Các phương pháp chế tạo vật liệu nano từ tính MnFe2O4 và CoFe2O4 đã được trình bày. Tính chất đặc trưng về từ tính và các ứng dụng tiên tiến nhất của hai vật liệu cũng được tổng hợp và trình bày chi tiết.
FACULTY OF MATERIALS SCIENCE AND ENGINEERING TOPIC: FERRIMAGNETIC NANOMATERIALS MnFe2O4 & CoFe2O4: FABRICATION, PROPERTY and APPLICATION Lecturers: Prof Anh-Tuan Le Master student: Mai Quan Doan – 21800028 CONTENT 01 INTRODUCTION • Magnetic domain • Ferrimagnetic nanomaterial • Ferrimagnetic MnFe2O4 & CoFe2O4: Properties and Applications 02 FABRICATONS and PROPERTIES of MnFe2O4 & CoFe2O4 nanomaterials 03 ANALYSIS of reported MnFe2O4 & CoFe2O4 and specific APPLICATIONS 04 CONCLUSION 01 INTRODUCTION What is Ferrimagnetic nanomaterials? Magnetic Domain: a region within a magnetic material in which the magnetization is in a uniform direction Magnetic Domain Structure (the arrangement of magnectic domain) in materials determines the properties of magnetic materials Bellow T , spins are aligned Ferromagnetic Domain Ferromagnetic Antiferromag netic Types of magnetic materials Domain wall Paramagnetic Ferrimagnetic Antiferromagnetic C parallel in magnetic domains Bellow TN, spins are aligned antiparallel in magnetic domains Paramagentic Spins are randomly oriented (any of the others above TC or TN) Ferrimagnetic Bellow TC, spins are aligned antiparallel but not cancel 02 INTRODUCTION A ferrimagnetic material is a material that has populations of atoms with opposing magnetic moments, these moments are unequal in magnitude so a spontaneous magnetization remains Popular structure of Ferrimagnetic materials: Spinel structure - AB2O4 (AOB2O3) (normal, inverse, mixed spinel structure) A is a divalent metal, B is a trivalent metal (Cations) Example: • • • • MnFe2O4 (MnOFe2O3) FeFe2O4 (FeOFe2O3 – Fe3O4) CoFe2O4 (CoOFe2O3) NiFe2O4 (NiOFe2O3) Cubic close-packed (fcc) structure of Ferrite Issa, Bashar, et al "Magnetic nanoparticles: surface effects and properties related to biomedicine applications." International journal of molecular sciences 14.11 (2013): 21266-21305 03 INTRODUCTION Crystal structure of Spinel Ferrite: MnFe2O4 and CoFe2O4 Ferrimagnetic Materials Crystal structure of spinel MnFe2O4 Crystal structure of spinel CoFe2O4 Islam, Riyajul, Junaid Jami, and J P Borah "Strain-Induced Electronic Structure and Magnetocrystalline Anisotropy Energy in MnFe2O4 From First-Principles Calculations." IEEE Transactions on Magnetics 57.3 (2021): 1-5 04 INTRODUCTION Characteristic Properties of Spinel Ferrite: MnFe2O4 and CoFe2O4 Ferrimagnetic Property • Spontaneous magnetization • Superparamagnetic material (nano metter) - Size - Shape - Temperature - Component - Structure - Interaction Easy to change the magnetic behavior • Through controlling the content of Cations in the Spinel structure • Distribution of Cations in the Spinel structure • Other contributions: Size, shape, temperature, component, structure, interaction Hysteresis loops measured at K, 100 K, 120 K, 180 K and 360 K of CoFe2O4 Zeng, Xue, et al "Direct observation of cation distributions of ideal inverse spinel CoFe2O4 nanofibres and correlated magnetic properties." Nanoscale 9.22 (2017): 7493-7500 05 INTRODUCTION Applications of Ferrite nanoparticles (MnFe2O4 and CoFe2O4) Properties: Biomedical: +) Superparamagnetic in the state at room temperature +) Biocompatibility +) None-cytotoxicity Catalyst, Wastewater treatment: excellent chemical reactivity, high adsorption capacity and reasonable MS value for easy of removal by external magnetic field Widely applied in many fields Technologies for synthesis Kefeni, Kebede K., Titus AM Msagati, and Bhekie B Mamba "Ferrite nanoparticles: synthesis, characterisation and applications in electronic device." Materials Science and Engineering: B 215 (2017): 37-55 06 FABRICATONS and PROPERTIES of MnFe2O4 & CoFe2O4 nanomaterials Synthesis Methods of Ferrite nanomaterials Co-precipitation Sol-gel Hydrothermal Microwave assisted Thermal decomposition Solvothermal Sonochemical Microemulsion Polyol 10.Electrochemical 11.Mechanical 12.Laser ablation Synthesis Process Key Parameters Characteristic Produces Mechanism Advantages and Disadvantages 07 FABRICATONS and PROPERTIES of MnFe2O4 & CoFe2O4 nanomaterials Co-precipitation Synthesis MnCl2.4H2O, Mn(NO3)2.4H2O) CoCl2.6H2O, Co(NO3)2.6H2O) FeCl3.6H2O Fe(NO₃)₃ NaOH NH4OH precipatate pH Distilled water Powder Stir and heat Stir Crystalline MnFe2O4 CoFe2O4 High-tem Heat annealing Low-tem Drying in vacuum 08 FABRICATONS and PROPERTIES of MnFe2O4 & CoFe2O4 nanomaterials Sol-gel method MnCl2.4H2O, Mn(NO3)2.4H2O) CoCl2.6H2O, Co(NO3)2.6H2O) FeCl3.6H2O Fe(NO₃)₃ NaOH NH4OH pH Distilled water Gelation Powder Stir and heat Stir Crystalline MnFe2O4 CoFe2O4 High-tem Heat annealing Low-tem Drying in vacuum 09 FABRICATONS and PROPERTIES of MnFe2O4 & CoFe2O4 nanomaterials Characteristic Produces Methods Co-precipitation Sol-gel Hydrothermal Microwave assisted Properties Structure • Spinel • Mn2+ (Co2+) : Fe3+ • Doping (A2+) • Spinel • Mn2+ (Co2+) : Fe3+ • Doping (A2+) • Spinel • Mn2+ (Co2+) : Fe3+ • Doping (A2+) • Spinel • Mn2+ (Co2+) : Fe3+ • Doping (A2+) Compostion • Mn2+ (Co2+) : Fe3+ • Doping (A2+) • Mn2+ (Co2+) : Fe3+ • Doping (A2+) • Mn2+ (Co2+) : Fe3+ • Doping (A2+) • Mn2+ (Co2+) : Fe3+ • Doping (A2+) Size, shape • Reaction time • Annealing temp • Surfactant • Reaction time • Annealing temp • Surfactant • Reaction time • Reaction temp • Surfactant • Reaction time • Reaction temp • Surfactant Functional Surface • Surfactant • Surfactant • Surfactant • Surfactant Interaction (composite, hybrid) • Core-shell • Composites • Core-shell • Composites • Core-shell • Composites • Core-shell • Composites Superparamgnetic property Electrcal Property (Eg) Compatibility Adsorption property 18 ANALYSIS of reported MnFe2O4 & CoFe2O4 and specific APPLICATIONS Specific Applications of MnFe2O4 & CoFe2O4 Biomedical Cancer treatment Drug delivery MnFe2O4 CoFe2O4 Biosensors Chemical Physical Wastewater treatment Sensors Biocompatibility Easily functionalized Recovery (superparamagnetic) Biocompatibility Easily functionalized Low cytotoxicity Superparamagnetic Easily functionalized High adsorption capacity Recovery Low-cost UV-Visible light irradiation Easily functionalized High adsorption capacity Electrical property 19 Metal organic frameworks combining CoFe2O4 magnetic nanoparticles as highly efficient SERS sensing platform for ultrasensitive detection of N-terminal pro-brain natriuretic peptide Ethylene Glycol solution Co(NO3)2.6H2O solution NaOH FeCl3 solution Magnetic stirring Teflon Heated at 180 0C for 10 h HAuCl4 CoFe2O4 NaBH4 CoFe2O4@Au SEM and TEM images of CoFe2O4 (A and B), XRD of CoFe2O4 (C) and UV-visible spectra of CoFe2O4 (red) and CoFe2O4@AuNPs (black) (D) CoFe2O4: Size: 80 nm Ms = 17 emu/g He, Yi, et al "Metal organic frameworks combining CoFe2O4 magnetic nanoparticles as highly efficient SERS sensing platform for ultrasensitive detection of N-terminal pro-brain natriuretic peptide." ACS applied materials & interfaces 8.12 (2016): 7683-7690 20 Metal organic frameworks combining CoFe2O4 magnetic nanoparticles as highly efficient SERS sensing platform for ultrasensitive detection of N-terminal pro-brain natriuretic peptide (a) CoFe2O4@Au/ NT-proBNP, (b) Au/ NT-proBNP CoFe2O4@Au/ NT-proBNP: • LOD = 0.37 pg/ml Superparamagnetic Property Recovery (enrich samples) Schematic diagram of the SERS-based immunosensor for the detection of NT-proBNP He, Yi, et al "Metal organic frameworks combining CoFe2O4 magnetic nanoparticles as highly efficient SERS sensing platform for ultrasensitive detection of N-terminal pro-brain natriuretic peptide." ACS applied materials & interfaces 8.12 (2016): 7683-7690 21 Tumor microenvironment-responsive multifunctional nanoplatform based on MnFe2O4-PEG for enhanced magnetic resonance imaging-guided hypoxic cancer radiotherapy Target: Enhanced hypoxic cancer radiotherapy performance Enhanced magnetic resonance imaging Cytotoxicity experiment Oxygen concentration In vivo MRI Schematic illustration of the MnFe2O4-PEG nanoparticles for reducing tumor hypoxia He, Zhenhu, et al "Tumor microenvironment-responsive multifunctional nanoplatform based on MnFe2O 4-PEG for enhanced magnetic resonance imaging-guided hypoxic cancer radiotherapy." Journal of Materials Chemistry B 9.6 (2021): 1625-1637 22 Tumor microenvironment-responsive multifunctional nanoplatform based on MnFe2O4-PEG for enhanced magnetic resonance imaging-guided hypoxic cancer radiotherapy (a) Transmission electron microscopy (TEM) image of MnFe2O4 (b) TEM elemental mapping images of Mn, Fe, and O (c) FTIR spectra of the MnFe2O4 and MnFe2O4-PEG (d) Detection of the Mn ions released in the PBS with different pH values Cytotoxicity experiment and In vitro enhanced radiotherapy of the MnFe2O4-PEG Low cytotoxicity Release large amounts of Mn ions 23 Tumor microenvironment-responsive multifunctional nanoplatform based on MnFe2O4-PEG for enhanced magnetic resonance imaging-guided hypoxic cancer radiotherapy MnO + 2H+ = Mn2+ + H2O Mn2+ + H2O2 = O2 + H+ Increases oxygen levels in cancer cells Enhanced hypoxic cancer radiotherapy performance PA tomography of the mice tumors with intravenous MnFe2O4-PEG and PEG Release of Mn2+ ions Enhanced magnetic resonance imaging T2-weighted coronal scan MRI of the tumor before and after intravenous MnFe2O4-PEG administration 24 Induction Heating Analysis of Surface-Functionalized Nanoscale CoFe2O4 for Magnetic Fluid Hyperthermia toward Noninvasive Cancer Treatment Fe(NO₃)₃ Co(NO3)2.6H2O Magnetic stirring Co-precipitation Heated CoFe2O4 Oleic acid (OA) CoFe2O4-OA Ethylene + H2O Experimental hyperthermia design Kharat, Prashant B., et al "Induction heating analysis of surface-functionalized nanoscale CoFe2O4 for magnetic fluid hyperthermia toward noninvasive cancer treatment." ACS omega 5.36 (2020): 23378-23384 25 Induction Heating Analysis of Surface-Functionalized Nanoscale CoFe2O4 for Magnetic Fluid Hyperthermia toward Noninvasive Cancer Treatment Hyperthermia curves for CoFe2O4-OA nanoparticles TGA plot, Fourier transform infrared (FT-IR) spectra, M−H plot of CoFe2O4-OA Ms = 74.76 emu/gam Thyperthermia (200 s) = 70 0C Kharat, Prashant B., et al "Induction heating analysis of surface-functionalized nanoscale CoFe2O4 for magnetic fluid hyperthermia toward noninvasive cancer treatment." ACS omega 5.36 (2020): 23378-23384 26 ANALYSIS of reported MnFe2O4 & CoFe2O4 and specific APPLICATIONS Specific Applications – Photocatalysis (wastewater treatment) Mn(NO3)2.4H2O ZnNO3 NH4OH La(NO3)3·6H2O Fe(NO₃)₃ Magnetic stirring Sol-gel Heated at 100 0C Mn1-xZnxLayFe2-yO4 Annealing 1000 0C Mn1-xZnxLayFe2-yO4 M-H loops of Mn1-xZnxLayFe2-yO4 nanoferrites (x = 0.0, 0.01, 0.03; y = 0.0, 0.02,0.04) Tauc plots for calculation energy band-gap Ms increasing from 0.53 to 9.27 emu/g Eg decreasing from 2.45 to 2.04 eV Kour, Satvinder, et al "Improving photocatalytic efficiency of MnFe2O4 ferrites via doping with Zn 2+/La 3+ ions: photocatalytic dye degradation for water remediation." Environmental Science and Pollution Research (2021): 1-16 27 ANALYSIS of reported MnFe2O4 & CoFe2O4 and specific APPLICATIONS Specific Applications – Photocatalysis (wastewater treatment) Potential mechanism of Photocatalysis Mn0.97Z n0.03La0.04Fe1.96O4 > Mn0.99Z n0.01La0.02Fe1.98O4 > MnFe2O4 with 96.1, 92.4, and 88.3% (a) Photodegradation curves under solar irradiation (b) Rate constants for different catalysts (c) Reusability of the prepared catalysts Kour, Satvinder, et al "Improving