CN116673050B - Bi with near infrared light response 2 O 2 CO 3 @CuBi 2 O 4 Heterojunction, in-situ synthesis method and application thereof - Google Patents
Bi with near infrared light response 2 O 2 CO 3 @CuBi 2 O 4 Heterojunction, in-situ synthesis method and application thereof Download PDFInfo
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- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 description 2
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- FBXVOTBTGXARNA-UHFFFAOYSA-N bismuth;trinitrate;pentahydrate Chemical compound O.O.O.O.O.[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FBXVOTBTGXARNA-UHFFFAOYSA-N 0.000 description 1
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- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 description 1
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- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
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Classifications
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/232—Carbonates
-
- 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
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- 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
- C02F2101/34—Organic compounds containing oxygen
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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
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
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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
- C02F2101/36—Organic compounds containing halogen
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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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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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
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a Bi with near infrared response 2 O 2 CO 3 @CuBi 2 O 4 Heterojunction, in-situ synthesis method and application thereof, bi 2 O 2 CO 3 @CuBi 2 O 4 The heterojunction is CuBi 2 O 4 In situ Bi synthesis on nanorods 2 O 2 CO 3 Particles, bi 2 O 2 CO 3 And CuBi 2 O 4 Forming a heterojunction therebetween. The one-dimensional rod-shaped Bi prepared by the invention 2 O 2 CO 3 @CuBi 2 O 4 The heterojunction has the characteristics of compact interface, large specific surface area and high catalytic activity, has good visible light absorption performance, near infrared characteristics and good stability, has high photoinduced charge transfer efficiency and good photocatalytic activation hydrogen peroxide effect, and can be applied to the fields of photocatalytic activation hydrogen peroxide, organic matter degradation and the like. Bi (Bi) 2 O 2 CO 3 @CuBi 2 O 4 Heterojunction at CuBi 2 O 4 In situ Bi synthesis on nanorods 2 O 2 CO 3 Forming heterojunction, compared with CuBi 2 O 4 The nanorods further improve the light response range and the photocatalysis performance, and improve the photon capturing efficiency; bi obtained by the present invention 2 O 2 CO 3 @CuBi 2 O 4 Heterojunction can efficiently activate H 2 O 2 The degradation rate constant of the acetaminophen can reach 0.0403min within 75min ‑1 And can activate H under wide pH and near infrared light 2 O 2 。
Description
Technical Field
The invention belongs to the technical field of photocatalysis, and particularly relates to Bi with near infrared light response 2 O 2 CO 3 @CuBi 2 O 4 Heterojunction, and in-situ synthesis method and application thereof.
Background
The pollution of organic pollutants to water environment is more and more paid attention to by the public due to the characteristics of high toxicity, difficult degradation and the like. Advanced Oxidation Processes (AOP) such as fenton oxidation, ozone oxidation, chlorine oxidation, persulfate oxidation, and electrochemical oxidation are effective methods for removing organic pollutants and heavy metal complex pollutants due to the efficient generation of oxidative free radicals at low temperatures. However, the disadvantages of low photo-generated electron yield, low transfer efficiency, low sunlight utilization rate and the like exist in the reaction process, so that the practical application is limited. And most of the current research is limited to the visible light range, and most of the photocatalysts cannot respond to near infrared light due to the wide band gap, i.e., do not react under near infrared light.
To solve these problems, efficient activated H with higher solar energy utilization efficiency and which can be extended to near infrared range is sought 2 O 2 The photocatalyst of (c) remains a great challenge. CuBi 2 O 4 Is a p-type semiconductor exhibiting a visible light response. Like other semiconductor photocatalysts, cuBi 2 O 4 And shows poor photocatalytic activity due to rapid recombination of photogenerated carriers.
The heterojunction system has strong oxidation-reduction capability due to the unique electron transfer path, and can effectively inhibit the recombination of photogenerated carriers. In recent years, it has received increasing attention. In the current research work, cuBi was prepared by ultrasonic or agitation methods from Jiu Guogong et al (CN 115069282A) 2 O 4 And Bi (Bi) 2 O 2 CO 3 And compounding to form a heterojunction structure. For another example, qin Yinghao et al (CN 108246306A) are prepared by first synthesizing CuBi 2 O 4 Then synthesizing a photocatalyst CuBi with visible light response by a one-pot method 2 O 4 /Bi 2 WO 6 A nanosphere. Zhang Lei et al (CN 111468138A) Na 2 S is dissolved in water, and CuBi is added 2 O 4 Stirring, transferring to an autoclave for reaction to obtain CuBi 2 O 4 /CuBi 2 S 4 . However, the heterojunction combining scheme reported so far is complex, two materials are needed to be respectively synthesized and then combined for construction, the operation is complex and complicated, or the interface combining failure leads to higher transfer resistance of the heterojunction interface, so that the degradation effect is reduced.
Disclosure of Invention
In view of the shortcomings of the prior art, the invention aims to provide Bi with near infrared response 2 O 2 CO 3 @CuBi 2 O 4 In-situ synthesis method of heterojunction, the in-situ synthesis method of the invention synthesizes Bi with near infrared response by one-step hydrothermal method 2 O 2 CO 3 @CuBi 2 O 4 Heterojunction of Bi 2 O 2 CO 3 @CuBi 2 O 4 The heterojunction has excellent and stable degradation capability on organic pollutants and a wider pH action range.
Another object of the present invention is to provide Bi obtained by the above-mentioned in-situ synthesis method 2 O 2 CO 3 @CuBi 2 O 4 Heterojunction of Bi 2 O 2 CO 3 @CuBi 2 O 4 Preparation of CuBi by heterojunction 2 O 4 At the same time introduce Bi 2 O 2 CO 3 Realize Bi 2 O 2 CO 3 In CuBi 2 O 4 In-situ synthesis with uniform distribution of Bi 2 O 2 CO 3 @CuBi 2 O 4 The heterojunction interface is compact, which is favorable for carrier transmission and separation, inhibits the recombination of electron hole pairs, improves the utilization rate of the transition of electrons from valence band to conduction band, and improves the photocatalytic activity.
