CN113135601A - Light response magnetic nano-particle with wettability reversible conversion and preparation method thereof - Google Patents

Light response magnetic nano-particle with wettability reversible conversion and preparation method thereof Download PDF

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CN113135601A
CN113135601A CN202110478671.9A CN202110478671A CN113135601A CN 113135601 A CN113135601 A CN 113135601A CN 202110478671 A CN202110478671 A CN 202110478671A CN 113135601 A CN113135601 A CN 113135601A
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ethanol
wettability
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张卫英
王桂雪
李晓
林畅
毛作东
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Fuzhou University
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G49/00—Compounds of iron
    • C01G49/02—Oxides; Hydroxides
    • C01G49/06—Ferric oxide (Fe2O3)
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
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    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
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    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
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    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • 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 belongs to the technical field of functional materials, and particularly relates to a preparation method of a light-responsive magnetic nanoparticle with wettability and reversible conversion. The method comprises the following steps: fe3O4Preparing magnetic nano particles; SiO 22Coated with Fe3O4Magnetic nanoparticles to obtain Fe3O4@SiO2A nanoparticle; fe3O4@SiO2Amination to give Fe3O4@SiO2‑NH2A nanoparticle; fe3O4@SiO2‑NH2Modification of azobenzene derivative AzoC6 acid to obtain Fe3O4@SiO2‑AzoC6 photo-responsive magnetic nanoparticles. The preparation method is simple, takes the fluorine-free azobenzene derivative as the photoresponse molecule, has low price, less environmental pollution, high photoresponse rate, excellent wettability reversible conversion characteristic, long-term stability, magnetic response performance and convenient recovery.

Description

Light response magnetic nano-particle with wettability reversible conversion and preparation method thereof
Technical Field
The invention belongs to the technical field of functional materials, and particularly relates to a photoresponsive magnetic nanoparticle with wettability and reversible conversion and a preparation method thereof.
Background
Wettability is an important property between solid-liquid contact surfaces. In recent years, research on infiltration materials has attracted extensive attention, and the existing single type infiltration materials cannot meet the requirements of actual production and life, and can respond to infiltration reversible switching materials of external stimuli, namely intelligent response type infiltration materials. In external stimulation, compared with other stimulation such as solvent stimulation, temperature stimulation and the like, light stimulation has the characteristics of no contact, high-precision positioning, low pollution and the like. Therefore, light responsive smart surfaces with wettability reversible conversion are of interest. In addition, the azobenzene derivative containing the fluorocarbon chain is often used for preparing an intelligent responsive infiltrated surface because the surface free energy is extremely low, but the organic matter containing the fluorocarbon chain has certain harm to the environment and is difficult to biodegrade, so that attention needs to be paid.
Disclosure of Invention
The invention aims to provide a photoresponse magnetic nanoparticle with wettability reversible conversion and a preparation method thereof, wherein the wettability of the particle can be reversibly converted between hydrophilic and hydrophobic water under the stimulation of light, and the rapid separation and recovery can be realized under the condition of an external magnetic field; the preparation method is simple and easy to implement, the raw materials are low in price, and the environmental pollution is small.
In order to achieve the purpose, the invention adopts the technical scheme that:
a preparation method of a photoresponse magnetic nanoparticle with wettability reversible conversion comprises the following four steps:
（1）Fe3O4preparing magnetic nanoparticles: FeCl3·6H2Dissolving O and sodium acetate in 30 mL of ethylene glycol, vigorously stirring at room temperature for 0.5-1 h, transferring the mixed solution into a high-pressure reaction kettle, placing the high-pressure reaction kettle in an oven for reaction, cooling to room temperature after the reaction is finished, performing solid-liquid separation by using a magnet, washing with ethanol, washing with water and drying in vacuum to obtain black Fe3O4Magnetic nanoparticles;
（2）SiO2coated with Fe3O4Magnetic nanoparticles: 0.1 g of Fe3O4Adding the magnetic nanoparticles into a mixed solution of 20-50 mL of absolute ethyl alcohol and deionized water, and adding 2.5mL of ammonia water after ultrasonic dispersion; dissolving TEOS in absolute ethanol, and transferring into Fe3O4Stirring the dispersion liquid of the granular ethanol at room temperature for reaction; after the reaction is finished, performing solid-liquid separation by using a magnet, then washing with water and drying in vacuum to obtain Fe3O4@SiO2A nanoparticle;
（3）Fe3O4@SiO2amination of the nanoparticles: 0.1 g of Fe3O4@SiO2Dissolving 3-aminopropyltriethoxysilane APTES (0.0664 g) and toluene (4 mL), ultrasonic treating at 200W for 20 min, reacting in a shaking table, separating solid and liquid with magnet, washing with ethanol, water and vacuum drying to obtain Fe3O4@SiO2-NH2A nanoparticle;
（4）Fe3O4@SiO2-NH2modifying the photoresponsive molecule: 0.1 gFe3O4@SiO2-NH2Adding the nano particles into 3 mL of absolute ethyl alcohol, and performing ultrasonic dispersion; reacting 6- [4- (2-phenylazo) phenoxy]The hexanoic acid AzoC6 acid and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride EDC were dissolved in 5mL of absolute ethanol and then added to Fe3O4@SiO2-NH2Stirring and reacting in the ethanol dispersion liquid; the reaction is finishedThen carrying out solid-liquid separation by using a magnet, washing by using ethanol, washing by using water and drying in vacuum to obtain Fe3O4@SiO2-azo c6 photo-responsive magnetic nanoparticles.
