CN114672233A - Photothermal super-hydrophobic coating based on MXene @ Au hybrid and preparation method thereof - Google Patents

Photothermal super-hydrophobic coating based on MXene @ Au hybrid and preparation method thereof Download PDF

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CN114672233A
CN114672233A CN202210251981.1A CN202210251981A CN114672233A CN 114672233 A CN114672233 A CN 114672233A CN 202210251981 A CN202210251981 A CN 202210251981A CN 114672233 A CN114672233 A CN 114672233A
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CN114672233B (en
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王佳莹
王志明
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Yangtze River Delta Research Institute of UESTC Huzhou
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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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • 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
    • 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
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08K3/08—Metals
    • C08K2003/0831—Gold
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives

Abstract

The invention provides a photothermal super-hydrophobic coating based on MXene @ Au hybrid and a preparation method thereof, wherein the preparation method comprises the following steps: (1) preparing MXene nanosheets; obtaining Au nano-particles by adopting a gold seed solution regrowth method; (2) forming MXene @ Au hybrid dispersion liquid from the MXene nanosheets and the dispersion liquid of the Au nanoparticles, and drying to obtain MXene @ Au hybrid powder; (3) adding the MXene @ Au hybrid powder into aqueous polyurethane to obtain aqueous polyurethane dispersion of MXene @ Au hybrid; preparing modified super-hydrophobic silicon oxide nano-particles; (4) and sequentially spraying, heating and drying the aqueous polyurethane dispersion liquid of the MXene @ Au hybrid and the dispersion liquid of the modified super-hydrophobic silicon oxide nano-particles to obtain the coating. The invention effectively improves the photothermal conversion capability of the MXene photothermal hydrophobic coating, and can be used in the fields of photothermal defrosting and deicing, remote optical drive, drug delivery and transfer and the like.

Description

Photothermal super-hydrophobic coating based on MXene @ Au hybrid and preparation method thereof
Technical Field
The invention belongs to the field of hydrophobic materials, and particularly relates to a photothermal super-hydrophobic coating based on MXene @ Au hybrid and a preparation method thereof.
Background
The super-hydrophobic surface has the properties of self-cleaning property, water repellency and the like; the contact angle of the super-hydrophobic material is larger than 150 degrees, and the rolling angle is smaller than 10 degrees. As one of the super-hydrophobic materials, the photo-thermal super-hydrophobic coating has great potential in the fields of building ice prevention, outdoor defrosting and deicing, flexible wearable equipment, remote light driving, medicine delivery assistance and the like. To obtain a photo-thermal super-hydrophobic coating with excellent performance, the photo-thermal material is selected to endow the coating with high photo-thermal conversion efficiency, and the surface of the coating has super-hydrophobic capability.
The photo-thermal conversion efficiency of the photo-thermal super-hydrophobic coating is not separated from that of the photo-thermal filler. The optical properties, thermal conductivity and dispersibility of the filler all affect the coating properties. MXene (titanium carbide) nano-materials have plasmon enhancement effect and wide absorption band, and have been widely applied to light absorption devices and photo-thermal conversion devices in view of good optical performance and rapid heat transfer. MXene is used as photo-thermal filler of the photo-thermal super-hydrophobic coating, and can promote quick and efficient high-heat conversion. CN109439188B provides a superhydrophobic photo-thermal coating and a preparation method thereof, the superhydrophobic photo-thermal coating includes: the modified multi-layer MXene compound, the modified single-layer MXene compound, ethyl acetate, polydimethylsiloxane and a curing agent; it has excellent mechanical, chemical and photo-thermal resistance. However, in consideration of fluidity of the spray solvent and dispersibility of the MXene nanomaterial in the spray solution, the photothermal conversion efficiency is not high when only a single photothermal filler is present.
Disclosure of Invention
The invention aims to provide a photothermal super-hydrophobic coating based on MXene @ Au hybrid and a preparation method thereof, and aims to solve the technical problem that the photothermal conversion efficiency of the photothermal super-hydrophobic coating is low.
