Comparison on Degradation of Reactive Black 5 (RB5) in Photocatalytic Fuel Cell (PFC) under UV and Solar Light

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1 Comparison on Degradation of Reactive Black 5 (RB5) in Photocatalytic Fuel Cell (PFC) under UV and Solar Light W. F. Khalik *, S. A. Ong *, L. N. Ho **, C. H. Voon **, Y. S. Wong *, N. A. Yusoff *, S. L. Lee **, S. Y. Yusuf * * Water Research Group (WAREG), School of Environmental Engineering, Universiti Malaysia Perlis, Arau, Perlis, Malaysia ( wanfadhilah@ymail.com; ongsoonan@yahoo.com; yswong@unimap.edu.my; athirah_yusoff@ymail.com; sarayasina@unimap.edu.my) ** School of Materials Engineering, Universiti Malaysia Perlis, Arau, Perlis, Malaysia ( lnho@unimap.edu.my; chvoon@unimap.edu.my; sinli_20@hotmail.com) Abstract PFC is an alternative to conventional treatment method to degrade organic pollutants which simultaneously generate electricity. A PFC comprise of photoanode externally connected with cathode electrode and organic pollutants. The purpose of this study was to compare the degradation of Reactive Black 5 (RB5) in PFC system under UV and solar light with ZnO/carbon felt as photoanode. The initial concentration of RB5 was 10 mg/l and reduced to and mg/l, respectively, under UV and solar light, after 6 h irradiation time. The open circuit voltage (V oc), short-circuit current density (J sc) and maximum power density (P max) for RB5 under UV light was 500 mv, ma/cm 2 and mw/cm 2, respectively, meanwhile, V oc, J sc and P max for RB5 under solar light irradiation was 550 mv, ma/cm 2 and mw/cm 2, respectively. It could be concluded that RB5 showed better degradation and would generate high electricity under solar light irradiation compared to UV light. Keywords Photocatalytic fuel cell; Reactive Black 5; Solar light; UV light; Voltage INTRODUCTION In these modern world which limited reserves of fossil fuels, it will become great effort for researchers to generate alternative renewable sources of energy, for example photocatalytic fuel cell (PFC) (Lianos, 2011;Antoniadou and Lianos, 2009), direct methanol fuel cell (DMFC) (Akbari et al., 2016; Garg et al., 2016; Liu et al., 2016), microbial fuel cell (MFC) (Deng et al., 2010; Fang et al., 2016; Sun et al., 2015) and alkaline polymer electrolyte fuel cell (APEFC) (Zhou et al., 2015; Hu et al., 2013; Lan et al., 2015).Besides being able to generate electricity, PFCs also can degrade organic pollutant which depends on the presence of light irradiation and photocatalyst. PFC consists of three main components which are photoanode, cathode electrode and pollutant itself. A photoanode electrode is carrying photocatalyst that responsible for the degradation of organic pollutant and externally connected with cathode electrode where this

2 electrode would support a reduction of electrocatalyst. Once the illumination of light is greater or equal to the band gap energy of photocatalyst, electron-hole pairs might be created (Antoniadou and Lianos, 2010). The hydroxyl radicals could be formed through reaction between holes andhydroxide ions or by decomposition of water molecules, meanwhile, electrons would react with electron acceptors such as oxygen molecules, sulphate ions and chloride ions to form superoxide radical anions. Some of electrons also would externally transfer from photoanode to cathode electrode and generate the voltage in PFC system. The process utilizes semiconductor catalyst as photoanode, for example TiO2 and ZnO which are inexpensive, largely available, nontoxic and leads to the total mineralization of organic chemicals to CO2. In this study, we compare the degradation of azo dye Reactive Black 5 (RB5) in PFC under UV and solar light with ZnO/carbon felt as photoanode. The application of ZnO/carbon felt as photocatalyst or photoanode in PFC can be considered as limited and ZnO itself has similar photodegradation mechanism with TiO2. MATERIALS AND METHODOLOGY Preparation of photoanode 500 ml of 0.1M sodium silicate was prepared and 5 g of ZnO powder was added into the solution. A carbon felt with dimension 3 cm x 4 cm was cut and dipped into the mixture for 1 h. The ZnO/carbon felt then was dried in an oven at 60 C for 3 h and this process was repeated for several times to make sure the surface of carbon felt was fully covered with ZnO. PFC procedure A stock solution of RB5 was prepared in 1.0 g/l concentration. The experiment was conducted in 500 ml beakers, well mixed with magnetic stirrer and exposed to UV light (Philips, PL-L 36W/10/4P) and solar light. The initial concentration of RB5 was 10 mg/l. The ZnO/carbon felt as photoanode and platinum loaded carbon (Pt/C) acted as cathode electrode where both of the electrode were connected with resistor box. The resistor value was 1000 Ω and this value was varied from 10 Ω to Ω in order to study its polarization curve. The experiment was conducted for 6 h and sample was taken out for every hour. The sample then was analyzed for its decolorization by UV-Vis spectrophotometer (Hitachi, U-2810). The voltage output was measured using digital multimeter (Sanwa Digital Multimeter CD800a). The solar light intensity was measured using Lux meter (Digital Lux Meter, MS6612) and its average was 868 x 100 Lux. RESULTS AND DISCUSSION

