CN108609649B - Preparation method of sea urchin-shaped magnetic hollow microspheres - Google Patents
Preparation method of sea urchin-shaped magnetic hollow microspheres Download PDFInfo
- Publication number
- CN108609649B CN108609649B CN201810526499.8A CN201810526499A CN108609649B CN 108609649 B CN108609649 B CN 108609649B CN 201810526499 A CN201810526499 A CN 201810526499A CN 108609649 B CN108609649 B CN 108609649B
- Authority
- CN
- China
- Prior art keywords
- polystyrene
- microspheres
- water
- iron oxyhydroxide
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
-
- 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)
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/34—Introducing sulfur atoms or sulfur-containing groups
- C08F8/36—Sulfonation; Sulfation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/42—Introducing metal atoms or metal-containing groups
-
- 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
-
- 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
Abstract
The invention relates to a preparation method of sea urchin-shaped magnetic hollow microspheres. The method comprises the following steps: (1) preparing polystyrene microspheres; (2) sulfonating polystyrene microspheres; (3) preparing hydroxyl ferric oxide/polystyrene composite microspheres; (4) preparing silicon dioxide or titanium dioxide/iron oxyhydroxide/polystyrene composite microspheres; (5) calcined silica or titanium dioxide/iron oxyhydroxide/polystyrene composite microspheres. The invention has the advantages of simple preparation process, mild reaction conditions, easy realization of industrial production and better industrial development prospect.
Description
Technical Field
The technical scheme of the invention relates to the field of organic, inorganic and high polymer materials, in particular to a preparation method of sea urchin-shaped magnetic hollow microspheres.
Background
The morphological characteristics are closely related to the physical and chemical properties of the material. With the development of nano materials, how to control the morphology of the nano materials so as to exert more excellent performance has become a key research point at home and abroad. Among the various nanostructures, the sea urchin-shaped hollow nanostructure has an ultra-high specific surface area and a strong enrichment capacity, so that the sea urchin-shaped hollow nanostructure attracts more attention in various potential applications such as a super capacitor, a solar cell, a sensor, a surface enhanced Raman spectrum, photocatalysis, cancer treatment and the like. (Y.Xiao, S.Liu, F.Li, A.Zhang, J.Zhao, S.Fang and D.Jia, adv.Funct.Mater.,2012,22, 4052; W.Q.Wu, Y.F.Xu, H.S.Rao, C.Y.Su and D.B.Kuang, J.Am.Chem.Soc.,2014,136,6437; D.P.Volander, A.A.Felix, M.O.Orlandi, G.Whitfield, D.J.Yang, E.Lono, H.L.Tullerand J.A.Varela, adv.Funct.Mater.,2013,23, 1759; X.Wang, D.P.Yang, P.Yang, M.C.Li, Li, F.Li, A.Zhang, J.C.E.Li, F.Li, A.J.C.T.T.J.C.T.T.T.T.T.T.T.T.T.T.T.T.C.T.T.T.T.T.T.T.T.T.T.T.T.C.T.T.T.T.T.T.T.T.T.T.T.T. C.T.T.T.T.T.T.T.T.T.T.T.T.T.T. 13, K.T.T.T.T.T.T.T.T.T.T.T.T.T.T.T.C.T.T.T.T.T.T.T.T.T. 13, D. WWhen the sea urchin-shaped hollow structure with silicon dioxide or titanium dioxide as the base material and paramagnetism are combined into the nano composite material, multiple functions can be integrated into a single nano whole, so that multiple characteristics of high specific surface area, easily modified surface, fast magnetic field response, good thermal stability, good biocompatibility and the like are shown. From patents reported in related research fields, it is known that core-shell structures are mainly used in the preparation of sea urchin-like magnetic nanocomposites (for example, Chinese patent No. CN102319564.B, patent name: a double-layer cavity structure and preparation method of sea urchin-like titanium dioxide magnetic microspheres; Chinese patent No. CN103157430.B, patent name: a sea urchin-like core-shell Fe3O4@TiO2Magnetic microspheres and preparation and application thereof; china, patent No.: cn105688794.a, patent name: a sea urchin-shaped magnetic nanosphere and its preparation method and application are provided. However, the mass transfer path and the material density are increased by the core in the structure, so that the application of the structure in the aspect of adsorption catalysis is limited, and the hollow structure has the advantages of low density, large specific surface area, short mass transfer path, semi-permeability and the like, so that the mass transfer resistance can be effectively reduced, the transfer of a substrate/product is accelerated, and the hollow structure is better used in the fields of load or photocatalysis and the like. Therefore, the preparation of the sea urchin-shaped hollow magnetic silicon dioxide or titanium dioxide nano material has important significance.
The patent designs and prepares the sea urchin-shaped magnetic hollow silicon dioxide or titanium dioxide microspheres, and the sea urchin-shaped magnetic hollow microspheres are prepared by a mode of combining sulfonation, in-situ hydrolysis and template removal. The microsphere skillfully combines a hollow structure, a sea urchin-shaped structure and magnetism, so that the material has great application value in the fields of catalysis, environment, biomedicine and the like.
Disclosure of Invention
The method comprises the steps of firstly sulfonating the crosslinked polystyrene microspheres as a template, growing iron oxyhydroxide tetragonal lepidocrocite (β -FeOOH) on the surfaces of the sulfonated polystyrene microspheres by using ferric trichloride, then hydrolyzing a silicon source or a titanium source on the surfaces of materials to generate a silicon dioxide or titanium dioxide shell layer, and finally removing the crosslinked polystyrene template by calcining and sintering β -FeOOH into magnetite so that the materials have great application value in the fields of load catalysis and the like.
