Nghiên cứu xúc tác tẩm chất lỏng ion (silp) và xúc tác nano vàng cho phản ứng chuyển hóa etylen = supported ionic liquid phase catalyst and nanogold catalyst for the conversion of ethylene

TRƯỜNG ĐẠI HỌC BÁCH KHOA HÀ NỘI LUẬN VĂN THẠC SĨ Nghiên cứu xúc tác tẩm chất lỏng ion (SILP) xúc tác nano vàng cho phản ứng chuyển hóa Etylen Vũ Tùng Lâm Lam.VT211199M@sis.hust.edu.vn Ngành Hóa Học Giảng viên hướng dẫn: GS.TS Lê Minh Thắng Chữ ký GVHD Bộ mơn: Cơng nghệ Hữu – Hóa dầu Viện: Kỹ thuật hóa học HÀ NỘI, 07/2022 CỘNG HỊA XÃ HỘI CHỦ NGHĨA VIỆT NAM Độc lập – Tự – Hạnh phúc BẢN XÁC NHẬN CHỈNH SỬA LUẬN VĂN THẠC SĨ Họ tên tác giả luận văn: Vũ Tùng Lâm Đề tài luận văn: Nghiên cứu xúc tác tẩm chất lỏng ion (SILP) xúc tác nano vàng cho phản ứng chuyển hóa Etylen Chuyên ngành: Hóa học Mã số SV: 20211199M Tác giả, Người hướng dẫn khoa học Hội đồng chấm luận văn xác nhận tác giả sửa chữa, bổ sung luận văn theo biên họp Hội đồng ngày 13/07/2022 với nội dung sau: − Chỉnh sửa lại bố cục chương cho gọn khoa học − Chỉnh sửa lỗi trình bày, tiếng Anh danh pháp − Đã bổ sung phần kết nghiên cứu công bố khoa học vào luận văn − Chỉnh sửa định dạng số tài liệu tham khảo Ngày Giáo viên hướng dẫn tháng năm Tác giả luận văn CHỦ TỊCH HỘI ĐỒNG ii HANOI UNIVERSITY OF SCIENCE AND TECHNOLOGY THESIS Supported ionic liquid phase catalyst and nanogold catalyst for the conversion of Ethylene Vu Tung Lam Lam.VT211199M@sis.hust.edu.vn Major: Chemistry Thesis advisor : Prof Le Minh Thang Department Institute : : Department of Chemistry Hanoi University of Science and Technology Hanoi, 7-2022 iii Acknowledgment “Now this is not the end It is not even the beginning of the end But it is, perhaps, the end of the beginning.” Winston Churchill My master’s thesis was the continuation from my engineer’s degree thesis, investigating the application of supported ionic liquid phase catalyst and gold catalyst in ethylene hydroformylation Following with the previous thesis, the application of a relatively new support in hydroformylation catalyst has been the upgrade from old catalysts on metal oxide support With high surface area and promising pore characteristics, the behavior and influence of these catalysts system in the hydroformylation are the primary discussion in this thesis Aside from that, this thesis concludes my years research at Hanoi University of Science and Technology, from an undergraduate to a master student I’d like to give my gratitude to Prof Le Minh Thang for all her hard work and dedication to me There are no words that can express my appreciation for everything that you have done for me I’m also extremely grateful to Dr Nguyen Van Chuc for everything he has taught me in the past year You played a decisive role in changing my way of thinking when it comes around science I would like to extend my sincere thanks to Dr Nguyen Ngoc Mai, who patiently helps me with editing and originlab’s tips Thank should also go to my lab mates Ta Dinh Quang, Khong Manh Hung and Tran Thi Thu Hien, who inspired me to push through the limits and be a better person Lastly, it is impossible to not mention my family, especially my parents, my sister, my brother-in-law and my nephews, who gave me the encouragement and emotional support along the way iv CONTENTS Abstract CHAPTER INTRODUCTION 1.1 1.2 1.3 Hydroformylation 1.1.1 History 1.1.2 Commercial application and statistics 1.1.3 Catalyst Evolution Alternatives development for the current catalyst .10 1.2.1 Implementation of Ionic Liquid as an organic phase 10 1.2.2 Application of different supports 12 1.2.3 Nano gold catalyst in Hydroformylation 13 The goal of this thesis .14 CHAPTER EXPERIMENT 15 2.1 2.2 Ordered mesoporous carbon synthesis 15 2.1.1 SBA-15 template synthesis 15 2.1.2 Fabrication of OMCs 15 Supported Ionic Liquid Phase Catalyst 16 2.2.1 Ligand synthesis 16 2.2.2 Catalyst synthesis 18 2.3 Gold catalyst on Ordered mesoporous carbon .19 2.4 Catalyst characteristics 20 2.4.1 Fourier-Transform Infrared Spectroscopy 20 2.4.2 Nitrogen adsorption-de adsorption Isotherm method 22 2.4.3 Electron paramagnetic resonance 23 2.4.4 Scanning electron microscopy/energy-dispersive X-ray spectroscopy 24 2.4.5 UV-Vis spectroscopy 24 2.4.6 Catalyst’s activity testing system 25 CHAPTER RESULTS AND DICUSSIONS 28 3.1 Synthesis and characterization of ordered mesoporous carbon 28 3.1.1 Ordered mesoporous carbon on SiO2 template 28 v 3.2 3.3 3.4 3.1.2 Ordered mesoporous carbon on SBA-15 template 30 3.1.3 Ordered mesoporous