Luận án tiến sĩ nghiên cứu sử dụng vật liệu nano từ tính cofe2o4 làm chất mang xúc tác cho phản ứng knoevenagel

ĐẠI HỌC QUỐC GIA TP HỒ CHÍ MINH TRƯỜNG ĐẠI HỌC BÁCH KHOA BÙI TẤN NGHĨA NGHIÊN CỨU SỬ DỤNG VẬT LIỆU NANO TỪ TÍNH CoFe2O4 LÀM CHẤT MANG XÚC TÁC CHO PHẢN ỨNG KNOEVENAGEL, SONOGASHIRA, SUZUKI, HECK LUẬN ÁN TIẾN SĨ KỸ THUẬT TP HỒ CHÍ MINH NĂM 2013 ĐẠI HỌC QUỐC GIA TP HCM TRƯỜNG ĐẠI HỌC BÁCH KHOA BÙI TẤN NGHĨA NGHIÊN CỨU SỬ DỤNG VẬT LIỆU NANO TỪ TÍNH CoFe2O4 LÀM CHẤT MANG XÚC TÁC CHO PHẢN ỨNG KNOEVENAGEL, SONOGASHIRA, SUZUKI, HECK Chuyên ngành: CÔNG NGHỆ HÓA HỌC CÁC CHẤT HỮU CƠ Mã số chuyên ngành: 62527505 Phản biện độc lập 1: GS.TS Đinh Thị Ngọ Phản biện độc lập 2: PGS.TS Nguyễn Thị Dung Phản biện 1: PGS.TS Nguyễn Thị Phương Phong Phản biện 2: PGS.TS Đặng Mậu Chiến Phản biện 3: PGS.TS Nguyễn Ngọc Hạnh NGƯỜI HƯỚNG DẪN KHOA HỌC PGS.TS Phan Thanh Sơn Nam PGS.TS Lê Thị Hồng Nhan LỜI CAM ĐOAN Tác giả xin cam đoan cơng trình nghiên cứu thân tác giả Các kết nghiên cứu kết luận luận án trung thực, không chép từ nguồn hình thức Việc tham khảo nguồn tài liệu thực trích dẫn ghi nguồn tài liệu tham khảo theo yêu cầu Tác giả luận án Bùi Tấn Nghĩa i TÓM TẮT LUẬN ÁN Hạt nano siêu thuận từ CoFe2O4 tổng hợp phương pháp vi nhũ biến tính cách kết hợp ligand palladium acetate để hình thành xúc tác phức với hàm lượng palladium 0,30 mmol/g Đặc tính xúc tác xác định phương pháp nhiễu xạ tia X (XRD), kính hiển vi điện tử quét (SEM), kính hiển vi điện tử truyền qua (TEM), phân tích nhiệt trọng lượng (TGA), từ kế mẫu rung (VSM), biến đổi Fourier hồng ngoại (FT-IR), quang phổ hấp thụ nguyên tử (AAS), phân tích hàm lượng nitơ Kết chứng minh hạt nano từ tính Pd(II)-CoFe2O4 xúc tác hiệu cho phản ứng ghép đôi carbon-carbon phản ứng Suzuki 4’-bromoacetophenone với phenylboronic acid, phản ứng Sonogashira 4’-bromoacetophenone với phenylacetylene, phản ứng Heck 4’-bromoacetophenone với styrene điều kiện gia nhiệt thơng thường có hỗ trợ vi sóng Hiệu xúc tác đánh giá qua độ chuyển hóa xác định sắc ký khí Xúc tác tái sử dụng nhiều lần mà hoạt tính khơng giảm ii ABSTRACT Cobalt superparamagnetic (CoFe2O4) nanoparticles were synthesized following a microemulsion method and functionalized by using the supported ligand and palladium acetate to form the immobilized palladium complex catalyst with a palladium loading of 0.30 mmol/g The catalyst was characterized by X-ray powder diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), thermogravimetric analysis (TGA), vibrating sample magnetometry (VSM), Fourier transform infrared (FT-IR), atomic absorption spectrophotometry (AAS), and nitrogen physisorption measurements The results proved that the Pd(II)-CoFe2O4 magnetic nanoparticles were as an efficient catalyst for several carbon-carbon couplings including for