(LUẬN án TIẾN sĩ) nghiên cứu tổng hợp tio2 AC, tio2 GO 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 3.7:The influence of Ethanol elimination method to catalyst performance 72 Fig 3.8: Comparing the best catalyst via hydrothermal and precipitation 73 Fig 3.9: Nitrogen isotherm of SG TiO2 and SG AC1200 TiO2 1/18 74 Fig 3.10: Pore size distribution of SG TiO2 and SG AC1200 TiO2 1/18 75 Fig 3.11: Morphology of SG AC-1200/Ti 1/18 (a) and SG AC-1200/Ti 3/1 (b) 76 viii [95] Guillard, C., Lachheb, H., Houas, A., Ksibi, M., Elaloui, E & Herrmann, J (2003) “Influence of chemical structure of dyes, of pH and of inorganic salts on their photocatalytic degradation by TiO2: Comparison of the efficiency of powder and supported TiO2” Journal of Photochemistry and Photobiology A: Chemistry, 158, 27–36 [96] Ao, Y., Xu, J., Fu, D., Shen, X & Yuan, C (2008) “Low temperature preparation of anatase TiO2 -activated carbon composite film” Applied Surface Science, 254, 4001–4006 [97] Jahromi, H., Taghdisian, H., Afshar, S & Tasharoffi, S (2009) “Effects of pH and polyethylene glycol on morphology of TiO2 thin film“ Surface and Coatings Technology, 203, 1991-1996 [98] M Uzunova-Bujnova, R Todorovska, M Milanova, R Kralchevska,, D Todorovsky (2009) On the spray-drying deposition of TiO2 photocatalytic films“ Applied Surface Science, 256, 830-837 [99] S., Lee, J., Yoo, K., Park, H., Kim, H & Lee, J (2008) “Adhesion properties of inorganic binders for the immobilization of photocatalytic ZnO and TiO2 nanopowders” Journal of Physics and Chemistry of Solids, 69,1461–1463 [100] Akira Fujishima Tata N Rao and Donald A Tryk, “Titanium dioxide photocatalysis” Journal of Photochemistry and Photobiology C: Photochemistry Reviews, 2000 - : Vol - pp 1-21 [101] Bin Gao George Z Chen,Gianluca Li Puma,“Carbon nanotubes/titanium dioxide (CNTs/TiO2) nanocomposites prepared by conventional and novel surfactant wrapping sol–gel methods exhibiting enhanced photocatalytic activity Applied Catalysis B: Environmental , 2009 - 3-4 : Vol 89 - pp 503-509 [102] Wang W Silva, C.G and Faria J.L “Photocatalytic Degradation of Chromotrope 2R using Nanocrystalline TiO2/Activated Carbon Composite Catalysts“, Applied Catalysis B: Enviromental - 2007 - 70 - pp 470-478 [103] Liu.J Rong.Y and Song-mei L, “Preparation and Application of Efficient TiO2/ACF Photocatalyst”, Journal of Environmental Science, 2006 - Vol - pp 979-982 [104] Tryba, B., Morawski, W & Inagaki, M (2003a) “A new route for preparation of TiO2 – mounted activated carbon” Applied Catalysis B: Environmental, 46, 203208 [105] Li.Y Zhang.S,Yu.Q and Yin.W, “The Effects of Activated Carbon Support on The Structure and Properties of TiO2 Nanoparticles Prepared by A Sol-gel Method“, Applied Surface Science 2007 Vol 253 - pp 9254- 9258 124 [106] Novoselov, K S., Geim, A K., Morozov, S V., Jiang, D., Zhang, Y., Dubonos, S V., Grigorieva, I V and Firsov, A A (2004), "Electric field in atomically thin carbon films", Science, Vol 306, No 5696, pp 666-669 [107] Wang, X., Zhi, L and Mullen, K (2007), "Transparent, Conductive Graphene Electrodes for Dye-Sensitized Solar Cells", Nano Letters, Vol 8, No 1, pp 323-327 [108] Allen, M J., Tung, V C and Kaner, R B (2009), "Honeycomb Carbon: A Review of Graphene", Chemical Reviews, Vol 