Another object of the present invention is to provide the above Bi 2 O 2 CO 3 @CuBi 2 O 4 Heterojunction as photocatalyst in activating H 2 O 2 The application in degrading pollutants.
The aim of the invention is achieved by the following technical scheme.
Bi with near infrared response 2 O 2 CO 3 @CuBi 2 O 4 The in-situ synthesis method of the heterojunction comprises the following steps:
step 1, uniformly mixing bismuth salt and water to obtain a solution A; uniformly mixing copper salt and water to obtain a solution B; dropwise adding the solution B into the solution A under the stirring condition, and uniformly stirring to obtain a solution C, wherein the ratio of bismuth to copper in the bismuth salt to copper salt is (1.8-2.2) 1;
in the step 1, the concentration of bismuth salt in the solution A is 0.060-0.066 mol/L, and the concentration of copper salt in the solution B is 0.030-0.033 mol/L.
In the step 1, the stirring time is at least 180min.
Step 2, adding polyvinylpyrrolidone (PVP) into the solution C, regulating the pH to 10-11 under the condition of stirring, stirring at room temperature, fully mixing to obtain a solution D, keeping the solution D at 180 ℃ for 22-25 hours, naturally cooling to room temperature to obtain a solid material, washing the solid material, and drying to obtain Bi 2 O 2 CO 3 @CuBi 2 O 4 The heterojunction, wherein, the ratio of the mass part of polyvinylpyrrolidone and the mass part of copper in copper salt is (40-120): 1, the unit of the mass part is g, and the unit of the mass part is mol.
In the step 2, naOH aqueous solution is added dropwise to adjust the pH, and the concentration of NaOH in the NaOH aqueous solution is 0.8-1.2 mol/L.
In the step 2, the stirring time at room temperature is 3-4 hours.
In step 2, distilled water and absolute ethanol are used for the washing.
In the step 2, the drying temperature is 60-80 ℃, and the drying time is 7-9 hours.
Bi (Bi) 2 O 2 CO 3 @CuBi 2 O 4 Heterojunction, cuBi 2 O 4 In situ Bi synthesis on nanorods 2 O 2 CO 3 Particles, bi 2 O 2 CO 3 And CuBi 2 O 4 Forming a heterojunction therebetween.
The Bi described above 2 O 2 CO 3 @CuBi 2 O 4 Heterojunction as photocatalyst in activating H 2 O 2 The application in degrading pollutants.
In the above technical solution, the contaminant is a mixture of one or more of Ciprofloxacin (CIP), tetracycline (TC), p-tert-butylphenol (PTBP), o-nitrophenol (ONP), p-acetaminophen (APAP), and iron complex (Fe-EDTA).
In the technical scheme, the degradation method comprises the following steps: bi is mixed with 2 O 2 CO 3 @CuBi 2 O 4 Adding the heterojunction into the solution to be degraded containing pollutants, stirring until adsorption is balanced under dark condition, and adding H 2 O 2 Aqueous solution, wherein H 2 O 2 H in aqueous solution 2 O 2 The concentration of (2) is 30wt%, bi 2 O 2 CO 3 @CuBi 2 O 4 Mass fraction of heterojunction and H 2 O 2 H in aqueous solution 2 O 2 The ratio of the parts by weight of the substances is 400 (2.5-3.5), the unit of the parts by weight is g, and the unit of the parts by weight of the substances is mol.
Compared with the prior art, the invention has the following beneficial effects:
1. prepared by the inventionOne-dimensional bar-shaped Bi 2 O 2 CO 3 @CuBi 2 O 4 The heterojunction has the characteristics of compact interface, large specific surface area and high catalytic activity, has good visible light absorption performance, near infrared characteristics and good stability, has high photoinduced charge transfer efficiency and good photocatalytic activation hydrogen peroxide effect, and can be applied to the fields of photocatalytic activation hydrogen peroxide, organic matter degradation and the like. Bi (Bi) 2 O 2 CO 3 @CuBi 2 O 4 Heterojunction at CuBi 2 O 4 In situ Bi synthesis on nanorods 2 O 2 CO 3 Forming heterojunction, compared with CuBi 2 O 4 The nanorods further improve the light response range and the photocatalysis performance, and improve the photon capturing efficiency; bi obtained by the present invention 2 O 2 CO 3 @CuBi 2 O 4 Heterojunction can efficiently activate H 2 O 2 The degradation rate constant of acetaminophen (APAP) can reach 0.0403min within 75min -1 And can activate H under wide pH and near infrared light 2 O 2 。
2. The in-situ synthesis method omits complicated pretreatment procedures, simplifies the preparation process and has low cost.
