CN112341859A - Polydopamine modified tungsten doped vanadium dioxide nanoparticle composite intelligent temperature control coating and preparation method thereof - Google Patents
Polydopamine modified tungsten doped vanadium dioxide nanoparticle composite intelligent temperature control coating and preparation method thereof Download PDFInfo
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- 229910021542 Vanadium(IV) oxide Inorganic materials 0.000 title claims abstract description 84
- GRUMUEUJTSXQOI-UHFFFAOYSA-N vanadium dioxide Chemical compound O=[V]=O GRUMUEUJTSXQOI-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 63
- 229920001690 polydopamine Polymers 0.000 title claims abstract description 38
- 150000003657 tungsten Chemical class 0.000 title claims abstract description 19
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- 238000000576 coating method Methods 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
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- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 28
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- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 14
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- 238000000137 annealing Methods 0.000 claims abstract description 12
- 239000007853 buffer solution Substances 0.000 claims abstract description 10
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 10
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229960001149 dopamine hydrochloride Drugs 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 27
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims description 26
- 239000011259 mixed solution Substances 0.000 claims description 16
- MUBZPKHOEPUJKR-UHFFFAOYSA-N oxalic acid group Chemical group C(C(=O)O)(=O)O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- 229960003638 dopamine Drugs 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 238000009210 therapy by ultrasound Methods 0.000 claims description 10
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 claims description 10
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical group O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 235000019441 ethanol Nutrition 0.000 claims description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims description 8
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 8
- FSJSYDFBTIVUFD-SUKNRPLKSA-N (z)-4-hydroxypent-3-en-2-one;oxovanadium Chemical compound [V]=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FSJSYDFBTIVUFD-SUKNRPLKSA-N 0.000 claims description 5
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 5
- 235000006408 oxalic acid Nutrition 0.000 claims description 5
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 5
- UUUGYDOQQLOJQA-UHFFFAOYSA-L vanadyl sulfate Chemical group [V+2]=O.[O-]S([O-])(=O)=O UUUGYDOQQLOJQA-UHFFFAOYSA-L 0.000 claims description 5
- 229940041260 vanadyl sulfate Drugs 0.000 claims description 5
- 229910000352 vanadyl sulfate Inorganic materials 0.000 claims description 5
- 235000019445 benzyl alcohol Nutrition 0.000 claims description 3
- HPLXJFZCZSBAAH-UHFFFAOYSA-N [V+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] Chemical compound [V+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] HPLXJFZCZSBAAH-UHFFFAOYSA-N 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 3
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- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 4
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- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G31/00—Compounds of vanadium
- C01G31/02—Oxides
Abstract
A preparation method of polydopamine modified tungsten doped vanadium dioxide nanoparticle composite intelligent temperature control coating comprises the following steps: mixing a vanadium source solution containing a reducing agent with a tungsten source solution containing hydrogen peroxide, carrying out hydrothermal reaction, drying a product, and carrying out high-temperature annealing treatment to obtain tungsten-doped vanadium dioxide; dispersing tungsten-doped vanadium dioxide in water, adding a buffer solution to adjust the pH value to 7.5-9.5, then adding dopamine hydrochloride with different mass ratios, and stirring for reaction to obtain the polydopamine modified tungsten-doped vanadium dioxide nanoparticles. The preparation method can obtain the polydopamine modified tungsten doped vanadium dioxide nano particle composite intelligent temperature control coating with high purity, uniform particle size distribution, high photo-thermal conversion efficiency, good biocompatibility, good dispersibility and strong adhesion.
Description
Technical Field
The invention belongs to the technical field of functional materials and nano materials, and particularly relates to a preparation method of a polydopamine modified tungsten doped vanadium dioxide nano particle composite intelligent temperature control coating.
Background
Vanadium dioxide is a thermochromic material with semiconductor-metal phase transition characteristics, and the phase transition temperature of pure vanadium dioxide is 68 ℃. The reversible transformation of infrared and near infrared from transmission to reflection is caused by the structural change before and after the phase change, so that the material has good thermochromic performance and excellent photo-thermal conversion performance. The method has wide application value in the fields of intelligent coating, optical storage equipment, infrared radiation detection and the like.
