Nghiên cứu khảo sát hoạt tính xúc tác của khung hữu cơ kim loại dựa trên nền cobalt trong phản ứng hữu cơ

BÁCH KHOA // Chuyên ngành: 602575 2013 - HCM PGS TS PGS TS n Tr Chí Minh ngày 25 Thành ph n H i ng ng i h c Bách Khoa, HQG Tp 2013 nh giá lu n v n th c s g m: PGS TSK PGS TS n PGS TS TS Xác nh n c a Ch t ch H i ng lý chuyên ngành sau lu n v n ã h giá c s a ch a (n u có) i i iii .2 1.3 Tí .4 1.3.2 Xúc tác .10 .11 14 15 1.4 N i dung nghiên c u 17 2.TH C NGHI M 21 2.1 T ng h p ZIF-67 kh o sát ho t tính xúc tác cho ph n .21 2.1.1 T ng h p ZIF-67 .21 2.1.2 Kh o sát ho t tính xúc tác ph n 22 2.2 T ng h p ZIF-9 kh o sát ho t tính xúc tác cho ph n ng oxy hóa benzylamine ghép chéo gi a benzylamine p-anisidine 22 2.2.1 T ng h p ZIF-9 23 2.2.2.1 Ph n ng oxy hóa benzylamine .23 2.2.2.2 Ph n ng ghép chéo gi a benzylamine p-anisidine .24 25 K T QU VÀ BÀN LU N 27 3.1 T ng h p ZIF-67 kh o sát ho t tính xúc tác cho ph n .27 3.1.1 K t qu phân tích hố lý c u trúc ZIF-67 27 3.1.1.1 K t qu XRD .27 ii 3.1.1.2 Ph FT-IR 27 3.1.1.3 Phân tích nhi t tr ng TGA .28 3.1.1.4 K t qu SEM, TEM 29 3.1.2 K t qu kh o sát ph n a 2-aminoacetophenone benzylamin 30 3.1.2.1 ng c a nhi chuy n hóa 30 3.1.2.2 ng c a t l mol tác ch t .31 3.1.2.3 ng c a t l mol xúc tác 32 3.1.2.4 ng c a tác nhân oxy hóa 33 3.1.2.5 ng c a dung môi 34 3.1.2.6 Ki m tra tính d th c a xúc tác 35 3.1.2.7 Kh o sát kh 3.1.2.8 i xúc tác .36 ng c a nhóm th benzylamine lên ph n ng 37 3.2.1.2 Ph FT-IR 38 3.2.1.3 Phân tích nhi t tr ng TGA .39 3.2.1.4 nh SEM, TEM 39 3.2.2 K t qu kh o sát ho t tính xúc tác cho ph n ng oxy hóa benzylamine ghép chéo gi a benzylamine p-anisidine .40 3.2.2.1 K t qu kh o sát ho t tính xúc tác cho ph n ng oxy hóa benzylamine 40 3.2.2.2 K t qu kh o sát ph n ng oxi hóa ghép chéo gi a p-anisidine benzylamine 44 K T LU N .50 TÀI LI U THAM KH O 51 iii Hình - hi ngâm .5 Hình 7: Hình 8: MOFs khác [7] .7 hexane carbaldehyde (a) benzaldehyde .9 -Mg làm xúc tác [14] .10 -nitrobenzaldehyde nitroalkanes [16] .10 -3 [17] 10 Hình 17: dimethoxymethylbenzene 11 11 12 - 12 12 13 -47/TBHP [25] 13 13 Hình 25: a) Ru-MOF- -phenylethanol [27] 14 14 .15 iv -101/DAAP [29] 15 -8 [30] 15 - -oxazolidone [20] 16 -Miyaura [31] 16 17 Hình 33 17 Hình 34 18 Hình 35 18 Hình 36 19 Hình 37 -Fe2O3 [33] .19 Hình 38 [41] 19 20 .20 Hình Hình 2: -67 27 - -67 (a) 2-methyl imidazole (b) .28 Hình 3: -67 .29 Hình 4: -67 .29 Hình 5: -67 30 Hình 6: -aminoacetophenone benzylamine .30 Hình 7: .31 Hình 8: -aminoacetophenone:benzylamine 32 Hình 9: - 33 Hình 10: 33 Hình 11: 34 Hình 12: 35 Hình 13: 36 Hình -67 36 37 Hình 16: IF-9 38 v Hình 17: FT- -9 (a)và benzimidazole (b) 38 Hình 18: - t hố .39 Hình 19: -9 40 Hình 20: -9 40 Hình 21: -9 làm xúc tác 41 Hình 22: ng c a nhi chuy n hoá c a 41 Hình 23: .42 Hình 24: 43 Hình 25: 44 Hình 26: -anisidine benzylamine .44 Hình 27: .45 Hình 28: 46 Hình 29 .47 48 Hình 31: -9 49 Hình 32: -anisidine