In order to solve the technical problems, the specific technical scheme of the photothermal super-hydrophobic coating based on MXene @ Au hybrid and the preparation method thereof is as follows:
a preparation method of a photo-thermal super-hydrophobic coating based on MXene @ Au hybrid comprises the following steps:
(1) etching MAX (aluminum titanium carbide) by using an MXene material and hydrochloric acid or hydrofluoric acid to obtain an MXene nanosheet; obtaining Au nano-particles by adopting a gold seed solution regrowth method;
(2) carrying out ultrasonic co-mixing on the MXene nanosheet and the dispersion liquid of the Au nanoparticles to form MXene @ Au hybrid dispersion liquid, and drying to obtain MXene @ Au hybrid powder;
(3) adding the MXene @ Au hybrid powder into aqueous polyurethane to obtain aqueous polyurethane dispersion of MXene @ Au hybrid; preparing silicon oxide nanoparticles by using a Stober method: coupling the silicon oxide nanoparticles with 1H, 2H, 3H, 4H-perfluoroalkyl triethoxysilane to obtain modified super-hydrophobic silicon oxide nanoparticles;
(4) and (3) sequentially spraying, heating and drying the aqueous polyurethane dispersion liquid of the MXene @ Au hybrid and the dispersion liquid of the modified super-hydrophobic silicon oxide nanoparticles by using a spray gun to obtain the photo-thermal super-hydrophobic coating based on the MXene @ Au hybrid.
Further, the MXene nano-sheet is Ti3C2TxThe nano material is a lamellar nano material, and the Au nano particles are spherical Au nano particles with the particle size of 25-35 nm.
Further, in the step (3), in the aqueous polyurethane dispersion of the MXene @ Au hybrid, the MXene nanosheet accounts for 1 to 4% of the aqueous polyurethane dispersion by mass.
Preferably, in the step (3), the MXene @ Au hybrid aqueous polyurethane dispersion liquid contains 3% of MXene nanosheets by mass.
Further, in the step (2), in the aqueous polyurethane dispersion of the MXene @ Au hybrid, the mass ratio of MXene to Au in the MXene @ Au hybrid powder is 12: 1 to 6: 1.
preferably, in the step (2), in the aqueous polyurethane dispersion of the MXene @ Au hybrid, the mass ratio of MXene to Au in the MXene @ Au hybrid powder is 8: 1.
further, in the step (3), the modified silica nanoparticles are 1.5 to 6% by mass of the aqueous polyurethane dispersion.
Preferably, in the step (3), the mass of the modified silica nanoparticles is 3.5% of the mass of the aqueous polyurethane dispersion.
The invention also provides a photo-thermal super-hydrophobic coating based on the MXene @ Au hybrid, and the photo-thermal super-hydrophobic coating is prepared by the method.
The photothermal super-hydrophobic coating based on the MXene @ Au hybrid and the preparation method thereof have the following advantages: the MXene and Au hybrid is used as photo-thermal filler, and the modified silicon oxide nanoparticles are sprayed on the MXene and Au hybrid photo-thermal coating, so that the photo-thermal super-hydrophobic performance of the MXene and Au hybrid photo-thermal coating is realized. The surface plasmon effect and the synergistic photothermal effect of the MXene @ Au hybrid in the photothermal super-hydrophobic coating effectively improve the photothermal conversion efficiency of the coating, and the spraying operation of the modified silicon oxide nano particles enables the photothermal super-hydrophobic coating to have stable and excellent super-hydrophobic performance.
