CN110075930B - Photocatalytic system with photoresponse switch and self-indicating property as well as preparation method and application - Google Patents
Photocatalytic system with photoresponse switch and self-indicating property as well as preparation method and application Download PDFInfo
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- CN110075930B CN110075930B CN201910388040.0A CN201910388040A CN110075930B CN 110075930 B CN110075930 B CN 110075930B CN 201910388040 A CN201910388040 A CN 201910388040A CN 110075930 B CN110075930 B CN 110075930B
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Abstract
The invention discloses a photocatalytic system with a photoresponse switch and self-indication property, a preparation method and application thereof, in particular to the universal application of the photocatalytic system in the field of controllable self-indication degradation of plastics. The invention relates to a photocatalyst system with a photoresponse switch and self-indication performance, which is constructed by utilizing the combination of a photocatalyst, a photo-generated electron-hole consumption agent and a photo-generated electron-hole consumption agent complex and utilizing the color change of the photo-generated electron-hole consumption agent and the photo-generated electron-hole consumption agent complex before and after reaction. In the initial stage of illumination, the photocatalytic system has a certain color and has no photocatalytic activity, and after the illumination is carried out for a certain time, the color of the photocatalytic system changes, so that the photocatalytic activity is high. The photocatalytic system can be added into plastics as a filler to provide controllable self-indicating degradability for the plastics. The plastic has high stability in the service life and high degradation efficiency in the waste period. And indicates to the consumer the beginning of the plastic waste period using a color change of the photocatalytic system.
Description
Technical Field
The invention belongs to the technical field of photocatalysis, relates to a photocatalysis system with a photoresponse switch and self-indication property, a preparation method and application in the field of plastic degradation, and particularly relates to application of the photocatalysis system in the aspects of controlling a plastic stabilization period, a degradation period and degradation efficiency and displaying the beginning of the plastic degradation period through color change.
Background
The non-decomposable plastic garbage produced in China every year reaches five million tons, which brings great burden to the environment. Biodegradable plastics can reduce plastic pollution, however, biodegradable plastics have not been widely popularized due to brittleness, low mechanical properties, low heat resistance, and low gas barrier properties. The traditional plastic has great market share due to good mechanical property, thermal stability, chemical and biological inertness and low price. However, due to the stability of the traditional plastics, the plastic wastes bring great harm to soil ecosystems and water ecosystems, in the process of plastic waste treatment, the landfill technology takes hundreds of thousands of years to degrade the traditional plastics, and the gas generated by the incineration technology brings secondary harm to the environment. How to develop the traditional plastic degradation technology improves the degradation efficiency of the plastic in the waste period on the basis of ensuring that the mechanical property, the thermal stability and the like of the plastic in the service period are not changed, and has important significance for environmental protection, sustainable development and the existing plastic industry.
According to the use requirement, an ideal plastic degradation technology should ensure that the plastic has good stability in the use period, has a fast degradation rate in the abandonment period, and can be completely mineralized in a short time, but no technology in the traditional plastic degradation technical field can meet the requirements at the same time.
In the field of traditional plastic degradation, the corresponding technologies can be divided into two categories: one is microbial degradation, and the plastic is degraded by using microbes in soil, water and compost, but the microbial degradation of the traditional plastic is extremely slow. The other type is non-biodegradable traditional plastic, and fillers such as an oxygen promoter and the like are added into the plastic to accelerate the degradation of the plastic under the assistance of light, heat and the like. The traditional plastic technology of non-biodegradation is divided into photo-assisted oxygen agent oxidation, thermal-assisted oxygen agent oxidation and photocatalytic degradation, however, the non-biodegradation requires long heating or illumination time for achieving complete degradation of the plastic. Due to the advantages and disadvantages of microbial degradation and non-biodegradable plastics, a more feasible research scheme at present is to use non-biodegradable pre-biodegradable plastics. Studies of Chiellini, E.and Portland, F. (Chiellini, E.; Corti, A.; D' Antone, S. Oxo-biodegradable hydrocarbon Polymer e biodegradation floor cement of thermally oxidized polyethylene in an aqueous medium. Polymer Degradation and stabilization 2007, 92, 1378-1383. Portland, F.; Yashchuk, O.; Hermida, E. Evaluation of the rate of oxidative and biological Degradation of oxidative polyethylene Polymer Testing 2016, 53, 58-69.) indicate that oxidation of the plastics using photo-and thermal-assisted oxidative pre-Degradation techniques results in incomplete Degradation of the plastics in subsequent thermal-assisted oxidative and oxidative Degradation, because of the high rate of partial mineralization of the plastics, and subsequent thermal-assisted oxidative Degradation of the plastics.
The photocatalytic pre-degradation technology has recently received much attention due to its high activity. However, the application of the photocatalyst in the field of plastic degradation meets the following two bottleneck problems that firstly, the plastic has no stable period due to the high efficiency of the photocatalyst, and the regulation and control of the stable period of the plastic cannot be realized (CN 101181678B); secondly, in the processes of storage, transportation, sale and use of the plastic, due to different environmental factors, the degradation degree of the plastic is different, and no indication system provides information whether the plastic is suitable for use for a user.
Disclosure of Invention
Aiming at the defects of the existing photocatalysis technology, the invention provides a photocatalysis system with photoresponse opening and self-indicating properties, a preparation method and application thereof in the field of plastic degradation.
The first purpose of the invention is to provide a photocatalytic system with photoresponse opening light and self-indicating property, the system has certain color in the initial illumination period and has no photocatalytic activity, and the color changes after a certain period of illumination to have the photocatalytic activity.
A second object of the present invention is to provide a method for the preparation of a photocatalytic system with open-light, self-indicating photo-response.
The third purpose of the invention is to provide a method for preparing a plastic product with controllable degradation efficiency by mixing a photocatalytic system with plastics, wherein the plastic product has the advantages of good stability, certain color in the service life, color change in the abandonment period and good photocatalytic degradation efficiency; the change in color of the plastic provides an indication to the user as to whether the plastic is suitable for use.
The specific technical scheme for realizing the purpose of the invention is as follows:
a photocatalysis system with photoresponse switch and self-indicating property is composed of the following raw materials in parts by weight:
1) 1 part of a photocatalyst; the photocatalyst consists of one or more of the following photocatalysts:
ultraviolet light responsive TiO2、ZnO、NiO、SrTiO3、KTaO3、K4Nb6O17And BaTiO3；
Visible light responsive modified TiO2Modified ZnO, SiC and CdSe;
oxides containing one or several of the following elements: fe. W, Bi, Ti, Ce, Cu, In, Ca, Y, Mo and V;
sulfides containing one or several of the following elements: mo, Ag, In, Cd, Ce and Cu;
nitrides containing one or several of the following elements: ta, O, C, La and Ti;
2) 0.01-10 parts of photocatalyst photo-generated electron-hole consuming agent; the photocatalyst photo-generated electron-hole consumption agent is a reversible redox couple or a photo-generated electron-hole couple trapping agent;
3) 0.00-20 parts of a photo-generated electron-hole consuming agent complex; the photo-generated electron-hole consuming agent complex includes, but is not limited to, starch and metal ion chelating agents; wherein:
the photo-response switch is characterized in that under the illumination of initial sunlight, a photo-induced electron-hole consumption agent of a photocatalyst in a photocatalytic system plays a role in inhibiting the photocatalytic activity of the photocatalyst, so that even if the photocatalyst generates photo-induced electron-hole pairs under the illumination, the photocatalyst cannot play the photocatalytic activity on substances outside the photocatalytic system; after 0.5 hour to 90 days of illumination, the photo-generated electron-hole consumption agent in the photo-catalytic system is invalid, and photo-generated electron-hole pairs generated by the photocatalyst can perform photo-catalytic action on substances outside the photo-catalytic system;
the self-indicating property is that when the photocatalytic system can not exert photocatalytic activity on substances outside the system, the self-indicating property has the following color: brown, purple, brown, orange, yellow, green, blue, bluish violet or purple red, and the color of the photocatalytic system changes to one of the following colors after 0.5 hours to 90 days of sunlight illumination: blue black, orange red, yellow, blue purple or white, and the photocatalytic system after color change has the function of exerting photocatalytic activity on substances outside the system.
In a photocatalytic system, the TiO2Including anatase, rutile, brookite, and amorphous; the ZnO comprises a hexagonal wurtzite structure, a cubic sphalerite structure, a cubic rock salt structure and an amorphous structure; the modified TiO2The modified ZnO is modified by one or more modification methods of metal element modification, nonmetal element modification, precious metal modification, metal element/nonmetal element co-modification and dye sensitization; TiO 22And ZnO can be in the form of powder, bulk, film or sol, as well as nanowires, nanotubes, nanospheres or nano-polygonal blocks and nano-irregular shapes.
In photocatalytic systems, the oxides containing one or several elements include, but are not limited to: fe2O3、WO3、Bi4Ti3O12、Ce2O3、Cu2O、In2O3、CaFe2O4、YFeO3、BiMoO6、BiVO4And InVO4(ii) a The sulfide containing one or several elements includes but is not limited to: MoS2、AgIn5S5、CdS、Ce2S3、CuIn5S2And In2S3(ii) a The nitride containing one or several elements includes, but is not limited to: TaON, C3N4、Ta3N5And LaTiO2N。
In photocatalytic systems, the reversible redox couple includes, but is not limited to: i is3 -/I-、I2/I-And Fe2+/Fe3+(ii) a The photogenerated electron-hole pair trapping agent includes but is not limited to AgNO3Formic acid, AgNO3Triethanolamine and KBrO3-sodium bicarbonate.
In photocatalytic systems, the metal ion chelating agents include, but are not limited to: 2,4, 6-tris (2-pyridyl) triazine and bathophenanthroline disulfonic acid disodium salt hydrate.
