CN113368882B - Cu 2 O-ZnO/g-C 3 N 4 Composite photocatalyst and preparation method and application thereof - Google Patents
Cu 2 O-ZnO/g-C 3 N 4 Composite photocatalyst and preparation method and application thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 40
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- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 claims abstract description 10
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- 238000006243 chemical reaction Methods 0.000 claims description 6
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- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical group [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 5
- 235000010323 ascorbic acid Nutrition 0.000 claims description 5
- 239000011668 ascorbic acid Substances 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 4
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical group [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 4
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- 238000005406 washing Methods 0.000 claims description 4
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 3
- 229910001431 copper ion Inorganic materials 0.000 claims description 3
- 230000000593 degrading effect Effects 0.000 claims description 3
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- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 2
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- 238000003917 TEM image Methods 0.000 description 2
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- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 2
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- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
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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
-
- B01J35/39—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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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
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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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
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
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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
Abstract
The invention discloses a Cu 2 O‑ZnO/g‑C 3 N 4 The preparation method of the composite photocatalyst comprises the following steps: firstly, mixing a zinc source and a carbon-nitrogen precursor, and roasting to obtain ZnO/g-C 3 N 4 Powder; then hydrothermal reaction is carried out on the ZnO/g-C 3 N 4 Powder surface loading Cu 2 And O, obtaining a final product. In the catalyst prepared by the invention, electrons and holes can be effectively separated from Cu by constructing a dual-action mechanism of Z-scheme and p-n heterojunction 2 Separation in O photocatalyst to suppress Cu 2 Photo-self-decomposition of O with Cu 2 The addition of O ensures that the photocatalytic performance of the ternary material is compared with that of ZnO/g-C 3 N 4 The improvement is more than 30 times; the material has excellent degradation performance on methyl orange water pollutants, and the degradation rate can still be kept above 92.6% after three times of cyclic utilization, so that the recycling performance is good.
Description
Technical Field
The invention belongs to the technical field of catalyst preparation, and particularly relates to Cu 2 O-ZnO/g-C 3 N 4 A composite photocatalyst and a preparation method and application thereof.
Background
In recent decades, with the development of economy and the progress of agriculture and industry, the shortage of energy and environmental pollution have become a very difficult problem for human beings, especially the treatment of organic pollutants in water. Based on the global energy crisis and the sustainability of sunlight, photocatalytic degradation is considered to be one of the most promising fields, and the search for photocatalytic materials capable of making full use of sunlight has attracted extensive attention. Of many semiconductor materials, cuprous oxide (Cu) 2 O) has increased significantly as a visible-light active semiconductor in the fields of photocatalysis and photoelectrochemistry, but due to Cu 2 The redox potential of O lies between the band gaps, and self-photoreduction or self-photooxidation inevitably occurs upon illumination.
The preparation of the photocatalytic composite material can well improve certain defects of a single semiconductor photocatalytic material, such as promotion of response to visible light, promotion of separation of photon-generated carriers, and reduction of photo-corrosion of the photocatalytic material by promotion of carrier migration. He at the design and photocatalytic property of ZnO/Cu 2 O core-shell nanocomposites, mater.lett,2016,184:148-151 2 O coupling to form a p-n heterojunction, which can utilize sunlight to the maximum extent and improve the electron-hole separation efficiency and photocatalytic activity. Wang et al in Oxygen defects-mediated Z-scheme charge separation in g-C 3 N 4 /ZnO photocatalysts for enhanced visible-light degradation of 4-chlorophenol and hydrogen evolution,Appl.Catal. B-Environ,2017,206, 406-416, the research in the publication shows that when ZnO is mixed with g-C, the reaction is carried out 3 N 4 When coupled to form a Z-scheme heterojunction, the charge separation follows the Z-scheme, which greatly improves the photocatalytic performance. From the above, with respect to Cu 2 More reports have been made on binary composites of O and semiconductor, and Cu 2 The reports of the O ternary composite material are few.
Disclosure of Invention
The object of the present invention is to provide a Cu 2 O-ZnO/g-C 3 N 4 A composite photocatalyst containing Cu 2 O、 ZnO、g-C 3 N 4 Three materials which can effectively lead electrons and holes from Cu through constructing a dual action mechanism of Z-scheme and p-n junction 2 Method of separation in O-photocatalyst, inhibition of Cu 2 The light of O is self-decomposed, and the photocatalytic performance is improved.
