CN116752249B - Binary metal magnetic separable nanocomposite fiber and preparation method thereof - Google Patents
Binary metal magnetic separable nanocomposite fiber and preparation method thereof Download PDFInfo
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 71
- 239000002184 metal Substances 0.000 title claims abstract description 71
- 239000000835 fiber Substances 0.000 title claims abstract description 45
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000002121 nanofiber Substances 0.000 claims abstract description 41
- 239000000725 suspension Substances 0.000 claims abstract description 37
- 239000002131 composite material Substances 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000007787 solid Substances 0.000 claims abstract description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 25
- 150000003839 salts Chemical class 0.000 claims abstract description 22
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 20
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000004202 carbamide Substances 0.000 claims abstract description 18
- 239000002122 magnetic nanoparticle Substances 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000011259 mixed solution Substances 0.000 claims abstract description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 14
- 239000007788 liquid Substances 0.000 claims abstract description 13
- 239000002657 fibrous material Substances 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 58
- 238000003756 stirring Methods 0.000 claims description 45
- 239000000047 product Substances 0.000 claims description 21
- 238000001816 cooling Methods 0.000 claims description 16
- 239000013067 intermediate product Substances 0.000 claims description 16
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 15
- 238000007789 sealing Methods 0.000 claims description 13
- 239000007789 gas Substances 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 238000003760 magnetic stirring Methods 0.000 claims description 9
- 230000001681 protective effect Effects 0.000 claims description 9
- 238000011049 filling Methods 0.000 claims description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 8
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 4
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 4
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 4
- 239000011148 porous material Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 2
- 239000005751 Copper oxide Substances 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 229910000431 copper oxide Inorganic materials 0.000 claims description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 2
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 2
- 230000001133 acceleration Effects 0.000 claims 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims 1
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- 238000005119 centrifugation Methods 0.000 claims 1
- 150000002505 iron Chemical class 0.000 claims 1
- 238000002604 ultrasonography Methods 0.000 claims 1
- 238000001354 calcination Methods 0.000 abstract description 10
- 238000011084 recovery Methods 0.000 abstract description 5
- 238000000926 separation method Methods 0.000 abstract description 5
- 238000001308 synthesis method Methods 0.000 abstract 1
- 235000019441 ethanol Nutrition 0.000 description 17
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 238000009210 therapy by ultrasound Methods 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- 230000002776 aggregation Effects 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- 238000004108 freeze drying Methods 0.000 description 4
- 238000004220 aggregation Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Fibers (AREA)
- Powder Metallurgy (AREA)
Abstract
本发明涉及一种二元金属磁性可分离纳米复合纤维及其制备方法，方法包括如下步骤：纳米纤维加入水中分散得到悬浮液A；将金属盐A和金属盐B加入到水和醇的混合溶液中分散并置于液氮中，然后置于冷冻干燥机中得到复合固体C；将复合固体C加入到悬浮液A中，随后加入尿素，缓慢滴加氨水并搅拌，置于反应釜并于烘箱反应后，离心收集产物，煅烧后得二元金属磁性可分离纳米复合纤维。本发明方法制备的二元金属磁性可分离纳米复合纤维整体呈现直径为10‑11μm的纤维状材料，表面覆盖的二元磁性纳米颗粒大小均一，分散均匀且回收分离效率高；反应过程简单易控，反应条件温和，不需要大型仪器设备，合成方法具有普适性。
The present invention relates to a binary metal magnetic separable nanocomposite fiber and a preparation method thereof, the method comprising the following steps: nanofibers are added to water and dispersed to obtain a suspension A; metal salt A and metal salt B are added to a mixed solution of water and alcohol, dispersed and placed in liquid nitrogen, and then placed in a freeze dryer to obtain a composite solid C; the composite solid C is added to the suspension A, urea is subsequently added, ammonia water is slowly dripped and stirred, placed in a reactor and reacted in an oven, the product is centrifuged and collected, and the binary metal magnetic separable nanocomposite fiber is obtained after calcination. The binary metal magnetic separable nanocomposite fiber prepared by the method of the present invention presents a fibrous material with a diameter of 10-11 μm as a whole, and the binary magnetic nanoparticles covered on the surface are uniform in size, uniformly dispersed, and have high recovery and separation efficiency; the reaction process is simple and easy to control, the reaction conditions are mild, no large-scale instruments and equipment are required, and the synthesis method has universal applicability.
Description
Technical Field
The invention relates to the technical field of nanofiber preparation, in particular to a binary metal magnetic separable nanocomposite fiber and a preparation method thereof.