carbon on γ-Al2O3 template 32 Supported Ionic liquid phase catalysts 36 3.2.1 Investigating ionic liquid impregnation in SILP catalyst 36 3.2.2 Surface area and pore distribution of SILP catalysts 38 3.2.3 SILP catalysts activity at different temperatures .41 3.2.4 SILP catalysts activity at 120°C 45 3.2.5 SILP catalysts activity at 140°C 48 3.2.6 Activity conclusion 51 3.2.7 Catalyst characteristics after the reaction .52 Nanogold catalysts on ordered mesoporous carbon 55 3.3.1 Gold catalysts electron paramagnetic resonance’s spectrum .55 3.3.2 Gold catalysts surface area and pore distribution 55 3.3.3 Gold catalysts UV-Vis spectra .58 3.3.4 Gold catalysts elemental mapping and EDX results 59 3.3.5 Gold catalyst activity 63 Au/OMC activity and others catalysts activity comparison .65 CONCLUSION 69 REFERENCE 70 vi LIST OF FIGURES Fig 1.1: Fischer - Tropsch Proces Fig 1.2: Disused Zollverein Coal Mine Industrial Coking plant Fig 1.3: Roelen's accidental discovery of hydroformylation Fig 1.4: First and second generations of hydroformyl catalyst Fig 1.5: Otto Roelen, in front of the Ruhrchemie’s plant based on his research Fig 1.6: Aldehydes product’s variation Fig 1.7: Verbund site in Nanjing, China: A joint industrial plant operated by BASF and SINOPEC, which houses the Butylene oxo s ynthesis plant Fig 1.8: Cobalt tetracarbonyl hydride - First generation of hydroformylation catalyst Fig 1.9: Cobalt catalyst salt formation Fig 1.10: Cobalt Phosphine-modified catalyst The second catalyst generation Fig 1.11: Low-pressure oxo process plant in Ponce, Puerto Rico (1971) Fig 1.12: Aqueous biphasic catalyst system Fig 1.13: Rhodium/TPPTS biphasic catalyst used in Ruhrchemie Oxo process.10 Fig 1.14: Ionic liquid cations and anions 11 Fig 1.15: Supported ionic liquid phase catalyst [22] 11 Fig 1.16: [BMIM][octylsulfate] Ionic liquid 12 Fig 1.17: Two methods to synthesize ordered mesoporous carbon 13 Fig 1.18: hydroformylation and Hydrogenation under the influence of Gold catalyst 13 Fig 2.1: Ordered mesoporous carbon hard-template method .16 Fig 2.2: Ligand synthesis using Schlenk line 17 Fig 2.3: The 3-steps ligand separation 17 Fig 2.4: SILP catalyst synthesis .19 Fig 2.5: Stretching and bending vibrations formation [41] 21 Fig 2.6: Nicolet iS50 FT-IR .21 Fig 2.7: Pre-treatment degassed system for sample 22 Fig 2.8: Gemini VII, Micromeritics Surface Area and Porosity 23 Fig 2.9: Bruker EMX-Micro EPR spectrometer 23 Fig 2.10: JCM-7000 NeoScope T M Benchtop SEM 24 Fig 2.11: Principle of UV-Vis spectroscopy .25 Fig 2.12: Avaspec 2048L, UV-Vis spectroscopy 25 Fig 2.13: Hydroformylation Catalyst’s activity testing system 25 Fig 2.14: Trace GC Ultra instrument to analyze products 26 Fig 3.1: FT-IR spectra of OMC-SiO2 28 vii Fig 3.2: Pore distribution of OMC-SiO2 30 Fig 3.3: FT-IR spectra of OMC-SBA-15 30 Fig 3.4: Pore distribution of OMC-SBA-15 32 Fig 3.5: FT-IR spectra of OMC-γ-Al2O3 33 Fig 3.6: Al-O formation in OMC-γ-Al2O3-4g 33 Fig 3.7: FT-IR spectra of OMC-γ-Al2O3 , excluding OMC-γ-Al2 O3-4g 34 Fig 3.8: Pore distribution of OMC-γ-Al2 O3 .35 Fig 3.9: FT-IR spectra of Cat-SILP samples 36 Fig 3.10: FT-IR spectra of different ionic liquid loading in SILP c atalysts 37 Fig 3.11: Pore distribution of Cat-SILP-2 at different temperatures .39 Fig 3.12: Pore distribution of Cat-SILP-2 and Cat-SILP-3 40 Fig 3.13: Pore size distribution of OMC-SiO2-3g and OMC-γ-Al2 O3-4g and SILP catalysts 41 Fig 3.14: Ethylene Conversion with time-on-stream over 0.15g powder CatSILP-2, gas flow rate 60mL/min, at bar 42 Fig 3.15: Propanal, propan-1-ol, propan-2-ol selectivity with time-on-stream over 0.15g powder Cat-SILP-2, gas flow rate 60mL/min, at bar 43 Fig 3.16: Propanal, propan-1-ol, propan-2-ol’s TOF with time-on-stream over 0.15g powder Cat-SILP-2, gas flow rate 60mL/min, at bar .44 Fig 3.17: Ethylene Conversion with time-on-stream over 0.15g powder CatSILP, gas flow rate 60mL/min, at bar and 120°C 45 Fig 3.18: Propanal, propan-1-ol, propan-2-ol selectivity with time-on-stream over 0.15g powder Cat-SILP, gas flow rate 60mL/min, at bar and 120°C 46 Fig 3.19: Propanal, propan-1-ol, propan-2-ol TOF with time-on-stream over 0.15g powder Cat-SILP, gas flow rate 60mL/min, at bar and 120°C .47 Fig 3.20: Ethylene Conversion with time-on-stream over 0.15g powder CatSILP, gas flow rate 60mL/min, at bar and 140°C 48 Fig 3.21: Propanal, propan-1-ol, propan-2-ol selectivity with time-on-stream over 0.15g powder Cat-SILP, gas flow rate 