The preparation method of the vanadium dioxide mainly comprises a thermal decomposition method, a sol-gel method and a hydrothermal method. Wherein, the hydrothermal method is completed in a single reaction step due to simple preparation operation process and easy control, and the product has high purity. And the hydrothermal reaction is carried out in a closed reaction kettle, so that the side reaction between the volatilized toxic substances and sensitive gas in the air can be effectively prevented, the preparation process is non-toxic and harmless, and the method is more environment-friendly, and is the most extensive method for preparing vanadium dioxide.
The application range of vanadium dioxide is greatly limited due to the higher phase transition temperature of vanadium dioxide. In order to widen the application field of the material, the material has a reversible conversion function from transmission to reflection of infrared and near infrared at room temperature, and the reduction of the phase transition temperature becomes one of important ways. Research shows that the phase transition temperature of vanadium dioxide can be effectively reduced to room temperature by an atomic doping method, wherein the effect of reducing the phase transition temperature by tungsten doping is most obvious. Therefore, the preparation of the tungsten-doped vanadium dioxide nano particles by a hydrothermal method has important significance.
Disclosure of Invention
The invention aims to provide a preparation method of polydopamine modified tungsten doped vanadium dioxide nanoparticle composite intelligent temperature control coating, and solves the problems of complex preparation process and low modification efficiency in the prior art. The technical scheme adopted by the invention is a preparation method of the polydopamine modified tungsten-doped vanadium dioxide nanoparticle composite intelligent temperature control coating, wherein a hydrothermal method is utilized to mix oxalic acid and reduce vanadium pentoxide to prepare vanadium dioxide, tungsten atoms are introduced by adding tungstic acid, annealing treatment is carried out after the reaction is finished, finally tungsten-doped vanadium dioxide nano powder is obtained, then dopamine aqueous solution is added to adjust PH, so that autopolymerization is initiated, and the polydopamine modified tungsten-doped vanadium dioxide nanoparticle is obtained.
The invention adopts the technical scheme that polydopamine modified tungsten-doped vanadium dioxide nanoparticles are prepared by a hydrothermal method, and the preparation method is implemented according to the following steps:
step 1: dissolving the weighed vanadium source in water, adding a reducing agent, and uniformly stirring to obtain a vanadium source solution reduced by the reducing agent;
step 2: dissolving the weighed tungsten source in a hydrogen peroxide solution, and performing ultrasonic treatment to obtain a tungsten source solution;
and step 3: adding the tungsten source solution obtained in the step 2 into the vanadium source solution obtained in the step 1, and uniformly stirring to obtain a mixed solution;
and 4, step 4: transferring the mixed solution obtained in the step (3) into a reaction kettle, and carrying out hydrothermal reaction to obtain a hydrothermal product;
and 5: the hydrothermal product obtained in the step (4) is washed by water and ethanol in a cross mode, and the product is placed in a drying oven to obtain a dried product;
step 6: carrying out high-temperature annealing treatment on the dried product obtained in the step 5 to obtain tungsten-doped vanadium dioxide nano powder;
and 7: dispersing the product obtained in the step 6 in a dilute nitric acid aqueous solution, washing with absolute ethyl alcohol, and centrifugally drying to obtain nano particles;
and 8: and (4) dispersing the nano powder obtained in the step (7) in deionized water, adding a buffer solution, adjusting the pH value, adding dopamine hydrochloride with different mass ratios, stirring to react completely, and centrifugally drying to obtain the polydopamine modified tungsten-doped vanadium dioxide nano particles.
