CN115999606A - Oxygen-doped carbon nitride modified nano calcium peroxide composite photocatalyst and preparation method and application thereof - Google Patents
Oxygen-doped carbon nitride modified nano calcium peroxide composite photocatalyst and preparation method and application thereof Download PDFInfo
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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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Abstract
The invention belongs to the technical field of photocatalytic materials, and particularly relates to an oxygen-doped carbon nitride modified nano calcium peroxide composite photocatalyst, and a preparation method and application thereof. The invention is realized by doping oxygen into carbon nitride O-C 3 N 4 With CaO 2 The ratio of the component (A) is adjusted, a high-performance photocatalytic material with high visible light response and low photon-generated carrier composite efficiency is synthesized by adopting a one-step method, and the high-efficiency degradation of phenols substances such as diclofenac and other antibiotics can be realized under the irradiation of visible light. The composite photocatalyst O-C prepared by the invention 3 N 4 /n‑CaO 2 O-C in (C) 3 N 4 Has high visible lightThe response and low photo-generated carrier composite efficiency can effectively utilize sunlight to generate electrons, and the photo-generated electrons can react with dissolved oxygen to generate superoxide anions and activate n-CaO 2 Generates hydroxyl free radicals, so that the catalytic performance of the composite material is improved. The composite photocatalyst has higher application potential and use value, and the preparation process lays a foundation for the application of the composite photocatalyst in the field of environmental improvement.
Description
Technical Field
The invention belongs to the technical field of photocatalytic materials, and particularly relates to an oxygen-doped carbon nitride modified nano calcium peroxide composite photocatalyst, and a preparation method and application thereof.
Background
Diclofenac (DCF) has strong antirheumatic, anti-inflammatory, analgesic and antipyretic effects, and is one of the common analgesic and anti-inflammatory drugs. On one hand, after the DCF is taken by people, the DCF cannot be completely metabolized, part of the DCF enters the urban sewage system along with excrement, and on the other hand, the waste liquid for producing the DCF is discharged into the environment to cause water pollution of the DCF. However, the conventional sewage treatment technology has poor DCF treatment effect, so that improvement of the water treatment technology in the prior art is needed.
CaO 2 Is a solid phase material, has wide application in the aspect of organic pollutant restoration, and on the one hand, caO 2 Can react with water to generate hydrogen peroxide (H) 2 O 2 ) The oxidant can be used for constructing Fenton-like systems for treating organic pollutants in sewage. CaO, on the other hand 2 As a high-efficiency oxygen release agent, oxygen can be slowly released in the water body, and the Dissolved Oxygen (DO) of the restored environmental medium is improved, so that the restoration effect on the anoxic water body can be improved. However, in practical application CaO 2 For water remediation, it is often necessary to add chemical activators such as metal ions (Fe 2+ 、Co 2+ Etc.) or nonmetallic compounds (SO 3 2- 、NO 2 - Etc.), but in the reaction systemIn turn, increases the potential for environmental pollution. Therefore, development of an environment-friendly, low-energy-consumption and efficient reagent coupling technology for water body restoration is urgently needed.
The photocatalysis technology using visible light as a light source is also commonly used for repairing polluted water, and the sunlight catalysis repair technology has the characteristics of green, high efficiency, low energy consumption, mild reaction, no secondary pollution and the like, is an environment-friendly water repair technology, and mainly converts organic matters into micromolecular organic matters and CO with low toxicity in the process of repairing the organic matter polluted water 2 、H 2 O and other inorganic salt substances, thereby achieving the purpose of harmless treatment. Wherein, the modified carbon nitride (g-C) has stable structure, high catalytic effect and visible light response 3 N 4 ) Catalysts have proven to be excellent materials for solar catalytic remediation.
