CN114751654A - High-transparency hydrophobic self-cleaning MOFs coating and preparation method thereof - Google Patents
High-transparency hydrophobic self-cleaning MOFs coating and preparation method thereof Download PDFInfo
- Publication number
- CN114751654A CN114751654A CN202210526895.7A CN202210526895A CN114751654A CN 114751654 A CN114751654 A CN 114751654A CN 202210526895 A CN202210526895 A CN 202210526895A CN 114751654 A CN114751654 A CN 114751654A
- Authority
- CN
- China
- Prior art keywords
- mofs
- glass substrate
- cleaning
- coating
- coatings
- 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.)
- Granted
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/70—Properties of coatings
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/11—Deposition methods from solutions or suspensions
- C03C2218/111—Deposition methods from solutions or suspensions by dipping, immersion
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/30—Aspects of methods for coating glass not covered above
- C03C2218/31—Pre-treatment
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2218/00—Methods for coating glass
- C03C2218/30—Aspects of methods for coating glass not covered above
- C03C2218/32—After-treatment
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Surface Treatment Of Glass (AREA)
Abstract
The invention belongs to the technical field of coatings, and particularly relates to a high-transparency self-cleaning MOFs coating and a preparation method thereof. On a glass substrate modified by 3-aminopropyltriethoxysilane, zirconium chloride and tetrafluoroterephthalic acid are used as raw materials, and a hydrophobic self-cleaning transparent MOFs coating is formed on a pre-functionalized glass substrate by using a hydrothermal synthesis method. By controlling the number of layers of the MOFs coating, the best balance between roughness, mechanical stability and light transmittance of the coating is achieved. The maximum light transmittance of the coating prepared by the invention can reach 92%, the water contact angle is 130 degrees, the water contact angle still keeps a hydrophobic state of 130 degrees after liquid impact, and the MOFs coating has high transparency, firmness and self-cleaning performance and has important significance in self-cleaning, antifouling, condensing, anti-icing and other applications.
Description
Technical Field
The invention belongs to the technical field of coatings, and particularly relates to a high-transparency hydrophobic self-cleaning MOFs coating and a preparation method thereof.
Background
The transparent hydrophobic self-cleaning surface has the capability of repelling low surface tension liquid, and has important significance in self-cleaning, antifouling, condensing, anti-icing and other applications. The use of micro-nano roughness while achieving robustness, transparency and hydrophobicity is very difficult, since increasing roughness increases liquid repellency but decreases transparency. Furthermore, in the report of transparent hydrophobic coatings, the impact resistance of the drop impact rather than the high-speed jet is proved, and the drop impact can be resisted but the drop impact cannot be borne, so that the manufacturing of the transparent hydrophobic coating with a firm micro-nano structure is extremely challenging.
The fundamental reason for the degradation of MOFs granules or powders due to their influence by water is due to their own instability to water and their ubiquity, and thus, the preparation of hydrophobic MOFs is the most promising solution. Generally, three strategies are used to overcome this challenge: modifying the MOFs surface by using a hydrophobic fluorine-containing alkyl substituent compound, modifying the MOFs surface by using a proper hydrophobic monolayer, and adding a hydrophobic polymer coating on the MOFs surface. MOFs films are used only for semiconductor devices, optical sensors, and gas sensors. Previously, in hydrophobic MOFs applications relied on physical adsorption of MOFs particles onto a substrate, Sun et al physically adsorbed hydrophobic UIO-66MOF onto a glass slide and recorded the contact angle. Recently, water-repellent lubricants have been injected into hydrophilic MOFs to obtain wet-slippery liquid porous surfaces with low hysteresis and anti-icing characteristics, however, such surfaces are vulnerable to lubricant consumption and poor mechanical stability.
To date, few research reports have been reported on transparent hydrophobic self-cleaning MOFs films, and therefore, further research is needed to design and construct mechanically stable, high-transparency hydrophobic self-cleaning MOFs surfaces.