The invention is also characterized in that:
the vanadium source is vanadium pentoxide, vanadyl acetylacetonate, ammonium metavanadate, vanadyl sulfate and triisopropoxyl vanadium oxide;
the reducing agent is oxalic acid, acetic acid, phthalic acid, citric acid, and benzyl alcohol;
the tungsten source is tungstic acid, sodium tungstate, ammonium tungstate or tungsten trioxide;
the PH value of the system is 7.5-9.5;
the mass ratio of dopamine to tungsten doped vanadium dioxide is 1:1, 2:1, 3:1 and 4: 1;
in step 1: controlling the temperature to be 40-80 ℃, and stirring for 20-60 min;
in step 2: controlling the temperature to be 30-70 ℃, and carrying out ultrasonic treatment for 10-50 min;
in step 3: controlling the temperature to be 40-80 ℃, and stirring for 0.5-2.5 h;
in step 4: the temperature is controlled to be 180-260 ℃, and the heating time is 5-9 h;
in step 5: the temperature is controlled to be 60-80 ℃, and the heating time is 6-12 h;
in step 6: the temperature is controlled to be 450-750 ℃, and the heating time is 1-5 h;
in step 7: the temperature is controlled to be 20-50 ℃, and the heating time is 1-4 h;
in step 8: controlling the pH value to be 7.5-9.5, controlling the dosage of dopamine to be 0.05-0.2 weight part, controlling the temperature to be 30-60 ℃, and heating for 12-36 hours;
the polydopamine modified tungsten doped vanadium dioxide nano particle prepared by the invention can be used for modifying polyurethane solid-solid phase change materials, and the modification effect can be seen in figure 3.
The invention has the beneficial effects that:
(1) according to the preparation method of the polydopamine modified tungsten doped vanadium dioxide nanoparticle composite intelligent temperature control coating, water is used as a solvent in a hydrothermal process, the polydopamine modified tungsten doped vanadium dioxide nanoparticle composite intelligent temperature control coating is non-toxic and pollution-free, the reaction efficiency can be improved, the modification conditions are mild, and the high-purity polydopamine modified tungsten doped vanadium dioxide nanoparticle composite intelligent temperature control coating can be obtained.
(2) The invention discloses a preparation method of polydopamine modified tungsten doped vanadium dioxide nanoparticle composite intelligent temperature control coating. By using a hydrothermal method, the reaction is milder and is easy to control, and the obtained product has uniform particle size. The selected tungsten source is added in the form of tungstic acid, the operation is simple and more economic, tungsten ions are ions with the highest efficiency of reducing the phase transition temperature by ion doping at present, and VO can be obviously improved after W doping2The thermochromic properties of the material. Dopamine as a biomass material has the characteristics of safety, environmental protection, good biocompatibility, photothermal conversion and the like, and has strong adhesion effectThe result is advantageous dispersion into the polymer matrix.
(3) The dispersion stability of the tungsten-doped vanadium dioxide nano particles in the polymer is poor, so that the thermochromism performance and the photothermal conversion performance of the tungsten-doped vanadium dioxide nano particles are easily reduced. Polydopamine as a substance with super-strong adhesion property can be modified on various organic or inorganic solid surfaces so as to be more easily dispersed in a polymer body, so that the polydopamine has wide application prospect in many fields. The basic principle is that dopamine is polymerized in an alkaline (PH = 8.5) aqueous solution to form a polydopamine membrane structure with strong adhesion property on the surface of a substrate, and the surface of the polydopamine polymerized and deposited membrane can chemically react with a plurality of active groups such as sulfydryl, amino and metal ions to obtain a functionalized surface. The polydopamine coating is formed by polymerizing dopamine on the surface of the polydopamine modified tungsten-doped vanadium dioxide nanoparticles, so that the dispersibility of the tungsten-doped vanadium dioxide nanoparticles in the polymer can be greatly improved, and the material has good thermochromic performance and biocompatibility.
Drawings
FIG. 1 is a DSC curve comparison of vanadium dioxide before and after tungsten doping; (a) vanadium dioxide undoped with tungsten, (b) vanadium dioxide doped with tungsten. As can be seen from the graph, the phase transition temperature after doping tungsten is significantly lowered because the addition of W atom changes VO2The crystal structure of the vanadium dioxide reduces the phase transition temperature of the vanadium dioxide.
