CN113318766A - Ag3PO4/g-C3N4Fenton-like catalytic material and preparation method and application thereof - Google Patents
Ag3PO4/g-C3N4Fenton-like catalytic material and preparation method and application thereof Download PDFInfo
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- 238000006731 degradation reaction Methods 0.000 claims description 23
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- 229910001961 silver nitrate Inorganic materials 0.000 claims description 10
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- 238000010438 heat treatment Methods 0.000 claims description 7
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- 239000010452 phosphate Substances 0.000 claims description 6
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- 229910000397 disodium phosphate Inorganic materials 0.000 claims description 4
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- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 4
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 4
- 239000001488 sodium phosphate Substances 0.000 claims description 4
- 235000011008 sodium phosphates Nutrition 0.000 claims description 4
- 238000009210 therapy by ultrasound Methods 0.000 claims description 4
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 2
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- XMEVHPAGJVLHIG-FMZCEJRJSA-N chembl454950 Chemical compound [Cl-].C1=CC=C2[C@](O)(C)[C@H]3C[C@H]4[C@H]([NH+](C)C)C(O)=C(C(N)=O)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O XMEVHPAGJVLHIG-FMZCEJRJSA-N 0.000 claims 3
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- YCIHPQHVWDULOY-FMZCEJRJSA-N (4s,4as,5as,6s,12ar)-4-(dimethylamino)-1,6,10,11,12a-pentahydroxy-6-methyl-3,12-dioxo-4,4a,5,5a-tetrahydrotetracene-2-carboxamide;hydrochloride Chemical compound Cl.C1=CC=C2[C@](O)(C)[C@H]3C[C@H]4[C@H](N(C)C)C(=O)C(C(N)=O)=C(O)[C@@]4(O)C(=O)C3=C(O)C2=C1O YCIHPQHVWDULOY-FMZCEJRJSA-N 0.000 description 25
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Images
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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
- B01J27/24—Nitrogen compounds
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/06—Controlling or monitoring parameters in water treatment pH
-
- 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
- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
Abstract
The present invention provides Ag3PO4/g‑C3N4Fenton-like catalytic material, Ag3PO4/g‑C3N4Ag in Fenton-like catalytic material3PO4Is a cubic phase, g-C3N4In a sheet/layer structure. The Ag is3PO4/g‑C3N4Fenton-like catalytic material and H2O2Under the combined action, the photocatalyst has high and stable non-photocatalytic oxidation activity and excellent visible light catalytic activity, can be used at night/in dark places, and can not generate iron mud and other adverse effects, g-C3N4As a promoter component, can be mixed with Ag3PO4Strong interaction occurs, so that surface Ag+Electrons are enriched around the catalyst to form an active center, so that the catalytic oxidation activity of the main catalyst is obviously improved. The invention also provides the Ag3PO4/g‑C3N4The preparation method of the Fenton-like catalytic material is simple in process, good in repeatability and suitable for industrial production.
Description
Technical Field
The invention relates to the field of inorganic composite materials, in particular to Ag3PO4/g-C3N4Fenton-like compounds, a preparation method thereof and application thereof in efficiently degrading tetracycline hydrochloride.
Background
With the development of economy, the water body pollution is increasingly serious, and the pollution becomes a great social problem threatening the health of human beings and the sustainable development of economy. The industrial wastewater contains a large amount of high-toxicity and high-stability organic pollutants which are difficult to decompose, such as residual antibiotics, organic dyes and the like, and the organic pollutants become one of important sources of water body pollution and bring serious harm to the health of human beings and other organisms. The removal of organic pollutants difficult to degrade in organic wastewater becomes a research hotspot and difficulty in the environmental field.
As a high-grade green oxidation technology, Fenton catalytic oxidation reaction utilizes hydroxyl free radicals with strong oxidizing property to thoroughly mineralize toxic organic pollutants which are difficult to decompose into nonhazardous CO2、H2O and other small molecular substances, and has the characteristics of simple process, safety, greenness, low cost and the like, so that the method is widely researched and used for removing various organic pollutants.
