CN113462207B - Photocatalytic self-cleaning composite coating and preparation method thereof - Google Patents
Photocatalytic self-cleaning composite coating and preparation method thereof Download PDFInfo
- Publication number
- CN113462207B CN113462207B CN202110805816.1A CN202110805816A CN113462207B CN 113462207 B CN113462207 B CN 113462207B CN 202110805816 A CN202110805816 A CN 202110805816A CN 113462207 B CN113462207 B CN 113462207B
- Authority
- CN
- China
- Prior art keywords
- mxene
- solution
- nanosheet
- composite coating
- titanium dioxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- 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
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
-
- 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/24—Electrically-conducting paints
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention provides a photocatalytic self-cleaning composite coating and a preparation method thereof, belonging to the field of self-cleaning materials. The coating comprises: the method comprises the steps of using an MXene precursor as a raw material, etching by using an etching agent to obtain MXene accordion-shaped nanosheets, intercalating and layering by using an intercalating agent to obtain MXene single-layer nanosheets, adding a cosolvent, titanium dioxide and silicate ester in a volume ratio of 1-3: 1-5: 6-10 to perform hydrolysis reaction, and diluting to obtain the MXene single-layer nanosheets/titanium dioxide photocatalytic self-cleaning composite coating, wherein the volume ratio of the titanium dioxide to the MXene single-layer nanosheets is 1-3: 5-15. The preparation method disclosed by the invention is simple in process and strong in operability, and the prepared coating has excellent aging resistance, antistatic property, super-hydrophilic property and photocatalytic activity, shows excellent antifouling potential and excellent weather resistance in the application of the self-cleaning coating, is easy to prepare on a large scale and has a wide application prospect.
Description
Technical Field
The invention relates to the field of self-cleaning materials, in particular to a photocatalytic self-cleaning composite coating and a preparation method thereof.
Background
In order to clean dirt such as dust, oil stain and the like on the surfaces of various objects such as walls, vehicles, glass panels and the like, people adopt four modes of manual scrubbing, water spraying flushing, machine scrubbing and preparation of self-cleaning surfaces. The traditional manual cleaning method is time-consuming, labor-consuming and extremely high in cost, and has huge hidden dangers in terms of personal safety of cleaning personnel. Self-cleaning techniques are highly appreciated for significantly reducing the number of operations and for reducing maintenance costs.
MXene is a two-dimensional material which is sought after in the field of new material research, and attracts the attention of research workers in different directions since being discovered in 2011. Selectively etching the A layer In the MAX phase of the precursor by HF acid to obtain MXene powder, wherein the 'A' In the MAX phase of the precursor represents elements of a third main group and a fourth main group, such as Ti, Si, Ge, Ga, In and Al; "M" in the MAX phase of the precursor is an early transition metal element, such as Sc, V, Cr, Ti, Sc, and the like; the "X" in the MAX phase of the precursor represents N, C. The two-dimensional material MXene has excellent conductivity, hydrophilicity and catalytic activity and is widely applied to the field of batteries, however, no MXene-based self-cleaning material coating exists.
Disclosure of Invention
Aiming at the technical problems, the invention provides a photocatalytic self-cleaning composite coating and a preparation method thereof, wherein an MXene precursor is adopted to prepare an MXene single-layer nanosheet through etching and intercalation; adding the MXene monolayer nanosheet into deionized water, centrifuging to form a stable colloidal solution, then adding silicate ester, a cosolvent and a titanium dioxide solution for hydrolysis reaction, diluting after complete hydrolysis, stirring and mixing uniformly to obtain the MXene monolayer nanosheet/titanium dioxide photocatalytic self-cleaning composite coating, which has excellent ageing resistance, antistatic property, super-hydrophilicity and photocatalytic activity. The preparation method provided by the invention is simple in process and strong in operability.
The invention provides a photocatalytic self-cleaning composite coating, which comprises: the method comprises the steps of taking an MXene precursor as a raw material, etching by using an etching agent to obtain MXene accordion-shaped nanosheets, intercalating and delaminating by using an intercalating agent to obtain MXene single-layer nanosheets, adding a cosolvent, 5wt% of a titanium dioxide solution and silicate ester to perform a hydrolysis reaction, and diluting until the mass concentration of the MXene single-layer nanosheets is below 1mg/mL to obtain the MXene single-layer nanosheet/titanium dioxide photocatalytic self-cleaning composite coating, wherein the volume ratio of the 5wt% of the titanium dioxide solution to the MXene single-layer nanosheet colloidal solution is 1-3: 5-15.
Preferably, the MXene precursor comprises Ti3SiC2、Ti2AlC、Nb2Any one of alcs.
Preferably, the intercalation agent includes any one of potassium hydroxide solution, isopropylamine solution, tetramethylammonium hydroxide.
Preferably, the concentration of the intercalating agent is 2-5mol/L, and the volume ratio of the MXene accordion-shaped nanosheets to the intercalating agent is 2-5: 15-65.
Preferably, the volume ratio of the co-solvent, 5wt% titania solution and silicate is 1-3: 1-5: 6-10.
