Table of Contents Author Guidelines Submit a Manuscript
Journal of Chemistry
Volume 2018, Article ID 9365147, 10 pages
https://doi.org/10.1155/2018/9365147
Research Article

Enhanced Photodecomposition of Methylene Blue in Water with Sr1−xKxTiO3−δ@PC-polyHIPEs under UV and Visible Light

1School of Environmental Science and Engineering, Taiyuan University of Technology, Taiyuan 030024, China
2Polymers Research Group, Institute for Frontier Materials, Deakin University, Locked Bag 20000, Geelong, VIC 3220, Australia

Correspondence should be addressed to Lizhen Gao; nc.ude.tuyt@nehziloag

Received 1 August 2017; Revised 26 December 2017; Accepted 24 January 2018; Published 17 April 2018

Academic Editor: Darren Sun

Copyright © 2018 Yonghua Gao 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

Photocatalytic method was investigated to remove water pollutant methylene blue (MB) produced in textile, plastic, and dye industries. PC-polyHIPEs were prepared by light-induced polymerization of dopamine in transparent polyHIPEs which were synthesized by polymerization within high internal phase emulsions. ( = 0–0.5) nanoparticles were incorporated and adhered to PC-polyHIPEs to form @PC-polyHIPEs for the first time. The catalysts were characterized by XRD, FTIR, TGA, UV-Vis DRS, and SEM and their photocatalytic properties for MB decomposition were measured over UV-Vis spectrometer. The PC-polyHIPEs were of interconnected porous structure with around 100 μm pores and 30 μm windows. Sr1−xKxTiO3−δ@PC-polyHIPEs showed excellent MB decomposition activity under either UV or visible light although Sr1−xKxTiO3−δ alone worked only under UV light. When = 0.3, Sr1−xKxTiO3−δ@PC-polyHIPEs showed the highest photocatalytic performance due to the existence of more oxygen vacancies. When the water solution with 50 mg L−1 MB and 1.6  L−1 Sr0.7K0.3TiO3−δ@PC-polyHIPEs was exposed to visible light for 160 min at room temperature, 88.3% of MB was decomposed. After being used for eight cycles, 87.6% activity of fresh Sr0.7K0.3TiO3−δ@PC-polyHIPEs still remained. The influences of salinity, temperature, and catalyst concentration on the catalytic activity were studied. For MB decomposition under visible light, the activation energy of Sr0.7K0.3TiO3−δ@PC-polyHIPEs was calculated to be 12.3 kJ mol−1 and the kinetics analysis revealed that the photocatalysis followed the second-order reaction. These findings demonstrated that Sr1−xKxTiO3−δ@PC-polyHIPEs were an effective candidate for real application in decomposition of MB in water.

1. Introduction

Methylene blue (MB) dye is produced as a water pollutant from textiles, cosmetics, printing, dyeing, food processing, and paper-making industries [1, 2]. Discharge of this colored effluent presents a major environmental problem for developing countries because of its toxic and carcinogenic effects on living beings [1]. There are several technologies adopted to remove MB in water like biological degradation, adsorption, Fenton’s reagent method, coagulation processes, photocatalytic decomposition, and so on [3]. Among these, photocatalytic method to degrade these pollutants is the most desirable as no second pollutants are generated in this process [4]. SrTiO3 has been an attractive catalyst for organics degradation under UV light [58]. However, there are some disadvantages hindering its real application, such as easy precipitation and agglomeration [9], low photocatalytic efficiency under visible light [1012], and the difficulty of collection and separation [13]. To overcome such disadvantages, incorporation of SrTiO3 into a catalyst support and substitution of potassium ion (K+) for part of Sr2+ in SrTiO3 to generate oxygen vacancy (Sr1−xKxTiO3−δ) may favour the improvement of its photocatalytic activity.

Up to now, different kinds of inorganic porous catalyst supports have been reported [14], but little porous polymer catalyst support has been used. Compared to inorganic supports, polymer owns the following advantages and is more suitable for water treatment: low density, big pores, inertia to acids and bases, flexibility, low cost, and high viscosity [1518]. Polydopamine coated polyHIPEs (PC-polyHIPEs) are a type of macroporous polymer, which has been confirmed to be an excellent catalyst support and has large attachment to inorganic catalyst particles. It is synthesized by light inducing polymerization of dopamine in transparent polyHIPEs obtained via polymerization within high internal phase emulsions (HIPEs) [1923]. The transparent substrate and macropores facilitate the adsorption of light, the mass transfer of substances like gases or liquids, and the host-guest interactions [24].

In this paper, with incorporation of Sr1−xKxTiO3−δ nanoparticles into PC-polyHIPEs, we obtained an efficient and durable material for photodecomposition of MB in model wastewater under visible light.

2. Experimental

2.1. Materials

Chemicals Ti(OBu)4, Sr(NO3)2·6H2O, KNO3, ethanol, ethylene glycol, anhydrous acetic acid, butyl acrylate, ethylene glycol dimethacrylate, sulfonated polystyrene, 2-hydroxy-2-methylpropiophenone, dopamine, and glycerol were purchased from Sigma-Aldrich.

