Appl Magn Reson DOI 10.

1007/s00723-011-0270-0

Applied Magnetic Resonance

Effect of Static Magnetic Field on Photocatalytic Degradation of Methylene Blue over ZnO and TiO2 Powders
Supawan Joonwichien Eiji Yamasue Hideyuki Okumura Keiichi N. Ishihara

Received: 13 May 2011 Springer-Verlag 2011

Abstract Magnetic eld effects (MFEs) on photocatalytic degradation of methylene blue (MB) solution over ZnO and TiO2 powders are investigated under static magnetic eld up to 0.7 T with light irradiation by ultraviolet (UV) light emitting diode. The UVvisible-near-infrared spectrometer is used to monitor the MB concentrations. The positive MFE is observed for ZnO, while the negative MFE for TiO2, and both MFEs are increased with the increase in the magnetic eld applied. By increasing the settling time (the time interval between the preparation of MB solution and the powder dispersion into the MB solution), the photodegradation abilities under MFEs are decreased for both the catalysts. The cause of MFE is discussed in terms of dissolved oxygen in the MB solution and magnetic adsorption of the constituent molecules.

1 Introduction There have been many experimental and theoretical studies for the effects of magnetic eld on chemical and biological systems [13]. The magnetic eld effects (MFEs) upon photochemical reactions are a newly developed research eld that has shown rapid progress since 1976 when the singlet sensitized photodecomposition reaction of dibenzoyl peroxide in toluene was found to be dependent on magnetic eld [4]. As for the mechanism of MFEs, the kinetics of photocatalytic reactions have long been considered [5, 6] not only in homogeneous systems [7], but also in heterogeneous systems [8, 9]. It was reported that one of the key factors of MFE proposed is the interaction between the radicals and the magnetic eld [10, 11] and
S. Joonwichien (&) E. Yamasue H. Okumura K. N. Ishihara Department of Socio-Environmental Energy Science, Graduate School of Energy Science, Kyoto University, Yoshida Honmachi, Sakyo-ku, Kyoto 606-8501, Japan e-mail: supawan@namihei.mtl.kyoto-u.ac.jp

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also documented that magnetic eld possibly affects the recombination process of electrons and holes [12]. However, as far as investigated, most of the previous publications on MFEs for heterogeneous photocatalytic reactions are limited to the TiO2-based catalyst system. Although authors have already reported existence of MFEs on photocatalytic degradation of methylene blue (MB) solution over ZnO powder [13, 14], the quantitative analyses as well as the examination on the possible cause were not performed, with less regard on the experimental temperature variation. Thus, the aim of the present study is to provide further details of MFE on the photodegradation of MB over ZnO powders compared with TiO2, both of which exhibit wide band gaps and similar photodegradation mechanisms through utilizing radical species [15, 16].

2 Experimental 2.1 Materials Powder zinc oxide (ZnO 99.9%, wurtzite structure, Wako Pure Chemical Ind. Ltd.) and titanium dioxide [TiO2 99.9%, ST-41 (anatase structure), Ishihara Sangyo Ltd.] were used as photocatalysts. The BET (BrunauerEmmettTeller) surface areas for ZnO and TiO2 powders were 3.8 m2/g (corresponding to a mean particle size of less than 5 lm) and 9.5 m2/g (0.2 lm), respectively. The granular MB solid and distilled water were received from Nacalai Tesque Inc., Kyoto, Japan, and the MB structure is given in Fig. 1. MB solution was prepared by authors as described in the following section. 2.2 Photocatalytic Measurement The granular MB was dissolved in distilled water to be 0.02 mmol/L followed by manual shaking for 5 min. After settling in the dark for another 5 min, 0.005 g of the photocatalyst powder was immediately mixed with the MB solution in a small reaction cell made of transparent quartz (inner volume of about 4 mL) with a plastic cap in order to prevent evaporation. The pH of 6.7 0.04 was observed for the MB solution, and no changes in pH values were registered during the experiment. Hereafter, the time interval between the preparation of the MB solution and the powder dispersion into the MB solution is called settling time. The concentration

Fig. 1 Molecular structure of MB

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MFE on Photocatalytic Degradation of Methylene Blue