60mL/min, at bar and 140°C 49 Fig 3.22: Propanal, propan-1-ol, propan-2-ol TOF with time-on-stream over 0.15g powder Cat-SILP, gas flow rate 60mL/min, at bar and 140°C .50 Fig 3.23: FT-IR spectrum of SILP-2 and SILP-3 catalyst before and after the reaction 52 Fig 3.24: Pore distribution of Cat-SILP-2 before and after the reaction 53 Fig 3.25: Pore distribution of Cat-SILP before and after the reaction 54 Fig 3.26: Gold catalysts EPR's spectrum 55 Fig 3.27: The pore distribution of Au catalysts and respective support .56 Fig 3.28: Pore size distribution of Cat-Au-2 pre-reaction and after the reaction 57 Fig 3.29: Pore distribution of Cat-Au-3 pre-reaction and after the reaction 58 viii Fig 3.30: UV-Vis spectra of Au catalysts and support 59 Fig 3.31: Cat-Au-2 elemental mapping at 5,000×magnification 59 Fig 3.32: Cat-Au-2-after SEM images at 5000×magnification 60 Fig 3.33: Cat-Au-2-after elemental mapping at 5,000×magnification 61 Fig 3.34: Cat-Au-3 elemental mapping at 5,000×magnification 62 Fig 3.35: Cat-Au-3-after elemental mapping at 5,000×magnification 62 Fig 3.36: Ethylene Conversion with time-on-stream over 0.15g powder Cat-Au, gas flow rate 60mL/min, at bar and 300°C .63 Fig 3.37: Product selectivity with time-on-stream over 0.15g powder Cat-Au, gas flow rate 60mL/min, at bar and 300°C .64 Fig 3.38: Product TOF with time-on-stream over 0.15g powder Cat-Au, gas flow rate 60mL/min, at bar and 300°C .65 Fig 3.39: Comparison of Cat-Au-2 at 300°C, Cat-SILP-3 and Cat-SILP-5 at 120°C ethylene conversion 66 Fig 3.40: Comparison of Cat-Au-2 at 300°C, Cat-SILP-3 and Cat-SILP-5 at 120°C selectivity 66 Fig 3.41: Comparison of Cat-Au-2 at 300°C, Cat-SILP-3 and Cat-SILP-5 at 120°C products’ TOF 67 Fig 3.42 68 ix LIST OF TABLES Table 1.1: Nameplate capacity (* 1000 tons) for productions of aldehydes by hydroformylation in 1998 Table 1.2: Aqueous biphasic catalyst specifications for Ruhrchemie oxo process Table 2.1: Synthesized OMC supports 16 Table 2.2: Supported Ionic liquid phase catalysts component and abbreviations 18 Table 2.3: Gold catalyst synthesized 19 Table 2.4: Activity testing system properties 26 Table 2.5: GC-FID gas flows and products’ retention time 27 Table 3.1: Surface area and porosity of OMC-SiO2 .29 Table 3.2: Pore characteristics of OMC-SBA-15 and SBA-15 template 31 Table 3.3: Surface area and porosity of OMC-γ-Al2O3 34 Table 4.1: Surface area and pore characteristics of Cat-SILP-2 at different degas temperature 38 Table 4.2: Surface area and pore characteristics of Cat-SILP-2 and Cat-SILP-3 39 Table 4.3: SILP catalysts on OMC- γ-Al2O3 and OMC-SiO2‘s surface area and pore characteristics 40 Table 4.4: Surface area and porosity of SILP catalysts before and after the reaction 52 Table 5.1: Surface area and pore characteristics of Au catalysts and support 56 Table 5.2: EDS results of Cat-Au-2 before and after the reaction 60 Table 5.3: EDS results of Cat-Au-3 61 x From Fig 3.31, the gold particles dispersed evenly on the surface of the OMC The elemental mapping also supports that, as Au gold is seen to distribute throughout the surface along with the carbon atoms Table 3.9: EDS results of Cat-Au-2 before and after the reaction Element atom% Element mass% Au O C Au O C 0.08 8.01 91.91 1.36 10.26 88.42 Cat-Au-2 0.07 8.15 91.78 1.07 10.46 88.46 0.10 6.70 93.20 1.54 8.61 89.86 Average 0.08 7.62 92.29 1.33 9.78 88.91 0.09 9.12 90.79 1.35 11.64 87.00 Cat-Au-20.03 8.70 91.28 0.41 11.22 88.38 after 0.02 7.48 92.50 0.26 9.70 90.04 Average 0.05 8.43 91.52 0.67 10.85 91.81 The EDS results from Table 3.9 also suggest that the Cat-Au-2 was synthesized successfully, as the average element mass percentage of Au in the catalyst is 1.33%, close to the theoretical 1% calculation Slightly differenc e in the mass calculation can be tolerated from the analysis Sample Fig 3.32: Cat-Au-2-after SEM images at 5000×magnification After the reaction, Au particles were still distributed evenly on the surface in Fig 3.32 However, the EDS results show that the mass percentage of Au decreases following the reaction It can be observed in Fig 3.33 that gold particles accumulated on the side of the carbon particles in some areas, resulting in lower dispersion across the whole surface and the mass percentage Despite 60 that, accumulation appeared only in some areas, not all of the surface The oxygen element attributed to the surface functional group can also be seen disappearing after the reaction, despite increasing mass percentage The increasing mass percentage is likely the result of lower gold mass percent At the same time, the disappearance in elemental mapping can be attributed to the elimination of the surface functional group during the reaction, as suggested in the previous section, either from heat treatment or interaction during hydroformylation Fig 3.33: Cat-Au-2-after elemental mapping at 5,000×magnification For Cat-Au-3, nearly no amount of Au mass percentage was detected in the EDS results This is likely owing to undispersed Au particles during the impregnation, or the size of Au particles was too small to be detected The Au particles can still be seen dispersing on the surface, though not concentrated as Cat-Au-2 in Fig 3.34 The EDS results from the respective Cat-Au-3 in Table 3.10 is calculated from different areas Table 3.10: EDS results of Cat-Au-3 Sample Cat-Au-3 Area Area Area Average Element mass% Au O C 0.01 5.42 94.56 0.22 6.89 92.89 0.12 6.16 93.73 61 Fig 3.34: Cat-Au-3 elemental mapping at 5,000×magnification The accumulation was clearly observed in the elemental mapping at 5000×magnification (Fig 3.35) Au particles accumulation to reduce high surface energy as nanoparticles can be the reason This is attributed to a lower activity with Cat-Au-3, which will be discussed in the following section Fig 3.35: Cat-Au-3-after elemental mapping at 5,000×magnification 62 3.3.5 Gold catalyst activity Cat-Au-2 and Cat-Au-3 hydroformylation’s activity was tested at 300°C and bar for hours Conversions for both catalysts are shown in Fig 3.36 Fig 3.36: Ethylene Conversion with time-on-stream over 0.15g powder Cat-Au, gas flow rate 60mL/min, at bar and 300°C Both catalysts increased conversion through time before reaching a stable state during the fifth hour of the reaction Cat-Au-3 came out slightly ahead of Cat-Au-2 in terms of conversion, reaching 83%, while the latter reached 74% after hours Noting that Au catalysts are active not only in hydroformylation but also in hydrogenation So, products such as ethane are also expected, which can contribute to the higher ethylene conversion, but not proportion to the effective of Au catalysts in hydroformylation Analogous to that, this also benefits the hydroformylation, as synthesized propanal converse directly into propan-2-ol or propan-1-ol, depending on the regioselectivity of the catalysts Propanal, propan-2-ol, and propan-1-ol’s selectivity are also calculated in Fig 3.37 63 Fig 3.37: Product selectivity with time-on-stream over 0.15g powder Cat-Au, gas flow rate 60mL/min, at bar and 300°C As expected, propanal selectivity for both catalysts was dim during the run For Cat-Au-2, the catalyst itself favors propan-1-ol during the start of the reaction, with 67% selectivity After that, the respective selectivity decreased through time to a 5% selectivity after hours However, the selectivity shifted slowly towards propan-2-ol, from 0% to 90% after hours On the other hand, the propan-2-ol’s selectivity for Cat-Au-3 ranged from around 76% to 92% after hours, followed by selectivity reducing to 43% after hours For propan-1-ol’s selectivity, the number was lower than estimated, with the highest selectivity reported at hours being only 25% Fig 3.38 shows the products’ TOF While selectivity can attribute to the catalyst’s effectiveness, the appearance of byproducts shadows the selectivity, even when products are produced steadily 64 Fig 3.38: Product TOF with time-on-stream over 0.15g powder Cat-Au, gas flow rate 60mL/min, at bar and 300°C Both Au catalysts show a low byproduct rate as the TOF trend is similar to selectivity Most of the products were propan-1-ol or propan-2-ol, with CatAu-2 favoring propan-2-ol Cat-Au-3 displayed low activity on both products, owing to the accumulation of gold particles Cat-Au-2 has better propan-2-ol TOF, along with high selectivity and a decent propan-1-ol TOF The reaction rate was also stable, as TOF rarely changed for hours As both templates possessed the carboxyl functional groups from the support, propanal was not observed in most of the run 3.4 Au/OMC activity and others catalysts activity comparison As Cat-Au-2 performed better than Cat-Au-3, the former activity is compared with the SILP-3 and SILP-5 at 120°C Both these SILP catalysts performed individually well on each respective propanol product, as well as the propanal’s TOF 65 Fig 3.39: Comparison of Cat-Au-2 at 300°C, Cat-SILP-3 and Cat-SILP-5 at 120°C ethylene conversion Ethylene’s