CN115155654B - Carbon nitride composite photocatalyst, preparation method thereof and herbicide wastewater treatment method - Google Patents
Carbon nitride composite photocatalyst, preparation method thereof and herbicide wastewater treatment method Download PDFInfo
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- CN115155654B CN115155654B CN202210689103.8A CN202210689103A CN115155654B CN 115155654 B CN115155654 B CN 115155654B CN 202210689103 A CN202210689103 A CN 202210689103A CN 115155654 B CN115155654 B CN 115155654B
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- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 169
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 88
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- 239000002135 nanosheet Substances 0.000 claims abstract description 84
- 150000003852 triazoles Chemical class 0.000 claims abstract description 36
- 239000000463 material Substances 0.000 claims description 47
- MXWJVTOOROXGIU-UHFFFAOYSA-N atrazine Chemical group CCNC1=NC(Cl)=NC(NC(C)C)=N1 MXWJVTOOROXGIU-UHFFFAOYSA-N 0.000 claims description 33
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0254—Nitrogen containing compounds on mineral substrates
-
- 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
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0244—Nitrogen containing compounds with nitrogen contained as ring member in aromatic compounds or moieties, e.g. pyridine
-
- B01J35/39—
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0036—Grinding
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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
-
- 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
- C02F2101/306—Pesticides
-
- 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
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
-
- 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
Abstract
The invention relates to a functional composite photocatalyst, and discloses a carbon nitride composite photocatalyst, a preparation method and a herbicide wastewater treatment method. The composite catalyst comprises graphite phase carbon nitride nano-sheets, and triazole and pyromellitic diamine which are modified on the surfaces of the graphite phase carbon nitride nano-sheets. The carbon nitride composite photocatalyst has the advantages of high photocatalytic activity, good photocatalytic stability, wide photoresponse range, high herbicide removal rate and good reusability.
Description
Technical Field
The invention relates to a functional composite photocatalyst, in particular to a carbon nitride composite photocatalyst, a preparation method and application thereof. In addition, the invention also relates to a method for treating herbicide wastewater.
Background
In recent years, the development of photocatalysis technology is rapid, and particularly, the removal of environmental pollutants by using a semiconductor-based photocatalytic degradation technology is widely focused by researchers, and the key of good catalytic performance is whether to have a semiconductor photocatalytic material with good performance. Therefore, designing and preparing efficient semiconductor photocatalytic materials is an important point of research in the current field of environmental photocatalysis.
Non-metallic graphite phase carbon nitrides have attracted considerable attention in terms of material selection and application. However, since the forbidden bandwidth of the graphite phase carbon nitride is 2.7eV, the absorption range of the graphite phase carbon nitride to visible light is limited to light within 460nm, the light response range is small, sunlight cannot be fully utilized, the catalytic degradation effect of the graphite phase carbon nitride material to pollutants in the environment cannot be improved, and the single catalyst cannot achieve a satisfactory photocatalytic effect.
Therefore, the obtained graphite-phase carbon nitride nano-sheet composite photocatalyst has high photocatalytic activity, good photocatalytic stability and wide photoresponse range, and has important significance for improving the catalytic degradation effect of graphite-phase carbon nitride on pollutants.
Disclosure of Invention
The invention aims to solve the problem that the catalytic degradation effect of a graphite phase carbon nitride material is to be improved in the prior art, and provides a carbon nitride composite photocatalyst, a preparation method and a herbicide wastewater treatment method.
In order to achieve the above object, according to one aspect of the present invention, there is provided a carbon nitride composite photocatalyst comprising graphite-phase carbon nitride nanoplatelets and triazole and diamine pyromellitic acid modified on the surfaces of the graphite-phase carbon nitride nanoplatelets.
Preferably, the ratio between the total mass of the triazole and the graphite phase carbon nitride nano-sheet and the mass of the pyromellitic diamine is 0.1-4:1, and the mass ratio of the triazole to the graphite phase carbon nitride nano-sheet is 1:7-13.
Further preferably, the mass ratio of the diamine pyromellitic acid, the triazole and the graphite phase carbon nitride nano-sheet is 1:0.4-1.5:7.2-12.5.
The second aspect of the present invention provides a method for preparing a carbon nitride composite photocatalyst, comprising the steps of:
s1, mixing and grinding graphite-phase carbon nitride nano-sheets and 3-amino-1, 2, 4-triazole to obtain precursor mixed powder;
s2, performing thermal condensation polymerization reaction I on the precursor mixed powder to obtain a triazole modified graphite-phase carbon nitride nano-sheet material;
s3, mixing and grinding the triazole modified graphite phase carbon nitride nanosheet material and pyromellitic dianhydride, and performing thermal condensation polymerization reaction II to obtain the carbon nitride composite photocatalyst.
Preferably, in step S1, the graphite-phase carbon nitride nano-sheet is a graphite-phase carbon nitride nano-sheet obtained by roasting urea.