2.2. Preparation of PC-polyHIPEs

PC-polyHIPEs were prepared according to the method described in our previous paper [22]. In a word, it was obtained by light inducing polymerization of dopamine in transparent polyHIPEs which was made via polymerization within high internal phase emulsions.

2.3. Preparation of Sr1−xKxTiO3−δ Nanoparticles

Sr1−xKxTiO3−δ nanoparticles were prepared by means of sol-gel. Typically, 1 mL of Ti(OBu)4 was mixed with 3 mL of ethanol and 0.3 mL of anhydrous acetic acid to form a titanium precursor solution. Sr(NO3)2 and KNO3 aqueous solution (1 M) were added dropwise to the as-prepared titanium precursor solution with the expected stoichiometry at room temperature. The resulting solution was stirred to turn into milky sol and finally transformed to gel. Afterwards, the wet gel was dried at 120°C overnight, and then the foamy solid was heated to 200°C in air in a tube furnace at a rate of 5°C min−1 to remove the organic ligands. Successively, the precursor was heated to 450°C and kept for 3 h to decompose the nitrates and calcined at 850°C for 4 h in air. Finally, it was ground to obtain Sr1−xKxTiO3−δ nanoparticles.

2.4. Preparation of Sr1−xKxTiO3−δ@PC-polyHIPEs

The photocatalyst Sr1−xKxTiO3−δ@PC-polyHIPEs was fabricated by chemical impregnation method [25]. In short, 100 mg of Sr1−xKxTiO3−δ nanoparticles was dispersed into 500 mL of mixed solvents (ethylene glycol : ethanol = 7 : 3, ) under sonication for 1 h, and then 80 mg of PC-polyHIPEs was immersed into the as-obtained solution. After 24 h, the as-formed Sr1−xKxTiO3−δ@PC-polyHIPEs were collected and washed repeatedly followed by drying at 110°C for 12 h. The dried Sr1−xKxTiO3−δ@PC-polyHIPEs were then centrifuged in water with 7000 rpm to make sure that only the stabilized imbedded Sr1−xKxTiO3−δ remained onto the PC-polyHIPEs.

2.5. Characterization

X-ray diffraction test was recorded on X’pert Powder diffractometer (XRD, PANalytical Company, Holland), using Cu ( = 0.1541 nm) radiation at 40 kV and 30 mA with a step scan of 0.065°. The Fourier transform infrared (FTIR) spectra were carried out on a Bruker Vertex 70 FTIR spectrometer from 4000 to 600 cm−1 with a resolution of 4 cm−1. The morphologies were observed with scanning electron microscopy (SEM, JSM-7800F, JEOL) at 3 kV. The Brunauer-Emmett-Teller (BET) specific surface area, pore volume, and pore width were operated on BET Tristar 3000 analyzer (Micromeritics, United States). TGA analyzer (Q50, TA instrument) was used to measure the weight loss and differential TG curves of the samples. Each time, about 5 mg of the sample was loaded in the platinum crucible and heated in air from room temperature to 800°C at a heating rate of 10°C min−1. The UV-Vis diffuse reflection spectroscopy (UV-Vis DRS) of samples was measured with a UV-Visible system (Agilent Varian Cary 100) equipped with a labsphere diffuse reflectance accessory.

2.6. Photocatalytic Activity Evaluation

The photocatalytic activities of Sr1−xKxTiO3−δ nanoparticles and Sr1−xKxTiO3−δ@PC-polyHIPEs were evaluated by decomposition of MB. In each run, Sr1−xKxTiO3−δ nanoparticles or Sr1−xKxTiO3−δ@PC-polyHIPEs were, respectively, dispersed into 100 mL MB aqueous solutions and then kept at dark for 2 h to establish the adsorption-desorption equilibrium. The initial concentration of MB was recorded after the equilibrium was established. Then all the experiments were conducted at room temperature with pH = 7 at various irradiation time under UV or visible light with an initial MB concentration of 50 mg L−1. The photocatalytic process was made over a homemade light exposure system under UV at wavelength of 365 nm or visible light at 450 nm. The average light intensity is 3.0 mW cm−2. The photocatalytic activity was obtained by measuring the concentration of MB solution recorded on a UV-Vis spectrometer (Cary 3 UV-Visible, Agilent, United States) at = 664 nm. Before MB concentration measurement, for Sr1−xKxTiO3−δ@PC-polyHIPEs, the sponge-like catalyst was readily removed, while, for Sr1−xKxTiO3−δ catalyst, the nanoparticle suspension solution was centrifuged at 7000 rpm for 30 min to precipitate the particles to make sure the measurement is accurate. The MB degradation efficiency ( can be calculated with the following:

In the equation, and correspond to the initial concentration and the concentration of MB at time , respectively. For comparison, the amount of Sr1−xKxTiO3−δ was kept the same in Sr1−xKxTiO3−δ and Sr1−xKxTiO3−δ@PC-polyHIPEs catalysts during the test (the loading concentration of Sr1−xKxTiO3−δ would be confirmed by TGA).