the Suzuki reaction between 4’bromoacetophenone with phenylboronic acid, and the Sonogashira reaction between 4’-bromoacetophenone with phenylacetylene, and the Heck reaction between 4’bromoacetophenone with styrene under conventional and microwave irradiation conditions Efficiency of catalysts in reactions was evaluated by conversion which was determined by gas chromatography The catalysts could be reused several times without significant degradation in catalytic activity iii LỜI CÁM ƠN Tôi xin trân trọng gởi lời cám ơn sâu sắc đến, Thầy PGS.TS Phan Thanh Sơn Nam, người thầy kính mến dẫn đường khoa học xuyên suốt cho luận án Cô PGS.TS Lê Thị Hồng Nhan, cô giáo tận tụy dành nhiều thời gian tâm huyết để hướng dẫn khoa học cho nghiên cứu Thầy PGS.TS Phạm Thành Quân, cô PGS.TS Nguyễn Ngọc Hạnh, thầy TS Tống Thanh Danh tập thể cán giảng viên mơn Kỹ thuật Hữu cơ, Khoa Kỹ thuật Hóa học, Đại học Bách Khoa Tp.HCM chân thành góp ý tạo điều kiện thuận lợi cho hồn thành luận án Có lúc khó khăn tưởng chừng vượt qua-vợ tôi- người đồng hành tơi vượt qua khó khăn trở ngại để hoàn thành nghiên cứu Cuối xin cảm ơn ba, má gia đình tạo nhiều động lực, nguồn cảm hứng cho học tập, nghiên cứu iv MỤC LỤC DANH MỤC CÁC HÌNH ẢNH .viii DANH MỤC BẢNG BIỂU xvii DANH MỤC CÁC TỪ VIẾT TẮT xviii GIỚI THIỆU CHƯƠNG 1: TỔNG QUAN 1.1 Giới thiệu 1.2 Phản ứng ghép đôi carbon-carbon xúc tác palladium mang chất mang polymer 1.3 Phản ứng ghép đôi carbon-carbon xúc tác palladium mang chất mang silica 13 1.4 Phản ứng ghép đôi carbon-carbon xúc tác nano palladium 20 1.5 Phản ứng ghép đôi carbon-carbon xúc tác palladium mang chất mang nano từ tính 22 1.5.1 Vật liệu từ tính 22 1.5.2 Vật liệu nano từ tính 27 1.5.3 Vật liệu nano từ tính ứng dụng làm chất mang xúc tác 28 CHƯƠNG 2: THỰC NGHIỆM 37 2.1 Nguyên vật liệu trang thiết bị 37 2.1.1 Nguyên vật liệu 37 2.1.2 Trang thiết bị 37 2.2 Tổng hợp xúc tác 39 2.2.1 Tổng hợp hạt nano từ tính CoFe2O4 (CoFe2O4 MNPs) 39 2.2.2 Làm giàu -OH bề mặt hạt nano từ tính CoFe2O4 39 2.2.3 Gắn nhóm chức amino lên hạt nano từ tính CoFe2O4 làm giàu –OH 39 2.2.4 Gắn nhóm base Schiff lên hạt nano từ tính amine hố 1N-MNPs, 2NMNPs 3N-MNPs 40 2.2.5 Cố định palladium hạt nano từ tính CoFe2O4 40 2.3 Khảo sát hoạt tính xúc tác 41 2.3.1 Phản ứng Knoevenagel 41 2.3.2 Phản ứng Sonogashira 41 2.3.3 Phản ứng Suzuki 43 v 2.3.4 Phản ứng Heck 44 2.3.5 Xử lý kết phân tích GC 45 CHƯƠNG 3: KẾT QUẢ VÀ BÀN LUẬN 47 3.1 Tổng hợp xúc tác 47 3.2 Kết thực phản ứng Knoevenagel 58 3.2.1 Kết khảo sát ảnh hưởng loại dung môi 59 3.2.2 Kết khảo sát ảnh hưởng hàm lượng xúc tác 60 3.2.3 Kết khảo sát ảnh hưởng nhóm vịng benzene benzaldehyde 61 3.2.4 Kết khảo sát tính dị thể xúc tác 62 3.2.5 Kết khảo sát khả thu hồi tái sử dụng xúc tác 63 3.2.6 Kết khảo sát tính chất đặc trưng xúc tác