CN111282559A - Preparation method of photocatalytic antibacterial porous adsorption air purification coating - Google Patents

Preparation method of photocatalytic antibacterial porous adsorption air purification coating Download PDF

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CN111282559A
CN111282559A CN202010183152.5A CN202010183152A CN111282559A CN 111282559 A CN111282559 A CN 111282559A CN 202010183152 A CN202010183152 A CN 202010183152A CN 111282559 A CN111282559 A CN 111282559A
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coating
air purification
preparation
parts
nano
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CN111282559B (en
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金小燕
曾亮亮
方桂煌
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Shaoxing Lanzhu New Material Technology Co Ltd
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Shaoxing Lanzhu New Material Technology Co Ltd
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Abstract

The invention discloses a preparation method of a photocatalytic antibacterial porous adsorption air purification coating, which is characterized in that an adsorption light guide coating which has an adsorption function and a rough and porous surface and can guide light is prepared by mixing an adsorption material, a light guide material and a photocatalyst and spraying the mixture on the surface of a substrate.

Description

Preparation method of photocatalytic antibacterial porous adsorption air purification coating
Technical Field
The invention relates to the technical field of air purification materials, in particular to a preparation method of a photocatalytic antibacterial porous adsorption air purification coating.
Background
With the continuous improvement of material preparation technology and technology, it is possible to coat a layer of coating with air purification function on the surface of base materials such as plastic, aluminum plate, ceramic tile, fiber composite board, etc., in order to realize the photocatalytic purification function on the surface of the base plate, the invention application with the patent application number of 201080051777.0 discloses a scheme for directly spraying a dense photocatalyst coating on the base plate to realize photocatalysis, but because the photocatalyst nano titanium dioxide is mainly added in a way of adhering to the surface layer of the base layer, many defects can appear to limit the application of the photocatalyst, and the way of directly spraying the nano titanium dioxide on the surface of the base plate, the nano titanium dioxide capable of effectively carrying out photocatalysis has small specific surface area and low catalytic efficiency.
Some existing products in the market simply add photocatalyst such as nano titanium dioxide into porous adsorptive material such as diatom ooze or shell powder to purify air. However, since the photocatalyst needs a light source for purifying air, it is far from sufficient to increase the specific surface area of the photocatalyst in contact with air, and the catalytic efficiency can be increased by increasing the utilization rate of the photocatalyst in the porous adsorption coating to light. And the porosity of the porous coating is high, microbes such as bacteria and fungi are easy to breed, organic and inorganic compounds in the adsorbed air become nutrients of the microbes, and if the photocatalytic performance of the porous coating is weak, the porous adsorption coating exposed in the air for a long time can generate peculiar smell to influence the air quality.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects of the prior art: provides a preparation method of a photocatalytic antibacterial porous adsorption air purification coating with porous adsorption and high photocatalytic efficiency.
The technical solution of the invention is as follows: a preparation method of a photocatalytic antibacterial porous adsorption air purification coating comprises the following steps:
1) the following components in parts by weight are fully mixed with deionized water to prepare the adsorption light guide spraying agent with the solid content of 1.0-20.0 wt%: 5-15 parts of shell powder, 1-7 parts of activated carbon powder, 2-8 parts of light guide agent, 1-6 parts of nano titanium dioxide, 0.5-2 parts of water-soluble cellulose, 0.1-2 parts of aluminum powder, 0.2-3 parts of hydrogen peroxide and 10-20 parts of silica sol; spraying the adsorption light guide spraying agent on the surface of a base material, and drying at 30-100 ℃ to prepare an adsorption light guide coating;
2) preparing silica sol into a solution with the mass fraction of silicon dioxide of 0.1-5%, adding copper nitrate, dissolving and stirring uniformly, controlling the pH value to be 6-9, and adding NaBH4Preparing a solution into a nano copper colloid with the Cu content of 0.01-5.0wt%, spraying the nano copper colloid on the adsorption light guide coating prepared in the step 1), and drying at 30-100 ℃ to prepare a double-layer composite coating;
3) hydrolyzing titanium salt in deionized water for precipitation, filtering, washing to remove soluble ions to obtain precipitated titanium hydrate, dissolving the precipitated titanium hydrate with hydrogen peroxide, adding silver nitrate, controlling pH to 4-8, stirring under ultraviolet irradiation to obtain the final product with Ag content of 0.001-1.0wt%, and TiO2Nano silver titanium dioxide colloid with the content of 0.5-5.0wt%, spraying the nano silver titanium dioxide colloid on the double-layer composite coating prepared in the step 2), and drying at the temperature of 100-300 ℃ to obtain the photocatalytic antibacterial porous adsorption coating consisting of the three layers of composite coatings.
