CN111592047B - Fluid method for continuously preparing iron oxide nanoparticles - Google Patents
Fluid method for continuously preparing iron oxide nanoparticles Download PDFInfo
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- 239000012530 fluid Substances 0.000 title claims abstract description 39
- 229940031182 nanoparticles iron oxide Drugs 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 37
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000000243 solution Substances 0.000 claims abstract description 32
- 239000000047 product Substances 0.000 claims abstract description 24
- 239000011248 coating agent Substances 0.000 claims abstract description 22
- 239000012071 phase Substances 0.000 claims abstract description 22
- 239000002243 precursor Substances 0.000 claims abstract description 22
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910021642 ultra pure water Inorganic materials 0.000 claims abstract description 19
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- 239000007789 gas Substances 0.000 claims abstract description 16
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- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 14
- 150000002505 iron Chemical class 0.000 claims abstract description 9
- 239000007788 liquid Substances 0.000 claims abstract description 9
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- 229940044631 ferric chloride hexahydrate Drugs 0.000 claims description 9
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims description 9
- DLRVVLDZNNYCBX-UHFFFAOYSA-N Polydextrose Polymers OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(O)O1 DLRVVLDZNNYCBX-UHFFFAOYSA-N 0.000 claims description 8
- 229960002089 ferrous chloride Drugs 0.000 claims description 8
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 8
- YASYEJJMZJALEJ-UHFFFAOYSA-N Citric acid monohydrate Chemical compound O.OC(=O)CC(O)(C(O)=O)CC(O)=O YASYEJJMZJALEJ-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
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- 229910052742 iron Inorganic materials 0.000 claims description 6
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- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 claims description 4
- 229920001100 Polydextrose Polymers 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- CXHHBNMLPJOKQD-UHFFFAOYSA-N methyl hydrogen carbonate Chemical compound COC(O)=O CXHHBNMLPJOKQD-UHFFFAOYSA-N 0.000 claims description 4
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- 238000001556 precipitation Methods 0.000 claims description 4
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- 229910001172 neodymium magnet Inorganic materials 0.000 claims description 3
- 230000010355 oscillation Effects 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 2
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- 238000010924 continuous production Methods 0.000 claims 2
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- 239000002245 particle Substances 0.000 description 12
- 229910001873 dinitrogen Inorganic materials 0.000 description 8
- 238000009826 distribution Methods 0.000 description 8
- 238000000975 co-precipitation Methods 0.000 description 7
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 5
- 239000002105 nanoparticle Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Natural products OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000006698 induction Effects 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- -1 iron ion Chemical class 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 239000003513 alkali Substances 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 3
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 3
- 229960004106 citric acid Drugs 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
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- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
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- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000002595 magnetic resonance imaging Methods 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
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- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
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- 229910000859 α-Fe Inorganic materials 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/06—Ferric oxide [Fe2O3]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/51—Particles with a specific particle size distribution
- C01P2004/52—Particles with a specific particle size distribution highly monodisperse size distribution
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Compounds Of Iron (AREA)
- Powder Metallurgy (AREA)
Abstract
The invention relates to a fluid method for continuously preparing iron oxide nano particles, which mainly comprises the following steps: respectively dissolving an iron salt precursor and a coating agent; mixing the coating agent solution with the ferric salt precursor solution; injecting the mixed solution into the T-shaped channel from the inlet 2 at a first flow rate through a fluid device, simultaneously inputting the mixed gas of nitrogen and ammonia gas into the T-shaped channel from the inlet 1 at a second flow rate, shearing the liquid phase fluid at the junction of the two phases by the gas phase to form a uniform liquid section distributed between the liquid phase and the gas phase in the output pipeline, simultaneously dissolving the ammonia gas in the liquid phase to form an alkaline environment to enable the precursor to have hydrolysis reaction, and curing the product in the pipeline; collecting the output product, washing the product for several times by using ultrapure water through an ultrafiltration or magnetic separation method to remove redundant ions, and thus obtaining the final product. The method is environment-friendly, low in cost, capable of realizing continuous and repeatable preparation of the iron oxide nanoparticles, and suitable for industrial application.
Description
Technical Field
The invention belongs to the field of inorganic nano material preparation, and particularly relates to a method for continuously preparing iron oxide nano particles by using a fluid device, which particularly comprises a method for continuously preparing the iron oxide nano particles by controlling reactants to be quickly and uniformly mixed and curing a product by using a fluid technology.
