WO2015196738A1 - Carbon nitride-modified titanium dioxide super-hydrophilic porous film and preparation method and use thereof - Google Patents

Carbon nitride-modified titanium dioxide super-hydrophilic porous film and preparation method and use thereof Download PDF

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WO2015196738A1
WO2015196738A1 PCT/CN2014/093047 CN2014093047W WO2015196738A1 WO 2015196738 A1 WO2015196738 A1 WO 2015196738A1 CN 2014093047 W CN2014093047 W CN 2014093047W WO 2015196738 A1 WO2015196738 A1 WO 2015196738A1
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titanium dioxide
carbon nitride
porous film
super
acid
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黄洪
陈炎丰
司徒粤
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华南理工大学
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
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    • C09K3/18—Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces

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  • the invention belongs to the technical field of functional material preparation, and particularly relates to a carbon nitride modified titanium dioxide super hydrophilic porous film and a preparation method and application thereof.
  • the super-hydrophilic film enables water droplets to diffuse on the surface and form a continuous or nearly continuous water film, so that the light is not disturbed, the light can be directly transmitted, and the glass or mirror has an excellent anti-fog effect, and further, by means of photocatalytic coating
  • the layer can degrade the organic pollutants adhering to the surface and remove the water film to achieve self-cleaning effect.
  • the ultra-thin water film formed on the surface is beneficial to the rapid evaporation of water, which is of great significance for the cooling of the cold plate. . Therefore, super-hydrophilic film technology has been widely used in the fields of anti-fog, self-cleaning and cold plate heat dissipation.
  • a primary object of the present invention is to provide a method for preparing a carbon nitride-modified titanium dioxide super-hydrophilic porous film.
  • Another object of the present invention is to provide a carbon nitride-modified titanium dioxide super-hydrophilic porous film obtained by the above production method.
  • Still another object of the present invention is to provide an application of the carbon nitride-modified titanium dioxide super-hydrophilic porous film obtained by the above production method.
  • a method for preparing a carbon nitride modified titanium dioxide super hydrophilic porous film comprising the following steps:
  • the carbon nitride nanosheet prepared in the step (1) is ultrasonically dispersed in absolute ethanol to obtain a carbon nitride dispersion, and then a titanium dioxide precursor is added, and then a double complexing agent acetylacetone and an alcohol amine are added, and the mixture is stirred. After uniformly obtaining a uniform solution, a mixed droplet of anhydrous ethanol, water and acid is added to the homogeneous solution, and the mixture is uniformly stirred to obtain a carbonitride/titanium dioxide composite sol, which is left to be aged for a period of time;
  • the calcination in the step (1) is: firstly, the precursor is heated at a temperature of 0.1 to 5 ° C / min to 400 to 600 ° C for 2 to 8 hours, and then the obtained solid is ground into a fine powder, and then the fine powder is further The temperature is raised from 1 to 10 ° C / min to 400 ⁇ 500 ° C for 2 ⁇ 6h to obtain carbon nitride nanosheets.
  • the concentration of the carbon nitride dispersion in the step (2) is 0.01 ⁇ 2 Mg/mL; volume ratio of carbon nitride dispersion, titanium dioxide precursor, acetylacetone, alcohol amine and mixed solution is (10 ⁇ 60): (1 ⁇ 20): (0.1 ⁇ 5): (0.1 ⁇ 5): (6.2 ⁇ 60), wherein the volume ratio of anhydrous ethanol, deionized water and acid in the mixed solution is (5 ⁇ 40): (1 ⁇ 15): (0.2 ⁇ 5).
  • the alcohol amine in the step (2) is at least one of monoethanolamine, diethanolamine and triethanolamine;
  • the titanium dioxide precursor is at least one of tetrabutyl titanate, isopropyl titanate and titanium sulfate.
  • the alcohol amine in the step (2) is at least one of monoethanolamine, diethanolamine and triethanolamine;
  • the titanium dioxide precursor is at least one of tetrabutyl titanate, isopropyl titanate and titanium sulfate.
  • the alcohol amine in the step (2) is at least one of monoethanolamine, diethanolamine and triethanolamine;
  • the titanium dioxide precursor is at least one of tetrabutyl titanate, isopropyl titanate and titanium sulfate.
  • the acid in the step (2) is at least one of 35% by mass of concentrated hydrochloric acid, 98% by mass of concentrated sulfuric acid and 65% by mass of concentrated nitric acid, and the aging time is 2 hours to 7 day.
  • the silica sol of the step (3) is prepared by adding ethyl orthosilicate to anhydrous ethanol A, adding a mixture of anhydrous ethanol B, deionized water and concentrated acid, and stirring. Uniform, aged for 2 hours to 4 days to prepare the silica sol;
  • the volume ratio of anhydrous ethanol A, ethyl orthosilicate and mixed solution is (10 ⁇ 70): (5 ⁇ 20): (6.1 ⁇ 58); anhydrous ethanol B, deionized water and
  • the volume ratio of concentrated acid is (5 ⁇ 40): (1 ⁇ 15): (0.1 ⁇ 3), concentrated acid is 35% mass fraction of concentrated hydrochloric acid, 98% by mass of concentrated sulfuric acid and 65% by mass of concentrated nitric acid. At least one of them.
  • the ultrasonically rinsing the substrate with the solvent in the step (3) means ultrasonically rinsing with acetone, absolute ethanol and water in sequence; the substrate is at least one of ordinary glass sheets, metal sheets and plastic products.
  • the substrate is at least one of ordinary glass sheets, metal sheets and plastic products.
  • the specific operation step of the step (4) is: spin coating the aged carbonitride/titanium dioxide composite sol at a speed of 100 to 3000 rpm for 10 to 50 seconds or at a speed of 1 to 10 cm/s. coated on a substrate manner pretreated, and coated with 1 to 5 times repeated, the coating obtained after drying at 80 ⁇ 150 °C, then 5 ⁇ 15W • m -2 ultraviolet light irradiation intensity of 5 to The carbon nitride-modified titanium dioxide super-hydrophilic porous film was obtained in 10 minutes.
  • the carbon nitride-modified titanium dioxide super-hydrophilic porous film obtained by the above preparation method is used in the field of anti-fog, self-cleaning or cold plate heat dissipation.
  • it can be used to prepare automobile glass rearview mirror anti-fog, anti-fog mirror, self-cleaning billboard, and the like.
  • the present invention has the following advantages and beneficial effects:
  • the preparation method of the invention can improve the super-hydrophilic realization condition of the titanium dioxide super-hydrophilic film and improve its photocatalytic activity under visible light conditions.
  • the invention is prepared by using cheap and easy-to-obtain raw materials, and the preparation conditions are easy to realize, and it is not required to be calcined under high temperature conditions, thereby reducing the cost of preparing the super-hydrophilic film product, and is advantageous for the popularization and application of the technology.
  • the carbonitride-modified titanium dioxide super-hydrophilic porous film of the present invention can be obtained on different substrates, and a variety of super-hydrophilic film products can be obtained.
  • the carbonitride-modified titanium dioxide super-hydrophilic porous film was prepared as follows:
  • the carbon nitride nanosheet prepared in the step (1) is ultrasonically dispersed in absolute ethanol to obtain 0.01. Mg/mL of carbonitride dispersion, then take 60 units of volume of carbonitride ethanol dispersion, add 20 units of tetrabutyl titanate, then add 5 units of acetylacetone and 5 units of monoethanolamine. Obtaining a homogeneous solution;
  • the glass piece is sequentially ultrasonically rinsed with acetone, absolute ethanol and water, dried, and the above silica sol is coated on the surface of the glass piece and dried to obtain a pretreated substrate;
  • step (3) Applying the carbonitride/titanium dioxide composite sol which has been aged in step (2) to the substrate after the pretreatment of step (3) by spin coating at 100 rpm for 50 seconds, and repeating the coating once.
  • the photodegradation activity of the obtained carbon nitride-modified titanium dioxide super-hydrophilic porous film was measured by the following procedure: 0.01 mmol•L -1 of methylene blue was used as a simulated pollutant, and the obtained porous film was used for degradation to achieve adsorption equilibrium.
  • the prepared carbon nitride-modified titanium dioxide super-hydrophilic porous film was tested to have a light transmittance of 89%, a water contact angle of 4.5°, and a methyl blue degradation rate of 53%.
  • the carbonitride-modified titanium dioxide super-hydrophilic porous film was prepared as follows:
  • the carbon nitride nanosheet prepared in the step (1) is ultrasonically dispersed in absolute ethanol to obtain a 2 mg/mL carbon nitride dispersion, and then 10 unit volume of a carbonitride ethanol dispersion is added, and 10 is added. a unit volume of isopropyl titanate, followed by 0.1 unit volume of acetylacetone and 0.1 unit volume of diethanolamine to obtain a uniform solution;
  • the iron piece is sequentially ultrasonically rinsed with acetone, absolute ethanol and water, dried, and the above silica sol is coated on the surface of the iron piece and dried to obtain a pretreated substrate;
  • the carbon nitride-modified titanium dioxide super-hydrophilic porous film prepared in the present Example was tested to have a light transmittance of 85% and a water contact angle of 4.9°; and the photodegradation activity of the obtained porous film was measured according to the method of Example 1, Finally, the methyl blue degradation rate was 83%.
  • the carbonitride-modified titanium dioxide super-hydrophilic porous film was prepared as follows:
  • the carbon nitride nanosheet prepared in the step (1) is ultrasonically dispersed in absolute ethanol to obtain a 1 mg/mL carbon nitride dispersion, and then 30 unit volume of a carbonitride ethanol dispersion is added, and 7 is added. a unit volume of isopropyl titanate, followed by the addition of 0.6 unit volume of acetylacetone and 0.4 unit volume of diethanolamine to obtain a homogeneous solution;
  • the iron piece is sequentially ultrasonically rinsed with acetone, absolute ethanol and water, dried, and the above silica sol is coated on the surface of the iron piece and dried to obtain a pretreated substrate;
  • step (3) Applying the carbonitride/titanium dioxide composite sol which has been aged in step (2) to the substrate after the pretreatment of step (3) by spin coating at 2000 rpm for 15 seconds, and repeating the coating three times.
  • the carbon nitride-modified titanium dioxide super-hydrophilic porous film prepared in the present Example was tested to have a light transmittance of 91% and a water contact angle of 4.5°; and the photodegradation activity of the obtained porous film was measured according to the method of Example 1, Finally, the methyl blue degradation rate was 89%.
  • the carbonitride-modified titanium dioxide super-hydrophilic porous film was prepared as follows:
  • the carbon nitride nanosheet prepared in the step (1) is ultrasonically dispersed in absolute ethanol to obtain a carbon nitride dispersion of 0.8 mg/mL, and then 40 parts by volume of a carbonitride ethanol dispersion is added. 10 unit volume of isopropyl titanate, followed by 2 units of acetylacetone and 2 units of diethanolamine to obtain a homogeneous solution;
  • the iron piece is sequentially ultrasonically rinsed with acetone, absolute ethanol and water, dried, and the above silica sol is coated on the surface of the iron piece and dried to obtain a pretreated substrate;
  • the carbonitride-modified titanium dioxide super-hydrophilic porous film prepared in the present Example was tested to have a light transmittance of 85% and a water contact angle of 5.0°; and the photodegradation activity of the obtained porous film was measured according to the method of Example 1, Finally, the methyl blue degradation rate was 87%.