Preferably, the silicate comprises any one or more of methyl orthosilicate, ethyl orthosilicate and propyl orthosilicate.
Preferably, the co-solvent comprises any one or more of isopropanol, ethanol, methanol, n-propanol.
Preferably, the diluent comprises any one or more of ethanol, propylene glycol methyl ether and methanol.
The invention also provides a preparation method of the photocatalytic self-cleaning composite coating, which comprises the following steps:
s1, preparing MXene precursor accordion-shaped nanosheets: adding an etchant into an MXene precursor serving as a raw material, controlling the temperature to be 25-40 ℃, violently stirring for 36-50h to obtain an MXene accordion-shaped nanosheet solution, and centrifuging for many times by using deionized water to remove the residual etchant to obtain the MXene accordion-shaped nanosheet solution;
s2, preparing MXene single-layer nanosheet stable colloidal solution: adding an intercalating agent into the obtained MXene accordion-shaped nanosheet solution according to the volume, violently stirring and reacting for 12-36h to obtain an MXene monolayer nanosheet solution, and washing to obtain a supernatant with the pH of 3-4 to obtain an MXene monolayer nanosheet stable colloidal solution;
s3, preparing the MXene single-layer nanosheet/titanium dioxide photocatalytic self-cleaning composite coating: adding a cosolvent, a 5wt% titanium dioxide solution and silicate ester into the stable colloidal solution of the MXene monolayer nanosheet according to the volume ratio for hydrolysis reaction, and adding a diluent to dilute until the mass concentration of the MXene monolayer nanosheet is below 1mg/mL after the hydrolysis is finished, so as to obtain the MXene monolayer nanosheet/titanium dioxide photocatalytic self-cleaning composite coating.
In steps S2 and S3, MXene single-layer nanosheet stable colloid presents strong acidity or alkalinity according to different intercalation agents, and the hydrolysis reaction of silicate ester is influenced. The silicate ester is hydrolyzed to form a silicon oxygen structure, and forms a connecting bond with a special two-dimensional structure of the MXene single-layer nano-sheet. On the other hand, the MXene single-layer nanosheet has excellent mounting property and certain adsorption property due to the two-dimensional structure; the method provides sites for the mounting and attachment of the titanium dioxide, is more beneficial to the MXene single-layer nanosheets to play the role of a cocatalyst, and improves the photocatalytic capacity of the titanium dioxide.
Preferably, the temperature of the hydrolysis reaction in step S3 is 35-40 ℃.
The technical scheme of the invention has the following advantages:
1. the preparation method disclosed by the invention is simple in process and strong in operability, and has excellent properties by utilizing the specific two-dimensional structure of the MXene single-layer nanosheet and the specific selection of the intercalator. For example, depending on whether the intercalating agent exhibits a strong acidity or basicity, this may affect the hydrolysis of the silicate; the silicate ester is hydrolyzed to form a silicon oxygen structure, and forms a connecting bond with a special two-dimensional structure of the MXene single-layer nanosheet; the stable colloid of the MXene single-layer nanosheet provides sites for the mounting and adsorption of the titanium dioxide due to the two-dimensional structure of the stable colloid, so that the stable colloid of the MXene single-layer nanosheet is more beneficial to the MXene single-layer nanosheet to exerting the property of a cocatalyst and improving the photocatalytic capacity of the titanium dioxide. The excellent aging resistance, the antistatic property, the super-hydrophilicity and the photocatalytic activity are simultaneously realized by utilizing the excellent properties of the MXene single-layer nanosheet and the connection, the mounting and the adsorption of silicate and titanium dioxide.
2. The MXene single-layer nanosheet prepared by the method can be used as a cocatalyst to effectively enhance the photocatalytic activity of titanium dioxide, and an excellent photocatalytic treatment effect under the condition of extremely small titanium dioxide addition amount is realized.
3. The MXene single-layer nanosheet prepared by the method can be treated by different intercalating agents so as to protect the MXene single-layer nanosheet from inhibiting photooxidation. Research shows that under the condition of simulating natural light aging by using a xenon lamp, the content of active oxygen generated by irradiating MXene single-layer nanosheets by using natural light simulated by the xenon lamp can be increased by induction, so that the oxidation rate is increased, and MXene aging is accelerated to lose hydrophilic groups. In comparison, in the preparation process of the paint, the alkaline intercalation agent and water are selected as the intercalation agent, and natural aging is simulated under the same condition. The water intercalation MXene single-layer nanosheet can only maintain the hydrophilicity for hours, and the MXene single-layer nanosheet prepared by the alkaline intercalating agent can still maintain the hydrophilicity after tens of hours.