Disclosure of Invention
In order to solve the technical problems pointed out in the background technology part, the invention provides a highly transparent hydrophobic self-cleaning MOFs coating and a preparation method thereof, wherein the preparation method comprises the following steps: firstly, immersing a glass substrate into a normal hexane solution of 3-aminopropyltriethoxysilane, then, immersing the 3-aminopropyltriethoxysilane functionalized glass substrate into an N, N-dimethylformamide solution of tetrafluoroterephthalic acid by using a hydrothermal synthesis method as raw materials, combining the tetrafluoroterephthalic acid with amino on the glass substrate through amidation reaction, then immersing the glass substrate into an N, N-dimethylformamide solution of zirconium chloride, and coordinately combining the zirconium chloride and the tetrafluoroterephthalic acid to form a growth cycle, repeating the growth cycle to deposit MOFs coatings layer by layer on the glass substrate to obtain MOFs coatings with different layers, finally immersing the MOFs coatings into trichloromethane, opening air holes, taking out and carrying out vacuum drying. According to the preparation method, different numbers of MOFs coatings are deposited layer by layer, so that the roughness, the mechanical stability and the light transmittance are optimally balanced, and the mechanically stable high-transparency hydrophobic self-cleaning MOFs coatings are obtained.
The preparation method mainly comprises the following steps:
(1) immersing the glass substrate into a n-hexane solution of 3-aminopropyltriethoxysilane, immersing for 2h at 25 ℃, taking out the immersed glass substrate, washing with n-hexane, and drying in a drying oven at 100 ℃ for 1 h;
wherein, the volume adding amount of the 3-aminopropyl triethoxysilane is 1 percent of that of the normal hexane.
(2) And (3) immersing the glass substrate soaked by the 3-aminopropyltriethoxysilane into 100mL of N, N-dimethylformamide solution of tetrafluoroterephthalic acid, performing closed reaction for 4 hours at 120 ℃ in a hydrothermal reaction kettle, and then immersing into 100mL of N, N-dimethylformamide solution of zirconium chloride for reaction for 20 minutes at 120 ℃, thereby finishing a growth cycle. The same procedure is circulated to deposit layer by layer on the glass substrate, and 2-9 layers of MOFs coatings are prepared;
wherein, the adding amount of the tetrafluoroterephthalic acid is 5.90-5.95g, and the adding amount of the zirconium chloride is 5.83-5.85 g.
(3) The sample with the MOFs coating prepared in the above way is immersed in chloroform for 24-72h, and is dried in vacuum at 100 ℃ for 12 h.
Compared with the prior art, the invention has the advantages that:
1. according to the invention, a glass substrate is immersed into n-hexane solution of 3-aminopropyltriethoxysilane, so that a 3-aminopropyltriethoxysilane-loaded glass substrate is obtained, and amino groups on the loaded glass substrate can perform amidation reaction with carboxyl groups of tetrafluoroterephthalic acid serving as a ligand of zirconium-based MOFs to generate amido bonds.
2. The invention adopts a hydrothermal synthesis method, the reaction time is accurately controlled, namely the reaction is controlled at 120 ℃ for 4h, carboxyl of the tetrafluoroterephthalic acid and amino on a glass substrate are subjected to amidation reaction to generate amido bond, the tetrafluoroterephthalic acid is connected on the glass substrate with amino functionalized, and fluorine atoms of the tetrafluoroterephthalic acid provide hydrophobicity for MOFs coatings.
3. According to the method, the MOFs films with different layers are prepared on the glass substrate by adopting a layer-by-layer deposition method, the water contact angles and the light transmittances of the MOFs films with different layers are different, the roughness, the mechanical stability and the light transmittance of the MOFs coating are well balanced by the method, and the transparent hydrophobic self-cleaning MOFs coating is obtained.
4. The MOFs coating is immersed in trichloromethane for 24-72 hours to open air holes of the MOFs coating, so that the refractive index of the coating can be reduced, and the MOFs coating is ensured to have higher light transmittance.
5. The MOFs coating prepared by the process has the light transmittance up to 92%, the water contact angle of 130 degrees after liquid impact is still kept, the lag angle of 10 degrees, the sand on the surface of the coating can be removed, the self-cleaning effect is good, and the MOFs coating has a great development prospect in the application of semiconductor devices, optical sensors and gas sensors.
