CN114433132A - Method for synthesizing Z-type heterojunction catalytic material by ultrasonic-assisted method - Google Patents
Method for synthesizing Z-type heterojunction catalytic material by ultrasonic-assisted method Download PDFInfo
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- 230000003197 catalytic effect Effects 0.000 title claims abstract description 31
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 103
- 239000003054 catalyst Substances 0.000 claims abstract description 53
- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical compound Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000000843 powder Substances 0.000 claims abstract description 21
- 238000002360 preparation method Methods 0.000 claims abstract description 6
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- 239000000243 solution Substances 0.000 claims description 98
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- 229910021641 deionized water Inorganic materials 0.000 claims description 97
- 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 claims description 57
- 235000011164 potassium chloride Nutrition 0.000 claims description 55
- 239000001103 potassium chloride Substances 0.000 claims description 55
- 235000013878 L-cysteine Nutrition 0.000 claims description 54
- 239000004201 L-cysteine Substances 0.000 claims description 54
- 238000001035 drying Methods 0.000 claims description 53
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- 238000005406 washing Methods 0.000 claims description 24
- 229910052797 bismuth Inorganic materials 0.000 claims description 22
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- 238000005303 weighing Methods 0.000 claims description 22
- 238000007664 blowing Methods 0.000 claims description 18
- 238000009210 therapy by ultrasound Methods 0.000 claims description 17
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- XMEVHPAGJVLHIG-FMZCEJRJSA-N chembl454950 Chemical group [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 description 9
- 239000011259 mixed solution Substances 0.000 claims description 9
- 229960004989 tetracycline hydrochloride Drugs 0.000 claims description 9
- 239000002135 nanosheet Substances 0.000 claims description 8
- 238000002604 ultrasonography Methods 0.000 claims description 7
- PWKSKIMOESPYIA-UHFFFAOYSA-N 2-acetamido-3-sulfanylpropanoic acid Chemical compound CC(=O)NC(CS)C(O)=O PWKSKIMOESPYIA-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
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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 description 9
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- SKLLMYPWXWGJTD-UHFFFAOYSA-N O.O.O.O.O.[N+](=O)([O-])[O-].[K+] Chemical compound O.O.O.O.O.[N+](=O)([O-])[O-].[K+] SKLLMYPWXWGJTD-UHFFFAOYSA-N 0.000 description 5
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- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
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- 229910052794 bromium Inorganic materials 0.000 description 1
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- 238000013329 compounding Methods 0.000 description 1
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- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- B01J35/39—
-
- 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
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
The invention belongs to the field of environmental engineering, relates to the technical field of advanced catalytic oxidation water treatment, and particularly relates to a method for synthesizing a Z-type heterojunction catalytic material by an ultrasonic-assisted method2S3Z-type heterojunction catalyst powder consisting of/BiOCl. The preparation method uses green and safe raw materials, is simple, has easy operation and continuous production, andthe method has low temperature requirement and less energy consumption during reaction, and the raw material reagent is cheap and easy to obtain, thereby showing the environmental friendliness of the catalytic material.
Description
Technical Field
The invention belongs to the field of environmental engineering, relates to the technical field of advanced catalytic oxidation water treatment, and particularly relates to a method for synthesizing a Z-type heterojunction catalytic material by an ultrasonic-assisted method.
Background
With the continuous development of industry, people's demand is continuously increased, and the environment is continuously damaged. Nowadays, the environmental problems caused by various human activities are highlighted and more paid attention from various aspects, and the prevention and treatment of environmental pollution is gradually brought forward by the nation, becoming one of the most concerned and all the time-sensitive matters. The development of environmental pollution treatment technology is urgent, and the pace of researching novel environment-friendly energy sources is not lacked.
The photocatalytic technology has received wide attention from scientists due to its characteristics of low energy consumption, high degradation efficiency, good economic feasibility, no secondary pollution, etc. The forbidden bandwidth of the photocatalytic material is too wide, and the photoproduction electrons and holes are easy to recombine, so that the photocatalytic efficiency is greatly influenced, and the application of the photocatalytic technology is limited. Therefore, the catalytic performance of the photocatalyst is enhanced by various methods such as metal and nonmetal doping, semiconductor compounding, surface defect, microstructure regulation and the like. Among many semiconductors, bismuth-based semiconductors are a promising new photocatalyst that can be used for visible light response. Bismuth oxyhalides BiOX (X ═ Cl, Br, I, etc.) are [ Bi ] interlaced by double-layer halogen atoms2O2]2+A novel layered semiconductor photocatalytic material formed by a layer structure. Wherein BiOCl is an indirect bandgap semiconductor. These characteristics facilitate the separation of photo-generated electron-hole pairs and improve the photocatalytic activity. However, its wide band gap and rapid recombination of photogenerated carriers limit its application in photocatalytic reactions.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a method for synthesizing a Z-type heterojunction catalytic material by an ultrasonic-assisted method, the preparation method uses green and safe raw materials, the method is simple, the process is easy to operate, continuous production can be realized, the temperature requirement is low during reaction, the energy consumption is low, raw material reagents are cheap and easy to obtain, and the environmental friendliness of the catalytic material is shown.
