CN114522709B - Three-dimensional porous graphite phase carbon nitride/bismuth oxyiodide/silver nanoparticle composite photocatalyst and preparation method and application thereof - Google Patents
Three-dimensional porous graphite phase carbon nitride/bismuth oxyiodide/silver nanoparticle composite photocatalyst and preparation method and application thereof Download PDFInfo
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 57
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- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 2
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/50—Silver
-
- 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
- B01J27/06—Halogens; Compounds thereof
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- B01J35/23—
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- B01J35/39—
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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
- C02F2101/34—Organic compounds containing oxygen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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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
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Abstract
The invention discloses a three-dimensional porous graphite phase carbon nitride/bismuth oxyiodide/silver nanoparticle composite photocatalyst, and a preparation method and application thereof. The composite photocatalyst is three-dimensional porous g-C with BiOI microspheres and nano Ag supported on the surface 3 N 4 A nano-sheet. The composite photocatalyst adopts three-dimensional porous g-C 3 N 4 The nano-sheet is used as a carrier, and the BiOI microsphere and the nano Ag are uniformly loaded on the three-dimensional porous g-C through a self-assembly and photochemical reduction two-step method 3 N 4 The surface of the nano-sheet. With a single three-dimensional porous g-C 3 N 4 Compared with BiOI microspheres, the three-dimensional porous graphite phase carbon nitride/bismuth oxyiodide/silver nanoparticle composite photocatalyst has more excellent visible light catalytic degradation activity on toxic organic matters in water.
Description
Technical Field
The invention belongs to the field of environmental functional materials, and particularly relates to a three-dimensional porous graphite phase carbon nitride/bismuth oxyiodide/silver nanoparticle composite photocatalyst, and a preparation method and application thereof.
Background
With the rapid development of the medical industry and livestock breeding industry, the use amount of antibiotics in the world continues to increase, so that a large amount of antibiotics are discharged into the environment and enter water in various ways, and serious environmental pollution is caused. Tetracyclines (TCs) are one of the most widely used antibiotics in the world and are widely used in human medicine, the pharmaceutical industry, livestock and poultry farming and aquaculture industry due to their broad spectrum and low cost. The residues of TC in the water environment have increasingly serious effects and hazards to the ecological environment and human health. The photocatalysis technology adopts green and environment-friendly photocatalyst, utilizes clean sunlight to drive reaction, is a technology for removing organic pollutants by advanced oxidation, and has huge potential application value in the field of water pollution treatment.
The photocatalyst is the core of the photocatalysis technology, and the activity of the photocatalyst is influenced by not only external reaction conditions, but also a band gap structure, a crystal structure, a morphology size, a specific surface area and other factors of the photocatalyst. In recent years, graphite-phase carbon nitride (g-C 3 N 4 ) Is widely focused in the field of photocatalysis, has a narrow band gap (eg=2.70 eV), and has visible light response performance. In addition, the catalyst has the advantages of higher chemical stability, easy modification, higher photocatalytic performance and the like. g-C since 2009 3 N 4 The method has very good application potential after being applied to the photo-decomposition of water to prepare hydrogen for the first time. However, due to g-C 3 N 4 The characteristics of the polymer have the defects of small specific surface area, narrow visible light response range, low photogenerated carrier separation efficiency and the like in the photocatalysis application process, and restrict g-C 3 N 4 Application in the field of photocatalysis. Thus, how to prepare novel high-efficiency g-C 3 N 4 The base photocatalyst is a problem to be solved in that the specific surface area of the photocatalyst can be increased, the utilization of visible light can be enhanced, and the catalytic activity of the base photocatalyst can be further increased. Currently researchers generally modify the electronic structure by adopting three methods of optimizing the electronic structure, optimizing the nano structure and constructing the heterojunction to expect improvement of g-C 3 N 4 Catalytic activity of the catalyst. Wherein, three-dimensional porous g-C 3 N 4 The photocatalytic material has rich reactive sites and larger specific surface area, and can be regulated and controlled by being compounded with other semiconductorsThe energy band structure of the material can optimize the reaction potential of photo-reduction and photo-oxidation, thereby improving the photocatalysis performance of the material and showing unique advantages and potential application value.