photocatalytic efficiency of MnFe2O4 ferrites via doping with Zn 2+/La 3+ ions: photocatalytic dye degradation for water remediation." Environmental Science and Pollution Research (2021): 1-16 28 ANALYSIS of reported MnFe2O4 & CoFe2O4 and specific APPLICATIONS Main Applications of MnFe2O4 & CoFe2O4 Biosensor Biosensor Magnetic resonance imaging Water treatment MnFe2O4 Drug delivery Cancer treatment Water treatment CoFe2O4 Cancer treatment Drug delivery 29 Potential commercial products Magnetic liquid for Magnetic resonance imaging (MRI) Water Treatment Food Quality monitoring and Disease Detection 30 CONCLUSION Spinel Ferrite NPs Fabrication Coprecipita tion Hydroth ermal Sol-gel Microwa ve assisted Fabrication Microem ulsion Thermal decompo sition Solvothe rmal Sonoche mical Property Application Superparamagnetic High Biocompatibility Low-cytotoxicty Easy functionalization High adsorption capacity Electrical property Photo-electrical property Composition Shape, size Temperature Interaction Structrure Biomedical Cancer treatment Sensor Applications Electronic devices Catalyst 31 REFERENCES [1] Issa, Bashar, et al "Magnetic nanoparticles: surface effects and properties related to biomedicine applications." International journal of molecular sciences 14.11 (2013): 21266-21305 [2] Islam, Riyajul, Junaid Jami, and J P Borah "Strain-Induced Electronic Structure and Magnetocrystalline Anisotropy Energy in MnFe2O4 From First-Principles Calculations." IEEE Transactions on Magnetics 57.3 (2021): 1-5 [3] Zeng, Xue, et al "Direct observation of cation distributions of ideal inverse spinel CoFe2O4 nanofibres and correlated magnetic properties." Nanoscale 9.22 (2017): 7493-7500 [4] Kefeni, Kebede K., Titus AM Msagati, and Bhekie B Mamba "Ferrite nanoparticles: synthesis, characterisation and applications in electronic device." Materials Science and Engineering: B 215 (2017): 37-55 [5] He, Yi, et al "Metal organic frameworks combining CoFe2O4 magnetic nanoparticles as highly efficient SERS sensing platform for ultrasensitive detection of N-terminal pro-brain natriuretic peptide." ACS applied materials & interfaces 8.12 (2016): 7683-7690 [6] He, Zhenhu, et al "Tumor microenvironment-responsive multifunctional nanoplatform based on MnFe2O 4-PEG for enhanced magnetic resonance imaging-guided hypoxic cancer radiotherapy." Journal of Materials Chemistry B 9.6 (2021): 1625-1637 [7] Kharat, Prashant B., et al "Induction heating analysis of surface-functionalized nanoscale CoFe2O4 for magnetic fluid hyperthermia toward noninvasive cancer treatment." ACS omega 5.36 (2020): 23378-23384 [8] Kour, Satvinder, et al "Improving photocatalytic efficiency of MnFe2O4 ferrites via doping with Zn 2+/La 3+ ions: photocatalytic dye degradation for water remediation." Environmental Science and Pollution Research (2021): 1-16 [9] Melo, R S., P Banerjee, and A Franco "Hydrothermal synthesis of nickel doped cobalt ferrite nanoparticles: optical and magnetic properties." Journal of Materials Science: Materials in Electronics 29.17 (2018): 14657-14667 [10] Sam, Susan, and A Samson Nesaraj "Preparation of MnFe2O4 nanoceramic particles by soft chemical routes." International Journal of Applied Science and Engineering 9.4 (2011): 223-239 32 ... Ferrimagnetic nanomaterial • Ferrimagnetic MnFe2O4 & CoFe2O4: Properties and Applications 02 FABRICATONS and PROPERTIES of MnFe2O4 & CoFe2O4 nanomaterials 03 ANALYSIS of reported MnFe2O4 & CoFe2O4. .. 0C for 10 h HAuCl4 CoFe2O4 NaBH4 CoFe2O4@ Au SEM and TEM images of CoFe2O4 (A and B), XRD of CoFe2O4 (C) and UV-visible spectra of CoFe2O4 (red) and CoFe2O4@ AuNPs (black) (D) CoFe2O4: Size: 80... FABRICATONS and PROPERTIES of MnFe2O4 & CoFe2O4 nanomaterials Co-precipitation & Sol-gel Methods Key parameters Materials MnFe2O4 CoFe2O4 Key parameters Prepared-nanomaterials Concentration ratio