Drawings
FIG. 1 is a flow chart of a preparation method of a MXene @ Au hybrid-based photo-thermal super-hydrophobic coating provided by the application;
FIG. 2 is a graph comparing the X-ray diffraction results of MXene @ Au hybrid powder prepared in example 1 with that of pure MXene material;
FIG. 3 is a scanning electron micrograph of a MXene @ Au hybrid prepared in example 1 and a transmission electron micrograph of a pure MXene material;
FIG. 4 is a graph comparing the X-ray photoelectron spectroscopy results of the MXene @ Au hybrid prepared in example 1 with that of a pure MXene material;
FIG. 5 is a comparison spectrum of light absorbance for the MXene photothermal coating and the MXene @ Au hybrid photothermal coating prepared in example 1;
FIG. 6 is a comparison of the photothermal properties of the MXene photothermal coating and the MXene @ Au hybrid photothermal coating prepared in example 1 under laser irradiation;
FIG. 7 is a surface and cross-sectional SEM images of a MXene @ Au hybrid photothermal superhydrophobic coating after spraying modified silica as prepared in example 1;
FIG. 8 is a graph of contact angle test data and rolling angle test data for a MXene @ Au hybrid-based photo-thermal superhydrophobic coating prepared in example 1;
FIG. 9 is a graph comparing the photothermal performance of an MXene @ Au hybrid photothermal superhydrophobic coating after spray coating of modified silica prepared in example 1 and an MXene photothermal superhydrophobic coating after spray coating of modified silica;
FIG. 10 is a graph of the contact angle test results of the MXene @ Au hybrid-based photothermal super-hydrophobic coating prepared in example 1 after undergoing multiple photothermal conversion cycles;
FIG. 11 is a graph showing the results of a contact angle test of the photo-thermal super-hydrophobic coating based on MXene @ Au hybrid prepared in example 1 under acid and alkali solutions;
FIG. 12 is a graph of the photoabsorption rate test of the photothermal superhydrophobic coatings based on MXene @ Au hybrid prepared in example 1 and example 2;
FIG. 13 is a photoabsorption test spectrum of the photothermal superhydrophobic coating based on MXene @ Au hybrid prepared in example 1 and example 3;
FIG. 14 is contact angle test data for photothermal superhydrophobic coatings based on MXene @ Au hybrids prepared in examples 1 and 4;
FIG. 15 is a photoabsorption test spectrum of the photo-thermal superhydrophobic coating based on MXene @ Au hybrid prepared in example 1 and example 4;
FIG. 16 is a test of defrosting performance of the photothermal superhydrophobic coating based on an MXene @ Au hybrid prepared in example 1 and the MXene @ Au hybrid photothermal coating of uncoated modified silica prepared according to comparative example 1;
FIG. 17 is a test of deicing performance for the photothermal superhydrophobic coating based on an MXene @ Au hybrid prepared in example 1 and the MXene @ Au hybrid photothermal coating of an uncoated modified silica prepared according to comparative example 1;
FIG. 18 is a photo-driven test of a photo-thermal superhydrophobic coating based on MXene @ Au hybrid prepared in example 1;
FIG. 19 is a test of MXene @ Au hybrid-based photothermal superhydrophobic coatings prepared in example 1 for drug transfer.
Detailed Description
In order to better understand the purpose, structure and function of the present invention, the photo-thermal super-hydrophobic coating based on MXene @ Au hybrid and the preparation method thereof are further described in detail below with reference to the accompanying drawings.
The core improvement point of the invention is that MXene @ Au hybrid is adopted to improve the photo-thermal conversion efficiency of the photo-thermal super-hydrophobic coating. The surface plasmon effect and the synergistic photothermal effect of the MXene @ Au hybrid in the photothermal super-hydrophobic coating effectively improve the photothermal conversion efficiency of the coating. Whereas the prior art relies only on MXene to provide photothermal effects.
FIG. 1 is a flow chart of the preparation of the MXene @ Au hybrid-based photothermal super-hydrophobic coating of the invention. The specific process is as follows: the MXene material is provided, and MAX (aluminum titanium carbide) is etched by hydrochloric acid or hydrofluoric acid to obtain MXene nanosheets, and related processes are disclosed by related documents. The gold nanoparticles can be obtained by a conventional seed solution growth method. Mixing MXene nanosheets and gold nanoparticle dispersion liquid, carrying out ultrasonic treatment for 0.5h together, and combining the MXene nanosheets and the gold nanoparticle dispersion liquid through electrostatic action to form MXene @ Au hybrid dispersion liquid. And drying to obtain MXene @ Au hybrid powder.
Adding MXene @ Au hybrid powder into aqueous polyurethane to obtain aqueous polyurethane dispersion of MXene @ Au hybrid, namely photo-thermal coating dispersion. Using the traditional Stober method, silica nanoparticles can be prepared: and coupling the silicon oxide nanoparticles with 1H, 2H, 3H, 4H-perfluoroalkyl triethoxysilane to obtain the modified super-hydrophobic silicon oxide nanoparticles. The super-hydrophobic silicon oxide nano-particles can be further used for preparing modified silicon oxide nano-dispersion liquid. And (3) spraying the photo-thermal coating dispersion liquid and the modified silicon oxide nanoparticle dispersion liquid on a substrate in sequence by using a spray gun, and heating and drying to obtain the photo-thermal super-hydrophobic coating of the MXene @ Au hybrid.
