Tổng Hợp Hệ Xúc Tác Trên Cơ Sở Pt SBA-15 Biến Tính Với Al Và Hoặc B Và Khả Năng Ứng Dụng Của Chúng

MINISTRY OF EDUCATION AND TRANING HANOI UNIVERSITY OF SCIENCE AND TECHNOLOGY NGO THI THANH HIEN Synthesis of catalysts based on Pt/SBA-15 modified with Al and/or B and their applicability on n-heptane hydroisomerization, tetralin hydrogenation and paracetamol detection CHEMICAL ENGINEERING DOCTORAL DISSERTATION Ha Noi – 2020 MINISTRY OF EDUCATION AND TRANING HANOI UNIVERSITY OF SCIENCE AND TECHNOLOGY NGO THI THANH HIEN Synthesis of catalysts based on Pt/SBA-15 modified with Al and/or B and their applicability on n-heptane hydroisomerization, tetralin hydrogenation and paracetamol detection Major: Chemical Engineering Code No: 9520301 CHEMICAL ENGINEERING DOCTORAL DISSERTATION ADVISORS: Assoc Prof Pham Thanh Huyen Prof Graziella Liana Turdean Ha Noi – 2020 STATUTORY DECLARATION I hereby declare that I myself have written this thesis book The data and results presented in the dissertation are true and have not been published by other authors Ha Noi, 25th September 2020 PhD Student Ngo Thi Thanh Hien ADVISORS: Assoc.Prof Pham Thanh Huyen Prof Graziella Liana Turdean i ACKNOWLEDGEMENT First of all, I would like to thank my advisors Assoc Prof Dr Pham Thanh Huyen and Prof Dr Graziella Liana Turdean for all support and encouragement which really helped me and motivated me during my research I would like to thank Prof Vasile I Parvulescu at Deparment of Organic Chemistry, Biochemistry and Catalysis, University of Bucharest, Romania for the support in hydroisomerization experiments I would like to thank my friends at HaNoi University of Science and Technology (HUST) and at “Babes- Bolyai” University (UBB) for all assistances and for the enjoyable time, friendly events we shared together I would like to acknowledge the Eramus+ Program with partner countries for the financial support of my stages at “Babes- Bolyai” University, Cluj –Napoca, Romania I want to extend my thanks to Assoc Prof Do Ngoc My – Rector of QuyNhon University (QNU), Dr Nguyen Le Tuan – Former Dean of Faculty of Chemistry, Dean of Faculty of Natural Sciences - QNU and my colleagues at QNU for their support Finally, I would like to express my deep thanks to my family for all their love, encouragement and unconditional support throughout my PhD studying ii CONTENTS STATUTORY DECLARATION i ACKNOWLEDGEMENT - ii CONTENTS - iii LIST OF ABBREVIATIONS - vii LIST OF FIGURES ix LIST OF TABLES xiii INTRODUCTION - THE NEW CONTRIBUTION OF THE DESSERTATION CHAPTER LITERATURE REVIEW - 1.1 Mesoporous material and ordered mesoporous silica SBA-15 - 1.2 The modified SBA-15 materials and applications - 1.3 The hydroisomerization of n-alkane over bifunctional catalysts 10 1.3.1 Metal function of bifunctional catalysts 11 1.3.2 Acid function of bifunctional catalysts -12 1.4 Hydrogenation of polynuclear aromatic hydrocarbon (PAHs) 17 1.4.1 Hydrogenation of polynuclear aromatic hydrocarbon (PAHs) 17 1.4.2 Catalysts for PAHs hydrogenation 20 1.5 Overview of paracetamol detection 24 1.5.1 Introduction of paracetamol 24 1.5.2 Electroanalytical methods based on using chemically modified electrodes (CMEs) for paracetamol detection 25 1.5.3 Chemically modified electrodes (CMEs) for PA detection 30 1.6 Conclusions 35 CHAPTER EXPERIMENTAL -37 2.1 Preparation of catalysts -37 2.1.1 Direct synthesis procedure of M-SBA-15 (where M=Al and/or B) -37 iii 2.1.2 Indirect synthesis of B/SBA-15 38 2.1.3 Synthesis of Pt/M-SBA-15 (where M=Al-, B- and Al-B-) catalysts 38 2.2 Electrochemical procedure -38 2.2.1 Preparation of Pt/M-SBA-15-GPE electrodes -38 2.2.2 Preparation of supporting electrolyte and standard solution of paracetamol -39 2.3 Catalyst characterization techniques 40 2.3.1 X-Ray Diffraction -40 2.3.2 Transmision electron microscopy (TEM) 41 2.3.3 Fourier Transformed Infrared Spectroscopy (FT-IR) -41 2.3.4 Temperature Programmed Desorption (NH3-TPD) -42 2.3.5 Nitrogen adsorption-desorption 42 2.3.6 Thermal analysis -43 2.3.7 Inductively coupled plasma optical emission spectrometry (ICP - OES) 44 2.3.8 Pyridine-FTIR 44 2.3.9 Energy Dispersive X-Ray Spectroscopy (EDS or EDX) -44 2.3.10 11B MAS NMR spectrocopy -45 2.4 Hydroisomerization activity test -45 2.5 Hydrogenation activity test -45 2.6 Electrochemical measurements 46 CHAPTER RESULTS AND DISCUSSION -49 3.1 Effect of preparation methods of support. 