  • the carbonitride-modified titanium dioxide super-hydrophilic porous film was prepared as follows:
  • the carbon nitride nanosheet prepared in the step (1) is ultrasonically dispersed in absolute ethanol to obtain a 0.3 mg/mL carbon nitride dispersion, and then 50 unit volume of a carbonitride ethanol dispersion is added. 12 unit volume of isopropyl titanate, followed by 1.5 unit volume of acetylacetone and 2.0 unit volume of diethanolamine to obtain a uniform solution;
  • the iron piece is sequentially ultrasonically rinsed with acetone, absolute ethanol and water, dried, and the above silica sol is coated on the surface of the iron piece and dried to obtain a pretreated substrate;
  • the carbon monoxide/titanium dioxide composite sol which has been aged in the step (2) is applied to the substrate after the pretreatment of the step (3) by spin coating at 1200 rpm for 30 seconds, and is repeatedly applied twice.
  • the carbonitride-modified titanium dioxide super-hydrophilic porous film prepared in the present Example was tested to have a light transmittance of 80% and a water contact angle of 3.5°; and the photodegradation activity of the obtained porous film was measured according to the method of Example 1, Finally, the methyl blue degradation rate was 90%.
  • the carbonitride-modified titanium dioxide super-hydrophilic porous film was prepared as follows:
  • the carbon nitride nanosheet prepared in the step (1) is ultrasonically dispersed in absolute ethanol to obtain a carbon nitride dispersion of 1.5 mg/mL, and then 60 parts by volume of a carbonitride ethanol dispersion is added. 10 unit volume of isopropyl titanate, followed by adding 3.5 unit volume of acetylacetone and 2.5 unit volume of diethanolamine to obtain a uniform solution;
  • the iron piece is sequentially ultrasonically rinsed with acetone, absolute ethanol and water, dried, and the above silica sol is coated on the surface of the iron piece and dried to obtain a pretreated substrate;
  • step (3) Applying the carbonitride/titanium dioxide composite sol which was aged in step (2) to the substrate after the pretreatment of step (3) by spin coating at 1800 rpm for 15 seconds, and repeating the coating 5 times.
  • the carbonitride-modified titanium dioxide super-hydrophilic porous film prepared in the present Example was tested to have a light transmittance of 83% and a water contact angle of 2.0°; the photodegradation activity of the obtained porous film was measured according to the method of Example 1, Finally, the methyl blue degradation rate was 92%.
  • the carbonitride-modified titanium dioxide super-hydrophilic porous film was prepared as follows:
  • the carbon nitride nanosheet prepared in the step (1) is ultrasonically dispersed in absolute ethanol to obtain a carbonitride dispersion of 0.08 mg/mL, and then 55 parts by volume of a carbonitride ethanol dispersion is added. 10 unit volume of isopropyl titanate, followed by 1.5 unit volume of acetylacetone and 2.5 unit volume of triethanolamine to obtain a uniform solution;
  • the glass piece is sequentially ultrasonically rinsed with acetone, absolute ethanol and water, dried, and the above silica sol is coated on the surface of the glass piece and dried to obtain a pretreated substrate;
  • the carbon monoxide/titanium dioxide composite sol which was aged in the step (2) was applied to the substrate after the pretreatment of the step (3) by spin coating at 2000 rpm for 20 seconds, and was repeatedly applied four times.
  • the carbonitride-modified titanium dioxide super-hydrophilic porous film prepared in the present Example was tested to have a light transmittance of 95% and a water contact angle of 3.5°; and the photodegradation activity of the obtained porous film was measured according to the method of Example 1, Finally, the methyl blue degradation rate was detected to be 68%.
  • the carbonitride-modified titanium dioxide super-hydrophilic porous film was prepared as follows:
  • the carbon nitride nanosheet prepared in the step (1) is ultrasonically dispersed in absolute ethanol to obtain a 0.5 mg/mL carbon nitride dispersion, and then 45 unit volume of a carbonitride ethanol dispersion is added. 15 unit volume of isopropyl titanate, followed by addition of 2.0 unit volume of acetylacetone and 2.0 unit volume of diethanolamine to obtain a uniform solution;
  • the glass piece is sequentially ultrasonically rinsed with acetone, absolute ethanol and water, dried, and the above silica sol is coated on the surface of the glass piece and dried to obtain a pretreated substrate;
  • step (3) Applying the carbonitride/titanium dioxide composite sol which has been aged in step (2) to the substrate after the pretreatment of step (3) by spin coating at 2,500 rpm for 10 seconds, and repeating the coating 5 times.
  • the carbonitride-modified titanium dioxide super-hydrophilic porous film prepared in the present Example was tested to have a light transmittance of 85% and a water contact angle of 3.5°; and the photodegradation activity of the obtained porous film was measured according to the method of Example 1, Finally, the methyl blue degradation rate was detected to reach 80%.
  • the carbonitride-modified titanium dioxide super-hydrophilic porous film was prepared as follows:
  • the carbon nitride nanosheet prepared in the step (1) is ultrasonically dispersed in absolute ethanol to obtain a carbon nitride dispersion of 1.0 mg/mL, and then 60 parts by volume of a carbonitride ethanol dispersion is added. 15 unit volume of tetrabutyl titanate, followed by 1.0 unit volume of acetylacetone and 1.5 unit volume of diethanolamine to obtain a uniform solution;
  • the iron piece is sequentially ultrasonically rinsed with acetone, absolute ethanol and water, dried, and the above silica sol is coated on the surface of the iron piece and dried to obtain a pretreated substrate;
  • the carbon nitride-modified titanium dioxide super-hydrophilic porous film prepared in the present Example was tested to have a light transmittance of 88% and a water contact angle of 4.5°; and the photodegradation activity of the obtained porous film was measured according to the method of Example 1, Finally, the methyl blue degradation rate was 86%.
  • the carbonitride-modified titanium dioxide super-hydrophilic porous film was prepared as follows:
  • the carbon nitride nanosheet prepared in the step (1) is ultrasonically dispersed in absolute ethanol to obtain a 1.2 mg/mL carbon nitride dispersion, and then 50 unit volume of a carbonitride ethanol dispersion is added. 15 units of isopropyl titanate, followed by 3 units of acetylacetone and 3 units of monoethanolamine to obtain a homogeneous solution;
  • the iron piece is sequentially ultrasonically rinsed with acetone, absolute ethanol and water, dried, and the above silica sol is coated on the surface of the iron piece and dried to obtain a pretreated substrate;
  • step (3) Applying the carbonitride/titanium dioxide composite sol which has been aged in step (2) to the substrate after the pretreatment of step (3) by spin coating at 4000 rpm for 10 seconds, and repeating the coating 5 times.
  • the carbonitride-modified titanium dioxide super-hydrophilic porous film prepared in the present Example was tested to have a light transmittance of 82% and a water contact angle of 1.0°; and the photodegradation activity of the obtained porous film was measured according to the method of Example 1, Finally, the methyl blue degradation rate was detected to be 78%.

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Abstract

A carbon nitride-modified titanium dioxide super-hydrophilic porous film and a preparation method and use thereof. The method comprises the following steps: calcining dicyandiamide or tripolycyanamide as a precursor, to prepare a carbon nitride nanosheet; ultrasonically dispersing the carbon nitride nanosheet in anhydrous ethanol so as to obtain a carbon nitride dispersion liquid, then adding a titanium dioxide precursor, diacetone and an alcohol amine, uniformly stirring to obtain a uniform solution, dropwise adding a mixed liquid prepared from the anhydrous ethanol, water and an acid into the uniform solution so as to obtain a carbon nitride/titanium dioxide composite sol, aging for a period of time, applying the carbon nitride/titanium dioxide composite sol on a preprocessed substrate, drying and irradiating using ultraviolet, so as to obtain a carbon nitride-modified titanium dioxide super-hydrophilic porous film. The film is prepared from the raw materials which are cheap and easily available, the preparation condition is easy to realize, and the film can be obtained without calcining at a high temperature, so that the preparation cost of a super-hydrophilic film article is reduced, facilitating the popularization and application of the technique.

Description

氮化碳改性二氧化钛超亲水多孔薄膜及其制备方法与应用  Carbon nitride modified titanium dioxide super hydrophilic porous film and preparation method and application thereof
技术领域Technical field
本发明属于功能材料制备技术领域，具体涉及一种氮化碳改性二氧化钛超亲水多孔薄膜及其制备方法与应用。The invention belongs to the technical field of functional material preparation, and particularly relates to a carbon nitride modified titanium dioxide super hydrophilic porous film and a preparation method and application thereof.
背景技术Background technique
超亲水薄膜能够使水滴在表面扩散并形成连续或接近连续的水膜，使光线免受干扰，光线可以直接透过，对于玻璃或者镜子有优异的防雾效果，进一步地，借助光催化涂层，可以对粘附在表面的有机污染物进行降解并利用水膜去除而达到自清洁效果，另一方面，表面形成的超薄水膜有利于水的迅速蒸发，对于冷板散热具有重要意义。因此，超亲水薄膜技术在防雾、自清洁以及冷板散热等领域都有广泛应用。The super-hydrophilic film enables water droplets to diffuse on the surface and form a continuous or nearly continuous water film, so that the light is not disturbed, the light can be directly transmitted, and the glass or mirror has an excellent anti-fog effect, and further, by means of photocatalytic coating The layer can degrade the organic pollutants adhering to the surface and remove the water film to achieve self-cleaning effect. On the other hand, the ultra-thin water film formed on the surface is beneficial to the rapid evaporation of water, which is of great significance for the cooling of the cold plate. . Therefore, super-hydrophilic film technology has been widely used in the fields of anti-fog, self-cleaning and cold plate heat dissipation.
对于超亲水薄膜的概念，一般认为当其表面水接触角小于5度即可视为具有超亲水性，传统的二氧化钛薄膜需要在紫外光的照射下才能实现超亲水性，这无疑限制了其使用，研究和制备出能够在自然光条件下具有超亲水性，并且具有一定光催化活性的二氧化钛薄膜对于其推广应用至关重要。而二氧化钛薄膜对基材的苛刻要求也无疑制约了二氧化钛亲水薄膜的应用，除了最常用的玻璃基材，对于一些塑料基材、钢铁基材，也是超亲水薄膜的重要应用载体。如塑料基材，二氧化钛薄膜由于具有光催化活性，能够与塑料基材发生反应，加快了塑料基材的老化。这些问题都是二氧化钛超亲水薄膜应用面临亟需解决的问题。For the concept of super-hydrophilic film, it is generally considered that when the surface water contact angle is less than 5 degrees, it can be regarded as super-hydrophilic, and the conventional titanium dioxide film needs to be super-hydrophilic under the irradiation of ultraviolet light, which is undoubtedly limited. Its use, research and preparation of titanium dioxide thin films which are super-hydrophilic under natural light conditions and have certain photocatalytic activity are essential for their popularization and application. The demanding requirements of the titanium dioxide film on the substrate undoubtedly restrict the application of the titanium dioxide hydrophilic film. In addition to the most commonly used glass substrates, it is also an important application carrier for super-hydrophilic films for some plastic substrates and steel substrates. Such as a plastic substrate, the titanium dioxide film has a photocatalytic activity, can react with the plastic substrate, and accelerates the aging of the plastic substrate. These problems are the problems that need to be solved in the application of titanium dioxide super-hydrophilic film.
