CN111346675B - Preparation method and application of acid-sensitive control type PAA @ Ag/AgCl/CN composite photocatalyst - Google Patents
Preparation method and application of acid-sensitive control type PAA @ Ag/AgCl/CN composite photocatalyst Download PDFInfo
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/069—Hybrid organic-inorganic polymers, e.g. silica derivatized with organic groups
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2305/10—Photocatalysts
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Abstract
The invention belongs to the technical field of environmental material preparation, and relates to a preparation method and application of an acid-sensitive control type PAA @ Ag/AgCl/CN composite photocatalyst; the method first prepares flake g-C 3 N 4 Preparing an Ag/AgCl/CN composite photocatalyst on the basis, adding the composite photocatalyst into a mixed solution of ethanol and MPS, carrying out constant-temperature water bath under the protection of nitrogen, centrifuging and drying a product to obtain a surface-modified binary material; adding acrylic acid and MBA into deionized water, and adding a surface modified binary material after ultrasonic treatment; and adding ammonium persulfate after stirring, washing a product after reaction by using deionized water and absolute ethyl alcohol, and drying in vacuum to obtain the PAA @ Ag/AgCl/CN composite photocatalyst. The invention can not cause resource waste and additional pollution, has simple and convenient operation and is a green and environment-friendly composite material; and the purpose of degrading antibiotics in the sewage by controlling the pH value of the surrounding environment is realized.
Description
Technical Field
The invention belongs to the technical field of preparation of environmental materials, and particularly relates to a preparation method and application of an acid-sensitive control type PAA @ Ag/AgCl/CN composite photocatalyst.
Background
With the rapid development of a large number of medical consumption and modern medical technology, the phenomenon of overuse of antibiotic medicines is more and more serious, and the pollution influence of antibiotic wastewater is more and more prominent. Antibiotics remaining in the water body can cause microbes and bacteria to develop drug resistance, disturbing the surrounding environment and ecosystem. In addition, a number of studies have shown that there are also a number of antibiotics in our daily drinking water, which in turn pose a potential threat to human health through the drinking water and food chain. Therefore, there is a strong need to find a method for effectively treating antibiotic residues.
At present, the technologies for removing antibiotics mainly comprise conventional treatment technologies, adsorption, membrane separation technologies, photocatalytic technologies and the like. Because the antibiotic wastewater has the characteristics of high biological toxicity, bacteriostatic substances and the like, the traditional conventional treatment technology has poor effect on treating the refractory toxic organic wastewater, particularly the wastewater containing residual trace antibiotics; the adsorption technology has the advantages of easy operation, low cost, high efficiency, no generation of high-toxicity byproducts and the like, but the mechanical strength stability of the adsorption technology is poor and the adsorption technology is difficult to recycle; the membrane separation technology is a physical method, toxic and harmful substances are not introduced, and the membrane separation technology is concerned about a water treatment process, but the membrane separation technology has higher cost and small flux and is difficult to be widely used; the photocatalysis technology has the advantages of simple method, low investment and operation cost, strong oxidation capability and high degradation rate, and is suitable for wide application. In addition, designing a high performance catalyst is crucial in photocatalytic technology.
g-C 3 N 4 As a novel two-dimensional semiconductor photocatalytic material, the material is easy to modify due to excellent physical characteristics and chemical stability, rich in raw material source, low in price and suitable in energy band structure, and has great research and application values in the field of photocatalytic degradation of antibiotics. Furthermore, flakes g-C 3 N 4 Comparative phase g-C 3 N 4 Has larger specific surface area, can provide more reactive active sites for reaction, and the catalyst and the antibiotic can be fully contacted, thereby improving the photocatalytic degradation performance of the catalyst. However, the capability of a semiconductor is often limited, so that it is necessary to select a suitable semiconductor and g-C 3 N 4 The compound acts on the photocatalytic degradation reaction. Silver chloride has photosensitivity and can change g-C 3 N 4 Electronic transmitterThe transmission path can prolong the service life of the current carrier, thereby improving the photocatalytic performance of the composite material.
An AgCl/g-C has been reported in the literature 3 N 4 The catalyst is prepared by a direct precipitation method, but the defect that the process for treating the antibiotic is seriously influenced by the surrounding environment still exists. Therefore, the present study invented a photocatalytic material with controllability to the surrounding environment during the treatment of antibiotics. Polyacrylic acid (PAA) is selected as an intelligent high polymer material in the research, and the polyacrylic acid can be used for constructing an intelligent response type composite photocatalytic material sensitive to acid so as to realize the regulation of the pH value of the surrounding environment in the photocatalytic degradation process. In addition, AgCl particles can generate a photo-corrosion phenomenon under the irradiation of light, and PAA serving as a protective layer can encapsulate the AgCl particles to prevent the loss of photosensitive materials. Therefore, the polyacrylic acid modified photocatalyst can prevent silver chloride from losing, realizes the controllability of the catalyst on the pH value of the surrounding environment, further optimizes the performance of the catalyst, and has good practical application value.
Disclosure of Invention
The invention aims to solve the technical defects of uncontrollable property to the surrounding environment, serious photo-corrosion, slow electron transmission rate, high electron hole recombination rate and the like of a photocatalyst, and the acid-sensitive control PAA @ Ag/AgCl/CN composite photocatalyst is prepared by taking a chemical precipitation method and an emulsion polymerization method as technical means and is applied to controllable degradation of antibiotics.
In order to achieve the technical purpose, the technical scheme adopted by the invention comprises the following steps:
(1) flake g-C 3 N 4 Preparation of (CN):
dissolving melamine and cyanuric acid in ethanol, stirring for a period of time, centrifugally drying, calcining in muffle furnace to obtain sheet g-C 3 N 4 Is marked as CN;
(2) preparing an Ag/AgCl/CN composite photocatalyst:
dissolving CN prepared in the step (1) in deionized water, stirring uniformly, and adding NaCl and AgNO 3 Stirring the solution again, and standingReacting under an ultraviolet lamp, centrifuging, washing and drying after the reaction to obtain a composite photocatalyst which is marked as Ag/AgCl/CN;
(3) preparing an acid-sensitive control type PAA @ Ag/AgCl/CN composite photocatalyst:
mixing ethanol and 3- (methacryloyloxy) propyl trimethoxy silane (MPS), adding the Ag/AgCl/CN prepared in the step (2), carrying out constant-temperature water bath for a period of time under the protection of nitrogen, centrifuging and drying the product to obtain a surface-modified binary material;
then, adding Acrylic Acid (AA) and N, N' -Methylene Bisacrylamide (MBA) into deionized water, and adding a surface modified binary material after ultrasonic treatment; stirring for a certain time, adding ammonium persulfate ((NH) 4 ) 2 S 2 O 6 ) Carrying out reaction; and repeatedly washing the product after reaction by using deionized water and absolute ethyl alcohol, and finally carrying out vacuum drying to obtain the final product, namely the acid-sensitive control type PAA @ Ag/AgCl/CN composite photocatalyst.