110, No 1, pp 132-145 [109] Huang, X., Qi, X., Boey, F and Zhang, H (2012), "Graphene-based composites", Chemical Society Reviews, Vol 41, No 2, pp 666-686 [110] Geim, A K and Novoselov, K S (2007), "The rise of graphene", Nature Materials, Vol 6, No 3, pp 183-191 [111] Guo, S and Dong, S (2011), "Graphene nanosheet: synthesis, molecular engineering, thin film, hybrids, and energy and analytical applications", Chemical Society Reviews, Vol 40, No 5, pp 2644-2672 [112] Feng, H., Cheng, R., Zhao, X., Duan, X and Li, J (2013), "A low-temperature method to produce highly reduced graphene oxide", Nature Communications, Vol 4, No pp 1539-1546 [113] Xu, Z., Sun, H., Zhao, X and Gao, C (2013), "Ultrastrong Fibers Assembled from Giant Graphene Oxide Sheets", Advanced Materials, Vol 25, No 2, pp 188-193 [114] Dreyer, D R., Park, S., Bielawski, C W and Ruoff, R S (2010), "The chemistry of graphene oxide", Chemical Society Reviews, Vol 39, No 1, pp 228-240 [115] Luo, J., Cote, L J., Tung, V C., Tan, A T L., Goins, P E., Wu, J and Huang, J (2010), "Graphene Oxide Nanocolloids", Journal of the American Chemical Society, Vol 132, No 50, pp 17667-17669 [116] Dikin, D A., Stankovich, S., Zimney, E J., Piner, R D., Dommett, G H B., Evmenenko, G., Nguyen, S T and Ruoff, R S (2007), "Preparation and characterization of graphene oxide paper", Nature, Vol 448, No 7152, pp 457460 [117] Park, S., An, J., Jung, I., Piner, R D., An, S J., Li, X., Velamakanni, A and Ruoff, R S (2009), "Colloidal suspensions of highly reduced graphene oxide in a wide variety of organic solvents", Nano Letters, Vol 9, No 4, pp 1593-1597 [118] Stankovich, S., Dikin, D A., Dommett, G H B., Kohlhaas, K M., Zimney, E J., Stach, E A., Piner, R D., Nguyen, S T and Ruoff, R S (2006), "Graphene-based composite materials", Nature, Vol 442, No 7100, pp 282-286 [119] Bai, H., Li, C and Shi, G (2011), "Functional composite materials based on chemically converted graphene", Advanced Materials, Vol 23, No 9, pp 10891115 125 [120] Zhu, X., Ning, G., Fan, Z., Gao, J., Xu, C., Qian, W and Wei, F (2012), "One-step synthesis of a graphene-carbon nanotube hybrid decorated by magnetic nanoparticles", Carbon, Vol 50, No 8, pp 2764-2771 [121] Liu, J., Bai, H., Wang, Y., Liu, Z., Zhang, X and Sun, D D (2010), "Selfassembling TiO2 nanorods on large graphene oxide sheets at a two-phase interface and their anti-recombination in photocatalytic applications", Advanced Functional Materials, Vol 20, No 23, pp 4175-4181 [122] Zhang, J., Xiong, Z and Zhao, X S (2011), "Graphene-metal-oxide composites for the degradation of dyes under visible light irradiation", Journal of Materials Chemistry, Vol 21, No 11, pp 3634-3640 [123] Kou, R., Shao, Y., Wang, D., Engelhard, M H., Kwak, J H., Wang, J., Viswanathan, V V., Wang, C., Lin, Y., Wang, Y., Aksay, I A and Liu, J (2009), "Enhanced activity and stability of Pt catalysts on functionalized graphene sheets for electrocatalytic oxygen reduction", Electrochemistry Communications, Vol 11, No 5, pp 954-957 [124] Chen, L C & Chou, T S (1994) “Photodecolorization of Methyl Orange Using Silver Ion Modified TiO2 as Photocatalyst” Industrial & Engineering Chemistry Research, 33, 1436-1443 [125] Al- Qaradawi, S & Salman, R S (2002) “Photocatalytic degradation of methyl orange as a model compound” Journal of Photochemistry and Photobiology A, 148, 161–168 [126] Arabatzis, I M., Stergiopoulos, T., Bernard, M C., Labou, D Neophytides, S G & Falaras, P.