3. Results and Discussion

3.1. Characterization of Sr1−xKxTiO3−δ

The XRD patterns of Sr1−xKxTiO3−δ are presented in Figure 1. All the main diffraction peaks can be readily assigned to the cubic perovskite structure of SrTiO3 (JCPDS 35-0734), demonstrating that the perovskite structure is still well maintained after K+ substitution. When ≥ 0.3, there are some weak diffraction peaks appearing at 2 = 30.23°, 44.60°, and 47.63° which are corresponding to TiO2 lattice diffraction. Furthermore, the perovskite structure diffraction peaks correspond to the lattice faces of (110), (111), (200), (211), (220), and (310) which turn to be much sharper (Figure 1(a)). The patterns shown in Figure 1(b) demonstrated that the lattice faces of (110) and (111) turn to be higher with increasing K-doping amount, suggesting that becomes smaller with the K-doping. Figure 2 illustrates SEM morphologies of PC-polyHIPEs, Sr0.7K0.3TiO3−δ, and Sr0.7K0.3TiO3−δ@PC-polyHIPEs. Figure 2(a) shows that PC-polyHIPEs has a well-developed interconnected macroporous structure, with smaller holes embedded in larger holes. It can be clearly observed that the PC-polyHIPEs owns ca. 100 μm pores and 30 μm windows as shown in the magnified micrograph of PC-polyHIPEs in Figure 2(b). Such kind of stable regular large scaled porous structure of PC-polyHIPEs is hard to be obtained for inorganic catalyst supports. Figure 2(c) indicates that when Sr0.7K0.3TiO3−δ nanoparticles are incorporated, the interconnected macroporous structure of PC-polyHIPEs is well preserved. The higher magnification micrograph demonstrated in Figure 2(d) confirms that well-defined cubic nanoparticles structure has been successfully incorporated into the PC-polyHIPEs. The average size of these cubic primary particles is 100 nm. However, some smaller nanoparticles with diameter about 10 nm coexist. Moreover, these nanoparticles are dispersed evenly without aggregation, which indicates Sr0.7K0.3TiO3−δ has strongly adhered to PC-polyHIPEs. The strong adherence between PC-polyHIPEs and Sr0.7K0.3TiO3−δ nanoparticles ensures the durability of catalyst when reacting with organic compounds in water. These results demonstrate that the high viscosity of PC-polyHIPEs plays an important role in producing an inorganic/polymer composite porous catalyst.

Figure 1: XRD patterns of the as-synthesized Sr1−xKxTiO3−δ.
Figure 2: SEM micrographs of (a) PC-polyHIPEs; (b) enlarged PC-polyHIPEs; (c) Sr0.7K0.3TiO3−δ@PC-polyHIPEs; (d) Sr0.7K0.3TiO3−δ. The long red arrow in Figure 2(b) shows that the PC-polyHIPEs own ca. 100 μm pores and the short red arrow shows that the PC-polyHIPEs own ca. 30 μm windows.

The formation of the hybrid Sr1−xKxTiO3−δ@PC-polyHIPEs catalyst is confirmed by FTIR. The spectra of Sr1−xKxTiO3−δ@PC-polyHIPEs, PC-polyHIPEs, and SrTiO3 are displayed in Figure 3. Pure SrTiO3 has an obvious peak at 1433 cm−1. PC-polyHIPEs showed three distinct peaks at 2962, 1726, and 1159 cm−1. Characteristic peaks appeared at 1433, 2962, 1726, and 1159 cm−1 in Sr1−xKxTiO3−δ@PC-polyHIPEs, indicating that potassium is successfully incorporated into SrTiO3 and is adhered to PC-polyHIPEs.

Figure 3: Ftir spectra of Sr1−xKxTiO3−δ@PC-polyHIPEs and PC-polyHIPEs.

The BET specific surface areas (SSA) of the Sr1−xKxTiO3−δ photocatalyst after K-doping are shown in Table 1. It can be seen that all the nanocatalysts Sr1−xKxTiO3−δ have larger SSA after calcination at 850°C. With the increasing amount of K-doping, the SSA of Sr1−xKxTiO3−δ gradually increases, and the nanocubic Sr0.7K0.3TiO3−δ has the largest SSA of 31.09 m2 g−1. However, when the amount of K substitution exceeds 30%, the SSA of the catalyst Sr1−xKxTiO3−δ decreases gradually. The SSA of Sr0.6K0.4TiO3−δ and Sr0.5K0.5TiO3−δ is 28.16 and 25.24 m2 g−1, respectively. When the doping amount is more than 30%, two phases of perovskite structure Sr1−xKxTiO3−δ and TiO2 are formed, which may cause the SSA to decrease.

Table 1: Specific surface areas of STi samples.

Taking Sr0.7K0.3TiO3−δ as an example, the N2 adsorption-desorption curves of Sr0.7K0.3TiO3−δ nanoparticles and Sr0.7K0.3TiO3−δ@PC-polyHIPEs are shown in Figure 4 after cooperating with the PC-polyHIPEs.

