CN110950344B - Silicon dioxide modified material for producing self-cleaning glass and preparation method thereof - Google Patents
Silicon dioxide modified material for producing self-cleaning glass and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the field of green building materials, and particularly relates to a silicon dioxide modified material for producing self-cleaning glass and a preparation method thereof, wherein the silicon dioxide modified material is characterized in that: the raw material formula of the silicon dioxide modified material comprises a copper source, a complex, silicon dioxide, a sulfur source, ammonia water, absolute ethyl alcohol and water, wherein Cu with molar mass in the copper source 2+ : s in sulfur source 2+ =1:1, complex with Cu 2+ The mass ratio of (1) 2 The mass ratio of the complex to the complexing substance is 2:1; s in silicon dioxide and sulfur source 2+ The proportion is 2:0.1-1, using three parts of water, wherein the mass volume ratio of the ammonia water to the second-time water is 3-5:50, the first part of water and the second part of water are the same in dosage, and the third part of water and absolute ethyl alcohol are a plurality of in amount. The self-cleaning glass prepared from the modified SiO2 is self-cleaned by utilizing the photocatalysis principle, and coating treatment is not needed, so that the problems that the self-cleaning glass film is not wear-resistant and is easy to damage are solved.
Description
Technical Field
The invention belongs to the field of green building materials, and particularly relates to a silicon dioxide modified material for producing self-cleaning glass and a preparation method thereof.
Background
As the environment deteriorates year by year, the human body is extremely harmful. People have higher and higher requirements on environmental protection, and the requirements on using green and environment-friendly materials are very urgent.
Glass is an ancient building material and is widely used, and various functional glasses have appeared so far. The self-cleaning glass which can automatically clean by utilizing natural conditions and beautify the environment meets the green and environment-friendly desire of people. The self-cleaning glass can automatically keep the surface of the glass clean by utilizing sunlight, air and rainwater, and the semiconductor on the glass can decompose organic matters in the air to purify the air and catalyze oxygen in the air to change the oxygen into negative oxygen ions, so that the air is fresh, and bacteria on the surface of the glass and bacteria in the air can be killed.
At present, tiO is plated on the surface of glass 2 Film, tiO 2 Under the condition of ultraviolet irradiation in sunlightThe glass can generate photocatalysis, and almost all organic matters on the surface of the glass can be decomposed. In addition, tiO 2 The film becomes hydrophilic under the condition of ultraviolet illumination, so that the glass can realize the functions of difficult recontamination, self-cleaning, fog prevention and the like. However, there are two major disadvantages to coating a glass surface. 1. In the solar radiation wave reaching the ground, there is only 3% -5% of the ultraviolet, and TiO 2 It is with this light source that the film decomposes organic contaminants. TiO 2 2 The film has a low utilization of solar energy. 2. The film is coated on the surface of the glass, the abrasion resistance of the film is poor, and the film is easy to damage, so that the self-cleaning function is lost.
Disclosure of Invention
In order to solve the technical problems, the invention provides a silicon dioxide material for producing self-cleaning glass and a preparation method thereof, which utilize the photocatalysis principle to carry out self-cleaning without coating treatment, thereby overcoming the problems that the film layer of the self-cleaning glass is not wear-resistant and is easy to damage.
The invention discloses a silicon dioxide modified material for producing self-cleaning glass, which solves the technical problems and is characterized in that: the raw material formula of the silicon dioxide modified material comprises a copper source, a complex and silicon dioxide (SiO) 2 ) Sulfur source, ammonia water, absolute ethyl alcohol and water, wherein the mass ratio of Cu in the copper source 2+ : s in sulfur source 2+ =1:1, complex with Cu 2+ The mass ratio of the silicon dioxide to the complexing agent is 1:1, S in silica and Sulfur Source 2+ The mass ratio is 2:0.1-1, using three parts of water, wherein the mass volume ratio of the ammonia water to the second part of water is 3-5:50, the first part of water and the second part of water are the same in dosage, and the third part of water and absolute ethyl alcohol are a plurality of.
The mass volume ratio of the ammonia water to the water is 3-5:200-500, the ratio of absolute ethyl alcohol to water is 1:1-2.
The copper source is copper chloride (CuCl) 2 ) Copper nitrate and copper sulfate, wherein the copper source in the optimized scheme is copper chloride; the water is distilled water.