Fig. 2 Schematic diagram of the experimental apparatus

of dissolved oxygen was monitored after the settling process by a multifunction meter equipped with dissolved oxygen (DO) electrode (OE-270AA, DKK-TOA Corp.). When the settling time is 5 min, the DO is 7.57 0.04 mg/L. The experimental setup is schematically shown in Fig. 2. The cell with the MB solution dispersed with a photocatalyst was irradiated from the bottom side by ultraviolet (UV) light emitting diode (LED) lamp (OMRON, ZUV-L8V, Kyoto, Japan) with the center light wavelength of 365 nm and with the light intensity of 600 mW/cm2. The distance from the UV light source to the cell was set to be 10 mm. As for the applied magnetic eld, external static magnetic eld intensities of 0.3, 0.5, and 0.7 T were applied by sandwiching the cell. For measurement of the MB concentration, the reaction cell with the sample was directly put into UVVisible (Vis)-near-infrared (NIR) spectrometer (Perkin-Elmer lambda 900) and then MB concentration was determined by comparison with the predetermined calibration curves between the MB concentration and the absorbance at 664 nm. Since the slope of the calibration curve decreases with temperature from 15 to 35C (the maximum increase of temperature due to light irradiation is 6C), another calibration curve for the slope and the temperature was also determined.

3 Results The photodegradation of MB over ZnO and TiO2 powders as a function of UV irradiation time is illustrated in Fig. 3a and b, respectively. The MFEs on the photodegradation are reproducibly observed (at least three times) for both photocatalysts. The ZnO powder exhibits positive MFE, while it is negative for TiO2. Interestingly, both the MFEs are gradually increased with the applied magnetic eld. In order to clarify the mechanism of MFEs, the settling time was varied from 5 min to 1, 3, and 24 h. Figures 4 and 5 show the photodegradation results after various MB settling times for ZnO and TiO2 particles, respectively. It is clear that

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Fig. 3 Magnetic eld dependences of the MB photodegradation using a ZnO and b TiO2 powders

the MFEs are decreased with increasing the settling time for both catalysts. Also the photodegradation abilities under 0 T magnetic eld are decreased with increasing the settling time for both catalysts. Although the opposite MFE tendency for the cases between ZnO and TiO2 seems to be curious, similar results have already been observed by Wakasa et al. [12, 17]. They investigated the MFE on photocatalytic decomposition of tert-butanol over TiO2 and Pt/TiO2 powders, and both systems similarly generated acetone and methane as the main products. However, the yields of acetone for the former were increased with increasing the magnetic eld strength from 0 to 1.5 T, while for the latter the decrease of acetone was observed. As for the possible mechanism, Wakasa et al. [12, 16] mentioned that the observed MFEs over both the photocatalysts are not caused by the reencounter of free radicals but are rather explained by magnetically induced acceleration of recombination of electrons and holes since the same particle types are used.

4 Discussion 4.1 Effect of DO under 0 T Magnetic Field Firstly, the relationship between the photodegradation ability under 0 T magnetic eld and the initial DO concentration will be considered. Figure 6 shows the relationship between the amount of DO in the initial MB solution and the settling time. It is found that the DO level decreases with increasing the settling time. Namely, through the shaking process, supersaturated small air bubbles (containing 21 vol% of oxygen gas) are introduced into the solution, which may react (possibly indirectly) with photogenerated electrons, resulting in the production of superoxide anions on and/or near the photocatalyst surface. Thus, the higher the DO concentration is, the more effective the photodegradation becomes. However, elongated settling time may cause the dissolution of air bubbles toward a steady-

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Fig. 4 Photodegradation of MB using ZnO under magnetic eld of 00.7 T for settling times: a 5 min (selected data from Fig. 2a), b 1 h, c 3 h, and d 24 h

state equilibrium, resulting in the reduction of photodegradation ability. Figure 7 shows the relationship between the change in concentration of MB after the reaction time of 80 min under 0 T magnetic eld and the initial DO concentration before light irradiation. They exhibit linear tendencies for both photocatalysts. This result supports the above speculation. Furthermore, similar slopes for different photocatalysts in Fig. 7 indicate that the photodegradation of MB is a diffusion-controlled process of DO species. Gerischer and Heller [18] investigated in detail the role of oxygen in the photodestruction of organics on catalyst surfaces. They developed kinetics models to predict the maximum electron uptake by oxygen and found that the latter depends on catalyst particle sizes and oxygen concentration in the solution. Early studies have shown that the adsorption of oxygen on illuminated TiO2 surface depends on the number of hydroxyl groups of the surface [1921]. The dependence of degradation rate constants of organics on the dissolved oxygen concentration can be

