CN111644185A - Bi stripping by cell crusher3O4Method for Cl and in photocatalytic reduction of CO2Application of aspects - Google Patents
Bi stripping by cell crusher3O4Method for Cl and in photocatalytic reduction of CO2Application of aspects Download PDFInfo
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- XMEVHPAGJVLHIG-FMZCEJRJSA-N chembl454950 Chemical compound [Cl-].C1=CC=C2[C@](O)(C)[C@H]3C[C@H]4[C@H]([NH+](C)C)C(O)=C(C(N)=O)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O XMEVHPAGJVLHIG-FMZCEJRJSA-N 0.000 claims abstract description 13
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- 229910052797 bismuth Inorganic materials 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
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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
-
- B01J35/39—
-
- B01J35/40—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/40—Carbon monoxide
Abstract
The invention provides a method for stripping Bi by using a cell crusher3O4Method for producing Cl with water as solvent and Bi (NO)3)3·5H2O is used as a Bi source, tetracycline hydrochloride is used as a Cl source, a hydrothermal method is adopted to prepare a Bi-O-Cl complex, and a sintering method is adopted to prepare a bulk Bi3O4Cl photocatalyst (B-Bi)3O4Cl), and then adding B-Bi3O4Cl is ultrasonically stripped through a cell crusher to prepare ultrathin Bi3O4Cl nanosheet (S-Bi)3O4Cl) to improve its photocatalytic properties. The invention consists ofBi prepared by combining hydrothermal method and sintering method3O4Cl photocatalyst, Bi prepared therefrom3O4The Cl is in an irregular block structure with the thickness of about 200 and 400 nm; prepared block Bi by utilizing cell crusher3O4Performing ultrasonic stripping on the Cl photocatalyst to ensure that Bi is3O4Stripping Cl from the block to Bi3O4The thickness of the nano-sheet is about 10-50 nm, and the ultrathin nano-sheet enables the migration rate of photo-generated carriers to be high, the separation efficiency to be high, and the good photocatalytic reduction of CO is realized2And (4) performance.
Description
Technical Field
The invention relates to preparation of chemical substances, in particular to a method for stripping Bi by using a cell crusher3O4Cl process, the invention also relates to Bi3O4Cl in reduction of CO2Application of the aspect.
Background
Energy is the material basis on which humans live and develop, and also the material basis on which society lives and develops. Nowadays, the traditional fossil energy is still in the leading position in the energy structure, but due to the limited and non-renewable nature of the fossil energy, the world will face the problem of resource exhaustion in the near future. Therefore, the development and utilization of new energy have become a hot spot of research. Among a plurality of new energy sources, solar energy is the focus of research because of inexhaustible advantages, and the photocatalysis technology is to directly utilize the solar energy through a semiconductor photocatalyst to convert the solar energy into chemical energy and electric energy, so that hydrogen and CO can be produced by decomposing water2Reduction, photocatalysis nitrogen fixation and other reactions, which enable the photocatalysis technology to show unique advantages and wide application prospects in the field of new energy.
In recent years, researchers have been working on novel highly efficient visible light-responsive photocatalysts including multi-element metal oxides, layered products, metal hydroxides, etc., wherein BiOX (X = Cl, Br, I) belongs to a novel bismuth-based photocatalyst having a layered structure characterized by [ Bi ]2O2]2+The double-layer halogen atoms are staggered, so that the recombination rate of photon-generated carriers can be obviously reduced, and the double-layer halogen atoms have the advantages of low toxicity, easiness in synthesis and the like, and attract wide attention of all countries in the world. However, most of BiOX can only be applied to ambient photocatalysis but not energy photocatalysis due to low position of a conduction band and weak reduction capability. Relevant studies have shown that Bi is rich in bismuth (dehalogenated) x O y X z The base photocatalyst has a layered structure similar to that of BiOX and more negative conduction band positionCompared with BiOX, the photocatalyst not only retains the advantages, but also makes up the deficiencies, and has more potential. Researchers are studying Bi x O y X z Some problems have also been found in the photocatalytic process, Bi x O y X z The photocatalytic efficiency is still low due to the weak carrier separation energy of (B), and thus, for Bi x O y X z Further modification is necessary to improve the photocatalytic activity. The construction of an ultrathin two-dimensional structure is one of effective ways for optimizing the photocatalytic performance. Ultrathin nanosheets are generally thinner than the space charge layer, and the photogenerated carriers can migrate from the interior of the nanosheet to the surface by simple diffusion, the thinner the nanosheet, the faster the carrier can diffuse from the interior to the surface. In addition, the number of exposed atoms on the surface of the ultrathin nanoflake is higher, which is also important for improving the solar energy absorption efficiency. Thus, Bi x O y X z Ultra-thin thickness is an effective way to achieve excellent photocatalytic performance. Bi3O4Cl as a Bi x O y X z The photocatalyst can generate a strong internal electric field due to the unique crystal structure, is beneficial to the effective separation of photo-generated charges, and Bi3O4Cl has high chemical and optical stability and is ideal for researching Bi x O y X z A photocatalytic material with ultra-thin thickness.
