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 – 2023 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 – 2023 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, March 14th 2023 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 12 1.4.1 Preparation of photocatalyst using sol-gel method .14 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 37 1.11 Kinetics study of phenol photodegradation .410 1.12 Summary …………………………………………………………………… 41 iii CHAPTER EXPERIMENTS 43 2.1 Materials and instruments 43 2.2 Catalyst preparation ………………………………………………………….42 2.2.1 Synthesis of mesoporous TiO2 452 2.2.2 Synthesis of TiO2 and AC/TiO2 by Sol-gel method 48 2.2.3 Synthesis of TiO2 GO by sol-gel method .49 2.2.4 Synthesis of TiO2 films on cordierite 51 2.3 Characterization of the catalysts 57 2.3.1 Morphology on the surface 57 2.3.2 Elemental surface composition and traces of impurities 59 2.3.3 Specific surface area, pore volume, and average pore size 59 2.3.4 Crystal structures formed and the crystallite diameter 60 2.3.5 Absorbance 61 2.3.6 UV-Vis DSR2.3.7 High-performance liquid chromatography analysis 62 2.4 Experimental set up 63 2.5 To calculate the efficiency of photocatalytic process .65 2.5.1 Construct calibration curve of methyl orange solution 65 2.5.2 Calculation the concentration via equation .66 CHAPTER RESULTS AND DISSCUSSIONS 67 3.1 Characterization and photocatalytic activity off mesoporous TiO2 synthesized by precipitation and hydrothermal using CTAB and P123 surfactants 67 3.1.1 Characterization of sampless 67 3.1.2.Photocatalytic activity… …………………………………………………71 3.2.Characterization and photocatalytic activity of TiO2/AC catalyst synthesized using sol-gel method 75 2.1 Characterization of samples .75 3.2.2 Photocatalytic activity of the synthesized samples .79 3.3 Chracterization and photocatalytic activity of GO-TiO2 catalysts by sol-gel method .85 3.3.1 Characterization of samples .85 3.3.2 MO photocatalytic degradation by TiO2 - GO ……………………… ………88 3.4 TiO2 films 91 iv 3.4.1 TiO2 films on Cordierite 91 3.4.2 TiO2 nanocatalysts thin film by the CVD method on various substrates102 3.5 Phenol photocatalytic degradation .109 CONCLUSIONS AND RECOMENDATONS 118 REFERENCES 121 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 Scanning electron microscopy 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 Summary of TiO2 and GO composites used as photocatalyst 30 Table 2.1: List of chemicals 43 Table 2.2: List of main instruments .44 Table 2.3: Catalyst synthesized by hydrothermal and precipitation methods using surfactant 47 Table 2.4 : AC/ TiO2 catalyst with various AC to TiO2 Ratio .49 Table 2.5: Catalysis films and powders synthesized by various methods with the low concetration of PEG 54 Table 2.6: Catalyst films and powders synthesized by various methods with higher concentration of PEG .55 Table 3.1: The surface characteristics of catalysts synthesized by hydrothermal and precipitation methods 67 Table 3.2: Crystalline sizes of catalysts 70 Table 3.3: Surface area of two samples by sol-gel synthesis 77 Table 3.4: Crystalline sizes of catalysts 79 Table 3.5: Surface area of GO-TiO2 catalysts 87 Table 3.6: Crystalline sizes of catalysts 88 Table 3.7: Effect of ratio mol TTIP:H2O to the catalyst mass coated 92 Table 3.8: Catalysts films coated cordierite 95 Table 3.9: Apparent first-order rate constant kapp and correlation coefficient R2 for phenol degradation by catalysts synthesized by various methods 111 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 113 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 114 Table 3.12: Apparent first-order rate constant kapp and correlation coefficient R2 for phenol degradation in visible light condition 116 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 [138] 34 Fig.1.8: Role of activated carbon [145] ……………………………………………………37 Fig 1.9: Mechanism 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Taiwan Inst Chem Eng 67:338–345 138 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