So far, three-dimensional porous g-C regulated by precious metal nano Ag is not seen 3 N 4 Related studies and reports of supported photocatalytic materials.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a three-dimensional porous graphite phase carbon nitride (g-C 3 N 4 ) Bismuth oxyiodide (BiOI)/silver nanoparticle composite photocatalyst, preparation method and application thereof, and novel structure of catalyst, three-dimensional porous g-C 3 N 4 The nano-sheet has higher specific surface area, and the BiOI microsphere with excellent visible light utilization rate forms a unique heterojunction, the nano Ag serving as an electron transfer layer can further accelerate the electron conduction rate, reduce the recombination probability of photo-generated electron-hole pairs, improve the photocatalysis efficiency and solve the problem of the existing block g-C 3 N 4 The photocatalyst has low activity.
The invention realizes the technical purposes by the following technical means: a three-dimensional porous graphite phase carbon nitride/bismuth oxyiodide/silver nanoparticle composite photocatalyst is a three-dimensional porous g-C with BiOI microspheres and nano Ag supported on the surface 3 N 4 A nano-sheet.
Preferably, the BiOI microsphere, three-dimensional porous g-C 3 N 4 The mass mol ratio of the nano-sheet to the nano-Ag is BiOI microsphere: three-dimensional porous g-C 3 N 4 Nanosheets: nano Ag= (200-700) mg (50-300) mg (0.15-0.6) mmol; more preferably, the BiOI microsphere, three-dimensional porous g-C 3 N 4 The mass mol ratio of the nano-sheet to the nano-Ag is BiOI microsphere: three-dimensional porous g-C 3 N 4 Nanosheets: nano ag=500 mg:100mg:0.3mmol.
The invention provides a preparation method of the three-dimensional porous graphite phase carbon nitride/bismuth oxyiodide/silver nanoparticle composite photocatalyst, and the preparation method of the composite photocatalystThe method comprises the steps of taking a three-dimensional porous g-C3N4 nano-sheet as a carrier, loading BiOI microspheres on the surface of the three-dimensional porous g-C3N4 nano-sheet through self-assembly, and loading nano Ag on the three-dimensional porous g-C through a photochemical reduction method 3 N 4 The surface of the nano-sheet.
Preferably, the preparation method of the composite photocatalyst comprises the following preparation steps:
(1) Mixing BiOI microsphere with three-dimensional porous g-C 3 N 4 Respectively dispersing the nano sheets in methanol by ultrasonic, and stirring the three-dimensional porous g-C 3 N 4 Dripping methanol solution of nanosheets into methanol solution of BiOI, heating the mixed solution until methanol is completely volatilized, washing and drying the obtained product to obtain three-dimensional porous g-C 3 N 4 BiOI nanoplatelets;
(2) The three-dimensional porous g-C obtained in the step (1) is subjected to 3 N 4 Adding the BiOI nano-sheet into a methanol-water solution of an Ag precursor, performing ultrasonic dispersion, and uniformly stirring under a dark condition; under the condition of light source irradiation, ag adsorbed on the three-dimensional porous nano-sheet + In-situ reducing to nano Ag to obtain three-dimensional porous g-C 3 N 4 BiOI/Ag composite photocatalyst.
Three-dimensional porous g-C in the present invention 3 N 4 The nano-sheet has a unique porous structure and a larger specific surface area, and forms a heterojunction with the BiOI microsphere with strong visible light absorption, and the nano-Ag serving as an electron conducting layer can effectively improve the electron conduction rate. Thus, the three-dimensional porous g-C prepared by the present invention 3 N 4 The BiOI/Ag composite photocatalyst has excellent photocatalytic enhancement effect under the condition of visible light.
Preferably, the three-dimensional porous g-C 3 N 4 The nano-sheet is prepared by the method comprising the following steps:
adding melamine and cyanuric acid into water, stirring and dissolving uniformly, washing and drying the obtained mixed solution, and calcining the obtained reaction product to obtain the three-dimensional porous g-C 3 N 4 A nano-sheet.
Preferably, the concentration of melamine in the mixed solution is 3-10 mM, the concentration of cyanuric acid in the mixed solution is 3-10 mM, the stirring time is 5-24 h, and the drying mode is freeze drying.
Preferably, the calcination temperature is 300-550 ℃ and the calcination time is 2-12 h.