Drawings
FIG. 1 shows Bi obtained by the preparation of examples 1 to 3 2 O 2 CO 3 @CuBi 2 O 4 Heterojunction and CuBi prepared in comparative example 2 2 O 4 An XRD pattern of (b);
FIG. 2 shows Bi obtained in example 2 2 O 2 CO 3 @CuBi 2 O 4 SEM image of heterojunction, wherein a is overall view, b is detail enlarged image;
FIG. 3 shows Bi obtained in example 2 2 O 2 CO 3 @CuBi 2 O 4 A TEM image and an HRTEM image of the heterojunction, wherein a is the TEM image, and b is the HRTEM image;
FIG. 4 shows Bi obtained in example 2 2 O 2 CO 3 @CuBi 2 O 4 Different environment pairs of heterojunction activated H 2 O 2 In (3), whereinA is degradation without adding background anions and with adding different background anions, b is degradation under different water bodies, c is degradation with different pollutant concentrations;
FIG. 5 shows Bi obtained in example 2 2 O 2 CO 3 @CuBi 2 O 4 Heterojunction at different pH vs H 2 O 2 The effect of activation, wherein a is the degradation curve of acetaminophen water solutions with different pH values (before degradation), b is the degradation rate of acetaminophen water solutions with different pH values (before degradation) during degradation for 75min, c is the change of pH value along with degradation;
FIG. 6 shows the activation of H by photocatalyst under irradiation of visible/near infrared light 2 O 2 The performance of degrading the acetaminophen, wherein a is a acetaminophen degradation curve of different photocatalysts under visible light irradiation, b is a first-order kinetic equation corresponding to the degradation of the acetaminophen by the different photocatalysts under visible light irradiation, c is a acetaminophen degradation curve of the different photocatalysts under near infrared light irradiation, and d is a first-order kinetic equation corresponding to the degradation of the acetaminophen by the different photocatalysts under near infrared light irradiation;
FIG. 7 shows Bi obtained in example 2 2 O 2 CO 3 @CuBi 2 O 4 Degradation rates of the heterojunction to different pollutants;
FIG. 8 shows Bi obtained in example 2 2 O 2 CO 3 @CuBi 2 O 4 A heterojunction continuous four-time degradation experimental diagram;
FIG. 9 shows Bi obtained in example 2 2 O 2 CO 3 @CuBi 2 O 4 Heterojunction and CuBi prepared in comparative example 2 2 O 4 Is a uv-visible diffuse reflectance graph of (a);
FIG. 10 shows Bi obtained in example 2 2 O 2 CO 3 @CuBi 2 O 4 Heterojunction and CuBi prepared in comparative example 2 2 O 4 (a) PL and (b) TRPL maps;
FIG. 11 shows Bi obtained in example 2 2 O 2 CO 3 @CuBi 2 O 4 Heterojunction and CuBi prepared in comparative example 2 2 O 4 (a) photocurrent and (b) EIS diagram;
FIG. 12 shows Bi obtained in example 2 2 O 2 CO 3 @CuBi 2 O 4 Heterojunction and CuBi prepared in comparative example 2 2 O 4 N of (a) 2 Adsorption stripping figure and (b) pore size distribution map;
FIG. 13 shows Bi obtained in example 1 2 O 2 CO 3 @CuBi 2 O 4 Heterojunction, bi prepared in example 2 2 O 2 CO 3 @CuBi 2 O 4 Heterojunction, bi prepared in example 3 2 O 2 CO 3 @CuBi 2 O 4 Heterojunction and CuBi prepared in comparative example 2 2 O 4 (a) Activation of H under irradiation of visible light 2 O 2 Degradation of contaminant patterns and (b) activation of H under irradiation of near infrared light 2 O 2 Degradation of the contaminant pattern.
Detailed Description
The technical scheme of the invention is further described below with reference to specific embodiments.
The raw materials and home information related to the following examples are as follows: bismuth nitrate pentahydrate: shanghai Ala Biochemical technology Co., ltd; copper nitrate trihydrate: shanghai Ala Biochemical technology Co., ltd; polyvinylpyrrolidone: beijing Ding Guo prosperous biotechnology limited liability company; sodium hydroxide: shanghai Ala Biochemical technology Co., ltd; aqueous hydrogen peroxide (30 wt%): tianjin, jiang Tian chemical technology Co., ltd;
the instruments and their model information involved in the following examples are as follows: xenon lamp light source system: beijing Zhongzhu Jiyuan technology Co., ltd; an agitator: tianjin Keno instruments Co., ltd; scanning Electron Microscope (SEM): hitachi SU8010; transmission Electron Microscope (TEM): JEOL JEM-2100F; powder x-ray diffraction (XRD): rigaku D/Max2200pc x-ray diffractometer; fluorescence spectrometer: FL S920P; ultraviolet-visible spectrophotometer: shimadzu; ultraviolet spectrophotometer: UV-6100s; electrochemical workstation: CHI660B; automatic gas adsorption analyzer: autosorb-IQ.
In Bi as follows 2 O 2 CO 3 @CuBi 2 O 4 In the heterojunction in-situ synthesis method, the adopted water is deionized water.
Examples 1 to 3
Bi with near infrared response 2 O 2 CO 3 @CuBi 2 O 4 The in-situ synthesis method of the heterojunction comprises the following steps:
step 1, bi (NO 3 ) 3 ·5H 2 O and water are uniformly mixed to obtain a solution A, cu (NO 3 ) 3 ·3H 2 Mixing O and water uniformly to obtain solution B, dropwise adding the solution B into the solution A under stirring, and stirring for 180min to obtain solution C, wherein Bi (NO 3 ) 3 ·5H 2 The concentration of O is 0.0625mol/L, cu (NO 3 ) 3 ·3H 2 The concentration of O is 0.03125mol/L, bi (NO 3 ) 3 ·5H 2 O and Cu (NO) 3 ) 3 ·3H 2 O is 2:1;
step 2, adding polyvinylpyrrolidone (PVP) into the solution C, dropwise adding 1mol/L NaOH aqueous solution under stirring to adjust the pH to 10.5, stirring at room temperature for 3 hours, fully mixing to obtain a solution D, placing the solution D into a steel autoclave lined with polytetrafluoroethylene of 100ml, keeping the solution D in a 180 ℃ oven for 24 hours, naturally cooling to room temperature to obtain a solid material, washing the solid material with distilled water and absolute ethyl alcohol for 3 times respectively, drying the solid material in a 70 ℃ vacuum oven for 8 hours, and grinding the solid material into powder to obtain Bi 2 O 2 CO 3 @CuBi 2 O 4 Heterojunction in which polyvinylpyrrolidone is present in parts by mass and Cu (NO 3 ) 3 ·3H 2 The ratio of the parts by weight of the O is X, the unit of the parts by weight is g, and the unit of the parts by weight is mol.
| Examples | X | Bi 2 O 2 CO 3 @CuBi 2 O 4 Numbering of heterojunction |
| Example 1 | 40:1 | Bi 2 O 2 CO 3 @CuBi 2 O 4 -1 |
| Example 2 | 80:1 | Bi 2 O 2 CO 3 @CuBi 2 O 4 -2 |
| Example 3 | 120:1 | Bi 2 O 2 CO 3 @CuBi 2 O 4 -3 |
Comparative example 1
CuBi 2 O 4 /Bi 2 O 2 CO 3 The method for synthesizing the heterojunction photocatalyst is disclosed in example 3 of the invention patent with publication number CN115069282A (the name of the invention: a copper bismuthate/bismuth oxide carbonate heterojunction photocatalyst, and a preparation method and application thereof). The method comprises the following steps:
step 1: 1.23 mmole of CuBi 2 O 4 Dispersing into 40mL of methanol, and carrying out ultrasonic treatment for 30 minutes to obtain a tan suspension A;
step 2: while magnetically stirring, 9.07mmolBi was added 2 O 2 CO 3 Dispersing the powder into the suspension A, stirring for 30min to obtain light brownIs a suspension B of (1);
step 3: precipitating suspension B, washing the precipitate with deionized water and absolute ethanol for 3 times, and drying at 70deg.C for 12 hr to obtain CuBi 2 O 4 /Bi 2 O 2 CO 3 Heterojunction photocatalysts.
Comparative example 2
CuBi 2 O 4 The synthesis method of (2) is basically the same as that of example 1, except that polyvinylpyrrolidone (PVP) is not added in step 2 of the comparative example to obtain CuBi 2 O 4 。
Comparative example 3
CuBi 2 O 4 With Bi 2 O 2 CO 3 The preparation method of the ultrasonic mixture comprises the following steps: respectively taking 5mg Bi 2 O 2 CO 3 Nanosheets with 35mg of CuBi 2 O 4 40mg of the mixture is added with 10mL of deionized water and ultrasonic treatment is carried out for 30min to obtain CuBi 2 O 4 With Bi 2 O 2 CO 3 Is a mixture of ultrasound.
The Bi described above 2 O 2 CO 3 The preparation method of the nano-sheet comprises the following steps: 70mL of ethanol and 4mL of deionized water were mixed and vigorously stirred at 300r/min for 10min, after which 600mg of cetyltrimethylammonium bromide (CTAB) was added and vigorously stirred until completely dissolved. 600mg of Hexamethylenetetramine (HMT) was then added and stirring continued until the solution became clear. Then, 1200mg of Na was added to the above system 2 CO 3 And 2g BiCl 3 Stirring vigorously for 1 hour, a precursor mixture was obtained. Subsequently, the prepared precursor mixture was put into a 100mL steel autoclave lined with polytetrafluoroethylene, heated at 140 ℃ for 12 hours, and then naturally cooled to room temperature to obtain a product. The obtained product is collected by centrifugation, washed 3 times with water and ethanol respectively, and dried in vacuum overnight to obtain Bi 2 O 2 CO 3 A nano-sheet.
The performance tests and characterizations of the above examples and comparative examples are as follows:
1. photocatalyst activating H under visible light 2 O 2 The method of (1):
0.04g of the photocatalyst was dissolved in 50mL of an aqueous acetaminophen solution having a acetaminophen concentration of 10mg/L and magnetically stirred in the dark for 15min to reach adsorption equilibrium. The solution which reached the adsorption equilibrium was taken and absorbance was measured at wavelength λ=242 nm. Adding H 2 O 2 Aqueous solution (H) 2 O 2 H in aqueous solution 2 O 2 The concentration of (2) is 30wt%) and a xenon lamp (adding optical filter to make lambda > 420 nm) is used as light source to make irradiation, in the course of which the stirring is continuously carried out, every 15min is sampled, the absorbance is measured, and the degradation rate of acetaminophen is calculated by means of absorbance value, in which the weight portion of photocatalyst and H 2 O 2 H in aqueous solution 2 O 2 The ratio of the parts by weight of the substances is 400:3, the unit of the parts by weight is g, and the unit of the parts by weight of the substances is mol.
2. Photocatalyst activation of H under near infrared light 2 O 2 The method of (1):
0.04g of the photocatalyst was dissolved in 50mL of an aqueous acetaminophen solution having a acetaminophen concentration of 10mg/L and magnetically stirred in the dark for 15min to reach adsorption equilibrium. The solution which reached the adsorption equilibrium was taken and absorbance was measured at wavelength λ=242 nm. Adding H 2 O 2 Aqueous solution (H) 2 O 2 H in aqueous solution 2 O 2 The concentration of (2) is 30wt%) and a xenon lamp (adding optical filter to make lambda > 800 nm) is used as light source to make irradiation, in the course of this process, stirring is continuously, every 15min sampling is made, the absorbance is measured, and the degradation rate of acetaminophen can be calculated by means of absorbance value, in which the weight portion of photocatalyst and H 2 O 2 H in aqueous solution 2 O 2 The ratio of the parts by weight of the substances is 400:3, the unit of the parts by weight is g, and the unit of the parts by weight of the substances is mol.
As can be seen from FIG. 1, the CuBi obtained in comparative example 2 was prepared using CuK radiation (λ=0.15418 nm) on a RigakuD/Max2200PC X-ray diffractometer 2 O 4 And Bi obtained by the preparation of examples 1 to 3 2 O 2 CO 3 @CuBi 2 O 4 Powder X-ray diffraction (XRD) is carried out on the heterojunction, and the synthesized CuBi 2 O 4 Diffraction peak and CuBi 2 O 4 The standard card (JCPCDS 72-0493) is highly coincident, indicating that it has good crystallinity. In addition, bi 2 O 2 CO 3 @CuBi 2 O 4 The heterojunction contains CuBi 2 O 4 And Bi (Bi) 2 O 2 CO 3 Is free of other impurity peaks, confirming CuBi 2 O 4 And Bi (Bi) 2 O 2 CO 3 Bi prepared by 2 O 2 CO 3 @CuBi 2 O 4 And coexist in the heterojunction.