Example 1
A preparation method of a photo-thermal super-hydrophobic coating based on MXene @ Au hybrid comprises the following steps:
(1) preparation of MXene nanosheet
10mL of concentrated hydrochloric acid (6mol/L) was slowly added to 10mL of deionized water, and stirred well. 1g of lithium fluoride powder was added to the solution, and stirred for 20min to dissolve it. Slowly adding 1g MAX powder into the solution for multiple times, stirring for 30min, turning on heating, and allowing the mixed solution to react at 55 deg.C and 400rpm for 24 h. After the reaction was complete, the reaction was washed with multiple ultrasonic centrifugal washes until the pH was close to 7. And (4) putting the centrifugal product into a vacuum drying oven, and drying at 40 ℃ overnight to obtain MXene nanosheets.
(2) Preparation of gold nanoparticle Dispersion
10mL of a 0.1mol/L cetyltrimethylammonium bromide solution was prepared, and 0.25mL of a 0.01mol/L chloroauric acid solution was added thereto and stirred for 15 min. 0.5mL of freshly prepared sodium borohydride solution with the concentration of 0.01mol/L is added, and the mixture is uniformly mixed and stirred. After that, the solution was stirred at 200rpm for 2 hours at room temperature to obtain a golden brown Au seed solution. 190mL of deionized water was added to 10mL of a 0.1mol/L hexadecyltrimethylammonium bromide solution, and after stirring uniformly, 4mL of a 0.01mol/L chloroauric acid solution was added thereto and stirred for 15 min. To this was added 15mL of a freshly prepared ascorbic acid solution with a concentration of 0.1mol/L, and the reaction was stirred for 15 min. To the solution, 0.12mL of the Au seed solution prepared in advance was added, and after slowly stirring, the growth solution was allowed to stand overnight. And centrifugally washing and collecting the dispersion liquid of the Au nanoparticles, and measuring the concentration of the Au nanoparticles in the obtained dispersion liquid to be 0.03mg/mL by using an inductively coupled plasma mass spectrometer.
(3) Preparation of MXene @ Au hybrid powder
MXene powder was weighed to prepare an aqueous solution of the MXene powder. According to the mass ratio of MXene to Au being 8: 1, a corresponding Au nanoparticle dispersion liquid was prepared. And (3) carrying out ultrasonic co-mixing on the aqueous solution of the MXene powder and the dispersion liquid of the Au nano particles for 0.5h to form the dispersion liquid of the MXene @ Au hybrid. And drying to obtain MXene @ Au hybrid powder.
As shown in fig. 2, MXene @ Au hybrid powder and simple MXene material were analyzed using X-ray diffraction spectroscopy. In the pattern of MXene @ Au hybrid powder, it can be seen that peaks at 38.4 °, 44.6 ° and 64.8 ° are respectively assigned to the (111), (200) and (220) crystal planes of metallic Au. Indicating that the Au nanoparticles were successfully doped in MXene.
Fig. 3 shows the morphology of MXene and MXene @ Au hybrid powders analyzed by Scanning Electron Microscopy (SEM). In the SEM results of MXene, MXene nanoplatelets are clearly visible as in fig. 3 (a).In the SEM results of MXene @ Au, Au nanoparticles can be seen to be distributed on MXene nano-sheets, as shown in FIG. 3(b), indicating that MXene @ Au hybrid is successfully prepared. By analyzing MXene @ Au with a Transmission Electron Microscope (TEM), Au nanoparticles distributed on MXene nanosheets can be clearly seen, as shown in FIG. 3 (c). As can be seen from the figure, the MXene nanosheet provided by the invention is Ti 3C2TxThe nano material is a lamellar nano material, and the Au nano particles are spherical Au nano particles with the particle size of 25-35 nm. The Au nano-particles with small particle size have large specific surface area, are very suitable for being combined with MXene nano-sheets through electrostatic acting force, and are also favorable for faster heat conduction.
As shown in FIG. 4, the composition of MXene and MXene @ Au hybrid powders can be characterized by X-ray photoelectron spectroscopy (XPS). In the XPS spectrum of MXene @ Au hybrid powder, peaks corresponding to Au 4d and Au 4f can be observed, which indicates that the metal Au is effectively doped on MXene.
