CN114950517A - Photocatalyst for efficiently degrading organic pollutants as well as preparation method and application thereof - Google Patents
Photocatalyst for efficiently degrading organic pollutants as well as preparation method and application thereof Download PDFInfo
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- CN114950517A CN114950517A CN202110213535.7A CN202110213535A CN114950517A CN 114950517 A CN114950517 A CN 114950517A CN 202110213535 A CN202110213535 A CN 202110213535A CN 114950517 A CN114950517 A CN 114950517A
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- 239000002957 persistent organic pollutant Substances 0.000 title claims abstract description 39
- 230000000593 degrading effect Effects 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- CBACFHTXHGHTMH-UHFFFAOYSA-N 2-piperidin-1-ylethyl 2-phenyl-2-piperidin-1-ylacetate;dihydrochloride Chemical compound Cl.Cl.C1CCCCN1C(C=1C=CC=CC=1)C(=O)OCCN1CCCCC1 CBACFHTXHGHTMH-UHFFFAOYSA-N 0.000 claims abstract description 46
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- 239000002131 composite material Substances 0.000 description 3
- 239000000356 contaminant Substances 0.000 description 3
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- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 3
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- 229910052797 bismuth Inorganic materials 0.000 description 2
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- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
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- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
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- FTLHORLYDROOSU-UHFFFAOYSA-N indium(3+);trinitrate;pentahydrate Chemical compound O.O.O.O.O.[In+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FTLHORLYDROOSU-UHFFFAOYSA-N 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
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- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 description 1
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- 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
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Abstract
The invention belongs to the field of environmental catalysis, and discloses a photocatalyst for efficiently degrading organic pollutants under visible light, and a preparation method and application thereof. The preparation method comprises the steps of preparing bismuth oxyiodide through water dispersion, constructing a supramolecular network through a nitrogen-rich compound, enabling the bismuth oxyiodide to be uniformly distributed in the supramolecular network as much as possible through constant-temperature reaction, and finally molding the photocatalyst through high-temperature roasting. Compared with the method of preparing graphite-phase carbon nitride and then constructing a heterojunction material, the photocatalyst has the advantages that the graphite-phase carbon nitride has special spherule shapes and is not in a traditional blocky or two-dimensional sheet layer shape, and more ideal surface distribution can effectively inhibit the recombination of photo-generated electrons and holes, so that more photo-generated electrons can reach the surface of the catalyst and are combined with oxygen molecules to form superoxide radicals, and better photocatalytic degradation capability is achieved (compared with 38 percent improvement).
Description
Technical Field
The invention belongs to the field of environmental catalysis, and particularly relates to a photocatalyst for efficiently degrading organic pollutants under visible light, and a preparation method and application thereof.
Background
The problem of environmental pollution is a great problem commonly faced by human beings in the 21 st century, and in the process of resisting environmental pollution, a plurality of technical means are vigorous, and the environmental catalysis technology is one of important technical means. The visible light photocatalytic technology is one of the major research directions in the current catalytic field, and has advantages of general catalytic technologies, such as mild reaction conditions, and other special advantages, such as providing energy required for reaction by using visible light with lower energy in sunlight (natural light), reducing energy consumption, and saving cost. When organic matters in the environmental pollutants are treated by adopting a visible light photocatalysis technology, the catalyst is irradiated by visible light to excite photoproduction electrons with reduction capability and holes with oxidation capability, and the photoproduction electrons are generated in a reaction system through certain oxidation-reduction reaction and can oxidize or mineralize and degrade the organic pollutants into small molecules or carbon dioxide and water, so that the removal of the organic pollutants is realized, and the aim of purifying the environment is fulfilled.