Background
The magnetic fiber is a fibrous magnetic material, and the composite material has very wide application in the fields of electromagnetic conversion, electromagnetic shielding, electromagnetic memory, medical treatment, biology, separation and purification and the like. The recoverable and separable magnetic nano composite fiber can be obtained by utilizing the magnetic nano particle solidified nano fiber, however, the preparation of the magnetic nano fiber composite material with the surface of the ultra-small nano particles uniformly dispersed is very difficult, and the further application of the magnetic nano fiber composite material is limited mainly due to the serious agglomeration and aggregation phenomenon among the magnetic nano particles. Therefore, controlling the dispersion of surface magnetic nanoparticles is a prerequisite for obtaining a magnetic fiber composite with a uniform surface and a high specific surface area during the preparation of the magnetic nanofibers. In addition, the binary metal magnetic nano particles can be introduced simultaneously to effectively improve various performances through the synergistic effect among metals. However, due to the nature differences between the various metals, the two phases tend to be non-fused, limiting further improvement in their performance. Therefore, the invention develops and prepares the binary magnetic nano composite fiber which is uniformly dispersed.
Disclosure of Invention
The invention aims to provide a binary metal magnetic separable nano composite fiber and a preparation method thereof, which are used for solving the problem of serious agglomeration and aggregation phenomenon among magnetic nano particles in the prior art.
In one aspect, the invention provides a method for preparing a binary metal magnetic separable nano composite fiber, comprising the following steps:
(1) Weighing 50-150 mg of nanofibers, adding the nanofibers into 30-50 mL of deionized water, and performing ultrasonic dispersion for 5-8 hours to obtain a uniformly dispersed suspension A;
(2) Adding metal salt A and metal salt B into a mixed solution of water and alcohol at the same time, dispersing uniformly to obtain a solution B with the concentration of 9-22 mmol/L, putting the solution B into liquid nitrogen, then putting the solution B into a freeze dryer, vacuumizing to 0.1-0.2kPa, drying for 36-48 h, and collecting to obtain fluffy composite solid C;
(3) Adding the composite solid C into the suspension A, and magnetically stirring to obtain a suspension D, wherein the mass ratio of the composite solid C to the nano fibers is 1:2.0-5.0;
(4) Adding urea into the suspension D, carrying out ultrasonic treatment for 20-35 min, magnetically stirring for 1-1.5 h, slowly dropwise adding ammonia water and stirring, wherein the mass ratio of the urea to the composite solid C is 1:0.7-1.5, and the volume ratio of the ammonia water to the suspension A is 1:0.2-0.8;
(5) Placing the solution obtained in the step (4) into a reaction kettle liner, sealing, placing the liner into an oven after being fixed in an outer kettle, reacting for 4-8 hours at 100-130 ℃, naturally cooling to room temperature after the hydrothermal reaction is finished, centrifugally collecting a product, alternately cleaning with water and alcohol, and placing in a vacuum drying oven for 15-24 hours to obtain an intermediate product E;
(6) And placing the intermediate product E in an aluminum oxide crucible, heating from room temperature to 450-650 ℃ at a heating rate of 5-8 ℃ per minute under protective gas, calcining for 1-2 hours, cooling to room temperature, and collecting the product to obtain the binary metal magnetic separable nano composite fiber.
Further, the diameter of the nanofiber in the step (1) is 5-15 μm.
Further, the metal salt A in the step (2) is one of nitrate, hydrochloride, acetate or sulfate of cobalt, nickel or copper, the metal salt B is ferric salt, specifically one of ferric nitrate, ferric chloride, ferric acetate or ferric sulfate, and the molar ratio of the metal salt A to the metal salt B is 1:0.8-1.2.
Further, the mixed solution of water and alcohol in the step (2) is a mixed solution of deionized water and absolute ethyl alcohol in a volume ratio of 1:0.8-1.2, the volume of the solution B placed in liquid nitrogen is 5-8mL, the dispersion is specifically ultrasonic dispersion, the ultrasonic power is 200-500W, and the temperature is 25-30 ℃.
Further, the solution B in the step (2) is placed in liquid nitrogen for freezing for 1-2min, and before being placed in a freeze dryer, the opening of the solution B is sealed by dust-free paper so as to ensure that the solution B is sufficiently dried under low pressure.
Further, in the step (3), the magnetic stirring speed is 400-600 r/min, and the stirring time is 1-1.5 h.