Subsequently, the sample obtained in example 2 was subjected to Scanning Electron Microscopy (SEM) using Hitachi SU8010
Bi 2 O 2 CO 3 @CuBi 2 O 4 The morphology and microstructure of the heterojunction were studied as shown in fig. 2. As can be seen from FIG. 2a, bi is obtained in example 2 2 O 2 CO 3 @CuBi 2 O 4 The heterojunction is of a one-dimensional rod-shaped structure; further magnification (b of FIG. 2) it was found that the surface after PVP addition became rough and at CuBi 2 O 4 Surface generation of a lot of Bi 2 O 2 CO 3 The XRD pattern of FIG. 1 confirms that the photocatalyst prepared in example 2 is Bi 2 O 2 CO 3 And CuBi 2 O 4 Is a coexistence of (1).
The Bi obtained in example 2 was observed by using a JEOL JEM-2100F Transmission Electron Microscope (TEM) 2 O 2 CO 3 @CuBi 2 O 4 The microstructure of the heterojunction is shown in FIG. 3, and FIG. 3 shows that CuBi 2 O 4 A plurality of Bi are distributed on the surface 2 O 2 CO 3 Nanoparticles (a of FIG. 3), bi 2 O 2 CO 3 @CuBi 2 O 4 High Resolution Transmission Electron Microscopy (HRTEM) of-2 clearly shows CuBi 2 O 4 (211) face and Bi 2 O 2 CO 3 The (110) plane of (C) is 0.310nm and 0.274nm, respectively. CuBi 2 O 4 And Bi (Bi) 2 O 2 CO 3 And a heterojunction interface in close contact is formed between the two layers, so that the transmission of photo-generated carriers at the interface is facilitated.
The application of photocatalytic technology in actual wastewater treatment is affected by a number of factors, such as dissolved natural organics and anions in the wastewater. Exploration of Bi in different environments 2 O 2 CO 3 @CuBi 2 O 4 Heterojunction activation H 2 O 2 Is a function of (a) and (b).
Exploration of additive vs. Bi 2 O 2 CO 3 @CuBi 2 O 4 -2 activation of H 2 O 2 The method of influence is as follows: 5 samples were prepared, each as follows: 0.04g Bi 2 O 2 CO 3 @CuBi 2 O 4 -2 was dissolved in 50mL of an aqueous acetaminophen solution prepared with deionized water, the concentration of acetaminophen in the aqueous acetaminophen solution being 10mg/L. The four samples were added with additives of 0.29g NaCl (0.1 mol/L) and 0.71g Na 2 SO 4 (0.1mol/L)、0.53gNa 2 CO 3 (0.1 mol/L) or 20mg humic acid (i.e. one additive was added to each of the first four samples), the last sample was not added with additives, and five samples were subjected to environmental conditions: first, magnetically stirring in the dark for 15min to reach adsorption equilibrium. Absorbance was measured at λ=242 nm for each solution that reached adsorption equilibrium. Then respectively adding H 2 O 2 Aqueous solution (H) 2 O 2 H in aqueous solution 2 O 2 The concentration of (2) was 30 wt%) and was irradiated with a xenon lamp (filter was added so that lambda > 420 nm) as a light source, during which stirring was continued, sampling was carried out every 15min, absorbance was measured, and the degradation rate of acetaminophen was calculated from the absorbance value, wherein Bi 2 O 2 CO 3 @CuBi 2 O 4 -2 parts by mass and H 2 O 2 H in aqueous solution 2 O 2 The ratio of the parts by weight of the substances is 400:3, the unit of the parts by weight is g, and the unit of the parts by weight of the substances is mol. As shown in FIG. 4 a, the result of the experiment is that common anions such as Cl - 、SO 4 2- 、CO 3 2- And humic acid has a negligible effect on degrading contaminants.
Exploration of water environment vs Bi 2 O 2 CO 3 @CuBi 2 O 4 -2 activation of H 2 O 2 Method of influencing, and the aforementioned "exploring additive vs. Bi 2 O 2 CO 3 @CuBi 2 O 4 -2 activation of H 2 O 2 The procedure of the test without additives was basically the same except that "the acetaminophen aqueous solution was prepared with deionized water, tap water or natural lake water (university of south-open Ma Dihu)", and the test results are shown in fig. 4 b. As shown in fig. 4 b, the degradation rate of pollutants in tap water and natural water is still kept above 75%.
Investigation of pollutant concentration versus Bi 2 O 2 CO 3 @CuBi 2 O 4 -2 activation of H 2 O 2 Method of influencing, with the aforementioned "photocatalyst activating H under visible light 2 O 2 The test steps in the method "of (2) are substantially identical, except that" the concentrations of the aqueous acetaminophen solutions are 5ppm, 10ppm, 20ppm and 50ppm, respectively, and the photocatalyst is Bi 2 O 2 CO 3 @CuBi 2 O 4 -2", the test results are shown in fig. 4 c. As shown in FIG. 4 c, the degradation rate of acetaminophen can still reach 75% with increasing or decreasing contaminant concentration.
