CN114620771A - Nano Fe with amino groups on surface3O4Preparation method of (1) - Google Patents
Nano Fe with amino groups on surface3O4Preparation method of (1) Download PDFInfo
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- 125000003277 amino group Chemical group 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title description 22
- 239000000243 solution Substances 0.000 claims abstract description 39
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229920006324 polyoxymethylene Polymers 0.000 claims abstract description 23
- 108010039918 Polylysine Proteins 0.000 claims abstract description 22
- 229920000656 polylysine Polymers 0.000 claims abstract description 22
- 238000002360 preparation method Methods 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 150000003839 salts Chemical class 0.000 claims abstract description 14
- 239000007864 aqueous solution Substances 0.000 claims abstract description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 239000008367 deionised water Substances 0.000 claims abstract description 6
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 6
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 6
- 239000001301 oxygen Substances 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 6
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 4
- 239000008187 granular material Substances 0.000 claims description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical group Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000002245 particle Substances 0.000 abstract description 18
- 239000002105 nanoparticle Substances 0.000 abstract description 6
- 229910021645 metal ion Inorganic materials 0.000 abstract description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 31
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 18
- -1 biomedicine Substances 0.000 description 6
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 5
- 229930040373 Paraformaldehyde Natural products 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 229910001447 ferric ion Inorganic materials 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 230000002829 reductive effect Effects 0.000 description 4
- 238000000975 co-precipitation Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 229910001385 heavy metal Inorganic materials 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 230000005415 magnetization Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000003223 protective agent Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000004729 solvothermal method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000013060 biological fluid Substances 0.000 description 1
- 238000005285 chemical preparation method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001784 detoxification Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 238000003018 immunoassay Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000011553 magnetic fluid Substances 0.000 description 1
- 239000006249 magnetic particle Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001184 polypeptide Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- 102000004196 processed proteins & peptides Human genes 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000011540 sensing material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000000015 thermotherapy Methods 0.000 description 1
- 230000017423 tissue regeneration Effects 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
- C01G49/08—Ferroso-ferric oxide [Fe3O4]
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/42—Magnetic properties
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- Organic Chemistry (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Compounds Of Iron (AREA)
Abstract
The invention discloses a nano Fe with amino groups on the surface3O4The preparation method comprises the following steps: dissolving trivalent ferric salt in aqueous solution of polyformaldehyde, and introducing N2To remove oxygen from the system; heating the reaction system to 30-90 ℃, adding polylysine with a certain mass into the solution, and mechanically stirring to obtain a transparent orange solution; transferring the orange solution to a hydrothermal reaction kettle for reaction to obtain bright black nano Fe3O4A solution; cooling the final reaction solution, separating by using a magnet, washing by deionized water and acetone for multiple times, and drying to obtain black superparamagnetic Fe3O4And (3) nanoparticles. The outer layer of the prepared particle is modified by polylysine, has high biological safety and compatibility, and metal ions have high adsorbability, and can be used in the field of biological medical treatment.
Description
Technical Field
The invention belongs to the technical field of nano materials, and particularly relates to nano Fe with amino groups on the surface3O4The preparation method of (1).
Background
Recently nano Fe3O4Is gradually the focus of research because of the nano Fe3O4Has unique superparamagnetic property. The performance can be widely applied to the fields of electronic and biological sensing materials, biomedicine, magnetic fluid, magnetic recording materials, magnetic recording media and the like. Nano Fe3O4The surface can be applied to the internal environment of a human body after being properly protected and modified, for example, the surface is functionalized and modified by nano Fe3O4Can be used for tissue repair, immunoassay, biological fluid detoxification, thermotherapy, drug delivery, and cell separation. Nano Fe3O4Applications in the above-mentioned fields, in particular biomedical applications, require high magnetization values, small particle sizes and narrow particle size distributions. Nano Fe3O4The chemical preparation method comprises a coprecipitation method, a hydrothermal reaction method, a sol-gel method, a solvothermal method and an ultrasonic method. Nano Fe prepared under general condition3O4For single crystal particles, a stabilizer is required for surface modification treatment to obtain functionalized magnetic particles. Common stabilizers include the following classes: monomer stabilizer (such as carboxyl compound and phosphate), inorganic substance (such as silicon and gold), and polymer (such as polyethylene glycol, polyvinyl alcohol and chitosan). In addition, the coprecipitation method and the gel-sol method are used for preparing the nano Fe3O4Poor water solubility of the particles; the particles prepared by the solvothermal method can be dissolved in an organic solvent but cannot be dissolved in water, and are expensive; the ultrasonic method cannot prepare nanoparticles on a large scale. Among all the preparation methods, the coprecipitation method is to prepare nano Fe3O4Most importantly and most frequentlyThe method is simple, effective and low in cost. However, the method produces Fe3O4The dispersion degree of the particle size is large, the crystal has defects, and the corresponding saturation magnetization is also low.