The technical scheme of the invention is as follows:
a preparation method of sea urchin-shaped magnetic hollow microspheres comprises the following steps:
(1) preparing polystyrene microspheres by adopting one of the following methods according to different crosslinking degrees:
the method comprises the following steps: preparation of polystyrene microsphere with crosslinking degree ranging from 0.5% to 50%
The crosslinked polystyrene microspheres are synthesized by an emulsion polymerization method: sequentially adding water and NaHCO into a reactor3Heating the mixture in a water bath to 70 ℃, introducing argon, mechanically stirring, adding a monomer (a mixture of styrene and divinylbenzene) into a reaction system, simultaneously heating an initiator potassium persulfate solution to 70 ℃, dropwise adding the mixture into the previous reactor, finishing dropping for 1 hour, stirring at the rotating speed of 180r/min, reacting at the constant temperature of 70 ℃ for 10-15 hours, removing the obtained emulsion, standing, and naturally volatilizing the solvent at room temperature to obtain a polystyrene microsphere template with the crosslinking degree of 0.5-50% for later use;
wherein, the material ratio is that the volume ratio is water: monomer (b): potassium persulfate solution 120: 20: 30, of a nitrogen-containing gas; the volume ratio of the monomers is styrene: divinylbenzene 20: 0.5 to 10; adding 0.01-0.60 g SDS and 0.1g NaHCO into 120mL water3(ii) a The concentration of the potassium persulfate solution is 30mL of distilled water in which 0.03-1.50 g of initiator potassium persulfate is dissolved;
the second method comprises the following steps: preparation of polystyrene microspheres with crosslinking degree ranging from 50% to 100%
The polystyrene microsphere is synthesized by adopting a dispersion polymerization method: adding polyvinylpyrrolidone, absolute ethyl alcohol and water into a reactor, mechanically stirring, controlling the stirring speed at 110r/min, introducing argon into a reaction system, and then placing the reaction system in a water bath at 75 ℃ for later use; adding styrene, divinylbenzene and azodiisobutyronitrile into a container, oscillating and dissolving, adding into the mixed solution for later use, keeping the mechanical stirring and argon protection state, reacting for 10-15 h, removing the obtained emulsion, standing, and volatilizing the solvent at room temperature to obtain polystyrene microspheres with the crosslinking degree of 50-100% for later use;
the material proportion is absolute ethyl alcohol by volume ratio: water: styrene: divinylbenzene 95: 10: 0.5-20: 20-0.5, 0.2g of azobisisobutyronitrile is dissolved in 20mL of monomer, and 1-4 g of polyvinylpyrrolidone is dissolved in 95mL of absolute ethyl alcohol;
(2) sulfonation of polystyrene microspheres
The method comprises the following steps: preparation of sulfonated polystyrene microsphere using concentrated sulfuric acid and acetic anhydride as sulfonation reagent
Vacuumizing the polystyrene microspheres obtained in the step (1), and injecting 1, 2-Dichloroethane (DCE) for swelling; dripping a sulfonation reagent in an ice water bath into the system, reacting for 6-24 hours at 20-80 ℃, taking out the sulfonation reagent, repeatedly washing the obtained material with ethanol and water to be neutral, and finally freeze-drying the obtained product to obtain the polystyrene microsphere modified by sulfonic acid groups;
wherein the sulfonation reagent is a mixture of 1, 2-dichloroethane, acetic anhydride and concentrated sulfuric acid, and the volume ratio is DCE: acetic anhydride: concentrated sulfuric acid is 6: 10: 3-8; volume ratio 1, 2-dichloroethane used in swelling: 1-10% of a sulfonation reagent: 20; adding 4ml of 1, 2-dichloroethane to 0.16g of the polystyrene microspheres obtained in the step (1);
the second method comprises the following steps: preparation of sulfonated polystyrene microsphere using concentrated sulfuric acid as sulfonation reagent
Immersing the polystyrene microspheres obtained in the drying step (1) in concentrated sulfuric acid, reacting at a constant temperature of 40-80 ℃ for 5-24 hours, taking out a sulfonation reagent after the reaction is finished, washing the sulfonation reagent with ethanol and water to be neutral, and freeze-drying the obtained product to obtain the polystyrene microspheres with sulfonic acid groups;
wherein the material ratio is that the polystyrene microsphere is prepared from the following materials in percentage by mass: concentrated sulfuric acid is 1: 10-40;
(3) the preparation of the hydroxyl ferric oxide/polystyrene composite microsphere is one of the following two methods:
the method comprises the following steps: alkaline preparation method
Respectively adding water and FeCl into the sulfonated polystyrene microspheres obtained in the step (2) under magnetic stirring3Urea and polyvinylpyrrolidone (PVP) are condensed and refluxed for 6-12 h in a water bath at the temperature of 60-90 ℃, and the obtained material is washed with absolute ethyl alcohol for three times and then naturally dried to obtain the iron oxyhydroxide/polystyrene composite microspheres;
the material proportion is water by volume ratio: FeCl3: urea: PVP 100: 0.1-0.6: 0.1-0.6: 0.01 to 1; adding 100ml of the mixed solution into every 0.1g of the sulfonated polystyrene microspheres obtained in the step (2);
the second method comprises the following steps: acidic preparation method
Respectively adding double distilled water and FeCl into the sulfonated polystyrene microspheres obtained in the step (2) under magnetic stirring3Condensing and refluxing hydrochloric acid (HCl) and polyvinylpyrrolidone (PVP) in a water bath at the temperature of 60-90 ℃ for 6-12 hours, washing the obtained material with absolute ethyl alcohol for three times, and naturally drying to obtain the iron oxyhydroxide/polystyrene composite microspheres;
the material proportion is water by volume ratio: FeCl3: HCl: PVP 100: 0.1-0.6: 0.1-0.6: 0.01 to 1; adding 100ml of the mixed solution into every 0.1g of the sulfonated polystyrene microspheres obtained in the step (2);
(4) the preparation of the silicon dioxide or titanium dioxide/iron oxyhydroxide/polystyrene composite microspheres is one of the following two methods:
the method comprises the following steps: preparation of silicon dioxide or titanium dioxide/iron oxyhydroxide/polystyrene microsphere by sol-gel method