FeCl in step (1)3·6H2The mass ratio of O to sodium acetate is 0.1-2.16.
And (2) placing the mixture in an oven for reaction in the step (1), wherein the temperature of the oven is 160-200 ℃, and the reaction time is 6-12 h.
The volume ratio of the ethanol to the deionized water in the step (2) is 10: 1-2: 1.
And (3) stirring and reacting for 1-5 h in the step (2).
0.2 g Fe in step (2)3O4The magnetic nanoparticles require TEOS in an amount of 200-1000. mu.L.
And (4) putting the mixture into a shaking table for reaction in the step (3), wherein the reaction temperature is 25-55 ℃, and the reaction time is 1-5 h.
The molar ratio of azoC6 acid to EDC in step (4) was 1: 10.
The reaction temperature of the stirring reaction in the step (4) is 25-55 ℃, and the reaction time is 14-20 h.
The structural formula of the azo C6 acid of the 6- [4- (2-phenylazo) phenoxy ] hexanoic acid in the step (4) is as follows:
Figure DEST_PATH_IMAGE002
(ii) a Specific preparation methods reference is made to the Synthesis of liquid-crystalline poly (meth) acrylates with
4-fluoro-azo-benzene-genic side-groups, Journal of Fluorine Chemistry 74 (1995) 185-189 and the literature Synthesis of a nitride functionalized stage-like polymeric compound as a high halogen effect nitride source and catalyst for the catalysis of the excitation of amines and substoice factors Synthesis of azo compounds of azo dye under solution-free conditions, Dyes and Pigments 117 (2015) 64-71.
The invention adopts a one-step solvothermal method to synthesize Fe with magnetic response3O4Nanoparticles, then passing through sol-gelIn the presence of Fe3O4The nano particles are coated with a layer of SiO2To obtain Fe3O4@SiO2Nanoparticles followed by APTES modification of Fe3O4@SiO2Obtaining the nano-particle Fe with amino groups on the surface3O4@SiO2-NH2Then the carboxyl of azobenzene reacts with the amino on the silicon dioxide coated ferroferric oxide after amination, and azobenzene derivative AzoC6 acid is grafted to obtain the nano-particle Fe with optical response and magnetic response3O4@SiO2-AzoC 6. EDC activates carboxyl on azobenzene to make it take part in reaction easily.
Compared with the prior art, the invention has the following advantages:
1. the light response magnetic nano-particles with wettability reversible conversion are prepared by adopting a sol-gel method on Fe3O4The surface of the nano-particles is coated with a layer of SiO2Improve Fe3O4The polymer has the defects of easy agglomeration and easy oxidation, and the stability is improved;
2. the photoresponse magnetic nanoparticle with wettability and reversible conversion has the advantages that the static Water Contact Angle (WCA) under Vis irradiation is 145.3 degrees, the magnetic nanoparticle is hydrophobic, the WCA is changed into 75.6 degrees after UV irradiation, the magnetic nanoparticle is hydrophilic, the hydrophobicity is restored after Vis irradiation, and the photoresponse magnetic nanoparticle has stable hydrophilic-hydrophobic reversible conversion characteristics;
3. the photoresponse magnetic nano-particle with wettability and reversible conversion has the advantages of simple preparation method, low price and less environmental pollution by taking the derivative without fluorine azobenzene as a photoresponse molecule, and magnetic response performance, and can be rapidly gathered around a magnet under the condition of an external magnetic field, thereby being convenient for recovery.