FIG. 2 is a comparison of UV-VIS-IR transmittance curves for different films; the dotted line represents 90 ℃ and the solid line 25 ℃. As can be seen from the figure, the optical transmittance of the blank film at low temperature is about 80%, the optical transmittance of the vanadium dioxide nanoparticle film is about 60%, the optical transmittance of the tungsten-doped vanadium dioxide nanoparticle film is about 55%, the optical transmittance of the polydopamine-coated tungsten-doped vanadium dioxide nanoparticle film at a wavelength of more than 1300nm is about 70%, and the optical transmittance at a wavelength of less than 1300nm is about 40%.
At high temperature, the light transmittance of the blank film is almost unchanged, and the vanadium dioxide nano particle film and the tungsten doped vanadium dioxide nano particle film are polishedThe optical transmittance is obviously reduced to about 20 percent, and the optical transmittance of the polydopamine-coated tungsten-doped vanadium dioxide nano particle film is also reduced. This is because the addition of W atom changes VO2The optical transmittance of the crystal structure of the tungsten-doped vanadium dioxide nano particles to infrared wavelength light is lower than that of pure vanadium dioxide, and in addition, the crystal structure of the tungsten-doped vanadium dioxide nano particles at high temperature has a transformation, so that infrared light is reflected at high temperature and the infrared light is transmitted at low temperature.
FIG. 3 shows the results of temperature adjustment tests of the polydopamine-coated tungsten-doped vanadium dioxide-modified PUPCM and the linear PUPCM under simulated sunlight.
Wherein a is a time-temperature change curve of the polydopamine-coated tungsten-doped vanadium dioxide modified PUPCM finished fabric, and b is a time-temperature change curve of the PUPCM finished fabric. c is the time-temperature curve of the unfinished fabric. In the heating process, the heating rate of the polydopamine-coated tungsten-doped vanadium dioxide modified PUPCM finished fabric is obviously higher than that of the PUPCM, the finished fabric and the unfinished fabric, and the temperature difference is about 8 ℃ at most; in the cooling process, the cooling rate of the unfinished fabric is obviously higher than that of the fabric finished by the polydopamine-coated tungsten-doped vanadium dioxide modified PUPCM, and the temperature difference is about 7 ℃ at most.
Detailed Description
The present invention will be described in detail with reference to the following embodiments.
The invention discloses a preparation method of polydopamine modified tungsten doped vanadium dioxide nanoparticle composite intelligent temperature control coating, which is implemented according to the following steps:
step 1, dissolving a weighed vanadium source in water, adding a reducing agent, and uniformly stirring to obtain a vanadium source solution reduced by the reducing agent, wherein the temperature is controlled to be 40-80 ℃, and the stirring time is 20-60 min;
step 2, dissolving the weighed tungsten source in a hydrogen peroxide solution, and performing ultrasonic treatment to obtain a tungsten source solution, wherein the temperature is controlled to be 30-70 ℃, and the ultrasonic treatment time is 10-50 min;
step 3, adding the tungsten source solution obtained in the step 2 into the vanadium source solution obtained in the step 1, and uniformly stirring to obtain a mixed solution, wherein the temperature is controlled to be 40-80 ℃, and the stirring time is 0.5-2.5 h;
step 4, transferring the mixed solution obtained in the step 3 into a reaction kettle, and carrying out hydrothermal reaction to obtain a hydrothermal product, wherein the temperature is controlled to be 180-260 ℃, and the heating time is 5-9 hours;
step 5, alternately washing the hydrothermal product obtained in the step 4 by using water and ethanol, and putting the product into a drying oven to obtain a dried product, wherein the temperature is controlled to be 60-80 ℃, and the heating time is 6-12 hours;
and 6, carrying out high-temperature annealing treatment on the dried product obtained in the step 5 to obtain the polydopamine modified tungsten doped vanadium dioxide nano particles, wherein the temperature is controlled to be 450-750 ℃, and the heating time is 1-5 h.