Therefore, there is a need to develop a new nano-Fe3O4。
Disclosure of Invention
The invention aims at: provides a nanometer Fe with amino groups on the surface3O4The above problems are solved by the preparation method of (1).
The technical scheme of the invention is as follows:
nano Fe with amino groups on surface3O4The preparation method comprises the following steps:
(1) dissolving trivalent ferric salt in aqueous solution of polyformaldehyde, and introducing N2Removing oxygen in the system to obtain a first solution;
(2) heating, adding polylysine into the first solution, and mechanically stirring to obtain a transparent orange solution;
(3) transferring the orange solution to a hydrothermal reaction kettle for reaction to obtain a bright black nano Fe3O4 solution;
(4) the nano Fe is added3O4Cooling the solution, separating with magnet, washing with deionized water and acetone for several times, and oven drying to obtain black nanometer Fe with amino groups on surface3O4And (3) granules.
Further, in the step (1), the ferric salt is FeCl3、Fe2(SO4)3And Fe (NO)3)3Any one of them.
Further, in the step (1), the polymerization degree n of the polyoxymethylene is 10 to 30, and the concentration of the polyoxymethylene is 0.1 to 3%.
Further, in the step (1), after the trivalent ferric salt is dissolved in the aqueous solution of the polyformaldehyde, the mass percentage of the trivalent ferric salt is 0.01-10%.
Further, N is described in step (1)2Is introduced for a time of30min。
Further, the temperature rise in the step (2) refers to that the temperature rises to 30-90 ℃.
Further, the polymerization degree of the polylysine in the step (2) is 5000-50000.
Further, the mass of the polylysine in the step (2) is 10-15 times of that of the ferric salt.
Further, the mechanical stirring time in the step (2) is 60-120 min.
Further, in the step (3), the reaction time in the hydrothermal reaction kettle is 3-6 hours, and the temperature is 100-250 ℃.
The invention has the advantages that:
1. nano Fe prepared by traditional method3O4The surface can be modified only by subsequent treatment, and the method can prepare the polylysine modified nano Fe in situ3O4；
2. The organic solvent and polylysine have the function of a protective agent and can control the nano Fe3O4The crystal grows, and the particle size distribution is more uniform;
3. the method utilizes the reducibility of polyformaldehyde and polylysine to prepare Fe by reducing ferric iron3O4The use of hydrazine hydrate, ammonia water and the like is avoided;
4. the polylysine can effectively protect the nano Fe3O4Has higher dispersibility and stability in aqueous solution, and the prepared nano Fe3O4The outer layer contains rich amino groups with high reactivity, and can be used for drug loading or heavy metal adsorption;
5. the polylysine is a typical polypeptide, is safe to human body and environment, has good biocompatibility and biodegradability, and can ensure the prepared nano Fe3O4Safety to human body and environment.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without inventive exercise. Wherein the content of the first and second substances,
FIG. 1 shows a nano Fe with amino groups on the surface3O4XRD pattern in example 1;
FIG. 2 shows a nano Fe with amino groups on the surface3O4SEM image of preparation method in example 1.
Detailed Description
The method utilizes a hydrothermal method, polyformaldehyde is decomposed into reductive formaldehyde under a high-temperature hydrothermal condition, and the reductive formaldehyde is cooperated with polylysine to reduce ferric ions, so that nano Fe is formed3O4. The nanometer Fe with perfect crystallization is prepared by a one-step reduction method3O4And (4) functional particles. To increase the nano Fe3O4And endows nano Fe with biosafety3O4The invention has excellent drug-loading and heavy metal adsorption performance, adopts polylysine as a protective agent, a dispersing agent, a reducing agent and a morphology control agent, and prepares the nano Fe with high solution dispersibility, high crystallization and surface amination by using a solvothermal and high-pressure reaction method3O4Particles.
