CN115889400B - Method for degrading PET plastic by photocatalysis - Google Patents
Method for degrading PET plastic by photocatalysis Download PDFInfo
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
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Abstract
The scheme belongs to the application field of photocatalysis, and particularly discloses a method for degrading PET (polyethylene terephthalate) plastic by photocatalysis, wherein the method is realized by alkali treatment, codeposition and photocatalysis, a catalyst of the photocatalysis is gradient alloy quantum dots modified by hexafluorophosphate, and an activator of the photocatalysis is palladium ions. The method for degrading PET plastic by using hexafluorophosphate modified gradient alloy quantum dots as the catalyst and palladium ions as the activating agent through illumination has the advantages of simple process, convenient operation, easy recovery, repeated utilization, high treatment efficiency, high degradation rate and the like, and has good application prospect in the actual treatment of plastic pollutants.
Description
Technical Field
The invention belongs to the field of photocatalysis application, and in particular relates to a method for degrading PET plastics by photocatalysis.
Background
Photocatalysis is an environment-friendly technology which uses solar energy as reaction driving energy, and has more and more important application prospects in the fields of energy and environment. In recent years, plastics have become widely used products worldwide due to their light weight, humanized design, chemical resistance, good thermal stability, and excellent electrical insulation properties. At present, most of huge amounts of plastic waste reserved in human production are accumulated in landfill sites or natural environments. A large amount of plastic is discharged into the natural environment through various routes, 21% to 42% of the plastic is deposited in landfills, and only 6% to 26% of the plastic is recycled. Existing methods of treating waste plastic materials include thermal degradation, catalytic degradation, mechanical degradation, chemical degradation, ozone oxidative degradation, and photo-oxidative degradation. These methods have various disadvantages, some of which produce contaminants, some of which consume large amounts of energy, and some of which waste resources. However, photocatalytic degradation is the utilization of abundant renewable solar energy, so photocatalytic degradation of polymers is energy efficient and inexpensive.
In recent years, quantum dots have become the first photosensitizer as a new generation of light emitting materials because of their high absorption coefficient, wide light absorption range, enhanced light stability, and ability to generate multiple excitons. Therefore, sensitization of the quantum dots to the semiconductor and quantum dot-based hybrid nanostructures facilitates the generation, separation and transport of carriers, thereby improving the photoelectrochemical response. The great interest from scientific research and industry has driven the practical application of quantum dots in various fields, such as solar cells, light emitting devices, and biomedical fields. Compared with the general quantum dots, the gradient alloy quantum dots have wider light absorption range and stronger light response intensity.
Plastics are synthetic polymers that are difficult to degrade under natural environmental conditions because of their high molecular mass density, and plastics take 250 to 500 years to degrade naturally, whereas chemical degradation often requires additional energy or can cause secondary pollution. Water pollution by micro-and nano-plastics, resulting from degradation of larger plastic fragments or direct release of cosmetic or cleaning products, has become a significant environmental and public health problem. In recent years, a method of solving the problem of white pollution has been sought.
Disclosure of Invention
In view of the above, the present invention aims to overcome at least one of the disadvantages in the prior art, and provides a method for degrading PET plastics by photocatalysis, wherein hexafluorophosphate modified gradient alloy quantum dots are used as catalysts, palladium ions are used as activators, and the method for degrading PET plastics by photocatalysis has the advantages of simple process, convenient operation, easy recovery, reusability, high treatment efficiency, high degradation rate and the like, and has good application prospects in the practical treatment of plastic pollutants.
In order to solve the technical problems, the following technical scheme is adopted: the invention provides a method for degrading PET plastics by photocatalysis, which is characterized in that the degradation of PET plastics is realized by alkali treatment, codeposition and photocatalysis in sequence, wherein a photocatalysis catalyst is hexafluorophosphate modified gradient alloy quantum dots, and a photocatalysis activator is palladium ions.
