CN110813376B - Polypyrrole-modified nano bismuth oxybromide photocatalytic material and preparation method and application thereof - Google Patents
Polypyrrole-modified nano bismuth oxybromide photocatalytic material and preparation method and application thereof Download PDFInfo
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- OZKCXDPUSFUPRJ-UHFFFAOYSA-N oxobismuth;hydrobromide Chemical compound Br.[Bi]=O OZKCXDPUSFUPRJ-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 57
- 239000000463 material Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 229920000128 polypyrrole Polymers 0.000 claims abstract description 53
- 239000002131 composite material Substances 0.000 claims abstract description 24
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims abstract description 11
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 26
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 238000001179 sorption measurement Methods 0.000 claims description 13
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 239000000178 monomer Substances 0.000 claims description 10
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 9
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- 229910052724 xenon Inorganic materials 0.000 claims description 6
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 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 description 4
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- 238000005286 illumination Methods 0.000 abstract description 4
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- 229910052757 nitrogen Inorganic materials 0.000 abstract description 3
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- 229910052799 carbon Inorganic materials 0.000 abstract description 2
- 125000000623 heterocyclic group Chemical group 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract description 2
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- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 15
- 229940012189 methyl orange Drugs 0.000 description 15
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- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 description 1
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The invention provides a polypyrrole-modified nano bismuth oxybromide photocatalytic material as well as a preparation method and application thereof, belonging to the field of photocatalysis. In the invention, polypyrrole is used as a heterocyclic conjugated conductive polymer with carbon and nitrogen coexisting, not only has excellent visible light absorption and conductive properties, but also has good chemical stability in most solvent systems, so that the polypyrrole conductive polymer has good recycling performance, and can be used for functionally modifying a bismuth oxybromide semiconductor, so that the light absorption performance of the polypyrrole conductive polymer can be effectively improved, the electron transfer between the mutual interfaces of semiconductor materials can be accelerated, the photoproduction electron hole separation efficiency under illumination can be effectively improved, the covalent attraction and the matching degree between the interface combinations greatly influence the electron hole separation efficiency, and further the generation efficiency of active free radicals can be influenced, and thus, a novel efficient composite photocatalytic material is obtained, and the photocatalytic degradation capability of the polypyrrole conductive polymer is improved.
Description
Technical Field
The invention relates to the technical field of photocatalysis, in particular to a polypyrrole-modified nano bismuth oxybromide photocatalytic material as well as a preparation method and application thereof.
Background
Among numerous semiconductor photocatalysts, the great potential of bismuth oxybromide semiconductors with appropriate band gaps (2.80eV) in the aspect of environmental pollution treatment causes people to pay attention to the photocatalyst, and the main reason is that the bismuth oxybromide semiconductors have good photocatalytic redox activity and environment-friendly performance under the irradiation of visible light or simulated sunlight. Nevertheless, the photocatalytic activity of BiOBr is still not ideal, and practical applications thereof are limited by, for example, rapid recombination of photogenerated charge carriers, difficulty in recovery of inorganic materials, and the like, and further improvement is required.
In general, the photocatalytic activity can be effectively improved through effective microstructure control or effective electron transfer paths; for example, carbon-based materials with excellent optics and excellent electron transfer performance, including carbon nanotubes, carbon quantum dots, graphene and graphene quantum dots, are added to improve the microstructure and accelerate and delay the recombination of electron hole species in a semiconductor, but the BiOBr-based photocatalytic material in the prior art still has the problem of poor catalytic effect.
Disclosure of Invention
In view of the above, the present invention aims to provide a polypyrrole-modified nano bismuth oxybromide photocatalytic material, and a preparation method and an application thereof. The polypyrrole-modified nano bismuth oxybromide photocatalytic material provided by the invention has excellent photocatalytic performance.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a polypyrrole-modified nano bismuth oxybromide photocatalytic material which comprises sheet bismuth oxybromide and polypyrrole coated on the surface of the sheet bismuth oxybromide, wherein the sheet bismuth oxybromide and the polypyrrole are bonded through covalent bonds.
Preferably, the mass ratio of the flaky bismuth oxybromide to the polypyrrole is 1: 2 to 6.
Preferably, the thickness of the flake of the polypyrrole-modified nano bismuth oxybromide photocatalytic material is 120-150 nm.