It is another object of the present invention to provide Cu as described above 2 O-ZnO/g-C 3 N 4 The preparation method of the composite photocatalyst comprises the following steps:
s1, roasting the mixed powder of the zinc source and the carbon-nitrogen precursor to obtain ZnO/g-C 3 N 4 Powder; preferably, the zinc source is ZnO or ZnCO 3 、ZnNO 3 、(CH 3 COO) 2 Zn、Zn(OH) 2 At least one of (a); the carbon-nitrogen precursor is at least one of melamine, urea, cyanamide, dicyandiamide and thiourea; the mass ratio of the zinc source to the carbon-nitrogen precursor is 1-5; the temperature of the roasting treatment is 500-700 ℃, and the time is 3-5 h. Further preferred, znCO 3 And melamine in a mass ratio of 1; the temperature of the roasting treatment is 550 ℃ and the time is 4 hours.
S2, adding ZnO/g-C into water 3 N 4 Mixing powder, surfactant and copper source, adding NaOH solution dropwise into water to gradually form blue floccule, mixing, and adding ascorbic Acid (AH) into water 2 ) To obtain a mixed solution, AH 2 The function of (A) is to be able to react with [ Cu (OH) 4 ] 2- Interaction to form anisotropic Cu 2 The shape of O; preferably, theThe copper source is CuCl 2 ·2H 2 O, the surfactant is Cetyl Trimethyl Ammonium Bromide (CTAB); the molar ratio of the copper ion content, the surfactant, naOH and the ascorbic acid in the copper source is 1.5-3. More preferably, the molar ratio of copper ions, surfactant, naOH, and ascorbic acid in the copper source is 1. The specific reaction formula is as follows:
Cu 2+ +2OH - →Cu(OH) 2 ↓ (3)
2Cu(OH) 4 2- +C 6 H 8 O 6 →Cu 2 O↓+C 6 H 6 O 6 +4OH - +3H 2 O (6)
s3, transferring the mixed solution into a reaction kettle, cooling to normal temperature after hydrothermal reaction, taking out the mixed solution, performing centrifugal separation to obtain a solid material, and washing, drying and grinding the solid material to obtain a final product, namely the nano Cu 2 O-ZnO/g-C 3 N 4 A composite photocatalyst.
As a preferable technical scheme, in the step S3, the temperature of the hydrothermal reaction is 100-180 ℃ and the time is 7-10 h; the drying temperature is 50-70 ℃ and the drying time is 3-6 h. Further preferably, the temperature of the hydrothermal reaction is 140 ℃ and the time is 9h; the drying temperature is 60 ℃ and the drying time is 4h.
It is a third object of the present invention to provide Cu as described above 2 O-ZnO/g-C 3 N 4 Application of composite photocatalyst and nano Cu 2 O-ZnO/g-C 3 N 4 The composite photocatalyst is used for degrading macromolecular pollutants in water. Further, the polymer pollutant is methyl orange.
The invention has the following beneficial effects:
(1) Cu synthesized by the invention 2 O-ZnO/g-C 3 N 4 The composite photocatalyst is prepared by mixing zinc source and carbon-nitrogen precursor and calcining to obtain ZnO and g-C 3 N 4 Meanwhile, the composite material is prepared in one step, the process is simple, the raw materials are low in cost, the preparation cost is low, and the photocatalytic activity of the ternary composite material prepared by the invention is higher than that of ZnO/g-C 3 N 4 The binary material is improved by 30 times.
(2) The nano Cu prepared by the invention 2 O-ZnO/g-C 3 N 4 Of materials of Cu 2 O、ZnO、g-C 3 N 4 The three materials can effectively lead electrons and holes to be separated from Cu by constructing a dual-action mechanism of Z-scheme and p-n junction 2 Separation in O photocatalyst to suppress Cu 2 The optical self-decomposition of O improves the photocatalytic performance; the proportion of the material for degrading methyl orange water pollutants in 150 minutes can reach 99.8 percent; after three times of cyclic utilization, the degradation rate can still be kept above 92.6%, and the recycling performance is good; and has no secondary pollution to the environment.
Drawings
FIG. 1 is Cu 2 O-ZnO/g-C 3 N 4 SEM picture of the composite photocatalyst;
FIG. 2 is Cu 2 O-ZnO/g-C 3 N 4 A TEM image of the composite photocatalyst;
FIG. 3 is Cu 2 O-ZnO/g-C 3 N 4 Composite photocatalyst and Cu 2 O、g-C 3 N 4 PL map of (2);
FIG. 4 is a graph of the degradation rate of methyl orange by different catalysts;
FIG. 5 shows Cu 2 O-ZnO/g-C 3 N 4 A degradation rate curve graph of the composite photocatalyst for methyl orange under different circulation times is provided.
Detailed Description
The present invention will be further described with reference to the following examples. It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The raw materials and reagents used in the following examples are all commercially available products;
examples
S1, mixing 1g of ZnCO 3 Fully grinding and mixing the mixture and 3g of melamine to obtain mixed powder, putting the mixed powder into a muffle furnace, roasting the mixed powder for 4 hours at the temperature of 550 ℃, cooling the mixed powder along with the furnace, and taking out the cooled mixed powder to obtain ZnO/g-C 3 N 4 Powder;
s2, weighing 0.1g of ZnO/g-C 3 N 4 Stirring the powder in 10mL deionized water for 30min, adding 1.822g CTAB, stirring for 30min, adding 0.85g CuCl 2 ·2H 2 Stirring for 30min, dropwise adding 12mL of 2.5mol/L NaOH solution to gradually generate blue floccules, continuously stirring for 30min, dropwise adding 25ml of 0.1mol/L ascorbic acid solution, and fully stirring for 30min to obtain a mixed solution.
S3, transferring the mixed solution into a polytetrafluoroethylene reaction kettle, and carrying out hydrothermal reaction for 9 hours at the temperature of 140 ℃; naturally cooling, taking out the mixed solution, centrifuging for 8min at 8000r/min to obtain solid, washing the solid with deionized water and anhydrous ethanol for three times respectively, drying in an air-blast drying oven at 60 deg.C for 4h, and grinding to obtain Cu sample 2 O-ZnO/g-C 3 N 4 (abbreviated as CZg) composite photocatalyst.
Comparative example
Cu 2 The preparation process comprises the following steps: dissolving 1.822g CTAB in 10ml deionized water, stirring for 30min, and adding 0.85g CuCl 2 ·2H 2 O in the mixed solution, stirring is continued for 30min, and then 12mL of 2.5mol/L NaOH solution is gradually added dropwiseBlue flocs appeared, and after stirring for 30min, 25mL of 0.1mol/L AH was added dropwise 2 The solution was stirred well for 1h, during which the solution turned from green to orange-yellow, finally giving a brick-red suspension. Transferring the prepared solution into a polytetrafluoroethylene reaction kettle, and reacting for 9 hours at the temperature of 140 ℃; and naturally cooling, taking out the mixed solution, performing centrifugal separation to obtain a solid, washing with deionized water and absolute ethyl alcohol for three times respectively, then placing in a forced air drying oven, drying at 60 ℃ for 3h, and grinding to obtain a sample.
g-C 3 N 4 : and (2) placing melamine in a muffle furnace for high-temperature roasting at 550 ℃ for 4h, setting the heating rate to be 5 ℃/min, cooling along with the furnace, and grinding to obtain yellow powder.
ZnO: znCO is reacted with 3 Placing the mixture in a muffle furnace for roasting at 550 ℃ for 4h, setting the heating rate at 5 ℃/min, cooling along with the furnace, and grinding to obtain white powder.
ZnO/g-C3N4: 1g of ZnCO 3 Fully grinding and uniformly mixing with 3g of melamine, putting the mixture into a muffle furnace, roasting the mixture at the high temperature of 550 ℃ for 4 hours, setting the heating rate to be 5 ℃/min, cooling the mixture along with the furnace, and grinding the mixture to obtain faint yellow powdered ZnO/g-C 3 N 4 A binary composite material.
Cu 2 O/g-C 3 N 4 : 0.1g of g-C is taken 3 N 4 Dissolving in 10ml deionized water, stirring for 30min, and repeating Cu 2 Preparation of O to obtain Cu 2 O/g-C 3 N 4 A binary composite material.
Cu 2 O/ZnO: dissolving 0.1g ZnO in 10ml deionized water, stirring for 30min, and repeating Cu process 2 Preparation of O to obtain Cu 2 An O/ZnO binary composite material.
Results and Performance testing
FIG. 1 shows Cu obtained in example 2 O-ZnO/g-C 3 N 4 SEM image of composite photocatalyst, and it can be seen from FIG. 1 that the composite photocatalyst is Cu 2 O, znO and g-C 3 N 4 The composite structure of (1). Wherein the columnar structure is ZnO, and the lamellar and small particles are g-C 3 N 4 And Cu 2 Composite structure of O, showing that the three materials are goodAre combined together.
FIG. 2 shows Cu obtained in example 2 O-ZnO/g-C 3 N 4 The TEM image of the composite photocatalyst shows that cuprous oxide particles with polyhedral morphology exist on the surface of the material from FIG. 2.
FIG. 3 shows Cu obtained in example 2 O-ZnO/g-C 3 N 4 Composite photocatalyst and Cu prepared by comparative example 2 O、 g-C 3 N 4 PL diagram of (a). From FIG. 3, it can be seen that Cu 2 O-ZnO/g-C 3 N 4 Photoluminescence intensity ratio Cu of composite photocatalyst 2 O、g-C 3 N 4 The photoluminescence intensity of the sample is low (because the peak intensity of ZnO is far higher than that of the rest 3 materials, a ZnO curve is not put in the figure), the photoluminescence signal is inhibited, and the recombination process is slow, the decay life of the photo-generated electron is long, and the recombination rate of the electron-hole pair is low.
FIG. 4 is a graph showing the degradation rate of methyl orange by different catalysts, specifically Cu prepared in the examples 2 O-ZnO/g-C 3 N 4 Composite photocatalyst and Cu prepared by comparative example 2 O/ZnO、Cu 2 O/g-C 3 N 4 、ZnO/g-C 3 N 4 Binary composite material and pure Cu 2 O、ZnO、g-C 3 N 4 The degradation rate curve of methyl orange under the condition of independent existence of seven photocatalysts can be seen from figure 4, under the condition of visible light (lambda is more than 400 nm), cu 2 O-ZnO/g-C 3 N 4 The degradation rate of the (CZg) composite photocatalyst to methyl orange within 150min is 99.8%, which is far higher than that of other materials, and the result shows that the prepared composite photocatalyst has very strong photocatalytic performance.
FIG. 5 shows Cu 2 O-ZnO/g-C 3 N 4 A degradation rate curve graph of the composite photocatalyst for methyl orange under different circulation times is provided. As can be seen from FIG. 5, after three times of recycling, the degradation rate can still be maintained above 92.6%, and the photocatalytic stability is very high.
Claims (9)
1. Cu 2 O-ZnO/g-C 3 N 4 The preparation method of the composite photocatalyst is characterized by comprising the following steps: the method comprises the following steps:
s1, roasting the mixed powder of the zinc source and the carbon-nitrogen precursor to obtain ZnO/g-C 3 N 4 Powder;
s2, adding ZnO/g-C into water 3 N 4 Uniformly mixing powder, a surfactant and a copper source, gradually adding a NaOH solution into water dropwise to generate blue floccules, uniformly mixing, and then adding ascorbic acid into the water to obtain a mixed solution;
s3, transferring the mixed solution into a reaction kettle, cooling to normal temperature after hydrothermal reaction, taking out the mixed solution, performing centrifugal separation to obtain a solid material, and washing, drying and grinding the solid material to obtain a final product, namely Cu 2 O-ZnO/g-C 3 N 4 A composite photocatalyst; the temperature of the hydrothermal reaction is 100-180 ℃.
2. The Cu of claim 1 2 O-ZnO/g-C 3 N 4 The preparation method of the composite photocatalyst is characterized by comprising the following steps: in step S1, the zinc source is ZnO or ZnCO 3 、ZnNO 3 、(CH 3 COO) 2 Zn、Zn(OH) 2 At least one of; the carbon-nitrogen precursor is at least one of melamine, urea, cyanamide, dicyandiamide and thiourea; the mass ratio of the zinc source to the carbon-nitrogen precursor is 1-5; the temperature of the roasting treatment is 500-700 ℃, and the time is 3-5 h.
