Luận án tiến sĩ nghiên cứu tổng hợp tio2ac, tio2go và đưa lên gốm cordierite làm xúc tác cho quá trình quang phân hủy metyl da cam và phenol

MINISTRY OF EDUCATION AND TRAINING HANOI UNIVERSITY OF SCIENCE AND TECHNOLOGY Nguyen Trung Hieu RESEARCH INTO TiO2/AC, TiO2/GO SYNTHESIS AND COATING ON CORDIERITE CERAMIC APPLIED AS CATALYSTS FOR PHOTODEGRADATION OF METHYL ORANGE AND PHENOL DOCTORAL DISSERTATION IN CHEMICAL ENGINEERING Hanoi – 2022 MINISTRY OF EDUCATION AND TRAINING HANOI UNIVERSITY OF SCIENCE AND TECHNOLOGY Nguyen Trung Hieu RESEARCH INTO TiO2/AC, TiO2/GO SYNTHESIS AND COATING ON CORDIERITE CERAMIC APPLIED AS CATALYSTS FOR PHOTODEGRADATION OF METHYL ORANGE AND PHENOL Major : Chemical Engineering Code No : 9520301 DOCTORAL DISSERTATION IN CHEMICAL ENGINEERING ADVISOR: Prof Le Minh Thang Hanoi – 2022 GUARANTEE The study has been conducted at the School of Chemical Engineering (SCE), Germany and Vietnam catalyst research center (Gevicat), Hanoi University of Science and Technology (HUST) I affirm that this is my own research The co-authors consented to the use of all the data and findings presented in the thesis and confirmed their veracity This study has not been published by anybody but me Hanoi, Octorber 25th 2022 Thesis Advisor PhD student Prof Le Minh Thang Nguyen Trung Hieu i ACKNOWLEDGEMENTS I would like to express my sincerest and heartfelt gratitude to the following people and organizations whose valuable contributions and assistances have made my research possible: To Hanoi University of Science and Technology, specifically to the School of Chemical Engineering, Department of Organic and Petrochemical Technology for providing the laboratory instruments and the equipment for me to accomplish my research To - Catalyst Program, for letting me be an official member of the sponsored research on modified TiO2 synthesis and methyl orange and phenol photocatalytic degradation at Hanoi University (HUST) and National Taiwan University (NTU) To my thesis adviser, Prof Dr Le Minh Thang, for giving me guidance and supervision as well as critiques and comments on my progress reports to bring me patience, finance, and power to finish this research To Prof Dr Jeffrey Chi-Sheng Wu, for allowing me to be a part of his research team under the RoHan Program and for training me in his Lab at NTU To my family and friends who always try to encourage and motivate me during my thesis course, especially since it is the late gift for my father in heaven now ii TABLE OF CONTENTS GUARANTEE i ACKNOWLEDGEMENTS ii TABLE OF CONTENTS iii LIST OF ABREVIATIONS .vi LIST OF TABLES vii LIST OF FIGURES viii INTRODUCTION 1 Necessity of the study Objectives of the study 3 Content of the thesis 4 Methodologies of the study Scope of the study Scientific and practical meanings Novelty of the study 8.Structure of the thesis CHAPTER LITERATURE REVIEW 1.1 Textile industry and Methyl Orange dye 1.2 Phenol in industry and its impact to the health 1.3 Titanium dioxide, TiO2 .9 1.4 Principles of Precipitation, sol-gel and hydrothermal synthesis methods 13 1.4.1 Preparation of photocatalyst using sol-gel method .15 1.5 Support and thin films 19 1.5.1 Overview of Cordierite 19 1.5.2 Mesoporous TiO2 and coating techniques 20 1.5.3 Catalyst Suspension and immobilization .21 1.6 TiO2/AC Materials 22 1.7 Graphene oxide (GO) 26 1.8 TiO2/GO Materials 28 1.9 MO photocatalytic degradation 31 