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Fig. 5 Photodegradation of MB using TiO2 under magnetic eld of 00.7 T for settling times: a 5 min (selected data from Fig. 2b), b 1 h, c 3 h, and d 24 h

Fig. 6 Relationship between the DO levels and the settling duration

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MFE on Photocatalytic Degradation of Methylene Blue Fig. 7 Relationship between the change in concentration of MB after the reaction time of 80 min under 0 T magnetic eld and the DO concentration

Fig. 8 Relationship between the apparent second-order rate constant of MB degradation and the DO concentration

well described by the LangmuirHinshelwood (LH) equation [2224]. In order to further study the effect of the DO variation on the kinetics of the MB photodegradation, the apparent reaction rate constant (k00 ) based on the LH approximation is plotted against the DO concentration (Fig. 8) where the secondorder kinetics is assumed as below: 1=Ct 1=C0 k00 t; 1

where Ct is the concentration of MB at any time t (min), C0 is the initial dye concentration (mmol/L), and k00 is the rate constant for second-order reaction (L/mmol min). The plot of 1/Ct versus time represents a straight line, where the slope obtained from the linear regression analysis equals the apparent second-order rate constant [13, 2528]. The best t of MB degradation agreed well with the

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second-order kinetics, indicating that the reaction takes place between the two adsorbed substances (MB molecule and DO) or the reaction, occurs between a radical in solution and an adsorbed substrate molecule (MB molecule and oxygen radical species). Figure 8 shows that the reaction rate constant decreases in proportion to the DO concentration regardless of the type of photocatalyst used. On the other hand, the reaction rate is changed at the lower DO concentration, which suggests that the diffusion of DO is the rate determining step through the liquid boundary layer. 4.2 Effect of DO on MFE and Mechanism of MFE As described in Sect. 1, MFEs were explained mostly in terms of the radical pair mechanism in the previous studies. Kiwi [8] explained that when radical species diffuse to the photocatalyst surface, an applied magnetic eld interferes with the reactivity of the radical species and the recombination rate of the photogenerated radicals become dependent on the strength of the magnetic eld. It is also reported that the MFEs may occur through variations on the reencounter of reactive free radicals [29, 30] or the recombination of electrons and holes [12]. Wakasa et al. [12, 16] claimed that the observed MFEs over the photocatalysts are not caused by the reencounter of free radicals, but by magnetically induced acceleration of recombination of photoexcited electrons and holes. Our experiments of varying the settling time, however, suggest that one of the critical factoring for MFE such as DO must be considered. In this respect, the following interesting reports may support our speculation; the diffusion of paramagnetic DO molecules in water [3133] (and also the dissolution of oxygen molecules into water [34]) is accelerated by a strong gradient static magnetic eld. Thus, it is possible that diffusion of DO molecules is increased and the dissolution of oxygen quickens under the magnetic eld [35, 36], resulting in the acceleration of the reaction due to the faster supply of consumed oxygen toward the powder surface [37]. Since the DO level is almost stable at 3 h settling time, but the MFE can be

Fig. 9 Adsorption of MB on a ZnO and b TiO2 in the dark under magnetic eld of 0 and 0.7 T

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Table 1 Comparison of photocatalysts used in this work and Refs. [12, 16] Referenced works TiO2 (anatase form) Particle size (*25 nm) BET surface area (not mentioned) Pt/TiO2 (anatase form) Particle size (\100,000 nm) BET surface area (not mentioned) Possible reaction: (referenced work)

Effect

Present work

Positive effect

ZnO

Particle size (\5,000 nm)

BET surface area (3.8 m2/g)

Negative effect

TiO2 (ST-41) (anatase form)

Particle size (*200 nm)

BET surface area (9.5 m2/g)

MFE on Photocatalytic Degradation of Methylene Blue

Possible reaction: (present work)