Drawings
FIG. 1 is a scanning electron micrograph of the surface of a photoresponsive magnetic nanoparticle with reversibly convertible wettability, magnified 10000 times.
Fig. 2 shows the reversible switching of WCA under Vis and UV alternating illumination of photoresponsive magnetic nanoparticles with wettability reversible switching.
FIG. 3 is a graph showing a comparison of the rapid concentration of photo-responsive magnetic nanoparticles having wettability reversible switching around a magnetite when dispersed in ethanol in the absence of an applied magnetic field (a) and in the presence of an applied magnetic field (b).
Detailed Description
In order to make the present invention easier to understand, the following examples will further illustrate the present invention, but the scope of the present invention is not limited to these examples.
The WCA measuring method of the invention for the light response magnetic nano-particles with wettability and reversible conversion comprises the following steps:
the invention adopts a video contact angle tester to measure the contact angle: and (3) taking 5 mu L of deionized water as a liquid drop, and measuring the contact angle by adopting an angulometry after the liquid drop is stabilized on the surface of the nano-particles for 60 s.
Example 1
(1) 1.08 g FeCl was weighed3·6H2Dissolving O and 3.0 g of sodium acetate in 30 mL of ethylene glycol, stirring at room temperature for 30 min, transferring the mixed solution into a high-pressure reaction kettle, placing the high-pressure reaction kettle into an oven, setting the temperature to be 200 ℃, reacting for 8 h, cooling the high-pressure reaction kettle to room temperature, and using Fe3O4The magnetism of (2) is subjected to solid-liquid separation by using a magnet, and is washed three times by using deionized water and ethanol respectively. After the cleaning is finished, the mixture is placed into a vacuum environment at 50 ℃ for drying for 10 h to obtain dry black Fe3O4And (3) nanoparticles.
(2) 0.1 g of Fe was weighed3O4And dispersing the particles in a mixed solution of 40 mL of absolute ethyl alcohol and 10 mL of deionized water, ultrasonically dispersing for 30 min, adding 2.5mL of ammonia water, and placing on a magnetic stirrer to stir for 10 min. 200 mul TEOS is measured and put into 10 mL absolute ethyl alcohol, and the absolute ethyl alcohol is transferred into Fe by a rubber dropper3O4The stirring was continued for 2 h at room temperature in a dispersion of particulate ethanol and deionized water. After the reaction, the magnetic powder was subjected to solid-liquid separation with a magnet, and washed with deionized water five times. After the cleaning, the mixture is put into a vacuum oven at 50 ℃ for drying for 10 hours, and the dried Fe powder is taken out to obtain the dried Fe powder3O4@SiO2。
(3) 0.1 g of Fe was weighed3O4@SiO2And 0.0664g of APTES in 4 mL of toluene, placing the mixture into a shaking table after ultrasonic treatment for 20 min, reacting for 1 h at room temperature, performing solid-liquid separation by using a magnet for powder magnetism, and washing with ethanol for three times and twice by using deionized water. After the cleaning is finished, putting the mixture into a vacuum drying chamber at 50 ℃ for 10 h to obtain dry black powdery Fe3O4@SiO2-NH2。
(4) 0.1 g of Fe was weighed3O4@SiO2-NH2Dispersing in 3 mL of absolute ethyl alcohol, and carrying out ultrasonic dispersion treatment for 20 min. 0.048 g of AzoC6 acid and 0.2876 g of EDC were weighed out, dissolved in 5mL of absolute ethanol, and then added to Fe3O4@SiO2-NH2In the ethanol dispersion, the temperature was set at 25 deg.C, stirring was continued for 18 h, and then solid-liquid separation was carried out with magnetite using the magnetism of the powder, as shown in FIG. 3, the resulting product was allowed to rapidly gather around the magnetite under an applied magnetic field, and washed with ethanol three times and twice with deionized water. After the cleaning is finished, putting the mixture into a vacuum drying chamber at 50 ℃ for 10 h to obtain dry black powdery Fe3O4@SiO2-AzoC6。Fe3O4@SiO2After 30 min of irradiation with visible light, the AzoC6 measured the contact angle of a static water drop on the surface to be 145 °, after 30 min of irradiation with ultraviolet light, the contact angle of a static water drop was 75 °, and the wettability response range was 70 °.