发明内容Summary of the invention
为解决现有技术的缺点和不足之处，本发明的首要目的在于提供一种氮化碳改性二氧化钛超亲水多孔薄膜的制备方法。In order to solve the disadvantages and deficiencies of the prior art, a primary object of the present invention is to provide a method for preparing a carbon nitride-modified titanium dioxide super-hydrophilic porous film.
本发明的另一目的在于提供上述制备方法得到的氮化碳改性二氧化钛超亲水多孔薄膜。Another object of the present invention is to provide a carbon nitride-modified titanium dioxide super-hydrophilic porous film obtained by the above production method.
本发明的再一目的在于提供上述制备方法得到的氮化碳改性二氧化钛超亲水多孔薄膜的应用。Still another object of the present invention is to provide an application of the carbon nitride-modified titanium dioxide super-hydrophilic porous film obtained by the above production method.
为实现上述发明目的，本发明采用如下技术方案：In order to achieve the above object, the present invention adopts the following technical solutions:
一种氮化碳改性二氧化钛超亲水多孔薄膜的制备方法，包括以下步骤：A method for preparing a carbon nitride modified titanium dioxide super hydrophilic porous film, comprising the following steps:
（1）以双氰胺或三聚氰胺为前驱体，经过煅烧，制得氮化碳纳米片；(1) using dicyandiamide or melamine as a precursor, and calcining to obtain a carbon nitride nanosheet;
（2）将步骤（1）制得的氮化碳纳米片在无水乙醇中超声分散，得到氮化碳分散液，然后加入二氧化钛前驱体，再加入双络合剂乙酰丙酮和醇胺，搅拌均匀得到均匀的溶液后，再将无水乙醇、水和酸配制成的混合液滴加到均匀的溶液中，搅拌均匀，得到氮化碳/二氧化钛复合溶胶，将其放置陈化一段时间；(2) The carbon nitride nanosheet prepared in the step (1) is ultrasonically dispersed in absolute ethanol to obtain a carbon nitride dispersion, and then a titanium dioxide precursor is added, and then a double complexing agent acetylacetone and an alcohol amine are added, and the mixture is stirred. After uniformly obtaining a uniform solution, a mixed droplet of anhydrous ethanol, water and acid is added to the homogeneous solution, and the mixture is uniformly stirred to obtain a carbonitride/titanium dioxide composite sol, which is left to be aged for a period of time;
（3）将基材用溶剂超声润洗，烘干后用硅溶胶涂膜，再烘干，得到预处理后的基材；(3) ultrasonically rinsing the substrate with a solvent, drying the film with a silica sol, and drying, to obtain a pretreated substrate;
（4）将步骤（2）陈化后的氮化碳/二氧化钛复合溶胶涂在步骤（3）预处理后的基材上，并将其烘干，之后用紫外线照射，得到所述氮化碳改性二氧化钛超亲水多孔薄膜。(4) Applying the carbonitride/titanium dioxide composite sol which has been aged in the step (2) to the substrate after the pretreatment of the step (3), and drying it, followed by irradiation with ultraviolet rays to obtain the carbon nitride. Modified titanium dioxide super hydrophilic porous film.
优选的，步骤（1）所述煅烧具体为：先将前驱体以0.1~5℃/min升温到400~600℃煅烧2~8h，然后将得到的固体研磨成细粉，再将细粉以1~10℃/min升温到400~500℃煅烧2~6h，得到氮化碳纳米片。Preferably, the calcination in the step (1) is: firstly, the precursor is heated at a temperature of 0.1 to 5 ° C / min to 400 to 600 ° C for 2 to 8 hours, and then the obtained solid is ground into a fine powder, and then the fine powder is further The temperature is raised from 1 to 10 ° C / min to 400 ~ 500 ° C for 2 ~ 6h to obtain carbon nitride nanosheets.
优选的，步骤（2）所述氮化碳分散液的浓度为0.01~2 mg/mL；氮化碳分散液、二氧化钛前驱体、乙酰丙酮、醇胺和混合液的体积比为（10~60）：（1~20）：（0.1~5）：（0.1~5）：（6.2~60），其中所述混合液中无水乙醇、去离子水和酸的体积比为（5~40）：（1~15）：（0.2~5）。Preferably, the concentration of the carbon nitride dispersion in the step (2) is 0.01~2 Mg/mL; volume ratio of carbon nitride dispersion, titanium dioxide precursor, acetylacetone, alcohol amine and mixed solution is (10~60): (1~20): (0.1~5): (0.1~5): (6.2~60), wherein the volume ratio of anhydrous ethanol, deionized water and acid in the mixed solution is (5~40): (1~15): (0.2~5).
优选的，步骤（2）所述醇胺为单乙醇胺、二乙醇胺和三乙醇胺中的至少一种；所述二氧化钛前驱体为钛酸四丁酯、钛酸异丙酯和硫酸钛中的至少一种。Preferably, the alcohol amine in the step (2) is at least one of monoethanolamine, diethanolamine and triethanolamine; the titanium dioxide precursor is at least one of tetrabutyl titanate, isopropyl titanate and titanium sulfate. Kind.
优选的，步骤（2）所述的酸为35%质量分数的浓盐酸、98%质量分数的浓硫酸和65%质量分数的浓硝酸的至少一种，所述陈化时间为2小时~7天。Preferably, the acid in the step (2) is at least one of 35% by mass of concentrated hydrochloric acid, 98% by mass of concentrated sulfuric acid and 65% by mass of concentrated nitric acid, and the aging time is 2 hours to 7 day.
优选的，步骤（3）所述硅溶胶通过如下步骤制备得到：将正硅酸乙酯加入无水乙醇A中，再加入无水乙醇B、去离子水和浓酸制成的混合液，搅拌均匀，陈化2小时~4天，制得所述硅溶胶；Preferably, the silica sol of the step (3) is prepared by adding ethyl orthosilicate to anhydrous ethanol A, adding a mixture of anhydrous ethanol B, deionized water and concentrated acid, and stirring. Uniform, aged for 2 hours to 4 days to prepare the silica sol;
其中无水乙醇A、正硅酸乙酯和混合液的体积比为（10~70）：（5~20）：（6.1~58）；所述混合液中无水乙醇B、去离子水和浓酸的体积比为（5~40）：（1~15）：（0.1~3），浓酸为35%质量分数的浓盐酸、98%质量分数的浓硫酸和65%质量分数的浓硝酸的至少一种。The volume ratio of anhydrous ethanol A, ethyl orthosilicate and mixed solution is (10~70): (5~20): (6.1~58); anhydrous ethanol B, deionized water and The volume ratio of concentrated acid is (5~40): (1~15): (0.1~3), concentrated acid is 35% mass fraction of concentrated hydrochloric acid, 98% by mass of concentrated sulfuric acid and 65% by mass of concentrated nitric acid. At least one of them.
优选的，步骤（3）中所述用溶剂超声润洗基材是指依次用丙酮、无水乙醇和水超声润洗；所述的基材为普通玻璃片、金属片和塑料制品中的至少一种。Preferably, the ultrasonically rinsing the substrate with the solvent in the step (3) means ultrasonically rinsing with acetone, absolute ethanol and water in sequence; the substrate is at least one of ordinary glass sheets, metal sheets and plastic products. One.
优选的，步骤（4）的具体操作步骤为：将陈化后的氮化碳/二氧化钛复合溶胶以100~3000 rpm速度旋涂10~50秒或者以1~10 cm/s的速度提拉的方式涂在预处理后的基材上，并重复涂1~5次，得到的涂层在80~150℃条件下烘干后，再用5~15W•m-2强度的紫外灯照射5~10分钟，得到所述氮化碳改性二氧化钛超亲水多孔薄膜。Preferably, the specific operation step of the step (4) is: spin coating the aged carbonitride/titanium dioxide composite sol at a speed of 100 to 3000 rpm for 10 to 50 seconds or at a speed of 1 to 10 cm/s. coated on a substrate manner pretreated, and coated with 1 to 5 times repeated, the coating obtained after drying at 80 ~ 150 ℃, then 5 ~ 15W • m -2 ultraviolet light irradiation intensity of 5 to The carbon nitride-modified titanium dioxide super-hydrophilic porous film was obtained in 10 minutes.
上述制备方法得到的氮化碳改性二氧化钛超亲水多孔薄膜。The carbon nitride-modified titanium dioxide super-hydrophilic porous film obtained by the above preparation method.
上述制备方法得到的氮化碳改性二氧化钛超亲水多孔薄膜在防雾、自清洁或冷板散热领域中的应用。例如可以将其制备汽车玻璃后视镜防雾、防雾镜子、自清洁广告牌等。The carbon nitride-modified titanium dioxide super-hydrophilic porous film obtained by the above preparation method is used in the field of anti-fog, self-cleaning or cold plate heat dissipation. For example, it can be used to prepare automobile glass rearview mirror anti-fog, anti-fog mirror, self-cleaning billboard, and the like.
与现有技术相比，本发明具有以下优点及有益效果：Compared with the prior art, the present invention has the following advantages and beneficial effects:
（1）本发明制备方法能改善二氧化钛超亲水薄膜的超亲水实现条件、提高其在可见光条件下的光催化活性。(1) The preparation method of the invention can improve the super-hydrophilic realization condition of the titanium dioxide super-hydrophilic film and improve its photocatalytic activity under visible light conditions.
（2）本发明采用廉价易得的原料制备，制备条件容易实现，不需要在高温条件下煅烧，降低了制备超亲水薄膜制品的成本，有利于该技术的推广应用。(2) The invention is prepared by using cheap and easy-to-obtain raw materials, and the preparation conditions are easy to realize, and it is not required to be calcined under high temperature conditions, thereby reducing the cost of preparing the super-hydrophilic film product, and is advantageous for the popularization and application of the technology.
（3）本发明氮化碳改性二氧化钛超亲水多孔薄膜可以在不同基材上得到，可以制得种类较多的超亲水薄膜制品。(3) The carbonitride-modified titanium dioxide super-hydrophilic porous film of the present invention can be obtained on different substrates, and a variety of super-hydrophilic film products can be obtained.
具体实施方式detailed description
下面结合实施例对本发明作进一步详细的描述，但本发明的实施方式不限于此。The present invention will be further described in detail below with reference to the embodiments, but the embodiments of the present invention are not limited thereto.