Most of the organic pollutants are caused by improper treatment or difficult treatment of organic compounds in the production process, and are naturally degraded slowly after being discharged into the environment due to higher physical and chemical stability, so that a certain influence is caused on an ecological system and even the balance of the local ecological system can be damaged. These compounds are important raw materials or products for social production and become pollutants when improperly handled and enter the natural environment. The problem of degrading organic pollutants is a scientific research and social environmental problem with great practical value due to the economic and environmental aspects of the organic pollutants. In the chinese patent publication CN111437856A, a heterojunction catalyst with excellent performance is prepared by preparing a graphite-phase carbon nitride nanotube, and then growing bismuth oxyhalide thereon through a hydrothermal reaction, thereby greatly improving the degradation rate of tetracycline under visible light. However, the preparation process needs to use concentrated sulfuric acid, which increases the operation requirement of the production process and increases the production risk; in addition, solvents such as methanol and ethylene glycol are used for a plurality of times in the preparation process, which is unfavorable for controlling the production cost, so that the method is unfavorable for large-scale popularization and application. In the chinese patent publication CN111097477A, the graphite-phase carbon nitride nanosheets are obtained by twice roasting urea, the composite of the graphite-phase carbon nitride nanosheets and graphene oxide is obtained by mixing and refluxing, and the composite is finally mixed and refluxed in a mixed solution of indium nitrate pentahydrate, cetyltrimethylammonium bromide and thioacetamide, so as to obtain the ultrathin two-dimensional layered composite photocatalytic material, which has a great effect on removing tetracycline. But may result in a lack of intimate bonding between the catalyst components and poor mechanical strength due to lack of high temperature sintering.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention mainly aims to provide a preparation method of a photocatalyst for efficiently degrading organic pollutants under visible light.
The invention also aims to provide the photocatalyst for efficiently degrading organic pollutants under visible light, which is prepared by the method.
The invention further aims to provide application of the photocatalyst for efficiently degrading organic pollutants under visible light in catalytic degradation of organic pollutants.
The purpose of the invention is realized by the following scheme:
a preparation method of a photocatalyst for efficiently degrading organic pollutants under visible light comprises the following three steps of firstly preparing a bismuth oxyiodide precursor and nitrogen-containing organic supermolecules, then fully mixing the bismuth oxyiodide precursor and the nitrogen-containing organic supermolecules, and then filtering, drying and roasting to obtain the catalyst.
The method specifically comprises the following steps:
(1) reacting pentahydrate bismuth nitrate and potassium iodide in water to prepare bismuth oxyiodide;
(2) heating the nitrogen-containing compound in water to self-assemble to prepare a supramolecular compound;
(3) mixing bismuth oxyiodide prepared in the step (1) with the supramolecular compound prepared in the step (2) for reaction to obtain a photocatalyst precursor;
(4) and putting the precursor into a ceramic crucible paved with aluminum foil, coating the aluminum foil outside the crucible to form a closed space, heating and roasting in a muffle furnace, and naturally cooling to obtain the photocatalyst.
The molar ratio of the bismuth nitrate pentahydrate to the potassium iodide in the step (1) is 1: 0.1-10; preferably 1: 1.
The reaction in the step (1) is stirred at room temperature for 30-480 min; preferably 240 min.
In the step (1), for a more complete reaction, it is preferable that the bismuth nitrate pentahydrate and the potassium iodide are dissolved in water to form an aqueous solution, and then mixed for reaction.
The nitrogen-containing compound in the step (2) is at least one of melamine, 5-aminotetrazole, azotriazole and cyanuric acid; melamine and cyanuric acid are preferred; more preferably, the molar ratio is 1:1 melamine and cyanuric acid.
The heating self-assembly in the step (2) is heating to 60-120 ℃ for reaction for 30-360 min.
In the step (2), for the purpose of more sufficient reaction, it is preferable that the nitrogen-containing compounds are dissolved in water, mixed, and then heated for self-assembly.
The mass ratio of the bismuth oxyiodide to the supramolecular compound in the step (3) is 1: 0.1-10; preferably 1: 4;
the mixing reaction in the step (3) refers to mixing reaction in an aqueous solution at the temperature of 60-120 ℃ for 30-360 min.
And (4) after the mixing reaction in the step (3) is finished, post-treatment operations such as filtering, washing, drying, grinding and the like are also included.
The heating and roasting in the step (4) refers to the reaction of raising the temperature from 1-10 ℃ to 350-650 ℃ for 30-360 min. Preferably, the temperature is raised to 500 ℃ at the heating rate of 10 ℃/min and the mixture is roasted for 2 hours at constant temperature.
The photocatalyst for efficiently degrading organic pollutants under visible light, which is prepared by the method, is composed of highly dispersible globular graphite phase carbon nitride and high-temperature resistant bismuth oxyiodide, wherein the high-temperature resistant bismuth oxyiodide is prepared by reacting bismuth oxyiodide with the supermolecular compound and then roasting at high temperature; the graphite phase carbon nitride is in a globular shape and is highly dispersed on the surface of the high-temperature resistant bismuth oxyiodide; the high temperature resistant bismuth oxyiodide is in a three-dimensional rosette shape with fewer lamellar units of bismuth oxyiodide than typical bismuth oxyiodide.
The photocatalyst for efficiently degrading organic pollutants under visible light is applied to catalytic degradation of organic pollutants.
The organic pollutant is one of tetracycline hydrochloride, methyl orange, phenol, parachlorophenol, rhodamine B, methylene blue and the like; preferably one of tetracycline hydrochloride, methyl orange and p-chlorophenol.
The mechanism of the invention is as follows:
the preparation method comprises the steps of preparing bismuth oxyiodide through water dispersion, constructing a supermolecular network through a nitrogen-rich compound, enabling the bismuth oxyiodide to be uniformly distributed in the supermolecular network as much as possible through constant-temperature reaction, and finally forming the photocatalyst through high-temperature roasting. On one hand, the dispersion medium used in the preparation process is water, and no other solvent is used, so that the technical requirements on reaction equipment can be greatly reduced, and the raw material cost and the separation cost in the production process can be saved. On the other hand, only one-time high-temperature roasting is needed in the preparation process, so that the graphite-phase carbon nitride and the bismuth oxyiodide are tightly combined while the energy consumption is saved, the interface electron conduction resistance is favorably reduced, and the photocatalytic activity is improved. Because the supermolecular compound generates ammonia gas and carbon dioxide gas in the constant-temperature roasting process, the formed graphite-phase carbon nitride is highly dispersed in the high-temperature resistant bismuth oxyiodide, and meanwhile, the morphology characteristics of the generated graphite-phase carbon nitride tend to be in a globular shape due to the space limitation of the three-dimensional rosette-shaped bismuth oxyiodide; for bismuth oxyiodide, ammonia gas and carbon dioxide gas have a gas stripping effect, so that the high-temperature-resistant bismuth oxyiodide is formed, the high-temperature-resistant bismuth oxyiodide is approximately consistent with the conventional bismuth oxyiodide in shape and is in a three-dimensional rosette shape, and compared with the typical bismuth oxyiodide, the high-temperature-resistant bismuth oxyiodide has fewer lamellar unit bismuth oxyiodide.
Compared with the prior art, the invention has the following advantages and beneficial effects:
compared with the method of preparing the graphite-phase carbon nitride and then constructing the heterojunction material (comparative example 3), the method has the advantages that the graphite-phase carbon nitride has special spherule shapes (figure 2) and is not a traditional blocky or two-dimensional sheet layer shape (figure 4), the more ideal surface distribution can effectively inhibit the recombination of photo-generated electrons and holes, more photo-generated electrons can reach the surface of the catalyst and are combined with oxygen molecules to form superoxide radicals, and the better photocatalytic degradation capability is realized (compared with the improvement of 38%).
The photocatalyst with high dispersity prepared by the invention can realize the purpose of efficiently degrading organic pollutants under the condition of visible light, and has certain reference value and practicability for removing the organic pollutants in wastewater treatment. The method has the advantages of easily available raw materials, low price, simple and convenient method, environmental protection and suitability for large-scale popularization and use.
Drawings
Fig. 1 is an SEM topography of the photocatalyst for efficient degradation of organic contaminants under visible light prepared in example 1.
Fig. 2 is a high resolution scanning electron microscope image of the photocatalyst for efficiently degrading organic contaminants under visible light prepared in example 1.
Fig. 3 is an element distribution diagram of the photocatalyst for efficiently degrading organic pollutants under visible light prepared in example 1.
FIG. 4 shows g-C for the photocatalyst prepared in comparative example 3 3 N 4 Field emission scanning electron microscope images of/BiOI.
FIG. 5 is a graph showing the comparison of the photocatalytic degradation activities of tetracycline hydrochloride in example 1 and comparative examples 1 and 2.
Fig. 6 is a graph comparing the activity of photocatalytic degradation methyl orange of example 1 and comparative examples 1, 2 and 3.
FIG. 7 is a graph comparing the activity of p-chlorophenol in photocatalytic degradation of example 1 and comparative examples 1 and 2.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the embodiments of the present invention are not limited thereto.