Comparative example 1
(1) 1.08 g FeCl was weighed3·6H2Dissolving O and 3.0 g of sodium acetate in 30 mL of ethylene glycol, stirring at room temperature for 30 min, transferring the mixed solution into a high-pressure reaction kettle, placing the high-pressure reaction kettle into an oven, setting the temperature to be 200 ℃, reacting for 8 h, cooling the high-pressure reaction kettle to room temperature, and using Fe3O4The magnetism of (2) is subjected to solid-liquid separation by using a magnet, and is washed three times by using deionized water and ethanol respectively. After the cleaning is finished, the mixture is placed into a vacuum environment at 50 ℃ for drying for 10 h to obtain dry black Fe3O4And (3) nanoparticles.
(2) 0.1 g of Fe was weighed3O4And 0.0664g of APTES in 4 mL of toluene, placing the mixture into a shaking table after ultrasonic treatment for 20 min, reacting for 1 h at room temperature, performing solid-liquid separation by using a magnet for powder magnetism, and washing with ethanol for three times and twice by using deionized water. After the cleaning is finished, putting the mixture into a vacuum drying chamber at 50 ℃ for 10 h to obtain dry black powdery Fe3O4-NH2。
(3) 0.1 g of Fe was weighed3O4-NH2Dispersing in 3 mL of absolute ethyl alcohol, and carrying out ultrasonic dispersion treatment for 20 min. 0.048 g of AzoC6 acid and 0.2876 g of EDC were weighed out, dissolved in 5mL of absolute ethanol, and then added to Fe3O4-NH2And (3) in the ethanol dispersion liquid, setting the temperature to 25 ℃, continuously stirring for 18 h, performing solid-liquid separation by using a magnet for magnetism of powder, quickly gathering the obtained product around the magnet under an external magnetic field, and washing with ethanol for three times and twice by using deionized water. After the cleaning is finished, putting the mixture into a vacuum drying chamber at 50 ℃ for 10 h to obtain dry black powdery Fe3O4-AzoC6。Fe3O4After 30 min of irradiation with visible light, the AzoC6 measured the contact angle of a static water drop on the surface to be 115 °, after 30 min of irradiation with ultraviolet light, the contact angle of a static water drop was 76 °, and the wettability response range was 39 °.
Comparative example 1 for Fe prepared3O4Without SiO coating2Directly carrying out amination by using a silane coupling agent APTES and then directly reacting with AzoC6 acid. Fe prepared in example 13O4@SiO2The contact angle change range of the static water drop of the azo C6 after the irradiation of visible light and ultraviolet light is obviously wider than that of the Fe prepared in the comparative example 13O4The contact angle of the static water drop of the azo C6 after irradiation of visible light and ultraviolet light is large because of the Fe3O4Wrapping SiO2Post-increasing the particle size and increasing Fe3O4Stability of (3), hydrolytic condensation of more APTES to-NH2Modified to SiO2Surface, illustrating the coated SiO of the invention2Is very critical.
Example 2
(1) 1.08 g FeCl was weighed3·6H2Dissolving O and 3.0 g of sodium acetate in 30 mL of ethylene glycol, stirring at room temperature for 1 h, transferring the mixed solution into a high-pressure reaction kettle, placing the high-pressure reaction kettle into an oven, setting the temperature to be 160 ℃, reacting for 12 h, cooling the high-pressure reaction kettle to room temperature, and using Fe3O4The magnetism of (2) is subjected to solid-liquid separation by using a magnet, and is washed three times by using deionized water and ethanol respectively. After the cleaning is finished, the mixture is placed into a vacuum environment at 50 ℃ for drying for 10 h to obtain dry black Fe3O4And (3) nanoparticles.
