CN112915988A - Titanium dioxide/carbon/manganese dioxide composite photocatalyst material, and preparation method and application thereof - Google Patents
Titanium dioxide/carbon/manganese dioxide composite photocatalyst material, and preparation method and application thereof Download PDFInfo
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 106
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 239000000463 material Substances 0.000 title claims abstract description 39
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 29
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 28
- 239000002131 composite material Substances 0.000 title claims abstract description 26
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 19
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- 102000004169 proteins and genes Human genes 0.000 claims abstract description 44
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- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000002904 solvent Substances 0.000 claims abstract description 22
- 238000004729 solvothermal method Methods 0.000 claims abstract description 21
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- 238000001354 calcination Methods 0.000 claims abstract description 17
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- 239000000203 mixture Substances 0.000 claims description 30
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 26
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- 238000003756 stirring Methods 0.000 description 58
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
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Abstract
A titanium dioxide/carbon/manganese dioxide composite photocatalyst material and a preparation method and application thereof are provided, the preparation method of the titanium dioxide/carbon/manganese dioxide composite photocatalyst material comprises the steps of extracting conchiolin from conchiolin; adding the shell protein into a solvent, mixing, and then adding butyl titanate, and mixing to obtain a mixed solution; carrying out solvothermal reaction on the mixed solution to obtain a solid, and calcining the solid under an oxygen-free condition to obtain TiO2C; will be provided withTiO2Adding the/C into a potassium permanganate solution for hydrothermal reaction to obtain the titanium dioxide/carbon/manganese dioxide composite photocatalyst material. The photocatalytic material prepared by the invention can improve the light absorption property, has the advantages of strong photon absorption, stable performance and the like, can be applied to the degradation of indoor VOCs, and has a strong market application prospect.
Description
Technical Field
The invention relates to the technical field of photocatalysts for degrading indoor mixed VOCs (volatile organic compounds), in particular to a titanium dioxide/carbon/manganese dioxide composite photocatalyst material as well as a preparation method and application thereof.
Background
According to statistics, at least 70% of the time of the people in one day is spent indoors, so that the guarantee of the indoor air quality safety is a big concern for the health of the public. Indoor air quality is affected by both outdoor and indoor sources of pollution. In 2010, the discharge amount of anthropogenic VOCs (volatile organic compounds) in China reaches 1335.6 ten thousand tons. With the improvement of living standard of people, the use amount of indoor building and decorative materials is increased rapidly, building syndrome (SBS), building association disease (BRI) and chemical substance allergy (MCS) are frequent, and the health and the living quality of people are seriously harmed.
Formaldehyde is an important agent for the manufacture of materials such as paints, synthetic resins, rayon, and plastics. These formaldehyde-containing materials are widely used in the wood industry, textile and preservative solutions. Toluene is used as a solvent for oils, resins, natural and synthetic rubbers, cellulose acetate, and also as a solvent for cellulosic paints and varnishes, and for photo-lithographical, ink. Toluene is also a raw material for organic synthesis of many dyes and the like. Formaldehyde and toluene are present in these materials for a long time and are difficult to be released completely in a short time, and have durability to indoor air pollution. The traditional Chinese medicine composition has great harm to human bodies, can damage respiratory systems and immune systems of the human bodies, causes symptoms of cough, chest distress and the like to the human bodies, and further develops respiratory diseases such as bronchitis, pneumonia, emphysema and the like in severe cases. In the publication No. 153 "Formaldehyde carcinogenesis" issued by the world health organization on 6/15/2004, it was confirmed that formaldehyde is a carcinogen. In 2017, the list of carcinogens published by the world health organization international cancer research institute is preliminarily collated and referenced, and toluene is also identified in the list of class 3 carcinogens. Therefore, the treatment of formaldehyde and toluene in the room is particularly important.