1.10 Phenol photocatalysis degradation 36 1.11 Summary 38 iii CHAPTER EXPERIMENTS 40 2.1 Materials and instruments 40 2.2 Catalyst preparation ………………………………………………………….42 2.2.1 Synthesis of mesoporous TiO2 42 2.2.2 Synthesis of TiO2 and AC/TiO2 by Sol-gel method 45 2.2.3 Synthesis of TiO2 GO by sol-gel method .46 2.2.4 Synthesis of TiO2 films on cordierite 48 2.3 Characterization of the catalysts 54 2.3.1 Morphology on the surface 54 2.3.2 Elemental surface composition and traces of impurities 56 2.3.3 Specific surface area, pore volume, and average pore size 56 2.3.4 Crystal structures formed and the crystallite diameter 57 2.3.5 Absorbance 58 2.3.6 UV-Vis DSR 60 2.3.7 High-performance liquid chromatography analysis 60 2.4 Experimental set up 62 2.5 To calculate the efficiency of photocatalytic process .63 2.5.1 Construct calibration curve of methyl orange solution 63 2.5.2 Calculation the concentration via equation .64 CHAPTER RESULTS AND DISSCUSSIONS 65 3.1 Mesoporous TiO2 synthesized by precipitation and hydrothermal with CTAB and P123 surfactants 65 3.1.1 Characterization results 65 3.1.2 MO photocatalytic degradation of mesoporous TiO2 photocatalysts prepared by precipitation and hydrothermal methods with surfactants (CTAB and P123) .69 3.2 TiO2/AC catalyst synthesized using sol-gel method .74 2.1 Characterization Catalyst 74 3.2.2 Photocatalytic activity of the MO in water .77 3.3 GO-TiO2 catalysts by sol-gel method 83 3.3.1 Characterization 83 3.3.2 MO photocatalytic degradation by TiO2 – GO ……………………… …….86 iv 3.4 TiO2 films 89 3.4.1 TiO2 films on Cordierite 89 3.4.2 TiO2 nanocatalysts thin film by the CVD method on various substrates100 3.5 Phenol photocatalytic degradation .107 CHAPTER 4: CONCLUSIONS AND RECOMENDATONS 115 REFERENCES 116 v LIST OF ABREVIATIONS Symbols Meaning UV Ultraviolet radiation MO methyl orange GO graphene oxide FTIR Fourier transform infrared spectroscopy SEM Scanning electron microscopy FE SEM Field Emission EDX Energy-dispersive X-ray spectroscopy P123 poly(ethylene glycol)-block-poly(propylene glycol)-block-poly (ethylene glycol) CNT carbon nanotube LPMOCVD Low pressure chemical vapor deposition AC activated carbon TTIP titanium tetraisopropoxide UV–VIS Ultraviolet- Visible HPLC High-performance liquid chromatography XRD X-ray diffraction BET Brunauer, Emmett and Teller SEM Scanning electron microscopy CTAB cetyl trimethyl ammonium bromide PEG polyethylene glycol vi LIST OF TABLES Table 1.1 The General Mechanism of the Photocatalytic Reaction Process on TiO2 [49] .11 Table 1.2 Summary of TiO2 and GO composites used as photocatalyst 30 Table 2.1: List of chemicals 40 Table 2.2: List of main instruments .41 Table 2.3: Catalyst synthesized by hydrothermal and precipitation methods using surfactant 44 Table 2.4 : AC to TiO2 Ratio with Corresponding Theoretical % Weight AC in AC/TiO2 catalyst 45 Table 2.5: Catalysis films and powders synthesized by various methods with the low concetration of PEG 50 Table 2.6: Catalyst films and powders synthesized by various methods with higher concentration of PEG .52 Table 3.1: The surface characteristics of catalysts synthesized by hydrothermal and precipitation methods 66 Table 3.2: Crystalline sizes of catalysts 68 Table 3.3: Surface area of two samples by sol-gel synthesis 75 Table 3.4: Crystalline sizes of catalysts 77 Table 3.5: Surface area of GO-TiO2 catalysts 85 Table 