Adding a silicon source or a titanium source, hydrochloric acid, absolute ethyl alcohol and water into a three-necked bottle with magnetons, and condensing and refluxing for 1-3 hours in a water bath at 40-80 ℃ to prepare silicon dioxide or titanium dioxide sol; under the condition of suction filtration, dropwise adding the sol onto the polystyrene microspheres with the iron oxyhydroxide obtained in the step (3), keeping for 5-15 min after dropwise adding, cleaning the polystyrene with ethanol, and then putting the material into an oven at 40-80 ℃ for gelation; after 1h, repeating the process of dropping sol, cleaning and gelling for 3-5 times to obtain the silicon dioxide or titanium dioxide/iron oxyhydroxide/polystyrene composite microspheres;
the material proportion is silicon source or titanium source by volume: hydrochloric acid: anhydrous ethanol: water 9: 0.5-20: 0.5-20: 0.5 to 30; dripping 10ml of sol into every 0.1g of the iron oxyhydroxide/polystyrene composite microspheres obtained in the step (3);
the second method comprises the following steps: preparation of silicon dioxide or titanium dioxide/iron oxyhydroxide/polystyrene composite microsphere by hydrolysis method
Respectively adding ethanol and water into the dried polystyrene microspheres with iron oxyhydroxide obtained in the step (3) under the condition of stirring, swelling for 5-12 h at 20-50 ℃, then dropwise adding a silicon source or a titanium source to react for 8-24 h, respectively washing the obtained material with absolute ethanol and distilled water, and then freeze-drying in freeze drying to obtain the polystyrene microsphere/silicon dioxide or titanium dioxide composite microspheres;
wherein, the material proportion is silicon source or titanium source for the volume ratio: anhydrous ethanol: water 1: 0.5-2.5: 0.01 to 2.5; adding 2ml of water into every 0.1g of the iron oxyhydroxide/polystyrene composite microspheres obtained in the step (3);
(5) calcined silicon dioxide or titanium dioxide/iron oxyhydroxide/polystyrene composite microsphere
Controlling the temperature of the dried silicon dioxide or titanium dioxide/iron oxyhydroxide/polystyrene composite microspheres by temperature programming, heating to 300 ℃ at a speed of 2-5 ℃/min under the protection of inert gas, keeping the temperature for 3-5 h, heating to 400-600 ℃ at the same speed, keeping the temperature for 4-6 h, and cooling to obtain sea urchin-shaped magnetic hollow silicon dioxide or titanium dioxide nanoparticles;
the silicon source is ethyl orthosilicate or 3-aminopropyl triethoxysilane;
the titanium source is butyl titanate, isopropyl titanate or titanium tetrachloride;
the invention has the substantive characteristics that:
according to the invention, ferric trichloride is utilized to grow the FeOOH tetragonal lepidocrocite on the surface of the sulfonated polystyrene microsphere, namely the nanorod on the surface of the sea urchin-shaped structure, and the FeOOH can be calcined into the ferroferric oxide to obtain magnetism by calcining the material, namely the hollow nanorod of which the magnetic part is the surface of the sea urchin-shaped structure. In the traditional method, a core-shell structure is utilized, monodisperse ferroferric oxide magnetic microspheres need to be prepared firstly, namely, the magnetic part of the material is a core consisting of the ferroferric oxide, the preparation method is complex, and the core-shell structure has smaller specific surface area and high density compared with a hollow structure.
The invention has the beneficial effects that:
(1) according to the invention, β -FeOOH tetragonal lepidocrocite is modified on the surface of the sulfonated polystyrene microsphere, and a sulfonic acid group on the surface of the polystyrene microsphere is used for inducing a silicon source or a titanium source to react to prepare the silicon dioxide or titanium dioxide/iron oxyhydroxide/polystyrene composite microsphere, and then the silicon dioxide or titanium dioxide/iron oxyhydroxide/polystyrene composite microsphere is calcined under the protection of inert gas to prepare the sea urchin-shaped magnetic hollow silicon dioxide or titanium dioxide nanoparticles.
(2) The sea urchin-shaped magnetic hollow silica or titanium dioxide nano-particles prepared by the invention are calcined on the surface of a material to form the magnetic hollow nano-rod after being prepared into silica or titanium dioxide/iron oxyhydroxide/polystyrene composite microspheres. The sea urchin-shaped magnetic microsphere prepared by the traditional method utilizes a core-shell structure, and needs to be prepared firstly, namely, the magnetic part of the material is a core consisting of ferroferric oxide.
(3) The sea urchin-shaped magnetic hollow silica or titanium dioxide nano-particles prepared by the invention mainly comprise silica or titanium dioxide in chemical composition, have good physical and chemical properties and excellent thermal stability and biocompatibility, and have great potential application value in the fields of high-temperature load catalysis, biological enzyme load catalysis and the like.
Drawings
FIG. 1: preparing sea urchin-shaped magnetic hollow microspheres;
FIG. 2: an electron micrograph of the polystyrene microsphere having a degree of crosslinking of 2% in example 1;
FIG. 3: electron microscope photograph of iron oxyhydroxide/polystyrene composite microsphere in example 1;
FIG. 4: electron micrographs of the echinoid magnetic hollow microspheres of example 1;
FIG. 5: a magnetic field response photo of the urchin-shaped magnetic hollow microsphere in example 1 under an external magnet;
Detailed Description
Example 1:
(1) preparation of polystyrene microspheres with a degree of crosslinking of 2%
0.1g NaHCO is taken30.2g of Sodium Dodecyl Sulfate (SDS) is dissolved in 120mL of distilled water, the solution is transferred to a reaction kettle, nitrogen is introduced, mechanical stirring is carried out, the temperature is raised to 70 ℃, after 30min of stirring, 20mL of monomer (a mixture of 19.6mL of styrene and 0.4mL of divinylbenzene) is added into a reaction system, 0.32g of potassium persulfate is weighed and dissolved in 30mL of distilled water, the reaction system is added, the stirring speed is controlled at 180r/min, the reaction is stopped after 13h of reaction, the obtained emulsion is moved out and stands, and the solvent is naturally volatilized at room temperature, so that the polystyrene microsphere with the crosslinking degree of 2 percent is obtained;
FIG. 2 shows that the polystyrene microspheres with a crosslinking degree of 2% are obtained by scanning polystyrene microspheres with a FEI Nano SEM 450 electron scanning electron microscope, and the polystyrene microspheres prepared by emulsion polymerization have uniform particle size.