The photocatalysis technology has the advantages of low energy consumption, mild reaction conditions, simple and convenient operation, no secondary pollution and the like, is widely applied to treating indoor air pollution in recent years, and obtains good treatment results. Titanium dioxide has the characteristics of good chemical stability, low cost, no toxicity and the like, and becomes the photocatalyst with the highest application potential, but because the band gap is wide (3.2eV), ultraviolet light (lambda is less than or equal to 387.5nm) is needed to excite the catalytic activity of the titanium dioxide, so that the application of the titanium dioxide is greatly limited, and the breakthrough of the application limit of the titanium dioxide through modification is always an important direction for research.
Disclosure of Invention
In view of the above, one of the main objectives of the present invention is to provide a titanium dioxide/carbon/manganese dioxide composite photocatalyst material, and a preparation method and an application thereof, so as to at least partially solve at least one of the above technical problems.
In order to achieve the above object, as an aspect of the present invention, there is provided a method for preparing a titanium dioxide/carbon/manganese dioxide composite photocatalyst material, comprising:
s1: extracting shell protein from the shell;
s2: adding the shell protein into a solvent, mixing, and then adding butyl titanate, and mixing to obtain a mixed solution;
s3: carrying out solvothermal reaction on the mixed solution to obtain a solid, and calcining the solid under an oxygen-free condition to obtain TiO2/C；
S4: adding TiO into the mixture2Adding the/C into a potassium permanganate solution for hydrothermal reaction to obtain the TiO2/C/MnO2A composite photocatalyst material.
As another aspect of the invention, the invention also provides a titanium dioxide/carbon/manganese dioxide composite photocatalyst material which is obtained by adopting the preparation method.
As a further aspect of the invention, the application of the titanium dioxide/carbon/manganese dioxide composite photocatalyst material in degrading mixed VOCs in a room is also provided.
Based on the technical scheme, compared with the prior art, the titanium dioxide/carbon/manganese dioxide composite photocatalyst material, the preparation method and the application have at least one or part of the following advantages:
1. the invention provides TiO for degrading indoor mixed VOCs (volatile organic compounds)2/C/MnO2The composite photocatalyst material and the preparation method modify and modify titanium dioxide, greatly increase the degradation efficiency of the titanium dioxide to formaldehyde and toluene mixed pollutants, are easy to recycle and are more beneficial to application in the environment; the prepared photocatalytic material can improve the light absorption property, has the advantages of strong photon absorption, stable performance and the like, can be applied to the degradation of indoor VOCs, and has a strong market application prospect;
2. the invention provides a method for synthesizing high-performance TiO by using protein in shells as a carbon source2/C/MnO2The method for degrading indoor formaldehyde and toluene by using the composite photocatalyst has the advantages of simple process, low price, easy popularization, good physical stability, good dispersibility, no volatilization, no dissolution, high heat-resistant temperature and no toxicity; tests prove that the catalyst obtained by the method has good stability and long catalytic life; the method utilizes protein in waste shells, has rich raw material resources and low price, and the whole preparation process is green and environment-friendly and is easy for industrial production.
Drawings
FIG. 1 shows TiO prepared by the preparation method provided by the embodiment of the invention2/C/MnO2A TEM image of (B);
FIG. 2 shows TiO prepared by the preparation method provided by the embodiment of the invention2/C/MnO2EDX of (D).
Detailed Description
In order that the objects, technical solutions and advantages of the present invention will become more apparent, the present invention will be further described in detail with reference to the accompanying drawings in conjunction with the following specific embodiments.
The invention discloses a preparation method of a titanium dioxide/carbon/manganese dioxide composite photocatalyst material, which comprises the following steps:
s1: extracting shell protein from the shell;
s2: adding the shell protein into a solvent, mixing, and then adding butyl titanate, and mixing to obtain a mixed solution;
s3: carrying out solvothermal reaction on the mixed solution to obtain a solid, and calcining the solid under an oxygen-free condition to obtain TiO2/C；
S4: adding TiO into the mixture2Adding the/C into a potassium permanganate solution for hydrothermal reaction to obtain the titanium dioxide/carbon/manganese dioxide composite photocatalyst material.
In some embodiments of the invention, the method for extracting conch protein in step S1 comprises adding dilute acid solution into the shell, immersing the shell, standing until the shell floats on the water surface, and separating insoluble protein.