4. The MXene single-layer nanosheet prepared by the method has excellent conductivity, and the coating prepared by the method has excellent antistatic property, so that the self-cleaning performance of the coating is further improved. Measuring the surface resistance of the alloy at 106-108And dust is not easy to attach.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a comparison of the efficiency of photocatalytic degradation of rhodamine b by a niobium carbide single-layer nanosheet/titanium dioxide composite material and titanium dioxide;
FIG. 2 is a comparison of water contact angles of a niobium carbide single-layer nanosheet/titanium dioxide photocatalytic self-cleaning composite coating (a) and a control group (b);
FIG. 3 is a comparison graph of a glass surface (a) and an uncoated glass surface (b) after application of a niobium carbide single-layer nanosheet/titanium dioxide photocatalytic self-cleaning composite coating;
FIG. 4 is a scanning electron microscope image of the niobium carbide single-layer nanosheet/titanium dioxide photocatalytic self-cleaning composite coating on a glass section (a) and a glass surface (b).
Detailed Description
Example 1:
(1) 1g of niobium aluminum carbide is taken as a precursor, and is vigorously stirred in 10mL of 40% hydrofluoric acid solution at the temperature of 35 ℃ for 48 hours to obtain niobium carbide;
(2) transferring the obtained niobium carbide into 10mL of isopropylamine solution, violently stirring for 24h to enable the niobium carbide to be intercalated to obtain niobium carbide single-layer nanosheets, centrifuging for many times by using deionized water after the reaction is finished to wash away the intercalant until the pH of a supernatant is 3-4, adding deionized water to a constant volume of 100mL, carrying out 3500rpm, and centrifuging for 60min to obtain a stable colloidal solution;
(3) 5mL of isopropanol serving as a cosolvent, 2mL of niobium carbide single-layer nanosheet colloidal solution, 4mL of 5wt% titanium dioxide solution and 20mL of ethyl orthosilicate are mixed, and hydrolysis reaction of the ethyl orthosilicate is carried out at the temperature of 25 ℃ and the rotating speed of 300 rpm;
(4) adding 12mL of ethanol, 8mL of propylene glycol methyl ether and 7mL of methanol into the obtained hydrolysis solution for dilution, and preparing the niobium carbide single-layer nanosheet/titanium dioxide photocatalytic self-cleaning composite coating;
(5) placing 5mL of the obtained composite photocatalytic coating into a beaker filled with 100mL of 25mg of organic pollutants, and carrying out dark reaction for 30 min;
(6) after the dark reaction was completed, the solution was irradiated with simulated visible light for 60min using a xenon lamp (300W, λ >420 nm). And calculating the concentration difference of the organic pollutants before and after the reaction is finished.
(7) The niobium carbide single-layer nanosheet/titanium dioxide photocatalytic self-cleaning composite coating is applied to catalytic degradation of organic matters (taking rhodamine b as an example). In order to compare the effects of the method, the titanium dioxide coating with the same addition amount is used as a control test, and a catalytic degradation experiment is carried out simultaneously with the niobium carbide single-layer nanosheet/titanium dioxide photocatalytic self-cleaning composite coating prepared by the method. Sampling at different time intervals to determine and analyze the residual concentration of rhodamine b, and recording the data as shown in the attached figure 1.
Compared with a pure titanium dioxide contrast test, the niobium carbide single-layer nanosheet/titanium dioxide photocatalytic self-cleaning composite coating has a very high removal rate of organic matters. On one hand, because the addition amount of the two groups of titanium dioxide in the experiment is lower than 1mg and is far lower than the addition amount of the common photocatalyst in the photocatalysis experiment, the effect of pure titanium dioxide is poor; on the other hand, under the condition of such low addition amount, the niobium carbide as the cocatalyst greatly improves the photocatalytic performance of the titanium dioxide and realizes high photocatalytic activity. In the use of self-cleaning coatings, exterior walls exposed to urban environments are often soiled by the attachment of organic matter. The self-cleaning coating prepared by the invention can degrade organic matters by utilizing high photocatalytic activity, thereby realizing the self-cleaning characteristic.
Example 2:
(1) the niobium carbide single-layer nanosheet/titanium dioxide photocatalytic self-cleaning composite coating is prepared in the same manner as in example 1.
(2) And (3) uniformly spraying the obtained photocatalytic self-cleaning composite coating on 30 cm-30 cm toughened glass by using a spray gun under the condition that the pressure of an air compressor is 0.5-0.6MPa, and naturally airing for 24 hours.
(3) Removing the cosolvent isopropanol in the preparation process of the niobium carbide single-layer nanosheet/titanium dioxide photocatalytic self-cleaning composite coating, and spraying and drying the composite coating on toughened glass as a control group in the same way.
(4) The contact angle measuring instrument is adopted to measure the water contact angle of the surface of toughened glass sprayed by the niobium carbide single-layer nanosheet/titanium dioxide photocatalytic self-cleaning composite coating as shown in figure 2(a), the water contact angle is 3.82 degrees, and the super-hydrophilicity is proved. The contact angle of the surface of the toughened glass sprayed by the control group is measured by a contact angle measuring instrument, as shown in fig. 2(b), the water contact angle is 27.58 degrees, and the toughened glass does not have super-hydrophilicity, so that the addition of the cosolvent isopropanol is a necessary component of the self-cleaning composite coating prepared by the invention.
Example 3:
(1) niobium carbide single-layer nanosheets were prepared in the same manner as in example 1.