实施例1Example 1
按以下步骤制备氮化碳改性二氧化钛超亲水多孔薄膜：The carbonitride-modified titanium dioxide super-hydrophilic porous film was prepared as follows:
（1）以双氰胺为前驱体，先将前驱体置于煅烧环境中，以0.1℃/min 的升温速度升温到400℃并保持温度煅烧8h，然后将得到的黄色固体研磨成细粉，再将细粉置于煅烧环境中，以1℃/min的升温速度升温到400℃并保持温度煅烧6h，制得氮化碳纳米片；(1) Using dicyandiamide as a precursor, first place the precursor in a calcination environment at 0.1 ° C / min The heating rate is raised to 400 ° C and the temperature is maintained for 8 h, and then the obtained yellow solid is ground into a fine powder, and the fine powder is placed in a calcination environment, and the temperature is raised to 400 ° C at a heating rate of 1 ° C / min and the temperature is maintained. 6h, producing carbon nitride nanosheets;
（2）将步骤（1）制得的氮化碳纳米片在无水乙醇中超声分散，得到0.01 mg/mL的氮化碳分散液，然后取60单位体积的氮化碳乙醇分散液，加入20单位体积的钛酸四丁酯，接着加入5单位体积的乙酰丙酮和5单位体积的单乙醇胺，得到均匀的溶液；(2) The carbon nitride nanosheet prepared in the step (1) is ultrasonically dispersed in absolute ethanol to obtain 0.01. Mg/mL of carbonitride dispersion, then take 60 units of volume of carbonitride ethanol dispersion, add 20 units of tetrabutyl titanate, then add 5 units of acetylacetone and 5 units of monoethanolamine. Obtaining a homogeneous solution;
再用40单位体积的无水乙醇、15单位体积的去离子水和5单位体积的浓硝酸（65%质量分数）配制成混合液后，将混合液缓慢滴加到上述均匀的溶液中，边滴加边搅拌均匀，得到氮化碳/二氧化钛复合溶胶，并将其陈化2小时；After further mixing 40 parts by volume of absolute ethanol, 15 units of deionized water and 5 units of concentrated nitric acid (65% by mass), the mixture is slowly added dropwise to the above homogeneous solution. Stirring while stirring, obtaining a carbonitride/titanium dioxide composite sol, and aging it for 2 hours;
（3）在10单位体积的无水乙醇中，加入5单位体积的正硅酸乙酯，再缓慢加入40单位体积的无水乙醇、1单位体积的去离子水和0.1单位体积的浓硝酸（65%质量分数）制成的混合液，搅拌均匀，并陈化2小时，制得硅溶胶；(3) Add 5 units of tetraethyl orthosilicate to 10 units of absolute ethanol, and slowly add 40 units of absolute ethanol, 1 unit volume of deionized water and 0.1 unit volume of concentrated nitric acid ( 65% by mass of the prepared mixture, stirred evenly, and aged for 2 hours to obtain a silica sol;
将玻璃片依次用丙酮、无水乙醇和水超声润洗，烘干，再将上述硅溶胶涂覆在玻璃片表面，烘干，得到预处理后的基材；The glass piece is sequentially ultrasonically rinsed with acetone, absolute ethanol and water, dried, and the above silica sol is coated on the surface of the glass piece and dried to obtain a pretreated substrate;
（4）将步骤（2）陈化后的氮化碳/二氧化钛复合溶胶以100rpm速度旋涂50秒的方式涂在步骤（3）预处理后的基材上，并重复涂1次，得到的涂层在80℃条件下烘干后，再用5W•m-2强度的紫外灯照射10分钟，得到所述氮化碳改性二氧化钛超亲水多孔薄膜（长×宽 = 2.5×3.5 cm2）。(4) Applying the carbonitride/titanium dioxide composite sol which has been aged in step (2) to the substrate after the pretreatment of step (3) by spin coating at 100 rpm for 50 seconds, and repeating the coating once. The coating was dried at 80 ° C, and then irradiated with a UV lamp of 5 W•m -2 intensity for 10 minutes to obtain the carbon nanotube-modified titanium dioxide super-hydrophilic porous film (length × width = 2.5 × 3.5 cm 2 ) ).
按照以下步骤测定制得的氮化碳改性二氧化钛超亲水多孔薄膜的光降解活性：用0.01 mmol•L-1的亚甲基蓝作为模拟污染物，用制得的多孔薄膜来降解，达到吸附平衡之后，用紫外可见分光光度计测其吸光值得出初始浓度C0，在100 mW•cm-2强度的模拟太阳光谱下照射24小时，在用紫外分光光度计测其测其最终浓度得出浓度为C，并根据公式计算降解率：降解率=(1-C0/C) ×100%。The photodegradation activity of the obtained carbon nitride-modified titanium dioxide super-hydrophilic porous film was measured by the following procedure: 0.01 mmol•L -1 of methylene blue was used as a simulated pollutant, and the obtained porous film was used for degradation to achieve adsorption equilibrium. The absorbance is measured by an ultraviolet-visible spectrophotometer to obtain an initial concentration of C 0 , which is irradiated for 24 hours under a simulated solar spectrum of 100 mW•cm -2 intensity, and the final concentration is measured by an ultraviolet spectrophotometer to obtain a concentration of C, and calculate the degradation rate according to the formula: degradation rate = (1-C 0 /C) × 100%.
对所制得的氮化碳改性二氧化钛超亲水多孔薄膜进行测试，其透光率为89%，水接触角为4.5º，甲基蓝降解率达到53%。The prepared carbon nitride-modified titanium dioxide super-hydrophilic porous film was tested to have a light transmittance of 89%, a water contact angle of 4.5°, and a methyl blue degradation rate of 53%.
实施例2Example 2
按以下步骤制备氮化碳改性二氧化钛超亲水多孔薄膜：The carbonitride-modified titanium dioxide super-hydrophilic porous film was prepared as follows:
（1）以三聚氰胺为前驱体，先将前驱体置于煅烧环境中，以5℃/min 的升温速度升温到600℃并保持温度煅烧2h，然后将得到的黄色固体研磨成细粉，再将细粉置于煅烧环境中，以10℃/min的升温速度升温到500℃并保持温度煅烧2h，制得氮化碳纳米片；(1) Using melamine as a precursor, first place the precursor in a calcination environment at 5 ° C / min The heating rate is raised to 600 ° C and the temperature is maintained for 2 h, and then the obtained yellow solid is ground into a fine powder, and the fine powder is placed in a calcination environment, and the temperature is raised to 500 ° C at a temperature rising rate of 10 ° C / min and the temperature is maintained. 2h, producing carbon nitride nanosheets;
（2）将步骤（1）制得的氮化碳纳米片在无水乙醇中超声分散，得到2mg/mL的氮化碳分散液，然后取10单位体积的氮化碳乙醇分散液，加入10单位体积的钛酸异丙酯，接着加入0.1单位体积的乙酰丙酮和0.1单位体积的二乙醇胺，得到均匀的溶液；(2) The carbon nitride nanosheet prepared in the step (1) is ultrasonically dispersed in absolute ethanol to obtain a 2 mg/mL carbon nitride dispersion, and then 10 unit volume of a carbonitride ethanol dispersion is added, and 10 is added. a unit volume of isopropyl titanate, followed by 0.1 unit volume of acetylacetone and 0.1 unit volume of diethanolamine to obtain a uniform solution;
再用40单位体积的无水乙醇、10单位体积的去离子水和3单位体积的浓盐酸（35%质量分数）配制成混合液后，将混合液缓慢滴加到上述均匀的溶液中，边滴加边搅拌均匀，得到氮化碳/二氧化钛复合溶胶，并陈化7天；After further mixing 40 parts by volume of absolute ethanol, 10 units of deionized water and 3 units of concentrated hydrochloric acid (35% by mass), the mixture is slowly added dropwise to the above homogeneous solution. Stirring while stirring, obtaining a carbon nitride/titanium dioxide composite sol, and aged for 7 days;
（3）在70单位体积的无水乙醇中，加入20单位体积的正硅酸乙酯，再缓慢加入5单位体积的无水乙醇、15单位体积的去离子水和3单位体积的浓硫酸（98%质量分数）制成的混合液，搅拌均匀，并陈化4天，制得硅溶胶；(3) In 70 units of volume of absolute ethanol, add 20 units of volume of orthosilicate, and then slowly add 5 units of absolute ethanol, 15 units of deionized water and 3 units of concentrated sulfuric acid ( 98% by mass of the prepared mixture, stirred evenly, and aged for 4 days to obtain a silica sol;
将铁片依次用丙酮、无水乙醇和水超声润洗，烘干，再将上述硅溶胶涂覆在铁片表面，烘干，得到预处理后的基材；The iron piece is sequentially ultrasonically rinsed with acetone, absolute ethanol and water, dried, and the above silica sol is coated on the surface of the iron piece and dried to obtain a pretreated substrate;
（4）将步骤（2）陈化后的氮化碳/二氧化钛复合溶胶以3000rpm速度旋涂10秒的方式涂在步骤（3）预处理后的基材上，并重复涂5次，得到的涂层在150℃条件下烘干后，再用15W•m-2强度的紫外灯照射5分钟，得到所述氮化碳改性二氧化钛超亲水多孔薄膜（长×宽 = 2.5×3.5 cm2）。(4) Applying the carbonitride/titanium dioxide composite sol which has been aged in step (2) to the substrate after the pretreatment of step (3) by spin coating at 3000 rpm for 10 seconds, and repeating the coating 5 times. After the coating was dried at 150 ° C, it was irradiated with a UV lamp of 15 W•m -2 intensity for 5 minutes to obtain the carbon nanotube-modified titanium dioxide super-hydrophilic porous film (length × width = 2.5 × 3.5 cm 2 ). ).
经检测本实施例制得的氮化碳改性二氧化钛超亲水多孔薄膜，其透光率为85%，水接触角为4.9º；按照实施例1的方法检测所得的多孔薄膜光降解活性，最后检测到其甲基蓝降解率达到83%。The carbon nitride-modified titanium dioxide super-hydrophilic porous film prepared in the present Example was tested to have a light transmittance of 85% and a water contact angle of 4.9°; and the photodegradation activity of the obtained porous film was measured according to the method of Example 1, Finally, the methyl blue degradation rate was 83%.