In some embodiments of the invention, the concentration of the dilute acidic solution is 5 to 10 wt.%, e.g., 5 wt.%, 6 wt.%, 7 wt.%, 8 wt.%, 9 wt.%, 10 wt.%.
In some embodiments of the invention, in step S2, the mass ratio of the conchiolin, the butyl titanate and the solvent is (2 to 8): 29: 473, for example 2: 29: 473. 3: 29: 473. 4: 29: 473. 5: 29: 473. 6: 29: 473. 7: 29: 473. 8: 29: 473.
in some embodiments of the invention, in step S2, the solvent comprises ethanol;
in step S2, the density of butyl titanate is 0.996g/em3。
In some embodiments of the invention, in step S3, the reaction temperature of the solvothermal reaction is 180 to 220 ℃, for example 180 ℃, 190 ℃, 200 ℃, 210 ℃, 220 ℃; the reaction time is 40 to 60h, for example 40h, 45h, 50h, 55h, 60 h.
In some embodiments of the invention, in step S4, the TiO is2TiO in/C2And potassium permanganate solids in a mass ratio of 0 to 1.5, wherein the mass ratio is different from 0, for example 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2, 1.3, 1.4, 1.5.
In some embodiments of the present invention, in step S4, the reaction time of the hydrothermal reaction is 40 to 60h, for example, 40h, 45h, 50h, 55h, 60 h.
The invention also discloses a titanium dioxide/carbon/manganese dioxide composite photocatalyst material which is obtained by adopting the preparation method.
The invention also discloses application of the titanium dioxide/carbon/manganese dioxide composite photocatalyst material in degrading indoor mixed VOCs.
In one exemplary embodiment, a TiO for degrading mixed VOCs in a room is provided2/C/MnO2The preparation method of the composite photocatalyst material comprises the following steps:
s1: extraction of conch protein: cleaning shell, adding dilute acid solution, submerging shell, standing until shell floats on water surface, and separating insoluble protein;
S2：TiO2c, synthesis: adding conchiolin into ethanol solvent at room temperature (e.g. 15-30 deg.C), stirring to mix thoroughly, adding butyl titanate after stirring, stirring to mix thoroughly, performing solvothermal reaction to obtain solid, washing the solid after reaction, and calcining in oxygen-free condition to obtain modified TiO2。
S3：TiO2/C/MnO2Synthesizing: adding TiO into the mixture2adding/C into the potassium permanganate solution, stirring until the mixture is fully and uniformly mixed, carrying out hydrothermal reaction after stirring to obtain a solid matter, washing and drying the solid matter to obtain the target catalyst TiO2/C/MnO2。
The protein in the shell of this example is rich in carbon and decomposes to produce amino acids during solvothermal processes, and is a natural surfactant, biological template, dopant and carbon source modified by titanium dioxide. In this example, insoluble proteins in shells were used as a biological template, surfactant, dopant and carbon source. Firstly, soaking a certain proportion of protein in an ethanol solution, and stirring for a certain time; adding a certain amount of butyl titanate, stirring for a certain time, carrying out solvothermal reaction, carrying out anaerobic calcination, and mixing with KMnO4Hydrothermal reaction, washing and drying, and synthesizing TiO2/C/MnO2The composite photocatalyst greatly improves the catalytic activity of the catalyst.
The mass concentration of the diluted acid solution in the step S1 in this embodiment is 5% to 10%. In the embodiment, the concentration of the dilute acid is not too low, otherwise, calcium carbonate cannot be dissolved; the concentration should not be too high, otherwise the protein structure is destroyed and cannot be collected; in the embodiment, the insoluble protein serving as an intelligent multifunctional template is decomposed into amino acid in the subsequent solvothermal process, and the amino acid serves as a surfactant, a dopant, a hydrogen donor and an important carbon source in the reaction process.
In this embodiment, the mass ratio of the protein, the butyl titanate and the ethanol in the step S2 is (2 to 8): 29: 473, in this example, the purpose of modifying titanium dioxide cannot be achieved due to too low protein addition, and formaldehyde cannot be effectively degraded; the addition amount of protein is too high, the reaction is not completed, and the formation of the composite catalyst is not facilitated due to too high carbon generation amount in the subsequent anaerobic calcination.