(2) Sulfonation of polystyrene microspheres
Immersing 1g of dried polystyrene microspheres into 40mL of concentrated sulfuric acid, reacting at a constant temperature of 40 ℃ for 8h, discarding liquid after the reaction is finished, washing until the pH value of a supernatant is unchanged, and freeze-drying the obtained product to obtain the polystyrene microspheres with sulfonic acid groups;
(3) preparation of iron oxyhydroxide/polystyrene composite microspheres
Taking 0.1g of dry polystyrene microspheres with sulfonic acid groups in a three-neck flaskUnder stirring, 100mL of distilled water and 0.5g of FeCl were added30.5g of urea, condensing for 6 hours in an oil bath at 80 ℃, washing the obtained material with absolute ethyl alcohol for 3 times, and drying under natural conditions to obtain the iron oxyhydroxide/polystyrene composite microspheres;
FIG. 3 is obtained by scanning FeI Nano SEM 450 electron scanning electron microscope with FeI Fei/polystyrene composite microsphere, and it can be seen from the figure that a uniform rod-like structure is formed on the surface of a single microsphere, which provides a basis for the magnetism and excellent morphology of the material. After the material is calcined, the iron oxyhydroxide nano-rod is calcined into a magnetite nano-tube, and the magnetite nano-tube rapidly responds to the magnetic field end under the action of an external magnetic field, so that the material has magnetism.
(4) Preparation of silicon dioxide/iron oxyhydroxide/polystyrene composite microspheres
Taking 0.1g of dried iron oxyhydroxide/polystyrene composite microspheres in a three-neck flask, respectively adding 10mL of ethanol and 2mL of distilled water under the condition of stirring, swelling for 10h at 25 ℃, dropwise adding 10mL of tetraethoxysilane for reacting for 12h, washing the obtained material with anhydrous ethanol and double distilled water for 3 times, and freeze-drying the material with a freeze dryer to obtain the silicon dioxide/iron oxyhydroxide/polystyrene composite microspheres;
(5) calcined silica/iron oxyhydroxide/polystyrene composite microspheres
Controlling the temperature rise of the dried silicon dioxide/iron oxyhydroxide/polystyrene composite microspheres by a program, raising the temperature to 300 ℃ at a speed of 4 ℃/min under the protection of inert gas, keeping the temperature for 4 hours, raising the temperature to 570 ℃ and keeping the temperature for 5 hours, and cooling to obtain the sea urchin-shaped magnetic hollow microspheres;
FIG. 4 is an electron micrograph of the urchin-like magnetic hollow microsphere obtained by removing the polystyrene template by FEI Nano SEM 450 electron scanning electron microscopy, and it is seen from the micrograph that the calcined material is in the shape of a hollow urchin, the nanotubes are hollow, and the particles are uniformly dispersed and have uniform size.
FIG. 5 shows the response of the sea urchin-like magnetic hollow microsphere to a magnetic field under the application of an external magnet, and the photo shows that the material has good magnetism.
Example 2:
(1) preparation of polystyrene microspheres with a degree of crosslinking of 3%
In a 500mL four-necked flask, 0.1g NaHCO was added30.3g of Sodium Dodecyl Sulfate (SDS) and 120mL of water are heated to 70 ℃ in a water bath, argon is introduced, mechanical stirring is carried out, then a mixed monomer (a mixture of 19.4mL of styrene and 0.6mL of divinylbenzene) is added into a reaction system, 0.5g of potassium persulfate is dissolved in 30mL of water and heated to 70 ℃, then the mixed monomer is dripped into the previous reactor, the stirring speed is 180r/min, the constant temperature reaction is carried out for 13h at 70 ℃, the obtained emulsion is kept stand, the solvent is naturally volatilized at room temperature, and the polystyrene microsphere with the crosslinking degree of 3 percent is obtained;
(2) sulfonation of polystyrene microspheres
Immersing 1g of dried crosslinked polystyrene microspheres in 40mL of concentrated sulfuric acid, reacting at the constant temperature of 40 ℃ for 12h, removing liquid after the reaction is finished, washing with water until the pH value of a supernatant is unchanged, and freeze-drying the obtained product to obtain the crosslinked polystyrene microspheres with sulfonic acid groups;
(3) preparation of iron oxyhydroxide/polystyrene composite microspheres
Taking 0.1g of dry polystyrene microspheres with sulfonic acid groups in a three-neck flask, and respectively adding 100mL of distilled water and 0.1g of FeCl under the condition of stirring30.6g of urea, condensing for 7 hours in oil bath at 70 ℃, washing the obtained material with absolute ethyl alcohol for 3 times, and drying under natural conditions to obtain the iron oxyhydroxide/polystyrene composite microspheres;
(4) preparation of titanium dioxide/iron oxyhydroxide/polystyrene composite microspheres
Taking 0.1g of dried iron oxyhydroxide/polystyrene composite microspheres in a three-neck flask, respectively adding 20mL of ethanol and 2mL of distilled water under the condition of stirring, swelling for 10h at 25 ℃, dropwise adding 10mL of butyl titanate, reacting for 13h, washing the obtained material with anhydrous ethanol and double distilled water for 3 times, and freeze-drying the material with a freeze-drying machine to obtain titanium dioxide/iron oxyhydroxide/polystyrene composite microspheres;
(5) calcined titanium dioxide/iron oxyhydroxide/polystyrene composite microspheres
Controlling the temperature rise of the dried titanium dioxide/iron oxyhydroxide/polystyrene composite microspheres by a program, raising the temperature to 300 ℃ at a speed of 2 ℃/min under the protection of inert gas, keeping the temperature for 4 hours, raising the temperature to 400 ℃ at the same speed, keeping the temperature for 5 hours, and cooling to obtain the sea urchin-shaped magnetic hollow microspheres;