3 RB5 concentration (mg/l) Figure 1 shows the decolorization of RB5 under UV and solar light after 6 h irradiation time. The concentration of RB5 under UV and solar light reduced to and mg/l, respectively. ZnO showed higher degradation efficiency for RB5 under solar light irradiation than UV light. The percentage degradation of RB5 under solar light irradiation and UV light was 78.32% and 45.63%, respectively. The enhancement of photodegradation rate of RB5 in the presence of ZnO under solar light irradiation may be attributed to the fact that it absorbs over a large fraction of UV spectrum and the corresponding threshold of ZnO is 425 nm. Moreover, solar light also contains 43% of visible light which is suitable for ZnO since it absorb the visible light to excite the electron from VB to CB, meanwhile in UV light, the percentage of visible light might be low than in solar light. Kansal et al. (2008) found that ZnO as catalyst showed higher degradation of lignin compared to TiO₂ or TiO2/ZnO under light irradiation. An effective degradation of RB5 led to the higher generation of voltage output. The open circuit voltage (Voc), short-circuit current density (Jsc) and maximum power density (Pmax) for RB5 under UV light was 500 mv, ma/cm 2 and mw/cm 2, respectively, meanwhile, Voc, Jsc and Pmax for RB5 under solar light irradiation was 550 mv, ma/cm 2 and mw/cm 2, respectively. The concentrationof RB5 under solar light rapidly decreased within 6 h irradiation time compared to UV light and this led to the higher voltage that generated during the process. The formation of electrons during photocatalytic process would react with electron acceptor to produce superoxide radical anions which responsible in enhancing the degradation of RB5, and some of the electrons might transfer from photoanode to the cathode electrode. The rapid decolorization of RB5 occurred due to the higher amount of electron-hole pairs that generated under solar light irradiation compared to UV light and increasing amount of electrons led to the higher generation of voltage in PFC system UV light Solar light Time (h) Figure 1. Comparison on the degradation of RB5 under UV and solar light

4 The mineralization of RB5 in PFC process also can be seen through decreased of its absorbance peak. There are several absorbance peaks that appeared in RB5 which is at 255, 285 and 598 nm. The main conjugated structure in RB5 includes azo linkage, benzene ring and naphthalene ring. The chromophore containing azo linkage has absorption in the visible region where in this case, the peak was at 598 nm, while benzene ring and naphthalene ring in the UV region. Both of the peak for benzene ring and naphthalene ring at 255 and 285 nm, respectively. Figure 2 illustrates the absorbance peak at azo linkage decreased after 6 h irradiation time when exposed under UV and solar light. This indicates that the OH attacked the azo bonds in RB5 initially which caused the cleavage of N=N double bonds. The azo bonds are easier to be destroyed compared to aromatic compounds because it has electrons and become the most active site in the dye molecule. The destruction of peak at azo bond might increase the peak at both benzene and naphthalene rings. Even though the peak of azo bond decreased as increased in irradiation time, however, the peak at benzene and naphthalene ring still increased. This might be due to the reason that aromatic compound still present in the RB5 and not fully mineralized. In order to achieve complete mineralization of RB5 in PFC system, the irradiation time under UV and solar light need to be prolonged Abs 0 h 0.5 h 1 h 1.5 h 2 h 3 h 4 h 5 h 6 h a Abs 0 h 0.5 h 1 h 1.5 h 2 h 3 h 4 h 5 h 6 h b nm nm Figure 2. The reduction of absorbance peaks of RB5 under (a) UV and (b) solar light for 6 h of irradiation time CONCLUSION It can be concluded that degradation of RB5 and generation of electricity showed better performance under solar light irradiation. The final concentration of RB5 under UV light and solar light was and mg/l, respectively. The Voc, Jsc and Pmax for RB5 under UV

5 light was 500 mv, ma/cm 2 and mw/cm 2, respectively, meanwhile, Voc, Jsc and Pmax for RB5 under solar light irradiation was 550 mv, ma/cm 2 and mw/cm 2, respectively. REFERENCES Akbari, E., Buntat, Z., Nikoukar, A., Kheirandish, A., Khaledian, M., Afroozeh, A Renewable and Sustainable Energy Reviews, 60, Garg, A., Panda, B.N., Lam, J.S.L Fuel, 183, Liu, G., Zhou, H., Ding, X., Li, X., Zou, D., Li, X., Wang, X., Lee, J.K Energy Conversion and Management, 122, Sun, Z., Cao, R., Huang, M., Chen, D., Zheng, W., Lin, L Journal of Photochemistry and Photobiology A: Chemistry, 300, Fang, Z., Song, H., Yu, R., Li, X Ecological Engineering, 94, Deng, Q., Li, X., Zuo, J., Ling, A., Logan, B.E Journal of Power Sources, Lan, C., Fang, J., Guan, Y., Zhou, H, Zhao, J Journal of Power Sources, 295, Hu, Q., Li, G., Pan, J., Tan, L., Lu, J., Zhuang, L International Journal of Hydrogen Energy, 38, Zhou, T., Shao, R., Chen., S., He, X., Qiao, J., Zhang, J Journal of Power Sources, 293, Antoniadou, M., Lianos, P Journal of Photochemistry and Photobiology A: Chemistry, 204, Lianos, P Journal of Hazardous Materials, 185, Antoniadou, M., Lianos, P Applied Catalysis B: Environmental, 99, Kansal, S.K., Singh, M., Sud, D Journal of Hazardous Materials, 153,

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