Description of the drawings:
FIG. 1 is a Fourier infrared spectrum of MOFs coatings obtained in example 2 of the present invention.
FIG. 2 is a transmission electron microscope picture of MOFs coatings obtained in example 2 of the present invention.
FIG. 3 is a graph showing the change of water contact angle of the MOFs coating obtained in example 2 of the present invention after an abrasion resistance test.
Fig. 4 is a self-cleaning picture of MOFs coatings obtained in embodiment 2 of the present invention.
Detailed Description
The present invention is further described below with reference to examples, but is not limited thereto.
Example 1
(1) Immersing the glass substrate into a normal hexane solution containing 1% of 3-aminopropyltriethoxysilane, immersing for 2h at 25 ℃, taking out the glass substrate, washing with normal hexane, and drying in a drying oven at 100 ℃ for 1 h;
(2) the 3-aminopropyltriethoxysilane-supported glass substrate was immersed in 100mL of an N, N-dimethylformamide solution containing 5.95g of tetrafluoroterephthalic acid in a hydrothermal reaction vessel at 120 ℃ for 4 hours in a closed state, and then immersed in 100mL of an N, N-dimethylformamide solution containing 5.83g of zirconium chloride in the hydrothermal reaction vessel at 120 ℃ for 20 minutes to complete one cycle. The same procedure was cycled 2 times to produce 2 layers of MOFs coatings on glass substrates.
(3) And (3) immersing the glass substrate carrying 2 MOFs coatings into chloroform for 48h, and carrying out vacuum drying at 100 ℃ for 12h to obtain the transparent hydrophobic self-cleaning MOFs coatings. The average light transmittance in the visible light range is up to 92.31 percent, the water contact angle is 117 degrees, and the lag angle is 20 degrees.
Example 2
The preparation of the glass substrate carrying 3-aminopropyltriethoxysilane was the same as in example 1.
(1) The 3-aminopropyltriethoxysilane-supported glass substrate was immersed in 100mL of an N, N-dimethylformamide solution containing 5.95g of tetrafluoroterephthalic acid in a hydrothermal reaction vessel at 120 ℃ for 4 hours in a closed state, and then immersed in 100mL of an N, N-dimethylformamide solution containing 5.83g of zirconium chloride in the hydrothermal reaction vessel at 120 ℃ for 20 minutes to complete one cycle. The same procedure was cycled 5 times to produce 5 layers of MOFs coatings on glass substrates.
(2) And (3) immersing the glass substrate carrying the 5-layer MOFs coating into chloroform for 48h, and carrying out vacuum drying at 100 ℃ for 12h to obtain the transparent hydrophobic self-cleaning MOFs coating. The average light transmittance in the visible light range is up to 92.26%, the water contact angle is 130 degrees, and the lag angle is 10 degrees.
Obtained from Fourier infrared spectrogram at 3448cm-1The absorption vibration peak of N-H is at 1660cm-1And 1571cm-1The tensile vibration of C ═ O and the asymmetric stretching of OCO are observed, which indicates that amidation reaction occurs between amino and carboxyl, and the subsequent MOFs coating on the glass substrate is favorably generated.
The growth state of 5 layers of MOFs was tracked by using a scanning electron microscope, and from the SEM image, MOF particles are obviously appeared and are mostly coarse particles.
The method comprises the steps of carrying 100g of object on a glass substrate carrying 5 MOFs coatings, enabling the object to move transversely on abrasive paper in 10cm cycle, measuring the change of water contact angles after 1, 2, 3, 4, 5, 6 and 7 times of cyclic abrasion, and measuring the change of the water contact angles after each abrasion cycle, wherein the change is small although the water contact angles slightly change, the water contact angles are always about 130 degrees, the lowest water contact angle can also reach 126 degrees, and the MOFs coatings have good mechanical stability.
The sand particles on the glass substrate with 5 MOFs coatings are easily removed by water drops sliding from the surface, and the self-cleaning property of the glass substrate can be confirmed.