The reagents used in the examples are commercially available without specific reference.
Example 1: preparation method of photocatalyst for efficiently degrading organic pollutants under visible light
A preparation method of a photocatalyst for efficiently degrading organic pollutants under visible light comprises the following steps:
(1) respectively weighing 2.425g of pentahydrate bismuth nitrate and 0.830g of potassium iodide, respectively dispersing in 130 ml of water and 20 ml of water at room temperature, and uniformly stirring; dropwise adding a potassium iodide solution (1 drop/second) into a bismuth nitrate solution, and continuously stirring for 120 minutes; filtering, washing and drying to obtain the bismuth oxyiodide.
(2) 1.261g of melamine and 1.291g of cyanuric acid are respectively weighed and respectively dispersed in 100ml of hot water at 90 ℃, and stirred for 30 minutes; dropwise adding a melamine solution (1 drop/second) into the melamine solution, and continuously stirring for 30 minutes; adding 0.528g of bismuth oxyiodide obtained in the step (1), and continuously stirring for 60 minutes; and filtering, washing and drying to obtain the photocatalyst precursor.
(3) And (3) putting the precursor obtained in the step (2) into a ceramic crucible, covering the ceramic crucible with a cover, putting the ceramic crucible into a muffle furnace, heating to 500 ℃ at a heating rate of 10 ℃/min under the air condition, roasting at a constant temperature for 2h, and naturally cooling to obtain the photocatalyst capable of efficiently degrading organic pollutants under visible light.
The SEM topography of the photocatalyst for efficient degradation of organic contaminants under visible light obtained in example 1 is shown in fig. 1, and it can be seen from fig. 1 that the catalyst body exhibits a three-dimensional structure, which may be formed due to the three-dimensional self-assembly of bismuth oxyiodide, while no significant layered stacking structure is observed for the graphite-phase carbon nitride, so we have performed higher resolution topography characterization to determine the morphology of the catalyst.
The high resolution scanning electron microscope image of the photocatalyst for efficiently degrading organic pollutants under visible light obtained in example 1 is shown in fig. 2, and it can be seen from fig. 2 that graphite phase carbon nitride presents a special island-like distribution on the surface of bismuth oxyiodide, and the graphite phase carbon nitride is not stacked in a traditional lamellar manner any more, so that the transmission path of carriers can be optimized, the recombination condition of photo-generated electron-hole pairs is reduced, the lifetime of photo-generated electrons is prolonged, and the photocatalytic activity is improved.
The element distribution diagram of the photocatalyst for efficiently degrading organic pollutants under visible light obtained in example 1 is shown in fig. 3, and it can be seen from fig. 3 that the element distribution of C, N, O, I, Bi and the like can be observed in the element distribution on the surface of the catalyst, which indicates that the catalyst may contain graphite phase carbon nitride and bismuth oxyiodide, and the graphite phase carbon nitride is relatively uniformly dispersed on the surface of the bismuth oxyiodide when the photocatalyst is combined with fig. 1 and fig. 2.
Comparative example 1: preparation method of graphite phase carbon nitride
The preparation method of the graphite phase carbon nitride comprises the following steps:
(1) 1.261g of melamine and 1.291g of cyanuric acid are respectively weighed and respectively dispersed in 100ml of hot water at 90 ℃, and stirred for 30 minutes; dropwise adding the melamine solution A into the melamine solution B (1 drop/second), and stirring for 30 minutes; and filtering, washing and drying to obtain the precursor of the comparative example 1.
(2) Putting the precursor obtained in the step (1) into a ceramic crucible, covering the ceramic crucible with a cover, putting the ceramic crucible into a muffle furnace, heating the ceramic crucible to 500 ℃ at a heating rate of 10 ℃/min under the air condition, roasting the ceramic crucible at a constant temperature for 2h, and naturally cooling the ceramic crucible to obtain the graphite-phase carbon nitride of the comparative example 1;
comparative example 2: preparation method of bismuth oxyiodide
A method for preparing bismuth oxyiodide of comparative example 2, comprising the steps of:
(1) respectively weighing 2.425g of pentahydrate bismuth nitrate and 0.830g of potassium iodide, respectively dispersing in 130 ml of water and 20 ml of water at room temperature, and uniformly stirring; dropwise adding a potassium iodide solution (1 drop/second) into a bismuth nitrate solution, and continuously stirring for 120 minutes; filtering, washing and drying to obtain the bismuth oxyiodide.
