CN115155654A - Carbon nitride composite photocatalyst, preparation method thereof and treatment method of herbicide wastewater - Google Patents
Carbon nitride composite photocatalyst, preparation method thereof and treatment method of herbicide wastewater Download PDFInfo
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- CN115155654A CN115155654A CN202210689103.8A CN202210689103A CN115155654A CN 115155654 A CN115155654 A CN 115155654A CN 202210689103 A CN202210689103 A CN 202210689103A CN 115155654 A CN115155654 A CN 115155654A
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- 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
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- 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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- 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
- C02F2101/306—Pesticides
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- 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
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Abstract
The invention relates to a functional composite photocatalyst, and discloses a carbon nitride composite photocatalyst, a preparation method thereof and a treatment method of herbicide wastewater. The composite catalyst comprises a graphite-phase carbon nitride nanosheet, and triazole and pyromellitic diamine modified on the surface of the graphite-phase carbon nitride nanosheet. The carbon nitride composite photocatalyst has the advantages of high photocatalytic activity, good photocatalytic stability, wide photoresponse range, high removal rate of herbicides and good reusability.
Description
Technical Field
The invention relates to a functional composite photocatalyst, and in particular relates to a carbon nitride composite photocatalyst as well as a preparation method and application thereof. In addition, the invention also relates to a method for treating the herbicide wastewater.
Background
In recent years, the development of photocatalytic technology is rapid, especially the application of semiconductor-based photocatalytic degradation technology to the removal of environmental pollutants is receiving wide attention of researchers, and the key to the excellence of catalytic performance is whether semiconductor photocatalytic materials with good performance are available. Therefore, designing and preparing high-efficiency semiconductor photocatalytic materials become the focus of research in the field of environmental photocatalysis at present.
Non-metallic graphite phase carbon nitride has attracted a great deal of attention in the selection and application of materials. However, since the forbidden band width of the graphite-phase carbon nitride is 2.7eV, the absorption range of the graphite-phase carbon nitride is limited to the illumination within 460nm, the photoresponse range is small, sunlight cannot be fully utilized, the catalytic degradation effect of the graphite-phase carbon nitride material on pollutants in the environment cannot be improved, and a single catalyst cannot achieve a satisfactory photocatalytic effect.
Therefore, the obtained graphite-phase carbon nitride nanosheet 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 needs to be improved in the prior art, and provides a carbon nitride composite photocatalyst, a preparation method thereof and a herbicide wastewater treatment method.
In order to achieve the above object, the present invention provides a carbon nitride composite photocatalyst, which comprises a graphite-phase carbon nitride nanosheet, and triazole and pyromellitic diamine modified on the surface of the graphite-phase carbon nitride nanosheet.
Preferably, the ratio of the total mass of the triazole and the graphite-phase carbon nitride nanosheets to the mass of the pyromellitic diamine is 0.1-4:1, and the mass ratio of the triazole to the graphite-phase carbon nitride nanosheets is 1:7-13.
Further preferably, the mass ratio of the pyromellitic diamine to the triazole to the graphite-phase carbon nitride nanosheets is 1.
The second aspect of the invention provides a preparation method of a carbon nitride composite photocatalyst, which comprises the following steps:
s1, mixing and grinding a graphite-phase carbon nitride nanosheet and 3-amino-1,2,4-triazole to obtain precursor mixed powder;
s2, carrying out thermal polycondensation reaction I on the precursor mixed powder to obtain a triazole modified graphite-phase carbon nitride nanosheet material;
and S3, mixing and grinding the triazole modified graphite-phase carbon nitride nanosheet material and pyromellitic dianhydride, and then carrying out thermal polycondensation reaction II to obtain the carbon nitride composite photocatalyst.
Preferably, in step S1, the graphite phase carbon nitride nanosheets are graphite phase carbon nitride nanosheets obtained by urea roasting.
Further preferably, the roasting conditions include: the temperature is 500-600 ℃, and the time is 3-5h.
More preferably, in the step S1, the mass ratio of the 3-amino-1,2,4-triazole to the graphite-phase carbon nitride nanosheets is 1:6-10.
Preferably, in step S2, the thermal polycondensation reaction I is carried out under conditions comprising a temperature of 500 to 600 ℃ and a time of 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 thermal polycondensation reaction II is carried out under the conditions of 300-350 ℃ and 3-5h.
