface OH oxygen increased slightly from 7.94 to 8.34% as a result of Ar plasma treatment.
Ti 3+ surface defects are some of the most important surface defects in TiO2 and an important reactive agent for many adsorbents. Hence, many surface reactions are influenced by these point defects. Sirisuk et al. reported that Ti 3+ sites play an essential role in photocatalytic process over TiO2 photocatalyst [52]. The reported methods to produce TiO2 containing Ti 3+ surface defect include UV irradiation [53,54], heating TiO2 under vacuum [55], thermal annealing to high temperatures (above 500 K) [56], and high-energy particle (neutron, Ar + , electron, or γ-ray) bombardment [57][58][59]. In this research, Ar plasma was generated Ti 3+ surface defect by changing Ti 4+ to Ti 3+ . XPS analysis was performed to further examine the effect of non-thermal Ar plasma on rutile TiO 2 nanoparticles. Figure 5 shows XPS spectra of non-immobilized treated and non-treated TiO 2 nanoparticles. Sharp peaks of C1s, Ti2p and O1s appeared the in the wide-scan spectra for both samples (Figure 5a). High resolution XPS (HR-XPS) spectra of Ti2p are depicted in Figure 5b. The two broad peaks shown in the spectrum of the unmodified sample at 464.09 and 458.38 eV are attributed to Ti2p1/2 and Ti2p3/2, respectively. After Ar plasma treatment, atomic percentages of Ti 3+ and Ti 2+ increased by 91.62 and 49.51%, respectively (increasing from 3.82% to 7.32% for Ti 3+ and from 1.03% to 1.54% for Ti 2+ ); while, atomic percentage was reduced by 4.4% for tetravalent Ti 4+ , which is in agreement with the results observed by Bharti et al. [51]. Therefore, oxidation state of Ti decreased after the plasma treatment. HR-XPS spectra of O1s are presented in Figure 5c. Deconvolution of the O1s peak revealed the presence of lattice and non-lattice/surface OH oxygen at 529.71 and 531.65 eV, respectively. Contribution of the non-lattice/surface OH oxygen increased slightly from 7.94 to 8.34% as a result of Ar plasma treatment.
Ti 3+ surface defects are some of the most important surface defects in TiO 2 and an important reactive agent for many adsorbents. Hence, many surface reactions are influenced by these point defects. Sirisuk et al. reported that Ti 3+ sites play an essential role in photocatalytic process over TiO 2 photocatalyst [52]. The reported methods to produce TiO 2 containing Ti 3+ surface defect include UV irradiation [53,54], heating TiO 2 under vacuum [55], thermal annealing to high temperatures (above 500 K) [56], and high-energy particle (neutron, Ar + , electron, or γ-ray) bombardment [57][58][59]. In this research, Ar plasma was generated Ti 3+ surface defect by changing Ti 4+ to Ti 3+ .