example 3:
(1) preparation of polystyrene microspheres with a crosslinking degree of 20%
Adding 1g of polyvinylpyrrolidone, 95mL of anhydrous ethanol and 10mL of water into a 250mL four-mouth bottle, controlling the stirring speed at 110r/min, introducing argon, placing the bottle in a 75 ℃ water bath for later use, adding 16mL of styrene, 4mL of divinylbenzene and 0.2g of azobisisobutyronitrile into a beaker, uniformly mixing, adding the mixture into the four-mouth bottle, carrying out argon protection, carrying out constant temperature reaction for 15 hours, removing and standing the obtained emulsion, and naturally volatilizing the solvent at room temperature to obtain the polystyrene microspheres with the crosslinking degree of 20%;
(2) functionalization of polystyrene microspheres
Immersing 1g of dried crosslinked polystyrene microspheres in 10mL of concentrated sulfuric acid, reacting at a constant temperature of 40 ℃ for 20h, removing liquid after the reaction is finished, washing with water until the pH value of a supernatant is unchanged, and freeze-drying the obtained product to obtain the crosslinked polystyrene microspheres with sulfonic acid groups;
(3) preparation of iron oxyhydroxide/polystyrene composite microspheres
Taking 0.1g of dry polystyrene microspheres with sulfonic acid groups in a three-neck flask, and respectively adding 100mL of distilled water and 0.15g of FeCl under the condition of stirring30.3g of urea, condensing for 9 hours in an oil bath at 60 ℃, washing the obtained material with absolute ethyl alcohol for 3 times, and drying under natural conditions to obtain the iron oxyhydroxide/polystyrene composite microspheres;
(4) preparation of silicon dioxide/iron oxyhydroxide/polystyrene composite microspheres
Taking 0.1g of dried iron oxyhydroxide/polystyrene composite microspheres in a three-neck flask, respectively adding 2mL of ethanol and 2mL of distilled water under the condition of stirring, swelling for 11h at 25 ℃, dropwise adding 1mL of tetraethoxysilane for reacting for 14h, washing the obtained material with anhydrous ethanol and double distilled water for 3 times, and freeze-drying the material with a freeze dryer to obtain the silicon dioxide/iron oxyhydroxide/polystyrene composite microspheres;
(5) calcining the silica/iron oxyhydroxide/polystyrene composite microspheres in the same manner as in the step (5) of the example 1;
example 4:
(1) preparation of polystyrene microspheres with a degree of crosslinking of 50%
Adding 1g of polyvinylpyrrolidone, 95mL of anhydrous ethanol and 10mL of water into a 250mL four-mouth bottle, controlling the stirring speed at 110r/min, introducing argon, placing the bottle in a 75 ℃ water bath for later use, adding 10mL of styrene, 10mL of divinylbenzene and 0.2g of azobisisobutyronitrile into a beaker, uniformly mixing, adding the mixture into the four-mouth bottle, carrying out argon protection, carrying out constant temperature reaction for 15 hours, removing and standing the obtained emulsion, and naturally volatilizing the solvent at room temperature to obtain polystyrene microspheres with the crosslinking degree of 50%;
(2) sulfonation of polystyrene microspheres
Immersing 1g of dried crosslinked polystyrene microspheres in 25mL of concentrated sulfuric acid, reacting at a constant temperature of 40 ℃ for 21h, after the reaction is finished, removing liquid, washing with water until the pH value of a supernatant is unchanged, and freeze-drying the obtained product to obtain the crosslinked polystyrene microspheres with sulfonic acid groups;
(3) preparation of iron oxyhydroxide/polystyrene composite microspheres
Taking 0.1g of dry polystyrene microspheres with sulfonic acid groups in a three-neck flask, and respectively adding 100mL of distilled water and 0.3g of FeCl under the condition of stirring30.35g of urea, condensing for 9 hours in an oil bath at 75 ℃, washing the obtained material with absolute ethyl alcohol for 3 times, and drying under natural conditions to obtain the iron oxyhydroxide/polystyrene composite microspheres;
(4) preparation of titanium dioxide/iron oxyhydroxide/polystyrene composite microspheres
Adding 8.4mL of butyl titanate, 1.5mL of hydrochloric acid, 2.7mL of water and 10mL of absolute ethyl alcohol into a three-necked bottle with magnetons, and condensing and refluxing for 1h in a water bath at 60 ℃ to obtain the titanium dioxide sol. And (3) slowly dripping the titanium sol onto 0.226g of the iron oxyhydroxide/polystyrene composite microspheres obtained in the step (3) under the condition of suction filtration, keeping for 5min after dripping, cleaning the material with ethanol, and washing the titanium sol on the surfaces of the composite microspheres. Then putting the filled material into a drying oven at 60 ℃ for gelation, filling for the second time after 1h, repeating the processes of dropping sol, cleaning and gelation for four times to obtain the titanium dioxide/iron oxyhydroxide/polystyrene composite microspheres;
(5) calcining the titanium dioxide/iron oxyhydroxide/polystyrene composite microspheres in the same manner as in the step (5) of the example 2;
example 5:
(1) the preparation of polystyrene microspheres with a crosslinking degree of 3% was the same as in step (1) of example 2;
(2) sulfonation of polystyrene microspheres
After evacuating 0.16g of the polystyrene microspheres obtained in step (1), 4mL of 1, 2-Dichloroethane (DCE) was injected and swollen. The sulfonation reagent (a mixture of 6mL of 1, 2-dichloroethane, 10mL of acetic anhydride, and 3.5mL of concentrated sulfuric acid) mixed in an ice-water bath was dropped into the system. Reacting for 10 hours at 40 ℃, taking out the sulfonation reagent, repeatedly washing the obtained material to be neutral by using ethanol and water, and finally freeze-drying the obtained product to obtain the polystyrene microsphere modified by the sulfonic acid group;