The preparation method of the photocatalytic system adopts a layer-by-layer modification method, and comprises the following specific steps:
step 1: adding a photocatalyst photo-generated electron-hole consumption agent into the solution, and stirring for 0.5 h-2 days at the temperature of 0-200 ℃; wherein the concentration of the photocatalyst photo-generated electron-hole consumption agent is 0.01-30 g/L; the solution is formed by mixing water with a polymer, or mixing water with citric acid and a polymer, or mixing water with an organic solvent and a polymer; the concentration of the polymer in the mixed solution of water and the polymer is 0.01-1.0 g/L; in the mixed solution of water, citric acid and polymer, the concentration of the citric acid is 0.00001-30g/L, and the concentration of the polymer is 0.01-1.0 g/L; in the mixed solution of water, organic solvent and polymer, the concentration of the polymer is 0.01-2.0g/L, and the concentration of the organic solvent is 5-300 g/L; the organic solvent is isopropanol, cyclohexane, acetone or ethanol; the polymer is hydroxyethyl cellulose, polyvinyl alcohol or polyethylene glycol; the photocatalyst photo-generated electron-hole consumption agent is a reversible redox couple or a photo-generated electron-hole couple trapping agent;
step 2: adding photocatalyst powder into the photocatalyst photo-generated electron-hole consuming agent mixed solution prepared in the step 1, stirring, refluxing or performing hydrothermal treatment for 0.5 h-2 days at the temperature of 0-200 ℃, or dropwise adding NaOH solution while stirring at the temperature of 0-200 ℃, filtering, and drying at the temperature of 25-200 ℃ to obtain powder; wherein the concentration of the NaOH solution is 1-160g/L, and the mass ratio of the NaOH to the photo-generated electron-hole consumption agent is 0.5-4: 1; the mass ratio of the photocatalyst to the photocatalyst photo-generated electron-hole consumption agent is 1: 0.01-10;
and step 3: adding the powder obtained in the step 2 into a mixed system consisting of a photo-generated electron-hole consuming agent complex and water, ethanol or a water-containing mixed solution, stirring and refluxing for 0.5 hour to 2 days at the temperature of 0 to 200 ℃, separating, adding into a water solution containing a polymer, stirring for 0 to 2 hours, separating, and drying at the temperature of 25 to 200 ℃ to obtain the photocatalytic system; wherein the concentration of the photo-generated electron-hole consuming agent complex is 0.01-10 w%; the aqueous mixed solution contains one or more of the following components: organic solvents, hydrochloric acid; if the aqueous mixed solution is mixed by water and an organic solvent, the volume ratio of the organic solvent to the water is 0.05-5:100, if the aqueous mixed solution is mixed by water and hydrochloric acid, the concentration of the hydrochloric acid is 0.05-1 mol/L; the organic solvent is isopropanol or ethanol; the polymer-containing aqueous solution has the concentration of 0.01-2.0 g/L; the polymer is selected from one of the following polymers: hydroxyethyl cellulose, polyvinyl alcohol or polyethylene glycol; the mass ratio of the photo-generated electron-hole consuming agent complex to the powder obtained in the step 2 is 0.00-20: 1; the photo-generated electron-hole consuming agent complex includes, but is not limited to, starch and metal ion chelating agents.
The preparation method of the photocatalytic system adopts a codeposition method for preparation, and comprises the following steps:
step 1: adding the photocatalyst, the photocatalyst photo-generated electron-hole consumption agent and the photo-generated electron-hole consumption agent complex into the solution for mixing, and carrying out stirring or reflux treatment at the temperature of 0-200 ℃ for 0.5 h-2 days; the solution consists of one or more of the following substances: water, organic solvents, polymers, hydrochloric acid and citric acid; if the solution consists of water and polymer, the concentration of the polymer is 0.01-1.0 g/L; if the solution consists of water, organic solvent and polymer, the concentration of the polymer is 0.01-2.0g/L, and the concentration of the organic solvent is 0.1-300 g/L; if the solution consists of water, polymer and hydrochloric acid, the concentration of the hydrochloric acid is 0.01-0.8mol/L, and the concentration of the polymer is 0.01-2.0 g/L; if the solution consists of water, polymer and citric acid, the concentration of the citric acid is 0.00001-30g/L, and the concentration of the polymer is 0.01-2.0 g/L; wherein the mass ratio of the photocatalyst to the photocatalyst photogenerated electron-hole consumption agent to the photogenerated electron-hole consumption agent complex is 1:0.01-10: 0.00-20; the concentration of the photocatalyst is 0.01-15 g/L; the organic solvent is isopropanol, cyclohexane, acetone or ethanol, and the polymer is hydroxyethyl cellulose, polyvinyl alcohol or polyethylene glycol;
step 2: filtering the mixture, and drying at 25-200 ℃ to obtain the photocatalytic system.
The preparation method of the photocatalytic system adopts photocatalyst sol preparation, and comprises the following steps:
step 1: mixing one or two photocatalyst precursors with absolute ethyl alcohol, stirring for 0.1-4h, controlling the temperature to be 25-100 ℃, dropwise adding the obtained mixed solution into a mixed solution containing water, and stirring for 0.5-72h to obtain photocatalyst sol; the photocatalyst precursor includes, but is not limited to: titanium alkoxide and zinc acetate, wherein the molar concentration of the titanium alkoxide and the zinc acetate is 0.5-2.5 mol/L; the mixed solution containing water comprises one or more of the following substances: water, acetylacetone, and an acid; the concentration of acetylacetone is 0.1-1.0mol/L, the concentration of acid is 0.1-1.0 mol/L; the volume ratio of the photocatalyst precursor to water is 1: 0.5-60; the acid is acetic acid, hydrochloric acid or nitric acid;
step 2: adding a photocatalyst photo-generated electron-hole consumption agent into the solution, and stirring for 0.5 h-2 days at the temperature of 0-200 ℃; wherein the concentration of the photocatalyst photo-generated electron-hole consumption agent is 0.01-30 g/L; the solution is formed by mixing water with a polymer, or mixing water with citric acid and a polymer, or mixing water with an organic solvent and a polymer; water and polymer mixed solution, the concentration of the polymer is 0.01-1.0 g/L; in the mixed solution of water, citric acid and polymer, the concentration of the citric acid is 0.00001-30g/L, and the concentration of the polymer is 0.01-1.0 g/L; mixing water, organic solvent and polymer, wherein the concentration of the polymer is 0.01-2.0g/L, and the concentration of the organic solvent is 5-300 g/L; the organic solvent is isopropanol, cyclohexane, acetone or ethanol; the polymer is hydroxyethyl cellulose, polyvinyl alcohol or polyethylene glycol; mixing the obtained mixed solution with photocatalyst sol, and stirring or refluxing at 0-200 deg.C for 0.5 hr-2 days; wherein the mass ratio of the photocatalyst photo-generated electron-hole consumption agent to the photocatalyst precursor in the photocatalyst sol is 0.001-7: 1;
and step 3: adding the photo-generated electron-hole consuming agent complex into a mixed system consisting of water, ethanol or a water-containing mixed solution, stirring and refluxing for 0.5 h-2 days at the temperature of 0-200 ℃, separating, adding into a water solution containing a polymer, stirring for 0-2h, separating, and drying at the temperature of 25-200 ℃; the aqueous mixed solution contains one or more of the following components: organic solvents, hydrochloric acid; if the water-containing mixed liquid is the mixture of water and an organic solvent, the volume of the organic solvent is 0.05-5%; if water is mixed with hydrochloric acid, the concentration of the hydrochloric acid is 0.05-1 mol/L; the organic solvent is isopropanol or ethanol; the polymer-containing aqueous solution has the concentration of 0.01-2.0 g/L; the polymer is selected from one of the following polymers: hydroxyethyl cellulose, polyvinyl alcohol or polyethylene glycol; the concentration of the photo-generated electron-hole consuming agent complex is 0.01-10 w%;
and 4, step 4: adding the mixture prepared in the step 3 into the mixture prepared in the step 2, and stirring or refluxing for 0.5 hour-2 days at the temperature of 0-200 ℃; wherein the mass ratio of the photo-generated electron-hole consuming agent complex to the photocatalyst precursor in the photocatalyst sol is 0.00-15: 1;
and 5: filtering the mixture, and drying at 25-200 ℃ to obtain the photocatalytic system.
A photocatalysis system with photoresponse switch and self-indicating property is composed of the following raw materials in parts by weight:
1 part of photocatalyst modified by photo-generated electron-hole consumption agent;
0.00-20 parts of a photo-generated electron-hole consuming agent complex.
In the photocatalytic system, the photocatalyst modified by the photo-generated electron-hole consuming agent is prepared by the following steps:
step 1: adding a photocatalyst and a photocatalyst photo-generated electron-hole consumption agent into the solution for mixing, and stirring or refluxing for 0.5 h-2 days at the temperature of 0-200 ℃, or dropwise adding a NaOH solution under stirring at the temperature of 0-200 ℃, wherein the concentration of the NaOH solution is 1-160g/L, and the mass ratio of NaOH to the photo-generated electron-hole consumption agent is 0.5-4: 1; the solution consists of one or more of the following substances: water, organic solvents, polymers and citric acid; if the solution consists of water and polymer, the concentration of the polymer is 0.01-1.0 g/L; if the solution consists of water, organic solvent and polymer, the concentration of the polymer is 0.01-2.0g/L, and the concentration of the organic solvent is 0.1-300 g/L; if the solution consists of water, citric acid and polymer, the concentration of the citric acid is 0.00001-30g/L, and the concentration of the polymer is 0.01-1.0 g/L; the organic solvent is isopropanol, cyclohexane, acetone or ethanol, and the polymer is hydroxyethyl cellulose, polyvinyl alcohol or polyethylene glycol; the mass ratio of the photocatalyst to the photo-generated electron-hole consumption agent is 1: 0.01-10; the concentration of the photocatalyst is 0.01-15 g/L;
step 2: and filtering the mixture, and drying at 25-200 ℃ to obtain the photocatalyst modified by the photocatalyst photo-generated electron-hole consumption agent.