Step 7, dispersing the product obtained in the step 6 in a dilute nitric acid aqueous solution, washing with absolute ethyl alcohol, and centrifugally drying to obtain nano particles; wherein the temperature is controlled to be 20-50 ℃, and the heating time is 1-4 h.
And 8, dispersing the nano powder obtained in the step 7 in deionized water, adding a buffer solution, adjusting the pH value, adding dopamine hydrochloride, stirring to react completely, and centrifugally drying to obtain the polydopamine modified tungsten-doped vanadium dioxide nano particles. Wherein the PH is controlled to be 7.5-9.5, the mass ratio of the dopamine to the tungsten-doped vanadium dioxide nanoparticles is controlled to be 1: 1-4: 1, the temperature is controlled to be 30-60 ℃, and the heating time is 12-36 hours.
Example 1
Step 1, dissolving the weighed vanadyl sulfate in water, adding oxalic acid, and stirring for 20min at 40 ℃ to obtain vanadyl sulfate solution reduced by oxalic acid;
step 2, dissolving the weighed tungstic acid in a hydrogen peroxide solution, and performing ultrasonic treatment for 10min at the temperature of 30 ℃ to obtain a tungstic acid solution;
step 3, adding the tungstic acid solution obtained in the step 2 into the vanadyl sulfate solution obtained in the step 1, and stirring for 0.5h at the temperature of 40 ℃ to obtain a mixed solution;
step 4, transferring the mixed solution obtained in the step 3 into a reaction kettle, and carrying out hydrothermal reaction for 5 hours at 180 ℃ to obtain a hydrothermal product;
step 5, alternately washing the hydrothermal product obtained in the step 4 with water and ethanol, and drying in a 60 ℃ drying oven for 6 hours to obtain a dried product;
and 6, annealing the dried product obtained in the step 5 at 450 ℃ for 1h to obtain the tungsten-doped vanadium dioxide nano particles.
Step 7, dispersing the product obtained in the step 6 in a dilute nitric acid aqueous solution, and ultrasonically heating for 1h at the temperature of 20 ℃ to obtain dried nano particles;
and 8, dispersing the nano powder obtained in the step 7 in deionized water, adding a buffer solution, adjusting the pH value to 7.5, controlling the mass ratio of dopamine to tungsten-doped vanadium dioxide nanoparticles to be 1:1, and stirring and reacting at 30 ℃ for 12 hours to obtain the polydopamine-modified tungsten-doped vanadium dioxide nanoparticles.
Example 2
Step 1, dissolving the weighed vanadium pentoxide in water, adding acetic acid, and stirring for 30min at 50 ℃ to obtain an acetic acid reduced vanadium pentoxide solution;
step 2, dissolving the weighed sodium tungstate into a hydrogen peroxide solution, and performing ultrasonic treatment at 40 ℃ for 20min to obtain a sodium tungstate solution;
step 3, adding the sodium tungstate solution obtained in the step 2 into the vanadium pentoxide solution obtained in the step 1, and stirring for 1 hour at the temperature of 50 ℃ to obtain a mixed solution;
step 4, transferring the mixed solution obtained in the step 3 into a reaction kettle, and carrying out hydrothermal reaction for 6 hours at 200 ℃ to obtain a hydrothermal product;
step 5, alternately washing the hydrothermal product obtained in the step 4 with water and ethanol, and drying in a 70 ℃ drying oven for 8 hours to obtain a dried product;
and 6, carrying out high-temperature annealing on the dried product obtained in the step 5 at 550 ℃ for 2h to obtain the tungsten-doped vanadium dioxide nano particles.
Step 7, dispersing the product obtained in the step 6 in a dilute nitric acid aqueous solution, and ultrasonically heating for 2 hours at the temperature of 30 ℃ to obtain dried nanoparticles;
and 8, dispersing the nano powder obtained in the step 7 in deionized water, adding a buffer solution, adjusting the pH value to 8.0, controlling the mass ratio of dopamine to tungsten-doped vanadium dioxide nanoparticles to be 2:1, and stirring and reacting at 40 ℃ for 18 hours to obtain the polydopamine-modified tungsten-doped vanadium dioxide nanoparticles.