(4) Adding the MXene @ Au hybrid powder into 500uL of aqueous polyurethane, wherein the mass fraction of MXene in the aqueous polyurethane dispersion liquid is 3%, and the mass ratio of MXene to Au is 8 to 1. And then ultrasonic mixing is carried out for 0.5h to obtain the aqueous polyurethane dispersion liquid of the MXene @ Au hybrid. The aqueous polyurethane can be commercial Jitian chemical F0401 type aqueous polyurethane.
(5) A2X 2cm quartz glass plate was provided as a substrate for spray coating, the substrate was heated on a hot stage at 120 ℃ and an aqueous polyurethane dispersion of MXene @ Au hybrid (photothermal coating dispersion) was sprayed by a spray gun using a gas pressure of 0.1 MPa. After drying, MXene @ Au hybrid photo-thermal coating is obtained on the glass substrate. For comparison, MXene photothermal coatings were obtained on substrates with the same operating procedure except that gold nanoparticles were added.
As shown in fig. 5, the absorption of the MXene @ Au photothermal coating was higher than that of the MXene photothermal coating. As shown in fig. 6(a), the photo-thermal temperature rise of the MXene @ Au hybrid photo-thermal coating is higher than that of the MXene photo-thermal coating under multiple laser irradiation of different powers. The irradiation power is 0.5W/cm2The maximum temperature rise equilibrium temperature of the MXene @ Au hybrid photo-thermal coating is 130.2 ℃, calculated according to the graph of FIG. 6(b)The calculated photothermal conversion efficiency was 87.1%; while the maximum temperature of the MXene photothermal coating was 110.3 ℃ and the corresponding photothermal conversion efficiency was 66.3% as calculated from FIG. 6 (c). After the MXene @ Au hybrid is formed by adding the Au to the MXene, the photo-thermal performance and the conversion efficiency are effectively improved. On one hand, the Au nanoparticles have a plasmon effect, and the MXene @ Au structure has higher light absorption rate due to the addition of Au, so that photo-thermal conversion is facilitated; on the other hand, the layered structure of the MXene nano-particles is suitable for doping and adding Au particles, the nano-layer is beneficial to rapidly conducting and diffusing heat generated by doping Au and heat generated by the nano-particles, the interaction of the heat generated by doping Au and the nano-particles enhances light absorption and improves the synergistic photo-thermal enhancement effect of photo-thermal and combines with the plasmon effect of Au, and finally the photo-thermal conversion of the MXene @ Au photo-thermal coating is greatly improved, so that the operation of doping the gold nano-particles is proved to have an important effect on photo-thermal.
(6) The silicon oxide nanoparticles are obtained by tetraethyl orthosilicate hydrolysis reaction by the Stober method. To 150mL of absolute ethanol, 8mL of aqueous ammonia and 20mL of deionized water were added, and the mixture was stirred and mixed. Then 4mL of tetraethyl orthosilicate was added and stirred for 12h for reaction, followed by drying and collection of silica nanoparticle powder.
(7) 1g of 1H, 2H, 3H, 4H-perfluoroalkyl triethoxysilane is added into 35mL of absolute ethanol and stirred for 30min, then 300mg of silicon oxide nanoparticle powder prepared in advance is added into the anhydrous ethanol, stirred for 3H, and dried to obtain the modified silicon oxide nanoparticles.
(8) And weighing 20mg of the modified silicon oxide nanoparticles, adding the weighed modified silicon oxide nanoparticles into 1mL of cyclohexane, and performing ultrasonic dispersion to obtain a dispersion liquid of the modified silicon oxide nanoparticles. The mass of the modified silica nanoparticles was about 3.5% of the aqueous polyurethane dispersion.
(9) And (3) placing the MXene @ Au hybrid photo-thermal coating on a heating table at 120 ℃, spraying the dispersion liquid of the modified silicon oxide nanoparticles on the surface of the MXene @ Au hybrid photo-thermal coating by using a spray gun, and drying for 2 hours to obtain the MXene @ Au hybrid-based photo-thermal super-hydrophobic coating.