benzylamine 49 vi MOF: metal-organic framework ZIF: zeolite imidazole framework NHPI: N-hydroxyphthalimide TBHP: tert-butyl hydroperoxide XRD: X-ray powder diffraction FT-IR: Fourier Transform Infrared Spectroscopy TGA: thermogravimetric analysis SEM: scanning electron microscopy TEM: transmission electron microscopy a Ngày nay, S d ng xúc tác có kh y ph n u su t trình ph n ng th i m th ng, ho c s n ph m có l n v i kim lo ng i l n vi c s n xu c ph ng l n ch t u tr ng s ng Vì th , tìm ki m m t lo i xúc tác d th m i có kh m th i gian ph n ng i tái s d ng nhi u l n, t h t u m t thách th d ng MOF ph n ng h kh o sát ng c bi t ph n ng oxy hóa Bên c kim lo i Cobalt kim lo i chuy n ti p có l p ngồi d ln tr ng th kh ng d ng c a Cobalt ph n ng oxi hóa r t cao Vì th , tác gi - 1.1 (metal-organic frameworks) nhóm [1] Hình 1: S ng c c công b n 1972-2010 [2] MOFs linh [2] ligand 44 [43] Hình 25: Sau nh n th ng c a nhóm nh lên ph n ng oxy hóa cs ng c a ZIF- n ph n ng oxy hóa s l a ch n ti p theo s d ng ZIF-9 làm xúc tác cho ph n ng oxy hóa ghép chéo gi a p-anisidine benzylamine 3.2.2.2 K t qu kh o sát ph n ng oxi hóa ghép chéo gi a p-anisidine benzylamine Hình 26: Ph n ng oxy hóa ghép chéo gi a p-anisidine benzylamine Trong nh ng y u t hoá c a pkho ng nhi c kh o sát, ng c a nhi chuy n c h t Theo nghiên c s d ng Nhóm tác gi Grirrane nhóm tác gi u kh o sát ph n ng oxy hóa ghép chéo 100oC [66,43] Trong Wei He c ng s c a s d ng 60oC [67] hay s d ng nhi phòng [62,68] Ph n c th c hi ng DMF, t l mol 45 p-anisidine:bezylamine 1:2 v i s có m t c a mol% ZIF-9 làm xúc tác, 70 oC, 80 oC, 90oC 100 oC K t qu cho th y nhi nhi k nt ch 70 oC, ph n ng x y v i t ph n ng T i nhi chuy n hoá c a p- c sau gi chuy n hoá c a p90oC 100 o r t ch m ng v i nhi t 100oC c sau gi Hình 27: ng c a nhi V i k t qu u t ti chuy lên ph n ng oxy hóa ghép chéo c kh o sát ng c a n ch n l c c a s n ph m Ph n c th c hi n 100oC ng DMF, t l mol p-anisidine:bezylamine 1:2 t i nhi v in ZIF-9 l 19 % pn t mol %, mol%, mol%, mol% K t qu n hoá sau gi n c xúc tác mol% Vi xúc tác t chuy n hoá c a benzylamine t 19% lên thành 71%, 73% Giá tr chuy n hoá dùng mol% ZIF-9 sau gi Trong m t s nghiên c ng th n kéo dài c dùng mol% [67], CuCl 0.5 mol% [43], CuI mol% [62] có th [63] nhiên th i gian ph n ng l i 46 Hình 28: ng c a n xúc tác lên ph n ng oxy hóa ghép chéo Trong ph n ng oxy hóa vi c l a ch tr ng t quan n hi u su t ph n ng Vì v y ti n hành ki m tra c a TBHP so sánh v i ch t oxy hóa khác lê c a s n ph m Ph n c th c hi chuy ng ch n l c ng DMF, t l mol p- anisidine:bezylamine 1:2 v i s có m t c a mol% ZIF-9 làm xúc tác t i nhi t 100 oC Các tác nhân s d ng TBHP, H2O2 khơng khí H2O2 TBHP làm tác nhân oxy hóa tert-butyl hypoiodite (tBuOI) [68], di-tert-butyldiaziridinone [69] s d ng nhi u nh t O2 [61,63,70] hay khơng khí [43,62,65,67] 47 Hình 29: ng c a tác nhân oxy hóa lên ph n ng oxy hóa ghép chéo ng c a dung môi