Example 3
The preparation of the glass substrate carrying 3-aminopropyltriethoxysilane was the same as in example 1.
(1) The 3-aminopropyltriethoxysilane supported glass substrate was immersed in 100mL of N, N-dimethylformamide solution containing 5.95g of tetrafluoroterephthalic acid in a hydrothermal reaction vessel at 120 ℃ for 4 hours in a closed state, and then immersed in 100mL of N, N-dimethylformamide solution containing 5.83g of zirconium chloride in 120 ℃ for 20 minutes to complete one cycle. The same procedure was cycled 6 times to produce 6 layers of MOFs coatings on glass substrates.
(2) And (3) immersing the glass substrate carrying the 6-layer MOFs coating into chloroform for 48h, and carrying out vacuum drying at 100 ℃ for 12h to obtain the transparent hydrophobic self-cleaning MOFs coating. The average light transmittance in the visible light range is up to 91.26%, the water contact angle is 130 degrees, and the lag angle is 10 degrees.
Example 4
The preparation of the glass substrate carrying 3-aminopropyltriethoxysilane was the same as in example 1.
(1) The 3-aminopropyltriethoxysilane-supported glass substrate was immersed in 100mL of an N, N-dimethylformamide solution containing 5.95g of tetrafluoroterephthalic acid in a hydrothermal reaction vessel at 120 ℃ for 4 hours in a closed state, and then immersed in 100mL of an N, N-dimethylformamide solution containing 5.83g of zirconium chloride in the hydrothermal reaction vessel at 120 ℃ for 20 minutes to complete one cycle. The same procedure was cycled 7 times to produce 7 layers of MOFs coatings on glass substrates.
(2) And (3) immersing the glass substrate carrying the 7-layer MOFs coating into trichloromethane for 48 hours, and carrying out vacuum drying at 100 ℃ for 12 hours to obtain the transparent hydrophobic self-cleaning MOFs coating. The average light transmittance in the visible light range is up to 90.93%, the water contact angle is 131 degrees, and the lag angle is 10 degrees.
Example 5
The preparation of 3-aminopropyltriethoxysilane supported on a glass substrate was the same as in example 1.
(1) The 3-aminopropyltriethoxysilane supported glass substrate was immersed in 100mL of N, N-dimethylformamide solution containing 5.95g of tetrafluoroterephthalic acid in a hydrothermal reaction vessel at 120 ℃ for 4 hours in a closed state, and then immersed in 100mL of N, N-dimethylformamide solution containing 5.83g of zirconium chloride in 120 ℃ for 20 minutes to complete one cycle. The same procedure was cycled 8 times to produce 8 layers of MOFs coatings on glass substrates.
(2) And (3) immersing the glass substrate carrying the 8-layer MOFs coating into trichloromethane for 48 hours, and carrying out vacuum drying at 100 ℃ for 12 hours to obtain the transparent hydrophobic self-cleaning MOFs coating. The average light transmittance in the visible light range is up to 88.45 percent, the water contact angle is 123 degrees, and the lag angle is 11 degrees.
Example 6
The preparation of the glass substrate carrying 3-aminopropyltriethoxysilane was the same as in example 1.
(1) The 3-aminopropyltriethoxysilane supported glass substrate was immersed in 100mL of N, N-dimethylformamide solution containing 5.95g of tetrafluoroterephthalic acid in a hydrothermal reaction vessel at 120 ℃ for 4 hours in a closed state, and then immersed in 100mL of N, N-dimethylformamide solution containing 5.83g of zirconium chloride in 120 ℃ for 20 minutes to complete one cycle. The same procedure was cycled 9 times to produce 9 MOFs coatings on glass substrates.
(2) And (3) immersing the glass substrate carrying the 9 MOFs coatings into chloroform for 48h, and carrying out vacuum drying at 100 ℃ for 12h to obtain the transparent hydrophobic self-cleaning MOFs coatings. The average light transmittance in the visible light range is up to 87.31 percent, the water contact angle is 120 degrees, and the lag angle is 11 degrees.
Example 7
The preparation of the glass substrate carrying 3-aminopropyltriethoxysilane was the same as in example 1.