Preferably, the BiOI microspheres and the three-dimensional porous g-C in the step (1) 3 N 4 The mass ratio of the nano-sheets is 200-700: 50 to 300 percent. Preferably, the mass volume ratio of the BiOI microspheres and the methanol in the methanol solution of the BiOI in the step (1) is (200-700) mg: (40-100 mL), three-dimensional porous g-C 3 N 4 Three-dimensional porous g-C in methanol solution of nano-sheet 3 N 4 The mass volume ratio of the nano-sheet to the methanol is (50-300) mg: (15-30) mL; and (3) stirring in the step (1) is magnetic stirring, and the stirring time is 0.5-24 h.
Preferably, the heating temperature in the step (1) is 65-100 ℃ and the heating time is 1-10 h; the drying temperature in the step (1) is 60-100 ℃ and the drying time is 1-5 h.
Preferably, the Ag precursor in the step (2) is silver nitrate or silver trifluoroacetate; the volume ratio of methanol to water in the methanol-water solution of the Ag precursor is 1 (1-10); the three-dimensional porous g-C 3 N 4 The mass molar ratio of the BiOI nano-sheet to the Ag precursor is three-dimensional porous g-C 3 N 4 BiOI nanosheets Ag precursor= (50-200) mg: (0.05-0.2) mmol, wherein the concentration of the Ag precursor in the methanol-water solution of the Ag precursor is 0.5-2.0 mM. More preferably, the three-dimensional porous g-C in the step (2) 3 N 4 The mass molar ratio of the BiOI nano-sheet to the Ag precursor is three-dimensional porous g-C 3 N 4 BiOI nanoplatelets Ag precursor = 200mg:0.1mmol.
Preferably, in the step (2), the stirring time is 0.5-24 h, and the light source is a xenon lamp with power of 300W.
The invention provides application of the three-dimensional porous graphite phase carbon nitride/bismuth oxyiodide/silver nanoparticle composite photocatalyst in degrading organic pollutants in water under visible light driving; preferably, the organic contaminant comprises a tetracycline, sulfonamide, or quinolone antibiotic drug.
The novel three-dimensional porous graphite phase carbon nitride/bismuth oxyiodide/silver nanoparticle composite photocatalyst prepared by the invention has the following advantages and beneficial effects:
(1) The invention uses the three-dimensional porous g-C with higher specific surface area and easy preparation 3 N 4 The nano sheet is used as a carrier, and the BiOI microsphere and the nano Ag are uniformly loaded on the three-dimensional porous g-C through a self-assembly and photochemical reduction two-step method 3 N 4 Preparing three-dimensional porous g-C on the surface of the nano sheet 3 N 4 BiOI/Ag nano particle composite photocatalyst. The composite photocatalyst has higher specific surface area, better visible light utilization capability, excellent photo-generated electron and hole separation efficiency and faster photo-generated electron transmission rate, and solves the problems of the traditional block g-C 3 N 4 The shortage of base photocatalysts.
(2) The invention prepares three-dimensional porous g-C 3 N 4 The BiOI/Ag nanoparticle photocatalyst has the advantages of simple process, high synthesis efficiency, low energy consumption, good repeatability, controllable content of each component of the ternary photocatalyst, and three-dimensional porous g-C of BiOI microspheres and nano Ag 3 N 4 The nano-sheets are uniformly attached and are not easy to fall off.
(3) The three-dimensional porous g-C prepared by the invention 3 N 4 The BiOI/Ag nanoparticle photocatalytic material has excellent visible light catalytic degradation activity on TC. The catalyst has wide application range and good market prospect.
(4) With a single three-dimensional porous g-C 3 N 4 Compared with BiOI microsphere, the three-dimensional porous g-C 3 N 4 The BiOI/Ag nano particle composite photocatalyst has more excellent visible light catalytic degradation activity on toxic organic matters in water.
Drawings
FIG. 1 is a Transmission Electron Microscope (TEM) image of the photocatalyst prepared in example 1 of the present invention.
FIG. 2 is a three-dimensional porous g-C 3 N 4 Effect of nanoplatelets (0.4 g/L) to degrade TC (30 mg/L) in water.
FIG. 3 is a graph showing the effect of BiOI microspheres (0.4 g/L) prepared in example 1 on the degradation of TC (30 mg/L) in water.
FIG. 4 is a three-dimensional porous g-C prepared in example 1 3 N 4 And (3) a TC effect diagram of visible light catalytic degradation of the BiOI/Ag nanoparticle composite photocatalyst.
