CN114672233B - 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 PDFInfo
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Abstract
The invention provides a photothermal super-hydrophobic coating based on MXene @ Au hybrid and a preparation method thereof, and the preparation method comprises the following steps: preparing MXene nano-sheets; 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 silica nanoparticles; (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 driving, drug delivery and transfer and the like.
Description
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 optical drive, assistance of drug delivery and the like. To obtain a photo-thermal super-hydrophobic coating with excellent properties, 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 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 comprises: a modified multi-layer MXene compound, a 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, so as 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 the 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 nano-particles with 1H,2H,3H, 4H-perfluoroalkyl triethoxysilane to obtain modified super-hydrophobic silicon oxide nano-particles;
(4) And (3) 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 in sequence by using a spray gun to obtain the photothermal super-hydrophobic coating based on the MXene @ Au hybrid.
Further, the MXene nanosheets are Ti 3 C 2 T x 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 liquid of the MXene @ Au hybrid, the mass fraction of the MXene nanosheets in the aqueous polyurethane dispersion liquid is 1% to 4%.
Preferably, in the step (3), in the aqueous polyurethane dispersion of the MXene @ Au hybrid, the MXene nanosheet accounts for 3% of the aqueous polyurethane dispersion 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 photothermal super-hydrophobic coating based on the MXene @ Au hybrid, and the photothermal super-hydrophobic coating is prepared by the method.
The photothermal super-hydrophobic coating based on MXene @ Au hybrid and the preparation method thereof have the following advantages: MXene @ Au hybrid is used as photo-thermal filler, and modified silicon oxide nanoparticles are sprayed on the MXene @ Au hybrid photo-thermal coating, so that the photo-thermal super-hydrophobic performance of the MXene @ 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 nanoparticles enables the photothermal super-hydrophobic coating to have stable and excellent super-hydrophobic performance.
Drawings
FIG. 1 is a flow chart of preparation 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 the scanning electron microscope image of MXene @ Au hybrid and simple MXene material prepared in example 1 and the transmission electron microscope image of MXene @ Au hybrid;
FIG. 4 is a graph comparing the X-ray photoelectron spectroscopy results of MXene @ Au hybrid prepared in example 1 and simple MXene material;
FIG. 5 is a graph comparing the light absorption rate of MXene photothermal coating prepared in example 1 with that of MXene @ Au hybrid photothermal coating;
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 scanning electron microscope image and a cross-sectional scanning electron microscope image of the MXene @ Au hybrid photothermal super-hydrophobic coating after spraying modified silica prepared in example 1;
FIG. 8 is a graph of contact angle test data and rolling angle test data for MXene @ Au hybrid-based photothermal superhydrophobic coatings prepared in example 1;
FIG. 9 is a graph comparing the photothermal performance of the MXene @ Au hybrid photothermal superhydrophobic coating after spraying modified silica and the MXene photothermal superhydrophobic coating after spraying modified silica prepared in example 1;
FIG. 10 is a graph of contact angle test results of the MXene @ Au hybrid-based photo-thermal superhydrophobic coating prepared in example 1 after undergoing multiple photo-thermal conversion cycles;
FIG. 11 is a graph of the contact angle test results of the photo-thermal super-hydrophobic coating based on MXene @ Au hybrid prepared in example 1 under acid and alkali solution;
FIG. 12 is a graph of photoabsorption rate test of the photothermal super hydrophobic coating based on MXene @ Au hybrid prepared in example 1 and example 2;
FIG. 13 is a graph of photoabsorption rate test of the photothermal super hydrophobic coating based on MXene @ Au hybrid prepared in example 1 and example 3;
FIG. 14 is contact angle test data of photo-thermal super-hydrophobic coating based on MXene @ Au hybrid prepared in example 1 and example 4;
FIG. 15 is a graph of photoabsorption rate test of the photothermal super hydrophobic coating based on MXene @ Au hybrid prepared in example 1 and example 4;
FIG. 16 is a defrosting performance test of the photothermal super hydrophobic coating based on MXene @ Au hybrid prepared in example 1 and the MXene @ Au hybrid photothermal coating prepared according to comparative example 1 without spray coating of modified silica;
FIG. 17 is a deicing performance test of the photothermal superhydrophobic coating based on MXene @ Au hybrid prepared in example 1 and the MXene @ Au hybrid photothermal coating prepared according to comparative example 1 without spray coating of modified silica;
FIG. 18 is a light driven test of the photothermal superhydrophobic coating based on MXene @ Au hybrid prepared in example 1;
FIG. 19 is the test of MXene @ Au hybrid-based photothermal superhydrophobic coating prepared in example 1 for drug transfer.