The third aspect of the invention provides a carbon nitride composite photocatalyst provided by the first aspect and application of the carbon nitride composite photocatalyst prepared by the preparation method provided by the second aspect in treatment of herbicide wastewater.
The fourth aspect of the present invention provides a method for treating herbicide wastewater, comprising the steps of:
(1) Under the condition of keeping out of the sun, mixing and adsorbing the carbon nitride composite photocatalyst provided by the first aspect and/or the prepared carbon nitride composite photocatalyst provided by the second aspect with the herbicide wastewater 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.
Further preferably, the herbicide is atrazine.
More preferably, the adsorption time is 15-25min.
Preferably, in the step (2), the wavelength λ 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 directional movement of photo-generated electrons and holes can be driven, and the utilization and absorption of the material to 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 to light energy can be 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 surface of the graphite-phase carbon nitride nanosheet is modified with triazole and pyromellitic diamine, so that the original plane structure can be changed, more active sites can be provided, the composite photocatalyst can be deformed, the space separation of an electron enrichment area and an electron depletion area can be generated, the separation of photo-generated electrons and holes can be promoted, the effective utilization rate of the photo-generated electrons of the photocatalyst can be improved, and the photocatalytic activity and the photocatalytic stability of the composite photocatalyst can be effectively improved.
(3) According to the preparation method of the carbon nitride composite catalyst, provided by the invention, triazole and pyromellitic diamine are gradually modified on the surface of the graphite-phase carbon nitride nanosheet through a thermal polycondensation reaction to prepare the composite photocatalyst with a plane deformation structure, so that a space separation can be generated in an electron enrichment area and an electron depletion area, the separation of photo-generated electrons and holes is promoted, the effective utilization rate of the 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 utilizes the carbon nitride radiation catalyst to carry out photocatalytic reaction on the herbicide wastewater, has the advantages of simple application method, low cost, high removal rate of the herbicide and the like, can realize effective degradation of the herbicide in the wastewater, and has good application prospect.
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 of graphite phase carbon nitride nanosheets (g-C) prepared in example 1 of the present invention 3 N 4 ) XRD patterns of a triazole modified graphite phase carbon nitride nanosheet material (TAC) and a carbon nitride composite photocatalyst (TACP);
FIG. 3 is a graph of graphite phase carbon nitride nanosheets (g-C) prepared in example 1 of the present invention 3 N 4 ) Ultraviolet-visible spectrum diffuse reflection diagrams of a triazole modified graphite phase carbon nitride nanosheet material (TAC) and a carbon nitride composite photocatalyst (TACP);
FIG. 4 is a graph of graphite phase carbon nitride nanosheets (g-C) prepared in example 1 of the present invention 3 N 4 ) The triazole modified graphite phase carbon nitride nanosheet material (TAC) and the carbon nitride composite photocatalyst (TACP) are in a visible light region (lambda)>420 nm) under photocatalysis activation, wherein the concentration of the atrazine changes along with time in the atrazine degradation process;
fig. 5 is a graph showing the effect of the removal rate of the carbon nitride composite photocatalyst in the case of recycling atrazine wastewater in example 1;
FIG. 6 is a graph showing the effect of the removal rate of the composite photocatalyst for carbon nitride synthesized by using different amounts of pyromellitic dianhydride in examples 1 and 4 to 7 according to the present invention in the recycling of atrazine wastewater;
FIG. 7 is a graph of graphite phase carbon nitride nanoplates (g-C) prepared in example 1 of the invention 3 N 4 ) And X-ray photoelectron energy spectrograms of the triazole modified graphite-phase carbon nitride nanosheet material (TAC) and the carbon nitride composite photocatalyst (TACP).
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and these ranges or values should be understood to encompass values close to these ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a carbon nitride composite photocatalyst, which comprises a graphite-phase carbon nitride nanosheet, and triazole and pyromellitic diamine modified on the surface of the graphite-phase carbon nitride nanosheet.