(1) The 3-aminopropyltriethoxysilane supported glass substrate was immersed in 100mL of N, N-dimethylformamide solution containing 5.95g of tetrafluoroterephthalic acid in a hydrothermal reaction vessel at 120 ℃ for 4 hours in a closed state, and then immersed in 100mL of N, N-dimethylformamide solution containing 5.83g of zirconium chloride in 120 ℃ for 20 minutes to complete one cycle. The same procedure was cycled 5 times to produce 5 layers of MOFs coatings on glass substrates.
(2) And (3) immersing the glass substrate carrying the 5-layer MOFs coating into chloroform for 24h, and carrying out vacuum drying at 100 ℃ for 12h to obtain the transparent hydrophobic self-cleaning MOFs coating. The average light transmittance in the visible light range is up to 89.59%, the water contact angle is 130 degrees, and the lag angle is 10 degrees.
Example 8
The preparation of the glass substrate carrying 3-aminopropyltriethoxysilane was the same as in example 1.
(1) The 3-aminopropyltriethoxysilane supported glass substrate was immersed in 100mL of N, N-dimethylformamide solution containing 5.95g of tetrafluoroterephthalic acid in a hydrothermal reaction vessel at 120 ℃ for 4 hours in a closed state, and then immersed in 100mL of N, N-dimethylformamide solution containing 5.83g of zirconium chloride in 120 ℃ for 20 minutes to complete one cycle. The same procedure was cycled 5 times to produce 5 layers of MOFs coatings on glass substrates.
(2) And (3) immersing the glass substrate carrying the 5-layer MOFs coating into chloroform for 72h, and carrying out vacuum drying at 100 ℃ for 12h to obtain the transparent hydrophobic self-cleaning MOFs coating. The average light transmittance in the visible light range is measured to be as high as 92.42 percent, the water contact angle is 108 degrees, and the lag angle is 20 degrees.
Comparative example 1
(1) Immersing the glass substrate into a normal hexane solution containing 1% of 3-aminopropyltriethoxysilane, soaking for 2h at 25 ℃, washing the glass substrate with normal hexane after taking out, and drying for 1h in a drying oven at 100 ℃;
(2) the 3-aminopropyltriethoxysilane-supported glass substrate was immersed in 100mL of an N, N-dimethylformamide solution containing 5.95g of tetrafluoroterephthalic acid in a hydrothermal reaction vessel at 120 ℃ for 4 hours in a closed state, and then immersed in 100mL of an N, N-dimethylformamide solution containing 5.83g of zirconium chloride in the hydrothermal reaction vessel at 120 ℃ for 20 minutes to complete one cycle. The same procedure was cycled 5 times to produce 5 layers of MOFs coatings on glass substrates.
(3) And (3) carrying the glass substrate with the 5-layer MOFs coating, and drying for 12h in vacuum at 100 ℃. The average light transmittance of the coating is 86.31 percent, and the water contact angle is 130 degrees.
Comparative example 2
(1) Immersing the glass substrate into a normal hexane solution containing 1% of 3-aminopropyltriethoxysilane, soaking for 2h at 25 ℃, washing the glass substrate with normal hexane after taking out, and drying for 1h in a drying oven at 100 ℃;
(2) the 3-aminopropyltriethoxysilane-supported glass substrate was immersed in 100mL of an N, N-dimethylformamide solution containing 5.95g of tetrafluoroterephthalic acid and 5.83g of zirconium chloride in a hydrothermal reaction vessel at 120 ℃ for a closed reaction for 4 hours, and one cycle was completed. The same procedure was cycled 5 times to produce 5 layers of MOFs coatings on glass substrates.
(3) And (3) immersing the glass substrate carrying the 5-layer MOFs coating into chloroform for 48h, and carrying out vacuum drying at 100 ℃ for 12 h. The average light transmittance of the coating is 90.63 percent, and the water contact angle is 70 degrees.
