CN111604083B - Graphite type carbon nitride composite photocatalytic material with oxygen vacancy bismuth tungstate/oxygen-enriched structure and preparation method and application thereof - Google Patents
Graphite type carbon nitride composite photocatalytic material with oxygen vacancy bismuth tungstate/oxygen-enriched structure and preparation method and application thereof Download PDFInfo
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 218
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- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 218
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- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 114
- 239000002131 composite material Substances 0.000 title claims abstract description 110
- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 101
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- 239000002351 wastewater Substances 0.000 claims abstract description 13
- VBIIFPGSPJYLRR-UHFFFAOYSA-M Stearyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C VBIIFPGSPJYLRR-UHFFFAOYSA-M 0.000 claims abstract description 11
- FBXVOTBTGXARNA-UHFFFAOYSA-N bismuth;trinitrate;pentahydrate Chemical compound O.O.O.O.O.[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FBXVOTBTGXARNA-UHFFFAOYSA-N 0.000 claims abstract description 10
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- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 6
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- B01J35/39—
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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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- B01J35/61—
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—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
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/343—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the pharmaceutical industry, e.g. containing antibiotics
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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
- C02F2305/02—Specific form of oxidant
- C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
-
- 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
Abstract
The invention discloses a graphite type carbon nitride composite photocatalytic material with an oxygen vacancy bismuth tungstate/oxygen-enriched structure, and a preparation method and application thereof. The composite photocatalytic material is formed by compounding oxygen vacancy bismuth tungstate and graphite type carbon nitride with an oxygen-enriched structure. The preparation method comprises the steps of firstly calcining dicyandiamide and ammonium tungstate serving as raw materials to synthesize graphite type carbon nitride with an oxygen-enriched structure, and then calcining the graphite type carbon nitride with bismuth nitrate pentahydrate, sodium tungstate dihydrate and the oxygen-enriched structure serving as raw materials by a hydrothermal method under the action of octadecyl trimethyl ammonium chloride to obtain the graphite type carbon nitride. The composite photocatalytic material has the advantages of strong stability, strong light capture capacity, high electron-hole pair separation efficiency, excellent photocatalytic performance and the like, and the preparation method has the advantages of mild reaction conditions, simple process flow, low energy consumption, less material consumption and the like, is suitable for large-scale popularization and application, has a good effect of removing antibiotics, and has a good application prospect in photocatalytic degradation of antibiotic wastewater.
Description
Technical Field
The invention belongs to the field of functional materials, relates to a composite photocatalytic material, and a preparation method and application thereof, and particularly relates to an oxygen vacancy bismuth tungstate/oxygen-enriched structure graphite type carbon nitride composite photocatalytic material, and a preparation method and application thereof.
Background
In recent years, the problem of water pollution caused by organic pollutants is becoming a serious environmental pollution problem, and especially the pollution caused by antibiotic organic matters is receiving attention all over the world. Antibiotics are used for the treatment of many bacterial infections due to their high efficacy and broad spectrum, but they are difficult to biodegrade, are stable in water, and are easily converted into teratogenic carcinogens, thus threatening the survival of humans and aquatic animals. Removal of antibiotics is therefore of widespread interest worldwide. Removal of antibiotics is difficult because antibiotics are readily soluble and very stable in water. Common antibiotic treatment techniques, such as membrane filtration, adsorption, oxidation, and biological treatment, are limited in practical application due to their high operating costs, complex processes, or the potential for the production of more toxic byproducts. In recent years, photocatalytic technology has been considered the most reliable and efficient method due to its green color and ease of operation. The core of the photocatalysis technology is photocatalyst, so that the key point for solving the problems is to obtain the photocatalyst which has high economic benefit and high degradation efficiency and can be recycled.
Semiconductor photocatalysts have been rapidly developed in recent years, and attract more people to pay attention to semiconductor photocatalytic technology. Bismuth tungstate is a semiconductor material having a typical perovskite layered structure, and is receiving attention due to its excellent photostability, non-toxicity and good photocatalytic activity. The band gap (2.8eV) of bismuth tungstate is narrow, and the bismuth tungstate has good light responsiveness in an ultraviolet-visible light region, but in practical application, the bismuth tungstate is still limited by rapid recombination of electron-hole pairs and limited light capture capability. It is reported that the construction of a heterojunction can solve the problem well, but the conventional heterojunction is easily constructed to cause the reduction of the redox performance. Therefore, the bismuth tungstate heterojunction which is simple in preparation process, low in cost, strong in stability, strong in light capture capacity, high in separation efficiency of electron-hole pairs, excellent in photocatalytic performance and environment-friendly is obtained.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, provides the graphite type carbon nitride composite photocatalytic material with the oxygen vacancy bismuth tungstate/oxygen-enriched structure, which has the advantages of strong stability, strong light capture capacity, high separation efficiency of electron-hole pairs, excellent photocatalytic performance and environmental friendliness, also provides the preparation method of the graphite type carbon nitride composite photocatalytic material with the oxygen vacancy bismuth tungstate/oxygen-enriched structure, which has the advantages of mild reaction conditions, simple process flow, environmental friendliness, low energy consumption and low cost, and correspondingly provides the application of the graphite type carbon nitride composite photocatalytic material with the oxygen vacancy bismuth tungstate/oxygen-enriched structure in photocatalytic degradation of antibiotics.
In order to solve the technical problems, the invention adopts the following technical scheme.