The invention provides a method for degrading PET plastics by photocatalysis, which comprises the steps of firstly carrying out alkali treatment and codeposition, and finally adopting gradient alloy quantum dots modified by hexafluorophosphate (PF - 6) as a novel photocatalyst, wherein palladium ions are used as an activating agent to activate polymers, degrading PET plastics by illumination, and effectively removing pollutants of the PET plastics and converting the pollutants into valuable industrial raw materials. The method provided by the invention has the advantages of simple process, convenient operation, easy recovery, repeated use, high treatment efficiency, high degradation rate and the like, and has good application prospect in the actual treatment of plastic pollutants. And the palladium ions used in the invention can be reduced into palladium solid finally for recovery, and the recovery rate of palladium is high.
The method for degrading PET plastic by photocatalysis comprises the following steps:
S1, carrying out alkali treatment on PET plastic;
S2, preparing a chloropalladite solution;
s3, co-depositing the PET plastic subjected to the alkali treatment of S1 and the chloropalladite solution prepared by S2;
s4, preparing hexafluorophosphate modified gradient alloy quantum dots;
s5, adopting gradient alloy quanta modified by hexafluorophosphate as a catalyst, and carrying out photocatalytic degradation on the product treated by the S3.
Further, the step S1 specifically includes: cutting PET plastic into small blocks of 0.8-2cm 2, adding into NaOH solution with concentration of 8-11mol/L, stirring at 35-80deg.C, reacting for 40-80 hr, taking out, centrifuging at 6000-10000rpm for 5-20min, oven drying at 60-75deg.C, and grinding to obtain plastic powder.
Further, the step S2 specifically includes: adding palladium chloride into deionized water, dropwise adding hydrochloric acid into the solution, controlling the ratio of the palladium chloride to the hydrogen chloride substance to be 1 (2-2.5), stirring the solution for 40-80min, and obtaining the palladium chloride acid solution with the concentration of 20-50mmol/L after constant volume.
Further, the step S3 specifically includes: adding the plastic powder in the step S1 into deionized water, adding the chloropalladite solution prepared in the step S2, adding 25% -35% hydrogen peroxide, stirring at 90-105 ℃, evaporating the solution, collecting and grinding the powder into powder containing palladium ions, wherein the ratio of the mass of the plastic powder, the volume of ionized water, the volume of the chloropalladite solution and the volume of hydrogen peroxide is controlled to be (0.4-0.7) g: (8-13) mL: (8-17) mL: (8-13) mL.
In the technical scheme, the hydrogen peroxide with the concentration of 25-35% is used for oxidizing the plastic powder, and the reverse reaction of alkali treatment in the step S1 is reduced.
Further, the step S4 specifically includes: dispersing gradient alloy quantum dots in ethyl acetate to obtain a solution A, wherein the volume ratio of the mass of the gradient alloy quantum dots to the ethyl acetate is 5g: (4-6) mL, adding ethanol solution with concentration of 15-25mmol/L hexafluorophosphate into the solution A, wherein the volume ratio of the solution A to the ethanol solution of hexafluorophosphate is (120-130): 1, stirring, centrifuging and drying to obtain the gradient alloy quantum dot modified by hexafluorophosphate.
Further, the step S5 specifically includes: adding the powder containing palladium ions obtained in the step S3 into deionized water, adding the gradient alloy quantum dots modified by hexafluorophosphate groups obtained in the step S4, regulating the pH to be 1.7-3.2, and stirring and illuminating for 5-7h.
In the step S5 of the technical scheme, palladium ions are used as an activating agent, polymers are activated, gradient alloy quantum dots modified by fluorophosphate are used as catalysts, and PET plastics are degraded by stirring illumination through adjusting the pH value.
Further, the hexafluorophosphate is ammonium hexafluorophosphate.
Further, the gradient alloy quantum dot is one of red gradient quantum dot Cd xZn1-xSeyS1-y or blue gradient quantum dot Zn 1-xCdx S, wherein x=0.7-0.98 and y=0.7-0.98.
Compared with the prior art, the scheme has the following beneficial effects: (1) The invention provides a novel photocatalyst, namely a gradient alloy quantum dot modified by fluorophosphate (PF - 6), which takes palladium ions as an activating agent to activate a polymer, and degrades PET plastic through illumination, so that the PET plastic pollutants are effectively removed, and the PET plastic pollutants can be converted into valuable industrial raw materials. The method has the advantages of simple process, convenient operation, easy recovery, repeated use, high treatment efficiency, high degradation rate and the like, and has good application prospect in the actual treatment of plastic pollutants.
(2) The invention provides a novel gradient alloy quantum dot catalyst modified by hexafluorophosphate, which is prepared by taking gradient alloy quantum dots, ethyl acetate, ammonium hexafluorophosphate and ethanol as raw materials and stirring and reacting. The catalyst has high absorption coefficient, wide light absorption range, enhanced light stability and capability of generating multiple excitons, is a novel visible light catalyst with excellent photocatalytic performance, and has good use value and application prospect.
(3) The palladium ion used in the invention is prepared by taking palladium chloride, deionized water and hydrochloric acid as raw materials and reacting the raw materials through heating and stirring. Has the advantages of high photocatalytic activity, high concentration, good stability and the like, and has high recovery rate after the reaction is finished.
Drawings
The drawings are for illustrative purposes only and are not to be construed as limiting the present solution; for better illustration of the present solution, some parts of the figures may be omitted, enlarged or reduced, and do not represent the dimensions of the actual product; it will be appreciated by those skilled in the art that certain well-known structures in the drawings and descriptions thereof may be omitted; the positional relationship described in the drawings is for illustrative purposes only and is not to be construed as limiting the present solution.
Fig. 1 is a photograph of the chloropalladate solution prepared in example 2.
Fig. 2 is a photograph of hexafluorophosphate (PF 6) -modified red gradient alloy quantum dots prepared in example 2.
FIG. 3 is a 1 H-NMR image of the alkali-treated plastic powder in example 2.
FIG. 4 is GCMS data of the alkali treated plastic powder of example 2.
FIG. 5 is a fluorescence spectrum of hexafluorophosphate (PF 6) -modified red gradient alloy quantum dots prepared in example 2.
FIG. 6 is a high performance liquid chromatogram of the solution after the completion of the light treatment in example 2.
Fig. 7 is a photograph of fluorophosphate (PF - 6) -modified blue gradient alloy quantum dots prepared in example 4.
FIG. 8 is a fluorescence spectrum of the fluorophosphate (PF - 6) -modified blue gradient alloy quantum dot prepared in example 4.
FIG. 9 is a FTIR contrast image of the solid obtained after evaporating the solution obtained after the light treatment of example 4 and comparative example 1.
Detailed Description
In order to enable those skilled in the art to better understand the technical solution of the present solution, the present solution is described in further detail below with reference to specific embodiments. The process methods used in the examples are conventional methods unless otherwise specified; the materials used, unless otherwise specified, are all commercially available.
In the embodiment of the invention, two gradient quantum dots are prepared by a laboratory, wherein the preparation method of red gradient alloy quantum dot Cd xZn1-xSeyS1-y (x=0.7-0.98 and y=0.7-0.98) (see ：Exploring different photocatalytic behaviors of Cd x Zn 1-x Se y S 1-y gradient-alloyed quantum dots via composition regulation,Catal. Sci.Technol,2021,11(17),5917-5930),, wherein the preparation method of blue gradient alloy quantum dot Zn 1-xCdx S (x=0.7-0.98) (see ：Thiocyanate-capped CdSe@Zn 1-X Cd X S gradient alloyed quantum dots for efficient photocatalytic hydrogen evolution,Chem.Eng.J.2020,402).
Example 1
The method for degrading PET plastic by photocatalysis comprises the following steps:
S1, carrying out alkali treatment on PET plastic, wherein the specific method comprises the following steps: cutting PET plastic into small pieces with the concentration of 0.8cm multiplied by 1cm, adding the small pieces into 8mol/L NaOH solution, heating to 35 ℃ and stirring, taking out 6000rpm after 40h of reaction, centrifuging for 5min, drying at 60 ℃ and grinding to form plastic powder.