(2003) “Silver-modified titanium dioxide thin films for efficient photodegradation of methyl orange” Applied Catalysis B: Environmental, 42, 187– 201 [127] Guettai, N & Amar, H A (2005) “Photocatalytic oxidation of methyl orange in presence of titanium dioxide in aqueous suspension Part I: Parametric study” Desalination, 185, 427–437 [128] Chen, J Q., Wang, D., Zhu, M X & Gao, C J (2006) “Study on degradation of methyl orange using pelagite as photocatalyst” Journal of Hazardous Materials B,138, 182–186 [129] Li, Y., Li, X., Li, J & Yin, J (2006) “Photocatalytic degradation of methyl orange by TiO2-coated” Water Research, 40, 1119 – 1126 [130] Sharma, S D., Singh, D., Saini, K K., Kant, C., Sharma, V., Jain, S C & Sharma, C P (2006) “Sol–gel-derived super-hydrophilic nickel doped TiO2 film as active photo-catalyst” Applied Catalysis A: General, 314, 40–46 126 [131] Kansal, S K., Singh, M & Sud, D (2007) “Studies on photodegradation of two commercial dyes in aqueous phase using different photocatalysts” Journal of Hazardous Materials, 141, 581-590 [132] Liu, Y & Sun, D (2007) “Development of Fe2O3 -CeO2 -TiO2/γ -Al2O3 as catalyst for catalytic wet air oxidation of methyl orange azo dye under room condition” Applied Catalysis B, Environmental, 72, 205-211 [133] Ma, H., Zhuo, Q & Wang, B (2007) “Characteristics of CuO-MoO3-P2O5 Catalyst and Its Catalytic Wet Oxidation (CWO) of Dye Wastewater under Extremely Mild Conditions” Environmental Science & Technology, 41, 7491-7496 [134] Rashed, M N & El-Amin, A A (2007) “Photocatalytic degradation of methyl orange in aqueous TiO2 under different solar irradiation sources“ International Journal of Physical Sciences, (3), 73-81 [135] Zhang, X., Yang, H., Zhang, F & Chen, K.W (2007) “Preparation and characterization of Pt–TiO2–SiO2 mesoporous materials and visible-light photocatalytic performance“ Materials Letters, 61, 2231–2234 [136] Huang, M., Xu, C., Wu, Z., Huang, Y., Lin, J & Wu, J (2008) “Photocatalytic discolorization of methyl orange solution by Pt modified TiO2 loaded on natural zeolite” Dyes and Pigments,77, 327-334 [137] Sohn, Y S., Smith, Y R., Misra, M & Subramanian, V (2008) “Electrochemically assisted photocatalytic degradation of methyl orange using anodized titanium dioxide nanotubes” Applied Catalysis B: Environmental, 84, 372–378 [138] Zhang, F., Xie, F., Fang, T., Zhang, K., Chen, T & Oh, W (2012) “Photocatalytic Degradation of Methyl Orange on Platinum and Palladium Co-doped TiO2 Nanoparticles, Synthesis and Reactivity in Inorganic, Metal-Organic, and NanoMetal Chemistry“, 42:5, 685-691 doi:10.1080/15533174.2011.615040 [139] Sun, M., Li, D., Li, W., Chen, Y., Chen, Z., He, Y & Fu, X (2008) “New Photocatalyst, Sb2S3, for Degradation of Methyl Orange under Visible-Light Irradiation” Journal of Physical Chemistry C, 112, 18076–18081 [140] Zhao, Q., Li, M., Chu, J., Jiang, T & Yin, H (2009) “Preparation, characterization of Au (or Pt)-loaded titania nanotubes and their photocatalytic activities for degradation of methyl orange” Applied Surface Science, 255, 3773–3778 [141] Zhu, Y., Xu, S & Yi, D (2010) “Photocatalytic degradation of methyl orange using polythiophene/titanium dioxide composites” Reactive & Functional Polymers, 70, 282-287 [142] Guo, C., Xu, J., He, Y., Zhang, Y & Wang, Y (2011) “Photodegradation of rhodamine B and methyl orange over one-dimensional TiO2 catalysts under simulated solar irradiation” Applied Surface Science, 257, 3798–3803 127 [143] Rauf, M & Ashraf, S (2009) „Fundamental principles and application of heterogeneous photocatalytic degradation of dye in solution“ Chemical Engineering Journal, 151, 10-18 [144] Bouzaida, I., Ferronato, C., Chovelon, J., Rammah, M & Herrmann J (2004) “Heterogeneous photocatalytic degradation of the anthraquinonic dye, acid blue 25 (AB25): A kinetic approach“ Journal of Photochemistry and Photobiology A: Chemistry, 168, 23 [145] S Kulkarni and D Kaware, "Review on Research for Removal of Phenol from Wastewater", International Journal of Scientific and Research Publications, (2013) 1-4 [146] Zaheen U Khan, Ayesha Kausar, Hidayat Ullah, Amin Badshah and Wasid U Khan (2015), "A review of graphene oxide, graphene buckypaper, and polymer/graphene composites: Properties and fabrication techniques", Journal of Plastic Film & Sheeting 0(0), tr 1-45 [147] X Xiong and Y Xu, "Synergetic Effect of Pt and Borate on the TiO2Photocatalyzed Degradation of Phenol in Water", The Journal of Physical Chemistry C, 120 (2016) 3906-3912 [148] W Wang, P Serp, P Kalck, J Luis Faria, “Photocatalytic degradation of phenol on MWNT and titania composite catalysts prepared by a modified sol–gel method”, Applied Catalysis B: Environmental 56 (2005) 305-312 [149] J Prince, F Tzompantzi, G Mendoza-Damian, F Hernandez-Beltran, J.S Valente, “Photocatalytic degradation of phenol by semiconducting mixed oxides derived from Zn(Ga)Al layered double hydroxides”, Applied Catalysis B: Environmental 163 (2015) 352-360 [150] M Umar and H Abdul, "Photocatalytic Degradation of Organic Pollutants in Water", Organic Pollutants - Monitoring, Risk and Treatment, 2013 [151] A Linsebigler, G Lu and J Yates, "Photocatalysis on TiO2 Surfaces: Principles, Mechanisms, and Selected Results", Chemical Reviews, 95 (1995) 735-758 [152] K Okamoto, Y Yamamoto, H Tanaka, M Tanaka and A Itaya, "Heterogeneous Photocatalytic Decomposition of Phenol over TiO2 Powder", Bulletin of the Chemical Society of Japan, 58 (1985) 2015- 2022 [153] N Khalid, E Ahmed, N Niaz, G Nabi, M Ahmad, M Tahir, M Rafique, M Rizwan and Y Khan, "Highly visible light responsive metal loaded N/TiO2 nanoparticles for photocatalytic conversion of CO2 into methane", Ceramics International, 43 (2017) 6771-6777 128 [154] N M Nghĩa and N T Huệ, "Nghiên cứu tính chất quang xúc tác TiO2 pha tạp Fe phủ hạt silica – gel," Tạp chí Khoa học ĐHQGHN: Khoa học Tự nhiên Công nghệ, vol 32, no 4, pp 24-29, 2016 [155] N.Q Tuấn et al, "Nghiên cứu chất quang xúc tác TiO2 biến tính Fe2O3 phương pháp sol-gel " Tạp chí hố học Việt Nam, vol 47, no 3, pp 292-299, 2008 [156] [3V] V H Sơn and L P Sơn, "Tổng hợp nano TiO2 cấu trúc anatase pha tạp neodymium phương pháp sol-gel," Tạp chí hóa học Việt Nam, vol 52, no 4, 2014 [157] N V Hưng et al, "Ảnh hưởng Nd3+ đến cấu trúc hoạt tính quang xúc tác bột Nd-TiO2 kích thước nano điều chế phương pháp thuỷ nhiệt thủy phân," Tạp chí Khoa học Cơng nghệ, vol 