3.6: Crystalline sizes of catalysts 86 Table 3.7: Effect of ratio mol TTIP:H2O to the catalyst mass coated 89 Table 3.8: Catalysts films coated cordierite 93 Table 3.9: Apparent first-order rate constant kapp and correlation coefficient R2 for phenol degradation by catalysts synthesized by various methods 109 Table 3.10: Apparent first-order rate constant kapp and correlation coefficient R2 for phenol degradation with various initial concentrations by P123-C25-450 catalyst 110 Table 3.11: Apparent first-order rate constant kapp and correlation coefficient R2 for phenol degradation by P123-C25-450 catalyst with various concentrations H2O2 112 Table 3.12: Apparent first-order rate constant kapp and correlation coefficient R2 for phenol degradation in visible light condition 113 vii LIST OF FIGURES Fig 1.1: Chemical structure of MO molecule [33,34] Fig 1.2: TiO2 Crystal Structures[44] Fig 1.3: The mechanism of photocatalytic activity of TiO2 [50] 11 Fig 1.4: Nanocrystalline Metal Oxide Preparation using Sol-Gel method 17 Fig 1.5: Structures of graphene, C60, CNT and graphite [109] 27 Fig 1.6: Structure of GO [110] 27 Fig 1.7: Possible mechanism of MO with TiO2 [142] 34 Fig 1.8: Production Distributions from Phenol Decomposition Reaction [152] 38 Fig 2.1 Flowchart of TiO2 synthesis using CTAB 42 Fig 2.2 Flowchart of TiO2 synthesis using P123 43 Fig 2.3: Flowchart of GO synthesis 46 Fig 2.4: Flowchart of GO-TiO2 (GO-ZnO) synthesis 47 Fig 2.5: Dip-coating TiO2 on the surface of cordierite 49 Fig 2.6: Experimental LPCVD set-up .53 Fig 2.7: Simplified internal structure of FESEM 54 Fig 2.8: Energy band diagram of a semiconductor (Zeghbroeck, 2007) .60 Fig 2.9: Principle diagram of a HPLC system 61 Fig 2.10a: Photocatalytic exerimental setup with UV-C lamp 62 Fig 2.10 b: Principle diagram of visible photocatalytic exerimental setup 63 Fig 3.1: Nitrogen isotherm of CTAB-NE and P123 C25-450 66 Fig 3.2: Pore size distribution of CTAB-NE and P123 C25-450 67 Fig 3.3: XRD paterns of catalysts synthesized with surfactants CTAB and P123 .68 Fig 3.4: FE-SEM images of CTAB-H (a) and P123 C25-450 (b) 69 Fig 3.5: Evaluation of the catalysts using CTAB by two hydrothermal and precipitation methods 70 Fig 3.6: The influence of citric acid amount to catalyst performance 71 Fig 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tổng hợp đến q trình tổng hộp xúc tác quang hóa TiO2 xử lý methyl da cam (MO)”, Tạp chí Hóa học, số T.55 (2e) 2017, tr 5-10 Nguyễn Trung Hiếu, Bùi Đức Huy, Le Minh Thắng (2018), “Nghiên cứu hoạt tính xúc tác TiO2 dạng màng mỏng cordierite xử lý methyl da cam”, Tạp chí Hóa học, số T.56 (3E12), tr 198-202 Nguyễn Trung Hiếu, Hoàng Thế Huynh, Trịnh Giang Khánh, Vũ Anh Tuấn, Lê Minh Thắng (2019), “Tổng hợp đánh giá hoạt tính xúc tác màng TiO2 gốm cordierite việc xử lý methyl da cam”, Tạp chí Hóa học, số T.57 (2e12) 1-5, tr 115-121 Nguyễn Trung Hiếu, Trịnh Huy Quang, Đào Quốc Tùy, Lê Minh Thắng (2019), “Nghiên cứu ảnh hưởng tỷ lệ grapheme oxide (GO) q trình biến tính xúc tác quang hóa TiO2 phương pháp sol-gel xử lý methyl da cam (MO)”, Tạp chí Hóa học, số T.57 (2e12) 1-5, tr 122-127 Trung Hieu Nguyen, Anh Tuan Vu, Van Han Dang, Jeffrey Chi-Sheng Wu, Minh Thang Le (2020), “Photocatalytic Degradation of Phenol and Methyl Orange with Titania-Based Photocatalysts Synthesized by Various Methods in Comparison with ZnO–Graphene Oxide Composite”, Topics in