Example 3
Step 1, dissolving the weighed vanadyl acetylacetonate in water, adding phthalic acid, and stirring at 60 ℃ for 40min to obtain a phthalic acid reduced vanadyl acetylacetonate solution;
step 2, dissolving the weighed ammonium tungstate into a hydrogen peroxide solution, and performing ultrasonic treatment at 50 ℃ for 30min to obtain an ammonium tungstate solution;
step 3, adding the ammonium tungstate solution obtained in the step 2 into the vanadyl acetylacetonate solution obtained in the step 1, and stirring for 1.5 hours at the temperature of 60 ℃ to obtain a mixed solution;
step 4, transferring the mixed solution obtained in the step 3 into a reaction kettle, and carrying out hydrothermal reaction for 7 hours at 220 ℃ to obtain a hydrothermal product;
step 5, alternately washing the hydrothermal product obtained in the step 4 with water and ethanol, and drying in an oven at 80 ℃ for 10 hours to obtain a dried product;
and 6, annealing the dried product obtained in the step 5 at 650 ℃ for 3h to obtain the tungsten-doped vanadium dioxide nano particles.
Step 7, dispersing the product obtained in the step 6 in a dilute nitric acid aqueous solution, and ultrasonically heating for 3 hours at 40 ℃ to obtain dried nanoparticles;
and 8, dispersing the nano powder obtained in the step 7 in deionized water, adding a buffer solution, adjusting the pH value to 8.5, controlling the mass ratio of dopamine to tungsten-doped vanadium dioxide nanoparticles to be 3:1, and stirring and reacting at 50 ℃ for 24 hours to obtain the polydopamine-modified tungsten-doped vanadium dioxide nanoparticles.
Example 4
Step 1, dissolving the weighed triisopropoxyl vanadium oxide in water, adding citric acid, and stirring for 50min at 70 ℃ to obtain a citric acid reduced triisopropoxyl vanadium oxide solution;
step 2, dissolving the weighed tungsten trioxide in a hydrogen peroxide solution, and performing ultrasonic treatment at 60 ℃ for 40min to obtain a tungsten trioxide solution;
step 3, adding the tungsten trioxide solution obtained in the step 2 into the triisopropoxyl vanadium oxide solution obtained in the step 1, and stirring for 2.5 hours at the temperature of 70 ℃ to obtain a mixed solution;
step 4, transferring the mixed solution obtained in the step 3 into a reaction kettle, and carrying out hydrothermal reaction for 8 hours at 240 ℃ to obtain a hydrothermal product;
step 5, alternately washing the hydrothermal product obtained in the step 4 with water and ethanol, and drying in an oven at 80 ℃ for 12 hours to obtain a dried product;
and 6, annealing the dried product obtained in the step 5 at 750 ℃ for 4h to obtain the tungsten-doped vanadium dioxide nano particles.
Step 7, dispersing the product obtained in the step 6 in a dilute nitric acid aqueous solution, and ultrasonically heating for 4 hours at 50 ℃ to obtain dried nanoparticles;
and 8, dispersing the nano powder obtained in the step 7 in deionized water, adding a buffer solution, adjusting the pH value to 9.0, controlling the mass ratio of dopamine to tungsten-doped vanadium dioxide nanoparticles to be 4:1, and stirring and reacting at 60 ℃ for 30 hours to obtain the polydopamine-modified tungsten-doped vanadium dioxide nanoparticles.