实施例3Example 3
按以下步骤制备氮化碳改性二氧化钛超亲水多孔薄膜：The carbonitride-modified titanium dioxide super-hydrophilic porous film was prepared as follows:
（1）以三聚氰胺为前驱体，先将前驱体置于煅烧环境中，以3℃/min 的升温速度升温到550℃并保持温度煅烧4h，然后将得到的黄色固体研磨成细粉，再将细粉置于煅烧环境中，以6℃/min的升温速度升温到490℃并保持温度煅烧3h，制得氮化碳纳米片；(1) Using melamine as a precursor, first place the precursor in a calcination environment at 3 ° C / min The heating rate is raised to 550 ° C and the temperature is maintained for 4 h. Then, the obtained yellow solid is ground into a fine powder, and the fine powder is placed in a calcination environment, and the temperature is raised to 490 ° C at a temperature rising rate of 6 ° C / min and the temperature is maintained. 3h, producing carbon nitride nanosheets;
（2）将步骤（1）制得的氮化碳纳米片在无水乙醇中超声分散，得到1mg/mL的氮化碳分散液，然后取30单位体积的氮化碳乙醇分散液，加入7单位体积的钛酸异丙酯，接着加入0.6单位体积的乙酰丙酮和0.4单位体积的二乙醇胺，得到均匀的溶液；(2) The carbon nitride nanosheet prepared in the step (1) is ultrasonically dispersed in absolute ethanol to obtain a 1 mg/mL carbon nitride dispersion, and then 30 unit volume of a carbonitride ethanol dispersion is added, and 7 is added. a unit volume of isopropyl titanate, followed by the addition of 0.6 unit volume of acetylacetone and 0.4 unit volume of diethanolamine to obtain a homogeneous solution;
再用30单位体积的无水乙醇、5单位体积的去离子水和2单位体积的浓盐酸（35%质量分数）配制成混合液后，将混合液缓慢滴加到上述均匀的溶液中，边滴加边搅拌均匀，得到氮化碳/二氧化钛复合溶胶，并陈化2天；After mixing 30 parts by volume of absolute ethanol, 5 units of deionized water and 2 units of concentrated hydrochloric acid (35% by mass), the mixture is slowly added dropwise to the above homogeneous solution. Stirring while stirring, obtaining a carbon nitride/titanium dioxide composite sol, and aging for 2 days;
（3）在50单位体积的无水乙醇中，加入15单位体积的正硅酸乙酯，再缓慢加入10单位体积的无水乙醇、8单位体积的去离子水和2单位体积的浓盐酸（35%质量分数）制成的混合液，搅拌均匀，并陈化1天，制得硅溶胶；(3) Add 15 units of volume of orthosilicate in 50 units of absolute ethanol, and then slowly add 10 units of absolute ethanol, 8 units of deionized water and 2 units of concentrated hydrochloric acid ( 35% by mass of the prepared mixture, stirred evenly, and aged for 1 day to obtain a silica sol;
将铁片依次用丙酮、无水乙醇和水超声润洗，烘干，再将上述硅溶胶涂覆在铁片表面，烘干，得到预处理后的基材；The iron piece is sequentially ultrasonically rinsed with acetone, absolute ethanol and water, dried, and the above silica sol is coated on the surface of the iron piece and dried to obtain a pretreated substrate;
（4）将步骤（2）陈化后的氮化碳/二氧化钛复合溶胶以2000rpm速度旋涂15秒的方式涂在步骤（3）预处理后的基材上，并重复涂3次，得到的涂层在120℃条件下烘干后，再用10W•m-2强度的紫外灯照射10分钟，得到所述氮化碳改性二氧化钛超亲水多孔薄膜（长×宽 = 2.5×3.5 cm2）。(4) Applying the carbonitride/titanium dioxide composite sol which has been aged in step (2) to the substrate after the pretreatment of step (3) by spin coating at 2000 rpm for 15 seconds, and repeating the coating three times. The coating was dried at 120 ° C, and then irradiated with a 10 W•m -2 intensity UV lamp for 10 minutes to obtain the carbon nitride-modified titanium dioxide super-hydrophilic porous film (length × width = 2.5 × 3.5 cm 2 ) ).
经检测本实施例制得的氮化碳改性二氧化钛超亲水多孔薄膜，其透光率为91%，水接触角为4.5º；按照实施例1的方法检测所得的多孔薄膜光降解活性，最后检测到其甲基蓝降解率达到89%。The carbon nitride-modified titanium dioxide super-hydrophilic porous film prepared in the present Example was tested to have a light transmittance of 91% and a water contact angle of 4.5°; and the photodegradation activity of the obtained porous film was measured according to the method of Example 1, Finally, the methyl blue degradation rate was 89%.
实施例4Example 4
按以下步骤制备氮化碳改性二氧化钛超亲水多孔薄膜：The carbonitride-modified titanium dioxide super-hydrophilic porous film was prepared as follows:
（1）以三聚氰胺为前驱体，先将前驱体置于煅烧环境中，以2℃/min 的升温速度升温到480℃并保持温度煅烧5h，然后将得到的黄色固体研磨成细粉，再将细粉置于煅烧环境中，以6℃/min的升温速度升温到500℃并保持温度煅烧3h，制得氮化碳纳米片；(1) Using melamine as a precursor, first place the precursor in a calcination environment at 2 ° C / min The heating rate is raised to 480 ° C and the temperature is maintained for 5 h. Then, the obtained yellow solid is ground into a fine powder, and the fine powder is placed in a calcination environment, and the temperature is raised to 500 ° C at a heating rate of 6 ° C / min and the temperature is maintained. 3h, producing carbon nitride nanosheets;
（2）将步骤（1）制得的氮化碳纳米片在无水乙醇中超声分散，得到0.8mg/mL的氮化碳分散液，然后取40单位体积的氮化碳乙醇分散液，加入10单位体积的钛酸异丙酯，接着加入2单位体积的乙酰丙酮和2单位体积的二乙醇胺，得到均匀的溶液；(2) The carbon nitride nanosheet prepared in the step (1) is ultrasonically dispersed in absolute ethanol to obtain a carbon nitride dispersion of 0.8 mg/mL, and then 40 parts by volume of a carbonitride ethanol dispersion is added. 10 unit volume of isopropyl titanate, followed by 2 units of acetylacetone and 2 units of diethanolamine to obtain a homogeneous solution;
再用25单位体积的无水乙醇、15单位体积的去离子水和1单位体积的浓硝酸（65%质量分数）配制成混合液后，将混合液缓慢滴加到上述均匀的溶液中，边滴加边搅拌均匀，得到氮化碳/二氧化钛复合溶胶，并陈化3天；After further mixing 25 parts by volume of absolute ethanol, 15 units of deionized water and 1 unit volume of concentrated nitric acid (65% by mass), the mixture is slowly added dropwise to the above homogeneous solution. Stirring while stirring, obtaining a carbon nitride/titanium dioxide composite sol, and aged for 3 days;
（3）在60单位体积的无水乙醇中，加入10单位体积的正硅酸乙酯，再缓慢加入20单位体积的无水乙醇、15单位体积的去离子水和2单位体积的浓盐酸（35%质量分数）制成的混合液，搅拌均匀，并陈化1天，制得硅溶胶；(3) Add 10 units of volume of ethyl orthosilicate to 60 units of absolute ethanol, and then slowly add 20 units of absolute ethanol, 15 units of deionized water and 2 units of concentrated hydrochloric acid ( 35% by mass of the prepared mixture, stirred evenly, and aged for 1 day to obtain a silica sol;
将铁片依次用丙酮、无水乙醇和水超声润洗，烘干，再将上述硅溶胶涂覆在铁片表面，烘干，得到预处理后的基材；The iron piece is sequentially ultrasonically rinsed with acetone, absolute ethanol and water, dried, and the above silica sol is coated on the surface of the iron piece and dried to obtain a pretreated substrate;
（4）将步骤（2）陈化后的氮化碳/二氧化钛复合溶胶以1000rpm速度旋涂10秒的方式涂在步骤（3）预处理后的基材上，并重复涂3次，得到的涂层在90℃条件下烘干后，再用10W•m-2强度的紫外灯照射10分钟，得到所述氮化碳改性二氧化钛超亲水多孔薄膜（长×宽 = 2.5×3.5 cm2）。(4) Applying the carbonitride/titanium dioxide composite sol which has been aged in step (2) to the substrate after the pretreatment of step (3) by spin coating at 1000 rpm for 10 seconds, and repeating the coating three times. coating at 90 deg.] C after drying, and then irradiated with an ultraviolet lamp 10W • m -2 strength 10 minutes to obtain the modified titanium dioxide carbon nitride porous film superhydrophilic (L × W = 2.5 × 3.5 cm 2 ).
经检测本实施例制得的氮化碳改性二氧化钛超亲水多孔薄膜，其透光率为85%，水接触角为5.0º；按照实施例1的方法检测所得的多孔薄膜光降解活性，最后检测到其甲基蓝降解率达到87%。The carbonitride-modified titanium dioxide super-hydrophilic porous film prepared in the present Example was tested to have a light transmittance of 85% and a water contact angle of 5.0°; and the photodegradation activity of the obtained porous film was measured according to the method of Example 1, Finally, the methyl blue degradation rate was 87%.
实施例5Example 5
按以下步骤制备氮化碳改性二氧化钛超亲水多孔薄膜：The carbonitride-modified titanium dioxide super-hydrophilic porous film was prepared as follows:
（1）以三聚氰胺为前驱体，先将前驱体置于煅烧环境中，以1℃/min 的升温速度升温到550℃并保持温度煅烧3h，然后将得到的黄色固体研磨成细粉，再将细粉置于煅烧环境中，以4℃/min的升温速度升温到500℃并保持温度煅烧2.5h，制得氮化碳纳米片；(1) Using melamine as a precursor, first place the precursor in a calcination environment at 1 ° C / min The heating rate is raised to 550 ° C and the temperature is maintained for 3 h, and then the obtained yellow solid is ground into a fine powder, and the fine powder is placed in a calcination environment, and the temperature is raised to 500 ° C at a heating rate of 4 ° C / min and the temperature is maintained. 2.5h, obtained carbon nitride nanosheets;
（2）将步骤（1）制得的氮化碳纳米片在无水乙醇中超声分散，得到0.3mg/mL的氮化碳分散液，然后取50单位体积的氮化碳乙醇分散液，加入12单位体积的钛酸异丙酯，接着加入1.5单位体积的乙酰丙酮和2.0单位体积的二乙醇胺，得到均匀的溶液；(2) The carbon nitride nanosheet prepared in the step (1) is ultrasonically dispersed in absolute ethanol to obtain a 0.3 mg/mL carbon nitride dispersion, and then 50 unit volume of a carbonitride ethanol dispersion is added. 12 unit volume of isopropyl titanate, followed by 1.5 unit volume of acetylacetone and 2.0 unit volume of diethanolamine to obtain a uniform solution;
再用30单位体积的无水乙醇、8单位体积的去离子水和2单位体积的浓盐酸（35%质量分数）配制成混合液后，将混合液缓慢滴加到上述均匀的溶液中，边滴加边搅拌均匀，得到氮化碳/二氧化钛复合溶胶，并陈化6天；After mixing with 30 units of absolute ethanol, 8 units of deionized water and 2 units of concentrated hydrochloric acid (35% by mass), the mixture is slowly added dropwise to the above homogeneous solution. Stirring while stirring, obtaining a carbon nitride/titanium dioxide composite sol, and aged for 6 days;
（3）在50单位体积的无水乙醇中，加入15单位体积的正硅酸乙酯，再缓慢加入10单位体积的无水乙醇、5单位体积的去离子水和5单位体积的浓硝酸（65%质量分数）制成的混合液，搅拌均匀，并陈化3天，制得硅溶胶；(3) In 50 units of volume of absolute ethanol, add 15 units of volume of orthosilicate, and then slowly add 10 units of absolute ethanol, 5 units of deionized water and 5 units of concentrated nitric acid ( 65% by mass of the prepared mixture, stirred evenly, and aged for 3 days to obtain a silica sol;
将铁片依次用丙酮、无水乙醇和水超声润洗，烘干，再将上述硅溶胶涂覆在铁片表面，烘干，得到预处理后的基材；The iron piece is sequentially ultrasonically rinsed with acetone, absolute ethanol and water, dried, and the above silica sol is coated on the surface of the iron piece and dried to obtain a pretreated substrate;
（4）将步骤（2）陈化后的氮化碳/二氧化钛复合溶胶以1200rpm速度旋涂30秒的方式涂在步骤（3）预处理后的基材上，并重复涂2次，得到的涂层在90℃条件下烘干后，再用15W•m-2强度的紫外灯照射10分钟，得到所述氮化碳改性二氧化钛超亲水多孔薄膜（长×宽 = 2.5×3.5 cm2）。(4) The carbon monoxide/titanium dioxide composite sol which has been aged in the step (2) is applied to the substrate after the pretreatment of the step (3) by spin coating at 1200 rpm for 30 seconds, and is repeatedly applied twice. The coating was dried at 90 ° C, and then irradiated with a UV lamp of 15 W•m -2 intensity for 10 minutes to obtain the carbon nanotube-modified titanium dioxide super-hydrophilic porous film (length × width = 2.5 × 3.5 cm 2 ) ).