The invention also provides a preparation method of the polypyrrole-modified nano bismuth oxybromide photocatalytic material, which comprises the following steps:
dispersing the flaky nano bismuth oxybromide in a dilute acid aqueous solution containing hexadecyl trimethyl ammonium bromide and ammonium persulfate to obtain a dispersion liquid;
and (3) in an ice bath, dropwise adding pyrrole monomers into the dispersion liquid, and then carrying out in-situ solution polymerization reaction to obtain the polypyrrole coated and modified nano bismuth oxybromide photocatalytic material.
Preferably, the mass concentration of the flaky nano bismuth oxybromide in the dispersion liquid is 2-8 mg/mL.
Preferably, the molar ratio of the hexadecyl trimethyl ammonium bromide to the ammonium persulfate is 0.2-0.8: 50-200.
Preferably, the dosage ratio of the flaky nano bismuth oxybromide to the pyrrole monomer is 15-35 mg: 0.2-0.5 mL.
Preferably, the pyrrole monomer is added dropwise at 0-10 ℃.
Preferably, the temperature of the in-situ solution polymerization reaction is 25-35 ℃ and the time is 15-20 h.
The invention also provides the polypyrrole-modified nano bismuth oxybromide photocatalytic material prepared by the preparation method in the technical scheme or the application of the polypyrrole-modified nano bismuth oxybromide photocatalytic material in the fields of dye adsorption and photocatalytic degradation.
The invention provides a polypyrrole-modified nano bismuth oxybromide photocatalytic material which comprises sheet bismuth oxybromide and polypyrrole coated on the surface of the sheet bismuth oxybromide, wherein the sheet bismuth oxybromide and the polypyrrole are bonded through covalent bonds. In the invention, polypyrrole is used as a heterocyclic conjugated conductive polymer with carbon and nitrogen coexisting, not only has excellent visible light absorption and conductive properties, but also has good chemical stability in most solvent systems, so that the polypyrrole conductive polymer has good recycling performance, and can be used for functionally modifying a bismuth oxybromide semiconductor, so that the light absorption performance of the polypyrrole conductive polymer can be effectively improved, the electron transfer between the mutual interfaces of semiconductor materials can be accelerated, the photoproduction electron hole separation efficiency under illumination can be effectively improved, the covalent attraction and the matching degree between the interface combinations greatly influence the electron hole separation efficiency, and further the generation efficiency of active free radicals can be influenced, and thus, a novel efficient composite photocatalytic material is obtained, and the photocatalytic degradation capability of the polypyrrole conductive polymer is improved. Compared with pure bismuth oxybromide, the polypyrrole-modified nano bismuth oxybromide photocatalytic material effectively improves the adsorption capacity, photodegradation capacity and cyclic degradation stability of dye. After the two-dimensional bismuth oxybromide and the polypyrrole are linked through covalent, on one hand, the defect that pure bismuth oxybromide is easy to agglomerate and low in catalytic effect is effectively overcome, the dispersibility of the bismuth oxybromide is improved, and the capacity of degrading pollutants through photocatalysis is improved; on the other hand, the in-situ covalent modification of the polypyrrole is beneficial to mutual contact between bismuth oxybromide and a polypyrrole conjugated structure, the light absorption range and the absorption intensity of the polypyrrole are effectively expanded, the separation efficiency of photo-generated electron holes is accelerated, and the efficient photocatalytic material is beneficial to obtaining. The data of the embodiment shows that the polypyrrole-modified nano bismuth oxybromide photocatalytic material provided by the invention has high adsorption capacity on methyl orange (5mg of the photocatalytic material adsorbs about 1.0mg of methyl orange in 40 min), and has excellent photocatalytic degradation efficiency (5mg of the photocatalytic material degrades about 0.4mg of methyl orange in 50 min) and cyclic adsorption and catalytic efficiency (5mg of the photocatalytic material adsorbs about 0.45mg of methyl orange in 40min, and degrades about 0.4mg of methyl orange in 50 min) under simulated sunlight, so that the polypyrrole-modified nano bismuth oxybromide photocatalytic material is an ideal recyclable organic-inorganic composite photocatalytic material. Compared with the existing bismuth oxybromide photocatalytic material, the photocatalytic material provided by the invention has the advantages of small using amount, excellent adsorption and catalysis efficiency, simple preparation process and the like, and can be rapidly realized in a large scale.
