Nghiên cứu tổng hợp và đặc trưng vật liệu mới, cấu trúc nano ứng dụng trong quang hóa xúc tác phân hủy thuốc nhuộm

VIN HN LM KHOA HC V CễNG NGH VIT NAM HC VIN KHOA HC V CễNG NGH Lấ TH MAI HOA NGHIấN CU TNG HP V C TRNG VT LIU MI, CU TRC NANO NG DNG TRONG QUANG HểA XC TC PHN HY THUC NHUM LUN N TIN S HểA HC Chuyờn ngnh: Húa lý thuyt v Húa lý Mó s: 62.44.01.19 Ngi hng dn khoa hc: PGS.TS V Anh Tun H ni, nm 2016 LI CM N Trc ht, em xin trõn trng cm n n PGS.TS V Anh Tun v cỏc thy, cụ giỏo ó tn tỡnh hng dn v truyn t kin thc, kinh nghim, h tr v giỳp em sut quỏ trỡnh em thc hin lun ỏn Tụi xin chõn thnh cm n th cỏn b phũng Húa lý B mtVin Húa hc- Vin Hn lõm Khoa hc v Cụng ngh Vit Nam ó nhit tỡnh giỳp tụi thi gian thc hin cỏc ni dung ca lun ỏn Tụi xin chõn thnh cm n sõu sc ti gia ỡnh, bn bố, ng nghip ti V Giỏo dc v o to, Dy ngh, Ban Tuyờn giỏo Trung ng ó quan tõm, ng viờn v to iu kin thun li giỳp tụi sut thi hc v nghiờn cu Tỏc gi lun ỏn Lờ Th Mai Hoa i LI CAM OAN Tụi xin cam oan, õy l cụng trỡnh nghiờn cu tụi thc hin di s hng dn ca ngi hng dn khoa hc Mt s nhim v nghiờn cu l thnh qu th ó c cỏc ng s cho phộp s dng Cỏc s liu v kt qu trỡnh by lun ỏn l trung thc v cha tng cụng b bt k cụng trỡnh lun ỏn no khỏc Tỏc gi lun ỏn Lờ Th Mai Hoa ii DANH MC CC T VIT TT GO Graphen oxit GOVS Graphen oxit búc lp bng vi súng GOSA Graphen oxit búc lp bng siờu õm rGO Graphen oxit kh v graphen AOPs H2O2 Phng phỏp oxy húa nõng cao (Advanced Oxidation Processes) Hydrogen peroxide *OH Hydroxyl TS Tng lng cht rn (Total Solids) SS Cht rn huyn phự (Suspended Solid) DO Hm lng oxy hũa tan (Disolved oxigen) BOD Nhu cu oxi húa sinh hc (Biochemical oxigen Demand) COD Nhu cu oxi húa hc (Chemical oxigen Demand) TOC Tng cacbon hu c (Total Organic Carbon) TOD Nhu cu oxy tng cng (Total Oxygen Demand) Fe3O4-GO Fe3O4 bc Graphen oxit (GO) CoFe2O4-GO Coban (Co), Fe2O4 bc Graphen oxit (GO) ZnFe2O4-GO Km (Zn), Fe2O4 bc Graphen oxit (GO) Fe0-Fe3O4-GO Fe, Fe3O4 bc Graphen oxit (GO) Fe(III)-GO Fe(III) oxo cluster Graphen oxit (GO) CVD Phng phỏp lng ng pha hi húa hc CNTs ng nano cacbon XRD Ph nhiu x Rnghen (X-ray Diffraction) FTIR BT Quang ph hng ngoi (Fourier Transform Infrared Spectroscopy) Ph in t quang tia X (X-ray Photoelectron Spectroscopy) Kớnh hin vi in t truyn qua (Transmission electron microscopy) Kớnh hin vi in t truyn qua phõn gii cao (High resolution Transmission electron microscopy) ng nhit hp ph kh nitrogen (Braunauer Emmett Teller) UV-Vis Ph hp th t ngoi kh kin VMS Phng phỏp xỏc nh t tớnh ca vt liu bng t k mu rung (Vibrating Sample Magnetometer) XPS TEM HR-TEM iii DANH MC CC HèNH V Hỡnh 1.1 Hỡnh 1.2 Hỡnh 