The common Fenton catalyst is an iron-containing compound, and the homogeneous phase iron-containing Fenton catalyst has the problem of secondary pollution caused by a large amount of iron mud generated by iron ion loss in the actual use process and is only suitable for the problem of an acidic solution. The catalyst is usually prepared into a heterogeneous catalyst to improve the stability of the catalyst, for example, Chinese patent CN201910812311.0 discloses an iron-containing Fenton heterogeneous multi-component solid-phase catalyst and a preparation method thereof, for example, Chinese patent CN201910670448.7 discloses a preparation method of a magnetic visible light heterogeneous iron-containing Fenton catalyst, and Chinese patent 201910874037.X provides a catalyst for photo-FentonFeVO of combined catalysis4/TiO2And the like. However, the existing heterogeneous iron-containing Fenton catalyst has the problem of insufficient activity. And generate iron sludge and other pollutants.
Therefore, the development of a novel heterogeneous Fenton-like catalyst becomes a hot research topic in the environmental field.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a novel efficient g-C3N4/Ag3PO4Heterogeneous Fenton-like catalyst and a preparation method thereof. The catalyst is used in the absence of light and H2O2Can efficiently oxidize and decompose the tetracycline hydrochloride and the dye under the synergistic effect of the components, and can be used in a wider pH range. Meanwhile, the catalyst can obviously improve the catalytic efficiency under the irradiation of visible light. The invention provides a new idea and solution for efficient and green pollutant treatment.
The present invention has been made to solve at least some of the problems occurring in the prior art, and in a first aspect of the present invention, there is provided Ag3PO4/g-C3N4Fenton-like catalytic material, the Ag3PO4/g-C3N4Ag in Fenton-like catalytic material3PO4Is a cubic phase, g-C3N4In a sheet/layer structure.
In a second aspect of the present invention, there is provided an Ag alloy as described in the first aspect of the present invention3PO4/g-C3N4The preparation method of the Fenton-like catalytic material comprises the following steps of:
step 1): roasting urea or melamine in air atmosphere to obtain g-C3N4；
Step 2): mixing a silver-containing compound with g-C obtained in step 1)3N4Dispersing in deionized water, stirring for 1-2 hours in the dark, adding soluble phosphate solution, stirring, ultrasonic processing, separating and drying to obtain the Ag3PO4/g-C3N4Fenton-like catalytic material.
In one or more embodiments of the invention, in the step 1), the roasting temperature is controlled to be 550-600 ℃; controlling the heating rate to be 3-5 ℃/min in the process of reaching the roasting temperature; the roasting time is controlled to be 1-5 hours, preferably 1-3 hours.
In one or more embodiments of the present invention, in the step 2), the soluble phosphate is selected from one or more of sodium dihydrogen phosphate, sodium hydrogen phosphate, and sodium phosphate; the molar ratio of the soluble phosphate to the silver-containing compound is 1: (1-3).
In one or more embodiments of the present invention, in the step 2), the silver-containing compound is silver acetate or silver nitrate; control of g-C3N4And the silver-containing compound has a mass ratio of 1: (1-4).
In one or more embodiments of the invention, in the step 2), the time of the ultrasonic treatment is controlled to be 1-2 hours, and the power of the ultrasonic treatment is controlled to be 100W.
In one or more embodiments of the invention, in the step 2), the drying temperature is controlled to be 80-100 ℃, and the drying time is controlled to be 8-12 hours.
In a third aspect of the present invention, the present invention provides Ag3PO4Or Ag3PO4/g-C3N4The Fenton-like catalytic material is applied to catalyzing degradation of tetracycline hydrochloride and/or rhodamine B. Preferably, the Ag is3PO4/g-C3N4Fenton-like catalytic material Ag according to the first aspect of the invention3PO4/g-C3N4Fenton-like catalytic material.
