Khảo sát hoạt tính xúc tác của vật liệu khung hữu cơ – kim loại tâm đồng trong các phản ứng oxy hóa ghép đôi

// TÂM Chuyên ngành: 602575 2013 -HCM ét : Tr Thành ph n H i ng ng i h c Bách Khoa, HQG Tp nh giá lu n v n th c s g m: 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) NAM T KHOA - - TP HCM, ngày : 602575 I » II Cu2(BPDC)2 IR, TGA 2-hydroxybenzaldehyde 1,4-dioxane 2-hydroxybenzaldehyde N,N-dimethylformamide 2(BPDC)2 III IV : 24/06/2013 : 23/05/2014 V Tp HCM, ng ày Cu2(BPDC)2 IR), phân Cu2(BPDC)2(BPY) - /g (tính theo ABSTRACT Highly porous metal organic framework copper active site Cu2(BPDC)2(BPY) was synthesized by a solvothermal method and characterized using a variety of different techniques, including X ray powder diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), thermogravimetric spectroscopy (FT analysis (TGA), Fourier transform infrared IR), atomic absorption spectrophotometry (AAS), and nitrogen physisorption measurements Highly crystalline porous Cu2(BPDC)2(BPY) was achieved with Langmuir surface areas of 1547 m2/g, respectively This material was used as an efficient heterogeneous catalyst for oxidative C direct C O coupling by H activation of ethers and formamides Cu2(BPDC)2(BPY) catalyst could be easily separated from the reaction mixture and could be reused several times without significant degradation in catalytic activity Furthermore, no contribution form homogenous catalysis of active species leaching into reaction solution was detected i iii ix 1.1 1.1.1 1.1.2 1.1.3 1.1.4 1.2 1.2.1 1.2.2 11 1.2.3 12 1.3 C C 15 1.3.1 C 15 1.3.2 O 18 22 2.1 2.1.1 2.1.2 2.2 22 22 Quy trình t 2(BPDC)2(BPY) 23 23 2.2.1 -hydroxybenzaldehyde 1,4-dioxane 23 2.2.2 -hydroxybenzaldehyde N,N dimethylformamide 24 2.3 25 i 27 3.1 2(BPDC)2 27 3.2 - hydroxybenzaldehyde 1,4-dioxane 32 3.3 a 2- hydroxybenzaldehyde N, N-dimethylformamide 57 84 86 ii F Hìn MOF UiO 66 làm xúc tác [11] 10 - 100 làm xúc tác [12] 11 [ZnF(Am2 Michael 12 2btec)(bpy) làm xúc tác 13 12 [16] 14 tách 2 [20] 16 [20] 16 C [20] 16 ine 17 -diester [26] 17 iii o -hydroxybenzaldehyde N,Nxúc tác Cu2(BPDC)2 o C - 2(BPDC)2 o - 2(BPDC)2 Hình 3.3.12 2(BPDC)2 -hydroxybenzaldehyde N,N-dimethylformamide Cu(NO3)2 - hydroxybenzaldehyde N,N- 75 Xúc tác Cu2(BPDC)2(BPY) o - hydroxybenzaldehyde N,NCu2(BPDC)2 -butyl hydroperoxide Xúc tác Cu2(BPDC)2 - Cu2(BPDC)2 (hình 3.3.13) xúc tác Cu2(BPDC)2 FT IR 4) o IR xúc tác Cu2(BPDC)2 trí 1640 cm-1 (hình 3.3.15) Cu2(BPDC)2 76 g cho Hình 3.3.13 - hydroxybenzaldehyde N,N- ác Cu2(BPDC)2(BPY) sau Hình 3.3.14 2(BPDC)2 77 Hình 3.3.15: 2(BPDC)2 O 2(BPDC)2 -hydroxybenzaldehyde N,N- 2- hydroxybenzaldehyde, methylsalicylate, 2- -hydroxyacetophenone, 2o nitrophenol phenol (hình 3.3.16) -dimethylformamidr 1:50, Cu2(BPDC)2 - N,N-dimethylformamide, enol sau - 78 hydroxyacetophenone N,N-dimethylformamide, -hy 2-dimethylformamide nghiên t 97% 92% sau 120 phút nitrophenol 2- - -me - - orthoOH, làm - Hình 3.3.16 -dimeth 2(BPDC)2(BPY) 79 - 2(BPDC)2 -hydroxybenzaldehyde N,N- - - - hydroxyacetophenone -dimethylformamide (DMF), N,N-diethylformamide (DEF) N- formylpiperidine (NFP) (hình 3.3.17 Cu2(BPDC)2 -butyl o -diethylformamide N-formylpiperidine -hydroxybenzaldehyde methylsalicylate, -diethylformamide N- di Khi -hydroxyacetophenone 2-diethylformamide N-formylpiperidine, N,N-dimethylformamide 2(BPDC)2(BPY) cho -carbonyl phenol formamide, -, para- 80 Hình 3.3.17 Cu2(BPDC)2(BPY) T kích có [62] 81 carbonyl tác Zn thay -napthaldehyde 4-phenylbenzaldehyde o [63] tác Cu2(BPDC)2 -butyl l, 4-phenylphenol 2- napthol (hình 3.3.18 -hydroxyben - - -napthol 2(BPDC)2 , bé o -phenylphenol 2-napthol Tuy nhiên, v cho 4-phenylphenol 2- - 82 Tuy nhiên, 2(BPDC)2 Hình 3.3.18 - 2(BPDC)2(BPY) 83 2(BPDC)2 -IR), phân tích n 2(BPDC)2 cao, tính Langmuir 1547 m2/g -hydroxybenzaldehyde 1,4-dioxane -hydroxybenzaldehyde N,N- -hydroxybenzaldehyde 1,4mol% xúc tác Cu2(BPDC)2 -hydroxybenzaldehyde 1,4- -butyl hy -hydroxybenzaldehyde 99% sau 84 -hydroxybenzaldehyde N,N- 2(BPDC)2 -hydroxybenzaldehyde N,N2(BPDC)2 (2013) 38 Expanding applications of copper-based metal organic frameworks in catalysis: Oxidative C O coupling by direct C H activation of ethers over Cu2(BPDC)2(BPY) as an efficient heterogeneous catalyst n Press, DOI : 10.1002/cctc.201300400 (IF = 5.181) organic framework as an efficient and recyclable catalyst for the oxidative cross 85 Irina P Beletskaya, A.V.C., Coordination Chemistry Reviews, 2004 248: p 2337 2364 B.F Hoskins, R.J.R., J Am Chem Soc, 1989 111: p 5962 O.M Yaghi, M.O.K., N.W Ockwig, H.K Chae, M Eddaoudi, J Kim, Nature 2003 423: p 705 00: p - 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O 56 -hydroxybenzaldehyde N,N- 2(BPDC)2(BPY) làm xúc tác 57 -hydroxybenzaldehyde N,N-dimethylformamide 58 -hydroxybenzaldehyde N,N 60 2(BPDC)2 -hydroxybenzaldehyde N,N-dimethylformamide... 61 -hydroxybenzaldehyde N,N- ng xúc tác Cu2(BPDC)2(BPY) 63 vi hydroxybenzaldehyde N,N-dimethylformamide 65 hydroxybenzaldehyde N,N- Cu2(BPDC)2(BPY) 67 -hydroxybenzaldehyde