经检测本实施例制得的氮化碳改性二氧化钛超亲水多孔薄膜，其透光率为80%，水接触角为3.5º；按照实施例1的方法检测所得的多孔薄膜光降解活性，最后检测到其甲基蓝降解率达到90%。The carbonitride-modified titanium dioxide super-hydrophilic porous film prepared in the present Example was tested to have a light transmittance of 80% and a water contact angle of 3.5°; and the photodegradation activity of the obtained porous film was measured according to the method of Example 1, Finally, the methyl blue degradation rate was 90%.
实施例6Example 6
按以下步骤制备氮化碳改性二氧化钛超亲水多孔薄膜：The carbonitride-modified titanium dioxide super-hydrophilic porous film was prepared as follows:
（1）以双氰胺为前驱体，先将前驱体置于煅烧环境中，以0.5℃/min 的升温速度升温到480℃并保持温度煅烧6h，然后将得到的黄色固体研磨成细粉，再将细粉置于煅烧环境中，以8℃/min的升温速度升温到450℃并保持温度煅烧3h，制得氮化碳纳米片；(1) Using dicyandiamide as the precursor, first place the precursor in a calcination environment at 0.5 ° C / min The heating rate is raised to 480 ° C and the temperature is maintained for 6 h. Then, the obtained yellow solid is ground into a fine powder, and the fine powder is placed in a calcination environment, and the temperature is raised to 450 ° C at a temperature rising rate of 8 ° C / min and the temperature is maintained. 3h, producing carbon nitride nanosheets;
（2）将步骤（1）制得的氮化碳纳米片在无水乙醇中超声分散，得到1.5mg/mL的氮化碳分散液，然后取60单位体积的氮化碳乙醇分散液，加入10单位体积的钛酸异丙酯，接着加入3.5单位体积的乙酰丙酮和2.5单位体积的二乙醇胺，得到均匀的溶液；(2) The carbon nitride nanosheet prepared in the step (1) is ultrasonically dispersed in absolute ethanol to obtain a carbon nitride dispersion of 1.5 mg/mL, and then 60 parts by volume of a carbonitride ethanol dispersion is added. 10 unit volume of isopropyl titanate, followed by adding 3.5 unit volume of acetylacetone and 2.5 unit volume of diethanolamine to obtain a uniform solution;
再用40单位体积的无水乙醇、1单位体积的去离子水和0.2单位体积的浓硫酸（98%质量分数）配制成混合液后，将混合液缓慢滴加到上述均匀的溶液中，边滴加边搅拌均匀，得到氮化碳/二氧化钛复合溶胶，并陈化5天；After further mixing 40 parts by volume of absolute ethanol, 1 unit volume of deionized water and 0.2 unit volume of concentrated sulfuric acid (98% by mass), the mixture is slowly added dropwise to the above homogeneous solution. Stirring while stirring, obtaining a carbon nitride/titanium dioxide composite sol, and aging for 5 days;
（3）在40单位体积的无水乙醇中，加入10单位体积的正硅酸乙酯，再缓慢加入15单位体积的无水乙醇、10单位体积的去离子水和1.5单位体积的浓盐酸（35%质量分数）制成的混合液，搅拌均匀，并陈化1天，制得硅溶胶；(3) In 40 units of volume of absolute ethanol, add 10 units of volume of orthosilicate, and then slowly add 15 units of absolute ethanol, 10 units of deionized water and 1.5 units of concentrated hydrochloric acid ( 35% by mass of the prepared mixture, stirred evenly, and aged for 1 day to obtain a silica sol;
将铁片依次用丙酮、无水乙醇和水超声润洗，烘干，再将上述硅溶胶涂覆在铁片表面，烘干，得到预处理后的基材；The iron piece is sequentially ultrasonically rinsed with acetone, absolute ethanol and water, dried, and the above silica sol is coated on the surface of the iron piece and dried to obtain a pretreated substrate;
（4）将步骤（2）陈化后的氮化碳/二氧化钛复合溶胶以1800rpm速度旋涂15秒的方式涂在步骤（3）预处理后的基材上，并重复涂5次，得到的涂层在110℃条件下烘干后，再用10W•m-2强度的紫外灯照射5分钟，得到所述氮化碳改性二氧化钛超亲水多孔薄膜（长×宽 = 2.5×3.5 cm2）。(4) Applying the carbonitride/titanium dioxide composite sol which was aged in step (2) to the substrate after the pretreatment of step (3) by spin coating at 1800 rpm for 15 seconds, and repeating the coating 5 times. The coating was dried at 110 ° C, and then irradiated with a UV lamp of 10 W•m -2 intensity for 5 minutes to obtain the carbon nanotube-modified titanium dioxide super-hydrophilic porous film (length × width = 2.5 × 3.5 cm 2 ) ).
经检测本实施例制得的氮化碳改性二氧化钛超亲水多孔薄膜，其透光率为83%，水接触角为2.0º；按照实施例1的方法检测所得的多孔薄膜光降解活性，最后检测到其甲基蓝降解率达到92%。The carbonitride-modified titanium dioxide super-hydrophilic porous film prepared in the present Example was tested to have a light transmittance of 83% and a water contact angle of 2.0°; the photodegradation activity of the obtained porous film was measured according to the method of Example 1, Finally, the methyl blue degradation rate was 92%.
实施例7Example 7
按以下步骤制备氮化碳改性二氧化钛超亲水多孔薄膜：The carbonitride-modified titanium dioxide super-hydrophilic porous film was prepared as follows:
（1）以三聚氰胺为前驱体，先将前驱体置于煅烧环境中，以4℃/min 的升温速度升温到500℃并保持温度煅烧5h，然后将得到的黄色固体研磨成细粉，再将细粉置于煅烧环境中，以6℃/min的升温速度升温到450℃并保持温度煅烧5h，制得氮化碳纳米片；(1) Using melamine as a precursor, first place the precursor in a calcination environment at 4 ° C / min The heating rate is raised to 500 ° C and the temperature is maintained for 5 h, and then the obtained yellow solid is ground into a fine powder, and the fine powder is placed in a calcination environment, and the temperature is raised to 450 ° C at a temperature rising rate of 6 ° C / min and the temperature is maintained. 5h, producing carbon nitride nanosheets;
（2）将步骤（1）制得的氮化碳纳米片在无水乙醇中超声分散，得到0.08mg/mL的氮化碳分散液，然后取55单位体积的氮化碳乙醇分散液，加入10单位体积的钛酸异丙酯，接着加入1.5单位体积的乙酰丙酮和2.5单位体积的三乙醇胺，得到均匀的溶液；(2) The carbon nitride nanosheet prepared in the step (1) is ultrasonically dispersed in absolute ethanol to obtain a carbonitride dispersion of 0.08 mg/mL, and then 55 parts by volume of a carbonitride ethanol dispersion is added. 10 unit volume of isopropyl titanate, followed by 1.5 unit volume of acetylacetone and 2.5 unit volume of triethanolamine to obtain a uniform solution;
再用30单位体积的无水乙醇、12单位体积的去离子水和4单位体积的浓盐酸（35%质量分数）配制成混合液后，将混合液缓慢滴加到上述均匀的溶液中，边滴加边搅拌均匀，得到氮化碳/二氧化钛复合溶胶，并陈化4天；After mixing with 30 units of absolute ethanol, 12 units of deionized water and 4 units of concentrated hydrochloric acid (35% by mass), the mixture is slowly added dropwise to the above homogeneous solution. The mixture was stirred while being added dropwise to obtain a carbon nitride/titanium dioxide composite sol, and aged for 4 days;
（3）在50单位体积的无水乙醇中，加入10单位体积的正硅酸乙酯，再缓慢加入20单位体积的无水乙醇、10单位体积的去离子水和1单位体积的浓盐酸（35%质量分数）制成的混合液，搅拌均匀，并陈化12小时，制得硅溶胶；(3) Add 10 units of volume of orthosilicate in 50 units of absolute ethanol, and slowly add 20 units of absolute ethanol, 10 units of deionized water and 1 unit of concentrated hydrochloric acid. 35% by mass of the prepared mixture, stirred evenly, and aged for 12 hours to obtain a silica sol;
将玻璃片依次用丙酮、无水乙醇和水超声润洗，烘干，再将上述硅溶胶涂覆在玻璃片表面，烘干，得到预处理后的基材；The glass piece is sequentially ultrasonically rinsed with acetone, absolute ethanol and water, dried, and the above silica sol is coated on the surface of the glass piece and dried to obtain a pretreated substrate;
（4）将步骤（2）陈化后的氮化碳/二氧化钛复合溶胶以2000rpm速度旋涂20秒的方式涂在步骤（3）预处理后的基材上，并重复涂4次，得到的涂层在130℃条件下烘干后，再用5W•m-2强度的紫外灯照射10分钟，得到所述氮化碳改性二氧化钛超亲水多孔薄膜（长×宽 = 2.5×3.5 cm2）。(4) The carbon monoxide/titanium dioxide composite sol which was aged in the step (2) was applied to the substrate after the pretreatment of the step (3) by spin coating at 2000 rpm for 20 seconds, and was repeatedly applied four times. The coating was dried at 130 ° C, and then irradiated with a UV lamp of 5 W•m -2 intensity for 10 minutes to obtain the carbon nanotube-modified titanium dioxide super-hydrophilic porous film (length × width = 2.5 × 3.5 cm 2 ) ).
经检测本实施例制得的氮化碳改性二氧化钛超亲水多孔薄膜，其透光率为95%，水接触角为3.5º；按照实施例1的方法检测所得的多孔薄膜光降解活性，最后检测到其甲基蓝降解率达到68%。The carbonitride-modified titanium dioxide super-hydrophilic porous film prepared in the present Example was tested to have a light transmittance of 95% and a water contact angle of 3.5°; and the photodegradation activity of the obtained porous film was measured according to the method of Example 1, Finally, the methyl blue degradation rate was detected to be 68%.