Further preferably, the conditions of the firing include: the temperature is 500-600 ℃ and the time is 3-5h.
More preferably, in step S1, the mass ratio of the 3-amino-1, 2, 4-triazole to the graphite phase carbon nitride nano-sheet is 1:6-10.
Preferably, in step S2, the conditions of the thermal polycondensation reaction I include a temperature of 500 to 600 ℃ for 3 to 5 hours.
Preferably, in step S3, the mass ratio of the triazole modified graphite phase carbon nitride nanosheet material to the pyromellitic dianhydride is 0.1-4:1.
Further preferably, the conditions of the thermal polycondensation reaction II include a temperature of 300 to 350℃for 3 to 5 hours.
The invention provides a carbon nitride composite photocatalyst provided in the first aspect and an application of the carbon nitride composite photocatalyst prepared by the preparation method provided in the second aspect in treating herbicide wastewater.
The fourth aspect of the invention provides a method for treating herbicide wastewater, comprising the following steps:
(1) Mixing and adsorbing the carbon nitride composite photocatalyst provided in the first aspect and/or the carbon nitride composite photocatalyst prepared and prepared in the second aspect with the herbicide wastewater under a light-shielding condition to obtain a mixed solution;
(2) And carrying out photocatalytic reaction on the mixed solution under the condition of visible light.
Preferably, in the step (1), the mass ratio of the carbon nitride composite photocatalyst to the herbicide is 40-120:1.
Further preferably, the herbicide is atrazine.
More preferably, the time of adsorption is 15-25min.
Preferably, in the step (2), the wavelength lambda of the visible light is more than 420nm, and the time of the photocatalytic reaction is 50-70min.
Through the technical scheme, the invention has the beneficial effects that:
(1) According to the carbon nitride composite catalyst provided by the invention, the triazole is used for modifying the surface of the graphite phase carbon nitride nanosheet, so that the orientated movement of photo-generated electrons and holes can be driven, and the utilization and absorption of the material on light energy can be improved; the pyromellitic diamine is modified on the surface of the graphite phase carbon nitride nanosheet, so that the directional movement of photo-generated electrons and holes can be further enhanced, and the utilization and absorption of the material on light energy are further improved. The carbon nitride composite photocatalyst provided by the invention has the advantages of high photocatalytic activity, wide photoresponse range and stable photocatalytic performance.
(2) According to the carbon nitride composite catalyst provided by the invention, the triazole and the diamine pyromellitic acid are modified on the surface of the graphite-phase carbon nitride nanosheet, so that the original planar structure can be changed, more active sites are provided, the composite photocatalyst can be deformed, the electron enrichment region and the electron depletion region can be spatially separated, the separation of photo-generated electrons and holes is promoted, the effective utilization rate of photo-generated electrons of the photocatalyst is improved, and the photocatalytic activity and the photocatalytic stability of the composite photocatalyst are effectively improved.
(3) According to the preparation method of the carbon nitride composite catalyst, the triazole and the diamine pyromellitic acid are gradually modified on the surface of the graphite-phase carbon nitride nanosheet through the thermal polycondensation reaction, so that the composite photocatalyst with a plane deformation structure is prepared, the space separation of an electron enrichment area and an electron depletion area can be generated, the separation of photo-generated electrons and holes is promoted, the effective utilization rate of photo-generated electrons of the photocatalyst is improved, and the photocatalytic activity and the photocatalytic stability of the composite photocatalyst are effectively improved. And has the advantages of simple preparation process, simple and convenient operation and low cost.
(4) The method for treating the herbicide wastewater, provided by the invention, has the advantages of simple application method, low cost, high herbicide removal rate and the like, can effectively degrade the herbicide in the wastewater, and has a good application prospect by utilizing the carbon nitride radiation catalyst to perform a photocatalytic reaction on the herbicide wastewater.
Drawings
FIG. 1 is a transmission electron microscope image of a triazole-modified graphite-phase carbon nitride nanosheet material (TAC) and a carbon nitride composite photocatalyst (TACP) prepared in example 1 of the present invention, wherein (A) is TAC and (B) is TACP;
FIG. 2 is a graph showing the graphite phase carbon nitride nanosheets (g-C) prepared in example 1 of the present invention 3 N 4 ) XRD pattern of triazole modified graphite phase carbon nitride nanosheet material (TAC) and carbon nitride composite photocatalyst (TACP);
FIG. 3 is a graph showing the graphite phase carbon nitride nanosheets (g-C) prepared in example 1 of the present invention 3 N 4 ) Ultraviolet-visible spectrum diffuse reflection diagram of triazole modified graphite phase carbon nitride nanosheet material (TAC) and carbon nitride composite photocatalyst (TACP);
FIG. 4 shows a graphite-phase carbon nitride nanosheet (g-C) prepared in example 1 of the present invention 3 N 4 ) Triazole modified graphite phase carbon nitride nanosheet material (TAC) and carbon nitride composite photocatalyst (TACP) in visible light region (lambda)>420 nm) and the relationship diagram of the concentration of atrazine in the degradation process of the atrazine by photocatalytic activation;
FIG. 5 is a graph showing the effect of removal rate of atrazine wastewater by circulating treatment with the carbon nitride composite photocatalyst in example 1 of the present invention;
FIG. 6 is a graph showing the effect of removal rate when the carbon nitride composite photocatalyst synthesized by using different amounts of pyromellitic dianhydride is used for circularly treating atrazine waste water in examples 1 and 4-7 of the present invention;
FIG. 7 is a graph showing the graphite phase carbon nitride nanosheets (g-C) prepared in example 1 of the present invention 3 N 4 ) An X-ray photoelectron spectrum of a triazole modified graphite phase carbon nitride nanosheet material (TAC) and a carbon nitride composite photocatalyst (TACP).