Optimal Plasma Treatment Conditions
Decolorization experiments were carried out based on the central composite design and the results are presented in Table 2. The response values (i.e., decolorization percentages) were fitted to the quadratic response function and the coefficients were determined by regression analysis. The obtained regression equation is shown in Equation (2): where Y is MG decolorization after 30 min of operation using each catalyst configuration, while X 1 and X 2 are coded values of plasma pressure and exposure time, respectively. A positive sign for the coefficients in the fitted model indicates that the decolorization efficiency increases with increase in the level of the corresponding factor. The statistical significance of the presented quadratic model was examined using analysis of variances (ANOVA). Coefficient of determination (R 2 ) was found to be 93.42%, which means that a high level of variation of MG decolorization was explained by the proposed model. Also, the value of adjusted coefficient of determination (R 2 adj ) was found to be 88.73%, which is close enough to the coefficient of determination and proves the significance of the model. The residuals plot against run number is depicted in Figure 6. According to this figure, residuals are distributed unevenly between experiments, confirming the reliability of obtained model [60]. Results of ANOVA analysis are tabulated in Table 3. The F-value of the model was 19.89, showing that proposed model was highly significant, which is double confirmed by the low P-value of 0.001. In order to study the effects of exposure time and plasma pressure, significance test of quadratic equation constants was performed and presented in Table 4. High F-value of 9.250 and P-value of 0.000 for B 2 term, which corresponds for plasma pressure, proves that pressure plays the main role in the decolorization efficiency of our plasma-treated photocatalyst.  Table 3. Analysis of variances for photocatalytic MG decolorization using plasma-treated immobilized TiO2 photocatalyst.  Figure 7 depicts a visual presentation of the correlation of the decolorization efficiency to plasma exposure time and pressure. Increase of plasma operation pressure led to higher decolorization percentage, while increase of plasma exposure time influenced the decolorization negatively. Operation pressure of the plasma treatment is inversely proportional to the plasma sheath thickness. The plasma sheath thickness is directly proportional to the velocity of Ar particles and the electrical field. Therefore, decrease of the pressure increases the thickness of the plasma sheath, which subsequently enhances the velocity and the electrical field [61]. Increase of the electrical field induces the electrons to collide with the surface of TiO2 with more power [62], damaging the surface of the nanoparticles. Therefore, higher pressure reduces the electric field and prevents the surface from being damaged. On the other hand, higher plasma exposure time increases collision of the electrons with the surface. These collisions damage the structure of TiO2 and reduce the photocatalytic activity.    Figure 7 depicts a visual presentation of the correlation of the decolorization efficiency to plasma exposure time and pressure. Increase of plasma operation pressure led to higher decolorization percentage, while increase of plasma exposure time influenced the decolorization negatively. Operation pressure of the plasma treatment is inversely proportional to the plasma sheath thickness. The plasma sheath thickness is directly proportional to the velocity of Ar particles and the electrical field. Therefore, decrease of the pressure increases the thickness of the plasma sheath, which subsequently enhances the velocity and the electrical field [61]. Increase of the electrical field induces the electrons to collide with the surface of TiO 2 with more power [62], damaging the surface of the nanoparticles. Therefore, higher pressure reduces the electric field and prevents the surface from being damaged. On the other hand, higher plasma exposure time increases collision of the electrons with the surface. These collisions damage the structure of TiO 2 and reduce the photocatalytic activity. Optimal operating conditions of the cold plasma treatment were predicted to be 21.7 min and 0.78 Torr for plasma exposure time and pressure, respectively. MG decolorization efficiency after 30 min was predicted to be 94.62% at these conditions, which is in a good agreement with the obtained experimental value of 94.94%. As expected, the optimized decolorization efficiency is higher than the decolorization percentage at any random conditions. For instance, the photocatalyst treated with Ar plasma for 50 min at a pressure of 0.22 Torr eliminates 69.03% MG solution after 30 min, which is very lower than the optimal decolorization efficiency of 94.94%. Figure 8 compares MG decolorization efficiency of the Ar-TiO2 sample, treated at the optimum plasma treatment conditions, with that of I-TiO2 photocatalyst and UV/H2O2 process in the absence of titanium dioxide. After 160 min of UVA irradiation in the presence of hydrogen peroxide, the decolorization efficiency reached 21%, which was boosted to 98% by the addition of TiO2immobilized (I-TiO2) glass plate. MG elimination using the optimized Ar-TiO2 sample reached 98% after 40 minutes, while I-TiO2 needed 160 min to achieve the same decolorization percentage. Kinetics of the MG decolorization can be expressed using the pseudo first order kinetic model [57]:

Decolorization Efficiency of Treated Catalyst vs Non-Treated Catalyst
where rdye, kobs and Cdye are decolorization rate, rate constant and dye concentration, respectively. Pseudo first order kinetic rate constant was 0.0972 min −1 for the optimized Ar-TiO2 (R 2 = 99.28%), which is 4.28 times greater than the rate constant (kobs = 0.0227 min −1 ) of the I-TiO2 photocatalyst (R 2 = 99.64%). Optimal operating conditions of the cold plasma treatment were predicted to be 21.7 min and 0.78 Torr for plasma exposure time and pressure, respectively. MG decolorization efficiency after 30 min was predicted to be 94.62% at these conditions, which is in a good agreement with the obtained experimental value of 94.94%. As expected, the optimized decolorization efficiency is higher than the decolorization percentage at any random conditions. For instance, the photocatalyst treated with Ar plasma for 50 min at a pressure of 0.22 Torr eliminates 69.03% MG solution after 30 min, which is very lower than the optimal decolorization efficiency of 94.94%. Figure 8 compares MG decolorization efficiency of the Ar-TiO 2 sample, treated at the optimum plasma treatment conditions, with that of I-TiO 2 photocatalyst and UV/H 2 O 2 process in the absence of titanium dioxide. After 160 min of UVA irradiation in the presence of hydrogen peroxide, the decolorization efficiency reached 21%, which was boosted to 98% by the addition of TiO 2 -immobilized (I-TiO 2 ) glass plate. MG elimination using the optimized Ar-TiO 2 sample reached 98% after 40 min, while I-TiO 2 needed 160 min to achieve the same decolorization percentage. Kinetics of the MG decolorization can be expressed using the pseudo first order kinetic model [57]:

Decolorization Efficiency of Treated Catalyst vs. Non-Treated Catalyst
where r dye , k obs and C dye are decolorization rate, rate constant and dye concentration, respectively. Pseudo first order kinetic rate constant was 0.0972 min −1 for the optimized Ar-TiO 2 (R 2 = 99.28%), which is 4.28 times greater than the rate constant (k obs = 0.0227 min −1 ) of the I-TiO 2 photocatalyst (R 2 = 99.64%). In order to study the effect of initial concentration of MG on the decolorization efficiency, additional experiments were performed at various concentrations of MG (Figure 9). Decolorization efficiencies of 5, 10, 15 and 20 mg/L initial dye concentrations were about 98% at different irradiation times of 30, 40, 60 and 85 min, respectively. It is clear from Figure 10 that after 30 min, the decolorization efficiency decreased from 98.7% to 72.1% with increasing dye concentration from 5 to 20 mg/L. Increase in MG concentration, decreases the ratio of available hydroxyl radicals to dye molecules, which results in a decreased degradation percentage. Another possible reason for this behavior is that at higher dye concentrations more organic pollutants are adsorbed on TiO2 surface; a large number of dye molecules shield the UV light, while fewer photons reach the TiO2 surface and fewer hydroxyl radicals are formed. Consequently, the photocatalytic degradation is decreased [63,64]. To demonstrate the catalytic activity of surface modified photocatalyst in decolorization of other dyestuff, treated and unmodified photocatalysts were used to decolorize the crystal violet (CV). The In order to study the effect of initial concentration of MG on the decolorization efficiency, additional experiments were performed at various concentrations of MG ( Figure 9). Decolorization efficiencies of 5, 10, 15 and 20 mg/L initial dye concentrations were about 98% at different irradiation times of 30, 40, 60 and 85 min, respectively. It is clear from Figure 10 that after 30 min, the decolorization efficiency decreased from 98.7% to 72.1% with increasing dye concentration from 5 to 20 mg/L. Increase in MG concentration, decreases the ratio of available hydroxyl radicals to dye molecules, which results in a decreased degradation percentage. Another possible reason for this behavior is that at higher dye concentrations more organic pollutants are adsorbed on TiO 2 surface; a large number of dye molecules shield the UV light, while fewer photons reach the TiO 2 surface and fewer hydroxyl radicals are formed. Consequently, the photocatalytic degradation is decreased [63,64]. In order to study the effect of initial concentration of MG on the decolorization efficiency, additional experiments were performed at various concentrations of MG ( Figure 9). Decolorization efficiencies of 5, 10, 15 and 20 mg/L initial dye concentrations were about 98% at different irradiation times of 30, 40, 60 and 85 min, respectively. It is clear from Figure 10 that after 30 min, the decolorization efficiency decreased from 98.7% to 72.1% with increasing dye concentration from 5 to 20 mg/L. Increase in MG concentration, decreases the ratio of available hydroxyl radicals to dye molecules, which results in a decreased degradation percentage. Another possible reason for this behavior is that at higher dye concentrations more organic pollutants are adsorbed on TiO2 surface; a large number of dye molecules shield the UV light, while fewer photons reach the TiO2 surface and fewer hydroxyl radicals are formed. Consequently, the photocatalytic degradation is decreased [63,64]. To demonstrate the catalytic activity of surface modified photocatalyst in decolorization of other dyestuff, treated and unmodified photocatalysts were used to decolorize the crystal violet (CV). The To demonstrate the catalytic activity of surface modified photocatalyst in decolorization of other dyestuff, treated and unmodified photocatalysts were used to decolorize the crystal violet (CV).
The experiments were performed at fixed initial dye concentration of 10 mg/L and H 2 O 2 concentration of 13 mM (similar to the MG decolorization conditions). Figure 10 demonstrates that the decomposition of CV in the presence of the optimized Ar-TiO 2 sample reached 98% within 100 min, while the decolorization with the I-TiO 2 photocatalyst needed about 190 min to reach the same decolorization percentage. A pseudo first order kinetic rate constant of 0.0429 min −1 was obtained for the treated photocatalyst (R 2 = 98.65%), which is 2.03 times higher than the rate constant (k obs = 0.0211 min −1 ) of the non-treated photocatalyst (R 2 = 99.95%).
