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Triiron tetraoxide is an inorganic substance with the chemical formula Fe3O4,CAS 1317-61-9. It is a black crystal with magnetism, so it is also called magnetic iron oxide. It cannot be regarded as "ferrous metaferrite" [Fe (FeO2)2], nor as a mixture of ferrous oxide (FeO) and ferric oxide (Fe2O3), but it can be approximately regarded as a compound of ferrous oxide and ferric oxide (FeO · Fe2O3). This substance is insoluble in water, alkali solution, ethanol, ether and other organic solvents. The natural ferric oxide is insoluble in acid solution, and it is easy to oxidize into ferric oxide (Fe2O3) in the air under humid conditions. It is usually used as pigment and polishing agent, and can also be used to make audio tapes and telecommunications equipment.
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Chemical Formula |
Fe3O42- |
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Exact Mass |
232 |
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Molecular Weight |
232 |
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m/z |
116 (100.0%), 115 (19.1%), 116 (6.9%), 114 (1.2%) |
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Elemental Analysis |
Fe, 72.36; O, 27.64 |
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Triiron tetraoxide (Fe ∝ O ₄), also known as magnetic iron oxide, is a black crystal with magnetic properties. It has stable chemical properties and unique physical characteristics, and is widely used in science, industry, and medicine.
1. Magnetic Materials and Data Storage
Iron tetroxide is the core material of magnetic recording media such as magnetic tapes, disks, and cores. Its magnetic properties make it a key material for data storage in electronic devices, such as the recording layer of old-fashioned magnetic tape recorders and video recorders made of iron oxide. In addition, iron oxide can also be used to manufacture magnetic sensors, hard magnetic materials, etc. It serves as a carrier for signal transmission in telecommunications equipment, supporting the development of communication technology.
2. Ironmaking and Metal Processing
Natural magnetite (containing Fe ∝ O ₄) is an important raw material for ironmaking, and iron can be extracted through reduction reactions. In metal surface treatment, iron oxide forms a dense oxide layer on the surface of steel through the "bluing" or "blackening" process, preventing rust and improving glossiness. This technology is widely used in fields such as automotive parts and tool manufacturing to extend the service life of products.
3. Pigments and Coatings
The deep black color of Fe3O4 makes it an ideal pigment for industries such as ceramics, plastics, and paints. It has excellent weather resistance and acid and alkali resistance, ensuring long-lasting and stable product color. For example, adding iron oxide to architectural coatings can provide decorative effects and enhance the coating's corrosion resistance.
4. Abrasives and polishing agents
Iron oxide has high hardness and can be used as an abrasive in fields such as metal processing and glass polishing. In the braking system of automobiles, iron oxide is used in the manufacturing of brake pads and brake shoes, achieving braking function through friction, and its wear resistance can reduce the wear and tear of the braking system.
5. Catalysts and Catalysts
Iron oxide is often used as a catalyst in chemical reactions, such as in desulfurization, hydrogenation, denitrification, and oxidation reactions, to accelerate reaction rates and increase yields. Its surface active sites are abundant and can reduce the activation energy of reactions, making it an important additive in chemical production.
Medical field: innovative applications from diagnosis to treatment
1. Magnetic resonance imaging (MRI) contrast agent
Iron oxide nanoparticles have superparamagnetism, which can rapidly magnetize in a magnetic field and quickly demagnetize after removing the magnetic field. This characteristic makes it the preferred material for MRI contrast agents, which enhances local magnetic field contrast, improves image clarity, and assists doctors in more accurately diagnosing diseases in the brain, liver, and other areas.
2. Magnetic targeted drug delivery
Iron oxide nanoparticles can be used as drug carriers to adsorb or encapsulate drugs on the surface, and accurately deliver them to the lesion site through external magnetic field guidance. This method can reduce the distribution of drugs in normal tissues, reduce side effects, and improve treatment efficiency, especially showing significant advantages in tumor treatment.
3. Magnetic Separation and Detection Technology
After binding with specific antibodies or ligands, iron oxide nanoparticles can quickly separate target cells or molecules from complex biological samples through magnetic field action.
This technology is widely used in disease diagnosis and biological research, such as isolating cancer cells, detecting pathogens, etc., providing technical support for precision medicine.
4. Magnetic Thermotherapy
Under the action of an alternating magnetic field, iron oxide nanoparticles can generate heat, which can be utilized for magnetic hyperthermia to kill tumor cells through local heating. This method has the advantages of non-invasive and precise treatment, which can reduce damage to surrounding normal tissues and is an emerging technology in the field of tumor treatment.
5. Biomarkers and Sensing
Iron oxide nanoparticles can serve as biomarkers for tracking cell movement, monitoring drug release processes, and detecting specific chemicals or biomolecules in the body. For example, in diabetes management, it can be used to monitor blood glucose levels in real time and provide data support for personalized treatment.
Emerging Technology Fields: Cross border Expansion from Energy to Environmental Protection
1. Energy storage materials
Iron tetroxide has both conductivity and magnetism, and can be used to prepare high-performance energy storage devices such as supercapacitors and lithium-ion batteries. Its high specific surface area and surface energy can improve energy storage and release efficiency, for example, as a negative electrode material in lithium-ion batteries, it can enhance the charging and discharging performance of the battery.
2. Catalysts and photocatalysts
Nano sized Fe3O4 has high catalytic activity and can be used in environmental protection fields such as the degradation of organic pollutants, water splitting for hydrogen production, etc. After being combined with other semiconductor materials, its photocatalytic performance is significantly improved. For example, it can efficiently remove heavy metal ions and organic pollutants in wastewater treatment, improving water quality.
3. Absorbing materials and stealth technology
Iron oxide nanoparticles have excellent absorbing properties and can be used to prepare anti UV materials and microwave absorbing materials. In the military field, as a key component of stealth coatings, Triiron tetraoxide can reduce radar reflection signals of aircraft, ships and other equipment, and enhance battlefield survival capabilities.
4. Sealing materials and sensors
The magnetic fluid formed by dispersing iron oxide in liquid can be used for gas and vacuum sealing of precision instruments and aerospace equipment.
Its magnetic properties and fluidity can also be used to manufacture pressure sensors, temperature sensors, and magnetic field sensors, achieving accurate measurement of various physical quantities.
4. Anti counterfeiting and data security
By utilizing the magnetic properties of Fe3O4, anti-counterfeit ink and anti-counterfeit labels can be prepared for product anti-counterfeit identification. In the field of data storage, its nanoscale particle size and high coercivity can improve the signal-to-noise ratio of magnetic recording materials, increase the storage density and read/write speed of media such as hard disks and magnetic tapes.
1. Precipitation method
Precipitation method is the most commonly used method for preparing nano particles because of its simple operation, low cost, high purity and uniform composition, which is suitable for large-scale production. At the same time, the dispersion of nanoparticles can be improved by adding organic dispersants or complexing agents to the precipitation mixture, and the disadvantage of easy agglomeration of nanoparticles can be overcome. Common precipitation methods include coprecipitation, hydrolytic precipitation, ultrasonic precipitation, alcohol salt solution and chelate decomposition.
By coprecipitation method, precipitants are added to the solution containing various cations to allow all ions to precipitate completely. In order to obtain uniform precipitation, the salt solution containing various cations is usually slowly added to the excessive precipitator for stirring, so that the concentration of all ions greatly exceeds the equilibrium concentration of precipitation, and all components are separated out at the same time in proportion as far as possible.
Its principle is Fe2++2Fe3++8OH - → Fe3O4+4H2O.
The molar ratio of Fe2+and Fe3+has a direct effect on the crystal structure of nano particles prepared by precipitation method; PH value of solution, ion concentration and reaction temperature all affect the size of particles. The main problem of precipitation method is how to prepare nanoparticles with single crystal structure and uniform particle size by controlling reaction conditions. The filtration and washing of external precipitator must also be considered.
The Fe3O4 nanoparticles obtained by coprecipitation method are mostly spherical in structure and small in size (5-10nm). However, due to the low temperature of the reaction, the crystallinity of the particles obtained is relatively poor. Moreover, the nano Fe3O4 particles prepared by this method are easy to agglomerate among particles during washing, filtering and drying, which will affect the performance of nano Triiron tetraoxide.
Hydrolysis precipitation method is to release OH- by hydrolysis of alkaline substances. Common alkaline substances include urea, hexamethylene diamine, etc. These substances release OH- slowly, which is conducive to the formation of uniform nanoparticles when preparing nano Fe3O4 particles. Generally, this method can produce nanoparticles with a particle distribution of 7 nm to 39 nm.
Ultrasound can produce cavitation effect in the solvent, and the cavitation bubble generated collapses in a very short time of 10-11 seconds, generating a high temperature of about 5000K in the bubble. Compared with the traditional stirring technology, this series of cavitation is easier to achieve mesoscopic uniform mixing, eliminate local concentration unevenness, improve reaction speed, stimulate the formation of new phases, and can also play a shear role in agglomeration, which is conducive to the formation of small particles. The application of ultrasonic technology has no special requirements on the properties of the system, as long as there is a liquid medium for energy transmission. Vijayakumar. R et al. used the radiation of high intensity ultrasound to prepare the superparamagnetic Fe3O4 particles with the particle size of 10 nm from the ferric acetate solution.
By using the reduction effect of sodium acetate ionizing in water to generate acetate, Fe was partially reduced to Fe at about 180 ℃ in a high-pressure reactor. Yonghui Deng and others heated FeCl3 sodium acetate and ethylene glycol in a high-pressure reactor at 200 ℃ for 8h to prepare superparamagnetic Fe3O4 nanoparticles.
The principle of this method is that metal ions and appropriate ligands form a stable complex at room temperature. At the appropriate temperature and pH value, the complex is destroyed. The metal ions are released again and react with OH ions in the solution and external precipitators and oxidants to generate insoluble metal oxides, hydroxides, salts and other precipitates of different valence. Further treatment can produce nanoparticles of certain size or even shape.
2. Hydrothermal (solvothermal) method:
Hydrothermal (solvothermal) reaction is a general term for chemical reactions carried out under high temperature and high pressure in fluids such as aqueous solution (organic solvent) or steam. Hydrothermal method is a kind of synthesis for preparing nano powder developed in recent ten years. Triiron tetraoxide prepared by this method has small particle size, uniform particle size, no need of high temperature calcination pretreatment, and can realize multivalent ion doping. However, the hydrothermal method requires the use of high temperature and high pressure resistant equipment, so the cost of this method is high and it is difficult to achieve large-scale production.
Nanometer Fe3O4 prepared by hydrothermal method mostly uses inorganic iron salts (FeCl3 · 6H2O, FeCl2 · 4H2O, FeSO4) and organic iron salts (ferrocene Fe (C5H5)2) as precursors, hydrazine, polyethylene glycol, PVP, etc. as surfactants, and is synthesized in alkaline solution below 200 ℃.
Shouheng Sun prepared superparamagnetic Fe3O4 particles with controllable particle size by hydrothermal method. First, Fe3O4 particles with a particle size of 4nm were prepared using Fe (acac) 3 as the Fe source, and then Fe3O4 nanoparticles with a particle size of 4nm were prepared by controlling the holding time and other factors.
Zhen Li et al. reported that Fe3O4 nanoparticles were prepared using common FeCl3 · H2O as precursor instead of expensive Fe (acac)3.
Yadong Li et al. reported that monodisperse Fe3O4 nanoparticles were prepared with FeCl3 · 6H2O, NaAC, EG and PEG as raw materials, and the particle size was adjustable.
3. Microemulsion method:
Microemulsion method refers to the formation of lotion by two immiscible solvents under the action of surfactant, that is, the amphiphilic molecules divide the continuous medium into small spaces to form a micro reactor, in which the reactants react to generate solid phase. Due to the limitation of the micro reactor in nucleation, crystal growth, coalescence, clustering and other processes, nano particles with a layer of surfactant and a certain condensed structure and morphology are formed.
The preparation of nanometer catalyst by micro lotion method has the advantages of simple equipment, mild experimental conditions and controllable particle size, which is incomparable to other methods. Therefore, it has become a very interesting technology in the synthesis of nano catalysts. The research on the preparation of nano catalyst by micro lotion method mostly focuses on the control of particle size, while the research on the control of particle monodispersity is relatively less.
4. Sol gel method
This method uses hydrolysis and polymerization of metal alkoxides to prepare uniform sol of metal oxides or metal hydroxides, and then condenses it into transparent gel. The gel is dried and heat treated to prepare oxide ultrafine powder. The disadvantage of Sol gel method is that the use of metal alkoxides as raw materials leads to high cost and long synthesis cycle in the gelling process. At the same time, the application of sol-gel method to prepare nanoparticles with particle size less than 100 nm has not been reported.
In addition, other preparation methods such as microwave method, pyrolytic carbonyl precursor method, ultrasonic method, air oxidation method, pyrolysis reduction method, polyol reduction method, etc. have been reported successively.
The black Fe3O4 nanoparticles can be obtained by adding FeSO4 solution to ammonia solution in the microwave oven for 8s. Alivasatos et al. prepared monodisperse γ- Fe3O4 nanoparticles, since then, this method has been widely used in the preparation of monodisperse magnetic oxide nanoparticles. Liu et al. prepared FePt magnetic nanoparticles with a diameter of 3nm by using the polyol reduction method and the reduction reaction of ferrous acetylacetonate and platinum acetylacetonate in the high-temperature liquid phase. The particles were monodisperse under the protection of surfactant. Meng Zhe et al. successfully prepared Triiron tetraoxide ultrafine powder with high purity, strong magnetism and spherical distribution by oxidation induction and air oxidation of Fe (OH)2 suspension at room temperature with pH=10 or so.
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