Detailed Description
In order to better understand the purpose, structure and function of the invention, the photothermal 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 photo-thermal super-hydrophobic coating of the invention. The specific process is as follows: the MXene material is provided, MAX (aluminum titanium carbide) is etched by hydrochloric acid or hydrofluoric acid to obtain MXene nano-sheets, 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 and Au to form MXene @ Au hybrid dispersion liquid under the electrostatic action. MXene @ Au hybrid powder can be obtained after drying.
Adding MXene @ Au hybrid powder into aqueous polyurethane to obtain aqueous polyurethane dispersion liquid of the MXene @ Au hybrid, namely photo-thermal coating dispersion liquid. Silicon oxide nanoparticles can be prepared using the traditional Stober method: coupling the silicon oxide nano-particles with 1H,2H,3H, 4H-perfluoroalkyl triethoxysilane to obtain the modified super-hydrophobic silicon oxide nano-particles. 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
10 mL of concentrated hydrochloric acid (6 mol/L) was slowly added to 10 mL of deionized water, and stirred uniformly. 1 g of lithium fluoride powder was added to the solution, and stirred for 20 min to dissolve. Slowly adding 1 g MAX powder into the solution for multiple times, stirring for 30 min, turning on heating, and allowing the mixed solution to react at 55 deg.C and 400 rpm 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
10 mL of a 0.1 mol/L cetyltrimethylammonium bromide solution was prepared, and 0.25 mL of a 0.01 mol/L chloroauric acid solution was added thereto and stirred for 15 min. 0.5 mL of freshly prepared sodium borohydride solution with the concentration of 0.01 mol/L is added, and the mixture is uniformly mixed and stirred. After that, the solution was stirred at 200 rpm for 2 hours at room temperature to obtain a golden brown Au seed solution. 190 mL of deionized water was added to 10 mL of a 0.1 mol/L hexadecyltrimethylammonium bromide solution, and after stirring uniformly, 4 mL of a 0.01 mol/L chloroauric acid solution was added thereto and stirred for 15 min. To this was added 15 mL of a freshly prepared ascorbic acid solution with a concentration of 0.1 mol/L, and the reaction was stirred for 15 min. To the solution was added 0.12 mL of the Au seed solution prepared in advance, 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 0.03 mg/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. Drying to obtain MXene @ Au hybrid powder.
As shown in FIG. 2, MXene @ Au hybrid powder and pure MXene material were analyzed by X-ray diffraction pattern. In the spectrum 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.
Figure 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 result 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), the Au nanoparticles distributed on the MXene nano-platelets can be clearly seen, as shown in FIG. 3 (c). As can be seen from the figure, the MXene nanosheets of the invention are Ti 3 C 2 T x 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, the corresponding peaks of 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 500 uL 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 8:1. And then ultrasonic mixing is carried out for 0.5h to obtain aqueous polyurethane dispersion liquid of MXene @ Au hybrid. The aqueous polyurethane can be commercial Jitian chemical F0401 type aqueous polyurethane.