(2) 0.1 g of Fe was weighed3O4And dispersing the particles in a mixed solution of 10 mL of absolute ethyl alcohol and 10 mL of deionized water, ultrasonically dispersing for 30 min, adding 2.5mL of ammonia water, and placing on a magnetic stirrer to stir for 10 min. Measuring 100 mu L TEOS, placing in 10 mL absolute ethyl alcohol, transferring into Fe with rubber dropper3O4The stirring was continued for 2 h at room temperature in a dispersion of particulate ethanol and deionized water. After the reaction, the magnetic powder was subjected to solid-liquid separation with a magnet, and washed with deionized water five times. After the cleaning, the mixture is put into a vacuum oven at 50 ℃ for drying for 10 hours, and the dried Fe powder is taken out to obtain the dried Fe powder3O4@SiO2。
(3) 0.1 g of Fe was weighed3O4@SiO2And 0.0664g of APTES in 4 mL of toluene, placing the mixture into a shaking table after ultrasonic treatment for 20 min, reacting for 1 h at room temperature, performing solid-liquid separation by using a magnet for powder magnetism, and washing with ethanol for three times and twice by using deionized water. After the cleaning is finished, putting the mixture into a vacuum drying chamber at 50 ℃ for 10 h to obtain dry black powdery Fe3O4@SiO2-NH2。
(4) 0.1 g of Fe was weighed3O4@SiO2-NH2Dispersing in 3 mL of absolute ethyl alcohol, and carrying out ultrasonic dispersion treatment for 20 min. 0.048 g of AzoC6 acid and 0.2876 g of EDC were weighed out, dissolved in 5mL of absolute ethanol, and then added to Fe3O4@SiO2-NH2In the ethanol dispersion, the temperature was set at 25 deg.CAfter stirring for 18 h, performing solid-liquid separation by using the magnetism of the powder and using a magnet to obtain a product which can be rapidly gathered around the magnet under an external magnetic field, and washing the product three times by using ethanol and twice by using deionized water. After washing, the mixture was dried in vacuum at 50 ℃ for 10 hours to obtain dry black powder Fe3O4@SiO2-AzoC6。Fe3O4@SiO2After 30 min of irradiation with visible light, AzoC6 measured the contact angle of a static drop of water on the surface at 142 °, after 30 min of irradiation with uv light, measured the contact angle of a static drop of water at 74 °, and the wettability response range at 68 °.
Example 3
(1) 1.08 g FeCl was weighed3·6H2Dissolving O and 3.0 g of sodium acetate in 30 mL of ethylene glycol, stirring at room temperature for 30 min, transferring the mixed solution into a high-pressure reaction kettle, placing the high-pressure reaction kettle into an oven, setting the temperature to be 200 ℃, reacting for 6 h, cooling the high-pressure reaction kettle to room temperature, and using Fe3O4The magnetism of (2) is subjected to solid-liquid separation by using a magnet, and is washed three times by using deionized water and ethanol respectively. After the cleaning is finished, the mixture is placed into a vacuum environment at 50 ℃ for drying for 10 h to obtain dry black Fe3O4And (3) nanoparticles.
(2) 0.1 g of Fe was weighed3O4And dispersing the particles in a mixed solution of 30 mL of absolute ethyl alcohol and 15mL of deionized water, ultrasonically dispersing for 30 min, adding 2.5mL of ammonia water, and placing on a magnetic stirrer to stir for 10 min. Measuring 100 mu L TEOS, placing in 10 mL absolute ethyl alcohol, transferring into Fe with rubber dropper3O4The stirring was continued for 5 h at room temperature in a dispersion of particulate ethanol and deionized water. After the reaction, the magnetic powder was subjected to solid-liquid separation with a magnet, and washed with deionized water five times. After the cleaning, the mixture is put into a vacuum oven at 50 ℃ for drying for 10 hours, and the dried Fe powder is taken out to obtain the dried Fe powder3O4@SiO2。
(3) 0.1 g of Fe was weighed3O4@SiO2And 0.0664g of APTES in 4 mL of toluene, ultrasonically treating for 20 min, placing in a shaking table at room temperature, reacting for 1 hThe powder is subjected to solid-liquid separation by using a magnet and washed twice by using ethanol and deionized water for three times. After the cleaning is finished, putting the mixture into a vacuum drying chamber at 50 ℃ for 10 h to obtain dry black powdery Fe3O4@SiO2-NH2。
(4) 0.1 g of Fe was weighed3O4@SiO2-NH2Dispersing in 3 mL of absolute ethyl alcohol, and carrying out ultrasonic dispersion treatment for 20 min. 0.048 g of AzoC6 acid and 0.2876 g of EDC were weighed out, dissolved in 5mL of absolute ethanol, and then added to Fe3O4@SiO2-NH2And (3) in the ethanol dispersion liquid, setting the temperature to 25 ℃, continuously stirring for 18 h, performing solid-liquid separation by using a magnet for magnetism of powder, quickly gathering the obtained product around the magnet under an external magnetic field, and washing with ethanol for three times and twice by using deionized water. After the cleaning is finished, putting the mixture into a vacuum drying chamber at 50 ℃ for 10 h to obtain dry black powdery Fe3O4@SiO2-AzoC6。Fe3O4@SiO2After 30 min of irradiation with visible light, AzoC6 measured the contact angle of a static water drop on the surface at 143 °, after 30 min of irradiation with ultraviolet light, measured the contact angle of a static water drop at 77 °, and the wettability response range at 66 °.
