Nghiên cứu tổng hợp vật liệu quang xúc tác lafeo3 cho phản ứng phân hủy hợp chất hữu cơ gây ô nhiễm trong nước thải

MINISTRY OF EDUCATION AND TRAINING HA NOI UNIVERSITY OF SCIENCES AND TECHNOLOGY PHAN CHI NHAN PHAN CHI NHAN CHEMICAL ENGINEERING SYNTHESIS LAFEO3 FOR PHOTODEGRADATION OF POLLUTANTS IN WASTEWATER MASTER THESIS YEAR : 2017 HA NOI - 2019 MINISTRY OF EDUCATION AND TRAINING HA NOI UNIVERSITY OF SCIENCES AND TECHNOLOGY - PHAN CHI NHAN SYNTHESIS LAFEO3 FOR PHOTODEGRADATION OF POLLUTANTS IN WASTEWATER CHEMICAL ENGINEERING MASTER THESIS SUPERVISOR ASSOCIATE PROFESSOR: PHAM THANH HUYEN HA NOI - 2019 Declaration statement I declare that: This is my own research work, the data and results presented in the thesis are true, are allowed to use by the authors and have never been published in any works Ha Noi, October, 2019 Phan Chi Nhan ACKNOWLEDGEMENT This work has been supported by the RoHan Project funded by the German Academic Exchange Service (DAAD, No 57315854) and the Federal Ministry for Economic Cooperation and Development (BMZ) inside the framework “SDG Bilateral Graduate school programme I would like to express my deep gratitude to my principal supervisor, Associate Professor Pham Thanh Huyen I thank Assc Prof Pham Huyen wholeheartedly for her great academic guidance, valuable advice, and constant encouragement I would like to give a big thank to Professor Malte Brasholz, who is my supervisor at this time I worked in Germany Thank you for giving me an opportunity to study in a good condition and learn more about interesting culture of Germany Countless thanks are also dedicated to my Mum, my sister and younger brother, my other family members and my friends who have always supported and accompanied me from my MsC Beginning to end Finally, I would like to thank my father, Mr Phan Van Huan (1945 – 2017), who brought me to science, give me a passion about chemistry and he is the motivation for me to finish this project This thesis is a present, which I want to give to my father Thank him for all TABLE OF CONTENTS ACKNOWLEDGEMENT TABLE OF CONTENT I CHAPTER 1: LITERATURE REVIEW 1 Introduction .1 Lanthanum Ferrite (LFO) Perovskite 2.1 Structure .3 2.2 Optical property 2.3 Magnetic property Lanthanum Ferrite as Visible-light Photocatalyst 3.1 Application in textile wastewater treatment 3.2 Photocatalytic mechanism Synthetic methods of LFO 10 4.1 Sol-gel method 11 4.2 Hydrothermal method .13 4.3 Sol-gel hydrothermal method 17 Factors affecting photocatalytic activity of LFO material 18 5.1 Surface area 18 5.2 Band gap energy 21 5.3 Morphology .22 5.4 Crystallinity .25 5.5 Dopants 27 CHAPTER 2: EXPERIMENTAL .30 Synthesis of LaFeO3 30 Characterization of LFO .30 Experiment of photocatalytic activity 31 CHAPTER RESULTS AND DICUSSION 33 Thermal Analysis .33 i XRD analysis 34 Morphological analysis 35 BET analysis .36 Band Gap energy result 37 Calibration curve of dyes and 17β-Estradiol 38 Photocatalytic activity of LFO nanoparticles .40 Efect of reaction condition on photodegradation efficiencies 42 Effect of catalytic concentration on photodegradation efficiencies 44 10 Effect of H2O2 concentration on photodegradation efficiencies .45 11 Comparison of catalytic activity for different dyes 46 12 Photodegradation of 17β-Estradiol 47 47 13 Effect of light intensity on photodegradation efficiencies 48 CONCLUSIONS .49 Recommendations for future research 49 REFERENCES 51 ii LIST OF TABLES Table Optical band gap values of LFO nanomaterials synthesized by various methods .5 Table Particle size and morphologies of LFO synthesized by sol-gel method using different templates 12 Table The influences of the hydrothermal temperature on the formation of LFO powders (Adopted from (Ji, Dai et al., 2013)) 17 Table Photocatalytic performance of LFO for the degradation of dyes .20 Table Degradation rate of dyes solution on different morphologies LFO nanoparticles 24 Table Effects of calcination temperature on the BET specific surface area and pore parameters of LFO nanoparticles 37 iii LIST OF FIGURES Figure Schematic crystalline structure of orthorhombic LFO (Misch, Birkel et al., 2014) Figure Schematic diagram of LFO antiferromagnetic order (Lee, Yun et al., 2014) Figure Schematic diagram of the reaction mechanism of LFO nanostructures for organic degradation (Adopted from (Thirumalairajan, Girija et al., 2013)) Figure FESEM images of LFO powders from (Feng, Liu et al., 2011) (a) and (Liu and Xu, 2011) (b) 13 Figure XRD patterns of different LFO nanostructures (Thirumalairajan, Girija et al., 2013) 15 Figure Image of LFO nanospheres by HRSEM (Dhinesh Kumar and Jayavel, 2014) 16 Figure RhB degradation % by using LFO samples with different particle sizes (Thirumalairajan, Girija et al., 2012) 19 Figure SEM images of LFO nanostructures with different morphologies: (a) nanocubes; (b) nanorodes; (c) nanospheres; (d) dendritic nanostructures (e) florallike nanosheets; (f) nanowires; (g) nanofibers (Yang, Huang et al., 2006; Leng, Li et al., 2010; Thirumalairajan, Girija et al., 2012; Thirumalairajan, Girija et al., 2013; Dhinesh Kumar and Jayavel, 2014; Thirumalairajan, Girija et al., 2014) 23 Figure (a) XRD pattern at different calcination temperatures; (b and c) degradation of RhB and MB in the presence of LFO calcined at 800°C (Thirumalairajan, Girija et al., 2014) 26 Figure 10 (a) XRD pattern of LFO samples calcined at different temperatures; (b) Degradation of RhB with the use of different LFO samples and P-25TiO2 (Su, Jing et al., 2010) 27 Figure 11 TGA curve of synthesized LaFeO3 sample 33 Figure 12 XRD patterns of LaFeO3 34 Figure 13 SEM images of (a) LFO-C600, (b) LFO-C700, (c) LFO-C800, and (d) LFO-C900 35 Figure.14 HRTEM image of the LFO-C800 .36 Figure.15 Nitrogen adsorption-desorption isotherms of the LFO nanoparticles calcined at different temperatures 36 Figure 16 (a) LFO solid UV-vis absorption spectrum and (b) Schematic of determination of band gap energy .38 Figure 17 Calibration curve of MB 38 39 iv Figure 18 Calibration curve of MB 39 Figure 19 Calibration curve of MO 39 Figure 20 Calibration curve of 17β-Estradiol 40 Fig 21 The photodegradation efficiencies of RhB under visible light irradation by different photocatalysts .40 Figure 22 The change in colour of RhB solution during the reaction 42 Fig.23 Photodegradation efficiencies of Metyl Orange under differences condition 43 Fig 24 Effect of catalytic concentration on photodegradation of MO 44 Fig.25 Effect of H2O2 concentration on photodegradation efficiencies 45 Fig.26 Photodegradation efficiencies for bleaching different dyes 46 Fig.27 The photodegradation efficiencies of 17β-Estradiol under visible light irradation 47 Fig.28 Photodegradation efficiencies of MB by different lamp 48 Fig.29 Photodegradation efficiencies of 7β-Estradiol by different lamp .48 v CHAPTER 1: LITERATURE REVIEW Introduction In recent years, environmental pollution issue, especially wastewater pollution has been increasing alarmingly Due to the rapid development of textile industry and lack of modern technologies for textile wastewater treatment, a considerable amount of harmful organic dyes has been discharged into environment (Yi, Chen et al., 2008) For several dyes with the concentration less than ppm, their presence in water could easily be observed and undesirable (Robinson, McMullan et al., 2001) Among these, the most notable ones include Rhodamine B (RhB), methylene blue (MB) and methyl orange (MO) which have been used as coloured substances for printing or dyeing cotton, leather, silk, wool (Gupta, Suhas et al., 2004) MB causes not only permanent injury to eye but also difficulty in breathing to human and animals (Tan, Ahmad et al., 2008) Meanwhile, experimental research has proven the negative effects arising from RhB and MO on human well-being and ecological environment, including carcinogenicity, toxicity, and mutagenicity (Khataee and Kasiri, 2010) Consequently, wastewater treatment targeting at minimising the levels of these organic compounds has become essential Conventional technologies for treatment of dye-containing water are not sufficiently effective to achieve the current stringent requirements for discharge To overcome the challenges, there has been much attention focusing on advanced oxidation processes (AOPs) which have been suggested as substitutions to previous treatment technologies Until now, there have been a variety of AOPs, including electrochemical oxidation (Gallios, Violintzis et al.,2010; 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Materials Letters 60(13): 1767-1770 Xiao, P., et al (2013) "Oxidative degradation of organic dyes over supported perovskite oxide LaFeO3/SBA-15 under ambient conditions." Catalysis letters 143(9): 887-894 Yao, W F., et al (2004) "Photocatalytic property of perovskite bismuth titanate." Applied Catalysis B: Environmental 52(2): 109-116 Yi, F and S Chen (2008) "Effect of activated carbon fiber anode structure and electrolysis conditions on electrochemical degradation of dye wastewater." Journal of Hazardous Materials 157(1): 79-87 65 ... LFO by light could take place in the following steps, as suggested by Chong et al (Chong, Jin et al., 2010) LaFeO3 + hν -> LaFeO3 + e-CB + h+VB e-CB + O2 -> O2•− O2•− + H2O -> HO2• + OH HO2• +... (m2/g) size (nm) LFO-110 Orthorhombic LaFeO3 18.6 50.5 LFO-140 Orthorhombic LaFeO3 23.6 32.8 LFO-170 Orthorhombic LaFeO3 25.8 36.5 LFO-200 Orthorhombic LaFeO3 15.5 71.2 and trace hexagonal La(OH)3... 2011) Thus, the study of LaFeO3 materials with properties suitable for photocatalytic requirements is really necessary So I decided to choose a topic : “ Synthesize LaFeO3 materials for photodegradation