In the photocatalytic system, the photocatalyst modified by the photo-generated electron-hole consuming agent is prepared by the following steps:
step 1: mixing one or two photocatalyst precursors with ethanol, stirring for 0.1-4h, controlling the temperature to be 25-100 ℃, dropwise adding the obtained mixed solution into a mixed solution containing water, and stirring for 0.5-72h to obtain photocatalyst sol; the photocatalyst precursor includes, but is not limited to: titanium alkoxide and zinc acetate, wherein the molar concentration of the titanium alkoxide and the zinc acetate is 0.5-2.5 mol/L; the mixed solution containing water comprises one or two or more of the following substances: water, acetylacetone, acid; the concentration of acetylacetone is 0.1-1.0mol/L, the concentration of acid is 0.1-1.0 mol/L; the volume ratio of the photocatalyst precursor to water is 1: 0.5-60; the acid is acetic acid, hydrochloric acid or nitric acid;
step 2: adding a photocatalyst photo-generated electron-hole consumption agent into the solution, and stirring for 0.5 h-2 days at the temperature of 0-200 ℃; wherein the concentration of the photocatalyst photo-generated electron-hole consumption agent is 0.01-30 g/L; the solution is formed by mixing water with a polymer, or mixing water with citric acid and a polymer, or mixing water with an organic solvent and a polymer; water and polymer mixed solution, the concentration of the polymer is 0.01-1.0 g/L; in the mixed solution of water, citric acid and polymer, the concentration of the citric acid is 0.00001-30g/L, and the concentration of the polymer is 0.01-1.0 g/L; mixing water, organic solvent and polymer, wherein the concentration of the polymer is 0.01-2.0g/L, and the concentration of the organic solvent is 5-300 g/L; the organic solvent is isopropanol, cyclohexane, acetone or ethanol; the polymer is hydroxyethyl cellulose, polyvinyl alcohol or polyethylene glycol; mixing the obtained mixed solution with photocatalyst sol, and stirring or refluxing at 0-200 deg.C for 0.5 hr-2 days; wherein the mass ratio of the photocatalyst photo-generated electron-hole consumption agent to the photocatalyst precursor in the photocatalyst sol is 0.001-7: 1;
and step 3: and (3) filtering the mixture obtained in the step (2), and drying at 25-200 ℃ to obtain the photocatalyst modified by the photocatalyst photo-generated electron-hole consumption agent.
An application of the photocatalytic system in the field of controllable degradation of plastics.
The application comprises the following specific steps:
step 1: dissolving plastic in water or one of the following organic solvents at 0-150 ℃: isopropanol, cyclohexane, acetone, ethanol, propanol, ethyl acetate, xylene or formic acid; the plastics include but are not limited to: polyethylene, polystyrene, polypropylene, polyamide, polyvinyl alcohol, and polyethylene glycol; the concentration of the plastic is 1-20 g/L;
step 2: adding the photocatalytic system to the solution containing the plastic in the step 1, wherein the mass ratio of the photocatalytic system to the plastic is 0.001-0.8;
and step 3: mixing at 25-200 deg.C for 0.5 hr-2 days;
and 4, step 4: coating the mixture prepared in the step 3 on a substrate, and drying at 25-200 ℃ to obtain a controllable degradation plastic product, wherein the plastic product has one of the following colors: brown, purple, brown, orange, yellow, green, blue, bluish violet or purple red, the weight loss of the plastic is 0.01-10% within 0.5-90 days of sunlight illumination, and the color of the plastic changes into one of the following colors after 0.5-90 days of sunlight illumination: the weight loss rate of the plastic product with changed color, blue black, orange red, yellow, blue purple or white, can be improved to 70-100% after the plastic product is continuously illuminated for 0.5h-90 days; the plastic product is taken as a coating on the surface of the substrate or is stripped from the substrate to independently exist; when the plastic article is used as a coating, the substrate is selected from, but not limited to, polyethylene, polystyrene, polypropylene, polyamide, glass, and quartz; when the plastic article is present alone, the substrate is selected from the group consisting of, but not limited to, glass, quartz, and low surface energy polymers; wherein the low surface energy polymers include, but are not limited to: polyvinylidene fluoride, polytetrafluoroethylene, and ethylene-tetrafluoroethylene copolymer.
The application comprises the following specific steps:
step 1: mixing a photocatalytic system with plastic particles, wherein the mass ratio of the photocatalytic system to the plastic particles is 0.001-0.8;
step 2: preparing a controllably degradable plastic article by extrusion using an extruder at a temperature of from 50 ℃ to 280 ℃, said plastic article having one of: brown, purple, brown, orange, yellow, green, blue, bluish violet or purple red, the weight loss of the plastic is 0.01-10% within 0.5-90 days of sunlight illumination, and the color of the plastic changes into one of the following colors after 0.5-90 days of sunlight illumination: the weight loss rate of the plastic product with changed color, blue black, orange red, yellow, blue purple or white, can be improved to 70-100% after the plastic product is continuously illuminated for 0.5h-90 days; wherein, the mixing mode of the photocatalysis system and the plastic particles is as follows:
the photocatalytic system and the plastic particle mixture are added into an extruder; or,
the plastic particles are firstly added into an extruder, and a photocatalysis system is added at the middle end of the extruder.
The application comprises the following specific steps:
step 1: dissolving plastic in water or one of the following organic solvents at 0-150 ℃: isopropanol, cyclohexane, acetone, ethanol, propanol, ethyl acetate, xylene or formic acid; the plastics include but are not limited to: polyethylene, polystyrene, polypropylene, polyamide, polyvinyl alcohol, and polyethylene glycol; the concentration of the plastic is 1-20 g/L;
step 2: adding a photocatalyst modified by a photocatalyst photo-generated electron-hole consumption agent into the solution containing the plastic in the step 1, wherein the mass ratio of the photocatalyst modified by the photocatalyst photo-generated electron-hole consumption agent to the plastic is 0.001-0.8;
and step 3: adding the photo-generated electron-hole consuming agent complex into water, ethanol or a water-containing mixed solution, and stirring to form a mixed system; wherein, the aqueous mixed solution contains one or more of the following components: organic solvents, hydrochloric acid; if the water-containing mixed liquid is the mixture of water and an organic solvent, the volume of the organic solvent is 0.05-5%; if water is mixed with hydrochloric acid, the concentration of the hydrochloric acid is 0.05-1 mol/L; the organic solvent is isopropanol or ethanol; the concentration of the photo-generated electron-hole consuming agent complex is 0.01-10 w%;
and 4, step 4: adding the liquid/suspension containing the photo-generated electron-hole consuming agent complex prepared in the step 3 into the mixture in the step 2; the mass ratio of the photoproduction electron-hole consumption agent complex to the plastic is 0.00-0.8;
and 5: mixing at 25-200 deg.C for 0.5 hr-2 days;
step 6: coating the mixture prepared in the step 5 on a substrate, and drying at 25-200 ℃ to obtain a controllable degradation plastic product, wherein the plastic product has one of the following colors: brown, purple, brown, orange, yellow, green, blue, bluish violet or purple red, the weight loss of the plastic is 0.01-10% within 0.5-90 days of sunlight illumination, and the color of the plastic changes into one of the following colors after 0.5-90 days of sunlight illumination: the weight loss rate of the plastic product with changed color, blue black, orange red, yellow, blue purple or white, can be improved to 70-100% after the plastic product is continuously illuminated for 0.5h-90 days; the plastic product is taken as a coating on the surface of the substrate or is stripped from the substrate to independently exist; when the plastic article is used as a coating, the substrate is selected from, but not limited to, polyethylene, polystyrene, polypropylene, polyamide, glass, and quartz; when the plastic article is present alone, the substrate is selected from the group consisting of, but not limited to, glass, quartz, and low surface energy polymers; wherein the low surface energy polymers include, but are not limited to: polyvinylidene fluoride, polytetrafluoroethylene, and ethylene-tetrafluoroethylene copolymer.
The application comprises the following specific steps:
step 1: adding the photo-generated electron-hole consuming agent complex into water, ethanol or a water-containing mixed solution, and stirring to form a mixed system; wherein the concentration of the photo-generated electron-hole consuming agent complex is 0.01-10 w%; the aqueous mixed solution contains one or more of the following components: organic solvents, hydrochloric acid; if the water-containing mixed liquid is the mixture of water and an organic solvent, the volume of the organic solvent is 0.05-5%; if water is mixed with hydrochloric acid, the concentration of the hydrochloric acid is 0.05-1 mol/L; the organic solvent is isopropanol and ethanol;
step 2: mixing plastic particles with the liquid obtained in the step (1), stirring for 0.5-12 h, and drying to prepare a photoproduction electron-hole consuming agent complex/plastic particle mixture; wherein the mass ratio of the photo-generated electron-hole consuming agent complex to the plastic particles is 0.00-0.8: 1;
and step 3: adding the photocatalyst modified by the photocatalyst photo-generated electron-hole consumption agent and the particle mixture prepared in the step (2) into an extruder, and extruding at the temperature of 50-280 ℃ to prepare a controllably degradable plastic product; the plastic product has one of the following colors: brown, purple, brown, orange, yellow, green, blue, bluish violet or purple red, the weight loss of the plastic is 0.01-10% within 0.5-90 days of sunlight illumination, and the color of the plastic changes into one of the following colors after 0.5-90 days of sunlight illumination: the weight loss rate of the plastic product with changed color, blue black, orange red, yellow, blue purple or white, can be improved to 70-100% after the plastic product is continuously illuminated for 0.5h-90 days; wherein the mass ratio of the photocatalyst modified by the photocatalyst photo-generated electron-hole consumption agent to the photo-generated electron-hole consumption agent complex/plastic particle mixture is 0.001-0.8: 1;
the photocatalyst modified by the photocatalyst photo-generated electron-hole consumption agent and the mixture of the photo-generated electron-hole consumption agent complex and the plastic particles are mixed in the following mode:
adding the photocatalyst modified by the photocatalyst photo-generated electron-hole consumption agent, the photo-generated electron-hole consumption agent complex and the plastic particle mixture into an extruder; or,
the mixture of the photo-induced electron-hole consumption agent complex and the plastic particles is firstly added into an extruder, and the photocatalyst modified by the photo-induced electron-hole consumption agent is added at the middle end of the extruder.
The photocatalytic system with light response opening and self-indicating property is proposed based on the following principle: when the photocatalyst is irradiated by light, photo-generated electron-hole pairs and O are generated2And H2O and the like react to generate active groups such as superoxide radical, hydroxyl radical and the like, which causes the photocatalyst to have high photocatalytic activity, and the photocatalytic activity is not selective. This activity results in the photocatalyst being unable to control the stabilization period and degradation period in the application of plastics, and the photocatalytic activity of the photocatalyst will start as long as light is present. In order to inhibit the photocatalytic activity of the photocatalyst and ensure that the plastic has good stability in the service life, a photo-generated electron-hole consumption agent is introduced into the surface or system of the photocatalyst, and the photo-generated electron-hole consumption agent can be a photo-generated electron-hole capture agent or a reversible redox couple. The photo-generated electron-hole consumption agent reacts with the photo-generated electron-hole pairs to inhibit the photocatalytic activity of the photocatalyst. Simultaneously, a photo-generated electron-hole consumption agent complex is introduced to carry out a complex reaction with the photo-generated electron-hole consumption agent, so that the slow release and consumption of the photo-generated electron-hole consumption agent are realized, and the photocatalytic activity inhibition of the photo-generated electron-hole consumption agent is regulated and controlledAnd further realizing the regulation and control of the plastic stabilization period. Meanwhile, the inhibition and the opening of the activity of the photocatalyst are indicated through the color change from the formation of the complex structure to the destruction process. Provides the user with information whether the plastic is suitable for use, and promotes the practical application of the photocatalytic degradable plastic with the photocatalyst filling.