(3) the preparation of the iron oxyhydroxide/polystyrene composite microspheres is the same as the step (3) of the example 2;
(4) preparation of silicon dioxide/iron oxyhydroxide/polystyrene composite microspheres
Adding 9mL of ethyl orthosilicate, 1mL of hydrochloric acid, 2mL of water and 8mL of absolute ethyl alcohol into a three-necked bottle with magnetons, and condensing and refluxing in a water bath at 70 ℃ for 2h to obtain the silicon dioxide sol. And (3) slowly dripping silica sol onto 0.2g of the iron oxyhydroxide/polystyrene composite microspheres obtained in the step (3) under the condition of suction filtration, keeping for 5min after dripping, cleaning the material with ethanol, and washing off the silica sol on the surfaces of the composite microspheres. Then putting the filled material into an oven at 70 ℃ for gelation, filling for the second time after 1h, repeating the process of dropping sol, cleaning and gelation for four times to obtain the silicon dioxide/iron oxyhydroxide/polystyrene composite microspheres;
(5) calcining the silica/iron oxyhydroxide/polystyrene composite microspheres in the same manner as in the step (5) of the example 1;
example 6:
(1) the preparation of polystyrene microspheres with a crosslinking degree of 2% was performed in the same manner as in example step (1);
(2) sulfonation of polystyrene microspheres
After evacuating 0.16g of the polystyrene microspheres obtained in step (1), 4mL of 1, 2-Dichloroethane (DCE) was injected and swollen. The sulfonation reagent (a mixture of 6mL of 1, 2-dichloroethane, 10mL of acetic anhydride, and 7mL of concentrated sulfuric acid) mixed in an ice-water bath was dropped into the system. Reacting at 60 ℃ for 12 hours, taking out the sulfonation reagent, repeatedly washing the obtained material to be neutral by using ethanol and water, and finally freeze-drying the obtained product to obtain the polystyrene microsphere modified by the sulfonic acid group;
(3) the preparation of the iron oxyhydroxide/polystyrene composite microspheres is the same as the step (3) of the example 2;
(4) the preparation of the titanium dioxide/iron oxyhydroxide/polystyrene composite microspheres is the same as the step (4) of the example 3;
(5) calcining the titanium dioxide/iron oxyhydroxide/polystyrene composite microspheres in the same manner as in the step (5) of the example 1;
the invention is not the best known technology.
Claims (1)
1. A preparation method of sea urchin-shaped magnetic hollow microspheres is characterized by comprising the following steps:
(1) preparing polystyrene microspheres by adopting one of the following methods according to different crosslinking degrees:
the method comprises the following steps: preparation of polystyrene microsphere with crosslinking degree ranging from 0.5% to 50%
The crosslinked polystyrene microspheres are synthesized by an emulsion polymerization method: sequentially adding water and NaHCO into a reactor3Heating the mixture in a water bath to 70 ℃, introducing argon, mechanically stirring, adding a mixture of styrene and divinylbenzene as a monomer into a reaction system, heating an initiator potassium persulfate solution to 70 ℃, dropwise adding the mixture into the previous reactor, finishing dripping for 1 hour, stirring at the rotating speed of 180r/min, reacting at the constant temperature of 70 ℃ for 10-15 hours,the obtained emulsion is moved out and kept stand, the solvent is naturally volatilized at room temperature, and a polystyrene microsphere template with the crosslinking degree within the range of 0.5-50% is obtained for later use;
wherein, the material ratio is that the volume ratio is water: monomer (b): potassium persulfate solution 120: 20: 30, of a nitrogen-containing gas; the volume ratio of the monomers is styrene: divinylbenzene 20: 0.5 to 10; adding 0.01-0.60 g SDS and 0.1g NaHCO into 120mL water3(ii) a The concentration of the potassium persulfate solution is 30mL of distilled water in which 0.03-1.50 g of initiator potassium persulfate is dissolved;
the second method comprises the following steps: preparation of polystyrene microspheres with crosslinking degree ranging from 50% to 100%
The polystyrene microsphere is synthesized by adopting a dispersion polymerization method: adding polyvinylpyrrolidone, absolute ethyl alcohol and water into a reactor, mechanically stirring, controlling the stirring speed at 110r/min, introducing argon into a reaction system, and then placing the reaction system in a water bath at 75 ℃ for later use; adding styrene, divinylbenzene and azodiisobutyronitrile into a container, oscillating and dissolving, adding into the mixed solution for later use, keeping the mechanical stirring and argon protection state, reacting for 10-15 h, removing the obtained emulsion, standing, and volatilizing the solvent at room temperature to obtain polystyrene microspheres with the crosslinking degree of 50-100% for later use;
the material proportion is absolute ethyl alcohol by volume ratio: water: styrene: divinylbenzene 95: 10: 0.5-20: 20-0.5, 0.2g of azobisisobutyronitrile is dissolved in 20mL of monomer, and 1-4 g of polyvinylpyrrolidone is dissolved in 95mL of absolute ethyl alcohol;
(2) sulfonation of polystyrene microspheres
The method comprises the following steps: preparation of sulfonated polystyrene microsphere using concentrated sulfuric acid and acetic anhydride as sulfonation reagent
Vacuumizing the polystyrene microspheres obtained in the step (1), and injecting 1, 2-Dichloroethane (DCE) for swelling; dripping a sulfonation reagent in an ice water bath into the system, reacting for 6-24 hours at 20-80 ℃, taking out the sulfonation reagent, repeatedly washing the obtained material with ethanol and water to be neutral, and finally freeze-drying the obtained product to obtain the polystyrene microsphere modified by sulfonic acid groups;