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The invention provides a carbon nitride composite photocatalyst, which comprises graphite phase carbon nitride nano-sheets, and triazole and pyromellitic diamine which are modified on the surfaces of the graphite phase carbon nitride nano-sheets.
The carbon nitride composite photocatalyst provided by the invention is a triazole and pyromellitic diamine secondary modified carbon nitride composite catalyst, and the triazole is modified on the surface of the graphite phase carbon nitride nanosheet, so that the orientated movement of photo-generated electrons and holes can be driven, and the utilization and absorption of the material on light energy can be improved; the pyromellitic diamine is modified on the surface of the graphite phase carbon nitride nanosheet, so that the directional movement of photo-generated electrons and holes can be further enhanced, and the utilization and absorption of the material on light energy are further improved. In addition, the triazole and the diamine pyromellitic acid are modified on the surface of the graphite-phase carbon nitride nanosheet, so that the original planar structure can be changed, more active sites are provided, the composite catalyst can be deformed, the electron enrichment region and the electron depletion region can be spatially separated, the separation of photo-generated electrons and holes is promoted, the effective utilization rate of photo-generated electrons of the material is improved, and the photo-catalytic activity and the photo-catalytic stability of the composite catalyst are effectively improved. The carbon nitride composite photocatalyst provided by the invention has the advantages of high photocatalytic activity, wide photoresponse range and stable photocatalytic performance.
In the carbon nitride composite photocatalyst, under the condition that the modification amount of the diamine pyromellitic acid on the surface of the graphite-phase carbon nitride nanosheet is low, the photocatalytic performance of the carbon nitride composite photocatalyst is improved along with the increase of the modification amount of the diamine pyromellitic acid, and the diamine pyromellitic acid can improve the light absorption capacity of the carbon nitride composite photocatalyst, promote the separation of photo-generated electrons and holes and improve the photocatalytic performance; with further increase of the specific gravity of the diamine pyromellitic acid in the carbon nitride composite photocatalyst, the photocatalytic performance of the carbon nitride composite photocatalyst is reduced mainly because: too much diamine pyromellitic acid can lead to insufficient heptazine ring units with photocatalytic activity in the catalyst of unit mass, and can weaken the photocatalytic performance of the material; on the other hand, too much diamine pyromellitic acid results in too dense a structure, so that the specific surface area of the catalyst is greatly reduced, resulting in a decrease in photocatalytic performance. Preferably, the ratio between the total mass of the triazole and the graphite phase carbon nitride nanoplatelets and the mass of the diamine pyromellitic acid is 0.1 to 4:1, and specifically may be 0.1:1, 0.5:1, 1:1, 1.5:1, 2:1, 2.5:1, 3:1, 3.5:1, 4:1, or any value between the two values; further preferably, the mass ratio of the total mass of the triazole and the graphite phase carbon nitride nano-sheet to the mass ratio of the pyromellitic diamine is 0.1-2:1, more preferably 0.1-1:1, and the carbon nitride composite photocatalyst has better catalytic performance. In order to further improve the photocatalytic activity of the carbon nitride composite photocatalyst, preferably, the mass ratio of the triazole to the graphite phase carbon nitride nanosheets is 1:7-13, and specifically may be 1:7, 1:8, 1:9, 1:10, 1:11, 1:12, 1:13, or any value between the two values; further preferably, the mass ratio of the triazole to the graphite phase carbon nitride nano-sheet is 1:8-10, more preferably 1:8. In view of further improving the photocatalytic activity of the carbon nitride composite photocatalyst, preferably, the mass ratio of the diamine pyromellitic acid, the triazole and the graphite-phase carbon nitride nanosheets is 1:0.4-1.5:7.2-12.5.
The second aspect of the present invention provides a method for preparing a carbon nitride composite photocatalyst, comprising the steps of:
s1, mixing and grinding graphite-phase carbon nitride nano-sheets and 3-amino-1, 2, 4-triazole to obtain precursor mixed powder;
s2, performing thermal condensation polymerization reaction I on the precursor mixed powder to obtain a triazole modified graphite-phase carbon nitride nano-sheet material;
s3, mixing and grinding the triazole modified graphite phase carbon nitride nanosheet material and pyromellitic dianhydride, and performing thermal condensation polymerization reaction II to obtain the carbon nitride composite photocatalyst.