Catalysis, Springer Nature 2020 https://doi.org/10.1007/s11244-020-01361-5 APPENDIX A TiO2/AC composites Calculation Example of Calculation: TiO2/AC at 5%wt: In preparation process 20ml Ti(OCH(CH3)2)4 was used The synthesis reaction was presented below Ti(OCH(CH3)2)4 information; the density is 0.97 kg/l, the molecular weight is 284.26 g/mol For TiO2, the molecular weight is 80 g/mol Ti{OCH(CH3)2}4 + H2O → TiO2 + (CH3)2CHOH So, 20ml Ti[OCH(CH3)2]4 can be produced TiO2; TiO ( g ) = 1mol Ti[OCH (CH 3)2 ]4 20ml  0.97kg / l   80 g / mol TiO2 284.26 g / molTi[OCH (CH 3)2 ]4 1mol TiO2 So the amount of TiO2 = 5.46 g The percent theoretical amount of AC percent in composite catalyst can be computed by % wt of AC = The amount of AC added, X =0.29 g X  100 X T 5% wt = X  100 X  5.46 APPENDIX B MO (methyl orange) photodegradation a b d c A: methyl orange MO in powder, B experimental setup for full range visible experiment, C MO sampling tube, D: MO absorbance by Avantes Uv-Vis device APPENDIX C Phenol photodegradation APPENDIX D BET pore results APPENDIX E XRD characterizations Faculty of Chemistry, HUS, VNU, D8 ADVANCE-Bruker - G1-18 600 500 300 d=3.527 Lin (Cps) 400 d=1.487 d=1.697 d=1.667 100 d=1.895 d=2.378 200 10 20 30 40 50 60 70 2-Theta - Scale File: HieuBK G1-18.raw - Type: 2Th/Th locked - Start: 5.000 ° - End: 70.010 ° - Step: 0.030 ° - Step time: 0.3 s - Temp.: 25 °C (Room) - Time Started: s - 2-Theta: 5.000 ° - Theta: 2.500 ° - Chi: 0.00 ° - Phi: 0.00 ° - X: 0.0 m 00-021-1272 (*) - Anatase, syn - TiO2 - Y: 82.49 % - d x by: - WL: 1.5406 - Tetragonal - a 3.78520 - b 3.78520 - c 9.51390 - alpha 90.000 - beta 90.000 - gamma 90.000 - Body-centered - I41/amd (141) - - 136.313 - I/Ic Faculty of Chemistry, HUS, VNU, D8 ADVANCE-Bruker - G1-24 600 500 d=3.520 300 d=3.360 d=1.481 d=1.700 d=1.890 100 d=1.370 200 d=2.378 Lin (Cps) 400 10 20 30 40 50 60 2-Theta - Scale File: HieuBK G1-24.raw - Type: 2Th/Th locked - Start: 2.000 ° - End: 70.010 ° - Step: 0.030 ° - Step time: 0.3 s - Temp.: 25 °C (Room) - Time Started: 14 s - 2-Theta: 2.000 ° - Theta: 1.000 ° - Chi: 0.00 ° - Phi: 0.00 ° - X: 0.0 1) Left Angle: 23.540 ° - Right Angle: 26.180 ° - Left Int.: 69.9 Cps - Right Int.: 94.8 Cps - Obs Max: 25.276 ° - d (Obs Max): 3.521 - Max Int.: 238 Cps - Net Height: 151 Cps - FWHM: 0.718 ° - Chord Mid.: 25.253 ° - Int Br 00-021-1272 (*) - Anatase, syn - TiO2 - Y: 50.21 % - d x by: - WL: 1.5406 - Tetragonal - a 3.78520 - b 3.78520 - c 9.51390 - alpha 90.000 - beta 90.000 - gamma 90.000 - Body-centered - I41/amd (141) - - 136.313 - I/Ic 70 Faculty of Chemistry, HUS, VNU, D8 ADVANCE-Bruker - G1-4 600 500 300 d=3.520 d=1.482 d=1.698 d=1.891 100 d=1.664 200 d=2.374 Lin (Cps) 400 10 20 30 40 50 60 2-Theta - Scale File: HieuBK G1-4.raw - Type: 2Th/Th locked - Start: 2.000 ° - End: 70.010 ° - Step: 0.030 ° - Step time: 0.3 s - Temp.: 25 °C (Room) - Time Started: 14 s - 2-Theta: 2.000 ° - Theta: 1.000 ° - Chi: 0.00 ° - Phi: 0.00 ° - X: 0.0 m 1) Left Angle: 22.820 ° - Right Angle: 27.560 ° - Left Int.: 71.2 Cps - Right Int.: 64.8 Cps - Obs Max: 25.280 ° - d (Obs Max): 3.520 - Max Int.: 234 Cps - Net Height: 167 Cps - FWHM: 0.742 ° - Chord Mid.: 25.271 ° - Int Br 00-021-1272 (*) - Anatase, syn - TiO2 - Y: 55.67 % - d x by: - WL: 1.5406 - Tetragonal - a 3.78520 - b 3.78520 - c 9.51390 - alpha 90.000 - beta 90.000 - gamma 90.000 - Body-centered - I41/amd (141) - - 136.313 - I/Ic 70