(2) Equally dividing the niobium carbide single-layer nanosheet into two parts, centrifuging and washing away the intercalation agent for multiple times by using deionized water after one part of the niobium carbide single-layer nanosheet is reacted until the pH of a supernatant is 3-4, adding deionized water to a constant volume of 50mL, carrying out 3500rpm, and centrifuging for 60min to obtain a stable colloidal solution; and taking the other part as a control group, directly adding deionized water to fix the volume to 50mL without washing the intercalation agent, carrying out 3500rpm, and centrifuging for 60min to obtain a stable colloidal solution.
(3) 5mL of isopropanol serving as a cosolvent, 2mL of niobium carbide single-layer nanosheet colloidal solution, 4mL of 5wt% titanium dioxide solution and 20mL of ethyl orthosilicate are mixed, and hydrolysis reaction of the ethyl orthosilicate is carried out at the temperature of 25 ℃ and the rotating speed of 300 rpm; the same 2mL of the control stable colloidal solution was mixed with 5mL of isopropanol, 4mL of 5wt% titanium dioxide solution and 20mL of ethyl orthosilicate, and hydrolysis of ethyl orthosilicate was carried out at 25 ℃ and 300 rpm.
(4) And adding 12mL of ethanol, 8mL of propylene glycol methyl ether and 7mL of methanol into the obtained two hydrolyzed solutions for dilution, and preparing the niobium carbide single-layer nanosheet/titanium dioxide photocatalytic self-cleaning composite coating and the control group coating.
And comparing the niobium carbide single-layer nanosheet solution prepared by the control group with the stable colloidal solution of niobium carbide single-layer nanosheets prepared by the invention. After the paint prepared by the control group according to the same method and the niobium carbide single-layer nanosheet/titanium dioxide photocatalytic self-cleaning composite paint are placed in a sample bottle for a period of time, the niobium carbide single-layer nanosheet solution of the control group precipitates, and the paint prepared by the control group can be rapidly gelled when placed in the bottle and cannot be sprayed for use. The niobium carbide single-layer nanosheet colloidal solution prepared by the method is stable and has good dispersibility.
Example 4:
(1) the niobium carbide single-layer nanosheet/titanium dioxide photocatalytic self-cleaning composite coating is prepared in the same manner as in example 1.
(2) The photocatalytic self-cleaning composite coating is sprayed on the toughened glass according to the same method as the embodiment 2 and naturally dried.
(3) In a xenon lamp aging test box, the blackboard temperature is 65 ℃, the temperature is 35 ℃, the humidity is 40 percent, and the irradiation intensity is 50W/m2After 108min of continuous operation, the panels were wetted with water sprays and continued to run for 18min as a cycle. Each cycle was 2 h. And after one cycle is finished, measuring the water contact angle on the surface of the toughened glass by using a contact angle measuring instrument.
(4) The cosolvent isopropanol in the hydrolysis reaction with the tetraethoxysilane is removed, and other preparation processes are unchanged and used as a control group. The aging experiment is carried out on the niobium carbide single-layer nanosheet/titanium dioxide photocatalytic self-cleaning composite coating prepared by the method under the same condition. The water contact angles of the surface of the tempered glass were measured at different aging times and the recorded data are shown in table 1.
TABLE 1 Water contact Angle Change in aging experiment of niobium carbide monolayer nanosheet/titanium dioxide photocatalytic self-cleaning composite coating
Compared with a control group, the niobium carbide single-layer nanosheet/titanium dioxide photocatalytic self-cleaning composite coating is excellent in ageing resistance. Under severe experimental conditions, the time to maintain hydrophilicity was much longer than the control coating. In the use of the self-cleaning coating, the long-time maintenance of the hydrophilicity is beneficial to the self-cleaning capability of the coating. In rainy days, the liquid drops on the surface of the substrate are fully contacted with the substrate due to hydrophilicity to spread out to form a water film. Because a water film exists between the pollutants and the super-hydrophilic self-cleaning coating, the pollutants such as dust and dirt are easily washed away by rainwater to realize the self-cleaning effect, and the coating has excellent weather resistance.
Example 5:
(1) the niobium carbide single-layer nanosheet/titanium dioxide photocatalytic self-cleaning composite coating is prepared in the same manner as in example 1.
(2) The photocatalytic self-cleaning composite coating is sprayed on the toughened glass according to the same method as the embodiment 2 and naturally dried.
(3) The surface resistance of the paint film was measured using an 1155TMF multifunctional insulation resistance tester. And (3) carrying out surface resistance test on the toughened glass which is not coated and the toughened glass coated with the niobium carbide single-layer nanosheet/titanium dioxide photocatalytic self-cleaning composite coating prepared by the invention under the same condition. The sheet resistance data are recorded as shown in table 2.
TABLE 2 surface resistance data of niobium carbide single-layer nanosheet/titanium dioxide photocatalytic self-cleaning composite coating
Generally considered to have a surface resistance of 106-108Omega is good in conductivity, has good antistatic property, is not easy to adsorb tiny dust, and can keep the surface of the base material clean. The surface resistance of the photocatalytic self-cleaning composite coating coated with niobium carbide single-layer nanosheets/titanium dioxide is 107Omega, has better antistatic property. The surface resistance of the uncoated glass is relatively high (10)10Omega) without antistaticAnd (4) electrical property.
