CN108212187B - Fe doped Bi2O2CO3Preparation method of photocatalyst and Fe-doped Bi2O2CO3Photocatalyst and process for producing the same - Google Patents
Fe doped Bi2O2CO3Preparation method of photocatalyst and Fe-doped Bi2O2CO3Photocatalyst and process for producing the same Download PDFInfo
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title claims description 26
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 22
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 22
- 239000002019 doping agent Substances 0.000 claims abstract description 17
- 238000002360 preparation method Methods 0.000 claims abstract description 17
- 239000001509 sodium citrate Substances 0.000 claims abstract description 16
- 239000003960 organic solvent Substances 0.000 claims abstract description 15
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims abstract description 13
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims description 25
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 2
- 150000001875 compounds Chemical class 0.000 claims 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims 1
- 244000248349 Citrus limon Species 0.000 claims 1
- 235000005979 Citrus limon Nutrition 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 16
- 239000013078 crystal Substances 0.000 abstract description 14
- 238000007146 photocatalysis Methods 0.000 abstract description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 39
- 230000000052 comparative effect Effects 0.000 description 23
- 239000000243 solution Substances 0.000 description 20
- 239000000047 product Substances 0.000 description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 230000000694 effects Effects 0.000 description 10
- 239000011259 mixed solution Substances 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- 239000012153 distilled water Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 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 5
- 229940012189 methyl orange Drugs 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 3
- 230000000593 degrading effect Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 238000000985 reflectance spectrum Methods 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 3
- 230000032900 absorption of visible light Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 239000004005 microsphere Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- PPNKDDZCLDMRHS-UHFFFAOYSA-N bismuth(III) nitrate Inorganic materials [Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PPNKDDZCLDMRHS-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
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Images
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/232—Carbonates
-
- B01J35/39—
-
- B01J35/61—
Abstract
Fe doped Bi2O2CO3Preparation method of photocatalyst and Fe-doped Bi2O2CO3A photocatalyst belongs to the technical field of photocatalysis. The preparation method comprises the following steps: will contain Fe3+In the presence of Bi (NO) dissolved in the dopant3)3And sodium citrate in alkaline organic solvent solution, and hydrothermal reaction in ammonia water. The photocatalyst was prepared according to the above preparation method. Capable of incorporating Fe into Bi2O2CO3In the crystal lattice of (2), Bi can be increased2O2CO3Absorb visible light, thereby improving Bi2O2CO3The photocatalytic activity of visible light.
Description
Technical Field
The invention relates to the technical field of photocatalysis, in particular to Fe-doped Bi2O2CO3Preparation method of photocatalyst and Fe-doped Bi2O2CO3A photocatalyst.
Background
With the rapid development of industry, the environmental pollution is more and more serious. The method for degrading pollutants by utilizing solar energy and a photocatalysis technology is an energy-saving and environment-friendly pollution treatment technology, and is considered to be the most effective and promising method for solving the environmental problems. Bi2O2CO3The photocatalyst is a novel photocatalyst, can degrade organic pollutants under ultraviolet light, and has higher activity than commercial P25. However, Bi2O2CO3Has a forbidden band width of about 3.4eV, and cannot absorb visible light. In addition, the ultraviolet light of sunlight accounts for only about 4.5%, while the visible light accounts for about 45%. Thus, Bi is caused to be2O2CO3In practiceIs greatly limited in application.
Therefore, it is necessary to take effective measures to increase Bi2O2CO3The sensitivity to visible light is enhanced in the absorption range of the visible light.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The invention aims to provide Fe-doped Bi2O2CO3Method for preparing photocatalyst capable of increasing Bi2O2CO3Absorb visible light, thereby improving Bi2O2CO3The photocatalytic activity of visible light.
Another object of the present invention is to provide a Bi-doped Fe2O2CO3The photocatalyst has enhanced absorption of visible light and enhanced photocatalytic activity of visible light.
The embodiment of the invention is realized by the following steps:
fe-doped Bi2O2CO3A method of preparing a photocatalyst, comprising: will contain Fe3+In the presence of Bi (NO) dissolved in the dopant3)3And sodium citrate in alkaline organic solvent solution, and hydrothermal reaction in ammonia water.
Fe-doped Bi2O2CO3A photocatalyst prepared according to the above-mentioned preparation method.