S2, preparing a chloropalladite solution, wherein the specific method comprises the following steps of: and adding palladium chloride into deionized water, dropwise adding hydrochloric acid into the solution, wherein the molar ratio of the palladium chloride to the hydrogen chloride is 1:2, stirring the solution for 40 minutes, and fixing the volume to obtain a palladium chloride acid solution with the concentration of 20 mmol/L.
S3, dissolving 0.4g of the plastic powder treated by the S1 in 8mL of deionized water, adding 8mL of the chloropalladite solution prepared by the S2 to be neutral, adding 8mL of 25% hydrogen peroxide, heating and stirring at 90 ℃, evaporating the solution, collecting and grinding into powder, and thus obtaining the palladium ion-containing powder.
S4, preparing hexafluorophosphate modified gradient alloy quantum dots, wherein the specific method comprises the following steps of: dispersing 5mg of red gradient alloy quantum dot Cd xZn1-xSeyS1-y (x=0.7-0.98 and y=0.7-0.98) in 4mL of ethyl acetate to obtain solution A, adding 33 mu L of 15mmol/L of ammonium hexafluorophosphate ethanol solution into the solution A, stirring for 30min, centrifuging for 5min at a centrifugal speed of 5000rpm, and drying in air to obtain hexafluorophosphate modified gradient alloy quantum dots.
S5, adding the powder containing palladium ions obtained in the step S3 into 100mL of deionized water, adding the hexafluorophosphate modified red gradient alloy quantum dots obtained in the step S4, adjusting the pH to 1.7, stirring, and carrying out illumination for 5h by using the maximum photocurrent of a xenon lamp 2/3.
Example 2
The method for degrading PET plastic by photocatalysis comprises the following steps:
s1, carrying out alkali treatment on PET plastic, wherein the specific method comprises the following steps: cutting PET plastic into 1cm×1cm pieces, adding into 10mol/L NaOH solution, heating at 60deg.C, stirring, reacting for 48 hr, taking out 7500rpm, centrifuging for 10min, oven drying at 70deg.C, and grinding to obtain powder.
S2, preparing a chloropalladite solution, wherein the specific method comprises the following steps of: and adding palladium chloride into deionized water, dropwise adding hydrochloric acid into the solution, wherein the molar ratio of the palladium chloride to the hydrogen chloride is 1:2, stirring for 60min, and fixing the volume to obtain a palladium chloride acid solution with the concentration of 30mmol/L, as shown in figure 1.
S3, dissolving 0.5g of the plastic powder treated by the S1 in 10mL of deionized water, adding 10mL of the chloropalladite solution prepared by the S2 to be neutral, adding 10mL of hydrogen peroxide, heating and stirring at 100 ℃, evaporating the solution, collecting and grinding into powder, namely palladium ion-containing powder.
S4, preparing hexafluorophosphate modified gradient alloy quantum dots, wherein the specific method comprises the following steps of: 5mg of red gradient alloy quantum dot Cd xZn1-xSeyS1-y (x=0.7-0.98 and y=0.7-0.98) is dispersed in 5mL of ethyl acetate to obtain solution A, 40 mu L of 20mmol/L of ethanol solution of ammonium hexafluorophosphate is added into the solution A, the solution A is stirred for 30min, the solution is centrifuged for 5min at 5000rpm and dried in air, and the hexafluorophosphate modified red gradient alloy quantum dot is obtained, and as shown in fig. 2, the fluorescence of the quantum dot is red, as can be seen from fig. 2.
S5, adding the palladium ion-containing powder obtained in the step S3 into 100mL of deionized water, adding the hexafluorophosphate modified red gradient alloy quantum dots obtained in the step S4, adjusting the pH to 2.5, stirring, and carrying out illumination for 6h by using a xenon lamp 2/3 maximum photocurrent.
The structure of the alkali-treated plastic powder in step S1 was confirmed by 1 H-NMR (Bruker AVANCE III MHz), the 1 H-NMR image of which is shown in FIG. 3, and GCMS data of the alkali-treated plastic powder was tested, as shown in FIG. 4.
With reference to fig. 3 and 4, it can be seen that the main components of the plastic powder obtained after the alkali treatment are ethylene glycol and terephthalate.
The fluorescence of the red gradient alloy quantum dots and the hexafluorophosphate modified red gradient alloy quantum dots in the S4 is tested, the fluorescence spectrum is shown in figure 5, and as can be seen from figure 5, after ligand exchange, the fluorescence intensity of the obtained hexafluorophosphate modified red gradient alloy quantum dots is obviously reduced, and the photocatalysis experiment is more facilitated.
The high performance liquid chromatograph of the solution after the illumination of the step S5 is tested by the high performance liquid chromatograph, the high performance liquid chromatograph is shown in figure 6, and the main component of the solution after the illumination degradation of the step S5 is oxalic acid, which is known to be converted into oxalic acid after the PET plastic is processed by the series of steps, thus being a valuable industrial raw material.
Example 3
The method for degrading PET plastic by photocatalysis comprises the following steps:
s1, carrying out alkali treatment on PET plastic, wherein the specific method comprises the following steps: cutting PET plastic into pieces of 2cm×1cm, adding into 11mol/L NaOH solution, heating to 80deg.C, stirring, reacting for 80 hr, taking out 10000rpm, centrifuging for 20min, oven drying at 75deg.C, and grinding to obtain powder.
S2, preparing a chloropalladite solution, wherein the specific method comprises the following steps of: and adding palladium chloride into deionized water, dropwise adding hydrochloric acid into the solution, wherein the molar ratio of the palladium chloride to the hydrogen chloride is 1:2.5, stirring the solution for 80 minutes, and fixing the volume to obtain a palladium chloride acid solution with the concentration of 50 mmol/L.
S3, dissolving 0.7g of the plastic powder treated by the S1 in 13mL of deionized water, adding 17mL of the chloropalladite solution prepared by the S2 to be neutral, adding 13mL of hydrogen peroxide, heating and stirring at 105 ℃, evaporating the solution, collecting and grinding into powder, and thus obtaining the palladium ion-containing powder.
S4, preparing hexafluorophosphate modified gradient alloy quantum dots, wherein the specific method comprises the following steps of: dispersing 5mg of red gradient alloy quantum dot Cd xZn1-xSeyS1-y (x=0.7-0.98 and y=0.7-0.98) in 6mL of ethyl acetate to obtain solution A, adding 47 mu L of an ethanol solution of 25mmol/L of ammonium hexafluorophosphate into the solution A, stirring for 30min, centrifuging for 5min at a centrifugal speed of 5000rpm, and drying in air to obtain the gradient alloy quantum dot modified by hexafluorophosphate.
S5, adding the palladium ion-containing powder obtained in the step S3 into 100mL of deionized water, adding the hexafluorophosphate modified gradient alloy quantum dot obtained in the step S4, adjusting the pH to 3.5, stirring, and carrying out illumination for 7h by using a xenon lamp 2/3 maximum photocurrent.
Example 4
S1, carrying out alkali treatment on PET plastic, wherein the specific method comprises the following steps: cutting PET plastic into 1cm×1cm pieces, adding into 10mol/L NaOH solution, heating at 60deg.C, stirring, reacting for 48 hr, taking out 7500rpm, centrifuging for 10min, oven drying at 70deg.C, and grinding to obtain powder.
S2, preparing a chloropalladite solution, wherein the specific method comprises the following steps of: and adding palladium chloride into deionized water, dropwise adding hydrochloric acid into the solution, wherein the molar ratio of the palladium chloride to the hydrogen chloride is 1:2, stirring the solution for 60 minutes, and fixing the volume to obtain a palladium chloride acid solution with the concentration of 30 mmol/L.
S3, dissolving 0.5g of the plastic powder treated by the S1 in 10mL of deionized water, adding a proper amount of 10mL of the chloropalladite solution prepared by the S2 to be neutral, adding 10mL of 30% hydrogen peroxide, heating and stirring at 100 ℃, evaporating the solution, collecting and grinding into powder, and thus obtaining the palladium ion-containing powder.
