CN115779942B - Modified fern-shaped bismuth vanadate photocatalytic nanomaterial as well as preparation method and application thereof - Google Patents
Modified fern-shaped bismuth vanadate photocatalytic nanomaterial as well as preparation method and application thereof Download PDFInfo
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- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 title claims abstract description 186
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 185
- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 184
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- 229960000583 acetic acid Drugs 0.000 claims description 4
- FBXVOTBTGXARNA-UHFFFAOYSA-N bismuth;trinitrate;pentahydrate Chemical group 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 description 4
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 4
- 239000000356 contaminant Substances 0.000 claims description 4
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- IHIXIJGXTJIKRB-UHFFFAOYSA-N trisodium vanadate Chemical group [Na+].[Na+].[Na+].[O-][V]([O-])([O-])=O IHIXIJGXTJIKRB-UHFFFAOYSA-N 0.000 claims description 4
- HTVITOHKHWFJKO-UHFFFAOYSA-N Bisphenol B Chemical compound C=1C=C(O)C=CC=1C(C)(CC)C1=CC=C(O)C=C1 HTVITOHKHWFJKO-UHFFFAOYSA-N 0.000 claims description 2
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- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 46
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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Abstract
The invention discloses a modified fern-shaped bismuth vanadate photocatalytic nanomaterial and a preparation method and application thereof. The preparation method comprises the following steps: the preparation method comprises the steps of preparing a fern-shaped bismuth vanadate nanomaterial by taking bismuth salt and vanadium salt as raw materials through hydrothermal reaction under the condition that the pH value is 3-4, and calcining the fern-shaped bismuth vanadate nanomaterial in a nitrogen atmosphere at the temperature of more than 350 ℃. The modified fern-shaped bismuth vanadate photocatalytic nanomaterial has the advantages of large specific surface area, multiple active sites, strong light absorption capability, wide light response range, low photogenerated electron-hole recombination rate, good conductivity, high photocatalytic activity, good stability and the like, is a novel bismuth vanadate catalyst which can be widely used and has excellent performance, and can realize rapid and thorough removal of organic pollutants in wastewater when being used for treating the wastewater of the organic pollutants, and has high use value and good application prospect.
Description
Technical Field
The invention belongs to the technical field of materials, relates to a functional nano material for treating environmental pollutants, a preparation method and application thereof, and in particular relates to a modified fern-shaped bismuth vanadate photocatalytic nano material, a preparation method thereof and application thereof in treating organic pollutants in water environment.
Background
Due to the rapid development of industrialization and city, the discharge of a large amount of industrial wastewater and domestic sewage and the use of chemical fertilizers and pesticides, a large amount of organic pollutants are discharged into the environment, most of the organic matters are toxic and easy to be biologically accumulated, and part of the organic matters also have three effects of teratogenesis, carcinogenesis and mutation, thus forming a great threat to human health, land and aquatic organisms. At present, the pollution of water environment has become an important issue for public health, which contains at least 51 toxic organic pollutants. For example, bisphenol A (BPA) is an endocrine disrupter with estradiol-like activity, and low doses can disrupt normal endocrine function, causing adverse effects such as metabolic disorders, precocity, sperm abnormalities, and cancer. The use of bisphenol a containing plastics in large quantities has been reported to result in their substantial exposure to food chains, water and soil, and more seriously, BPA can enter the human body through dietary and non-dietary sources and thus prolonged exposure to BPA contaminated environments can have disastrous consequences. Therefore, the effective removal of bisphenol A and other organic pollutants in the environment is a technical problem which needs to be solved in the current stage.
Photocatalytic technology has been widely used to degrade organic pollutants in water environments, wherein obtaining a catalyst with excellent photocatalytic performance is a key point for effectively degrading organic pollutants. Bismuth vanadate (BiVO) 4 ) As a common semiconductor nano material, the material has proper energy band width (2.4 eV), good photochemical stability and controllable morphology, and can be used as catalystThe chemosing agent is used to degrade organic contaminants, however, existing bivos 4 The material still has the defects of low carrier mobility, short diffusion distance of photo-generated holes, serious carrier recombination and the like, so that the photoelectric conversion efficiency is low, and the expected catalytic effect still cannot be achieved. In addition, the method comprises the following steps. Existing BiVO 4 The following drawbacks still exist for materials: the existing BiVO has the defects of small specific surface area, few active sites, weak light absorption capability, narrow light response range, high photo-generated electron-hole recombination rate, poor photocatalytic activity, poor stability and the like 4 Materials still have difficulty in efficiently removing organic contaminants in aqueous environments. In addition, the existing defect introducing method still has the defects of complex process, harsh treatment conditions, large potential safety hazard and the like, and the defects are easily introduced into a deep layer (inside) in the defect introducing process, so that the original structure of the crystal is easily damaged, the stability of the crystal is poor, the reduction of the recombination rate of photo-generated electrons and holes is also unfavorable, and the photocatalytic activity of the crystal is still poor. So far, no reference to "fern-like BiVO" has been found 4 Related reports of materials ". Therefore, the modified fern-shaped bismuth vanadate photocatalytic nanomaterial which has the advantages of large specific surface area, multiple active sites, strong light absorption capacity, wide light response range, low photo-generated electron-hole recombination rate, good conductivity, high photocatalytic activity and good stability, and the preparation method matched with the modified fern-shaped bismuth vanadate photocatalytic nanomaterial, which has the advantages of simple process, convenient operation, low cost and high yield, has very important significance for improving the removal effect of the bismuth vanadate photocatalytic nanomaterial on organic pollutants in the environment and realizing the effective removal of the organic pollutants in the environment.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, provide a modified fern-shaped bismuth vanadate photocatalytic nanomaterial which has the advantages of large specific surface area, multiple active sites, strong light absorption capability, wide light response range, low photo-generated electron-hole recombination rate, good conductivity, high photocatalytic activity and good stability, and also provide a preparation method of the modified fern-shaped bismuth vanadate photocatalytic nanomaterial, which has the advantages of mild reaction condition, safety, reliability, simple process, convenient operation, low cost and high yield, and the application of the modified fern-shaped bismuth vanadate photocatalytic nanomaterial in treating organic pollutant wastewater.