Different from the traditional hydrothermal method, the principle is that polyformaldehyde is used as a reducing agent and can be decomposed into formaldehyde micromolecules with stronger reducibility at high temperature, so that ferric ions are reduced, the decomposition process is slow, and the reducibility of formaldehyde is moderate, so that the ferric ions can be controlled to be slowly reduced into the ferrous ions, nano ferroferric oxide is formed, excessive reduction is prevented from forming elementary iron, the yield is improved, the reaction process is slow, and the polylysine has a protection effect, so that the particle size of the formed nano particles is smaller, and the generation of micron-sized particles is avoided. Prepared nano Fe3O4Has good dispersibility and heavy metal adsorption capacity in aqueous solution. The specific preparation method comprises the following steps:
(1) dissolving trivalent ferric salt in aqueous solution of polyformaldehyde, and introducing N2Removing oxygen in the system for 30min, wherein the polymerization degree n of polyformaldehyde is 10-30, the concentration of polyformaldehyde is 0.1% -3%, and the trivalent ferric salt is FeCl3、Fe2(SO4)3Or Fe (NO)3)3The mass percentage of the ferric iron salt in the polyformaldehyde aqueous solution is 0.01-10%;
(2) heating the reaction system to 30-90 ℃, adding polylysine with a certain mass into the solution, and mechanically stirring for 60-120 min to obtain a transparent orange solution, wherein the polymerization degree of the polylysine is 5000-50000; the mass of the added polylysine is 10-15 times of that of the ferric salt;
(3) transferring the orange solution into a hydrothermal reaction kettle to react for 3-6h at the temperature of 100-250 ℃ to obtain bright black nano Fe3O4A solution;
(4) cooling the final reaction solution, separating by using a magnet, washing by deionized water and acetone for multiple times, and drying to obtain black superparamagnetic Fe3O4And (3) nanoparticles.
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with figures are further described below. The invention is not limited to the embodiments listed but also comprises any other known variations within the scope of the invention as claimed.
First, the references herein to "one embodiment" or "an embodiment" refer to a particular feature, structure, or characteristic that may be included in at least one implementation of the invention. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
The present invention is described in detail by using the schematic structural diagrams, etc., and for convenience of illustration, the schematic diagrams are not enlarged partially according to the general scale when describing the embodiments of the present invention, and the schematic diagrams are only examples, which should not limit the scope of the present invention. In addition, the actual fabrication process should include three-dimensional space of length, width and depth.
Example one
The method prepares the nano Fe with amino groups on the surface according to the following steps3O4：
1. 0.5g of FeCl was taken3Adding into 50g of polyformaldehyde aqueous solution, and fully stirring for 10min to obtain FeCl with the mass percentage of 1%3An aqueous solution of polyoxymethylene, said solution being charged with N2Fully removing dissolved oxygen in the solution for 30 min;
2. the reaction system was warmed to 70 ℃ and 2g polylysine was added to FeCl3Mechanically stirring the polyformaldehyde solution for 1 hour to obtain an orange transparent solution;
3. transferring the reaction system to a hydrothermal reaction kettle, and reacting for 3 hours at 150 ℃ to obtain bright black nano Fe3O4A solution;
4. cooling the final reaction solution, separating by using a magnet, circularly washing by using deionized water and acetone for three times, and drying to finally obtain the polylysine-protected brownish black nano Fe3O4And (3) granules.
Referring to fig. 1 and 2, fig. 1 is a nano Fe with amino groups on the surface according to the present invention3O4XRD pattern in example 1; FIG. 2 shows a nano Fe with amino groups on the surface3O4SEM image of preparation method in example 1. As shown in FIG. 1, nano Fe3O4XRD diffraction peak and Fe of3O4The XRD standard spectrogram completely corresponds to the standard, and 7 diffraction peaks respectively correspond to Fe3O4The diffraction peaks of (220), (311), (400), (422), (511), (440) and (622) crystal planes of (see standard card JCPDS No. 21-1272) prove that the nanometer Fe3O4And (4) generating. As shown in FIG. 2, Fe3O4Is triangular or irregular polygon, and has uniform particle size less than 30 nm. Therefore, the prepared particles are nano-sized, and micron-sized agglomerated particles do not appear, which indicates that the nano-particles have good dispersibility.
Example two
The method prepares the nano Fe with amino groups on the surface according to the following steps3O4：
1. 0.5g of Fe (NO) was taken3)3Adding into 50g polyformaldehyde water, stirring thoroughly for 30min to obtain Fe (NO) with mass percent of 1%3)3An aqueous solution of polyoxymethylene, said solution being charged with N2Fully removing dissolved oxygen in the solution for 30 min;
2. the reaction system was warmed to 70 ℃ and 2g of polylysine was added to Fe (NO)3)3Mechanically stirring the polyformaldehyde aqueous solution for 1 hour to obtain an orange transparent solution;
3. transferring the reaction system to a hydrothermal reaction kettle, and reacting for 3 hours at 220 ℃ to obtain bright black nano Fe3O4A solution;
4. cooling the final reaction solution, separating by using a magnet, circularly washing by using deionized water and acetone for three times, and drying to finally obtain polylysine-protected brown black nano Fe3O4And (3) granules.
In conclusion, the nano Fe with amino groups on the surface3O4The preparation method utilizes the slow decomposition of polyformaldehyde into formaldehyde at high temperature so as to reduce Fe3+The formaldehyde has moderate reducibility, prevents excessive reduction from generating elemental iron, improves the yield, and prevents the particle size from increasing due to too high reduction speed. In addition, the outer layer of the prepared particles is modified by polylysine, so that the particles have high biological safety and compatibility, and metal ions have high adsorbability, and can be used in the field of biological medical treatment. The following table 1 shows the specific comparison with other methods.
TABLE 1
It should be noted that the above-mentioned embodiments are only for illustrating the technical solutions of the present invention and not for limiting, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, which should be covered by the claims of the present invention.
Claims (10)
1. Nano Fe with amino groups on surface3O4The preparation method is characterized by comprising the following steps:
(1) dissolving trivalent ferric salt in aqueous solution of polyformaldehyde, and introducing N2Removing oxygen in the system to obtain a first solution;
(2) heating, adding polylysine into the first solution, and mechanically stirring to obtain a transparent orange solution;
(3) transferring the orange solution to a hydrothermal reaction kettle for reaction to obtain bright black nano Fe3O4A solution;
(4) the nano Fe is added3O4Cooling the solution, separating by using a magnet, washing the solution by using deionized water and acetone for multiple times, and drying to obtain black nano Fe with amino groups on the surface3O4And (3) granules.
2. The nano Fe with amino groups on the surface as claimed in claim 13O4The preparation method is characterized by comprising the following steps: in the step (1), the ferric salt is FeCl3、Fe2(SO4)3And Fe (NO)3)3Any one of them.
3. The nano Fe with amino groups on the surface as claimed in claim 13O4The preparation method is characterized by comprising the following steps: in the step (1), the polymerization degree n of the polyformaldehyde is 10-30, and the concentration of the polyformaldehyde is 0.1-3%.
4. The nano Fe with amino groups on the surface as claimed in claim 13O4The preparation method is characterized by comprising the following steps: in the step (1), the trivalent ferric salt is dissolved inAfter the polyformaldehyde is in the aqueous solution, the mass percent of the trivalent ferric salt is 0.01-10%.
5. The nano Fe with amino groups on the surface as claimed in claim 13O4The preparation method is characterized by comprising the following steps: n in step (1)2The flow-in time of (2) was 30 min.
6. The nano Fe with amino groups on the surface as claimed in claim 13O4The preparation method is characterized by comprising the following steps: in the step (2), the temperature rise refers to the temperature rise to 30-90 ℃.
7. The nano Fe with amino groups on the surface as claimed in claim 13O4The preparation method is characterized by comprising the following steps: the polymerization degree of the polylysine in the step (2) is 5000-50000.
8. The nano Fe with amino groups on the surface as claimed in claim 13O4The preparation method is characterized in that: and (3) in the step (2), the mass of the polylysine is 10-15 times of that of the ferric salt.
9. The nano Fe with amino groups on the surface as claimed in claim 13O4The preparation method is characterized by comprising the following steps: and (3) mechanically stirring for 60-120 min in the step (2).
10. The nano Fe with amino groups on the surface as claimed in claim 13O4The preparation method is characterized by comprising the following steps: in the step (3), the reaction time in the hydrothermal reaction kettle is 3-6h, and the temperature is 100-250 ℃.
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