S4, preparing hexafluorophosphate modified gradient alloy quantum dots, wherein the specific method comprises the following steps of: 5mg of blue gradient alloy quantum dot Zn 1-xCdx S (x=0.7-0.98) is dispersed in 5mL of ethyl acetate to obtain solution A, 40 mu L of 20mmol/L of ammonium hexafluorophosphate ethanol solution is added into the solution A, and the solution A is stirred for 30min, centrifuged at 5000rpm for 5min and dried in air to obtain hexafluorophosphate modified blue gradient alloy quantum dot, and as shown in figure 7, the fluorescence of the quantum dot is blue.
S5, adding the powder obtained in the step S3 into 100mL of deionized water, adding the hexafluorophosphate modified blue gradient alloy quantum dot obtained in the step S4, adjusting the pH to 2.5, stirring, and carrying out illumination for 6h by using the maximum photocurrent of a xenon lamp 2/3.
The fluorescence of the blue gradient alloy quantum dots and the hexafluorophosphate modified blue gradient alloy quantum dots in the step S4 is tested, the fluorescence spectrum is shown in figure 8, and as can be seen from figure 8, after ligand exchange, the fluorescence intensity of the obtained hexafluorophosphate modified blue gradient alloy quantum dots is obviously reduced, so that the photocatalysis experiment is more facilitated.
Comparative example 1
Referring to example 4, other conditions were unchanged and blue gradient alloy quantum dots were not added.
The solution after the light treatment of the example 4 and the comparative example 2 is filtered, the solid obtained after the filtrate is evaporated to dryness is subjected to infrared spectrum test, and FTIR images are obtained, as shown in figure 9, the blue gradient alloy quantum dots modified by adding hexafluorophosphate can be seen from figure 9, and the degradation of PET plastic pollutants is obviously improved.
High performance chromatograms of the solutions of examples 1,3,4 and comparative example 1 after the light treatment were obtained by high performance chromatography, and the conversion and oxalic acid yield of the plastics of examples 1 to 4 and comparative example 1 were calculated as shown in table 1.
TABLE 1 conversion of plastics and oxalic acid yield
| Conversion of plastics% | Oxalic acid yield mg/L | |
| Example 1 | 85％ | 412 |
| Example 2 | 88％ | 417 |
| Example 3 | 83％ | 409 |
| Example 4 | 93％ | 425 |
| Comparative example 1 | 75％ | 192 |
As can be seen from Table 1, the conversion rates of the plastics of examples 1 to 4 are all very high, which means that the degradation rate of the PET plastics by the method for photocatalytic degradation of PET plastics provided by the invention is high, and the oxalic acid yield of comparative example 1 is significantly lower than that of example 4 although the conversion rates of the PET plastics of examples 1 to 4 and comparative example 1 after treatment are all converted into oxalic acid, which is a valuable industrial raw material. The data of comparative example 4 and comparative example 1 show that the conversion rate of comparative example 1 is much lower than that of example 4, which shows that the hexafluorophosphate modified blue gradient alloy quantum dot provided by the invention is used as a photocatalysis catalyst, and the degradation of PET plastic pollutants is obviously improved.
The solutions after the photoreaction in the step S5 of examples 1 to 4 and comparative example 1 were filtered, the filter residues were collected, and the filter residues were dried and weighed, and the recovery of palladium was calculated to be 99.1%, 99.8%, 99.5%, 98.3% and 25.3%, respectively, so that it was found that palladium ions used in the present invention could be converted into palladium, and the palladium ions could be recovered and utilized with high recovery rate.
The invention provides a method for degrading PET plastic by photocatalysis, which comprises the steps of firstly treating with alkali, codeposition, and finally using gradient alloy quantum dots modified by hexafluorophosphate (PF - 6) as a novel photocatalyst, using palladium ions as an activating agent, and carrying out photocatalysis to degrade the PET plastic, thereby realizing effective removal of PET plastic pollutants and converting the PET plastic pollutants into valuable industrial raw material oxalic acid. The method has the advantages of simple process, convenient operation, easy recovery, repeated use, high treatment efficiency, high degradation rate and the like, and has good application prospect in the actual treatment of plastic pollutants. And the palladium ions used in the invention can be reduced into solid finally for recovery, and the recovery rate of palladium is high.