Preferably, in the step (1), the molar ratio of the melamine to the cyanuric acid is 1: 1-3; the dosage of the ethanol is 80-120 mL;
preferably, in the step (1), the stirring is carried out for 12-24 hours; the calcining temperature is 500-600 ℃, the calcining speed is 2-2.5 ℃/min, and the calcining time is 4-8 h.
Preferably, in step (2), the CN, the deionized NaCl and the AgNO 3 The dosage ratio of (A) is 0.4-0.8 g: 80-120 mL: 0.0326-0.1468 g: 2.9-13.1 mL; the AgNO 3 The concentration of the solution was 1 mol/L.
Preferably, in the step (2), the reaction time under the ultraviolet lamp is 20-40 min.
Preferably, in the step (3), the dosage ratio of the Ag/AgCl/CN, the ethanol and the 3- (methacryloyloxy) propyl trimethoxy silane is 0.3-0.5 g: 80-100 mL: 8-10 mL.
Preferably, in the step (3), the temperature of the thermostatic water bath is 50 ℃ and the time is 12 h.
Preferably, in the step (3), the use amount ratio of acrylic acid, N' -methylene bisacrylamide, deionized water, the surface-modified binary material and ammonium persulfate is 0.1-0.13 g: 0.01-0.03 g: 30-50 mL: 0.3-0.5 g: 0.1-0.3 mL. The ultrasonic treatment time is 30-60 min.
Preferably, in the step (3), the stirring is carried out for 2 to 3 hours; the concentration of the ammonium persulfate is 0.1 mol/L; the time for adding ammonium persulfate to carry out reaction is 12-24 hours.
Preferably, in the step (3), the temperature of the vacuum drying is 60 ℃ and the time is 12 h.
The Ag/AgCl/CN composite photocatalyst is prepared by the preparation method, wherein the AgCl accounts for 10-45% of the CN by mass, and the preferable mass percentage is 40%.
The acid-sensitive controlled PAA @ Ag/AgCl/CN composite photocatalyst obtained by the preparation method is applied to degrading antibiotics in antibiotic wastewater.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention adopts a template-free method to synthesize CN and blocky g-C 3 N 4 Compared with the prior art, the method has the advantages that the contact area is increased, the transmission distance of carriers is shortened, the separation efficiency of electron hole pairs is improved, and the photocatalysis efficiency is improved. Moreover, the method is simple and convenient and is easy for mass preparation.
(2) The AgCl has photosensitivity, not only can change an electron transmission path of CN, but also can increase the separation of electron hole pairs, thereby improving the photocatalytic performance of the composite material; after AgCl is loaded on CN, two semiconductors generate synergistic action in the photocatalytic degradation process; AgCl is loaded on CN, is not easy to agglomerate, and the electron transmission rate and the photocatalytic performance are improved.
(3) The polyacrylic acid is selected to modify Ag/AgCl/CN, can prevent AgCl loss, can effectively transfer electrons, improves the separation efficiency of photo-generated electrons and hole pairs, shortens the degradation time and improves the photocatalytic degradation efficiency, can realize the controllability of the catalyst on the pH value of the surrounding environment in the degradation process, and has higher photocatalytic activity and practical application value than CN and Ag/AgCl/CN.
(4) The acid-sensitive control type PAA @ Ag/AgCl/CN composite photocatalyst takes visible light as excitation, realizes a special catalytic effect through the interface interaction with antibiotic molecules, and enables surrounding oxygen and water molecules to be excited into substances with strong oxidizing property such as oxygen free radicals and hydroxyl free radicals with strong oxidizing property, thereby achieving the purpose of degrading harmful organic substances in the environment; compared with the prior art, the method does not cause resource waste and additional pollution, is simple and convenient to operate, and is an environment-friendly high-efficiency treatment technology; in addition, the invention realizes the purpose of degrading antibiotics in sewage by the controllability of the PAA @ Ag/AgCl/CN composite photocatalyst on the pH value of the surrounding environment.
Drawings
FIG. 1 is an XRD pattern of Ag/AgCl/CN in different ratios, wherein a represents Ag/AgCl-10/CN, b represents Ag/AgCl-20/CN, c represents Ag/AgCl-30/CN, d represents Ag/AgCl-35/CN, e represents Ag/AgCl-40/CN, and f represents Ag/AgCl-45/CN; panel B is an XRD pattern of CN, AgCl, Ag/AgCl-40/CN and PAA @ Ag/AgCl-40/CN, wherein a represents CN, B represents AgCl, c represents Ag/AgCl-40/CN, and d represents PAA @ Ag/AgCl-40/CN.
In FIG. 2, A and B are SEM pictures of CN, C and D are SEM pictures of Ag/AgCl-40/CN, and E and F are SEM pictures of PAA @ Ag/AgCl-40/CN composite photocatalyst.
In FIG. 3, A is a photo current diagram of the composite photocatalyst of CN, AgCl, Ag/AgCl-40/CN and PAA @ Ag/AgCl-40/CN; b is an impedance diagram of the CN, AgCl, Ag/AgCl-40/CN and PAA @ Ag/AgCl-40/CN composite photocatalyst; wherein a represents CN, b represents AgCl, c represents Ag/AgCl-40/CN, and d represents PAA @ Ag/AgCl-40/CN composite photocatalyst.
FIG. 4 is a PL diagram for CN, Ag/AgCl-40/CN and PAA @ Ag/AgCl-40/CN composite photocatalysts; wherein a represents CN, b represents Ag/AgCl-40/CN, and c represents PAA @ Ag/AgCl-40/CN composite photocatalyst.