sau thu hồi tái sử dụng 64 3.3 Kết thực phản ứng Sonogashira 68 3.3.1 Kết khảo sát ảnh hưởng loại base 69 3.3.2 Kết khảo sát ảnh hưởng nhiệt độ cường độ chiếu xạ vi sóng 72 3.3.3 Kết khảo sát ảnh hưởng hàm lượng xúc tác 74 3.3.4 Kết khảo sát ảnh hưởng hàm lượng đồng xúc tác CuI 76 3.3.5 Kết khảo sát tỷ lệ mol phenylacetylene: 4’-bromoacetophenone 78 3.3.6 Kết khảo sát tỷ lệ mol K3PO4:4’-bromoacetophenone 80 3.3.7 Kết khảo sát ảnh hưởng nhóm halogen vòng benzene acetophenone 82 3.3.8 Kết khảo sát ảnh hưởng vị trí nhóm Br- vòng benzene acetophenone 83 3.3.9 Kết khảo sát ảnh hưởng nhóm vịng benzene bromobenzene 85 3.3.10 Kết so sánh hoạt tính xúc tác Pd-1N-MNPs, Pd-2N-MNPs Pd-3NMNPs 87 3.3.11 Kết khảo sát tính dị thể xúc tác 91 3.3.12 Kết khảo sát khả thu hồi tái sử dụng xúc tác 93 3.4 Kết thực phản ứng Suzuki 94 3.4.1 Kết khảo sát ảnh hưởng loại base 95 3.4.2 Kết khảo sát ảnh hưởng nhiệt độ 97 vi 3.4.3 Kết khảo sát ảnh hưởng hàm lượng xúc tác 98 3.4.4 Kết khảo sát ảnh hưởng tỷ lệ mol phenylboronic acid: 4’bromoacetophenone 100 3.4.5 Kết khảo sát ảnh hưởng vị trí nhóm Br- vịng benzene acetophenone 101 3.4.6 Kết khảo sát ảnh hưởng nhóm 103 3.4.7 Kết khảo sát ảnh hưởng nhóm halogen vòng benzene acetophenone 105 3.4.8 Kết so sánh hoạt tính xúc tác Pd-1N-MNPs, Pd-2N-MNPs Pd-3NMNPs 107 3.4.9 Kết khảo sát tính dị thể xúc tác 110 3.4.10 Kết khảo sát khả thu hồi tái sử dụng xúc tác 112 3.5 Kết thực phản ứng Heck 113 3.5.1 Kết khảo sát ảnh hưởng loại base 114 3.5.2 Kết khảo sát ảnh hưởng hàm lượng xúc tác 117 3.5.3 Kết khảo sát ảnh hưởng nhiệt độ 120 3.5.4 Kết khảo sát ảnh hưởng tỷ lệ mol styrene: 4’-bromoacetophenone 121 3.5.5 Kết khảo sát ảnh hưởng tỷ lệ mol base: 4’-bromoacetophenone 122 3.5.6 Kết khảo sát ảnh hưởng nhóm vòng benzene bromobenzene 123 3.5.7 Kết khảo sát ảnh hưởng nhóm halogen vịng benzene acetophenone 125 3.5.8 Kết khảo sát ảnh hưởng vị trí nhóm Br- vòng benzene acetophenone 128 3.5.9 Kết khảo sát tính dị thể xúc tác 129 3.5.10 Kết so sánh hoạt tính xúc tác Pd-1N-MNPs, Pd-2N-MNPs Pd-3NMNPs 130 3.5.11 Kết khảo sát khả thu hồi tái sử dụng xúc tác 133 KẾT LUẬN VÀ KIẾN NGHỊ 135 CÁC TÀI LIỆU CÔNG BỐ CỦA TÁC GIẢ 138 TÀI LIỆU THAM KHẢO 139 vii DANH MỤC CÁC HÌNH ẢNH Hình 1.1 Phản ứng Heck dẫn xuất aryl halide styrene Hình 1.2 Phản ứng Suzuki dẫn xuất aryl halide phenylboronic acid Hình 1.3 Phản ứng Sonogashira dẫn xuất aryl halide phenylacetylene Hình 1.4 Sơ đồ tổng hợp phức Palladium(II) chất mang polysiloxane [37] Hình 1.5 Sơ đồ tổng hợp xúc tác phức palladium chất mang ghép poly(Nvinylpyrrolidone) – silica [39] Hình 1.6 Sơ đồ tổng hợp xúc tác Pd – PHEMA/CMK-1[41] Hình 1.7 Sơ đồ tổng hợp xúc tác Hydrogel – Pd(II) [42] Hình 1.8 Xúc tác palladium chất mang Click ionic copolymer [46] 10 Hình 1.9 Cấu trúc polyamic acid [50] 11 Hình 