The embodiment of the invention has the beneficial effects that:
the Fe doped Bi provided by the invention2O2CO3The preparation method of the photocatalyst is found by the research of the inventor that Fe3+Doping into Bi2O2CO3In the crystal lattice of (B), Bi can be effectively increased2O2CO3Absorb visible light, thereby effectively improving Bi2O2CO3The photocatalytic activity of visible light. The inventors also found that Fe is added3+In an alkaline organic solvent solution, Fe3+In Bi2O2CO3The doping effect in the crystal lattice is good, and the particle size of the synthesized substance is small, the specific surface area is large, so that the prepared Bi2O2CO3The photocatalytic activity of the visible light is further improved.
The Fe doped Bi provided by the invention2O2CO3The photocatalyst is prepared by the preparation method, so that the photocatalyst has the advantages of enhanced absorption of visible light and enhanced visible light photocatalytic activity.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
FIG. 1 is a scanning electron micrograph of a comparative example of the present invention;
FIG. 2 is a scanning electron microscope image of a test example of the present invention;
FIG. 3 is XRD patterns of a test example of the present invention and a comparative example;
FIG. 4 shows the experimental example and comparative example in FIG. 3, where 2 θ is 30.2o(ii) a magnified map of (a);
FIG. 5 shows XPS high resolution spectra of experimental examples of the present invention;
FIG. 6 is a UV-VIS diffuse reflectance spectrum of a test example of the present invention and a comparative example;
FIG. 7 is a graph showing the comparative activity of the test examples and comparative examples of the present invention against the degradation of methyl orange.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
Following Fe-doped Bi of the examples of the invention2O2CO3Preparation method of photocatalyst and Fe-doped Bi2O2CO3The photocatalyst is specifically described.
The invention provides Fe-doped Bi2O2CO3A method of preparing a photocatalyst, comprising: will contain Fe3+In the presence of Bi (NO) dissolved in the dopant3)3And sodium citrate in alkaline organic solvent solution, and hydrothermal reaction in ammonia water.
Bi2O2CO3Is a typical bismuth-based composite oxide, consisting of Bi2O2 2+And CO3 2–The bent space structure of the composite material shows unique photocatalytic performance under the irradiation of ultraviolet-visible light. The inventor researches and discovers that Fe3+Doping into Bi2O2CO3In the crystal lattice of (B), Bi can be effectively increased2O2CO3Absorb visible light, thereby effectively improving Bi2O2CO3The photocatalytic activity of visible light.
Containing Fe3+As an iron source, providing Fe3+Into Bi2O2CO3In the crystal lattice of (1). In some embodiments of the invention, the Fe-containing compound3+The doping agent adopts Fe-containing3+The inorganic salt of (A) provides Fe3+. Further, in some preferred embodiments, the Fe-containing material comprises Fe3+The dopant of (A) is Fe (NO)3)3. In addition, in some other embodiments of the present invention, the Fe-containing compound3+The dopant of (A) may also be FeCl3、Fe2(SO4)3And (3) equistrong acid and weak base salt.
Using the above iron source as the Fe-containing3+In Bi2O2CO3The doping effect in the crystal lattice is good; meanwhile, the production of byproducts can be effectively avoided, thereby improving the quality of products.
In a specific embodiment of the invention, Fe3+Doping ofIn Bi (NO)3)3And sodium citrate, adding iron source into the solution system, and then adding ammonia water to carry out hydrothermal reaction.
Bi(NO3)3And the solution system of sodium citrate is an alkaline organic solution system. The inventor researches and discovers that the Fe-containing alloy contains Fe3+Is doped in an alkaline agent, Fe3+In Bi2O2CO3The doping effect in the crystal lattice is good; at the same time, Fe3+The doping agent of (2) can be controlled in an organic solvent to form a catalyst with smaller particle size, so that the specific surface area is increased, and the photocatalytic activity of the catalyst is improved. In some preferred embodiments of the invention, the basic organic solvent is N, N-dimethylformamide.
The addition of ammonia water can control Fe3+Doping of (3). In a preferred embodiment of the present invention, the mass concentration of the ammonia water is 25-35%. Preferably, the concentration is 25 to 30%. More preferably 28%, but of course also for example: 25%, 26%, 27%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, etc.
The inventor researches and discovers that Bi (NO) is controlled3)3Sodium citrate, alkaline organic solvent, Fe-containing3+The dosage ratio of the doping agent to the ammonia water is 0.8-1.2 g: 0.15-0.45 g: 8-12 ml: 0.02 g-0.15 g: 3-8 ml of Fe3+In Bi2O2CO3The doping in the crystal lattice has better effect; the obtained substance has small particle size, large specific surface area and strong visible light photocatalysis performance.
Preferably, the Bi (NO)3)3Sodium citrate, alkaline organic solvent, Fe-containing3+The dosage ratio of the doping agent to the ammonia water is 0.9-1.1 g: 0.25-0.35 g: 9-11 ml: 0.05 g-0.15 g: 4-6 ml.
Further, the Bi (NO)3)3Sodium citrate, alkaline organic solvent, Fe-containing3+The dosage of the doping agent and the ammonia water is preferably controlled to be 0.97 g: 0.3 g: 10 ml: 0.1 g: 5 ml.
The hydrothermal reaction is transferred to a hydrothermal kettle after the ammonia water is added. In a preferred embodiment of the present invention, the reaction temperature is kept at 170-190 ℃ during the hydrothermal reaction, and the temperature is kept for 1-12 h, so as to ensure the reactants in the hydrothermal reaction to fully react and avoid the generation of byproducts as far as possible. Preferably, the reaction temperature is 175-185 ℃, and the reaction time is 9-11 h. Further preferably, the reaction temperature is 170 ℃ and the reaction time is 10 hours.
After the hydrothermal reaction is finished, washing and drying the product after the hydrothermal kettle is cooled, and obtaining the prepared Bi2O2CO3A photocatalyst.
And in the washing operation, distilled water and ethanol are used for alternately washing the precipitate obtained by the reaction until the product is washed clean.
The drying is preferably carried out at a temperature of 55 to 65 ℃ and maintained at the temperature for 7 to 9 hours. In some embodiments of the present invention, the drying temperature is preferably 60 ℃, and the drying time is preferably 8 hours, so that the drying effect is good, and the influence on the performance of the product is avoided.
The invention provides Fe-doped Bi2O2CO3The photocatalyst is prepared by the preparation method, so that the photocatalyst has the advantages of good absorption effect on visible light, small particle size, large specific surface area and the like, and has strong visible light photocatalytic activity.
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1
Fe-doped Bi2O2CO3A method of preparing a photocatalyst, comprising:
s1, 0.97gBi (NO)3)3And 0.3g of sodium citrate was dissolved in 10ml of N, N-dimethylformamide to obtain a reaction solution.
S2, adding 0.1g Fe (NO) into the reaction solution3)3Stirring evenly, and adding 5ml of ammonia water with the mass concentration of 28% to obtain a reaction mixed solution.
S3, transferring the reaction mixed solution into a hydrothermal kettle, preserving the heat for 12 hours at the temperature of 170 ℃, cooling, and carrying out solid-liquid separation to obtain a primary product.
S4, alternately cleaning the primary product with distilled water and ethanol, and drying at 60 ℃ for 8h to obtain Bi2O2CO3A photocatalyst.
Fe-doped Bi prepared according to the preparation method2O2CO3A photocatalyst.
Example 2
Fe-doped Bi2O2CO3A method of preparing a photocatalyst, comprising:
s1, 0.8gBi (NO)3)3And 0.15g of sodium citrate was dissolved in 8ml of N, N-dimethylformamide to obtain a reaction solution.
S2, adding 0.02g Fe (NO) into the reaction solution3)3Stirring evenly, adding 3ml of ammonia water with the mass concentration of 35% to obtain a reaction mixed solution.
S3, transferring the reaction mixed solution into a hydrothermal kettle, preserving the heat for 11 hours at the temperature of 175 ℃, cooling, and carrying out solid-liquid separation to obtain a primary product.
S4, alternately cleaning the primary product with distilled water and ethanol, and drying at 60 ℃ for 8h to obtain Bi2O2CO3A photocatalyst.
Fe-doped Bi prepared according to the preparation method2O2CO3A photocatalyst.
Example 3
Fe-doped Bi2O2CO3A method of preparing a photocatalyst, comprising:
s1, 0.9 (NO) 0.9gBi3)3And 0.25g of sodium citrate was dissolved in 9ml of N, N-dimethylformamide to obtain a reaction solution.
S2, adding 0.05g Fe (NO) into the reaction solution3)3Stirring evenly, adding 4ml ammonia water with mass concentration of 30% to obtain reaction mixed liquid.
S3, transferring the reaction mixed solution into a hydrothermal kettle, preserving the heat for 9 hours at the temperature of 185 ℃, cooling, and carrying out solid-liquid separation to obtain a primary product.
S4, mixing the primary productCleaning with distilled water and ethanol alternately, drying at 55 deg.C for 9h to obtain Bi2O2CO3A photocatalyst.
Fe-doped Bi prepared according to the preparation method2O2CO3A photocatalyst.
Example 4
Fe-doped Bi2O2CO3A method of preparing a photocatalyst, comprising:
s1, 1.1gBi (NO)3)3And 0.35g of sodium citrate was dissolved in 11ml of N, N-dimethylformamide to obtain a reaction solution.
S2, adding 0.05g Fe (NO) into the reaction solution3)3Stirring evenly, adding 6ml ammonia water with mass concentration of 30% to obtain reaction mixed liquid.
S3, transferring the reaction mixed solution into a hydrothermal kettle, preserving the heat for 8 hours at the temperature of 190 ℃, cooling, and carrying out solid-liquid separation to obtain a primary product.
S4, alternately cleaning the primary product with distilled water and ethanol, and drying at 60 ℃ for 8h to obtain Bi2O2CO3A photocatalyst.
Fe-doped Bi prepared according to the preparation method2O2CO3A photocatalyst.
Example 5
Fe-doped Bi2O2CO3A method of preparing a photocatalyst, comprising:
s1, 1.2 (NO) 1.2gBi3)3And 0.45g of sodium citrate was dissolved in 12ml of N, N-dimethylformamide to obtain a reaction solution.
S2, adding 0.15g Fe (NO) into the reaction solution3)3Stirring evenly, adding 8ml of ammonia water with the mass concentration of 25% to obtain a reaction mixed solution.
S3, transferring the reaction mixed solution into a hydrothermal kettle, preserving the heat for 10 hours at the temperature of 180 ℃, cooling, and carrying out solid-liquid separation to obtain a primary product.
S4, alternately cleaning the primary product with distilled water and ethanol, and heating to 65 deg.CDrying for 7h to obtain Bi2O2CO3A photocatalyst.
Fe-doped Bi prepared according to the preparation method2O2CO3A photocatalyst.
Fe doped Bi from example 12O2CO3The photocatalyst used as a test example was conventional Bi2O2CO3The photocatalyst was used as a comparative example.
The experimental examples and comparative examples were analyzed by scanning electron microscopy. FIG. 1 is a scanning electron micrograph of a comparative example, conventional Bi2O2CO3The structure of the photocatalyst is flower-shaped microspheres. FIG. 2 is a scanning electron micrograph of a test example in which Fe was doped3+Of Bi2O2CO3The structure of the photocatalyst was a cyclic microsphere similar to that of the comparative example. Illustrating the doping with Fe in the test examples3+Of Bi2O2CO3Photocatalyst and Bi conventional in comparative example2O2CO3The photocatalyst has a similar microstructure.
Meanwhile, as can be seen from fig. 1 and 2, the experimental examples were doped with Fe3+Of Bi2O2CO3The radius of the sphere of the photocatalyst is obviously smaller than that of the conventional Bi in the comparative example2O2CO3The radius of the flower ball of the photocatalyst shows that the Fe doped Bi prepared by the preparation method provided by the invention2O2CO3The photocatalyst has smaller particle size and larger specific surface area, and is beneficial to improving the photocatalytic performance of the product.
The X-ray diffraction analysis was performed on the test examples and the comparative examples, and the XRD patterns of the test examples and the comparative examples were obtained in fig. 3, and fig. 4 was obtained in the case where 2 θ was 30.2 in the test examples and the comparative examples of fig. 3oA magnified map of (a).
As can be seen from FIG. 3, in the test examples, Fe was doped3+Of Bi2O2CO3Photocatalyst and Bi conventional in comparative example2O2CO3All diffraction peaks of the photocatalyst correspond to tetragonal phase Bi2O2CO3(JCPDSNo41-1488) No other miscellaneous peak indicates that the doping of Fe does not change Bi2O2CO3The crystal structure of (1).
As can be seen from fig. 4, the (010) diffraction peak having 2 θ of 30.2 ° was carefully observed, and it was found that Fe was doped in the test example3+Of Bi2O2CO3This peak of the photocatalyst is relative to the conventional Bi in the comparative example2O2CO3The peak of the photocatalyst is slightly shifted due to Bi2O2CO3Bi3 with a part of large radius in crystal lattice+Fe with small ion envelope radius3+Ion is substituted for Fe3+Ions enter Bi2O2CO3The crystal lattice of (1).
The test examples were subjected to X-ray photoelectron spectroscopy, and XPS high-resolution spectra of the test examples were obtained as shown in FIG. 5.
As can be seen from FIG. 5, in the test examples, Fe was doped3+Of Bi2O2CO3Two peaks of Fe2p of photocatalyst, Fe2p3/2 at 711.5eV and Fe2p1/2 at 724eV, corresponding to Fe3+The chemical state of the element(s). The binding energy of the Fe2p3/2 peak is obviously higher than that of Fe2O3Middle Fe3+Binding energy of (2) also indicates Fe3+Replace Bi2O2CO3Bi in the crystal lattice3+。
Ultraviolet-visible diffuse reflectance spectrum analysis was performed on the test examples and comparative examples, and fig. 6 is an external-visible diffuse reflectance spectrum of the test examples and comparative examples.
As can be seen from FIG. 6, Bi conventional in the comparative example2O2CO3The photocatalyst does not absorb visible light, and the test examples are doped with Fe3+Of Bi2O2CO3The photocatalyst has obvious absorption at the wavelength of 400-600 nm, which shows that the doping of Fe improves Bi2O2CO3Absorption of visible light.
The activities of the test examples and the comparative examples for degrading methyl orange are compared, and fig. 7 is a graph comparing the activities of the test examples and the comparative examples for degrading methyl orange.
From FIG. 7As is known, Bi conventional in the comparative example2O2CO3The photocatalyst hardly degraded methyl orange after two hours, while the test examples were doped with Fe3+Of Bi2O2CO3The photocatalyst degrades about 98 percent of methyl orange, which shows that the doping of Fe obviously improves Bi2O2CO3Is optically active.
In summary, the Fe doped Bi in the embodiments of the invention2O2CO3Preparation method of photocatalyst and Fe-doped Bi2O2CO3Photocatalyst of Fe3+Doping into Bi2O2CO3In the crystal lattice of (B), Bi can be effectively increased2O2CO3Absorption of visible light; will contain Fe3 +In an alkaline organic solvent solution, Fe3+In Bi2O2CO3The doping effect in the crystal lattice is good, and the synthesized substance has small grain diameter and large specific surface area. Thereby effectively improving Bi2O2CO3The photocatalytic activity of visible light.
The embodiments described above are some, but not all embodiments of the invention. The detailed description of the embodiments of the present invention is not intended to limit the scope of the invention as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Claims (14)
1. Fe-doped Bi2O2CO3A method for preparing a photocatalyst, comprising: will contain Fe3+In the presence of Bi (NO) dissolved in the dopant3）3And sodium citrate in alkaline organic solvent solution, and carrying out hydrothermal reaction under the condition of containing ammonia water, wherein:
the basic organic solvent comprises N, N-dimethylformamide;
the Bi (NO)3）3The lemon isSodium citrate, the basic organic solvent, the Fe-containing3+The dosage ratio of the doping agent to the ammonia water is 0.8-1.2 g: 0.15-0.45 g: 8-12 ml: 0.02 g-0.15 g: 3-8 ml;
the reaction temperature of the hydrothermal reaction is 170-190 ℃, and the reaction time is 8-12 h.
2. The method according to claim 1, wherein the Fe-containing compound is3+The dopant is Fe-containing3+The inorganic salt of (1).
3. The method of claim 2, wherein the Fe is contained3+The dopant is Fe-containing3+The strong acid and weak base salt of (2).
4. The method according to claim 3, wherein the Fe-containing compound is3+The dopant of (A) is Fe (NO)3)3。
5. The method according to claim 1, wherein the aqueous ammonia has a mass concentration of 25 to 35%.
6. The method according to claim 5, wherein the ammonia water has a mass concentration of 25 to 30%.
7. The production method according to claim 6, wherein the mass concentration of the aqueous ammonia is 28%.
8. The method according to claim 1, wherein said Bi (NO)3）3The sodium citrate, the alkaline organic solvent, the Fe-containing3+The dosage ratio of the doping agent to the ammonia water is 0.9-1.1 g: 0.25-0.35 g: 9-11 ml: 0.05 g-0.15 g: 4-6 ml.
9. The method according to claim 8, wherein said Bi (NO)3）3The sodium citrate, the alkaline organic solvent, the Fe-containing3+The dosage ratio of the doping agent to the ammonia water is 0.97 g: 0.3 g: 10 ml: 0.1 g: 5 ml.
10. The method according to claim 1, wherein the hydrothermal reaction is carried out at a temperature of 175 to 185 ℃ for 9 to 11 hours.
11. The method according to claim 10, wherein the hydrothermal reaction is followed by washing and drying.
12. The method according to claim 11, wherein the drying temperature is 55 to 65 ℃ and the drying time is 7 to 9 hours.
13. The method according to claim 12, wherein the drying temperature is 60 ℃ and the drying time is 8 hours.
14. Fe-doped Bi prepared by the preparation method of any one of claims 1 to 132O2CO3A photocatalyst.
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