ph n ng y u t giá ng lên ph n ng H n h p ph n c l a ch n ti ng g m: t l mol p- anisidine:bezylamine 1:2 v i s có m t c a mol% ZIF-9 làm xúc tác t i nhi t 100 oC Các dung môi DMF, DMSO, toluen p-xylen Ph n hành 50 oC v i n ZIF-9 mol% p-anisidine DMA, p-xylene toluene ph n ng x y v V i dung môi chuy kho ng 58-63% sau gi Khi chuy n sang dung mơi phân c c khác chuy n hố c ti n 77% sau gi c DMF 48 Hình 30: ng c chuy n hóa c a ph n ng 100 oC dung môi DMF - p-anisidine:benzylamine 1:2 mmol tách - p-anisidine ZIF-9 làm p-anisidine khơng thay -9 hồn tồn 49 Hình 31: Thí nghi m ki m tra tính d th c a ZIF-9 M t nh kh t tr i c a xúc tác d th so v i tái s d ng c - ng th c thu h i sau ph n ng b ng cách g n tách kh i h n h p s n ph m, r a nh v i m t DMF r i s y chân không uv in 170 oC gi , r t Ph n ng d ng l i cho ph n ng ban c th c hi n gi a p-anisidine benzylamine v i t l mol 1:2 dung môi DMF 100 oC, s d ng TBHP làm tác nhân oxy hóa mol% ZIF-9 K t qu cho th chuy n hoá c a p-anisidine sau l n thu h i ch Hình 32: c 57% chuy n hoá c a ph n ng gi a p-anisidine benzylamine s d ng ZIF-9 sau l n thu h i 50 K T LU N - ZIF-67 -IR), phân ZIF-67 - u oxy hóa P oxy -aminoacetophenone benzylamine oxy hóa ghép -anisidine benzylamine ZIF - -aminoacetophenone benzylamine mol% ZIF-67 1:1.2 2-aminoacetophenone : benzylamine TBHP 2-aminoacetophenone sau - 2% p-anisidine benzylamine mol% ZIF-9 1:2 p-anisidine : benzylamine TBHP p-anisidine sau 77% ZIF ZIF oxy hóa - hai thác , 226231 (2013) 51 TÀI LI U THAM KH O Yaghi, O M et al Reticular synthesis and the design of new materials Nature 423, 705 714 (2003) and applications of metal-organic frameworks Science 341, 1230444 (2013) Eddaoudi, M et al Systematic design of pore size and functionality in isoreticular MOFs and their application in methane storage Science 295, 469 472 (2002) Park, K S et al Exceptional chemical and thermal stability of zeolitic imidazolate frameworks Proc Natl Acad Sci U S A 103, 10186 10191 (2006) Uribe-romo, F J., Knobler, C B., Keeffe, M O., Yaghi, O M & Spectus, C O N Synthesis, Structure, and Carbon Dioxide Capture Properties of Zeolitic Imidazolate Frameworks xxx, (2009) Bruinsma, R F., Gennes, P G De, Freund, J B & Levine, D A route to high surface area , porosity and inclusion of large molecules in crystals Nature 427, 523 527 (2004) Furukawa, H et al Ultrahigh porosity in metal-organic frameworks Science 329, 424 428 (2010) Banerjee, R et al Control of pore size and functionality in isoreticular zeolitic imidazolate frameworks and their carbon dioxide selective capture properties J Am Chem Soc 131, 3875 3877 (2009) Morris, W et al A combined experimental-computational investigation of carbon dioxide capture in a series of isoreticular zeolitic imidazolate frameworks J Am Chem Soc 132, 11006 11008 (2010) 10 Pérez-Mayoral, E et al Synthesis of quinolines via Friedländer reaction catalyzed by CuBTC metal-organic-framework Dalton Trans 41, 4036 4044 (2012) 52 11 Miralda, C M., Macias, E E., Zhu, M., Ratnasamy, P & Carreon, M a Zeolitic Imidazole Framework-8 Catalysts in the Conversion of CO to Chloropropene Carbonate ACS Catal 2, 180 183 (2012) 12 Opanasenko, M et al Comparison of the catalytic activity of MOFs and zeolites in Knoevenagel condensation Catal Sci Technol (2012) doi:10.1039/c2cy20586f 13 Lin, X.