Detailed Description
The technical solution of the present invention will be further described in detail with reference to the following specific examples. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention. The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.
Melamine (C) used in the present invention 3 H 6 N 6 ) Cyanuric acid (C) 3 H 3 N 3 O 3 ) Sodium chloride (NaCl), silver nitrate (AgNO) 3 ) 3- (methacryloyloxy) propyltrimethoxysilane (C) 10 H 20 O 5 Si 8 ) Acrylic acid (C) 3 H 4 O 2 ) N, N' -methylenebisacrylamide (C) 7 H 10 N 2 O 2 ) Ammonium persulfate (NH) 4 ) 2 S 2 O 6 Absolute ethanol (C) 2 H 5 OH) are all analytically pure and purchased from chemical reagents of national drug group, Inc.; the tetracycline antibiotic is a standard product and is purchased from Shanghai Shubo bioengineering Co.
Photocatalytic activity evaluation of the photocatalyst prepared in the present invention: irradiating with visible light lamp in DW-01 type photochemical reactor (purchased from technologies, Inc. of city, Yangzhou university), adding 100mL tetracycline simulation wastewater with concentration of 20mg/L into the reactor, measuring initial value, adding the prepared photocatalyst, magnetically stirring, introducing air to maintain the catalyst in suspension or floating state, sampling and analyzing at 15min interval during illumination, centrifuging, collecting supernatant, and placing in spectrophotometer lambda max Absorbance was measured at 357nm and by the formula: dr ═ 1-A i /A 0 ]The degradation rate was calculated by X100%, where A 0 Absorbance of the tetracycline solution to equilibrium for adsorption, A i The absorbance of the tetracycline solution was determined for the timed samples.
Comparative example 1:
(1) preparation of CN: dissolving melamine and cyanuric acid in a molar ratio of 1:1 in 120mL ethanol, stirring for 12h, centrifugally drying, calcining in a muffle furnace at 550 ℃ and a speed of 2.5 ℃/min for 8h, and fully grinding the obtained product to obtain CN;
(2) preparing an Ag/AgCl/CN composite photocatalyst: weighing 0.4g CN to be dissolved in 120mL deionized water, fully stirring, adding 0.0326g solid NaCl, stirring for 4h, and dropwise adding 2.9mL AgNO with concentration of 1mol/L 3 Fully stirring the solution to ensure that the reaction is completely carried out, continuously reacting for 20min under an ultraviolet lamp, centrifuging, washing and drying in an oven to obtain the Ag/AgCl-10/CN composite photocatalyst;
(3) and (3) taking the sample in the step (2) to carry out a photocatalytic degradation test in a photochemical reactor, and measuring that the degradation rate of the photocatalyst to tetracycline reaches 46.63% within 2 h.
Comparative example 2:
(1) preparation of CN: dissolving melamine and cyanuric acid in 100mL of ethanol at a molar ratio of 1:2, stirring for 18h, centrifugally drying, calcining in a muffle furnace at 500 ℃ and a speed of 2.3 ℃/min for 6h, and fully grinding the obtained product to obtain CN;
(2) preparing an Ag/AgCl/CN composite photocatalyst: weighing 0.4g CN to be dissolved in 120mL deionized water, fully stirring, adding 0.0326g solid NaCl, stirring for 4h, and dropwise adding 2.9mL AgNO with concentration of 1mol/L 3 Fully stirring the solution to ensure that the reaction is completely carried out, continuously reacting for 20min under an ultraviolet lamp, centrifuging, washing and drying in an oven to obtain the Ag/AgCl-10/CN composite photocatalyst;
(3) and (3) carrying out a photocatalytic degradation test on the sample in the step (2) in a photochemical reactor, and measuring that the degradation rate of the photocatalyst to tetracycline reaches 40.87% within 2 h.
Comparative example 3:
(1) preparation of CN: dissolving melamine and cyanuric acid in 80mL of ethanol in a molar ratio of 1:3, stirring for 24h, centrifugally drying, calcining for 4h in a muffle furnace at a temperature of 600 ℃ and a speed of 2 ℃/min, and fully grinding the obtained product to obtain CN;
(2) preparing an Ag/AgCl/CN composite photocatalyst: weighing 0.4g CN to be dissolved in 120mL deionized water, fully stirring, adding 0.0326g solid NaCl, stirring for 4h, and dropwise adding 2.9mL AgNO with concentration of 1mol/L 3 Fully stirring the solution to ensure that the reaction is completely carried out, continuously reacting for 20min under an ultraviolet lamp, centrifuging, washing and drying in an oven to obtain the Ag/AgCl-10/CN composite photocatalyst;
(3) and (3) taking the sample in the step (2) to carry out a photocatalytic degradation test in a photochemical reactor, and measuring that the degradation rate of the photocatalyst to tetracycline reaches 36.24% within 2 h.
Comparative example 4:
(1) preparation of CN: dissolving melamine and cyanuric acid in a molar ratio of 1:1 in 120mL ethanol, stirring for 12h, centrifugally drying, calcining in a muffle furnace at 550 ℃ and a speed of 2.5 ℃/min for 8h, and fully grinding the obtained product to obtain CN;
(2) preparing an Ag/AgCl/CN composite photocatalyst: weighing 0.4g CN to be dissolved in 120mL deionized water, fully stirring, adding 0.0326g solid NaCl, stirring for 4h, and dropwise adding 2.9mL AgNO with concentration of 1mol/L 3 Fully stirring the solution to ensure that the reaction is completely carried out, continuously reacting for 20min under an ultraviolet lamp, centrifuging, washing and drying in an oven to obtain the Ag/AgCl-10/CN composite photocatalyst;
(3) and (3) taking the sample in the step (2) to carry out a photocatalytic degradation test in a photochemical reactor, and measuring that the degradation rate of the photocatalyst to tetracycline reaches 46.63% within 2 h.