In order to solve the technical problems, the invention adopts the following technical scheme.
A modified fern-shaped bismuth vanadate photocatalytic nanomaterial comprises a fern-shaped bismuth vanadate nanomaterial, wherein nitrogen and oxygen defects are introduced into the surface of the fern-shaped bismuth vanadate nanomaterial.
The modified fern-shaped bismuth vanadate photocatalytic nanomaterial is further improved, and the modified fern-shaped bismuth vanadate photocatalytic nanomaterial is prepared by calcining the fern-shaped bismuth vanadate nanomaterial in a nitrogen atmosphere; the fern-shaped bismuth vanadate nanomaterial is prepared by taking bismuth salt and vanadium salt as raw materials and performing hydrothermal treatment under the condition that the pH value is 3-4; bismuth vanadate nanoparticles are distributed on the surface of the fern-shaped bismuth vanadate nanomaterial.
The invention also provides a preparation method of the modified fern-shaped bismuth vanadate photocatalytic nanomaterial, which comprises the following steps of:
s1, dissolving bismuth salt in water, adding vanadium salt, and stirring to obtain a mixed solution;
s2, regulating the pH value of the mixed solution to 3-4, and performing hydrothermal reaction to obtain a fern-shaped bismuth vanadate nanomaterial;
and S3, heating the fern-shaped bismuth vanadate nanomaterial obtained in the step S2 to above 350 ℃ under the nitrogen atmosphere, and calcining to obtain the modified fern-shaped bismuth vanadate photocatalytic nanomaterial.
In the preparation method, further improved, in the step S3, the calcining temperature is 350-650 ℃.
In the preparation method, further improved, in the step S3, the calcining temperature is 400-600 ℃.
In the step S1, the mass fraction of bismuth salt in the mixed solution is 1.25-mg-1.5 mg/mL, and the mass fraction of vanadium salt is 1.5-2.5 mg/mL; the bismuth salt is bismuth nitrate pentahydrate; the vanadium salt is sodium orthovanadate; the stirring time is 5-10 min.
In the preparation method, in step S2, glacial acetic acid is adopted to adjust the pH value of the mixed solution; the temperature of the hydrothermal reaction is 110-200 ℃; the hydrothermal reaction time is 10-12 h.
In the preparation method, which is further improved, in the step S3, the calcination time is 2-3 hours; the modified fern-shaped bismuth vanadate photocatalytic nanomaterial comprises a fern-shaped bismuth vanadate nanomaterial, and nitrogen and oxygen defects are introduced into the surface of the fern-shaped bismuth vanadate nanomaterial.
As a technical conception in the method, the invention also provides an application of the modified fern-shaped bismuth vanadate photocatalytic nanomaterial or the modified fern-shaped bismuth vanadate photocatalytic nanomaterial prepared by the preparation method in treating organic pollutant wastewater.
The above application, further improved, said application comprising the steps of: mixing the modified fern-shaped bismuth vanadate photocatalytic nanomaterial with organic pollutant wastewater, stirring, and performing photocatalytic reaction to treat organic pollutants in the wastewater; the addition amount of the modified fern-shaped bismuth vanadate photocatalytic nanomaterial is 0.5 g-1.5 g of the modified fern-shaped bismuth vanadate photocatalytic nanomaterial added into each liter of organic pollutant wastewater.
The application is further improved, and the organic pollutants in the organic pollutant wastewater are at least one of bisphenol A, bisphenol B and bisphenol F; the initial concentration of the organic pollutants in the organic pollutant wastewater is 20mg/L.
In the application, further improved, the stirring time is 30min; the time of the photocatalytic reaction is 60min.