In a further optimized scheme, the copper chloride is CuCl 2 ·2H 2 O。
The sulfur source is thiourea (CH) 4 N 2 S), thioacetamide, sodium sulfide and the like, wherein the sulfur source in the optimized scheme is thiourea.
The mass ratio of the copper chloride to the thiourea is 32:38, molar mass of Cu in copper chloride 2+ The ratio of thiourea to mass is 1:38; the mass ratio of silicon dioxide to thiourea is 2:0.38-3.8.
The complex is diethyl triaminepentaacetic acid (DTPA), thioacetamide and sodium sulfide, and the complex in the optimized scheme is diethyl triaminepentaacetic acid.
Ammonia provides more OH-; copper chloride, DTPA, silicon dioxide SiO 2 Thiourea (CH) 4 N 2 S) and ammonia water are analytically pure raw materials, and distilled water is prepared by self.
The first part of water is used for dissolving a copper source, the second part of water is used for dissolving thiourea, and the third part of water and absolute ethyl alcohol are used for washing and suction filtration; cu in the copper source aqueous solution 2+ The amount content of the substance is 0.1-1.0mol/L, and the optimized scheme is that Cu in the copper source water solution 2+ The content of substances is 0.5mol/L; the amount concentration of thiourea is 0.1-1.0mol/L.
The invention discloses a preparation method of a silicon dioxide material for producing self-cleaning glass, which comprises the following steps:
(1) Preparing raw materials, and dividing water into three parts;
(2) Weighing a copper source with required dosage, adding the copper source into the first part of water, and uniformly stirring;
(3) Weighing the complex, adding into the copper source solution, stirring, heating to 50-70 deg.C, and maintaining at constant temperature for 4-6min; the temperature increase helped the DTPA dissolve.
(4) Mixing silicon dioxide (SiO) 2 ) Adding the powder into the solution, and magnetically stirring at constant temperature of 50-70 deg.C for 40min to form uniform suspension; silicon dioxide powder is used as a carrier.
(5) And weighing the sulfur source with the required dosage, adding the sulfur source into the second part of water, uniformly stirring, adding ammonia water, and uniformly stirring by magnetic force for 4-5 min. Adding ammonia water to provide more OH - 。
(6) Uniformly adding the solution in the step (5) into the suspension in the step (4), continuously stirring by magnetic force and keeping the set temperature, wherein the reaction time is 4.5-5.5h; the reaction was complete when the suspension became a uniform grey-black color.
(7) And (4) washing and filtering the solution obtained in the step (6) by using absolute ethyl alcohol and distilled water to obtain solid sample powder, and drying at the drying temperature of 55-65 ℃ for 7-9h to obtain the nano-silver-zinc-tin-zinc-tin alloy.
In the optimized scheme, the reaction time in the step (6) is 5h.
In the step (7), the drying temperature is 60 ℃, and the drying time is 8h.
The particle size of the silicon dioxide powder is 20-40 microns. SiO2 2 The smaller the particles, the better the effect. The particles are small, the specific surface area is large, the number of the foot points of the loaded particles is large, the loaded particles are large and dispersed, and the agglomeration phenomenon is reduced.
In the optimized scheme, the invention adopts a chemical deposition method to select SiO of one of the glass raw materials 2 As carrier, cu is selected 2+ The compound is a copper source, the diethyltriaminepentaacetic acid DTPA is a complexing agent, and the thiourea CH 4 N 2 S is a sulfur source, and the ammonia water provides hydroxide ions OH-.
With CuCl 2 ·2H 2 O is an example to illustrate the reaction mechanism in the present invention, as follows:
where n =5 and 6, cu during complexation 2+ Complexes with coordination numbers 5 and 6 were formed simultaneously with DTPA.
CH 4 N 2 S+OH - →CH 2 N 2 +HS - +H 2 O
HS - +OH - →S 2- +H 2 O
Cu 2+ +S 2- →CuS↓
The preparation method of the invention generates CuS, has simple process and does not need to be carried out at high temperature, thereby reducing the production cost. CuS is a narrow-band-gap semiconductor, has a forbidden band width of 2.31-2.58eV, is a stable and efficient novel photo-thermal material, and is compared with the traditional TiO 2 (the forbidden band width is about 3.2 eV), the utilization efficiency of solar radiation by the CuS is higher. CuS is a hydrophobic material, siO 2 Is a hydrophilic material, and CuS is loaded on SiO 2 The silica modified composite material is formed, the composite material has hydrophilic performance, pollutants are not easy to gather when the silica modified composite material is used for preparing glass, and the surface fogging can be prevented in the occasions with high indoor temperature.