Detailed Description
In order to make the objects, features and advantages of the present invention more obvious and understandable, the technical solutions of the embodiments of the present invention will be clearly and completely described below, and it is apparent that the embodiments described below are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
1. Preparation of photocatalytic materials
(1) BiOI microspheres prepared by hydrothermal reaction (the preparation method is as described in reference 3D-2D-3D BiOI/porius g-C 3 N 4 Per graphene hydrogel composite photocatalyst with synergy of adsorption-photocatalysis in static and flow systems. Journal of Alloys and Compounds 850 (2021) 156778. Method), naturally cooling to room temperature, then centrifugally washing the BiOI microspheres 3 times with deionized water, drying the precipitate in a drying oven at 60℃for 4 hours to obtain BiOI microsphere powder, and placing in a dryer for later use;
(2) The mass ratio is 5:1 and three-dimensional porous g-C 3 N 4 The nano-sheets are respectively dissolved in methanol, and after ultrasonic treatment for 30min at room temperature, uniform solution is obtained. Three-dimensional porous g-C 3 N 4 Slowly dripping methanol solution of nanosheets into methanol solution of BiOI microspheres, magnetically stirring for 2.0h, heating the obtained uniform solution in an oil bath pot at 80 ℃ until methanol is completely volatilized, washing the obtained product with deionized water for 3 times, and drying in a baking oven at 60 ℃ to obtain three-dimensional porous g-C 3 N 4 BiOI nanoplatelets.
(3) Under the magnetic stirring condition, the three-dimensional porous g-C obtained in the step (2) is subjected to 3 N 4 BiOI nanoplatelets and AgNO 3 Solution(1 mM) 200mg in terms of mass to volume ratio: mixing 100mL, performing ultrasonic treatment at room temperature for 30min, magnetically stirring for 1.0h under dark condition, performing photochemical reduction reaction with 300W xenon lamp as light source, washing the obtained product with deionized water for 3 times, and oven drying at 60deg.C to obtain three-dimensional porous g-C 3 N 4 BiOI/Ag nano particle composite photocatalyst.
FIG. 1 shows a three-dimensional porous g-C prepared in this example 3 N 4 TEM image of BiOI/Ag nanoparticle composite photocatalyst; as can be seen from FIG. 1, g-C prepared in this example 3 N 4 The three-dimensional porous nano-sheet is formed by uniformly dispersing BiOI microspheres and nano Ag particles in three-dimensional porous g-C 3 N 4 On the nanoplatelets.
2. Performance test:
FIGS. 2 to 4 show three-dimensional porous g-C 3 N 4 Nanoplatelets, biOI microspheres prepared in example 1 and g-C prepared in example 1 3 N 4 Effect graph of BiOI/Ag composite photocatalyst (amount: 0.4 g/L) for degrading TC (30 mg/L) in water. As shown in FIGS. 2-4, three-dimensional porous g-C 3 N 4 Nanoplatelets, biOI microspheres and g-C 3 N 4 The degradation rate of the composite photocatalyst of the BiOI/Ag nano particles to TC within 165min is 80.4%,86.9% and 91.8%, respectively. The results show that the three-dimensional porous g-C is combined with single three-dimensional porous g-C 3 N 4 Compared with BiOI microspheres, the novel three-dimensional porous composite photocatalysis material has better adsorption capacity and excellent visible light photocatalytic activity, and is a novel photocatalysis material with wide application prospect.
Example 2
(1) BiOI microspheres prepared by hydrothermal reaction (the preparation method is as described in reference 3D-2D-3D BiOI/porius g-C 3 N 4 Per graphene hydrogel composite photocatalyst with synergy of adsorption-photocatalysis in static and flow systems. Journal of Alloys and Compounds 850 (2021) 156778. Method), naturally cooling to room temperature, then centrifugally washing the BiOI microspheres 3 times with deionized water, drying the precipitate in a drying oven at 60℃for 4 hours to obtain BiOI microsphere powder, and placing in a dryer for later use;
(2) The mass ratio is 5:1 and three-dimensional porous g-C 3 N 4 The nano-sheets are respectively dissolved in methanol, and after ultrasonic treatment for 30min at room temperature, uniform solution is obtained. Three-dimensional porous g-C 3 N 4 Slowly dripping methanol solution of nanosheets into methanol solution of BiOI microspheres, magnetically stirring for 2.0h, heating the obtained uniform solution in an oil bath pot at 80 ℃ until methanol is completely volatilized, washing the obtained product with deionized water for 3 times, and drying in a baking oven at 60 ℃ to obtain three-dimensional porous g-C 3 N 4 BiOI nanoplatelets.