The graphite type carbon nitride composite photocatalytic material with the oxygen vacancy bismuth tungstate/oxygen enrichment structure is formed by compounding the oxygen vacancy bismuth tungstate and graphite type carbon nitride with the oxygen enrichment structure, and the composite photocatalytic material is in a three-dimensional structure.
Preferably, the mass ratio of the oxygen vacancy-containing bismuth tungstate to the oxygen-rich graphite type carbon nitride in the composite photocatalytic material is 1-5: 1.
As a general technical concept, the invention also provides a preparation method of the graphite type carbon nitride composite photocatalytic material with the oxygen vacancy bismuth tungstate/oxygen-enriched structure, which comprises the following steps:
s1, uniformly mixing dicyandiamide and ammonium tungstate, and calcining at 450-550 ℃ for 3-6 h to obtain graphite type carbon nitride with an oxygen-enriched structure;
s2, mixing sodium tungstate dihydrate with octadecyl trimethyl ammonium chloride, dissolving in water, adding bismuth nitrate pentahydrate under stirring, and continuously stirring to obtain a mixed solution containing sodium tungstate and bismuth nitrate;
s3, mixing the mixed solution obtained in the step S2 with the graphite type carbon nitride with the oxygen-rich structure obtained in the step S1, stirring and performing ultrasonic treatment to obtain a precursor mixed solution; carrying out hydrothermal reaction on the precursor mixed solution for 20-24 h at 120-160 ℃, filtering and drying to obtain the graphite type carbon nitride composite photocatalytic material with the oxygen vacancy bismuth tungstate/oxygen-enriched structure.
Preferably, in the step S1, the molar ratio of dicyandiamide to ammonium tungstate is 95-105: 1.
Preferably, in the preparation method of the graphite type carbon nitride composite photocatalytic material with the oxygen vacancy bismuth tungstate/oxygen-enriched structure, the mass ratio of the graphite type carbon nitride with the oxygen-enriched structure adopted in the step S3 to the sodium tungstate dihydrate and the bismuth nitrate pentahydrate in the step S2 is 0.38-1.9: 0.98-1.02: 2.42-2.44, and the mass ratio of the sodium tungstate dihydrate to the octadecyl trimethyl ammonium chloride is 22-27: 1. Wherein the addition amount of the sodium tungstate dihydrate and the bismuth nitrate pentahydrate in the step (2) is 0.59-0.62: 1 in terms of molar ratio of W to Bi.
Preferably, in the step S3, the precursor mixed solution undergoes a hydrothermal reaction at 140 ℃ for 24 hours.
In the preparation method of the graphite type carbon nitride composite photocatalytic material with the oxygen vacancy bismuth tungstate/oxygen-enriched structure, preferably, in the step S2, the dissolving is carried out by stirring for 0-60 min at the rotating speed of 400-1200 r/min; the rotating speed of the continuous stirring is 400 r/min-1200 r/min, and the time of the continuous stirring is 60 min-180 min.
Preferably, in the step S3, the stirring speed is 400r/min to 1200r/min, the stirring time is 60min to 180min, and the ultrasound time is 5min to 30 min.
As a general technical concept, the invention also provides an application of the graphite type carbon nitride composite photocatalytic material with the oxygen vacancy bismuth tungstate/oxygen-enriched structure or the graphite type carbon nitride composite photocatalytic material with the oxygen vacancy bismuth tungstate/oxygen-enriched structure prepared by the preparation method in photocatalytic degradation of antibiotic wastewater.
The above application, preferably, comprises the following steps: mixing the graphite type carbon nitride composite photocatalytic material with the oxygen vacancy bismuth tungstate/oxygen-enriched structure with antibiotic wastewater, performing dark treatment, and performing photocatalytic treatment under the illumination condition; the antibiotic in the antibiotic wastewater is tetracycline, the concentration of the tetracycline is 5 mg/L-30 mg/L, the mass ratio of the composite photocatalytic material to the tetracycline is 5-40: 1, the dark treatment is stirring for 20 min-60 min under the dark condition, and the photocatalytic treatment is specifically stirring for 30 min-120 min under the illumination condition with the wavelength of 300 nm-800 nm and the rotating speed of 300 r/min-1000 r/min.
Compared with the prior art, the invention has the advantages that:
(1) the graphite type carbon nitride composite photocatalytic material with the oxygen vacancy bismuth tungstate/oxygen-enriched structure is formed by compounding the oxygen vacancy bismuth tungstate and the graphite type carbon nitride with the oxygen-enriched structure. Wherein oxygen vacancies can form local defect energy levels (CB) below the conduction band, improve the light trapping capability, can effectively trap light-induced electrons, and are favorable for adsorbing pollutants. The graphite type carbon nitride with the oxygen-enriched structure has an energy band matched with oxygen vacancy bismuth tungstate, a hole on a graphite type carbon nitride valence band of the oxygen-enriched structure and an electron on an oxygen vacancy bismuth tungstate conduction band are combined to form a Z-type charge transfer system, a strong oxidation-reduction potential can be reserved, photo-generated charges can be transferred rapidly, electron-hole recombination is avoided, and the wavelength range of light absorption is widened.