Disclosure of Invention
The invention aims to solve the technical problem of providing a method for peeling a block Bi by using a cell crusher3O4Cl to obtain nanosheet, and application of the nanosheet to photocatalytic reduction of CO2The use of (1).
In order to solve the technical problems, the technical scheme adopted by the invention is as follows: bi stripping by cell crusher3O4The Cl method uses water as a solvent and Bi (NO)3)3·5H2O is used as a Bi source, tetracycline hydrochloride is used as a Cl source, and hydrothermal treatment is adoptedPreparing Bi-O-Cl complex by the method, and preparing block Bi by a sintering method3O4Cl photocatalyst (namely B-Bi)3O4Cl), and then adding B-Bi3O4Cl is ultrasonically stripped through a cell crusher to prepare ultrathin Bi3O4Cl nanosheet (noted as S-Bi)3O4Cl) to improve its photocatalytic properties; the method comprises the following steps:
⑴ weighing 0.4-1 g Bi (NO)3)3·5H2Fully stirring and dissolving O in 30-35 ml of deionized water, then adding 0.2-0.5 g of tetracycline hydrochloride, stirring for 30-60 min, putting into a 40 ml stainless steel kettle hydrothermal kettle with a polytetrafluoroethylene lining, and reacting for 15-24 h at 140-180 ℃;
⑵, taking out the sample after the hydrothermal reaction obtained in the step ⑴, centrifuging for 3-10 min at 10000 r/min each time by using a centrifuge, washing and centrifuging and precipitating for a plurality of times by using distilled water and ethanol respectively, finally drying in an oven at 60-100 ℃ for 12-24 h to obtain a black Bi-O-Cl complex precursor, weighing 0.2-2 g of the dried precursor, putting the dried precursor into a muffle furnace, sintering for 2-10 h at 450-600 ℃, raising the temperature at the rate of 1-5 ℃/min, naturally cooling to room temperature, and collecting the sample to obtain the block Bi3O4A Cl photocatalyst;
⑶ weighing 300 mg of the bulk Bi prepared in step ⑵3O4Adding 0-200 ml of deionized water, 0-500 ml of absolute ethyl alcohol and 0-500 ml of ethylene glycol into a Cl sample in a 1000 ml beaker, carrying out ultrasonic stripping by using a cell crusher, wherein the ultrasonic power is 40-80%, carrying out ultrasonic treatment after cooling to room temperature after 15-30 min of each ultrasonic treatment, supplementing absolute ethyl alcohol each time until the solution reaches 500 ml, accumulating the ultrasonic treatment for 4-8 h, standing and precipitating, washing and precipitating the precipitate by using distilled water and ethanol for a plurality of times, finally drying in an oven at 60-100 ℃ for 12-24 h to obtain an ultrathin sample, and carrying out XRD, SEM, DRS and photocurrent test on Bi by using the technical means of3O4The phase composition, the micro morphology, the charge separation and the photocatalytic performance of the Cl photocatalyst are researched.
The water content of the ethylene glycol is less than 0.01% (V/V).
The water content of the ethanol is less than 0.01% (V/V).
The hydrothermal temperature is 140 ℃ and 180 ℃.
The Bi (NO)3)3·5H2The molar ratio of O to tetracycline hydrochloride is 1.8-2: 1.
the total volume of the deionized water, the absolute ethyl alcohol and the glycol is 500 ml.
The invention adopts the technical scheme to strip Bi by using the cell crusher3O4Cl method, firstly preparing Bi by combining hydrothermal method and sintering method3O4Cl photocatalyst, Bi prepared therefrom3O4The Cl is in an irregular block structure with the thickness of about 200 and 400 nm; then the prepared block Bi is subjected to cell crushing by a cell crusher3O4Performing ultrasonic stripping on the Cl photocatalyst to ensure that Bi is3O4Stripping Cl from the block to Bi3O4The thickness of the nano-sheet is about 10-50 nm, and the ultrathin nano-sheet enables the migration rate of photo-generated carriers to be high, the separation efficiency to be high, and the good photocatalytic reduction of CO is realized2And (4) performance.
