CN110833836A - Two-dimensional ultrathin bismuth-rich bismuth oxychloride nanosheet prepared by hydrothermal method and application thereof - Google Patents
Two-dimensional ultrathin bismuth-rich bismuth oxychloride nanosheet prepared by hydrothermal method and application thereof Download PDFInfo
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- 229940073609 bismuth oxychloride Drugs 0.000 title claims abstract description 36
- 238000001027 hydrothermal synthesis Methods 0.000 title claims abstract description 33
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- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims description 4
- RCJVRSBWZCNNQT-UHFFFAOYSA-N dichloridooxygen Chemical compound ClOCl RCJVRSBWZCNNQT-UHFFFAOYSA-N 0.000 claims description 4
- QYIGOGBGVKONDY-UHFFFAOYSA-N 1-(2-bromo-5-chlorophenyl)-3-methylpyrazole Chemical compound N1=C(C)C=CN1C1=CC(Cl)=CC=C1Br QYIGOGBGVKONDY-UHFFFAOYSA-N 0.000 claims description 3
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- 239000003054 catalyst Substances 0.000 claims description 3
- BEQZMQXCOWIHRY-UHFFFAOYSA-H dibismuth;trisulfate Chemical compound [Bi+3].[Bi+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BEQZMQXCOWIHRY-UHFFFAOYSA-H 0.000 claims description 3
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- FBXVOTBTGXARNA-UHFFFAOYSA-N bismuth;trinitrate;pentahydrate Chemical compound O.O.O.O.O.[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FBXVOTBTGXARNA-UHFFFAOYSA-N 0.000 description 3
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- B01J35/39—Photocatalytic properties
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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Abstract
The invention belongs to the technical field of functionalized nano materials, and relates to a two-dimensional ultrathin bismuth-rich bismuth oxychloride nanosheet prepared by a hydrothermal method and application thereof. Firstly, mixing polyol, a bismuth source and a surfactant to obtain a solution, then dropwise adding a sodium chloride solution, adjusting the pH to 10-13 by using a sodium hydroxide solution, carrying out hydrothermal reaction on the reaction kettle at the temperature of 140-180 ℃ for 2-12 h, cooling to room temperature, centrifuging a product, and sequentially washing by using ethanol and deionized water to obtain the bismuth-containing nano-particles. According to the invention, a one-step hydrothermal method is utilized to prepare the two-dimensional ultrathin material, compared with a bulk material, the prepared ultrathin nanosheet has high-efficiency photocatalytic carbon dioxide reduction performance, a new thought and method is provided for the design and synthesis of a functional photocatalytic material, and CO is realized2Provides a new way for the high-efficiency catalytic reduction, and provides a theoretical basis for the application of the photocatalytic carbon dioxide reduction technology in solving the environmental problems, energy shortage and the like caused by the greenhouse effect. The method has the advantages of mild and controllable reaction conditions, simple operation, strong practicability and convenience for large-scale popularization.
Description
Technical Field
The invention belongs to the technical field of functionalized nano materials, and particularly relates to a two-dimensional ultrathin bismuth-rich bismuth oxychloride nanosheet prepared by a hydrothermal method and application thereof.
Background
Along with the rapid development of economy, the demand of human beings on energy is more and more, the most widely used fossil energy still is fossil energy at present, the use of fossil energy can produce carbon dioxide, sulfur dioxide and the like, carbon dioxide is greenhouse gas, can cause global temperature rise, glacier melts, and then makes sea level rise, and sulfur dioxide is the leading cause that causes acid rain, and the use of fossil energy can cause serious environmental problem anyhow. In addition, fossil energy is becoming exhausted, and development and use of new clean energy are becoming more and more difficult.
At present, the renewable clean energy mainly comprises solar energy, hydrogen energy, tidal energy, wind energy and the like. Solar energy is the most widely distributed renewable energy source, and the total energy reaching the earth per second is approximately equal to the energy released by the combustion of 500 million tons of coal. By using clean and pollution-free solar energy to reduce carbon dioxide into chemical fuels such as hydrocarbons or alcohols, the content of carbon dioxide in the atmosphere is reduced, and the obtained product can be recycled, so that the photocatalytic reduction of carbon dioxide has a good prospect. The raw materials are simple and easy to obtain in the process, the solar energy is directly utilized without consuming auxiliary energy, and the carbon can be really recycled, so that the method is regarded as the technology with the greatest prospect.
In the photocatalytic reduction of carbon dioxide, a catalyst occupies an indispensable position, and the catalyst with strong selectivity and high activity can improve the solar energy utilization rate, so that the conversion efficiency of the reaction is improved. The two-dimensional ultrathin nanosheet has a large specific surface area, and can effectively promote oxidation-reduction reaction. Compared with a block material, more reaction active sites can be exposed, and the catalytic activity of the reaction is effectively improved. Therefore, the two-dimensional ultrathin bismuth-rich bismuth oxychloride nanosheet material is expected to greatly improve the performance of photocatalytic reduction of carbon dioxide.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a method for preparing a two-dimensional ultrathin bismuth-rich bismuth oxychloride nanosheet by a hydrothermal method.
A method for preparing a two-dimensional ultrathin bismuth-rich bismuth oxychloride nanosheet material by a hydrothermal method comprises the following steps:
(1) adding deionized water into a polytetrafluoroethylene lining reaction kettle, respectively adding polyol, a bismuth source and a surfactant, and mixing to obtain a solution, wherein the molar volume ratio of the polyol to the bismuth source to the surfactant to the deionized water is (2-300 mmol): 0.5-1.5 mmol: 4-16 mmol: 25-40 ml;
(2) slowly dropwise adding a sodium chloride solution, and keeping stirring at a high speed, wherein the concentration of the sodium chloride solution is 6.2mmol/L, and the stirring speed is more than 1000 r/min; continuously dropwise adding a sodium hydroxide solution, adjusting the pH to 10-13, preferably 11.85, and continuously stirring for more than 10 min; wherein the sodium hydroxide solution is 2 mol/L; the volume ratio of the mixed solution to the sodium chloride solution to the sodium hydroxide solution is 25-40 ml: 1-5 ml: 0.8-1.3 ml, preferably 25ml: 5ml: 1 ml;
(3) and carrying out hydrothermal reaction for 2-12 h at 140-180 ℃, preferably for 3h at 160 ℃, cooling to room temperature, centrifuging the product, and sequentially washing with ethanol and deionized water to obtain the two-dimensional ultrathin bismuth-rich bismuth oxychloride nanosheet.
In the preferred embodiment of the present invention, the polyol in step (1) is mannitol, ethylene glycol or glycerol, preferably mannitol.
In a preferred embodiment of the present invention, the bismuth source in step (1) is bismuth nitrate, bismuth acetate, bismuth chloride, or bismuth sulfate, preferably bismuth nitrate.
In a preferred embodiment of the present invention, the surfactant in step (1) is polyvinylpyrrolidone (PVP), cetyltrimethylammonium chloride, and an ionic liquid, preferably polyvinylpyrrolidone (PVP).
In a preferred embodiment of the present invention, when the polyhydric alcohol in the step (1) is mannitol, the bismuth source is bismuth nitrate, and the surfactant is polyvinylpyrrolidone, the molar volume ratio is 2.5 mmol: 1 mmol: 4 mmol: 25 mL.
The inventor finds that: when Bi (NO)3)3Upon addition to water, the solution immediately turned into a white suspension due to Bi (NO)3)3Hydrolysis occurs to form micro-particlesDissolved BiONO3. However, when the aqueous solution is added with mannitol, then Bi (NO) is added3)3Stirring continuously to form clear solution, which shows that bismuth ions added into the solution are coordinated with mannitol to avoid BiONO3. The method is favorable for uniform nucleation and growth of bismuth oxychloride in later hydrothermal reaction and formation of an ultrathin nano structure. Glycol, glycerol, etc. can replace mannitol, and have similar effects. Polyvinylpyrrolidone (PVP) is used as a synthetic water-soluble high molecular compound and plays a role of a surfactant in the synthesis process of the nano material. In the process of crystal growth of the nano material, in order to reduce the surface energy of the system, PVP molecules can be strongly adsorbed on a certain crystal face of the crystal, so that more nano particles are prevented from being adsorbed and grown on the crystal face, the growth of the crystal in a certain crystal direction is limited, and finally a two-dimensional ultrathin structure is formed. Cetyl trimethyl ammonium chloride and ionic liquid can replace PVP to be used as a surfactant, and the ultrathin nano structure of bismuth oxychloride can be formed.
According to the powder sample prepared by the method, the thickness of the ultrathin nanosheet is about 2-3 nm, and the nanosheet is proved to have an ultrathin structure.
The crystal structure and phase were investigated by X-ray diffraction (XRD), and as shown in FIG. 1, the diffraction peak of the sample was indexed to Bi in the tetragonal phase12O17Cl2(JCPDS No. 370702), bismuth oxychloride in general has the formula BiOCl and is therefore defined as bismuth-rich. The morphology and size of the samples were characterized using Transmission Electron Microscopy (TEM). As shown in FIG. 2, the low-resolution transmission electron microscope image shows a two-dimensional sheet-like morphology and almost transparent characteristics, which indicates that the film has an ultrathin property, and the size is about 100-200 nm. The thickness of the nanoplatelets was further analyzed by Atomic Force Microscope (AFM) images and corresponding height profile.
It is a further object of the present invention to use the prepared material for photocatalytic reduction of carbon dioxide.
Photocatalytic CO of the obtained sample by adopting a Beijing Pophyi Labsolar-6a photocatalytic system2Reduction ActivityEvaluation was carried out: suspending 30mg of photocatalyst powder in 50ml of water, and violently stirring at 1000r/min until the photocatalyst powder is uniformly dispersed; before light source irradiation, vacuum treatment is carried out on the instrument to keep the temperature of a reaction system at about 5 ℃ so as to improve CO2(ii) a solubility of (a); pure CO is mixed2The gas was pumped into a 100ml reactor at a pressure of 0.08mpa, a 300w xenon lamp was used as the light source, and the photocatalytic CO was analyzed by a gas chromatograph (Cotrun GC2002, FID) during irradiation2The gaseous product of the reduction.
To verify the structural superiority of the ultrathin nanosheets, CO was performed2And (3) a photocatalytic reduction experiment, namely evaluating the photocatalytic activity of a synthesized sample and eliminating the influence of a sacrificial agent and a cocatalyst. The gas chromatographic analysis shows that CO is Bi12O17Cl2Ultrathin nanosheet and Bi12O17Cl2Bulk major product, no CH detected4And CH3OH and the like. As shown in FIG. 4, the yield of CO gradually increased with the increase of irradiation time, and Bi was added12O17Cl2The conversion rate of the ultrathin nano-sheets is about 64.3 mu mol g-1·h-1Is Bi12O17Cl2Bulk material (2.3. mu. mol. g)-1·h-1) About 28 times of the total weight of the product. In a control experiment carried out in the dark in the absence of the photocatalyst, no CO signal was detected, confirming that CO is derived from CO on the photocatalyst2By photocatalytic reduction.
Advantageous effects
The invention utilizes a one-step hydrothermal method to prepare the ultrathin bismuth-rich bismuth oxychloride nanosheet material with high specific surface area and more active sites. The inventor prepares the two-dimensional ultrathin material by regulating pH, reaction temperature and the like and adopting a simple one-step hydrothermal method, compared with a block material, the prepared ultrathin nanosheet has efficient photocatalytic carbon dioxide reduction performance, not only provides a new thought and method for the design and synthesis of a novel functional photocatalytic material, but also realizes CO2Provides a new way for the high-efficiency catalytic reduction, and provides a theoretical basis for the application of the photocatalytic carbon dioxide reduction technology in solving the environmental problems, energy shortage and the like caused by the greenhouse effect. TheThe method has the advantages of mild and controllable reaction conditions, simple operation, strong practicability and convenience for large-scale popularization.
Drawings
FIG. 1 is an X-ray powder diffraction analysis (XRD) of the two-dimensional ultrathin bismuth-rich oxychloride nanosheet material obtained in example 1;
FIG. 2 is a transmission image (TEM) of low power field emission of the two-dimensional ultrathin bismuth-rich oxychloride nanoplatelets obtained in example 1;
FIG. 3 is an atomic force microscopy electron microscope (AFM) image of the two-dimensional ultrathin bismuth oxychloride nanoplatelet material obtained in example 1;
FIG. 4 shows the carbon dioxide reduction performance test of the two-dimensional ultrathin bismuth-rich oxychloride nanosheet material obtained in example 1.
Detailed Description
The present invention will be described in detail below with reference to examples to enable those skilled in the art to better understand the present invention, but the present invention is not limited to the following examples.
Unless otherwise defined, terms (including technical and scientific terms) used herein should be construed to have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. It will be further understood that terms used herein should be interpreted as having a meaning that is consistent with their meaning in the context of this specification and the relevant art, and should not be interpreted in an idealized or overly formal sense unless expressly so defined herein.
Example 1
A method for preparing a two-dimensional ultrathin bismuth-rich bismuth oxychloride nanosheet material by a hydrothermal method comprises the following steps:
adding 25mL of deionized water into a 50mL polytetrafluoroethylene inner liner, keeping stirring, adding 0.455 g of mannitol, adding 0.486 g of bismuth nitrate pentahydrate after complete dissolution, adding 0.400 g of polyvinylpyrrolidone after complete dissolution, then slowly adding 5mL of a solution containing 0.059 g of sodium chloride, and adding 2 mol/L of sodium hydroxide solution to adjust the pH value of the solution to 11.85. Putting the obtained solution into a reaction kettle, screwing down the solution, putting the solution into an oven, and heating the solution for 3 hours at 160 ℃. And (3) continuously carrying out solid-liquid separation on the obtained suspension for 3 min at the rotating speed of 13000 r/min by using a high-speed centrifuge, and washing the solid collection for 3 times by using ethanol and deionized water respectively to obtain the two-dimensional ultrathin bismuth-rich bismuth oxychloride nanosheet material.
Subjecting the obtained two-dimensional ultrathin bismuth-rich bismuth oxychloride nanosheet to CO2In the photocatalytic reduction experiment, the yield of CO is gradually increased along with the increase of the irradiation time, and Bi is12O17Cl2The conversion rate of the ultrathin nano-sheets is about 64.1 mu mol g-1·h-1。
Example 2
A method for preparing a two-dimensional ultrathin bismuth-rich bismuth oxychloride nanosheet material by a hydrothermal method comprises the following steps:
adding 15 mL of deionized water into a 25mL polytetrafluoroethylene inner liner, keeping stirring, adding 0.228 g of mannitol, adding 0.243 g of bismuth nitrate pentahydrate after complete dissolution, adding 0.200 g of polyvinylpyrrolidone after complete dissolution, then slowly adding 2.5mL of a solution containing 0.059 g of sodium chloride, and adding 2 mol/L of sodium hydroxide solution to adjust the pH value of the solution to 11.85. Putting the obtained solution into a reaction kettle, screwing down the solution, putting the solution into an oven, and heating the solution for 3 hours at 160 ℃. And (3) continuously carrying out solid-liquid separation on the obtained suspension for 3 min at the rotating speed of 13000 r/min by using a high-speed centrifuge, and washing the solid collection for 3 times by using ethanol and deionized water respectively to obtain the two-dimensional ultrathin bismuth-rich bismuth oxychloride nanosheet material.
Subjecting the obtained two-dimensional ultrathin bismuth-rich bismuth oxychloride nanosheet to CO2In the photocatalytic reduction experiment, the yield of CO is gradually increased along with the increase of the irradiation time, and Bi is12O17Cl2The conversion rate of the ultrathin nano-sheets is about 65.0 mu mol g-1·h-1。
Example 3
A method for preparing a two-dimensional ultrathin bismuth-rich bismuth oxychloride nanosheet material by a hydrothermal method comprises the following steps:
50mL of deionized water was added to a 100mL polytetrafluoroethylene liner, stirring was maintained, 0.900 g of mannitol was added, 0.972 g of bismuth nitrate pentahydrate was added after complete dissolution, 0.800 g of polyvinylpyrrolidone was added after complete dissolution, 10 mL of a solution containing 0.059 g of sodium chloride was slowly added, and 2 mol/L of sodium hydroxide solution was added to adjust the pH of the solution to 11.85. Putting the obtained solution into a reaction kettle, screwing down the solution, putting the solution into an oven, and heating the solution for 3 hours at 160 ℃. And (3) continuously carrying out solid-liquid separation on the obtained suspension for 3 min at the rotating speed of 13000 r/min by using a high-speed centrifuge, and washing the solid collection for 3 times by using ethanol and deionized water respectively to obtain the two-dimensional ultrathin bismuth-rich bismuth oxychloride nanosheet material.
Subjecting the obtained two-dimensional ultrathin bismuth-rich bismuth oxychloride nanosheet to CO2In the photocatalytic reduction experiment, the yield of CO is gradually increased along with the increase of the irradiation time, and Bi is12O17Cl2The conversion rate of the ultrathin nano-sheets is about 61.2 mu mol g-1·h-1。
Example 4
A method for preparing a two-dimensional ultrathin bismuth-rich bismuth oxychloride nanosheet material by a hydrothermal method comprises the following steps:
(1) adding deionized water into a polytetrafluoroethylene lining reaction kettle, respectively adding mannitol, bismuth acetate and polyvinylpyrrolidone, mixing to obtain a solution, wherein the molar volume ratio of the polyhydric alcohol to the bismuth source to the surfactant to the deionized water is 2.5 mmol: 1 mmol: 4 mmol: 25 ml;
(2) slowly dropwise adding a sodium chloride solution, and keeping stirring at a high speed, wherein the concentration of the sodium chloride solution is 6.2mmol/L, and the stirring speed is more than 1000 r/min; continuously dropwise adding sodium hydroxide solution, adjusting the pH value to 11.85, and continuously stirring for more than 10 min; the sodium hydroxide solution is 2 mol/L; the volume ratio of the mixed solution to the sodium chloride solution to the sodium hydroxide solution is 25ml: 5ml: 1 ml;
(3) and carrying out hydrothermal reaction for 3h at 160 ℃ in the reaction kettle, cooling to room temperature, centrifuging the product, and sequentially washing with ethanol and deionized water to obtain the two-dimensional ultrathin bismuth-rich bismuth oxychloride nanosheet.
Subjecting the obtained two-dimensional ultrathin bismuth-rich bismuth oxychloride nanosheet to CO2In the photocatalytic reduction experiment, the yield of CO is gradually increased along with the increase of the irradiation time, and Bi is12O17Cl2The conversion rate of the ultrathin nano-sheets is about 58.3 mu mol g-1·h-1。
Example 5
A method for preparing a two-dimensional ultrathin bismuth-rich bismuth oxychloride nanosheet material by a hydrothermal method comprises the following steps:
(4) adding deionized water into a polytetrafluoroethylene lining reaction kettle, respectively adding mannitol, bismuth sulfate and polyvinylpyrrolidone, mixing to obtain a solution, wherein the molar volume ratio of the polyhydric alcohol to the bismuth source to the surfactant to the deionized water is 2.5 mmol: 1 mmol: 4 mmol: 25 ml;
(5) slowly dropwise adding a sodium chloride solution, and keeping stirring at a high speed, wherein the concentration of the sodium chloride solution is 6.2mmol/L, and the stirring speed is more than 1000 r/min; continuously dropwise adding sodium hydroxide solution, adjusting the pH value to 11.85, and continuously stirring for more than 10 min; the sodium hydroxide solution is 2 mol/L; the volume ratio of the mixed solution to the sodium chloride solution to the sodium hydroxide solution is 25ml: 5ml: 1 ml;
(6) and carrying out hydrothermal reaction for 3h at 160 ℃ in the reaction kettle, cooling to room temperature, centrifuging the product, and sequentially washing with ethanol and deionized water to obtain the two-dimensional ultrathin bismuth-rich bismuth oxychloride nanosheet.
Subjecting the obtained two-dimensional ultrathin bismuth-rich bismuth oxychloride nanosheet to CO2In the photocatalytic reduction experiment, the yield of CO is gradually increased along with the increase of the irradiation time, and Bi is12O17Cl2The conversion rate of the ultrathin nano-sheets is about 65.7 mu mol g-1·h-1。
Example 6
A method for preparing a two-dimensional ultrathin bismuth-rich bismuth oxychloride nanosheet material by a hydrothermal method comprises the following steps:
(7) adding deionized water into a polytetrafluoroethylene lining reaction kettle, respectively adding glycerol, bismuth nitrate and polyvinylpyrrolidone, mixing to obtain a solution, wherein the molar volume ratio of the polyhydric alcohol to the bismuth source to the surfactant to the deionized water is 300 mmol: 1 mmol: 4 mmol: 25 ml;
(8) slowly dropwise adding a sodium chloride solution, and keeping stirring at a high speed, wherein the concentration of the sodium chloride solution is 6.2mmol/L, and the stirring speed is more than 1000 r/min; continuously dropwise adding sodium hydroxide solution, adjusting the pH value to 11.85, and continuously stirring for more than 10 min; the sodium hydroxide solution is 2 mol/L; the volume ratio of the mixed solution to the sodium chloride solution to the sodium hydroxide solution is 25ml: 5ml: 1 ml;
(9) and carrying out hydrothermal reaction for 3h at 160 ℃ in the reaction kettle, cooling to room temperature, centrifuging the product, and sequentially washing with ethanol and deionized water to obtain the two-dimensional ultrathin bismuth-rich bismuth oxychloride nanosheet.
Subjecting the obtained two-dimensional ultrathin bismuth-rich bismuth oxychloride nanosheet to CO2In the photocatalytic reduction experiment, the yield of CO is gradually increased along with the increase of the irradiation time, and Bi is12O17Cl2The conversion rate of the ultrathin nano-sheets is about 60.5 mu mol g-1·h-1。
Example 7
A method for preparing a two-dimensional ultrathin bismuth-rich bismuth oxychloride nanosheet material by a hydrothermal method comprises the following steps:
(10) adding deionized water into a polytetrafluoroethylene lining reaction kettle, respectively adding mannitol, bismuth nitrate and hexadecyl trimethyl ammonium chloride, and mixing to obtain a solution, wherein the molar volume ratio of the polyhydric alcohol to the bismuth source to the surfactant to the deionized water is 300 mmol: 1 mmol: 2 mmol: 25 ml;
(11) slowly dropwise adding a sodium chloride solution, and keeping stirring at a high speed, wherein the concentration of the sodium chloride solution is 6.2mmol/L, and the stirring speed is more than 1000 r/min; continuously dropwise adding sodium hydroxide solution, adjusting the pH value to 11.85, and continuously stirring for more than 10 min; the sodium hydroxide solution is 2 mol/L; the volume ratio of the mixed solution to the sodium chloride solution to the sodium hydroxide solution is 25ml: 5ml: 1 ml;
(12) and carrying out hydrothermal reaction for 3h at 160 ℃ in the reaction kettle, cooling to room temperature, centrifuging the product, and sequentially washing with ethanol and deionized water to obtain the two-dimensional ultrathin bismuth-rich bismuth oxychloride nanosheet.
Subjecting the obtained two-dimensional ultrathin bismuth-rich bismuth oxychloride nanosheet to CO2In the photocatalytic reduction experiment, the yield of CO is gradually increased along with the increase of the irradiation time, and Bi is12O17Cl2The conversion rate of the ultrathin nano-sheets is about 62.3 mu mol g-1·h-1。
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes performed by the present invention or directly or indirectly applied to other related technical fields are included in the scope of the present invention.
Claims (10)
1. A method for preparing a two-dimensional ultrathin bismuth-rich bismuth oxychloride nanosheet material by a hydrothermal method is characterized by comprising the following steps:
(1) adding deionized water into a polytetrafluoroethylene lining reaction kettle, respectively adding polyol, a bismuth source and a surfactant, and mixing to obtain a solution, wherein the molar volume ratio of the polyol to the bismuth source to the surfactant to the deionized water is (2-300 mmol): 0.5-1.5 mmol: 4-16 mmol: 25-40 ml;
(2) slowly dropwise adding a sodium chloride solution, and keeping stirring at a high speed, wherein the concentration of the sodium chloride solution is 6.2mmol/L, and the stirring speed is more than 1000 r/min; continuously dropwise adding a sodium hydroxide solution, adjusting the pH value to 10-13, and continuously stirring for more than 10 min; wherein the sodium hydroxide solution is 2 mol/L; the volume ratio of the mixed solution to the sodium chloride solution to the sodium hydroxide solution is 25-40 ml: 1-5 ml: 0.8-1.3 ml;
(3) and carrying out hydrothermal reaction for 2-12 h at 140-180 ℃ in the reaction kettle, cooling to room temperature, centrifuging a product, and sequentially washing with ethanol and deionized water to obtain the catalyst.
2. The hydrothermal process of claim 1, wherein: the polyhydric alcohol in the step (1) is mannitol, ethylene glycol or glycerol, and preferably mannitol.
3. The hydrothermal process of claim 1, wherein: in the step (1), the bismuth source is bismuth nitrate, bismuth acetate, bismuth chloride and bismuth sulfate, and bismuth nitrate is preferred.
4. The hydrothermal process of claim 1, wherein: the surfactant in the step (1) is polyvinylpyrrolidone, hexadecyl trimethyl ammonium chloride and ionic liquid, preferably polyvinylpyrrolidone.
5. The hydrothermal process of claim 1, wherein: when the polyhydric alcohol is mannitol, the bismuth source is bismuth nitrate and the surfactant is polyvinylpyrrolidone in the step (1), the molar volume ratio is 2.5 mmol: 1 mmol: 4 mmol: 25 mL.
6. The hydrothermal process of claim 1, wherein: and (3) continuously dropwise adding the sodium hydroxide solution in the step (2), adjusting the pH value to 11.85, and continuously stirring for more than 10 min.
7. The hydrothermal process of claim 1, wherein: the volume ratio of the mixed solution, the sodium chloride solution and the sodium hydroxide solution in the step (2) is 25ml to 5ml to 1 ml.
8. The hydrothermal process of claim 1, wherein: and (3) carrying out hydrothermal reaction on the reaction kettle for 3 hours at the temperature of 160 ℃.
9. The two-dimensional ultrathin bismuth-rich oxychloride nanosheet material prepared by the method of any one of claims 1 to 8, wherein: the thickness of the ultrathin nanosheet is about 2-3 nm.
10. The use of the two-dimensional ultrathin bismuth oxychloride nanosheet material as defined in claim 9, wherein: it is applied to photocatalytic reduction of carbon dioxide.
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