The reaction time during the solvothermal reaction in the step S2 described in this example was 40 to 60 h. The solvent thermal reaction time is less than 40 hours, so that the yield is too low to be practically applied; reaction time longer than 60 hours will produce a large amount of high molecular polymer, reduce the efficiency of degrading formaldehyde.
In this example, the density of butyl titanate in the S2 step was 0.996g/cm3。
TiO 3 step described in this example2And KMnO4The mass ratio is 0 to 1.5, wherein the mass ratio is not 0.
The embodiment also discloses a photocatalyst, which adopts the method for synthesizing the high-performance TiO2/C/MnO2The photocatalyst for degrading indoor formaldehyde and toluene is prepared by the preparation method.
The TiO for degrading indoor mixed VOCs provided by the embodiment2/C/MnO2The preparation method of the composite photocatalyst material has simple process, low price and easy popularization; the titanium dioxide prepared by the method has good physical stability, no volatilization, no dissolution, high heat-resistant temperature, no toxicity and long catalytic life; the invention utilizes protein in waste shellsThe quality, the raw material resources are rich, the price is low, the whole preparation process is green and environment-friendly, and the industrial production is easy to realize.
The technical solution of the present invention is further illustrated by the following specific embodiments in conjunction with the accompanying drawings. It should be noted that the following specific examples are given by way of illustration only and the scope of the present invention is not limited thereto.
The chemicals and raw materials used in the following examples were either commercially available or self-prepared by a known preparation method.
Example 1
Cleaning shell, adding 5-10% acetic acid solution to submerge the shell, standing until the shell floats on water surface, and separating insoluble protein. Adding 0.2g of shell protein into 60mL of ethanol solvent at room temperature, stirring until the mixture is fully and uniformly mixed, adding 3mL of butyl titanate after stirring is finished, continuously stirring until the mixture is fully and uniformly mixed, carrying out solvothermal reaction after stirring is finished, wherein the reaction time is 50h, washing a solid after the reaction is finished, and carrying out anaerobic calcination to obtain TiO2and/C. 0.75g of TiO was taken2Dispersing the/C into 30mL of water, stirring the mixture until the mixture is fully mixed, performing hydrothermal reaction after stirring, and washing and drying a solid matter after the reaction is finished to obtain TiO2/C/MnO2. The removal rate of the photocatalytic material for degrading indoor formaldehyde under visible light for 45min is 85%, and the removal rate of toluene is 65%. As shown in FIGS. 1 and 2, TiO prepared for this example2/C/MnO2The synthesized TiO was verified by characterization with an electron microscope (TEM) and an energy dispersive X-ray spectrometer (EDX)2/C/MnO2The composition of the components (A) and (B).
Example 2
Cleaning shell, adding 5-10% acetic acid solution to submerge the shell, standing until the shell floats on water surface, and separating insoluble protein. Adding 0.4g of conchiolin into 60mL of ethanol solvent at room temperature, stirring until the conchiolin is fully and uniformly mixed, adding 3mL of butyl titanate after stirring is finished, continuously stirring until the conchiolin is fully and uniformly mixed, carrying out solvothermal reaction after stirring is finished, wherein the reaction time is 50h, washing a solid after the reaction is finished, and carrying out anaerobic calcination to obtain the solidTo TiO2and/C. 0.75g of TiO was taken2Dispersing the/C into 30mL of 0.005 mol.L-1KMnO4Stirring to mix thoroughly, hydrothermal reacting, washing and drying to obtain TiO2/C/MnO2. The removal rate of the photocatalytic material for degrading indoor formaldehyde for 45min under visible light is 90%, and the removal rate of toluene is 80%.