Background
Magnetic iron oxide nanoparticles have good biocompatibility and magnetic properties, and have a wide application prospect in the fields of biomedicine, environmental remediation, electronics and the like, and for example, magnetic iron oxide nanoparticles have been used for targeted drug delivery, magnetic resonance imaging, tumor thermotherapy, immunoassay, sewage treatment, magnetic ink printing, microwave absorption, magnetic memory devices and the like, thereby attracting the attention of a large number of researchers. The chemical methods for synthesizing magnetic iron oxide nanoparticles include coprecipitation, pyrolysis, microemulsion, sol-gel, and hydrothermal methods. The coprecipitation method is simple, effective, environment-friendly and easy to realize batch production, and is the most commonly applied preparation method at present. However, the coprecipitation preparation method involves complex iron ion hydrolysis reaction, the reaction is rapid and difficult to control, and high-quality magnetic iron oxide nanoparticles with uniform appearance, uniform particle size distribution and good crystallization are difficult to prepare.
The magnetic iron oxide nanoparticles are prepared by a coprecipitation method, and mainly by mixing an alkaline solution and an iron salt precursor solution, iron ions are hydrolyzed and precipitated under an alkaline condition to generate the iron oxide nanoparticles. The coprecipitation reaction is sensitive to pH, and local differences in pH caused by uneven mixing of reaction solutions can cause inconsistency of reaction routes and reaction speeds, thereby causing nonuniformity in morphology, particle size and composition of final products. The repeatability between different batches of prepared iron oxide nanoparticles is difficult to guarantee. The iron oxide nanoparticles have magnetism, and the small size effect and the surface effect of the nanoparticles enable the particles to be easily agglomerated. Therefore, some monomolecular stabilizers (citrate, phosphate and the like), polymer stabilizers (polyethylene glycol, polysaccharide and the like), inorganic material protective layers (gold, silver, silicon dioxide and the like) and the like are commonly used for modifying the surfaces of the iron oxide nanoparticles and improving the stability and the dispersibility of the iron oxide nanoparticles in a water phase.
Aiming at the problems of uneven appearance, uneven particle size and poor repeatability of iron oxide nano-particle products prepared by a coprecipitation method, the invention provides a novel method for continuously preparing iron oxide nano-particles by combining a fluid technology. Firstly, a mixed solution of an iron salt precursor and a coating agent is input through one end of a fluid reactor to form a stable water-phase fluid, then an immiscible gas-phase fluid (nitrogen) is input through a T-shaped pipe, and the continuous liquid-phase fluid is cut into liquid segments by gas phases at the junction of two phases, so that uniform liquid segments distributed among the gas segments are formed in an output pipeline. On the basis, ammonia gas with a certain proportion is skillfully mixed in the nitrogen gas as an alkali source, and the ammonia gas is partially dissolved in a liquid phase to form an alkaline environment in the process of converging two phases, so that the precursor is subjected to hydrolysis precipitation reaction to generate the ferric oxide nanoparticles. The method uses a mode of mixing gas-liquid two-phase fluid under a micro scale to replace the traditional mixing modes of dripping, injecting and the like, improves the mass transfer efficiency of the reaction, and utilizes the high heat transfer efficiency of a fluid pipeline to cure the product. Meanwhile, the roughness effect of the inner surface of the fluid pipeline and the compressibility of the gas promote the internal mixing of the reaction solution, and further improve the uniformity of reactant mixing. According to the invention, ferric oxide nanoparticles with uniform particle size and morphology are prepared by taking citric acid monohydrate and polydextrose sorbitol carboxymethyl ether (PSC, molecular weight is 10 KDa) as coating agents respectively. Besides the coprecipitation method, the method is also suitable for preparing magnetic iron oxide nano particles by an oxidation hydrolysis method, and meanwhile, the method can also be adopted for preparing other oxides and hydroxides of iron and various inorganic nano materials such as silicon dioxide, manganese oxide, manganese ferrite and the like, and is particularly suitable for the reaction by taking ammonia as an alkali source.
