CN111167464B - Preparation of double Z-type V based on in-situ synthesis method2O5/FeVO4/Fe2O3Method for preparing photocatalyst and its application - Google Patents
Preparation of double Z-type V based on in-situ synthesis method2O5/FeVO4/Fe2O3Method for preparing photocatalyst and its application Download PDFInfo
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- CN111167464B CN111167464B CN202010093073.5A CN202010093073A CN111167464B CN 111167464 B CN111167464 B CN 111167464B CN 202010093073 A CN202010093073 A CN 202010093073A CN 111167464 B CN111167464 B CN 111167464B
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- 238000011065 in-situ storage Methods 0.000 title claims abstract description 9
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- GNTDGMZSJNCJKK-UHFFFAOYSA-N Vanadium(V) oxide Inorganic materials O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims abstract description 86
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 86
- 238000001354 calcination Methods 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
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- 229960001180 norfloxacin Drugs 0.000 claims description 46
- OGJPXUAPXNRGGI-UHFFFAOYSA-N norfloxacin Chemical compound C1=C2N(CC)C=C(C(O)=O)C(=O)C2=CC(F)=C1N1CCNCC1 OGJPXUAPXNRGGI-UHFFFAOYSA-N 0.000 claims description 40
- 239000000243 solution Substances 0.000 claims description 24
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- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 2
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
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- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical class [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 2
- 229910003145 α-Fe2O3 Inorganic materials 0.000 description 2
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- 102000004169 proteins and genes Human genes 0.000 description 1
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- FDDDEECHVMSUSB-UHFFFAOYSA-N sulfanilamide Chemical compound NC1=CC=C(S(N)(=O)=O)C=C1 FDDDEECHVMSUSB-UHFFFAOYSA-N 0.000 description 1
- 150000003456 sulfonamides Chemical class 0.000 description 1
- 239000011206 ternary composite Substances 0.000 description 1
- 229960002180 tetracycline Drugs 0.000 description 1
- 229930101283 tetracycline Natural products 0.000 description 1
- 229940040944 tetracyclines Drugs 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
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- 150000003952 β-lactams Chemical class 0.000 description 1
- 229910006297 γ-Fe2O3 Inorganic materials 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
- 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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- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/847—Vanadium, niobium or tantalum or polonium
- B01J23/8472—Vanadium
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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
- C02F2101/38—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
- C02F2305/10—Photocatalysts
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Abstract
The invention relates to a method for preparing double Z-type V based on an in-situ synthesis method2O5/FeVO4/Fe2O3A method of photocatalyst and its application. Will V2O5Suspension and Fe2O3Fully stirring and uniformly mixing the suspension; then placing the mixture in a microwave hydrothermal synthesizer, treating the mixture for 30 minutes at the temperature of 150 ℃ under the pressure of 4.0MPa, centrifuging and drying the obtained product, grinding the product, and calcining the product for 1 to 4 hours at the temperature of 500-700 ℃ to obtain a target product V2O5/FeVO4/Fe2O3. Invention pair V2O5And Fe2O3The two materials are compounded in situ to generate FeVO4Constructed double Z-type photocatalyst V2O5/FeVO4/Fe2O3And organic pollutants in water can be efficiently degraded in a photocatalytic manner under the action of visible light.
Description
Technical Field
The invention belongs to the field of photocatalysts, and particularly relates to a method for preparing double Z-shaped V by adopting a microwave hydrothermal method and an in-situ synthesis method2O5/FeVO4/Fe2O3A photocatalyst and application thereof in catalyzing and degrading antibiotics in water under sunlight.
Background
Antibiotics (antibiotics) are a class of secondary metabolites with anti-pathogen or other activities generated by microorganisms (including bacteria, molds and other microorganisms) or higher animals and plants in the life process, and are chemical substances with the function of interfering the development of other living cells. Is mainly used for treating bacterial infection caused by micro-pathogens and the like. Common antibiotics can be classified into the following classes according to their structure and mechanism of action: quinolones, tetracyclines, sulfonamides, beta lactams, macrolides, and the like.