Modified SiO in the invention during the process of preparing glass 2 Directly mixing with other glass raw materials, and producing according to conventional glass production method. SiO, unlike other coatings which are only applied to glass surfaces 2 The raw materials are originally involved in the preparation of the glass and are completely fused in the glass.
The invention is silicon dioxide SiO as a raw material of self-cleaning glass 2 Modified by using the modified SiO 2 When the self-cleaning glass is prepared, self-cleaning is carried out by utilizing the photocatalysis principle, and coating treatment is not needed, so that the problems that the self-cleaning glass film layer is not wear-resistant and is easy to damage are solved.
Drawings
The invention will be described in further detail with reference to the following drawings and detailed description:
FIG. 1 is a flow chart of a process for preparing a silica material according to the present invention
FIG. 2 is a schematic diagram of a performance testing apparatus according to the present invention
Detailed Description
The invention will be further illustrated with reference to specific embodiments:
example 1
A modified silicon dioxide material for preparing self-cleaning glass is prepared from copper source, complex and silicon dioxide (SiO) 2 ) Sulfur source, ammonia water, absolute ethyl alcohol and water, wherein the copper source is the same as the copper sourceCu of molar mass 2+ : s in sulfur source 2+ =1:1, complex with Cu 2+ The mass ratio of the silicon dioxide to the complexing agent is 1:1, S in silica and Sulfur Source 2+ The proportion is 2:0.1, the mass ratio of silicon dioxide to thiourea is 2:0.38-3.8 of water is used for three times, and the mass volume ratio of the ammonia water to the second water is 4:50, the first water and the second water are used in the same amount, and the third water and absolute ethyl alcohol are used in a plurality of amounts.
The first part of water dissolves a copper source, the second part of water dissolves thiourea, and the third part of water and absolute ethyl alcohol are used for washing and suction filtration; cu in the copper source aqueous solution 2+ The content of the substance was 0.2mol/L, and the concentration of the thiourea was 0.3mol/L.
Example 2
A modified silicon dioxide material for preparing self-cleaning glass is prepared from copper source, complex and silicon dioxide (SiO) 2 ) Sulfur source, ammonia water, absolute ethyl alcohol and water, wherein Cu in molar mass is in the copper source 2+ : s in sulfur source 2+ =1:1, complex with Cu 2+ The mass ratio of the silicon dioxide to the complexing agent is 1:1, S in silica and Sulfur Source 2+ The proportion is 2:1, using water for three times, wherein the mass-volume ratio of the ammonia water to the water for the second time is 5:50, the first water and the second water are used in the same amount, and the third water and absolute ethyl alcohol are used in a plurality of amounts.
The first part of water dissolves a copper source, the second part of water dissolves thiourea, and the third part of water and absolute ethyl alcohol are used for washing and suction filtration; cu in the copper source aqueous solution 2+ The amount of the substance was 0.5mol/L, and the amount concentration of the thiourea was 0.5mol/L.
Example 3
A modified silicon dioxide material for preparing self-cleaning glass is prepared from copper source, complex and silicon dioxide (SiO) 2 ) Sulfur source, ammonia water, absolute ethyl alcohol and water, wherein Cu in molar mass is in the copper source 2+ : s in sulfur source 2+ =1:1, complex with Cu 2+ The mass ratio of 1:2, the mass ratio of the silicon dioxide to the complexing agent is 2:1, S in silica and Sulfur Source 2+ The proportion is 2:0.and 5, using water for three times, wherein the mass-volume ratio of the ammonia water to the water for the second time is 3:50, the first water and the second water are used in the same amount, and the third water and the absolute ethyl alcohol are used in a plurality of amounts.
The first part of water dissolves a copper source, the second part of water dissolves thiourea, and the third part of water and absolute ethyl alcohol are used for washing and suction filtration; cu in the copper source aqueous solution 2+ The amount of the substance was 0.6mol/L, and the amount concentration of the thiourea was 0.4mol/L.