Furthermore, the preparation method provided by the invention has simple and efficient overall process, the dispersion concentration of the bismuth oxybromide can be regulated and controlled by controlling the using amount of the dispersing agent, the covalent linkage between the compounds has strong stability and high load stability, is easy to recover, enhances the circulating photocatalytic degradation capability of the bismuth oxybromide on pollutants, and has better industrial application prospect.
The invention has the advantages that:
1. the bismuth oxybromide/polypyrrole composite photocatalytic material is prepared by preparing a two-dimensional bismuth oxybromide semiconductor material by a one-step photochemical reaction method and then linking the semiconductor material and pyrrole through a stable covalent bond by using an in-situ solution polymerization method. Compared with pure bismuth oxybromide, the composite material effectively improves the adsorption capacity of the composite material to dye, the photocatalytic efficiency and the cyclic catalysis stability. After the two-dimensional bismuth oxybromide and the polypyrrole are covalently linked by the method, on one hand, the defect that pure bismuth oxybromide is easy to agglomerate and low in catalytic effect is effectively overcome, the dispersibility of the bismuth oxybromide is improved, and the capability of degrading pollutants by photocatalysis is improved; on the other hand, the mutual contact between the semiconductor material and the polypyrrole conjugated organic material is facilitated by the in-situ modification of the polypyrrole, the light absorption range of the polypyrrole conjugated organic material is expanded, the separation efficiency of a photoproduction electron hole is accelerated, the load stability of the polypyrrole conjugated organic material is improved, the circulating photocatalytic degradation capability of the polypyrrole conjugated organic material on pollutants is further enhanced, the polypyrrole conjugated organic material is easy to recover, the high recovery rate and the good recycling performance are achieved, and the polypyrrole conjugated organic material has a good industrial application prospect.
2. The polypyrrole covalent modified flaky bismuth oxybromide photocatalytic material is prepared by bismuth oxybromide and pyrrole in a dilute acid environment through a one-step solution polymerization method. The dispersion concentration of the bismuth oxybromide can be regulated and controlled by controlling the using amount of the dispersing agent, the covalent linkage stability is strong, the preparation process is simple, the feasibility is strong, and the practical application of photocatalysis is facilitated.
Drawings
FIG. 1 is an XRD pattern of pure Ppy, pure BiOBr and BiOBr/Ppy obtained in example 1;
FIG. 2 is a Raman spectrum of pure Ppy, pure BiOBr and BiOBr/Ppy obtained in example 1;
FIG. 3 is an XPS plot of pure BiOBr and BiOBr/Ppy from example 1, wherein a is a full spectrum plot of pure BiOBr and BiOBr/Ppy and b is a partial spectrum plot taken from the full spectrum plot;
FIG. 4 is an SEM image of pure BiOBr and BiOBr/Ppy made in example 1, where a is an SEM image of pure BiOBr and b is an SEM image of BiOBr/Ppy;
FIG. 5 is a TEM image of BiOBr/Ppy prepared in example 1 at different magnifications;
FIG. 6 is a graph of the UV-VIS absorption spectra of pure BiOBr and BiOBr/Ppy obtained in example 1;
FIG. 7 is a graph showing the effect of BiOBr/Ppy prepared from pure Ppy, pure BiOBr and examples 1-3 on the photocatalytic degradation of methyl orange at different times;
FIG. 8 is a graph of the fluorescence spectra of pure BiOBr and BiOBr/Ppy obtained in example 1;
FIG. 9 is a graph of the degradation activity of BiOBr/Ppy from example 1, the catalyst from the comparative example, and pure BiOBr versus methyl orange at 50 mL1.5mg/mL;
FIG. 10 is a stability test curve of BiOBr/Ppy obtained in example 1.
Detailed Description
The invention provides a polypyrrole-modified nano bismuth oxybromide photocatalytic material (BiOBr/PPy), which comprises sheet bismuth oxybromide and polypyrrole coated on the surface of the sheet bismuth oxybromide, wherein the sheet bismuth oxybromide and the polypyrrole are bonded through a covalent bond.