The carbon nitride composite photocatalyst provided by the invention is a carbon nitride composite catalyst secondarily modified by triazole and pyromellitic diamine, and the triazole is modified on the surface of a graphite-phase carbon nitride nanosheet, so that the directional movement of photo-generated electrons and holes can be driven, and the utilization and absorption of the material to 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 to light energy can be further improved. Moreover, the original plane structure can be changed by modifying the triazole and the pyromellitic diamine on the surface of the graphite-phase carbon nitride nanosheet, more active sites can be provided, the composite catalyst can be deformed, the electron enrichment area and the electron depletion area can be separated spatially, the separation of photo-generated electrons and holes can be promoted, the effective utilization rate of the photo-generated electrons of the material can be improved, and the photo-catalytic activity and the photo-catalytic stability of the composite photocatalyst can be 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 pyromellitic diamine 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 pyromellitic diamine, because the pyromellitic diamine can improve the light absorption capacity of the carbon nitride composite photocatalyst, can promote the separation of photo-generated electrons and holes, and improves the photocatalytic performance; with the further increase of the proportion of pyromellitic diamine in the carbon nitride composite photocatalyst, the photocatalytic performance of the carbon nitride composite photocatalyst is reduced, which is mainly due to the following reasons: excessive pyromellitic diamine can cause insufficient heptazine ring units with photocatalytic activity in the catalyst per unit mass, and can weaken the photocatalytic performance of the material; on the other hand, too much pyromellitic diamine leads to an excessively compact structure, so that the specific surface area of the catalyst is greatly reduced, and the photocatalytic performance is reduced. Preferably, the ratio of the total mass of the triazole and the graphite-phase carbon nitride nanosheets to the mass of the pyromellitic diamine is 0.1-4:1, and specifically may be 0.1, 0.5; further preferably, the mass ratio of the total mass of the triazole and the graphite-phase carbon nitride nanosheet to the pyromellitic diamine is 0.1-2:1, more preferably 0.1-1:1, and at this time, 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; more preferably, the mass ratio of the triazole to the graphite-phase carbon nitride nanosheets is 1:8-10, and is more preferably 1:8. From the viewpoint of further improving the photocatalytic activity of the carbon nitride composite photocatalyst, the mass ratio of the pyromellitic diamine, the triazole and the graphite-phase carbon nitride nanosheets is preferably 1.4-1.5.
The second aspect of the invention provides a preparation method of a carbon nitride composite photocatalyst, which comprises the following steps:
s1, mixing and grinding graphite-phase carbon nitride nanosheets and 3-amino-1,2,4-triazole to obtain precursor mixed powder;
s2, carrying out thermal polycondensation reaction I on the precursor mixed powder to obtain a triazole modified graphite-phase carbon nitride nanosheet material;
and S3, mixing and grinding the triazole modified graphite-phase carbon nitride nanosheet material and pyromellitic dianhydride II, and then carrying out thermal polycondensation reaction II to obtain the carbon nitride composite photocatalyst.
According to the carbon nitride composite photocatalyst provided by the invention, triazole and pyromellitic diamine are respectively modified on the surface of the graphite-phase carbon nitride nanosheet through two thermal polycondensation reactions to prepare the composite photocatalyst material with a plane deformation structure, so that a space separation can be generated in an electron enrichment region and an electron depletion region, the separation of photo-generated electrons and holes is promoted, the effective utilization rate of the 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, in step S1, the graphite-phase carbon nitride nanosheets are preferably obtained by calcining urea. The temperature and time of the calcination can be determined by those skilled in the art according to the actual circumstances. In order to further improve the photocatalytic activity of the prepared composite photocatalyst, preferably, the calcination conditions include: the temperature is 500-600 deg.C, specifically 500 deg.C, 520 deg.C, 540 deg.C, 560 deg.C, 580 deg.C, 600 deg.C, or any value therebetween, and the time is 3-5h, specifically 3h, 3.5h, 4h, 4.5h, 5h, or any value therebetween. In the invention, the heating rate of roasting is 3-8 ℃/min.
Preferably, in the step S1, the mass ratio of the 3-amino-1,2,4-triazole to the graphite-phase carbon nitride nanosheets is 1:6-10. In the course of research, the inventors found that under the condition of the mass ratio, the active sites 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 actual conditions. In order to further improve the action effect of the 3-amino-1,2,4-triazole and the graphite phase carbon nitride nanosheet, the grinding time I is preferably 10-60min.