The granularity range of the shell powder is less than 100 um.
The particle size range of the activated carbon powder is less than 200 um.
The light guide agent is nano silicon dioxide, and the particle size is less than 100 nm.
The nano titanium dioxide powder is in an anatase crystal form, the particle size is not more than 100nm, and the optimal average particle size range is 5-10 nm.
The granularity of the aluminum powder is less than 20 um.
The mass fraction of the hydrogen peroxide in the hydrogen peroxide is 30 percent.
The mass fraction of silicon dioxide in the silica sol liquid is 20-30%.
The water-soluble cellulose is one or a mixture of more of cellulose acetate butyrate, carboxymethyl cellulose, hydroxymethyl cellulose, hydroxypropyl methyl cellulose and hydroxyethyl cellulose.
The titanium salt is one or more of ethyl titanate, butyl titanate, titanium isopropoxide, titanium tetrachloride and titanyl sulfate.
The base material comprises one or more of inorganic building materials, organic building materials, metal materials or fiber materials.
The inorganic building material is ceramic tile, glass, clay plate and concrete.
The organic building material is wood, bamboo composite board and aluminum composite board.
The metal material comprises an aluminum net, an iron net and an aluminum honeycomb.
The fiber material comprises a carbon fiber net, a glass fiber net and a textile fabric.
The spraying amount of the adsorption light-guide spraying agent is 100-300ml/m2。
The spraying amount of the nano copper colloid is 10-120 ml/m2。
The spraying amount of the nano silver titanium dioxide colloid is 50-200 ml/m2。
The invention has the beneficial effects that: the adsorption light guide coating which has adsorption function and is rough in surface, porous and light-conductive is prepared by mixing an adsorption material, a light guide material and a photocatalyst and spraying the mixture on the surface of a substrate. Then, an antibacterial scattering nano layer is introduced on the adsorption light guide coating, the layer is a nano copper silicon dioxide transparent layer, a layer of nano copper colloid is uniformly coated on the surface of the adsorption light guide coating which is mainly provided with a concave-convex porous structure on the substrate, nano copper particles are uniformly distributed in the nano copper colloid, light entering the coating has a light reflection effect on the nano copper particles, a Tyndall effect is generated, and the utilization rate of the photocatalysis light is further improved; in addition, the antibacterial performance of the porous adsorption light guide coating can be improved by introducing the nano copper. The silver-doped titanium dioxide photocatalytic nano coating on the outermost layer improves the specific surface of the catalyst due to the porous concave-convex coating of the porous adsorption light guide coating, can realize sufficient contact with air, and has photocatalytic air purification and antibacterial functions, wherein nano silver titanium dioxide colloid has higher photocatalytic activity, and the heterojunction made of different materials and the nano structural characteristic of the nano copper silicon dioxide transparent layer and the nano silver titanium dioxide layer are favorable for effectively separating titanium dioxide photo-generated electron-hole pairs and promoting photocatalytic air purification reaction. The photocatalytic antibacterial porous adsorption coating disclosed by the invention is simple in preparation process, the thickness of each single film and the proportion of each film layer can be controlled by spraying, the coating is easy to coat, the coating can be produced, popularized and applied in a large scale, and the coating is suitable for the surfaces of various substrates and has a good effect.
Detailed Description
The present invention will be described in further detail with reference to the following examples, but the present invention is not limited to the following examples.