(2) Respectively weighing 1.261g of bismuth oxyiodide and 1.291g of bismuth oxyiodide, respectively dispersing in 100ml of 90 ℃ hot water, and stirring for 30 minutes; dropwise adding the bismuth oxyiodide solution A into the bismuth oxyiodide solution B dropwise (1 drop/second), and stirring for 30 minutes; adding 0.528g of bismuth oxyiodide, and continuing stirring for 60 minutes; and filtering, washing and drying to obtain the precursor of the comparative example 2.
(3) Putting the precursor obtained in the step (2) into a ceramic crucible, covering the ceramic crucible with a cover, putting the ceramic crucible into a muffle furnace, heating the ceramic crucible to 500 ℃ at a heating rate of 10 ℃/min under the air condition, roasting the ceramic crucible at a constant temperature for 2h, and naturally cooling the ceramic crucible to obtain the bismuth oxyiodide of the comparative example 2;
comparative example 3: photocatalyst g-C 3 N 4 Preparation method of/BiOI
Photocatalyst of comparative example 3 g-C 3 N 4 The preparation method of the/BiOI comprises the following steps:
(1) respectively weighing 2.425g of pentahydrate bismuth nitrate and 0.830g of potassium iodide, respectively dispersing in 130 ml of water and 20 ml of water at room temperature, and uniformly stirring; dropwise adding a potassium iodide solution (1 drop/second) into a bismuth nitrate solution, and continuously stirring for 120 minutes; filtering, washing and drying to obtain the bismuth oxyiodide.
(2) 1.261g of melamine and 1.291g of cyanuric acid are respectively weighed and respectively dispersed in 100ml of hot water at 90 ℃, and stirred for 30 minutes; dropwise adding the melamine solution A into the melamine solution B (1 drop/second), and stirring for 90 minutes; filtering, washing and drying to obtain the precursor of the graphite-phase carbon nitride.
(3) Putting the precursor obtained in the step (2) into a ceramic crucible, covering the ceramic crucible with a cover, putting the ceramic crucible into a muffle furnace, heating the ceramic crucible to 500 ℃ at a heating rate of 10 ℃/min under the air condition, roasting the ceramic crucible at a constant temperature for 2h, and naturally cooling the ceramic crucible to obtain graphite-phase carbon nitride;
(4) putting all the graphite-phase carbon nitride obtained in the step (3) and 0.528g of bismuth oxyiodide obtained in the step (1) into a stainless steel reaction kettle with a perfluoroethylene lining, sealing, putting the reaction kettle into a temperature programming drying box, keeping the temperature of the reaction kettle at 140 ℃ for 12 hours, cooling, performing suction filtration to obtain a product, and adding deionized waterAnd absolute ethyl alcohol are respectively washed for three times; the washed product was placed in a vacuum oven and dried at 80 ℃ for 12h to obtain the photocatalyst g-C of comparative example 3 3 N 4 /BiOI。
Photocatalyst g-C prepared in comparative example 3 3 N 4 A field emission scanning electron micrograph of the/BiOI is shown in FIG. 4. Compared with the method of preparing the graphite-phase carbon nitride and then constructing the heterojunction material (comparative example 3), the method has the advantages that the graphite-phase carbon nitride has special spherule shapes (figure 2) and is not a traditional blocky or two-dimensional sheet layer shape (figure 4), the more ideal surface distribution can effectively inhibit the recombination of photo-generated electrons and holes, more photo-generated electrons can reach the surface of the catalyst and are combined with oxygen molecules to form superoxide radicals, and the better photocatalytic degradation capability is realized (compared with the improvement of 38%).
The photocatalyst prepared in the embodiment 1 of the invention is used for degrading tetracycline hydrochloride, and when the dosage of the catalyst is 30mg and simulated wastewater of the tetracycline hydrochloride (10mg/L, 100mL) is continuously illuminated for 60 minutes, the degradation rate of the tetracycline hydrochloride is 82.2%, and under the same conditions, the degradation rate of the tetracycline hydrochloride is 8.6% in the comparative example 1 and 64.8% in the comparative example 2. As shown in particular in fig. 5.