Compared with the prior art, the invention provides a method and a principle for preparing a photocatalytic system with a photoresponse switch and a self-indicating function. The photocatalysis system has adjustable photocatalysis activity, has no photocatalysis activity under the condition of initial illumination, presents a certain color, and has photocatalysis activity after the color changes after illumination for a period of time. The photocatalysis system can be applied to the field of plastic degradation, realizes that the plastic has good stability in the service life and high-efficiency degradation efficiency in the waste period, and simultaneously prompts whether the plastic is in the high-speed degradation period or not by color change. The technology has important significance for relieving the harm of white pollution to the environment, promoting the degradation of the traditional petrochemical plastics and improving the sustainable development of the traditional petrochemical plastics. The photocatalytic system can also be applied to other fields of photocatalysts which need to be adjustable and have self-indicating property.
Drawings
Fig. 1 is an external view of a sample 4 of a photocatalytic system of the present invention;
FIG. 2 is a schematic representation of the controlled self-indicating phenol-degrading activity of sample 4 of the photocatalytic system of the present invention;
FIG. 3 is a schematic view of the controllable self-indicating photocatalytic degradation of the controllably degradable polyethylene film sample 15 of the present invention.
Detailed Description
The present invention will be described in detail below with reference to specific examples.
Example 1
Step 1: will I2And KI according to a molar ratio I2KI =1:2, adding to 0.25g/L hydroxyethylcellulose solution (molecular weight 90000), and stirring to obtain a homogeneous solution, wherein I2The mass ratio of the cellulose to the hydroxyethyl cellulose is 1: 1. Adding anatase TiO into the mixed solution2Powder, TiO2Powders of the compounds I2The mass ratio of (A) to (B) is 1: 2. The mixture was stirred for 24h, separated by filtration and then dried in an oven at 35 ℃. Grinding to obtain I3 -/I-Modified TiO2And (3) powder.
Step 2: soaking 0.1g amylose in 1mL ethanol, adding 9mL NaOH solution (1 mol/L), heating in boiling water bath for 10min, cooling to room temperature, and diluting with water to 100mL to obtain amylose mixture with concentration of 1 mg/mL.
And step 3: adjusting the pH value of the amylose mixed solution to 6.5-7.5 by using HCl to prepare the amylose mixed solution with the pH value of 6.5-7.5.
And 4, step 4: the prepared I3 -/I-Modified TiO2Adding the powder into amylose mixed solution with pH of 6.5-7.5, stirring at room temperature for 24h, I3 -/I-Modified TiO2The mass ratio of the powder to the starch is 1: 1. The sample was separated by filtration, and then washed 3 times by centrifugation with anhydrous ethanol, and dried at 35 ℃. And grinding to obtain a photocatalytic system sample 1 with photoresponsive switch and self-indicating property.
Example 2
The difference is that I is the same as example 12And KI according to a molar ratio I2KI =1:2, 0.25g/L of a polyvinyl alcohol solution containing 2w% of acetone, I2The concentration of (2) was 0.5 g/L. A photocatalytic system sample 2 having a photoresponsive switch and self-indicating properties was prepared.
Example 3
Sample 3, which is a photocatalytic system having a photoresponsive switch and self-indicating properties, was prepared as in example 1, except that isopropanol was used instead of ethanol and 100 ℃ reflux was used instead of a boiling water bath.
Example 4
Will I2And KI according to a molar ratio I2KI =1:2, adding into 0.5g/L hydroxyethyl cellulose solution (molecular weight 90000), and stirring2The mass ratio of the cellulose to the hydroxyethyl cellulose is 1: 2. Adding TiO into the obtained mixed solution2Powder, TiO2Powders of the compounds I2The mass ratio of (A) to (B) is 1:2, and stirring. TiO 22The crystal structure is 75% anatase and 25% rutile. Adding 1mg/mL amylose mixed solution with the pH of 6.5-7.5 into the mixture, wherein the starch and the TiO are2Is stirred for 24 hours, the sample is filtered, washed for 3 times by ethanol and dried at the temperature of 35 ℃. Grinding to obtain a photocatalytic system sample 4 with a photoresponse switch and self-indicating property; the appearance of which is shown in fig. 1.
Phenol is used as a simulated pollutant, and phenol and commercial TiO are adsorbed in a dark place by a sample 42P25 photocatalytic degradation of phenol was used as a control. 0.1g of sample 4 was weighed and added to 100mL of 0.01g/L phenol solution, and the resulting mixture was placed under a xenon lamp for light test, and the degradation efficiency of phenol and the color change of the mixture were shown in FIG. 2. The results show that the phenol concentration is essentially unchanged within 10-60 minutes of the reaction, indicating no significant degradation, and that the mixture appears blue in color. After 60 minutes, the mixture became light in color and phenol degradation began, and after 5 hours the phenol degradation rate reached 55%, at which time the mixture was white. Behavior of degrading phenol and commercial TiO by photocatalyst2Comparison of the P25 degradation behavior of phenol shows that sample 4 has a light responsive switch and self indicating function.
Example 5
Will I2、KI、TiO2Adding the mixture solution of 1mg/mL amylose into 0.25g/L hydroxyethyl cellulose solution containing 0.1w% isopropanol, I2:KI:TiO2Amylose-hydroxyethyl cellulose =2:1:1:1: 0.5. Stirring for 12h at room temperature, filtering the mixture, drying at 35 ℃, and grinding to obtain a photocatalytic system sample 5 with photoresponse switch and self-indication.
Example 6
1mL of acetylacetone was added to 30mL of a nitric acid solution at a nitric acid concentration of 0.2 mol/L. A mixture of 5mL of n-tetrabutyltitanate and 5mL of ethanol was added dropwise to the nitric acid solution. Stirring for 12h to obtain transparent TiO2And (3) sol.
Will I2And KI according to a molar ratio I2KI =1:2 ratio, 500mL of 0.25g/L hydroxyethylcellulose solution (molecule)In amount 90000), stirring until homogeneous, wherein I2The mass ratio of the cellulose to the hydroxyethyl cellulose is 1: 1.
500mL of a solution containing I2Hydroxyethyl cellulose solution with KI and 3mL TiO2Mixing the sol, stirring for 1h, and refluxing at 100 deg.C for 6 h. The resulting mixture was cooled to room temperature under stirring.
Amylose-containing mixture was obtained by dispersing 0.125g of amylose in 25mL of an isopropanol solution containing 0.1mol/L of NaOH and stirring for 4 hours.
Adding the mixed solution containing amylose into the mixed solution containing TiO cooled to room temperature2The mixture of (1) was stirred for 24 hours. Centrifuging, filtering and cleaning with ethanol for three times, and drying at 35 deg.C. And grinding to obtain a photocatalytic system sample 6 with photoresponsive switch and self-indicating property.
Example 7
FeCl is added2And FeCl3Adding into hydroxyethyl cellulose water solution containing citric acid at a molar ratio of 1:1, wherein the hydroxyethyl cellulose concentration is 0.25g/L, the citric acid concentration is 0.04g/L, and Fe2+The mass ratio of the cellulose to the hydroxyethyl cellulose is 1: 1. Stirring for 4 h. Adding TiO into the obtained mixed solution2Powder, TiO2Powder and Fe2+The mass ratio of (A) to (B) is 1: 1. Dripping 1mol/L NaOH solution, NaOH and FeCl into the solution2And FeCl3The mass ratio of the components is 1:1, the mixture is stirred for 4 hours, filtered and separated, and then the mixture is put into an oven to be dried at 80 ℃. Grinding to obtain Fe2+/Fe3+Modified TiO2And (3) powder.
2,4, 6-tri (2-pyridyl) triazine is dissolved by hydrochloric acid with the concentration of 6mol/L, and 27mL of hydrochloric acid solution with the concentration of 6mol/L is needed for dissolving 1g of 2,4, 6-tri (2-pyridyl) triazine. The resulting solution was then diluted with purified water to give a solution of 2,4, 6-tris (2-pyridyl) triazine at a concentration of 0.7 g/L.
0.5g of prepared Fe2+/Fe3+Modified TiO2Adding the powder into 500mL of 2,4, 6-tri (2-pyridyl) triazine solution, stirring for 30min, centrifuging, adding 0.25g/L hydroxyethyl cellulose, stirring for 30min, drying in an oven at 60 deg.C, and grinding to obtain the final product with photoresponseSwitch, self-indicating photocatalytic system sample 7.
Example 8
FeCl is added2And FeCl3Adding into hydroxyethyl cellulose water solution containing citric acid at a molar ratio of 1:1, wherein the hydroxyethyl cellulose concentration is 0.25g/L, the citric acid concentration is 0.04g/L, and Fe2+The mass ratio of the cellulose to the hydroxyethyl cellulose is 1: 1. Stirring for 4 h. Adding TiO into the obtained mixed solution2Powder, TiO2Powder and Fe2+The mass ratio of (A) to (B) is 1: 1. Dripping 1mol/L NaOH solution, NaOH and FeCl into the solution2And FeCl3The mass ratio of the components is 1:1, the mixture is refluxed for 12 hours at 80 ℃, filtered and separated, and then the mixture is put into an oven to be dried at 80 ℃. Grinding to obtain Fe2+/Fe3+Modified TiO2And (3) powder.
0.5g of prepared Fe2+/Fe3+Modified TiO2The powder is mixed with 400mL of aqueous solution containing 0.25g/L of hydroxyethyl cellulose and 350mL of ethanol solution containing 1g/L of 2,4, 6-tri (2-pyridyl) triazine, stirred for 30 minutes, then centrifugally separated, dried in an oven at 60 ℃, and ground to prepare a photocatalytic system sample 8 with a light response switch and self-indicating property.
Example 9
FeCl is added2、FeCl3ZnO, the solution of 2,4, 6-tris (2-pyridyl) triazine prepared in example 7, was added to a solution of hydroxyethylcellulose having a concentration of 1g/L, FeCl2:FeCl3ZnO to 2,4, 6-tri (2-pyridyl) triazine solution to hydroxyethyl cellulose in a mass ratio =1:1:2:0.8: 1. Ultrasonic dispersing for 15min, and refluxing at 80 deg.C for 4 h. Filtering and separating, drying in an oven at 80 ℃, and grinding to obtain a photocatalytic system sample 9 with a photoresponse switch and self-indicating property.