Disclosure of Invention
The invention provides a fluid method for continuously preparing iron oxide nano particles based on a fluid reactor technology. Firstly, a mixed solution of an iron salt precursor and a coating agent is input through one end of a fluid reactor to form a stable water-phase fluid, then an immiscible gas-phase fluid (nitrogen) is input through a T-shaped pipe, and the continuous liquid-phase fluid is cut into liquid segments by gas phases at the junction of two phases, so that uniform liquid segments distributed among the gas segments are formed in an output pipeline. On the basis, ammonia gas with a certain proportion is skillfully mixed in the nitrogen gas as an alkali source, and the ammonia gas is partially dissolved in a liquid phase to form an alkaline environment in the process of converging two phases, so that the precursor is subjected to hydrolysis precipitation reaction to generate the ferric oxide nanoparticles. The method uses a mode of mixing gas-liquid two-phase fluid under a micro scale to replace the traditional mixing modes of dripping, injecting and the like, improves the mass transfer efficiency of the reaction, and utilizes the high heat transfer efficiency of a fluid pipeline to cure the product. Meanwhile, the roughness effect of the inner surface of the fluid pipeline and the compressibility of the gas promote the internal mixing of the reaction solution, and further improve the uniformity of reactant mixing. The iron oxide nanoparticles prepared by the method have uniform particle size distribution and uniform appearance, can improve the repeatability among different batches of products, and can be used for continuously preparing the iron oxide nanoparticles.
The invention discloses a fluid method for continuously preparing iron oxide nano particles, which mainly comprises the following steps:
1) respectively adding an iron salt precursor and a coating agent into ultrapure water for ultrasonic dissolution;
2) adding a certain amount of coating agent solution into ferric salt precursor solution and carrying out ultrasonic mixing;
3) injecting the mixed solution in the step 2) into a T-shaped pipe through an inlet 2 at a first flow rate through a fluid reaction device, simultaneously inputting mixed gas of nitrogen and ammonia into the T-shaped pipe through an inlet 1 at a second flow rate, shearing liquid phase fluid into a liquid phase at the joint of two phases of the T-shaped pipe, so as to form a uniform liquid phase distributed with the gas phase in an output pipeline, and partially dissolving the ammonia into the liquid phase to form an alkaline environment in the process, so that the precursor is subjected to hydrolysis precipitation reaction;
4) connecting a PTFE pipe with a certain length at the outlet of the T-shaped pipe, and placing the T-shaped pipe in an alcohol bath, a water bath or an electromagnetic induction heating equipment coil with a certain temperature to control the reaction temperature so as to cure the product;
5) collecting the output product, introducing nitrogen for protection, and washing the product by ultra-filtration or magnetic separation with ultrapure water for several times to remove redundant ions to obtain the final product.
In a specific embodiment of the invention, the precursor in the step 1) comprises ferrous chloride tetrahydrate and ferric chloride hexahydrate, and the coating agent comprises one of citric acid monohydrate and polydextrose sorbitol carboxymethyl ether (PSC, molecular weight is 10 KDa) or no coating agent.
Further, the molar ratio of the precursor ferrous chloride tetrahydrate and ferric chloride hexahydrate in the step 1) is 0.4-0.6, preferably 0.5.
Further, the total iron molar concentration of the mixed reaction solution in the step 2) is 3-60mM, preferably 6-45 mM;
further, the mol ratio of the coating agent to the ferric salt precursor is 0-2: 1. When the coating agent is citric acid monohydrate, the molar ratio of the citric acid monohydrate to the iron is 1:8-2:5, preferably 1: 3; when the coating agent is PSC, the mass ratio of the coating agent to ferric chloride hexahydrate is 4:5-2:1, preferably 9: 8; if the coating agent is not used, adding a proper amount of ultrapure water to dilute the ferric salt precursor solution to the required concentration.
Further, the first flow rate in step 3) is 0.2-3ml/min, preferably 0.5-2 ml/min; the second flow rate is 6-30 sccm, preferably 10-20 sccm.
Further, the mixing ratio of the ammonia gas and the nitrogen gas in the mixed gas in the step 3) is 1:5-1:2, preferably 1:4-1: 3.
Further, the inner diameter of the PTFE tube used in the step 4) is 1.6 mm or 2.2 mm, preferably 2.2 mm; the PTFE tube has a length of 0.1 to 20 m, preferably 0.15 to 10 m.