g-C 3 N 4 The band gap width is 2.7 eV, the potentials of the valence band and the conduction band are respectively +1.8V and-0.9V (vs NHE), and the band gap is typically visible light response, conduction band leading type (e - And. O 2 ˉ As the main active substance) catalyst, to overcome g-C 3 N 4 Photogeneration e - And h + Is often modified by element vacancies (O, P, N and S, etc.). Wherein oxygen modifies g-C 3 N 4 （O-C 3 N 4 ) The electron and hole utilization rate of the catalyst is enhanced on the basis of retaining the original structure, and the modified material has high catalytic activity under wide spectrum visible light. For example, chinese patent publication No. CN108686692a discloses an oxygen-doped carbon nitride photocatalyst, a method for preparing the same and application thereof, which discloses an oxygen-doped carbon nitride (O-C) by using a thermal polymerization method 3 N 4 ) The photocatalyst has visible light response performance, can degrade PPCPs in water, but has a narrow application object range, low adaptability and can not effectively degrade phenols and compounds thereof.
Based on CaO 2 Can utilize the characteristics of visible light catalyst and CaO 2 Constructing an oxidation-photocatalysis composite system and introducingThe photo-generated electrons generated by the OCN photocatalyst under the visible light can effectively excite the n-CaO 2 Make up for the disadvantage of adding extra chemicals. At the same time, the method can also adjust O-C 3 N 4 And n-CaO 2 The addition amount is such that O-C 3 N 4 Photogeneration e generated in sunlight - On the one hand, continuously and efficiently generate O 2 - On the other hand, partial overproducing photogeneration e - Activation of n-CaO 2 Forming OH, effectively strengthening the photo-generation e of the photo-catalytic activation system - Action efficacy, promote system generation. O 2 - OH.
Based on this, n-CaO was searched for 2 Synergistic O-C 3 N 4 The catalytic activity for photocatalysis will provide theoretical support for practical application in constructing an "oxidation-photocatalysis" composite system.
Disclosure of Invention
In order to solve the technical problems in the prior art, the invention adopts the method of doping oxygen into carbon nitride (O-C 3 N 4 ) With CaO 2 The ratio of the (B) is adjusted, and a one-step method is adopted to synthesize the high-performance photocatalytic material (O-C) with high visible light response and low photon-generated carrier composite efficiency 3 N 4 /n-CaO 2 Composite photocatalyst) and can realize the high-efficiency degradation of phenols such as diclofenac and other antibiotics under the irradiation of visible light.
The invention also provides an oxygen-doped carbon nitride modified nano calcium peroxide composite photocatalyst (O-C) 3 N 4 /n-CaO 2 ) Is prepared by the preparation method of (1).
The invention further provides the oxygen-doped carbon nitride modified nano calcium peroxide composite photocatalyst (O-C) 3 N 4 /n-CaO 2 ) Is used in the application of (a).
In order to achieve the technical purpose, the invention adopts the following technical scheme:
oxygen-doped carbon nitride catalytic material (O-C 3 N 4 ) The preparation method of (2) comprises the following steps:
calcining semicarbazide hydrochloride at the temperature of 540-560 ℃ for 3-6 hours, cooling to room temperature,obtaining a powdery product, grinding and sieving the powdery product to obtain the oxygen-doped carbon nitride catalytic material (O-C 3 N 4 ）。
Further, the screen mesh used in sieving is 100-200 mesh.
Preferably, the calcination time is 3-5 h, and the temperature rising rate during calcination is 4-6 ℃/min.
Based on a general inventive concept, the invention improves the oxygen-doped carbon nitride catalytic material by using a nano calcium peroxide modification mode, and provides a preparation method of an oxygen-doped carbon nitride modified nano calcium peroxide composite photocatalyst, which comprises the following steps:
1) Adding calcium chloride into a mixed solvent of water and ammonia water, and then adding polyethylene glycol (PEG 2000) while stirring to obtain a solution A;
2) Adding hydrogen peroxide into the solution A obtained in the step 1), and stirring for 1-3 hours to obtain a solution B; adjusting the pH value of the solution B to 11-12 to obtain a suspension, centrifuging to obtain a solid precipitate, drying the solid precipitate, grinding and sieving to obtain powdery nano calcium peroxide (n-CaO) 2 ）；
3) Oxygen-doped carbon nitride catalytic material (O-C 3 N 4 ) Dissolving the powdery nano calcium peroxide prepared in the step 2) in a mixed solvent of water and ethanol, heating in a water bath, evaporating water to dryness, calcining to obtain powdery solid, grinding, and sieving to obtain the composite photocatalyst O-C 3 N 4 /n-CaO 2 。
In step 1), the dosage ratio of calcium chloride to polyethylene glycol (PEG 2000) is 1g (30-40 mL), preferably 1g:40mL.