Example one
1) Fully mixing the following components in parts by weight with deionized water to prepare the adsorption light-guiding spraying agent with the solid content of 10.0 wt%: 8 parts of shell powder (average particle size of 20 um), 3 parts of activated carbon powder (average particle size of 40 um), 5 parts of nano silicon dioxide (average particle size of 20 nm), 4 parts of nano titanium dioxide (average particle size of 5 nm), 1 part of hydroxypropyl methyl cellulose, 0.5 part of aluminum powder (average particle size of 5 um), 1 part of hydrogen peroxide (mass fraction of 30%), and silica sol (SiO 2)2Content mass fraction 20%) 14 portions; spraying the adsorption light-guiding spraying agent on a bamboo composite boardDrying the surface of the base material at 30-100 ℃ to prepare an adsorption light guide coating;
2) preparing the silica sol into a solution with the mass fraction of silicon dioxide of 2.5 percent, adding 0.5g of copper nitrate, dissolving and stirring uniformly, controlling the pH value to be 8, and adding NaBH under the condition of rapid stirring4Solution (0.4 g NaBH)4Dissolving in 10ml of deionized water), fully reacting, changing the sol liquid from semitransparent light blue into dark brown to prepare nano copper colloid with the Cu content of 0.10wt%, spraying the nano copper colloid on the adsorption light guide coating prepared in the step 1), and drying at 30-100 ℃ to prepare a double-layer composite coating;
3) adding 5ml of ethyl titanate into 100ml of deionized water, slowly stirring to hydrolyze and precipitate titanium salt, standing for 2 hours, filtering and washing to remove soluble ions to obtain white precipitated hydrate, mixing the white precipitated hydrate with 50ml of deionized water, adding 5ml of hydrogen peroxide, stirring for dissolving, adding 0.1g of silver nitrate, controlling the pH value to be 6, uniformly stirring under the irradiation of an ultraviolet lamp (wavelength of 254nm and power of 10 w), diluting with deionized water to obtain the product with Ag content of 0.03wt%, TiO2Nano silver titanium dioxide colloid with the content of 0.9wt%, spraying the nano silver titanium dioxide colloid on the double-layer composite coating prepared in the step 2), and drying at 100 ℃ to obtain the photocatalytic antibacterial porous adsorption coating consisting of the three-layer composite coating.
Comparative example 1
Making adsorption light-conducting coating
Fully mixing the following components in parts by weight with deionized water to prepare the adsorption light-guiding spraying agent with the solid content of 10.0 wt%: 8 parts of shell powder (average particle size of 20 um), 3 parts of activated carbon powder (average particle size of 40 um), 5 parts of nano silicon dioxide (average particle size of 20 nm), 4 parts of nano titanium dioxide (average particle size of 5 nm), 1 part of hydroxypropyl methyl cellulose, 0.5 part of aluminum powder (average particle size of 5 um), 1 part of hydrogen peroxide (mass fraction of 30%), and silica sol (SiO 2)2Content mass fraction 20%) 14 portions; and spraying the adsorption light guide spraying agent on the surface of the bamboo composite board substrate, and drying at 30-100 ℃ to prepare the adsorption light guide coating.
Comparative example No. two
Making adsorption coating without light guide function
Fully mixing the following components in parts by weight with deionized water to prepare the adsorption light-guiding spraying agent with the solid content of 10.0 wt%: 8 parts of shell powder (average particle size of 20 um), 3 parts of activated carbon powder (average particle size of 40 um), 4 parts of nano titanium dioxide (average particle size of 5 nm), 1 part of hydroxypropyl methyl cellulose, 0.5 part of aluminum powder (average particle size of 5 um), 1 part of hydrogen peroxide (mass fraction of 30%), and silica Sol (SiO)2Content mass fraction 20%) 14 portions; the adsorption light-guiding spraying agent is sprayed on the surface of a bamboo composite board substrate and dried at 30-100 ℃ to prepare an adsorption light-guiding coating
Comparative example No. three
Preparation of double-layer composite coating with adsorption function
1) Fully mixing the following components in parts by weight with deionized water to prepare the adsorption light-guiding spraying agent with the solid content of 10.0 wt%: 8 parts of shell powder (average particle size of 20 um), 3 parts of activated carbon powder (average particle size of 40 um), 5 parts of nano silicon dioxide (average particle size of 20 nm), 4 parts of nano titanium dioxide (average particle size of 5 nm), 1 part of hydroxypropyl methyl cellulose, 0.5 part of aluminum powder (average particle size of 5 um), 1 part of hydrogen peroxide (mass fraction of 30%), and silica sol (SiO 2)2Content mass fraction 20%) 14 portions; spraying the adsorption light guide spraying agent on the surface of the bamboo composite board substrate, and drying at 30-100 ℃ to prepare an adsorption light guide coating;
2) preparing the silica sol into a solution with the mass fraction of silicon dioxide of 2.5 percent, adding 0.5g of copper nitrate, dissolving and stirring uniformly, controlling the pH value to be 8, and adding NaBH under the condition of rapid stirring4Solution (0.4 g NaBH)4Dissolving in 10ml of deionized water), fully reacting, changing the sol liquid from semitransparent light blue into dark brown, preparing nano copper colloid with the Cu content of 0.10wt%, spraying the nano copper colloid on the adsorption light guide coating prepared in the step 1), and drying at 30-100 ℃ to obtain the double-layer composite coating.