Investigation of different pH vs Bi 2 O 2 CO 3 @CuBi 2 O 4 -2 activation of H 2 O 2 Is a function of (a) and (b). Will be 0.04gBi 2 O 2 CO 3 @CuBi 2 O 4 -2 is dissolved in 50mL of an aqueous acetaminophen solution, pH adjusted to pH3, 5, 7, 9 or 11, respectively, using 1mol/L NaOH or 1mol/L HCl in water, wherein the concentration of acetaminophen in the aqueous acetaminophen solution is 10mg/L. After adjusting the pH, magnetic stirring was carried out in the dark for 15min to reach adsorption equilibrium, at which time measurement was carried out using a pH meter and defined as initial pH. The solution which reached the adsorption equilibrium was taken and absorbance was measured at wavelength λ=242 nm. AddingIn H 2 O 2 Aqueous solution (H) 2 O 2 H in aqueous solution 2 O 2 The concentration of (2) was 30 wt%) and a xenon lamp (filter was added so that lambda > 800 nm) was used as a light source for irradiation, during which stirring was continued for 75min, and after completion of stirring for 75min, the pH of the solution was measured using a pH meter and defined as Final pH, wherein samples were taken at 15min intervals and absorbance was measured during continuous stirring for 75min, and the degradation rate of acetaminophen was calculated from the absorbance value.
As can be seen from FIG. 5 a and FIG. 5 b, bi 2 O 2 CO 3 @CuBi 2 O 4 -2 maintains a high reactivity in the initial pH range 3-9. The change in system pH at different initial pH values was thus studied further. From fig. 5 c, it is shown that the pH decreases with increasing reaction time. Possible reasons include the production of small organic acids and the release of protons during the degradation of APAP.
Investigation of different photocatalysts for activating H under visible light/near-infrared light irradiation 2 O 2 Degrading the pollutants. The activation of H under visible light according to the aforementioned "photocatalyst", respectively 2 O 2 Process for the "and" photocatalyst activation of H under near infrared light 2 O 2 The procedure of (2) was carried out with the photocatalyst Bi obtained in examples 1 to 3 2 O 2 CO 3 @CuBi 2 O 4 Heterojunction, cuBi prepared in comparative example 1 2 O 4 /Bi 2 O 2 CO 3 Heterojunction photocatalyst and CuBi prepared in comparative example 2 2 O 4 And comparative example 3 CuBi 2 O 4 With Bi 2 O 2 CO 3 Is a mixture of ultrasound. The photocatalyst is Bi prepared in example 2 2 O 2 CO 3 @CuBi 2 O 4 Heterojunction, cuBi prepared in comparative example 1 2 O 4 /Bi 2 O 2 CO 3 Heterojunction photocatalyst and CuBi prepared in comparative example 2 2 O 4 And comparative example 3 CuBi 2 O 4 With Bi 2 O 2 CO 3 The results of the experiment of the ultrasonic mixture of (2) are shown in FIG. 6, the photocatalyst isBi obtained by the preparation of examples 1 to 3 2 O 2 CO 3 @CuBi 2 O 4 Heterojunction and CuBi prepared in comparative example 2 2 O 4 The experimental results of (A) are shown in FIG. 13, (CBO, CBO-2, physical mixture, BOC in FIG. 6 are CuBi prepared in comparative example 2 in this order) 2 O 4 Bi obtained in example 2 2 O 2 CO 3 @CuBi 2 O 4 Heterojunction, cuBi prepared in comparative example 3 2 O 4 With Bi 2 O 2 CO 3 CuBi prepared in comparative example 1 and ultrasonic mixture of (2) 2 O 4 /Bi 2 O 2 CO 3 The heterojunction photocatalyst, shown in FIG. 13 as CBO-1, CBO-2, CBO-3 and CBO, is Bi prepared in example 1 2 O 2 CO 3 @CuBi 2 O 4 Heterojunction, bi prepared in example 2 2 O 2 CO 3 @CuBi 2 O 4 Heterojunction, bi prepared in example 3 2 O 2 CO 3 @CuBi 2 O 4 Heterojunction and CuBi prepared in comparative example 2 2 O 4 ) Bi under the irradiation condition of visible light/near infrared light 2 O 2 CO 3 @CuBi 2 O 4 When-2 is used as a photocatalyst, the degradation rate of acetaminophen (APAP) exceeds 90% after 75min degradation, so Bi 2 O 2 CO 3 @CuBi 2 O 4 2 as a photocatalyst, has stronger catalytic oxidation activity on pollutants under the condition of visible light/near infrared light.
FIG. 6a shows Bi under irradiation with visible light 2 O 2 CO 3 @CuBi 2 O 4 The degradation rate of APAP by heterojunction is superior to that of comparative example 1, comparative example 2 and comparative example 3, and b of FIG. 6 shows Bi prepared in example 2 2 O 2 CO 3 @CuBi 2 O 4 Degradation rate constant of heterojunction (0.0403 min) -1 ) CuBi obtained by comparative example 2 2 O 4 (0.0113min -1 ) And CuBi prepared in comparative example 1 2 O 4 /Bi 2 O 2 CO 3 Heterojunction photocatalyst (0.0047 min) -1 ) 3.6 times and 8.6 times of (a). FIG. 6 c shows Bi obtained in example 2 under near infrared irradiation 2 O 2 CO 3 @CuBi 2 O 4 The degradation effect of the heterojunction on APAP is also better than CuBi 2 O 4 FIG. 6 d shows Bi obtained in example 2 2 O 2 CO 3 @CuBi 2 O 4 Degradation rate constant of heterojunction (0.0255 min) -1 ) Respectively CuBi 2 O 4 (0.0111min -1 ) And CuBi 2 O 4 /Bi 2 O 2 CO 3 Heterojunction photocatalyst (0.009 min) -1 ) 2.3 times and 28.3 times of (a). In addition, with Bi 2 O 2 CO 3 @CuBi 2 O 4 Comparative example 3 preparation of CuBi compared to heterojunction 2 O 4 With Bi 2 O 2 CO 3 The degradation performance of the ultrasonic mixture on APAP is obviously poorer, which indicates that Bi synthesized in situ 2 O 2 CO 3 @CuBi 2 O 4 CuBi in heterojunction 2 O 4 And Bi (Bi) 2 O 2 CO 3 The tighter interface interactions between the heterojunctions may promote interfacial electron transfer.