Comparative example 5:
(1) preparation of CN: dissolving melamine and cyanuric acid in a molar ratio of 1:1 in 120mL ethanol, stirring for 12h, centrifugally drying, calcining in a muffle furnace at 550 ℃ and a speed of 2.5 ℃/min for 8h, and fully grinding the obtained product to obtain CN;
(2) preparing an Ag/AgCl/CN composite photocatalyst: weighing 0.4g CN to be dissolved in 120mL deionized water, adding 0.0652g solid NaCl after fully stirring, dropwise adding 5.8mL AgNO with the concentration of 1mol/L after stirring for 4h 3 Fully stirring the solution to ensure that the reaction is completely carried out, continuously reacting for 20min under an ultraviolet lamp, centrifuging, washing and drying in an oven to obtain the Ag/AgCl-20/CN composite photocatalyst;
(3) and (3) taking the sample in the step (2) to carry out a photocatalytic degradation test in a photochemical reactor, and measuring that the degradation rate of the photocatalyst to tetracycline reaches 59.28% within 2 h.
Comparative example 6:
(1) preparation of CN: dissolving melamine and cyanuric acid in a molar ratio of 1:1 in 120mL ethanol, stirring for 12h, centrifugally drying, calcining in a muffle furnace at 550 ℃ and a speed of 2.5 ℃/min for 8h, and fully grinding the obtained product to obtain CN;
(2) preparing an Ag/AgCl/CN composite photocatalyst: weighing 0.4g CN to be dissolved in 120mL deionized water, adding 0.0978g solid NaCl after fully stirring, stirring for 4h, and dropwise adding 8.7mL AgNO with the concentration of 1mol/L 3 Fully stirring the solution to ensure that the reaction is completely carried out, continuously reacting for 20min under an ultraviolet lamp, centrifuging, washing and drying in an oven to obtain the Ag/AgCl-30/CN composite photocatalyst;
(3) and (3) taking the sample in the step (2) to carry out a photocatalytic degradation test in a photochemical reactor, and measuring that the degradation rate of the photocatalyst to tetracycline reaches 64.67% within 2 h.
Comparative example 7:
(1) preparation of CN: dissolving melamine and cyanuric acid in a molar ratio of 1:1 in 120mL ethanol, stirring for 12h, centrifugally drying, calcining in a muffle furnace at 550 ℃ and a speed of 2.5 ℃/min for 8h, and fully grinding the obtained product to obtain CN;
(2) preparing an Ag/AgCl/CN composite photocatalyst: weighing 0.4g CN to be dissolved in 120mL deionized water, adding 0.1141g solid NaCl after fully stirring, stirring for 4h, and dropwise adding 10.2mL AgNO with the concentration of 1mol/L 3 Fully stirring the solution to ensure that the reaction is completely carried out, continuously reacting for 20min under an ultraviolet lamp, centrifuging, washing and drying in an oven to obtain the Ag/AgCl-35/CN composite photocatalyst;
(3) and (3) taking the sample in the step (2) to carry out a photocatalytic degradation test in a photochemical reactor, and measuring that the degradation rate of the photocatalyst to tetracycline reaches 70.62% within 2 h.
Comparative example 8:
(1) preparation of CN: dissolving melamine and cyanuric acid in a molar ratio of 1:1 in 120mL ethanol, stirring for 12h, centrifugally drying, calcining in a muffle furnace at 550 ℃ and a speed of 2.5 ℃/min for 8h, and fully grinding the obtained product to obtain CN;
(2) preparing an Ag/AgCl/CN composite photocatalyst: weighing 0.4Dissolving CN g in 120mL of deionized water, fully stirring, adding 0.1304g of solid NaCl, stirring for 4 hours, and dropwise adding 11.6mL of AgNO with the concentration of 1mol/L 3 Fully stirring the solution to ensure that the reaction is completely carried out, continuously reacting for 20min under an ultraviolet lamp, centrifuging, washing and drying in an oven to obtain the Ag/AgCl-40/CN composite photocatalyst;
(3) and (3) taking the sample in the step (2) to carry out a photocatalytic degradation test in a photochemical reactor, and measuring that the degradation rate of the photocatalyst to tetracycline reaches 75.75% within 2 h.
Comparative example 9:
(1) preparation of CN: dissolving melamine and cyanuric acid in a molar ratio of 1:1 in 120mL ethanol, stirring for 12h, centrifugally drying, calcining in a muffle furnace at 550 ℃ and a speed of 2.5 ℃/min for 8h, and fully grinding the obtained product to obtain CN;
(2) preparing an Ag/AgCl/CN composite photocatalyst: weighing 0.4g CN to be dissolved in 120mL deionized water, adding 0.1468g solid NaCl after fully stirring, dropwise adding 13.1mL AgNO with the concentration of 1mol/L after stirring for 4h 3 Fully stirring the solution to ensure that the reaction is completely carried out, continuously reacting for 20min under an ultraviolet lamp, centrifuging, washing and drying in an oven to obtain the Ag/AgCl-45/CN composite photocatalyst;
(3) and (3) taking the sample in the step (2) to carry out a photocatalytic degradation test in a photochemical reactor, and measuring that the degradation rate of the photocatalyst to tetracycline reaches 72.27% within 2 h.
Example 1:
(1) preparation of CN: preparation of CN: dissolving melamine and cyanuric acid in a molar ratio of 1:1 in 120mL ethanol, stirring for 12h, centrifugally drying, calcining in a muffle furnace at 550 ℃ and a speed of 2.5 ℃/min for 8h, and fully grinding the obtained product to obtain CN;
(2) preparing an Ag/AgCl-40/CN composite photocatalyst:
preparing an Ag/AgCl/CN composite photocatalyst: weighing 0.4g of CN to be dissolved in 120mL of deionized water, fully stirring, adding 0.1304g of solid NaCl, stirring for 4 hours, and dropwise adding 11.6mL of AgNO with the concentration of 1mol/L 3 Solution, fillingStirring to complete the reaction, continuing the reaction for 20min under an ultraviolet lamp, centrifuging, washing and drying in an oven to obtain the Ag/AgCl/CN composite photocatalyst, wherein the mass of AgCl accounts for 40% of CN at the moment, and the Ag/AgCl-40/CN composite photocatalyst is called as Ag/AgCl-40/CN in the following;
(3) preparing an acid-sensitive control type PAA @ Ag/AgCl-40/CN composite photocatalyst:
0.5g of Ag/AgCl-40/CN was dispersed in 100mL of ethanol and 10mL of 3- (methacryloyloxy) propyltrimethoxysilane, and the mixture was subjected to a constant temperature water bath at 50 ℃ for 12 hours under the protection of nitrogen, and the product was centrifuged and dried to complete the surface modification of the binary material. Then, 0.13g of acrylic acid and 0.03g N, N' -methylene bisacrylamide are weighed, 50mL of deionized water is added, ultrasonic treatment is carried out for 30min, 0.3g of surface-modified binary material is added, stirring is carried out for 2h, and 0.1mL of ammonium persulfate (0.1mol/L) is added as an initiator to react for 12 h. Finally, repeatedly washing the product by deionized water and absolute ethyl alcohol, and drying the product in vacuum at 60 ℃ for 12 hours; obtaining the PAA @ Ag/AgCl-40/CN composite photocatalyst.