Comparative example 3
(1) Immersing the glass substrate into a normal hexane solution containing 1% of 3-aminopropyltriethoxysilane, soaking for 2h at 25 ℃, washing the glass substrate with normal hexane after taking out, and drying for 1h in a drying oven at 100 ℃;
(2) the 3-aminopropyltriethoxysilane-supported glass substrate was immersed in 100mL of an N, N-dimethylformamide solution containing 4.95g of 2, 5-dihydroxyterephthalic acid in a hydrothermal reaction kettle at 120 ℃ for a closed reaction for 4 hours, and then immersed in 100mL of an N, N-dimethylformamide solution containing 5.83g of zirconium chloride in a reaction kettle at 120 ℃ for 20 minutes, thereby completing one cycle. The same procedure was cycled 5 times to produce 5 layers of MOFs coatings on glass substrates.
(3) And (2) immersing the glass substrate carrying the 5-layer MOFs coating into trichloromethane for 48 hours, carrying out vacuum drying at 100 ℃ for 12 hours to obtain a hydrophilic MOFs coating, then immersing into a normal hexane solution containing 1% trichlorooctadecylsilane for 2 hours, and carrying out drying at 120 ℃ for 2 hours. The average light transmittance of the coating is 92.31 percent, and the water contact angle is 117 degrees.
Comparative example 4
(1) The unmodified glass substrate is immersed into a 100mL N, N-dimethylformamide solution containing 5.95g of tetrafluoroterephthalic acid in a hydrothermal reaction kettle at 120 ℃ for 4 hours in a closed manner, and then immersed into a 100mL N, N-dimethylformamide solution containing 5.83g of zirconium chloride for 20 minutes at 120 ℃, so that one cycle is finished. The same procedure was cycled 5 times to produce 5 layers of MOFs coatings on glass substrates.
(2) And (3) immersing the glass substrate carrying the 5-layer MOFs coating into chloroform for 48h, and carrying out vacuum drying at 100 ℃ for 12 h. The average light transmittance of the coating is 92.31 percent, and the water contact angle is 63 degrees.
The present invention is not limited to the above-described embodiments, and any obvious improvements, substitutions or modifications can be made by those skilled in the art without departing from the spirit of the present invention.
Claims (8)
1. A preparation method of a high-transparency hydrophobic self-cleaning MOFs coating is characterized by comprising the following steps:
(1) adding 3-aminopropyltriethoxysilane into n-hexane at 25 ℃, then immersing the glass substrate into the n-hexane, taking out the glass substrate, washing the glass substrate with n-hexane, and drying the glass substrate for 1 hour at 100 ℃;
(2) taking tetrafluoroterephthalic acid and zirconium chloride as raw materials, generating MOFs coatings on a glass substrate soaked by 3-aminopropyltriethoxysilane by adopting a hydrothermal synthesis method, circulating the same program, and depositing MOFs coatings with different layers on the glass substrate layer by layer;
(3) and (3) immersing the glass substrate loaded with the MOFs coatings with different layers obtained in the step (2) into chloroform, and drying in a vacuum drying oven.
2. The method of preparing highly transparent hydrophobic self-cleaning MOFs coatings according to claim 1, wherein: in the step (1), the volume addition amount of 3-aminopropyltriethoxysilane is 1% of that of n-hexane; the glass substrate immersion time was 2 h.
3. The method of preparing highly transparent hydrophobic self-cleaning MOFs coatings according to claim 1, wherein: the hydrothermal method in the step (2) comprises the following specific synthesis method: the 3-aminopropyltriethoxy functionalized glass substrate was put into a polytetrafluoroethylene reaction kettle of 100mL of a N, N-dimethylformamide solution of tetrafluoroterephthalic acid, reacted at 120 ℃ for 4 hours, and then immersed into 100mL of an N, N-dimethylformamide solution of zirconium chloride, reacted at 120 ℃ for 20 minutes, which is one growth cycle.
4. The method of preparing highly transparent hydrophobic self-cleaning MOFs coatings according to claim 3, wherein: the addition amount of the tetrafluoroterephthalic acid is 5.90-5.95g, and the addition amount of the zirconium chloride is 5.83-5.85 g.