3. The Cu of claim 1 2 O-ZnO/g-C 3 N 4 The preparation method of the composite photocatalyst is characterized by comprising the following steps: in step S2, the copper source is CuCl 2 ·2H 2 O, and the surfactant is cetyl trimethyl ammonium bromide.
4. The Cu of claim 3 2 O-ZnO/g-C 3 N 4 The preparation method of the composite photocatalyst is characterized by comprising the following steps: in step S2, the copper ion content, the surfactant and Na in the copper sourceThe molar ratio of OH to ascorbic acid is 1.
5. Cu according to claim 1 2 O-ZnO/g-C 3 N 4 The preparation method of the composite photocatalyst is characterized by comprising the following steps: in the step S3, the time of the hydrothermal reaction is 7-10 h.
6. Cu according to claim 1 2 O-ZnO/g-C 3 N 4 The preparation method of the composite photocatalyst is characterized by comprising the following steps: in the step S3, the drying temperature is 50-70 ℃ and the drying time is 3-6 h.
7. Cu 2 O-ZnO/g-C 3 N 4 The composite photocatalyst is characterized in that: which is carried out using a Cu as claimed in any of claims 1 to 6 2 O-ZnO/g-C 3 N 4 The composite photocatalyst is prepared by the preparation method.
8. Cu according to claim 7 2 O-ZnO/g-C 3 N 4 The application of the composite photocatalyst is characterized in that: the Cu 2 O-ZnO/g-C 3 N 4 The composite photocatalyst is used for degrading macromolecular pollutants in water.
9. Cu according to claim 8 2 O-ZnO/g-C 3 N 4 The application of the composite photocatalyst is characterized in that: the polymer pollutant is methyl orange.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105032468A (en) * | 2015-08-03 | 2015-11-11 | 中南大学 | Cu2O-TiO2/g-C3N4 ternary complex and preparation and application method thereof |
| CN107199045A (en) * | 2017-06-22 | 2017-09-26 | 武汉纺织大学 | A kind of preparation method and applications of g C3N4 Cu2O composite catalysts |
| CN108704655A (en) * | 2018-05-31 | 2018-10-26 | 武汉大学 | A kind of preparation method of cuprous oxide and graphite phase carbon nitride heterojunction photocatalyst |
| CN110124723A (en) * | 2019-06-14 | 2019-08-16 | 辽宁大学 | ZnO/g-C3N4Composite photo-catalyst and its preparation method and application |
| CN111229285A (en) * | 2020-03-24 | 2020-06-05 | 电子科技大学 | ZnO/TiO2/g-C3N4Composite photocatalyst and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110102312B (en) * | 2019-05-14 | 2021-03-30 | 福州大学 | One-dimensional cuprous oxide/silver/zinc oxide nanorod photocatalytic composite material and preparation method and application thereof |
-
2021
- 2021-05-19 CN CN202110545072.4A patent/CN113368882B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105032468A (en) * | 2015-08-03 | 2015-11-11 | 中南大学 | Cu2O-TiO2/g-C3N4 ternary complex and preparation and application method thereof |
| CN107199045A (en) * | 2017-06-22 | 2017-09-26 | 武汉纺织大学 | A kind of preparation method and applications of g C3N4 Cu2O composite catalysts |
| CN108704655A (en) * | 2018-05-31 | 2018-10-26 | 武汉大学 | A kind of preparation method of cuprous oxide and graphite phase carbon nitride heterojunction photocatalyst |
| CN110124723A (en) * | 2019-06-14 | 2019-08-16 | 辽宁大学 | ZnO/g-C3N4Composite photo-catalyst and its preparation method and application |
| CN111229285A (en) * | 2020-03-24 | 2020-06-05 | 电子科技大学 | ZnO/TiO2/g-C3N4Composite photocatalyst and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| CuO/ZnO/g-C3N4 heterostructures as efficient visible light-driven photocatalysts;Mohammed AbdullahBajiri等;《Journal of Environmental Chemical Engineering》;20190913;第7卷(第5期);第1-8页 * |
| Hydrothermal synthesis of Cu2O with morphology evolution and its effect on visible-light photocatalysis;Xudong Chen等;《Materials Letters》;20210423;第297卷;第1-4页 * |
| ZnO/g-C_3N_4复合材料的制备及其光催化性能研究;刘艳丽等;《湖南大学学报(自然科学版)》;20171225(第12期);第45-51页 * |
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