(3) Under the magnetic stirring condition, the three-dimensional porous g-C obtained in the step (2) is subjected to 3 N 4 BiOI nanoplatelets and AgNO 3 Solution (0.5 mM) 200mg in mass to volume ratio: mixing 100mL, performing ultrasonic treatment at room temperature for 30min, magnetically stirring for 1.0h under dark condition, performing photochemical reduction reaction with 300W xenon lamp as light source, washing the obtained product with deionized water for 3 times, and oven drying at 60deg.C to obtain three-dimensional porous g-C 3 N 4 BiOI/Ag nano particle composite photocatalyst.
Three-dimensional porous g-C of this example 3 N 4 The micro-morphology of the BiOI/Ag nanoparticle composite photocatalyst is highly similar to that of the composite photocatalyst prepared in example 1, and the composite photocatalyst has excellent visible light photocatalytic activity on TC, and the degradation rate of TC (30 mg/L) is up to 91.1% within 165min at the dosage of 0.4 g/L.
Example 3
(1) BiOI microspheres prepared by hydrothermal reaction (the preparation method is as described in reference 3D-2D-3D BiOI/porius g-C 3 N 4 Per graphene hydrogel composite photocatalyst with synergy of adsorption-photocatalysis in static and flow systems. Journal of Alloys and Compounds 850 (2021) 156778. Method), naturally cooling to room temperature, then centrifugally washing the BiOI microspheres 3 times with deionized water, drying the precipitate in a drying oven at 60℃for 4 hours to obtain BiOI microsphere powder, and placing in a dryer for later use;
(2) The mass ratio is 5:1 and three-dimensional porous g-C 3 N 4 The nano-sheets are respectively dissolved in methanol,after 30min of ultrasonic treatment at room temperature, a uniform solution was obtained. Three-dimensional porous g-C 3 N 4 Slowly dripping methanol solution of nanosheets into methanol solution of BiOI microspheres, magnetically stirring for 2.0h, heating the obtained uniform solution in an oil bath pot at 80 ℃ until methanol is completely volatilized, washing the obtained product with deionized water for 3 times, and drying in a baking oven at 60 ℃ to obtain three-dimensional porous g-C 3 N 4 BiOI nanoplatelets.
(3) Under the magnetic stirring condition, the three-dimensional porous g-C obtained in the step (2) is subjected to 3 N 4 BiOI nanoplatelets and AgNO 3 Solution (2.0 mM) in a mass to volume ratio of 200mg: mixing 100mL, performing ultrasonic treatment at room temperature for 30min, magnetically stirring for 1.0h under dark condition, performing photochemical reduction reaction with 300W xenon lamp as light source, washing the obtained product with deionized water for 3 times, and oven drying at 60deg.C to obtain three-dimensional porous g-C 3 N 4 BiOI/Ag nano particle composite photocatalyst.
Three-dimensional porous g-C of this example 3 N 4 The micro-morphology of the BiOI/Ag nanoparticle composite photocatalyst is highly similar to that of the composite photocatalyst prepared in example 1, and the composite photocatalyst has excellent visible light photocatalytic activity on TC, and the degradation rate of TC (30 mg/L) is up to 90.9% within 165min at the dosage of 0.4 g/L.