Formaldehyde removal performance test
Composite coated sheets prepared according to the methods of example 1, comparative example 2 and comparative example 3 were cut to a size of 1000X1000mm and placed at 1m3In the test chamber, comparative test is carried out under the same conditions according to JC/T1074-2008 & lt & gt indoorThe test steps in the purification efficiency of 6.5 in the standard of air purification function coating material purification performance are carried out according to the test of photocatalysis materials, and the formaldehyde photocatalysis performance is measured by selecting the illumination test time to be 2h in order to obtain the formaldehyde removal effect contrast test of four composite coating plates.
Figure DEST_PATH_IMAGE001
From the test results, the formaldehyde purification efficiency of the coating after the light guide agent is added is improved, the middle layer of the silicon dioxide uniformly dispersed by nano-copper is introduced into the composite coating, the formaldehyde is favorably removed by photocatalysis, and the formaldehyde removal effect of the photocatalytic antibacterial porous adsorption coating consisting of the three layers of the composite coating is higher.
Test of coating Sterilization Properties
The composite coating is prepared by spraying on the aluminum-plastic plate according to the preparation method of the coating in the example 1, the comparative example 1 and the comparative example 3, the aluminum-plastic plate is cut into the size of 100mmx100mm, a sealing circle (the height of the edge of the circle is 5 mm) with the diameter of 70mm is adhered on the plate, the Escherichia coli strain liquid can be dripped into the sealing circle, the bacterial liquid can not leak out of the circle, and the sterilization treatment is carried out before the bacteria taking and culturing. Testing according to 5.5 operation steps in GB/T23763-2009 evaluation of antibacterial properties of photocatalytic antibacterial materials and products, sterilizing, inoculating, culturing for 24h, and testing photocatalytic sample conditions (the sample is irradiated to a sample plate with a UVA ultraviolet lamp with a light intensity of 0.01mW/cm2-0.1mW/cm2Test, see GB/T23763-2009), dark condition test (test without light). Respectively eluting and counting a blank sample, a light sample and a dark sample after culture (refer to GB/T4789.2), and calculating the sterilization rate R of the samplesGeneral assembly. The numerical values are expressed in%, and the calculation formula is as follows
RGeneral assembly=[（C0-C1）/C0]×100
In the formula: c0The number of viable counts in cfu of the control samples after incubation under light conditions
C1-the value of viable count of the photo-catalyzed sample after incubation under bright conditions,unit cfu
The antibacterial contribution value of the photocatalytic material under UVA irradiation is RLight (es)The numerical value is expressed in percent, and the calculation formula is as follows
RLight (es)=[（B1-C1）/B1]×100
In the formula: b is1The number of viable counts, in cfu, of the photocatalytic samples cultured in the dark
Figure DEST_PATH_IMAGE002
According to the test results, the sterilization efficiency can be improved by adding the nano copper silicon dioxide layer in the middle layer, the bacterial reproduction of the porous adsorption bottom layer is reduced, the air purification is facilitated, and the antibacterial performance of the photocatalytic antibacterial porous adsorption coating formed by the three layers of composite coatings is obviously improved.