In order to further visually represent the excellent property that the antistatic property is difficult to adsorb fine dust, fine dust with the particle size of below 50 microns is adopted and lightly sprayed on the surface of the glass coated with the niobium carbide single-layer nanosheet/titanium dioxide photocatalytic self-cleaning composite coating, the dust adhesion condition is observed by naked eyes as shown in figure 3(a), and the fine dust is hardly adhered, so that the antistatic property is proved. Under the same test conditions, the surface to which the glass was not applied was as shown in FIG. 3(b), and the adhesion of fine dust was evident, demonstrating no antistatic property.
Example 6:
(1) 1g of niobium aluminum carbide is taken as a precursor, and is vigorously stirred in 10mL of 40% hydrofluoric acid solution at the temperature of 35 ℃ for 48 hours to obtain accordion-shaped multilayer niobium carbide;
(2) transferring the obtained accordion-shaped multilayer niobium carbide into an isopropylamine solution, wherein the volume ratio of the accordion-shaped multilayer niobium carbide to an intercalator is 5:65, violently stirring for 24 hours to ensure that the niobium carbide is intercalated to obtain niobium carbide single-layer nanosheets, centrifuging for many times by using deionized water after the reaction is finished to wash off the intercalator until the pH of a supernatant is 3-4, adding deionized water to a constant volume of 100mL, and centrifuging for 60 minutes to obtain a stable colloidal solution;
(3) 6mL of isopropanol serving as a cosolvent, 2mL of niobium carbide single-layer nanosheet colloidal solution, 10mL of 5wt% titanium dioxide solution and 20mL of ethyl orthosilicate are mixed, and ethyl orthosilicate hydrolysis reaction is carried out at the temperature of 25 ℃ and the rotating speed of 300rpm, wherein the volume ratio of titanium dioxide to MXene single-layer nanosheets is 1: 15, and the volume ratio of the cosolvent, the titanium dioxide and silicate is 3: 5: 10;
(4) adding 12mL of ethanol, 8mL of propylene glycol methyl ether and 7mL of methanol into the obtained hydrolysis solution for dilution, and preparing the niobium carbide single-layer nanosheet/titanium dioxide photocatalytic self-cleaning composite coating;
and (3) uniformly spraying the obtained photocatalytic self-cleaning composite coating on toughened glass by using a spray gun under the condition that the pressure of an air compressor is 0.5-0.6MPa, and naturally airing for 24 hours. By comparing the composite coating obtained in this example with the composite coating obtained in example 1, it is considered that the two coatings are not significantly different and have excellent aging resistance, antistatic property, super-hydrophilic property and photocatalytic activity.
Example 7:
(1) 1g of niobium aluminum carbide is taken as a precursor, and is vigorously stirred in 10mL of 40% hydrofluoric acid solution at the temperature of 35 ℃ for 48 hours to obtain accordion-shaped multilayer niobium carbide;
(2) transferring the obtained accordion-shaped multilayer niobium carbide into an isopropylamine solution, wherein the volume ratio of the accordion-shaped multilayer niobium carbide to an intercalator is 2:15, violently stirring for 24 hours to ensure that the niobium carbide is intercalated to obtain niobium carbide single-layer nanosheets, centrifuging for many times by using deionized water after the reaction is finished to wash off the intercalator until the pH of a supernatant is 3-4, adding deionized water to a constant volume of 100mL, and centrifuging for 60 minutes to obtain a stable colloidal solution;
(3) mixing 15mL of isopropanol serving as a cosolvent, 2mL of niobium carbide single-layer nanosheet colloidal solution, 15mL of 5wt% titanium dioxide solution and 30mL of ethyl orthosilicate, and carrying out ethyl orthosilicate hydrolysis reaction at the temperature of 25 ℃ and the rotating speed of 300rpm, wherein the volume ratio of titanium dioxide to MXene single-layer nanosheets is 2:15, and the volume ratio of the cosolvent, the titanium dioxide and silicate is 1: 2;
(4) adding 12mL of ethanol, 8mL of propylene glycol methyl ether and 7mL of methanol into the obtained hydrolysis solution for dilution, and preparing the niobium carbide single-layer nanosheet/titanium dioxide photocatalytic self-cleaning composite coating;
and (3) uniformly spraying the obtained photocatalytic self-cleaning composite coating on toughened glass by using a spray gun under the condition that the pressure of an air compressor is 0.5-0.6MPa, and naturally airing for 24 hours. By comparing the composite coating obtained in this example with the composite coatings obtained in examples 1 and 6, it is considered that the three coatings are not obviously different and have excellent aging resistance, antistatic property, super-hydrophilic property and photocatalytic activity.