In order to further improve the photocatalytic activity of the prepared composite photocatalyst, preferably, in step S2, the conditions of the thermal polycondensation reaction I include a temperature of 500 to 600 ℃, specifically 500 ℃, 520 ℃, 540 ℃, 560 ℃, 580 ℃, 600 ℃, 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 invention, in the thermal polycondensation reaction I, the heating 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. In the course of research, the inventors found that, under the condition of the mass ratio, the activation sites 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, the mass ratio of the triazole-modified graphite-phase carbon nitride nanosheet material to the pyromellitic dianhydride is preferably 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 a person skilled in the art according to actual conditions. In order to further improve the action effect of the triazole modified graphite-phase carbon nitride nanosheet material and pyromellitic dianhydride, the grinding II is preferably performed for 10-60min.
In order to further improve the photocatalytic activity of the prepared composite photocatalyst, it is further preferable that the conditions of the thermal polycondensation reaction II include a temperature of 300-350 ℃, specifically 300 ℃, 310 ℃, 320 ℃, 330 ℃, 340 ℃, 350 ℃, or any value between the two values, and a time of 3-5h, specifically 3h, 3.5h, 4h, 4.5h, 5h, or any value between the two values. In the invention, in the thermal polycondensation reaction I, the heating rate is 5-10 ℃/min.
The third aspect of the invention provides a carbon nitride composite photocatalyst provided by the first aspect and application of the carbon nitride composite photocatalyst prepared by the preparation method provided by the second aspect in treatment of herbicide wastewater. The carbon nitride composite photocatalyst provided by the invention can carry out photocatalytic reaction on herbicide wastewater, realizes efficient degradation and removal of the 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 present invention, the herbicide-containing wastewater is a wastewater containing a herbicide.
The fourth aspect of the present invention provides a method for treating herbicide wastewater, comprising the steps of:
(1) Under the condition of keeping out of the sun, mixing and adsorbing the carbon nitride composite photocatalyst provided by the first aspect and/or the prepared carbon nitride composite photocatalyst provided by the second aspect with the herbicide wastewater 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 provided carbon nitride composite catalyst has higher removal rate to herbicide, and has lower cost and simple method.
According to the invention, the dosage of the herbicide and the carbon nitride composite photocatalyst in the wastewater is not particularly limited, and the herbicide can be degraded and removed by applying the carbon nitride composite photocatalyst and performing photocatalysis. Preferably, in the step (1), the mass ratio of the carbon nitride composite photocatalyst to the herbicide is 40-120. Further preferably, the concentration of the herbicide in the herbicide wastewater can be adjusted to 1-15mg/L by water, and the addition amount of the carbon nitride composite photocatalyst in the wastewater is 0.2-1 g/L.
Preferably, the herbicide is atrazine. The composite photocatalyst has a better atrazine removing effect.
According to the invention, the adsorption time is preferably 15-25min, and specifically may be 15min, 17min, 19min, 21min, 23min, 25min, or any value between the two values.
According to the invention, in order to further improve the efficiency of treating the herbicide wastewater, preferably, in the step (2), the wavelength λ of the visible light is more than 420nm, and a xenon lamp can be particularly used as a light source of the visible light; the conditions of the photocatalytic reaction include: the temperature is 5-40 deg.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 above two values; the time is 50-70min, specifically 50min, 55min, 60min, 65min, 70min, or any value between the above 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) Putting urea in a crucible, heating from room temperature to 500-600 ℃ at the heating rate of 3-8 ℃/min, sintering for 3-5h, 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 nanosheet 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) in a crucible, heating to 500-600 ℃ from room temperature at the 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 in 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 sintered 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 in a dark environment (the mass ratio of the carbon nitride composite photocatalyst to the atrazine is 40-120: 1), and adsorbing for 15-25min to obtain a mixed solution;
(6) And (3) under the condition of visible light (the wavelength lambda is more than 420 nm), placing the mixed solution obtained in the step (5) into a photocatalytic reaction device, and reacting for 50-70min.
In the preferred embodiment, atrazine has a higher removal rate.
The present invention will be described in detail below by way of examples.
In the following examples, the concentration of atrazine was measured by high performance liquid chromatography (mobile phase methanol: water =70, flow rate 1mL/min column temperature 30 ℃, monitoring wavelength 275 nm). The high performance liquid chromatograph is purchased from Agilent company, and the instrument model is 1290Infinity II; the scanning transmission electron microscope is purchased from Zeiss company, and the instrument model is Sigma HD; the XRD analyzer is purchased from Bruker, 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 analyzer is U-4100; the light source system of visible light is PLS-SXE 300D xenon lamp, which is purchased from Beijing Pofely science and technology Limited; x-ray photoelectron spectroscopy was purchased from Sammerfei, inc. under the instrument model Thermo Fisher ESCALB Xi +.
In the following examples, the raw materials and instruments used are all conventional commercial products unless otherwise specified, wherein 3-amino-1,2,4-triazole is available from Michael corporation under product number A800538; pyromellitic dianhydride is purchased from Aladdin company, the product number is M158458, herbicide wastewater adopts self-prepared atrazine solution as simulated wastewater, atrazine is purchased from Meclin company, and the product number is A821828.
In the following examples, unless otherwise specified, the data obtained are the average of three or more replicates at room temperature of 25. + -. 5 ℃.
Example 1
(1) Putting 10g of urea into a crucible, heating from room temperature to 550 ℃ at the heating rate of 5 ℃/min, sintering for 4h, 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 8g of graphite-phase carbon nitride nanosheets obtained in the step (1) for 30min to obtain precursor mixed powder;
(3) Placing the precursor mixed powder obtained in the step (2) in a crucible, heating from room temperature to 550 ℃ at the heating rate of 5 ℃/min, sintering for 4h, and cooling to obtain a triazole modified graphite phase carbon nitride nanosheet 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 the heating rate of 7 ℃/min, sintering the mixture for 4h, and cooling the sintered mixture to obtain the carbon nitride composite photocatalyst (TACP).
Example 2
(1) Putting 10g of urea into a crucible, heating from room temperature to 500 ℃ at the heating rate of 3 ℃/min, sintering for 5h, 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 6g of graphite-phase carbon nitride nanosheets obtained in the step (1) for 10min to obtain precursor mixed powder;
(3) Placing the precursor mixed powder obtained in the step (2) in a crucible, heating from room temperature to 500 ℃ at the heating rate of 3 ℃/min, sintering for 5h, and cooling to obtain a triazole modified graphite phase carbon nitride nanosheet material (TAC);
(4) And (3) mixing and grinding 2.5g of the triazole modified graphite-phase carbon nitride nanosheet material obtained in the step (3) and 5g of pyromellitic dianhydride for 10min, then placing the mixture in a crucible, heating the mixture from room temperature to 300 ℃ at the heating rate of 5 ℃/min, sintering the mixture for 5h, and cooling the sintered mixture to obtain the carbon nitride composite photocatalyst (TACP).
Example 3
(1) Putting 25g of urea in a crucible, heating from room temperature to 600 ℃ at the heating rate of 7 ℃/min, sintering for 3h, 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 nanosheets obtained in the step (1) for 60min to obtain precursor mixed powder;
(3) Placing the precursor mixed powder obtained in the step (2) in a crucible, heating from room temperature to 600 ℃ at the heating rate of 7 ℃/min, sintering for 3h, and cooling to obtain a triazole modified graphite phase carbon nitride nanosheet 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 the heating rate of 10 ℃/min, sintering the mixture for 3h, and cooling the sintered mixture to obtain the carbon nitride composite photocatalyst (TACP).
Example 4
A carbon nitride composite catalyst was prepared by the method of example 1, except that in the step (4), pyromellitic dianhydride was added in an amount of 20g.
Example 5
A carbon nitride composite catalyst was prepared by the method of example 1, except that in the step (4), pyromellitic dianhydride was added in an amount of 10g.
Example 6
A carbon nitride composite catalyst was prepared by the method of example 1, except that in the step (4), pyromellitic dianhydride was added in an amount of 3g.
Example 7
A carbon nitride composite catalyst was prepared by the method of example 1, except that in the step (4), pyromellitic dianhydride was added in an amount of 2g.
Test example 1
The Transmission Electron Microscope (TEM) analysis of the triazole-modified graphite-phase carbon nitride nanosheet material (TAC) and the carbon nitride composite photocatalyst (TACP) prepared in example 1 is shown in fig. 1, where (1) is a TEM image of TAC and (B) is a TEM image of TACP. As can be seen from fig. 1, TAC exhibits a nanosheet structure with curled edges, whereas TACP is thinner, and the curled structure is retained at the nanosheet edges. The curling structure of the edge of the nano-sheet mainly comes from modified triazole and pyromellitic diamine, which can provide more active sites for a catalyst on one hand, and can construct an electron donor-conjugate-electron acceptor structure based on a 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 on light energy is further improved.
