CN110052285B - Bismuth-based composite photocatalyst and synthesis method thereof - Google Patents
Bismuth-based composite photocatalyst and synthesis method thereof Download PDFInfo
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 110
- 239000002131 composite material Substances 0.000 title claims abstract description 93
- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 85
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 238000001308 synthesis method Methods 0.000 title claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 65
- 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 claims abstract description 37
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 32
- 238000001816 cooling Methods 0.000 claims abstract description 19
- 238000001035 drying Methods 0.000 claims abstract description 19
- 238000003756 stirring Methods 0.000 claims abstract description 19
- 238000005406 washing Methods 0.000 claims abstract description 19
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 11
- 238000000926 separation method Methods 0.000 claims abstract description 11
- 239000007788 liquid Substances 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 150000005846 sugar alcohols Polymers 0.000 claims abstract description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 53
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 12
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 12
- 229910002651 NO3 Inorganic materials 0.000 claims description 10
- 229920005862 polyol Polymers 0.000 claims description 5
- 150000003077 polyols Chemical class 0.000 claims description 5
- 229940068918 polyethylene glycol 400 Drugs 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims 6
- 230000001699 photocatalysis Effects 0.000 abstract description 17
- 239000000243 solution Substances 0.000 description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 12
- 239000012153 distilled water Substances 0.000 description 9
- 238000001228 spectrum Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- 238000000985 reflectance spectrum Methods 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 230000015556 catabolic process Effects 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 238000006731 degradation reaction Methods 0.000 description 5
- 238000007146 photocatalysis Methods 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002135 nanosheet Substances 0.000 description 3
- 239000002957 persistent organic pollutant Substances 0.000 description 3
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 3
- 229940043267 rhodamine b Drugs 0.000 description 3
- 241000282414 Homo sapiens Species 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 229910002900 Bi2MoO6 Inorganic materials 0.000 description 1
- 229910002915 BiVO4 Inorganic materials 0.000 description 1
- 150000001621 bismuth Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000007849 functional defect Effects 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 230000001089 mineralizing effect Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
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- 238000012827 research and development Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000007847 structural defect Effects 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 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
- B01J27/24—Nitrogen compounds
- B01J27/25—Nitrates
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Abstract
The invention discloses a bismuth-based composite photocatalyst and a synthesis method thereof, wherein the synthesis method comprises the following steps: mixing bismuth nitrate, cetyl trimethyl ammonium bromide and a polyalcohol solvent, and uniformly stirring to form a reaction solution, wherein the molar ratio of the bismuth nitrate to the cetyl trimethyl ammonium bromide in the reaction solution is 1: 3-1: 6; and (3) reacting the reaction solution at 90-130 ℃ for 4-24h, and after the reaction is finished, cooling, carrying out solid-liquid separation, washing and drying to obtain the bismuth-based composite photocatalyst. The synthesis method of the bismuth-based composite photocatalyst provided by the invention has the advantages of simple process, mild conditions, high yield, high photocatalytic activity of the obtained composite photocatalyst and good stability.
Description
Technical Field
The invention relates to the technical field of photocatalysis, in particular to a bismuth-based composite photocatalyst and a synthesis method thereof.
Background
Environmental pollution is a major challenge facing human beings at present and is also a major subject that must be considered in priority for implementing the strategy of sustainable development in our country. Environmental problems caused by toxic and refractory organic pollutants have become a great problem affecting human survival and health in the 21 st century. The pollutants have stable structure, high toxicity and low concentration, and are difficult to treat by the existing environmental technology, so that the research of a new method for effectively controlling toxic and nondegradable organic pollutants becomes a very concerned and troublesome subject at home and abroad.
The photocatalysis can convert the solar energy with low density into chemical energy and electric energy with high density, and can directly utilize the solar energy with low density to degrade and mineralize various pollutants in water and air, so the photocatalysis has great potential in the aspects of environmental purification and new energy development. The heterogeneous photocatalysis process using semiconductor micro-nano material as photocatalyst is an ideal environmental pollution treatment technology due to the unique properties of being capable of reacting at room temperature, directly utilizing sunlight, mineralizing organic pollutants, having no secondary pollution and the like.
In recent years, the bismuth-based composite oxide photocatalyst has attracted great interest to researchers due to its unique electronic structure, excellent visible light absorption capability and high organic matter degradation capability. At present, bismuth-based photocatalytic materials have been developed mainly comprising Bi2WO6、Bi2MoO6、BiVO4、BiPO4And the like. However, the reported bismuth-based photocatalyst has still to be improved in photocatalytic activity and stability due to its own structural and functional defects. Therefore, the research and development of novel bismuth-based photocatalytic materials become hot spots in the current chemical and material research fields.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides the bismuth-based composite photocatalyst and the synthesis method thereof, the synthesis method has the advantages of simple process, mild conditions and high yield, and the obtained composite photocatalyst has high photocatalytic activity and good stability.
The invention provides a synthesis method of a bismuth-based composite photocatalyst, which comprises the following steps: mixing bismuth nitrate, cetyl trimethyl ammonium bromide and a polyalcohol solvent, and uniformly stirring to form a reaction solution, wherein the molar ratio of the bismuth nitrate to the cetyl trimethyl ammonium bromide in the reaction solution is 1: 3-1: 6; and (3) reacting the reaction solution at 90-130 ℃ for 4-24h, and after the reaction is finished, cooling, carrying out solid-liquid separation, washing and drying to obtain the bismuth-based composite photocatalyst.
Preferably, the polyol solvent is one or more of ethylene glycol, glycerol, diethylene glycol and polyethylene glycol 400.
Preferably, the polyol solvent is ethylene glycol.
Preferably, the concentration of bismuth nitrate in the reaction solution is 0.02 to 0.08 mol/L.
Preferably, the molar ratio of bismuth nitrate to cetyltrimethylammonium bromide in the reaction solution is 1: 3.
preferably, the synthesis method of the bismuth-based composite photocatalyst comprises the following steps: adding 0.0012mol of bismuth nitrate and 0.0036-0.0072mol of hexadecyl trimethyl ammonium bromide into 15-60ml of ethylene glycol, and uniformly stirring to form a reaction solution; and (3) placing the reaction solution in a round-bottom flask, reacting for 4-24h at 90-130 ℃, naturally cooling after the reaction is finished, and washing and drying the obtained solid after centrifugal separation to obtain the bismuth-based composite photocatalyst.
Preferably, the synthesis method of the bismuth-based composite photocatalyst comprises the following steps: adding 0.0012mol of bismuth nitrate and 0.0036-0.0072mol of hexadecyl trimethyl ammonium bromide into 45ml of ethylene glycol, and uniformly stirring to form a reaction solution; and (3) placing the reaction solution in a round-bottom flask, reacting for 7 hours at 110 ℃, naturally cooling after the reaction is finished, and washing and drying the obtained solid after centrifugal separation to obtain the bismuth-based composite photocatalyst.
The invention also provides a bismuth-based composite photocatalyst, which is prepared by adopting the synthesis method of the bismuth-based composite photocatalyst.
In the synthesis method of the bismuth-based composite photocatalyst, bismuth nitrate and cetyl trimethyl ammonium bromide are used as raw materials, and the molar ratio of the bismuth nitrate to the cetyl trimethyl ammonium bromide is controlled to be 1: 3-1: 6, the temperature and the time of the reaction are adjusted simultaneously, and the bismuth-based composite photocatalyst is synthesized in one step and is BiOBr and [ Bi6O4(OH)4](NO3)6(H2O)4The composite material has simple process, mild condition, yield near 95%, high catalytic activity and high stability.
Drawings
FIG. 1 shows X-ray diffraction patterns and BiOBr and [ Bi ] of photocatalysts prepared in examples 1 and 2 of the present invention and comparative example 16O4(OH)4](NO3)6(H2O)4XRD standard card of (1);
FIG. 2 is an XPS high resolution spectrum of Bi 4f in the bismuth-based composite photocatalyst synthesized in example 1 of the present invention;
FIG. 3 is an XPS high resolution spectrum of O1 s in the bismuth-based composite photocatalyst synthesized in example 1 of the present invention;
FIG. 4 is an XPS high resolution spectrum of Br 3d in the bismuth-based composite photocatalyst synthesized in example 1 of the present invention;
FIG. 5 is an XPS high resolution spectrum of N1 s in the bismuth-based composite photocatalyst synthesized in example 1 of the present invention;
figure 6 is an SEM photograph of the bibbr photocatalyst synthesized in comparative example 1 of the present invention;
FIG. 7 is an SEM photograph of the bismuth-based composite photocatalyst synthesized in example 1 of the present invention;
figure 8 is a diffuse reflectance spectrum of a BiOBr photocatalyst synthesized in comparative example 1 of the present invention;
FIG. 9 is a diffuse reflectance spectrum of the bismuth-based composite photocatalyst synthesized in example 1 of the present invention;
FIG. 10 is a diffuse reflectance spectrum of the bismuth-based composite photocatalyst synthesized in example 2 of the present invention;
FIG. 11 is a graph showing the degradation efficiency of an aqueous solution of rhodamine B under UV-visible light irradiation in the presence of the photocatalyst synthesized in example 1, example 2 and comparative example 1 as a catalyst and in the absence of the catalyst;
FIG. 12 is a graph showing the photocatalytic cycle efficiency of the bismuth-based composite photocatalyst synthesized in example 1 of the present invention;
fig. 13 is a graph showing photocurrent curves of photocatalysts obtained in example 1 and example 2 of the present invention and comparative example 1.
Detailed Description
The technical solution of the present invention will be described in detail below with reference to specific examples.
Example 1
The invention provides a synthesis method of a bismuth-based composite photocatalyst, which comprises the following steps: adding 0.0012mol of bismuth nitrate and 0.0036mol of hexadecyl trimethyl ammonium bromide into 45ml of ethylene glycol, and uniformly stirring to form a reaction solution; and (3) placing the reaction solution in a round-bottom flask, reacting for 7 hours at 110 ℃, naturally cooling to room temperature after the reaction is finished, centrifugally separating, washing the obtained solid with distilled water, and drying for 8 hours at 60 ℃ to obtain the bismuth-based composite photocatalyst.
Example 2
The invention provides a synthesis method of a bismuth-based composite photocatalyst, which comprises the following steps: adding 0.0012mol of bismuth nitrate and 0.0072mol of hexadecyl trimethyl ammonium bromide into 45ml of ethylene glycol, and stirring uniformly to form a reaction solution; and (3) placing the reaction solution in a round-bottom flask, reacting for 7 hours at 110 ℃, naturally cooling to room temperature after the reaction is finished, centrifugally separating, washing the obtained solid with distilled water, and drying for 8 hours at 60 ℃ to obtain the bismuth-based composite photocatalyst.
Comparative example 1
A synthetic method of a BiOBr photocatalyst comprises the following steps: adding 0.0012mol of bismuth nitrate and 0.0012mol of hexadecyl trimethyl ammonium bromide into 45ml of ethylene glycol, and stirring uniformly to form a reaction solution; and (3) placing the reaction solution into a round-bottom flask, reacting for 7h at 110 ℃, naturally cooling to room temperature after the reaction is finished, centrifugally separating, washing the obtained solid with distilled water, and drying for 8h at 60 ℃ to obtain the BiOBr photocatalyst.
Example 3
The invention provides a synthesis method of a bismuth-based composite photocatalyst, which comprises the following steps: adding 0.0012mol of bismuth nitrate and 0.0036mol of hexadecyl trimethyl ammonium bromide into 30ml of ethylene glycol, and stirring uniformly to form a reaction solution; and (3) placing the reaction solution in a round-bottom flask, reacting at 90 ℃ for 24 hours, naturally cooling to room temperature after the reaction is finished, centrifugally separating, washing the obtained solid with distilled water, and drying at 50 ℃ for 11 hours to obtain the bismuth-based composite photocatalyst.
Example 4
The invention provides a synthesis method of a bismuth-based composite photocatalyst, which comprises the following steps: adding 0.0012mol of bismuth nitrate and 0.0072mol of hexadecyl trimethyl ammonium bromide into 60ml of ethylene glycol, and stirring uniformly to form a reaction solution; and (3) placing the reaction solution in a round-bottom flask, reacting for 4 hours at 130 ℃, naturally cooling to room temperature after the reaction is finished, centrifugally separating, washing the obtained solid with distilled water, and drying for 6 hours at 80 ℃ to obtain the bismuth-based composite photocatalyst.
Example 5
The invention provides a synthesis method of a bismuth-based composite photocatalyst, which comprises the following steps: adding 0.0012mol of bismuth nitrate and 0.0048mol of hexadecyl trimethyl ammonium bromide into 15ml of ethylene glycol, and stirring uniformly to form a reaction solution; and (3) placing the reaction solution in a round-bottom flask, reacting for 10 hours at 100 ℃, naturally cooling to room temperature after the reaction is finished, centrifugally separating, washing the obtained solid with distilled water, and drying for 7 hours at 70 ℃ to obtain the bismuth-based composite photocatalyst.
Example 6
The invention provides a synthesis method of a bismuth-based composite photocatalyst, which comprises the following steps: adding 0.002mol of bismuth nitrate and 0.01mol of hexadecyl trimethyl ammonium bromide into a solvent consisting of 25ml of ethylene glycol and 30ml of polyethylene glycol 400, and uniformly stirring to form a reaction solution; and (3) placing the reaction solution in a round-bottom flask, reacting for 17 hours at the temperature of 98 ℃, naturally cooling to room temperature after the reaction is finished, centrifugally separating, washing the obtained solid with distilled water, and drying for 7 hours at the temperature of 65 ℃ to obtain the bismuth-based composite photocatalyst.
Example 7
The invention provides a synthesis method of a bismuth-based composite photocatalyst, which comprises the following steps: adding 0.002mol of bismuth nitrate and 0.007mol of hexadecyl trimethyl ammonium bromide into 80ml of glycerol, and stirring uniformly to form a reaction solution; and (3) placing the reaction solution in a round-bottom flask, reacting for 20h at 112 ℃, naturally cooling to room temperature after the reaction is finished, centrifugally separating, washing the obtained solid with distilled water, and drying for 8h at 60 ℃ to obtain the bismuth-based composite photocatalyst.
The invention also provides a bismuth-based composite photocatalyst which is prepared by adopting the synthesis method of the bismuth-based composite photocatalyst and is BiOBr and [ Bi6O4(OH)4](NO3)6(H2O)4The composite material with the multilevel structure is formed.
Example 8
The invention provides a synthesis method of a bismuth-based composite photocatalyst, which comprises the following steps: adding 0.003mol of bismuth nitrate and 0.009mol of hexadecyl trimethyl ammonium bromide into a round-bottom flask, then adding 20ml of ethylene glycol and 60ml of diethylene glycol, uniformly stirring, reacting at 105 ℃ for 9 hours, naturally cooling to room temperature after the reaction is finished, filtering, washing the obtained filter cake with distilled water, and drying at 60 ℃ for 8 hours to obtain the bismuth-based composite photocatalyst.
The invention also provides a bismuth-based composite photocatalyst, which is prepared by adopting the synthesis method of the bismuth-based composite photocatalyst.
Example 9
The invention provides a synthesis method of a bismuth-based composite photocatalyst, which comprises the following steps: mixing bismuth nitrate, cetyl trimethyl ammonium bromide and ethylene glycol, and uniformly stirring to form a reaction solution, wherein the concentration of the bismuth nitrate is 0.08mol/L, and the molar ratio of the bismuth nitrate to the cetyl trimethyl ammonium bromide is 1: 3; and (3) reacting the reaction solution at 130 ℃ for 4 hours, and after the reaction is finished, cooling, carrying out solid-liquid separation, washing and drying to obtain the bismuth-based composite photocatalyst.
The invention also provides a bismuth-based composite photocatalyst, which is prepared by adopting the synthesis method of the bismuth-based composite photocatalyst.
Example 10
The invention provides a synthesis method of a bismuth-based composite photocatalyst, which comprises the following steps: mixing bismuth nitrate, cetyl trimethyl ammonium bromide and a polyol solvent, and uniformly stirring to form a reaction solution, wherein the concentration of bismuth nitrate in the reaction solution is 0.02mol/L, and the molar ratio of bismuth nitrate to cetyl trimethyl ammonium bromide is 1: 6, the polyalcohol solvent is a mixture of glycerol and diethylene glycol; and (3) reacting the reaction solution at 90 ℃ for 24 hours, and after the reaction is finished, cooling, carrying out solid-liquid separation, washing and drying to obtain the bismuth-based composite photocatalyst.
The invention also provides a bismuth-based composite photocatalyst, which is prepared by adopting the synthesis method of the bismuth-based composite photocatalyst.
Example 11
The invention provides a synthesis method of a bismuth-based composite photocatalyst, which comprises the following steps: mixing bismuth nitrate, cetyl trimethyl ammonium bromide and a polyalcohol solvent, and uniformly stirring to form a reaction solution, wherein the concentration of bismuth nitrate in the reaction solution is 0.06mol/L, and the molar ratio of bismuth nitrate to cetyl trimethyl ammonium bromide is 1: 5, the polyalcohol solvent is a mixture of glycol and polyethylene glycol 400; and (3) reacting the reaction solution at 115 ℃ for 18h, and after the reaction is finished, cooling, carrying out solid-liquid separation, washing and drying to obtain the bismuth-based composite photocatalyst.
The invention also provides a bismuth-based composite photocatalyst, which is prepared by adopting the synthesis method of the bismuth-based composite photocatalyst.
FIG. 1 shows X-ray diffraction patterns and BiOBr and [ Bi ] of photocatalysts prepared in examples 1 and 2 of the present invention and comparative example 16O4(OH)4](NO3)6(H2O)4XRD standard card of (1), wherein [ Bi6O4(OH)4](NO3)6(H2O)4The XRD standard card of (1) is JCPDS No.84-2189, a is the X-ray diffraction pattern of the photocatalyst obtained in example 2, b is the X-ray diffraction pattern of the photocatalyst obtained in example 1, c is the X-ray diffraction pattern of the photocatalyst obtained in comparative example 1, and the XRD standard card of BiOBr is JCPDS No.09-0393, wherein the characteristic peaks in JCPDS No.84-2189 are marked with # in a, b and c, and the characteristic peaks in JCPDS No.09-0393 are marked with # in a, b and c; as can be seen from fig. 1, in the preparation of the photocatalyst, when Bi: the molar ratio of Br is 1: at 1 (i.e., a molar ratio of bismuth nitrate to cetyltrimethylammonium bromide of 1: 1), the resulting sample was phase-pure BiOBr (JCPDS No. 09-0393); when the Bi is increased: the molar ratio of Br is 1: at 3 (i.e., a molar ratio of bismuth nitrate to cetyltrimethylammonium bromide of 1: 3), the XRD diffraction pattern of the resulting product exhibited [ Bi6O4(OH)4](NO3)6(H2O)4A phase (JCPDS No.84-2189), namely a bismuth-based composite photocatalyst [ Bi ] is formed6O4(OH)4](NO3)6(H2O)4-BiOBr; increasing Bi again: the molar ratio of Br is 1: when the molar ratio of the bismuth nitrate to the hexadecyl trimethyl ammonium bromide is 1: 6, the obtained product is still the bismuth-based composite photocatalyst [ Bi6O4(OH)4](NO3)6(H2O)4-BiOBr。
FIG. 2 is an XPS high resolution spectrum of Bi 4f in the bismuth-based composite photocatalyst synthesized in example 1 of the present invention; in FIG. 2, two peaks with binding energies of 158.97eV and 164.31eV correspond to Bi 4f7/2And Bi 4f5/2Thus, it is shown that the Bi element in the sample of the composite photocatalyst obtained in example 1 is Bi3+The form exists;
FIG. 3 is an XPS high resolution spectrum of O1 s in the bismuth-based composite photocatalyst synthesized in example 1 of the present invention; as can be seen from FIG. 3, the only XPS peak is at 531.9eV, indicating that the valence of the O element in the sample is-2;
FIG. 4 is an XPS high resolution spectrum of Br 3d in the bismuth-based composite photocatalyst synthesized in example 1 of the present invention; as can be seen from FIG. 4, it can be fitted with two peaks 68.01eV and 69.11eV, corresponding to Br 3d5/2And Br 3d3/2Thus, it was shown that Br is an element Br in the sample of the composite photocatalyst obtained in example 1-The form exists;
FIG. 5 is an XPS high resolution spectrum of N1 s in the bismuth-based composite photocatalyst synthesized in example 1 of the present invention; as can be seen from FIG. 5, the only peak is located at 402.08eV, which indicates that the valence of N element in the sample of the composite photocatalyst obtained in example 1 is +5, i.e., NO3 -Exists in the form of (1);
figure 6 is an SEM photograph of the bibbr photocatalyst synthesized in comparative example 1 of the present invention; as can be seen from fig. 6, the synthesized BiOBr photocatalyst is a multi-stage structure assembled by nanosheets;
FIG. 7 is an SEM photograph of the bismuth-based composite photocatalyst synthesized in example 1 of the present invention; as can be seen from fig. 7, the obtained product is still a multi-level structure assembled by the nanosheets, and many nanoparticles with smaller sizes appear on the surface of the assembled unit of the nanosheets;
figure 8 is a diffuse reflectance spectrum of a BiOBr photocatalyst synthesized in comparative example 1 of the present invention; as can be seen from fig. 8, the band gap of the obtained product BiOBr photocatalyst is about 2.97 eV;
FIG. 9 is a diffuse reflectance spectrum of the bismuth-based composite photocatalyst synthesized in example 1 of the present invention; as can be seen from FIG. 9, the band gap of the obtained composite photocatalyst product is about 2.89 eV;
FIG. 10 is a diffuse reflectance spectrum of the bismuth-based composite photocatalyst synthesized in example 2 of the present invention; as can be seen from FIG. 10, the band gap of the obtained composite photocatalyst product is about 2.84 eV;
fig. 11 is a degradation efficiency curve of rhodamine B aqueous solution degraded under ultraviolet-visible light irradiation under the conditions of using the photocatalysts synthesized in example 1, example 2 and comparative example 1 as catalysts and no catalyst, and it can be known from fig. 11 that the bismuth-based composite photocatalyst obtained in example 1 exhibits the best photocatalytic activity, the degradation efficiency of the rhodamine B aqueous solution with the concentration of 40mg/L is as high as 96.2% after 12 minutes of light irradiation, which is far greater than the degradation efficiency under the photocatalytic conditions of other two photocatalytic samples and no catalyst.
FIG. 12 is a graph showing the photocatalytic cycle efficiency of the bismuth-based composite photocatalyst synthesized in example 1 of the present invention; as can be seen from fig. 12, the obtained product exhibited excellent photocatalytic stability, and no significant decay of photocatalytic activity occurred after four cycles.
FIG. 13 is a graph showing photocurrent curves of photocatalysts obtained in examples 1 and 2 according to the present invention and comparative example 1; as can be seen from fig. 13, the composite photocatalyst obtained in example 1 has the highest photocurrent density, which indicates that it has better photo-generated charge separation efficiency, and thus exhibits the best photocatalytic activity.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (8)
1. A synthesis method of a bismuth-based composite photocatalyst is characterized by comprising the following steps: mixing bismuth nitrate, cetyl trimethyl ammonium bromide and a polyalcohol solvent, and uniformly stirring to form a reaction solution, wherein the molar ratio of the bismuth nitrate to the cetyl trimethyl ammonium bromide in the reaction solution is 1: 3-1: 6; placing the reaction solution in a round-bottom flask, reacting for 4-24h at 90-130 ℃, and after the reaction is finished, cooling, carrying out solid-liquid separation, washing and drying to obtain the bismuth-based composite photocatalyst;
wherein the bismuth-based composite photocatalyst is [ Bi6O4(OH)4](NO3)6(H2O)4-a composite material of BiOBr.
2. The method for synthesizing the bismuth-based composite photocatalyst as claimed in claim 1, wherein the polyol solvent is one or a mixture of more of ethylene glycol, glycerol, diethylene glycol and polyethylene glycol 400.
3. The method for synthesizing the bismuth-based composite photocatalyst as claimed in claim 1 or 2, wherein the polyol solvent is ethylene glycol.
4. The method for synthesizing the bismuth-based composite photocatalyst as claimed in claim 1 or 2, wherein the concentration of bismuth nitrate in the reaction solution is 0.02 to 0.08 mol/L.
5. The method for synthesizing the bismuth-based composite photocatalyst as claimed in claim 1 or 2, wherein the molar ratio of bismuth nitrate to cetyltrimethylammonium bromide in the reaction solution is 1: 3.
6. the method for synthesizing the bismuth-based composite photocatalyst as claimed in claim 1 or 2, which is characterized by comprising the following steps: adding 0.0012mol of bismuth nitrate and 0.0036-0.0072mol of hexadecyl trimethyl ammonium bromide into 15-60ml of ethylene glycol, and uniformly stirring to form a reaction solution; and (3) placing the reaction solution in a round-bottom flask, reacting for 4-24h at 90-130 ℃, naturally cooling after the reaction is finished, and washing and drying the obtained solid after centrifugal separation to obtain the bismuth-based composite photocatalyst.
7. The method for synthesizing the bismuth-based composite photocatalyst as claimed in claim 1 or 2, which is characterized by comprising the following steps: adding 0.0012mol of bismuth nitrate and 0.0036-0.0072mol of hexadecyl trimethyl ammonium bromide into 45ml of ethylene glycol, and uniformly stirring to form a reaction solution; and (3) placing the reaction solution in a round-bottom flask, reacting for 7 hours at 110 ℃, naturally cooling after the reaction is finished, and washing and drying the obtained solid after centrifugal separation to obtain the bismuth-based composite photocatalyst.
8. A bismuth-based composite photocatalyst, which is characterized by being prepared by the synthesis method of the bismuth-based composite photocatalyst as claimed in any one of claims 1 to 7.
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