49 3.2 Characterizations of modified SBA-15 supports 53 3.2.1 X-ray diffraction (XRD) 54 3.2.2 Nitrogen physisorption isotherms -54 3.2.3 Transition electron microscopy (TEM) -56 3.2.4 Fourier-transform infrared spectroscopy (FTIR) -57 iv 3.2.5 EDX analysis -58 3.2.6 11B MAS-NMR spectroscopy -60 3.2.7 Ammonia Temperature- Programmed Desorption (NH3-TPD) -60 3.2.8 FTIR spectra of chemisorbed pyridine 63 3.3 Characterizations of Pt/modified SBA-15 catalysts 63 3.3.1 Nitrogen physisorption isotherms 63 3.3.2 X-ray diffraction (XRD) 64 3.3.3 Transition electron microscopy (TEM) -65 3.3.4 NH3-TPD profiles -65 3.4 Performance of platinum supported on modified SBA-15 catalysts for hydroisomerization of n-heptane 68 3.4.1 Effect of the acidic supports on hydroisomerization activity of catalysts 68 3.4.2 Effect of temperature and reaction time in the hydroisomerization of nheptane 70 3.4.3 Cracked product yield and coke formation -72 3.5 Performance of platinum supported on modified SBA-15 catalysts for hydrogenation of tetralin -75 3.5.1 The results of GC-MS analysis of hydrogenation of tetralin -75 3.5.2 Effect of reaction temperature and pressure on catalytic activity -76 3.5.3 Effect of the acidity of modified supports on catalytic activity -78 3.5.4 Coke formation -80 3.6 The mesoporous catalysts of Pt loaded on modified SBA-15 material for the paracetamol detection 82 3.6.1 Characterization of 1%Pt/Al-SBA-15 catalyst 83 3.6.2 Electrochemical characterization of Pt/Al-SBA-15-GPE electrode material -85 3.6.3 Electrochemical impedance spectroscopy measurements at Pt/Al-SBA15-GPE electrode 88 v 3.6.4 Analytical characterization of Pt/Al-SBA-15-GPE electrode material -89 3.6.5 Interference study 91 3.6.6 Real sample analysis -92 CONCLUSIONS 94 PUBLICATIONS OF THE DISSERTATION -96 REFERENCES 97 vi LIST OF ABBREVIATIONS AA Ascorbic acid BET Brunauer-Emmet-Teller CE Counter electrode CMEs Chemically modified electrodes CN Cetane Number CV Cyclic voltammetry DTA Differential thermal analysis EIS Electrochemical impedance spectroscopy FCC Fluid catalytic cracking FT-IR Fourier transformed infrared spectroscopy FWHM Full width at half maximum GCE Glassy carbon electrode GPE Graphite paste electrode ICP Inductively coupled plasma method LCO Light cycle oil LOD Limit of detection MSA Amorphous silica-alumina NH3-TPD Ammonia Temperature- Programmed Desorption PA Paracetamol PAHs Polynuclear aromatic hydrocarbons PBS Phosphate buffer solution Py-FTIR FTIR spectra of chemisorbed pyridine RE Reference electrode SAPO-n Silicoaluminophosphate vii SBA-15 Santa Barbara Amorphous No 15 SWV Square wave voltammetry TEM Transmision electron microscopy TEOS Tetraethyl orthosilicate TGA Thermogra vimetric analysis TMOS Tetramethyl orthosilicate UA Uric acid WE Working electrode XRD X-ray diffraction viii Phú (2006), “Tổng hợp, đặc trưng vật liệu mao quản nano Al-SBA-15 có tỷ số SiAl khác nhau,” in Hội nghị khoa học lần thứ 20 - Đại học Bách Khoa Hà Nội, 2006, pp 34–37 [27] Hoàng Văn Đức, Đặng Tuyết Phương, Nguyễn Hữu Phú (2007), “Nghiên cứu tính chất hóa lý vật liệu mao quản trung bình Ti-SBA-15 tổng hợp phương pháp trực tiếp,” Tạp chí hóa học, vol 45, no 5, pp 595–599 [28] Nguyễn Thị Hồng Hoa, Đặng Tuyết Phương, Nguyễn Thị Ngọc Linh (2013) “Tổng hợp vật liệu mao quản trung bình SBA-15 sử dụng làm chất mang cố định enzym DAAO,” Tạp chí Khoa học Công nghệ, vol 2, no 12, pp 15–19 [29] Tuyet Phuong D., Anh Tuan V., Gia Thanh V., Vinh Thang H., Cao Thang D., Hoang Yen, Kim Hoa T., Kim Lan L., Huu Phu N (2006), “Photocatalytic oxidation of phenylsulfophtalein by hydrogen peroxide over Ti containing SBA15 mesoporous materials,” Study Surf Scien Catal., vol 165, pp 663–666 [30] Nguyen Tien Thao, Bui The Thien, Pham Thi Hien, Nguyen Thi Nhu (2016) “Oxidation of styrene with hydrogen peroxide over Cu/SBA-15 catalyst,” Vietnam J Chem., vol 54, pp 133–138 [31] Trần Văn Nhân, Hoàng Hiệp, Hoa Hữu Thu, Lê Thanh Sơn, Khúc Quang Đạt (2008), “Tổng hợp nghiên cứu xúc tác Cu/SBA-15 phản ứng oxi hóa hồn tồn LPG,” Tạp chí hóa học, vol 46, no 4, pp 411–415 [32] Ngô Thị Thuận, Phạm Xuân Núi (2007), “Xúc tác Pt/WO3-ZrO2 vật liệu mao quản trung bình SBA-15 phản ứng isome hóa n-heptan,” Tạp chí hóa học, vol 45, no 1, pp 77–82 [33] A Goguet, S Shekhtman, F Cavallaro, C Hardacre, and F C Meunier (2008), “Effect of the carburization of MoO3-based catalysts on the activity for butane hydroisomerization,” Appl Catal A Gen, vol 344, no 1–2, pp 30–35 [34] W Wang, C.-J Liu, and W Wu (2019), “ Bifunctional catalysts for the hydroisomerization of n -alkanes: the effects of metal–acid balance and textural structure ,” Catal Sci Technol., vol 9, no 16, pp 4162–4187 [35] K Park and S Ihm (2000), “Comparison of Pt / zeolite catalysts for n 100 hexadecane hydroisomerization,” Appl Catal A, vol 203, pp 201–209 [36] M Guisnet (2013), “‘ Ideal ’ bifunctional catalysis over Pt-acid zeolites,” Catal Today, vol 218–219, pp 123–134 [37] P Liu, J Wang, and R Wei, X Ren, X Zhang (2008), “A Highly Efficient H β Zeolite Supported Pt Catalyst Promoted by Chromium for the Hydroisomerization of n -Heptane A Highly Efficient H b Zeolite Supported Pt Catalyst Promoted by Chromium for the Hydroisomerization of n -Heptane,” Catal Lett, 126, pp 346-352 [38] A De Lucas, P Sa, A Fu, and L Valverde (2006), “Liquid-Phase Hydroisomerization of n -Octane over Platinum-Containing Zeolite-Based Catalysts with and without Binder,” Ind Eng Chem Res, vol 45, pp 8852– 8859 [39] H Deldari (2005), “Suitable catalysts for hydroisomerization of long-chain normal paraffins,” Appl Catal A, vol 293, pp 1–10 [40] M A Arribas, F Márquez, and A Martínez (2000), “Activity, selectivity, and sulfur resistance of Pt/WOx-ZrO2 and Pt/Beta catalysts for the simultaneous hydroisomerization of n-heptane and hydrogenation of benzene,” J Catal., vol 190, no 2, pp 309–319 [41] P Munnik, P E De Jongh, and K P De Jong (2015), “Recent Developments in the Synthesis of Supported Catalysts,” Chem Rev., vol 115, no 14, pp 6687– 6718 [42] E Blomsma, J A Martens, and P A Jacobs (1996), “Mechanisms of heptane isomerization on bifunctional Pd/H-beta zeolites,” J Catal., vol 159, no 2, pp 323–331 [43] E Blomsma, J A Martens, and P A Jacobs (1997), “Isomerization and hydrocracking of heptane over bimetallic bifunctional PtPd/H-beta and PtPd/USY zeolite catalysts,” J Catal., vol 165, no 2, pp 241–248 [44] O B Yang and S I Woo (1993), “Characterization and Catalytic Properties of Pt-Ir Small Bimetallic Cluster in NaY,” Stud Surf Sci Catal., vol 75, no C, pp 101 671–680 [45] F Bauer, K Ficht, M Bertmer, W D Einicke, T Kuchling, and R Gläser (2014), “Hydroisomerization of long-chain paraffins over nano-sized bimetallic Pt-Pd/H-beta catalysts,” Catal Sci Technol., vol 4, no 11, pp 4045–4054 [46] I Eswaramoorthi and N Lingappan (2003), “Hydroisomerisation of n-hexane over bimetallic bifunctional silicoaluminophosphate based molecular sieves,” Appl Catal A Gen., vol 245, no 1, pp 119–135 [47] I Eswaramoorthi and N Lingappan (2004), “Ni-Pt loaded silicoaluminophosphate molecular sieves for hydroisomerisation of n-heptane,” J Mol Catal A Chem., vol 218, no 2, pp 229–239 [48] A G Bhavani, N Lingappa, I Eswaramoorthi (2003), “Activity, Selectivity and Stability of Ni-Pt Loaded Zeolite-β and Mordenite Catalysts for Hydroisomerisation of nHeptane,” Appl Catal A Gen., vol 253, pp 469–486 [49] A Corma, A Martinez, S Pergher, S Peratello, C Perego (1997), “Hydrocracking-hydroisomerization of n-decane on amorphous silica-alumina with uniform pore diameter,” Appl Catal A, vol 152, pp 107–125 [50] V Calemma, S Peratello, C Perego (2000), “Hydroisomerization