Under the same illumination condition, methyl orange is continuously illuminated by the photocatalyst prepared in example 1 of the invention, the degradation rate of the methyl orange is 99.4 percent when the catalyst dosage is 30mg and the simulated wastewater of the methyl orange (10mg/L, 100mL) is continuously illuminated for 30 minutes, and the degradation rate of the methyl orange is 18.8 percent in comparative example 1, 64.8 percent in comparative example 2 and g-C of the photocatalyst in comparative example 3 3 N 4 The degradation rate of the/BiOI is 72.1%. As shown in particular in fig. 6.
Under the same illumination conditions, the photocatalyst prepared in example 1 of the present invention was continuously used to illuminate chlorophenol, and the degradation rate of the chlorophenol was 27.9% in the simulated wastewater of the chlorophenol (10mg/L, 100mL) continuously illuminated for 60 minutes with 30mg of the catalyst, compared with 1.3% in comparative example 1 and 16.3% in comparative example 2. As shown in particular in fig. 7.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A preparation method of a photocatalyst for efficiently degrading organic pollutants under visible light is characterized by comprising the following steps:
(1) reacting pentahydrate bismuth nitrate and potassium iodide in water to prepare bismuth oxyiodide;
(2) heating the nitrogen-containing compound in water to self-assemble to prepare a supramolecular compound;
(3) mixing the bismuth oxyiodide prepared in the step (1) with the supramolecular compound prepared in the step (2) for reaction to obtain a photocatalyst precursor;
(4) and putting the precursor into a ceramic crucible paved with aluminum foil, coating the aluminum foil outside the crucible to form a closed space, heating and roasting in a muffle furnace, and naturally cooling to obtain the photocatalyst.
2. The method for preparing the photocatalyst for efficiently degrading organic pollutants under visible light according to claim 1, which is characterized in that:
the molar ratio of the bismuth nitrate pentahydrate to the potassium iodide in the step (1) is 1: 0.1-10;
the reaction in the step (1) is stirred at room temperature for 30-480 min.
3. The method for preparing the photocatalyst for efficiently degrading organic pollutants under visible light according to claim 1, which is characterized in that:
the nitrogen-containing compound in the step (2) is at least one of melamine, 5-aminotetrazole, azotriazole and cyanuric acid;
the heating self-assembly in the step (2) is heating to 60-120 ℃ for reaction for 30-360 min.
4. The method for preparing the photocatalyst for efficiently degrading organic pollutants under visible light according to claim 1, which is characterized in that:
the nitrogen-containing compounds in the step (2) are melamine and cyanuric acid;
the heating self-assembly in the step (2) is heating to 60-120 ℃ for reaction for 30-360 min.
5. The method for preparing the photocatalyst for efficiently degrading organic pollutants under visible light according to claim 1, wherein the method comprises the following steps:
the nitrogen-containing compound in the step (2) is prepared by mixing the following components in a molar ratio of 1:1 melamine and cyanuric acid;
the heating self-assembly in the step (2) refers to heating to 60-120 ℃ for reaction for 30-360 min.
6. The method for preparing the photocatalyst for efficiently degrading organic pollutants under visible light according to claim 1, wherein the method comprises the following steps:
the mass ratio of the bismuth oxyiodide to the supramolecular compound in the step (3) is 1: 0.1-10;
the mixing reaction in the step (3) refers to mixing reaction in an aqueous solution at the temperature of 60-120 ℃ for 30-360 min.
7. The method for preparing the photocatalyst for efficiently degrading organic pollutants under visible light according to claim 1, which is characterized in that:
the heating and roasting in the step (4) refers to the reaction of raising the temperature from 1-10 ℃ to 350-650 ℃ for 30-360 min.
8. A photocatalyst for degrading organic pollutants with high efficiency under visible light, which is prepared according to the method of any one of claims 1 to 7.
9. The use of the photocatalyst for efficiently degrading organic pollutants under visible light according to claim 8 in the catalytic degradation of organic pollutants.
10. The use of the photocatalyst for efficiently degrading organic pollutants under visible light according to claim 9 in the catalytic degradation of organic pollutants, wherein:
the organic pollutant is one of tetracycline hydrochloride, methyl orange, phenol, parachlorophenol, rhodamine B and methylene blue.
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