wherein the sulfonation reagent is a mixture of 1, 2-dichloroethane, acetic anhydride and concentrated sulfuric acid, and the volume ratio is DCE: acetic anhydride: concentrated sulfuric acid is 6: 10: 3-8; volume ratio 1, 2-dichloroethane used in swelling: 1-10% of a sulfonation reagent: 20; adding 4ml of 1, 2-dichloroethane to 0.16g of the polystyrene microspheres obtained in the step (1);
the second method comprises the following steps: preparation of sulfonated polystyrene microsphere using concentrated sulfuric acid as sulfonation reagent
Immersing the polystyrene microspheres obtained in the drying step (1) in concentrated sulfuric acid, reacting at a constant temperature of 40-80 ℃ for 5-24 hours, taking out a sulfonation reagent after the reaction is finished, washing the sulfonation reagent with ethanol and water to be neutral, and freeze-drying the obtained product to obtain the polystyrene microspheres with sulfonic acid groups;
wherein the material ratio is that the polystyrene microsphere is prepared from the following materials in percentage by mass: concentrated sulfuric acid is 1: 10-40;
(3) the preparation of the hydroxyl ferric oxide/polystyrene composite microsphere is one of the following two methods:
the method comprises the following steps: alkaline preparation method
Respectively adding water and FeCl into the sulfonated polystyrene microspheres obtained in the step (2) under magnetic stirring3Urea and polyvinylpyrrolidone (PVP) are condensed and refluxed for 6-12 h in a water bath at the temperature of 60-90 ℃, and the obtained material is washed with absolute ethyl alcohol for three times and then naturally dried to obtain the iron oxyhydroxide/polystyrene composite microspheres;
the material proportion is water by volume ratio: FeCl3: urea: PVP 100: 0.1-0.6: 0.1-0.6: 0.01 to 1; adding 100ml of the mixed solution into every 0.1g of the sulfonated polystyrene microspheres obtained in the step (2);
the second method comprises the following steps: acidic preparation method
Respectively adding double distilled water and FeCl into the sulfonated polystyrene microspheres obtained in the step (2) under magnetic stirring3Condensing and refluxing hydrochloric acid (HCl) and polyvinylpyrrolidone (PVP) in a water bath at the temperature of 60-90 ℃ for 6-12 hours, washing the obtained material with absolute ethyl alcohol for three times, and naturally drying to obtain the iron oxyhydroxide/polystyrene composite microspheres;
the material proportion is water by volume ratio: FeCl3：HCl：PVP＝100：0.1～0.6：0.1～0.6：0.01～1(ii) a Adding 100ml of the mixed solution into every 0.1g of the sulfonated polystyrene microspheres obtained in the step (2);
(4) the preparation of the silicon dioxide or titanium dioxide/iron oxyhydroxide/polystyrene composite microspheres is one of the following two methods:
the method comprises the following steps: preparation of silicon dioxide or titanium dioxide/iron oxyhydroxide/polystyrene microsphere by sol-gel method
Adding a silicon source or a titanium source, hydrochloric acid, absolute ethyl alcohol and water into a three-necked bottle with magnetons, and condensing and refluxing for 1-3 hours in a water bath at 40-80 ℃ to prepare silicon dioxide or titanium dioxide sol; under the condition of suction filtration, dropwise adding the sol onto the polystyrene microspheres with the iron oxyhydroxide obtained in the step (3), keeping for 5-15 min after dropwise adding, cleaning the polystyrene with ethanol, and then putting the material into an oven at 40-80 ℃ for gelation; after 1h, repeating the process of dropping sol, cleaning and gelling for 3-5 times to obtain the silicon dioxide or titanium dioxide/iron oxyhydroxide/polystyrene composite microspheres;
the material proportion is silicon source or titanium source by volume: hydrochloric acid: anhydrous ethanol: water 9: 0.5-20: 0.5-20: 0.5 to 30; dripping 10ml of sol into every 0.1g of the iron oxyhydroxide/polystyrene composite microspheres obtained in the step (3);
the second method comprises the following steps: preparation of silicon dioxide or titanium dioxide/iron oxyhydroxide/polystyrene composite microsphere by hydrolysis method
Respectively adding ethanol and water into the dried polystyrene microspheres with iron oxyhydroxide obtained in the step (3) under the condition of stirring, swelling for 5-12 h at 20-50 ℃, then dropwise adding a silicon source or a titanium source to react for 8-24 h, respectively washing the obtained material with absolute ethanol and distilled water, and then freeze-drying in freeze drying to obtain the polystyrene microsphere/silicon dioxide or titanium dioxide composite microspheres;
wherein, the material proportion is silicon source or titanium source for the volume ratio: anhydrous ethanol: water 1: 0.5-2.5: 0.01 to 2.5; adding 2ml of water into every 0.1g of the iron oxyhydroxide/polystyrene composite microspheres obtained in the step (3);
(5) calcined silicon dioxide or titanium dioxide/iron oxyhydroxide/polystyrene composite microsphere
Controlling the temperature of the dried silicon dioxide or titanium dioxide/iron oxyhydroxide/polystyrene composite microspheres by temperature programming, heating to 300 ℃ at a speed of 2-5 ℃/min under the protection of inert gas, keeping the temperature for 3-5 h, heating to 400-600 ℃ at the same speed, keeping the temperature for 4-6 h, and cooling to obtain sea urchin-shaped magnetic hollow silicon dioxide or titanium dioxide nanoparticles;
the silicon source is tetraethoxysilane or 3-aminopropyl triethoxysilane;
the titanium source is butyl titanate, isopropyl titanate or titanium tetrachloride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810526499.8A CN108609649B (en) | 2018-05-22 | 2018-05-22 | Preparation method of sea urchin-shaped magnetic hollow microspheres |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810526499.8A CN108609649B (en) | 2018-05-22 | 2018-05-22 | Preparation method of sea urchin-shaped magnetic hollow microspheres |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108609649A CN108609649A (en) | 2018-10-02 |