It is apparent that the above examples of the present solution are merely examples for clearly illustrating the present solution and are not limiting of the embodiments of the present solution. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present solution should be included in the protection scope of the present solution claims.
Claims (7)
1. A method for degrading PET plastics by photocatalysis is characterized in that the method realizes degradation of PET plastics by alkali treatment, codeposition and photocatalysis in sequence, wherein a photocatalysis catalyst is hexafluorophosphate modified gradient alloy quantum dots, and a photocatalysis activator is palladium ions;
The method for degrading PET plastic by photocatalysis comprises the following steps:
s1, carrying out alkali treatment on PET plastic to obtain plastic powder;
S2, preparing a chloropalladite solution;
S3, co-depositing the plastic powder obtained by the alkali treatment of S1 and the chloropalladite solution prepared by S2;
s4, preparing hexafluorophosphate modified gradient alloy quantum dots;
s5, adopting hexafluorophosphate modified gradient alloy quantum dots as catalysts, and carrying out photocatalytic degradation on the product treated by the S3;
The specific method of the step S3 is as follows: adding the plastic powder in the step S1 into deionized water, adding the chloropalladite solution prepared in the step S2, adding 25% -35% hydrogen peroxide, stirring at 90-105 ℃, evaporating the solution, collecting and grinding the powder into powder containing palladium ions, wherein the ratio of the mass of the plastic powder, the volume of ionized water, the volume of the chloropalladite solution and the volume of hydrogen peroxide is controlled to be (0.4-0.7) g: (8-13) mL: (8-17) mL: (8-13) mL;
The specific method of the step S4 is as follows: dispersing gradient alloy quantum dots in ethyl acetate to obtain a solution A, wherein the ratio of the mass of the gradient alloy quantum dots to the volume of the ethyl acetate is 5g: and (4-6) mL, adding an ethanol solution with the concentration of 15-25 mmol/L hexafluorophosphate into the solution A, wherein the volume ratio of the solution A to the ethanol solution of hexafluorophosphate is (120-130) 1, stirring, centrifuging and drying to obtain the hexafluorophosphate modified gradient alloy quantum dot.
2. The method for degrading PET plastic by photocatalysis according to claim 1, wherein the specific method in step S1 is as follows: cutting PET plastic into small blocks with the concentration of 0.8-2 cm < 2 >, adding the small blocks into a NaOH solution with the concentration of 8-11 mol/L, stirring at the temperature of 35-80 ℃, reacting for 40-80 hours, taking out, centrifuging at the centrifugal speed of 6000-10000 rpm for 5-20 min, and then drying and grinding at the temperature of 60-75 ℃ to form plastic powder.
3. The method for degrading PET plastic by photocatalysis according to claim 1, wherein the specific method in step S2 is as follows: and adding palladium chloride into deionized water, dropwise adding hydrochloric acid into the solution, controlling the ratio of the palladium chloride to the hydrogen chloride substance to be 1 (2-2.5), stirring the solution for 40-80 min, and obtaining the palladium chloride acid solution with the concentration of 20-50 mmol/L after constant volume.
4. The method for photocatalytic degradation of PET plastic according to claim 2, characterized in that said step S5 is specifically: adding the powder containing palladium ions obtained in the step S3 into deionized water, adding the gradient alloy quantum dots modified by hexafluorophosphate groups obtained in the step S4, adjusting the pH to be 1.7-3.2, and stirring and illuminating for 5-7 h.
5. The method of claim 1, wherein the hexafluorophosphate salt is ammonium hexafluorophosphate.
6. The method of claim 1, wherein the gradient alloy quantum dot is one of a red gradient quantum dot or a blue gradient quantum dot.
7. The method for photocatalytic degradation of PET plastic according to claim 6, wherein the red gradient quantum dot is CdxZn1-xSeyS1-y, and the blue gradient quantum dot is Zn1-xCdxS, wherein x=0.7 to 0.98, and y=0.7 to 0.98.
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