Luận văn thạc sĩ nghiên cứu tổng hợp vật liệu composite nife2o4 graphen oxit biến tính ứng dụng làm chất xúc tác quang phân hủy chất hữu cơ ô nhiễm trong môi trường nước

i LỜI CAM ĐOAN Tơi xin cam đoan cơng trình kết nghiên cứu riêng tôi, thực hướng dẫn khoa học PGS TS Nguyễn Thị Vƣơng Hoàn TS Lê Thị Thanh Thúy Các số liệu, kết nêu luận văn trung thực chưa công bố cơng trình nghiên cứu Tơi xin chịu tránh nhiệm nghiên cứu Học Viên Nguyễn Thị Thúy e ii LỜI CẢM ƠN Tôi xin bày tỏ lòng biết ơn sâu sắc tới PGS TS Nguyễn Thị Vƣơng Hoàn TS Lê Thị Thanh Thúy – tận tình hướng dẫn, giúp đỡ, bảo động viên tơi hồn thành tốt luận văn Trong q trình thực luận văn tơi nhận nhiều quan tâm tạo điều kiện Thầy, Cô khoa Khoa học tự nhiên - Trường Đại học Quy Nhơn Tơi xin bày tỏ lịng cảm ơn chân thành tới quý Thầy, Cô Tôi xin chân thành cảm ơn gia đình, bạn bè tập thể lớp Cao học Hóa K21 ln động viên, khích lệ tinh thần suốt trình học tập nghiên cứu khoa học Mặc dù cố gắng thời gian thực luận văn cịn hạn chế kiến thức thời gian, kinh nghiệm nghiên cứu nên khơng tránh khỏi thiếu sót Rất mong nhận thông cảm ý kiến đóng góp q báu từ q Thầy, Cơ để luận văn hồn thiện Tơi xin chân thành cảm ơn! Bình Định, tháng năm 2020 Học Viên Nguyễn Thị Thúy e iii MỤC LỤC Trang Trang phụ bìa LỜI CAM ĐOAN……………………………………………………………i LỜI CẢM ƠN……………………………………………………………….ii MỤC LỤC………………………………………………………………… iii DANH MỤC CHỮ VIẾT TẮT, KÍ HIỆU……………………………… vi DANH MỤC CÁC BẢNG…………………………………………………vii DANH MỤC CÁC HÌNH VẼ, ĐỒ THỊ………………………………….viii MỞ ĐẦU Chƣơng 1: TỔNG QUAN 1.1 Tổng quan graphit 1.2 Tổng quan graphen oxit graphen oxit biến tính 1.2.1 Graphen oxit (GO) 1.2.2 Graphen oxit biến tính 12 1.3 Vật liệu ferrite spinel NiFe2O4 16 1.3.1 Cấu trúc vật liệu ferrite spinel 16 1.3.2 Tính chất từ vật liệu ferrite spinel 17 1.3.3 Các yếu tố ảnh hưởng đến tính chất từ hệ hạt nano ferrite spinel 18 1.3.4 Các phương pháp tổng hợp vật liệu ferrite spinel MFe2O4 25 1.3.5 Ứng dụng ferrite spinel MFe2O4 28 1.4 Vật liệu nanocomposite MFe2O4/GO GO biến tính 28 1.5 Giới thiệu xúc tác quang 30 1.5.1 Khái niệm xúc tác quang 30 1.5.2 Cơ chế phản ứng quang xúc tác 31 e iv 1.6 Giới thiệu thuốc nhuộm hoạt tính RhB MB 37 1.6.1 Thuốc nhuộm hoạt tính RhB 37 1.6.2 Xanh metylen (MB) 38 Chƣơng 2: PHƢƠNG PHÁP NGHIÊN CỨU VÀ THỰC NGHIỆM 40 2.1 Thực nghiệm 40 2.1.1 Thiết bị hóa chất 40 2.1.2 Tổng hợp vật liệu 41 2.2 Các phƣơng pháp nghiên cứu 43 2.2.1 Phương pháp nhiễu xạ tia X (XRD)… 43 2.2.2 Phương pháp quang phổ hồng ngoại (FT-IR) 45 2.2.3 Phương pháp quang phổ tia X phân tán lượng (EDX) 46 2.2.4 Ảnh hiển vi điện tử quét (SEM) 47 2.2.5 Phương pháp hiển vi điện tử truyền qua (TEM) 47 2.2.6 Phổ quang điện tử tia X (EDX) 48 2.2.7 Từ kế mẫu rung (VSM) 49 2.2.8 Phương pháp phân tích nhiệt 49 2.2.9 Phương pháp đẳng nhiệt hấp phụ - khử hấp phụ nitơ (BET) 50 2.2.10 Phương pháp phổ phản xạ khuếch tán tử ngoại – khả kiến (UVVis DRS) 50 2.3 Khảo sát hoạt tính quang xúc tác phản ứng phân hủy RhB 53 2.3.1 Xây dựng đường chuẩn 53 2.3.2.Khảo sát hoạt tính quang xúc tác vật liệu phản ứng phân hủy RhB 55 2.3.3 Nghiên cứu động học trình xúc tác 59 Chƣơng 3: KẾT QUẢ VÀ THẢO LUẬN 62 3.1 Đặc trƣng vật liệu 62 3.1.1 Vật liệu niken ferrite (NF) 62 e v 3.1.2 Vật liệu graphen oxit, graphen oxit biến tính 69 3.1.3 Vật liệu composite NF/ GO-N NF/ GO-N,S 