Example 8:
(1) selecting titanium aluminum carbide as a precursor, slowly dissolving 2.0g of lithium fluoride in 40mL of hydrochloric acid, stirring for 10min to fully dissolve the lithium fluoride, slowly adding 1g of titanium aluminum carbide, and violently stirring for 24h at the temperature of 35 ℃ to obtain titanium carbide;
(2) transferring the obtained titanium carbide into 10mL of isopropylamine solution, violently stirring for 24h to enable the titanium carbide to be intercalated to obtain titanium carbide single-layer nanosheets, centrifuging for many times by using deionized water after the reaction is finished to wash away the intercalating agent until the pH of a supernatant is 3-4, adding deionized water to a constant volume of 100mL, carrying out 3500rpm, and centrifuging for 60min to obtain a stable colloidal solution;
(3) 5mL of isopropanol serving as a cosolvent, 2mL of titanium carbide single-layer nanosheet colloidal solution, 4mL of 5wt% titanium dioxide solution and 20mL of ethyl orthosilicate are mixed, and hydrolysis reaction of the ethyl orthosilicate is carried out at the temperature of 25 ℃ and the rotating speed of 300 rpm;
(4) adding 12mL of ethanol, 8mL of propylene glycol methyl ether and 7mL of methanol into the obtained hydrolysis solution for dilution, and preparing the titanium carbide single-layer nanosheet/titanium dioxide photocatalytic self-cleaning composite coating;
and (3) uniformly spraying the obtained photocatalytic self-cleaning composite coating on toughened glass by using a spray gun under the condition that the pressure of an air compressor is 0.5-0.6MPa, and naturally airing for 24 hours. It should be noted that, by comparing the composite coating obtained in this example with the composite coating obtained in example 1, the properties thereof are not significantly different, and the composite coating has excellent aging resistance, antistatic property, super-hydrophilic property and photocatalytic activity.
Example 9:
(1) the silicon titanium carbide in the MXene precursor is selected, 1g of titanium aluminum carbide is added into 30mL of 40% hydrofluoric acid solution, and the bottle is placed in an ice-water bath, the temperature is controlled to be 5 ℃, and overheating is prevented. Then transferring the mixture into a water bath kettle at the temperature of 40 ℃, and violently stirring for 48 hours to obtain titanium carbide;
(2) transferring the obtained titanium carbide into 10mL of isopropylamine solution, violently stirring for 24h to enable the titanium carbide to be intercalated to obtain titanium carbide single-layer nanosheets, centrifuging for many times by using deionized water after the reaction is finished to wash away the intercalating agent until the pH of a supernatant is 3-4, adding deionized water to a constant volume of 100mL, carrying out 3500rpm, and centrifuging for 60min to obtain a stable colloidal solution;
(3) 5mL of isopropanol serving as a cosolvent, 2mL of titanium carbide single-layer nanosheet colloidal solution, 4mL of 5wt% titanium dioxide solution and 20mL of ethyl orthosilicate are mixed, and hydrolysis reaction of the ethyl orthosilicate is carried out at the temperature of 25 ℃ and the rotating speed of 300 rpm;
(4) adding 12mL of ethanol, 8mL of propylene glycol methyl ether and 7mL of methanol into the obtained hydrolysis solution for dilution, and preparing the titanium carbide single-layer nanosheet/titanium dioxide photocatalytic self-cleaning composite coating;
and (3) uniformly spraying the obtained photocatalytic self-cleaning composite coating on toughened glass by using a spray gun under the condition that the pressure of an air compressor is 0.5-0.6MPa, and naturally airing for 24 hours. It should be noted that, by comparing the composite coating obtained in this example with the composite coating obtained in example 1, the properties thereof are not significantly different, and the composite coating has excellent aging resistance, antistatic property, super-hydrophilic property and photocatalytic activity.
Example 10:
(1) 1g of niobium aluminum carbide is taken as a precursor, and is vigorously stirred in 10mL of 40% hydrofluoric acid solution at the temperature of 35 ℃ for 48 hours to obtain niobium carbide;
(2) transferring the obtained niobium carbide into 10mL of isopropylamine solution, violently stirring for 24h to enable the niobium carbide to be intercalated to obtain niobium carbide single-layer nanosheets, centrifuging for many times by using deionized water after the reaction is finished to wash away the intercalant until the pH of a supernatant is 3-4, adding deionized water to a constant volume of 100mL, carrying out 3500rpm, and centrifuging for 60min to obtain a stable colloidal solution;
(3) the selected silicate is methyl orthosilicate, 5mL of cosolvent isopropanol, 2mL of niobium carbide single-layer nanosheet colloidal solution, 4mL of 5wt% titanium dioxide solution and 20mL of methyl orthosilicate are mixed, and hydrolysis reaction of the methyl orthosilicate is carried out at the temperature of 25 ℃ and the rotating speed of 300 rpm;
(4) adding 12mL of ethanol, 8mL of propylene glycol methyl ether and 7mL of methanol into the obtained hydrolysis solution for dilution, and preparing the niobium carbide single-layer nanosheet/titanium dioxide photocatalytic self-cleaning composite coating;
and (3) uniformly spraying the obtained photocatalytic self-cleaning composite coating on toughened glass by using a spray gun under the condition that the pressure of an air compressor is 0.5-0.6MPa, and naturally airing for 24 hours. It should be noted that, by comparing the composite coating obtained in this example with the composite coating obtained in example 1, the properties thereof are not significantly different, and the composite coating has excellent aging resistance, antistatic property, super-hydrophilic property and photocatalytic activity.