Figure 4: N2 adsorption-desorption isotherms of Sr0.7K0.3TiO3−δ, PC-polyHIPEs, and Sr0.7K0.3TiO3−δ@PC-polyHIPEs.

According to IUPAC classification, the N2 adsorption-desorption curves of these three samples belong to the IV-type curve with hysteresis loop. The hysteresis loop of Sr0.7K0.3TiO3−δ is located at 0.5~0.96 (), indicating that there are micropores and mesopores in Sr0.7K0.3TiO3−δ. Based on this result, the average pore width of Sr0.7K0.3TiO3−δ is 20.89 nm. And the hysteresis loop position ( = 0.96) of the support PC-polyHIPEs and the composite material Sr0.7K0.3TiO3−δ@PC-polyHIPEs are almost the same, indicating that the samples are of macroporous structure [26]. As the pores in PC-polyHIPEs are 30~100 μm in diameter, over such material, the N2 adsorption-desorption isothermal curve does not exactly reflect the pore situation. The SSA of the pure support PC-polyHIPEs is 0.113 m2 g−1. After adding Sr0.7K0.3TiO3−δ, the SSA of the composite Sr0.7K0.3TiO3−δ@PC-polyHIPEs is increased to 2.041 m2 g−1, indicating that the large surface of Sr0.7K0.3TiO3−δ is successfully incorporated into the PC-polyHIPEs.

Figure 5 shows the TG-DTG plot of the pure Sr0.7K0.3TiO3−δ nanoparticles, PC-polyHIPEs, and the composite Sr0.7K0.3TiO3−δ@PC-polyHIPEs. The weight loss of pure Sr0.7K0.3TiO3−δ (Figure 5(a)) is very tiny with 0.8 wt.% during the heating process from 20 to 800°C, suggesting that the as-fabricated Sr0.7K0.3TiO3−δ is extremely steady. By contrast, the weight loss of PC-polyHIPEs is almost 100% (Figure 5(b)), indicating the total combustion in air. The PC-polyHIPEs exhibits marked mass loss peaks at around 264°C, 369°C, and 455°C, while the composite material Sr0.7K0.3TiO3−δ@PC-polyHIPEs also has significant mass loss at the above-mentioned temperatures. After incorporating Sr0.7K0.3TiO3−δ into PC-polyHIPEs, the residual weight is 45.4 wt.%, demonstrating Sr1−xKxTiO3−δ constitutes 45.4 wt.% of Sr1−xKxTiO3−δ@PC-polyHIPEs.

Figure 5: TG-DTG curves of (a) Sr0.7K0.3TiO3-δ; (b) PC-polyHIPEs; and (c) Sr0.7K0.3TiO3−δ@PC-polyHIPEs.
3.2. The Photocatalytic Property of Sr1−xKxTiO3@PC-polyHIPEs
3.2.1. The Effect of K-Doping

The catalytic performance of Sr1−xKxTiO3−δ (x = 0~0.5) under UV light is shown in Figure 6. The catalytic performance of Sr1−xKxTiO3−δ (x = 0.1~0.5) is better than pure SrTiO3. Moreover, the catalytic activity of Sr1−xKxTiO3−δ increases with the addition of potassium till x = 0.3. The catalyst Sr0.7K0.3TiO3−δ was the best, over which the degradation rate of MB reached 42% ( = 0.58) when the UV-irradiation time was 20 min. However, when > 0.3, the photodegradation activity of Sr1−xKxTiO3−δ declined. When = 0.4, 0.5, the degradation efficiency of Sr1−xKxTiO3−δ for MB was 40% and 36%, respectively, with 20 min UV-irradiation. The photodegradation performance of all the catalysts was significantly improved with the prolongation of the irradiation time. The higher efficiency of Sr1−xKxTiO3−δ under UV light can be ascribed to oxygen vacancy generation when potassium doped onto SrTiO3.

Figure 6: Photocatalytic decomposition of MB over Sr1−xKxTiO3−δ under UV (365 nm) irradiation.

According to the results of Figure 6, the optimum K-doping amount is 30% for Sr1−xKxTiO3−δ catalysts. Therefore, we choose Sr0.7K0.3TiO3−δ catalyst and catalyst support PC-polyHIPEs to form new composite Sr0.7K0.3TiO3@PC-polyHIPEs and then study its photodecomposition activity for MB under both UV and visible light. Its photodegradation performance is shown in Figure 7. When PC-polyHIPEs are added, the new photocatalyst Sr0.7K0.3TiO3−δ@PC-polyHIPEs has a very high MB catalytic activity, and the degradation rate can be achieved about 71.9% only under 20 min UV-irradiation. In contrast, Sr0.7K0.3TiO3−δ has a degradation rate of only 42% when irradiated under UV light for 20 min, showing that the degradation efficiency of Sr0.7K0.3TiO3−δ@PC-polyHIPEs under UV light was increased by 71.4%. After incorporation, the higher efficiency of Sr0.7K0.3TiO3−δ@PC-polyHIPEs under UV light can be ascribed to a better dispersion of Sr0.7K0.3TiO3−δ onto PC-polyHIPEs, which increases the active sites of catalyst exposed to MB. Some small particles around 10 nm attached inside the pores of PC-polyHIPEs may cause quantum efficiency enhancement [27].