Since the discovery of penicillin (also known as penicillin) by a bacteriologist of England alexander Freimine in 1929, various antibiotics have been widely used for the prevention and treatment of human and animal diseases. While benefiting mankind, the problems of abuse of antibiotics, abandonment of waste, random discharge of production wastewater and the like also bring serious pollution to the environment. China is not only a large producing country of antibiotics, but also a super large country in use. According to the relevant data released by Chinese academy of sciences, the daily usage of antibiotics in our country is 5.7 times that in UK and 5.5 times that in USA. In 16.2 ten thousand tons of antibiotics used in 2013 in China, the human use amount reaches 48%, and the veterinary use amount reaches 52%. However, these antibiotics are only partially metabolized in humans and animals, resulting in a large amount of residues being released into the environment in the form of technical substances or metabolites and accumulating constantly. In addition, the pharmaceutical industry waste water is directly discharged without treatment or incompletely discharged after treatment, and the expired antibiotics are directly discarded, so that the environment is polluted. Due to the lack of biodegradability of antibiotics, the removal of antibiotics in sewage treatment plants is mainly achieved by bioadsorption rather than biodegradation. This results in the inability of a significant portion of the antibiotics to be effectively removed prior to discharge of the wastewater, inevitably leading to natural water. These antibiotics, which are released into the environment, require a long enough half-life to be degraded, which inevitably leads to the development of resistance in humans if ingested through the food chain for a long period of time. The simultaneous existence of multiple antibiotics with different concentrations in the environment can also accelerate the appearance of super microorganisms with extremely strong drug resistance genes and drug resistance, and the drug resistance genes can be transferred to human again through multiple ways, thereby causing serious threat to the health and the ecological system balance of human. Compared with other types of wastewater, the antibiotic wastewater has the characteristics of high toxicity, complex components, high organic matter concentration, poor biodegradability and the like, and has higher treatment difficulty. Therefore, an effective method for treating the antibiotic wastewater is necessary to be found, and the advanced oxidation method has wide application prospect in the field of antibiotic wastewater treatment.
Vanadium pentoxide (V)2O5) Is an n-type semiconductor with a narrow forbidden band width. Due to the orthogonal layered structure, the material has highly anisotropic electrical and optical properties, has strong absorption capacity on visible light, and can store a large amount of ions. In addition, V2O5The chemical property is relatively stable, and the characteristics of unique optical property, catalytic performance and the like have attracted wide attention of people. In recent years, the relevant photocatalysts have been widely used for degradation of organic pollutants in the environment.
Among the metal vanadates, iron vanadate (FeVO)4) The compound is an n-type semiconductor, is yellow solid powder in a normal state, is a multifunctional compound, has photocatalytic reaction performance when being used as a semiconductor material, and can be used for photodegradation of organic pollutants. Three-oblique phase FeVO4The catalyst can exist stably at normal temperature and normal pressure, has a forbidden band width of about 2.06-2.7 eV, is a highly stable and highly selective catalyst, and has good visible light absorption capacity. Has wide application in degrading organic pollutant with photocatalysis.
Iron (Fe) oxide2O3) Has the characteristics of high temperature resistance, alkali resistance, low cost, no toxicity and the like, and is widely applied to the aspects of industrial production, organic pollutant degradation and the like. Fe2O3Has three structures:α-Fe2O3，β-Fe2O3，γ-Fe2O3among them, the most common is α -Fe2O3。α-Fe2O3Belongs to a hexagonal system, is a semiconductor material, has strong absorption capacity in a visible light region, can absorb more than 40 percent of energy in sunlight, and is a photocatalyst with extremely potential application value.