Example 4
(1) 1.08 g FeCl was weighed3·6H2Dissolving O and 10.8 g of sodium acetate in 30 mL of ethylene glycol, stirring at room temperature for 30 min, transferring the mixed solution into a high-pressure reaction kettle, placing the high-pressure reaction kettle into an oven, setting the temperature to be 180 ℃, reacting for 8 h, cooling the high-pressure reaction kettle to room temperature, and using Fe3O4The magnetism of (2) is subjected to solid-liquid separation by using a magnet, and is washed three times by using deionized water and ethanol respectively. After the cleaning is finished, the mixture is placed into a vacuum environment at 50 ℃ for drying for 10 h to obtain dry black Fe3O4And (3) nanoparticles.
(2) 0.1 g of Fe was weighed3O4And dispersing the particles in a mixed solution of 40 mL of absolute ethyl alcohol and 10 mL of deionized water, ultrasonically dispersing for 30 min, adding 2.5mL of ammonia water, and placing on a magnetic stirrer to stir for 10 min. 1000 mul TEOS is measured and put into 10 mL absolute ethyl alcoholIn the middle, the Fe-Fe alloy is transferred to Fe by a rubber head dropper3O4The stirring was continued for 2 h at room temperature in a dispersion of particulate ethanol and deionized water. After the reaction, the magnetic powder was subjected to solid-liquid separation with a magnet, and washed with deionized water five times. After the cleaning, the mixture is put into a vacuum oven at 50 ℃ for drying for 10 hours, and the dried Fe powder is taken out to obtain the dried Fe powder3O4@SiO2。
(3) 0.1 g of Fe was weighed3O4@SiO2And 0.0664g of APTES in 4 mL of toluene, placing the mixture into a shaking table after ultrasonic treatment for 20 min, reacting for 1 h at room temperature, performing solid-liquid separation by using a magnet for powder magnetism, and washing with ethanol for three times and twice by using deionized water. After the cleaning is finished, putting the mixture into a vacuum drying chamber at 50 ℃ for 10 h to obtain dry black powdery Fe3O4@SiO2-NH2。
(4) 0.1 g of Fe was weighed3O4@SiO2-NH2Dispersing in 3 mL of absolute ethyl alcohol, and carrying out ultrasonic dispersion treatment for 20 min. 0.048 g of AzoC6 acid and 0.2876 g of EDC were weighed out, dissolved in 5mL of absolute ethanol, and then added to Fe3O4@SiO2-NH2And (3) in the ethanol dispersion liquid, setting the temperature to 25 ℃, continuously stirring for 14 h, performing solid-liquid separation by using a magnet for magnetism of powder, quickly gathering the obtained product around the magnet under an external magnetic field, and washing with ethanol for three times and twice by using deionized water. Performing solid-liquid separation by using powder magnetism and using a magnet, and washing the powder with ethanol for three times and washing the powder with deionized water for two times. After washing, the mixture was dried in vacuum at 50 ℃ for 10 hours to obtain dry black powder Fe3O4@SiO2-AzoC6。Fe3O4@SiO2After 30 min of irradiation of the azo c6 with visible light, the contact angle of the static water drop on the measurement surface was 146 °, after 30 min of irradiation with ultraviolet light, the contact angle of the static water drop was 82 °, and the wettability response range was 64 °.
Example 5
(1) 1.08 g FeCl was weighed3·6H2O and 0.5 g of ethyleneDissolving sodium acid in 30 mL of ethylene glycol, stirring at room temperature for 30 min, transferring the mixed solution into a high-pressure reaction kettle, placing the high-pressure reaction kettle into an oven, setting the temperature at 200 ℃, reacting for 8 h, cooling the high-pressure reaction kettle to room temperature, and then using Fe3O4The magnetism of (2) is subjected to solid-liquid separation by using a magnet, and is washed three times by using deionized water and ethanol respectively. After the cleaning is finished, the mixture is placed into a vacuum environment at 50 ℃ for drying for 10 h to obtain dry black Fe3O4And (3) nanoparticles.