Figure 7: Photocatalytic properties over MB of Sr0.7K0.3TiO3−δ and Sr0.7K0.3TiO3−δ@PC-polyHIPEs under UV (365 nm) and Vis (450 nm) irradiation.

It can be observed from Figure 7 that pure Sr0.7K0.3TiO3−δ has no photocatalytic activity under visible light, so do PC-polyHIPEs. However, after incorporation, Sr0.7K0.3TiO3−δ@PC-polyHIPEs have excellent catalytic efficiency for MB degradation under visible light. The MB degradation rate can reach 56.5% after visible light irradiation for 20 min, which is impossible for pure Sr0.7K0.3TiO3−δ alone. When the aqueous suspension containing 50 mg L−1 MB and 1.6  L−1 Sr0.7K0.3TiO3−δ@PC-polyHIPEs is exposed to visible light for 160 min at room temperature, 88.3% of MB is decomposed.

To further explore the photocatalytic activity of Sr0.7K0.3TiO3−δ@PC-polyHIPEs under visible light irradiation, UV-Vis DRS spectra of Sr0.7K0.3TiO3-δ@PC-polyHIPEs and neat SrTiO3 were recorded (Figure 8). The light absorption of SrTiO3 ranges from 200 to 400 nm, confirming that it does not absorb visible light. However, the absorption of Sr0.7K0.3TiO3-δ@PC-polyHIPEs ranges from 200 to 640 nm, covering both UV and visible range. Without addition of noble metal dopants in the Sr0.7K0.3TiO3−δ perovskite, the uncommon visible light response of Sr0.7K0.3TiO3−δ@PC-polyHIPEs may be explained by the dye-sensitization or ligand-to-metal charge transfer that occurs between Sr0.7K0.3TiO3−δ nanoparticles and PC-polyHIPEs [2830].

Figure 8: UV-Vis DRS spectra of Sr0.7K0.3TiO3−δ@PC-polyHIPEs and neat SrTiO3.
3.2.2. The Effect of Catalyst Concentration

Since the catalyst concentration has a significant effect on the catalyst activity, the effect of the concentration of Sr0.7K0.3TiO3−δ@PC-polyHIPEs on the activity of photocatalytic degradation of MB is investigated. The concentration of catalyst Sr0.7K0.3TiO3−δ@PC-polyHIPEs is set as 0.4, 0.8, 1.6, and 2.4  L−1, and the light source is visible light. The experimental results show that the degradation efficiency of the catalyst Sr0.7K0.3TiO3−δ@PC-polyHIPEs increases with the increase of the catalyst concentration in the range 0.4~1.6  L−1, as the number of reactive sites increases with rising catalyst concentration [28]. However, when the catalyst concentration reaches 2.4  L−1, the degradation efficiency starts to drop.

3.2.3. The Effect of Salinity

Nowadays, a lot of waste water from dyeing has been discharged into the sea. However, the sea water is different from the freshwater resources. It has certain salinity which can affect the activity of catalyst. Therefore, the effect of salinity on the catalytic activity of the composite catalyst is investigated in order to provide a theoretical basis for further industrial applications of the catalyst. Figure 9 shows the photocatalytic degradation properties of Sr0.7K0.3TiO3−δ@PC-polyHIPEs at different salinity (: 10, 20, 40 g L−1). It can be seen that the salinity of seawater affects the degradation activity of MB at different levels under visible light compared with the deionized water. When the salinity is increased, the catalytic activity turns low. Therefore, the effect order of salinity on the degradation rate of MB over Sr0.7K0.3TiO3−δ@PC-polyHIPEs under visible light from high to low is 40 g L−1 > 20 g L−1 > 10 g L−1. It has been reported that chloride ions may combine with the photocatalyst to affect the excited electron-hole pairing, which has a hindrance effect on the photocatalytic reaction rate [31].

Figure 9: Influence of salinity over Sr0.7K0.3TiO3−δ@PC-polyHIPEs for photocatalytic decomposition MB under visible irradiation.
3.2.4. The Effect of Temperature

In actual water purification process, the water temperature between summer and winter varies. In order to explore the optimum operating conditions of Sr0.7K0.3TiO3−δ@PC-polyHIPEs, the effect of temperature (0~40°C) on the photocatalytic degradation for MB under visible light is studied and its result is shown in Figure 10. The degradation rates of Sr0.7K0.3TiO3@PC-polyHIPEs are 52.9%, 56.5%, and 59.3% at 0°C, 20°C, and 40°C, respectively, under visible light for 20 min. It can be seen that, with the increase of temperature, the photocatalytic degradation rate is increasing. This is due to the fact that the effective collisions between Sr0.7K0.3TiO3−δ@PC-polyHIPEs and MB are enhanced as the molecules become more active at a higher temperature.