Further, in the step (4), the ultrasonic power is 100-300W, the ultrasonic is performed at the temperature of 25-30 ℃, the magnetic stirring speed is 200-300 r/min, the ammonia water dripping speed is 5-7 s/drop, stirring is performed while dripping, the stirring speed is 200-300 r/min, and the stirring time is 2-3 h.
Further, in the step (5), the filling ratio of the solution obtained in the step (4) to the lining of the reaction kettle is 35-55%, and water and alcohol are alternately cleaned and filtered or centrifuged for 6-10 times.
Further, the shielding gas in the step (6) is N2 or Ar, and before the temperature is raised, the shielding gas is introduced for 1-2 hours, and the cooling rate is 2-5 ℃ per minute.
The invention further provides a binary metal magnetic separable nano composite fiber, binary metal magnetic nano particles are uniformly wrapped on the surface of the nano fiber, the binary metal magnetic nano particles are a mixture of ferroferric oxide and any one of cobalt oxide, nickel oxide and copper oxide, the diameter of the nano fiber is 5-15 mu m, the particle size of the binary metal magnetic nano particles is 5-200 nm, the binary metal magnetic separable nano composite fiber is a fibrous material with the diameter of 5-18 mu m, the binary metal magnetic separable nano composite fiber is a micropore-mesopore concurrent secondary pore structure, micropores are smaller than 2nm, and mesopores are 2-10 nm.
The technical scheme of the invention has the beneficial effects that:
According to the invention, ferric salt and another metal salt are used as composite metal precursors, a mixed solution of water and alcohol is used as a dissolving agent, uniform and fluffy composite metal salt is formed through freeze drying, nano fibers are used as a carrier, urea and ammonia water are used as precipitants, parameters such as metal salt proportion, metal salt and fiber proportion, precipitant dripping rate and the like are cooperatively regulated and controlled, and uniform binary metal magnetic nano composite fiber preparation is realized through a hydrothermal-calcining method.
1) The method has universality, simple synthesis path, easy control, low cost, high efficiency and high product yield, can be suitable for industrial production, and can be expanded to the preparation of the multi-element metal magnetic separable nano composite fiber;
2) The binary metal magnetic separable nano composite fiber is prepared by mixing and freeze-drying the metal salt precursor and the nano fiber before compositing, so that binary metal sites can be composited uniformly and the particle size of nano particles on the surface of the fiber is reduced, the particle size of the prepared binary metal magnetic separable nano composite fiber is uniform and smaller, the electron transmission of the magnetic nano particles and the surface of the nano fiber is facilitated, and the number of active sites is increased;
3) The used metal precursor dissolvent is the mixed solution of absolute ethyl alcohol and deionized water, and the polarity of the mixed solution is utilized to form a droplet-shaped metal precursor, so that the generation of smaller nanometer particle size on the surface of the nanofiber is determined;
4) The method provided by the invention forms a secondary pore structure with concurrent micropores and mesopores, wherein the micropores are beneficial to adsorption of reaction substances, and the mesopores are beneficial to transportation of the reaction substances;
5) Ammonia water is slowly and dropwise added into the suspension, so that the ultra-small particle size of the metal nano particles is maintained, and the occurrence of side reactions is reduced;
6) Firstly, carrying out ultrasonic dispersion on the nanofiber, and then adding a metal salt precursor to enable binary metal ions to be uniformly coordinated with the surface of the nanofiber, so that chemical bonds are formed, the stability of the structure is facilitated, and the charge transmission between the binary metal ions is quickened;
7) The calcination condition has a key effect on the nano composite fiber forming the secondary pore structure, the temperature rising rate is 5-8 ℃ per minute under the protection of argon or nitrogen, the too fast temperature rising rate can lead to the aggregation of metal particles on the surface of the fiber, meanwhile, the temperature is higher than 650 ℃, the magnetic performance can be destroyed, and the mesoporous structure cannot be formed when the temperature is lower than 450 ℃.
Drawings
FIG. 1 is a low power scanning electron microscope image of the product prepared in example 1 of the present invention;
FIG. 2 is a high power scanning electron microscope image of the product prepared in example 1 of the present invention;
FIG. 3 is a scanning electron microscope image of the product prepared in comparative example 1 of the present invention;
FIG. 4 shows the results of the separation and recovery of the product of example 1 of the present invention under the action of a magnet.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments of the present invention.
Example 1
Step one, weighing 100mg of nano fibers with the diameter of 10 mu m, adding the nano fibers into 40mL of deionized water, and performing ultrasonic dispersion for 6 hours to obtain a uniformly dispersed suspension A;
Adding 5mmol of copper nitrate and 5mmol of ferric nitrate into 1L of mixed solution of water and alcohol in a volume ratio of 1:1 at the same time, performing ultrasonic dispersion uniformly to obtain a solution B, taking 6mL of solution, putting into liquid nitrogen for 1min, sealing an opening by using dust-free paper, then putting into a freeze dryer, vacuumizing for 0.1kPa, drying for 48h, and collecting to obtain fluffy composite solid C;
Adding the composite solid C into the solution A, magnetically stirring for 500r/min, and stirring for 1h to obtain a suspension D, wherein the mass ratio of the composite solid C to the nanofiber is 1:2;
adding urea into the suspension D, performing ultrasonic treatment for 30min, performing magnetic stirring for 1h, slowly adding ammonia water dropwise at a speed of 6 s/drop, stirring while dripping, wherein the stirring speed is 200r/min, and the stirring time is 2h, wherein the mass ratio of the urea to the composite solid C is 1:1, and the volume ratio of the ammonia water to the suspension A is 1:0.5;
Placing the solution obtained in the step four in a reaction kettle liner, sealing, wherein the filling ratio of the solution to the reaction liner is 40%, placing the liner in an oven after being fixed in an outer kettle, reacting for 6 hours at 120 ℃, cooling to room temperature after the hydrothermal reaction is finished, centrifugally collecting a product, alternately centrifuging with water and alcohol for 8 times, and placing in a vacuum drying oven for 20 hours to obtain an intermediate product E;
And step six, placing the intermediate product E in an aluminum oxide crucible, heating from room temperature to 550 ℃ at a heating rate of 6 ℃ per minute under protective gas Ar, calcining for 1.5h, cooling to room temperature at a speed of 3 ℃ per minute, and collecting the product to obtain the binary metal magnetic separable nano composite fiber.
Example 2
Firstly, weighing 50mg of nano fibers with the diameter of 5 mu m, adding the nano fibers into 30mL of deionized water, and performing ultrasonic dispersion for 5 hours to obtain a uniformly dispersed suspension A;
Adding 5mmol of cobalt acetate and 4mmol of ferric chloride into 1L of mixed solution of water and alcohol in a volume ratio of 1:0.8 at the same time, performing ultrasonic dispersion uniformly to obtain a solution B, taking 5mL of the solution, placing the solution into liquid nitrogen for 1min, sealing an opening by using dust-free paper, placing the solution into a freeze dryer, vacuumizing to 0.1kPa, drying for 36h, and collecting the fluffy composite solid C;
adding the composite solid C into the solution A, magnetically stirring for 400r/min, and stirring for 1h to obtain a suspension D, wherein the mass ratio of the composite solid C to the nanofiber is 1:2;
Adding urea into the suspension D, carrying out ultrasonic treatment for 20min, magnetically stirring for 1h, slowly adding ammonia water dropwise at a speed of 5 s/drop, stirring while dripping, wherein the stirring speed is 200r/min, and the stirring time is 2h, wherein the mass ratio of the urea to the composite solid C is 1:0.7, and the volume ratio of the ammonia water to the suspension A is 1:0.2;
Placing the solution obtained in the step four in a reaction kettle liner, sealing, wherein the filling ratio of the solution to the reaction liner is 35%, placing the liner in an oven after being fixed in an outer kettle, reacting for 4 hours at 100 ℃, cooling to room temperature after the hydrothermal reaction is finished, centrifugally collecting a product, alternately centrifuging with water and alcohol for 6 times, and placing in a vacuum drying oven for 15 hours to obtain an intermediate product E;
And step six, placing the intermediate product E in an aluminum oxide crucible, heating from room temperature to 450 ℃ at a heating rate of 5 ℃ per minute under protective gas Ar, calcining for 1h, cooling to room temperature at a speed of 2 ℃ per minute, and collecting the product to obtain the binary metal magnetic separable nano composite fiber.
Example 3
Firstly, weighing 150mg of nano fibers with the diameter of 15 mu m, adding the nano fibers into 50mL of deionized water, and performing ultrasonic dispersion for 8 hours to obtain a uniformly dispersed suspension A;
Adding 10mmol of nickel chloride and 12mmol of ferric chloride into 1L of mixed solution of water and alcohol in a volume ratio of 1:1.2 at the same time, performing ultrasonic dispersion uniformly to obtain a solution B, taking 8mL of the solution, putting the solution into liquid nitrogen for 2min, sealing an opening by using dust-free paper, then putting the solution into a freeze dryer, vacuumizing for 0.2kPa, drying for 48h, and collecting the fluffy composite solid C;
Adding the composite solid C into the solution A, magnetically stirring for 600r/min, and stirring for 1.5h to obtain a suspension D, wherein the mass ratio of the composite solid C to the nanofiber is 1:5;
adding urea into the suspension D, performing ultrasonic treatment for 35min, performing magnetic stirring for 1.5h, slowly adding ammonia water dropwise at a speed of 7 s/drop, stirring while dripping, wherein the stirring speed is 300r/min, the stirring time is 3h, the mass ratio of the urea to the composite solid C is 1:1.5, and the volume ratio of the ammonia water to the suspension A is 1:0.8;
Placing the solution obtained in the step four in a reaction kettle liner, sealing, wherein the filling ratio of the solution to the reaction liner is 55%, placing the liner in an oven after being fixed in an outer kettle, reacting for 8 hours at 140 ℃, cooling to room temperature after the hydrothermal reaction is finished, centrifugally collecting a product, alternately centrifuging for 10 times by using water and alcohol, and placing in a vacuum drying oven for 24 hours to obtain an intermediate product E;
and step six, placing the intermediate product E in an aluminum oxide crucible, heating from room temperature to 650 ℃ for calcining for 2 hours at a heating rate of 8 ℃ per minute under the protection gas N2, cooling to room temperature at a speed of 5 ℃ per minute, and collecting the product to obtain the binary metal magnetic separable nano composite fiber.
Example 4
Firstly, weighing 50mg of nano fibers with the diameter of 8 mu m, adding the nano fibers into 35mL of deionized water, and performing ultrasonic dispersion for 6 hours to obtain a uniformly dispersed suspension A;
adding 8mmol of cobalt nitrate and 7mmol of ferric sulfate into 1L of mixed solution of water and alcohol in a volume ratio of 1:1.1 at the same time, performing ultrasonic dispersion uniformly to obtain a solution B, taking 7mL of solution, putting the solution into liquid nitrogen for 1.5min, sealing an opening by using dust-free paper, then putting the solution into a freeze dryer, vacuumizing for 0.2kPa, drying for 40h, and collecting the fluffy composite solid C;
Adding the composite solid C into the solution A, magnetically stirring for 550r/min, and stirring for 1.2h to obtain a suspension D, wherein the mass ratio of the composite solid C to the nanofiber is 1:3;
adding urea into the suspension D, performing ultrasonic treatment for 28min, performing magnetic stirring for 1.1h, slowly adding ammonia water dropwise at a speed of 5 s/drop, stirring while dripping, wherein the stirring speed is 250r/min, and the stirring time is 2.5h, wherein the mass ratio of urea to composite solid C is 1:0.9, and the volume ratio of ammonia water to suspension A is 1:0.6;
Placing the solution obtained in the step four in a reaction kettle liner, sealing, wherein the filling ratio of the solution to the reaction liner is 40%, placing the liner in an oven after being fixed in an outer kettle, reacting for 7 hours at 130 ℃, cooling to room temperature after the hydrothermal reaction is finished, centrifugally collecting a product, alternately centrifuging with water and alcohol for 8 times, and placing in a vacuum drying oven for 18 hours to obtain an intermediate product E;
And step six, placing the intermediate product E in an aluminum oxide crucible, heating from room temperature to 600 ℃ at a heating rate of 7 ℃ per minute under protective gas Ar, calcining for 1.5h, cooling to room temperature at a speed of 3 ℃ per minute, and collecting the product to obtain the binary metal magnetic separable nano composite fiber.
Example 5
Step one, weighing 120mg of nano fibers with the diameter of 13 mu m, adding the nano fibers into 40mL of deionized water, and performing ultrasonic dispersion for 7 hours to obtain a uniformly dispersed suspension A;
Adding 9mmol of copper sulfate and 10mmol of ferric sulfate into 1L of mixed solution of water and alcohol in a volume ratio of 1:0.9 at the same time, performing ultrasonic dispersion uniformly to obtain a solution B, taking 6mL of solution, putting into liquid nitrogen for 1.5min, sealing an opening by using dust-free paper, then putting into a freeze dryer, vacuumizing for 0.1kPa, drying for 45h, and collecting to obtain fluffy composite solid C;
adding the composite solid C into the solution A, magnetically stirring for 450r/min, and stirring for 1h to obtain a suspension D, wherein the mass ratio of the composite solid C to the nanofiber is 1:4;
Adding urea into the suspension D, performing ultrasonic treatment for 30min, performing magnetic stirring for 1h, slowly adding ammonia water dropwise at a speed of 7 s/drop, stirring while dripping, wherein the stirring speed is 200r/min, the stirring time is 2h, the mass ratio of the urea to the composite solid C is 1:1.2, and the volume ratio of the ammonia water to the suspension A is 1:0.6;
placing the solution obtained in the step four in a reaction kettle liner, sealing, wherein the filling ratio of the solution to the reaction liner is 55%, placing the liner in an oven after being fixed in an outer kettle, reacting for 5 hours at 100 ℃, cooling to room temperature after the hydrothermal reaction is finished, centrifugally collecting a product, alternately centrifuging with water and alcohol for 6 times, and placing in a vacuum drying oven for 24 hours to obtain an intermediate product E;
and step six, placing the intermediate product E in an aluminum oxide crucible, heating from room temperature to 450 ℃ at a heating rate of 5 ℃ per minute under protective gas Ar, calcining for 2 hours, cooling to room temperature at a speed of 4 ℃ per minute, and collecting the product to obtain the binary metal magnetic separable nano composite fiber.
Comparative example 1
Step one, weighing 100mg of nano fibers with the diameter of 10 mu m, adding the nano fibers into 40mL of deionized water, and performing ultrasonic dispersion for 6 hours to obtain a uniformly dispersed suspension A;
Adding 5mmol of copper nitrate and 5mmol of ferric nitrate into 1L of mixed solution of water and alcohol in a volume ratio of 1:1 simultaneously, performing ultrasonic dispersion uniformly to obtain a solution B, and putting 6mL of the solution into liquid nitrogen for 1min to obtain a substance C;
adding a substance C into the solution A, magnetically stirring for 500r/min, and stirring for 1h to obtain a suspension D, wherein the mass ratio of the substance C to the nanofiber is 1:2;
adding urea into the suspension D, performing ultrasonic treatment for 30min, performing magnetic stirring for 1h, slowly adding ammonia water dropwise at a speed of 6 s/drop, stirring while dripping, wherein the stirring speed is 200r/min, the stirring time is 2h, the mass ratio of urea to the substance C is 1:1, and the volume ratio of the ammonia water to the suspension A is 1:0.5;
Placing the solution obtained in the step four in a reaction kettle liner, sealing, wherein the filling ratio of the solution to the reaction liner is 40%, placing the liner in an oven after being fixed in an outer kettle, reacting for 6 hours at 120 ℃, cooling to room temperature after the hydrothermal reaction is finished, centrifugally collecting a product, alternately centrifuging with water and alcohol for 8 times, and placing in a vacuum drying oven for 20 hours to obtain an intermediate product E;
And step six, placing the intermediate product E in an aluminum oxide crucible, heating from room temperature to 550 ℃ at a heating rate of 6 ℃ per minute under protective gas Ar, calcining for 1.5h, cooling to room temperature at a speed of 3 ℃ per minute, and collecting the product to obtain the binary metal magnetic separable nano composite fiber.
The whole binary metal magnetic separable nano composite fiber prepared in the embodiment 1 of the method of the invention presents a fibrous material with the diameter of 10-11 mu m, the surface of the fibrous material is uniformly covered with a plurality of small binary magnetic nano particles as shown in figure 1, the particle size of the binary metal magnetic nano particles is 20-30nm, the particle size is uniform and the dispersion is uniform as shown in figure 2, however, the binary magnetic nano particles on the surface of the nano composite fiber material obtained in the step of freeze drying experiment are not uniformly dispersed in the comparative example 1, the size is not uniform, the initial freeze drying step is very important for forming the uniformly dispersed binary magnetic nano particles, in addition, the separation and recovery experiment is carried out on the binary metal magnetic separable nano composite fiber prepared in the embodiment 1, as shown in figure 4, the original quality of the material is recovered for the 0 th time through 6 times of experiments, the recovery rate is as high as 98.5%, and the recovery and separation efficiency is high.
It should be noted that the above embodiments are merely for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the above embodiments, it should be understood by those skilled in the art that the technical solution described in the above embodiments may be modified or some or all of the technical features may be equivalently replaced, and these modifications or substitutions do not make the essence of the corresponding technical solution deviate from the scope of the technical solution of the embodiments of the present invention.
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