Example 11:
(1) the niobium carbide single-layer nanosheet/titanium dioxide photocatalytic self-cleaning composite coating is prepared in the same manner as in example 1.
(2) And (3) uniformly spraying the obtained photocatalytic self-cleaning composite coating on toughened glass by using a spray gun under the condition that the pressure of an air compressor is 0.5-0.6MPa, and naturally airing for 24 hours.
FIG. 4 is a scanning electron microscope image of the niobium carbide single-layer nanosheet/titanium dioxide photocatalytic self-cleaning composite coating on the glass section and the glass surface. As shown in fig. 4(a), the composite coating and the glass form obvious layering, the thickness of the coating formed by the composite coating is 176.7nm, the texture is uniform, and rough bulges appear on the surface; as shown in fig. 4(b), the composite coating forms a compact coating on the glass surface, and coarse particles are attached, and the coarse particles are single-layer nano sheets of niobium carbide wrapped in the coating of the composite coating. This shows that the composite coating has good adhesion effect and uniform distribution, and forms a stable rough surface on the glass surface.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (6)
1. A photocatalytic self-cleaning composite coating is characterized by comprising: the method comprises the steps of using an MXene precursor as a raw material, etching with an etchant to obtain an MXene accordion-shaped nanosheet solution, intercalating and layering with an intercalator to obtain an MXene monolayer nanosheet solution, removing the intercalator to obtain an MXene monolayer nanosheet stable colloidal solution, adding a cosolvent, 5wt% of a titanium dioxide solution and silicate ester to perform a hydrolysis reaction, and diluting to obtain an MXene monolayer nanosheet/titanium dioxide photocatalytic self-cleaning composite coating, wherein the volume ratio of the 5wt% of the titanium dioxide solution to the MXene monolayer nanosheet stable colloidal solution is 1-3: 5-15; the intercalation agent comprises any one of potassium hydroxide solution, isopropylamine solution and tetramethylammonium hydroxide; the MXene precursor comprises Ti3SiC2、Ti2AlC、Nb2Any one of AlC; the volume ratio of the MXene accordion-shaped nanosheet solution to the intercalating agent is 2-5: 15-65; the volume ratio of the cosolvent, the 5wt% titanium dioxide solution and the silicate ester is 1-3: 1-5: 6-10; the cosolvent comprises any one or more of isopropanol, ethanol, methanol and n-propanol;
the preparation method comprises the following steps:
s1, preparing MXene accordion-shaped nanosheet solution: adding an etchant into an MXene precursor serving as a raw material, controlling the temperature to be 25-40 ℃, violently stirring for 36-50h to obtain an MXene accordion-shaped nanosheet solution, and centrifuging for many times by using deionized water to remove the residual etchant to obtain the MXene accordion-shaped nanosheet solution;
s2, preparing MXene single-layer nanosheet stable colloidal solution: adding an intercalating agent into the obtained MXene accordion-shaped nanosheet solution according to the volume ratio, violently stirring and reacting for 12-36h to obtain an MXene monolayer nanosheet solution, and washing to obtain a supernatant with the pH of 3-4 to obtain an MXene monolayer nanosheet stable colloidal solution;
s3, preparing the MXene single-layer nanosheet/titanium dioxide photocatalytic self-cleaning composite coating: adding a cosolvent, a 5wt% titanium dioxide solution and silicate ester into the stable colloidal solution of the MXene monolayer nanosheet according to the volume ratio for hydrolysis reaction, and adding a diluent for dilution after the hydrolysis is finished to obtain the MXene monolayer nanosheet/titanium dioxide photocatalytic self-cleaning composite coating.
2. The photocatalytic self-cleaning composite coating material as claimed in claim 1, wherein the etchant includes any one of hydrofluoric acid and hydrochloric acid.
3. The photocatalytic self-cleaning composite coating material as claimed in claim 1, wherein the concentration of the intercalation agent is 2-5 mol/L.
4. The photocatalytic self-cleaning composite coating material as claimed in claim 1, wherein the silicate ester comprises any one or more of methyl orthosilicate, ethyl orthosilicate and propyl orthosilicate.
5. The photocatalytic self-cleaning composite coating material as claimed in claim 1, wherein the diluent comprises any one or more of ethanol, propylene glycol methyl ether and methanol.