| CN108609649B true CN108609649B (en) | 2020-06-09 |
Family
ID=63664375
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810526499.8A Expired - Fee Related CN108609649B (en) | 2018-05-22 | 2018-05-22 | Preparation method of sea urchin-shaped magnetic hollow microspheres |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108609649B (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109704347B (en) * | 2019-01-30 | 2021-05-18 | 北京科技大学 | Silicon dioxide hollow sphere nano composite material and preparation and application thereof |
| CN109824934B (en) * | 2019-01-31 | 2021-06-11 | 济南大学 | Polyethylene-titanium oxide micron nano multilevel structure composite microsphere material and application |
| CN110586026A (en) * | 2019-10-09 | 2019-12-20 | 东南大学 | Adsorbent for removing heavy metal arsenic and preparation method and application thereof |
| CN110961162B (en) * | 2019-12-09 | 2021-01-19 | 北京化工大学 | Catalyst carrier, precious metal catalyst, and preparation method and application thereof |
| CN111498911B (en) * | 2020-04-22 | 2021-11-05 | 常熟理工学院 | Purple Fe with monodisperse hollow structure3O4@SiO2Material and preparation method |
| CN112694093A (en) * | 2021-01-28 | 2021-04-23 | 山东瑞利泰阳新材料科技有限公司 | Low dielectric loss silicon dioxide microsphere and preparation method thereof |
| CN114433084B (en) * | 2021-12-29 | 2023-09-08 | 杭州臻尚环境科技有限公司 | Preparation method and application of hollow carbon/silicon composite microsphere catalyst with core-shell structure |
| CN114874560B (en) * | 2022-03-18 | 2023-07-25 | 北京林业大学 | Modified polystyrene composite material and preparation method and application thereof |
| CN115261023B (en) * | 2022-08-11 | 2024-04-12 | 河南大学 | Preparation method and application of soil-water body heavy metal passivating agent of nano silicon/iron oxyhydroxide |
| CN115710417A (en) * | 2022-11-28 | 2023-02-24 | 江西省萍乡市轩品塑胶制品有限公司 | Biodegradable sheet lunch box master batch and preparation method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102580783B (en) * | 2012-01-09 | 2014-03-26 | 兰州交通大学 | Method for preparing TiO2/PS/Fe3O4 magnetic nanoparticle photocatalyst |
| CN103157412A (en) * | 2013-03-25 | 2013-06-19 | 哈尔滨工业大学 | Preparation method of electromagnetic composite hollow microspheres |
| CN106710773B (en) * | 2016-12-12 | 2019-09-10 | 北京大学深圳研究生院 | A kind of monodisperse magnetic porous silica microballoon and preparation method thereof |
-
2018
- 2018-05-22 CN CN201810526499.8A patent/CN108609649B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN108609649A (en) | 2018-10-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108609649B (en) | Preparation method of sea urchin-shaped magnetic hollow microspheres | |
| Hua et al. | Hierarchically structural PAN/UiO-66-(COOH) 2 nanofibrous membranes for effective recovery of Terbium (III) and Europium (III) ions and their photoluminescence performances | |
| Ma et al. | Magnetic lignin-based carbon nanoparticles and the adsorption for removal of methyl orange | |
| Luo et al. | Adsorptive removal of Lead from water by the effective and reusable magnetic cellulose nanocomposite beads entrapping activated bentonite | |
| Wang et al. | Hydrothermal synthesis of hierarchical core–shell manganese oxide nanocomposites as efficient dye adsorbents for wastewater treatment | |
| Yang et al. | Monodisperse core-shell structured magnetic mesoporous aluminosilicate nanospheres with large dendritic mesochannels | |
| Wei et al. | Rapid and efficient uranium (VI) capture by phytic acid/polyaniline/FeOOH composites | |
| Shi et al. | Electrospinning fabrication of flexible Fe3O4 fibers by sol-gel method with high saturation magnetization for heavy metal adsorption | |
| Shi et al. | A general strategy to fabricate soft magnetic CuFe2O4@ SiO2 nanofibrous membranes as efficient and recyclable Fenton-like catalysts | |
| Guo et al. | Silver nanoparticles/polydopamine coated polyvinyl alcohol sponge as an effective and recyclable catalyst for reduction of 4-nitrophenol | |
| CN103880020B (en) | Chirality mesoporous organic silica nanotube or core-shell type nanometer rod and preparation method thereof | |
| CN107585758A (en) | A kind of graphene aerogel and its preparation method and application | |
| Wang et al. | Spherical montmorillonite-supported nano-silver as a self-sedimentary catalyst for methylene blue removal | |
| CN104759635B (en) | A kind of preparation method of loaded nano zero-valent iron composite material | |
| CN105664936A (en) | Method for preparing nano composite material having core-shell structure with dopamine as carbon source | |
| CN105458295B (en) | A kind of multi-pore micron copper ball and preparation method thereof | |
| Du et al. | Novel yolk-shell polymer/carbon@ Au nanocomposites by using dendrimer-like mesoporous silica nanoparticles as hard template | |
| CN103864032B (en) | A kind of preparation method of nano material | |
| CN104439276B (en) | A kind of quick method and product preparing hollow porous silica/argentum nano composite material | |
| CN105600833B (en) | A kind of spherical mesoporous iron oxide and preparation method thereof | |
| Zhuang et al. | Alcohol-assisted self-assembled 3D hierarchical iron (hydr) oxide nanostructures for water treatment | |
| Tan et al. | Synthesis of a novel magnetically recyclable starch-based adsorbent for efficient adsorption of crystal violet dye | |
| CN102689917B (en) | Method for preparing barium sulfate porous microspheres and titanium dioxide nano-particles by using titanium sulfate | |
| Zhang et al. | Preparation and catalytic properties of magnetic rectorite-chitosan-Au composites | |
| Wang et al. | Oyster shell derived hydroxyapatite microspheres as an effective adsorbent for remediation of Coomassie brilliant blue |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20200609 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |