CN113145158A - Stripped tubular carbon nitride photocatalyst and preparation method and application thereof - Google Patents
Stripped tubular carbon nitride photocatalyst and preparation method and application thereof Download PDFInfo
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- XMEVHPAGJVLHIG-FMZCEJRJSA-N chembl454950 Chemical compound [Cl-].C1=CC=C2[C@](O)(C)[C@H]3C[C@H]4[C@H]([NH+](C)C)C(O)=C(C(N)=O)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O XMEVHPAGJVLHIG-FMZCEJRJSA-N 0.000 claims description 79
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- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 claims description 14
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- IPZJNJPAVPZHJM-UHFFFAOYSA-N n-[(2,2-dimethylchromen-6-yl)methyl]-3,4-dimethoxy-n-phenylbenzenesulfonamide Chemical compound C1=C(OC)C(OC)=CC=C1S(=O)(=O)N(C=1C=CC=CC=1)CC1=CC=C(OC(C)(C)C=C2)C2=C1 IPZJNJPAVPZHJM-UHFFFAOYSA-N 0.000 description 23
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- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
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- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B15/00—Peroxides; Peroxyhydrates; Peroxyacids or salts thereof; Superoxides; Ozonides
- C01B15/01—Hydrogen peroxide
- C01B15/027—Preparation from water
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
- C01B21/0605—Binary compounds of nitrogen with carbon
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/01—Crystal-structural characteristics depicted by a TEM-image
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Abstract
The invention discloses a stripped tubular carbon nitride photocatalyst and a preparation method and application thereof, wherein the preparation method of the stripped tubular carbon nitride photocatalyst comprises the following steps: the method comprises the steps of mixing a nitrogen-containing raw material and potassium halide to prepare a mixed solution, and carrying out hydrothermal reaction and calcination to obtain the stripped tubular carbon nitride photocatalyst. The stripped tubular carbon nitride photocatalyst prepared by the invention has the advantages of large specific surface area, more active sites, low recombination rate of photo-generated electron-hole pairs and visible lightStrong absorption capacity, high photocatalytic activity and the like, is a novel visible light catalyst with novel appearance structure and excellent photocatalytic performance, can be widely used for degrading organic pollutants and producing H2O2The practical application value is high; meanwhile, the preparation method does not need an additional template, does not need a hazardous reagent, does not adopt raw materials harmful to the environment, has the advantages of simple process, easy operation, low cost, high safety, high preparation efficiency and the like, is suitable for large-scale preparation, and is beneficial to industrial application.
Description
Technical Field
The invention belongs to the field of visible light catalysis, and relates to a stripped tubular carbon nitride photocatalyst, and a preparation method and application thereof.
Background
With the rapid development of social economy, environmental and energy problems have become the problem which needs to be solved urgently today. Pollution and harm of organic pollutants to the environment are common environmental pollution problems, wherein the organic pollutants comprise antibiotics, dyes and the like. Taking an antibiotic as an example, the antibiotic is a common organic pollutant, and the antibiotic is the most common medical drug and has been widely used in a plurality of fields such as medical industry, animal husbandry, aquaculture industry and the like, however, the antibiotic used in an excessive amount can cause the antibiotic to be incompletely metabolized in the organism and enter natural water, sewage, soil and other environment media, and the unmetabolized antibiotic entering the environment media can promote the environment organism to generate drug-resistant strains, thereby bringing adverse effects on the ecological environment and human health. At present, the methods for treating antibiotics in the environment mainly include physical treatment methods, chemical treatment methods and biological treatment methods. Since the physical treatment method cannot fundamentally degrade antibiotics, the biological treatment method takes a long time, and thus the chemical treatment method is the most common. Photocatalysis has been widely studied as a new approach to chemical treatment, and the study of photocatalysts with high photocatalytic performance is the key to photocatalytic applications. Besides the field of environmental remediation, photocatalysis also plays an important role in the field of energy production. Hydrogen peroxide has received increasing attention in recent years as a new type of liquid solar fuel and disinfectant. The traditional technologies such as the traditional anthraquinone method, the electrocatalytic oxygen reduction method and the like have complex processes and high cost, so the semiconductor photocatalysis technology taking solar energy as a driving force is considered to be an effective strategy for solving the current energy crisis.
Among the numerous photocatalysts, the traditional photocatalysts such as TiO2CdS and ZnO can only absorb ultraviolet light due to their large forbidden band width, and thus cannot effectively utilize sunlight. Graphitized carbon nitride (g-C)3N4) The photocatalyst has the advantages of proper forbidden band width, effective response to visible light, strong stability, low preparation cost and the like, and is considered to be one of ideal photocatalysts. The nanostructure and morphology of the photocatalyst are closely related to their physicochemical properties. g-C3N4Mainly comprises block, rod, tube, quantum dots and the like, wherein the traditional block g-C3N4The defects of small specific surface area, high photo-generated charge recombination rate, low quantum efficiency and the like exist, and the application of the quantum well is limited in practice; rod-like g-C3N4The same disadvantage of small specific surface area, g-C3N4The quantum dots are easy to agglomerate. g-C in bulk and rod form3N4Tubular carbon nitride exhibits higher photocatalytic performance due to its large specific surface area. However, conventional tubular shapes existg-C3N4The defects of thicker pipe wall, insufficient exposure of the surface of the catalyst, less active sites, higher photo-generated charge recombination efficiency and the like exist, so that the photocatalysis effect is not ideal enough. Therefore, how to solve the defects and shortcomings of the tubular carbon nitride is a technical problem which needs to be solved urgently at present.
To solve this problem, tubular g-C with a split tube wall was synthesized3N4Is effective. However, the commonly used methods for stripping carbon nitride mainly include strong acid stripping, high temperature calcination stripping, ultrasonic stripping and the like, and these methods are dangerous in operating environment, harsh in conditions and long in time consumption, so that it is necessary to research a stripping method which is safe in operation and mild in conditions; at the same time, the severe reaction conditions can lead to destruction of the tubular structure during the stripping process. Therefore, the method for preparing the stripped tubular carbon nitride photocatalyst with the advantages of simple process, mild conditions, low cost, high safety, large specific surface area, many active sites, strong light absorption capacity, low photo-generated charge recombination efficiency and strong photocatalytic activity is obtained, and organic pollutants (such as antibiotics) in the environment are degraded and H is increased2O2The yield of (A) has very important significance.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, provides a stripped tubular carbon nitride photocatalyst with large specific surface area, more active sites, strong light absorption capacity, low photo-generated charge recombination efficiency and strong photocatalytic activity, also provides a preparation method of the stripped tubular carbon nitride photocatalyst with simple process, low treatment cost and high safety performance, and the stripped tubular carbon nitride photocatalyst is used for degrading organic pollutants and preparing H2O2The use of (1).
In order to solve the technical problems, the invention adopts the following technical scheme:
a preparation method of a stripped tubular carbon nitride photocatalyst comprises the following steps:
s1, mixing the nitrogen-containing raw material and potassium halide to prepare a mixed solution;
s2, carrying out hydrothermal reaction on the mixed solution in the step S1 to obtain a precursor;
and S3, calcining the precursor in the step S2 to obtain the stripped tubular carbon nitride photocatalyst.
In the step S1, the mass ratio of the nitrogen-containing raw material to the potassium halide is 1.0-5.5: 1.
In a further improvement of the above preparation method, in step S1, the nitrogen-containing raw material is at least one of melamine, dicyandiamide, cyanuric acid, and urea; the potassium halide is at least one of potassium chloride, potassium bromide and potassium iodide.
In the above preparation method, further improvement, in step S1, the step of preparing the mixed solution is:
s1-1, mixing the nitrogenous raw material with a solvent, and stirring to dissolve the nitrogenous raw material into the solution to obtain a nitrogenous raw material solution;
and S1-2, mixing the nitrogen-containing raw material solution with potassium halide, and stirring to dissolve the potassium halide in the nitrogen-containing raw material solution to obtain a mixed solution.
In the preparation method, further improvement is provided, in step S1-1, the solvent is water; the stirring is carried out at the temperature of 60-90 ℃; the rotating speed of the stirring is 300-600 rpm; the stirring time is 0.5-1.5 h.
In a further improvement of the above preparation method, in step S1-2, the stirring is performed at a temperature of 60 ℃ to 90 ℃; the rotating speed of the stirring is 300-600 rpm; the stirring time is 0.5 h-1.0 h.
In the preparation method, the preparation method is further improved, in step S2, the temperature of the hydrothermal reaction is more than or equal to 150 ℃; the time of the hydrothermal reaction is 8-12 h; the hydrothermal reaction further comprises the following treatment steps: washing, filtering and drying the product solution; the filtration is carried out at a temperature of 20 ℃ to 50 ℃: the drying is carried out at the temperature of 60-85 ℃; the drying time is 6-12 h.
In a further improvement of the above preparation method, in step S3, the calcination is performed in a nitrogen atmosphere; the heating rate in the calcining process is 2-5 ℃/min; the calcining temperature is 450-650 ℃; the calcining time is 2-6 h.
As a general technical concept, the invention also provides a stripped tubular carbon nitride photocatalyst prepared by the preparation method.
As a general technical concept, the invention also provides the application of the stripped tubular carbon nitride photocatalyst in degrading organic pollutants or preparing H2O2The use of (1).
The application is further improved, when the stripped tubular carbon nitride photocatalyst is used for degrading organic pollutants in water, the method comprises the following steps: mixing the stripped tubular carbon nitride photocatalyst with the organic pollutant water body, stirring, and carrying out photocatalytic reaction to finish the degradation of the organic pollutant in the water body; the proportion of the stripped tubular carbon nitride photocatalyst to the organic pollutant water body is 0.3-1 g: 1L; the organic pollutants in the organic pollutant water body are antibiotics; the antibiotic is tetracycline hydrochloride; the initial concentration of the organic pollutants in the organic pollutant water body is less than or equal to 20 mg/L; the rotating speed of the stirring is 300-600 rpm; the stirring time is 30-60 min; the photocatalytic reaction is carried out under the irradiation of a xenon lamp; the optical power of the xenon lamp is 45-50W; the photocatalytic reaction is carried out at the rotating speed of 300-600 rpm; the temperature of the photocatalytic reaction is 25-35 ℃; the time of the photocatalytic reaction is 30-150 min.
The application is further improved, and the stripped tubular carbon nitride photocatalyst is used for preparing H2O2The method comprises the following steps: mixing the stripped tubular carbon nitride photocatalyst with water, adding sacrificial agent, introducing oxygen, stirring, and carrying out photocatalytic reaction to obtain H2O2Preparing; the ratio of the stripped tubular carbon nitride photocatalyst to water is 0.3-1 g: 1L; the volume ratio of the sacrificial agent to the water is 0.1-0.25: 1; the sacrificial agent is isopropanol and/or ethanol; the introducing time of the oxygen is 30-60 min; the rotating speed of the stirring is 300-600 rpm; the stirring time is 30-60 min; the above-mentionedThe photocatalytic reaction is carried out under the irradiation of a xenon lamp; the optical power of the xenon lamp is 45-50W; the photocatalytic reaction is carried out at the rotating speed of 300-600 rpm; the temperature of the photocatalytic reaction is 25-35 ℃; the time of the photocatalytic reaction is 30-150 min.
Compared with the prior art, the invention has the advantages that:
(1) the invention provides a preparation method of a stripped tubular carbon nitride photocatalyst, which forms a tubular carbon nitride nanotube precursor through supermolecule self-assembly, and takes potassium bromide as a stripping regulator to play a role in regulating the structure of the supermolecule precursor in the hydrothermal reaction process of a nitrogenous raw material, so as to play a stripping role in the calcining process of the tubular carbon nitride nanotube precursor, realize the stripping and separation of the wall of the tubular carbon nitride nanotube and finally obtain tubular carbon nitride with a stripped wall structure. Compared with the conventional carbon nitride, the stripped tubular carbon nitride photocatalyst prepared by the preparation method has the advantages of large specific surface area, more active sites, low recombination rate of photo-generated electron-hole pairs, strong visible light absorption capacity, high photocatalytic activity and the like, is a novel visible light photocatalyst with novel morphology and structure and excellent photocatalytic performance, can be widely used for degrading organic pollutants and producing H2O2And the practical application value is high.
(2) In the preparation method of the stripped tubular carbon nitride photocatalyst, the mass ratio of the nitrogen-containing raw material to the potassium halide is optimized, the optimal potassium halide usage amount is obtained, the stripping effect of the tubular carbon nitride can be further realized on the premise of ensuring that the tubular structure is not damaged, and the stripped tubular carbon nitride photocatalyst with better performance is obtained.
(3) The preparation method of the stripped tubular carbon nitride photocatalyst does not need an additional template, does not need dangerous reagents, does not adopt raw materials harmful to the environment, has the advantages of simple process, easy operation, low cost, high safety, high preparation efficiency and the like, is suitable for large-scale preparation, and is beneficial to industrial application.
(4) The invention also provides the application of the stripped tubular carbon nitride photocatalyst in degrading organic pollutants, the stripped tubular carbon nitride photocatalyst is mixed with the organic pollutant water body for carrying out photocatalytic reaction, so that the organic pollutants in the water body can be effectively removed, and the method has the advantages of simple process, convenience in operation, low cost, high treatment efficiency, good removal effect and the like, and has good application prospect. By taking tetracycline hydrochloride as an example, the stripping tubular carbon nitride photocatalyst has the degradation efficiency of 83% to the tetracycline hydrochloride, and compared with the conventional carbon nitride, the stripping tubular carbon nitride photocatalyst has the degradation efficiency improved by 32%, realizes the efficient removal of the tetracycline, and can meet the requirements of practical application.
(5) The invention also provides a method for preparing H by stripping the tubular carbon nitride photocatalyst2O2The application of the method comprises mixing stripped tubular carbon nitride (KCN) photocatalyst with pure water, and performing photocatalytic reaction in isopropanol as sacrificial agent to produce H2O2The method has the advantages of simple process, convenient operation, low cost, high production efficiency and the like, and has good application prospect. In the present invention, the stripped tubular carbon nitride photocatalyst produces H2O2The efficiency is up to 6650 mu M.h-1·g-1Production of H compared with conventional carbon nitride2O2The efficiency is improved by 2 times, and H is realized2O2The high-efficiency production can meet the actual production requirement.
Drawings
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention.
FIG. 1 is a scanning electron microscope image of a stripped tubular carbon nitride photocatalyst (KCN-2) prepared in example 1 of the present invention, an unmodified monomeric carbon nitride photocatalyst (CN) prepared in comparative example 1, and an un-stripped tubular carbon nitride photocatalyst (TCN) prepared in comparative example 2, wherein (a) is CN, (b) is TCN, and (c) is KCN.
FIG. 2 is a transmission electron microscope image of a stripped tubular carbon nitride photocatalyst (KCN-2) prepared in example 1 of the present invention, an unmodified monomeric carbon nitride photocatalyst (CN) prepared in comparative example 1, and an un-stripped tubular carbon nitride photocatalyst (TCN) prepared in comparative example 2, wherein (a) is CN, (b) is TCN, and (c) is KCN.
FIG. 3 is an X-ray diffraction pattern of the exfoliated tubular carbon nitride photocatalyst (KCN-1, KCN-2, KCN-3) prepared in example 1 of the present invention, the unmodified monomeric carbon nitride photocatalyst (CN) prepared in comparative example 1, and the unexfoliated tubular carbon nitride photocatalyst (TCN) prepared in comparative example 2.
Fig. 4 is a nitrogen adsorption-desorption graph of the stripped tubular carbon nitride photocatalyst (KCN-2) prepared in example 1 of the present invention, the unmodified monomeric carbon nitride photocatalyst (CN) prepared in comparative example 1, and the unstripped tubular carbon nitride photocatalyst (TCN) prepared in comparative example 2.
FIG. 5 is a graph showing the distribution of pore diameters of a stripped tubular carbon nitride photocatalyst (KCN-2) prepared in example 1 of the present invention, an unmodified monomeric carbon nitride photocatalyst (CN) prepared in comparative example 1, and an unstripped tubular carbon nitride photocatalyst (TCN) prepared in comparative example 2.
FIG. 6 is a graph comparing UV-visible diffuse reflectance spectra of the exfoliated tubular carbon nitride photocatalyst (KCN-1, KCN-2, KCN-3) prepared in example 1 of the present invention and the unmodified monomeric carbon nitride photocatalyst (CN) prepared in comparative example 1 and the unstripped tubular carbon nitride photocatalyst (TCN) prepared in comparative example 2.
FIG. 7 is a graph comparing photoluminescence spectra of a stripped tubular carbon nitride photocatalyst (KCN-2) prepared in example 1 of the present invention, an unmodified monomeric carbon nitride photocatalyst (CN) prepared in comparative example 1, and an un-stripped tubular carbon nitride photocatalyst (TCN) prepared in comparative example 2.
FIG. 8 is a graph showing the effect of stripping tubular carbon nitride photocatalysts (KCN-1, KCN-2 and KCN-3), unmodified monomeric carbon nitride photocatalyst (CN) and un-stripped tubular carbon nitride photocatalyst (TCN) on the degradation of tetracycline hydrochloride in water in example 2 of the present invention.
FIG. 9 is a graph showing the degradation effect of the stripped tubular carbon nitride photocatalyst (KCN-2) on tetracycline hydrochloride in water bodies of different pH values in example 3 of the present invention.
FIG. 10 is a graph showing the effect of stripping the tubular carbon nitride photocatalyst (KCN-2) on the repeated degradation of tetracycline hydrochloride in water in example 4 of the present invention.
FIG. 11 is a graph showing the effect of the tubular carbon nitride photocatalyst stripped in example 5 on tetracycline hydrochloride (TCH) treatment under different conditions of the radical scavenger.
FIG. 12 is a diagram illustrating the mechanism of degrading tetracycline hydrochloride by stripping the tubular carbon nitride photocatalyst according to the present invention.
FIG. 13 shows the H production of stripped tubular carbon nitride photocatalysts (KCN-1, KCN-2 and KCN-3), unmodified monomeric carbon nitride photocatalyst (CN) and un-stripped tubular carbon nitride photocatalyst (TCN) in example 6 of the present invention2O2And (5) effect diagrams.
FIG. 14 shows the production of H by the stripped tubular carbon nitride photocatalyst (KCN-2) under different conditions of radical scavenger in example 7 of the present invention2O2The effect diagram of (1).
FIG. 15 shows the production of H by stripping tubular carbon nitride photocatalyst according to the present invention2O2Schematic diagram of (1).
Detailed Description
The invention is further described below with reference to the drawings and specific preferred embodiments of the description, without thereby limiting the scope of protection of the invention.
The starting materials and equipment used in the following examples are commercially available. In the examples of the present invention, unless otherwise specified, the adopted process is a conventional process, the adopted equipment is conventional equipment, and the obtained data are average values of three or more repeated experiments.
Examples
A preparation method of a stripped tubular carbon nitride photocatalyst comprises the following steps: mixing a nitrogen-containing raw material with a solvent (the solvent is preferably water, but not limited to the solvent), and stirring for 0.5-1.5 h at the temperature of 60-90 ℃ and the rotating speed of 300-600 rpm to dissolve the nitrogen-containing raw material into the solution to obtain a nitrogen-containing raw material solution; mixing the nitrogen-containing raw material solution with potassium halide, and stirring for 0.5-1.0 h at the temperature of 60-90 ℃ and the rotating speed of 300-600 rpm to dissolve the potassium halide into the nitrogen-containing raw material solution to obtain a mixed solution; placing the mixed solution at a temperature of more than or equal to 150 ℃ for hydrothermal reaction for 8-12 h, washing the product solution, filtering at a temperature of 20-50 ℃, and drying at a temperature of 60-85 ℃ for 6-12 h to obtain a precursor; and under the nitrogen atmosphere, heating the precursor to 450-650 ℃ according to the heating rate of 2-5 ℃/min, and calcining for 2-6 h to obtain the stripped tubular carbon nitride photocatalyst. In a further improvement, the mass ratio of the nitrogen-containing raw material to the potassium halide is 1.0-5.5: 1. The nitrogen-containing raw material is at least one of melamine, dicyandiamide, cyanuric acid and urea; the potassium halide is at least one of potassium chloride, potassium bromide and potassium iodide.
The application of the stripped tubular carbon nitride photocatalyst in degrading organic pollutants comprises the following steps: mixing the stripped tubular carbon nitride photocatalyst with the organic pollutant water body, stirring at the rotating speed of 300-600 rpm for 30-60 min, and carrying out photocatalytic reaction at the temperature of 25-35 ℃ and the rotating speed of 300-600 rpm for 30-150 min to finish the degradation of the organic pollutant in the water body. In further improvement, the ratio of the stripped tubular carbon nitride photocatalyst to the organic pollutant water body is 0.3-1 g: 1L; the organic pollutants in the organic pollutant water body are antibiotics; the antibiotic is tetracycline hydrochloride; the initial concentration of the organic pollutants in the organic pollutant water body is less than or equal to 20 mg/L.
Preparation of H by stripping tubular carbon nitride photocatalyst2O2The application of the stripped tubular carbon nitride photocatalyst in preparing H2O2The method comprises the following steps: mixing the stripped tubular carbon nitride photocatalyst with water, adding a sacrificial agent, introducing oxygen for 30-60 min, stirring at the rotating speed of 300-600 rpm for 30-60 min, carrying out photocatalytic reaction at the temperature of 25-35 ℃ and the rotating speed of 300-600 rpm for 30-150 min, and finishing the reaction on H2O2And (4) preparing. Further improvementsThe ratio of the stripped tubular carbon nitride photocatalyst to water is 0.3-1 g: 1L; the volume ratio of the sacrificial agent to the water is 0.1-0.25: 1; the sacrificial agent is isopropanol and/or ethanol.
Example 1
A method for preparing a stripped tubular carbon nitride photocatalyst is prepared by taking melamine and potassium bromide as raw materials through a hydrothermal process and calcination, and comprises the following steps:
s1, 1.26g of melamine is taken in 80mL of pure water, heated in a water bath at 80 ℃ and stirred at the rotating speed of 300rpm for 1h, so that the melamine is completely dissolved in the water to obtain a clear solution.
S2, adding 0.357g of potassium bromide into the clear solution obtained in the step S1, continuing to heat in the water bath at 80 ℃ and stirring for 30min at the rotating speed of 300rpm to obtain a clear mixed solution.
S3, transferring the mixed solution obtained in the step S2 into a 100mL autoclave, carrying out hydrothermal reaction for 10h at 180 ℃, naturally cooling, washing the obtained reaction product with pure water for 3 times, carrying out suction filtration at 40 ℃, and drying for 12h at 60 ℃ to obtain the precursor.
S4, placing the precursor obtained in the step S3 into a crucible, placing the crucible into a muffle furnace, heating to 550 ℃ at a heating rate of 5 ℃/min in a nitrogen atmosphere, calcining, keeping the temperature at 550 ℃ for 2 hours, taking out after natural cooling, and grinding to obtain the stripped tubular carbon nitride photocatalyst, which is recorded as KCN-2.
Meanwhile, in the embodiment, stripped tubular carbon nitride photocatalysts (KCN-1 and KCN-3) are also prepared, and the mass ratio of corresponding melamine to potassium bromide is 6.6: 1 and 2.1: 1 respectively.
Comparative example 1
Unmodified monomer carbon nitride (g-C)3N4) The preparation method of the photocatalyst comprises the following steps: putting 5g of melamine into a crucible, putting the crucible into a muffle furnace, heating the melamine to 550 ℃ at the heating rate of 2.3 ℃/min under the nitrogen atmosphere, preserving the heat at 550 ℃ for 240min, taking out the melamine after natural cooling, and grinding the melamine to obtain a yellow powder sample, namely an unmodified monomer carbon nitridePhotocatalyst, noted CN.
Comparative example 2
A preparation method of an unstripped tubular carbon nitride photocatalyst comprises the following steps
S1, 1.26g of melamine is taken in 80mL of pure water, heated in a water bath at 80 ℃ and stirred at 500rpm for 1h to completely dissolve the melamine in the water, so that a clear solution is obtained.
S2, transferring the clear solution obtained in the step S1 into a 100mL high-pressure kettle, carrying out hydrothermal reaction for 10h at 180 ℃, naturally cooling, washing the obtained reaction product with pure water for 3 times, carrying out suction filtration at 40 ℃, and drying for 12h at 60 ℃ to obtain the precursor.
S3, placing the precursor obtained in the step S2 into a crucible, placing the crucible into a muffle furnace, heating to 550 ℃ at a heating rate of 5 ℃/min under a nitrogen atmosphere, calcining, keeping the temperature at 550 ℃ for 2h, taking out after natural cooling, and grinding to obtain an unstripped tubular carbon nitride photocatalyst, which is recorded as TCN.
Performance testing
FIG. 1 is a scanning electron microscope image of a stripped tubular carbon nitride photocatalyst (KCN-2) prepared in example 1 of the present invention, an unmodified monomeric carbon nitride photocatalyst (CN) prepared in comparative example 1, and an un-stripped tubular carbon nitride photocatalyst (TCN) prepared in comparative example 2, wherein (a) is CN, (b) is TCN, and (c) is KCN. FIG. 2 is a transmission electron microscope image of a stripped tubular carbon nitride photocatalyst (KCN-2) prepared in example 1 of the present invention, an unmodified monomeric carbon nitride photocatalyst (CN) prepared in comparative example 1, and an un-stripped tubular carbon nitride photocatalyst (TCN) prepared in comparative example 2, wherein (a) is CN, (b) is TCN, and (c) is KCN. As can be seen from fig. 1 and 2, the unmodified monomeric carbon nitride photocatalyst (CN) prepared in comparative example 1 has a bulk structure, a small specific surface area and no nano-pores on the surface; the unstripped tubular carbon nitride photocatalyst (TCN) prepared in comparative example 2 had a distinct hollow tubular structure; the stripped tubular carbon nitride photocatalyst (KCN) prepared by the invention not only has an obvious hollow tubular structure, but also has an obvious stripping phenomenon on the tube wall.
FIG. 3 is an X-ray diffraction pattern of the exfoliated tubular carbon nitride photocatalyst (KCN-1, KCN-2, KCN-3) prepared in example 1 of the present invention, the unmodified monomeric carbon nitride photocatalyst (CN) prepared in comparative example 1, and the unexfoliated tubular carbon nitride photocatalyst (TCN) prepared in comparative example 2. As can be seen from FIG. 3, two distinct XRD diffraction peaks, which are typical of the (100) and (002) crystal planes of graphite-phase carbon nitride, appear at 12.9 DEG and 27.5 DEG, confirming that the products produced are both g-C3N4. Compared with the unmodified monomer carbon nitride photocatalyst (CN), the un-stripped tubular carbon nitride photocatalyst (TCN) and the stripped tubular carbon nitride photocatalysts (KCN-1, KCN-2 and KCN-3) with different proportions, the diffraction peak intensity is weakened, the crystallization is weakened, the thickness is thinned, and the tubular structure is successfully formed.
Fig. 4 is a nitrogen adsorption-desorption graph of the stripped tubular carbon nitride photocatalyst (KCN-2) prepared in example 1 of the present invention, the unmodified monomeric carbon nitride photocatalyst (CN) prepared in comparative example 1, and the unstripped tubular carbon nitride photocatalyst (TCN) prepared in comparative example 2. FIG. 5 is a graph showing the distribution of pore diameters of a stripped tubular carbon nitride photocatalyst (KCN-2) prepared in example 1 of the present invention, an unmodified monomeric carbon nitride photocatalyst (CN) prepared in comparative example 1, and an unstripped tubular carbon nitride photocatalyst (TCN) prepared in comparative example 2. From fig. 4 it can be found that: the specific surface areas of the stripped tubular carbon nitride photocatalyst (KCN-2) and the un-stripped tubular carbon nitride photocatalyst (TCN) are obviously larger than that of the monomer Carbon Nitride (CN) photocatalyst, and the stripped tubular carbon nitride photocatalyst (KCN-2) has the largest specific surface area. As can be seen from fig. 5, the pore diameter of the synthesized catalyst is mainly mesoporous, and the exfoliated tubular carbon nitride photocatalyst (KCN-2) has the largest pore volume. As can be seen from fig. 4 and 5, the stripped tubular carbon nitride photocatalyst of the present invention has the advantages of large surface area, large pore volume, large pore diameter, many active sites, etc.
FIG. 6 is a graph comparing UV-visible diffuse reflectance spectra of the exfoliated tubular carbon nitride photocatalyst (KCN-1, KCN-2, KCN-3) prepared in example 1 of the present invention and the unmodified monomeric carbon nitride photocatalyst (CN) prepared in comparative example 1 and the unstripped tubular carbon nitride photocatalyst (TCN) prepared in comparative example 2. As can be seen from FIG. 6, the absorption wavelength of the unmodified monomeric carbon nitride photocatalyst (CN) is about 455nm, and the absorption wavelength of the non-stripped tubular carbon nitride photocatalyst (TCN) is about 460nm, while the absorption wavelength of the stripped tubular carbon nitride photocatalyst (KCN-1, KCN-2, KCN-3) of the invention is widened to be more than 475nm, so that the light absorption range is increased, and the visible light absorption capacity of the stripped tubular carbon nitride photocatalyst (KCN-1, KCN-2, KCN-3) is higher than that of the monomeric carbon nitride photocatalyst (CN), so that the light utilization rate is improved.
FIG. 7 is a graph comparing photoluminescence spectra of a stripped tubular carbon nitride photocatalyst (KCN-2) prepared in example 1 of the present invention, an unmodified monomeric carbon nitride photocatalyst (CN) prepared in comparative example 1, and an un-stripped tubular carbon nitride photocatalyst (TCN) prepared in comparative example 2. As can be seen from fig. 7, the stripped tubular carbon nitride photocatalyst (KCN-2) prepared in the present invention has the lowest Photoluminescence (PL) intensity, which indicates that the stripped tubular carbon nitride photocatalyst has the lowest recombination efficiency of photo-generated electron-hole pairs and improved photocatalytic ability.
Example 2
An application of a stripped tubular carbon nitride photocatalyst in degrading organic pollutants, in particular to a method for degrading tetracycline hydrochloride in a water body by utilizing the stripped tubular carbon nitride photocatalyst (KCN-1, KCN-2 and KCN-3) prepared in example 1, which comprises the following steps:
taking the stripped tubular carbon nitride photocatalyst (KCN-1, KCN-2 and KCN-3) prepared in the example 1, the unmodified monomer carbon nitride photocatalyst (CN) prepared in the comparative example 1 and the un-stripped tubular carbon nitride photocatalyst (TCN) prepared in the comparative example 2, respectively taking 20mg, respectively adding the 20mg into 50mL tetracycline hydrochloride (TCH) solution with the concentration of 10mg/L, pH value of 4.86, uniformly mixing, carrying out dark reaction on the tetracycline hydrochloride under the conditions of room temperature and 300rpm, and reaching the adsorption-desorption balance after 30 min; placing the mixed solution after reaching the adsorption equilibrium under a xenon lamp (lambda is more than 420nm), and carrying out photocatalytic reaction for 90min under the conditions of room temperature and 300rpm to finish the treatment of tetracycline hydrochloride (TCH).
FIG. 8 is a graph showing the effect of stripping tubular carbon nitride photocatalysts (KCN-1, KCN-2 and KCN-3), unmodified monomeric carbon nitride photocatalyst (CN) and un-stripped tubular carbon nitride photocatalyst (TCN) on the degradation of tetracycline hydrochloride in water in example 2 of the present invention. In FIG. 8, (a) - (b) are a degradation effect graph and a mineralization effect graph in sequence. As can be seen from FIG. 8(a), the effect of the stripped tubular carbon nitride photocatalyst (KCN-1, KCN-2, KCN-3) prepared by the invention on tetracycline hydrochloride (TCH) treatment is better than that of the unmodified monomer carbon nitride photocatalyst (CN) and the unreleased tubular carbon nitride photocatalyst (TCN), wherein the removal rates of the KCN-1, KCN-2, KCN-3, CN and TCN on tetracycline hydrochloride are respectively 79.5%, 83%, 77.7%, 51% and 73%. Compared with KCN-1 and KCN-3, KCN-2 has an optimal stripped tubular structure, so that the effect of photocatalytic degradation of tetracycline hydrochloride (TCH) is higher than that of KCN-1 and KCN-3. Compared with CN, KCN-2 has larger specific surface area, lower light absorption capacity and lower photogenerated charge recombination efficiency, thereby showing higher efficiency of degrading tetracycline hydrochloride (TCH) by photocatalysis. Compared with TCN, KCN-2 has larger specific surface area and lower photogenerated charge recombination efficiency, thereby showing higher efficiency of photocatalytic degradation of tetracycline hydrochloride (TCH). As can be seen from FIG. 8(b), the mineralization effect of the stripped tubular carbon nitride photocatalyst (KCN-2) prepared by the invention on tetracycline hydrochloride (TCH) is better than that of an unmodified monomer carbon nitride photocatalyst (CN) and an un-stripped tubular carbon nitride photocatalyst (TCN), wherein the mineralization rates of the KCN-2, CN and TCN on tetracycline hydrochloride are respectively 80.6%, 44.4% and 67.8%, and the KCN-2 has stronger visible light catalytic capability, so that the tetracycline hydrochloride (TCH) mineralization capability is better than that of the CN and the TCN.
Example 3
An application of a stripped tubular carbon nitride photocatalyst in degrading organic pollutants, in particular to a method for degrading tetracycline hydrochloride in water bodies with different pH values by using the stripped tubular carbon nitride photocatalyst (KCN-2) prepared in example 1, which comprises the following steps:
taking 5 parts of the stripped tubular carbon nitride photocatalyst (KCN-2) prepared in the example 1, respectively taking 20mg, respectively adding the obtained materials into tetracycline hydrochloride (TCH) solutions with initial pH values of 3, 5, 7, 9 and 11 (the volumes of the solutions are all 50mL, and the concentrations are all 10mg/L), uniformly mixing, carrying out dark reaction on the tetracycline hydrochloride under the conditions of room temperature and 300rpm, and reaching adsorption-desorption equilibrium after 30 min; placing the mixed solution after reaching the adsorption equilibrium under a xenon lamp (lambda is more than 420nm), and carrying out photocatalytic reaction for 90min under the conditions of room temperature and 300rpm to finish the treatment of tetracycline hydrochloride (TCH).
FIG. 9 is a graph showing the degradation effect of the stripped tubular carbon nitride photocatalyst (KCN-2) on tetracycline hydrochloride in water bodies of different pH values in example 3 of the present invention. Fig. 9 shows that the treatment effect of the prepared stripped tubular carbon nitride photocatalyst (KCN-2) on tetracycline hydrochloride (TCH) is basically kept stable under different pH conditions, which indicates that the prepared stripped tubular carbon nitride photocatalyst has high environmental stability and a wide application range.
Example 4
An application of a stripped tubular carbon nitride photocatalyst in degrading organic pollutants, in particular to a method for repeatedly degrading tetracycline hydrochloride in a water body by utilizing the stripped tubular carbon nitride photocatalyst (KCN-2) prepared in example 1, which comprises the following steps:
(1) adding 20mg of the stripped tubular carbon nitride photocatalyst (KCN-2) prepared in the example 1 into 50mL of tetracycline hydrochloride (TCH) solution with the concentration of 10mg/L, pH value of 4.86, uniformly mixing, carrying out dark reaction on the tetracycline hydrochloride under the conditions of room temperature and 300rpm, and reaching adsorption-desorption equilibrium after 30 min; placing the mixed solution after reaching the adsorption equilibrium under a xenon lamp (lambda is more than 420nm), and carrying out photocatalytic reaction for 90min under the conditions of room temperature and 300rpm to finish the treatment of tetracycline hydrochloride (TCH).
(2) And (2) carrying out solid-liquid separation on the product solution obtained in the step (1), carrying out suction filtration and washing on the obtained solid material for three times by using distilled water, and drying at 60 ℃ for 12h to obtain the regenerated stripped tubular carbon nitride photocatalyst.
(3) And (3) repeating the steps (1) and (2), and repeatedly degrading the tetracycline hydrochloride in the water body by using the stripped tubular carbon nitride photocatalyst.
FIG. 10 is a graph showing the effect of stripping the tubular carbon nitride photocatalyst (KCN-2) on the repeated degradation of tetracycline hydrochloride in water in example 4 of the present invention. As shown in fig. 10, the stripped tubular carbon nitride photocatalyst (KCN-2) still maintains good tetracycline hydrochloride (TCH) treatment capacity after 4 rounds of recycling, which indicates that the prepared stripped tubular carbon nitride photocatalyst has high stability.
Example 5
Considering the application of the stripped tubular carbon nitride photocatalyst in the generation of free radicals in the process of degrading tetracycline hydrochloride (TCH) solution, the stripped tubular carbon nitride (KCN-2) photocatalyst prepared in example 1 is added with tetracycline hydrochloride (TCH) solution containing different free radical trapping agents, and the method comprises the following steps:
(1) 4 parts of the stripped tubular carbon nitride (KCN-2) photocatalyst prepared in example 1, 20mg of the stripped tubular carbon nitride (KCN-2) photocatalyst, are respectively added into 50mL of tetracycline hydrochloride (TCH) solution with the concentration of 10mg/L, pH value of 4.86, the solution is uniformly mixed, the tetracycline hydrochloride is subjected to dark reaction under the conditions of room temperature and 300rpm, and the adsorption equilibrium is reached after 30 min.
(2) Adding 1mmol of disodium ethylene diamine tetraacetate (EDTA-2 Na) into the mixture after adsorption equilibrium obtained in step (1) for capture+) 1mmol of tetramethylpiperidinoxide (TEMPOL, for trapping. O)2 -) 1mmol of isopropanol (IPA for capturing. OH), one part without any capture agent.
(3) And (3) placing each mixed solution obtained in the step (2) under a xenon lamp (lambda is more than 420nm), and carrying out photocatalytic reaction for 90min at room temperature and 300rpm to finish the treatment of tetracycline hydrochloride (TCH).
FIG. 11 is a graph showing the effect of the tubular carbon nitride photocatalyst stripped in example 5 on tetracycline hydrochloride (TCH) treatment under different conditions of the radical scavenger. In fig. 11, (a) - (d) are sequentially graphs of the treatment effect of the stripped tubular carbon nitride photocatalyst on tetracycline hydrochloride (TCH) under different conditions of the radical scavenger; a percentage contribution rate graph of different free radical trapping agents to the degradation of tetracycline hydrochloride (TCH) by the stripped tubular carbon nitride photocatalyst; superoxide radical (. O) at different durations2 -) Electron spin resonance signal maps of (a); electron spin resonance signal profiles of hydroxyl radical (. OH) at different durations. As can be seen from FIG. 11(a), the release produced by the present inventionTubular carbon nitride photocatalyst in tetracycline hydrochloride (TCH) treatment process, h+Is the main active substance, O2 -Is next to h+The important active substance, OH, has minimal effect on the processing of tetracycline hydrochloride (TCH). As can be seen from FIG. 11(b), the stripped tubular carbon nitride photocatalyst prepared by the present invention is used in the treatment of tetracycline hydrochloride (TCH)+Has the largest contribution rate,. O2 -Is next to h+The contribution of. OH is the smallest. As can be seen from FIGS. 11(c) and 11(d), the ESR characterization results of the exfoliated tubular carbon nitride photocatalyst prepared according to the present invention also confirmed O2 -And OH, and the concentration of the active ingredient increases with the VSL irradiation time.
FIG. 12 is a diagram illustrating the mechanism of degrading tetracycline hydrochloride by stripping the tubular carbon nitride photocatalyst according to the present invention. As can be seen from FIG. 12, the valence band of the exfoliated tubular carbon nitride photocatalyst excited photo-generated carriers under light irradiation, and photo-generated electrons transferred to the catalyst conduction band and reacted with oxygen to form O2 -，·O2 -Mineralization of tetracycline hydrochloride (TCH) to CO2And H2And O. At the same time, the cavity remaining in the valence band also mineralizes tetracycline hydrochloride (TCH) to CO2And H2And O. The reaction equation is as follows:
h++TCH→CO2+H2O (3)
example 6
An application of a stripped tubular carbon nitride photocatalyst in green energy, specifically an H photocatalytic production method by using the stripped tubular carbon nitride photocatalysts (KCN-1, KCN-2 and KCN-3) prepared in example 12O2The method comprises the following steps:
respectively taking 20mg of the stripped tubular carbon nitride photocatalyst (KCN-1, KCN-2 and KCN-3) prepared in the example 1, the unmodified monomer carbon nitride photocatalyst (CN) prepared in the comparative example 1 and the unreleased tubular carbon nitride photocatalyst (TCN) prepared in the comparative example 2, respectively adding into 40mL of pure water, respectively adding 10mL of isopropanol serving as a sacrificial agent, uniformly mixing, pumping oxygen in the dark under the conditions of room temperature and 300rpm, and reaching oxygen saturation after 30 min; placing the mixed solution saturated with oxygen in xenon lamp (lambda)>420nm) under the conditions of room temperature and 300rpm for 60min to finish H production2O2And (4) processing.
FIG. 13 shows the H production of stripped tubular carbon nitride photocatalysts (KCN-1, KCN-2 and KCN-3), unmodified monomeric carbon nitride photocatalyst (CN) and un-stripped tubular carbon nitride photocatalyst (TCN) in example 6 of the present invention2O2And (5) effect diagrams. In FIG. 13, (a) - (d) are sequential for H production2O2Effect diagram H2O2Decomposition efficiency map of (1), H2O2Generating a rate constant (Kf) and decomposition rate constant (Kd) map and producing H2O2The cycle effect diagram of (1). As can be seen from FIG. 13(a), the stripped tubular carbon nitride photocatalyst (KCN-1, KCN-2, KCN-3) prepared by the present invention produces H2O2The effect is superior to that of unmodified monomer carbon nitride photocatalyst (CN) and un-stripped tubular carbon nitride photocatalyst (TCN), wherein the products of KCN-1, KCN-2, KCN-3, CN and TCN are H2O2The efficiency was 93. mu.M in order (i.e.H production within 1 hour per gram of catalyst)2O2The amount is 4650. mu.M.h-1·g-1)、133μM(6650μM·h-1·g-1)、81μM(4050μM·h-1·g-1)、67μM(3350μM·h-1·g-1)、84μM(4200μM·h-1·g-1) The reason may be that KCN-2 has an optimum exfoliated tubular structure and thus produces H photocatalytically2O2The effect of (B) is higher than that of KCN-1 and KCN-3; KCN-2 has strong light absorption capacity and low photogenerated charge recombination efficiency, so that the KCN-2 generates a large amount of photogenerated electrons and holes under visible light radiation and generates a large amount of O2 -To promote H production2O2The efficiency of (c); KCN-2 has large surface area and can adsorb a large amount of oxygen molecules in the oxygen pumping process to produce H2O2Provide more reaction substrates, and thus KCN-2 shows higher photocatalytic H production2O2Efficiency. As can be seen from FIG. 13(b), the exfoliated tubular carbon nitride photocatalyst (KCN-2) prepared by the present invention is directed to H2O2Has a decomposition capability lower than that of an unmodified monomeric carbon nitride photocatalyst (CN), an unstripped tubular carbon nitride photocatalyst (TCN), wherein KCN-2, CN and H of TCN2O2The decomposition efficiency was 0.52%, 0.9%, 1.3% in this order. FIG. 13(c) also shows that the stripped tubular carbon nitride photocatalyst (KCN-2) prepared by the present invention has the highest H yield2O2Ability of (D) and minimum decomposition H2O2The capability shows that the stripped tubular carbon nitride photocatalyst prepared by the invention is good for producing H2O2The photocatalyst of (1). FIG. 13(d) shows that the stripped tubular carbon nitride photocatalyst (KCN-2) prepared by the present invention still maintains good H yield after 4 rounds of recycling2O2The capability of the invention shows that the stripped tubular carbon nitride photocatalyst prepared by the invention has high stability.
Example 7
Investigating the production of hydrogen peroxide (H) by peeling off a tubular carbon nitride photocatalyst2O2) The application of the generation condition of free radicals in the process is to utilize the stripped tubular carbon nitride photocatalyst (KCN-2) prepared in the example 1 to carry out photocatalytic H generation in pure water containing different free radical trapping agents2O2The method comprises the following steps:
(1) 3 parts of the stripped tubular carbon nitride (KCN-2) photocatalyst prepared in example 1, 20mg of each part, are added into 40mL of pure water respectively, 10mL of isopropanol is used as a sacrificial agent, the mixture is uniformly mixed, oxygen is pumped in the dark under the conditions of room temperature and 300rpm, and the oxygen saturation is achieved after 30 min.
(2) Adding 1mmol of silver nitrate (AgNO) into 3 parts of the mixed solution which is obtained in the step (1) and is saturated by oxygen respectively3For capturing e-) 1mmol of tetramethylpiperidinyloxyCompounds (TEMPOL, for trapping. O)2 -) One part of the mixture is not added with any capture agent.
(3) Placing each mixed solution obtained in the step (2) in a xenon lamp (lambda)>420nm) under the conditions of room temperature and 300rpm for 60min to finish H production2O2。
FIG. 14 shows the production of H by the stripped tubular carbon nitride photocatalyst (KCN-2) under different conditions of radical scavenger in example 7 of the present invention2O2The effect diagram of (1). In FIG. 14, (a) - (b) are sequential H production under different radical scavenger conditions2O2Effect diagram of (2) and different radical pair production H2O2Is shown in the percentage contribution ratio. As can be seen from FIG. 14(a), the stripped tubular carbon nitride photocatalyst (KCN-2) prepared by the present invention is in the production of H2O2In the process, e-is the main active substance, O2Is an important active next to e-. As can be seen from FIG. 14(b), the stripped tubular carbon nitride photocatalyst (KCN-2) prepared by the present invention is in H production2O2Maximum contribution of e-in the process,. O2The contribution of-is second only to the contribution of e-.
FIG. 15 shows the production of H by stripping tubular carbon nitride photocatalyst according to the present invention2O2Schematic diagram of (1). As can be seen from fig. 15, under the light irradiation condition, the valence band of the stripped tubular carbon nitride photocatalyst excites the photo-generated carriers, the photo-generated electrons are transferred to the catalyst conduction band, and H is generated through the one-step two-electron path and the two-part one-electron path2O2At the same time, the hole on the valence band also sacrifices isopropanol to react and provide extra proton to supplement H production2O2The desired proton. The reaction equation is as follows:
O2+2e-+2H+→H2O2 (8)
comprehensively, compared with the conventional carbon nitride, the stripped tubular carbon nitride photocatalyst prepared by the preparation method has the advantages of large specific surface area, more active sites, low recombination rate of photo-generated electron-hole pairs, strong visible light absorption capacity, high photocatalytic activity and the like, is a novel visible light photocatalyst with novel morphology structure and excellent photocatalytic performance, can be widely used for degrading organic pollutants and producing H2O2And the practical application value is high. Meanwhile, the preparation method of the stripped tubular carbon nitride photocatalyst does not need an additional template, does not need a dangerous reagent, does not adopt raw materials harmful to the environment, has the advantages of simple process, easy operation, low cost, high safety, high preparation efficiency and the like, is suitable for large-scale preparation, and is beneficial to industrial application.
The above examples are merely preferred embodiments of the present invention, and the scope of the present invention is not limited to the above examples. All technical schemes belonging to the idea of the invention belong to the protection scope of the invention. It should be noted that modifications and embellishments within the scope of the invention may be made by those skilled in the art without departing from the principle of the invention, and such modifications and embellishments should also be considered as within the scope of the invention.
Claims (10)
1. A preparation method of a stripped tubular carbon nitride photocatalyst is characterized by comprising the following steps:
s1, mixing the nitrogen-containing raw material and potassium halide to prepare a mixed solution;
s2, carrying out hydrothermal reaction on the mixed solution in the step S1 to obtain a precursor;
and S3, calcining the precursor in the step S2 to obtain the stripped tubular carbon nitride photocatalyst.
2. The method according to claim 1, wherein in step S1, the mass ratio of the nitrogen-containing raw material to the potassium halide is 1.0-5.5: 1.
3. The method according to claim 2, wherein in step S1, the nitrogen-containing raw material is at least one of melamine, dicyandiamide, cyanuric acid, and urea; the potassium halide is at least one of potassium chloride, potassium bromide and potassium iodide.
4. The method according to any one of claims 1 to 3, wherein in step S1, the step of preparing the mixed solution comprises:
s1-1, mixing the nitrogenous raw material with a solvent, and stirring to dissolve the nitrogenous raw material into the solution to obtain a nitrogenous raw material solution;
and S1-2, mixing the nitrogen-containing raw material solution with potassium halide, and stirring to dissolve the potassium halide in the nitrogen-containing raw material solution to obtain a mixed solution.
5. The method according to claim 4, wherein in step S1-1, the solvent is water; the stirring is carried out at the temperature of 60-90 ℃; the rotating speed of the stirring is 300-600 rpm; the stirring time is 0.5 h-1.5 h;
in step S1-2, the stirring is carried out at a temperature of 60 ℃ to 90 ℃; the rotating speed of the stirring is 300-600 rpm; the stirring time is 0.5 h-1.0 h.
6. The preparation method according to any one of claims 1 to 3, wherein in step S2, the temperature of the hydrothermal reaction is 150 ℃ or higher; the time of the hydrothermal reaction is 8-12 h; the hydrothermal reaction further comprises the following treatment steps: washing, filtering and drying the product solution; the filtration is carried out at a temperature of 20 ℃ to 50 ℃: the drying is carried out at the temperature of 60-85 ℃; the drying time is 6-12 h;
in step S3, the calcination is performed under a nitrogen atmosphere; the heating rate in the calcining process is 2-5 ℃/min; the calcining temperature is 450-650 ℃; the calcining time is 2-6 h.
7. The stripped tubular carbon nitride photocatalyst is characterized by being prepared by the preparation method of any one of claims 1-6.
8. Use of the stripped tubular carbon nitride photocatalyst according to claim 7 in degrading organic pollutants or preparing H2O2The use of (1).
9. The use of claim 8, wherein the use of a stripped tubular carbon nitride photocatalyst for degrading organic contaminants in a body of water comprises the steps of: mixing the stripped tubular carbon nitride photocatalyst with the organic pollutant water body, stirring, and carrying out photocatalytic reaction to finish the degradation of the organic pollutant in the water body; the proportion of the stripped tubular carbon nitride photocatalyst to the organic pollutant water body is 0.3-1 g: 1L; the organic pollutants in the organic pollutant water body are antibiotics; the antibiotic is tetracycline hydrochloride; the initial concentration of the organic pollutants in the organic pollutant water body is less than or equal to 20 mg/L; the rotating speed of the stirring is 300-600 rpm; the stirring time is 30-60 min; the photocatalytic reaction is carried out under the irradiation of a xenon lamp; the optical power of the xenon lamp is 45-50W; the photocatalytic reaction is carried out at the rotating speed of 300-600 rpm; the temperature of the photocatalytic reaction is 25-35 ℃; the time of the photocatalytic reaction is 30-150 min.
10. Use according to claim 8, wherein a lift-off tubular carbon nitride photocatalyst is used for the preparation of H2O2The method comprises the following steps: mixing the stripped tubular carbon nitride photocatalyst with water, adding sacrificial agent, and introducingOxygen, stirring, and carrying out photocatalytic reaction to obtain H2O2Preparing; the ratio of the stripped tubular carbon nitride photocatalyst to water is 0.3-1 g: 1L; the volume ratio of the sacrificial agent to the water is 0.1-0.25: 1; the sacrificial agent is isopropanol and/or ethanol; the introducing time of the oxygen is 30-60 min; the rotating speed of the stirring is 300-600 rpm; the stirring time is 30-60 min; the photocatalytic reaction is carried out under the irradiation of a xenon lamp; the optical power of the xenon lamp is 45-50W; the photocatalytic reaction is carried out at the rotating speed of 300-600 rpm; the temperature of the photocatalytic reaction is 25-35 ℃; the time of the photocatalytic reaction is 30-150 min.
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