Compared with the prior art, the invention has the advantages that:
(1) Aiming at the defects of small specific surface area, few active sites, weak light absorption capacity, narrow light response range, low carrier mobility, short photogenerated hole diffusion distance, high photogenerated electron-hole recombination rate, poor photocatalytic activity, poor stability and the like of the bismuth vanadate material, the invention creatively provides a modified fern-shaped bismuth vanadate photocatalytic nanomaterial, which comprises a fern-shaped bismuth vanadate nanomaterial, wherein the surface of the fern-shaped bismuth vanadate nanomaterial is introducedHas nitrogen and oxygen defects. Compared with other different shapes, the fern-shaped bismuth vanadate nanomaterial adopted in the invention has the following advantages: as a nano material with unique fern bionic morphology, the fern bismuth vanadate nano material has larger specific surface area and more active sites, can obviously shorten the diffusion distance of photo-generated carriers while improving a large number of active sites, is beneficial to improving the separation efficiency of the photo-generated carriers, can obviously improve the reaction kinetics, and promotes the full contact of target pollutants in solution and the material, thereby being more beneficial to promoting the rapid treatment of the target pollutants by the material. On the basis, in the invention, nitrogen and oxygen defects are introduced on the surface of the fern-shaped bismuth vanadate nanomaterial, so that the following advantages are further brought: oxygen defects are introduced on the surface of the fern-shaped bismuth vanadate nanomaterial through nitrogen doping, on one hand, the oxygen defects serve as an electron donor, so that most of carrier density can be increased, electron traps are provided, photo-generated carrier separation in the fern-shaped bismuth vanadate nanomaterial is promoted, and the oxygen defects can also improve BiVO by generating impurity energy levels near the side of a Conduction Band (CB) or a Valence Band (VB) 4 The electronic structure of the fern-shaped nano material ensures that the fern-shaped bismuth vanadate nano material has higher conductivity and thermal stability, so that the light absorption capacity of the material can be promoted and improved, the light energy utilization rate and the photon-generated carrier separation efficiency of the fern-shaped bismuth vanadate nano material are obviously improved, meanwhile, more active sites can be introduced by doping nitrogen, more importantly, a synergistic promotion effect exists between doping nitrogen and oxygen defects, the band gap of the material can be effectively reduced, the excitation of carriers to a conduction band is enhanced, and the transfer of electrons in oxidation-reduction reaction is facilitated. Compared with the existing conventional bismuth vanadate photocatalytic nanomaterial, the modified fern-shaped bismuth vanadate photocatalytic nanomaterial has the advantages of large specific surface area, multiple active sites, strong light absorption capacity, wide light response range, low photo-generated electron-hole recombination rate, good conductivity, high photocatalytic activity, good stability and the like, is a novel bismuth vanadate catalyst which can be widely used and has excellent performance, and can realize the treatment of organic pollutants in wastewater when being used for treating the organic pollutant wastewaterThe method has the advantages of quick and thorough removal, high use value and good application prospect.
(2) Aiming at the defects of harsh reaction conditions, high potential safety hazards, easiness in damaging a crystal structure, poor photocatalytic activity, poor stability and the like of the bismuth vanadate nanomaterial caused by the severe reaction conditions and the high potential safety hazards in the preparation method, the invention creatively provides the preparation method of the modified fern-shaped bismuth vanadate photocatalytic nanomaterial, which comprises the steps of preparing a mixed solution by taking bismuth salt and vanadium salt as raw materials, regulating the pH value of the mixed solution to 3-4 and performing simple hydrothermal treatment to prepare the fern-shaped bismuth vanadate nanomaterial with unique fern bionic morphology, and then placing the fern-shaped bismuth vanadate nanomaterial in a nitrogen atmosphere to be heated to more than 350 ℃ for calcination, so that nitrogen doping can be introduced into the surface of the fern-shaped bismuth vanadate nanomaterial to generate oxygen defects. Meanwhile, the preparation method provided by the invention has the advantages of simple process, convenience in operation, low cost, high yield and the like, is suitable for large-scale preparation, and is convenient for industrial utilization.
(3) According to the preparation method of the modified fern-shaped bismuth vanadate photocatalytic nanomaterial, the calcination temperature is optimized, so that oxygen defects are more favorably introduced into the surface of the material, and the oxygen defects can be effectively prevented from entering the inside of crystals, so that the modified fern-shaped bismuth vanadate photocatalytic nanomaterial with more excellent photocatalytic performance and better stability can be obtained, and compared with the calcination temperature of 350 ℃ or 650 ℃, for example, the modified fern-shaped bismuth vanadate photocatalytic nanomaterial prepared at 400-600 ℃ has weaker fluorescence emission signals and stronger photocurrent signals, and the modified fern-shaped bismuth vanadate photocatalytic nanomaterial prepared by the method has more excellent photocatalytic performance. In particular, it is difficult to pass N when the calcination temperature is lower than 350 DEG C 2 The atmosphere calcination method successfully introduces N element, and above 650 ℃, bulk defects are formed, and the bulk defects serve as recombination centers of the photo-generated carrier, so that the catalytic activity of the catalyst is reduced.
(4) The invention also provides application of the modified fern-shaped bismuth vanadate photocatalytic nanomaterial in treating organic pollutant wastewater, and the modified fern-shaped bismuth vanadate photocatalytic nanomaterial and the organic pollutant wastewater are mixed for photocatalytic reaction, so that the efficient removal of organic pollutants in the wastewater can be realized, and the modified fern-shaped bismuth vanadate photocatalytic nanomaterial has the advantages of simple process, low operation method, low cost, high treatment efficiency, good removal effect and the like, and is beneficial to realizing the effective treatment of the organic pollutant wastewater. Taking bisphenol A as an example, the removal rate of bisphenol A after 60min of treatment by adopting the modified pteridophyte bismuth vanadate photocatalytic nanomaterial of the invention is up to 97.16%, and the modified pteridophyte bismuth vanadate photocatalytic nanomaterial shows very excellent removal capability, compared with the conventional BiVO 4 The removal rate of the nano-sheet to bisphenol A is only 49.51%, and meanwhile, when the modified fern-shaped bismuth vanadate photocatalytic nano-material disclosed by the invention is used for circularly treating bisphenol A wastewater, after the wastewater is circularly used for 4 times, the effective removal of bisphenol A in the wastewater can still be realized, so that the recycling property is good, and the treatment cost is reduced.
Drawings
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention.
FIG. 1 is an SEM image of a fern-shaped bismuth vanadate nanomaterial (a) prepared in example 1, a modified fern-shaped bismuth vanadate photocatalytic nanomaterial (b), and a sheet-shaped bismuth vanadate nanomaterial (c) prepared in comparative example 1, wherein a is "fern-shaped" BiVO 4 B is N/O v /BiVO 4 -450, c is BiVO 4 A nano-sheet.