and hydrocracking of long chain n-alkanes on Pt/amorphous SiO2-Al2O3 catalyst,” Appl Catal A Gen., vol 190, no 1–2, pp 207–218 [51] M Y Wen, I Wender, J W Tierney (1990), “Hydroisomerization and Hydrocracking of n-Heptane and n-Hexadecane on Solid Superacids,” Energy and Fuels, vol 4, no 4, pp 372–379 [52] S Zhang, Y Zhang, J W Tierney, and I Wender (2000), “Hydroisomerization of normal hexadecane with platinum-promoted tungstate-modified zirconia catalysts,” Appl Catal A Gen., vol 193, no 1–2, pp 155–171 [53] M C Claude, G Vanbutsele, J A Martens (2001), “Dimethyl branching of long n-alkanes in the range from decane to tetracosane on pt/H-ZSM-22 bifunctional catalyst,” J Catal., vol 203, no 1, pp 213–231 [54] G Wang, Q Liu, W Su, X Li, Z Jiang, X Fang, C Han, C Li (2008), 102 “Hydroisomerization activity and selectivity of n-dodecane over modified Pt/ZSM-22 catalysts,” Appl Catal A Gen., vol 335, no 1, pp 20–27 [55] M Zhang, C Li, Y Chen, C W Tsang, Q Zhang, C Liang (2016), “Hydroisomerization of hexadecane over platinum supported on EU-1/ZSM-48 intergrowth zeolite catalysts,” Catal Sci Technol., vol 6, no 22, pp 8016– 8023 [56] C L Z Yang, Y Liu, J Zhao, J Gou, K Sun (2017), “Zinc-modified Pt/SAPO-11 for improving the isomerization selectivity to dibranched alkanes,” Chinese J Catal., vol 38, pp 509–517 [57] A K Sinha, S Sivasanker, P Ratnasamy ((1998), “Hydroisomerization of nalkanes over Pt-SAPO-11 and Pt-SAPO-31 synthesized from aqueous and nonaqueous media,” Ind Eng Chem Res., vol 37, no 6, pp 2208–2214 [58] M Y Kim, K Lee, M Choi (2014), “Cooperative effects of secondary mesoporosity and acid site location in Pt/SAPO-11 on n-dodecane hydroisomerization selectivity,” J Catal., vol 319, pp 232–238 [59] R S Arẳjo, D C S Azevedo, E Rodríguez-Castellón, A Jiménez-López, C L Cavalcante (2008), “Al and Ti-containing mesoporous molecular sieves: Synthesis, characterization and redox activity in the anthracene oxidation,” J Mol Catal A Chem., vol 281, no 1–2, pp 154–163 [60] Y Zhang, D Liu, B Lou, R Yu, Z Men, M Li, Z Li (2018), “Hydroisomerization of n-decane over micro/mesoporous Pt-containing bifunctional catalysts: Effects of the MCM-41 incorporation with Y zeolite,” Fuel, vol 226, no November 2017, pp 204–212 [61] P Liu, J Wang, R Wei (2008), “A Highly Efficient H b Zeolite Supported Pt Catalyst Promoted by Chromium for the Hydroisomerization of n -Heptane,” Catal Letters, vol 126, pp 346–352 [62] P Liu, J Wang, X Zhang, R Wei, X Ren (2009), “Catalytic performances of dealuminated Hβ zeolite supported Pt catalysts doped with Cr in hydroisomerization of n-heptane,” Chem Eng J., vol 148, no 1, pp 184–190 103 [63] V M Akhmedov and & S H Al‐Khowaiter (2007), “Recent Advances and Future Aspects in the Selective Isomerization of High n‐Alkanes,” Catal Rev., vol 49, pp 33–139 [64] K C Mouli, O Choudhary, K Soni, A K Dalai (2012), “Improvement of cetane number of LGO by ring opening of naphthenes on Pt / Al-SBA-15 catalysts,” Catal Today, vol 198, no 1, pp 69–76 [65] Z YuaShiyou Xing, Pengmei Lv, Junying Fu, Jiayan Wang, Pei Fan, Lingmei Yang, Zhenhong Yuann (2017), “Direct synthesis and characterization of porebroadened Al-SBA-15,” Microporous Mesoporous Mater., vol 239, pp 316– 327 [66] Ngô Thị Thuận, Phạm Xuân Núi, Nguyễn Hữu Phú (2005), “Nghiên cứu đặc trưng xúc tác MoO3/ZrO2-SO4 phản ứng isome hóa n-heptan,” in Tuyển tập cơng trình hội nghị khoa học cơng nghệ hóa hữu tồn quốc lần thứ III, 2005, pp 514–518 [67] Nguyễn Hữu Trịnh (2007), “Nghiên cứu phản ứng isome hóa n-hexan xúc tác Pt/gamma Al2O3,” Tạp chí hóa học, vol 45, no 4, pp 403–406 [68] T K T Dao and C L Luu (2015), “n-Hexane hydro-isomerization over promoted Pd/HZSM-5 catalysts,” Adv Nat Sci Nanosci Nanotechnol., vol 6, no 3, pp 035014–035020 [69] S C Korre, M T Klein, R J Quann (1997), “Hydrocracking of polynuclear aromatic hydrocarbons Development of rate laws through inhibition studies,” Ind Eng Chem Res., vol 36, no 6, pp 2041–2050 [70] M F Williams, B Fonfé, C Woltz, A Jentys, J