CN116116450A - Carbon-nitrogen photocatalyst rich in bulk defects and preparation method and application thereof - Google Patents
Carbon-nitrogen photocatalyst rich in bulk defects and preparation method and application thereof Download PDFInfo
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 38
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 230000007547 defect Effects 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 52
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 46
- NJYZCEFQAIUHSD-UHFFFAOYSA-N acetoguanamine Chemical compound CC1=NC(N)=NC(N)=N1 NJYZCEFQAIUHSD-UHFFFAOYSA-N 0.000 claims abstract description 40
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- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
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- 239000001301 oxygen Substances 0.000 claims abstract description 16
- 230000001699 photocatalysis Effects 0.000 claims abstract description 16
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- 239000001257 hydrogen Substances 0.000 claims abstract description 5
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- 238000000034 method Methods 0.000 claims description 21
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- 238000004519 manufacturing process Methods 0.000 claims description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
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- 229910052757 nitrogen Inorganic materials 0.000 description 5
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 5
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- 239000007791 liquid phase Substances 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
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- 238000012986 modification Methods 0.000 description 3
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- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
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- 125000000524 functional group Chemical group 0.000 description 1
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
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- 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
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B15/00—Peroxides; Peroxyhydrates; Peroxyacids or salts thereof; Superoxides; Ozonides
- C01B15/01—Hydrogen peroxide
- C01B15/027—Preparation from water
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Abstract
The invention relates to a carbon-nitrogen photocatalyst rich in bulk phase defects, a preparation method and application thereof, wherein the preparation method is based on hydrogen bond self-assembly of melamine and cyanuric acid, and introduces 2-methyl-4, 6-diamino-1, 3, 5-triazine acetoguanamine with a similar structure with melamine to form bulk phase defects in a carbon-nitrogen material from bottom to top, and specifically comprises the following steps: weighing melamine and 2-methyl-4, 6-diamino-1, 3, 5-triazine acetoguanamine with proper proportions, dissolving in deionized water, and fully stirring and dissolving to obtain a reaction solution A; dissolving a proper amount of cyanuric acid in deionized water, and fully stirring and dissolving to obtain a reaction solution B; and slowly dripping the reaction solution B into the turbid solution obtained in the reaction solution A, and washing and drying to obtain the carbon-nitrogen photocatalyst rich in bulk defects. The preparation method is simple and feasible and has low cost; the carbon-nitrogen photocatalyst rich in bulk defects can remarkably improve the photocatalytic activity and selectivity, and can remarkably improve the hydrogen peroxide yield when applied to the preparation of hydrogen peroxide by photocatalytic oxygen reduction.
Description
Technical Field
The invention belongs to the technical field of photocatalysts, and particularly relates to a carbon-nitrogen photocatalyst rich in bulk defects, and a preparation method and application thereof.
Background
Hydrogen peroxide (H) 2 O 2 ) Is a high-value multifunctional chemical product and is widely applied to the fields of chemical synthesis, medical disinfection, wastewater treatment, semiconductor cleaning and the like. In recent years, H 2 O 2 As a novel energy carrier for efficient and environment-friendly oxidants and fuel cells, applications in the environment-friendly and energy fields are receiving a great deal of attention. Hydrogen peroxide (H) 2 O 2 ) As a multifunctional and clean redox agent, the reaction product is H due to the high active oxygen content 2 O and O 2 The environment-friendly and safe environment-friendly oxidizing agent is an efficient and green oxidizing agent for environmental remediation, and is widely applied to degradation of pollutants by advanced oxidation technologies (AOPs).
At present, the industrial production of hydrogen peroxide mainly utilizes an anthraquinone process with high cost, complex process and multiple byproducts, and the transportation process of high-concentration hydrogen peroxide also has great risks. Photocatalytic 2 e-oxygen reduction (ORR) to H 2 O 2 Is a green, sustainable and energy-saving H 2 O 2 The production method. Among the numerous photocatalysts, graphitic carbon nitride (g-C 3 N 4 ) Is a metal-free low-cost semiconductor and has been widely used for photocatalysis of H 2 O 2 Has been attracting attention, because of its suitable energy band structure, certain light response capability and good stability. However, due to insufficient visible light absorption, the photo-generated carriers recombine severely, lack effective active sites, original g-C 3 N 4 Is relatively low. The construction of defect engineering on the photocatalyst surface is a common and effective method for improving the photocatalytic conversion efficiency. By introducing surface defects such as surface vacancies and surface functional groups to g-C 3 N 4 The modification can greatly improve the photocatalysisSelectivity and activity of the reaction. However, in the case of synthesis defect g-C 3 N 4 During the process of (a) adding an alkali metal reagent or borohydride (e.g. NaBH 4 Or KBH 4 ) At this time, defects and doping together regulate the electronic structure, thereby affecting the photocatalytic activity. At present, research on improving hydrogen peroxide yield by photocatalyst bulk defects is lacking.
Disclosure of Invention
In one aspect, the invention provides an environment-friendly carbon-nitrogen photocatalyst and a simple and easy preparation method thereof with low cost, and the catalyst regulates and controls the defect degree by a bottom-up method to form the carbon-nitrogen photocatalyst rich in bulk defects, thereby remarkably improving the photocatalytic activity.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
preparation method of carbon-nitrogen photocatalyst rich in bulk defects
The preparation method is based on hydrogen bond self-assembly of melamine and cyanuric acid, and introduces 2-methyl-4, 6-diamino-1, 3, 5-triazine acetoguanamine with a similar structure with melamine to form bulk defects in a carbon-nitrogen material from bottom to top.
Some technical schemes comprise the following steps:
weighing melamine and 2-methyl-4, 6-diamino-1, 3, 5-triazine acetoguanamine with proper proportions, dissolving in deionized water, and fully stirring and dissolving to obtain a reaction solution A;
dissolving a proper amount of cyanuric acid in deionized water, and fully stirring and dissolving to obtain a reaction solution B;
and slowly dripping the reaction solution B into the turbid solution obtained in the reaction solution A, and washing and drying to obtain the carbon-nitrogen photocatalyst rich in bulk defects.
In some embodiments, the ratio of the melamine to the 2-methyl-4, 6-diamino-1, 3, 5-triazine acetoguanamine is 1: (0.6-3.0).
In some embodiments, the amount of melamine and 2-methyl-4, 6-diamino-1, 3, 5-triazine acetoguanamine is in a ratio of 1:1.2.
In some embodiments, the ratio of the sum of the amounts of the melamine and the benzene ring-containing substance of 2-methyl-4, 6-diamino-1, 3, 5-triazine acetoguanamine to the amount of the benzene ring-containing substance in cyanuric acid is 1:1.
On the other hand, the invention further provides the application of the carbon-nitrogen photocatalyst rich in bulk defects, prepared by the preparation method, in the production of hydrogen peroxide by photocatalytic oxygen reduction, and the yield of the hydrogen peroxide can be remarkably improved.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the method comprises the following steps: adding a certain amount of carbon-nitrogen photocatalyst rich in phase defects into an aqueous solution, introducing oxygen, and matching with visible light irradiation.
The technical scheme adopted by the invention has at least the following beneficial effects:
1. the defect degree of the catalyst construction is regulated and controlled by adopting a bottom-up method, and a carbon-nitrogen photocatalyst rich in bulk defects is formed, so that the separation efficiency of photo-generated carriers is increased while the higher visible light absorption of the carbon-nitrogen photocatalyst is ensured, and the photocatalytic activity and selectivity are further improved;
2. the carbon-nitrogen photocatalyst rich in bulk defects is applied to a process for producing hydrogen peroxide by photocatalytic oxygen reduction, so that the yield of the hydrogen peroxide can be remarkably improved, and the preparation process is simple and convenient to operate;
3. the method is characterized in that a photocatalysis system is used for producing hydrogen peroxide, a solar light excitation light-emitting catalyst is used for carrying out efficient catalytic reaction, no sacrificial agent is needed to be added, oxygen is reduced to produce hydrogen peroxide, utilization and conversion of light energy are realized, and meanwhile, a high-value product is obtained;
4. the chemical reagents used in the preparation process of the photocatalyst are all common reagents, are low in cost and easy to obtain, and have mild synthesis and reaction conditions, simple synthesis method, convenient operation and zero pollution; the prepared catalyst has the advantages of good stability, large specific surface area, strong light absorption capacity, rapid charge transfer, high activity and good cycle stability.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the reference numerals and their signs used in the embodiments will be briefly described below, and it is obvious that the drawings described below are only some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 shows a carbon-nitrogen photocatalyst (DCN) obtained in example 2 1.2 ) XRD pattern of the sample (CN) compared therewith;
FIG. 2 is a DCN obtained in example 2 1.2 Is a field emission scanning electron microscope image;
FIG. 3 is a graph showing the activity of the DCN produced in examples 1-3 in producing hydrogen peroxide at various ratios to the comparative sample CN;
FIG. 4 is a DCN obtained in example 2 of the present application 1.2 ESR diagram with CN.
Detailed Description
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following description will explain the specific embodiments of the present invention with reference to the accompanying drawings. It is evident that the drawings in the following description are only examples of the invention, from which other drawings and other embodiments can be obtained by a person skilled in the art without inventive effort.
For simplicity of the drawing, only the parts relevant to the invention are schematically shown in each drawing, and they do not represent the actual structure thereof as a product. Additionally, in order to simplify the drawing for ease of understanding, components having the same structure or function in some of the drawings are shown schematically with only one of them, or only one of them is labeled. Herein, "a" means not only "only this one" but also "more than one" case.
It should be further understood that the term "and/or" as used in this specification and the appended claims refers to any and all possible combinations of one or more of the associated listed items, and includes such combinations.
Carbon nitride as organic semiconductorThe bulk nonmetallic photocatalyst has the advantages of simplicity and easiness in implementation, meeting the environmental protection requirement and low cost in the process of producing hydrogen peroxide by photocatalytic oxygen reduction, and the original graphite carbon nitride (g-C) 3 N 4 ) Insufficient visible light absorption, severe recombination of photogenerated carriers, and lack of effective active sites; therefore, the applicant adopts a strategy of defect construction and surface modification, and specifically introduces 2-methyl-4, 6-diamino-1, 3, 5-triazine acetoguanamine with a structure similar to melamine into self-assembly based on hydrogen bonds of melamine and cyanuric acid to form bulk defects from bottom to top in a carbon-nitrogen material, so that the separation efficiency of photo-generated carriers is improved while the higher visible light absorption of a carbon-nitrogen photocatalyst is ensured, and the photocatalytic activity and selectivity are further improved.
The technical scheme of the present invention will be clearly and completely described in the following in connection with specific embodiments. The following examples are only for more clearly illustrating the technical aspects of the present invention, and are not intended to limit the scope of the present invention.
Comparative example 1
Adding 0.5g of melamine into 50mL of water, stirring and heating to 70 ℃ to dissolve completely, adding another 0.568g of cyanuric acid into 50mL of water, stirring and heating to 70 ℃ to dissolve completely, slowly dripping the cyanuric acid solution into the mixed solution, reacting for 30min at the same temperature, washing, centrifuging, drying, transferring into a tube furnace, heating to 550 ℃ under nitrogen, preserving heat for 4 hours, cooling, and taking out to obtain a comparative sample Catalyst (CN).
0.01g of the sample powder obtained in example 1 was weighed, added to 60mL of an aqueous solution having a pH value of 3, oxygen was introduced, the solution was irradiated with visible light of 420nm, the solution was stirred constantly to uniformly distribute the catalyst in the liquid phase system, and 2mL of the sample was taken and the concentration of hydrogen peroxide was detected by the DPD method.
Example 1
The ratio of melamine to the amount of 2-methyl-4, 6-diamino-1, 3, 5-triazine acetoguanamine material was 1.5:1. Adding 0.378g of melamine and 0.250g of 2-methyl-4, 6-diamino-1, 3, 5-triazine acetoguanamine into 50mL of water, stirring and heating to 70 ℃ to dissolve completely, and adding 0.645g of cyanuric acid into the mixtureAdding into 50mL of water, stirring and heating to 70deg.C for complete dissolution, slowly dripping cyanuric acid solution into the mixed solution, reacting at the same temperature for 30min, washing, centrifuging, drying, transferring into a tube furnace, heating to 550deg.C under nitrogen condition, maintaining for 4 hr, cooling, and taking out to obtain carbon-nitrogen photocatalyst DCN 0.7 。
0.01g of the sample powder obtained in example 1 was weighed, added to 60mL of an aqueous solution having a pH value of 3, oxygen was introduced, the solution was irradiated with visible light of 420nm, the solution was stirred constantly to uniformly distribute the catalyst in the liquid phase system, and 2mL of the sample was taken and the concentration of hydrogen peroxide was detected by the DPD method.
Example 2
The ratio of melamine to the amount of 2-methyl-4, 6-diamino-1, 3, 5-triazine acetoguanamine material was 1:1.2. Adding 0.252g of melamine and 0.300g of 2-methyl-4, 6-diamino-1, 3, 5-triazine acetoguanamine into 50mL of water, stirring and heating to 70 ℃ to dissolve completely, adding 0.568g of cyanuric acid into 50mL of water, stirring and heating to 70 ℃ to dissolve completely, slowly dripping the cyanuric acid solution into the mixed solution, reacting for 30min at the same temperature, washing, centrifuging, drying, transferring into a tube furnace, heating to 550 ℃ under nitrogen condition, preserving heat for 4 hours, cooling and taking out to obtain the carbon nitrogen photocatalyst DCN 1.2 。
0.01g of the sample powder obtained in example 1 was weighed, added to 60mL of an aqueous solution having a pH value of 3, oxygen was introduced, the solution was irradiated with visible light of 420nm, the solution was stirred constantly to uniformly distribute the catalyst in the liquid phase system, and 2mL of the sample was taken and the concentration of hydrogen peroxide was detected by the DPD method.
Example 3
The ratio of the content of melamine to the content of 2-methyl-4, 6-diamino-1, 3, 5-triazine acetoguanamine is 1:3. Adding 0.252g of melamine and 0.751g of 2-methyl-4, 6-diamino-1, 3, 5-triazine acetoguanamine into 50mL of water, stirring and heating to 70 ℃ to dissolve completely, adding 1.032g of cyanuric acid into 50mL of water, stirring and heating to 70 ℃ to dissolve completely, slowly dripping cyanuric acid solution into the mixed solution, reacting for 30min at the same temperature, washing, centrifuging, drying, and transferring into a tube furnaceUnder the condition of nitrogen, heating to 550 ℃, preserving heat for 4 hours, cooling and taking out to obtain the carbon-nitrogen photocatalyst DCN 3.0 。
0.01g of the sample powder obtained in example 1 was weighed, added to 60mL of water solution with pH value of 3, oxygen was introduced, the solution was irradiated with visible light of 420nm, the solution was stirred constantly to uniformly distribute the catalyst in the liquid phase system, and 2mL of the sample was taken and the concentration of hydrogen peroxide was detected by the DPD method.
Comparative example 2
The present example is substantially the same as the embodiment 1, except that: in the process of producing hydrogen peroxide by photocatalytic oxygen reduction in this example, air is directly introduced for reaction. DCN under the same reaction conditions 1.2 The hydrogen peroxide production rate in the air is 233 mu mol/(g) cat H) the rate of hydrogen peroxide production in oxygen was 292. Mu. Mol/(g) cat H), description O 2 In the photocatalytic synthesis of H 2 O 2 Plays an important role in the process.
It should be noted that, in comparative examples 1 to 2 and examples 1 to 3, the molar ratio of benzene rings in the self-assembly reaction based on hydrogen bonding between melamine and/or a similar substance and cyanuric acid is 1:1, and in examples 1-3, by designing the ratio of melamine to 2-methyl-4, 6-diamino-1, 3, 5-triazine acetoguanamine to be 1.5:1, 1:1.2 and 1:3, respectively, the best synthesis ratio was studied, and the specific ratios involved were all calculated and rounded approximations, which did not substantially affect the implementation effect of the present case.
The product prepared by the invention is structurally characterized by the following means: structural analysis of the sample was performed using X-ray diffraction measured on a Japanese national science Rigaku D/Max-RB type X-ray diffractometer; scanning electron micrographs obtained by using a scanning electron microscope of the Hitachi S-4800 type in Japan; catalyst defects were analyzed using a 300E ESR analyzer from Bruker, germany.
Referring to FIG. 1, a carbon-nitrogen photocatalyst (DCN) prepared in example 2 of the present application 1.2 ) XRD contrast pattern with (CN) obtained in comparative example 1 shows the preparation of carbon-nitrogen photocatalysisThe diffraction peak corresponding to the agent corresponds to the original graphite carbon nitride material, and the phase composition consistent with the diffraction peak and the original graphite carbon nitride material can be obtained; and the (002) plane diffraction peak intensity of the carbon-nitrogen photocatalyst of example 2 was reduced, indicating that the layered superposition of carbon-nitrogen materials was weakened, facilitating the exposure of more active sites.
Referring to FIG. 2, a field emission scanning electron microscope image of the carbon-nitrogen photocatalyst prepared in example 2 shows that the prepared carbon-nitrogen photocatalyst is in a loose layered structure, and the specific surface area can reach 66.052m 2 /g。
Referring to FIG. 3, graphs showing the activity of the different carbon nitrogen photocatalysts of comparative example 1 and examples 1-3 in producing hydrogen peroxide are shown in CN, DCN 0.7 、DCN 1.2 、DCN 3.0 The reaction rates for producing hydrogen peroxide were 96. Mu. Mol/(g), respectively cat ·h)、120μmol/(g cat ·h)、175μmol/(g cat ·h)、80μmol/(g cat H) the synthesis ratio of the optimal sample is 1:1.2.
Referring to FIG. 4, CN and DCN obtained in comparative example 1 and example 2 are shown 1.2 The ESR diagram of the photocatalyst shows that the g of the two materials is 2.0024, and the two materials form nitrogen vacancies and DCN 1.2 The peak intensity of (2) is about 5.0, which is far higher than the defect peak intensity of CN by 0.5, indicating DCN 1.2 The defect degree is stronger, and the activity of producing hydrogen peroxide is higher.
The foregoing examples illustrate only a few embodiments of the invention and are described in detail herein without thereby limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of the invention should be assessed as that of the appended claims.
It should be understood by those skilled in the art that while the present invention has been described in terms of several embodiments, not every embodiment contains only one independent technical solution. The description is given for clearness of understanding only, and those skilled in the art will understand the description as a whole and will recognize that the technical solutions described in the various embodiments may be combined with one another to understand the scope of the present invention.
Claims (8)
1. A preparation method of a carbon-nitrogen photocatalyst rich in bulk defects is characterized in that,
the preparation method is based on hydrogen bond self-assembly of melamine and cyanuric acid, and introduces 2-methyl-4, 6-diamino-1, 3, 5-triazine acetoguanamine with a similar structure with melamine to form bulk defects in a carbon-nitrogen material from bottom to top.
2. The method of manufacturing according to claim 1, comprising the steps of:
weighing melamine and 2-methyl-4, 6-diamino-1, 3, 5-triazine acetoguanamine with proper proportions, dissolving in deionized water, and fully stirring and dissolving to obtain a reaction solution A;
dissolving a proper amount of cyanuric acid in deionized water, and fully stirring and dissolving to obtain a reaction solution B;
and slowly dripping the reaction solution B into the turbid solution obtained in the reaction solution A, and washing and drying to obtain the carbon-nitrogen photocatalyst rich in bulk defects.
3. The method according to claim 2, wherein,
the ratio of the amount of melamine to the amount of 2-methyl-4, 6-diamino-1, 3, 5-triazine acetoguanamine is 1: (0.6-3.0).
4. The method according to claim 2, wherein,
the ratio of the amount of melamine to the amount of 2-methyl-4, 6-diamino-1, 3, 5-triazine acetoguanamine is 1:1.2.
5. the method according to claim 2, wherein,
the ratio of the sum of the amounts of the substances of benzene rings contained in melamine and 2-methyl-4, 6-diamino-1, 3, 5-triazine acetoguanamine to the amount of the substances of benzene rings contained in cyanuric acid is 1:1.
6. A carbon-nitrogen photocatalyst enriched in bulk defects prepared by the method of any one of claims 1-5.
7. Use of a carbon-nitrogen photocatalyst enriched in bulk defects as claimed in claim 6 as a photocatalyst for photocatalytic oxygen reduction to hydrogen peroxide.
8. The use according to claim 7, characterized in that it comprises the steps of:
adding a certain amount of carbon-nitrogen photocatalyst rich in phase defects into an aqueous solution, introducing oxygen, and matching with visible light irradiation.
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