Example 10
FeCl is added2And FeCl3Adding into 0.25g/L polyethylene glycol solution containing 1w% ethanol and Fe at a molar ratio of 1:12+The mass ratio of the polyethylene glycol to the polyethylene glycol is 1: 1. Stirring for 4 h. Adding TiO into the obtained mixed solution2Powder, TiO2Powder and Fe2+The mass ratio of (1):1. carrying out hydrothermal treatment for 12h at 90 ℃. The mixture was filtered and separated, and then dried in an oven at 80 ℃. Grinding to obtain Fe2+/Fe3+Modified TiO2And (3) powder.
0.5g of the obtained Fe2+/Fe3+Modified TiO2The powder was added to 300mL of a 2.5mmol/L bathophenanthroline disulfonic acid disodium salt hydrate solution, and 12.5mL of concentrated hydrochloric acid was added to the solution, followed by stirring for 30 minutes. And then centrifugally separating, adding the mixture into 500mL0.25g/L hydroxyethyl cellulose, stirring for 30 minutes, centrifugally separating, drying in an oven at 60 ℃, and grinding to obtain the photocatalytic system sample 10 with a photoresponse switch and self-indicating property.
Example 11
Mixing KBrO3And NaHCO3Adding into 0.5g/L hydroxyethyl cellulose solution, stirring, and mixing3With NaHCO3The mass ratio of (A) to (B) is 2:1, and the concentrations are 1g/L and 0.5g/L respectively. And adding 1g of ZnO powder into 500mL of the solution, stirring for 24h, filtering, separating, washing with purified water, drying in an oven at 40 ℃, and grinding to obtain a photocatalytic system sample 11 with a photoresponse switch and self-indicating property.
Example 12
Adding 0.5 TiO2Adding into 500mL of 1g/L silver nitrate solution, stirring for 1h, filtering, separating, adding the obtained powder into 500mL of 0.5g triethanolamine-containing hydroxyethyl cellulose solution with hydroxyethyl cellulose concentration of 0.25g/L, ultrasonic treating for 10min, and stirring for 30 min. Filtering, separating, drying and grinding to obtain the photocatalytic system sample 12 with photoresponse switch and self-indicating property.
Example 13
Adding 0.5 TiO2Adding into 500mL of 1g/L silver nitrate solution, stirring for 1h, filtering, separating, adding the obtained powder into 500mL of 0.5g formic acid-containing hydroxyethyl cellulose solution with hydroxyethyl cellulose concentration of 0.25g/L, ultrasonic treating for 10min, and stirring for 30 min. Filtering, separating and grinding to obtain the photocatalytic system sample 13 with photoresponsive switch and self-indicating property.
Example 14
Will I2And KI according to a molar ratio I2KI =1:2, adding to 0.25g/L hydroxyethylcellulose solution (molecular weight 90000), and stirring to obtain a homogeneous solution, wherein I2The mass ratio of the cellulose to the hydroxyethyl cellulose is 1: 1. Adding anatase TiO into the mixed solution2Powder, TiO2Powders of the compounds I2The mass ratio of (A) to (B) is 1: 2. The mixture was stirred for 24h, separated by filtration and then dried in an oven at 35 ℃. Grinding to obtain I3 -/I-Modified TiO2Powder; the photocatalyst sample 14 modified by the photocatalyst photo-generated electron-hole consuming agent is obtained.
Example 15
Polyethylene was dissolved in a cyclohexane solution at 70 ℃ to prepare a 10g/L polyethylene solution, which was stirred for 2 hours. And (3) adding the sample 4 into the solution, stirring, wherein the mass ratio of the sample 4 to the polyethylene is 0.1:1, ultrasonically dispersing for 15min, and stirring for 24 h. And coating the obtained mixed solution on the surface of the cleaned glass sheet, and drying for 1d at room temperature. The film was then peeled from the glass surface to produce controlled degradation polyethylene film sample 15.
The control sample was a polyethylene film sample 15 with controlled degradation and a pure polyethylene film prepared under the same conditions. Placing into xenon lamp aging test box at 340nm 0.7w/m2The experiment was performed under the illumination condition to test the weight loss of the film, and the results are shown in fig. 3. The results show that the polyethylene film sample 15 remained essentially of unchanged quality for 36 hours prior to the reaction, indicating no significant degradation, and the film appeared blue in color. After 36 hours, sample 15 began to fade and the polyethylene film began to degrade, and after 325 hours the film weight loss reached 27%, at which time sample 15 was white. The test result shows that the polyethylene film sample 15 has a controllable self-indicating degradation function.
Example 16
1g of polystyrene was added to 100mL of ethyl acetate and dissolved by sonication. Then, sample 3 was added to the solution, sonicated for 15min, and stirred for 12 h. The mass ratio of sample 3 to polystyrene was 0.001: 1. And coating the obtained mixed solution on the surface of the cleaned glass sheet, and drying for 2d at room temperature. The film was then peeled from the glass surface to produce a controlled degradation polystyrene film sample 16.
Example 17
1g of polyamide (PA6) was added to 100mL of formic acid solution and dissolved with stirring. Sample 1 was then added to the solution and stirred for 12 h. The mass ratio of sample 1 to polyamide was 0.01: 1. And coating the obtained mixed solution on the surface of the cleaned glass sheet, and drying for 2d at room temperature. The film was then peeled from the glass surface to produce controlled degradation polyamide film sample 17.
Example 18
1g of polypropylene was added to 100mL of xylene solution and dissolved at 120 ℃ under reflux, and then sample 5 was added to the solution and stirred for 12 hours. The mass ratio of sample 5 to polypropylene was 0.05: 1. And coating the obtained mixed solution on the surface of the cleaned glass sheet, and drying for 1d at room temperature. The film was then peeled from the glass surface to produce sample 18 of a controlled degradation polypropylene film.
Example 19
1g of polyvinyl alcohol was added to 100mL of the aqueous solution and dissolved with stirring at 95 ℃ and then sample 4 was added to the solution and stirred for 12 hours. The mass ratio of sample 4 to polyvinyl alcohol was 0.001: 1. And coating the obtained mixed solution on the surface of the cleaned glass sheet, and drying for 2d at room temperature. The film was then peeled from the glass surface to produce a controlled degradation polyvinyl alcohol film sample 19.
Example 20
1g of polyethylene glycol was added to 100mL of the aqueous solution, dissolved with stirring at room temperature, and then sample 4 was added to the solution and stirred for 12 hours. The mass ratio of sample 4 to polyethylene glycol was 0.001: 1. And coating the obtained mixed solution on the surface of the cleaned glass sheet, and drying for 2d at the temperature of 60 ℃. The film was then peeled from the glass surface to prepare a controlled degradation polyethylene glycol film sample 20.
Example 21
The same as example 20, except that isopropyl alcohol was used instead of the aqueous solution, a controlled degradation polyethylene glycol film sample 21 was prepared.
Example 22
The same as example 20, except that acetone was used instead of the aqueous solution, a controlled degradation polyethylene glycol film sample 22 was prepared.
Example 23
The same as example 20, except that ethanol was used instead of the aqueous solution, a controlled degradation polyethylene glycol film sample 23 was prepared.
Example 24
The same as example 20, except that propanol was used instead of the aqueous solution, a controlled degradation polyethylene glycol film sample 24 was prepared.
Example 25
1mL of acetylacetone was added to 30mL of a nitric acid solution at a nitric acid concentration of 0.2 mol/L. A mixture of 5mL of n-tetrabutyltitanate and 5mL of ethanol was added dropwise to the nitric acid solution. Stirring for 12h to obtain transparent TiO2And (3) sol.
Will I2And KI according to a molar ratio I2KI =1:2, to 500mL of a 0.25g/L hydroxyethylcellulose solution (molecular weight 90000), and stirring the mixture to homogeneity, wherein I2The mass ratio of the cellulose to the hydroxyethyl cellulose is 1: 1.
500mL of a solution containing I2Hydroxyethyl cellulose solution with KI and 3mL TiO2Mixing the sol, stirring for 1h, and refluxing at 100 deg.C for 6 h. Centrifuging the mixture, drying at 35 deg.C, and grinding to obtain I3 -/I-Modified TiO2And obtaining a photocatalyst sample 25 modified by the photocatalyst photo-generated electron-hole consuming agent.
Example 26
1g of polyvinyl alcohol was added to 100mL of the aqueous solution and dissolved with stirring at 95 ℃ and then 0.01g of sample 11 was added to the solution and stirred for 12 hours. And coating the obtained mixed solution on the surface of the cleaned glass sheet, and drying for 2d at room temperature. The film was then peeled from the glass surface to produce a controlled degradation polyvinyl alcohol film sample 26.
Example 27
1g of polyvinyl alcohol was added to 100mL of the aqueous solution and dissolved with stirring at 95 ℃ and then 0.02g of sample 25 was added to the solution and stirred for 12 hours. 10mL of 1mg/mL amylose mixture was added to the solution containing polyvinyl alcohol and sample 25, dispersed by ultrasound for 20min, and stirred for 12 h. The obtained mixed solution is coated on the surface of polystyrene and dried for 2 days at room temperature. A controlled degradation polyvinyl alcohol film sample 27 was prepared.
Example 28
The low density polyethylene was mixed with sample 1 at a mass ratio of sample 1 to low density polyethylene of 0.05: 1. The mixture was fed into a twin-screw extruder having L/D =40 and D =16mm, the extruder having 10 temperature-controlled zones, wherein in the extrusion direction, a mixture of the low-density polyethylene and the sample was fed into the extruder at the feed port of the first stage at a temperature of 180 ℃ at the feed ports of the first and sixth stages, respectively, and the screw was extruded at a rotational speed of 100 rpm. A controllably degradable low density polyethylene sample 28 was prepared.
Example 29
Low density polyethylene was fed to the first stage feed port of the extruder described in example 28, and extruded at 180 ℃ and 100rpm, the temperature in the first to sixth temperature control zones was 180 ℃, sample 2 was fed to the feed port of the sixth temperature control zone, and the temperature in the seventh to tenth temperature control zones was 170 ℃. The mass ratio of sample 2 to low density polyethylene was 0.05: 1. A controllably degradable low density polyethylene sample 29 was prepared.