(2) 0.1 g of Fe was weighed3O4And dispersing the particles in a mixed solution of 40 mL of absolute ethyl alcohol and 4 mL of deionized water, ultrasonically dispersing for 30 min, adding 2.5mL of ammonia water, and placing on a magnetic stirrer to stir for 10 min. Measuring 150 mu L TEOS, placing into 10 mL absolute ethyl alcohol, transferring into Fe with rubber dropper3O4The stirring was continued for 2 h at room temperature in a dispersion of particulate ethanol and deionized water. After the reaction, the magnetic powder was subjected to solid-liquid separation with a magnet, and washed with deionized water five times. After the cleaning, the mixture is put into a vacuum oven at 50 ℃ for drying for 10 hours, and the dried Fe powder is taken out to obtain the dried Fe powder3O4@SiO2。
(3) 0.1 g of Fe was weighed3O4@SiO2And 0.0664g of APTES in 4 mL of toluene, placing the mixture into a shaking table after ultrasonic treatment for 20 min, reacting for 1 h at room temperature, performing solid-liquid separation by using a magnet for powder magnetism, and washing with ethanol for three times and twice by using deionized water. After the cleaning is finished, putting the mixture into a vacuum drying chamber at 50 ℃ for 10 h to obtain dry black powdery Fe3O4@SiO2-NH2。
(4) 0.1 g of Fe was weighed3O4@SiO2-NH2Dispersing in 3 mL of absolute ethyl alcohol, and carrying out ultrasonic dispersion treatment for 20 min. 0.048 g of AzoC6 acid and 0.2876 g of EDC were weighed out, dissolved in 5mL of absolute ethanol, and then added to Fe3O4@SiO2-NH2Stirring at 55 deg.C for 20 hr in ethanol dispersion, performing solid-liquid separation with magnetic powder, and collecting the productTo gather around the magnetite rapidly under the applied magnetic field, and wash with ethanol and three times deionized water twice. After the cleaning is finished, putting the mixture into a vacuum drying chamber at 50 ℃ for 10 h to obtain dry black powdery Fe3O4@SiO2-AzoC6。Fe3O4@SiO2After 30 min of irradiation with visible light, the AzoC6 measured the contact angle of a static water drop on the surface at 141 °, after 30 min of irradiation with ultraviolet light, the contact angle of a static water drop was 73 °, and the wettability response range was 68 °.
FIG. 1 illustrates Fe prepared3O4@SiO2-azoC6 is nanoparticle with particle size of about 0.22-0.32 μm.
FIG. 2 illustrates Fe prepared3O4@SiO2The measured static water contact angle of the azo C6 is about 145 degrees after the visible light irradiation for 30 min, and the measured static water contact angle is about 75 degrees after the ultraviolet light irradiation for 30 min, which indicates that the prepared Fe3O4@SiO2The wettability of the azo C6 can realize the conversion in the hydrophilic-hydrophobic range, and the response can be cycled.
FIG. 3 illustrates Fe prepared3O4@ SiO2The azo-C6 can be uniformly dispersed in ethanol and water, and Fe when an external magnetic field is applied3O4@SiO2The azo 6 can be totally and rapidly gathered near the magnetite as shown in the figure (b), and the solution is in a clear state and shows good magnetic field stimulation response performance.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.

Claims (10)

1. A method for preparing optical response magnetic nano particles with wettability reversible conversion is characterized in that Fe is firstly carried out3O4Preparing magnetic nano particles; then made of SiO2Coated with Fe3O4Magnetic nanoparticles to obtain Fe3O4@SiO2A nanoparticle; fe3O4@SiO2Amination to give Fe3O4@SiO2-NH2A nanoparticle; last Fe3O4@SiO2-NH2Modifying light-responsive molecules, in particular by Fe3O4@SiO2-NH2Modified azobenzene derivative 6- [4- (2-phenylazo) phenoxy]The hexanoic acid AzoC6 acid gives Fe3O4@SiO2-azo c6 photo-responsive magnetic nanoparticles.
2. The method of claim 1, wherein the Fe is selected from the group consisting of Fe, Mn3O4Preparing magnetic nanoparticles: FeCl3·6H2Dissolving O and sodium acetate in 30 mL of ethylene glycol, vigorously stirring at room temperature for 0.5-1 h, transferring the mixed solution into a high-pressure reaction kettle, placing the high-pressure reaction kettle in an oven for reaction, cooling to room temperature after the reaction is finished, performing solid-liquid separation by using a magnet, washing with ethanol, washing with water and drying in vacuum to obtain black Fe3O4Magnetic nanoparticles.