FIG. 7 shows SEM surface and cross section of photo-thermal super-hydrophobic coating based on MXene @ Au hybrid after spraying modified silica, and modified oxygen can be observed The silicon oxide nano-particles are uniformly distributed on the surface of the coating. The resulting photothermal superhydrophobic coatings based on MXene @ Au hybrids were further tested. As shown in fig. 8, the contact angle was 153 ° and the rolling angle was 4.5 °, so that the prepared coating had good superhydrophobic capability. The photo-thermal performance test of the prepared photo-thermal super-hydrophobic coating based on MXene @ Au hybrid was performed as shown in FIG. 9. As shown in fig. 9(a), the photothermal super-hydrophobic coating exhibits stable photothermal conversion capability during multiple cyclic photothermal conversion processes. As shown in FIGS. 9(b) and 9(c), under milder light (0.5W/cm)2) The MXene @ Au photo-thermal super-hydrophobic coating sprayed with the silicon oxide nano-particles has the temperature rise equilibrium temperature of up to 121 ℃ and the corresponding photo-thermal conversion efficiency of 85.8 percent; the equilibrium temperature of the MXene photo-thermal super-hydrophobic coating sprayed with the silicon oxide is 108 ℃, and the corresponding photo-thermal efficiency is calculated to be 76.9%. The result shows that the gold-doped MXene @ Au structure plays a role in improving the photo-thermal conversion performance of the photo-thermal super-hydrophobic coating after the modified silicon oxide is sprayed.
As shown in fig. 10, the contact angle test results of the photo-thermal superhydrophobic coating still showed excellent superhydrophobic characteristics after being subjected to the multiple photo-thermal tests as in fig. 9. The modified silicon oxide modified hybrid photo-thermal coating prepared by the invention has obvious super-hydrophobicity and lasting chemical stability: as shown in fig. 11, the photo-thermal super-hydrophobic coating shows stable super-hydrophobic ability and acid and alkali resistance in a contact angle test under an acid and alkali solution.
Example 2
A photo-thermal superhydrophobic coating containing only MXene was prepared according to the same procedure as in example 1 (MXene powder was 1%, 2% and 4% by mass of aqueous polyurethane dispersion, and was not doped with Au). As shown in fig. 12, for the photo-thermal super-hydrophobic coatings containing different mass fractions of MXene, which were prepared separately, when the mass fraction of MXene powder in the aqueous polyurethane dispersion was 3%, the absorption spectrum of the coating showed the best performance, so it was optimized based on this that the mass fraction of MXene powder in the aqueous polyurethane dispersion was set to 3%. When the mass fraction of the MXene nanosheets in the aqueous polyurethane dispersion liquid is less than 3%, the light absorption rate of the prepared coating increases with the increase of the mass fraction of the MXene; when the mass fraction of the MXene nanosheets in the aqueous polyurethane dispersion liquid exceeds 3%, the light absorption rate of the prepared coating is reduced along with the increase of the mass fraction of the MXene nanosheets, and the MXene nanosheets are easy to agglomerate and are not beneficial to spraying and dispersing when the content of the MXene nanosheets is too much. When the mass fraction of the MXene nanosheets in the aqueous polyurethane dispersion liquid is too high, the viscosity of the dispersion liquid is too high, so that the spraying process is not uniform, and too much powder is easy to agglomerate. When the mass fraction of the MXene nanosheet in the aqueous polyurethane dispersion liquid is too low, the active ingredients for photothermal conversion are few, and a good photothermal conversion effect cannot be achieved. The mass fraction of MXene nanoplatelets in the aqueous polyurethane dispersion in the appropriate range is advantageous for improving the efficiency of the photothermal coating.
Example 3
A photothermal super hydrophobic coating layer containing MXene @ Au was prepared according to the same procedure as in example 1, except that in the procedure (3), the corresponding photothermal super hydrophobic coating layers were prepared in the mass ratios of MXene to Au of 12: 1, 10: 1 and 6: 1, respectively. As shown in fig. 13, for the coatings containing different mass ratios of MXene to Au prepared in examples 1 and 3, respectively, the absorptance spectrum of the coating is best represented when the mass ratio of MXene to Au is 8 to 1, so that it is optimized according to this to set the mass ratio of MXene to Au to 8 to 1. When the mass ratio of MXene to Au in the MXene @ Au hybrid dispersion liquid is too high, the content of Au particles is low, the plasmon effect and the photo-thermal synergistic effect are not obvious, and the coating absorptivity and the photo-thermal conversion performance are not high. When the mass ratio of MXene to Au in the MXene @ Au hybrid is too low, the content of Au particles is high, the plasmon effect is deteriorated due to the agglomeration and adsorption of the particles, and the photo-thermal performance is poor.