In one or more embodiments of the invention, the Ag3PO4/g-C3N4The Fenton-like catalytic material is Ag according to the second aspect of the invention3PO4/g-C3N4The Fenton-like catalytic material is prepared by the preparation method.
In one or more embodiments of the invention, the degradation of tetracycline hydrochloride and/or rhodamine B is catalyzed by the method under the condition of keeping out light.
In a fourth aspect of the invention, the invention provides Ag3PO4The application of the compound in catalyzing the degradation of tetracycline hydrochloride and/or rhodamine B.
In one or more embodiments of the invention, Ag3PO4The preparation method comprises the following steps: dispersing silver acetate in deionized water under the condition of keeping out of the sun, and then adding a sodium dihydrogen phosphate solution into the solution, wherein the molar ratio of the sodium dihydrogen phosphate to the silver nitrate is 1: 3, stirring for 0.5 hour, centrifugally separating, and drying at 80 ℃ for 12 hours to obtain Ag3PO4。
In one or more embodiments of the invention, the degradation of tetracycline hydrochloride and/or rhodamine B is catalyzed by the method under the condition of keeping out light.
g-C prepared by the preparation method provided by the invention3N4/Ag3PO4The Fenton-like catalytic material comprises Ag3PO4Main catalytic component and g-C3N4A co-catalytic component; wherein, Ag3PO4Is cubic phase, with particle size of tens of nanometers to several micrometers, g-C3N4In a sheet/layer structure. The catalyst is a novel Fenton-like catalyst and is protected from light and H2O2Can efficiently oxidize and decompose the tetracycline hydrochloride and the dye under the synergistic effect of the components, and can be used in a wider pH range. Meanwhile, the catalyst can obviously improve the catalytic efficiency under the irradiation of visible light. The composite catalytic material is also suitable for removing other organic pollutants.
g-C provided by the invention3N4/Ag3PO4The heterogeneous Fenton catalytic material has a catalytic mechanism probably as follows: g-C3N4With Ag3PO4There is a strong interaction between them, electrons from g-C3N4Transfer to Ag3PO4To make surface Ag+The surrounding is enriched with electrons to become active center, and at the same time, surface Ag+And Ag will also react with H2O2Hydroxyl free radicals with strong oxidizing property are generated,hydroxyl radicals and superoxide anion radicals, which oxidize most organic pollutants to CO2And H2O and other small molecular products.
Tetracycline hydrochloride having the molecular formula C22H25ClN2O8CAS number 64-75-5.
Compared with the prior art, the invention has the following advantages and beneficial effects:
1. the invention provides Ag3PO4/g-C3N4Fenton-like catalytic material, the Ag3PO4/g-C3N4Fenton-like catalytic material and H2O2Under the combined action, the photocatalyst has high and stable non-photocatalytic oxidation activity and excellent visible light catalytic activity, and can be used at night/in dark places compared with a pure photocatalyst material.
2. The invention provides Ag3PO4/g-C3N4Fenton-like catalytic material, the Ag3PO4/g-C3N4The Fenton-like catalytic material is a novel Fenton-like catalyst, the catalytic mechanism of the Fenton-like catalytic material is different from that of the Fe-containing Fenton-like catalyst, and adverse effects such as iron mud and the like cannot be generated, g-C3N4As a promoter component, can be mixed with Ag3PO4Strong interaction occurs, so that surface Ag+Electrons are enriched around the catalyst to form an active center, so that the catalytic oxidation activity of the main catalyst is obviously improved.
3. The invention provides Ag3PO4/g-C3N4Fenton-like catalytic material, the Ag3PO4/g-C3N4The Fenton-like catalytic material is a novel Fenton-like catalyst, can be recycled for multiple times, and hardly reduces the efficiency of degrading organic pollutants such as tetracycline hydrochloride and the like.
4. The invention provides Ag3PO4/g-C3N4The preparation method of the Fenton-like catalytic material is simple in process, environment-friendly, easy in raw material obtaining, good in repeatability and suitable for industrial production.
5. The invention provides Ag3PO4/g-C3N4The Fenton-like catalytic material is applied to catalyzing degradation of tetracycline hydrochloride and/or rhodamine B. The Ag is3PO4/g-C3N4The Fenton-like catalytic material has high degradation efficiency in catalyzing tetracycline hydrochloride and/or rhodamine B, can efficiently oxidize and decompose organic pollutants such as tetracycline hydrochloride and the like, and can be used in a wider pH range.
Drawings
FIG. 1 shows Ag prepared in example 13PO4/g-C3N4Transmission electron microscopy images of Fenton-like catalytic materials.
Detailed Description
The scheme of the invention will be explained with reference to the examples. It will be appreciated by those skilled in the art that the following examples are illustrative of the invention only and should not be taken as limiting the scope of the invention. The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications. The methods used are conventional methods known in the art unless otherwise specified, and the consumables and reagents used are commercially available unless otherwise specified. Unless otherwise defined, technical and scientific terms used herein have the same meaning as is familiar to those skilled in the art. In addition, any methods or materials similar or equivalent to those described herein can also be used in the present invention.
Example 1
Firstly, putting urea into a muffle furnace, roasting for 3 hours at 550 ℃ in air atmosphere, and obtaining g-C with the heating rate of 5 ℃/min3N4. Then adding silver acetate and g-C3N4Dispersed in deionized water, wherein g-C3N4And silver acetate in a mass ratio of 1: and 2.3, stirring for 1 hour in the dark, and then adding a sodium dihydrogen phosphate solution into the solution, wherein the molar ratio of the sodium dihydrogen phosphate to the silver acetate is 1: 1.4. ultrasonic treating under stirring and 100W power for 1 hr, centrifuging, drying at 80 deg.C for 12 hr to obtain Ag3PO4/g-C3N4Fenton-like catalytic material.
Preparation of sample TransmissionFIG. 1 shows the electron micrograph, in which Ag is3PO4Particle size of tens to hundreds of nanometers, g-C3N4In a sheet/layer structure. XRD result shows that Ag is contained3PO4Is a cubic phase.
Example 2
Firstly, putting urea into a muffle furnace, roasting for 3 hours at 550 ℃ in air atmosphere, and obtaining g-C with the heating rate of 3 ℃/min3N4. Then adding silver acetate and g-C3N4Dispersed in deionized water, wherein g-C3N4And silver acetate in a mass ratio of 1: and 4, stirring for 1 hour in the dark, and then adding a sodium dihydrogen phosphate solution into the solution, wherein the molar ratio of the sodium dihydrogen phosphate to the silver acetate is 1: 2. ultrasonic treating under stirring and 100W power for 1 hr, centrifuging, drying at 100 deg.C for 8 hr to obtain Ag3PO4/g-C3N4Fenton-like catalytic material.
Example 3
Firstly, melamine is put into a muffle furnace and roasted for 1 hour at 600 ℃ in the air atmosphere, the heating rate is 3 ℃/min, and g-C is obtained3N4. Then silver nitrate and g-C are added3N4Dispersed in deionized water, wherein g-C3N4And silver nitrate in a mass ratio of 1: stirring for 2 hours in the dark, and then adding a sodium hydrogen phosphate solution into the solution, wherein the molar ratio of the sodium hydrogen phosphate to the silver nitrate is 1: 1. ultrasonic treating under stirring and 100W power for 2 hr, centrifuging, drying at 90 deg.C for 10 hr to obtain Ag3PO4/g-C3N4Fenton-like catalytic material.
Example 4
Firstly, melamine is put into a muffle furnace and roasted for 2 hours at 570 ℃ under the air atmosphere, the heating rate is 4 ℃/min, and g-C is obtained3N4. Then silver nitrate and g-C are added3N4Dispersed in deionized water, wherein g-C3N4And silver nitrate in a mass ratio of 1: and 2.3, stirring for 1.5 hours in a dark place, and then adding a sodium phosphate solution into the solution, wherein the molar ratio of the sodium phosphate to the silver nitrate is 1: 3. in the stirring andultrasonic treating at 100W power for 1.5 hr, centrifuging, drying at 80 deg.C for 12 hr to obtain Ag3PO4/g-C3N4Fenton-like catalytic material.
Comparative example 1
Placing urea in a muffle furnace, roasting for 3 hours at 550 ℃ in air atmosphere, wherein the heating rate is 5 ℃/min to obtain g-C3N4。
Comparative example 2
Dispersing silver acetate in deionized water under the condition of keeping out of the sun, and then adding a sodium dihydrogen phosphate solution into the solution, wherein the molar ratio of the sodium dihydrogen phosphate to the silver nitrate is 1: 3, stirring for 0.5 hour, centrifugally separating, and drying at 80 ℃ for 12 hours to obtain Ag3PO4。
Example 5
In order to examine the degradation effect of the catalyst prepared in the embodiment and the comparative example in the catalytic oxidation of tetracycline hydrochloride or/and rhodamine B, the inventor tests the performance of the catalyst in degrading tetracycline hydrochloride or/and rhodamine B according to the following method.
The test procedure was as follows: 50mg of the catalyst samples prepared in the different examples and comparative examples were dispersed in a solution of tetracycline hydrochloride (70mg/L) at 40 ℃ and 2mL of H was added2O2In the absence of light or/and illumination (200W xenon lamp, wavelength)>420nm) and reacting for 1.5 hours under different pH conditions, measuring the concentration change of tetracycline hydrochloride or/and rhodamine B by an ultraviolet-visible spectrophotometry and calculating a degradation reaction rate constant. The degradation rate constants of the catalysts prepared in examples 1-4 and comparative examples 1 and 2 for catalytic oxidation of tetracycline hydrochloride under different reaction conditions are shown in the following table 1.
TABLE 1 degradation rate constants of catalysts prepared in examples 1-4 and comparative examples 1 and 2 for catalytic oxidation of tetracycline hydrochloride under different reaction conditions
The results in Table 1 show that Ag provided by the present invention3PO4/g-C3N4The Fenton-like composite catalytic material can be used in the absence of light and H2O2Can effectively oxidize and decompose tetracycline hydrochloride under the existence condition; as shown by the test results of Nos. 1 to 3, Ag3PO4/g-C3N4The applicable pH range of the Fenton-like composite catalytic material catalytic degradation reaction is wide (the pH is 4-9.1); as shown by comparison of the test results of Nos. 1 and 4, Ag was observed under light irradiation3PO4/g-C3N4The catalytic degradation activity of the Fenton-like composite catalytic material is higher than that of a dark place; as can be seen from comparison of the test results of Nos. 1, 5, 6 and 7, Ag obtained by different preparation methods3PO4/g-C3N4The catalytic degradation efficiency of the Fenton-like composite catalytic material is different; as shown by comparing the test results of Nos. 1, 8 and 9, Ag3PO4/g-C3N4The catalytic degradation effect of the Fenton-like composite catalytic material is obviously better than that of g-C3N4And Ag3PO4A material.
Example 6
The test procedure was as follows: 50mg of the catalyst samples prepared in the different examples and comparative examples were dispersed in a rhodamine B (10mg/L) solution at 40 ℃ for 10 minutes, and then 2mL of H was added2O2In the absence of light or/and illumination (200W xenon lamp, wavelength)>420nm) and reacting under different pH conditions, sampling, measuring the concentration change of the rhodamine B by an ultraviolet-visible spectrophotometry, and calculating the degradation reaction rate constant of the rhodamine B. The rate constants of the catalytic degradation reaction of rhodamine B oxide by the catalysts prepared in examples 1-4 and comparative example 1 under different reaction conditions are shown in the following table 2.
Table 2 rate constants of catalytic degradation reaction of rhodamine B under different reaction conditions for catalysts prepared in example 1 and comparative example 1
As is clear from the results in Table 2, the present invention provides Ag3PO4/g-C3N4The Fenton-like composite catalytic material can be used in the absence of light and H2O2Under the existing condition, the rhodamine B is effectively degraded under the acidic condition.