Figure 10: Influence of temperature over Sr0.7K0.3TiO3@PC-polyHIPEs for photocatalytic decomposition MB under visible irradiation.

The activation energy () and reaction order of catalytic reaction are extremely important to studying the process and mechanism of catalytic reactions. Accordingly, the activation energy of Sr0.7K0.3TiO3−δ@PC-polyHIPEs was estimated according to the Ozawa plots. Based on the above results, the activation energy of Sr0.7K0.3TiO3−δ@PC-polyHIPEs for MB decomposition under visible light is calculated to be 12.3 kJ mol−1. The concentration of MB in the photocatalytic reaction with Sr0.7K0.3TiO3−δ@PC-polyHIPEs under visible light is measured at different time with results shown in Table 2. According to the rate equation using the integral method, if the reaction followed the first-order kinetics, this means that versus t (Time) should give a straight line; if the reaction followed the second-order kinetics, this means that versus t should give a straight line. As shown in Figure 11, the versus gives a straight line; therefore, it can be concluded that the photocatalysis between Sr0.7K0.3TiO3−δ@PC-polyHIPEs and MB under visible light follows the second-order reaction.

Table 2: MB concentration at different time with STi@PC-polyHIPEs under visible light (450 nm).
Figure 11: The kinetics analysis of Sr0.7K0.3TiO3−δ@PC-polyHIPEs for photocatalytic decomposition MB under visible irradiation.
3.2.5. The Effect of Cycle Times

Figure 12 displays the photocatalytic degradation of MB for 160 min reaction under visible light when Sr0.7K0.3TiO3−δ@PC-polyHIPEs are utilized eight times, yet the photocatalytic activity is well preserved with 87.6% of fresh catalyst degradation ratio even after the eighth cycle. It can be concluded that Sr0.7K0.3TiO3−δ@PC-polyHIPEs have excellent durability and reusability under visible light. Moreover, Sr1−xKxTiO3@PC-polyHIPEs own many other merits. Firstly, they are flexible and can be separated and collected easily from MB solution. Secondly, the novel material is of low density so it can be floated and easily fixed in water solution, causing high contacting area between catalyst and MB. Thirdly, it is stable either in acid or in base environment and could be suitable for various water conditions. As a kind of low-cost and environment-friendly hybrid material, Sr1−xKxTiO3@PC-polyHIPEs can be a promising photocatalyst for water purification under visible light.

Figure 12: Degradation ratio of MB solutions in the presence of Sr0.7K0.3TiO3−δ@PC-polyHIPEs at eight cycle times.

4. Conclusions

PC-polyHIPEs with large and interconnected pores were fabricated by light-induced polymerization of dopamine in transparent polyHIPEs which were prepared by polymerization within high internal phase emulsions. Sr1−xKxTiO3−δ nanoparticles were successfully incorporated and adhered to PC-polyHIPEs to form a novel catalyst compound Sr1−xKxTiO3−δ@PC-polyHIPEs. The catalyst showed excellent MB decomposition performance under either UV or visible light although Sr1−xKxTiO3−δ alone worked only under UV light. When = 0.3, Sr1−xKxTiO3−δ@PC-polyHIPEs showed the highest photocatalytic performance due to the existence of more oxygen vacancies. When the aqueous suspension with 50 mg L−1 MB and 1.6  L−1 Sr0.7K0.3TiO3−δ@PC-polyHIPEs is exposed to visible light for 160 min at room temperature, 88.3% of MB was decomposed. After being used for eight cycles, 87.6% activity of fresh Sr0.7K0.3TiO3−δ@PC-polyHIPEs still remained. The influences of salinity, temperature, and catalyst concentration on the photocatalytic activity were studied. For MB decomposition under visible light, the activation energy of Sr0.7K0.3TiO3−δ@PC-polyHIPEs was calculated to be 12.3 kJ mol−1 and the kinetics analysis revealed that the photocatalyst was the second-order reaction. These findings demonstrated that Sr1−xKxTiO3−δ@PC-polyHIPEs were an effective catalyst in real application for MB degradation.

Conflicts of Interest

The authors declare that there are no conflicts of interest regarding the publication of this paper.

Acknowledgments

Yonghua Gao was supported by China Scholarship Council for Young Scholars (Grant no. 201406935028), the Specialized Joint Research Fund for the Doctoral Program of Higher Education in China (Grant no. 20121402110014), and the Natural Science Foundation Fund of Shanxi Province (Grant no. 2013011041-4).