-M., Li, T.-T., Wang, Y.-W., Zhang, L & Su, C.-Y Two Zn(II) metalorganic frameworks with coordinatively unsaturated metal sites: structures, adsorption, and catalysis Chem Asian J 7, 2796 804 (2012) 14 Links, D A., Saha, D., Sen, R & Koner, S Porous magnesium carboxylate framework: synthesis, X-ray crystal structure, gas adsorption property and heterogeneous catalytic aldol condensation reaction Dalt Trans 41, 7399 7408 (2012) 15 Saha, D., Maity, T., Sen, R & Koner, S Heterogeneous catalysis over a barium carboxylate framework compound: Synthesis, X-ray crystal structure and aldol condensation reaction Polyhedron 43, 63 70 (2012) 16 Gu, J.-M., Kim, W.-S & Huh, S Size-dependent catalysis by DABCOfunctionalized Zn-MOF with one-dimensional channels Dalton Trans 40, 10826 10829 (2011) 17 Gascon, J., Aktay, U., Hernandez-alonso, M D., Klink, G P M Van & Kapteijn, F Amino-based metal-organic frameworks as stable , highly active basic catalysts J Catal 261, 75 87 (2009) 18 Park, J et al A versatile metal organic framework for carbon dioxide capture and cooperative catalysis Chem Commun 48, 9995 9997 (2012) 19 Shi, L.-X & Wu, C.-D A nanoporous metal-organic framework with accessible Cu2+ sites for the catalytic Henry reaction Chem Commun (Camb) 47, 2928 2930 (2011) 20 Arai, T., Kawasaki, N & Kanoh, H Magnetically Separable Cu-Carboxylate MOF Catalyst for the Henry Reaction Synlett 23, 1549 1553 (2012) 53 21 Catalytic oxidation of aromatic oxygenates by the heterogeneous catalyst CoZIF-9 Appl Catal A Gen 394, 79 85 (2011) 22 Zhang, A., Li, L., Li, J., Zhang, Y & Gao, S Epoxidation of olefins with O2 and isobutyraldehyde catalyzed by cobalt (II)-containing zeolitic imidazolate framework material Catal Commun 12, 1183 1187 (2011) 23 Dhakshinamoorthy, A., Alvaro, M & Garcia, H Metal organic frameworks as heterogeneous catalysts for oxidation reactions Catal Sci Technol 1, 856 867 (2011) 24 Dhakshinamoorthy, A., Alvaro, M., Garcia, H & Valencia, D Aerobic Oxidation of Styrenes Catalyzed by an Iron Metal Organic Framework ACS Catal 1, 836 840 (2011) 25 Leus, K et al The remarkable catalytic activity of the saturated metal organic framework V-MIL-47 in the cyclohexene oxidation Chem Commun (Camb) 46, 5085 5087 (2010) 26 Fu, Y., Sun, D., Qin, M., Huang, R & Li, Z Cu ( II ) -and Co ( II ) containing metal organic frameworks ( MOFs ) as catalysts for cyclohexene oxidation with oxygen under solvent-free conditions RSC Adv 2, 3309 3314 (2012) 27 