Example 4
A photothermal super hydrophobic coating containing MXene @ Au was prepared by following the same procedure as in example 1, except that in said step (8), the modified silica nanoparticles were 1.5% and 6% by mass of the aqueous polyurethane dispersion. As shown in fig. 14, for examples 1 and 4, when the mass of the modified silica nanoparticles is lower than the mass fraction of the aqueous polyurethane dispersion (1.5%), the hydrophobic property of the coating is not ideal, and when the mass of the modified silica nanoparticles is 3.5% and 6% of the mass fraction of the aqueous polyurethane dispersion, the prepared coating has super-hydrophobic property. As shown in fig. 15, when the mass of the modified silica nanoparticles was 3.5% of the mass of the aqueous polyurethane dispersion, the absorption spectrum showed better. According to the optimization, the mass of the modified silicon oxide nano particles is set to be 3.5 percent of the mass of the aqueous polyurethane dispersion liquid. The modified silicon oxide sprayed on the surface of the photo-thermal coating plays a role in improving the super-hydrophobic property of the coating. When the mass fraction of the modified silicon oxide nanoparticles is too high, the silicon oxide layer formed by spraying is too thick, so that the light absorbed by the photothermal filler MXene @ Au is reduced, and the photothermal performance is reduced. When the mass fraction of the modified silicon oxide nano particles is too low, the modified silicon oxide is too little, so that the super-hydrophobic property of the prepared coating is not high.
Comparative example 1
Photo-thermal coatings of non-hydrophobically modified MXene @ Au hybrids were prepared following the same procedure of example 1, except that spray-modified silica nanoparticles were not performed.
The photothermal super-hydrophobic coating based on MXene @ Au hybrid prepared based on the method of the embodiment is provided with the following specific application scenes:
defrosting
The coatings prepared in example 1 and comparative example 1 were placed on a-10 ℃ cold stand, respectively, and after the frost covered the entire coating surface, the power was 0.5W/cm2The 808nm laser beam of (1) was irradiated thereto. The melting process of the frost on the surface of the coating was recorded with a video camera. The superhydrophobic photothermal coating described in fig. 16 demonstrates better defrosting performance due to its high photothermal conversion capability and superhydrophobic capability.
Deicing
The coatings prepared by the method of example 1 and comparative example 1 were placed on a-15 ℃ cold plate, respectively, and ice disks of the same size and 3mm thickness were placed on the coatings, respectively. The power consumption is 0.5W/cm2The 808nm laser beam of (1) was irradiated thereto. The melting process of the ice on the coated surface was recorded with a video camera. FIG. 1 shows a schematic view of aThe superhydrophobic photothermal coating described in 7 shows better deicing performance. The super-hydrophobic property enables water formed after ice melts to flow away rapidly, light absorption on the surface of the coating is not affected by the melted water, and the ice surface is melted more rapidly due to the high light-heat conversion capacity of the super-hydrophobic light-heat coating, so that a better deicing effect is achieved.
Optical drive
The photo-thermal superhydrophobic coating was prepared on filter paper according to the procedure of example 1, and cut into appropriate shape and size. The power consumption is 2W/cm2The 808nm laser irradiates different positions of the coating, and remote optical drive can be realized. FIG. 18 is a photo-driven test of a photothermal superhydrophobic coating based on MXene @ Au hybrid prepared according to example 1. The forward driving of the photo-thermal super-hydrophobic coating can be realized by irradiating the back side of the square coating filter paper. Illuminating different positions of the triangular coated filter paper can achieve clockwise and counterclockwise rotational light driven behavior.
Drug transfer
The photo-thermal superhydrophobic coating was prepared on filter paper according to the procedure of example 1, and cut into a suitable shape and size according to the size of the drug-carrying capsule. The power consumption is 2W/cm2The 808nm laser irradiates the coating and the carried marking medicine, and the light-driven medicine transfer can be realized. FIG. 19 is a test of photothermal superhydrophobic coatings based on MXene @ Au hybrid prepared according to example 1 for drug transfer. The drug transfer is divided into that the photo-thermal super-hydrophobic coating carries a labeled drug to a site and the drug capsule is melted and released under the photo-thermal action. In the process of carrying the marked medicine, the super-hydrophobic property of the prepared coating reduces the resistance of the coating to light-driven motion on the water surface. In the process of drug melting and releasing, the high light-heat conversion capability of the prepared coating enables the transparent drug capsule to be melted rapidly at high temperature and successfully release the marked drug.