Example 30
A sample 30 of controllably degradable low density polyethylene was prepared by mixing 100g of low density polyethylene masterbatch with 1L of a 1mg/mL amylose solution, stirring for 4h, drying at 60℃, mixing the dried masterbatch with 1g of sample 14, feeding the mixture into the first stage feed port of the extruder described in example 27, and extruding at 100rpm at 180℃.
Example 31
1000g of low density polyethylene master batch was mixed with 10L of 1mg/mL amylose solution, stirred for 4h, dried at 60 ℃ and the dried product was extruded at 100rpm at 180 ℃ from the first section feed inlet of the extruder described in example 27, with the temperature of the first to sixth temperature control zones being 180 ℃ and the sample 25 being added at the feed inlet of the sixth temperature control zone and the temperature of the seventh to tenth temperature control zones being 170 ℃. The mass ratio of sample 25 to low density polyethylene was 0.05: 1. A controllably degradable low density polyethylene sample 31 was prepared.
Example 32
The same as example 1 except that ZnO was used in place of TiO2A photocatalytic system sample 32 having a photoresponsive switch and self-indicating properties was prepared.
Example 33
The difference from example 1 is that NiO is used instead of TiO2A photocatalytic system sample 33 having a photoresponsive switch and self-indicating properties was prepared.
Example 34
The difference from example 1 is that SrTiO is used3Replacement of TiO2A photocatalytic system sample 34 having a photoresponsive switch, self-indicating, was prepared.
Example 35
The difference from example 1 is that KTaO was used3Replacement of TiO2A sample 35 of a photocatalytic system having a photoresponsive switch and self-indicating properties was prepared.
Example 36
The difference from example 1 is that K is used4Nb6O17Replacement of TiO2A photocatalytic system sample 36 having a photoresponsive switch and self-indicating properties was prepared.
Example 37
The same as example 1 except that BaTiO was used3Replacement of TiO2A sample of a photocatalytic system having a photoresponsive switch and self-indicating properties was prepared 37.
Example 38
The same as example 1 except that silver modified TiO having visible light activity was used2Replacement of TiO2A photocatalytic system sample 38 having a photoresponsive switch, self-indicating, was prepared.
Example 39
The same as example 1 except that nitrogen-modified ZnO having visible light activity was used in place of TiO2A photocatalytic system sample 39 having a photoresponsive switch and self-indicating properties was prepared.
Example 40
The difference from example 1 is that SiC was used instead of SiCBy replacing TiO2A sample of a photocatalytic system 40 having a photoresponsive switch and self-indicating properties is prepared.
EXAMPLE 41
The difference from example 1 is that CdSe is used instead of TiO2A photocatalytic system sample 41 having a photoresponsive switch and self-indicating properties was prepared.
Example 42
The difference from example 1 is that Fe is used2O3Replacement of TiO2A photocatalytic system sample 42 having a photoresponsive switch and self-indicating properties is prepared.
Example 43
The difference from example 1 is that WO is used3Replacement of TiO2A photocatalytic system sample 43 having a photoresponsive switch and self-indicating properties was prepared.
Example 44
The difference from example 1 is that Bi is used4Ti3O12Replacement of TiO2A sample 44 of a photocatalytic system having a photoresponsive switch and self-indicating properties was prepared.
Example 45
The difference from example 1 is that Ce is used2O3Replacement of TiO2A sample 45 of a photocatalytic system having a photoresponsive switch and self-indicating properties was prepared.
Example 46
The difference from example 1 is that Cu is used2Substitution of O for TiO2A sample 46 of a photocatalytic system having a photoresponsive switch and self-indicating properties was prepared.
Example 47
The difference from example 1 is that In is used2O3Replacement of TiO2A photocatalytic system sample 47 having a photoresponsive switch and self-indicating properties was prepared.
Example 48
The difference from example 1 is that CaFe is used2O4Replacement of TiO2A photocatalytic system sample 48 having a photoresponsive switch and self-indicating properties was prepared.
Example 49
The difference from example 1 is that YFeO is used3Replacement of TiO2A sample 49 of a photocatalytic system having a photoresponsive switch and self-indicating properties was prepared.
Example 50
The difference from example 1 is that BiMoO was used6Replacement of TiO2A sample of a photocatalytic system 50 having a photoresponsive switch and self-indicating properties is prepared.
Example 51
The difference from example 1 is that BiVO was used4Replacement of TiO2A sample 51 of a photocatalytic system having a photoresponsive switch and self-indicating properties was prepared.
Example 52
The difference from example 1 is that InVO is used4Replacement of TiO2A photocatalytic system sample 52 having a photoresponsive switch, self-indicating, is prepared.
Example 53
The difference from example 1 is that MoS is used2Replacement of TiO2A photocatalytic system sample 53 having a photoresponsive switch and self-indicating properties was prepared.
Example 54
The difference from example 1 is that AgIn is used5S5Replacement of TiO2A photocatalytic system sample 54 with photoresponsive switching, self-indicating properties was prepared.
Example 55
Same as example 1, except that CdS was used instead of TiO2A sample 55 of a photocatalytic system with photoresponsive switching, self-indicating properties was prepared.
Example 56
The difference from example 1 is that Ce is used2S3Replacement of TiO2A photocatalytic system sample 56 having a photoresponsive switch, self-indicating, was prepared.
Example 57
The difference from example 1 is that CuIn is used5S2Replacement of TiO2Preparation of lightSample photocatalytic system 57 that responds to switching, self-indicating.
Example 58
The difference from example 1 is that In is used2S3Replacement of TiO2A photocatalytic system sample 58 having a photoresponsive switch and self-indicating properties was prepared.
Example 59
The same as example 1 except that TaON was used in place of TiO2A photocatalytic system sample 59 having a photoresponsive switch and self-indicating properties was prepared.
Example 60
The difference from example 1 is that C is used3N4Replacement of TiO2A sample 60 of a photocatalytic system having a photoresponsive switch and self-indicating properties was prepared.
Example 61
The difference from example 1 is that Ta3N5Replacement of TiO2A photocatalytic system sample 61 having a photoresponsive switch and self-indicating properties was prepared.
Example 62
The difference from example 1 is that LaTiO is used2Substitution of TiO by N2A photocatalytic system sample 62 having a photoresponsive switch and self-indicating properties was prepared.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles and protocols described herein may be applied to other embodiments without the use of inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (11)
1. The photocatalysis system is characterized by comprising the following raw materials in parts by weight:
1) 1 part of a photocatalyst; the photocatalyst consists of one or more of the following photocatalysts:
ultraviolet light responsive TiO2、ZnO、NiO、SrTiO3、KTaO3、K4Nb6O17And BaTiO3；
Visible light responsive modified TiO2Modified ZnO, SiC and CdSe;
oxides containing one or several of the following elements: fe. W, Bi, Ti, Ce, Cu, In, Ca, Y, Mo and V;
sulfides containing one or several of the following elements: mo, Ag, In, Cd, Ce and Cu;
nitrides containing one or several of the following elements: ta, O, C, La and Ti;
2) 0.01-10 parts of photocatalyst photo-generated electron-hole consuming agent; the photocatalyst photo-generated electron-hole consumption agent is a reversible redox couple or a photo-generated electron-hole couple trapping agent;
3) 0.00-20 parts of a photo-generated electron-hole consuming agent complex; the photo-generated electron-hole consuming agent complex comprises starch and a metal ion chelating agent; wherein:
the photo-response switch is characterized in that under the illumination of initial sunlight, a photo-induced electron-hole consumption agent of a photocatalyst in a photocatalytic system plays a role in inhibiting the photocatalytic activity of the photocatalyst, so that even if the photocatalyst generates photo-induced electron-hole pairs under the illumination, the photocatalyst cannot play the photocatalytic activity on substances outside the photocatalytic system; after 0.5 hour to 90 days of illumination, the photo-generated electron-hole consumption agent in the photo-catalytic system is invalid, and photo-generated electron-hole pairs generated by the photocatalyst can perform photo-catalytic action on substances outside the photo-catalytic system;
the self-indicating property is that when the photocatalytic system can not exert photocatalytic activity on substances outside the system, the self-indicating property has the following color: brown, purple, brown, orange, yellow, green, blue, bluish violet or purple red, and the color of the photocatalytic system changes to one of the following colors after 0.5 hours to 90 days of sunlight illumination: the photocatalyst system after color change has the function of playing the photocatalytic activity on substances outside the system;
the TiO is2Including anatase, rutile, brookite, and amorphous; the ZnO comprises a hexagonal wurtzite structure, a cubic sphalerite structure, a cubic rock salt structure and an amorphous structure; the modified TiO2The modified ZnO is modified by one or more modification methods of metal element modification, nonmetal element modification, metal element/nonmetal element co-modification and dye sensitization; TiO 22And ZnO can be in powder, block, film or sol form, and can also be in nanowire, nanotube, nanosphere or nanometer irregular shape;
the oxide containing one or several elements includes: fe2O3、WO3、Bi4Ti3O12、Ce2O3、Cu2O、In2O3、CaFe2O4、YFeO3、BiMoO6、BiVO4And InVO4(ii) a The sulfide containing one or several elements includes: MoS2、AgIn5S5、CdS、Ce2S3、CuIn5S2And In2S3(ii) a The nitride containing one or several elements includes: TaON, C3N4、Ta3N5And LaTiO2N；
The reversible redox couple includes: i is3 -/I-、I2/I-And Fe2+/Fe3+(ii) a The photogenerated electron-hole pair trapping agent comprises: AgNO3Formic acid, AgNO3Triethanolamine and KBrO3-sodium bicarbonate;
the metal ion chelating agent includes: 2,4, 6-tris (2-pyridyl) triazine and bathophenanthroline disulfonic acid disodium salt hydrate;
the photocatalytic system is prepared by adopting a layer-by-layer modification method, a codeposition method or a photocatalyst sol method.