The above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (8)
1. The preparation method of the three-dimensional porous graphite-phase carbon nitride/bismuth oxyiodide/silver nanoparticle composite photocatalyst for degrading organic pollutants in water under the drive of visible light is characterized in that the organic pollutants comprise tetracycline, sulfanilamide or quinolone antibiotic drugs;
the preparation method of the composite photocatalyst comprises the steps of preparing three-dimensional porous g-C 3 N 4 The nano-sheet is used as a carrier, and the BiOI microsphere is loaded on the three-dimensional porous g-C through self-assembly 3 N 4 The nano Ag is loaded on the surface of the nano sheet by a photochemical reduction method on the three-dimensional porous g-C 3 N 4 The surfaces of the nano-sheets;
the BiOI microsphere and the three-dimensional porous g-C 3 N 4 The mass mol ratio of the nano-sheet to the nano-Ag is BiOI microsphere: three-dimensional porous g-C 3 N 4 Nanosheets: nano Ag= (200-700) mg (50-300) mg (0.15-0.6) mmol;
the three-dimensional porous g-C 3 N 4 The nano-sheet is prepared by the method comprising the following steps: adding melamine and cyanuric acid into water, stirring and dissolving uniformly, washing and drying the obtained mixed solution, and calcining the obtained reaction product to obtain the three-dimensional porous g-C 3 N 4 A nanosheet;
the preparation method of the composite photocatalyst comprises the following preparation steps:
(1) Mixing BiOI microsphere with three-dimensional porous g-C 3 N 4 Respectively dispersing the nano sheets in methanol by ultrasonic, and stirring the three-dimensional porous g-C 3 N 4 Dripping methanol solution of nanosheets into methanol solution of BiOI, heating the mixed solution until methanol is completely volatilized, washing and drying the obtained product to obtain three-dimensional porous g-C 3 N 4 BiOI nanoplatelets;
(2) The three-dimensional porous g-C obtained in the step (1) is subjected to 3 N 4 Adding the BiOI nano-sheet into a methanol-water solution of an Ag precursor, performing ultrasonic dispersion, and uniformly stirring under a dark condition; under the condition of light source irradiation, ag adsorbed on the three-dimensional porous nano-sheet + In-situ reducing to nano Ag to obtain the three-dimensional porous graphite phase carbon nitride/bismuth oxyiodide/silver nanoparticle composite photocatalyst.
2. The method for preparing the three-dimensional porous graphite phase carbon nitride/bismuth oxyiodide/silver nanoparticle composite photocatalyst according to claim 1, which is characterized in thatThe BiOI microsphere and the three-dimensional porous g-C in the step (1) 3 N 4 The mass ratio of the nano-sheets is 200-700: 50 to 300 percent.
3. The method for preparing the three-dimensional porous graphite phase carbon nitride/bismuth oxyiodide/silver nanoparticle composite photocatalyst according to claim 1, wherein the heating temperature in the step (1) is 65-100 ℃ and the heating time is 1-10 h; the drying temperature in the step (1) is 60-100 ℃ and the drying time is 1-5 h.
4. The method for preparing the three-dimensional porous graphite phase carbon nitride/bismuth oxyiodide/silver nanoparticle composite photocatalyst according to claim 1, wherein the Ag precursor in the step (2) is silver nitrate or silver trifluoroacetate; the volume ratio of methanol to water in the methanol-water solution of the Ag precursor is 1 (1-10); the three-dimensional porous g-C 3 N 4 The mass molar ratio of the BiOI nano-sheet to the Ag precursor is three-dimensional porous g-C 3 N 4 BiOI nanosheets Ag precursor= (50-200) mg: (0.05-0.2) mmol, wherein the concentration of the Ag precursor in the methanol-water solution of the Ag precursor is 0.5-2.0 mM.
5. The method for preparing the three-dimensional porous graphite phase carbon nitride/bismuth oxyiodide/silver nanoparticle composite photocatalyst according to claim 1, wherein in the step (2), the stirring time is 0.5-24 h, and the light source is a xenon lamp with power of 300W.
6. The method for preparing the three-dimensional porous graphite phase carbon nitride/bismuth oxyiodide/silver nanoparticle composite photocatalyst according to claim 1, wherein the BiOI microsphere and the three-dimensional porous g-C are prepared by 3 N 4 The mass mol ratio of the nano-sheet to the nano-Ag is BiOI microsphere: three-dimensional porous g-C 3 N 4 Nanosheets: nano ag=500 mg:100mg:0.3mmol.
7. A three-dimensional porous graphite-phase carbon nitride/bismuth oxyiodide/silver nanoparticle composite photocatalyst for degrading organic pollutants in water under visible light driving, prepared by the preparation method of any one of claims 1-6, wherein the organic pollutants comprise tetracycline, sulfanilamide or quinolone antibiotic drugs.
8. The use of the three-dimensional porous graphite-phase carbon nitride/bismuth oxyiodide/silver nanoparticle composite photocatalyst according to claim 7 for degrading organic pollutants in water under visible light driving; the organic contaminants include tetracyclines, sulfonamides or quinolones.
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