Test example 2
Graphite-phase carbon nitride nanosheets (g-C) prepared in example 1 3 N 4 ) XRD analysis of TAC and TACP was performed, and the results are shown in FIG. 2. As can be seen from FIG. 2, g-C 3 N 4 Typical diffraction peaks of carbon nitride are shown, the basic structure of the carbon nitride is kept in the TAC, and more amorphous carbon structures are generated due to the modification of triazole. In addition to retention of g-C in TACP 3 N 4 And a series of typical pyromellitic diamine diffraction peaks appear in the amorphous carbon structure derived from triazole modification, which shows that the graphite-phase carbon nitride nanosheets modified by triazole and pyromellitic diamine have been successfully compounded, and the basic structure of the graphite-phase carbon nitride nanosheets is not changed in compounding, so that the method has a 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) was performed for TAC and TACP, and the results are shown in FIG. 3. As can be seen from FIG. 3, g-C 3 N 4 The TAC has stronger absorption between the wavelength of 460nm and 600nm, and the TACP has further enhanced absorption between the wavelength of 460nm and 600 nm. This is mainly due to the fact that the photo-generated electrons in the partially deformed carbon nitride composite photocatalyst are easier to be photo-generatedThe energy is generated under excitation, the absorption capacity of the material in visible light is improved, the photoresponse range of the material is widened, the absorption capacity of the material to the whole spectrum is improved, and therefore the utilization and conversion efficiency of light energy is improved. In addition, as the carbon nitride composite photocatalyst has an electron structure of electron donor-conjugated-electron acceptor, photo-generated charges and holes can be more easily directionally transferred in the material.
Test example 4
(1) Weighing 20mg of TACP prepared in example 1, adding the TACP into 50mL of atrazine wastewater with the initial concentration of 5mg/L in a dark environment, adsorbing for 20min, and placing the mixture in a photocatalytic reaction device;
(2) And (3) performing a photocatalytic reaction for 60min in a visible light region (lambda is more than 420 nm) by using a 300W xenon lamp as a light source to finish the treatment of the atrazine in the wastewater.
Sampling at the photocatalytic reaction time t of 0min, 20min, 40min and 60min, filtering with a filter membrane of 0.22 μm, and detecting the concentration of atrazine in the solution. Analyzing and measuring the atrazine concentration by a high performance liquid chromatograph, combining a standard curve to obtain the atrazine concentration C corresponding to different illumination times, and obtaining the atrazine concentration C according to a formula (D = (C) 0 -C)/C 0 X 100% where C 0 Initial concentration of atrazine) was calculated, and the results are shown in fig. 4, in which the atrazine removal rate D was calculated for different light irradiation times.
In addition, 20mg of g-C prepared in example 1 were weighed out separately 3 N 4 And TAC, repeating the steps of atrazine wastewater treatment to respectively obtain the atrazine removal rate of the two photocatalysts in the wastewater at different illumination time, and the result is shown in figure 4.
As can be seen from FIG. 4, the removal rate of atrazine by TACP of the invention can reach 95% within 60min, which is g-C 3 N 4 Both (36%) and TAC (42%) are high, and the photocatalytic efficiency is remarkably improved, namely the composite photocatalyst has higher catalytic efficiency and better removal effect. Thus, the carbon nitride composite photocatalyst has the ratio of g-C 3 N 4 And TAC has a higher photocatalytic activity.
Test example 5
(1) And (3) centrifugally separating the reaction solution after the photocatalytic reaction in test example 4, collecting the carbon nitride composite photocatalyst, then alternately cleaning the carbon nitride composite photocatalyst by using water and ethanol for 2 times, and drying the carbon nitride composite photocatalyst in an oven at 60 ℃ for 12 hours to obtain the 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 into 50mL of atrazine wastewater with the initial concentration of 5mg/L in a dark environment, adsorbing for 20min, and placing the mixture 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 is more than 420 nm).
(4) Repeating the steps (1) - (3) 4 times.