Example 7
To examine the reusability of the catalyst of the present invention, Ag prepared in example 1 was used3PO4/g-C3N4The Fenton-like composite catalytic material is repeatedly used for 3 times for photophobic degradation of tetracycline hydrochloride, and the test process for 3 times photophobic degradation of tetracycline hydrochloride is as follows: for the first time: 50mg of Ag prepared in example 1 were added at 40 deg.C3PO4/g-C3N4The Fenton-like composite catalytic material is dispersed in tetracycline hydrochloride (70mg/L) solution, and then 2mL of H is added2O2And reacting for 1.5 hours under the conditions of keeping out of the light and pH 4.04, measuring the concentration change of tetracycline hydrochloride or/and rhodamine B by an ultraviolet-visible spectrophotometry method, and calculating a degradation reaction rate constant. And (3) for the second time: except for Ag used3PO4/g-C3N4The Fenton-like composite catalytic material is Ag recycled for the first time3PO4/g-C3N4And (3) performing the test according to the first test process except for the Fenton-like composite catalytic material. And thirdly: except for Ag used3PO4/g-C3N4The Fenton-like composite catalytic material is Ag recycled for the second time3PO4/g-C3N4And (3) performing the test according to the first test process except for the Fenton-like composite catalytic material. The test results are shown in Table 3, and show that Ag prepared by the preparation method of the invention3PO4/g-C3N4The catalytic activity of the Fenton-like composite catalytic material after repeated use is not obviously reduced, the catalytic activity is relatively stable, and the characterization result shows that the composition and the property of the composite catalytic material are not obviously changed, which shows that the composite catalytic material provided by the invention has good stability.
Table 3 Ag prepared in example 13PO4/g-C3N4Fenton-like composite catalysisDegradation reaction rate constant of material for three times of catalytic oxidation of tetracycline hydrochloride
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (10)
1. Ag3PO4/g-C3N4Fenton-like catalytic material, characterized in that the Ag is3PO4/g-C3N4Ag in Fenton-like catalytic material3PO4Is a cubic phase, g-C3N4In a sheet/layer structure.
2. The Ag of claim 13PO4/g-C3N4The preparation method of the Fenton-like catalytic material is characterized by comprising the following steps of:
step 1): roasting urea or melamine in air atmosphere to obtain g-C3N4；
Step 2): mixing a silver-containing compound with g-C obtained in step 1)3N4Dispersing in deionized water, stirring for 1-2 hours in the dark, adding soluble phosphate solution, stirring, ultrasonic processing, separating and drying to obtain the Ag3PO4/g-C3N4Fenton-like catalytic material.
3. Ag according to claim 23PO4/g-C3N4The preparation method of the Fenton-like catalytic material is characterized in that in the step 1), the roasting temperature is controlled to be 550-600 ℃; controlling the heating rate to be 3-5 ℃/min; the roasting time is controlled to be 1-5 hours, preferably 1-3 hours。
4. Ag according to claim 23PO4/g-C3N4The preparation method of the Fenton-like catalytic material is characterized in that in the step 2), the soluble phosphate is selected from one or more of sodium dihydrogen phosphate, sodium hydrogen phosphate and sodium phosphate; the molar ratio of the soluble phosphate to the silver-containing compound is 1: (1-3).
5. Ag according to claim 23PO4/g-C3N4The preparation method of the Fenton-like catalytic material is characterized in that in the step 2), the silver-containing compound is silver acetate or silver nitrate; control of g-C3N4And the silver-containing compound has a mass ratio of 1: (1-4).
6. Ag according to claim 23PO4/g-C3N4The preparation method of the Fenton-like catalytic material is characterized in that in the step 2), the ultrasonic treatment time is controlled to be 1-2 hours, and the ultrasonic treatment power is controlled to be 100W.