2. A method for preparing the photocatalytic system according to claim 1, wherein the photocatalytic system is prepared by a layer-by-layer modification method, comprising the following steps:
step 1: adding a photocatalyst photo-generated electron-hole consumption agent into the solution, and stirring for 0.5 h-2 days at the temperature of 0-200 ℃; wherein the concentration of the photocatalyst photo-generated electron-hole consumption agent is 0.01-30 g/L; the solution is formed by mixing water with a polymer, or mixing water with citric acid and a polymer, or mixing water with an organic solvent and a polymer; the concentration of the polymer in the mixed solution of water and the polymer is 0.01-1.0 g/L; in the mixed solution of water, citric acid and polymer, the concentration of the citric acid is 0.00001-30g/L, and the concentration of the polymer is 0.01-1.0 g/L; in the mixed solution of water, organic solvent and polymer, the concentration of the polymer is 0.01-2.0g/L, and the concentration of the organic solvent is 5-300 g/L; the organic solvent is isopropanol, cyclohexane, acetone or ethanol; the polymer is hydroxyethyl cellulose, polyvinyl alcohol or polyethylene glycol; the photocatalyst photo-generated electron-hole consumption agent is a reversible redox couple or a photo-generated electron-hole couple trapping agent;
step 2: adding photocatalyst powder into the photocatalyst photo-generated electron-hole consuming agent mixed solution prepared in the step 1, stirring, refluxing or hydro-thermal treating for 0.5 h-2 days at the temperature of 0-200 ℃, or dropwise adding NaOH solution while stirring at the temperature of 0-200 ℃, filtering, and drying at the temperature of 25-200 ℃ to obtain powder; wherein the concentration of the NaOH solution is 1-160g/L, and the mass ratio of the NaOH to the photo-generated electron-hole consumption agent is 0.5-4: 1; the mass ratio of the photocatalyst to the photocatalyst photo-generated electron-hole consumption agent is 1: 0.01-10;
and step 3: adding the powder obtained in the step 2 into a mixed system consisting of a photo-generated electron-hole consuming agent complex and water, ethanol or a water-containing mixed solution, stirring and refluxing for 0.5 hour to 2 days at the temperature of 0 to 200 ℃, separating, adding into a water solution containing a polymer, stirring for 0 to 2 hours, separating, and drying at the temperature of 25 to 200 ℃ to obtain the photocatalytic system; wherein the concentration of the photo-generated electron-hole consuming agent complex is 0.01-10 w%; the aqueous mixed solution contains one or more of the following components: organic solvents, hydrochloric acid; if the aqueous mixed solution is mixed by water and an organic solvent, the volume ratio of the organic solvent to the water is 0.05-5:100, if the aqueous mixed solution is mixed by water and hydrochloric acid, the concentration of the hydrochloric acid is 0.05-1 mol/L; the organic solvent is isopropanol or ethanol; the polymer-containing aqueous solution has the concentration of 0.01-2.0 g/L; the polymer is selected from one of the following polymers: hydroxyethyl cellulose, polyvinyl alcohol or polyethylene glycol; the mass ratio of the photo-generated electron-hole consuming agent complex to the powder obtained in the step 2 is 0.00-20: 1; the photo-generated electron-hole consuming agent complex includes, but is not limited to, starch and metal ion chelating agents.
3. A process for the preparation of the photocatalytic system according to claim 1, characterized by the fact that it is prepared by codeposition, with the following steps:
step 1: adding the photocatalyst, the photocatalyst photo-generated electron-hole consumption agent and the photo-generated electron-hole consumption agent complex into the solution for mixing, and carrying out stirring or reflux treatment at the temperature of 0-200 ℃ for 0.5 h-2 days; the solution consists of one or more of the following substances: water, organic solvents, polymers, hydrochloric acid and citric acid; if the solution consists of water and polymer, the concentration of the polymer is 0.01-1.0 g/L; if the solution consists of water, organic solvent and polymer, the concentration of the polymer is 0.01-2.0g/L, and the concentration of the organic solvent is 0.1-300 g/L; if the solution consists of water, polymer and hydrochloric acid, the concentration of the hydrochloric acid is 0.01-0.8mol/L, and the concentration of the polymer is 0.01-2.0 g/L; if the solution consists of water, polymer and citric acid, the concentration of the citric acid is 0.00001-30g/L, and the concentration of the polymer is 0.01-2.0 g/L; wherein the mass ratio of the photocatalyst to the photocatalyst photogenerated electron-hole consumption agent to the photogenerated electron-hole consumption agent complex is 1:0.01-10: 0.00-20; the concentration of the photocatalyst is 0.01-15 g/L; the organic solvent is isopropanol, cyclohexane, acetone or ethanol, and the polymer is hydroxyethyl cellulose, polyvinyl alcohol or polyethylene glycol;
step 2: filtering the mixture, and drying at 25-200 ℃ to obtain the photocatalytic system.
4. A process for the preparation of the photocatalytic system according to claim 1, characterized by using a photocatalyst sol, which comprises the following steps:
step 1: mixing one or two photocatalyst precursors with absolute ethyl alcohol, stirring for 0.1-4h, controlling the temperature to be 25-100 ℃, dropwise adding the obtained mixed solution into a mixed solution containing water, and stirring for 0.5-72h to obtain photocatalyst sol; the photocatalyst precursor includes: titanium alkoxide and zinc acetate, wherein the molar concentration of the titanium alkoxide and the zinc acetate is 0.5-2.5 mol/L; the mixed solution containing water comprises one or more of the following substances: water, acetylacetone, and an acid; the concentration of acetylacetone is 0.1-1.0mol/L, the concentration of acid is 0.1-1.0 mol/L; the volume ratio of the photocatalyst precursor to water is 1: 0.5-60; the acid is acetic acid, hydrochloric acid or nitric acid;
step 2: adding a photocatalyst photo-generated electron-hole consumption agent into the solution, and stirring for 0.5 h-2 days at the temperature of 0-200 ℃; wherein the concentration of the photocatalyst photo-generated electron-hole consumption agent is 0.01-30 g/L; the solution is formed by mixing water with a polymer, or mixing water with citric acid and a polymer, or mixing water with an organic solvent and a polymer; water and polymer mixed solution, the concentration of the polymer is 0.01-1.0 g/L; in the mixed solution of water, citric acid and polymer, the concentration of the citric acid is 0.00001-30g/L, and the concentration of the polymer is 0.01-1.0 g/L; mixing water, organic solvent and polymer, wherein the concentration of the polymer is 0.01-2.0g/L, and the concentration of the organic solvent is 5-300 g/L; the organic solvent is isopropanol, cyclohexane, acetone or ethanol; the polymer is hydroxyethyl cellulose, polyvinyl alcohol or polyethylene glycol; mixing the obtained mixed solution with photocatalyst sol, and stirring or refluxing at 0-200 deg.C for 0.5 hr-2 days; wherein the mass ratio of the photocatalyst photo-generated electron-hole consumption agent to the photocatalyst precursor in the photocatalyst sol is 0.001-7: 1;
and step 3: adding the photo-generated electron-hole consuming agent complex into a mixed system consisting of water, ethanol or a water-containing mixed solution, stirring and refluxing for 0.5 h-2 days at the temperature of 0-200 ℃, separating, adding into a water solution containing a polymer, stirring for 0-2h, separating, and drying at the temperature of 25-200 ℃; the aqueous mixed solution contains one or more of the following components: organic solvents, hydrochloric acid; if the water-containing mixed liquid is the mixture of water and an organic solvent, the volume of the organic solvent is 0.05-5%; if water is mixed with hydrochloric acid, the concentration of the hydrochloric acid is 0.05-1 mol/L; the organic solvent is isopropanol or ethanol; the polymer-containing aqueous solution has the concentration of 0.01-2.0 g/L; the polymer is selected from one of the following polymers: hydroxyethyl cellulose, polyvinyl alcohol or polyethylene glycol; the concentration of the photo-generated electron-hole consuming agent complex is 0.01-10 w%;
and 4, step 4: adding the mixture prepared in the step 3 into the mixture prepared in the step 2, and stirring or refluxing for 0.5 hour-2 days at the temperature of 0-200 ℃; wherein the mass ratio of the photo-generated electron-hole consuming agent complex to the photocatalyst precursor in the photocatalyst sol is 0.00-15: 1;
and 5: filtering the mixture, and drying at 25-200 ℃ to obtain the photocatalytic system.
5. The photocatalysis system is characterized by comprising the following raw materials in parts by weight:
1 part of photocatalyst modified by photo-generated electron-hole consumption agent;
0.00-20 parts of a photo-generated electron-hole consuming agent complex; wherein:
the photocatalyst modified by the photo-generated electron-hole consumption agent comprises the following preparation steps:
step 1: adding a photocatalyst and a photocatalyst photo-generated electron-hole consumption agent into the solution for mixing, and stirring or refluxing for 0.5 h-2 days at the temperature of 0-200 ℃, or dropwise adding a NaOH solution under stirring at the temperature of 0-200 ℃, wherein the concentration of the NaOH solution is 1-160g/L, and the mass ratio of NaOH to the photo-generated electron-hole consumption agent is 0.5-4: 1; the solution consists of one or more of the following substances: water, organic solvents, polymers and citric acid; if the solution consists of water and polymer, the concentration of the polymer is 0.01-1.0 g/L; if the solution consists of water, organic solvent and polymer, the concentration of the polymer is 0.01-2.0g/L, and the concentration of the organic solvent is 0.1-300 g/L; if the solution consists of water, citric acid and polymer, the concentration of the citric acid is 0.00001-30g/L, and the concentration of the polymer is 0.01-1.0 g/L; the organic solvent is isopropanol, cyclohexane, acetone or ethanol, and the polymer is hydroxyethyl cellulose, polyvinyl alcohol or polyethylene glycol; the mass ratio of the photocatalyst to the photo-generated electron-hole consumption agent is 1: 0.01-10; the concentration of the photocatalyst is 0.01-15 g/L;
step 2: filtering the mixture, and drying at 25-200 ℃ to obtain the photocatalyst modified by the photocatalyst photo-generated electron-hole consumption agent;
the photo-generated electron-hole consuming agent complex comprises starch and a metal ion chelating agent; the metal ion chelating agent includes: 2,4, 6-tris (2-pyridyl) triazine and bathophenanthroline disulfonic acid disodium salt hydrate.