(4) And (3) keeping the pH value of the sample in the photochemical reactor to be 12 for carrying out a photocatalytic degradation test, and measuring that the degradation rate of the photocatalyst to tetracycline reaches 81.98% within 2 h.
Example 2:
(1) preparation of CN: dissolving melamine and cyanuric acid in a molar ratio of 1:1 in 120mL ethanol, stirring for 12h, centrifugally drying, calcining in a muffle furnace at 550 ℃ and a speed of 2.5 ℃/min for 8h, and fully grinding the obtained product to obtain CN;
(2) preparing an Ag/AgCl-40/CN composite photocatalyst:
preparing an Ag/AgCl/CN composite photocatalyst: weighing 0.4g CN, dissolving in 120mL deionized water, fully stirring, adding 0.1304g solid NaCl, stirring for 4h, and dropwise adding 11.6mL AgNO with concentration of 1mol/L 3 Fully stirring the solution to ensure that the reaction is completely carried out, continuing the reaction for 20min under an ultraviolet lamp, centrifuging, washing and putting into an oven for drying to obtain the Ag/AgCl/CN composite photocatalyst, wherein the mass of AgCl accounts for 40% of CN at the moment, and the Ag/AgCl-40/CN composite photocatalyst is called as Ag/AgCl-40/CN later;
(3) preparing an acid-sensitive control type PAA @ Ag/AgCl-40/CN composite photocatalyst:
0.3g of Ag/AgCl-40/CN was dispersed in 80mL of ethanol and 8mL of 3- (methacryloyloxy) propyltrimethoxysilane, and the mixture was subjected to a constant temperature water bath at 50 ℃ for 12 hours under the protection of nitrogen, and the product was centrifuged and dried to complete the surface modification of the binary material. Then, 0.1g of acrylic acid and 0.01g N, N' -methylenebisacrylamide were weighed, 30mL of deionized water was added, and after 30min of sonication, 0.4g of the surface-modified binary material was added. After stirring for 2h, 0.2mL ammonium persulfate (0.1mol/L) was added as an initiator and reacted for 18 h. Finally, repeatedly washing the product by deionized water and absolute ethyl alcohol, and drying the product in vacuum at 60 ℃ for 12 hours; obtaining the PAA @ Ag/AgCl-40/CN composite photocatalyst.
(4) And (3) keeping the pH value of the composite photocatalyst in the step (3) to be 12 in a photochemical reactor to carry out a photocatalytic degradation test, and measuring that the degradation rate of the photocatalyst to tetracycline reaches 74.36% within 2 h.
Example 3:
(1) preparation of CN: dissolving melamine and cyanuric acid in a molar ratio of 1:1 in 120mL ethanol, stirring for 12h, centrifugally drying, calcining in a muffle furnace at 550 ℃ and a speed of 2.5 ℃/min for 8h, and fully grinding the obtained product to obtain CN;
(2) preparing an Ag/AgCl-40/CN composite photocatalyst:
preparing an Ag/AgCl/CN composite photocatalyst: weighing 0.4g CN, dissolving in 120mL deionized water, fully stirring, adding 0.1304g solid NaCl, stirring for 4h, and dropwise adding 11.6mL AgNO with concentration of 1mol/L 3 Fully stirring the solution to ensure that the reaction is completely carried out, continuing the reaction for 20min under an ultraviolet lamp, centrifuging, washing and putting into an oven for drying to obtain the Ag/AgCl/CN composite photocatalyst, wherein the mass of AgCl accounts for 40% of CN at the moment, and the Ag/AgCl-40/CN composite photocatalyst is called as Ag/AgCl-40/CN later;
(3) the preparation of the acid-sensitive controlled PAA @ Ag/AgCl-40/CN composite photocatalyst comprises the following steps:
0.4g of Ag/AgCl-40/CN is dispersed in 90mL of ethanol and 9mL of 3- (methacryloyloxy) propyl trimethoxy silane, and the mixture is subjected to constant temperature water bath for 12h at 50 ℃ under the protection of nitrogen, and the product is centrifuged and dried to complete the surface modification of the binary material. Then, 0.12g of acrylic acid and 0.02g N, N' -methylenebisacrylamide were weighed, 50mL of deionized water was added, and after 30min of sonication, 0.5g of the surface-modified binary material was added. After stirring for 2h, 0.3mL ammonium persulfate (0.1mol/L) was added as an initiator for 24 h. Finally, repeatedly washing the product by deionized water and absolute ethyl alcohol, and drying the product in vacuum at 60 ℃ for 12 hours; obtaining the PAA @ Ag/AgCl-40/CN composite photocatalyst.
(4) And (3) keeping the pH value of the composite photocatalyst in the step (3) to be 12 in a photochemical reactor to carry out a photocatalytic degradation test, and measuring that the degradation rate of the photocatalyst to tetracycline reaches 71.24 within 2 h.