Supplementary Materials

Data of photocatalytic decomposition of MB for 160 min under visible light when Sr1−xKxTiO3−δ@poly-HIPEs were used. (Supplementary Materials)

References

  1. H. Mohammad, S. H. Hossein, and S. N. Masoud, “Degradation of methylene blue and Rhodamine B as water pollutants via green synthesized Co3O4/ZnO nanocomposite,” Journal of Molecular Liquids, vol. 229, pp. 293–299, 2017. View at Google Scholar
  2. Ü. Geçgel, G. Özcan, and G. Ç. Gürpınar, “Modelling and interpretation of adsorption isotherms,” Journal of Chemistry, vol. 2017, pp. 1–11, 2017. View at Google Scholar
  3. H. Park, Y. Park, W. Kim, and W. Choi, “Surface modification of TiO2 photocatalyst for environmental applications,” Journal of Photochemistry and Photobiology C: Photochemistry Reviews, vol. 15, no. 2, pp. 1–20, 2013. View at Publisher · View at Google Scholar · View at Scopus
  4. Y. Li, J. Wang, H. Yao, L. Dang, and Z. Li, “Efficient decomposition of organic compounds and reaction mechanism with BiOI photocatalyst under visible light irradiation,” Journal of Molecular Catalysis A: Chemical, vol. 334, no. 1-2, pp. 116–122, 2011. View at Publisher · View at Google Scholar · View at Scopus
  5. S. Kawasaki, R. Takahashi, K. Akagi et al., “Electronic structure and photoelectrochemical properties of an Ir-doped SrTiO3 photocatalyst,” The Journal of Physical Chemistry C, vol. 118, no. 35, pp. 20222–20228, 2014. View at Publisher · View at Google Scholar · View at Scopus
  6. X. Zhang, K. Huo, L. Hu, Z. Wu, and P. K. Chu, “Synthesis and photocatalytic activity of highly ordered TiO2 and SrTiO3/TiO2 nanotube arrays on Ti substrates,” Journal of the American Ceramic Society, vol. 93, no. 9, pp. 2771–2778, 2010. View at Publisher · View at Google Scholar · View at Scopus
  7. R. Konta, T. Ishii, H. Kato, and A. Kudo, “Photocatalytic activities of noble metal ion doped SrTiO3 under visible light irradiation,” The Journal of Physical Chemistry B, vol. 108, no. 26, pp. 8992–8995, 2004. View at Publisher · View at Google Scholar · View at Scopus
  8. M. Miyauchi, M. Takashio, and H. Tobimatsu, “Photocatalytic activity of SrTiO3 codoped with Nitrogen and lanthanum under visible light illumination,” Langmuir, vol. 20, no. 1, pp. 232–236, 2004. View at Publisher · View at Google Scholar · View at Scopus
  9. R. Niishiro, S. Tanaka, and A. Kudo, “Hydrothermal-synthesized SrTiO3 photocatalyst codoped with rhodium and antimony with visible-light response for sacrificial H2 and O2 evolution and application to overall water splitting,” Applied Catalysis B: Environmental, vol. 150-151, pp. 187–196, 2014. View at Publisher · View at Google Scholar · View at Scopus
  10. Y. Jia, S. Shen, D. Wang et al., “Composite Sr2TiO4/SrTiO3(La,Cr) heterojunction based photocatalyst for hydrogen production under visible light irradiation,” Journal of Materials Chemistry A, vol. 1, no. 27, pp. 7905–7912, 2013. View at Publisher · View at Google Scholar · View at Scopus
  11. T.-H. Xie, X. Sun, and J. Lin, “Enhanced photocatalytic degradation of RhB driven by visible light-induced MMCT of Ti(IV)-O-Fe(II) formed in Fe-doped SrTiO3,” The Journal of Physical Chemistry C, vol. 112, no. 26, pp. 9753–9759, 2008. View at Publisher · View at Google Scholar · View at Scopus
  12. J. Wang, S. Yin, Q. Zhang, F. Saito, and T. Sato, “Mechanochemical synthesis of SrTiO3-xFx with high visible light photocatalytic activities for nitrogen monoxide destruction,” Journal of Materials Chemistry, vol. 13, no. 9, pp. 2348–2352, 2003. View at Publisher · View at Google Scholar · View at Scopus
  13. C. W. Lim and I. S. Lee, “Magnetically recyclable nanocatalyst systems for the organic reactions,” Nano Today, vol. 5, no. 5, pp. 412–434, 2010. View at Publisher · View at Google Scholar · View at Scopus
  14. D. Wang, J. H. Ye, T. Kako, and T. Kimura, “Photophysical and photocatalytic properties of SrTiO3 doped with Cr cations on different sites,” The Journal of Physical Chemistry B, vol. 110, no. 32, pp. 15824–15830, 2006. View at Publisher · View at Google Scholar · View at Scopus
  15. A. Desforges, R. Backov, H. Deleuze, and O. Mondain-Monval, “Generation of palladium nanoparticles within macrocellular polymeric supports: Application to heterogeneous catalysis of the Suzuki-Miyaura coupling reaction,” Advanced Functional Materials, vol. 15, no. 10, pp. 1689–1695, 2005. View at Publisher · View at Google Scholar · View at Scopus
  16. F. Su, C. L. Bray, B. Tan, and A. I. Cooper, “Rapid and reversible hydrogen storage in clathrate hydrates using emulsion-templated polymers,” Advanced Materials, vol. 20, no. 14, pp. 2663–2666, 2008. View at Publisher · View at Google Scholar · View at Scopus
  17. C. Féral-Martin, M. Birot, H. Deleuze, A. Desforges, and R. Backov, “Integrative chemistry toward the first spontaneous generation of gold nanoparticles within macrocellular polyHIPE supports (Au@polyHIPE) and their application to eosin reduction,” Reactive and Functional Polymers, vol. 67, no. 10, pp. 1072–1082, 2007. View at Publisher · View at Google Scholar · View at Scopus
  18. I. Pulko, J. Wall, P. Krajnc, and N. R. Cameron, “Ultra-high surface area functional porous polymers by emulsion templating and hypercrosslinking: Efficient nucleophilic catalyst supports,” Chemistry - A European Journal, vol. 16, no. 8, pp. 2350–2354, 2010. View at Publisher · View at Google Scholar · View at Scopus
  19. Y. Wu, T. Zhang, Z. Xu, and Q. Guo, “High internal phase emulsion (HIPE) xerogels for enhanced oil spill recovery,” Journal of Materials Chemistry A, vol. 3, no. 5, pp. 1906–1909, 2015. View at Publisher · View at Google Scholar · View at Scopus
  20. T. Zhang, Y. Wu, Z. Xu, and Q. Guo, “Hybrid high internal phase emulsion (HIPE) organogels with oil separation properties,” Chemical Communications, vol. 50, no. 89, pp. 13821–13824, 2014. View at Publisher · View at Google Scholar · View at Scopus
  21. T. Zhang, Z. Xu, Y. Wu, and Q. Guo, “Assembled block copolymer stabilized high internal phase emulsion hydrogels for enhancing oil safety,” Industrial & Engineering Chemistry Research, vol. 55, no. 16, pp. 4499–4505, 2016. View at Publisher · View at Google Scholar · View at Scopus
  22. T. Zhang and Q. Guo, “Isorefractive high internal phase emulsion organogels for light induced reactions,” Chemical Communications, vol. 52, no. 24, pp. 4561–4564, 2016. View at Publisher · View at Google Scholar · View at Scopus
  23. T. Zhang and Q. Guo, “Continuous preparation of polyHIPE monoliths from ionomer-stabilized high internal phase emulsions (HIPEs) for efficient recovery of spilled oils,” Chemical Engineering Journal, vol. 307, pp. 812–819, 2017. View at Publisher · View at Google Scholar · View at Scopus
  24. X. Li, G. Sun, Y. Li et al., “Porous TiO2 materials through pickering high-internal phase emulsion templating,” Langmuir, vol. 30, no. 10, pp. 2676–2683, 2014. View at Publisher · View at Google Scholar · View at Scopus
  25. J. Xu, J. Liu, Z. Zhao et al., “Easy synthesis of three-dimensionally ordered macroporous La1-xKxCoO3 catalysts and their high activities for the catalytic combustion of soot,” Journal of Catalysis, vol. 282, no. 1, pp. 1–12, 2011. View at Publisher · View at Google Scholar · View at Scopus
  26. X. Wei, G. Xu, Z. Ren et al., “Single-crystal-like mesoporous SrTiO3 spheres with enhanced photocatalytic performance,” Journal of the American Ceramic Society, vol. 93, no. 5, pp. 1297–1305, 2010. View at Publisher · View at Google Scholar · View at Scopus
  27. H. Zhang, G. Liu, L. Shi, H. Liu, T. Wang, and J. Ye, “Engineering coordination polymers for photocatalysis,” Nano Energy, vol. 22, pp. 149–168, 2016. View at Publisher · View at Google Scholar · View at Scopus
  28. G. Zhang, G. Kim, and W. Choi, “Visible light driven photocatalysis mediated via ligand-to-metal charge transfer (LMCT): An alternative approach to solar activation of titania,” Energy & Environmental Science, vol. 7, no. 3, pp. 954–966, 2014. View at Publisher · View at Google Scholar · View at Scopus
  29. B. Subash, B. Krishnakumar, M. Swaminathan, and M. Shanthi, “Highly efficient, solar active, and reusable photocatalyst: Zr-loaded Ag-ZnO for reactive red 120 dye degradation with synergistic effect and dye-sensitized mechanism,” Langmuir, vol. 29, no. 3, pp. 939–949, 2013. View at Publisher · View at Google Scholar · View at Scopus
  30. Y. Li, W. Guo, H. Hao et al., “Enhancing photoelectrical performance of dye-sensitized solar cell by doping SrTiO3:Sm3+@SiO2 core-shell nanoparticles in the photoanode,” Electrochimica Acta, vol. 173, Article ID 25049, pp. 656–664, 2015. View at Publisher · View at Google Scholar · View at Scopus
  31. M. Pelaez, N. T. Nolan, S. C. Pillai et al., “A review on the visible light active titanium dioxide photocatalysts for environmental applications,” Applied Catalysis B: Environmental, vol. 125, pp. 331–349, 2012. View at Publisher · View at Google Scholar · View at Scopus