50, no 3, pp 367-374, 2012 [158] H T K Xuân et al, “Nghiên cứu biến tính TiO2 anatase KF khảo sát hoạt tính quang hóa vùng khả kiến”," Tạp chí phát triển khoa học cơng nghệ ĐH Quốc Gia TP.HCM, vol 13, no T1, pp 22-28, 2010 [159] Malekshoar G, Pal K, He Q, Yu A, Ray AK (2014) Enhanced solar photocatalytic degradation of phenol with coupled graphene- based titanium dioxide and zinc oxide Indust Eng Chem Res 53:18824–18832 [160] Alam S, Sharma N, Kumar L (2017) “Synthesis of graphene oxide (GO) by Modified Hummers method and its thermal reduction to obtain reduced graphene oxide rGO” Graphene 6:1–18 [161] Mai Phuong P, „Study on the impregnation procedures to prepare catalytic complexes for the treatment of motobiker ‘s exhaust gases“, a PhD dissertation 2013 HUST [162] I Syauqiyah, M Elma, M D Putra1, A Rahma, Amalia E Pratiwi and E L A Rampun, “Interlayer-free Silica-carbon Template Membranes from Pectin and P123 for Water Desalination“, MATEC Web Conf Volume 280, 2019 [163] A Ban Mazin, S Asma, Khalil, „Characterization of TiO2 Nanorods and Nanotubes Synthesized by Sol Gel Template Method“, Engineering and Technology Journal Vol 36, Part C, No 2, 2018 [164] Shaohua, ShenLiang, Zhao Liejin Guo, “Crystallite, optical and photocatalytic properties of visible-light-driven ZnIn2S4 photocatalysts synthesized via a surfactant-assisted hydrothermal method“, Materials Research Bulletin, Volume 44, Issue 1, January 2009, Pages 100-105 [165] H Annika, H Marwa, S Franceb , J Jouguetb , D Dappozze ,G Chantal, "Impact of Rutile and Anatase Phase on the Photocatalytic Decomposition of Lactic Acid“, 129 Applied Catalysis B: Environmental ,Volume 253, 15 September 2019, Pages 96104 [166] G Jayakumar, A Albert Irudayaraj, A Dhayal Raj, “Particle Size Effect on the Properties of Cerium Oxide (CeO2) Nanoparticles Synthesized by Hydrothermal Method“, Mechanics, Materials Science & Engineering, April 2017 – ISSN 24125954 [167] Katie A.Cychosz, T Matthias, “Progress in the Physisorption Characterization of Nanoporous Gas Storage Materials“, Engineering, Volume 4, Issue 4, August 2018, Pages 559-566 [168] M.Pas-Garzón, A.Gómez-Avilés, C.BelverJ.J.Rodriguez, J.Bedia, “Degradation pathways of emerging contaminants using TiO2-activated carbon heterostructures in aqueous solution under simulated solar light“, Chemical Engineering Journal Volume 392, 15 July 2020, 124867 [169] O Kingsley,J Iwuozorab, O Joshua, E.Ighalocd, “Adsorption of methyl orange: A review on adsorbent performance,“ Current Research in Green and Sustainable Chemistry Volume 4, 2021, 100179 -174 [170] Abdollah Karami, Reem Shomal , Rana Sabouni , Mohammad H Al-Sayah and Ahmed Aidan, “Parametric Study of Methyl Orange Removal Using Metal–Organic Frameworks Based on Factorial Experimental Design Analysis”, Energies 2022, 15, 4642 [171] Reda S Salama, Sohier A El-Hakama, Salem E Samraa, Shady M El-Dafrawya and Awad I.Ahmeda, “Adsorption, Equilibrium and kinetic studies on the removal of methyl orange dye from aqueous solution by the use of copper metal organic framework (Cu-BDC)”, International Journal of Modern Chemistry, 2018, 10(2): 195-207 [172] Xian-Tai Zhou, Hong-Bing Ji, andXing-Jiao Huang, “Photocatalytic Degradation of Methyl Orange over Metalloporphyrins Supported on TiO2 Degussa