5. The method for preparing highly transparent hydrophobic self-cleaning MOFs coatings according to claim 1, wherein said method comprises the following steps: the number of the MOFs coating layers deposited layer by layer in the step (2) is 2-9.
6. The method of preparing highly transparent hydrophobic self-cleaning MOFs coatings according to claim 1, wherein: immersing in chloroform for 24-72h in the step (3).
7. The method of preparing highly transparent hydrophobic self-cleaning MOFs coatings according to claim 1, wherein: and (3) drying for 12 hours in a vacuum drying oven at 100 ℃.
8. Highly transparent hydrophobic self-cleaning MOFs coating prepared according to the process of any one of claims 1 to 7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210526895.7A CN114751654B (en) | 2022-05-16 | 2022-05-16 | High-transparency hydrophobic self-cleaning MOFs coating and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210526895.7A CN114751654B (en) | 2022-05-16 | 2022-05-16 | High-transparency hydrophobic self-cleaning MOFs coating and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114751654A true CN114751654A (en) | 2022-07-15 |
| CN114751654B CN114751654B (en) | 2023-08-01 |
Family
ID=82335955
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210526895.7A Active CN114751654B (en) | 2022-05-16 | 2022-05-16 | High-transparency hydrophobic self-cleaning MOFs coating and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114751654B (en) |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1887760A (en) * | 2006-07-20 | 2007-01-03 | 杭州钱塘江特种玻璃技术有限公司 | Self-cleaning household appliance glass capable of shielding electromagnetic radiation and its prepn |
| US7485343B1 (en) * | 2005-04-13 | 2009-02-03 | Sandia Corporation | Preparation of hydrophobic coatings |
| CN101362632A (en) * | 2007-08-08 | 2009-02-11 | 中国科学院宁波材料技术与工程研究所 | Method for preparing transparent hydrophobic coating |
| CN102153950A (en) * | 2011-02-28 | 2011-08-17 | 武汉理工大学 | Metal organic compound collosol/organic silicone compound icing-proof coating and preparation method thereof |
| US20130337226A1 (en) * | 2012-06-08 | 2013-12-19 | University Of Houston | Self-cleaning coatings and methods for making same |
| CN103951276A (en) * | 2014-05-04 | 2014-07-30 | 江南大学 | Self-cleaning anti-reflection film and preparation method thereof |
| CN106950618A (en) * | 2017-05-04 | 2017-07-14 | 鲁东大学 | A kind of method that utilization bionic super-hydrophobic structure prevents optical lens fogging |
| CN110791066A (en) * | 2019-10-18 | 2020-02-14 | 于素阁 | Flame-retardant MOFs-CNTs modified polylactic acid super-hydrophobic material and preparation method thereof |
| CN110845149A (en) * | 2019-11-16 | 2020-02-28 | 中建材蚌埠玻璃工业设计研究院有限公司 | Preparation method of super-hydrophobic glass |
| CN113713636A (en) * | 2021-08-27 | 2021-11-30 | 中国石油大学(华东) | Mixed matrix membrane based on PIM-1 and preparation method thereof |
| CN113754308A (en) * | 2021-09-30 | 2021-12-07 | 常州大学 | Preparation method of super-amphiphobic antifouling transparent coating |
-
2022
- 2022-05-16 CN CN202210526895.7A patent/CN114751654B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7485343B1 (en) * | 2005-04-13 | 2009-02-03 | Sandia Corporation | Preparation of hydrophobic coatings |
| CN1887760A (en) * | 2006-07-20 | 2007-01-03 | 杭州钱塘江特种玻璃技术有限公司 | Self-cleaning household appliance glass capable of shielding electromagnetic radiation and its prepn |
| CN101362632A (en) * | 2007-08-08 | 2009-02-11 | 中国科学院宁波材料技术与工程研究所 | Method for preparing transparent hydrophobic coating |
| CN102153950A (en) * | 2011-02-28 | 2011-08-17 | 武汉理工大学 | Metal organic compound collosol/organic silicone compound icing-proof coating and preparation method thereof |
| US20130337226A1 (en) * | 2012-06-08 | 2013-12-19 | University Of Houston | Self-cleaning coatings and methods for making same |
| CN103951276A (en) * | 2014-05-04 | 2014-07-30 | 江南大学 | Self-cleaning anti-reflection film and preparation method thereof |