In the mixed solvent of the step 1), the volume ratio of water to ammonia water is (1.2-2.8): 1.
Preferably, the mixed solvent of water and ammonia water is prepared from 20-40 mL of water and 15-mL ammonia solution with the concentration of 1-3M.
Further, in the step 1), the dosage ratio of the calcium chloride to the mixed solvent of water and ammonia water is (1-4) g: (35-55 mL), preferably 1g:15mL.
Further, in the step 2), the concentration of hydrogen peroxide is 20-30%.
Further, in the step 2), naOH solution is used for adjusting the pH value of the solution B to 11-12; it is further preferred to adjust the pH of solution B to 11.5 using NaOH solution.
Further, in the step 2), the drying temperature is 70-80 ℃ and the drying time is 1-2 hours.
In the step 3), the mixed solvent of water and ethanol is prepared from water and ethanol with a volume ratio of (1.5-4): (0.5-1.5), and the preferred volume ratio is 3:1.
Further, in step 3), the oxygen-doped carbon nitride catalytic material (O-C 3 N 4 ) The dosage ratio of the mixed solvent of water and ethanol is 1g: (25-70 mL), preferably 1 g/25 mL.
Further, in step 3), the oxygen-doped carbon nitride catalytic material (O-C 3 N 4 ) The mass ratio of the powder nano calcium peroxide prepared in the step 2) to the powder nano calcium peroxide is (0.1-1): 1-2, and is preferably 1:1 or 1:2.
Further, in the step 3), the water bath heating temperature is 60-70 ℃, the calcining temperature is 280-320 ℃, the calcining time is 2-4 h, and the heating rate during calcining is 3-6 ℃/min.
Further, the screen mesh used in sieving is 100-200 mesh.
The method improves the oxygen-doped carbon nitride catalytic material by using a nano calcium peroxide modification mode to prepare the oxygen-doped carbon nitride modified nano calcium peroxide composite photocatalyst O-C 3 N 4 /n-CaO 2 。
Furthermore, the invention also provides application of the oxygen-doped carbon nitride modified nano calcium peroxide composite photocatalyst in photocatalytic degradation of water pollutants.
Specifically, the water body is domestic sewage, industrial sewage, agricultural sewage, river water, lake water or seawater, etc.
Specifically, the contaminants are one or more of antibiotics, anti-inflammatory drugs, phenolic compounds, and organic dyes.
Furthermore, the composite photocatalyst can realize repeated utilization when the pollutants in the water body are degraded by photocatalysis, and the repeated utilization times are 1-5 times.
Preferably, the application of the oxygen-doped carbon nitride modified nano calcium peroxide composite photocatalyst in photocatalytic degradation of phenolic compounds in wastewater.
Further preferably, the phenolic compound is phenol, bisphenol a, bisphenol F, bisphenol S or Diclofenac (DCF).
Further, the invention also provides a method for carrying out photocatalytic degradation on water pollutants by using the oxygen-doped carbon nitride modified nano calcium peroxide composite photocatalyst, in particular to a method for carrying out photocatalytic degradation on Diclofenac (DCF) by using the oxygen-doped carbon nitride modified nano calcium peroxide composite photocatalyst, which comprises the following steps:
the composite photocatalyst (O-C 3 N 4 /n-CaO 2 ) Mixing with DCF solution, placing in a photochemical reactor, using a xenon lamp as a light source, irradiating the solution for 5-60 min under visible light, and measuring the DCF content in the solution.