实施例8Example 8
按以下步骤制备氮化碳改性二氧化钛超亲水多孔薄膜：The carbonitride-modified titanium dioxide super-hydrophilic porous film was prepared as follows:
（1）以双氰胺为前驱体，先将前驱体置于煅烧环境中，以1.5℃/min 的升温速度升温到400℃并保持温度煅烧7h，然后将得到的黄色固体研磨成细粉，再将细粉置于煅烧环境中，以5℃/min的升温速度升温到450℃并保持温度煅烧4h，制得氮化碳纳米片；(1) Using dicyandiamide as a precursor, first place the precursor in a calcination environment at 1.5 ° C / min The heating rate is raised to 400 ° C and the temperature is maintained for 7 h. Then, the obtained yellow solid is ground into a fine powder, and the fine powder is placed in a calcination environment, and the temperature is raised to 450 ° C at a heating rate of 5 ° C / min and the temperature is maintained. 4h, producing carbon nitride nanosheets;
（2）将步骤（1）制得的氮化碳纳米片在无水乙醇中超声分散，得到0.5mg/mL的氮化碳分散液，然后取45单位体积的氮化碳乙醇分散液，加入15单位体积的钛酸异丙酯，接着加入2.0单位体积的乙酰丙酮和2.0单位体积的二乙醇胺，得到均匀的溶液；(2) The carbon nitride nanosheet prepared in the step (1) is ultrasonically dispersed in absolute ethanol to obtain a 0.5 mg/mL carbon nitride dispersion, and then 45 unit volume of a carbonitride ethanol dispersion is added. 15 unit volume of isopropyl titanate, followed by addition of 2.0 unit volume of acetylacetone and 2.0 unit volume of diethanolamine to obtain a uniform solution;
再用40单位体积的无水乙醇、10单位体积的去离子水和2单位体积的浓硝酸（65%质量分数）配制成混合液后，将混合液缓慢滴加到上述均匀的溶液中，边滴加边搅拌均匀，得到氮化碳/二氧化钛复合溶胶，并陈化1天；After further mixing 40 parts by volume of absolute ethanol, 10 units of deionized water and 2 units of concentrated nitric acid (65% by mass), the mixture is slowly added dropwise to the above homogeneous solution. Stirring while stirring, obtaining a carbon nitride/titanium dioxide composite sol, and aging for 1 day;
（3）在50单位体积的无水乙醇中，加入15单位体积的正硅酸乙酯，再缓慢加入15单位体积的无水乙醇、15单位体积的去离子水和2单位体积的浓盐酸（35%质量分数）制成的混合液，搅拌均匀，并陈化18小时，制得硅溶胶；(3) Add 15 units of volume of tetraethyl orthosilicate to 50 units of absolute ethanol, and then slowly add 15 units of absolute ethanol, 15 units of deionized water and 2 units of concentrated hydrochloric acid ( 35% by mass of the prepared mixture, stirred evenly, and aged for 18 hours to obtain a silica sol;
将玻璃片依次用丙酮、无水乙醇和水超声润洗，烘干，再将上述硅溶胶涂覆在玻璃片表面，烘干，得到预处理后的基材；The glass piece is sequentially ultrasonically rinsed with acetone, absolute ethanol and water, dried, and the above silica sol is coated on the surface of the glass piece and dried to obtain a pretreated substrate;
（4）将步骤（2）陈化后的氮化碳/二氧化钛复合溶胶以2500rpm速度旋涂10秒的方式涂在步骤（3）预处理后的基材上，并重复涂5次，得到的涂层在140℃条件下烘干后，再用15W•m-2强度的紫外灯照射5分钟，得到所述氮化碳改性二氧化钛超亲水多孔薄膜（长×宽 = 2.5×3.5 cm2）。(4) Applying the carbonitride/titanium dioxide composite sol which has been aged in step (2) to the substrate after the pretreatment of step (3) by spin coating at 2,500 rpm for 10 seconds, and repeating the coating 5 times. The coating was dried at 140 ° C, and then irradiated with a UV lamp of 15 W•m -2 intensity for 5 minutes to obtain the carbon nanotube-modified titanium dioxide super-hydrophilic porous film (length × width = 2.5 × 3.5 cm 2 ) ).
经检测本实施例制得的氮化碳改性二氧化钛超亲水多孔薄膜，其透光率为85%，水接触角为3.5º；按照实施例1的方法检测所得的多孔薄膜光降解活性，最后检测到其甲基蓝降解率达到80%。The carbonitride-modified titanium dioxide super-hydrophilic porous film prepared in the present Example was tested to have a light transmittance of 85% and a water contact angle of 3.5°; and the photodegradation activity of the obtained porous film was measured according to the method of Example 1, Finally, the methyl blue degradation rate was detected to reach 80%.
实施例9Example 9
按以下步骤制备氮化碳改性二氧化钛超亲水多孔薄膜：The carbonitride-modified titanium dioxide super-hydrophilic porous film was prepared as follows:
（1）以三聚氰胺为前驱体，先将前驱体置于煅烧环境中，以2℃/min 的升温速度升温到550℃并保持温度煅烧4h，然后将得到的黄色固体研磨成细粉，再将细粉置于煅烧环境中，以5℃/min的升温速度升温到500℃并保持温度煅烧4h，制得氮化碳纳米片；(1) Using melamine as a precursor, first place the precursor in a calcination environment at 2 ° C / min The heating rate is raised to 550 ° C and the temperature is maintained for 4 h. Then, the obtained yellow solid is ground into a fine powder, and the fine powder is placed in a calcination environment, and the temperature is raised to 500 ° C at a heating rate of 5 ° C / min and the temperature is maintained. 4h, producing carbon nitride nanosheets;
（2）将步骤（1）制得的氮化碳纳米片在无水乙醇中超声分散，得到1.0mg/mL的氮化碳分散液，然后取60单位体积的氮化碳乙醇分散液，加入15单位体积的钛酸四丁酯，接着加入1.0单位体积的乙酰丙酮和1.5单位体积的二乙醇胺，得到均匀的溶液；(2) The carbon nitride nanosheet prepared in the step (1) is ultrasonically dispersed in absolute ethanol to obtain a carbon nitride dispersion of 1.0 mg/mL, and then 60 parts by volume of a carbonitride ethanol dispersion is added. 15 unit volume of tetrabutyl titanate, followed by 1.0 unit volume of acetylacetone and 1.5 unit volume of diethanolamine to obtain a uniform solution;
再用30单位体积的无水乙醇、10单位体积的去离子水和1.5单位体积的浓盐酸（35%质量分数）配制成混合液后，将混合液缓慢滴加到上述均匀的溶液中，边滴加边搅拌均匀，得到氮化碳/二氧化钛复合溶胶，并陈化2天；After mixing with 30 units of absolute ethanol, 10 units of deionized water and 1.5 units of concentrated hydrochloric acid (35% by mass), the mixture is slowly added dropwise to the above homogeneous solution. Stirring while stirring, obtaining a carbon nitride/titanium dioxide composite sol, and aging for 2 days;
（3）在60单位体积的无水乙醇中，加入15单位体积的正硅酸乙酯，再缓慢加入25单位体积的无水乙醇、10单位体积的去离子水和2单位体积的浓盐酸（35%质量分数）制成的混合液，搅拌均匀，并陈化2天，制得硅溶胶；(3) Add 15 units of volume of tetraethyl orthosilicate to 60 units of absolute ethanol, and slowly add 25 units of absolute ethanol, 10 units of deionized water and 2 units of concentrated hydrochloric acid ( 35% by mass of the prepared mixture, stirred evenly, and aged for 2 days to obtain a silica sol;
将铁片依次用丙酮、无水乙醇和水超声润洗，烘干，再将上述硅溶胶涂覆在铁片表面，烘干，得到预处理后的基材；The iron piece is sequentially ultrasonically rinsed with acetone, absolute ethanol and water, dried, and the above silica sol is coated on the surface of the iron piece and dried to obtain a pretreated substrate;
（4）将步骤（2）陈化后的氮化碳/二氧化钛复合溶胶以900rpm速度旋涂30秒的方式涂在步骤（3）预处理后的基材上，并重复涂3次，得到的涂层在110℃条件下烘干后，再用15W•m-2强度的紫外灯照射10分钟，得到所述氮化碳改性二氧化钛超亲水多孔薄膜（长×宽 = 2.5×3.5 cm2）。(4) The carbonitride/titanium dioxide composite sol which was aged in step (2) was applied to the substrate after the pretreatment of step (3) by spin coating at 900 rpm for 30 seconds, and was repeatedly applied three times. After the coating was dried at 110 ° C, it was further irradiated with a UV lamp of 15 W•m -2 intensity for 10 minutes to obtain the carbon nanotube-modified titanium dioxide super-hydrophilic porous film (length × width = 2.5 × 3.5 cm 2 ). ).
经检测本实施例制得的氮化碳改性二氧化钛超亲水多孔薄膜，其透光率为88%，水接触角为4.5º；按照实施例1的方法检测所得的多孔薄膜光降解活性，最后检测到其甲基蓝降解率达到86%。The carbon nitride-modified titanium dioxide super-hydrophilic porous film prepared in the present Example was tested to have a light transmittance of 88% and a water contact angle of 4.5°; and the photodegradation activity of the obtained porous film was measured according to the method of Example 1, Finally, the methyl blue degradation rate was 86%.