Drawings
FIG. 1 is a powder X-ray diffraction pattern of samples obtained in examples 1 and 2 of the present invention;
FIG. 2 is a scanning electron micrograph of samples obtained in examples 1 and 2 of the present invention;
FIG. 3 is a graph showing the UV-visible diffuse reflectance spectra of samples obtained in examples 1 and 2 of the present invention;
FIG. 4 is a graph showing the photocurrent response of samples obtained in examples 1 and 2 of the present invention;
FIG. 5 shows the photocatalytic reduction of CO for samples obtained in examples 1 and 2 of the present invention2And (4) performance.
Detailed Description
The invention relates to a method for stripping Bi by using a cell crusher3O4The Cl method uses water as a solvent and Bi (NO)3)3·5H2O is used as a Bi source, tetracycline hydrochloride is used as a Cl source, a hydrothermal method is adopted to prepare a Bi-O-Cl complex, and a sintering method is adopted to prepare a bulk Bi3O4Cl photocatalyst (namely B-B)i3O4Cl), and then adding B-Bi3O4Cl is ultrasonically stripped through a cell crusher to prepare ultrathin Bi3O4Cl nanosheet (noted as S-Bi)3O4Cl) to improve its photocatalytic properties.
The invention relates to a method for stripping Bi by using a cell crusher3O4Method example 1 for Cl, the method steps are:
⑴ weighing 1 g Bi (NO)3)3·5H2Dissolving O in 35 ml of deionized water under stirring, adding 0.5 g of tetracycline hydrochloride, stirring for 30 min, transferring the mixed solution into a 40 ml stainless steel kettle hydrothermal kettle with a polytetrafluoroethylene lining, and reacting for 16 h at 160 ℃. Taking out the sample after the hydrothermal reaction, and centrifuging for 10min at 10000 r/min each time by using a centrifuge. Washing the precipitate with distilled water and ethanol for several times, and drying in an oven at 80 deg.C for 24 hr to obtain black Bi-O-Cl complex precursor. Weighing 0.2 g of dried precursor, putting the precursor into a muffle furnace, sintering at 550 ℃ for 3 h at the heating rate of 5 ℃/min, naturally cooling to room temperature, and collecting a sample to obtain a block Bi3O4A Cl photocatalyst;
⑵ weighing 300 mg of the block Bi prepared in the step (1)3O4Cl samples were placed in a 1000 ml beaker and 100 ml deionized water, 200 ml absolute ethanol and 200 ml ethylene glycol were added. Carrying out ultrasonic stripping by using a cell crusher, wherein the ultrasonic power is 40%, carrying out ultrasonic treatment after cooling to room temperature after 20 min of ultrasonic treatment each time, supplementing absolute ethyl alcohol each time until the solution reaches 500 ml, accumulating the ultrasonic treatment for 4h, standing for precipitation, washing the precipitate by using distilled water and ethyl alcohol for several times, and finally drying in an oven at 60 ℃ for 24h to obtain the ultrathin sample.
The invention relates to a method for stripping Bi by using a cell crusher3O4Method example 2 for Cl, the method steps are:
⑴ weighing 0.8 g Bi (NO)3)3·5H2Dissolving O in 33 ml deionized water under stirring, adding 0.35 g tetracycline hydrochloride, stirring for 40 min, transferring the mixed solution into 40 ml stainless steel kettle hydrothermal kettle with polytetrafluoroethylene lining, and reacting at 180 deg.C for 1And 6 h. Taking out a sample after the hydrothermal reaction, centrifuging for 8 min at 10000 r/min each time by using a centrifuge, washing the centrifugal precipitate for a plurality of times by using distilled water and ethanol respectively, and finally drying in an oven at 60 ℃ for 18 h to obtain a black Bi-O-Cl complex precursor. Weighing 0.2 g of dried precursor, putting the precursor into a muffle furnace, sintering at 500 ℃ for 5 h at the heating rate of 2 ℃/min, naturally cooling to room temperature, and collecting a sample to obtain a block Bi3O4A Cl photocatalyst;
⑵ weighing 300 mg of the block Bi prepared in the step (1)3O4Cl samples were placed in 1000 ml beakers and 300 ml absolute ethanol and 200 ml ethylene glycol were added. Carrying out ultrasonic stripping by using a cell crusher, wherein the ultrasonic power is 60%, carrying out ultrasonic treatment after cooling to room temperature after 15 min of ultrasonic treatment each time, supplementing absolute ethyl alcohol each time until the solution reaches 500 ml, accumulating ultrasonic treatment for 6 h, standing for precipitation, washing the precipitate by using distilled water and ethyl alcohol for several times, and finally drying in an oven at 60 ℃ for 24h to obtain the ultrathin sample.
The invention relates to a method for stripping Bi by using a cell crusher3O4Method example 3 for Cl, the method steps are:
⑴ weighing 0.5 g Bi (NO)3)3·5H2Dissolving O in 33 ml deionized water under stirring, adding 0.28 g tetracycline hydrochloride, stirring for 30 min, transferring the mixed solution into a 40 ml stainless steel kettle hydrothermal kettle with a polytetrafluoroethylene lining, and reacting at 180 deg.C for 24 h. Taking out a sample after the hydrothermal reaction, centrifuging for 8 min at 10000 r/min each time by using a centrifuge, washing the centrifugal precipitate for a plurality of times by using distilled water and ethanol respectively, and finally drying in an oven at 60 ℃ for 18 h to obtain a black Bi-O-Cl complex precursor. Weighing 0.2 g of dried precursor, putting the precursor into a muffle furnace, sintering the precursor for 5 h at 450 ℃, heating at the rate of 1 ℃/min, naturally cooling to room temperature, and collecting a sample to obtain a block Bi3O4A Cl photocatalyst;
⑵ weighing 300 mg of the block Bi prepared in the step (1)3O4Cl sample in a 1000 ml beaker 100 ml deionized water, 300 ml absolute ethanol and 100 ml ethylene glycol were added. Ultrasonic peeling with cell pulverizer with ultrasonic power of 80%, per unitAnd performing ultrasonic treatment after the ultrasonic treatment is performed for 20 min, cooling to room temperature, performing ultrasonic treatment again, supplementing absolute ethyl alcohol each time until the solution reaches 500 ml, accumulating the ultrasonic treatment for 7 h, standing and precipitating, washing and precipitating the precipitate with distilled water and ethanol for a plurality of times, and finally drying in an oven at 60 ℃ for 24h to obtain the ultrathin sample.
The invention relates to a method for stripping Bi by using a cell crusher3O4Method example 4 for Cl, the method steps are:
⑴ weighing 0.8 g Bi (NO)3)3·5H2Dissolving O in 33 ml of deionized water under stirring, adding 0.35 g of tetracycline hydrochloride, stirring for 40 min, transferring the mixed solution into a 40 ml stainless steel kettle hydrothermal kettle with a polytetrafluoroethylene lining, and reacting for 16 h at 180 ℃. Taking out the sample after the hydrothermal reaction, and centrifuging for 8 min at 10000 r/min each time by using a centrifuge. Washing the precipitate with distilled water and ethanol for several times, and drying in an oven at 60 deg.C for 18 h to obtain black Bi-O-Cl complex precursor. Weighing 0.2 g of dried precursor, putting the precursor into a muffle furnace, sintering at 550 ℃ for 5 h at the heating rate of 5 ℃/min, naturally cooling to room temperature, and collecting a sample to obtain a block Bi3O4A Cl photocatalyst;
⑵ weighing 300 mg of the block Bi prepared in the step (1)3O4The Cl sample was placed in a 1000 ml beaker and 200 ml deionized water, 150 ml absolute ethanol and 150 ml ethylene glycol were added. Carrying out ultrasonic stripping by using a cell crusher, wherein the ultrasonic power is 60%, carrying out ultrasonic treatment after cooling to room temperature after carrying out ultrasonic treatment for 18 min each time, supplementing absolute ethyl alcohol each time until the solution reaches 500 ml, accumulating the ultrasonic treatment for 6 h, standing for precipitation, washing the precipitate by using distilled water and ethyl alcohol for precipitation for a plurality of times, and finally drying in an oven at 60 ℃ for 24h to obtain the ultrathin sample.
The invention relates to a method for stripping Bi by using a cell crusher3O4Method example 5 for Cl, the method steps are:
⑴ weighing 1 g Bi (NO)3)3·5H2Dissolving O in 33 ml deionized water under stirring, adding 0.48 g tetracycline hydrochloride, stirring for 40 min, transferring the mixed solution into 40 ml stainless steel kettle hydrothermal kettle with polytetrafluoroethylene lining,the reaction was carried out at 180 ℃ for 16 h. Taking out a sample after the hydrothermal reaction, centrifuging for 8 min at 10000 r/min each time by using a centrifuge, washing the centrifugal precipitate for a plurality of times by using distilled water and ethanol respectively, and finally drying in an oven at 60 ℃ for 18 h to obtain a black Bi-O-Cl complex precursor. Weighing 0.2 g of dried precursor, putting the precursor into a muffle furnace, sintering at 500 ℃ for 5 h at the heating rate of 2 ℃/min, naturally cooling to room temperature, and collecting a sample to obtain a block Bi3O4A Cl photocatalyst.
⑵ weighing 300 mg of the block Bi prepared in the step (1)3O4Adding 200 ml of deionized water, 100 ml of absolute ethyl alcohol and 200 ml of ethylene glycol into a 1000 ml beaker, ultrasonically stripping by using a cell crusher, wherein the ultrasonic power is 70%, carrying out ultrasonic treatment after cooling to room temperature after carrying out ultrasonic treatment for 16 min each time, supplementing the absolute ethyl alcohol each time until the solution reaches 500 ml, accumulating the ultrasonic treatment for 5 h, standing and precipitating, washing and precipitating the precipitate by using distilled water and ethanol for a plurality of times, and finally drying in an oven at 80 ℃ for 24h to obtain the ultrathin sample.
The invention utilizes Bi stripped by a cell crusher3O4Photocatalytic reduction of CO with Cl2Example 6:
photocatalytic reduction of CO2CO is generated by a photocatalytic reaction by utilizing a catalyst2Reduction to CO and CH4The solar energy fuel has important significance for relieving the problems of energy shortage, greenhouse effect and the like at present. The specific operation flow is as follows: adopts a gas-sealed quartz reactor of Beijing Pofely science and technology company, the volume of the reactor is 350 mL, a 300W high-pressure xenon lamp is used as a light source, and the photocatalysis CO is carried out on an off-line system2And (4) carrying out reduction experiments. 0.05 g of a photocatalyst Bi3O4Cl was uniformly dispersed in 28.26 cm2On a round quartz plate, 1.7 g NaHCO was added to the bottom of the reactor3Before irradiation, the system was subjected to vacuum treatment to completely remove the air in the reactor. Then 4M H2SO4(5 mL) was injected into the reaction cell with NaHCO3Reaction to 1atm CO2A gas. The temperature of the light reaction device is kept by adopting a DC-0506 low-temperature constant-temperature bath systemThe temperature was maintained at 20 ℃. At given time intervals, about 1 ml of gas was withdrawn using a syringe and the CO was chromatographed using a gas chromatograph2The reduction product is measured, and the gas detected by the chromatogram is CO and CH4And CO2The amount of production was quantified by a standard curve.
FIG. 1 is a powder X-ray diffraction pattern of the samples obtained in examples 1 and 2, from which it can be seen that S-Bi3O4The diffraction spectrum of the Cl sample has several strong peaks at 2 theta =24.0 degrees, 29.1 degrees, 29.7 degrees, 31.4 degrees, 31.6 degrees and 45.3 degrees, and the peak positions and the Bi3O4The peaks of the Cl standard PDF (36-0760) card are consistent, and the peaks correspond to Bi3O4Monoclinic structure of Cl, XRD diffraction pattern thereof and Bi3O4Compared with the Cl standard PDF (36-0760) card, the card has no other miscellaneous peaks and no shift of the peak position, which indicates that the cell crusher is Bi3O4The Cl is subjected to ultrasonic stripping and the phase composition is changed, and the obtained ultra-thin sample is still Bi3O4Cl is pure phase, and the crystal form of the sample is better. FIG. 2 is a scanning electron micrograph of the samples obtained in examples 1 and 2, (a) B-Bi3O4Cl；（b）S-Bi3O4Cl, B-Bi prepared3O4The Cl appearance is an irregular block structure with the thickness of about 200-400 nm, and the sample S-Bi after ultrasonic stripping3O4Most of Cl is ultrathin nanosheets stripped from blocks, and the thickness of the nanosheets is about 10-50 nm, which indicates that a cell crusher is used for successfully stripping a sample. FIG. 3 is a graph showing the UV-visible diffuse reflectance spectra of the samples obtained in examples 1 and 2, as seen from B-Bi3O4Cl phase, S-Bi3O4The Cl sample has a higher absorption intensity in the visible region and the absorption range extends over the entire visible region. FIG. 4 is the photocurrent response of the samples obtained in examples 1 and 2, from which S-Bi can be seen3O4Cl has a ratio of B-Bi3O4Higher photocurrent intensity of Cl than B-Bi3O4Cl increased by about 2. mu.A.cm-2。
FIG. 5 shows an embodiment of the present invention1 and 2 photocatalytic reduction of CO in the samples obtained2Properties, as can be seen in the figure, S-Bi3O4Cl sample vs bulk B-Bi3O4Cl sample in CO2The reaction for converting into CO shows higher photocatalytic efficiency and selectivity. The yield of CO gas generated by the prepared samples increased with the irradiation time and accumulated linearly with time. S-Bi3O4The rate of formation of CO of Cl was 1.89. mu. mol g-1h-1Compared with B-Bi3O4CO formation rate of Cl 0.30. mu. mol g-1h-1The performance is nearly 6 times higher.
Claims (7)
1. Bi stripping by cell crusher3O4Cl process, characterized in that it uses water as solvent and Bi (NO)3)3·5H2O is used as a Bi source, tetracycline hydrochloride is used as a Cl source, a hydrothermal method is adopted to prepare a Bi-O-Cl complex, and a sintering method is adopted to prepare a bulk Bi3O4Cl photocatalyst (B-Bi)3O4Cl), and then adding B-Bi3O4Cl is ultrasonically stripped through a cell crusher to prepare ultrathin Bi3O4Cl nanosheet (S-Bi)3O4Cl) to improve its photocatalytic properties; the method comprises the following steps:
⑴ weighing 0.4-1 g Bi (NO)3)3·5H2Fully stirring and dissolving O in 30-35 ml of deionized water, then adding 0.2-0.5 g of tetracycline hydrochloride, stirring for 30-60 min, putting into a 40 ml stainless steel kettle hydrothermal kettle with a polytetrafluoroethylene lining, and reacting for 15-24 h at 140-180 ℃;
⑵, taking out the sample after the hydrothermal reaction obtained in the step ⑴, centrifuging for 3-10 min at 10000 r/min each time by using a centrifuge, washing and centrifuging and precipitating for a plurality of times by using distilled water and ethanol respectively, finally drying in an oven at 60-100 ℃ for 12-24 h to obtain a black Bi-O-Cl complex precursor, weighing 0.2-2 g of the dried precursor, putting the dried precursor into a muffle furnace, sintering for 2-10 h at 450-600 ℃, raising the temperature at the rate of 1-5 ℃/min, naturally cooling to room temperature, and collecting the sample to obtain the block Bi3O4A Cl photocatalyst;
⑶ weighing 300 mg of the bulk Bi prepared in step ⑵3O4Adding 0-200 ml of deionized water, 0-500 ml of absolute ethyl alcohol and 0-500 ml of ethylene glycol into a Cl sample in a 1000 ml beaker, carrying out ultrasonic stripping by using a cell crusher, wherein the ultrasonic power is 40-80%, carrying out ultrasonic treatment after cooling to room temperature after 15-30 min of each ultrasonic treatment, supplementing absolute ethyl alcohol each time until the solution reaches 500 ml, accumulating the ultrasonic treatment for 4-8 h, standing and precipitating, washing and precipitating the precipitate by using distilled water and ethanol for a plurality of times, finally drying in an oven at 60-100 ℃ for 12-24 h to obtain an ultrathin sample, and carrying out XRD, SEM, DRS and photocurrent test on Bi by using the technical means of3O4The phase composition, the micro morphology, the charge separation and the photocatalytic performance of the Cl photocatalyst are researched.
2. The method of claim 1 for stripping Bi by using a cell crusher3O4Cl, characterized in that said ethylene glycol has a water content of less than 0.01% (V/V).
3. The method of claim 1 for stripping Bi by using a cell crusher3O4Cl, characterized in that the ethanol has a water content of less than 0.01% (V/V).
4. The method of claim 1 for stripping Bi by using a cell crusher3O4The Cl method is characterized in that the hydrothermal temperature is 140-180 ℃.
5. The method of claim 1 for stripping Bi by using a cell crusher3O4Cl, characterized in that said Bi (NO)3)3·5H2The molar ratio of O to tetracycline hydrochloride is 1.8-2: 1.
6. the method of claim 1 for stripping Bi by using a cell crusher3O4Cl, characterized in that the total volume of said deionized water, absolute ethanol and ethylene glycol is 500 ml.
7. The Bi of claim 1 exfoliated using a cell disruptor3O4Photocatalytic reduction of CO with Cl2Application of the aspect.
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