6. The photocatalytic self-cleaning composite coating material as claimed in claim 1, wherein the temperature of the hydrolysis reaction in step S3 is 35-40 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110805816.1A CN113462207B (en) | 2021-07-16 | 2021-07-16 | Photocatalytic self-cleaning composite coating and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110805816.1A CN113462207B (en) | 2021-07-16 | 2021-07-16 | Photocatalytic self-cleaning composite coating and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113462207A CN113462207A (en) | 2021-10-01 |
| CN113462207B true CN113462207B (en) | 2022-01-28 |
Family
ID=77880751
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110805816.1A Active CN113462207B (en) | 2021-07-16 | 2021-07-16 | Photocatalytic self-cleaning composite coating and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113462207B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115463677B (en) * | 2022-09-06 | 2023-10-27 | 大连工业大学 | Composite photocatalytic material attached with MXene phase promoter, preparation method and application |
| CN115594998B (en) * | 2022-11-02 | 2024-07-30 | 中南林业科技大学 | Composite coating with photocatalysis self-cleaning capability, preparation method and application |
| CN116694219B (en) * | 2023-04-06 | 2024-09-24 | 江苏苏博特新材料股份有限公司 | Visible light-induced MXene/waterborne polyurethane antibacterial self-repairing composite coating and preparation method thereof |
| CN118048062A (en) * | 2024-02-18 | 2024-05-17 | 中煤科工重庆工程技术有限公司 | Self-cleaning nano material applied to photovoltaic module and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1631999A (en) * | 2004-12-02 | 2005-06-29 | 上海大学 | Process for preparing self-cleaning titanium dioxide photo-catalytic coating liquid |
| CN108384448A (en) * | 2017-05-17 | 2018-08-10 | 东华大学 | A kind of composite Nano corrosion-inhibiting coating of imitative clam shell feature and preparation method thereof |
| CN109439188A (en) * | 2018-11-15 | 2019-03-08 | 北京林业大学 | A kind of super-hydrophobic photo-thermal coating and preparation method thereof |
| CN111591992A (en) * | 2020-06-10 | 2020-08-28 | 哈尔滨工业大学 | Single-layer MXene nanosheet and preparation method thereof |
-
2021
- 2021-07-16 CN CN202110805816.1A patent/CN113462207B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1631999A (en) * | 2004-12-02 | 2005-06-29 | 上海大学 | Process for preparing self-cleaning titanium dioxide photo-catalytic coating liquid |
| CN108384448A (en) * | 2017-05-17 | 2018-08-10 | 东华大学 | A kind of composite Nano corrosion-inhibiting coating of imitative clam shell feature and preparation method thereof |
| CN109439188A (en) * | 2018-11-15 | 2019-03-08 | 北京林业大学 | A kind of super-hydrophobic photo-thermal coating and preparation method thereof |
| CN111591992A (en) * | 2020-06-10 | 2020-08-28 | 哈尔滨工业大学 | Single-layer MXene nanosheet and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113462207A (en) | 2021-10-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113462207B (en) | Photocatalytic self-cleaning composite coating and preparation method thereof | |
| CN101333075B (en) | Method for preparing self-cleaning toughened glass | |
| Kesmez et al. | Sol–gel preparation and characterization of anti-reflective and self-cleaning SiO2–TiO2 double-layer nanometric films | |
| CN102241939B (en) | Organic-inorganic hybrid super-hydrophilic coating as well as preparation method and application thereof | |
| JP3732247B2 (en) | Titanium oxide coating film-forming liquid composition for photocatalyst and process for producing the same | |
| CN102382490A (en) | Preparation method and use of hydrophilic automatically-cleaning coating with photocatalytic activity | |
| CN110317476B (en) | Nano functional coating and preparation method and application thereof | |
| TWI441678B (en) | Photocatalyst coating and photocatalyst coating solution | |
| CN101549959B (en) | A method of nano self-cleaning glass production in the float glass production line | |
| CN111534162B (en) | Montmorillonite-based photocatalytic super-hydrophobic coating and preparation method thereof | |
| CN103359954A (en) | Preparation method of silicon dioxide super-hydrophobic thin film and super-hydrophobic material | |
| CN102503554B (en) | Method for preparing oil-water-soaked light-operated reversible SiO2/TiO2 composite coating on silicon substrate surface | |
| CN102718410B (en) | Method for preparing self-cleaning antifogging coating film | |
| CN104817858A (en) | Preparation method of antifog and self-cleaning nanomaterial | |
| CN109206017A (en) | A kind of graphene doped-glass coating liquid and preparation method thereof | |
| CN109439042A (en) | A kind of hydrophilic surface layer coating, relevant stainless steel sink and preparation method | |
| CN106082692A (en) | Self-cleaning surface structure of Nanometer dustproof and preparation method thereof | |
| CN109385122A (en) | A kind of preparation method of graphene doping self-cleaning glass coating liquid | |
| CN110436795A (en) | A method of preparing the silica membrane of the structure of shape containing Egg Tarts | |
| WO2016143297A1 (en) | Glass plate provided with coating film and method for manufacturing same | |
| CN1194922C (en) | Nano self-cleaning super hydrophilic glass product production method | |
| CN117926382A (en) | Preparation method of inorganic super-hydrophobic protective coating of aluminum alloy | |
| US20110129662A1 (en) | Substrates Supplied with a Dust and Aerosol-Repellent Coating, Method for the Production Thereof g and Materials for this Purpose | |
| JP4012930B1 (en) | A method for producing a composite comprising tourmaline and silicon oxide. | |
| Cai et al. | Preparation and characterization of SiO2–TiO2 superhydrophilic coatings with photocatalytic activity induced by low temperature |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |