CN106964380B - Three-dimensional cadmium sulfide/bismuth oxybromide heterojunction photocatalyst, and preparation method and application thereof - Google Patents
Three-dimensional cadmium sulfide/bismuth oxybromide heterojunction photocatalyst, 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 119
- 229910052980 cadmium sulfide Inorganic materials 0.000 title claims abstract description 97
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 title claims abstract description 86
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- 238000002360 preparation method Methods 0.000 title claims abstract 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 claims abstract description 40
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 39
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- 239000000047 product Substances 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 18
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims description 10
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- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 14
- VUXKVKAHWOVIDN-UHFFFAOYSA-N Cyclohexyl formate Chemical compound O=COC1CCCCC1 VUXKVKAHWOVIDN-UHFFFAOYSA-N 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 4
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- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
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- 239000000969 carrier Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
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- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- -1 BiOBr compound Chemical class 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
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- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 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
- 229910052799 carbon Inorganic materials 0.000 description 1
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
Classifications
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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
- B01J27/06—Halogens; Compounds thereof
- B01J27/138—Halogens; Compounds thereof with alkaline earth metals, magnesium, beryllium, zinc, cadmium or mercury
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/37—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups
- C07C45/39—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups being a secondary hydroxyl group
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
Abstract
The invention specifically discloses a three-dimensional cadmium sulfide/bismuth oxybromide heterojunction photocatalyst, which comprises the following raw material components: bismuth nitrate, cetyl trimethyl ammonium bromide, ethylene glycol and cadmium sulfide; the preparation method comprises the following steps: firstly, mixing a bismuth nitrate/ethylene glycol mixed solution with a hexadecyl trimethyl ammonium bromide/ethylene glycol mixed solution to obtain a bismuth oxybromide precursor solution, reacting to obtain a precipitate A, centrifugally separating the precipitate A, washing, drying, and finally baking to obtain the bismuth oxybromide microspheres; and then, mixing cadmium sulfide and bismuth oxybromide microspheres, adding deionized water, stirring to obtain a three-dimensional cadmium sulfide/bismuth oxybromide heterojunction precursor solution, reacting to obtain a precipitate B, centrifugally separating the precipitate B, washing and drying to obtain the cadmium sulfide/bismuth oxybromide heterojunction precursor solution. The preparation method of the three-dimensional cadmium sulfide/bismuth oxybromide heterojunction photocatalyst has the advantages of simple process, controllable appearance and environmental friendliness, and is used for photocatalytic reduction of CO2Improving the photocatalytic reduction of CO2The reaction rate of (c).
Description
Technical Field
The invention relates to the technical field of heterojunction photocatalysts, in particular to a three-dimensional cadmium sulfide/bismuth oxybromide heterojunction photocatalyst, a preparation method and application thereof.
Background
The global energy consumption is mainly fossil fuel mainly comprising petroleum, coal and natural gas. Fossil fuels come from millionsThe plankton buried underground is formed through the long geological time evolution year by year, belongs to the exhausted energy source, and simultaneously emits greenhouse gases, particularly CO, into the atmosphere in the combustion process of fossil fuel2Gases, have an adverse and irreversible impact on the global environment. CO in the atmosphere2The increase in the content causes global warming, which has become the most serious environmental problem. Thus, reduction of atmospheric CO2The content of (b) and the development of renewable, clean energy are two major problems that need to be solved at present. Simulating photosynthesis in nature to convert CO2The fixation or conversion into the high value-added hydrocarbon fuel can simultaneously solve the problems of energy supply and environmental warming.
CO2Is itself a carbon source and can be converted into CH4、CH3Organic compounds such as OH but due to CO2The molecular structure is stable, and the reduction is not easy under mild conditions, so that the reaction rate is slow, and the product selectivity is poor. The photocatalytic technology is considered as a potential solution for global energy shortage and environmental pollution, and particularly from the viewpoint of photosynthesis of natural green plants, various semiconductors are used as catalysts to carry out photocatalytic reduction on CO in water2There are many reports of reducing agents, such as TiO2And ZnO, but the catalysts can only absorb ultraviolet light with the wavelength less than 387nm due to wide band gap, and the ultraviolet light only accounts for 4 percent of the total amount of solar energy, so that the utilization of the catalysts to the solar energy is limited. In addition, the activity of the catalyst is related to factors such as particle size, morphology and surface area, and many researches show that the photocatalyst with the three-dimensional layered structure, which is composed of the one-dimensional nanorods and the nanotubes, shows good catalytic activity. Bismuth oxybromide (BiOBr) is a novel ternary semiconductor oxide with a layered structure and high photochemical stability, a band gap width of 2.9eV, and a conduction band position (E)CBNhe pH 7 ═ 0.1V vs. BiOBr shows good photocatalytic degradation activity under the action of visible light, but the application of the catalyst is limited due to the high photogenerated electron-hole recombination rate of the BiOBr.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a three-dimensional cadmium sulfide/bismuth oxybromideThe preparation method has simple process and controllable shape, and can be used for photocatalytic reduction of CO2To enhance the photocatalytic reduction of CO2The reaction rate of (c).
In order to achieve the purpose, the invention is realized by adopting the following technical scheme.
The three-dimensional cadmium sulfide/bismuth oxybromide heterojunction photocatalyst is characterized by comprising the following raw material components: bismuth nitrate, cetyl trimethyl ammonium bromide, ethylene glycol and cadmium sulfide.
(II) a preparation method of a three-dimensional cadmium sulfide/bismuth oxybromide heterojunction photocatalyst, which is characterized by comprising the following steps:
step 1, preparing bismuth oxybromide microspheres; mixing the bismuth nitrate/ethylene glycol mixed solution with a hexadecyl trimethyl ammonium bromide/ethylene glycol mixed solution to obtain a bismuth oxybromide precursor solution; transferring the bismuth oxybromide precursor solution into a reaction kettle for reaction to obtain a precipitate A; centrifugally separating the precipitate A, washing with deionized water and ethanol, drying to obtain a dried product, and roasting the dried product to obtain the bismuth oxybromide microspheres with the three-dimensional structures;
step 2, preparing a three-dimensional cadmium sulfide/bismuth oxybromide heterojunction; firstly, mixing cadmium sulfide and the three-dimensional bismuth oxybromide prepared in the step 1 to prepare a cadmium sulfide/bismuth oxybromide mixture; adding the cadmium sulfide/bismuth oxybromide mixture into deionized water, and fully stirring to form a three-dimensional cadmium sulfide/bismuth oxybromide heterojunction precursor solution; transferring the three-dimensional cadmium sulfide/bismuth oxybromide heterojunction precursor solution into a reaction kettle for reaction to obtain a precipitate B; and (3) centrifugally separating the precipitate B, washing and drying by using deionized water and ethanol to obtain the three-dimensional cadmium sulfide/bismuth oxybromide heterojunction photocatalyst.
Preferably, in step 1, the bismuth nitrate/ethylene glycol mixed solution is formed by mixing bismuth nitrate and ethylene glycol, and the concentration of bismuth nitrate in the bismuth nitrate/ethylene glycol mixed solution is 0.05-0.06 mol/L.
Preferably, in the step 1, the cetyl trimethyl ammonium bromide/ethylene glycol mixed solution is formed by mixing cetyl trimethyl ammonium bromide and ethylene glycol, and the concentration of the cetyl trimethyl ammonium bromide in the cetyl trimethyl ammonium bromide/ethylene glycol mixed solution is 0.05-0.08 mol/L.
Preferably, in step 1, the volume ratio of the bismuth nitrate/ethylene glycol mixed solution to the cetyltrimethylammonium bromide/ethylene glycol mixed solution is 1: 1.
Preferably, in the step 1, the reaction temperature of the reaction in the reaction kettle is 160 ℃, and the reaction time is 12 hours. In the step 1, the drying temperature is 80 ℃, and the drying time is 10 hours.
Preferably, in step 1, the roasting temperature is 400 ℃, and the roasting time is 2 hours.
Preferably, in the step 2, the mass percentage of cadmium sulfide in the cadmium sulfide/bismuth oxybromide mixture is 1-7%.
Preferably, in the step 2, the molar concentration of the three-dimensional cadmium sulfide/bismuth oxybromide heterojunction precursor solution is 0.016-0.02 mol/L.
Preferably, in the step 2, the reaction temperature of the reaction in the reaction kettle is 140 ℃ and the reaction time is 12 hours.
Three-dimensional cadmium sulfide/bismuth oxybromide heterojunction photocatalyst for photocatalytic reduction of CO2The use of (1).
The three-dimensional structure bismuth oxybromide (BiOBr) composed of the staggered nano-sheets can obtain stronger light absorption through multi-surface reflection of light, and the graded microspheres have larger illumination area than the photocatalyst with a two-dimensional sheet structure, and can meet the requirement of reducing CO at present2The light energy utilization rate is low in the process. The catalyst surface is loaded with the cocatalyst, which can effectively promote the separation of photon-generated carriers and improve the photocatalytic activity. CdS is a narrow band gap semiconductor with a band gap width of 2.4eV and a conduction band position (E)CBAdding a proper amount of CdS into BiOBr, the response of BiOBr in a visible light region can be effectively widened, the separation of photon-generated carriers can be promoted, and CO can be promoted at the position of a conduction band with more negative CdS2Reduction of (2). At present, the CdS/BiOBr compound is simpleThe preparation by a precipitation method has poor crystallinity and catalytic activity is not well reflected. Heterojunction photocatalyst CdS/BiOBr with three-dimensional structure and application of heterojunction photocatalyst CdS/BiOBr in photocatalytic reduction of CO2The research of the method is not reported, and in view of the problems, the development of a CdS/BiOBr heterojunction photocatalyst with high activity and good visible light response is very meaningful.
The invention aims at the photocatalytic reduction of CO under the action of visible light in the prior art2Low utilization rate of visible light and CO generation in the process2Firstly preparing bismuth oxybromide microspheres, then loading cadmium sulfide nanoparticles on the surfaces of the microspheres to form a three-dimensional cadmium sulfide/bismuth oxybromide heterojunction photocatalyst, and carrying out photocatalytic reduction on CO in cyclohexanol2The catalyst shows good catalytic performance in an activity test, and can reduce CO with other heterojunction photocatalysts under the action of visible light2Compared with the prior art, the preparation method of the three-dimensional CdS/BiOBr heterojunction photocatalyst has the advantages of simple preparation process, controllable appearance, environmental friendliness and the like.
Drawings
The invention is described in further detail below with reference to the figures and specific embodiments.
FIG. 1 is a scanning electron micrograph of three-dimensional bismuth oxybromide prepared in example 1;
FIG. 2 is a scanning electron microscope image of the three-dimensional cadmium sulfide/bismuth oxybromide heterojunction photocatalyst prepared in example 1;
FIG. 3 shows the photocatalytic reduction of CO in cyclohexanol by the photocatalyst of cadmium sulfide/bismuth oxybromide heterojunction prepared in example 12And the quantity of the generated Cyclohexyl Formate (CF) is subjected to esterification reaction along with the change of time; in the figure, the abscissa is the reaction time and the ordinate is the yield of Cyclohexyl Formate (CF);
FIG. 4 shows the photocatalytic reduction of CO in cyclohexanol by the photocatalyst of cadmium sulfide/bismuth oxybromide heterojunction prepared in example 12Graph of the amount of cyclohexanol oxidized to Cyclohexanone (CH) as a function of time; in the figure, the abscissa represents the reaction time, and the ordinate represents the production amount of Cyclohexanone (CH).
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention.
Example 1
The embodiment provides a preparation method of a three-dimensional CdS/BiOBr heterojunction photocatalyst, which comprises the following steps:
step 1, preparing bismuth oxybromide microspheres; mixing the bismuth nitrate/ethylene glycol mixed solution with a hexadecyl trimethyl ammonium bromide/ethylene glycol mixed solution to obtain a bismuth oxybromide precursor solution; transferring the bismuth oxybromide precursor solution into a reaction kettle, and reacting at 160 ℃ for 12 hours to obtain a precipitate A; centrifugally separating the precipitate A, washing the precipitate A with deionized water and ethanol, and drying the precipitate A at 80 ℃ for 10 hours to obtain a dried product; finally, roasting the dried product at 400 ℃ for 2h to obtain the three-dimensional bismuth oxybromide; wherein the bismuth nitrate/ethylene glycol mixed solution is formed by mixing bismuth nitrate and ethylene glycol, and the concentration of the bismuth nitrate in the bismuth nitrate/ethylene glycol mixed solution is 0.05 mol/L; the cetyl trimethyl ammonium bromide/ethylene glycol mixed solution is formed by mixing cetyl trimethyl ammonium bromide and ethylene glycol, and the concentration of the cetyl trimethyl ammonium bromide in the cetyl trimethyl ammonium bromide/ethylene glycol mixed solution is 0.05 mol/L; and the volume ratio of the bismuth nitrate/ethylene glycol mixed solution to the cetyl trimethyl ammonium bromide/ethylene glycol mixed solution is 1: 1.
Step 2, preparing a three-dimensional cadmium sulfide/bismuth oxybromide heterojunction; mixing cadmium sulfide with the three-dimensional bismuth oxybromide prepared in the step 1 to obtain a cadmium sulfide/bismuth oxybromide mixture, wherein the mass percentage of the cadmium sulfide in the cadmium sulfide/bismuth oxybromide mixture is 5%; adding the cadmium sulfide/bismuth oxybromide mixture into deionized water, fully stirring to form a three-dimensional cadmium sulfide/bismuth oxybromide heterojunction precursor solution with the concentration of 0.016mol/L, transferring the three-dimensional cadmium sulfide/bismuth oxybromide heterojunction precursor solution into a reaction kettle, and reacting for 12 hours at 140 ℃ to obtain a precipitate B; and (3) centrifugally separating the precipitate B, washing with deionized water and ethanol, and drying to obtain the three-dimensional cadmium sulfide/bismuth oxybromide heterojunction photocatalyst.
Example 2
The embodiment provides a preparation method of a three-dimensional CdS/BiOBr heterojunction photocatalyst, which comprises the following steps:
step 1, preparing bismuth oxybromide microspheres; mixing the bismuth nitrate/ethylene glycol mixed solution with a hexadecyl trimethyl ammonium bromide/ethylene glycol mixed solution to obtain a bismuth oxybromide precursor solution; transferring the bismuth oxybromide precursor solution into a reaction kettle, and reacting at 160 ℃ for 12 hours to obtain a precipitate A; centrifugally separating the precipitate A, washing the precipitate A with deionized water and ethanol, and drying the precipitate A at 80 ℃ for 10 hours to obtain a dried product; finally, roasting the dried product at 400 ℃ for 2h to obtain the three-dimensional bismuth oxybromide; wherein the bismuth nitrate/ethylene glycol mixed solution is formed by mixing bismuth nitrate and ethylene glycol, and the concentration of the bismuth nitrate in the bismuth nitrate/ethylene glycol mixed solution is 0.06 mol/L; the cetyl trimethyl ammonium bromide/ethylene glycol mixed solution is formed by mixing cetyl trimethyl ammonium bromide and ethylene glycol, and the concentration of the cetyl trimethyl ammonium bromide in the cetyl trimethyl ammonium bromide/ethylene glycol mixed solution is 0.06 mol/L; and the volume ratio of the bismuth nitrate/ethylene glycol mixed solution to the cetyl trimethyl ammonium bromide/ethylene glycol mixed solution is 1: 1.
Step 2, preparing a three-dimensional cadmium sulfide/bismuth oxybromide heterojunction; mixing cadmium sulfide and the three-dimensional bismuth oxybromide prepared in the step 1 to obtain a cadmium sulfide/bismuth oxybromide mixture, wherein the mass percentage of the cadmium sulfide in the cadmium sulfide/bismuth oxybromide mixture is 1%; adding the cadmium sulfide/bismuth oxybromide mixture into deionized water, fully stirring to form a three-dimensional cadmium sulfide/bismuth oxybromide heterojunction precursor solution with the concentration of 0.018mol/L, transferring the three-dimensional cadmium sulfide/bismuth oxybromide heterojunction precursor solution into a reaction kettle, and reacting for 12 hours at 140 ℃ to obtain a precipitate B; and (3) centrifugally separating the precipitate B, washing with deionized water and ethanol, and drying to obtain the three-dimensional cadmium sulfide/bismuth oxybromide heterojunction photocatalyst.
Example 3
The embodiment provides a preparation method of a three-dimensional CdS/BiOBr heterojunction photocatalyst, which comprises the following steps:
step 1, preparing bismuth oxybromide microspheres; mixing the bismuth nitrate/ethylene glycol mixed solution with a hexadecyl trimethyl ammonium bromide/ethylene glycol mixed solution to obtain a bismuth oxybromide precursor solution; transferring the bismuth oxybromide precursor solution into a reaction kettle, and reacting at 160 ℃ for 12 hours to obtain a precipitate A; centrifugally separating the precipitate A, washing the precipitate A with deionized water and ethanol, and drying the precipitate A at 80 ℃ for 10 hours to obtain a dried product; finally, roasting the dried product at 400 ℃ for 2h to obtain the three-dimensional bismuth oxybromide; wherein the bismuth nitrate/ethylene glycol mixed solution is formed by mixing bismuth nitrate and ethylene glycol, and the concentration of the bismuth nitrate in the bismuth nitrate/ethylene glycol mixed solution is 0.06 mol/L; the cetyl trimethyl ammonium bromide/ethylene glycol mixed solution is formed by mixing cetyl trimethyl ammonium bromide and ethylene glycol, and the concentration of the cetyl trimethyl ammonium bromide in the cetyl trimethyl ammonium bromide/ethylene glycol mixed solution is 0.08 mol/L; and the volume ratio of the bismuth nitrate/ethylene glycol mixed solution to the cetyl trimethyl ammonium bromide/ethylene glycol mixed solution is 1: 1.
Step 2, preparing a three-dimensional cadmium sulfide/bismuth oxybromide heterojunction; mixing cadmium sulfide with the three-dimensional bismuth oxybromide prepared in the step 1 to obtain a cadmium sulfide/bismuth oxybromide mixture, wherein the mass percentage of the cadmium sulfide in the cadmium sulfide/bismuth oxybromide mixture is 3%; adding the cadmium sulfide/bismuth oxybromide mixture into deionized water, fully stirring to form a three-dimensional cadmium sulfide/bismuth oxybromide heterojunction precursor solution with the concentration of 0.02mol/L, transferring the three-dimensional cadmium sulfide/bismuth oxybromide heterojunction precursor solution into a reaction kettle, and reacting for 12 hours at 140 ℃ to obtain a precipitate B; and (3) centrifugally separating the precipitate B, washing with deionized water and ethanol, and drying to obtain the three-dimensional cadmium sulfide/bismuth oxybromide heterojunction photocatalyst.
Example 4
The embodiment provides a preparation method of a three-dimensional CdS/BiOBr heterojunction photocatalyst, which comprises the following steps:
step 1, preparing bismuth oxybromide microspheres; mixing the bismuth nitrate/ethylene glycol mixed solution with a hexadecyl trimethyl ammonium bromide/ethylene glycol mixed solution to obtain a bismuth oxybromide precursor solution; transferring the bismuth oxybromide precursor solution into a reaction kettle, and reacting at 160 ℃ for 12 hours to obtain a precipitate A; centrifugally separating the precipitate A, washing the precipitate A with deionized water and ethanol, and drying the precipitate A at 80 ℃ for 10 hours to obtain a dried product; finally, roasting the dried product at 400 ℃ for 2h to obtain the three-dimensional bismuth oxybromide; wherein the bismuth nitrate/ethylene glycol mixed solution is formed by mixing bismuth nitrate and ethylene glycol, and the concentration of the bismuth nitrate in the bismuth nitrate/ethylene glycol mixed solution is 0.06 mol/L; the cetyl trimethyl ammonium bromide/ethylene glycol mixed solution is formed by mixing cetyl trimethyl ammonium bromide and ethylene glycol, and the concentration of the cetyl trimethyl ammonium bromide in the cetyl trimethyl ammonium bromide/ethylene glycol mixed solution is 0.08 mol/L; and the volume ratio of the bismuth nitrate/ethylene glycol mixed solution to the cetyl trimethyl ammonium bromide/ethylene glycol mixed solution is 1: 1.
Step 2, preparing a three-dimensional cadmium sulfide/bismuth oxybromide heterojunction; mixing cadmium sulfide with the three-dimensional bismuth oxybromide prepared in the step 1 to obtain a cadmium sulfide/bismuth oxybromide mixture, wherein the mass percentage of the cadmium sulfide in the cadmium sulfide/bismuth oxybromide mixture is 7%; adding the cadmium sulfide/bismuth oxybromide mixture into deionized water, fully stirring to form a three-dimensional cadmium sulfide/bismuth oxybromide heterojunction precursor solution with the concentration of 0.02mol/L, transferring the three-dimensional cadmium sulfide/bismuth oxybromide heterojunction precursor solution into a reaction kettle, and reacting for 12 hours at 140 ℃ to obtain a precipitate B; and (3) centrifugally separating the precipitate B, washing with deionized water and ethanol, and drying to obtain the three-dimensional cadmium sulfide/bismuth oxybromide heterojunction photocatalyst.
SEM tests are respectively carried out on the three-dimensional bismuth oxybromide and the three-dimensional cadmium sulfide/bismuth oxybromide heterojunction photocatalyst prepared in the embodiment 1, the test results are shown in figures 1 and 2, and as can be seen from figure 1, scanning electron microscope photos of the bismuth oxybromide prepared by the hydrothermal method provided by the invention show three-dimensional microspheres with mutually staggered nano sheets; as can be seen from FIG. 2, the scanning electron microscope of the three-dimensional cadmium sulfide/bismuth oxybromide heterojunction shows that the surface of the three-dimensional microsphere is loaded with clearly visible cadmium sulfide nanoparticles.
The three-dimensional cadmium sulfide/bismuth oxybromide heterojunction photocatalyst prepared in the example 1 is applied to photocatalytic reduction of CO2In the method, a photocatalysis test is carried out in a slurry bed reactor at normal temperature and normal pressure, a 500W halogen lamp is used as a light source and is matched with a 400nm optical filter for use; the specific operation process is as follows: 10mg of the cadmium sulfide/bismuth oxybromide heterojunction photocatalyst prepared in example 1 was added to 10mL of cyclohexanol, and high-purity CO was introduced into the solution before the reaction started2(99.99%) for 30min to remove dissolved oxygen from the solution; sealing the reactor, turning on a light source, and starting a magnetic stirrer to start reaction; after reacting for a certain time, the liquid phase product was centrifuged and detected by gas chromatography.
FIGS. 3 and 4 respectively show the photocatalytic reduction of CO in cyclohexanol2The graph shows that the cyclohexanol has photocatalytic CO reduction under normal temperature and pressure and visible light effect2Cyclohexanol is oxidized to cyclohexanone and produces hydrogen protons, CO2Reduced to formic acid and cyclohexanol undergoes esterification reaction to produce cyclohexyl formate. The formation amount of the target products cyclohexanone and cyclohexyl formate is increased along with the prolonging of the reaction time, the formation amount of the product is increased along with the increase of the content of cadmium sulfide, when the percentage content of cadmium sulfide reaches 5%, the formation amount of the product reaches the maximum, and the formation amount of the product is reduced due to the fact that the content of cadmium sulfide in bismuth oxybromide is continuously increased.
The product cyclohexyl formate is a spice and is mainly used for making ice food and baked food; cyclohexanone is an organic chemical raw material, is a main intermediate for producing monomer caprolactam and adipic acid of nylon 66, and can also be used as an industrial solvent for paint containing nitrocellulose, vinyl chloride polymer and copolymer; both products have good application value.
Although the present invention has been described in detail in this specification with reference to specific embodiments and illustrative embodiments, it will be apparent to those skilled in the art that modifications and improvements can be made thereto based on the present invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (8)
1. Photocatalytic reduction of CO in cyclohexanol under normal temperature and pressure and visible light action by three-dimensional cadmium sulfide/bismuth oxybromide heterojunction photocatalyst2The use of (a);
the preparation method of the three-dimensional cadmium sulfide/bismuth oxybromide heterojunction photocatalyst comprises the following steps:
step 1, preparing bismuth oxybromide microspheres; mixing the bismuth nitrate/ethylene glycol mixed solution with a hexadecyl trimethyl ammonium bromide/ethylene glycol mixed solution to obtain a bismuth oxybromide precursor solution; transferring the bismuth oxybromide precursor solution into a reaction kettle for reaction to obtain a precipitate A; centrifugally separating the precipitate A, washing with deionized water and ethanol, drying to obtain a dried product, and roasting the dried product to obtain the bismuth oxybromide microspheres with the three-dimensional structures;
step 2, preparing a three-dimensional cadmium sulfide/bismuth oxybromide heterojunction; firstly, mixing cadmium sulfide and the three-dimensional bismuth oxybromide prepared in the step 1 to prepare a cadmium sulfide/bismuth oxybromide mixture; adding the cadmium sulfide/bismuth oxybromide mixture into deionized water, and fully stirring to form a three-dimensional cadmium sulfide/bismuth oxybromide heterojunction precursor solution; transferring the three-dimensional cadmium sulfide/bismuth oxybromide heterojunction precursor solution into a reaction kettle for reaction to obtain a precipitate B; and (3) centrifugally separating the precipitate B, washing and drying by using deionized water and ethanol to obtain the three-dimensional cadmium sulfide/bismuth oxybromide heterojunction photocatalyst.
2. The application of the bismuth nitrate/ethylene glycol composite material as claimed in claim 1, wherein in the step 1, the bismuth nitrate/ethylene glycol composite solution is formed by mixing bismuth nitrate and ethylene glycol, and the concentration of the bismuth nitrate in the bismuth nitrate/ethylene glycol composite solution is 0.05-0.06 mol/L; the cetyl trimethyl ammonium bromide/ethylene glycol mixed solution is formed by mixing cetyl trimethyl ammonium bromide and ethylene glycol, and the concentration of the cetyl trimethyl ammonium bromide in the cetyl trimethyl ammonium bromide/ethylene glycol mixed solution is 0.05-0.08 mol/L.
3. The use according to claim 1, wherein in step 1, the volume ratio of the bismuth nitrate/ethylene glycol mixed solution to the cetyltrimethylammonium bromide/ethylene glycol mixed solution is 1: 1.
4. The application of claim 1, wherein in the step 1, the reaction temperature of the reaction in the reaction kettle is 160 ℃, and the reaction time is 12 hours; the roasting temperature is 400 ℃, and the roasting time is 2 hours.
5. The use according to claim 1, wherein in step 1, the drying temperature is 80 ℃ and the drying time is 10 hours.
6. The application of the cadmium sulfide/bismuth oxybromide composite material as claimed in claim 1, wherein in the step 2, the mass percentage of the cadmium sulfide in the cadmium sulfide/bismuth oxybromide mixture is 1-7%.
7. The use according to claim 1, wherein in the step 2, the molar concentration of the three-dimensional cadmium sulfide/bismuth oxybromide heterojunction precursor solution is 0.016-0.02 mol/L.
8. The use according to claim 1, wherein in step 2, the reaction temperature in the reaction kettle is 140 ℃ and the reaction time is 12 hours.
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| "Cr(VI),Pb(II),Cd(II) adsorption properties of nanostructured BiOBr microspheres and their application in a continuous filtering removal device for heavy metal ions";Xingqi Wang et al;《Journal of materials Chemistry A》;20131129;第2卷;第2599-2608页 * |
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