As can be seen from FIG. 13, bi obtained by the preparation of examples 1 and 3 2 O 2 CO 3 @CuBi 2 O 4 Heterojunction can obtain Bi obtained in example 2 2 O 2 CO 3 @CuBi 2 O 4 Technical effect of heterojunction approach.
Investigation of Bi 2 O 2 CO 3 @CuBi 2 O 4 -2 degrading different contaminants. With the aforementioned photocatalyst, H is activated under visible light 2 O 2 The only difference is that the aforementioned "acetaminophen" is replaced with "Ciprofloxacin (CIP), tetracycline (TC), p-tert-butylphenol (PTBP), o-nitrophenol (ONP) or complex iron contaminants (Fe-EDTA)". As can be seen from FIG. 7, bi 2 O 2 CO 3 @CuBi 2 O 4 -2 has high degradation rate for different pollutants, showing Bi 2 O 2 CO 3 @CuBi 2 O 4 Wide applicability of-2.
Investigation of Bi 2 O 2 CO 3 @CuBi 2 O 4 Stability of-2, bi is used 2 O 2 CO 3 @CuBi 2 O 4 -2 activation of H under visible light as photocatalyst according to the "photocatalyst" described above 2 O 2 The process "four times, at each time" photocatalyst activates H under visible light 2 O 2 After the end of the process of (2), the photocatalyst was washed with deionized water and then dried for the next time "photocatalyst was activated with H under visible light 2 O 2 Is a method of (2). As can be seen from FIG. 8, bi 2 O 2 CO 3 @CuBi 2 O 4 -2 shows excellent degradation rate to pollutants four times in succession, showing Bi 2 O 2 CO 3 @CuBi 2 O 4 Good stability of-2.
Measurement of CuBi obtained in comparative example 2 by ultraviolet-visible Spectrophotometer (Shimadzu) 2 O 4 And Bi obtained in example 2 2 O 2 CO 3 @CuBi 2 O 4 -2 ultraviolet/visible-near infrared diffuse reflectance spectrum. The test results are shown in FIG. 9, and it can be seen from FIG. 9 that CuBi obtained in comparative example 2 2 O 4 Exhibits strong absorption in the ultraviolet and visible wavelength ranges of 823nm, and the heterojunction structure enhances Bi obtained in example 2 2 O 2 CO 3 @CuBi 2 O 4 -2, the absorption capacity in the near infrared region, shows a pronounced red-shift enhancement.
Photoluminescence spectra (PL) were measured at 325nm excitation wavelength using a FL S920P fluorescence spectrometer from Edinburgh instruments, to further demonstrate the Bi obtained in example 2 2 O 2 CO 3 @CuBi 2 O 4 Effective charge separation of-2, steady state Photoluminescence (PL) emission tests were performed. Generally, PL analysis is mainly used to reveal the migration, transfer and separation efficiency of photoexcited electrons and holes in semiconductors. The lower the illumination intensity, the lower the electron-hole pair recombination rate. As shown in FIG. 10 a, the CuBi obtained in comparative example 2 2 O 4 And implementationBi obtained in EXAMPLE 2 2 O 2 CO 3 @CuBi 2 O 4 -2 emission spectrum at 325nm excitation. With the CuBi obtained in comparative example 2 2 O 4 In comparison, bi obtained in example 2 2 O 2 CO 3 @CuBi 2 O 4 The PL emission intensity of-2 drops rapidly, and the formation of heterojunction suppresses the recombination of photogenerated electron-hole pairs. In addition, in order to evaluate carrier lifetime, time Resolved Photoluminescence (TRPL) technique was used, as shown in FIG. 10 b, bi obtained in example 2 2 O 2 CO 3 @CuBi 2 O 4 -2 carrier lifetime maximum (τ ave =2.95 ns), indicating that more photogenerated electrons can participate in H 2 O 2 Is activated by the activation of (a).
Investigation of CuBi-containing 2 O 4 Or Bi 2 O 2 CO 3 @CuBi 2 O 4 -2 photo-electric properties of the photo-anode. 0.02g of photocatalyst, 1mL of ethanol and 20. Mu.L of naphthol were mixed and dropped on Indium Tin Oxide (ITO) glass to obtain a photo anode. The prepared photoanode was subjected to a photoelectric performance test (saturated calomel electrode reference electrode, platinum plate counter electrode) using an electrochemical workstation (CHI 660B; three electrode quartz cell system for Shanghai Chenhua Co.) in which the electrolyte was 0.1M Na 2 SO 4 An aqueous solution. The photocatalyst is CuBi 2 O 4 Or Bi 2 O 2 CO 3 @CuBi 2 O 4 -2。
As shown in FIG. 11 a, bi obtained in example 2 2 O 2 CO 3 @CuBi 2 O 4 -2 has the highest photocurrent, indicating Bi 2 O 2 CO 3 With CuBi 2 O 4 The photogenerated electrons and holes at the interface are effectively separated. It is well known that the surface charge density is proportional to the amount of positive charge accumulated on the surface. The measured transient photocurrent density was subtracted by the photocurrent steady state value and time integrated, bi obtained in example 2 2 O 2 CO 3 @CuBi 2 O 4 The surface charge density of-2 is the CuBi obtained in comparative example 2 2 O 4 More than twice of Bi obtained in example 2 2 O 2 CO 3 @CuBi 2 O 4 -2 more charge is involved in H at the surface 2 O 2 Is activated by the activation of (a). FIG. 11 b shows the Electrochemical Impedance Spectroscopy (EIS) of Bi obtained in example 2 2 O 2 CO 3 @CuBi 2 O 4 The smaller arc radius observed for-2 suggests that the heterojunction structure is beneficial for reducing the charge transfer resistance.