6. The photocatalytic system of claim 5, wherein the photocatalyst is a photocatalyst modified by an electron-hole consuming agent, and is prepared by the steps of:
step 1: mixing one or two photocatalyst precursors with ethanol, stirring for 0.1-4h, controlling the temperature to be 25-100 ℃, dropwise adding the obtained mixed solution into a mixed solution containing water, and stirring for 0.5-72h to obtain photocatalyst sol; the photocatalyst precursor includes, but is not limited to: titanium alkoxide and zinc acetate, wherein the molar concentration of the titanium alkoxide and the zinc acetate is 0.5-2.5 mol/L; the mixed solution containing water comprises one or two or more of the following substances: water, acetylacetone, acid; the concentration of acetylacetone is 0.1-1.0mol/L, the concentration of acid is 0.1-1.0 mol/L; the volume ratio of the photocatalyst precursor to water is 1: 0.5-60; the acid is acetic acid, hydrochloric acid or nitric acid;
step 2: adding a photocatalyst photo-generated electron-hole consumption agent into the solution, and stirring for 0.5 h-2 days at the temperature of 0-200 ℃; wherein the concentration of the photocatalyst photo-generated electron-hole consumption agent is 0.01-30 g/L; the solution is formed by mixing water with a polymer, or mixing water with citric acid and a polymer, or mixing water with an organic solvent and a polymer; water and polymer mixed solution, the concentration of the polymer is 0.01-1.0 g/L; in the mixed solution of water, citric acid and polymer, the concentration of the citric acid is 0.00001-30g/L, and the concentration of the polymer is 0.01-1.0 g/L; mixing water, organic solvent and polymer, wherein the concentration of the polymer is 0.01-2.0g/L, and the concentration of the organic solvent is 5-300 g/L; the organic solvent is isopropanol, cyclohexane, acetone or ethanol; the polymer is hydroxyethyl cellulose, polyvinyl alcohol or polyethylene glycol; mixing the obtained mixed solution with photocatalyst sol, and stirring or refluxing at 0-200 deg.C for 0.5 hr-2 days; wherein the mass ratio of the photocatalyst photo-generated electron-hole consumption agent to the photocatalyst precursor in the photocatalyst sol is 0.001-7: 1;
and step 3: and (3) filtering the mixture obtained in the step (2), and drying at 25-200 ℃ to obtain the photocatalyst modified by the photocatalyst photo-generated electron-hole consumption agent.
7. Use of the photocatalytic system according to claim 1 or 5 in the field of the controlled degradation of plastics.
8. The application according to claim 7, characterized by comprising the following specific steps:
step 1: dissolving plastic in water or one of the following organic solvents at 0-150 ℃: isopropanol, cyclohexane, acetone, ethanol, propanol, ethyl acetate, xylene or formic acid; the plastic comprises: polyethylene, polystyrene, polypropylene, polyamide, polyvinyl alcohol, and polyethylene glycol; the concentration of the plastic is 1-20 g/L; wherein the organic solvent for dissolving the polyethylene is cyclohexane; the organic solvent for dissolving the polystyrene is ethyl acetate; the organic solvent for dissolving the polyamide is formic acid; the organic solvent for dissolving the polypropylene is dimethylbenzene; the solvent for dissolving the polyvinyl alcohol is water; solvents for dissolving polyethylene glycol include water, isopropanol, acetone, ethanol and propanol;
step 2: adding the photocatalytic system to the solution containing the plastic in the step 1, wherein the mass ratio of the photocatalytic system to the plastic is 0.001-0.8;
and step 3: mixing at 25-200 deg.C for 0.5 hr-2 days;
and 4, step 4: coating the mixture prepared in the step 3 on a substrate, and drying at 25-200 ℃ to obtain a controllable degradation plastic product, wherein the plastic product has one of the following colors: brown, purple, brown, orange, yellow, green, blue, bluish violet or purple red, the weight loss of the plastic is 0.01-10% within 0.5-90 days of sunlight illumination, and the color of the plastic changes into one of the following colors after 0.5-90 days of sunlight illumination: the weight loss rate of the plastic product with changed color, blue black, orange red, yellow, blue purple or white, can be improved to 70-100% after the plastic product is continuously illuminated for 0.5h-90 days; the plastic product is taken as a coating on the surface of the substrate or is stripped from the substrate to independently exist; when the plastic product is used as a coating, the substrate is selected from the group consisting of polyethylene, polystyrene, polypropylene, polyamide, glass and quartz; when the plastic article is present alone, the substrate is selected from glass, quartz, and low surface energy polymers; wherein the low surface energy polymer comprises: polyvinylidene fluoride, polytetrafluoroethylene, and ethylene-tetrafluoroethylene copolymer.
9. The application according to claim 7, characterized by comprising the following specific steps:
step 1: mixing a photocatalytic system with plastic particles, wherein the mass ratio of the photocatalytic system to the plastic particles is 0.001-0.8;
step 2: preparing a controllably degradable plastic article by extrusion using an extruder at a temperature of from 50 ℃ to 280 ℃, said plastic article having one of: brown, purple, brown, orange, yellow, green, blue, bluish violet or purple red, the weight loss of the plastic is 0.01-10% within 0.5-90 days of sunlight illumination, and the color of the plastic changes into one of the following colors after 0.5-90 days of sunlight illumination: the weight loss rate of the plastic product with changed color, blue black, orange red, yellow, blue purple or white, can be improved to 70-100% after the plastic product is continuously illuminated for 0.5h-90 days; wherein, the mixing mode of the photocatalysis system and the plastic particles is as follows:
the photocatalytic system and the plastic particle mixture are added into an extruder; or,
the plastic particles are firstly added into an extruder, and a photocatalysis system is added at the middle end of the extruder.
10. The application according to claim 7, characterized by comprising the following specific steps:
step 1: dissolving plastic in water or one of the following organic solvents at 0-150 ℃: isopropanol, cyclohexane, acetone, ethanol, propanol, ethyl acetate, xylene or formic acid; the plastic comprises: polyethylene, polystyrene, polypropylene, polyamide, polyvinyl alcohol, and polyethylene glycol; the concentration of the plastic is 1-20 g/L; wherein the organic solvent for dissolving the polyethylene is cyclohexane; the organic solvent for dissolving the polystyrene is ethyl acetate; the organic solvent for dissolving the polyamide is formic acid; the organic solvent for dissolving the polypropylene is dimethylbenzene; the solvent for dissolving the polyvinyl alcohol is water; solvents for dissolving polyethylene glycol include water, isopropanol, acetone, ethanol and propanol;
step 2: adding a photocatalyst modified by a photocatalyst photo-generated electron-hole consumption agent into the solution containing the plastic in the step 1, wherein the mass ratio of the photocatalyst modified by the photocatalyst photo-generated electron-hole consumption agent to the plastic is 0.001-0.8;
and step 3: adding the photo-generated electron-hole consuming agent complex into water, ethanol or a water-containing mixed solution, and stirring to form a mixed system; wherein, the aqueous mixed solution contains one or more of the following components: organic solvents, hydrochloric acid; if the water-containing mixed liquid is the mixture of water and an organic solvent, the volume of the organic solvent is 0.05-5%; if water is mixed with hydrochloric acid, the concentration of the hydrochloric acid is 0.05-1 mol/L; the organic solvent is isopropanol or ethanol; the concentration of the photo-generated electron-hole consuming agent complex is 0.01-10 w%;
and 4, step 4: adding the liquid/suspension containing the photo-generated electron-hole consuming agent complex prepared in the step 3 into the mixture in the step 2; the mass ratio of the photoproduction electron-hole consumption agent complex to the plastic is 0.00-0.8;
and 5: mixing at 25-200 deg.C for 0.5 hr-2 days;
step 6: coating the mixture prepared in the step 5 on a substrate, and drying at 25-200 ℃ to obtain a controllable degradation plastic product, wherein the plastic product has one of the following colors: brown, purple, brown, orange, yellow, green, blue, bluish violet or purple red, the weight loss of the plastic is 0.01-10% within 0.5-90 days of sunlight illumination, and the color of the plastic changes into one of the following colors after 0.5-90 days of sunlight illumination: the weight loss rate of the plastic product with changed color, blue black, orange red, yellow, blue purple or white, can be improved to 70-100% after the plastic product is continuously illuminated for 0.5h-90 days; the plastic product is taken as a coating on the surface of the substrate or is stripped from the substrate to independently exist; when the plastic product is used as a coating, the substrate is selected from the group consisting of polyethylene, polystyrene, polypropylene, polyamide, glass and quartz; when the plastic article is present alone, the substrate is selected from glass, quartz, and low surface energy polymers; wherein the low surface energy polymer comprises: polyvinylidene fluoride, polytetrafluoroethylene, and ethylene-tetrafluoroethylene copolymer.
11. The application according to claim 7, characterized by comprising the following specific steps:
step 1: adding the photo-generated electron-hole consuming agent complex into water, ethanol or a water-containing mixed solution, and stirring to form a mixed system; wherein the concentration of the photo-generated electron-hole consuming agent complex is 0.01-10 w%; the aqueous mixed solution contains one or more of the following components: organic solvents, hydrochloric acid; if the water-containing mixed liquid is the mixture of water and an organic solvent, the volume of the organic solvent is 0.05-5%; if water is mixed with hydrochloric acid, the concentration of the hydrochloric acid is 0.05-1 mol/L; the organic solvent is isopropanol and ethanol;
step 2: mixing plastic particles with the liquid obtained in the step (1), stirring for 0.5-12 h, and drying to prepare a photoproduction electron-hole consuming agent complex/plastic particle mixture; wherein the mass ratio of the photo-generated electron-hole consuming agent complex to the plastic particles is 0.00-0.8: 1;
and step 3: adding the photocatalyst modified by the photocatalyst photo-generated electron-hole consumption agent and the particle mixture prepared in the step (2) into an extruder, and extruding at the temperature of 50-280 ℃ to prepare a controllably degradable plastic product; the plastic product has one of the following colors: brown, purple, brown, orange, yellow, green, blue, bluish violet or purple red, the weight loss of the plastic is 0.01-10% within 0.5-90 days of sunlight illumination, and the color of the plastic changes into one of the following colors after 0.5-90 days of sunlight illumination: the weight loss rate of the plastic product with changed color, blue black, orange red, yellow, blue purple or white, can be improved to 70-100% after the plastic product is continuously illuminated for 0.5h-90 days; wherein the mass ratio of the photocatalyst modified by the photocatalyst photo-generated electron-hole consumption agent to the photo-generated electron-hole consumption agent complex/plastic particle mixture is 0.001-0.8: 1;
the photocatalyst modified by the photocatalyst photo-generated electron-hole consumption agent and the mixture of the photo-generated electron-hole consumption agent complex and the plastic particles are mixed in the following mode:
adding the photocatalyst modified by the photocatalyst photo-generated electron-hole consumption agent, the photo-generated electron-hole consumption agent complex and the plastic particle mixture into an extruder; or,
the mixture of the photo-induced electron-hole consumption agent complex and the plastic particles is firstly added into an extruder, and the photocatalyst modified by the photo-induced electron-hole consumption agent is added at the middle end of the extruder.
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