According to the carbon nitride composite photocatalyst provided by the invention, the triazole and the diamine pyromellitic acid are respectively modified on the surface of the graphite-phase carbon nitride nanosheet through twice thermal shrinkage polymerization reaction, so that the composite photocatalyst material with a plane deformation structure is prepared, the electron enrichment region and the electron depletion region can be spatially separated, the separation of photo-generated electrons and holes is promoted, the effective utilization rate of photo-generated electrons of the photocatalyst is improved, and the photocatalytic activity and the photocatalytic stability of the composite photocatalyst are effectively improved. And has the advantages of simple preparation process, simple and convenient operation and low cost.
In order to further improve the photocatalytic activity of the prepared composite photocatalyst, preferably, in step S1, the graphite-phase carbon nitride nanosheets are graphite-phase carbon nitride nanosheets obtained by urea calcination. The temperature and time of the calcination may be determined by those skilled in the art according to the actual circumstances. From the viewpoint of further improving the photocatalytic activity of the produced composite photocatalyst, preferably, the conditions of the calcination include: the temperature is 500-600deg.C, specifically 500 deg.C, 520 deg.C, 540 deg.C, 560 deg.C, 580 deg.C, 600 deg.C, or any value between the above two values, and the time is 3-5h, specifically 3h, 3.5h, 4h, 4.5h, 5h, or any value between the above two values. In the invention, the temperature rising rate of roasting is 3-8 ℃/min.
Preferably, in step S1, the mass ratio of the 3-amino-1, 2, 4-triazole to the graphite phase carbon nitride nano-sheet is 1:6-10. The inventor finds that under the condition of the mass ratio, the activation site of the catalyst can be further increased, and the photocatalytic activity of the catalyst can be further improved.
According to the invention, the grinding I can be mechanical grinding or manual grinding, and the grinding time can be determined by a person skilled in the art according to the actual situation. In order to further improve the action and effect of the 3-amino-1, 2, 4-triazole and the graphite phase carbon nitride nano-sheet, it is preferable that the time of grinding I is 10-60min.
In order to further improve the photocatalytic activity of the prepared composite photocatalyst, preferably, in the step S2, the condition of the thermal shrinkage polymerization reaction I includes that the temperature is 500-600 ℃, specifically 500 ℃, 520 ℃, 540 ℃, 560 ℃, 580 ℃, 600 ℃, or any value between the two values, and the time is 3-5h, specifically 3.5h, 4h, 4.5h, 5h, or any value between the two values. In the thermal polycondensation reaction I, the temperature rising rate is 3-8 ℃/min.
Preferably, in step S3, the mass ratio of the triazole modified graphite phase carbon nitride nanosheet material to the pyromellitic dianhydride is 0.1-4:1. The inventor finds that under the condition of the mass ratio, the activation site of the catalyst can be further increased, and the photocatalytic activity of the catalyst can be further improved. From the viewpoint of further improving the photocatalytic activity of the catalyst, it is preferable that the mass ratio of the triazole-modified graphite-phase carbon nitride nanosheet material to the pyromellitic dianhydride is 0.1 to 2:1. More preferably, the mass ratio of the triazole modified graphite phase carbon nitride nanosheet material to the pyromellitic dianhydride is 0.1-1:1.
According to the invention, the grinding II can be mechanical grinding or manual grinding, and the grinding time can be determined by the person skilled in the art according to the actual situation. In order to further improve the action effect of the triazole modified graphite phase carbon nitride nanosheet material and pyromellitic dianhydride, the grinding time of the grinding II is preferably 10-60min.
In order to further improve the photocatalytic activity of the prepared composite photocatalyst, it is further preferable that the condition of the thermal polycondensation reaction II includes a temperature of 300 to 350 ℃, specifically 300 ℃, 310 ℃, 320 ℃, 330 ℃, 340 ℃, 350 ℃, or any value between the two values, and a time of 3 to 5 hours, specifically 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours, or any value between the two values. In the thermal polycondensation reaction I, the temperature rising rate is 5-10 ℃/min.
The invention provides a carbon nitride composite photocatalyst provided in the first aspect and an application of the carbon nitride composite photocatalyst prepared by the preparation method provided in the second aspect in treating herbicide wastewater. The carbon nitride composite photocatalyst provided by the invention can perform photocatalytic reaction on herbicide wastewater, realizes efficient degradation and removal of herbicide in the wastewater, and has the advantages of stable photocatalytic performance, good reusability, simple application method, low cost and the like.
According to the invention, the herbicide wastewater is wastewater containing herbicide.