P25”, Molecules 2012, 17(2), 1149-1158 [173] S LasseS, S RenSua, W StefanWendt, H PeterHald, M ArefMamakhel, Y Chuanxu, B Yudong Huang, B,B Iversenc Flemming, “The influence of crystallite size and crystallinity of anatase nanoparticles on the photo-degradation of phenol”, Journal of Catalysis Volume 310, February 2014, Pages 100-108 [174] Lathasree, S., Rao, A.N., SivaSankar, B., Sadasivam, V., Rengaraj, K., “Heterogeneous photocatalytic mineralization of phenols in aqueous solutions“, J Mol Catal A: Chem 223, (2004) 130 [175] N.N.Bahrudin, “Evaluation of degradation kinetic and photostability of immobilized TiO2/activated carbon bilayer photocatalyst for phenol removal”, Applied Surface Science Advances Volume 7, February 2022, 100208 [176] Daneshvar, N., Behnajady, M.A., Asghar,Y.Z.,“Photooxidative degradation of 4-nitrophenol in UV/H2O2 process: Influence of operational parameters and reaction mechanism“, J Hazard Mat., B139, (2007) 275-279 [177] Sobczynski, A., Duczmal, L., Zmudzinski, W, “Phenol destruction by photocatalysis on TiO2: An attempt to solve the reaction mechanism“, J Mol Catal A: Chem 213, (2004) 225-230 [178] Behnajady, M.A., Modirshshla, N., Shokri, M., “Photodestruction of acid orange (AO7) in aqueous solution by UV/H2O2: Influence of operational parameters“, Chemosphere 55 (2003) 129-134 [179] Roenfeldt, E.J., Linden, K.G., Canonica, S., Gunten, U V.,“Comparison of the efficiency of OH radical formation during ozonation and the advanced oxidation processes O3/H2O2 and UV/H2O2“, Water Res 40 (2006) 3695-3704 [180] Yonar, T., Kestioglu, K., Azbar, N, “Treatability studies on domestic wastewater using UV/H2O2 process“, Appl Catal B: Environ., 67, (2006) 223-228 [181] Raja A, Selvakumar K, Rajasekaran P, Arunpandian M, Ashok- kumar S, Kaviyarasu K, Asath Bahadur S, Swaminathan M (2019), “Visible active reduced graphene oxide loaded titania for photo- decomposition of ciprofloxacin and its antibacterial activity“ Colloids Surf A 564:23–30 [182] Fu CC, Juang RS, Huq MM, Hsieh CT (2016), “Enhanced adsorption and photodegradation of phenol in aqueous suspensions of titania/graphene oxide composite catalysts“ J Taiwan Inst Chem Eng 67:338–345 131 THE COLLECTION OF PUBLICATIONS Nguyễn Trung Hiếu, Phạm Thị Mai Phương, Đào Quốc Tùy, Lê Minh Thắng (2016), “Nghiên cứu ảnh hưởng chủng loại hàm lượng than hoạt tính vật liệu AC/TiO2 đến trình quang phân hủy methyl orange (MO)”, Tạp chí hóa học, số T54 (5e1,2) 1-5 2016, tr 343-347 Nguyễn Trung Hiếu, Đào Quốc Tùy, Filip Verschaeren, Lê Minh Thắng (2017), “Nghiên cứu ảnh hưởng chất hoạt động bề mặt phương pháp 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 ... Jiang et al 2011 TiO2/ GO 30 nm 10 wt% Methyl blue Nguyen et al 2011 TiO2/ GO - GO :TiO2 = 1.5 wt Methyl orange Pu et al 2013 TiO2/ GO 10 nm 0.03 mg GO Methyl blue Yoo D-H et al 2011 TiO2/ GO 4-5 nm 3.3... Diphenhydramine and methyl orange Pastrana et al 2010 TiO2/ GO 15 nm ~10% Rhodamine B Liang et al 2010 TiO2/ GO 10 nm GO :TiO2 = 3:2 wt Methyl orange Gao et al 2010 TiO2/ GO 6-9 nm wt% Methylene blue Kim et al... TiO2 particle size Pt -GO -TiO2/ GR 30 nm TiO2- GO and TiO2- GR GO content Pollutant Ref 0.5 wt% Dodecylbenzenesulfonate Neppolian et al 2012 5-15 nm 90 wt% Methylene blue Ismail et al 2013 2013 TiO2/ GO