1.3 Hỡnh 1.4 Hỡnh 1.5 Hỡnh 1.6 Hỡnh 1.7 Hỡnh 1.8 Hỡnh 1.9 Hỡnh 1.10 Hỡnh 1.11 Hỡnh 1.12 Hỡnh 1.13 Hỡnh 2.1 Hỡnh 2.2 Hỡnh 2.3 Hỡnh 2.4 Hỡnh 2.5 Hỡnh 2.6 Hỡnh 2.7 Hỡnh 2.8 Hỡnh 2.9 Hỡnh 2.10 Hỡnh 2.11 Hỡnh 2.12 Hỡnh 2.13 Hỡnh 2.14 Graphen - vt liu cú cu trỳc c bn (2D) cho cỏc vt liu cacbon khỏc (0D, 1D, v 3D) Cỏc liờn kt ca mi nguyờn t cacbon mng graphen Phng phỏp tỏch lp graphit bng bng dớnh C ch to mng graphen bng phng phỏp nung nhit SiC Quỏ trỡnh oxi húa t graphit thnh GO (a) v quỏ trỡnh kh GO bng hydrazine (b) c xut C ch ngh ca quỏ trỡnh tng hp GO v graphen Nc thi dt nhum Cụng thc cu to ca RR195 Cỏc phng phỏp loi b mu thuc nhum Phn ng Fenton ng th v Fenton d th C ch phn ng ca TiO2/graphen vi Methylene blue C ch phn ng ca ZnO vi cỏc cht hu c C ch phn ng ca Fe3O4/graphen vi cỏc cht hu c S tng hp graphen oxit vi súng (GOVS) v graphen oxit siờu õm (GOSA) t graphen oxit S tng hp Fe3O4-GO S tng hp CoFe2O4-GO S tng hp ZnFe2O4-GO S tng hp Fe0-Fe3O4-GO ng chun v ph UV-Vis ca thuc nhum RR195 th lgC theo t i vi phn ng bc S chựm tia ti v chựm tia nhiu x trờn tinh th tự ca pic phn x gõy kớch thc ht Quỏ trỡnh phỏt quang in t Nguyờn tc phỏt x tia X dựng ph S nguyờn lý s to nh phõn gii cao HRTEM Cỏc dng ng ng nhit hp ph-kh hp ph theo phõn loi IUPAC Bc chuyn ca cỏc electron phõn t iv 10 12 13 14 15 19 31 41 42 44 46 47 48 50 51 52 55 57 57 59 61 63 64 65 Hỡnh 3.1 Hỡnh 3.2 Hỡnh 3.3 Hỡnh 3.4a Hỡnh 3.4b Hỡnh 3.5 Hỡnh 3.6 Hỡnh 3.7 Hỡnh 3.8 Hỡnh 3.9 Hỡnh 3.10 Hỡnh 3.11 Hỡnh 3.12 Hỡnh 3.13 Hỡnh 3.14 Hỡnh 3.15 Hỡnh 3.16 Hỡnh 3.17 Hỡnh 3.18 Hỡnh 3.19 Hỡnh 3.20 Hỡnh 3.21 Hỡnh 3.22 Hỡnh 3.23 Hỡnh 3.24 Hỡnh 3.25 Gin XRD ca graphen oxit v graphen nh HR-TEM ca GOSA (graphen siờu õm) (a), GOVS (graphen vi súng) (b) v rGO (c) Ph FT-IR ca GOSA, GOVS v rGO sau tng hp Ph XPS ca GOSA (a,b), GOVS (c,d) v rGO (e,f) Ph XPS ca rGOSA kh nhit t GOSA Gin XRD ca graphen oxit (GO) Gin XRD ca Fe3O4-GO Gin XRD ca CoFe2O4-GO Gin XRD ca ZnFe2O4 GO Gin XRD ca Fe0-Fe3O4-GO Gin XRD ca GO v Fe(III)-GO nh HR- TEM ca Fe3O4-GO vi phúng i khỏc nh HR- TEM ca CoFe2O4-GO nh HR- TEM ca ZnFe2O4 -GO nh HR- TEM ca Fe0-Fe3O4-GO nh HR- TEM ca Fe(III)-GO vi cỏc phúng i khỏc Ph FTIR ca Fe3O4-GO Ph FTIR ca CoFe2O4-GO Ph FTIR ca ZnFe2O4-GO Ph FTIR ca Fe0-Fe3O4-GO Ph FTIR ca Fe(III)-GO v GO Ph XPS ca Fe3O4-GO: (a)- Ph XPS tng ca Fe3O4-GO; (b)- Ph XPS Fe2p tỏch ca Fe3O4-GO; (c)- Ph XPS O1s tỏch ca Fe3O4-GO; (d) Ph XPS C1s tỏch ca Fe3O4-GO Ph XPS ca Fe0-Fe3O4-GO: (a)- Ph XPS tng ca Fe0Fe3O4-GO; (b)- Ph XPS Fe2p tỏch ca Fe0- Fe3O4-GO; (c)Ph XPS O1s tỏch ca Fe0-Fe3O4-GO; (d) Ph XPS C1s tỏch ca Fe0-Fe3O4-GO Ph XPS ca vt liu Fe(III)- GO: (a)- Ph XPS tng ca Fe(III)-GO; (b)- Ph XPS O1s tỏch ca Fe(III)-GO; (c)- Ph XPS Fe2p tỏch ca Fe(III)-GO; (d) Ph XPS C1s tỏch ca Fe(III)-GO Phõn b mao qun ca Fe0-Fe3O4-GO v Fe3O4-GO ng ng nhit hp ph - kh hp ph N2 ca Fe0-Fe3O4- v 67 68 69 71 72 73 74 75 76 76 77 78 78 79 79 80 81 81 82 83 83 84 85 87 88 88 Hỡnh 3.26 Hỡnh 3.27 Hỡnh 3.28 Hỡnh 3.29 Hỡnh 3.30 Hỡnh 3.31 Hỡnh 3.32 Hỡnh 3.33 Hỡnh 3.34 Hỡnh 3.35 Hỡnh 3.36 Hỡnh 3.37 Hỡnh 3.38 Hỡnh 3.39 Hỡnh 3.40 Hỡnh 3.41 Hỡnh 3.42 Hỡnh 3.43 Hỡnh 3.44 Hỡnh 3.45 GO v Fe3O4-GO ng ng nhit hp ph - kh hp ph N2 ca ZnFe2O4-GO Phõn b mao qun ca ZnFe2O4-GO ng cong t tr ca Fe0-Fe3O4-GO v Fe3O4-GO ng cong t tr ca ZnFe3O4-GO Hot tớnh quang xỳc tỏc Fe3O4-GO S ph thuc chuyn húa theo thi gian phn ng cỏc iu kin khỏc ca CoFe2O4 GO bn xỳc tỏc qua cỏc ln chy phn ng quỏ trỡnh phõn hy RR195 trờn CoFe2O4-GO Ph UV_Vis quỏ trỡnh phõn hy RR195 di iu kin chiu x (A) v khụng chiu x (B) trờn CoFe2O4-GO S ph thuc chuyn húa theo thi gian phn ng cỏc iu kin khỏc ca ZnFe2O4-GO bn xỳc tỏc qua cỏc ln chy phn ng khỏc quỏ trỡnh phõn hy RR195 trờn ZnFe2O4-GO Ph UV_Vis quỏ trỡnh phõn hy RR195 di iu kin chiu x trờn ZnFe2O4-GO Ph UV_Vis quỏ trỡnh phõn hy RR195 di iu kin khụng chiu x trờn ZnFe2O4-GO S ph thuc chuyn húa theo thi gian phn ng cỏc iu kin khỏc trờn Fe0 -Fe3O4-GO Hot tớnh xỳc tỏc ca Fe0-Fe3O4-GO v Fe304-GO Ph UV_Vis quỏ trỡnh phõn hy RR195 di iu kin chiu x trờn Fe0-Fe3O4-GO Ph UV_Vis quỏ trỡnh phõn hy RR195 di iu kin khụng chiu x trờn Fe0-Fe3O4-GO bn xỳc tỏc qua cỏc ln chy phn ng quỏ trỡnh phõn hy RR195 trờn Fe0-Fe3O4-GO S ph thuc chuyn húa theo thi gian phn ng cỏc iu kin khỏc trờn Fe(III)-GO S ph thuc t l nng C/C0 ca thuc nhum hot tớnh RR195 theo thi gian phn ng cỏc iu kin khỏc trờn CoFe2O4-GO S ph thuc t l nng C/C0 ca thuc nhum hot tớnh vi 89 90 91 92 94 95 97 97 98 99 100 100 101 103 103 104 104 106 108 109 RR195 theo thi gian tip xỳc trờn CoFe2O4-GO ln v ln Hỡnh 3.46 Hỡnh 3.47 Hỡnh 3.48 Hỡnh 3.49 Hỡnh 3.50 Hỡnh 3.51 Hỡnh 3.52 Hỡnh 3.53 Hỡnh 3.54 Hỡnh 3.55 Hỡnh 3.56 Quỏ trỡnh phõn hy RR195 trờn cỏc loi xỳc tỏc khỏc Fe(III)-GO; Fe0-Fe3O4-GO; CoFe3O4-GO; ZnFe2O4-GO; Fe3O4-GO Kh nng t phõn hy ca RR195 mụi trng pH khỏc vi s cú mt H2O2 nh hng pH n kh nng phõn hy RR195 trờn Fe0-Fe3O4GO nh hng ca nng H2O2 n quỏ trỡnh phõn hy RR195 trờn Fe0-Fe3O4-GO nh hng ca nng RR195 ban u n quỏ trỡnh phõn hy RR195 trờn Fe0-Fe3O4-GO ng hc quỏ trỡnh xỳc tỏc quang húa phn ng phõn hy RR195 trờn Fe(III)-GO bc ng hc quỏ trỡnh xỳc tỏc quang húa phn ng phõn hy RR195 trờn Fe(III)-GO bc ng hc quỏ trỡnh xỳc tỏc quang húa phn ng phõn hy RR195 trờn Fe(III)-GO bc ng hc quỏ trỡnh xỳc tỏc quang húa phn ng phõn hy RR195 trờn Fe0-Fe3O4-GO bc ng hc quỏ trỡnh xỳc tỏc quang húa phn ng phõn hy RR195 trờn Fe0-Fe3O4-GO bc ng hc quỏ trỡnh xỳc tỏc quang húa phn ng phõn hy RR195 trờn Fe0-Fe3O4-GO bc vii 111 112 113 114 115 117 118 118 120 120 121 DANH MC CC BNG Bng 1.1 Bng 1.2 Bng 1.3 Bng 1.4 Bng 1.5 Bng 1.6 Bng 1.7 Bng Bng 3.1 Bng 3.2 Bng 3.3 Bng 3.4 Bng 3.5 Bng 3.6 Tớnh cht ca Graphen n lp u v nhc im ca mt s phng phỏp x lý cỏc hp cht hu c cú mu Th oxi hoỏ ca mt s tỏc nhõn oxi hoỏ thng gp Mt s phng phỏp AOPs ph bin hin ang s dng x lý nc thi Bng thng kờ mt vi nghiờn cu v TiO2/graphen Bng thng kờ mt vi nghiờn cu v oxit kim loi/graphen Bng thng kờ mt vi nghiờn cu v hn hp oxit/graphen Túm tt phn ng bc 0, 1, v n Thnh phn % cỏc nguyờn t ph XPS ca GO v rGO Cỏc thụng s c trng ca Fe3O4-GO Cỏc thụng s c trng ca Fe0-Fe3O4-GO Cỏc thụng s c trng ca ZnFe2O4-GO Nng RR195 trc v sau quỏ trỡnh quang phõn s dng xỳc tỏc Fe(III)-GO ti cỏc nng khỏc Nng RR195 trc v sau quỏ trỡnh quang phõn s dng xỳc tỏc Fe0-Fe3O4-GO ti cỏc nng khỏc viii 19 27 29 39 42 45 54 73 89 89 90 116-117 119 MC LC LI CM N i LI CAM OAN ii DANH MC CC T VIT TT iii DANH MC CC HèNH V iv DANH MC CC BNG viii T VN CHNG TNG QUAN TI LIU 1.1 Vt liu graphen v ng dng x lý cht mu 1.1.1 Vt liu trờn c s graphen 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chúng tôi lựa chọn đề tài luận án Nghiên cứu tổng hợp và đặc trưng vật liệu mới, cấu trúc nano ứng dụng trong quang hóa xúc tác phân hủy thuốc nhuộm” đã được thực hiện Mục tiêu nghiên cứu của luận án 2 Tổng... Tình hình nghiên cứu và áp dụng các quá trình oxi hóa nâng cao hiện nay ……………………………………………………………… 1.3.5 Các hệ xúc tác trong xử lý chất màu hữu cơ ………………… 36 36 38 1.3.5.1 Xúc tác quang hóa TiO2/ graphen …………………………… 38 1.3.5.2 Xúc tác quang hóa composite oxit kim loại/graphen ……… 40 1.3.5.3 Xúc tác quang hóa composit ion kim loại/graphen có từ tính 43 CHƯƠNG 2 THỰC NGHIỆM VÀ PHƯƠNG PHÁP NGHIÊN CỨU 45... nano composit trên cơ sở oxit kim loại có từ tính/graphen oxit; nghiên cứu đánh giá hoạt tính xúc tác của các hệ vật liệu tổng hợp được trên thuốc nhuộm hoạt tính và ứng dụng làm xúc tác quang hóa mới, hiệu quả cao, có khả năng thu hồi và tái sử dụng trong phản ứng phân hủy chất màu, thuốc nhuộm hoạt tính để xử lý nước thải dệt nhuộm Nội dung nghiên cứu của luận án - Tổng hợp được một số vật liệu nano. .. hưởng pH đến khả năng phân hủy thuốc nhuộm hoạt tính RR195 trên Fe0-Fe3O4-GO ………………………………………… 3.4.2 Ảnh hưởng của nồng độ H2O2 đến quá trình phân hủy thuốc nhuộm hoạt tính RR195 trên Fe0-Fe3O4-GO ……………………… 3.4.3 Ảnh hưởng của nồng độ thuốc nhuộm hoạt tính RR195 ban đầu đến quá trình phân hủy trên Fe0-Fe3O4-GO ………………………… 3.5 Động học của quá trình xúc tác quang hóa trong phản ứng phân hủy thuốc nhuộm... đổi ion - Đặc trưng các vật liệu tổng hợp được bằng các phương pháp hóa lý hiện đại như XRD, FTIR, TEM, XPS, BET, UV-Vis - Đánh giá hoạt tính đối với các hệ xúc tác tổng hợp được - Nghiên cứu các điều kiện ảnh hưởng như pH, nồng độ H2O2, nồng độ thuốc nhuộm hoạt tính RR195 ban đầu đến hoạt tính xúc tác của vật liệu tổng hợp - Nghiên cứu động học quá trình xúc tác quang hóa trong phản ứng phân hủy thuốc... GO là có độ âm điện lớn khi phân tán trong nước từ kết quả đo thế zeta Đó là do sự ion hóa của nhóm axit cacboxylic và phenolic hydroxyl Sự phân tán ổn định của GO trong nước không chỉ do tính ưa nước mà còn do lực đẩy tĩnh điện của nó Ngoài ra còn có thể tách lớp graphit oxit để tạo thành GO bằng phương pháp vi sóng, hỗn hợp được đặt trong lò vi sóng với công suất 700W trong 1 phút, nhiệt độ tăng... sinh học, mà chỉ xác định lượng oxy cần thiết trong 5 ngày đầu (BOD5) ở nhiệt độ 20oC trong bóng tối (để tránh hiện tượng quang hợp ở trong nước) 16 Nhu cầu oxy hóa học (COD- chemical oxigen Demand) COD được định nghĩa là lượng oxy cần thiết cho quá trình oxi hóa toàn bộ các chất hữu cơ có trong mẫu thành CO2 và H2O Chỉ số COD được dùng rộng rãi để đặc trưng cho hàm lượng chất hữu cơ của nước thải... nhuộm màu có cấu trúc polymer cao phân tử bền vững Hơn nữa, thành phần các chất màu trong nước thải thường gây độc cho quần xã hoặc quần thể vi sinh vật sử dụng trong bùn Các phương pháp loại bỏ màu thuốc nhuộm có thể được chia thành hai nhóm phân huỷ và không phân huỷ (Hình 1.9) Bảng 1.2 đã tổng kết các ưu điểm và nhược điểm của một số phương pháp hiện nay đang sử dụng trong công nghệ loại bỏ thuốc nhuộm... hai cơ chế được nghiên cứu: thứ nhất là cơ chế phân hủy nhiệt của một số cacbua kim loại, thứ hai là cơ chế tạo màng đơn tinh thể của graphen trên đế kim loại hoặc đế cacbua kim loại bởi sự lắng đọng hơi hóa học (Chemical Vapor Deposition) của các hydrocarbon Cơ chế phân hủy nhiệt: Thường được tiến hành với đế silic cacbua (SiC) ở 1300oC trong môi trường chân không cao hoặc ở 1650oC trong môi trường... nước và dễ dàng phân tán trong nước Graphit oxit được phân tán trong nước theo tỉ lệ 1mg/ml và sử dụng phương pháp siêu âm để tách lớp thành graphen oxit Các tấm graphit ban đầu có độ dày 0,34 nm, tấm GO được cho là dày hơn do sự dịch chuyển của nguyên tử cacbon sp3 lên trên hoặc dưới so với mặt phẳng graphen gốc và sự có mặt của các nguyên tử oxy liên kết hóa trị Kết quả tương tự khi pha phân tán là các