7. Ag according to claim 23PO4/g-C3N4The preparation method of the Fenton-like catalytic material is characterized in that in the step 2), the drying temperature is controlled to be 80-100 ℃, and the drying time is controlled to be 8-12 hours.
8.Ag3PO4Or Ag3PO4/g-C3N4The Fenton-like catalytic material is applied to catalyzing degradation of tetracycline hydrochloride and/or rhodamine B.
9. Use according to claim 8, wherein the Ag is3PO4/g-C3N4The Fenton-like catalytic material is Ag described in claims 2-73PO4/g-C3N4Fenton-like catalystsThe chemical material is prepared by the preparation method.
10. The use according to claim 8, wherein the catalysis of degradation of tetracycline hydrochloride and/or rhodamine B is to catalyze degradation of tetracycline hydrochloride and/or rhodamine B under dark conditions.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103028428A (en) * | 2013-01-16 | 2013-04-10 | 华东理工大学 | Method for preparing composite visual light catalytic material Ag3PO4 and g-C3N4 |
| CN103506141A (en) * | 2013-09-29 | 2014-01-15 | 太原理工大学 | Method for preparing visible light photocatalytic material and application thereof |
| CN105195185A (en) * | 2015-09-18 | 2015-12-30 | 武汉理工大学 | Efficient light fenton catalyst Ag3PO4/CuO and preparation method thereof |
| CN107298477A (en) * | 2017-06-22 | 2017-10-27 | 武汉纺织大学 | A kind of method for being catalyzed organic pollution in persulfate degrading waste water |
| CN109012721A (en) * | 2017-06-08 | 2018-12-18 | 南京理工大学 | A kind of preparation method of silver orthophosphate/graphite phase carbon nitride composite photo-catalyst |
-
2021
- 2021-06-07 CN CN202110630161.9A patent/CN113318766A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103028428A (en) * | 2013-01-16 | 2013-04-10 | 华东理工大学 | Method for preparing composite visual light catalytic material Ag3PO4 and g-C3N4 |
| CN103506141A (en) * | 2013-09-29 | 2014-01-15 | 太原理工大学 | Method for preparing visible light photocatalytic material and application thereof |
| CN105195185A (en) * | 2015-09-18 | 2015-12-30 | 武汉理工大学 | Efficient light fenton catalyst Ag3PO4/CuO and preparation method thereof |
| CN109012721A (en) * | 2017-06-08 | 2018-12-18 | 南京理工大学 | A kind of preparation method of silver orthophosphate/graphite phase carbon nitride composite photo-catalyst |
| CN107298477A (en) * | 2017-06-22 | 2017-10-27 | 武汉纺织大学 | A kind of method for being catalyzed organic pollution in persulfate degrading waste water |
Non-Patent Citations (6)
| Title |
|---|
| FENG-JUN ZHANG: "A novel photofunctional g-C3N4/Ag3PO4 bulk heterojunction for decolorization of Rh.B", 《CHEMICAL ENGINEERING JOURNAL》 * |
| JIANKUI JIA: "Fabrication of g-C3N4/Ag3PO4-H2O2 heterojunction system with enhanced visible-light photocatalytic activity and mechanism insight", 《JOURNAL OF ALLOYS AND COMPOUNDS》 * |
| QIQI DING: "Complete degradation of ciprofloxacin over g-C3N4-iron oxide composite via heterogeneous dark Fenton reaction", 《JOURNAL OF ENVIRONMENTAL MANAGEMENT》 * |
| ZHENG HU: "Role of reactive oxygen species in the photocatalytic degradation of methyl orange and tetracycline by Ag3PO4 polyhedron modified with g-C3N4", 《MATERIALS SCIENCE IN SEMICONDUCTOR PROCESSING》 * |
| 徐苏倩等: "具有双反应活性中心Cu-Al2O3-g-C3N4类芬顿催化剂及•OH选择性转化机理", 《环境科学学报》 * |
| 韩长日等: "《电子及信息用化学品生产工艺与技术》", 31 March 2019, 科学技术文献出版社 * |
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