Example 5
Step 1, dissolving the weighed ammonium metavanadate in water, adding benzyl alcohol, and stirring for 60min at 80 ℃ to obtain an ammonium metavanadate solution reduced by the benzyl alcohol;
step 2, dissolving the weighed tungstic acid in a hydrogen peroxide solution, and performing ultrasonic treatment for 50min at the temperature of 70 ℃ to obtain a tungstic acid solution;
step 3, adding the tungstic acid solution obtained in the step 2 into the ammonium metavanadate solution obtained in the step 1, and stirring for 3 hours at the temperature of 80 ℃ to obtain a mixed solution;
step 4, transferring the mixed solution obtained in the step 3 into a reaction kettle, and carrying out hydrothermal reaction at 260 ℃ for 9 hours to obtain a hydrothermal product;
step 5, alternately washing the hydrothermal product obtained in the step 4 with water and ethanol, and drying in an oven at 80 ℃ for 12 hours to obtain a dried product;
and 6, carrying out high-temperature annealing on the dried product obtained in the step 5 at 550 ℃ for 5h to obtain the tungsten-doped vanadium dioxide nano particles.
Step 7, dispersing the product obtained in the step 6 in a dilute nitric acid aqueous solution, and ultrasonically heating for 2 hours at the temperature of 30 ℃ to obtain dried nanoparticles;
and 8, dispersing the nano powder obtained in the step 7 in deionized water, adding a buffer solution, adjusting the pH value to 9.5, controlling the mass ratio of dopamine to tungsten-doped vanadium dioxide nanoparticles to be 3:1, and stirring and reacting at 60 ℃ for 36 hours to obtain the polydopamine-modified tungsten-doped vanadium dioxide nanoparticles.
The poly dopamine modified tungsten doped vanadium dioxide nano particles prepared by the preparation method of the poly dopamine modified tungsten doped vanadium dioxide nano particle composite intelligent temperature control coating are characterized: the polydopamine modified tungsten doped vanadium dioxide nano particles have uniform particle size distribution, lower phase transition temperature and good photo-thermal conversion efficiency. The method has great application potential in the fields of intelligent coating, optical storage equipment, infrared radiation detection and the like.
Claims (7)
1. A preparation method of polydopamine modified tungsten doped vanadium dioxide nanoparticle composite intelligent temperature control coating is characterized by comprising the following steps:
mixing a vanadium source solution containing a reducing agent with a tungsten source solution containing hydrogen peroxide, carrying out hydrothermal reaction, drying a product, and carrying out high-temperature annealing treatment to obtain tungsten-doped vanadium dioxide;
dispersing tungsten-doped vanadium dioxide in water, adding a buffer solution to adjust the pH value to 7.5-9.5, then adding dopamine hydrochloride, and stirring for reaction to obtain the polydopamine modified tungsten-doped vanadium dioxide nanoparticles.
2. The method of claim 1, wherein the vanadium source is vanadyl sulfate, vanadium pentoxide, vanadyl acetylacetonate, vanadium triisopropoxide oxide, ammonium metavanadate; the reducing agent is oxalic acid, acetic acid, phthalic acid, citric acid and benzyl alcohol; the tungsten source is tungstic acid, sodium tungstate, ammonium tungstate or tungsten trioxide.
3. The method of claim 1, wherein the mass ratio of dopamine to tungsten doped vanadium dioxide is (1-4): 1.
4. The method of claim 1, wherein the tungsten-doped vanadium dioxide is prepared by carrying out a hydrothermal reaction at 180-260 ℃ for 5-9 h and then carrying out a high-temperature annealing treatment at 450-750 ℃ for 1-5 h.
5. The method of claim 1, wherein when the tungsten-doped vanadium dioxide reacts with the dopamine hydrochloride, the pH is controlled to be 7.5-9.5, and the tungsten-doped vanadium dioxide is stirred and reacts at 30-60 ℃ for 12-36 hours.