Specifically, the composite photocatalyst (O-C 3 N 4 /n-CaO 2 ) The dosage ratio of the aqueous solution to the DCF solution is (0.01-0.02) g: (50-100) mL.
Specifically, the concentration of the DCF solution is 1-4 mgL -1 。
Specifically, the power of the xenon lamp is 300W-350W.
Although n-CaO 2 As an environmental functional material, there are many advantages but there are also disadvantages such as n-CaO 2 Depending on the external supply of energy to maintain its stable production of active substances, the excessive addition of chemicals limits its application. O-C used in the invention 3 N 4 Is an excellent catalyst which can be effectively excited by sunlight to generate photo-generated electrons and holes, has low recombination rate of the photo-generated electrons and the holes, and can react with dissolved oxygen to generate superoxide anions and further derive a large amount of active substances. The book is provided withThe invention is implemented by mixing O-C 3 N 4 Doped with n-CaO 2 After that, the photo-generated electrons can react with dissolved oxygen to excite the n-CaO 2 The active substances generated in the two aspects can cooperatively remove organic pollutants.
Compared with the prior art, the invention has the advantages that:
1. O-C according to the invention 3 N 4 /n-CaO 2 The preparation method of the composite photocatalyst adopts a simple thermal polymerization method, the composite material has the advantages of simple synthesis method, low cost, good stability and good repeatability, has basic conditions of large-scale production, has higher application potential and use value, and lays a foundation for the application of the composite photocatalyst in the field of environmental improvement.
2. O-C according to the invention 3 N 4 /n-CaO 2 O-C in composite photocatalyst 3 N 4 The composite material has high visible light response and low photon-generated carrier composite efficiency, can effectively utilize sunlight to generate electrons, and simultaneously has O-C 3 N 4 Has strong electron storage and transfer capability, and the photo-generated electrons can react with dissolved oxygen to generate superoxide anions and activate n-CaO 2 Generates hydroxyl free radicals, so that the catalytic performance of the composite material is improved.
Drawings
FIG. 1 is O-C in example 1 3 N 4 Scanning electron microscope images;
FIG. 2 is n-CaO in example 2 2 Scanning electron microscope images;
FIG. 3 is O-C in example 3 3 N 4 /n-CaO 2 Scanning electron microscope images;
FIG. 4 is O-C of example 1 3 N 4 n-CaO of example 2 2 And O-C of example 3 3 N 4 /n-CaO 2 Degradation performance profile for DCF;
FIG. 5 is O-C in example 3 3 N 4 /n-CaO 2 A degradation performance diagram of DCF in different water bodies;
FIG. 6 is O-C in example 3 3 N 4 /n-CaO 2 Catalytic reduction for 5 continuous cyclesA degradation rate graph of DCF in the water;
FIG. 7 is O-C in example 3 3 N 4 /n-CaO 2 A degradation performance diagram of DCF in water added with different ions;
FIG. 8 is O-C in example 3 3 N 4 /n-CaO 2 And the degradation performance of different medicines in the water body is shown.
Detailed Description
The invention will be further illustrated by the following examples in conjunction with the accompanying drawings. The embodiment is implemented on the premise of the technical scheme of the invention, and detailed implementation modes and processes are given, but the protection scope of the invention is not limited to the following embodiment. The experimental methods in which specific conditions are not specified in the following examples are generally carried out under conventional conditions, and the raw materials and reagents used are commercially available products without any particular explanation.
The materials and instruments used in the examples below are all commercially available; wherein the photochemical reactor is XPA-7, purchased from Nanjing Jiang electric works, and the lamp source is 350W xenon lamp.
Semicarbazide hydrochloride (Aminourea hydrochloride), CAS number 563-41-7, 99% pure, ala Ding Shiji (Shanghai) Limited.
Example 1
Example 1 provides an O-C 3 N 4 The preparation method of the photocatalyst comprises the following specific steps:
weighing 120g of semicarbazide hydrochloride, placing the semicarbazide hydrochloride into an alumina crucible, transferring the alumina crucible into a muffle furnace, heating to 550 ℃ at a heating rate of 5 ℃/min, calcining at 550 ℃ for 5 hours, cooling to room temperature, grinding by an agate mortar, and sieving (100-200 meshes of screen) to obtain O-C 3 N 4 The product is obtained.
Example 2
Example 2 provides a calcium peroxide nanomaterial n-CaO 2 The preparation method comprises the following specific steps:
1) Adding 3 g calcium chloride into a mixed solvent of distilled water and ammonia water, uniformly stirring, and adding 120 mL of PEG 2000 liquid in the stirring process to obtain a solution A; wherein, the mixed solvent of distilled water and ammonia water is prepared by 30 mL distilled water and 15mL ammonia solution with the concentration of 1M;
2) Adding 15mL of 30% hydrogen peroxide into the solution A obtained in the step 1) at the speed of 3 drops per minute, and stirring for 2h to obtain a transparent light yellow solution, namely a solution B;
3) Dropwise adding 0.1mol/L NaOH solution into the solution B in the step 2), regulating the pH value of the solution to 11.5, obtaining a white suspension at the moment, centrifuging to obtain a white precipitate, washing the precipitate for 3 times by using 0.1mol/L NaOH solution, washing the precipitate with distilled water until the final pH value of the filtrate is 8.4, drying the obtained precipitate in a vacuum drying oven at 80 ℃ for 2h to obtain a powdery solid product n-CaO 2 。
Example 3
Example 3 provides an oxygen-doped carbon nitride modified nano calcium peroxide composite photocatalyst (O-C 3 N 4 /n-CaO 2 ) The preparation method comprises the following specific steps:
0.8 of the O-C prepared in example 1 was weighed out 0.8 g 3 N 4 Placing into an alumina crucible, adding 15mL ultrapure water, 5mL ethanol and 0.8. 0.8 g n-CaO prepared by example 2 2 Dissolving the powder by ultrasonic treatment, heating in a water bath at 65 ℃ while stirring until the water is evaporated to dryness, then placing the powder into a muffle furnace, heating to 300 ℃ at a heating rate of 5 ℃/min, calcining 3 h at 300 ℃ to obtain powdery solid, cooling to room temperature, grinding by an agate mortar, and sieving (100-200 mesh screen) to obtain the composite photocatalyst O-C 3 N 4 /n-CaO 2 。
Characterization of the preparation results
O-C prepared in example 1 3 N 4 The photocatalyst scanning electron microscope is shown in FIG. 1, and it can be seen from FIG. 1 that O-C 3 N 4 Is porous and has rich pore structure.
The calcium peroxide nanomaterial n-CaO prepared in example 2 2 The scanning electron microscope image is shown in FIG. 2, and it can be seen from FIG. 2 that n-CaO 2 Is in a fine particle state and has larger specific surface area.
Example 3 preparationIs of composite photocatalyst O-C 3 N 4 /n-CaO 2 The scanning electron microscope is shown in FIG. 3, and it can be seen from FIG. 3 that O-C 3 N 4 With n-CaO 2 Preferably bonded together to form a composite.
Test example 1
O-C using example 1 3 N 4 n-CaO of example 2 2 And O-C of example 3 3 N 4 /n-CaO 2 The degradation test of Diclofenac (DCF) is carried out, and the specific steps are as follows:
1. 0.01g of O-C was weighed out separately 3 N 4 、n-CaO 2 And O-C 3 N 4 /n-CaO 2 Placed in a photolysis tube of a photochemical reactor and added with a concentration of 50 mL to 4mg L -1 In the Diclofenac (DCF) solution, stirring for 30 min in the dark to make the solution reach adsorption equilibrium.