Example 4
A silicon dioxide modified material for producing self-cleaning glass is prepared from CuCl 2 ·2H 2 O, diethyl triaminepentaacetic acid (DTPA), silicon dioxide (SiO) 2 ) Thiourea (CH) 4 N 2 S), ammonia water, absolute ethyl alcohol and water, wherein CuCl 2 ·2H 2 Cu of molar mass in O 2+ : heavy thiourea =1:3.8, DTPA and Cu 2+ The mass ratio of (1) 2 The mass ratio of the DTPA to the DTPA is 2:1, the mass ratio of silicon dioxide to thiourea is 2:1.6.
the water is used in three parts, and the mass volume ratio of the ammonia water to the second part of water is 3:50, the first part of water and the second part of water are the same in dosage, and the third part of water and absolute ethyl alcohol are a plurality of. The first part of water dissolves a copper source, the second part of water dissolves thiourea, and the third part of water and absolute ethyl alcohol are used for washing and suction filtration; cu in aqueous solution of copper source 2+ The amount of the substance was 0.8mol/L, and the mass concentration of thiourea was 0.5mol/L.
The silica powder particle size was 30 microns.
The invention adopts a chemical deposition method to select silicon dioxide SiO which is one of glass raw materials 2 Copper chloride CuCl is selected as a carrier 2 ·2H 2 O is copper source, DTPA is complexing agent, thiourea CH 4 N 2 S is a sulfur source, and the ammonia provides hydroxide ions OH-. The reaction mechanism is as follows:
where n =5 and 6, in the networkIn-process Cu 2+ Complexes with coordination numbers 5 and 6 were formed simultaneously with DTPA.
CH 4 N 2 S + OH - →CH 2 N 2 + HS - +H 2 O
HS - +OH - →S 2- +H 2 O
Cu 2+ +S 2- →CuS↓
The preparation method has the process flow diagram shown in figure 1, and comprises the following specific steps: :
(1) Preparing raw materials, and dividing water into three parts;
(2) Weighing a copper source with required dosage, adding the copper source into the first part of water, and uniformly stirring;
(3) Weighing diethyl triaminepentaacetic acid, adding into the copper source solution, stirring, heating to 60 deg.C, and maintaining at constant temperature for 56min; warming helped the DTPA dissolve. The solubility of DTPA was 5g/L at 20 ℃ and the dissolution of DTPA in water was facilitated by increasing the temperature.
(4) Adding silicon dioxide powder into the solution, and magnetically stirring for 40min at constant temperature of 60 ℃ to form uniform suspension; silicon dioxide powder is used as a carrier.
(5) Weighing thiourea with the required dosage, adding the thiourea into the second part of water, uniformly stirring, adding ammonia water, and uniformly stirring by magnetic force for 4min. Ammonia was added to provide more OH-.
(6) Uniformly adding the solution in the step (5) into the suspension in the step (4), continuously stirring by magnetic force and keeping the set temperature, wherein the reaction time is 5 hours; the reaction was complete when the suspension became a uniform grey-black color.
(7) And (4) washing and filtering the solution obtained in the step (6) by using absolute ethyl alcohol and distilled water to obtain solid sample powder, and drying at the drying temperature of 60 ℃ for 8 hours to obtain the nano-silver-coated zinc oxide.
Example 5
Silicon dioxide for producing self-cleaning glassThe material is prepared from copper nitrate, diethyltriaminepentaacetic acid, silicon dioxide, thioacetamide, ammonia water, anhydrous ethanol and distilled water, wherein Cu in molar mass is in the copper nitrate 2+ : thiourea =1:3.8, DTPA and Cu 2+ The mass ratio of (1) 2 The mass ratio of the DTPA to the DTPA is 2:1, the mass ratio of silicon dioxide to thiourea is 2:0.5 Cu in aqueous solution of copper source 2+ The mass content is 0.6mol/L, and the mass concentration of thiourea is 0.1mol/L. The mass volume ratio of the ammonia water to the water is 3:200, the ratio of absolute ethyl alcohol to water is 1:1; using distilled water in three parts, wherein the mass volume ratio of the ammonia water to the second part of distilled water is 4:50, the first part of distilled water and the second part of distilled water are used in the same amount, and the third part of distilled water and absolute ethyl alcohol are used in a plurality of amounts. The first part of distilled water dissolves the copper source, the second part of distilled water dissolves thiourea, and the third part of distilled water and absolute ethyl alcohol are used for washing and suction filtration. The silica powder particle size was 40 microns.
The preparation method comprises the following steps:
(1) Preparing raw materials, and dividing water into three parts;
(2) Weighing a copper source with required dosage, adding the copper source into the first part of water, and uniformly stirring;
(3) Weighing diethyl triaminepentaacetic acid, adding into the copper source solution, stirring, heating to 50 deg.C, and maintaining at constant temperature for 6min; the temperature increase helped the DTPA dissolve.