Carson, F et al Ruthenium complexation in an aluminium metal-organic framework and its application in alcohol oxidation catalysis Chemistry 18, 15337 15344 (2012) 28 Bromberg, L & Hatton, T A Aldehyde-Alcohol Reactions Catalyzed under Mild Conditions by Chromium(III) Terephthalate Metal Organic Framework (MIL-101) and Phosphotungstic Acid Composites ACS Appl Mater Interfaces 3, 4756 4764 (2011) 29 Wang, S., Bromberg, L., Schreuder-gibson, H & Hatton, T A Organophophorous Ester Degradation by Chromium(III) Terephthalate Metal -101) Chelated to N , N - Dimethylaminopyridine 54 and Related Aminopyridines ACS Appl Mater Interfaces 5, 1267 1278 (2013) 30 Dang, T T et al Palladium Nanoparticles Supported on ZIF - As an Efficient Heterogeneous Catalyst for Aminocarbonylation ACS Catal 5, 1406 1410 (2013) 31 Huang, Y et al Palladium nanoparticles supported on amino functionalized metal-organic frameworks as highly active catalysts for the Suzuki Miyaura cross-coupling reaction Catal Commun 14, 27 31 (2011) 32 Huang, Y et al Palladium Nanoparticles Supported on Mixed-Linker Metal Organic Frameworks as Highly Active Catalysts for Heck Reactions Chempluschem 77, 106 112 (2012) 33 Anand, N., Reddy, K H P., Satyanarayana, T., Rao, K S R & Burri, D R A magneticall -Fe2O3 nanocatalyst for the synthesis of 2- phenylquinazolines under solvent-free conditions Catal Sci Technol 2, 570 574 (2012) 34 quinazolinones and quinazolines Tetrahedron 61, 10153 10202 (2005) 35 Erba, E., Pocar, D & Valle, M -Triazolines Part 41 A new synthesis of 2-alkylquinazolines and , 9-dialkylpyrimido [ , 5- b ] indoles J Chem Soc 1, 421 425 (1999) 36 Hiroaki, O Y O Y T S O N F Ynamides: a modern functional group for the new millennium Org Lett 12, 3963 3965 (2010) 37 Mori, K., Yamaguchi, K., Mizugaki, T., Ebitani, K & Kaneda, K Catalysis of a hydroxyapatite-bound Ru complex: efficient heterogeneous oxidation of primary amines to nitriles in the presence of molecular oxygen Chem Commun 461 462 (2001) doi:10.1039/b009944i 38 Cenini, S., Porta, F & Pizzotti, M Low oxidation states ruthenium chemistry VI Stoichiometric and catalytic oxidation by molecular oxygen of primary amines bound to dichlorobis(triphenylphosphine)ruthenium(II) J Mol Catal 15, 297 308 55 39 Tang, R., Diamond, S E., Neary, N & Mares, F Homogeneous catalytic oxidation of amines and secondary alcohols by molecular oxygen J Chem Soc Chem Commun 562 (1978) doi:10.1039/c39780000562 40 Porta, F., Crotti, C & Cenini, S Oxidation of amines in the presence of ruthenium complexes: molecular oxygen and iodosylbenzene as oxidants J Mol Catal 50, 333 341 41 Lang, X., Ji, H., Chen, C., Ma, W & Zhao, J Selective formation of imines by aerobic photocatalytic oxidation of amines on TiO2 Angew Chem Int Ed Engl 50, 3934 3937 (2011) 42 Su, F et al Aerobic oxidative coupling of amines by carbon nitride photocatalysis with visible light