The composite photocatalytic material is integrally combined into a three-dimensional structure by a two-dimensional sheet structure, the specific surface area is large, more active sites can be provided, and photo-generated charges can reach the surface of the material more quickly, so that the transfer of the photo-generated charges is facilitated; the graphite type carbon nitride with the oxygen-rich structure is a visible light response photocatalytic material, can absorb sunlight with the wavelength less than 800nm, is rich in pi-pi bonds, can improve the adsorption capacity of the composite material on organic pollutants, has outstanding conductive property, can be used as an electron acceptor, plays a role in 'electron library' effect, is beneficial to a semiconductor to generate charge transfer under illumination, prolongs the service life of photo-generated charges and further improves the photocatalytic activity; by compounding oxygen vacancy-containing bismuth tungstate with graphite type carbon nitride of an oxygen-rich structure, the adsorption of organic pollutants is enhanced, and simultaneously the charge separation efficiency is effectively promoted. Compared with an oxygen vacancy-containing bismuth tungstate monomer and an oxygen-enriched graphite type carbon nitride monomer, the composite photocatalytic material disclosed by the invention has the advantages of strong stability, strong light capture capability, high electron-hole pair separation efficiency, excellent photocatalytic performance, environmental friendliness and the like, and has good application value and application prospect.
(2) The preparation method of the graphite type carbon nitride composite photocatalytic material with the oxygen vacancy bismuth tungstate/oxygen-enriched structure comprises the steps of calcining dicyandiamide and ammonium tungstate serving as raw materials to synthesize graphite type carbon nitride with the oxygen-enriched structure, and then using sodium tungstate dihydrate, bismuth nitrate pentahydrate and graphite type carbon nitride with the oxygen-enriched structure as raw materials to prepare the graphite type carbon nitride composite photocatalytic material with the oxygen vacancy bismuth tungstate/oxygen-enriched structure, which has excellent electronic conductivity and photocatalytic performance, in one step through a hydrothermal method under the action of octadecyl trimethyl ammonium chloride.
The method for obtaining the oxygen vacancy is simple and mild in condition, common methods for obtaining the oxygen vacancy in the prior art such as alkali etching, hydrogen heat treatment or high-temperature calcination at 300-400 ℃ are not used, and auxiliary agents such as vinyl alcohol, sodium borohydride and the like are not added2WO6And the composite photocatalytic material of the invention is generated while synthesizing the oxygen vacancy-containing bismuth tungstateOne-step operation, simple method and low energy consumption.
The preparation method of the invention has the advantages of small using amount of octadecyl trimethyl ammonium chloride, being beneficial to obtaining oxygen vacancy in bismuth tungstate, greatly reducing cost and having great significance for industrial popularization.
The graphite type carbon nitride with the oxygen-enriched structure has the blackbody property, and can improve the light capture capacity of the composite material.
The graphite type carbon nitride with the oxygen-enriched structure can generate a small amount of hydrogen peroxide, and because a tungsten source is required to be introduced to synthesize the graphite type carbon nitride with the oxygen-enriched structure, a small amount of tungsten oxide is generated under a high-temperature condition, the hydrogen peroxide can be accelerated to be converted into dissolved oxygen, so that more superoxide radicals are generated, and the oxidation and degradation of antibiotic wastewater are facilitated.
(3) The graphite type carbon nitride composite photocatalytic material with the oxygen vacancy bismuth tungstate/oxygen enrichment structure is applied to photocatalytic degradation of antibiotic wastewater, has high degradation efficiency, such as the degradation efficiency of tetracycline is up to 96.2%, is simple to operate, short in period, easy to recycle, mild in condition, capable of reacting in a greenhouse, free of special equipment, good in anti-interference capability, applicable to different water body environments, and good in application prospect in antibiotic wastewater treatment.
The composite photocatalytic material has better dispersibility, can be uniformly dispersed in the wastewater to be treated, is beneficial to fully contacting with the antibiotics to be treated, has good stability, and can be recycled by simple centrifugation. The graphite type carbon nitride with an oxygen-rich structure and the oxygen vacancy-containing bismuth tungstate form a Z-type charge transfer channel in the composite photocatalytic material, so that the separation of photoinduced charge carriers can be promoted, and a stronger oxidation-reduction potential can be kept. The photo-generated electrons generated by the bismuth tungstate can be quickly conducted, the electrons are transferred to the surface of the composite photocatalytic material to react with dissolved oxygen to generate superoxide radicals with strong oxidability, such as formulas (1) and (2), a small amount of hydroxyl radicals are also generated, such as formula (3), and the radicals can participate in oxidation-reduction reaction to degrade tetracycline, such as formulas (4) and (5). The process improves the separation efficiency of the photo-generated electron-hole pairs and effectively enhances the photocatalytic activity of the composite photocatalytic material. On the other hand, the graphite type carbon nitride with the oxygen-enriched structure can generate a small amount of hydrogen peroxide, and a small amount of tungsten oxide is generated in the process of synthesizing the graphite type carbon nitride with the oxygen-enriched structure, so that the hydrogen peroxide can be accelerated to be converted into dissolved oxygen, as shown in formula (6), and more superoxide radicals are generated to carry out oxidative degradation on tetracycline.
BWO-OV/OCN+hν→e-+h+ (1)
O2+e-→·O2 - (2)
h++H2O→·OH (3)
h++ TC → degradation product (4)
·O2 -+ TC → degradation product (5)
H2O2-2e-→O2+2H+ (6)
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 an SEM image of a graphite type carbon nitride composite photocatalytic material 4BWO-OV/OCN with an oxygen vacancy bismuth tungstate/oxygen-rich structure prepared in example 2 of the present invention.
FIG. 2 is a TEM image of the graphite type carbon nitride composite photocatalytic material 4BWO-OV/OCN with oxygen vacancy bismuth tungstate/oxygen-rich structure prepared in example 2 of the present invention.
FIG. 3 is an XPS diagram of Bi 4f of the graphite type carbon nitride composite photocatalytic material 4BWO-OV/OCN having an oxygen vacancy bismuth tungstate/oxygen-rich structure prepared in example 2 of the present invention.
FIG. 4 is a low-temperature solid-state Electron Paramagnetic Resonance (EPR) diagram of the graphite-type carbon nitride composite photocatalytic material 4BWO-OV/OCN with an oxygen-vacancy bismuth tungstate/oxygen-rich structure prepared in example 2 of the present invention.
FIG. 5 is an XRD (X-ray diffraction) diagram of the graphite type carbon nitride composite photocatalytic material with the oxygen-vacancy-containing bismuth tungstate/oxygen-enriched structure prepared in examples 1 to 5 and comparative example 1, 5BWO-OV/OCN, 4BWO-OV/OCN, 3BWO-OV/OCN, 2BWO-OV/OCN, 1BWO-OV/OCN and 0.33BWO-OV/OCN, the graphite type carbon nitride OCN with the oxygen-enriched structure prepared in comparative example 2 and the bismuth tungstate BWO-OV with the oxygen vacancy-containing structure prepared in comparative example 3.
FIG. 6 is a graph showing the effect of the graphite type carbon nitride composite photocatalytic material containing oxygen vacancy bismuth tungstate/oxygen-enriched structure prepared in examples 1 to 5 and comparative example 1 of the present invention on tetracycline degradation by 5BWO-OV/OCN, 4BWO-OV/OCN, 3BWO-OV/OCN, 2BWO-OV/OCN, 1BWO-OV/OCN, 0.33BWO-OV/OCN, the graphite type carbon nitride OCN containing oxygen-enriched structure prepared in comparative example 2, and BWO-OV prepared in comparative example 3.
FIG. 7 is a graph showing a degradation rate of the oxygen-vacancy-containing bismuth tungstate/oxygen-enriched graphite type carbon nitride composite photocatalytic material 5BWO-OV/OCN, 4BWO-OV/OCN, 3BWO-OV/OCN, 2BWO-OV/OCN, 1BWO-OV/OCN, 0.33BWO-OV/OCN prepared in examples 1 to 5 and comparative example 1, the oxygen-enriched graphite type carbon nitride OCN prepared in comparative example 2, and BWO-OV prepared in comparative example 3, with respect to tetracycline, and the ordinate is-ln (the ratio of the concentration of tetracycline degraded at a certain time to the initial concentration thereof) and the initial concentration is the concentration after adsorption equilibrium.
Fig. 8 is a graph of the degradation effect of the graphite type carbon nitride composite photocatalytic material 4BWO-OV/OCN with the oxygen-vacancy bismuth tungstate/oxygen-rich structure prepared in example 2 of the present invention on tetracycline in different water environments, where the ordinate is the ratio of the concentration of tetracycline degraded at a certain time to the initial concentration thereof, and the initial concentration is the concentration after adsorption equilibrium, where DW is pure water, TW is tap water, LW is lake water, and RW is river water.
Fig. 9 is a graph of the degradation effect of the graphite type carbon nitride composite photocatalytic material 4BWO-OV/OCN having an oxygen vacancy bismuth tungstate/oxygen-rich structure prepared in example 2 of the present invention on tetracycline in the presence of common acid ions, where the ordinate is the ratio of the concentration of tetracycline degraded at a certain time to the initial concentration thereof, and the initial concentration is the concentration after adsorption equilibrium.
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.
In the examples of the present invention, the raw materials and instruments used are commercially available unless otherwise specified. The data obtained are the average of three or more replicates.
Example 1
The invention relates to a graphite type carbon nitride composite photocatalytic material with an oxygen vacancy bismuth tungstate/oxygen-enriched structure, which is formed by compounding oxygen vacancy bismuth tungstate and graphite type carbon nitride with an oxygen-enriched structure, wherein the composite material is in a three-dimensional structure, and the mass ratio of the oxygen vacancy bismuth tungstate to the graphite type carbon nitride with the oxygen-enriched structure in the composite photocatalytic material is 5: 1.
The preparation method of the graphite type carbon nitride composite photocatalytic material containing the oxygen vacancy bismuth tungstate/oxygen-rich structure comprises the following steps:
s1, uniformly mixing 50mmol of dicyandiamide and 0.5mmol of ammonium tungstate, putting the mixture into a crucible with a cover and the diameter of 50mm, and calcining the mixture for 4 hours at 500 ℃ to obtain the graphite type carbon nitride OCN with the oxygen-enriched structure.
S2, weighing 1.0g of sodium tungstate dihydrate and 40mg of octadecyl trimethyl ammonium chloride, mixing, stirring at the rotation speed of 800r/min for 60min to completely dissolve the sodium tungstate dihydrate and the octadecyl trimethyl ammonium chloride in 40mL of deionized water, adding 2.43g of bismuth nitrate pentahydrate under the stirring condition, keeping the rotation speed unchanged, and continuing stirring for 120min to obtain a mixed solution containing sodium tungstate and bismuth nitrate, wherein the molar ratio of W to Bi in the mixed solution is 0.6: 1;
s3, mixing the mixed solution containing the sodium tungstate and the bismuth nitrate obtained in the step S2 with 0.38g of the graphite type carbon nitride with the oxygen-rich structure prepared in the step S1, stirring for 120min at the rotating speed of 800r/min, and performing ultrasonic treatment for 30min to obtain a precursor mixed solution; carrying out hydrothermal reaction on the precursor mixed solution at 140 ℃ for 24h, cooling to room temperature, filtering and drying to obtain oxygen vacancy-containing bismuth tungstate (Bi)2WO6) Graphite type nitrogen of oxygen-enriched structureThe carbon composite photocatalytic material is 5 BWO-OV/OCN.
Example 2
The graphite type carbon nitride composite photocatalytic material containing the oxygen vacancy bismuth tungstate/the oxygen-enriched structure is basically the same as the composite photocatalytic material in the embodiment 1, and the difference is only that: the mass ratio of oxygen vacancy bismuth tungstate to oxygen-enriched graphite type carbon nitride in the composite photocatalytic material is 4: 1.
The preparation method of the graphite type carbon nitride composite photocatalytic material containing the oxygen vacancy bismuth tungstate/oxygen-rich structure in the embodiment is basically the same as that of the preparation method in the embodiment 1, and the difference is only that: and (4) 0.475g of graphite type carbon nitride with the oxygen-enriched structure in the step (S3) to obtain the graphite type carbon nitride composite photocatalytic material 4BWO-OV/OCN with the oxygen vacancy bismuth tungstate/oxygen-enriched structure.
FIG. 1 is an SEM photograph of 4BWO-OV/OCN obtained in example 2 of the present invention. As can be seen from figure 1, the graphite type carbon nitride composite photocatalytic material containing oxygen vacancy bismuth tungstate/oxygen-rich structure, which is prepared by the invention, is integrally combined by two-dimensional sheets. The oxygen vacancy-containing bismuth tungstate monomer has a smooth surface, and fig. 1 obviously shows that a layer of substance is attached to one substance, so that the surface of the material becomes rough and layered, and the successful compounding of the two materials is proved.
FIG. 2 is a TEM image of 4BWO-OV/OCN obtained in example 2 of the present invention. The figure shows different crystal lattices which respectively correspond to the crystal lattices of the graphite type carbon nitride OCN with the oxygen-enriched structure prepared in the comparative example 2 and the crystal lattices of the bismuth tungstate BWO-OV with the oxygen vacancy prepared in the comparative example 3, and the composite photocatalytic material prepared by the invention is shown to be successfully compounded with the graphite type carbon nitride with the oxygen-enriched structure. Wherein the lattice spacing of 0.25nm in the oxygen-rich structure of the graphite type carbon nitride is slightly larger than that of the existing graphite type carbon nitride (0.24nm), which is probably due to the formation of the oxygen-rich structure.
FIG. 3 is an XPS map of Bi 4f of 4BWO-OV/OCN obtained in example 2 of the present invention. Except for common Bi3+Has two additional peaks at 159.2eV and 164.5eV, which are derived from Bi having a lower valence(3-x)+This may be associated with the loss of oxygen atoms in BWO-OV.
FIG. 4 is a diagram of the low temperature solid state Electron Paramagnetic Resonance (EPR) of 4BWO-OV/OCN made in accordance with example 2 of the present invention, wherein the EPR signal at g 2.0002 is due to the presence of oxygen vacancies, thereby verifying the presence of oxygen vacancies.
Example 3
The graphite type carbon nitride composite photocatalytic material containing the oxygen vacancy bismuth tungstate/the oxygen-enriched structure is basically the same as the composite photocatalytic material in the embodiment 1, and the difference is only that: the mass ratio of oxygen vacancy bismuth tungstate to oxygen-enriched graphite type carbon nitride in the composite photocatalytic material is 3: 1.
The preparation method of the graphite type carbon nitride composite photocatalytic material containing the oxygen vacancy bismuth tungstate/oxygen-rich structure in the embodiment is basically the same as that of the preparation method in the embodiment 1, and the difference is only that: and (4) 0.63g of graphite type carbon nitride with the oxygen-enriched structure in the step (S3) to obtain the graphite type carbon nitride composite photocatalytic material 3BWO-OV/OCN with the oxygen vacancy bismuth tungstate/oxygen-enriched structure.
Example 4
The graphite type carbon nitride composite photocatalytic material containing the oxygen vacancy bismuth tungstate/the oxygen-enriched structure is basically the same as the composite photocatalytic material in the embodiment 1, and the difference is only that: the mass ratio of oxygen vacancy-containing bismuth tungstate to oxygen-rich graphite type carbon nitride in the composite photocatalytic material is 2: 1.
The preparation method of the graphite type carbon nitride composite photocatalytic material containing the oxygen vacancy bismuth tungstate/oxygen-rich structure in the embodiment is basically the same as that of the preparation method in the embodiment 1, and the difference is only that: and (4) 0.95g of graphite type carbon nitride with the oxygen-enriched structure in the step (S3) to obtain the graphite type carbon nitride composite photocatalytic material 2BWO-OV/OCN with the oxygen-containing vacancy bismuth tungstate/oxygen-enriched structure.
Example 5
The graphite type carbon nitride composite photocatalytic material containing the oxygen vacancy bismuth tungstate/the oxygen-enriched structure is basically the same as the composite photocatalytic material in the embodiment 1, and the difference is only that: the mass ratio of oxygen vacancy bismuth tungstate to oxygen-enriched graphite type carbon nitride in the composite photocatalytic material is 1: 1.
The preparation method of the graphite type carbon nitride composite photocatalytic material containing the oxygen vacancy bismuth tungstate/oxygen-rich structure in the embodiment is basically the same as that of the preparation method in the embodiment 1, and the difference is only that: and (4) 1.9g of graphite type carbon nitride with the oxygen-enriched structure in the step (S3) to obtain the graphite type carbon nitride composite photocatalytic material 1BWO-OV/OCN with the oxygen vacancy bismuth tungstate/oxygen-enriched structure.
Comparative example 1
A graphite type carbon nitride composite photocatalytic material containing an oxygen vacancy bismuth tungstate/oxygen-enriched structure is basically the same as the composite photocatalytic material in the embodiment 1, and the difference is only that: the mass ratio of oxygen vacancy bismuth tungstate to oxygen-enriched graphite type carbon nitride in the composite photocatalytic material is 0.33: 1.
A preparation method of a graphite type carbon nitride composite photocatalytic material containing an oxygen vacancy bismuth tungstate/oxygen-enriched structure is basically the same as that of the preparation method in the embodiment 1, and the difference is only that: 0.5g of sodium tungstate dihydrate, 1.215g of bismuth nitrate pentahydrate and 2.85g of graphite type carbon nitride with an oxygen-enriched structure in the step S3 in the step S2, so that the graphite type carbon nitride composite photocatalytic material with the oxygen vacancy bismuth tungstate/oxygen-enriched structure is obtained, wherein the weight of the graphite type carbon nitride composite photocatalytic material is 0.33 BWO-OV/OCN.
Comparative example 2
A preparation method of graphite type carbon nitride with an oxygen-enriched structure comprises the following steps:
taking 50mmol of dicyandiamide and 0.5mmol of ammonium tungstate, uniformly mixing, putting into a crucible with a cover and the diameter of 50mm, and calcining for 4 hours at 500 ℃ to obtain the graphite type carbon nitride OCN with the oxygen-enriched structure.
Comparative example 3
A preparation method of oxygen vacancy-containing bismuth tungstate comprises the following steps:
s1, weighing 1.0g of sodium tungstate dihydrate and 40mg of octadecyl trimethyl ammonium chloride, mixing and completely dissolving the sodium tungstate dihydrate and the octadecyl trimethyl ammonium chloride in 40mL of deionized water, adding 2.43g of bismuth nitrate pentahydrate under the stirring condition, and continuously stirring to obtain a mixed solution containing bismuth nitrate and sodium tungstate, wherein the molar ratio of W to Bi in the mixed solution is 0.6: 1;
s2, carrying out hydrothermal reaction on the mixed solution containing bismuth nitrate and sodium tungstate obtained in the step S1 at the temperature of 140 ℃ for 24 hours, cooling to room temperature, filtering, and drying to obtain oxygen vacancy-containing bismuth tungstate BWO-OV.
FIG. 5 is XRD graphs of graphite type carbon nitride composite photocatalytic materials containing oxygen vacancy bismuth tungstate/oxygen-enriched structure prepared in comparative example 1, 5BWO-OV/OCN, 4BWO-OV/OCN, 3BWO-OV/OCN, 2BWO-OV/OCN, 1BWO-OV/OCN, 0.33BWO-OV/OCN, OCN prepared in comparative example 2 and BWO-OV prepared in comparative example 3 in examples 1 to 5 of the present invention. As can be seen from FIG. 5, the crystal face of the composite photocatalytic material prepared by the method is basically consistent with the crystal face of the oxygen vacancy-containing bismuth tungstate monomer, but the peak width of the crystal face of the composite photocatalytic material 131 is widened, which means the successful compounding of the oxygen vacancy-containing bismuth tungstate and the oxygen-rich graphite type carbon nitride.
Example 6
The invention relates to an application of a graphite type carbon nitride composite photocatalytic material with an oxygen vacancy bismuth tungstate/oxygen-enriched structure in photocatalytic degradation of antibiotic wastewater, which comprises the following steps:
taking degradable tetracycline as an example, taking 5BWO-OV/OCN, 4BWO-OV/OCN, 3BWO-OV/OCN, 2BWO-OV/OCN, 1BWO-OV/OCN, 0.33BWO-OV/OCN prepared in the comparative example 1, and BWO-OV prepared in the comparative example 3 as the mass ratio of the composite photocatalytic material to the tetracycline in the solution of the embodiment 1-5, respectively adding the materials into the tetracycline solution with the initial concentration of 10mg/L for dark treatment for 60min, after reaching adsorption equilibrium, carrying out photocatalytic treatment for 60min under the condition of illumination with the wavelength of 300 nm-800 nm at the rotating speed of 800r/min, respectively sampling and measuring the concentration of the tetracycline at the time of 0min, 15min, 30min, 45min and 60min after the reaction is finished, carrying out solid-liquid separation, and recovering the composite photocatalytic material.
As shown in FIG. 6, the 4BWO-OV/OCN prepared in example 2 of the present invention has the best photocatalytic degradation effect on tetracycline after 60min of photocatalytic treatment, and the tetracycline removal rate is as high as 96.2%, which is greatly improved compared with 62.9% for BWO-OV and 30.2% for OCN. The removal rate of 5BWO-OV/OCN to tetracycline is 68.9%, although only a little OCN is compounded, the removal rate of the tetracycline is still better than that of monomer BWO-OV; the tetracycline removal rate of 0.33BWO-OV/OCN is 30.6%, although only a little BWO-OV is compounded, the tetracycline removal rate is also better than that of monomer OCN. The different proportions of BWO-OV and OCN in the composite photocatalytic materials in FIG. 6 indicate that the degradation effect of the composite photocatalytic materials on tetracycline is different, and the difference of the degradation effect on tetracycline indicates that one monomer material can cover or cover the active sites on the surface if the monomer material is too much or too little, so that the quantity of photo-generated electrons is reduced, the photocatalytic activity of the material is influenced, the content of any monomer is too much or too little, which is not beneficial to the improvement of the material performance, and the excessive monomer material can even cause negative effects. In the content range limited by the invention, the graphite type carbon nitride composite photocatalytic material with the oxygen vacancy bismuth tungstate/oxygen-enriched structure can achieve better degradation effect on tetracycline by 1BWO-OV/OCN, 2BWO-OV/OCN, 3BWO-OV/OCN, 4BWO-OV/OCN and 5 BWO-OV/OCN.
The degradation rate is shown in FIG. 7, the 4BWO-OV/OCN prepared in the embodiment 1 of the invention has the fastest photocatalytic degradation rate to tetracycline, and the rate reaches 0.04747min-1The graphite type carbon nitride composite photocatalytic material with the oxygen vacancy bismuth tungstate/oxygen-enriched structure can rapidly degrade tetracycline in water, and the degradation rate of the graphite type carbon nitride composite photocatalytic material with the oxygen vacancy bismuth tungstate/oxygen-enriched structure to the tetracycline is 0.01656min respectively-1、0.02969min-1、0.03577min-1、0.01391min-1Obviously higher than 0.01119min of oxygen vacancy-containing bismuth tungstate-1And graphite type carbon nitride with oxygen-enriched structure for 0.00218min-1. Therefore, the graphite type carbon nitride composite photocatalytic material with the oxygen vacancy bismuth tungstate/oxygen-enriched structure can realize the rapid degradation of tetracycline in water by 1BWO-OV/OCN, 2BWO-OV/OCN, 3BWO-OV/OCN, 4BWO-OV/OCN and 5 BWO-OV/OCN.
Example 7
The degradation efficiency of the graphite type carbon nitride composite photocatalytic material containing oxygen vacancy bismuth tungstate/oxygen-enriched structure to tetracycline in different water bodies is investigated.
According to the mass ratio of the graphite type carbon nitride composite photocatalytic material with the oxygen vacancy bismuth tungstate/oxygen-enriched structure to tetracycline in a tetracycline solution being 20: 1, 4 parts of 4BWO-OV/OCN prepared in example 2 are respectively added into four solutions of pure water DW, tap water TW, lake water LW and river RW of which the initial concentrations are 10mg/L, stirred for 60min under a dark condition, after adsorption balance is achieved, photocatalytic treatment is carried out for 60min under the stirring condition with the rotating speed of 800r/min and the illumination condition with the wavelength of 300 nm-800 nm, samples are respectively taken for measuring the tetracycline concentration when the photocatalytic treatment is carried out for 0min, 15min, 30min, 45min and 60min, solid-liquid separation is carried out after reaction is completed, and the composite photocatalytic material is recovered.
The results are shown in fig. 8, and the removal rates of tetracycline in pure water DW, tap water TW, lake water LW and river water RW by 4BWO-OV/OCN prepared in example 2 of the present invention are 96.2%, 85.8%, 78.5% and 84.8%, respectively, which indicates that the graphite type carbon nitride composite photocatalytic material containing oxygen vacancy bismuth tungstate/oxygen-rich structure of the present invention exhibits high photocatalytic performance for tetracycline in different water environments, and thus, the graphite type carbon nitride composite photocatalytic material containing oxygen vacancy bismuth tungstate/oxygen-rich structure of the present invention can be widely used for processing tetracycline in different water environments, and has good practical application prospects in the field of photocatalysis.
Example 8
The anti-interference situation of the graphite type carbon nitride composite photocatalytic material with the oxygen vacancy bismuth tungstate/oxygen-enriched structure on common acid radical ions in wastewater during the photocatalytic degradation of tetracycline is investigated.
According to the mass ratio of the graphite type carbon nitride composite photocatalytic material with the oxygen vacancy bismuth tungstate/oxygen-enriched structure to the tetracycline in the tetracycline solution of 20: 1, 3 parts of 4BWO-OV/OCN prepared in example 2 are respectively added into the solution containing PO4 3-、SO4 2-、Cl-、NO3 -In the tetracycline solution, the concentration of the tetracycline is 10mg/L, the tetracycline is firstly stirred for 60min under the dark condition, after the adsorption balance is achieved, the photocatalytic treatment is carried out for 60min under the stirring condition with the rotating speed of 800r/min and the illumination condition with the wavelength of 300 nm-800 nm, samples are respectively taken for measuring the concentration of the tetracycline when the photocatalytic treatment is carried out for 0min, 15min, 30min, 45min and 60min, the solid-liquid separation is carried out after the reaction is finished, and the composite photocatalytic material is recovered。
The results are shown in FIG. 9, in which PO was added to 4BWO-OV/OCN obtained in example 2 of the present invention4 3-、SO4 2-、Cl-、NO3 -The removal rates of tetracycline in the water body are respectively 74.0%, 85.5%, 86.7% and 92.8%, and the high-efficiency photocatalytic performance is shown, so that the composite photocatalytic material disclosed by the invention is strong in anti-interference capability, and the composite photocatalytic material disclosed by the invention is proved to have good practical application prospects.
In conclusion, the application of the graphite type carbon nitride composite photocatalytic material with the oxygen vacancy bismuth tungstate/oxygen enrichment structure in photocatalytic degradation of antibiotic wastewater has the advantages of simple operation steps, short period, easiness in separation and reuse, high degradation efficiency, good anti-interference capability and the like, can effectively remove antibiotics (such as tetracycline) in different water bodies under illumination with wider wavelength, and has good practical application prospect.
The foregoing is merely a preferred embodiment of the invention and is not intended to limit the invention in any manner. Although the present invention has been described with reference to the preferred embodiments, it is not intended to be limited thereto. Those skilled in the art can make many possible variations and modifications to the disclosed embodiments, or equivalent modifications, without departing from the spirit and scope of the invention, using the methods and techniques disclosed above. Therefore, any simple modification, equivalent replacement, equivalent change and modification made to the above embodiments according to the technical essence of the present invention are still within the scope of the protection of the technical solution of the present invention.
Claims (7)
1. A preparation method of a graphite type carbon nitride composite photocatalytic material with an oxygen vacancy bismuth tungstate/oxygen-enriched structure is characterized by comprising the following steps:
s1, uniformly mixing dicyandiamide and ammonium tungstate, and calcining at 450-550 ℃ for 3-6 h to obtain graphite type carbon nitride with an oxygen-enriched structure;
s2, mixing sodium tungstate dihydrate with octadecyl trimethyl ammonium chloride, dissolving in water, adding bismuth nitrate pentahydrate under stirring, and continuously stirring to obtain a mixed solution containing sodium tungstate and bismuth nitrate;
s3, mixing the mixed solution obtained in the step S2 with the graphite type carbon nitride with the oxygen-rich structure obtained in the step S1, stirring and performing ultrasonic treatment to obtain a precursor mixed solution; carrying out hydrothermal reaction on the precursor mixed solution at the temperature of 140-160 ℃ for 20-24 h, filtering and drying to obtain a graphite type carbon nitride composite photocatalytic material with an oxygen vacancy bismuth tungstate/oxygen-enriched structure, wherein the composite photocatalytic material is formed by compounding oxygen vacancy bismuth tungstate and graphite type carbon nitride with an oxygen-enriched structure, and the composite photocatalytic material is in a three-dimensional structure;
the mass ratio of the graphite type carbon nitride with the oxygen-enriched structure adopted in the step S3 to the sodium tungstate dihydrate and the bismuth nitrate pentahydrate in the step S2 is 0.38-1.9: 0.98-1.02: 2.42-2.44, and the mass ratio of the sodium tungstate dihydrate to the octadecyl trimethyl ammonium chloride is 22-27: 1.
2. The preparation method of the graphite type carbon nitride composite photocatalytic material containing the oxygen vacancy bismuth tungstate/oxygen-rich structure as claimed in claim 1, wherein in the step S1, the molar ratio of dicyandiamide to ammonium tungstate is 95-105: 1.
3. The method for preparing the graphite type carbon nitride composite photocatalytic material containing the oxygen vacancy bismuth tungstate/oxygen-rich structure as claimed in claim 1, wherein in the step S3, the precursor mixed solution undergoes a hydrothermal reaction at 140 ℃ for 24 hours.
4. The method for preparing the graphite type carbon nitride composite photocatalytic material containing the oxygen vacancy bismuth tungstate/the oxygen-rich structure according to any one of claims 1 to 3, wherein in the step S2, the dissolving is performed by stirring for 0 to 60min at a rotation speed of 400 to 1200 r/min; the rotating speed of the continuous stirring is 400 r/min-1200 r/min, and the time of the continuous stirring is 60 min-180 min.
5. The method for preparing the graphite type carbon nitride composite photocatalytic material containing the oxygen vacancy bismuth tungstate/oxygen enrichment structure as claimed in any one of claims 1 to 3, wherein in the step S3, the rotation speed of stirring is 400r/min to 1200r/min, the stirring time is 60min to 180min, and the ultrasonic time is 5min to 30 min.
6. An application of the graphite type carbon nitride composite photocatalytic material containing oxygen vacancy bismuth tungstate/oxygen-rich structure prepared by the preparation method of any one of claims 1-5 in photocatalytic degradation of antibiotic wastewater.
7. Use according to claim 6, characterized in that it comprises the following steps: mixing the graphite type carbon nitride composite photocatalytic material with the oxygen vacancy bismuth tungstate/oxygen-enriched structure with antibiotic wastewater, performing dark treatment, and performing photocatalytic treatment under the illumination condition; the antibiotic in the antibiotic wastewater is tetracycline, the concentration of the tetracycline is 5 mg/L-30 mg/L, the mass ratio of the composite photocatalytic material to the tetracycline is 5-40: 1, the dark treatment is stirring for 20 min-60 min under the dark condition, and the photocatalytic treatment is specifically stirring for 30 min-120 min under the illumination condition with the wavelength of 300 nm-800 nm and the rotating speed of 300 r/min-1000 r/min.
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