The MXene @ Au hybrid is formed by doping gold into MXene, and the doping operation and the preparation proportion of the super-hydrophobic coating are optimized, so that the photothermal super-hydrophobic coating based on the MXene @ Au hybrid is obtained. Compared with the photothermal super-hydrophobic coating based on MXene, the photothermal super-hydrophobic coating doped with Au nanoparticles has the advantages that the light absorption rate, the heating balance temperature and the photothermal conversion efficiency are effectively improved. The photothermal super-hydrophobic coating based on the MXene @ Au hybrid provided by the invention is rapid in temperature rise, high in photothermal conversion efficiency and stable in acid and alkali resistant super-hydrophobic surface. The photo-thermal super-hydrophobic coating can be used for photo-thermal defrosting and deicing and has great potential in the fields of remote light driving, drug delivery and transfer and the like.
It is to be understood that the present invention has been described with reference to certain embodiments and that various changes in form and details may be made therein by those skilled in the art without departing from the spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from the essential scope thereof. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed, but that the invention will include all embodiments falling within the scope of the appended claims.

Claims (9)

1. A preparation method of a photo-thermal super-hydrophobic coating based on MXene @ Au hybrid is characterized by comprising the following steps:
(1) utilizing MXene material, and etching titanium aluminum carbide by using hydrochloric acid or hydrofluoric acid to obtain MXene nanosheets; obtaining Au nano particles by adopting a gold seed solution regrowth method;
(2) carrying out ultrasonic co-mixing on the MXene nanosheet and the dispersion liquid of the Au nanoparticles to form MXene @ Au hybrid dispersion liquid, and drying to obtain MXene @ Au hybrid powder;
(3) adding the MXene @ Au hybrid powder into waterborne polyurethane to obtain waterborne polyurethane dispersion liquid of an MXene @ Au hybrid; preparing silicon oxide nanoparticles by using a Stober method: coupling the silicon oxide nanoparticles with 1H, 2H, 3H, 4H-perfluoroalkyl triethoxysilane to obtain modified super-hydrophobic silicon oxide nanoparticles;
(4) and (3) sequentially spraying, heating and drying the aqueous polyurethane dispersion liquid of the MXene @ Au hybrid and the dispersion liquid of the modified super-hydrophobic silicon oxide nanoparticles by using a spray gun to obtain the photo-thermal super-hydrophobic coating based on the MXene @ Au hybrid.
2. The method of claim 1, wherein the MXene nanoplatelets are Ti 3C2TxThe Au nano particles are spherical Au nano particles with the particle size of 25-35 nm.
3. The method for preparing the photothermal super hydrophobic coating based on MXene @ Au hybrid of claim 2, wherein in the step (3), the weight percentage of MXene nanosheets in the aqueous polyurethane dispersion of MXene @ Au hybrid is 1% to 4%.
4. The method for preparing the photothermal super hydrophobic coating based on MXene @ Au hybrid of claim 3, wherein in the step (3), the weight percentage of MXene nanosheets in the aqueous polyurethane dispersion of MXene @ Au hybrid is 3%.
5. The method for preparing the photothermal super hydrophobic coating based on MXene @ Au hybrid of claim 1, wherein in the step (2), the weight ratio of MXene to Au in the MXene @ Au hybrid powder is 12: 1 to 6: 1.
6. the method for preparing the photothermal super hydrophobic coating based on MXene @ Au hybrid of claim 5, wherein in the step (2), the weight ratio of MXene to Au in the MXene @ Au hybrid powder is 8: 1.
7. The method for preparing the photothermal superhydrophobic coating based on the MXene @ Au hybrid of claim 1, wherein in the step (3), the mass of the modified silica nanoparticles is 1.5% to 6% of the mass of the aqueous polyurethane dispersion.
8. The method for preparing the photothermal super hydrophobic coating based on MXene @ Au hybrid according to claim 7, wherein in the step (3), the modified silica nanoparticle mass is 3.5% of the aqueous polyurethane dispersion mass.
9. The photothermal super-hydrophobic coating based on MXene @ Au hybrid is characterized by being prepared by the preparation method of photothermal super-hydrophobic coating based on MXene @ Au hybrid according to any one of claims 1 to 9.
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