A R Van Veen, and J A Lercher (2007), “Hydrogenation of tetralin on silica – alumina-supported Pt catalysts II Influence of the support on catalytic activity,” J Catal., vol 251, pp 497–506 [71] K Sato, Y Iwata, Y Miki, H Shimada (1999), “Hydrocracking of Tetralin over NiW / USY Zeolite Catalysts : For the Improvement of Heavy-Oil Upgrading Catalysts,” J Catal., vol 186, pp 45–56 104 [72] Z Cao, X Xu, Y Qi, S Lu, B Qi (2010), “Petroleum Science and Technology Hydrocracking of Tetralin over Mo – Ni / Usy Dual Functional Catalysts,” Pet Sci Technol., no October 2013, pp 37–41 [73] S G A Ferraz, F M Z Zotin, L R Raddi Araujo, J L Zotin (2010), “Applied Catalysis A : General Influence of support acidity of NiMoS catalysts in the activity for hydrogenation and hydrocracking of tetralin,” Applied Catal A, Gen., vol 384, no 1–2, pp 51–57 [74] M C Carrio, B R Manzano, F A Jalo (2005), “Influence of the metallic precursor in the hydrogenation of tetralin over Pd – Pt supported zirconium doped mesoporous silica,” Green Chem., vol 7, pp 793–799 [75] M A Arribas and A Martínez (2002), “The influence of zeolite acidity for the coupled hydrogenation and ring opening of 1-methylnaphthalene on Pt/USY catalysts,” Appl Catal A Gen., vol 230, no 1–2, pp 203–217 [76] K C Park, D J Yim, and S K Ihm (2002), “Characteristics of Al-MCM-41 supported Pt catalysts: Effect of Al distribution in Al-MCM-41 on its catalytic activity in naphthalene hydrogenation,” Catal Today, vol 74, no 3–4, pp 281– 290 [77] S G A Ferraz, B M Santos, F M Z Zotin, L R R Araujo, and J L Zotin (2015), “Influence of Support Acidity of NiMo Sul fi de Catalysts for Hydrogenation and Hydrocracking of Tetralin and Its Reaction Intermediates,” Ind Eng Chem Res., vol 54, pp 2646–2656 [78] J Lee, Y Choi, J Shin, and J K Lee (2015), “Selective hydrocracking of tetralin for light aromatic hydrocarbons,” Catal Today, vol 265, pp 1–10 [79] R C Santana, P T Do, M Santikunaporn, W A Alvarez, J D Taylor, E L Sughrue, D E Resasco (2006),, “Evaluation of different reaction strategies for the improvement of cetane number in diesel fuels,” Fuel, vol 85, no 5–6, pp 643–656 [80] M Chareonpanich, Z G Zhang, and A Tomita (1996), “Hydrocracking of aromatic hydrocarbons over USY-zeolite,” Energy and Fuels, vol 10, no 4, pp 105 927–931 [81] X M Yue, X Y Wei, B Sun, Y H Wang, Z M Zong, X Fan, Z W Liu (2012)., “A new solid acid for specifically cleaving the C arC alk bond in di(1naphthyl)methane,” Appl Catal A Gen., vol 425–426, pp 79–84 [82] H Matsuhashi, S Nishiyama, H Miura, K Eguchi, K Hasegawa, Y Iizuka, A Igarashi, N Katada, J Kobayashi, T Kubota, T Mori, K Nakai, N Okazaki, M Sugioka, T Umeki, Y Yazawa, D Lu (2004), “Effect of preparation conditions on platinum metal dispersion and turnover frequency of several reactions over platinum-supported on alumina catalysts,” Appl Catal A Gen., vol 272, no 1– 2, pp 329–338 [83] H Fan, B Han, T Jiang, J Guo, Q Wang, Y Cheng, S Wu (2011), “Hydrocracking of anthracene to ethyl biphenyl promoted by coupling supercritical water and cracking catalysts,” ChemCatChem, vol 3, no 9, pp 1474–1479 [84] H Fan, Q Wang, J Guo, T Jiang, Z Zhang, G Yang, B Han (2012), “Elimination of the negative effect of nitrogen compounds by CO2-water in the hydrocracking of anthracene,” Green Chem., vol 14, no 7, pp 1854–1858 [85] V Calemma, R Giardino, and M Ferrari (2010), “Upgrading of LCO by partial hydrogenation of aromatics and ring opening of naphthenes over bi-functional catalysts,” Fuel Process Technol., vol 91, no 7, pp 770–776 [86] R Galiasso Tailleur and J R Nascar (2008), “The effect of aromatics on paraffin mild hydrocracking reactions (WNiPd/CeY-Al2O3),” Fuel Process Technol., vol 89, no 8, pp 808–818 [87] A Haas, S Rabl, M Ferrari, V Calemma, and J Weitkamp (2012), “Ring opening of decalin via hydrogenolysis on Ir/- and Pt/silica catalysts,” Appl Catal A Gen., vol 425–426, pp 97–109 [88] C Guan, Z Wang, S Yu, A Guo, and G Que (2004), “Upgrading petroleum residue by two-stage hydrocracking,” Fuel