conversion for Cat-Au-2 is lower than Cat-SILP-3, gradually increasing over hours Fig 3.40: Comparison of Cat-Au-2 at 300°C, Cat-SILP-3 and Cat-SILP-5 at 120°C selectivity 66 Fig 3.41: Comparison of Cat-Au-2 at 300°C, Cat-SILP-3 and Cat-SILP-5 at 120°C products’ TOF From both the product’s selectivity and product’s TOF in Fig 3.40 and Fig 3.41, it is clear that Cat-Au-2 has higher selectivity in propan-2-ol, as propan-2-ol was the main product for gold catalysts Despite functional groups suppressing hydrogenation, gold metal favors the hydrogenation, possibly conflicting with the functional groups, resulting in lower TOF for all products Analogous to that, the TOF for all products of gold catalysts was considerably lower than both SILP catalysts This can be attributed to hydroformylation favoring homogeneous catalysts, as reactants need to be dispersed evenly in the catalysts or the opposite in the case of SILP Still, Cat-Au-2 avoided the byproduct formation, even with a tendency for hydrogenation, which is one advantage over the SILP catalysts To further investigate the improvement with these SILP catalysts, SILP catalysts, which used TiO2 as a support, were compared TiO2-SILP catalysts were synthesized with the same weight percentage of Rhodium, ionic liquid, ligand/rhodium ratio; with the only difference is the ligand, using TPPTS-Na3 67 Fig 3.42: Propan-2-ol with time-on-stream over 0.5g powder 0,2%Rh - 10%IL - L/Rh = 10/TiO2 , TPPTS - Na3 , gas flow rate 60mL/min, at bar and bar From Fig 3.42, it is clear that SILP catalysts with metal oxide support has relatively low TOF than SILP catalysts with OMC support Low TOF are likely the results of multi factors, from low surface area, un-dissolving ligand in methanol solvent during catalyst synthesizing step At bar, ethylene shows barely any sign of transformation to either propanal or propanol after hours of reaction, but over at bar, propan-2-ol was observed 68 CONCLUSION To conclude, the ethylene conversion was investigated in the hydroformyl reaction to convert ethylene into propanal or propanol Understand that the drawbacks of the present hydroformylation catalysts are mass transfers and catalyst leaching, the implementation of supported ionic liquid phase catalyst and the nanogold heterogeneous catalyst were executed The development of mesoporous carbon materials as a support to avoid both disadvantages was undergoing, and activity for both catalysts’ concepts were tested • Ordered mesoporous carbon materials were synthesized successfully using the hard-template method, with a relatively high specific surface area With different templates, the OMC-SiO2 support has pore concentrated at 70Å, OMC using SBA-15 template pore focused in 44Å, and a potential by-effect during the synthesis of OMC-γ-Al2O3 has been observed Another difference between these OMCs was the surface functional groups, which are the carboxyl groups reported with OMC-SiO2 and OMC-γ-Al2O3, influencing the catalyst behaviour • After synthesizing, SILP catalysts with 30% ionic liquid loading reported a drop in surface area and pore volume Despite that, all SILP components are observed through the FT-IR spectra From the SILP catalyst activity testing, it is clear that the catalyst benefiting from the surface functional groups leads to enlarging n/iso ratio product compared to others In addition, the functional groups suppress the hydrogenation reaction, which explains less propanol formation than propanal On the other hand, catalysts with no surface functional groups report higher propan-2-ol formation (iso product) At higher temperatures, the reaction shifts toward hydrogenation, leading to further byproducts, and lowering the selectivity of the reaction for SILP catalysts • Analogous to SILP catalysts, the absence of an ionic liquid layer was likely different from the surface area of gold catalysts Both Cat-Au-2 and Cat-Au-3 have specific surface areas and pore volumes close to the original supports The UV/Vis spectra also suggested the homogeneity in Au particles size, along with a plasmon surface phenomenon reported at 524 nm • Gold catalysts using OMC with γ-Al2 O3 and SiO2 templates showed relatively high selectivity and conversion, with only a tiny number of byproducts However, due to its nature, gold catalysts tended to favor hydrogenation products rather than hydroformylation, resulting in lower product formation than SILP catalysts 69 REFERENCE [1] [2] [3] [4] [5] [6] [7] [8] [9] [10] [11] [12] [13] [14] [15] [16] A M Trzeciak, “Hydroformylation,” Compr Inorg Chem II (Second Ed From Elem to Appl., vol 6, pp 25–46, 2013, doi: 10.1016/B978-0-08097774-4.00602-1 Kirk-Othmer, “Encyclopedia of Chemical Technology, v 22,” p 709, 1983 B Zhang, D Pa Fuentes, and A Bưrner, “Hydroformylation,” ChemTexts, vol 8, no 1, 2022, doi: 10.1007/s40828-021-00154-x R Tudor and A Shah, “ Industrial Low Pressure Hydroformylation: FortyFive Years of Progress for the LP Oxo SM Process ,” Johnson Matthey Technol Rev., vol 61, no 3, pp 246–256, 2017, doi: 10.1595/205651317x695875 K Ahuja and S Singh, “Global Oxo alcohols Market Size, Share and Industry Analysis Report by Product (N-Butanol, 2-Ethylhexanol and Isobutanol), By Application (Plasticizers, Acrylate, Acetate, Glycol Ether, Solvents, Adhesives and Lube Oil Additive) Regional Outlook, Competi,” 2020 doi: Report ID: GMI2224 H W Bohnen and B Cornils, “Hydroformylation of alkenes: An industrial view of the status and importance,” Adv Catal., vol 47, pp 1–64, 2002, doi: 10.1016/s0360-0564(02)47005-8 IHS Markit /S&P Global, “Oxo chemicals,” in Chemical economic handbook, 2021 W P Mul, “Shell Hydroformylation (SHF),” 1953 H Van Rensburg, R P Tooze, D F Foster, S Andrews, S Technology, and S Africa, “CCP ~ Ph,” no c, pp 247–254, 2006 M P Mitoraj and A Michalak, “σ-Donor and π-acceptor properties of phosphorus ligands: An insight from the natural orbitals for chemical valence,” Inorg Chem., vol 49, no 2, pp 578–582, 2010, doi: 10.1021/ic901736n W P Mul, “Shell Hydroformylation Process,” US8017811B2, 2008 G Victor, “Chapter Five,” Soc SecBeveridge Ils 191, pp 113–128, 2020, doi: 10.4324/9781315007717-17 C W Kohlpaintner, R W Fischer, and B Cornils, “Aqueous biphasic catalysis: Ruhrchemie/Rhône-Poulenc oxo process,” Appl Catal A Gen., vol 221, no 1–2, pp 219–225, 2001, doi: 10.1016/S0926-860X(01)007918 H Mao, H Yu, J Chen, and X Liao, “Biphasic catalysis using amphiphilic polyphenols-chelated noble metals as highly active and selective catalysts,” Sci Rep., vol 3, pp 1–5, 2013, doi: 10.1038/srep02226 E N Kusumawati and M Shirai, “Recent progress in biphasic catalytic systems using ionic liquids,” Curr Opin Green Sustain Chem., vol 35, p 100613, Jun 2022, doi: 10.1016/J.COGSC.2022.100613 M Schörner, P Wolf, and M Haumann, “Monolithic membrane reactors 70 [17] [18] [19] [20] [21] [22] [23] [24] [25] [26] [27] [28] [29] based on supported ionic liquid phase (SILP) materials – hydroformylation and water-gas shift case studies,” Green Chem Eng., vol 2, no 4, pp 339–341, Dec 2021, doi: 10.1016/J.GCE.2021.07.004 H P Steinrück and P Wasserscheid, “Ionic liquids in catalysis,” Catal Letters, vol 145, no 1, pp 380–397, 2015, doi: 10.1007/s10562-0141435-x J G McDaniel and A Verma, “On the Miscibility and Immiscibility of Ionic Liquids and Water,” J Phys Chem B, vol 123, no 25, pp 5343– 5356, 2019, doi: 10.1021/acs.jpcb.9b02187 R S Kalb, Toward Industrialization of Ionic Liquids 2020 doi: 10.1007/978-3-030-35245-5_11 J A Fuentes, “Effect of Ligand Backbone on the Selectivity and Stability of Rhodium Hydroformylation Catalysts Derived from PhospholanePhosphites,” Organometallics, vol 40, no 23, pp 3966–3978, 2021, doi: 10.1021/acs.organomet.1c00540 J Joni, M Haumann, and P Wasserscheid, “Continuous gas-phase isopropylation of toluene and cumene using highly acidic Supported Ionic Liquid Phase (SILP) catalysts,” Appl Catal A Gen., vol 372, no 1, pp 8– 15, 2010, doi: 10.1016/j.apcata.2009.09.048 F T U Kohler, “Surface-functionalized ionic liquid crystal-supported ionic liquid phase materials: Ionic liquid crystals in mesopores,” ChemPhysChem, vol 12, no 18, pp 3539–3546, 2011, doi: 10.1002/cphc.201100379 F Jin, Q Liu, Z Quan, M Kang, X Wang, and H Song, “Phosphoruscontaining polymeric ionic liquids-supported rhodium catalyst for hydroformylation of dihydrofurans,” Mol Catal., vol 521, no November 2021, p 112207, 2022, doi: 10.1016/j.mcat.2022.112207 J Flieger and M Flieger, “Ionic liquids toxicity—benefits and threats,” Int J Mol Sci., vol 21, no 17, pp 1–41, 2020, doi: 10.3390/ijms21176267 M S Alvarez, C Houzé, S Groni, B Schöllhorn, and C Fave, “Halogen bonding effect on electrochemical anion oxidation in ionic liquids,” Org Biomol Chem., vol 19, no 35, pp 7587–7593, 2021, doi: 10.1039/d1ob01031j J Guo, S B Fan, X H Gao, Q X Ma, J L Zhang, and T S Zhao, “Study on catalytic performance of Co-Ni-B/SBA-15 for hydroformylation of 1-octene,” Ranliao Huaxue Xuebao/Journal