77 3.2 hảo sát hoạt t nh úc tác quang vật liệu 91 3.2.1 hảo sát thời gian đạt cân b ng hấp phụ 91 3.2.2 Đánh giá hoạt tính xúc tác quang vật liệu phản ứng phân hủy RhB 92 3.2.3 hảo sát yếu tố ảnh hưởng đến hiệu suất xúc tác quang vật liệu 94 3.3 Nghiên cứu động học phản ứng quang úc tác vật liệu composite NF/GO-N,S 97 3.4 Nghiên cứu chế phản ứng 100 3.5 tái sử dụng vật liệu 103 ẾT LUẬN VÀ IẾN NGHỊ 105 I KẾT LUẬN 105 II KIẾN NGHỊ 107 DANH MỤC CƠNG TRÌNH KHOA HỌC ĐÃ CƠNG BỐ 108 TÀI LIỆU THAM KHẢO 109 QUYẾT ĐỊNH GIAO ĐỀ TÀI LUẬN VĂN THẠC SĨ( Bản sao) e vi DANH MỤC CÁC TỪ VIẾT TẮT, Í HIỆU AOPs Q trình oxi hóa nâng cao (Advance Oxidation Process) BET Phương pháp đẳng nhiệt hấp phụ - khử hấp phụ nitơ (BnenceuerEmmett- Teller) CB Vùng dẫn (Conduction Band) e CB- Electron quang sinh (Photoelectron electron) EDX Phương pháp phổ tán xạ lượng tia X (Energy Dispersive XRay Spectroscopy) Eg Năng lượng vùng cấm (Band gap energy) GO Graphen oxit (Graphene oxide) h+VB Lỗ trống quang sinh (Optical birth hole) HĐBM Hoạt động bề mặt (Surface active agent) IR Phương pháp phổ hồng ngoại (Infrared Spectroscopy) MB Xanh Methylen NF Niken ferrite (NiFe2O4) RhB Rhodamine B SEM Phương pháp hiển vi điện tử quét (Scanning Electron Microscopy) TEM UV-Vis Hiển vi điện tử truyền qua (Transmission Electron Microscopy) Phổ hấp thụ phân tử (Ultraviolet-visible) UV-Vis DRS Phương pháp phổ phản xạ khuếch tán tử ngoại-khả kiến (Ultraviolet-visible Diffuse Reflectance Spectra) VB Vùng hóa trị (Valence band) VSM Từ kế mẫu rung (Vibrating Sample Magnetmeter) XPS Phổ quang điện tử tia X( X-ray photoelectron spectroscopy-XPS) XRD Nhiễu xạ tia X( X-Ray Diffraction) e vii DANH MỤC CÁC BẢNG BIỂU Bảng 1 Thơng số bán kính số ion kim loại ·························· 16 Bảng Phân bố ion vị trí cấu trúc spine ······················ 17 Bảng Tính chất từ số hệ hạt nano có hình dạng khác nhau.····· 19 Bảng Ảnh hưởng thành phần đến tính chất từ ····················· 22 Bảng Thế oxi hóa chất oxy hóa điển hình ························· 33 Bảng Các loại hóa chất sử dụng đề tài ························ 40 Bảng 2 Các thí nghiệm chuẩn bị xây dựng đường chuẩn RhB·············· 53 Bảng Các thí nghiệm chuẩn bị xây dựng đường chuẩn MB ·············· 54 Bảng Thành phần nguyên tử nguyên tố có NF ·················· 67 Bảng Thành phần phần trăm nguyên tử nguyên tố graphit; GO GO-N, GO-N,S ······················································· 77 Bảng 3 Các thông số đặc trưng của NF/GO-N NF/GO-N,S ········ 82 Bảng Phần trăm nguyên tố mẫu NF; NF/GO; NF/GO-N; NF/GO-N,S ······························································ 83 Bảng Năng lượng vùng cấm vật liệu ······························· 93 Bảng Hằng số tốc độ k phản ứng theo mơ hình Langmuir – Hinshelwood ····························································· 98 Bảng Hằng số tốc độ phản ứng theo mơ hình Langmuir – Hinshelwood ··························································· 100 Bảng Hiệu suất xúc tác quang chất xúc tác NF/GO-N,S với chất dập tắt ··································································· 102 e viii DANH MỤC HÌNH VẼ, ĐỒ THỊ Hình 1.1 Cấu trúc tinh thể kim cương graphit (3D)······················ Hình Sơ đồ tạo Graphen oxit từ graphit ······································ Hình Cấu trúc GO theo Lerf – Klinowski ······························· Hình Liên kết hydro lớp graphit oxit ······························ 10 Hình Cấu tạo liên kết nguyên tử nitrogen N-graphene········· 13 Hình Cấu trúc hình thành vật liệu nanocomposite MnO2/N-GO····· 14 Hình Sơ đồ tổng hợp graphen dopping N,S ································· 15 Hình 8.Cấu trúc tinh thể củaferrite spinel ······································ 16 Hình Sự phụ thuộc Ms vào nồng độ pha tạp Zn2+ hệ nano ZnxM1-x Fe2O4 (M=Fe, Mn) ············································· 21 Hình 10 Sự phụ thuộc mômen từ vào từ trường H (a) H/T (b) nhiệt độ khác hạt nano Fe có kích thước D = 4,4 nm ···· 23 Hình 11 Lực kháng từ phụ thuộc vào kích thước hạt···················· 24 Hình 12 Đường M(H) với kích thước khác (a) phụ thuộc lực kháng từ vào kích thước hệ hạt nano Fe3O4 300 K (b) ···· 25 Hình 13 Đường M(H) với kích thước khác (a) phụ thuộc lực kháng từ vào kích thước mẫu Co0,4Fe2,6O4(b) ··············· 25 Hình 14 Cơ chế phản ứng xúc tác quang hóa dị thể ························· 32 Hình 15 Sơ đồ biểu diễn chế oxi hóa ······································ 34 Hình 16 Sơ đồ biểu diễn chế khử ··········································· 35 Hình 17 Cơ chế xúc tác quang vật liệu biến tính A B chất bán dẫn ····················································································· 36 Hình 18 Cơng thức hóa học RhB ·········································· 38 Hình 1.19 Cơng thức 3,7-bis(Dimethylamino)-phenothiazin-5-ium chloride (hay xanh metylen) ··········································· 38 e ix Hình Sơ đồ nhiễu xạ Rơnghen ··············································· 44 Hình 2 Sơ đồ tia tới tia························································ 44 Hình Độ tù peak phản xạ gây kích thước hạt ···················· 44 Hình Phổ UV- Vis RhB ··················································· 53 Hình Đường chuẩn Rhodamine B (RhB) ······························· 54 Hình Phổ UV- Vis MB ···················································· 55 Hình Đường chuẩn xanh metylen (MB) ································ 55 Hình Giản đồ XRD NF nung nhiệt độ 3500C (a), 4000C (b), 4500C (c), 5000C (d) 7000C (e) ······································ 62 Hình 3.2 Giản đồ phân tích nhiệt NF ········································· 63 Hình 3 Ảnh TEM mẫu NF-4500C (a), NF-5000C (b) NF-7000C (c) ·········································································· 64 Hình Giản đồ XRD NF tỉ lệ mol Fe3+ Ni2+ khác nhau······ 65 Hình Phổ EDX vật liệu NF tỉ lệ khác nhau······················ 66 Hình Đường cong từ trễ mẫu NF tổng hợp tỉ lệ mol Fe3+ Ni2+ khác nhau···························································· 67 Hình Đồ thị biểu diễn phụ thuộc C/Co theo thời gian vật liệu NF tỉ lệ ································································· 68 Hình Phổ XPS tồn phần (a), Ni2p (b), Fe2p (c) O1s (d) vật liệu NF 2,0:1,0 ································································· 70 Hình Giản đồ nhiễu xạ tia X GO; GO-N1,0 ; GO-N1,5 GO-N2,0 ·································································· 71 Hình 10 Giản đồ nhiễu xạ tia X GO; GO-N,S1,0 ; GO-N,S1,5 GO-N,S2,0 ···························································· 72 Hình 11 Phổ FT-IR mẫu GO mẫu GO-N-1; GO-N-1,5 ; GO-N-2,0 ································································ 74 Hình 12 Phổ FT-IR mẫu GO mẫu GO-N,S1,0 ; GO-N,S1,5; e x GO-N,S2,0 ······························································ 74 Hình 3.13 Đồ thị biểu diễn phụ thuộc C/Co theo thời gian mẫu vật liệu GO-N tỉ lệ khác ············································ 75 Hình 14 Đồ thị biểu diễn phụ thuộc C/Co theo thời gian mẫu vật liệu GO-N,S tỉ lệ khác ···································· 76 Hình 15 Giản đồ nhiễu xạ tia X GO, NF, NF/GO-N NF/ GO-N,S ····························································· 78 Hình 16 Phổ IR GO; GO-N; GO-N,S; NF; NF– GO-N NF– GO-N,S ··························································· 78 Hình 17 Ảnh SEM composite NF/GO-N, NF/GO-N,S ············ 79 Hình 18 Ảnh TEM composite NF/GO-N NF/GO-N,S ········· 80 Hình 19 Đường đẳng nhiệt hấp phụ- khử hấp phụ N2 77 K NF/GO-N NF/GO-N,S ·························································· 80 Hình 20 Đường cong từ trễ NF, NF/GO-N NF/GO-N,S ············ 81 Hình 21 Phổ XPS tồn phần NF, NF/GO NF/GO-N; NF/GO-N,S ··· ·························································································· 82 Hình 22 Phổ XPS phân giải cao C1s NF/GO-N,S ················ 84 Hình 23 Phổ XPS phân giải cao O1s NF/GO-N,S ················ 84 Hình 24 Phổ XPS Fe2p NF, NF/GO-N, NF/GO-N,S ············ 85 Hình 25 Phổ XPS Ni2p NF/GO-N,S ······························· 86 Hình 26 Phổ XPS N1s, S2p NF/GO-N,S ························· 87 Hình 27 Phổ XPS phân giải cao O1s NF, NF/GO-N, NF/GO-N,S······························································ 88 Hình 28 Phổ UV-Vis trạng thái rắn NF, NF/GO-N NF/GO-N,S··· 89 Hình 29 Đồ thị phụ thuộc (F(R)hϑ)2 theo lượng ánh sáng bị hấp thụ NF, NF/GO-N NF/GO-N,S ························· 90 Hình 30 Dung lượng hấp phụ RhB theo thời gian mẫu NF, GO-N, e 109 TÀI LIỆU THAM HẢO TÀI LIỆU TIẾNG VIỆT [1] Lê Thị Mai Hoa, Hà Quang Ánh, Lê Hà Giang, Nguyễn Kế Quang, Ngô Tiến Quyết, Quản Thị Thu Trang Vũ Anh Tuấn, Study on dye reactive RR 195 photodegradation ability from aqueous solution by CoFe2O4/ GO composite, Tạp chí Xúc tác hấp phụ, ISSN 0866-7411, T4, N0 2, 39-44 (2015) [2] Lê Thị Mai Hoa, Hà Quang Ánh, Lê Hà Giang, Nguyễn Kế Quang, Đào Đức Cảnh, Nguyễn Thị Phương, Trần Thị Kim Hoa, Đặng Tuyết Phương Vũ Anh Tuấn, Synthesis, characterization and application of novel MnFe2O4- rGO composite in photocatalytic degradation of reactive dye, Proceedings of IWNA 2015,11-14 November 2015, Vung Tau, Viet Nam pp 513-516 [3] Nguyễn Hữu Đức (2008), Vật liệu từ cấu trúc nano điện t spin, Nhà xuất đại học Quốc gia Hà Nội: pp 49-53 [4] Nguyễn Hữu Hiếu, Đặng Thị Minh Kiều, Phan Thị Hoài Diễm, Tổng hợp Fe3O4/ graphen oxit nanocomposit để x lý nước thải, Tạp chí phát triển KH&CN, tập 18, số T6, 212-220 (2015) [5] Nguyen Thi Vuong Hoan , Nguyen Ngoc Minh, Thoi Thi Kim Nhi, Nguyen Van Thang, Vu Anh Tuan , Vo Thang Nguyen, Nguyen Mau Thanh, Nguyen Van Hung and Dinh Quang Khieu, TiO2/Diazonium/Graphene Oxide Composites: Synthesis and Visible-Light-Driven Photocatalytic Degradation of Methylene Blue, Journal of Nanomaterials Volume 2020, Article ID 4350125, 15 pages [6] Nguyen Thi Vuong Hoan, Nguyen Thi Anh Thu, Hoang Van Duc, Nguyen Duc Cuong, Dinh Quang Khieu, and Vien 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oxit