FIG. 2 shows a fern-like bismuth vanadate nanomaterial ("fern-like" BiVO) prepared in example 1 of the present invention 4 ) Modified fern-like bismuth vanadate photocatalytic nanomaterial (N/O) v /BiVO 4 -450) and the sheet bismuth vanadate nanomaterial (BiVO) prepared in comparative example 1 4 Nanoplatelets) nitrogen adsorption-desorption isotherm plot.
FIG. 3 shows a fern-like bismuth vanadate nanomaterial ("fern-like" BiVO) prepared in example 1 of the present invention 4 ) Modified fern-shaped bismuth vanadate photocatalytic nanoMaterial (N/O) v /BiVO 4 -350、N/O v /BiVO 4 -450、N/O v /BiVO 4 -550、N/O v /BiVO 4 -650) and the sheet bismuth vanadate nanomaterial (BiVO) prepared in comparative example 1 4 Nanoplatelets) uv-diffuse spectral reflectance.
FIG. 4 shows a fern-like bismuth vanadate nanomaterial ("fern-like" BiVO) prepared in example 1 of the present invention 4 ) Modified fern-like bismuth vanadate photocatalytic nanomaterial (N/O) v /BiVO 4 -350、N/O v /BiVO 4 -450、N/O v /BiVO 4 -550、N/O v /BiVO 4 -650) and the sheet bismuth vanadate nanomaterial (BiVO) prepared in comparative example 1 4 Nanoplatelets) photoluminescence fluorescence spectrum.
FIG. 5 shows a fern-like bismuth vanadate nanomaterial prepared in example 1 of the present invention ("fern-like" BiVO) 4 ) Modified fern-like bismuth vanadate photocatalytic nanomaterial (N/O) v /BiVO 4 -350、N/O v /BiVO 4 -450、N/O v /BiVO 4 -550、N/O v /BiVO 4 -650) and the sheet bismuth vanadate nanomaterial (BiVO) prepared in comparative example 1 4 Nanoplatelets) is used.
FIG. 6 shows a fern-like bismuth vanadate nanomaterial prepared in example 1 of the present invention ("fern-like" BiVO) 4 ) And modified fern-like bismuth vanadate photocatalytic nanomaterial (N/O) v /BiVO 4 -350、N/O v /BiVO 4 -450、N/O v /BiVO 4 -550、N/O v /BiVO 4 -650) XPS O1s profile.
FIG. 7 shows a fern-like bismuth vanadate nanomaterial ("fern-like" BiVO) prepared in example 1 of the present invention 4 ) And modified fern-like bismuth vanadate photocatalytic nanomaterial (N/O) v /BiVO 4 -350、N/O v /BiVO 4 -450、N/O v /BiVO 4 -550、N/O v /BiVO 4 -650) XPS N1s profile.
FIG. 8 shows the modified fern-shaped bismuth vanadate photocatalytic nanomaterial (N/O) prepared in example 2 of the present invention v /BiVO 4 -450), fern-like bismuth vanadate nanomaterials ("fern)Shape "BiVO 4 ) Sheet bismuth vanadate nanomaterial (BiVO) 4 Nanoplatelets) the concentration of bisphenol a during photodegradation as a function of photocatalytic time.
FIG. 9 is a graph showing the effect of the modified fern-shaped bismuth vanadate photocatalytic nanomaterial on the cyclic treatment of bisphenol A wastewater in example 3 of the present invention.
Detailed Description
The invention is further described below in connection with the drawings and the specific preferred embodiments, but the scope of protection of the invention is not limited thereby. The materials and instruments used in the examples below are all commercially available.
Example 1:
the modified fern-shaped bismuth vanadate photocatalytic nanomaterial is characterized by comprising a fern-shaped bismuth vanadate nanomaterial, wherein nitrogen and oxygen defects are introduced into the surface of the fern-shaped bismuth vanadate nanomaterial.
In the embodiment, the modified fern-shaped bismuth vanadate photocatalytic nanomaterial is prepared by calcining a fern-shaped bismuth vanadate nanomaterial in a nitrogen atmosphere, wherein the fern-shaped bismuth vanadate nanomaterial is prepared by performing hydrothermal treatment on bismuth salt and vanadium salt serving as raw materials under the condition of pH value of 3-4.
In the embodiment, bismuth vanadate nanoparticles are distributed on the surface of the fern-shaped bismuth vanadate nanomaterial.
The preparation method of the modified fern-shaped bismuth vanadate photocatalytic nanomaterial in the embodiment comprises the following steps:
(1) 60mg of bismuth nitrate pentahydrate is dissolved in 40mL of deionized water, and 100mg of sodium orthovanadate is added after uniform stirring, and stirring is carried out for 10min, thus obtaining a mixed solution A.
(2) And (3) regulating the pH value of the mixed solution A obtained in the step (1) to 4.0 by glacial acetic acid to obtain a mixed solution B.
(3) Transferring the mixed solution B obtained in the step (3) into a liner of a reaction kettle, installing the liner into a steel sleeve of a hydrothermal reaction kettle, performing hydrothermal reaction for 12 hours at the temperature of 110 ℃, naturally cooling to room temperature after the hydrothermal reaction is completed, and performing vacuum drying for 6 hours at the temperature of 45 ℃ to obtain a fern-shaped bismuth vanadate nanomaterial, namely "fern-shaped" BiVO 4 。
(4) Placing the fern-shaped bismuth vanadate nanomaterial obtained in the step (d) in a clean quartz crucible, heating to 450 ℃ at a heating rate of 3 ℃/min under nitrogen atmosphere, calcining for 3 hours, introducing nitrogen element into the fern-shaped bismuth vanadate nanomaterial by calcining and generating oxygen defects, and obtaining the modified fern-shaped bismuth vanadate photocatalytic nanomaterial, which is denoted as N/O v /BiVO 4 -450。
In the embodiment, the influence of different calcination temperatures on the performance of the pteridophyte bismuth vanadate nanomaterial is also examined, wherein the modified pteridophyte bismuth vanadate photocatalytic nanomaterial obtained by calcination at the temperature of 350 ℃,550 ℃ and 650 ℃ is sequentially recorded as N/O v /BiVO 4 -350、N/O v /BiVO 4 -550、N/O v /BiVO 4 -650。
Comparative example 1:
the preparation method of the flaky bismuth vanadate nanomaterial comprises the following steps of:
(1) 60mg of bismuth nitrate pentahydrate is dissolved in 40mL of deionized water, and 100mg of sodium orthovanadate is added after uniform stirring, and stirring is carried out for 10min, thus obtaining a mixed solution A.
(2) And (3) regulating the pH value of the mixed solution A obtained in the step (1) to 6.0 by glacial acetic acid to obtain a mixed solution B.
(3) Transferring the mixed solution B obtained in the step (3) into a liner of a reaction kettle, installing the liner into a steel sleeve of a hydrothermal reaction kettle, performing hydrothermal reaction for 12 hours at the temperature of 110 ℃, naturally cooling to room temperature after the hydrothermal reaction is completed, and performing vacuum drying for 6 hours at the temperature of 45 ℃ to obtain a sheet bismuth vanadate nano material, which is marked as BiVO 4 A nano-sheet.
The fern-like bismuth vanadate nanomaterial prepared in example 1 ("fern-like" BiVO) 4 ) Modified fern-like bismuth vanadate photocatalytic nanomaterial (N/O) v /BiVO 4 -450) and the sheet bismuth vanadate nanomaterial (BiVO) prepared in comparative example 1 4 Nanoplatelets) were subjected to SEM analysis, and the results are shown in fig. 1. FIG. 1 is an SEM image of a pteridoshaped bismuth vanadate nanomaterial (a) prepared in example 1, a modified pteridoshaped bismuth vanadate photocatalytic nanomaterial (b), and a flaky bismuth vanadate nanomaterial (c) prepared in comparative example 1, wherein a is "pteridoshaped”BiVO 4 B is N/O v /BiVO 4 -450, c is BiVO 4 A nano-sheet. As can be seen from FIGS. 1a and 1b, biVO in a "fern-like" form 4 N/O v /BiVO 4 -450 all show fern-like morphology with a size of 500nm, particles with a diameter of 10nm are uniformly distributed on the surface of the fern-like morphology, and the unique bionic morphology structure brings a larger specific surface area. Meanwhile, as can be seen from FIGS. 1a and 1b, a "fern-like" BiVO 4 N/O v /BiVO 4 The morphology of-450 remained almost uniform, indicating that calcination under nitrogen does not destroy BiVO 4 Is of a specific morphology. In addition, as can be seen from FIG. 1c, biVO 4 The nanoplatelets exhibit a typical platelet structure and a smooth surface.
The fern-like bismuth vanadate nanomaterial prepared in example 1 ("fern-like" BiVO) 4 ) Modified fern-like bismuth vanadate photocatalytic nanomaterial (N/O) v /BiVO 4 -450) and the sheet bismuth vanadate nanomaterial (BiVO) prepared in comparative example 1 4 Nanoplatelets) were separately subjected to nitrogen adsorption and desorption tests, and the results are shown in fig. 2. FIG. 2 shows a fern-like bismuth vanadate nanomaterial ("fern-like" BiVO) prepared in example 1 of the present invention 4 ) Modified fern-like bismuth vanadate photocatalytic nanomaterial (N/O) v /BiVO 4 -450) and the sheet bismuth vanadate nanomaterial (BiVO) prepared in comparative example 1 4 Nanoplatelets) nitrogen adsorption-desorption isotherm plot. After BET calculation, "fern-like" BiVO 4 11.65m 2 /g，N/O v /BiVO 4 -450 is 20.59m 2 /g，BiVO 4 The nano sheet is 1.22m 2 And/g. It can be seen that compared to BiVO 4 Nanoplatelets, N/O v /BiVO 4 -450 and "fern-like" BiVO 4 The catalyst has larger specific surface area, is beneficial to increasing the contact area of the catalyst and environmental pollutants and increases the reaction sites.
For the fern-like bismuth vanadate nanomaterial prepared in example 1 ("fern-like" BiVO) 4 ) Modified fern-like bismuth vanadate photocatalytic nanomaterial (N/O) v /BiVO 4 -350、N/O v /BiVO 4 -450、N/O v /BiVO 4 -550、N/O v /BiVO 4 -650) and the tablets prepared in comparative example 1Bismuth vanadate nanomaterial (BiVO) 4 Nanoplatelets) were subjected to uv-diffuse spectral reflectance analysis, respectively, the results of which are shown in fig. 3. FIG. 3 shows a fern-like bismuth vanadate nanomaterial ("fern-like" BiVO) prepared in example 1 of the present invention 4 ) Modified fern-like bismuth vanadate photocatalytic nanomaterial (N/O) v /BiVO 4 -350、N/O v /BiVO 4 -450、N/O v /BiVO 4 -550、N/O v /BiVO 4 -650) and the sheet bismuth vanadate nanomaterial (BiVO) prepared in comparative example 1 4 Nanoplatelets) uv-diffuse spectral reflectance. As can be seen from FIG. 3, "fern-like" BiVO 4 Is relative to BiVO 4 The nano-sheet is lifted to a certain extent; modified fern-shaped bismuth vanadate photocatalytic nanomaterial (N/O) v /BiVO 4 -350、N/O v /BiVO 4 -450、N/O v /BiVO 4 -550、N/O v /BiVO 4 -650) visible light absorption edge relative to simple "fern" BiVO 4 A certain red shift occurs, and the N/O is in the range of less than 500nm with the increase of the calcination temperature v /BiVO 4 The absorption of x is slightly enhanced. From this, it can be seen that BiVO in "fern-like" form 4 Compared with lamellar BiVO 4 Has better light absorption capacity, and at the same time, the introduction of nitrogen and oxygen defects can further improve the 'fern' -shaped BiVO 4 Thereby being more beneficial to improving the light energy utilization rate of the material.
For the fern-like bismuth vanadate nanomaterial prepared in example 1 ("fern-like" BiVO) 4 ) Modified fern-like bismuth vanadate photocatalytic nanomaterial (N/O) v /BiVO 4 -350、N/O v /BiVO 4 -450、N/O v /BiVO 4 -550、N/O v /BiVO 4 -650) and the sheet bismuth vanadate nanomaterial (BiVO) prepared in comparative example 1 4 Nanoplatelets) were subjected to photoluminescence fluorescence spectroscopy and photocurrent response signal analysis, and the results are shown in fig. 4 and 5. FIG. 4 shows a fern-like bismuth vanadate nanomaterial ("fern-like" BiVO) prepared in example 1 of the present invention 4 ) Modified fern-like bismuth vanadate photocatalytic nanomaterial (N/O) v /BiVO 4 -350、N/O v /BiVO 4 -450、 N/O v /BiVO 4 -550、N/O v /BiVO 4 -650) and the sheet bismuth vanadate nanomaterial (BiVO) prepared in comparative example 1 4 Nanoplatelets) photoluminescence fluorescence spectrum. FIG. 5 shows a fern-like bismuth vanadate nanomaterial prepared in example 1 of the present invention ("fern-like" BiVO) 4 ) Modified fern-like bismuth vanadate photocatalytic nanomaterial (N/O) v /BiVO 4 -350、N/O v /BiVO 4 -450、 N/O v /BiVO 4 -550、N/O v /BiVO 4 -650) and the sheet bismuth vanadate nanomaterial (BiVO) prepared in comparative example 1 4 Nanoplatelets) is used. Fluorescence is caused by recombination of photogenerated carriers, and can reflect the separation, transfer and migration rules of the carriers. Fern-like bismuth vanadate nanomaterial (fern-like BiVO) 4 ) Modified fern-like bismuth vanadate photocatalytic nanomaterial (N/O) v /BiVO 4 -350、N/O v /BiVO 4 -450、N/O v /BiVO 4 -550、N/O v /BiVO 4 -650) and the sheet bismuth vanadate nanomaterial (BiVO) prepared in comparative example 1 4 Steady state fluorescence emission spectrum (lambda) of nanoplatelets ex 365 nm), as shown in FIG. 4, in which BiVO 4 The fluorescence intensity of the nano-sheet is obviously higher than that of 'fern-shaped' BiVO 4 The carrier loading rate of the former is shown to be much higher than that of the latter. However, modified fern-like bismuth vanadate photocatalytic nanomaterial (N/O v /BiVO 4 -350、N/O v /BiVO 4 -450、N/O v /BiVO 4 -550、 N/O v /BiVO 4 -650) are lower than the "fern-like" BiVO 4 And shows a tendency of decreasing before increasing with increasing calcination temperature, indicating that the recombination of photoelectron-hole pairs decreases before increasing. The photocurrent response signal shown in fig. 5 also has the same characteristics, N/O v /BiVO 4 -450 photocurrent signal is stronger than N/O v /BiVO 4 -550 and N/O v /BiVO 4 -650. From this, it is known that the modified fern-shaped bismuth vanadate photocatalytic nanomaterial has a higher N doping level with an increase in the calcination temperature, and thus generates more bulk oxygen defects, which are involved in the recombination as a photogenerated carrier when the bulk oxygen defects increaseThe heart also leads to a decrease in the catalytic activity of the catalyst. Therefore, compared with the method, the method is carried out at 400-600 ℃, is more beneficial to introducing surface oxygen defects on the surface of the material, and the surface oxygen defects can be used as carrier traps and adsorption sites of active substances, so that the photo-generated electron-hole recombination can be more effectively inhibited, and the method is consistent with the results in fig. 4 and 5, namely, fluorescence emission signals are weakened, photocurrent signals are enhanced, and particularly, when the calcining temperature is 450 ℃, the prepared modified pteridophytate bismuth vanadate photocatalytic nanomaterial has more proper oxygen defect surfaces and shows very excellent photocatalytic performance.
For the fern-like bismuth vanadate nanomaterial prepared in example 1 ("fern-like" BiVO) 4 ) Modified fern-like bismuth vanadate photocatalytic nanomaterial (N/O) v /BiVO 4 -350、N/O v /BiVO 4 -450、N/O v /BiVO 4 -550、N/O v /BiVO 4 -650) and the sheet bismuth vanadate nanomaterial (BiVO) prepared in comparative example 1 4 Nanoplatelets) were subjected to XPS analysis, and the results are shown in fig. 6 and 7.
FIG. 6 shows a fern-like bismuth vanadate nanomaterial prepared in example 1 of the present invention ("fern-like" BiVO) 4 ) And modified fern-like bismuth vanadate photocatalytic nanomaterial (N/O) v /BiVO 4 -350、N/O v /BiVO 4 -450、N/O v /BiVO 4 -550、N/O v /BiVO 4 -650) XPS O1s profile. In FIG. 6, the characteristic peaks of O1s can be divided into O L ,O V And O A Three, respectively representing lattice oxygen (O L ) Oxygen defect region (O) v ) And oxygen (O) chemically absorbed from water A ). As can be seen from fig. 6 and table 1, the peak area of Ov increases with increasing calcination temperature, which indicates an increase in defective oxygen.
TABLE 1 preparation of fern-like bismuth vanadate nanomaterial ("fern-like" BiVO) 4 ) And modified fern-like bismuth vanadate photocatalytic nanomaterial (N/O) v /BiVO 4 -350、N/O v /BiVO 4 -450、N/O v /BiVO 4 -550、N/O v /BiVO 4 -650) high resolution XPS peak calculated O L 、O v And O c Peak area of (2)
FIG. 7 shows a fern-like bismuth vanadate nanomaterial ("fern-like" BiVO) prepared in example 1 of the present invention 4 ) And modified fern-like bismuth vanadate photocatalytic nanomaterial (N/O) v /BiVO 4 -350、N/O v /BiVO 4 -450、N/O v /BiVO 4 -550、N/O v /BiVO 4 -650) XPS N1s profile. As can be seen from fig. 7 and table 2, as the calcination temperature increases, the nitrogen element content of the surface of the modified fern-shaped bismuth vanadate photocatalytic nanomaterial also increases.
Table 2: is prepared from fern-shaped bismuth vanadate nano material (fern-shaped BiVO) 4 ) And modified fern-like bismuth vanadate photocatalytic nanomaterial (N/O) v /BiVO 4 -350、N/O v /BiVO 4 -450、N/O v /BiVO 4 -550、N/O v /BiVO 4 -650) peak area of nitrogen characteristic peak calculated from high resolution XPS peak
| Material | Characteristic peak area |
| N/O v /BiVO 4 -350 | 2159.16 |
| N/O v /BiVO 4 -450 | 2599.13 |
| N/O v /BiVO 4 -550 | 3355.31 |
| N/O v /BiVO 4 -650 | 3414.60 |
Example 2
The application of the modified fern-shaped bismuth vanadate photocatalytic nanomaterial in treating organic pollutant wastewater, in particular to the application of the modified fern-shaped bismuth vanadate photocatalytic nanomaterial in treating bisphenol A wastewater, comprising the following steps of:
(1) 50mg of the modified fern-shaped bismuth vanadate photocatalytic nanomaterial (N/O) prepared in example 1 was weighed v /BiVO 4 -450) was added to 50mL of bisphenol a wastewater having an initial concentration of 20mg/L in a dark environment, adsorbed for 30min under stirring, and then placed in a photocatalytic reaction device.
(2) And carrying out photocatalytic reaction for 60min by adopting a 300W xenon lamp, and finishing the treatment of bisphenol A in the wastewater.
In the treatment process, the absorbance value of the reaction solution at the time t at the wavelength of 271nm is measured, the concentration C of bisphenol A at the time t is obtained by combining a standard curve, and the concentration C is calculated according to the formula D= (C) 0 －C)/C 0 X100% calculation modified fern-shaped bismuth vanadate photocatalytic nanomaterial (N/O) v /BiVO 4 -450) removal rate D of bisphenol A, wherein C 0 The bisphenol A removal rate is shown in FIG. 1 for the initial concentration of bisphenol A.
In addition, 50mg of the fern-shaped bismuth vanadate nanomaterial prepared in example 1 ("fern-shaped" BiVO) was weighed separately 4 ) And the sheet bismuth vanadate nanomaterial prepared in comparative example 1 (BiVO 4 Nanoplatelets), bisphenol a wastewater was treated according to the above procedure, and their results on bisphenol a removal rate from the wastewater are shown in fig. 1.
FIG. 1 shows a modified fern-shaped bismuth vanadate photocatalytic nanomaterial (N/O) prepared in example 2 of the present invention v /BiVO 4 -450), fernBismuth vanadate nanomaterial ('fern' BiVO) 4 ) Sheet bismuth vanadate nanomaterial (BiVO) 4 Nanoplatelets) the concentration of bisphenol a during photodegradation as a function of photocatalytic time. As can be seen from FIG. 1, the modified fern-shaped bismuth vanadate photocatalytic nanomaterial (N/O v /BiVO 4 -450) bisphenol A removal after 60min of photocatalytic treatment was 97.16%, whereas "fern" BiVO 4 The removal rate of bisphenol A is 71.47 percent and BiVO 4 The removal rate of the nano-sheet to bisphenol A is 49.51 percent. From this, it is clear that BiVO is more than that of BiVO 4 Nanosheets, modified fern-like bismuth vanadate photocatalytic nanomaterial (N/O) v /BiVO 4 -450), fern-like bismuth vanadate nanomaterial ("fern-like" BiVO) 4 ) Has higher photocatalytic activity, and the modified fern-shaped bismuth vanadate photocatalytic nanomaterial (N/O) v /BiVO 4 -450) has a significantly higher photocatalytic activity than "fern-like" BiVO 4 。
Example 3
The application of the modified fern-shaped bismuth vanadate photocatalytic nanomaterial in treating organic pollutant wastewater, in particular to the repeated treatment of bisphenol A wastewater by using the modified fern-shaped bismuth vanadate photocatalytic nanomaterial, comprising the following steps of:
centrifugally separating and collecting the modified fern-shaped bismuth vanadate photocatalytic nanomaterial after the reaction in the embodiment 2, washing the nano material with water and ethanol in a large amount, and drying the nano material in an oven at 45 ℃ for 10 hours to obtain a regenerated modified fern-shaped bismuth vanadate photocatalytic nanomaterial; the bisphenol a solution was repeatedly treated 4 times in total using the regenerated modified fern-shaped bismuth vanadate photocatalytic nanomaterial according to the treatment method in example 1.
After 4 times of photocatalysis experiments are detected, the removal rate of bisphenol A by the modified pteridophyte bismuth vanadate photocatalysis nano material is detected, and the result of the cycling experiments is shown in figure 9. FIG. 9 is a graph showing the effect of the modified fern-shaped bismuth vanadate photocatalytic nanomaterial on the cyclic treatment of bisphenol A wastewater in example 3 of the present invention. As can be seen from FIG. 9, in the 4 th photocatalytic experiment, the photocatalytic removal rate of bisphenol A by the modified fern-shaped bismuth vanadate photocatalytic nanomaterial is not obviously reduced, and the removal rate can still reach more than 90%, which indicates that the modified fern-shaped bismuth vanadate photocatalytic nanomaterial has good photocatalytic stability and good recycling performance, and can be widely used for treating organic pollutant wastewater.
In conclusion, the modified fern-shaped bismuth vanadate photocatalytic nanomaterial disclosed by the invention has the advantages of large specific surface area, more active sites, strong light absorption capacity, wide light response range, low photo-generated electron-hole recombination rate, good conductivity, high photocatalytic activity, good stability and the like, is a novel bismuth vanadate catalyst which can be widely used and has excellent performance, can realize rapid and thorough removal of organic pollutants in wastewater when being used for treating organic pollutant wastewater, has high use value and good application prospect, and has important significance for effectively purifying organic pollutant water bodies.
The above description is only of the preferred embodiment of the present invention, and is not intended to limit the present invention in any way. While the invention has been described in terms of preferred embodiments, it is not intended to be limiting. Any person skilled in the art can make many possible variations and modifications to the technical solution of the present invention or equivalent embodiments using the method and technical solution disclosed above without departing from the spirit and technical solution of the present invention. Therefore, any simple modification, equivalent substitution, equivalent variation and modification of the above embodiments according to the technical substance of the present invention, which do not depart from the technical solution of the present invention, still fall within the scope of the technical solution of the present invention.
Claims (7)
1. The preparation method of the modified fern-shaped bismuth vanadate photocatalytic nanomaterial is characterized by comprising the following steps of:
s1, dissolving bismuth salt in water, adding vanadium salt, and stirring to obtain a mixed solution; the bismuth salt is bismuth nitrate pentahydrate; the vanadium salt is sodium orthovanadate;
s2, adjusting the pH value of the mixed solution to 3-4 by using glacial acetic acid, and performing hydrothermal reaction to obtain a fern-shaped bismuth vanadate nanomaterial;
and S3, heating the fern-shaped bismuth vanadate nanomaterial obtained in the step S2 to 350-650 ℃ in a nitrogen atmosphere, and calcining to obtain the modified fern-shaped bismuth vanadate photocatalytic nanomaterial.
2. The method according to claim 1, wherein in step S3, the calcination temperature is 400 ℃ to 600 ℃.
3. The preparation method according to claim 1 or 2, wherein in step S1, the mass fraction of bismuth salt in the mixed solution is 1.25 mg/mL to 1.5mg/mL, and the mass fraction of vanadium salt is 1.5mg/mL to 2.5mg/mL; the stirring time is 5-10 min;
in the step S2, the temperature of the hydrothermal reaction is 180-200 ℃; the hydrothermal reaction time is 10 h-12 h;
in the step S3, the calcination time is 2 h-3 h; the modified fern-shaped bismuth vanadate photocatalytic nanomaterial comprises a fern-shaped bismuth vanadate nanomaterial, and nitrogen and oxygen defects are introduced into the surface of the fern-shaped bismuth vanadate nanomaterial.
4. Use of the modified fern-like bismuth vanadate photocatalytic nanomaterial prepared by the preparation method of any of claims 1-3 in treating organic pollutant wastewater.
5. The application according to claim 4, characterized in that it comprises the following steps: mixing the modified fern-shaped bismuth vanadate photocatalytic nanomaterial with organic pollutant wastewater, stirring, and performing photocatalytic reaction to treat organic pollutants in the wastewater; the addition amount of the modified fern-shaped bismuth vanadate photocatalytic nanomaterial is 0.5 g-1.5 g g of the modified fern-shaped bismuth vanadate photocatalytic nanomaterial added into per liter of organic pollutant wastewater.
6. The use according to claim 5, wherein the organic contaminant in the organic contaminant wastewater is at least one of bisphenol a, bisphenol B, bisphenol F; the initial concentration of the organic pollutants in the organic pollutant wastewater is 20mg/L.
7. The use according to claim 5 or 6, wherein the stirring time is 30min; the time of the photocatalytic reaction is 60min.
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| Additive-free hydrothermal synthesis of novel bismuth Vanadium oxideden dritic structures as highly efficient visible-light photocatalysts;Bing-Xin Lei et al.;《Materials Science in Semiconductor Processin》(第30期);429-434 * |
| Simultaneous enhancements in photon absorption and charge transport of bismuth vanadate photoanodes for solar water splitting;Tae Woo Kim et al.;《NATURE COMMUNICATIONS》;1-10 * |
| Tuning the morphology of electrosprayed BiVO4 from nanopillars to nanoferns via pH control for solar water splitting;Min-Woo Kim;Tuning the morphology of electrosprayed BiVO4 from nanopillars to nanoferns via pH control for solar water splitting(第167期);1-26 * |
| 三维纳米结构单斜相BIVO4光催化材料研究进展;刘伟等;《化工新型材料》;第46卷(第11期);63-66 * |
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