Example 4:
(1) preparation of CN: preparation of CN: dissolving melamine and cyanuric acid in a molar ratio of 1:1 in 120mL ethanol, stirring for 12h, centrifugally drying, calcining in a muffle furnace at 550 ℃ and a speed of 2.5 ℃/min for 8h, and fully grinding the obtained product to obtain CN;
(2) preparing an Ag/AgCl-40/CN composite photocatalyst:
preparing an Ag/AgCl/CN composite photocatalyst: weighing 0.4g CN, dissolving in 120mL deionized water, fully stirring, adding 0.1304g solid NaCl, stirring for 4h, and dropwise adding 11.6mL AgNO with concentration of 1mol/L 3 Fully stirring the solution to ensure that the reaction is completely carried out, continuing the reaction for 20min under an ultraviolet lamp, centrifuging, washing and putting into an oven for drying to obtain the Ag/AgCl/CN composite photocatalyst, wherein the mass of AgCl accounts for 40% of CN at the moment, and the Ag/AgCl-40/CN composite photocatalyst is called as Ag/AgCl-40/CN later;
(3) preparing an acid-sensitive control type PAA @ Ag/AgCl-40/CN composite photocatalyst:
0.5g of Ag/AgCl-40/CN was dispersed in 100mL of ethanol and 10mL of 3- (methacryloyloxy) propyltrimethoxysilane, and the mixture was subjected to a constant temperature water bath at 50 ℃ for 12 hours under the protection of nitrogen, and the product was centrifuged and dried to complete the surface modification of the binary material. Then, 0.13g of acrylic acid and 0.03g N, N' -methylenebisacrylamide were weighed, 50mL of deionized water was added, and after 30min of sonication, 0.3g of the surface-modified binary material was added. After stirring for 2h, 0.1mL ammonium persulfate (0.1mol/L) was added as an initiator for 12 h. Finally, repeatedly washing the product by deionized water and absolute ethyl alcohol, and drying the product in vacuum at 60 ℃ for 12 hours; obtaining the PAA @ Ag/AgCl-40/CN composite photocatalyst.
(4) And (3) keeping the pH value of the composite photocatalyst in the step (3) to be 10 in a photochemical reactor to carry out a photocatalytic degradation test, and measuring that the degradation rate of the photocatalyst to tetracycline reaches 77.04 within 2 h.
Example 5:
(1) preparation of CN: preparation of CN: dissolving melamine and cyanuric acid in a molar ratio of 1:1 in 120mL ethanol, stirring for 12h, centrifugally drying, calcining in a muffle furnace at 550 ℃ and a speed of 2.5 ℃/min for 8h, and fully grinding the obtained product to obtain CN;
(2) preparing an Ag/AgCl-40/CN composite photocatalyst:
preparing an Ag/AgCl/CN composite photocatalyst: weighing 0.4g CN, dissolving in 120mL deionized water, fully stirring, adding 0.1304g solid NaCl, stirring for 4h, and dropwise adding 11.6mL AgNO with concentration of 1mol/L 3 Fully stirring the solution to ensure that the reaction is completely carried out, continuing the reaction for 20min under an ultraviolet lamp, centrifuging, washing and putting into an oven for drying to obtain the Ag/AgCl/CN composite photocatalyst, wherein the mass of AgCl accounts for 40% of CN at the moment, and the Ag/AgCl-40/CN composite photocatalyst is called as Ag/AgCl-40/CN later;
(3) preparing an acid-sensitive control type PAA @ Ag/AgCl-40/CN composite photocatalyst:
dispersing 0.5g of Ag/AgCl-40/CN into 100mL of ethanol and 10mL of 3- (methacryloyloxy) propyl trimethoxy silane, carrying out constant-temperature water bath for 12h at 50 ℃ under the protection of nitrogen, centrifuging and drying a product, and finishing the surface modification of the binary material; then, 0.13g of acrylic acid and 0.03g N, N' -methylene bisacrylamide are weighed, 50mL of deionized water is added, ultrasonic treatment is carried out for 30min, 0.3g of surface-modified binary material is added, stirring is carried out for 2h, and 0.1mL of ammonium persulfate (0.1mol/L) is added as an initiator to react for 12 h. Finally, repeatedly washing the product by deionized water and absolute ethyl alcohol, and drying the product in vacuum at 60 ℃ for 12 hours; obtaining the PAA @ Ag/AgCl-40/CN composite photocatalyst.
(4) And (3) keeping the pH value of the composite photocatalyst in the step (3) to be 8 in a photochemical reactor to carry out a photocatalytic degradation test, and measuring that the degradation rate of the photocatalyst to tetracycline reaches 74.72 within 2 h.
Example 6:
(1) preparation of CN: preparation of CN: dissolving melamine and cyanuric acid in a molar ratio of 1:1 in 120mL ethanol, stirring for 12h, centrifugally drying, calcining in a muffle furnace at 550 ℃ and a speed of 2.5 ℃/min for 8h, and fully grinding the obtained product to obtain CN;
(2) preparing an Ag/AgCl-40/CN composite photocatalyst:
preparing an Ag/AgCl/CN composite photocatalyst: weighing 0.4g CN, dissolving in 120mL deionized water, fully stirring, adding 0.1304g solid NaCl, stirring for 4h, and dropwise adding 11.6mL AgNO with concentration of 1mol/L 3 Fully stirring the solution to ensure that the reaction is completely carried out, continuing the reaction for 20min under an ultraviolet lamp, centrifuging, washing and putting into an oven for drying to obtain the Ag/AgCl/CN composite photocatalyst, wherein the mass of AgCl accounts for 40% of CN at the moment, and the Ag/AgCl-40/CN composite photocatalyst is called as Ag/AgCl-40/CN later;
(3) preparing an acid-sensitive control type PAA @ Ag/AgCl-40/CN composite photocatalyst:
0.5g of Ag/AgCl-40/CN was dispersed in 100mL of ethanol and 10mL of 3- (methacryloyloxy) propyltrimethoxysilane, and the mixture was subjected to a constant temperature water bath at 50 ℃ for 12 hours under the protection of nitrogen, and the product was centrifuged and dried to complete the surface modification of the binary material. Then, 0.13g of acrylic acid and 0.03g N, N' -methylenebisacrylamide were weighed, 50mL of deionized water was added, and after 30min of sonication, 0.3g of the surface-modified binary material was added. After stirring for 2h, 0.1mL ammonium persulfate (0.1mol/L) was added as an initiator for 12 h. Finally, repeatedly washing the product by deionized water and absolute ethyl alcohol, and drying the product in vacuum at 60 ℃ for 12 hours; obtaining the PAA @ Ag/AgCl-40/CN composite photocatalyst.
