CN113430858B - Self-cleaning modification method for paper surface - Google Patents
Self-cleaning modification method for paper surface Download PDFInfo
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- CN113430858B CN113430858B CN202110829791.9A CN202110829791A CN113430858B CN 113430858 B CN113430858 B CN 113430858B CN 202110829791 A CN202110829791 A CN 202110829791A CN 113430858 B CN113430858 B CN 113430858B
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H25/00—After-treatment of paper not provided for in groups D21H17/00 - D21H23/00
- D21H25/04—Physical treatment, e.g. heating, irradiating
- D21H25/06—Physical treatment, e.g. heating, irradiating of impregnated or coated paper
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/03—Non-macromolecular organic compounds
- D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
- D21H17/07—Nitrogen-containing compounds
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/63—Inorganic compounds
- D21H17/64—Alkaline compounds
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/63—Inorganic compounds
- D21H17/67—Water-insoluble compounds, e.g. fillers, pigments
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The application provides a self-cleaning modification method for a paper surface, which comprises the following steps: 1) activating the paper by using low-temperature plasma; 2) uniformly attaching a titanium source to the surface of the paper; 3) treating paper by using an alkaline solution and a urea solution, and then placing the paper in a constant-temperature treatment box for treatment to promote the generation of titanium dioxide and nitrogen doping; 4) and continuously treating the paper by using the plasma generated in the nitrogen atmosphere to realize secondary nitrogen doping. The method can generate titanium dioxide on the surface of paper in situ and carry out nitrogen doping, improve the photocatalytic performance of the titanium dioxide in a visible light region, remove bacterial colonies and organic pollutants on the surface of the paper by utilizing the photocatalytic oxidation reaction of the titanium dioxide in the visible light, and realize self-cleaning of the surface of the paper.
Description
Technical Field
The application relates to the technical field of paper cleaning, in particular to a paper surface self-cleaning modification method.
Background
The main components of the paper are plant fibers including cellulose, hemicellulose, lignin and other substances, so that a plurality of polar groups exist on the surface of the paper, the paper is easy to be infected with a plurality of organic pollutants, a loose and porous structure on the surface of the paper provides a plurality of attached sites for the pollutants, the pollutants are deposited and adsorbed on the surface of the paper and are not easy to remove, polymers such as polysaccharide, monosaccharide and the like in the paper material provide nutrient substances for the growth of bacterial spores, and due to the characteristics, the pollution such as stains, mildew and the like easily appears on the surface of the paper in the storage process, the pollution not only influences the normal use of the paper, but also accelerates the aging of the paper and shortens the service life of the paper. Therefore, the paper is cleaned regularly to remove harmful pollutants and bacterial colonies on the surface of the paper.
At present, foreign pollutants on the surface of paper are removed by physical wiping and washing for many times by using a cleaning agent, and the specific cleaning effect is related to the types of the cleaning agent and the paper by using a disinfectant to remove bacterial colonies on the surface of the paper. The measures can only realize temporary cleaning protection of the paper, and after the cleaned paper is stored for a certain time, new pollutants and bacterial colonies appear on the surface of the paper, so that the aging of the paper is accelerated. If the paper is cleaned by using the cleaning agent and the disinfectant for multiple times, the surface appearance and the structure of the paper can be influenced, for example, information on the surface of the paper is damaged, and the surface of the paper is wrinkled, yellowed and embrittled and the like. For the more aged paper, this direct contact type cleaning is not suitable.
With the development of semiconductor photocatalysis technology, the oxidation effect generated by semiconductor photocatalysis can be utilized to destroy bacteria on the surface of paper and decompose organic pollutants into small molecular compounds which are easy to remove. However, because the semiconductor has a large forbidden band width and needs a light source of a specific wavelength band for excitation, the photocatalytic performance of the semiconductor under visible light is not obvious, which greatly limits the application of the semiconductor.
Disclosure of Invention
Based on the above, there is a need to provide a method for self-cleaning modification of paper surface, which can realize self-cleaning modification of paper surface and continuous protection of paper without affecting the topography and structure of paper surface.
The technical scheme provided by the invention is as follows: a method for self-cleaning modification of paper surfaces comprises the following steps:
1) activating the paper by using low-temperature plasma;
2) uniformly attaching a titanium source to the surface of the paper;
3) treating paper by using an alkaline solution and a urea solution, and then placing the paper in a constant-temperature treatment box for treatment to promote the generation of titanium dioxide and nitrogen doping;
4) and continuously treating the paper by using the plasma generated in the nitrogen atmosphere to realize secondary nitrogen doping.
According to the technical scheme, the paper is pretreated by adopting low-temperature plasma, the number of polar groups exposed on the surface of the paper is increased by activating the surface of the paper, and then the paper is immersed in the titanium source solution, so that the titanium source solution is uniformly attached to the surface of the paper. Then, alkaline solution and urea solution are used for treating paper surface, then the paper is placed in a constant temperature treatment box for treatment, the generation and nitrogen doping of titanium dioxide are promoted, and finally, the paper loaded with titanium dioxide is treated by plasma under the nitrogen atmosphere.
The alkaline solution treatment can promote the titanium source solution to hydrolyze to generate titanium dioxide, meanwhile, the paper surface can be fully swelled to destroy cellulose molecular chains with small degree of polymerization on the paper surface, the cellulose molecules are coated by the urea solution, and then the titanium dioxide is firmly loaded on the paper surface. Finally, the paper is subjected to plasma treatment in the nitrogen atmosphere, so that the doping of a urea nitrogen source and titanium dioxide can be promoted, and meanwhile, nitrogen atoms in the working gas are doped into titanium dioxide crystal lattices, so that secondary nitrogen doping is realized, and the nitrogen doping degree of the titanium dioxide in the paper is improved. The method can form titanium dioxide on the surface of the paper in situ and reinforce the titanium dioxide, can complete nitrogen doping of the titanium dioxide, effectively reduces the forbidden bandwidth of the titanium dioxide, and improves the photocatalytic performance of the titanium dioxide in a visible light region, thereby realizing self-cleaning of the surface of the paper under visible light.
Several alternatives are provided below, but not as an additional limitation to the above general solution, but merely as a further addition or preference, each alternative being combinable individually for the above general solution or among several alternatives without technical or logical contradictions.
Optionally, the activating treatment in step 1) includes: and (3) placing the paper in a low-temperature plasma treatment chamber, and performing discharge treatment for 1-8min, wherein the discharge gas is air or oxygen-argon mixed gas. The oxygen-containing active substances in the plasma can be increased by taking the oxygen-containing gas as the reaction gas, so that the number of oxygen-containing groups loaded on the surface of the paper is increased, and finally, the loading amount of the titanium source solution on the surface of the paper is increased.
Optionally, the low temperature plasma is generated by corona discharge, glow discharge or dielectric barrier discharge.
Optionally, the attaching in step 2) includes: and (3) immersing the paper into the titanium source solution for treatment for 1-5min, and taking out.
Optionally, the titanium source solution is a tetrabutyl titanate solution, a titanyl sulfate solution or a titanium tetrachloride solution. The selected titanium source solution is easy to hydrolyze, and can be hydrolyzed in situ on the surface of paper under certain conditions to generate titanium dioxide.
Optionally, a buffering agent is added into the titanium source solution; the buffer is an absolute ethyl alcohol solution, a glacial acetic acid solution or a diethanolamine solution. Since the selected titanium source solution is very easy to hydrolyze, when the titanium source solution is loaded on the surface of paper, a buffering agent is added to inhibit the hydrolysis of the titanium source solution.
Optionally, the alkaline solution in step 3) is a sodium hydroxide solution, potassium hydroxide, an ammonia water solution or a calcium hydroxide solution. The alkaline solution treatment can be used for swelling the paper, destroying the cellulose molecular chains with low polymerization degree stacked on the surface of the paper, and simultaneously matching with the urea solution to perform inclusion on the cellulose molecules, so that the fixation of the titanium dioxide on the surface of the paper is realized.
Optionally, the pH of the alkaline solution in step 3) is 9 to 10.
Optionally, the mass fraction of the urea solution in the step 3) is 0.1-1 wt%, and more preferably 0.4-0.6 wt%.
Optionally, in the step 3), the paper is placed in a constant temperature treatment box for treatment, wherein the treatment temperature is 50-80 ℃, and the treatment time is 6-24 hours. The treatment in the constant temperature treatment box can increase the internal energy of molecules, accelerate the diffusion between titanium dioxide and urea molecules and improve the nitrogen doping speed of the titanium dioxide.
Optionally, the continuing of the processing in step 4) includes: putting the paper treated in the step 3) into a microwave plasma treatment chamber, introducing nitrogen, adjusting the working pressure to be 1-2 pa, and treating the paper for 10-60min by using microwave electron cyclotron resonance plasma. Compared with the traditional discharge plasma, the electrolysis degree and the decomposition efficiency of the gas are higher, the plasma density is higher, the microwave plasma essentially belongs to non-equilibrium low-temperature plasma, and the paper substrate cannot be influenced in the treatment process. In the treatment process, energy-carrying particles in the plasma are in inelastic collision with nitrogen molecules and urea, the energy is converted into internal energy of the molecules, the molecules are excited and dissociated, and the generated activated nitrogen atoms bombard titanium dioxide to replace oxygen in crystal lattices of the titanium dioxide, so that the doping of nitrogen is realized.
Optionally, the microwave power of the microwave plasma processing chamber is 200-800W.
The invention has the following beneficial effects:
(1) according to the method, titanium dioxide is generated by hydrolysis of a titanium source solution, and the hydrolysis process is promoted and the titanium dioxide is fixed by using an alkaline solution and a urea solution, so that the titanium dioxide is generated in situ on the surface of the paper, and the stability of the titanium dioxide loaded on the surface of the paper is improved.
(2) According to the invention, the urea molecules and the microwave electron cyclotron resonance plasma are utilized to carry out nitrogen doping on the titanium dioxide loaded on the surface of the paper, so that secondary nitrogen doping of the titanium dioxide can be realized, and the nitrogen doping effect of the titanium dioxide is improved.
(3) According to the invention, nitrogen is used for doping titanium dioxide, so that the forbidden bandwidth is reduced, the photocatalytic performance of the titanium dioxide under visible light is increased, organic pollutants on the surface of paper can be degraded under the visible light through the photocatalytic action, and bacterial colonies are removed.
Detailed Description
The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to specific embodiments of the present application, and it should be apparent that the described embodiments are only a part of the embodiments of the present application, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein in the description of the present application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application.
Example 1
And (3) placing the paper to be treated in a glow discharge plasma treatment chamber for treatment, wherein the discharge gas is air, and the discharge treatment time is 5 min. Adding 5ml of tetrabutyl titanate solution into 50ml of absolute ethyl alcohol solution, uniformly mixing, immersing the paper into the solution for treatment for 2min, taking out, treating the paper with a sodium hydroxide solution with the pH value of 10 and a urea solution with the weight percent of 0.5, after 3min of treatment, placing the paper in a constant-temperature treatment box with the temperature of 70 ℃ for nitrogen doping treatment for 8h, after the treatment, washing the paper with deionized water for multiple times, and drying for later use.
And (3) putting the dried paper into a microwave plasma processing chamber, introducing 99.99% nitrogen into the microwave plasma processing chamber with the flow rate of 50sccm, adjusting the working air pressure to be 1-2 pa by a vacuum pump, adjusting the microwave power to be 400W, and processing the paper by using microwave electron cyclotron resonance plasma for 30 min. Thus finishing the secondary nitrogen doping of the titanium dioxide on the surface of the paper.
Performance analysis:
carrying out ultrasonic oscillation treatment on the paper loaded with the titanium dioxide in an ethanol solution, carrying out XPS (X-ray diffraction) tests before and after the oscillation treatment, and calculating the change of the relative content of the titanium element, namely the change of the relative content of the titanium element relative to the carbon element, so as to represent the stability of the titanium dioxide load. And then, the forbidden bandwidth of the titanium dioxide is calculated by analyzing the ultraviolet-visible absorption spectrum of the nitrogen-doped titanium dioxide loaded on the surface of the paper, so as to represent the nitrogen doping degree of the titanium dioxide.
The XPS test of the paper loaded with titanium dioxide in example 1 can calculate that the relative content of titanium is 0.74%, after the ultrasonic oscillation treatment, the relative content of titanium is 0.67%, and the relative content difference between titanium before and after the ultrasonic oscillation treatment is small, which indicates that the titanium dioxide is stably loaded and does not fall off greatly during the ultrasonic oscillation treatment. Then, the forbidden bandwidth of the nitrogen-doped titanium dioxide is characterized, the forbidden bandwidth of the titanium dioxide which is not doped with any element is calculated to be 3.09eV, and the forbidden bandwidth of the titanium dioxide doped with the nitrogen element in the embodiment 1 is calculated to be 2.96 eV. Indicating successful doping of the titanium dioxide on the surface of the paper with nitrogen atoms.
Comparative example 1
And (3) placing the paper to be treated in a glow discharge plasma treatment chamber for treatment, wherein the discharge gas is air, and the discharge treatment time is 5 min. Adding 5ml of tetrabutyl titanate solution into 50ml of absolute ethyl alcohol solution, uniformly mixing, immersing the paper into the solution for treatment for 2min, taking out, treating the paper with a sodium hydroxide solution with the pH value of 10 and a urea solution with the weight percent of 0.5, after 3min of treatment, placing the paper in a constant-temperature treatment box with the temperature of 70 ℃ for nitrogen doping treatment for 8h, after the treatment, washing the paper with deionized water for multiple times, and drying for later use.
Performance analysis:
the paper loaded with titanium dioxide in comparative example 1 was subjected to XPS testing, and the testing and calculation methods were the same as those in example 1, and it was calculated that the relative content of titanium before the ultrasonic oscillation treatment was 0.78%, and after the ultrasonic oscillation treatment, the relative content of titanium was 0.66%, and before and after the ultrasonic oscillation treatment, the relative content of titanium did not change significantly, because titanium dioxide was loaded on the paper surface only by physical adsorption, and the loading was unstable, and could fall off under the ultrasonic oscillation. The forbidden band width of the titanium dioxide doped with the nitrogen element is calculated and obtained to be 3.02eV through an ultraviolet visible absorption spectrum. The nitrogen doping degree of the titanium dioxide on the surface of the paper is lower due to the diffusion effect of urea molecules without subsequent plasma nitrogen doping treatment, which is obviously higher than that of the embodiment 1.
Comparative example 2
And (3) placing the paper to be treated in a glow discharge plasma treatment chamber for treatment, wherein the discharge gas is air, and the discharge treatment time is 5 min. Adding 5ml of tetrabutyl titanate solution into 50ml of absolute ethyl alcohol solution, uniformly mixing, immersing the paper into the solution for treatment for 2min, taking out, then treating the paper with a sodium hydroxide solution with the pH value of 10 for 3min, placing the paper in a constant-temperature treatment box at 70 ℃ for 8h after the treatment is finished, washing the paper with deionized water for multiple times after the treatment is finished, and drying for later use.
And (3) putting the dried paper into a microwave plasma processing chamber, introducing 99.99% nitrogen into the microwave plasma processing chamber with the flow rate of 50sccm, adjusting the working air pressure to be 1-2 pa by a vacuum pump, adjusting the microwave power to be 400W, and processing the paper by using microwave electron cyclotron resonance plasma for 30 min. Thus finishing the secondary nitrogen doping of the titanium dioxide on the surface of the paper.
Performance analysis:
the paper loaded with titanium dioxide in comparative example 2 was subjected to XPS testing, and the testing and calculation methods were the same as those in example 1, and the relative content of titanium before the ultrasonic oscillation treatment was calculated to be 0.72%, and after the ultrasonic oscillation treatment, the relative content of titanium was calculated to be 0.51%, and after the ultrasonic oscillation treatment, the relative content of titanium was decreased. This is because the urea solution lacks the coating effect on the cellulose molecules and titanium dioxide, so that the fixation effect of the paper surface on the titanium dioxide is reduced, and thus the paper easily falls off under the action of ultrasonic vibration. The forbidden band width of the titanium dioxide doped with the nitrogen element is calculated and obtained to be 3.06eV through an ultraviolet visible absorption spectrum. The forbidden band width of the titanium dioxide is obviously higher than that of the titanium dioxide in the embodiment 1, because the plasma treatment is only carried out in the nitrogen atmosphere without the existence of urea molecules, so that the titanium dioxide cannot be effectively doped with nitrogen, and finally, the nitrogen doping degree of the titanium dioxide is lower, and the forbidden band width is reduced less.
Comparative example 3
Adding 5ml of tetrabutyl titanate solution into 50ml of absolute ethyl alcohol solution, mixing uniformly, directly immersing paper into the solution for treatment for 2min, taking out, treating the paper with 0.5 wt% of urea solution for 3min, placing the paper in a constant temperature treatment box at 70 ℃ for nitrogen doping treatment after the treatment is finished, wherein the treatment time is 8h, washing the paper with deionized water for multiple times after the treatment is finished, and drying for later use.
And (3) putting the dried paper into a microwave plasma processing chamber, introducing 99.99% nitrogen into the microwave plasma processing chamber with the flow rate of 50sccm, adjusting the working air pressure to be 1-2 pa by a vacuum pump, adjusting the microwave power to be 400W, and processing the paper by using microwave electron cyclotron resonance plasma for 30 min. Thus finishing the secondary nitrogen doping of the titanium dioxide on the surface of the paper.
Performance analysis:
the XPS test was performed on the paper loaded with titanium dioxide in comparative example 2, and the test and calculation methods are the same as those in example 1, and the relative content of titanium element before the ultrasonic oscillation treatment was calculated to be 0.35%, and after the ultrasonic oscillation treatment, the relative content of titanium element was 0.16%, and after the ultrasonic oscillation treatment, the relative content of titanium element was greatly reduced, because the content of the titanium source solution loaded on the surface of the paper was not high, hydrolysis was incomplete, and the load was unstable, and it was easy to fall off under the external effect without plasma pretreatment and alkaline solution treatment. And then calculating by an ultraviolet visible absorption spectrum to obtain the forbidden band width of the titanium dioxide doped with the nitrogen element to be 3.01 eV. The forbidden band width of the titanium dioxide is obviously higher than that of the embodiment 1, which is attributed to the low content of the titanium dioxide and incomplete hydrolysis of the titanium source solution, so that effective nitrogen doping can not be carried out.
Example 2
The procedure of example 1 was repeated except that the titanium source solution in example 1 was adjusted to 3g of titanyl sulfate and 50ml of glacial acetic acid solution was added. Finally, the forbidden band width of the titanium dioxide after nitrogen doping is calculated to be 2.97 eV.
Example 3
The procedure of example 1 was repeated except for adjusting the titanium source solution in example 1 to 5g of titanium tetrachloride and adding 50ml of an anhydrous ethanol solution. And finally calculating to obtain the forbidden band width of the titanium dioxide after the nitrogen doping to be 2.95 eV.
Example 4
The same procedure as in example 1 was repeated except that the alkali solution in the process of swelling the paper sheet in example 1 was changed to a calcium hydroxide solution having a pH of 9. Finally, the forbidden band width of the titanium dioxide after nitrogen doping is calculated to be 3.00 eV.
Example 5
The temperature of the oven was adjusted to 60 ℃ in example 1 and the treatment time was increased to 12 hours, the same procedure as in example 1 being followed. And finally calculating to obtain the forbidden band width of the titanium dioxide after the nitrogen doping to be 2.98 eV.
Example 6
The microwave plasma treatment of the paper of example 1 was carried out with the power from the microwave set at 600W, and the operation procedure was the same as that of example 1. And finally calculating to obtain the forbidden band width of the titanium dioxide after the nitrogen doping to be 2.95 eV.
Claims (10)
1. A method for self-cleaning modification of a paper surface is characterized by comprising the following steps:
1) activating the paper by using low-temperature plasma;
2) uniformly attaching a titanium source to the surface of the paper;
3) treating paper by using an alkaline solution and a urea solution, and then placing the paper in a constant-temperature treatment box for treatment to promote the generation of titanium dioxide and nitrogen doping;
4) and continuously treating the paper by using the plasma generated in the nitrogen atmosphere to realize secondary nitrogen doping.
2. The method for self-cleaning modification of paper surfaces according to claim 1, wherein the activation treatment in step 1) comprises: and (3) placing the paper in a low-temperature plasma treatment chamber, and performing discharge treatment for 1-8min, wherein the discharge gas is air or oxygen-argon mixed gas.
3. The method for self-cleaning modification of the surface of paper according to claim 2, wherein the low temperature plasma is generated by corona discharge, glow discharge or dielectric barrier discharge.
4. The method of self-cleaning modification of paper surfaces as recited in claim 1 wherein the attaching in step 2) comprises: and (3) immersing the paper into the titanium source solution for treatment for 1-5min, and taking out.
5. The method for self-cleaning modification of the surface of paper as recited in claim 4 wherein the titanium source solution is a tetrabutyl titanate solution, a titanyl sulfate solution, or a titanium tetrachloride solution.
6. The method for self-cleaning modification of the surface of paper as claimed in claim 4, wherein a buffer is added to the titanium source solution; the buffer is an absolute ethyl alcohol solution, a glacial acetic acid solution or a diethanolamine solution.
7. The method for self-cleaning modification of the surface of paper as claimed in claim 1, wherein the alkaline solution in step 3) is sodium hydroxide solution, potassium hydroxide, ammonia water solution or calcium hydroxide solution.
8. The method for self-cleaning modification of the surface of the paper sheet as claimed in claim 1, wherein the paper sheet is treated in the step 3) in a constant temperature treatment box, wherein the treatment temperature is 50-80 ℃ and the treatment time is 6-24 h.
9. The method of self-cleaning modification of paper surfaces as recited in claim 1 wherein the continuing of the process in step 4) comprises: putting the paper treated in the step 3) into a microwave plasma treatment chamber, introducing nitrogen, adjusting the working pressure to be 1-2 pa, and treating the paper for 10-60min by using microwave electron cyclotron resonance plasma.
10. The method for self-cleaning modification of the surface of paper as claimed in claim 9, wherein the microwave plasma treatment chamber has a microwave power of 200-800W.
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| CN102354605A (en) * | 2011-09-22 | 2012-02-15 | 中国矿业大学 | Method for preparing doping-type crystalline titanium dioxide photoelectrode at low temperature by virtue of microwave auxiliary reaction supercharge method |
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| US7445671B2 (en) * | 2000-06-29 | 2008-11-04 | University Of Louisville | Formation of metal oxide nanowire networks (nanowebs) of low-melting metals |
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| CN102354605A (en) * | 2011-09-22 | 2012-02-15 | 中国矿业大学 | Method for preparing doping-type crystalline titanium dioxide photoelectrode at low temperature by virtue of microwave auxiliary reaction supercharge method |
| CN106320094A (en) * | 2016-09-13 | 2017-01-11 | 福建农林大学 | PVC (polyvinyl chloride) wallpaper with function of photocatalytically degrading formaldehyde in visible light and method for preparing PVC wallpaper |
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