Example 3
Cleaning shell, adding 5-10% acetic acid solution to submerge the shell, standing until the shell floats on water surface, and separating insoluble protein. Adding 0.6g of shell protein into 60mL of ethanol solvent at room temperature, stirring until the mixture is fully and uniformly mixed, adding 3mL of butyl titanate after stirring is finished, continuously stirring until the mixture is fully and uniformly mixed, carrying out solvothermal reaction after stirring is finished, wherein the reaction time is 50h, washing a solid after the reaction is finished, and carrying out anaerobic calcination to obtain TiO2and/C. 0.75g of TiO was taken2Dispersing the/C into 30mL of 0.01 mol.L-1KMnO4Stirring to mix thoroughly, hydrothermal reacting, washing and drying to obtain TiO2/C/MnO2. The removal rate of the photocatalytic material for degrading indoor formaldehyde for 45min under visible light is 90%, and the removal rate of toluene is 70%.
Example 4
Cleaning shell, adding 5-10% acetic acid solution to submerge the shell, standing until the shell floats on water surface, and separating insoluble protein. Adding 0.8g of shell protein into 60mL of ethanol solvent at room temperature, stirring until the mixture is fully and uniformly mixed, adding 3mL of butyl titanate after stirring is finished, continuously stirring until the mixture is fully and uniformly mixed, carrying out solvothermal reaction after stirring is finished, wherein the reaction time is 50h, washing a solid after the reaction is finished, and carrying out anaerobic calcination to obtain TiO2and/C. 0.75g of TiO was taken2the/C is dispersed to 30mL of 0.02mol.L-1KMnO4Stirring to mix thoroughly, hydrothermal reacting, washing and drying to obtain TiO2/C/MnO2. The photocatalytic material degrades indoor armor under visible lightThe removal rate of aldehyde for 45min was 97%, and the removal rate of toluene was 90%.
Example 5
Cleaning shell, adding 5-10% acetic acid solution to submerge the shell, standing until the shell floats on water surface, and separating insoluble protein. Adding 0.8g of shell protein into 60mL of ethanol solvent at room temperature, stirring until the mixture is fully and uniformly mixed, adding 3mL of butyl titanate after stirring is finished, continuously stirring until the mixture is fully and uniformly mixed, carrying out solvothermal reaction after stirring is finished, wherein the reaction time is 40h, washing a solid after the reaction is finished, and carrying out anaerobic calcination to obtain TiO2and/C. 0.75g of TiO was taken2Dispersing the/C into 30mL of 0.05 mol.L-1KMnO4Stirring to mix thoroughly, hydrothermal reacting, washing and drying to obtain TiO2/C/MnO2. The removal rate of the photocatalytic material for degrading indoor formaldehyde for 45min under visible light is 87%, and the removal rate of toluene is 85%.
Example 6
Cleaning shell, adding 5-10% acetic acid solution to submerge the shell, standing until the shell floats on water surface, and separating insoluble protein. Adding 0.8g of shell protein into 60mL of ethanol solvent at room temperature, stirring until the mixture is fully and uniformly mixed, adding 3mL of butyl titanate after stirring is finished, continuously stirring until the mixture is fully and uniformly mixed, carrying out solvothermal reaction after stirring is finished, wherein the reaction time is 60h, washing a solid after the reaction is finished, and carrying out anaerobic calcination to obtain TiO2and/C. 0.75g of TiO was taken2Dispersing the/C into 30mL of 0.1 mol.L-1KMnO4Stirring to mix thoroughly, hydrothermal reacting, washing and drying to obtain TiO2/C/MnO2. The removal rate of the photocatalytic material for degrading indoor formaldehyde in visible light for 45min is 82%, and the removal rate of toluene is 85%. .
Comparative example 1
Cleaning shell, adding 5-10% acetic acid solution to submerge the shell, standing until the shell floats on water surface, and separating insoluble protein. At room temperature, 0.8g shell proteinAdding the mixture into 60mL of ethanol solvent, stirring the mixture until the mixture is fully mixed, adding 3mL of butyl titanate after the stirring is finished, continuously stirring the mixture until the mixture is fully mixed, carrying out solvothermal reaction after the stirring is finished for 30 hours, washing a solid after the reaction is finished, and carrying out anaerobic calcination to obtain TiO2and/C. 0.75g of TiO was taken2Dispersing the/C into 30mL of 0.02mol.L-1KMnO4Stirring to mix thoroughly, hydrothermal reacting, washing and drying to obtain TiO2/C/MnO2. The removal rate of the photocatalytic material for degrading indoor formaldehyde in visible light for 45min is 75%, and the removal rate of toluene is 70%. Thus, the efficiency of removing formaldehyde and toluene is reduced when the reaction time is too short.