(4) Adding silicon dioxide powder into the solution, and magnetically stirring at constant temperature of 50 ℃ for 40min to form uniform suspension; silicon dioxide powder is used as a carrier.
(5) Weighing thiourea with the required dosage, adding the thiourea into the second part of water, uniformly stirring, adding ammonia water, and uniformly stirring by magnetic force for 5min.
(6) Adding the solution in the step (5) into the suspension in the step (4) at a uniform speed, continuing magnetic stirring and keeping the set temperature, wherein the reaction time is 4.5h; the reaction was complete when the suspension became a uniform grey-black color.
(7) And (4) washing and filtering the solution obtained in the step (6) by using absolute ethyl alcohol and distilled water to obtain solid sample powder, and drying at the drying temperature of 55 ℃ for 9 hours to obtain the nano-silver-coated zinc oxide.
Example 6
A silicon dioxide modified material for producing self-cleaning glass comprises copper sulfate, diethyltriaminepentaacetic acid, silicon dioxide, sodium sulfide, ammonia water, anhydrous ethanol and distilled water, wherein Cu in molar mass in copper sulfate 2+ : thiourea =1:3.8, DTPA and Cu 2+ 1.5, silicon dioxide SiO 2 The mass ratio of the DTPA to the DTPA is 2:1, the mass ratio of silicon dioxide to thiourea is 2:3, cu in aqueous solution of copper source 2+ The amount of the substance was 0.8mol/L, and the amount concentration of the thiourea was 1.0mol/L. The mass volume ratio of the ammonia water to the water is 4:500, the ratio of absolute ethyl alcohol to water is 1:2. the water is used in three parts, and the mass volume ratio of the ammonia water to the second part of water is 5:50, the first part of water and the second part of water are the same in dosage, and the third part of water and absolute ethyl alcohol are a plurality of in amount. The first part of water dissolves the copper source, the second part of water dissolves thiourea, and the third part of water and absolute ethyl alcohol are used for washing and suction filtration.
The silica powder particle size was 20 microns.
(1) Preparing raw materials, and dividing water into three parts;
(2) Weighing a copper source with required dosage, adding the copper source into the first part of water, and uniformly stirring;
(3) Weighing diethyl triaminepentaacetic acid, adding into the copper source solution, stirring, heating to 70 deg.C, and holding at constant temperature for 4min.
(4) Adding silicon dioxide powder into the solution, and magnetically stirring for 40min at constant temperature of 70 ℃ to form uniform suspension; silicon dioxide powder is used as a carrier.
(5) Weighing thiourea with the required dosage, adding the thiourea into the second part of water, uniformly stirring, adding ammonia water, and uniformly stirring by magnetic force for 4min.
(6) Uniformly adding the solution in the step (5) into the suspension in the step (4), continuously stirring by magnetic force and keeping the set temperature, wherein the reaction time is 5.5h; the reaction was complete when the suspension became a uniform grey-black color.
(7) And (4) washing and filtering the solution obtained in the step (6) by using absolute ethyl alcohol and distilled water to obtain solid sample powder, and drying at the drying temperature of 65 ℃ for 7 hours to obtain the nano-silver-coated zinc oxide.
Example 7
(1) Weighing a certain amount of CuCl 2 ·2H 2 O is added into 50ml of distilled water and stirred uniformly. Cu 2+ The content is 0.1mol/L
(0.32 g of Cu 2+ )。
(2) Weighing 1g of DTPA, adding the DTPA into the copper chloride solution, continuing to stir by magnetic force, heating to a set temperature and keeping the temperature constant. The temperature of the invention can be controlled between 50 and 70 ℃.
(3) Weighing SiO 2 2.0g of powder as a carrier was added to the solution in step (2), and magnetic stirring was continued at constant temperature for 40min to form a uniform suspension.
(4) Weighing 0.38g of thiourea CH 4 N 2 S is added into 50ml of distilled water and stirred evenly.
(5) 4ml of ammonia water was measured and added to the solution of step (4) to provide more OH - . The mixture was stirred magnetically for about 5 minutes. The stirring rate is moderate, and in a magnetic stirrer, the rate can be controlled from a solution phenomenon. While stirring, the rate was gradually increased, and when the solution in the beaker swirled and the liquid did not splash, the rate was better at this time.