(5) A 2 × 2 cm piece of quartz glass was provided as a substrate for spray coating, the substrate was heated on a hot stage at 120 ℃, and an aqueous polyurethane dispersion (photothermal coating dispersion) of mxene @ au hybrid was spray coated using a spray gun with 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 absorptivity of MXene @auphoto-thermal coating is higher than that of MXene photo-thermal coating. As shown in fig. 6 (a), the photothermal temperature rise of the MXene @auhybrid photothermal coating is higher than that of the MXene photothermal coating under multiple laser irradiation of different powers. Under the irradiation of 0.5W/cm 2 When the temperature rise equilibrium maximum temperature of the MXene @ Au hybrid photo-thermal coating is 130.2 ℃, the photo-thermal conversion efficiency calculated according to the figure 6 (b) is 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 is added with Au to form MXene @ Au hybrid, the photothermal performance and the conversion efficiency are effectively improved. On one hand, the Au nano particles have a plasmon effect, and the light absorption rate of the MXene @ Au structure is higher due to the addition of Au, so that photo-thermal conversion is facilitated; on the other hand, the layered structure of the MXene nanosheet is suitable for doping and adding Au particles, the nanosheet layer is beneficial to rapid conduction and diffusion of heat generated by doping Au and heat generated by the nanosheet, the interaction of the Au and the nanosheet enhances light absorption, the photo-thermal synergistic enhancement effect is improved, the plasmon effect of Au is combined, and finally the photo-thermal conversion of the MXene @ Au photo-thermal coating is greatly improved.
(6) The silicon oxide nanoparticles are obtained by tetraethyl orthosilicate hydrolysis reaction by the Stober method. To 150 mL of absolute ethanol, 8 mL of aqueous ammonia and 20 mL of deionized water were added, and the mixture was stirred and mixed. Then 4 mL of tetraethyl orthosilicate was added and stirred for 12 h for reaction, followed by drying and collection of the silica nanoparticle powder.
(7) 1 g of 1H,2H,3H, 4H-perfluoroalkyltriethoxysilane was added to 35 mL of anhydrous ethanol and stirred for 30 min, and then 300 mg of the previously prepared silica nanoparticle powder was added thereto, stirred for 3h, and dried to obtain modified silica nanoparticles.
(8) And weighing 20 mg 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 a dispersion liquid of modified silicon oxide nano particles on the surface of the MXene @ Au hybrid photo-thermal coating by using a spray gun, and drying for 2h to obtain the MXene @ Au hybrid-based photo-thermal super-hydrophobic coating.
Fig. 7 shows SEM surface and cross section of the photo-thermal super-hydrophobic coating based on mxene @ au hybrid after spraying modified silica, and it can be observed that the modified silica nanoparticles 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 prepared photothermal super-hydrophobic coating based on MXene @ Au hybrid was subjected to photothermal performance test as shown in FIG. 9. As shown in fig. 9 (a), the photo-thermal superhydrophobic coating exhibits stable photo-thermal conversion capability during multiple cycles of photo-thermal conversion. As shown in FIGS. 9 (b) and 9 (c), under relatively mild 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 as high as 121 ℃ and the corresponding photo-thermal conversion efficiency is calculated to be 85.8 percent; the temperature rising equilibrium temperature of the MXene photo-thermal super-hydrophobic coating sprayed with the silicon oxide is 1The photothermal efficiency was calculated to be 76.9% at 08 ℃. 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 show 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 lower than 3%, the light absorption rate of the prepared coating is increased along 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, because 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 the powder is too much and is easy to agglomerate. And when the mass fraction of the MXene nanosheets in the aqueous polyurethane dispersion liquid is too low, the effective components for photothermal conversion are less, and a good photothermal conversion effect cannot be achieved. The mass fraction of the MXene nanosheets in the aqueous polyurethane dispersion in the appropriate range is advantageous for improving the efficiency of the photothermal coating.
Example 3
The photo-thermal superhydrophobic coating containing MXene @ Au was prepared according to the same procedure as in example 1, except that in the procedure (3), the corresponding photo-thermal superhydrophobic coatings were prepared according to MXene to Au mass ratios of 12 to 1, 10 to 1, and 6 to 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 photo-thermal synergistic effect are not obvious, and the conditions that the coating absorptivity is not high and the photo-thermal conversion performance is not high are shown. When the mass ratio of MXene to Au in the MXene @ Au hybrid is too low, the content of Au particles is high, the aggregation and adsorption of the particles cause the plasmon effect to be poor, and the photo-thermal performance is poor.