The fourth aspect of the invention provides a method for treating herbicide wastewater, comprising the following steps:
(1) Mixing and adsorbing the carbon nitride composite photocatalyst provided in the first aspect and/or the carbon nitride composite photocatalyst prepared and prepared in the second aspect with the herbicide wastewater under a light-shielding condition to obtain a mixed solution;
(2) And carrying out photocatalytic reaction on the mixed solution under the condition of visible light.
The inventor finds that the carbon nitride composite catalyst provided by the invention has higher removal rate to herbicide, and has lower cost and simple method in the research process.
According to the invention, the amount of the herbicide and the carbon nitride composite photocatalyst in the wastewater is not particularly limited, and the herbicide is subjected to photocatalysis to degrade and remove the herbicide by applying the carbon nitride composite photocatalyst. Preferably, in the step (1), the mass ratio of the carbon nitride composite photocatalyst to the herbicide is 40-120:1. Further preferably, the concentration of the herbicide in the herbicide wastewater can be adjusted to 1-15mg/L by using water, and further the carbon nitride composite photocatalyst is added to the wastewater in an amount of 0.2-1g/L, and the inventors have found that the efficiency of removing the herbicide by the photocatalytic reaction can be effectively improved in this preferred embodiment.
Preferably, the herbicide is atrazine. The composite photocatalyst has better atrazine removing effect.
According to the invention, the time of adsorption is preferably 15-25min, and may be specifically 15min, 17min, 19min, 21min, 23min, 25min, or any value between the two values.
According to the present invention, in order to further improve the efficiency of treating herbicide wastewater, preferably, in the step (2), the wavelength λ of visible light is greater than 420nm, and specifically, a xenon lamp may be used as a light source of visible light; the conditions of the photocatalytic reaction include: the temperature is 5-40deg.C, specifically 5 deg.C, 10 deg.C, 15 deg.C, 20 deg.C, 25 deg.C, 30 deg.C, 35 deg.C, 40 deg.C, or any value between the two values; the time is 50-70min, and can be specifically 50min, 55min, 60min, 65min, 70min, or any value between the two values.
According to a particularly preferred embodiment of the present invention, there is provided a method for treating herbicide wastewater, comprising the steps of:
(1) Placing urea into a crucible, heating from room temperature to 500-600deg.C at a heating rate of 3-8deg.C/min, sintering for 3-5 hr, and cooling to obtain graphite phase carbon nitride nanosheets (g-C) 3 N 4 )；
(2) Mixing and grinding 3-amino-1, 2, 4-triazole and the graphite-phase carbon nitride nano-sheet obtained in the step (1) for 10-60min according to the mass ratio of 1:7-13 to obtain precursor mixed powder;
(3) Placing the precursor mixed powder obtained in the step (2) into a crucible, heating from room temperature to 500-600 ℃ at a heating rate of 3-8 ℃/min, sintering for 3-5h, and cooling to obtain a triazole modified graphite-phase carbon nitride nanosheet material (TAC);
(4) Mixing and grinding the triazole modified graphite-phase carbon nitride nanosheet material obtained in the step (3) and pyromellitic dianhydride according to a mass ratio of 0.1-4:1 for 10-60min, then placing the mixture in a crucible, heating the mixture from room temperature to 300-350 ℃ at a heating rate of 5-10 ℃/min, sintering the mixture for 3-5h, and cooling the mixture to obtain a carbon nitride composite photocatalyst (TACP);
(5) Adding the carbon nitride composite photocatalyst obtained in the step (4) into atrazine wastewater with the initial concentration of 5-15mg/L (the mass ratio of the carbon nitride composite photocatalyst to atrazine is 40-120:1) in a light-shielding environment, and adsorbing for 15-25min to obtain a mixed solution;
(6) And (3) under the condition of visible light (wavelength lambda >420 nm), placing the mixed solution obtained in the step (5) into a photocatalytic reaction device for reaction for 50-70min.
In the above preferred embodiment, atrazine has a higher removal rate.
The present invention will be described in detail by examples.
In the following examples, atrazine concentration was measured by high performance liquid chromatography (mobile phase: methanol: water=70:30, flow rate 1mL/min column temperature 30 ℃, monitoring wavelength 275 nm). The high performance liquid chromatograph is purchased from Agilent corporation, and the instrument model is 1290 Infinicity II; scanning transmission electron microscope is purchased from Zeiss company, and the instrument model is Sigma HD; XRD analyzer is purchased from Bruce company, and the model of the XRD analyzer is D8 advance; the ultraviolet-visible spectrum diffuse reflection analyzer is purchased from Hitachi, and the model of the ultraviolet-visible spectrum diffuse reflection analyzer is U-4100; the visible light source system is a PLS-SXE 300D xenon lamp, which is purchased from Beijing Porphy technology Co., ltd; x-ray photoelectron spectroscopy was purchased from Siemens, apparatus model Thermo Fisher ESCALAB Xi +.