(4) And (3) keeping the pH value of the composite photocatalyst in the step (3) to be 6 in a photochemical reactor to carry out a photocatalytic degradation test, and measuring that the degradation rate of the photocatalyst to tetracycline reaches 67.38% within 2 h.
Example 7:
(1) preparation of CN: preparation of CN: dissolving melamine and cyanuric acid in a molar ratio of 1:1 in 120mL ethanol, stirring for 12h, centrifugally drying, calcining in a muffle furnace at 550 ℃ and a speed of 2.5 ℃/min for 8h, and fully grinding the obtained product to obtain CN;
(2) preparing an Ag/AgCl-40/CN composite photocatalyst:
preparing an Ag/AgCl/CN composite photocatalyst: weighing 0.4g CN, dissolving in 120mL deionized water, fully stirring, adding 0.1304g solid NaCl, stirring for 4h, and dropwise adding 11.6mL AgNO with concentration of 1mol/L 3 Fully stirring the solution to ensure that the reaction is completely carried out, continuing the reaction for 20min under an ultraviolet lamp, centrifuging, washing and putting into an oven for drying to obtain the Ag/AgCl/CN composite photocatalyst, wherein the mass of AgCl accounts for 40% of CN at the moment, and the Ag/AgCl-40/CN composite photocatalyst is called as Ag/AgCl-40/CN later;
(3) the preparation of the acid-sensitive controlled PAA @ Ag/AgCl-40/CN composite photocatalyst comprises the following steps:
0.5g of Ag/AgCl-40/CN was dispersed in 100mL of ethanol and 10mL of 3- (methacryloyloxy) propyltrimethoxysilane, and the mixture was subjected to a constant temperature water bath at 50 ℃ for 12 hours under the protection of nitrogen, and the product was centrifuged and dried to complete the surface modification of the binary material. Then, 0.13g of acrylic acid and 0.03g N, N' -methylenebisacrylamide were weighed, 50mL of deionized water was added, and after 30min of sonication, 0.3g of the surface-modified binary material was added. After stirring for 2h, 0.1mL ammonium persulfate (0.1mol/L) was added as an initiator for 12 h. Finally, repeatedly washing the product by deionized water and absolute ethyl alcohol, and drying the product in vacuum at 60 ℃ for 12 hours; obtaining the PAA @ Ag/AgCl-40/CN composite photocatalyst.
(4) And (3) keeping the pH value of the composite photocatalyst in the step (3) to be 4 in a photochemical reactor to carry out a photocatalytic degradation test, and measuring that the degradation rate of the photocatalyst to tetracycline reaches 64.55 within 2 h.
Example 8:
(1) preparation of CN: preparation of CN: dissolving melamine and cyanuric acid in 120mL of ethanol at a molar ratio of 1:1, stirring for 12h, centrifugally drying, calcining in a muffle furnace at 550 ℃ and a speed of 2.5 ℃/min for 8h, and fully grinding the obtained product to obtain CN;
(2) preparing an Ag/AgCl-40/CN composite photocatalyst:
Ag/AgCl/CN composite photocatalystPreparation of the reagent: weighing 0.4g CN, dissolving in 120mL deionized water, fully stirring, adding 0.1304g solid NaCl, stirring for 4h, and dropwise adding 11.6mL AgNO with concentration of 1mol/L 3 Fully stirring the solution to ensure that the reaction is completely carried out, continuing the reaction for 20min under an ultraviolet lamp, centrifuging, washing and putting into an oven for drying to obtain the Ag/AgCl/CN composite photocatalyst, wherein the mass of AgCl accounts for 40% of CN at the moment, and the Ag/AgCl-40/CN composite photocatalyst is called as Ag/AgCl-40/CN later;
(3) preparing an acid-sensitive control type PAA @ Ag/AgCl-40/CN composite photocatalyst:
dispersing 0.5g of Ag/AgCl-40/CN into 100mL of ethanol and 10mL of 3- (methacryloyloxy) propyl trimethoxy silane, carrying out constant-temperature water bath for 12h at 50 ℃ under the protection of nitrogen, centrifuging and drying a product, and finishing the surface modification of the binary material; then, 0.13g of acrylic acid and 0.03g N, N' -methylenebisacrylamide were weighed, 50mL of deionized water was added, and after 30min of sonication, 0.3g of the surface-modified binary material was added. After stirring for 2h, 0.1mL ammonium persulfate (0.1mol/L) was added as an initiator for 12 h. Finally, repeatedly washing the product by deionized water and absolute ethyl alcohol, and drying the product in vacuum at 60 ℃ for 12 hours; obtaining the PAA @ Ag/AgCl-40/CN composite photocatalyst.
(4) And (3) keeping the pH value of the composite photocatalyst in the step (3) to be 2 in a photochemical reactor to carry out a photocatalytic degradation test, and measuring that the degradation rate of the photocatalyst to tetracycline reaches 61.97 within 2 h.
FIG. 1 is an XRD pattern of Ag/AgCl/CN in different ratios, wherein a represents an Ag/AgCl-10/CN catalyst, b represents an Ag/AgCl-20/CN catalyst, c represents an Ag/AgCl-30/CN catalyst, d represents an Ag/AgCl-35/CN catalyst, e represents an Ag/AgCl-40/CN catalyst, and f represents an Ag/AgCl-45/CN catalyst; and the B picture is an XRD picture of CN, AgCl, Ag/AgCl-40/CN and PAA @ Ag/AgCl-40/CN, wherein a represents a CN monomer, B represents an AgCl monomer, c represents an Ag/AgCl-40/CN catalyst, and d represents PAA @ Ag/AgCl-40/CN catalyst. The characteristic peaks of CN and AgCl are clearly shown in the figure, the characteristic peaks of CN and AgCl are detected in the Ag/AgCl-40/CN composite photocatalyst, but the characteristic peak of Ag is not detected, probably caused by the reason that the content of Ag nanoparticles is low, and in addition, the acid-sensitive control type PAA @ Ag/AgCl-40/CN composite photocatalyst is found not to change the crystal structure of the Ag/AgCl-40/CN photocatalyst.