6. The method of claim 1, comprising the steps of:
1) dissolving a vanadium source in water, adding a reducing agent, and stirring at 40-80 ℃ for 20-60 min to obtain a vanadium source solution reduced by the reducing agent;
2) dissolving a tungsten source in a hydrogen peroxide solution, and performing ultrasonic treatment at 30-70 ℃ for 10-50 min to obtain a tungsten source solution;
3) adding the tungsten source solution obtained in the step 2) into the vanadium source solution obtained in the step 1), and stirring at 40-80 ℃ for 0.5-2.5 h to obtain a mixed solution;
4) transferring the mixed solution obtained in the step 3) into a reaction kettle, and carrying out hydrothermal reaction at 180-260 ℃ for 5-9 h to obtain a hydrothermal product;
5) cross washing the hydrothermal product obtained in the step 4) with water and ethanol, and drying at 60-80 ℃ for 6-12 h;
6) annealing the dried product obtained in the step 5) at the high temperature of 450-750 ℃ for 1-5 h to obtain tungsten-doped vanadium dioxide nanoparticles;
7) dispersing the product obtained in the step 6) in a dilute nitric acid aqueous solution, washing with absolute ethyl alcohol, centrifuging, and drying at 20-50 ℃ for 1-4 h;
8) dispersing the product obtained in the step 7) in deionized water, adding a buffer solution, adjusting the pH value to 7.5-9.5, adding dopamine hydrochloride, stirring and reacting at 30-60 ℃ for 12-36 h, centrifuging, and drying to obtain the polydopamine modified tungsten doped vanadium dioxide nanoparticles.
7. The polydopamine modified tungsten doped vanadium dioxide nano particle composite intelligent temperature control coating obtained by the method of any one of claims 1 to 6.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113185802A (en) * | 2021-04-26 | 2021-07-30 | 济南大学 | Melamine-formaldehyde resin coated vanadium dioxide photothermal response composite nano-particle and preparation method thereof |
| CN113925968A (en) * | 2021-10-18 | 2022-01-14 | 上海市第六人民医院 | Multifunctional vanadium carbide/polydopamine nanosheet and preparation method and application thereof |
| CN114767711A (en) * | 2022-05-17 | 2022-07-22 | 深圳市优色生物科技有限公司 | Efficient redox nano enzyme for tumor treatment and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070007512A1 (en) * | 2005-07-09 | 2007-01-11 | Nada Dimitrijevic | Bio-inorganic conjugates |
| CN102976307A (en) * | 2012-12-04 | 2013-03-20 | 北京化工大学 | Carbon nano tube surface functionalization method |
| CN105680021A (en) * | 2016-03-26 | 2016-06-15 | 上海大学 | Poly-dopamine coated nano-micro powder and preparation method thereof |
| CN109399710A (en) * | 2018-10-26 | 2019-03-01 | 西安理工大学 | Witch culture temperature induced color changing VO2Nano material and its preparation method and application |
-
2020
- 2020-12-28 CN CN202011575925.0A patent/CN112341859A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070007512A1 (en) * | 2005-07-09 | 2007-01-11 | Nada Dimitrijevic | Bio-inorganic conjugates |
| CN102976307A (en) * | 2012-12-04 | 2013-03-20 | 北京化工大学 | Carbon nano tube surface functionalization method |
| CN105680021A (en) * | 2016-03-26 | 2016-06-15 | 上海大学 | Poly-dopamine coated nano-micro powder and preparation method thereof |
| CN109399710A (en) * | 2018-10-26 | 2019-03-01 | 西安理工大学 | Witch culture temperature induced color changing VO2Nano material and its preparation method and application |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113185802A (en) * | 2021-04-26 | 2021-07-30 | 济南大学 | Melamine-formaldehyde resin coated vanadium dioxide photothermal response composite nano-particle and preparation method thereof |
| CN113925968A (en) * | 2021-10-18 | 2022-01-14 | 上海市第六人民医院 | Multifunctional vanadium carbide/polydopamine nanosheet and preparation method and application thereof |
| CN114767711A (en) * | 2022-05-17 | 2022-07-22 | 深圳市优色生物科技有限公司 | Efficient redox nano enzyme for tumor treatment and preparation method thereof |
| CN114767711B (en) * | 2022-05-17 | 2023-10-20 | 恩祺生物科技(上海)有限公司 | Redox nano-enzyme for tumor treatment and preparation method thereof |
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