experiments were performed at fixed initial dye concentration of 10 mg/L and H2O2 concentration of 13 mM (similar to the MG decolorization conditions). Figure 10 demonstrates that the decomposition of CV in the presence of the optimized Ar-TiO2 sample reached 98% within 100 min, while the decolorization with the I-TiO2 photocatalyst needed about 190 min to reach the same decolorization percentage. A pseudo first order kinetic rate constant of 0.0429 min −1 was obtained for the treated photocatalyst (R 2 = 98.65%), which is 2.03 times higher than the rate constant (kobs = 0.0211 min −1 ) of the non-treated photocatalyst (R 2 = 99.95%). The superior performance of the Ar-TiO2 catalyst can be explained using the differences in characteristics of the treated and non-treated catalysts. Interaction of plasma with titanium dioxide is a complicated process due to the presence of ions, photons, radicals and electrons in various excited energy levels. Applying electrical current to the electrodes in the plasma chamber ionizes the argon gas molecules to electrons and positive ions (Equation (4)) [56]. Electrons can subsequently participate in a reaction with titanium dioxide (Equation (5)), generating oxygen vacancy on the surface of the catalyst [58].
The results presented in Section 3.1. showed that Ar plasma treatment did not alter the crystalline phase of rutile TiO2 nanoparticles, which is the most thermodynamically stable phase of natural titania. The UV-DRS analyses showed that the band gap energy also remained almost unchanged and only decreased by a small margin. However, XPS analyses demonstrated an increase in Ti 3+ molar ratio and a decline of oxygen to titanium ratio, which resulted in oxygen and titanium defects on the surface of the catalyst. Surface oxygen vacancies can act as active sites and enhance activity of the titanium dioxide as photocatalyst [30,59]. Furthermore, the observed increase of surface hydroxyl group aids the formation of hydroxyl radicals, increasing the degradation rate of organic pollutants [65].
Pan et al. [59] have found that adsorption of oxygen molecule on perfect neutral titanium dioxide surface is not possible. They have reported that oxygen is adsorbed only on a surface with excess negative charge or when there is oxygen vacancy. Due to the existence of oxygen vacancies, adsorbed O2 and H2O molecules capture photo-generated electrons and improve charge transportation. This The superior performance of the Ar-TiO 2 catalyst can be explained using the differences in characteristics of the treated and non-treated catalysts. Interaction of plasma with titanium dioxide is a complicated process due to the presence of ions, photons, radicals and electrons in various excited energy levels. Applying electrical current to the electrodes in the plasma chamber ionizes the argon gas molecules to electrons and positive ions (Equation (4)) [56]. Electrons can subsequently participate in a reaction with titanium dioxide (Equation (5)), generating oxygen vacancy on the surface of the catalyst [58].
Ti 4+ : 1s 2 /2s 2 2p 6 /3s 2 3p 6 /4s 0 3d 0 4p 0 + e − → Ti 3+ : 1s 2 /2s 2 2p 6 /3s 2 3p 6 /4s 1 3d 0 4p 0 The results presented in Section 3.1. showed that Ar plasma treatment did not alter the crystalline phase of rutile TiO 2 nanoparticles, which is the most thermodynamically stable phase of natural titania. The UV-DRS analyses showed that the band gap energy also remained almost unchanged and only decreased by a small margin. However, XPS analyses demonstrated an increase in Ti 3+ molar ratio and a decline of oxygen to titanium ratio, which resulted in oxygen and titanium defects on the surface of the catalyst. Surface oxygen vacancies can act as active sites and enhance activity of the titanium dioxide as photocatalyst [30,59]. Furthermore, the observed increase of surface hydroxyl group aids the formation of hydroxyl radicals, increasing the degradation rate of organic pollutants [65].
Pan et al. [59] have found that adsorption of oxygen molecule on perfect neutral titanium dioxide surface is not possible. They have reported that oxygen is adsorbed only on a surface with excess negative charge or when there is oxygen vacancy. Due to the existence of oxygen vacancies, adsorbed O 2 and H 2 O molecules capture photo-generated electrons and improve charge transportation. This generates highly reactive species such as superoxide radical anions (O − 2 ) and hydroxyl radicals [60] which subsequently decolorize the solutions by oxidizing dye molecules.
Another reason for increased performance of the plasma-treated samples may be related to increased surface area of the optimized Ar-TiO 2 sample. Khataee et al. reported change in the physical surface structure of Ar cold plasma-treated pyrite [61,62]. As it was shown in Figure 3, Ar plasma-treated surface poses cracks over the surface. This phenomenon may result in an increase in effective surface available for photocatalytic reactions, improving its overall performance.