Recording N using an Autosorb-IQ automatic gas adsorption analyzer (Quantachrome) 2 Adsorption-desorption isotherms, bi was determined using BET and BJH 2 O 2 CO 3 @CuBi 2 O 4 -2 and CuBi obtained in comparative example 2 2 O 4 SSA and pore size. As shown in fig. 12, cuBi 2 O 4 And Bi (Bi) 2 O 2 CO 3 @CuBi 2 O 4 Form IV N of-2 2 Adsorption-desorption isotherms showed compliance with IUPAC classification rules. CuBi 2 O 4 And Bi (Bi) 2 O 2 CO 3 @CuBi 2 O 4 BET surface areas of-2 are 90.2 and 126.2m, respectively 2 Per g, bi with PVP addition 2 O 2 CO 3 @CuBi 2 O 4 -2 increases the specific surface area.
The foregoing has described exemplary embodiments of the invention, it being understood that any simple variations, modifications, or other equivalent arrangements which would not unduly obscure the invention may be made by those skilled in the art without departing from the spirit of the invention.
Claims (10)
1. Bi with near infrared response 2 O 2 CO 3 @CuBi 2 O 4 The in-situ synthesis method of the heterojunction is characterized by comprising the following steps of:
step 1, uniformly mixing bismuth salt and water to obtain a solution A; uniformly mixing copper salt and water to obtain a solution B; dropwise adding the solution B into the solution A under the stirring condition, and uniformly stirring to obtain a solution C, wherein the ratio of bismuth to copper in the bismuth salt to copper salt is (1.8-2.2) 1;
step 2, adding polyethylene into the solution CPyrrolidone, adjusting pH to 10-11 under stirring, stirring at room temperature, mixing thoroughly to obtain solution D, maintaining solution D at 180deg.C for 22-25 hr, naturally cooling to room temperature to obtain solid material, washing the solid material, and drying to obtain Bi 2 O 2 CO 3 @CuBi 2 O 4 The heterojunction, wherein, the ratio of the mass part of polyvinylpyrrolidone and the mass part of copper in copper salt is (40-120): 1, the unit of the mass part is g, and the unit of the mass part is mol.
2. The in situ synthesis process according to claim 1, wherein in step 1 the concentration of bismuth salt in the solution a is between 0.060 and 0.066mol/L.
3. The in situ synthesis process according to claim 2, wherein the concentration of copper salt in solution B is 0.030 to 0.033mol/L.
4. The in situ synthesis process according to claim 1, wherein in step 1, the stirring is performed for a period of at least 180 minutes.
5. The in situ synthesis process according to claim 1, wherein in step 2, the pH is adjusted by dropwise addition of an aqueous NaOH solution having a NaOH concentration of 0.8-1.2 mol/L.
6. The in situ synthesis process according to claim 1, wherein in step 2, the stirring time at room temperature is 3 to 4 hours; in step 2, distilled water and absolute ethanol are used for the washing.
7. The in situ synthesis process according to claim 1, wherein in step 2, the drying temperature is 60 to 80 ℃ and the drying time is 7 to 9 hours.
8. Bi obtained by the in situ synthesis method according to any one of claims 1 to 7 2 O 2 CO 3 @CuBi 2 O 4 Heterojunction as photocatalyst in activating H 2 O 2 The application in degrading pollutants.
9. The use according to claim 8, wherein the contaminant is a mixture of one or more of ciprofloxacin, tetracycline, p-tert-butylphenol, o-nitrophenol, acetaminophen and iron complex.
10. The use according to claim 8 or 9, wherein the degradation method is: bi is mixed with 2 O 2 CO 3 @CuBi 2 O 4 Adding the heterojunction into the solution to be degraded containing pollutants, stirring until adsorption is balanced under dark condition, and adding H 2 O 2 Aqueous solution for activating H under irradiation of visible light/near infrared light 2 O 2 Wherein H is 2 O 2 H in aqueous solution 2 O 2 The concentration of (2) is 30wt%, bi 2 O 2 CO 3 @CuBi 2 O 4 Mass fraction of heterojunction and H 2 O 2 H in aqueous solution 2 O 2 The ratio of the parts by weight of the substances is 400 (2.5-3.5), the unit of the parts by weight is g, and the unit of the parts by weight of the substances is mol.
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| CN111468138A (en) * | 2020-05-27 | 2020-07-31 | 辽宁大学 | One-dimensional rod-shaped CuBi2O4@CuBi2S4Visible light catalyst and preparation method and application thereof |
| CN112337476A (en) * | 2020-11-27 | 2021-02-09 | 台州学院 | Copper tungstate/copper bismuthate composite photocatalyst and preparation method thereof |
| CN113275023A (en) * | 2021-05-28 | 2021-08-20 | 南开大学 | Bi3O4Br/CuBi2O4Preparation method and application of bimetallic heterojunction catalyst |
| CN115069282A (en) * | 2022-07-26 | 2022-09-20 | 陕西科技大学 | Copper bismuthate/bismuthate carbonate heterojunction photocatalyst and preparation method and application thereof |
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| CN111468138A (en) * | 2020-05-27 | 2020-07-31 | 辽宁大学 | One-dimensional rod-shaped CuBi2O4@CuBi2S4Visible light catalyst and preparation method and application thereof |
| CN112337476A (en) * | 2020-11-27 | 2021-02-09 | 台州学院 | Copper tungstate/copper bismuthate composite photocatalyst and preparation method thereof |
| CN113275023A (en) * | 2021-05-28 | 2021-08-20 | 南开大学 | Bi3O4Br/CuBi2O4Preparation method and application of bimetallic heterojunction catalyst |
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