In the present invention, the mass ratio of the flaky bismuth oxybromide to the polypyrrole is preferably 1: 2-6, more preferably 1: 3.
in the invention, the flake thickness of the polypyrrole-modified nano bismuth oxybromide photocatalytic material is preferably 120-150 nm.
The invention also provides a preparation method of the polypyrrole-modified nano bismuth oxybromide photocatalytic material, which comprises the following steps:
dispersing the flaky nano bismuth oxybromide in a dilute acid aqueous solution containing hexadecyl trimethyl ammonium bromide and ammonium persulfate to obtain a dispersion liquid;
and (3) in an ice bath, dropwise adding pyrrole monomers into the dispersion liquid, and then carrying out in-situ solution polymerization reaction to obtain the polypyrrole coated and modified nano bismuth oxybromide photocatalytic material.
In the invention, the preparation method of the flaky nano bismuth oxybromide is preferably as follows: dissolving bismuth nitrate and potassium bromide in a dilute nitric acid aqueous solution, and carrying out one-step photochemical reaction treatment under the irradiation of simulated sunlight to obtain sheet-shaped nano bismuth oxybromide, wherein the mass fraction of the dilute nitric acid is 3-8%, and the volume of the dilute nitric acid, the molar weight of the bismuth nitrate and the molar weight of the potassium bromide are in a ratio of 15-25 mL: 0.8-1.5 mmol: 0.8-1.5 mmol; the illumination light source of the simulated sunlight is a 500W xenon lamp, and the reaction time is 0.5-3 h.
In the invention, the mass concentration of the flaky nano bismuth oxybromide in the dispersion liquid is preferably 2-8 mg/mL.
In the invention, the molar ratio of the hexadecyl trimethyl ammonium bromide to the ammonium persulfate is preferably 0.2-0.8: 50-200.
In the invention, the preferable dosage ratio of the flaky nano bismuth oxybromide to the pyrrole monomer is 15-35 mg: 0.2-0.5 mL.
In the invention, the dilute acid aqueous solution is preferably dilute hydrochloric acid with the concentration of 0.5-1.5 mol/L.
In a specific embodiment of the invention, the volume of the dilute hydrochloric acid, the amount of the cetyl trimethyl ammonium bromide, the ammonium persulfate, the flaky nano bismuth oxybromide and the pyrrole monomer is preferably 2-8 mL: 0.0182: 0.0228: 15-35 mg: 0.35 mL.
In the invention, the dripping is preferably carried out at 0-10 ℃, and the dripping speed is preferably 0.1-0.2 mL/min.
In the invention, the temperature of the in-situ solution polymerization reaction is preferably 25-35 ℃, and the time is preferably 15-20 h.
After the in-situ solution polymerization reaction is finished, the BiOBr/PPy is preferably prepared by washing the obtained in-situ solution polymerization reaction product with deionized water and absolute ethyl alcohol and then drying the product in vacuum at room temperature.
In the invention, the temperature of the vacuum drying is preferably 25-35 ℃, and the time is preferably 15-20 h.
The invention also provides the polypyrrole-modified nano bismuth oxybromide photocatalytic material prepared by the preparation method in the technical scheme or the application of the polypyrrole-modified nano bismuth oxybromide photocatalytic material in the fields of dye adsorption and photocatalytic degradation.
In the present invention, the application is preferably carried out at a pH of 7.
In the present invention, the application is preferably: suspending the polypyrrole-modified nano bismuth oxybromide photocatalytic material in an organic pollutant aqueous solution, adjusting the pH of the system to 7, uniformly mixing, and stirring for a period of time to achieve adsorption balance; and then carrying out photocatalytic reaction on the mixed solution under the irradiation of sunlight or simulated sunlight.
In order to further illustrate the present invention, the polypyrrole-modified nano bismuth oxybromide photocatalytic material provided by the present invention, the preparation method and the application thereof are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
(1) Respectively adding 0.8mmol of bismuth nitrate pentahydrate and 0.8mmol of potassium bromide into 15mL of dilute nitric acid with the mass fraction of 3%, completely dissolving, carrying out photoreaction under the irradiation of a 500W xenon lamp, controlling the reaction time to be 0.5h, and after the reaction is finished, centrifuging, washing for multiple times, and drying in vacuum to obtain the flaky nano bismuth oxybromide.
(2) 0.0182g of hexadecyl trimethyl ammonium bromide and 0.0228g of ammonium persulfate are weighed and added into 5mL of dilute hydrochloric acid with the concentration of 1mol/L, after uniform dissolution, 25mg of flaky bismuth oxybromide obtained by the reaction is dispersed in the dilute hydrochloric acid, then 0.35mL of pyrrole monomer is dropwise added in an ice bath, the reaction and polymerization are carried out for 18h at room temperature (25 ℃), and the product is centrifuged, washed and vacuum-dried to obtain the nano bismuth oxybromide composite material (BiOBr/Ppy) modified by brown polypyrrole.
FIG. 1 shows XRD patterns of BiOBr/Ppy composites of pure Ppy, pure BiOBr and example 1, wherein Ppy is a conjugated conductive polymer and is mostly amorphous polymer, and as can be seen from FIG. 1, the diffraction peak 2 theta of pure Ppy is mainly located between 13 DEG and 30 DEG and shows a wider diffraction peak, and the main peak is located near 21 DEG, indicating that Ppy is an amorphous structure with a very low degree of order. The diffraction peaks of pure BiOBr are mainly located at 11.0 degrees, 21.9 degrees, 25.3 degrees, 31.8 degrees, 32.2 degrees, 39.4 degrees, 46.2 degrees, 57.3 degrees and the corresponding crystal faces are (001), (002), (011), (012), (110), (112), (020), (212), and correspond to standard cards (JCPDSNo.09-0393) one by one, which shows that the purity of BiOBr prepared by adopting photochemical reaction is higher, while for BiOBr/Ppy composite materials, the diffraction peaks corresponding to pure BiOBr appear, but the sharpness degree of the diffraction peaks is broadened, and the amorphous Ppy is uniformly modified on the surface of the BiOBr.
FIG. 2 is a Raman spectrum of pure Ppy, pure BiOBr and BiOBr/Ppy composites made in example 1. Through the comparison of Raman spectra, the pure Ppy is observed to be 1580cm-1About 1330cm of C-C stretching vibration on the pyrrole skeleton-1A relatively high disorder degree appears nearby, and no corresponding peak appears in pure BiOBr; in the BiOBr/Ppy composite material, the thickness is 1580cm-1The C ═ C stretching vibration peak on the corresponding pyrrole skeleton appears nearby, and the peak is 1330cm-1The degree of nearby disorder is relatively reduced; the wave number was shifted compared to pure Ppy, indicating that BiOBr is compared to pure PpyThe strong interaction of Ppy allows Ppy to form a more broadly conjugated system with BiOBr.
FIG. 3 is an XPS plot of BiOBr/Ppy of BiOBr and BiOBr/Ppy of example 1, wherein a is a full spectrum plot of BiOBr and BiOBr/PPy, and the comparison shows that five elements of Br, Bi, C, O and N exist in BiOBr/PPy, b is a partial spectrum cut from the full spectrum plot, and b shows that Bi 4f in BiOBr/PPy is compared with the full BiOBr7/2And Bi 4f5/2The binding energy of (b) is significantly increased, indicating that there is a strong interfacial interaction between the BiOBr and PPy. The increase of the surface atomic bonding energy of Bi 4f shows that BiOBr/PPy is more stable under the irradiation of simulated sunlight than pure BiOBr.
FIG. 4 is an SEM image of pure BiOBr and BiOBr/Ppy obtained in example 1, wherein a is the SEM image of pure BiOBr, from which it can be seen that BiOBr shows a flake structure with different sizes and flake thicknesses of about 80-100 nm, and b is the SEM image of BiOBr/Ppy, from which it can be seen that BiOBr is coated by Ppy, the flake size is obviously reduced, and the flake thickness is increased to 120-150 nm.
FIG. 5 is a TEM image of BiOBr/Ppy prepared in example 1 at different magnifications. It can be seen from the figure that BiOBr/Ppy is a composite material formed by coating Ppy on sheet BiOBr and mutually overlapping, the formed BiOBr/PPy has a large contact area, strong interaction exists between the BiOBr/PPy and the sheet BiOBr/PPy, the lattice fringes of the BiOBr can be obviously seen from a high resolution image of the BiOBr/PPy, and the measured result, the interplanar spacing d is 0.281nm and corresponds to the (012) crystal plane of the BiOBr.
The UV-VIS absorption spectra of pure BiOBr and BiOBr/Ppy obtained in example 1 in FIG. 6 show that pure BiOBr and BiOBr/Ppy have good light absorption in the UV region; after BiOBr is coated and modified by PPy, the absorption range of BiOBr/Ppy in a visible light area is subjected to red shift relative to BiOBr, and the absorption intensity of BiOBr/Ppy in the visible light area is obviously increased; meanwhile, according to a formula Eg-1239.18/lambdag (absorption wavelength threshold), the energy gap width of BiOBr can be calculated to be about 2.75eV, and the energy gap width of BiOBr/Ppy is calculated to be about 1.5eV, so that the BiOBr/Ppy composite material coated with Ppy effectively widens the absorption range and the absorption intensity of BiOBr to visible light, and simultaneously reduces the band gap width, thereby being beneficial to improving the photocatalytic performance of the BiOBr/Ppy composite material under sunlight.
FIG. 8 is a fluorescence spectrum of pure BiOBr and BiOBr/Ppy obtained in example 1. As can be seen from FIG. 8, BiOBr has an emission peak at 400-500 nm, which is mainly caused by the recombination of valence band photogenerated holes and conduction band electrons. After PPy is coated, the fluorescence intensity of the emission peak of the BiOBr/Ppy composite material is obviously weakened, which shows that energy level structure coupling occurs in the interaction of BiOBr and Ppy, and the introduction of a conjugated conductive structure effectively promotes the separation of electrons and holes generated under visible light, so that the intensity of the emission peak of a fluorescence spectrum is weakened, and the photocatalysis capability of BiOBr/Ppy is enhanced.
Example 2
(1) Respectively adding 0.8mmol of bismuth nitrate pentahydrate and 0.8mmol of potassium bromide into 15mL of dilute nitric acid with the mass fraction of 3%, completely dissolving, carrying out photoreaction under the irradiation of a 500W xenon lamp, controlling the reaction time to be 0.5h, and after the reaction is finished, centrifuging, washing for multiple times, and drying in vacuum to obtain the flaky nano bismuth oxybromide.
(2) Weighing 0.0182g of hexadecyl trimethyl ammonium bromide and 0.0228g of ammonium persulfate, adding the weighed materials into 5mL of dilute hydrochloric acid with the concentration of 1mol/L, uniformly dissolving, dispersing 15mg of flaky bismuth oxybromide obtained by the reaction in the diluted hydrochloric acid, dropwise adding 0.35mL of pyrrole monomer in an ice bath, reacting and polymerizing for 18h at room temperature (25 ℃), and centrifuging, washing and vacuum drying the product to obtain the nano bismuth oxybromide composite material modified by the tan polypyrrole, wherein the name of the nano bismuth oxybromide composite material is BiOBr/Ppy.
Example 3
(1) Respectively adding 0.8mmol of bismuth nitrate pentahydrate and 0.8mmol of potassium bromide into 15mL of dilute nitric acid with the mass fraction of 3%, completely dissolving, carrying out photoreaction under the irradiation of a 500W xenon lamp, controlling the reaction time to be 0.5h, and after the reaction is finished, centrifuging, washing for multiple times, and drying in vacuum to obtain the flaky nano bismuth oxybromide.
(2) Weighing 0.0182g of hexadecyl trimethyl ammonium bromide and 0.0228g of ammonium persulfate, adding the weighed materials into 5mL of dilute hydrochloric acid with the concentration of 1mol/L, uniformly dissolving, dispersing 35mg of flaky bismuth oxybromide obtained by the reaction in the diluted hydrochloric acid, dropwise adding 0.35mL of pyrrole monomer in an ice bath, reacting and polymerizing for 18h at room temperature (25 ℃), and centrifuging, washing and vacuum drying the product to obtain the nano bismuth oxybromide composite material modified by the tan polypyrrole, wherein the name of the nano bismuth oxybromide composite material is BiOBr/Ppy.
The BiOBr/Ppy composite photocatalytic material prepared in the embodiment 1-3 is applied to a photocatalytic degradation experiment of an organic dye methyl orange, and the specific process and steps are as follows:
the BiOBr/Ppy composite photocatalytic material prepared in the embodiment 1-3 is dispersed in 50mL of methyl orange solution (the concentration is 30mg/L), and after the dispersion is uniform, the mixture is stirred for a period of time to enable the mixture to reach adsorption and desorption balance; and then transferring the dispersion liquid into a xenon lamp light catalytic reaction instrument (under the irradiation of simulated sunlight), sampling every 10min after the start of a photocatalytic reaction, after 50min of reaction, centrifugally separating the extracted dispersion liquid, transferring the dispersion liquid into a quartz cuvette, and measuring the absorbance at different photocatalytic times by using an ultraviolet-visible spectrophotometer, thereby obtaining the photocatalytic degradation effect of the photocatalytic material on the methyl orange at different times. The results are shown in FIG. 7, where 15mg BiOBr/Ppy in FIG. 7 represents BiOBr/Ppy prepared using 15mg BiOBr in example 2, 25mg BiOBr/Ppy represents BiOBr/Ppy prepared using 25mg BiOBr in example 1, and 35mg BiOBr/Ppy represents BiOBr/Ppy prepared using 35mg BiOBr in example 3. As can be seen from the figure, compared with pure BiOBr, photolysis experiments under dark conditions and methyl orange prove that the adsorption performance and the photodegradation performance of the composite material to methyl orange are obviously improved, the adsorption performance and the photodegradation performance of the composite material are changed along with the addition ratio of BiOBr, the core-shell type BiOBr/PPy (25mg) has higher adsorption performance and photodegradation performance, the degradation efficiency to methyl orange in simulated sunlight within 50min is 88%, and under the same conditions, the degradation efficiencies of the core-shell type BiOBr/Py (15mg), BiOBr/PPy (35mg) and pure BiOBr to methyl orange are about 13%, 40% and 10%.
Meanwhile, stability tests are carried out on the BiOBr/Ppy prepared in example 1, and the results are shown in FIG. 10, which shows that the photocatalytic efficiency of the recovered product for three-cycle degradation of methyl orange is still maintained at 40% within 50min of illumination, thus demonstrating that the BiOBr/Ppy prepared by the invention has stable photocatalytic performance.
Comparative example 1
The same as in example 1, except that the temperature of the in situ solution polymerization reaction was 50 ℃.
FIG. 9 shows the degradation activity curves of BiOBr/Ppy prepared in example 1, the catalyst prepared in comparative example and pure BiOBr on 50mL1.5mg/mL methyl orange, and it can be seen from FIG. 9 that the temperature of the in situ solution polymerization reaction has a great influence on the catalytic effect of the product.
The foregoing is merely a preferred embodiment of the invention and is not intended to limit the invention in any manner. It should be noted that, for those skilled in the art, without departing from the principle of the present invention, several improvements and modifications can be made, and these improvements and modifications should also be construed as the protection scope of the present invention.
Claims (2)
1. A polypyrrole-modified nano bismuth oxybromide photocatalytic material is characterized by comprising sheet bismuth oxybromide and polypyrrole coated on the surface of the sheet bismuth oxybromide, wherein the sheet bismuth oxybromide and the polypyrrole are bonded through covalent bonds;
the preparation method of the polypyrrole-modified nano bismuth oxybromide photocatalytic material comprises the following steps:
(1) respectively adding 0.8mmol of bismuth nitrate pentahydrate and 0.8mmol of potassium bromide into 15mL of dilute nitric acid with the mass fraction of 3%, completely dissolving, carrying out photoreaction under the irradiation of a 500W xenon lamp, controlling the reaction time to be 0.5h, and after the reaction is finished, centrifuging, washing for multiple times and drying in vacuum to obtain the flaky nano bismuth oxybromide;
(2) weighing 0.0182g of hexadecyl trimethyl ammonium bromide and 0.0228g of ammonium persulfate, adding the weighed materials into 5mL of dilute hydrochloric acid with the concentration of 1mol/L, uniformly dissolving, dispersing 25mg of flaky bismuth oxybromide obtained by the reaction in the diluted hydrochloric acid, dropwise adding 0.35mL of pyrrole monomer in an ice bath, reacting and polymerizing for 18h at room temperature, and centrifuging, washing and vacuum drying the product to obtain the brown polypyrrole modified nano bismuth oxybromide composite material.
2. The polypyrrole-modified nano bismuth oxybromide photocatalytic material of claim 1 is applied to the fields of dye adsorption and photocatalytic degradation.
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