| CN106950618A (en) * | 2017-05-04 | 2017-07-14 | 鲁东大学 | A kind of method that utilization bionic super-hydrophobic structure prevents optical lens fogging |
| CN110791066A (en) * | 2019-10-18 | 2020-02-14 | 于素阁 | Flame-retardant MOFs-CNTs modified polylactic acid super-hydrophobic material and preparation method thereof |
| CN110845149A (en) * | 2019-11-16 | 2020-02-28 | 中建材蚌埠玻璃工业设计研究院有限公司 | Preparation method of super-hydrophobic glass |
| CN113713636A (en) * | 2021-08-27 | 2021-11-30 | 中国石油大学(华东) | Mixed matrix membrane based on PIM-1 and preparation method thereof |
| CN113754308A (en) * | 2021-09-30 | 2021-12-07 | 常州大学 | Preparation method of super-amphiphobic antifouling transparent coating |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114751654B (en) | 2023-08-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhuang et al. | Transparent superhydrophobic PTFE films via one-step aerosol assisted chemical vapor deposition | |
| JP3628692B2 (en) | Composite material having high refractive index, method for producing the composite material, and optically active material including the composite material | |
| Li et al. | A facile layer-by-layer deposition process for the fabrication of highly transparent superhydrophobic coatings | |
| JP3930884B2 (en) | Anti-glare and anti-reflection coating of surface activated nanoparticles | |
| JP4581608B2 (en) | Thin film manufacturing method, optical component manufacturing method, and film forming apparatus | |
| JP3708429B2 (en) | Method for manufacturing vapor deposition composition, method for manufacturing optical component having vapor deposition composition and antireflection film | |
| CN101344601B (en) | Method for preparing anti-fog anti-reflection coating layer based on layered packaging technique | |
| Fu et al. | Testing of the superhydrophobicity of a zinc oxide nanorod array coating on wood surface prepared by hydrothermal treatment | |
| KR20100019959A (en) | A coating composition endowing transparent substrate with anti-reflection effect and a preparing method for transparent substrate with anti-reflection effect using the composition | |
| GB2210378A (en) | Process for processing a polyurethane lens | |
| WO2015157880A1 (en) | Coating method used for nano surface coating of irregularly-shaped metal | |
| Liu et al. | Durable and self-healing superhydrophobic polyvinylidene fluoride (PVDF) composite coating with in-situ gas compensation function | |
| Lu et al. | Superhydrophobic wood fabricated by epoxy/Cu2 (OH) 3Cl NPs/stearic acid with performance of desirable self-cleaning, anti-mold, dimensional stability, mechanical and chemical durability | |
| US20230313444A1 (en) | Hydrophobic and oleophobic coating, preparation method therefor, and product | |
| Luo et al. | Preparation of fluorine-free superhydrophobic and wear-resistant cotton fabric with a UV curing reaction for self-cleaning and oil/water separation | |
| Huang et al. | Durable silica antireflective coating prepared by combined treatment of ammonia and KH570 vapor | |
| CN114751654A (en) | High-transparency hydrophobic self-cleaning MOFs coating and preparation method thereof | |
| WO2020099290A1 (en) | Easy to clean coating | |
| Sun et al. | Design and preparation of superhydrophobic, broadband and double-layer antireflective coatings | |
| Yi et al. | Preparation of microstructure-controllable superhydrophobic polytetrafluoroethylene porous thin film by vacuum thermal-evaporation | |
| CN111501354A (en) | Oil-proof antifouling self-cleaning functional fabric and preparation method thereof | |
| CN115542434A (en) | Anti-reflection composite film and preparation method thereof | |
| JP2003014904A (en) | Method for manufacturing optical member having water- repellent thin film | |
| CA2305513C (en) | Transparent substrate bearing an anti-stain, hydrophobic coating, and process for making it | |
| JPS63296002A (en) | Surface reforming method for inorganic coating film |
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 |