Reusability of Plasma-Modified Catalyst
Another important factor in determination of performance of the catalyst is its ability to maintain its reaction efficiency over time. In order to evaluate the reusability of Ar-TiO 2 sample, a single glass plate with immobilized plasma-modified rutile TiO 2 was utilized in UV/TiO 2 /H 2 O 2 process to decolorize a 10 mg/L MG solution for 8 cycles of 40 min. After each cycle, the Ar-TiO 2 sample was thoroughly rinsed with deionized water and dried in an oven at a temperature of 70 • C. Figure 11 demonstrates the reusability results after 8 consecutive cycles. generates highly reactive species such as superoxide radical anions (O ) and hydroxyl radicals [60] which subsequently decolorize the solutions by oxidizing dye molecules. Another reason for increased performance of the plasma-treated samples may be related to increased surface area of the optimized Ar-TiO2 sample. Khataee et al. reported change in the physical surface structure of Ar cold plasma-treated pyrite [61,62]. As it was shown in Figure 3, Ar plasmatreated surface poses cracks over the surface. This phenomenon may result in an increase in effective surface available for photocatalytic reactions, improving its overall performance.

Reusability of Plasma-Modified Catalyst
Another important factor in determination of performance of the catalyst is its ability to maintain its reaction efficiency over time. In order to evaluate the reusability of Ar-TiO2 sample, a single glass plate with immobilized plasma-modified rutile TiO2 was utilized in UV/TiO2/H2O2 process to decolorize a 10 mg/L MG solution for 8 cycles of 40 min. After each cycle, the Ar-TiO2 sample was thoroughly rinsed with deionized water and dried in an oven at a temperature of 70 °C. Figure 11 demonstrates the reusability results after 8 consecutive cycles. The results showed that decolorization efficiency dropped from 97.85% after 40 min of operation in the first run to 91.19% after eight consecutive runs. The relative performance of the catalyst was 93.19% after a total of 320 min photocatalytic decolorization process. Therefore, Ar-TiO2 photocatalyst was able to maintain a high performance level in a long run and its reusability results were promising.

Materials
TiO2 nanoparticles (rutile phase, 99.9%, 30 nm) were purchased from US Research Nanomaterials Co. (Houston, TX, USA) Malachite green oxalate and crystal violet were obtained from Sigma Aldrich (St. Louis, MO, USA). H2O2 (30-35%) and NaOH were supplied from Mojallali Co. Ltd. (Tehran, Iran). HCl (37%) was purchased from Merck (Darmstadt, Germany). All solutions were prepared with distilled water. The results showed that decolorization efficiency dropped from 97.85% after 40 min of operation in the first run to 91.19% after eight consecutive runs. The relative performance of the catalyst was 93.19% after a total of 320 min photocatalytic decolorization process. Therefore, Ar-TiO 2 photocatalyst was able to maintain a high performance level in a long run and its reusability results were promising.  (30-35%) and NaOH were supplied from Mojallali Co. Ltd. (Tehran, Iran). HCl (37%) was purchased from Merck (Darmstadt, Germany). All solutions were prepared with distilled water.

Apparatus
A 6 W UV-A lamp (F6T5, Hitachi, Tokyo, Japan) provided the irradiation. A UV-vis spectrophotometer (1700 UV-vis Shimadzu, Kyoto, Japan) was used to determine dye concentration. Scanning electron microscopy (SEM) images and EDX analysis were carried out using MIRA3FEG-SEM (TescanBrno, Brno, Czech Republic). X-ray diffraction (XRD) analysis was performed using a D5000 system (Siemens, Berlin, Germany) equipped with a copper anode (λ = 0.15406 nm). UV-vis Diffuse Reflectance Spectra (UV-DRS) were collected using an Avaspec-2048-TEC spectrometer (Avantes, Apeldoorn, Netherlands). X-ray Photoelectron Spectroscopy (XPS) analysis was performed using a K-Alpha spectrometer (Thermo Scientific, Waltham, MA, USA) with an aluminum anode (Al Kα = 1468.3 eV) at an electron take-off angle of 90. The binding energy scale was calibrated by assigning the C1 s peak at 284.5 eV. A Sonoplus ultrasonic homogenizer (Sonic 6D, James Products, Inc., Northampton, England) was applied for sonication. pH value of the solutions was measured with a PHT-110 pH-meter (Labtron, Tehran, Iran).

Immobilization of TiO 2 and Plasma Treatment
The heat attachment method was used to immobilize TiO 2 nanoparticles on glass plates. Surface of glass plates was modified with hydroxyl groups by soaking in NaOH solution (1N) for 2 h. Then, 0.5 g of rutile TiO 2 nanoparticles was suspended in 50 mL of distilled water. The desired amount of HCl (1N) was injected into the solution to obtain a pH value of 3. After 30 min of sonication, the solution was poured onto glass plates and allowed to dry at 80 • C. Finally, the plates were washed with distilled water and put at 480 • C for 5 h to complete the heat attachment process. This sample is called I-TiO 2 in this paper.
To modify the surface of rutile TiO 2 nanoparticles immobilized on glass plates, cold plasma in Argon atmosphere was implemented. Schematic of the plasma treatment setup is shown in Figure 12. The chamber of plasma reactor is made of Pyrex tube sealed with two aluminum bonnets on both sides. Rotary and molecular pumps were used to reach low pressures. The plasma reactor was flushed several times with Argon gas to remove any impurities in the chamber. The flow of gas was adjusted with a mass flow controller and alternative current (AC) was applied to aluminum electrode to generate cold plasma. The plasma-modified sample is referred to as Ar-TiO 2 in this paper.

Apparatus
A 6 W UV-A lamp (F6T5, Hitachi, Tokyo, Japan) provided the irradiation. A UV-vis spectrophotometer (1700 UV-vis Shimadzu, Kyoto, Japan) was used to determine dye concentration. Scanning electron microscopy (SEM) images and EDX analysis were carried out using MIRA3FEG-SEM (TescanBrno, Brno, , Czech Republic). X-ray diffraction (XRD) analysis was performed using a D5000 system (Siemens, Berlin, Germany) equipped with a copper anode (λ = 0.15406 nm). UV-vis Diffuse Reflectance Spectra (UV-DRS) were collected using an Avaspec-2048-TEC spectrometer (Avantes, Apeldoorn, Netherlands). X-ray Photoelectron Spectroscopy (XPS) analysis was performed using a K-Alpha spectrometer (Thermo Scientific, Waltham, MA, USA) with an aluminum anode (Al Kα = 1468.3 eV) at an electron take-off angle of 90. The binding energy scale was calibrated by assigning the C1 s peak at 284.5 eV. A Sonoplus ultrasonic homogenizer (Sonic 6D, James Products, Inc., Northampton, England) was applied for sonication. pH value of the solutions was measured with a PHT-110 pH-meter (Labtron, Tehran, Iran).

Immobilization of TiO2 and Plasma Treatment
The heat attachment method was used to immobilize TiO2 nanoparticles on glass plates. Surface of glass plates was modified with hydroxyl groups by soaking in NaOH solution (1N) for 2 h. Then, 0.5 g of rutile TiO2 nanoparticles was suspended in 50 mL of distilled water. The desired amount of HCl (1N) was injected into the solution to obtain a pH value of 3. After 30 min of sonication, the solution was poured onto glass plates and allowed to dry at 80 °C. Finally, the plates were washed with distilled water and put at 480 °C for 5 h to complete the heat attachment process. This sample is called I-TiO2 in this paper.
To modify the surface of rutile TiO2 nanoparticles immobilized on glass plates, cold plasma in Argon atmosphere was implemented. Schematic of the plasma treatment setup is shown in Figure  12. The chamber of plasma reactor is made of Pyrex tube sealed with two aluminum bonnets on both sides. Rotary and molecular pumps were used to reach low pressures. The plasma reactor was flushed several times with Argon gas to remove any impurities in the chamber. The flow of gas was adjusted with a mass flow controller and alternative current (AC) was applied to aluminum electrode to generate cold plasma. The plasma-modified sample is referred to as Ar-TiO2 in this paper.

Photocatalytic Batch Reactor
Photochemical decolorization was conducted in a rectangular batch reactor (3 cm × 3 cm × 21 cm) containing TiO 2 nanoparticles immobilized on glass plates. A glass plate (3 cm × 3 cm × 20 cm) containing 0.16 g of immobilized rutile TiO 2 nanoparticles was placed at the bottom of the reactor for each experiment. The UV lamp was placed at the top of the reactor to provide irradiation. The batch reactor was filled with 100 mL of dye solution (10 mg/L) and H 2 O 2 (13 mM) was injected into the dye solution at the beginning of each experiment. This specific concentration of H 2 O 2 was determined by performing preliminary MG decolorization experiments to maximize the efficiency of the process at a MG concentration of 10 mg/L and various H 2 O 2 concentrations from 5 to 15 mM was examined. Decolorization process was carried out in a shaker incubator at 25 • C and a rotation speed of 10 rpm. Dye concentration was monitored by a UV spectrophotometer at the maximum wavelength of 618 nm and 595 nm for Malachite green and Crystal violet, respectively. Decolorization percentage was calculated using the following equation (Equation (6)) [66]: where C 0 and C t are the concentrations of the sample solution at times 0 and t, respectively.

Response Surface Methodology and Experimental Design
Experimental design and optimization were carried out using response surface methodology by the aid of Minitab 16.2 software (Minitab Inc., State College, PA, USA). Each independent variable was coded as 'X i ' using the following equation (Equation (7)): where X i is the coded value, x 0 denotes the value of x i at the center point and δx is the step change value. The plasma exposure time (X 1 ) and pressure (X 2 ) are the critical factors in preparing the plasma-treated photocatalyst. Optimization of these factors will increase the efficiency of the photocatalyst and maximize the decolorization. The decolorization percentage after 30 min of reaction in presence of H 2 O 2 (13 mM) was chosen as the response (i.e., dependent variable). Each codified variable was studied at five levels (−1.41, −1, 0, 1, +1.41). Table 5 shows levels and values of coded variables. Ar glow discharge plasma formed in pressures below 0.8 Torr (1 Torr = 133.32 Pa), therefore the upper limit for plasma pressure was set to be 0.78 Torr in our design. A second order polynomial Equation (8) was employed to correlate the response to the independent variables X 1 and X 2 : where Y is the predicted response, B 0 is the interception term, B i are the linear coefficients, B ii are the quadratic coefficients, B ij are the interaction coefficients, X i are the coded variables and n is the number of independent variables.

Conclusions
In this study, the cold plasma treatment was applied to modify the surface properties of immobilized rutile TiO 2 nano particles on the glass plates. A five-level central composite design was employed to model and optimize the photocatalytic decolorization efficiency by considering the plasma exposure time and pressure as the independent variables, and the decolorization efficiency as the dependent variable using response surface methodology. Results showed that optimizing plasma pressure and exposure time (parameters that are usually overlooked) had significant effect on enhancing activity of the photocatalyst. Plasma pressure was found to be the most important parameter to adjust, and its increase, enhanced decolorization efficiency. On the other hand, increase of plasma exposure time decreased the decolorization efficiency. The optimum values of the exposure time and pressure of plasma treatment process were 21.7 min and 0.78 Torr, respectively. The plasma treatment decreased the oxygen to titanium ratio and created oxygen vacancy on the surface of the catalyst. As a result, the plasma-treated catalyst showed superior performance than the non-treated catalyst in decolorization of the aqueous solutions of Malachite green and Crystal violet. It can be concluded that cold plasma is an effective method for enhancing the photocatalytic performance of rutile titanium dioxide without addition of any impurities. The Ar plasma-modified rutile phase maintained its low band gap energy, making it a better competitor for anatase titanium dioxide in visible light operations.