In the following examples, unless otherwise specified, the materials and equipment used were conventional commercial products, wherein 3-amino-1, 2, 4-triazole was purchased from microphone company under the product number A800538; pyromellitic dianhydride is purchased from Allatin company, the product number is M158458, the herbicide wastewater adopts self-prepared atrazine solution as simulation wastewater, atrazine is purchased from Milin company, and the product number is A821828.
In the following examples, the data obtained are the average of three or more replicates at room temperature of 25.+ -. 5 ℃ unless otherwise specified.
Example 1
(1) 10g of urea is placed in a crucible, heated from room temperature to 550 ℃ at a heating rate of 5 ℃/min, sintered for 4 hours, cooled to obtain graphite-phase carbon nitride nanosheets (g-C) 3 N 4 )；
(2) Mixing and grinding 1g of 3-amino-1, 2, 4-triazole and 8g of graphite-phase carbon nitride nano-sheet obtained in the step (1) for 30min to obtain precursor mixed powder;
(3) Placing the precursor mixed powder obtained in the step (2) into a crucible, heating from room temperature to 550 ℃ at a heating rate of 5 ℃/min, sintering for 4 hours, and cooling to obtain a triazole modified graphite-phase carbon nitride nano sheet material (TAC);
(4) And (3) mixing and grinding 5g of the triazole modified graphite-phase carbon nitride nanosheet material obtained in the step (3) and 5g of pyromellitic dianhydride for 30min, then placing the mixture in a crucible, heating the mixture from room temperature to 325 ℃ at a heating rate of 7 ℃/min, sintering the mixture for 4h, and cooling the mixture to obtain the carbon nitride composite photocatalyst (TACP).
Example 2
(1) 10g of urea is placed in a crucible, heated from room temperature to 500 ℃ at a heating rate of 3 ℃/min, sintered for 5 hours, cooled to obtain graphite-phase carbon nitride nanosheets (g-C) 3 N 4 )；
(2) Mixing and grinding 1g of 3-amino-1, 2, 4-triazole and 6g of graphite-phase carbon nitride nano-sheet obtained in the step (1) for 10min to obtain precursor mixed powder;
(3) Placing the precursor mixed powder obtained in the step (2) into a crucible, heating from room temperature to 500 ℃ at a heating rate of 3 ℃/min, sintering for 5 hours, and cooling to obtain a triazole modified graphite-phase carbon nitride nano sheet material (TAC);
(4) 2.5g of the triazole modified graphite-phase carbon nitride nanosheet material obtained in the step (3) and 5g of pyromellitic dianhydride are mixed and ground for 10min, then placed in a crucible, heated from room temperature to 300 ℃ at a heating rate of 5 ℃/min, sintered for 5h, and cooled to obtain the carbon nitride composite photocatalyst (TACP).
Example 3
(1) Placing 25g urea into a crucible, heating from room temperature to 600 ℃ at a heating rate of 7 ℃/min, sintering for 3 hours, and cooling to obtain graphite-phase carbon nitride nanosheets (g-C) 3 N 4 )；
(2) Mixing and grinding 1g of 3-amino-1, 2, 4-triazole and 10g of graphite-phase carbon nitride nano-sheet obtained in the step (1) for 60min to obtain precursor mixed powder;
(3) Placing the precursor mixed powder obtained in the step (2) into a crucible, heating from room temperature to 600 ℃ at a heating rate of 7 ℃/min, sintering for 3 hours, and cooling to obtain a triazole modified graphite-phase carbon nitride nano sheet material (TAC);
(4) And (3) mixing and grinding 7.5g of the triazole modified graphite-phase carbon nitride nanosheet material obtained in the step (3) and 5g of pyromellitic dianhydride for 60min, then placing the mixture in a crucible, heating the mixture from room temperature to 350 ℃ at a heating rate of 10 ℃/min, sintering the mixture for 3h, and cooling the mixture to obtain the carbon nitride composite photocatalyst (TACP).
Example 4
A carbon nitride composite catalyst was prepared in the same manner as in example 1 except that in step (4), pyromellitic dianhydride was added in an amount of 20g.
Example 5
A carbon nitride composite catalyst was prepared in the same manner as in example 1 except that in step (4), pyromellitic dianhydride was added in an amount of 10g.
Example 6
A carbon nitride composite catalyst was prepared in the same manner as in example 1 except that in step (4), pyromellitic dianhydride was added in an amount of 3g.
Example 7
A carbon nitride composite catalyst was prepared in the same manner as in example 1 except that in step (4), pyromellitic dianhydride was added in an amount of 2g.
Test example 1
The triazole-modified graphite-phase carbon nitride nano-sheet material (TAC) and the carbon nitride composite photocatalyst (TACP) prepared in example 1 were subjected to Transmission Electron Microscopy (TEM) analysis, and the results are shown in fig. 1, wherein (1) is a TEM image of TAC and (B) is a TEM image of TACP. As can be seen from fig. 1, TAC exhibits an edge-curled nano-sheet structure, while TACP is thinner in thickness, and the nano-sheet edge retains the curled structure. The curled structure of the nano sheet edge mainly comes from modified triazole and pyromellitic diamine, which can provide more active sites for the catalyst on one hand, and can construct an electron donor-conjugated-electron acceptor structure based on the graphite phase carbon nitride nano sheet structure on the other hand, so that the directional migration of photo-generated charges and holes can be promoted, and the utilization rate of the material to light energy is further improved.
Test example 2
The graphite-phase carbon nitride nanosheets (g-C) 3 N 4 ) XRD analysis was performed with TAC and TACP, and the results are shown in FIG. 2. As can be seen from FIG. 2, g-C 3 N 4 Typical carbon nitride diffraction peaks are shown, TAC retains the basic structure of carbon nitride, while more amorphous carbon structure occurs due to the modification of triazole. In addition to g-C reserved in TACP 3 N 4 And an amorphous carbon structure modified by triazole, a series of typical diamine pyromellitic acid diffraction peaks also appear, which shows that the graphite-phase carbon nitride nano-sheets modified by the triazole and the diamine pyromellitic acid together are successfully compounded, and the basic structure of the graphite-phase carbon nitride nano-sheets is not changed in the compounding, so that the method has very important significance for maintaining the excellent photocatalytic performance of the composite material.
Test example 3
For g-C prepared in example 1 3 N 4 The ultraviolet-visible spectrum diffuse reflectance analysis (UV-vis), TAC, and TACP were performed, respectively, and the results are shown in fig. 3. As can be seen from FIG. 3, g-C 3 N 4 Only the light with the wavelength smaller than 460nm has an absorption effect, TAC has stronger absorption between the wavelength of 460nm and 600nm, and the absorption of TACP between the wavelength of 460nm and 600nm is further enhanced. The photo-generated electrons in the partially deformed carbon nitride composite photocatalyst are easier to generate under the excitation of light energy, so that the absorption capacity of the material in visible light is improved, the light response range of the material is widened, the absorption capacity of the material to the whole spectrum is improved, and the utilization and conversion efficiency of the light energy are improved. In addition, since the carbon nitride composite photocatalyst has an electron structure of electron donor-conjugate-electron acceptor, photo-generated charges and holes are more likely to directionally migrate in the material.
Test example 4
(1) Weighing 20mg of TACP prepared in example 1, adding the TACP into 50mL of atrazine wastewater with initial concentration of 5mg/L in a dark environment, adsorbing for 20min, and placing the TACP in a photocatalytic reaction device;
(2) And (3) adopting a 300W xenon lamp as a light source, and carrying out photocatalytic reaction for 60min in a visible light region (lambda >420 nm) to finish the treatment of atrazine in the wastewater.
Sampling when the photocatalytic reaction time t is 0min, 20min, 40min and 60min, and detecting the atrazine concentration in the solution after filtering by a filter membrane with the thickness of 0.22 mu m. The atrazine concentration is analyzed and measured by a high performance liquid chromatograph, and the atrazine concentration C corresponding to different illumination time is obtained by combining a standard curve, and the atrazine concentration C is calculated according to a formula (D= (C) 0 -C)/C 0 X 100%, where C 0 For the initial concentration of atrazine) the removal rate D of atrazine corresponding to different illumination times was calculated, and the result was shown in fig. 4.
In addition, 20mg of g-C prepared in example 1 was weighed out separately 3 N 4 And TAC, repeating the steps of atrazine wastewater treatment to obtain the atrazine removal rate of the two photocatalysts in wastewater at different illumination time, and the result is shown in figure 4.
As can be seen from FIG. 4, the TACP of the present invention has a removal rate of atrazine up to 95% in 60min, and a specific ratio of g-C 3 N 4 The (36%) and the TAC (42%) are high, and the photocatalytic efficiency is obviously improved, namely, the composite photocatalyst has faster catalytic efficiency and better removal effect. It can be seen that the ratio of the carbon nitride composite photocatalyst of the invention to g-C 3 N 4 And TAC has higher photocatalytic activity.
Test example 5
(1) The reaction solution after the photocatalytic reaction in test example 4 was subjected to centrifugal separation, and the carbon nitride composite photocatalyst was collected, then washed with water and ethanol alternately 2 times, and dried in an oven at 60 ℃ for 12 hours, to obtain a regenerated carbon nitride composite photocatalyst.
(2) Weighing 2mg of the regenerated carbon nitride composite photocatalyst (TACP) prepared in the step (1), adding the regenerated carbon nitride composite photocatalyst (TACP) into 50mL of atrazine wastewater with initial concentration of 5mg/L in a light-resistant environment, adsorbing for 20min, and then placing the atrazine wastewater in a photocatalytic reaction device.
(3) A300W xenon lamp is used as a light source, and the photocatalytic reaction is carried out for 60min in a visible light region (lambda >420 nm).
(4) Repeating the steps (1) - (3) for 4 times.
After each cycle test was completed, the atrazine concentration in the reaction solution was measured, and the atrazine concentration C corresponding to each cycle test was obtained by combining the standard curve, according to the formula (d= (C) 0 -C)/C 0 X 100%, where C 0 For the initial concentration of atrazine) the removal rate D of atrazine corresponding to each cycle test was calculated, and the result is shown in fig. 5. As can be seen from FIG. 5, in the 4 th photocatalytic experiment, the photocatalytic removal rate of the carbon nitride composite photocatalyst of the present invention is not significantly reduced, and the removal rate can still reach 80%, which indicates that the composite photocatalyst of the present invention has good photocatalytic stability and recycling performance.
Test example 6
The catalysts prepared in example 1 and examples 4 to 7 were tested according to the test method in test 4, and the removal rate of atrazine within 60 minutes was calculated as shown in fig. 6, which illustrates that the composite catalysts prepared in example 1, example 4 and example 5 have better removal rates of atrazine.
Test example 7
For g-C prepared in example 1 3 N 4 The X-ray photoelectron spectroscopy N1s narrow spectrum analysis was performed on TAC and TACP, respectively, and the results are shown in fig. 7. As can be seen from FIG. 7, compared with g-C 3 N 4 TAC and N-C in TACP due to modification of triazole group 3 The peak area of the group is significantly increased. At the same time, due to the triazole and g-C 3 N 4 The binding energy position of the N-H peak in TACP and TAC is higher than that of g-C 3 N 4 Higher.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (10)
1. The preparation method of the carbon nitride composite photocatalyst comprises the following steps:
s1, mixing and grinding graphite-phase carbon nitride nano-sheets and 3-amino-1, 2, 4-triazole to obtain precursor mixed powder;
s2, performing thermal condensation polymerization reaction I on the precursor mixed powder to obtain a triazole modified graphite-phase carbon nitride nano-sheet material;
s3, mixing and grinding the triazole modified graphite phase carbon nitride nanosheet material and pyromellitic dianhydride, and performing thermal condensation polymerization reaction II to obtain a carbon nitride composite photocatalyst;
the mass ratio of the 3-amino-1, 2, 4-triazole to the graphite-phase carbon nitride nano-sheet is 1:8, and the mass ratio of the triazole-modified graphite-phase carbon nitride nano-sheet material to the pyromellitic dianhydride is 0.25-1:1.
2. The preparation method of the carbon nitride composite photocatalyst is characterized by comprising the following steps of:
s1, mixing and grinding graphite-phase carbon nitride nano-sheets and 3-amino-1, 2, 4-triazole to obtain precursor mixed powder;
s2, performing thermal condensation polymerization reaction I on the precursor mixed powder to obtain a triazole modified graphite-phase carbon nitride nano-sheet material;
s3, mixing and grinding the triazole modified graphite phase carbon nitride nanosheet material and pyromellitic dianhydride, and performing thermal condensation polymerization reaction II to obtain a carbon nitride composite photocatalyst;
the mass ratio of the 3-amino-1, 2, 4-triazole to the graphite-phase carbon nitride nano-sheet is 1:8, and the mass ratio of the triazole-modified graphite-phase carbon nitride nano-sheet material to the pyromellitic dianhydride is 0.25-1:1.
3. The method according to claim 2, wherein in step S1, the graphite-phase carbon nitride nanosheets are graphite-phase carbon nitride nanosheets obtained by urea calcination.
4. A method of preparing according to claim 3, wherein the firing conditions include: the temperature is 500-600 ℃ and the time is 3-5h.
5. The process according to any one of claims 2 to 4, wherein in step S2, the conditions for the thermal polycondensation reaction I comprise a temperature of 500 to 600 ℃ for a period of 3 to 5 hours.
6. The process according to any one of claims 2 to 4, wherein the conditions for the thermal polycondensation reaction II comprise a temperature of 300 to 350 ℃ for a period of 3 to 5 hours.
7. Use of the carbon nitride composite photocatalyst according to claim 1 or the carbon nitride composite photocatalyst prepared by the preparation method according to any one of claims 2 to 5 in the treatment of herbicide wastewater.
8. The herbicide wastewater treatment method is characterized by comprising the following steps:
(1) Mixing and adsorbing the carbon nitride composite photocatalyst prepared by the preparation method of any one of claims 1 and/or 2-5 with the herbicide wastewater under the light-shielding condition to obtain a mixed solution;
(2) And carrying out photocatalytic reaction on the mixed solution under the condition of visible light.
9. The method according to claim 8, wherein in the step (1), the mass ratio of the carbon nitride composite photocatalyst to the herbicide is 40-120:1;
the herbicide is atrazine;
the adsorption time is 15-25min.
10. The process according to claim 8 or 9, wherein in step (2), the visible light has a wavelength λ >420nm and the photocatalytic reaction takes 50-70min.
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