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P photocatalyst (ZnO, TiO2), BET Brunauer-Emmett-Teller

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observed, indicating involvement of other possible factors, i.e. the complex formation of dye with oxygen molecules prior to the UV irradiation must inuence the photocatalysis [38] as well as the corresponding MFE. From this point of view, the speculation is, the amount of oxygen molecules chemically or physically adsorbed on the photocatalyst powder and the complex formation of the MB-dye with oxygen molecules is formed [14], so-called MB-O2 complex before UV illuminating. In order to conrm the possibility of this speculation, the concentration of DO in the solution for 5 min, 1 h, 3 h, and 24 h are calculated to be 0.47, 0.42, 0.39, and 0.38 mmol/L, respectively. This suggested that the amount of DO in the solution is sufcient to form MB-O2 complex since the concentration of oxygen is much larger than MB dye concentration (0.02 mmol/L) for all cases. The fast supply of oxygen molecules is prompted by magnetic eld around the powder, the produced electron by light irradiation could be efciently consumed through DO. Besides, the possible involvement of MB-O2 complex can be represented by the second-order kinetics reaction, considering each elementary step involved with the MB-O2 degradation. Moreover, the variation of settling time could be ascribed to the MB-O2 complex formation as well [39]. However, this explains only the positive MFE as exhibited in the case of ZnO. In order to explain the negative MFE exhibited in this study for TiO2, the disincentive factor of the reaction is further considered, where the magnetic adsorptionthe MFE on acceleration or deceleration of the MB adsorption toward the powder surfaceis focused. Figure 9a and b shows the decrease in MB concentration for ZnO and TiO2, respectively, when each powder is dispersed into the solution in the dark. In the case of ZnO, the concentration of MB under magnetic eld (0.7 T) reproducibly (at least three times) decreases more than that without magnetic eld (0 T), indicating the acceleration of MB adsorption on the surface of ZnO under magnetic eld, while slight deceleration for TiO2. Although the MFE on adsorption of DO is not measured directly, it is possible that some sort of change is generated because magnetic adsorptions of gas were sometimes reported [4042]. It is also reported that the increment of adsorption oxygen on the catalyst surface increased under magnetic eld of 80 mT, depending on types of metal oxide and its structure [43]. If this speculation holds, the magnetic eld affects the adsorption of DO molecules and the reaction is inuenced by the settling time. Since an opposite MFEs is found between ZnO and TiO2 according to our analysis, this effect may also caused by the unique physical properties of the photocatalyst and the quantity of oxygen adsorbed [43]. Consequently, it can be said that the direction of MFE on the photodegradation is explained by the combination of positive and negative effects. As shown in Table 1, although opposite MFEs are observed between the present work and Wakasas report [12, 16] even for similar TiO2 photocatalysts, it can be phenomenologically explained by a combination of positive and negative factors under magnetic eld. The cause of the MFE is the action of DO molecule, which involves DO short-range diffusion (micron-order distance) or molecular transport, adsorption including MBO2 complex formation, chemical reaction (photodegradation), scavenging (or supplying) electrons or holes, and the spin-state (singlet-triplet) variation [4446]. One of them could be also the deciding factor for the recombination of electron and

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hole [12, 17]. However, the detailed discussion of MFE on the photoreaction is beyond the scope of this paper. Further investigation is required to elucidate the mechanism of the novel phenomena.

5 Conclusion MFEs on photocatalytic degradation of MB solution over ZnO and TiO2 powders are investigated under static magnetic eld up to 0.7 T with light irradiation by UV-LED. With the conditions investigated in this study, the ZnO powder exhibits a positive MFE, while it is negative for TiO2, and the results are reproducible. Both MFEs are increased with the increase in the applied magnetic eld. By increasing the settling time of the MB solution, the photodegradation abilities under MFEs are signicantly reduced for both catalysts. The cause of MFE is phenomenologically explained by alteration of the dissolved oxygen molecules in the MB solution and the magnetic adsorption of the constituent molecules that include water, MB dye, and oxygen.
Acknowledgments Financial support from Global Center of Excellence (GCOE) Program and Grantin-Aid for Scientic Research (B) by the Ministry of Education, Culture, Sports, Science and Technology, Japan are gratefully acknowledged.

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