Disclosure of Invention
The invention aims to synthesize FeVO in situ4And V and2O5and Fe2O3The ternary composite photocatalytic system is directly formed, the photoresponse range of the semiconductor photocatalyst is widened, the recombination rate of electrons and holes is reduced, and sunlight is fully utilized, so that the photocatalytic capacity of the semiconductor material is improved. The invention provides a composite double Z-shaped photocatalyst capable of responding sunlight more efficiently by compounding three semiconductor photocatalysts capable of responding to different wavelength ranges.
Another object of the present invention is to utilize a composite double Z-type photocatalyst V2O5/FeVO4/Fe2O3Catalyzing and degrading antibiotics in water.
The technical scheme adopted by the invention is as follows: preparation of double Z-type V based on in-situ synthesis method2O5/FeVO4/Fe2O3A method of photocatalyst comprising the steps of: get V2O5And Fe2O3Dispersing in deionized water, and adding V2O5Suspension and Fe2O3Fully stirring the suspension, uniformly mixing, placing in a microwave hydrothermal synthesizer, treating for 30 minutes at the temperature of 150 ℃ under the pressure of 4.0MPa, centrifuging and drying the obtained product, grinding, and calcining for 1-4 hours at the temperature of 700 ℃ to obtain a target product V2O5/FeVO4/Fe2O3。
Further, the above method, in terms of particle number ratio, V2O5:Fe2O3＝(4-6):1。
Further, the method as described above, said V2O5The preparation method comprises the following steps: dissolving ammonium metavanadate in deionized water, adding sulfuric acid, adjusting the pH value of the solution to 2.0, transferring the obtained mixed solution into a polytetrafluoroethylene-lined stainless steel autoclave, preserving the temperature for 30min at 150 ℃ under 4.0MPa, naturally cooling to room temperature, washing with deionized water, centrifuging, drying, and calcining for 2h at 500 ℃ to obtain V2O5And (3) nanoparticles.
Further, the above method, the Fe2O3The preparation method comprises the following steps: dissolving ferric trichloride hexahydrate and urea in deionized water, transferring the obtained mixed solution into a stainless steel autoclave with a polytetrafluoroethylene lining, preserving the temperature at 180 ℃ for 30min under 4.0MPa, naturally cooling to room temperature, washing with deionized water, filtering, centrifuging, drying, and calcining at 500 ℃ for 2h to obtain Fe2O3And (3) nanoparticles.
Double Z type V prepared by the method2O5/FeVO4/Fe2O3Application of the photocatalyst in degrading antibiotics under visible light.
Further, the method is as follows: adding the above-mentioned double Z-type V into solution containing antibiotic2O5/FeVO4/Fe2O3And (3) irradiating the photocatalyst for 2-4h under the sunlight.
Further, in the solution containing the antibiotic, the initial concentration of the antibiotic is adjusted to 2.5-20 mg/L.
Further, double Z-shaped V2O5/FeVO4/Fe2O3The addition amount of the photocatalyst is 0.5-2.0 g/L.
Further, the antibiotic is norfloxacin.
The invention has the beneficial effects that: the invention aims to efficiently utilize sunlight by using two photocatalysts V with different photoresponse ranges2O5And Fe2O3Compounding and generating a third photocatalyst FeVO in situ4The symmetrical double-Z-shaped structure is directly and efficiently formed, and the generation of effective sites of the Z-shaped photocatalyst is improved. And broadens the photoresponse range of the photocatalytic system and reducesElectron (e)-) And a cavity (h)+) The photocatalytic activity is improved.
Drawings
FIG. 1 is V2O5X-ray diffraction pattern of (a).
FIG. 2 is FeVO4X-ray diffraction pattern of (a).
FIG. 3 is Fe2O3X-ray diffraction pattern of (a).
FIG. 4 is V2O5/FeVO4X-ray diffraction pattern of (a).
FIG. 5 is Fe2O3/FeVO4X-ray diffraction pattern of (a).
FIG. 6 is V2O5/FeVO4/Fe2O3X-ray diffraction pattern of (a).
FIG. 7 is V2O5/FeVO4/Fe2O3Scanning electron microscopy of (a).