Process Technol., vol 85, no 2–3, pp 165–172 106 [89] P A Rautanen, J R Aittamaa, and A O I Krause (2001), “Liquid phase hydrogenation of tetralin on Ni/Al2Ỏ3,” Chem Eng Sci., vol 56, pp 1247–1254 [90] O A Verónica A.Valles, Brenda C.Ledesma, Lorena P Rivoira, Jorgelina Cussa, A R Anunziata, and Beltramone (2016), “Experimental design optimization of the tetralin hydrogenation over Ir–Pt-SBA-15,” Catal Today, vol 271, pp 140–148 [91] K C Mouli, O Choudhary, K Soni, and A K Dalai (2012), “Improvement of cetane number of LGO by ring opening of naphthenes on Pt/Al-SBA-15 catalysts,” Catal Today, vol 198, no 1, pp 69–76 [92] O J D Souza, R J Mascarenhas, T Thomas, B M Basaveraja, A K Saxena, K Mukhopadhyay, D Roy (2015), “Platinum decorated multi-walled carbon nanotubes / Triton X-100 modified carbon paste electrode for the sensitive amperometric determination of Paracetamol,” J Electroanal Chem., vol 739, pp 49–57 [93] X Liu, W Na, H Liu, and X Su (2017), “Fluorescence turn-off-on probe based on polypyrrole/graphene quantum composites for selective and sensitive detection of paracetamol and ascorbic acid,” Biosens Bioelectron., vol 98, pp 222–226 [94] M E Bosch, A J S Ruiz, and C B Ojeda (2006), “Determination of paracetamol : Historical evolution,” Jounal Pharm Biomed Anal., vol 42, pp 291–321 [95] C M A Brett, A N A Maria, and O Brett (1994), "Electrochemistry: Principles , Methods , and Applications", Oxford University Press, New York, USA [96] A J Bard, L R Faulkner, E Swain, and C Robey (2001), "Electrochemical methods: Fundamentals and Applications", John Wiley & Son, INC [97] V Mirceski, R Gulaboski, M Lovric, I Bogeski, and R Kappl (2013), “Square-Wave Voltammetry : A Review on the Recent Progress,” vol 25, pp 1– 11 107 [98] E Bayram and E Akyilmaz (2016), “Sensors and Actuators B : Chemical Development of a new microbial biosensor based on conductive polymer / multiwalled carbon nanotube and its application to paracetamol determination,” Sensors Actuators B Chem., vol 233, pp 409–418 [99] A C Durst, R A, Baumner A.J, Murray R.W, Buck R.P (2007), “Chemically modified electrodes: Recommended terminology and definitions (IUPAC Recommendations 1997),” Pure Appl Chem., vol 69, no 6, pp 1317–1324 [100] K E Labuda J., Vanícková M., Bučková M (2000), “Development in Voltammetric Analysis with Chemically Modified Electrodes and Biosensors,” Chem Pap., vol 54, pp 95–103 [101] I Noviandri and R Rakhmana (2012), “Carbon Paste Electrode Modified with Carbon Nanotubes and Poly ( 3-Aminophenol ) for Voltammetric Determination of Paracetamol” , Int J Electrochem, Sci vol 7, pp 4479–4487 [102] J Luo, J Sun, J Huang, and X Liu (2016), “Preparation of water-compatible molecular imprinted conductive polyaniline nanoparticles using polymeric micelle as nanoreactor for enhanced paracetamol detection,” Chem Eng J., vol 283, pp 1118–1126 [103] Y Teng, L Fan, Y Dai, M Zhong, X Lu, and X Kan (2015), “Biosensors and Bioelectronics Electrochemical sensor for paracetamol recognition and detection based on catalytic and imprinted composite film,” Biosens Bioelectron., vol 71, pp 137–142 [104] P K Kalambate and A K Srivastava (2016), “Sensors and Actuators B : Chemical Simultaneous voltammetric determination of paracetamol , cetirizine and phenylephrine using a multiwalled carbon nanotube-platinum nanoparticles nanocomposite modified carbon paste electrode,” Sensors Actuators B Chem., vol 233, pp 237–248 [105] R Olivé-monllau, F X Mu, and E Baldrich (2013), “Sensors and Actuators B : Chemical Characterization and optimization of carbon nanotube electrodes produced by magnetic entrapment : Application to paracetamol detection,” 108 Sensors Actuators B vol 185, pp 685–693 [106] P A Raymundo-pereira, A M Campos, C D Mendonc, M L Calegaro, S A S Machado, and O N O Jr (2017), “Sensors and Actuators B : Chemical Printex 6L Carbon Nanoballs used in Electrochemical Sensors for Simultaneous Detection of Emerging Pollutants Hydroquinone and Paracetamol,” vol 252, pp 