Example 4
A photothermal super hydrophobic coating containing MXene @ Au was prepared according to the same procedure as in example 1, except that in the procedure (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. Optimized according to the method, 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 coating of MXene @ Au hybrid without hydrophobic modification was prepared by following the same procedure as in example 1, except that the operation of spray-coating modified silica nanoparticles was 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 by the methods of example 1 and comparative example 1 were placed on respective substrates
On a cooling table at 10 ℃ and after the frost covered the entire coating surface, the power was 0.5W/cm 2 The 808 nm 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 methods of example 1 and comparative example 1 were placed on the respective substrates
On a cooling table at 15 ℃ ice disks of the same size and 3 mm thickness were placed on the coating, respectively. The power consumption is 0.5W/cm 2 808 nm laser light of (2) was irradiated thereto. The melting process of the ice on the coated surface was recorded with a video camera. The superhydrophobic photothermal coating described in fig. 17 demonstrates 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. With a power of 2W/cm 2 The 808 nm 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 super-hydrophobic 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/cm 2 The 808 nm laser irradiates the coating and the carried marking medicine, and the light-driven medicine transfer can be realized. Fig. 19 is a test of the photothermal superhydrophobic coating 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 invention obtains the photothermal super-hydrophobic coating based on the MXene @ Au hybrid by doping gold into MXene to form the MXene @ Au hybrid and optimizing the doping operation and the preparation ratio of the super-hydrophobic coating. Compared with the photo-thermal super-hydrophobic coating based on MXene, the photo-thermal super-hydrophobic coating doped with Au nanoparticles has the advantages that the light absorption rate, the heating balance temperature and the photo-thermal conversion efficiency are effectively improved. The photothermal super-hydrophobic coating based on the MXene @ Au hybrid has the advantages of rapid temperature rise, high photothermal conversion efficiency and stable acid-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 the features and embodiments, or equivalent substitutions 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 (8)
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 aqueous polyurethane to obtain aqueous polyurethane dispersion of MXene @ Au hybrid; preparing silicon oxide nanoparticles by using a Stober method: coupling the silicon oxide nano-particles with 1H,2H,3H, 4H-perfluoroalkyl triethoxysilane to obtain modified super-hydrophobic silicon oxide nano-particles;
(4) 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 by using a spray gun to obtain a photo-thermal super-hydrophobic coating based on the MXene @ Au hybrid;
the MXene nanosheet is Ti 3 C 2 T x The Au nano particles are spherical Au nano particles with the particle size of 25-35 nm.
2. The method for preparing the photothermal super-hydrophobic coating based on the MXene @ Au hybrid of claim 1, wherein in the step (3), the MXene nanosheet accounts for 1 to 4% of the aqueous polyurethane dispersion liquid in the aqueous polyurethane dispersion liquid of the MXene @ Au hybrid.
3. The preparation method of the MXene @ Au hybrid-based photo-thermal superhydrophobic coating according to claim 2, wherein in the step (3), the MXene @ Au hybrid aqueous polyurethane dispersion liquid comprises 3% of MXene nanosheets in mass percentage of the aqueous polyurethane dispersion liquid.
4. The method for preparing the photothermal superhydrophobic coating based on the MXene @ Au hybrid of claim 1, wherein in the step (2), in the aqueous polyurethane dispersion liquid of the MXene @ Au hybrid, the mass ratio of MXene to Au in the MXene @ Au hybrid powder is 12:1 to 6:1.
5. the method for preparing the photothermal super-hydrophobic coating based on MXene @ Au hybrid according to claim 4, wherein 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.
6. the method for preparing the photothermal super hydrophobic coating based on MXene @ Au hybrid according to claim 1, wherein in the step (3), the modified super hydrophobic silica nanoparticles mass is 1.5% to 6% of the aqueous polyurethane dispersion mass.
7. The method for preparing the photothermal superhydrophobic coating based on the MXene @ Au hybrid according to claim 6, wherein in the step (3), the mass of the modified superhydrophobic silicon oxide nanoparticles is 3.5% of the mass of the aqueous polyurethane dispersion liquid.
8. The photothermal super-hydrophobic coating based on the MXene @ Au hybrid is characterized by being prepared by the preparation method of the photothermal super-hydrophobic coating based on the MXene @ Au hybrid according to any one of claims 1-7.
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| CN113019867A (en) * | 2019-12-24 | 2021-06-25 | 华中科技大学 | Method for preparing photo-thermal film based on spraying method |
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