Fuel Chem Technol., vol 49, no 7, pp 945–951, 2021, doi: 10.1016/S1872-5813(21)60048-8 Y Zhao, X Zhang, J Sanjeevi, and Q Yang, “Hydroformylation of 1octene in Pickering emulsion constructed by amphiphilic mesoporous silica nanoparticles,” J Catal., vol 334, pp 52–59, 2016, doi: 10.1016/j.jcat.2015.11.011 F Marras, J Wang, M O Coppens, and J N H Reek, “Ordered mesoporous materials as solid supports for rhodium-diphosphine catalysts with remarkable hydroformylation activity,” Chem Commun., vol 46, no 35, pp 6587–6589, 2010, doi: 10.1039/c0cc00924e J Yao, W Song, D Wang, H Sun, and Y Li, “Multi-scale pore network 71 [30] [31] [32] [33] [34] [35] [36] [37] [38] [39] [40] [41] [42] modelling of fluid mass transfer in nano-micro porous media,” Int J Heat Mass Transf., vol 141, pp 156–167, 2019, doi: 10.1016/j.ijheatmasstransfer.2019.06.077 L Xu, H Zhao, H Song, and L Chou, “Ordered mesoporous alumina supported nickel based catalysts for carbon dioxide reforming of methane,” Int J Hydrogen Energy, vol 37, no 9, pp 7497–7511, 2012, doi: 10.1016/j.ijhydene.2012.01.105 F Yu and F.-S Xiao, “Mesostructured materials,” Ref Modul Chem Mol Sci Chem Eng., Jan 2021, doi: 10.1016/B978-0-12-823144-9.00006-6 D P Zhuchkov, M V Nenasheva, M V Terenina, Y S Kardasheva, D N Gorbunov, and E A Karakhanov, “Polymeric Heterogeneous Catalysts in the Hydroformylation of Unsaturated Compounds,” Pet Chem., vol 61, no 1, pp 1–14, 2021, doi: 10.1134/S0965544121010011 B Török, C Schäfer, and A Kokel, Heterogeneous catalytic rearrangements and other transformations 2022 doi: 10.1016/b978-0-12817825-6.00012-4 M Sankar et al., “Role of the Support in Gold-Containing Nanoparticles as Heterogeneous Catalysts,” Chem Rev., vol 120, no 8, pp 3890–3938, 2020, doi: 10.1021/acs.chemrev.9b00662 L Vu, “Nghiên cứu tổng hợp xúc tác tẩm chất lỏng ion SILP xúc tác nano vàng cho phản ứng chuyển hóa Etylen,” Engineer's thesis, Hanoi University of Science and Technology, 2021 K Dinh, “Nghiên cứu phản ứng hydroformyl hóa etylen hệ xúc tác tẩm chất lỏng ion hệ xúc tác nano vàng,” Engineer's thesis, Hanoi University of Science and Technology, 2019 S Wang, J Wang, X Zhu, J Wang, O Terasaki, and Y Wan, “Sizecontrol growth of thermally stable Au nanoparticles encapsulated within ordered mesoporous carbon framework,” Cuihua Xuebao/Chinese J Catal., vol 37, no 1, pp 61–72, 2016, doi: 10.1016/S18722067(15)60917-2 H Do, “Synthesis and characterization of the imidazolium ionic liquid phase catalyst containing rhodium complex on solid supports for the hydroformylation of ethylene,” Doctorate dissertation, Hanoi Universitiy of Science and Technology, 2016 B Cornils, H Springer, and P E Siegel, “United States Patent ( 19 ),” no 19, 1984 A Townshen, Principles of Instrumental Analysis, vol 152 1983 doi: 10.1016/s0003-2670(00)84936-3 H Yu, X Bai, G Qian, H Wei, X Gong, J Lin, Z Li “Impact of ultraviolet radiation on the aging properties of SBS-modified asphalt binders,” Polymers (Basel)., vol 11, no 7, 2019, doi: 10.3390/polym11071111 M Hydrodynamics, J Zhang, W Chiu, M Hydrodynamics, and E Cryomicroscopy, Encyclopedia of Biophysics 2013 doi: 10.1007/978-3-64216712-6 72 [43] C O Colpan, Y Nalbant, and M Ercelik, “Fundamentals of Fuel Cell Technologies,” Compr Energy Syst., vol 4–5, pp 1107–1130, 2018, doi: 10.1016/B978-0-12-809597-3.00446-6 [44] H Xu, W Pei, X Li, and J Zhang, “Highly Efficient Adsorption of Phenylethanoid Glycosides on Mesoporous Carbon,” Front Chem., vol 7, no November, pp 1–11, 2019, doi: 10.3389/fchem.2019.00781 [45] M Shenbagapushpam, Carbon Ratio Controlled in-situ Synthesis of Ordered Mesoporous Hybrid Silica/Carbon Materials via Soft Template Method 2021 doi: 10.1007/s12633-021-01453-1 [46] Petrović, “Mechanism of sorption of pertechnetate onto ordered mesoporous carbon,” J Radioanal Nucl Chem., vol 302, no 1, pp 217– 224, 2014, doi: 10.1007/s10967-014-3249-0 [47] B Chao, “The Effects of Ordered Mesoporous Carbon ( OMC ) Structure on the Adsorption Capacity for Resorcinol Removal : Laboratory and Simulation Approaches A Thesis Presented to the Graduate Faculty of the University of Louisiana at Lafayette In Partial Fulfillme,” 2016 [48] Y Zhai, Y Wan, Y Cheng, Y Shi, Y Zhang, F Zhang, B Tu, D Zhao “The influence of carbon source on the wall structure of ordered mesoporous carbons,” J Porous Mater., vol 15, no 5, pp 601–611, 2008, doi: 10.1007/s10934-007-9139-x [49] C Liu, K Shih, Y Gao, F Li, and L Wei, “Dechlorinating transformation of propachlor through nucleophilic substitution by dithionite on the surface of alumina,” J Soils Sediments, vol 12, no 5, pp 724–733, 2012, doi: 10.1007/s11368-012-0506-0 [50] Y Ku and H M Chiou, “The adsorption of fluoride ion from aqueous solution by activated alumina,” Water Air Soil Pollut., vol 133, no 1–4, pp 349–361, 2002, doi: 10.1023/A:1012929900113 [51] H Knözinger, “Dehydration of Alcohols on Aluminum Oxide,” Angew Chemie Int Ed English, vol 7, no 10, pp 791–805, 1968, doi: 10.1002/anie.196807911 [52] C T P da Silva, F R Veregue, M P Moisés, M R Guilherme, and A W Rinaldi, “Synthesis of Al O3-nanowhisker-based HKUST1 MOF composites,” Mater Chem Phys., vol 232, no May, pp 446–451, 2019, doi: 10.1016/j.matchemphys.2019.05.009 [53] O Levy-Ontman, D Blum, R Golden, E Pierschel, S Leviev, and A Wolfson, “Palladium Based-Polysaccharide Hydrogels as Catalysts in the Suzuki Cross-Coupling Reaction,” J Inorg Organomet Polym Mater., vol 30, no 3, pp 622–636, 2020, doi: 10.1007/s10904-019-01221-0 [54] C Xinlan, L Peng, Z Lei, P Hong, and Z Lun, “Some New Water Soluble Phosphines with the Involvement of the Trivalent Rare Earth Ion,” vol 3, no 1, pp 86–91, 1998 [55] S A Dharaskar, K L Wasewar, M N Varma, D Z Shende, and C K Yoo, “Synthesis, characterization and application of 1-butyl-3methylimidazolium tetrafluoroborate for extractive desulfurization of liquid fuel,” Arab J Chem., vol 9, no 4, pp 578–587, 2016, doi: 10.1016/j.arabjc.2013.09.034 73 [56] H G M Edwards, A F Johnson, and I R Lewis, “A vibrational spectroscopic study of tris triphenyl phosphine rhodium (I) chloride,” Spectrochim Acta Part A Mol Spectrosc., vol 49, no 5–6, pp 707–714, 1993, doi: 10.1016/0584-8539(93)80093-P [57] R Knapp, A Jentys, and J A Lercher, “Impact of supported ionic liquids on supported Pt catalysts,” Green Chem., vol 11, no 5, pp 656–66, 2009, doi: 10.1039/b901318k [58] J Lemus, J Palomar, M A Gilarranz, and J J Rodriguez, “Characterization of Supported Ionic Liquid Phase (SILP) materials prepared from different supports,” Adsorption, vol 17, no 3, pp 561–571, 2011, doi: 10.1007/s10450-011-9327-5 [59] S Nouri, “Effect of functional groups and pH on the affinity and adsorption capacity of activated carbon: Comparison of homogeneous and binary langmuir model parameters,” Adsorpt Sci Technol., vol 21, no 6, pp 511–524, 2003, doi: 10.1260/026361703771953578 [60] K N Ruckart, R A O’Brien, S M Woodard, K N West, and T G Glover, “Porous Solids Impregnated with Task-Specific Ionic Liquids as Composite Sorbents,” J Phys Chem C, vol 119, no 35, pp 20681– 20697, 2015, doi: 10.1021/acs.jpcc.5b04646 [61] S Lee, A Patra, P Christopher, D G Vlachos, and S Caratzoulas, “Theoretical Study of Ethylene Hydroformylation on Atomically Dispersed Rh/Al2O3Catalysts: Reaction Mechanism and Influence of the ReOxPromoter,” ACS Catal., vol 11, no 15, pp 9506–9518, 2021, doi: 10.1021/acscatal.1c00705 [62] M Tan, “Enhancing catalytic performance of activated carbon supported Rh catalyst on heterogeneous hydroformylation of 1-hexene via introducing surface oxygen-containing groups,” Appl Catal A Gen., vol 527, pp 53–59, 2016, doi: 10.1016/j.apcata.2016.08.024 [63] E Romb., “Modifications induced by pretreatments on Au/SBA-15 and their influence on the catalytic activity for low temperature CO oxidation,” Phys Chem Chem Phys., vol 11, no 3, pp 593–602, 2009, doi: 10.1039/b813982b [64] F Saira, N Firdous, R Qureshi, and A Ihsan, “Preparation and catalytic evaluation of Au/γ-Al2O3 nanoparticles for the conversion of 4-nitrophenol to 4-aminophenol by spectrophotometric method,” Turkish J Chem., vol 44, no 2, pp 448–460, 2020, doi: 10.3906/KIM-1910-21 [65] S Veziroglu, “Plasmonic and non-plasmonic contributions on photocatalytic activity of Au-TiO2 thin film under mixed UV–visible light,” Surf Coatings Technol., vol 389, p 125613, 2020, doi: 10.1016/j.surfcoat.2020.125613 74 ... tên tác giả luận văn: Vũ Tùng Lâm Đề tài luận văn: Nghiên cứu xúc tác tẩm chất lỏng ion (SILP) xúc tác nano vàng cho phản ứng chuyển hóa Etylen Chuyên ngành: Hóa học Mã số SV: 20211199M Tác giả,... TECHNOLOGY THESIS Supported ionic liquid phase catalyst and nanogold catalyst for the conversion of Ethylene Vu Tung Lam Lam.VT211199M@sis.hust.edu.vn Major: Chemistry Thesis advisor : Prof Le Minh... master’s thesis was the continuation from my engineer’s degree thesis, investigating the application of supported ionic liquid phase catalyst and gold catalyst in ethylene hydroformylation Following