165–174 [107] A Kutluay and M Aslanoglu (2013), “Chemical Modification of electrodes using conductive porous layers to confer selectivity for the voltammetric detection of paracetamol in the presence of ascorbic acid , dopamine and uric acid,” Sensors Actuators B Chem., vol 185, pp 398–404 [108] I Sadok and K Tyszczuk-rotko (2016), “Chemical Bismuth particles Nafion covered boron-doped diamond electrode for simultaneous and individual voltammetric assays of paracetamol and caffeine,” Sensors Actuators B , vol 235, pp 263–272, 2016 [109] P K Kalambate, B J Sanghavi, S P Karna, and A K Srivastava (2015), “Sensors and Actuators B : Chemical Simultaneous voltammetric determination of paracetamol and domperidone based on a graphene / platinum nanoparticles / nafion composite modified glassy carbon electrode,” Sensors Actuators B Chem., vol 213, pp 285–294 [110] X Kang, J Wang, H Wu, J Liu, I A Aksay, and Y Lin (2010), “A graphenebased electrochemical sensor for sensitive detection of paracetamol,” Talanta, vol 81, no 3, pp 754–759 [111] S B Tanuja, B E K Swamy, and K V Pai (2017), “Electrochemical determination of paracetamol in presence of folic acid at nevirapine modi fi ed carbon paste electrode : A cyclic voltammetric study,” J Electroanal Chem., vol 798, no May, pp 17–23 [112] M Zidan, T A N W E E Tee, and A H Abdullah (2011), “Electrochemical Oxidation of Paracetamol Mediated by MgB Microparticles Modified Glassy Carbon Electrode,” E-Jounal of Chemistry, vol 8, no 2, pp 553–560 109 [113] N T A Thu, H Van Duc, N Hai Phong, N D Cuong, N T V Hoan, and D Quang Khieu (2018), “Electrochemical Determination of Paracetamol Using Fe3O4/Reduced Graphene-Oxide-Based Electrode,” J Nanomater., vol 2018, pp 1–15 [114] F Chang, G Wang, Y Xie, M Zhang, and J Zhang (2013), “Synthesis of TiO nanoparticles on mesoporous aluminosilicate Al-SBA-15 in supercritical CO for photocatalytic decolorization of methylene blue,” Ceram Int., vol 39, no 4, pp 3823–3829 [115] A Sacara, F Pitzalis, A Salis, G L Turdean, and L M Muresan (2019), “Glassy Carbon Electrodes Modi fi ed with Ordered Mesoporous Silica for the Electrochemical Detection of Cadmium Ions,” ACS Omega, vol 4, pp 1410– 1415 [116] N Lashgari, A Badiei, and G M Ziarani (2017), “A novel functionalized nanoporous SBA-15 as a selective fluorescent sensor for the detection of multianalytes (Fe3+ and Cr2O72-) in water,” J Phys Chem Solids, vol 103, pp 238–248 [117] D Lin, Y Jiang, Y Wang, and S Sun (2008), “Silver Nanoparticles Confined in SBA-15 Mesoporous Silica and the Application as a Sensor for Detecting Hydrogen Peroxide,” J Nanomater., vol 2008, 1–10 [118] M Yadavi, A Badiei, and G Mohammadi (2013), “Applied Surface Science A novel Fe + ions chemosensor by covalent coupling fluorene onto the mono , diand tri-ammonium functionalized nanoporous silica type,” Appl Surf Sci., vol 279, pp 121–128 [119] S.-G S and X.-C S Rui-Xiang Wang, Jing-Jing Fan, You-Jun Fan, Jing-Ping Zhong, Li Wang (2014), “Platinum nanoparticles on porphyrin functionalized graphene nanosheets as superior catalyst for methanol electrooxidation,” R Soc Chem., vol 6, no 24, pp 14999–15007 [120] Lê Viết Hải, Trần Đại Lâm (chủ biên), Nguyễn Tuấn Dung, Nguyễn Lê Huy (2017), Các phương pháp phân tích hóa lý vật liệu NXB Khoa học tự nhiên 110 công nghệ [121] ThermoScientific (2013), “Introduction to Fourier Transform Infrared Spectroscopy.” Thermo Fisher Scientific [122] J Lynch (2003), "Physico-chemical analysis of industrial catalysts" Institut Francai du Pe1trole Publication [123] W Yu, Y Tang, L Mo, P Chen, H Lou, and X Zheng (2011), “Bifunctional Pd / Al-SBA-15 catalyzed one-step hydrogenation – esteri fi cation of furfural and acetic acid : A model reaction for catalytic upgrading of bio-oil SBA-15,” CATCOM, vol 13, no 1, pp 35–39 [124] D Zhao, Y Wan, W Zhou (2013), "Ordered mesoporous materials", Wiley VCH Verlag GmbHz & CoKGaA [125] G M Kumaran, S Garg, K Soni, M Kumar, and L D Sharma (2007), “Effect of Al-SBA-15 Support on Catalytic Functionalities