FIG. 8a is V2O5、FeVO4、Fe2O3And V2O5/FeVO4/Fe2O3Ultraviolet-visible diffuse reflection absorption spectrogram.
FIG. 8b is V2O5、FeVO4And Fe2O3Effective band gap energy map of (1).
Figure 9 is a graph of the ultraviolet absorption of norfloxacin solution.
Detailed Description
Example 1
Double Z-shape V2O5/FeVO4/Fe2O3The preparation method of the photocatalyst comprises the following steps:
1) synthesis of V by microwave hydrothermal method2O5Nano-particles: 11.619g of NH4VO3Dissolved in 100mL of deionized water and stirred for 2 hours to obtain a light yellow solution. Dilute sulfuric acid (H) is added2SO4/H2O1: 4v/v), adjusting the pH of the solution to 2.0, transferring the obtained mixed solution into a stainless steel autoclave with a polytetrafluoroethylene lining, preserving the temperature at 150 ℃ for 30min under 4.0MPa, and naturally cooling to room temperature. Is removed fromRepeatedly washing with water, centrifuging, drying at 80 deg.C for 24 hr, calcining at 500 deg.C for 2 hr to obtain V2O5And (3) nanoparticles.
2) Synthesis of Fe by microwave hydrothermal method2O3Nano-particles: FeCl is added3·6H2O (6.75g, 2.5mmol) and urea (30g, 0.05mol) were dissolved in 100mL of deionized water to give a yellow solution. Transferring the obtained yellow solution into a polytetrafluoroethylene-lined stainless steel autoclave, preserving heat for 30min at 180 ℃ under 4.0MPa, naturally cooling to room temperature, washing with deionized water, filtering, centrifugally collecting red precipitate, drying at 80 ℃ for 24h, and calcining at 500 ℃ for 2h to obtain Fe2O3And (3) nanoparticles.
3) Will V2O5And Fe2O3The powder is respectively dissolved in 100mL deionized water according to the particle number ratio of (4:1), (5:1) and (6:1), then the mixture is fully stirred and uniformly mixed, and then the mixture is placed in a microwave hydrothermal synthesizer and treated for 30 minutes at the temperature of 150 ℃ under the pressure of 4.0 MPa. The obtained products are respectively centrifuged, dried and fully ground to respectively obtain samples V with different particle number ratios2O5/FeVO4。
3.1) sample V obtained by mixing particles in the ratio of (4:1), (5:1) and (6:1)2O5/FeVO4Calcining in 600 deg.C muffle furnace for 2 hr, naturally cooling, grinding again to obtain double Z-type V particles with different particle number ratios2O5/FeVO4/Fe2O3Photocatalysts, and respectively designated V2O5/FeVO4/Fe2O3(4:1,600-2)、 V2O5/FeVO4/Fe2O3(5:1,600-2)、V2O5/FeVO4/Fe2O3(6:1,600-2)。
3.2) sample V obtained with a particle number ratio of 5:12O5:Fe2O3Calcining in muffle furnace at 500 deg.C, 600 deg.C and 700 deg.C for 2 hr, naturally cooling, grinding again to obtain double Z-type V with different calcining temperatures2O5/FeVO4/Fe2O3Photocatalysts, and respectively designated V2O5/FeVO4/Fe2O3(5:1,500-2)、V2O5/FeVO4/Fe2O3(5:1,600-2)、 V2O5/FeVO4/Fe2O3(5:1,700-2)。
3.3) sample V obtained with a particle number ratio of 5:12O5:Fe2O3Calcining in 600 deg.C muffle furnace for 1 hr, 3 hr, and 4 hr, naturally cooling, grinding again to obtain double Z-shaped V with different calcining time2O5/FeVO4/Fe2O3Photocatalysts, and respectively designated V2O5/FeVO4/Fe2O3(5:1,600-1)、V2O5/FeVO4/Fe2O3(5:1,600-3)、 V2O5/FeVO4/Fe2O3(5:1,600-4)。
(II) comparative example
Synthesis of FeVO by microwave hydrothermal method4Nano-particles: 9.6960g of Fe (NO)3)3·9H2O into 100mL of deionized water, 2.7886g of NH4VO3Dissolved in 100mL of deionized water. Reacting NH4VO3Dropwise addition of the solution to Fe (NO)3)3In the solution, the solution was stirred until a yellow precipitate appeared, and the resulting reaction system was transferred to a 100mL autoclave lined with tetrafluoroethylene. Sealing the autoclave, keeping the temperature at 180 ℃ for 30min under 4.0MPa, naturally cooling to room temperature, repeatedly cooling with deionized water, collecting precipitate, drying at 80 ℃ for 12h, and calcining at 600 ℃ for 2h to obtain FeVO4And (3) nanoparticles.
(III) characterization of the catalyst
As shown in FIG. 1, V2O5The characteristic peak of the protein is consistent with that of a standard card (JCPDS 75-0547, JCPDS 89-0612). The results show that V was successfully prepared2O5。
In FIG. 2, FeVO prepared by microwave hydrothermal method4Can be matched with the characteristic peak of a standard card (JCPDS 14-0688, JCPDS 89-0618)Inosculating, thus synthesized, FeVO4No impurities.
FIG. 3 is Fe2O3XRD pattern of (1), Fe2O3The characteristic peaks of (a) are in one-to-one correspondence with a standard card (PDF # 33-0664). The results show that Fe was successfully produced2O3。
FIG. 4 is V2O5/FeVO4XRD pattern of (1), V2O5And FeVO4All the characteristic peaks are shown on the graph, and the result shows that V is successfully prepared2O5/FeVO4。
FIG. 5 is Fe2O3/FeVO4XRD pattern of (1), Fe2O3And FeVO4The characteristic peaks are also shown on the graph, and the result shows that Fe is successfully prepared2O3/FeVO4。
FIG. 6 shows a double Z-shaped V2O5/FeVO4/Fe2O3XRD pattern of photocatalyst, from which V can be found2O5、FeVO4And Fe2O3The characteristic peak position of the compound has no obvious movement, which indicates that the structures of the compound, the compound and the compound are not changed, and also indicates that V is successfully prepared2O5/FeVO4/Fe2O3And (3) compounding a catalyst.
FIG. 7 is V2O5/FeVO4/Fe2O3Scanning electron microscopy of (a). As can be seen in the figure, the V is in the form of a block2O5And Fe of cubic rhombus shape2O3FeVO with spherule in between4The test result shows that V2O5And Fe2O3Effectively compound and generate FeVO4This indicates a double Z form V2O5/FeVO4/Fe2O3The composite catalyst was successfully prepared. In addition, it can be seen from the images that their crystal sizes are dispersed between about 100-500 nm.
FIG. 8a is V2O5、FeVO4、Fe2O3And V2O5/FeVO4/Fe2O3Ultraviolet-visible diffuse reflection absorption spectrogram. V prepared as shown in FIG. 8a2O5/FeVO4/Fe2O3The nanoparticles have an absorption wavelength at 550-700 nm.
FIG. 8b is V2O5、FeVO4And Fe2O3Effective band gap energy map of (1). V was obtained by calculation based on the ultraviolet-visible diffuse reflectance absorption spectrum as shown in FIG. 8b2O5、FeVO4And Fe2O3Respectively at 2.1eV, 2.16eV and 1.95 eV.
Fig. 9 is a uv-vis spectrum of a solution of Norfloxacin (NFX) degraded under different conditions under visible light irradiation. As can be seen, all three catalysts have a degrading effect on NFX, wherein, under the irradiation of visible light, double Z-type V2O5/FeVO4/Fe2O3The catalyst has the most obvious effect on the degradation of NFX solution.
EXAMPLE 2 Effect of catalyst on degradation of norfloxacin
Influence of catalyst calcination time on norfloxacin degradation rate
Visible light photocatalytic degradation: 30mL of norfloxacin solution with an initial concentration of 10.0mg/L were measured in a quartz tube, and the double Z form V prepared in example 1 was added for different calcination times2O5/FeVO4/Fe2O330mg of photocatalyst, irradiating for 4h under visible light, centrifuging, filtering, and measuring the ultraviolet absorbance of the supernatant in the wavelength range of 200-800 nm. And taking the absorbance value at 274.9nm, substituting the absorbance value into a standard curve formula, and calculating the response concentration so as to calculate the degradation rate of norfloxacin. The results are shown in Table 1.
Percent degradation rate (%) (1-C/C)0) X 100% (wherein C)0: the concentration of the stock solution; c: concentration of sample).
TABLE 1 Effect of calcination time on the photodegradation of antibiotic-norfloxacin
As can be seen from Table 1, the bis Z form V was obtained under the condition that the solid phase calcination time was 2 hours2O5/FeVO4/Fe2O3The degradation rate of the photocatalyst is high and reaches 70.01 percent.
Influence of (II) catalyst calcination temperature on norfloxacin degradation rate
Visible light photocatalytic degradation: 30mL of norfloxacin solution with initial concentration of 10.0mg/L was measured in a quartz tube, and the double Z form V prepared in example 1 with different calcination temperatures was added2O5/FeVO4/Fe2O330mg of photocatalyst, irradiating for 4h under visible light, centrifuging, filtering, and measuring the ultraviolet absorbance of the supernatant in the wavelength range of 200-800 nm. And taking the absorbance value at 274.9nm, substituting the absorbance value into a standard curve formula, and calculating the response concentration so as to calculate the degradation rate of norfloxacin. The results are shown in Table 2.
Percent degradation rate (%) (1-C/C)0) X 100% (wherein C)0: the concentration of the stock solution; c: concentration of sample).
TABLE 2 influence of the calcination temperature of the solid phase on the photodegradation of the antibiotic norfloxacin
As can be seen from Table 2, the bis Z form V was obtained at a calcination temperature of 600 deg.C2O5/FeVO4/Fe2O3The degradation rate of the photocatalyst is high and reaches 70.01 percent.
Influence of different particle number ratios of (III) catalyst on degradation rate of norfloxacin
Visible light photocatalytic degradation: 30mL of norfloxacin solution with initial concentration of 10.0mg/L was measured in a quartz tube, and the double Z form V prepared in example 1 with different particle number ratios was added2O5/FeVO4/Fe2O330mg of photocatalyst, irradiating for 4h under visible light, centrifuging, filtering, and measuring the ultraviolet absorbance of the supernatant in the wavelength range of 200-800 nm. Take 274.9nAnd substituting the absorbance value at the position m into a standard curve formula, and calculating the response concentration so as to calculate the degradation rate of the norfloxacin. The results are shown in Table 3.
Percent degradation rate (%) (1-C/C)0) X 100% (wherein C)0: the concentration of the stock solution; c: concentration of sample).
TABLE 3 Effect of different particle number ratios on the photodegradation of antibiotic-norfloxacin
As can be seen from Table 3, the double Z form V was obtained at a particle number ratio of 6:12O5/FeVO4/Fe2O3The degradation rate of the photocatalyst is high and reaches 70.81%.
Influence of (IV) different catalysts on norfloxacin degradation rate
Visible light photocatalytic degradation: 30mL of norfloxacin solution with the initial concentration of 10.0mg/L is measured in a quartz tube, different photocatalysts 30mg are added as shown in Table 4, the mixture is irradiated for 4 hours under visible light, centrifuged and filtered, and the ultraviolet absorbance of the supernatant is measured within the wavelength range of 200-800 nm. And taking the absorbance value at 274.9nm, substituting the absorbance value into a standard curve formula, and calculating the response concentration so as to calculate the degradation rate of norfloxacin. The results are shown in Table 4.
Percent degradation rate (%) (1-C/C)0) X 100% (wherein C)0: the concentration of the stock solution; c: concentration of sample).
TABLE 4 Effect of different catalysts on the photodegradation of antibiotic-norfloxacin
As can be seen from Table 4, V in the use of the present invention2O5/FeVO4/Fe2O3Under the condition of the photocatalyst, the degradation rate of pollutants is high and reaches 70.01 percent.
(V) influence of degradation time on norfloxacin degradation rate
Visible light photocatalytic degradation: 30mL of norfloxacin solution with initial concentration of 10.0mg/L is measured in a quartz tube, and V is added2O5/FeVO4/Fe2O3(5:1,600-2)30mg, irradiating for different times under visible light, centrifuging, filtering, and measuring the ultraviolet absorbance of the supernatant in the wavelength range of 200-800 nm. And taking the absorbance value at 274.9nm, substituting the absorbance value into a standard curve formula, and calculating the response concentration so as to calculate the degradation rate of norfloxacin. The results are shown in Table 5.
Percent degradation rate (%) (1-C/C)0) X 100% (wherein C)0: the concentration of the stock solution; c: concentration of sample).
TABLE 5 Effect of different irradiation times on the photodegradation of antibiotic-norfloxacin
As can be seen from table 5, the degradation rate increased with increasing irradiation time. When irradiated for 240min, the degradation rate reached a maximum of 73.02%. The degradation rate remained essentially unchanged as the irradiation time continued to increase. In comparison, norfloxacin degrades at the fastest rate over the 0-90min range.
(VI) influence of different adding amounts of catalyst on degradation rate of norfloxacin
Visible light photocatalytic degradation: 30mL of norfloxacin solution with initial concentration of 10.0mg/L is measured in a quartz tube, and different doses of V are added2O5/FeVO4/Fe2O3(5:1,600-2) the catalyst, irradiating for 3h under visible light, centrifuging, filtering, and measuring the ultraviolet absorbance of the supernatant in the wavelength range of 200-800 nm. Get274.9nm, substituting the absorbance value into a standard curve formula, calculating the response concentration, and further calculating the degradation rate of norfloxacin, wherein the results are shown in Table 6.
Percent degradation rate (%) (1-C/C)0) X 100% (wherein C)0: the concentration of the stock solution; c: concentration of sample).
TABLE 6 Effect of different dosages on the photodegradation of antibiotic-norfloxacin
As can be seen from Table 6, the degradation rate increased with increasing catalyst addition. When the catalyst addition is 2.0g/L, V2O5/FeVO4/Fe2O3The degradation rate in the system is 74.39%.
(VII) influence of different initial concentrations on degradation rate of norfloxacin
Visible light photocatalytic degradation: 30mL of norfloxacin solutions with different initial concentrations are measured in a quartz tube, and V is added2O5/FeVO4/Fe2O3(5:1,600-2)30mg of catalyst, irradiating for 3h under visible light, centrifuging, filtering, and measuring the ultraviolet absorbance of the supernatant in the wavelength range of 200-800 nm. The absorbance value at 274.9nm was taken and substituted into the standard curve formula to calculate the response concentration and further the degradation rate of norfloxacin, the results are shown in table 7.
Percent degradation rate (%) (1-C/C)0) X 100% (wherein C)0: the concentration of the stock solution; c: concentration of sample).
TABLE 7 Effect of different initial concentrations on the photodegradation of antibiotic-norfloxacin
Watch with watch7 it can be seen that the degradation rate increases with decreasing initial norfloxacin concentration. When the initial concentration of norfloxacin is 2.5 g/L, V2O5/FeVO4/Fe2O3The degradation rate in the system is 91.78%.
(VIII) Effect of changing catalyst use times on degradation rate of norfloxacin
Visible light photocatalytic degradation: 30mL of 10.0mg/L norfloxacin solution was weighed into a quartz tube, and V was added2O5/FeVO4/Fe2O3(5:1,600-2)30mg of catalyst, irradiating for 3h under visible light, centrifuging, filtering, and measuring the ultraviolet absorbance of the supernatant in the wavelength range of 200-800 nm. The absorbance value at 274.9nm was taken and substituted into the standard curve formula to calculate the response concentration and further the degradation rate of norfloxacin, the results are shown in table 8.
Percent degradation rate (%) (1-C/C)0) X 100% (wherein C)0: the concentration of the stock solution; c: concentration of sample).
TABLE 8 Effect of the number of uses on the photodegradation of the antibiotic norfloxacin
As can be seen from Table 8, the degradation rate of norfloxacin was more stable. This means that V is measured in five consecutive cycles2O5/FeVO4/Fe2O3The photocatalytic system exhibits excellent photodegradation activity. Therefore, when the pollutants in water are removed, the catalyst can be reused for 5 times, and the catalytic system still has good stability.
In the above examples, norfloxacin was used as the antibiotic, but norfloxacin is not a limitation to the antibiotic degraded by the present invention, and the method of the present invention is suitable for degrading any antibiotic, such as tetracycline, sulfanilamide, etc.
Claims (8)
1. Preparation of double Z-type V based on in-situ synthesis method2O5/FeVO4/Fe2O3Method for preparing photocatalystThe method is characterized by comprising the following steps: get V2O5And Fe2O3Dispersing in deionized water, and adding V2O5Suspension and Fe2O3Fully stirring the suspension, uniformly mixing, placing in a microwave hydrothermal synthesizer, treating for 30 minutes at the temperature of 150 ℃ under the pressure of 4.0MPa, centrifuging and drying the obtained product, grinding, and calcining for 1-4 hours at the temperature of 700 ℃ to obtain a target product V2O5/FeVO4/Fe2O3(ii) a In terms of the number ratio of particles, V2O5:Fe2O3=（4-6）: 1。
2. The method of claim 1, wherein V is2O5The preparation method comprises the following steps: dissolving ammonium metavanadate in deionized water, adding sulfuric acid, adjusting the pH value of the solution to 2.0, transferring the obtained mixed solution into a polytetrafluoroethylene-lined stainless steel autoclave, preserving the temperature for 30min at 150 ℃ under 4.0MPa, naturally cooling to room temperature, washing with deionized water, centrifuging, drying, and calcining for 2h at 500 ℃ to obtain V2O5And (3) nanoparticles.
3. The method of claim 1, wherein the Fe2O3The preparation method comprises the following steps: dissolving ferric trichloride hexahydrate and urea in deionized water, transferring the obtained mixed solution into a stainless steel autoclave with a polytetrafluoroethylene lining, preserving the temperature at 180 ℃ for 30min under 4.0MPa, naturally cooling to room temperature, washing with deionized water, filtering, centrifuging, drying, and calcining at 500 ℃ for 2h to obtain Fe2O3And (3) nanoparticles.
4. Bis Z form V prepared according to the process of claim 1 or 2 or 32O5/FeVO4/Fe2O3Application of the photocatalyst in degrading antibiotics under visible light.
5. The use according to claim 4,the method comprises the following steps: adding double Z type V into solution containing antibiotics2O5/FeVO4/Fe2O3And (3) irradiating the photocatalyst for 2-4h under the sunlight.
6. Use according to claim 5, characterized in that in the solution containing the antibiotic, the initial concentration of the antibiotic is adjusted to be 2.5-20 mg/L.
7. Use according to claim 6, characterised in that the double Z-shaped V is2O5/FeVO4/Fe2O3The addition amount of the photocatalyst is 0.5-2.0 g/L.
8. The use according to any one of claims 5 to 7, wherein the antibiotic is norfloxacin.
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| CN2378113Y (en) * | 1999-05-11 | 2000-05-17 | 中国科学院广州能源研究所 | Photocatalysis air processing device |
| CN1618516A (en) * | 2004-09-28 | 2005-05-25 | 北京联合大学生物化学工程学院 | Composite nano-photo-catalyst used for purifying air |
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