3. The method of claim 2, wherein FeCl is used as a material for preparing the photo-responsive magnetic nanoparticles with wettability reversible conversion3·6H2The mass ratio of O to sodium acetate is 0.1-2.16; wherein the reaction conditions in the oven are as follows: the temperature of the oven is 160-200 ℃, and the reaction time is 6-12 h.
4. The method of claim 1, wherein the SiO is in the form of a porous silica film2Coated with Fe3O4Magnetic nanoparticles: 0.1 g of Fe3O4Adding the magnetic nanoparticles into a mixed solution of 20-50 mL of absolute ethyl alcohol and deionized water, and adding 2.5mL of ammonia water after ultrasonic dispersion; tetraethyl orthosilicate TEOS is dissolved in absolute ethyl alcohol and is transferred into Fe3O4Stirring and reacting in the dispersion liquid of the granular ethanol; after the reaction is finished, performing solid-liquid separation by using a magnet, then washing with water and drying in vacuum to obtain Fe3O4@SiO2Nano-particlesAnd (4) granulating.
5. The method for preparing the light-responsive magnetic nanoparticle with wettability and reversible conversion as claimed in claim 4, wherein the volume ratio of ethanol to deionized water is 10: 1-2: 1; stirring and reacting for 1-5 h; 0.2 g Fe3O4The magnetic nanoparticles require TEOS in an amount of 200-1000. mu.L.
6. The method of claim 1, wherein the Fe is selected from the group consisting of Fe, Mn3O4@SiO2Amination of (a): 0.1 g of Fe3O4@SiO2Dissolving 0.0664g of 3-aminopropyl triethoxy APTES in toluene, performing ultrasonic treatment, placing in a shaking table for reaction, performing solid-liquid separation by using a magnet after the reaction is finished, and then washing by ethanol, washing by water and drying in vacuum to obtain Fe3O4@SiO2-NH2And (3) nanoparticles.
7. The method for preparing the photoresponsive magnetic nanoparticle with wettability and reversible conversion according to claim 6, wherein the ultrasonic treatment is specifically as follows: the power is 200W, and the time is 20 min later; and reacting in the shaking table at the temperature of 25-55 ℃ for 1-5 h.
8. The method of claim 1, wherein the Fe is selected from the group consisting of Fe, Mn3O4@SiO2-NH2Modifying the photoresponsive molecule: 0.1 g of Fe3O4@SiO2-NH2Adding the nano particles into 3 mL of absolute ethyl alcohol, and performing ultrasonic dispersion; reacting 6- [4- (2-phenylazo) phenoxy]The hexanoic acid AzoC6 acid and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride EDC were dissolved in 5mL of absolute ethanol and then added to Fe3O4@SiO2-NH2Stirring and reacting in the ethanol dispersion liquid; after the reaction is finished, carrying out solid-liquid separation by using a magnet, and then carrying out ethanol treatmentWashing, water washing and vacuum drying to obtain Fe3O4@SiO2-azo c6 photo-responsive magnetic nanoparticles.
9. The method for preparing the photo-responsive magnetic nanoparticles with wettability reversible conversion according to claim 8, wherein the molar ratio of AzoC6 acid to EDC is 1: 10; the stirring reaction temperature is 25-55 ℃, and the reaction time is 14-20 h.
10. A photo-responsive magnetic nanoparticle having wettability reversible switching obtained by the method of any one of claims 1 to 9.
CN202110478671.9A 2021-04-30 2021-04-30 Light response magnetic nano-particle with wettability reversible conversion and preparation method thereof Pending CN113135601A (en)

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20160114476A (en) * 2015-03-24 2016-10-05 부산대학교 산학협력단 DUAL STIMULI-RESPONSIVE CORE-SHELL MAGNETIC NANOPARTICLE HAVING UV-LIGHT RESPONSIVITY AND pH-RESPONSIVITY, AND DRUG DELIVERY COMPISING THE SAME

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20160114476A (en) * 2015-03-24 2016-10-05 부산대학교 산학협력단 DUAL STIMULI-RESPONSIVE CORE-SHELL MAGNETIC NANOPARTICLE HAVING UV-LIGHT RESPONSIVITY AND pH-RESPONSIVITY, AND DRUG DELIVERY COMPISING THE SAME

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
KATHRIN ISENBÜGEL ET AL.: ""Photo-Switchable Behavior of Azobenzene-Dye-Modifi ed Silica Nanoparticles and Their Assembly With Cyclodextrin Derivatives"", 《MACROMOL. CHEM. PHYS.》 *

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Application publication date: 20210720