Further, the reaction temperature of the alcohol bath, water bath or electromagnetic induction heating device with different temperatures in the step 4) is controlled within the range of 0-90 ℃, preferably 0-60 ℃.
Further, the electromagnetic induction heating device used in the step 4) is a high-frequency or medium-frequency induction heating device, and the oscillation frequency is 50-1500 kHz, preferably 700-1500 kHz; the power is 5-10 kW, preferably 6-10 kW; the current intensity is 5-30A, preferably 8-20A; the inner diameter of the coil is 2.5-5cm, preferably 4-5 cm.
Further, the nitrogen gas used for the nitrogen protection in step 5) is flowed at a rate of 10 to 50 sccm, preferably 15 to 30 sccm.
Further, the ultrafiltration tube used in the ultrafiltration washing in step 5) has a molecular weight cut-off of 10-50 kDa, preferably 30 kDa; the centrifugal speed is 4000-8000 rpm, preferably 5000 rpm; the time for each centrifugation is 5-10 min, preferably 6 min; the centrifugation temperature is 0-30 ℃, preferably 25 ℃; repeatedly ultrafiltering for several times to remove excessive ions to obtain final product.
Further, in the step 5), the magnetic separation is to use a neodymium iron boron magnet to adsorb the magnetic product to the bottom of the container, remove the supernatant, add ultrapure water to ultrasonically disperse the product, and repeatedly remove redundant ions for 5-10 times to obtain the final product.
The invention has the beneficial effects that:
1) the method does not involve any organic solvent, toxic precursor or excessively high reaction temperature, is environment-friendly and low in cost, can realize continuous and repeatable preparation of the iron oxide nanoparticles, and is suitable for industrial application.
2) The method has high mass transfer efficiency, and simultaneously the coarse effect of the inner surface of the fluid pipeline and the compressibility of the gas promote the internal mixing of the reaction solution, further improve the uniformity of reactant mixing, and the obtained iron oxide nanoparticles have uniform particle size distribution and uniform appearance.
3) The fluid process has high heat transfer efficiency and can cure the product more effectively in a short time.
Drawings
Fig. 1 is a schematic structural view of a gas-liquid two-phase continuous fluid device.
Fig. 2 is a transmission electron microscope picture and a particle size distribution histogram of citric acid modified iron oxide nanoparticles.
Fig. 3 is a transmission electron microscope picture and a particle size distribution histogram of PSC-modified iron oxide nanoparticles.
Fig. 4 is a transmission electron microscope picture and a particle size distribution bar of unmodified bare iron oxide nanoparticles.
Wherein, the tube is a 1-T type tube.
The specific implementation mode is as follows:
for the purpose of promoting an understanding of the invention, reference will now be made in detail to the embodiments of the invention illustrated in the accompanying drawings.
The following non-limiting examples are presented to enable those of ordinary skill in the art to more fully understand the present invention and are not intended to limit the invention in any way. In the following examples, unless otherwise specified, the experimental methods used were all conventional.
Example one
Ferrous chloride tetrahydrate (89.5 mg) and ferric chloride hexahydrate (243.3 mg) were ultrasonically dissolved in 20 ml of ultrapure water, and citric acid monohydrate (63 mg) as a coating agent was ultrasonically dissolved in 10 ml of ultrapure water. The above solutions were mixed ultrasonically and placed in a 50 ml syringe. The injection rate of the reaction solution was set to 500. mu.l/min, the flow rate of ammonia gas was set to 3.5 sccm, and the flow rate of nitrogen gas was set to 14 sccm. A PTFE tube having an inner diameter of 2.2 mm and a length of 10m was connected to the reactor and placed in an alcohol bath at 1 ℃ to thereby obtain a residence time of the reaction solution in the PTFE tube of about 3 min. The reaction apparatus and experimental implementation are shown in FIG. 1. Collecting the product at room temperature, introducing 20 sccm nitrogen for protection, and repeatedly performing ultrafiltration washing on the sample by using ultrapure water until the solution is neutral to obtain citric acid modified iron oxide nanoparticles with uniform particle size and morphology distribution, as shown in FIG. 2. The centrifugal speed used in the ultrafiltration process is 5000 rpm, the time of each centrifugation is 6 min, the centrifugation temperature is 25 ℃, and the molecular weight cut-off of the ultrafiltration tube is 30 kDa.
Example two
Ferrous chloride tetrahydrate (29.8 mg) and ferric chloride hexahydrate (81.1 mg) were ultrasonically dissolved in 20 ml of ultrapure water, and the coating agent PSC (90 mg) was ultrasonically dissolved in 10 ml of ultrapure water. The above solutions were mixed ultrasonically and placed in a 50 ml syringe. The injection rate of the reaction solution was set to 500. mu.l/min, the flow rate of ammonia gas was set to 3.5 sccm, and the flow rate of nitrogen gas was set to 14 sccm. A PTFE tube having an inner diameter of 2.2 mm and a length of 10m was connected to the reactor and placed in an alcohol bath at 1 ℃ to thereby obtain a residence time of the reaction solution in the PTFE tube of about 3 min. And (3) collecting the product at room temperature, introducing 20 sccm nitrogen for protection, and repeatedly performing ultrafiltration washing on the sample by using ultrapure water until the solution is neutral to obtain PSC-modified iron oxide nanoparticles with uniform particle size and morphology distribution, as shown in FIG. 3. The centrifugal speed used in the ultrafiltration process is 5000 rpm, the time of each centrifugation is 6 min, the centrifugation temperature is 25 ℃, and the molecular weight cut-off of the ultrafiltration tube is 30 kDa.
EXAMPLE III
Ferrous chloride tetrahydrate (29.8 mg) and ferric chloride hexahydrate (81.1 mg) were ultrasonically dissolved in 30 ml of ultrapure water, and the reaction solution was placed in a 50 ml syringe. The solution injection rate was set at 2 ml/min, the ammonia gas flow rate was set at 5sccm, and the nitrogen gas flow rate was set at 15 sccm. A PTFE tube having an inner diameter of 2.2 mm and a length of 15 cm was connected to the reactor and left at room temperature, and the residence time of the reaction solution in the PTFE tube was about 3 seconds. The product was passed directly into a three-necked flask, collected at room temperature and blanketed with 20 sccm nitrogen, and the reaction was continued with stirring at 600 rpm for 1 h. After the reaction is finished, the sample is repeatedly washed by using ultrapure water through magnetic separation until the solution is neutral, and the bare iron oxide nanoparticles without modification are obtained, as shown in fig. 4. The magnet used for magnetic separation is a neodymium iron boron magnet.
Example four
Ferrous chloride tetrahydrate (89.5 mg) and ferric chloride hexahydrate (243.3 mg) were ultrasonically dissolved in 20 ml of ultrapure water, and coating agent PSC (324.4 mg) was ultrasonically dissolved in 10 ml of ultrapure water. The above solutions were mixed ultrasonically and placed in a 50 ml syringe. The injection rate of the reaction solution was set to 2 ml/min, the flow rate of ammonia gas was set to 2sccm, and the flow rate of nitrogen gas was set to 8 sccm. A PTFE tube 9 m having an inner diameter of 2.2 mm and a total length of 10m was placed at room temperature, and 1 m was wound into a coil and placed in a coil of an electromagnetic induction heating apparatus, as shown in FIG. 1. The residence time of the reaction solution in the PTFE tube is about 6 min, wherein the reaction solution is heated in the coil of the electromagnetic induction heating device for about 36 s, and the generated magnetic iron oxide nanoparticles are heated and aged under the action of the alternating magnetic field generated by the electromagnetic induction device. The electromagnetic induction heating equipment is high-frequency induction heating equipment, the oscillation frequency of the high-frequency induction heating equipment is 1400 kHz, the maximum power is 6 kW, the current intensity is adjusted to 14A, and the diameter of the coil is 4 cm. The product was passed directly into a three-necked flask, collected at room temperature and blanketed with 20 sccm of nitrogen. And after the reaction is finished, closing the electromagnetic induction heating equipment, and repeatedly performing ultrafiltration washing on the sample by using ultrapure water until the solution is neutral after the temperature of the reaction product is reduced to room temperature to obtain the PSC modified iron oxide nanoparticles subjected to magnetic induction heating and curing. The centrifugal speed used in the ultrafiltration process is 5000 rpm, the time of each centrifugation is 6 min, the centrifugation temperature is 25 ℃, and the molecular weight cut-off of the ultrafiltration tube is 30 kDa.
The technical means disclosed by the scheme of the invention are not limited to the technical means disclosed by the technical means, and also comprise the technical scheme formed by equivalent replacement of the technical features. The present invention is not limited to the details given herein, but is within the ordinary knowledge of those skilled in the art.
Claims (7)
1. A fluid method for continuously preparing iron oxide nanoparticles is characterized by being realized by a gas-liquid two-phase continuous fluid device: the device comprises a T-shaped pipe (1), wherein the T-shaped pipe (1) is divided into an inlet 1, an inlet 2 and an outlet, the outlet is connected with a spirally bent PTFE pipe 4, and the PTFE pipe 4 is placed in an alcohol bath, a water bath or an electromagnetic induction heating equipment coil; the method specifically comprises the following steps:
1) respectively adding an iron salt precursor and a coating agent into ultrapure water for ultrasonic dissolution to respectively form an iron salt precursor solution and a coating agent solution;
2) adding the coating agent solution into the ferric salt precursor solution, and carrying out ultrasonic mixing to form a mixed solution;
3) injecting the mixed solution in the step 2) into a T-shaped pipe (1) through an inlet 2 at a rate of 0.2-3ml/min by using a fluid reaction device, simultaneously inputting the mixed gas of nitrogen and ammonia gas into the T-shaped pipe (1) through the inlet 1 at a rate of 6-30 sccm, and shearing the liquid phase fluid into a liquid phase at the joint of two phases of the T-shaped pipe (1) to form a uniform liquid phase distributed between the liquid phase and the gas phase in an output pipeline, wherein the ammonia gas is partially dissolved in the liquid phase to form an alkaline environment in the process, so that the precursor is subjected to hydrolysis precipitation reaction;
4) connecting a PTFE tube with a length of 0.1-20 m at the outlet of the T-shaped tube (1), aging the product by placing the tube in a 0-90 deg.C alcohol bath, water bath or electromagnetic induction heating equipment coil to control the reaction temperature, wherein the inner diameter of the PTFE tube is 1.6 mm or less
2.2 mm；
5) Collecting the output product, introducing nitrogen for protection, wherein the flow of the nitrogen is 10-50 sccm, and washing the product by using ultrapure water by an ultrafiltration or magnetic separation method for several times to remove redundant ions to obtain the final product.
2. The fluid method for continuous preparation of iron oxide nanoparticles according to claim 1, wherein in step 1), the iron salt precursor comprises ferrous chloride tetrahydrate and ferric chloride hexahydrate, the molar ratio of the ferrous chloride tetrahydrate to the ferric chloride hexahydrate is 0.4-0.6, the coating agent is one of citric acid monohydrate and polydextrose sorbitol carboxymethyl ether, the molecular weight of the polydextrose sorbitol carboxymethyl ether is 10KDa, and the molar ratio of the coating agent to the iron salt precursor is 0-2: 1.
3. The fluidic method for continuous preparation of iron oxide nanoparticles according to claim 1, characterized in that, in step 2), the total iron molar concentration of the mixed solution is 3-60 mM.
4. The fluid method for continuous production of iron oxide nanoparticles according to claim 1, wherein the mixing ratio of the mixed gas of ammonia and nitrogen in step 3) is (1: 5) - (1: 2).
5. The fluid method for continuous production of iron oxide nanoparticles according to claim 1, wherein the electromagnetic induction heating apparatus used is a high-frequency or medium-frequency electromagnetic induction heating apparatus having an oscillation frequency of 50 to 1500 kHz, a power of 5 to 10 kW, a current intensity of 5 to 30A, and an inner diameter of a coil of 2.5 to 5 cm.
6. The fluid method for continuously preparing iron oxide nanoparticles as claimed in claim 1, wherein the molecular weight cut-off of the ultrafiltration tube used in the ultrafiltration washing in step 5) is 10-50 kDa, the centrifugation speed is 4000-8000 rpm, the time for each centrifugation is 5-10 min, the centrifugation temperature is 0-30 ℃, and the final product is obtained by repeatedly performing ultrafiltration for several times.
7. The fluid method for continuously preparing the iron oxide nanoparticles according to claim 1, wherein the magnetic separation in the step 5) is to adsorb the magnetic product to the bottom of the container by using a neodymium iron boron magnet, remove the supernatant, add ultrapure water to ultrasonically disperse the product, and repeatedly remove redundant ions for 5-10 times to obtain the final product.
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