Angew Chem Int Ed Engl 50, 657 660 (2011) 43 Patil, R D & Adimurthy, S Copper-Catalyzed Aerobic Oxidation of Amines to Imines under Neat Conditions with Low Catalyst Loading Adv Synth Catal 353, 1695 1700 (2011) 44 Kegnæs, S., Mielby, J., Mentzel, U V., Christensen, C H & Riisager, A Formation of imines by selective gold-catalysed aerobic oxidative coupling of alcohols and amines under ambient conditions Green Chem 12, 1437 1441 (2010) 45 So, M.-H., Liu, Y., Ho, C.-M & Che, C.-M Graphite-supported gold nanoparticles as efficient catalyst for aerobic oxidation of benzylic amines to imines and N-substituted 1,2,3,4-tetrahydroisoquinolines to amides: synthetic applications and mechanistic study Chem Asian J 4, 1551 61 (2009) 46 Aschwanden, L., Mallat, T., Krumeich, F & Baiker, A A simple preparation of an efficient heterogeneous gold catalyst for aerobic amine oxidation J Mol Catal A Chem 309, 57 62 (2009) 47 Grirrane, A., Corma, A & Garcia, H Highly active and selective gold catalysts for the aerobic oxidative condensation of benzylamines to imines and one-pot, two-step synthesis of secondary benzylamines J Catal 264, 138 144 (2009) 56 48 Jiang, L et al Direct and mild palladium-catalyzed aerobic oxidative synthesis of imines from alcohols and amines under ambient conditions Chem Commun (Camb) 47, 10833 (2011) 49 Dhakshinamoorthy, A., Alvaro, M & Garcia, H Aerobic Oxidation of Benzyl Amines to Benzyl Imines Catalyzed by Metal-Organic Framework Solids ChemCatChem 2, 1438 1443 (2010) 50 Gross, A F., Sherman, E & Vajo, J J Aqueous room temperature synthesis of cobalt and zinc sodalite zeolitic imidizolate frameworks Dalt Trans 41, 5458 5460 (2012) 51 Qian, J., Sun, F & Qin, L Hydrothermal synthesis of zeolitic imidazolate framework-67 ( ZIF-67 ) nanocrystals Mater Lett 82, 220 223 (2012) 52 Huang, Y., Lin, Z & Cao, R Palladium nanoparticles encapsulated in a metal-organic framework as efficient heterogeneous catalysts for direct C2 arylation of indoles Chemistry 17, 12706 12 (2011) 53 Li, P et al Hydrogen-bonding 2D metal-organic solids as highly robust and efficient heterogeneous green catalysts for Biginelli reaction Tetrahedron Lett 52, 6220 6222 (2011) 54 Dhakshinamoorthy, A., Alvaro, M & Garcia, H Claisen-Schmidt Condensation Catalyzed by Metal-Organic Frameworks Adv Synth Catal 352, 711 717 (2010) 55 Pérez- -Organic Framework Catalyst for the Friedländer Reaction ChemCatChem 3, 157 159 (2011) 56 Lv, Y et al Copper-catalyzed annulation of amidines for quinazoline synthesis Chem Commun (Camb) 49, 6439 6441 (2013) 57 Han, B et al Efficient aerobic oxidative synthesis of 2-aryl quinazolines via benzyl C-H bond amination catalyzed by 4-hydroxy-TEMPO Chem Commun (Camb) 47, 7818 7820 (2011) 58 Guo, S., Wang, J., Fan, X., Zhang, X & Guo, D Synthesis of Pyrazolo[1,5c]quinazoline Derivatives through Copper- Catalyzed Tandem Reaction of 5- 57 (2-Bromoaryl)-1H-pyrazoles with Carbonyl Compounds and Aqueous Ammonia J Org Chem (2013) 59 Ohta, Y., Tokimizu, Y., Oishi, S., Fujii, N & Ohno, H Direct Synthesis of Quinazolines through Copper-Catalyzed Reaction of Aniline-Derived Benzamidines Org Lett., 12, 3963 3965 (2010) 60 Li, Q & Kim, H Hydrogen production from NaBH4 hydrolysis via Co-ZIF-9 catalyst Fuel Process Technol 100, 43 48 (2012) 61 Liu, L., Zhang, S., Fu, X & Yan, C.