实施例10Example 10
按以下步骤制备氮化碳改性二氧化钛超亲水多孔薄膜：The carbonitride-modified titanium dioxide super-hydrophilic porous film was prepared as follows:
（1）以双氰胺为前驱体，先将前驱体置于煅烧环境中，以4℃/min 的升温速度升温到500℃并保持温度煅烧5h，然后将得到的黄色固体研磨成细粉，再将细粉置于煅烧环境中，以7℃/min的升温速度升温到500℃并保持温度煅烧3h，制得氮化碳纳米片；(1) Using dicyandiamide as the precursor, first place the precursor in the calcination environment at 4 ° C / min The heating rate is raised to 500 ° C and the temperature is maintained for 5 h. Then, the obtained yellow solid is ground into a fine powder, and the fine powder is placed in a calcination environment, and the temperature is raised to 500 ° C at a heating rate of 7 ° C / min and the temperature is maintained. 3h, producing carbon nitride nanosheets;
（2）将步骤（1）制得的氮化碳纳米片在无水乙醇中超声分散，得到1.2mg/mL的氮化碳分散液，然后取50单位体积的氮化碳乙醇分散液，加入15单位体积的钛酸异丙酯，接着加入3单位体积的乙酰丙酮和3单位体积的单乙醇胺，得到均匀的溶液；(2) The carbon nitride nanosheet prepared in the step (1) is ultrasonically dispersed in absolute ethanol to obtain a 1.2 mg/mL carbon nitride dispersion, and then 50 unit volume of a carbonitride ethanol dispersion is added. 15 units of isopropyl titanate, followed by 3 units of acetylacetone and 3 units of monoethanolamine to obtain a homogeneous solution;
再用40单位体积的无水乙醇、10单位体积的去离子水和3单位体积的浓盐酸（35%质量分数）配制成混合液后，将混合液缓慢滴加到上述均匀的溶液中，边滴加边搅拌均匀，得到氮化碳/二氧化钛复合溶胶，并陈化3天；After further mixing 40 parts by volume of absolute ethanol, 10 units of deionized water and 3 units of concentrated hydrochloric acid (35% by mass), the mixture is slowly added dropwise to the above homogeneous solution. Stirring while stirring, obtaining a carbon nitride/titanium dioxide composite sol, and aged for 3 days;
（3）在60单位体积的无水乙醇中，加入10单位体积的正硅酸乙酯，再缓慢加入20单位体积的无水乙醇、10单位体积的去离子水和3单位体积的浓硫酸（98%质量分数）制成的混合液，搅拌均匀，并陈化3天，制得硅溶胶；(3) Add 10 units of volume of orthosilicate in 60 units of absolute ethanol, and then slowly add 20 units of absolute ethanol, 10 units of deionized water and 3 units of concentrated sulfuric acid ( 98% by mass of the prepared mixture, stirred evenly, and aged for 3 days to obtain a silica sol;
将铁片依次用丙酮、无水乙醇和水超声润洗，烘干，再将上述硅溶胶涂覆在铁片表面，烘干，得到预处理后的基材；The iron piece is sequentially ultrasonically rinsed with acetone, absolute ethanol and water, dried, and the above silica sol is coated on the surface of the iron piece and dried to obtain a pretreated substrate;
（4）将步骤（2）陈化后的氮化碳/二氧化钛复合溶胶以4000rpm速度旋涂10秒的方式涂在步骤（3）预处理后的基材上，并重复涂5次，得到的涂层在100℃条件下烘干后，再用10W•m-2强度的紫外灯照射8分钟，得到所述氮化碳改性二氧化钛超亲水多孔薄膜（长×宽 = 2.5×3.5 cm2）。(4) Applying the carbonitride/titanium dioxide composite sol which has been aged in step (2) to the substrate after the pretreatment of step (3) by spin coating at 4000 rpm for 10 seconds, and repeating the coating 5 times. The coating was dried at 100 ° C, and then irradiated with a UV lamp of 10 W•m -2 intensity for 8 minutes to obtain the carbon nanotube-modified titanium dioxide super-hydrophilic porous film (length × width = 2.5 × 3.5 cm 2 ) ).
经检测本实施例制得的氮化碳改性二氧化钛超亲水多孔薄膜，其透光率为82%，水接触角为1.0º；按照实施例1的方法检测所得的多孔薄膜光降解活性，最后检测到其甲基蓝降解率达到78%。The carbonitride-modified titanium dioxide super-hydrophilic porous film prepared in the present Example was tested to have a light transmittance of 82% and a water contact angle of 1.0°; and the photodegradation activity of the obtained porous film was measured according to the method of Example 1, Finally, the methyl blue degradation rate was detected to be 78%.
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述实施例的限制，其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化，均应为等效的置换方式，都包含在本发明的保护范围之内。The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and combinations thereof may be made without departing from the spirit and scope of the invention. Simplifications should all be equivalent replacements and are included in the scope of the present invention.

Claims (10)

  1. 一种氮化碳改性二氧化钛超亲水多孔薄膜的制备方法，其特征在于，包括以下步骤： A method for preparing a carbon nitride modified titanium dioxide super-hydrophilic porous film, comprising the steps of:
    （1）以双氰胺或三聚氰胺为前驱体，经过煅烧，制得氮化碳纳米片；(1) using dicyandiamide or melamine as a precursor, and calcining to obtain a carbon nitride nanosheet;
    （2）将步骤（1）制得的氮化碳纳米片在无水乙醇中超声分散，得到氮化碳分散液，然后加入二氧化钛前驱体，再加入双络合剂乙酰丙酮和醇胺，搅拌均匀得到均匀的溶液后，再将无水乙醇、水和酸配制成的混合液滴加到均匀的溶液中，搅拌均匀，得到氮化碳/二氧化钛复合溶胶，将其放置陈化一段时间；(2) The carbon nitride nanosheet prepared in the step (1) is ultrasonically dispersed in absolute ethanol to obtain a carbon nitride dispersion, and then a titanium dioxide precursor is added, and then a double complexing agent acetylacetone and an alcohol amine are added, and the mixture is stirred. After uniformly obtaining a uniform solution, a mixed droplet of anhydrous ethanol, water and acid is added to the homogeneous solution, and the mixture is uniformly stirred to obtain a carbonitride/titanium dioxide composite sol, which is left to be aged for a period of time;
    （3）将基材用溶剂超声润洗，烘干后用硅溶胶涂膜，再烘干，得到预处理后的基材；(3) ultrasonically rinsing the substrate with a solvent, drying the film with a silica sol, and drying, to obtain a pretreated substrate;
    （4）将步骤（2）陈化后的氮化碳/二氧化钛复合溶胶涂在步骤（3）预处理后的基材上，并将其烘干，之后用紫外线照射，得到所述氮化碳改性二氧化钛超亲水多孔薄膜。 (4) Applying the carbonitride/titanium dioxide composite sol which has been aged in the step (2) to the substrate after the pretreatment of the step (3), and drying it, followed by irradiation with ultraviolet rays to obtain the carbon nitride. Modified titanium dioxide super hydrophilic porous film.
  2. 根据权利要求1所述的制备方法，其特征在于，步骤（1）所述煅烧具体为：先将前驱体以0.1~5℃/min升温到400~600℃煅烧2~8h，然后将得到的固体研磨成细粉，再将细粉以1~10℃/min升温到400~500℃煅烧2~6h，得到氮化碳纳米片。The preparation method according to claim 1, wherein the calcination in the step (1) is specifically: first heating the precursor at 0.1 to 5 ° C / min to 400 to 600 ° C for 2 to 8 hours, and then obtaining the obtained The solid is ground into a fine powder, and the fine powder is heated at 400 to 500 ° C for 2 to 6 hours at 1 to 10 ° C / min to obtain a carbon nitride nanosheet.
  3. 根据权利要求1所述的制备方法，其特征在于，步骤（2）所述氮化碳分散液的浓度为0.01~2 mg/mL；氮化碳分散液、二氧化钛前驱体、乙酰丙酮、醇胺和混合液的体积比为（10~60）：（1~20）：（0.1~5）：（0.1~5）：（6.2~60），其中所述混合液中无水乙醇、去离子水和酸的体积比为（5~40）：（1~15）：（0.2~5）。The preparation method according to claim 1, wherein the concentration of the carbon nitride dispersion in the step (2) is 0.01 to 2 Mg/mL; volume ratio of carbon nitride dispersion, titanium dioxide precursor, acetylacetone, alcohol amine and mixed solution is (10~60): (1~20): (0.1~5): (0.1~5): (6.2~60), wherein the volume ratio of anhydrous ethanol, deionized water and acid in the mixed solution is (5~40): (1~15): (0.2~5).
  4. 根据权利要求1所述的制备方法，其特征在于，步骤（2）所述醇胺为单乙醇胺、二乙醇胺和三乙醇胺中的至少一种；所述二氧化钛前驱体为钛酸四丁酯、钛酸异丙酯和硫酸钛中的至少一种。The preparation method according to claim 1, wherein the alcohol amine in the step (2) is at least one of monoethanolamine, diethanolamine and triethanolamine; the titania precursor is tetrabutyl titanate, titanium At least one of isopropyl acid ester and titanium sulfate.
  5. 根据权利要求1所述的制备方法，其特征在于，步骤（2）所述的酸为35%质量分数的浓盐酸、98%质量分数的浓硫酸和65%质量分数的浓硝酸的至少一种，所述陈化时间为2小时~7天。The preparation method according to claim 1, wherein the acid in the step (2) is at least one of 35% by mass of concentrated hydrochloric acid, 98% by mass of concentrated sulfuric acid, and 65% by mass of concentrated nitric acid. The aging time is 2 hours to 7 days.
  6. 根据权利要求1所述的制备方法，其特征在于，步骤（3）所述硅溶胶通过如下步骤制备得到：将正硅酸乙酯加入无水乙醇A中，再加入一定体积的无水乙醇B、去离子水和浓酸制成的混合液，搅拌均匀，陈化2小时~4天，制得所述硅溶胶；The preparation method according to claim 1, wherein the silica sol of the step (3) is prepared by adding ethyl orthosilicate to anhydrous ethanol A, and adding a certain volume of absolute ethanol B. a mixture of deionized water and concentrated acid, stirred uniformly, aged for 2 hours to 4 days to prepare the silica sol;
    其中无水乙醇A、正硅酸乙酯和混合液的体积比为（10~70）：（5~20）：（6.2~58）；所述混合液中无水乙醇B、去离子水和浓酸的体积比为（5~40）：（1~15）：（0.1~3），浓酸为35%质量分数的浓盐酸、98%质量分数的浓硫酸和65%质量分数的浓硝酸的至少一种。The volume ratio of anhydrous ethanol A, ethyl orthosilicate and mixed solution is (10~70): (5~20): (6.2~58); anhydrous ethanol B, deionized water and The volume ratio of concentrated acid is (5~40): (1~15): (0.1~3), concentrated acid is 35% mass fraction of concentrated hydrochloric acid, 98% by mass of concentrated sulfuric acid and 65% by mass of concentrated nitric acid. At least one of them.
  7. 根据权利要求1所述的制备方法，其特征在于，步骤（3）中所述用溶剂超声润洗基材是指依次用丙酮、无水乙醇和水超声润洗；所述的基材为普通玻璃片、金属片和塑料制品中的至少一种。The preparation method according to claim 1, wherein the ultrasonically rinsing the substrate with the solvent in the step (3) means sequentially washing with acetone, absolute ethanol and water; the substrate is ordinary. At least one of a glass sheet, a metal sheet, and a plastic article.
  8. 根据权利要求1所述的制备方法，其特征在于，步骤（4）的具体操作步骤为：将陈化后的氮化碳/二氧化钛复合溶胶以100~3000 rpm速度旋涂10~50秒或者以1~10 cm/s的速度提拉的方式涂在预处理后的基材上，并重复涂1~5次，得到的涂层在80~150℃条件下烘干后，再用5~15W•m-2强度的紫外灯照射5~10分钟，得到所述氮化碳改性二氧化钛超亲水多孔薄膜。The preparation method according to claim 1, wherein the specific operation step of the step (4) is: spin coating the aged carbonitride/titanium dioxide composite sol at a speed of 100 to 3000 rpm for 10 to 50 seconds or Apply 1~10 cm/s at the speed of the pretreated substrate and repeat the coating for 1~5 times. The obtained coating is dried at 80~150 °C, then 5~15W. • The m- 2 intensity ultraviolet lamp is irradiated for 5 to 10 minutes to obtain the carbon nitride-modified titanium dioxide super-hydrophilic porous film.
  9. 一种氮化碳改性二氧化钛超亲水多孔薄膜，由权利要求1~8任一项所述制备方法得到。A carbon nitride-modified titanium dioxide super-hydrophilic porous film obtained by the production method according to any one of claims 1 to 8.
  10. 权利要求9所述氮化碳改性二氧化钛超亲水多孔薄膜在防雾、自清洁或冷板散热领域中的应用。The use of the carbon nitride-modified titanium dioxide super-hydrophilic porous film according to claim 9 in the field of anti-fog, self-cleaning or cold plate heat dissipation.
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