2. The solution is irradiated by a 350W xenon lamp light source for photocatalysis experiments, the reaction temperature is 25 ℃, after a certain period of reaction, the residual concentration C of DCF in the reaction solution is detected by a high performance liquid chromatograph, and the residual concentration C is detected according to the formula N= (C) 0 -C)/C 0 * The removal rate was calculated at 100%. Wherein C is 0 Is the initial concentration of DCF.
The test results are shown in Table 1 and FIG. 4, table 1 shows a comparison of 40 minutes degradation rate, FIG. 4 shows the O-C of example 1 3 N 4 n-CaO of example 2 2 And O-C of example 3 3 N 4 /n-CaO 2 Degradation performance profile for diclofenac. As can be seen from Table 1 and FIG. 4, O-C 3 N 4 、n-CaO 2 And O-C 3 N 4 /n-CaO 2 The degradation rate of DCF in 40 minutes is 33.6%, 26.9% and 99.0% respectively.
TABLE 1 degradation of DCF by different catalysts
Test example 2
O-C using the composite photocatalyst of example 3 3 N 4 /n-CaO 2 The degradation test of the medicine (DCF) in different water bodies is carried out, and the specific steps are as follows:
the test method of test example 1 was used to test O-C in example 3 by taking river water, lake water, and ultrapure water containing DCF in a certain place as test subjects 3 N 4 /n-CaO 2 Wherein the concentration of DCF, the ratio of photocatalyst to DCF used was the same as in test example 1.
The test results are shown in Table 2 and FIG. 5, wherein Table 2 is a comparative table of 40 minutes degradation rate, and FIG. 5 is a composite photocatalyst O-C of example 3 3 N 4 /n-CaO 2 And the degradation performance of diclofenac in different water bodies is shown.
As can be seen from Table 2 and FIG. 5, the degradation of DCF in ultrapure water is the best, the degradation rate in 40 minutes reaches more than 99.0%, and the degradation of DCF in river water, river water and lake water is inhibited to different degrees, which is related to the existence of a plurality of inorganic salt ions in the actual water body, but in general, O-C 3 N 4 /n-CaO 2 The reactivity in the actual water body is also higher.
TABLE 2O-C in example 3 3 N 4 /n-CaO 2 Degradation rate of DCF in different water bodies
Test example 3
O-C using the composite photocatalyst of example 3 3 N 4 /n-CaO 2 And (3) carrying out a cycle performance test of DCF degradation, and examining the recycling performance of the photocatalyst, wherein the method comprises the following specific steps of:
the DCF degradation test method in test example 1 was used, and the cycle was operated 5 times, in which the concentration of DCF, the ratio of photocatalyst to DCF used was the same as in test example 1.
The test results are shown in FIG. 6, FIG. 6 is the O-C in example 3 3 N 4 /n-CaO 2 And (3) a degradation rate diagram of the diclofenac degradation cycle experiment.
As can be seen from FIG. 6, pass 5Sub-cycle O-C 3 N 4 /n-CaO 2 The degradation performance of DCF is maintained above 89%. The material has good recycling performance and certain practical application potential.
Test example 4
Test example 4 test of composite photocatalyst O-C of example 3 when different ions are contained in Water 3 N 4 /n-CaO 2 The method for degrading the DCF comprises the following specific steps of:
the composite photocatalyst O-C of example 3 was tested using the DCF degradation test method of test example 1 3 N 4 /n-CaO 2 The degradation performance of DCF in water added with different ions, wherein the concentration of DCF and the dosage ratio of photocatalyst to DCF are the same as those of test example 1, and the degradation reaction is 40min.
The concentration of the ions (chloride ion, carbonate ion, nitrate ion and sulfate ion) added into the water body is 5 mg L -1 The control group is DCF-containing water body without ions.
The test results are shown in fig. 7, and it can be seen from fig. 7 that chloride ions, carbonate ions, nitrate ions and sulfate ions all have a certain inhibition effect on DCF degradation. Of these, the inhibition of nitrate and carbonate ions was most pronounced, with inhibition of 8.87% and 13.36%.
Test example 5
Test example 5 test example 3 composite photocatalyst O-C 3 N 4 /n-CaO 2 The degradation performance of different medicines in the water body is as follows:
the composite photocatalyst O-C of example 3 was tested using the DCF degradation test method of test example 1 3 N 4 /n-CaO 2 The degradation performance of different drugs in the water body, wherein the concentration of each drug and the dosage ratio of the photocatalyst to the drug are the same as those of test example 1, and the degradation reaction is 40min.
The test drugs were bisphenol a (BPA, diphenolpropane), bisphenol F (BPF, 4-dihydroxydiphenyl methane), bisphenol S (BPS, 4' -dihydroxydiphenyl sulfone), and Diclofenac (DCF), respectively.
The test results are shown in the figure8, as can be seen from FIG. 8, the composite photocatalyst O-C of example 3 3 N 4 /n-CaO 2 The degradation effect on different medicines is achieved, the degradation rate of DCF reaches 100% within 40 minutes, and the degradation rates of BPA, BPF, BPS are 64.83%, 74.09% and 50.68% respectively. Illustrating the composite photocatalyst O-C prepared by the invention 3 N 4 /n-CaO 2 Has good degradation effect on different medicines and has certain universality.
Finally, it should be noted that: the above embodiments are only for illustrating the technical aspects of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the above embodiments, it should be understood by those of ordinary skill in the art that: modifications and equivalents may be made to the specific embodiments of the invention without departing from the spirit and scope of the invention, which are intended to be covered by the scope of the claims.
Claims (10)
1. The preparation method of the oxygen-doped carbon nitride modified nano calcium peroxide composite photocatalyst is characterized by comprising the following steps of:
1) Adding calcium chloride into a mixed solvent of water and ammonia water, and then adding polyethylene glycol while stirring to obtain a solution A;
2) Adding hydrogen peroxide into the solution A obtained in the step 1), and stirring for 1-3 hours to obtain a solution B; adjusting the pH value of the solution B to 11-12 to obtain a suspension, then centrifugally separating to obtain a solid precipitate, drying the solid precipitate, grinding and sieving to obtain powdery nano calcium peroxide;
3) Dissolving the oxygen-doped carbon nitride catalytic material and the powdery nano calcium peroxide prepared in the step 2) in a mixed solvent of water and ethanol, heating in a water bath until the water is evaporated to dryness, calcining to obtain powdery solid, grinding and sieving to obtain a final product.
2. The preparation method of claim 1, wherein in the step 1), the ratio of the amount of the mixed solvent of calcium chloride, water and ammonia water is (1-4) g: (35-55) mL.
3. The method according to claim 1, wherein in the step 1), the ratio of the calcium chloride to the polyethylene glycol is 1g (30-40 mL).
4. The method according to claim 1, wherein in the step 2), the drying temperature is 70-80 ℃ and the drying time is 1-2 hours.
5. The method according to claim 1, wherein in the step 3), the ratio of the amount of the oxygen-doped carbon nitride catalyst material mixed with the water and ethanol is 1g: (25-70) mL.
6. The preparation method of claim 1, wherein in the step 3), the mass ratio of the oxygen-doped carbon nitride catalytic material to the powdery nano calcium peroxide prepared in the step 2) is (0.1-1): 1-2.
7. The preparation method according to claim 1, wherein in the step 3), the water bath heating temperature is 60-70 ℃, the calcining temperature is 280-320 ℃, the calcining time is 2-4 hours, and the heating rate during calcining is 3-6 ℃/min.
8. The oxygen-doped carbon nitride modified nano calcium peroxide composite photocatalyst prepared by the method of any one of claims 1-7.
9. The application of the oxygen-doped carbon nitride modified nano calcium peroxide composite photocatalyst in photocatalytic degradation of water pollutants in the field of water treatment.
10. The application of the nano calcium peroxide composite photocatalyst according to claim 9, wherein the application of the nano calcium peroxide composite photocatalyst modified by the oxygen-doped carbon nitride in photocatalytic degradation of phenolic compounds in wastewater.
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