1.10 Cơ chế phản ứng Sonogashira sử dụng xúc tác [CuIPdIIPA][BF4]3 [50] 12 Hình 1.11 Sơ đồ tổng hợp xúc tác phức Pd(II)–PPh2–PMO(Et) [52] 12 Hình 1.12 Sơ đồ tổng hợp phức Pd–NHC mang Silica [53] 13 Hình 1.13 Sơ đồ tổng hợp phức Pd-NHC ghép hợp chất silica hữu [54] 14 Hình 1.14 Sơ đồ tổng hợp phức palladium-phosphine cố định chất mang silica [55] 15 Hình 1.15 Sơ đồ tổng hợp xúc tác phức palladium chất mang 3-mercaptopropyl ghép silica gel [56] 15 Hình 1.16 Xúc tác phức palladium chất mang silica gel [57] 15 Hình 1.17 Sơ đồ tổng hợp xúc tác nano Pd(0)/SDPP [58] 16 Hình 1.18 Quy trình điều chế xúc tác palladium chất mang silica [59] 16 Hình 1.19 Sơ đồ tổng hợp xúc tác phức Pd(II)-MCM-41 [60] 17 Hình 1.20 Cấu trúc xúc tác MCM-41-Pd [61] 17 Hình 1.21 Sơ đồ tổng hợp xúc tác MCM-41-2N-Pd(II) [62] 18 Hình 1.22 Sơ đồ tổng hợp xúc tác phức SBA-15@DABCO-Pd [64] 18 Hình 1.23 Sơ đồ tổng hợp xúc tác phức [Ph-SBA-15-PPh3-Pd] cố định chất mang SBA-15 [65] 19 Hình 1.24 Hình minh họa domain vật liệu từ ferromagnetic ferrimagnetic [87] 23 Hình 1.25 Mơ tả trạng thái domain vật liệu từ ferromagnetic ferrimagnetic áp đặt từ trường [88] 24 viii tăng làm cho trạng thái Pd(0) bền, mạch amine dài giảm hiệu ứng không gian nên khả tác chất công vào tâm kim loại palladium dễ dàng Bên cạnh hiệu xúc tác, chất tác động lên phản ứng xúc tác chất mang nano từ tính chứng minh dị thể tất dạng ghép đôi carboncarbon khảo sát hoạt tính xúc tác khơng giảm đáng kể sau lần thu hồi, tái sử dụng Điều cho thấy liên kết tâm xúc tác palladium với chất mang hạt nano từ tính CoFe2O4 thơng qua ligand base Schiff bền q trình thực phản ứng ghép đơi Sonogashira, Suzuki, Heck Như vậy, thấy ngồi dễ dàng trình thu hồi sau phản ứng hiệu cao tái sử dụng nhiều lần mà hoạt tính khơng giảm đáng kể, xúc tác chất mang nano từ tính cịn thể độ bền vượt trội cấu trúc lõi hạt nano từ tính sau nhiều tác động mơi trường Điều làm tảng cho nghiên cứu mở rộng ứng dụng hạt nano từ tính làm chất mang xúc tác khác dạng phản ứng khác II Kiến nghị Cần nghiên cứu thêm ảnh hưởng môi trường chiếu xạ vi sóng lên tính chất từ hạt nano từ tính, độ bền liên kết cấu trúc hữu với hạt nano từ tính, khả đứt liên kết tâm palladium với ligand base Schiff Phổ biến quy trình tổng hợp xúc tác palladium chất mang nano từ tính sử dụng xúc tác nghiên cứu tổng hợp vật liệu kỹ thuật cao, loại dược phẩm có giá trị dựa phản ứng ghép đôi Suzuki, Sonogashira, Heck… 137 CÁC TÀI LIỆU CÔNG BỐ CỦA TÁC GIẢ Phan Thanh Son Nam, Bui Tan Nghia, Dinh Tuan Hoang, Le Vu Ha, “Microwaveassisted Sonogashira reaction using a palladium catalyst immobilized on superparamagnetic nanoparticles,” Tạp chí Khoa học Cơng nghệ, tập 50 – số 3B, trang 275-284, 2012 Phan Thanh Son Nam, Le Khac Anh Ky, 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