After each circulation test is finished, measuring the concentration of the atrazine in the reaction solution, combining a standard curve to obtain the concentration C of the atrazine corresponding to each circulation test, and obtaining the concentration C according to a formula (D = (C) 0 -C)/C 0 X 100% where C 0 Initial concentration of atrazine) was calculated, and the removal rate D of atrazine corresponding to each cycle test was calculated, and the results are 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 still 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 examples 1 and 4 to 7 were tested in the test manner of test 4, and the atrazine removal rate in 60min was calculated as shown in fig. 6, which illustrates that the composite catalysts prepared in examples 1, 4 and 5 have a better atrazine removal rate.
Test example 7
For g-C prepared in example 1 3 N 4 The results of narrow spectrum analysis of X-ray photoelectron spectroscopy N1s by TAC and TACP are shown in fig. 7. As can be seen from FIG. 7, the ratio is compared with that of g-C 3 N 4 N-C in TAC and TACP due to modification of the triazolyl group 3 The peak area of the radical is obviously increased. Meanwhile, due to triazole and g-C 3 N 4 The position of the binding energy of the N-H peak in TACP and TAC is higher than that of g-C 3 N 4 And higher.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (10)
1. The composite carbon nitride photocatalyst is characterized by comprising a graphite-phase carbon nitride nanosheet, and triazole and pyromellitic diamine modified on the surface of the graphite-phase carbon nitride nanosheet.
2. The carbon nitride composite photocatalyst of claim 1, wherein the ratio of the total mass of the triazole and the graphite-phase carbon nitride nanosheets to the mass of the pyromellitic diamine is 0.1-4:1, and the mass ratio of the triazole to the graphite-phase carbon nitride nanosheets is 1:7-13;
preferably, the mass ratio of the pyromellitic diamine to the triazole to the graphite-phase carbon nitride nanosheets is 1.4-1.5.
3. A preparation method of a carbon nitride composite photocatalyst is characterized by comprising the following steps:
s1, mixing and grinding a graphite-phase carbon nitride nanosheet and 3-amino-1,2,4-triazole to obtain precursor mixed powder;
s2, carrying out thermal polycondensation reaction I on the precursor mixed powder to obtain a triazole modified graphite-phase carbon nitride nanosheet material;
and S3, mixing and grinding the triazole modified graphite-phase carbon nitride nanosheet material and pyromellitic dianhydride, and then carrying out thermal polycondensation reaction II to obtain the carbon nitride composite photocatalyst.
4. The production method according to claim 3, wherein in step S1, the graphite-phase carbon nitride nanosheets are graphite-phase carbon nitride nanosheets obtained by urea roasting;
preferably, the conditions of the calcination include: the temperature is 500-600 ℃, and the time is 3-5h;
preferably, the mass ratio of the 3-amino-1,2,4-triazole to the graphite phase carbon nitride nanosheet is 1:6-10.
5. The process according to claim 3 or 4, wherein in step S2, the conditions of the thermal polycondensation reaction I comprise a temperature of 500 to 600 ℃ and a time of 3 to 5 hours.
6. The preparation method according to claim 3 or 4, wherein 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;
preferably, the conditions of the thermal polycondensation reaction II include a temperature of 300-350 ℃ and a time of 3-5h.
7. The use of the carbon nitride composite photocatalyst as defined in claim 1 or 2 and the carbon nitride composite photocatalyst prepared by the preparation method as defined in any one of claims 3 to 6 for treating herbicide wastewater.
8. A method for treating herbicide wastewater is characterized by comprising the following steps:
(1) Mixing and adsorbing the carbon nitride composite photocatalyst of claim 1 or 2 and/or the prepared carbon nitride composite photocatalyst of any one of claims 3 to 6 with the herbicide wastewater under a dark condition to obtain a mixed solution;
(2) And carrying out photocatalytic reaction on the mixed solution under the condition of visible light.
9. The treatment method as claimed in claim 8, wherein in the step (1), the mass ratio of the carbon nitride composite photocatalyst to the herbicide is 40-120;
preferably, the herbicide is atrazine;
preferably, the adsorption time is 15-25min.
10. The process according to claim 8 or 9, characterized in that, in step (2), the wavelength λ of the visible light is >420nm and the time of the photocatalytic reaction is 50-70min.
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