-H Metal-free aerobic oxidative coupling of amines to imines Chem Commun (Camb) 47, 10148 10150 (2011) 62 Tian, H., Yu, X., Li, Q., Wang, J & Xu, Q General, Green, and Scalable Synthesis of Imines from Alcohols and Amines by a Mild and Efficient Copper-Catalyzed Aerobic Oxidative Reaction in Open Air at Room Temperature Adv Synth Catal 354, 2671 2677 (2012) 63 Zhang, C & Jiao, N Copper-Catalyzed Aerobic Oxidative Dehydrogenative Coupling of Anilines Leading to Aromatic Azo Compounds using Dioxygen as an Oxidant Angew Chemie 122, 6310 6313 (2010) 64 Nguyen, L T L., Le, K K a., Truong, H X & Phan, N T S Metal organic frameworks for catalysis: the Knoevenagel reaction using zeolite imidazolate framework ZIF-9 as an efficient heterogeneous catalyst Catal Sci Technol 2, 521 528 (2012) 65 Largeron, M & Fleury, M.-B A biologically inspired Cu(I)/topaquinone-like co-catalytic system for the highly atom-economical aerobic oxidation of primary amines to imines Angew Chem Int Ed Engl 51, (2012) 66 Grirrane, A., Corma, A & García, H Gold-catalyzed synthesis of aromatic azo compounds from anilines and nitroaromatics Science 322, 1661 1664 (2008) 67 Cai, S et al Room Temperature Activation of Oxygen by Monodispersed Metal Nanoparticles: Oxidative Dehydrogenative Coupling of Anilines for Azobenzene Syntheses ACS Catal 3, 478 486 (2013) 58 68 Takeda, Y., Okumura, S & Minakata, S Oxidative dimerization of aromatic amines using tBuOI: entry to unsymmetric aromatic azo compounds Angew Chem Int Ed Engl 51, 7804 7808 (2012) 69 Zhu, Y & Shi, Y Facile Cu(I)-catalyzed oxidative coupling of anilines to azo compounds and hydrazines with diaziridinone under mild conditions Org Lett 15, 1942 1945 (2013) 70 Grirrane, A., Corma, A & García, H Gold-catalyzed synthesis of aromatic azo compounds from anilines and nitroaromatics Science 322, 1661 1664 (2008) ... nhiên h n ch c a xúc tác giá thành cao Vì th , nghiên c u h xúc tác khác có giá r ng th i thu h khoa h c tìm tịi phát tri n tác gi c nhi u l c nhà o sát ho t tính xúc tác c a h xúc tác NHPI/Fe(BTC)... benzene kh o sát ho t tính xúc tác cho ph n ng cyanosilyl hóa h p ch t carbonyl K t qu ng minh c hi u qu xúc tác c a MOF-Zn so v i Cu3(BTC)2 ho t tính xúc tác sau l n thu h [13] c tác gi Cheng-Yong... DMSO, Toluen, p-xylene - Ki m tra tính d th c a xúc tác - Kh o sát kh - Kh o sát i ng c a nhóm th chuy n hóa c a ph n ng 2.2 T ng h p ZIF-9 kh o sát ho t tính xúc tác cho ph n ng oxy hóa benzylamine