The above are merely characteristic embodiments of the present invention, and do not limit the scope of the present invention in any way. All technical solutions formed by equivalent exchanges or equivalent substitutions fall within the protection scope of the present invention.

Claims (10)

1. A preparation method of a photocatalytic antibacterial porous adsorption air purification coating is characterized by comprising the following steps:
1) the following components in parts by weight are fully mixed with deionized water to prepare the adsorption light guide spraying agent with the solid content of 1.0-20.0 wt%: 5-15 parts of shell powder, 1-7 parts of activated carbon powder, 2-8 parts of light guide agent, 1-6 parts of nano titanium dioxide, 0.5-2 parts of water-soluble cellulose, 0.1-2 parts of aluminum powder, 0.2-3 parts of hydrogen peroxide and 10-20 parts of silica sol; spraying the adsorption light guide spraying agent on the surface of a base material, and drying at 30-100 ℃ to prepare an adsorption light guide coating;
2) preparing silica sol into a solution with the mass fraction of silicon dioxide of 0.1-5%, adding copper nitrate, dissolving and stirring uniformly, controlling the pH value to be 6-9, and adding NaBH4Preparing a solution into a nano copper colloid with the Cu content of 0.01-5.0wt%, spraying the nano copper colloid on the adsorption light guide coating prepared in the step 1), and drying at 30-100 ℃ to prepare a double-layer compositeCoating;
3) hydrolyzing titanium salt in deionized water for precipitation, filtering, washing to remove soluble ions to obtain precipitated titanium hydrate, dissolving the precipitated titanium hydrate with hydrogen peroxide, adding silver nitrate, controlling pH to 4-8, stirring under ultraviolet irradiation to obtain the final product with Ag content of 0.001-1.0wt%, and TiO2Nano silver titanium dioxide colloid with the content of 0.5-5.0wt%, spraying the nano silver titanium dioxide colloid on the double-layer composite coating prepared in the step 2), and drying at the temperature of 100-300 ℃ to obtain the photocatalytic antibacterial porous adsorption coating consisting of the three layers of composite coatings.
2. The preparation method of the photocatalytic antibacterial porous adsorption air purification coating as claimed in claim 1, wherein the particle size range of the shell powder is less than 100um, the particle size range of the activated carbon powder is less than 200um, the light guide agent is nano-silica with a particle size of less than 100nm, and the nano-titania powder is in an anatase crystal form with a particle size of no more than 100 nm.
3. The preparation method of the photocatalytic antibacterial porous adsorption air purification coating as claimed in claim 1, wherein the aluminum powder particle size is less than 20 um.
4. The preparation method of the photocatalytic antibacterial porous adsorption air purification coating as claimed in claim 1, wherein the mass fraction of hydrogen peroxide in hydrogen peroxide is 30%.
5. The preparation method of the photocatalytic antibacterial porous adsorption air purification coating as claimed in claim 1, wherein the mass fraction of silica in the silica sol liquid is 20-30%.
6. The preparation method of the photocatalytic antibacterial porous adsorption air purification coating according to claim 1, wherein the water-soluble cellulose is one or a mixture of more of cellulose acetate butyrate, carboxymethyl cellulose, hydroxymethyl cellulose, hydroxypropyl methyl cellulose and hydroxyethyl cellulose.
7. The preparation method of the photocatalytic antibacterial porous adsorption air purification coating according to claim 1, wherein the titanium salt is one or more of ethyl titanate, butyl titanate, titanium isopropoxide, titanium tetrachloride and titanyl sulfate.
8. The preparation method of the photocatalytic antibacterial porous adsorption air purification coating as claimed in claim 1, wherein the base material comprises one or more of inorganic building materials, organic building materials, metal materials or fiber materials.
9. The method for preparing the photocatalytic antibacterial porous adsorption air purification coating as claimed in claim 1, wherein the spraying amount of the adsorption light guide spraying agent is 100-300ml/m2。
10. The preparation method of the photocatalytic antibacterial porous adsorption air purification coating as claimed in claim 1, wherein the spraying amount of the sprayed nano copper colloid is 10-120 ml/m2The spraying amount of the nano silver titanium dioxide colloid is 50-200 ml/m2。
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