(6) And (3) uniformly adding the solution in the step (5) into the suspension in the step (3). Magnetic stirring was continued and the set temperature was maintained. After 5 hours of reaction, the suspension became a uniform gray black and the reaction was complete. The reaction mixture was washed three times with distilled water, each time requiring 100ml of water and a total of 300ml of water. The absolute ethanol is washed twice with 100ml each time, and a total of 200ml absolute ethanol is needed.
(7) And then washing the suspension with absolute ethyl alcohol and distilled water, carrying out suction filtration, and finally placing the obtained solid sample powder in an oven for drying. The temperature of the oven is set to 60 ℃, and the drying time is 8h.
Example 8
(1) Weighing a certain amount of CuCl 2 ·2H 2 O is added to 50ml of distilled water and stirred uniformly. Cu (copper) 2+ The content was 0.25mol/L (0.8 g of Cu) 2+ )。
(2) Weighing 1g of DTPA, adding the DTPA into the copper chloride solution, continuing to stir by magnetic force, heating to a set temperature and keeping the temperature constant. The temperature of the invention can be controlled between 50 and 70 ℃.
(3) Weighing SiO 2 2.0g of powder as a carrier was added to the solution in step (2), and magnetic stirring was continued at constant temperature for 40min to form a uniform suspension.
(4) Weighing 0.95g of thiourea CH 4 N 2 S is added into 50ml of distilled water and stirred evenly.
(5) An amount of 4ml of ammonia was added to the solution of step (4) to provide more OH-. The mixture was stirred magnetically for about 5 minutes. The stirring rate is moderate, and in a magnetic stirrer, the rate can be controlled from a solution phenomenon. While stirring, the rate was gradually increased, and when the solution in the beaker swirled and the liquid did not splash, the rate was better at this time.
(6) And (3) uniformly adding the solution in the step (5) into the suspension in the step (3). Magnetic stirring was continued and the set temperature was maintained. After 5 hours of reaction, the suspension became a uniform gray-black color, and the reaction was terminated. The reaction mixture was washed three times with distilled water, each time requiring 100ml of water and a total of 300ml of water. The absolute ethanol is washed twice with 100ml each time, and a total of 200ml absolute ethanol is needed.
(7) And then washing the suspension with absolute ethyl alcohol and distilled water, carrying out suction filtration, and finally placing the obtained solid sample powder in an oven for drying. The oven temperature was set at 62 ℃ and the drying time was 7.5h.
Example 9
The rest is as in example 4, where Cu 2+ Cu in an amount of 0.5mol/L (CuCl2.2H2O 4.26g,1.6g 2+ ) 1.9g of thiourea, 4ml of aqueous ammonia, 2.0g of SiO2 powder, 1g of DTPA, and 50ml of distilled water in which thiourea was dissolved were added.
Example 10
The rest is as in example 4, where Cu 2+ The content was 0.75mol/L (2.4 g of Cu) 2+ ) 2.85g of thiourea, 4ml of ammonia water, 2.0g of SiO2 powder, and 1g of DTPA were added. The distilled water for dissolving thiourea was 50ml again.
Example 11
The rest is as in example 4, where Cu 2+ The content was 1mol/L (3.2 g)Cu of (2) 2+ ) 3.8g of thiourea, 4ml of aqueous ammonia, 2.0g of SiO2 powder, and 1g of DTPA, to which distilled water was added. The amount of distilled water for dissolving thiourea was 50ml.
Test No. 1
The dry sample is used for decomposing organic pollutants for performance test, and the methyl orange solution is taken as a target degradation product in the specific steps. The degradation testing apparatus for methyl orange solution is shown in fig. 2.
The methyl orange is prepared into a solution of 10mg/L, then 50mg of the products in the examples 7 to 11 are weighed and added into 50ml of the methyl orange solution, and the mixture is magnetically stirred under the illumination condition of a fluorescent lamp. After 2h of testing, the degradation rates were determined as in Table 1 below.
Through a test of 2h, the degradation rate of methyl orange is 83-90%. Wherein, when the adding amount of the copper source is 4.26g, the degradation rate is the highest.
Methyl orange is selected as a representative of the organic pollutants, and methyl blue and the like can also be used as a representative of the organic pollutants.
According to the invention, silicon dioxide SiO2 which is one of raw materials of the self-cleaning glass is modified, and when the self-cleaning glass is prepared by using the modified SiO2, the self-cleaning glass is self-cleaned by utilizing a photocatalysis principle without coating treatment, so that the problems that a self-cleaning glass film layer is not wear-resistant and is easy to damage are solved.