In FIG. 2, A and B are SEM pictures of CN, C and D are SEM pictures of Ag/AgCl-40/CN, and E and F are SEM pictures of PAA @ Ag/AgCl-40/CN composite photocatalyst; CN with a flaky appearance can be obtained from the graphs A and B, AgCl particles in the graphs (C, D) are uniformly dispersed on the CN, and Ag/AgCl particles in the graphs (E, F) and the CN have a layer of substances on the surface, which indicates that Ag/AgCl-40/CN has been successfully modified by polyacrylic acid.
In FIG. 3, A is a photo current diagram of CN, AgCl, Ag/AgCl-40/CN and PAA @ Ag/AgCl-40/CN composite photocatalysts; b is an impedance diagram of the CN, AgCl, Ag/AgCl-40/CN and PAA @ Ag/AgCl-40/CN composite photocatalyst; wherein a represents CN monomer, b represents AgCl monomer, c represents Ag/AgCl-40/CN catalyst, and d represents PAA @ Ag/AgCl-40/CN composite photocatalyst; FIG. A shows that PAA @ Ag/AgCl-40/CN has the highest photocurrent intensity compared with monomer CN, indicating that the composite material has high efficiency of separating electrons from holes; in the graph B, the PAA @ Ag/AgCl-40/CN has the smallest arc radius, which indicates that the carrier recombination rate of the catalyst is low, and the photocatalytic performance is improved.
FIG. 4 is a PL diagram for CN, Ag/AgCl-40/CN and PAA @ Ag/AgCl-40/CN composite photocatalysts; wherein a represents CN, b represents Ag/AgCl-40/CN, and c represents PAA @ Ag/AgCl-40/CN composite photocatalyst;
the strong emission peak of CN is concentrated at 460nm, which shows that the recombination probability of the photo-generated electron hole pair is high, but the carrier separation efficiency of the PAA @ Ag/AgCl-40/CN composite photocatalyst is obviously improved. The photo-generated electron hole pair of the PAA @ Ag/AgCl-40/CN composite material can be efficiently transferred at a heterojunction interface and has higher photo-catalytic activity than CN and Ag/AgCl-40/CN.
Description of the drawings: the above embodiments are only used to illustrate the present invention and do not limit the technical solutions described in the present invention; thus, while the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted; all such modifications and variations are intended to be included herein within the scope of this disclosure and the present invention and protected by the following claims.
Claims (9)
1. A preparation method of an acid-sensitive controlled PAA @ Ag/AgCl/CN composite photocatalyst is characterized by comprising the following specific steps:
(1) mixing melamine and cyanuric acid, dissolving in ethanol, stirring for a period of time, centrifugally drying, calcining in muffle furnace to obtain sheet g-C 3 N 4 Is marked as CN;
(2) dissolving CN prepared in the step (1) in deionized water, stirring uniformly, and adding NaCl and AgNO 3 Stirring the solution again, placing the solution under an ultraviolet lamp for reaction, centrifuging, washing and drying the solution after the reaction to obtain a composite photocatalyst which is marked as Ag/AgCl/CN;
(3) mixing ethanol and 3- (methacryloyloxy) propyl trimethoxy silane, adding the Ag/AgCl/CN prepared in the step (2), carrying out constant-temperature water bath for a period of time under the protection of nitrogen, centrifuging and drying a product to obtain a surface modified binary material; the dosage ratio of the Ag to the AgCl to the CN to the ethanol to the 3- (methacryloyloxy) propyl trimethoxy silane is 0.3-0.5 g: 80-100 mL: 8-10 mL;
then, adding acrylic acid and N, N' -methylene bisacrylamide into deionized water, and adding a surface modified binary material after ultrasonic treatment; stirring for a certain time, and then adding ammonium persulfate to react; repeatedly washing the product after reaction by using deionized water and absolute ethyl alcohol, and finally carrying out vacuum drying to obtain the acid-sensitive control type PAA @ Ag/AgCl/CN composite photocatalyst; the use amount ratio of the acrylic acid, the N' -methylene bisacrylamide, the deionized water, the surface-modified binary material and the ammonium persulfate is 0.1-0.13 g: 0.01-0.03 g: 30-50 mL: 0.3-0.5 g: 0.1-0.3 mL.
2. The preparation method of the acid-sensitive controlled PAA @ Ag/AgCl/CN composite photocatalyst according to claim 1, wherein in the step (1), the molar ratio of the melamine to the cyanuric acid is 1: 1-3; the dosage of the ethanol is 80-120 mL.
3. The method for preparing the acid-sensitive controlled PAA @ Ag/AgCl/CN composite photocatalyst according to claim 1, wherein in the step (1), the stirring is carried out for 12-24 hours; the calcining temperature is 500-600 ℃, the calcining speed is 2-2.5 ℃/min, and the calcining time is 4-8 h.
4. The method for preparing the acid-sensitive controlled PAA @ Ag/AgCl/CN composite photocatalyst according to claim 1, wherein in the step (2), the CN, the deionized water, the NaCl and the AgNO are 3 The dosage ratio of (A) is 0.4-0.8 g: 80-120 mL: 0.0326-0.1468 g: 2.9-13.1 mL; the AgNO 3 The concentration of the solution was 1 mol/L.
5. The preparation method of the acid-sensitive controlled PAA @ Ag/AgCl/CN composite photocatalyst according to claim 1, wherein in the step (2), the reaction time under the ultraviolet lamp is 20-40 min.
6. The method for preparing the acid-sensitive controlled PAA @ Ag/AgCl/CN composite photocatalyst according to claim 1, wherein in the step (3), the temperature of the thermostatic water bath is 50 ℃ and the time is 12 hours.
7. The method for preparing the acid-sensitive controlled PAA @ Ag/AgCl/CN composite photocatalyst according to claim 1, wherein in the step (3), the ultrasonic time is 30-60 min.
8. The method for preparing the acid-sensitive controlled PAA @ Ag/AgCl/CN composite photocatalyst according to claim 1, wherein in the step (3), the stirring is carried out for 2-3 h; the concentration of the ammonium persulfate is 0.1 mol/L; the time for adding ammonium persulfate to carry out reaction is 12-24 hours; the temperature of the vacuum drying is 60 ℃, and the time is 12 h.
9. Use of the acid-sensitive controlled PAA @ Ag/AgCl/CN composite photocatalyst prepared by the method according to any one of claims 1 to 8 for degrading antibiotics in wastewater.
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