Comparative example 2
Cleaning shell, adding 5-10% acetic acid solution to submerge the shell, standing until the shell floats on water surface, and separating insoluble protein. Adding 0.8g of shell protein into 60mL of ethanol solvent at room temperature, stirring until the mixture is fully and uniformly mixed, adding 3mL of butyl titanate after stirring is finished, continuously stirring until the mixture is fully and uniformly mixed, carrying out solvothermal reaction after stirring is finished, wherein the reaction time is 65h, washing a solid after the reaction is finished, and carrying out anaerobic calcination to obtain TiO2and/C. 0.75g of TiO was taken2Dispersing the/C into 30mL of 0.02mol.L-1KMnO4Stirring to mix thoroughly, hydrothermal reacting, washing and drying to obtain TiO2/C/MnO2. The removal rate of the photocatalytic material for degrading indoor formaldehyde for 45min under visible light is 70%, and the removal rate of toluene is 68%. Which indicates that the formaldehyde and the toluene are removed with low efficiency for a long time.
Comparative example 3
Cleaning shell, adding 5-10% acetic acid solution to submerge the shell, standing until the shell floats on water surface, and separating insoluble protein. At room temperature, adding 0.1g of conchiolin into 60mL of ethanol solvent, stirring until the mixture is fully mixed, adding 3mL of butyl titanate after stirring, continuing stirring until the mixture is fully mixed, carrying out solvothermal reaction after stirring, and reacting for timeThe reaction time is 50h, and after the reaction is finished, the solid matter is washed and subjected to anaerobic calcination to obtain TiO2and/C. 0.75g of TiO was taken2Dispersing the/C into 30mL of 0.02mol.L-1KMnO4Stirring to mix thoroughly, hydrothermal reacting, washing and drying to obtain TiO2/C/MnO2. The removal rate of the photocatalytic material for degrading indoor formaldehyde in visible light for 45min is 67%, and the removal rate of toluene is 60%. Thus showing that the removal efficiency of formaldehyde and toluene is reduced when the addition amount of the shell protein is too small.
Comparative example 4
Cleaning shell, adding 5-10% acetic acid solution to submerge the shell, standing until the shell floats on water surface, and separating insoluble protein. Adding 1.5g of shell protein into 60mL of ethanol solvent at room temperature, stirring until the mixture is fully and uniformly mixed, adding 3mL of butyl titanate after stirring is finished, continuously stirring until the mixture is fully and uniformly mixed, carrying out solvothermal reaction after stirring is finished, wherein the reaction time is 50h, washing a solid after the reaction is finished, and carrying out anaerobic calcination to obtain TiO2and/C. 0.75g of TiO was taken2Dispersing the/C into 30mL of 0.02mol.L-1KMnO4Stirring to mix thoroughly, hydrothermal reacting, washing and drying to obtain TiO2/C/MnO2. The removal rate of the photocatalytic material for degrading indoor formaldehyde in visible light for 45min is 60%, and the removal rate of toluene is 50%. Thus showing that the removal efficiency of formaldehyde and toluene is reduced when the shell protein is added in an excessive amount.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of a titanium dioxide/carbon/manganese dioxide composite photocatalyst material comprises the following steps:
s1: extracting shell protein from the shell;
s2: adding the shell protein into a solvent, mixing, and then adding butyl titanate, and mixing to obtain a mixed solution;
s3: carrying out solvothermal reaction on the mixed solution to obtain a solid, and calcining the solid under an oxygen-free condition to obtain TiO2/C；
S4: adding TiO into the mixture2Adding the/C into a potassium permanganate solution for hydrothermal reaction to obtain the titanium dioxide/carbon/manganese dioxide composite photocatalyst material.
2. The production method according to claim 1,
in step S1, the method for extracting shell protein comprises adding dilute acid solution into shell, immersing the shell, standing until the shell floats on water surface, and separating insoluble protein.
3. The production method according to claim 2,
the concentration of the dilute acid solution is 5 to 10 wt.%.
4. The production method according to claim 1,
in step S2, the mass ratio of the shell protein to the butyl titanate to the solvent is (2-8) to 29: 473.
5. The production method according to claim 1,
in step S2, the solvent includes ethanol;
in step S2, the density of butyl titanate is 0.996g/cm3。
6. The production method according to claim 1,
in step S3, the reaction temperature of the solvothermal reaction is 180 to 220 ℃, and the reaction time is 40 to 60 hours.
7. The production method according to claim 1,
in step S4, TiO2TiO in/C2And potassium permanganate solids in a mass ratio of 0 to 1.5, wherein the mass ratio is different from 0.
8. The production method according to claim 1,
in step S4, the reaction time of the hydrothermal reaction is 40 to 60 hours.
9. A titanium dioxide/carbon/manganese dioxide composite photocatalyst material is obtained by adopting the preparation method of any one of 1 to 8.
10. The use of the titanium dioxide/carbon/manganese dioxide composite photocatalyst material of claim 9 in degrading mixed VOCs in a room.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114588892A (en) * | 2022-03-22 | 2022-06-07 | 扬州海华环境技术有限公司 | Titanium modified manganese-based catalyst and preparation method thereof |
| CN115364841A (en) * | 2022-09-21 | 2022-11-22 | 电子科技大学长三角研究院(湖州) | Simple synthesis of superfine TiO 2 @C 7 H 8 O@C photocatalyst method and application technical field of formaldehyde degradation |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104014357A (en) * | 2014-06-23 | 2014-09-03 | 武汉理工大学 | Preparation method for nitrogen-doped TiO2 (titanium dioxide) powder of reticulated porous structure |
| CN109529866A (en) * | 2018-09-28 | 2019-03-29 | 天津大学 | A kind of preparation method and application for the layered metal oxide that potassium permanganate is modified |
| CN110327915A (en) * | 2019-06-28 | 2019-10-15 | 杭州同净环境科技有限公司 | Photochemical catalyst and preparation method |
| US20200269216A1 (en) * | 2019-02-25 | 2020-08-27 | China Jiliang University | Nano-catalyst composite for decomposing formaldehyde at room temperature and preparation method thereof |
-
2021
- 2021-01-26 CN CN202110107381.3A patent/CN112915988B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104014357A (en) * | 2014-06-23 | 2014-09-03 | 武汉理工大学 | Preparation method for nitrogen-doped TiO2 (titanium dioxide) powder of reticulated porous structure |
| CN109529866A (en) * | 2018-09-28 | 2019-03-29 | 天津大学 | A kind of preparation method and application for the layered metal oxide that potassium permanganate is modified |
| US20200269216A1 (en) * | 2019-02-25 | 2020-08-27 | China Jiliang University | Nano-catalyst composite for decomposing formaldehyde at room temperature and preparation method thereof |
| CN110327915A (en) * | 2019-06-28 | 2019-10-15 | 杭州同净环境科技有限公司 | Photochemical catalyst and preparation method |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114588892A (en) * | 2022-03-22 | 2022-06-07 | 扬州海华环境技术有限公司 | Titanium modified manganese-based catalyst and preparation method thereof |
| CN114588892B (en) * | 2022-03-22 | 2023-08-01 | 扬州海华环境技术有限公司 | Titanium modified manganese-based catalyst and preparation method thereof |
| CN115364841A (en) * | 2022-09-21 | 2022-11-22 | 电子科技大学长三角研究院(湖州) | Simple synthesis of superfine TiO 2 @C 7 H 8 O@C photocatalyst method and application technical field of formaldehyde degradation |
| CN115364841B (en) * | 2022-09-21 | 2024-03-26 | 电子科技大学长三角研究院(湖州) | Simple and easy synthetic superfine TiO 2 @C 7 H 8 O@C photocatalyst method and formaldehyde degradation application technical field |
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