The photocatalysis principle is based on the oxidation-reduction capability of the photocatalyst under the condition of illumination, so that the aim of purifying pollutants is fulfilled. When the surface of the silicon dioxide is loaded with photocatalysis, the photocatalyst obtains energy under the irradiation of the sun, and electron transition occurs to leave a cavity. The electron-hole pair has a strong oxidizing property, and particularly, for organic substances, can decompose the organic substances into carbon dioxide and water. Thereby achieving the purpose of cleaning the surface of the glass.
While the foregoing shows and describes the fundamental principles and principal features of the invention, together with the advantages thereof, the foregoing embodiments and description are illustrative only of the principles of the invention, and various changes and modifications can be made therein without departing from the spirit and scope of the invention, which will fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (10)
1. A silica modified material for producing self-cleaning glass, characterized in that: the raw material formula of the silicon dioxide modified material comprises a copper source, a complex, silicon dioxide, a sulfur source, ammonia water, absolute ethyl alcohol and water, wherein the mass ratio of the copper source to the Cu in the anhydrous ethyl alcohol is Cu 2+ : s in sulfur source 2+ =1:1, complex with Cu 2+ The mass ratio of (1: 0.32) - (3.2) and silicon dioxide SiO 2 The mass ratio of the complex to the complexing substance is 2:1; s in silica and sulfur source 2+ The mass ratio is 2:0.1-1, using three parts of water, wherein the mass volume ratio of the ammonia water to the second part of water is (3-5): 50, the first part of water and the second part of water are the same in dosage, and the third part of water and absolute ethyl alcohol are a plurality of in quantity;
the mass volume ratio of the ammonia water to the water is 3-5:200-500, wherein the mass volume ratio of the absolute ethyl alcohol to the water is 1:1-2;
the preparation method of the silicon dioxide modified material comprises the following steps:
(1) Preparing raw materials, and dividing water into three parts;
(2) Weighing a copper source with required dosage, adding the copper source into the first part of water, and uniformly stirring;
(3) Weighing the complex, adding into the copper source solution, stirring, heating to 50-70 deg.C, and maintaining at constant temperature for 4-6min;
(4) Adding silicon dioxide powder into the solution, and magnetically stirring at constant temperature of 50-70 ℃ for 40min to form uniform suspension;
(5) Weighing a sulfur source with required dosage, adding the sulfur source into the second part of water, uniformly stirring, adding ammonia water, and uniformly stirring by magnetic force for 4-5min:
(6) Uniformly adding the solution in the step (5) into the suspension in the step (4), continuously stirring by magnetic force and keeping the set temperature, wherein the reaction time is 4.5-5.5h;
(7) And (4) washing and filtering the solution obtained in the step (6) by using absolute ethyl alcohol and a third part of water to obtain solid sample powder, and drying at the temperature of 55-65 ℃ for 7-9h to obtain the product.
2. A silica-modified material for the production of self-cleaning glass according to claim 1, characterized in that: the copper source is copper chloride, copper nitrate and copper sulfate; the water is distilled water.
3. A silica-modified material for the production of self-cleaning glass according to claim 2, characterized in that: the copper source is copper chloride.
4. A silica-modified material for the production of self-cleaning glass according to claim 3, characterized in that: the copper chloride is CuCl 2 ·2H 2 O 。
5. A silica-modified material for the production of self-cleaning glass according to claim 1, characterized in that: the sulfur source is thiourea, thioacetamide and sodium sulfide.
6. A silica-modified material for the production of self-cleaning glass according to claim 5, characterized in that: the sulfur source is thiourea.
7. A silica-modified material for the production of self-cleaning glass according to claim 1, characterized in that: the complex is diethyl triaminepentaacetic acid and thioacetamide.
8. The method for preparing the silica modified material for producing self-cleaning glass according to claim 1, wherein the method comprises the following steps: the particle size of the silicon dioxide powder is 20-40 microns.
9. The method for preparing the silica modified material for producing self-cleaning glass according to claim 1, wherein the method comprises the following steps: in the step (7), the drying temperature is 60 ℃, and the drying time is 8h.
10. The method for preparing the silica modified material for producing self-cleaning glass according to claim 1, wherein the method comprises the following steps: the reaction time in the step (6) is 5h.
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