of Hydrotreating Catalysts II Effect of Variation of Molybdenum and Promoter Contents on Catalytic Functionalities,” Industrial & Engineering Chemistry Research, pp 4747–4754 [126] J Berlin (2011), “Analysis of Boron with Energy Dispersive X-ray Spectrometry: Advances in light element analysis with SDD technology,” Imaging Microsc., vol 13, pp 19–21 [127] G M Kumaran, S Garg, K Soni, M Kumar, and J K Gupta (2008), “Synthesis and characterization of acidic properties of Al-SBA-15 materials with varying Si / Al ratios,” vol 114, pp 103–109, 2008 [128] J R Regalbuto, A Navada, S Shadid, M L Bricker, and Q Chen (1999), “An Experimental Verification of the Physical Nature of Pt Adsorption onto Alumina,” J Catal., vol 348, pp 335–348 [129] T Sugii, R Ohnishi, J Zhang, A Miyaji, and Y Kamiya (2006), “Acidityattenuated heteropolyacid catalysts : Acidity measurement using benzonitrileTPD and catalytic performance in the skeletal isomerization of n -heptane,” J vol 116, pp 179–183, 2006 [130] L Gao, Z Shi, U Etim, W Xing, P Wu, D Han, S Mintova, P Bai, Z Yan 111 (2019), “Beta-MCM-41 micro-mesoporous catalysts in the hydroisomerization of n-heptane: Definition of an indexed isomerization factor as a performance descriptor,” Microporous Mesoporous Mater., vol 277, pp 17–28 [131] L Valverde, P Sa, A De Lucas, and F Dorado (2005), “Hydroisomerization of n -octane over platinum catalysts with or without binder,” Applied Catalysis A, vol 282, pp 15–24 [132] W Zhang and P G Smirniotis (1999), “Effect of Zeolite Structure and Acidity on the Product Selectivity and Reaction Mechanism for n-Octane Hydroisomerization and Hydrocracking,” Jounal of Catalysis, vol 416, pp 400– 416 [133] M Guisnet and P Magnoux (2001), “Organic chemistry of coke formation,” Appl Catal A Gen., vol 212, no 1–2, pp 83–96 [134] Veronica A Valles, Brenda C Ledesma, Lorena P Rivoira, Jorgelina Cussa, Oscar A Anunziata, Andrea R Beltramone (2015), “Experimental design optimization of the tetralin hydrogenation over Ir-Pt-SBA-15; Catalysis Today, vol 271, pp 140-148 [135] D E Siriporn Jongpatiwut, Zhongrui Li, G W Resasco, Walter E Alvarez, Ed L Sughrue, and Dodwell (2004), “Competitive hydrogenation of poly-aromatic hydrocarbons on sulfur-resistant bimetallic Pt-Pd catalysts,” Appl Catal A, vol 262, pp 241–253 [136] J Chan and C Tan (2006), “Hydrogenation of Tetralin over Pt / γ -Al O in Trickle-Bed Reactor in the Presence of Compressed CO2,” Enegy & Fuels, vol 20, no 15, pp 771–777 [137] M M Rusu, C I Fort, L C Cote, A Vulpoi, M Todea, G L Turdean, V Danciu, I C Popescu, L Baia (2018), “Insights into the morphological and structural particularities of highly sensitive porous bismuth-carbon nanocomposites based electrochemical sensors,” Sensors Actuators, B Chem., vol 268, pp 398–410 [138] F J Burpo, E A Nagelli, L A Morris, and J P Mcclure (2017), “Direct 112 solution-based reduction synthesis of Au , Pd , and Pt aerogels,” Jounal Mater Res., vol 22, pp 4153–4165 [139] W Y Su and S H Cheng (2010), “Electrochemical oxidation and sensitive determination of acetaminophen in pharmaceuticals at poly(3,4-ethylenedioxythiophene)-modified screen-printed electrodes,” Electroanalysis, vol 22, no 6, pp 707–714 [140] J Song, J Yang, J Zeng, J Tan, and L Zhang (2011), “Graphite oxide filmmodified electrode as an electrochemical sensor for acetaminophen,” Sensors Actuators, B Chem., vol 155, no 1, pp 220–225 113 APPENDIX 114 ... TEM images of 0.5 %Pt/ Al -SBA-15; 0.5 %Pt/ Al- B -SBA-15 and 0.5 %Pt/ B -SBA-15 66 Fig 3.16 NH3-TPD curves of 0.5% Pt/ Al -SBA-15; 0.5% Pt/ Al- B -SBA-15 and 0.5% Pt/ B -SBA-15 catalyst ... (A); Al -SBA-15 (B) ; Al- B -SBA-15 (C) and BSBA-15 (D) 57 Fig 3.8 FTIR spectra of SBA-15 and modified SBA-15 samples 58 Fig 3.9 EDX spectras of Al -SBA-15 (A); Al- B -SBA-15 (B) ; B -SBA-15. .. 3.10 1 1B MAS-NMR for B -SBA-15 sample 60 Fig 3.11 NH3-TPD curves of Al -SBA-15; Al- B -SBA-15; B -SBA-15 samples 61 Fig 3.12 The Py-FTIR spectras of Al -SBA-15 (A), Al- B -SBA-15 (B) , B- SBA-15