In order to achieve the technical purpose, the technical scheme of the invention is as follows:
a method for synthesizing a Z-type heterojunction catalytic material by an ultrasonic-assisted method comprises the following steps:
step 1, weighing bismuth nitrate pentahydrate, and dissolving the bismuth nitrate pentahydrate into deionized water to obtain a bismuth dissolved solution; weighing L-cysteine, dissolving the L-cysteine in deionized water, and completely dissolving to obtain an L-cysteine solution;
step 2, adding the L-cysteine solution obtained in the step 1 into a bismuth solution, and carrying out normal-temperature ultrasonic treatment for 25min to obtain a precipitate;
step 4, weighing bismuth nitrate pentahydrate, and dissolving the bismuth nitrate pentahydrate into deionized water to obtain a bismuth dissolved solution; weighing potassium chloride, dissolving the potassium chloride in deionized water, and completely dissolving to obtain a potassium chloride solution;
step 5, adding a potassium chloride solution into the bismuth dissolving solution to obtain a mixed solution;
step 6, carrying out ultrasonic treatment on the mixed solution for 25min by adopting an ultrasonic machine at normal temperature to obtain a precipitate;
step 7, washing the precipitate obtained in the step 6 by using deionized water and absolute ethyl alcohol for several times, and then drying the precipitate in an electrothermal drying oven at 60 ℃ to obtain BiOCl catalyst powder;
step 8, weighing bismuth nitrate pentahydrate, and dissolving the bismuth nitrate pentahydrate into deionized water to obtain a bismuth dissolved solution; weighing L-cysteine, dissolving the L-cysteine in deionized water, and completely dissolving to obtain an L-cysteine solution; weighing potassium chloride, dissolving the potassium chloride in deionized water, and completely dissolving to obtain a potassium chloride solution;
step 9, respectively and simultaneously adding the potassium chloride solution and the L-cysteine solution into the bismuth solution, and carrying out normal-temperature ultrasound for 25min by using an ultrasonic machine to obtain a ternary mixed solution;
In step 1, 2.42535g of bismuth nitrate pentahydrate was dissolved in 300mL of deionized water, and 0.121g of L-cysteine was dissolved in 25mL of deionized water.
In step 4, 2.42535g of bismuth nitrate pentahydrate was dissolved in 300mL of deionized water, and 0.7455g of potassium chloride was dissolved in 25mL of deionized water.
In the step 8, 2.42535g of bismuth nitrate pentahydrate is dissolved in 300mL of deionized water, 0.7455g of potassium chloride is dissolved in 25mL of deionized water, and the L-cysteine is dissolved in 25mL of deionized water, and the addition amounts of the L-cysteine are respectively 0.02g, 0.04g, 0.06g, 0.08g and 0.10 g.
The Bi2S3the/BiOCl Z-type heterojunction catalyst is prepared by the method, is of a spherical structure stacked by nano sheets, and has excellent visible light catalytic activity, high catalytic efficiency, good stability and good reusability. The Bi2S3the/BiOCl Z-type heterojunction catalyst is a nanosheet.
Bi2S3The application of the/BiOCl Z-type heterojunction catalyst comprises the following preparation method:
a1, preparing an organic pollutant solution with the concentration of 20mg/L in a volumetric flask with the capacity of 1L;
a2, preparing 25mg of Bi2S3the/BiOCl flake catalyst powder is put into a 50mL beaker, and the prepared 50mL organic pollutant solution with the concentration of 20mg/L is used for dissolving Bi2S3A BiOCl Z-type heterojunction catalyst powder;
a3, stirring the solution obtained in the step a2 in the dark for 60min, turning on an LED light source to irradiate and stir for 30min, and extracting 1mL of solution sample every 5 min;
a4, centrifuging and filtering the solution sample obtained in the step a3, and detecting the concentration of pollutants every 5min by using an ultraviolet-visible spectrophotometry method;
a5, carrying out 5 times of cycle performance tests on the screened catalyst with the best catalytic performance, and researching the prepared Bi2S3Method for preparing/BiOCl Z-type heterojunction catalystAnd (4) stability.
In the a1, tetracycline hydrochloride is adopted as the organic pollutant.
In the a1, the concentration of the organic pollutants is 20 mg/L.
In a2, Bi2S3The use amount of the/BiOCl Z-type heterojunction catalyst powder is 25 mg.
In the a2, the use amount of the organic pollutants is 50 mL.
In the a3, the reaction time was 30min under stirring.
The catalyst can be applied to degrading organic pollutants in organic wastewater under natural conditions.
From the above description, it can be seen that the present invention has the following advantages:
1. the preparation method of the invention uses green and safe raw materials, has simple method and simple process, is easy to operate, can realize continuous production, has low temperature requirement and less energy consumption when in reaction, has cheap and easily obtained raw material reagents, and shows the environmental friendliness of the catalytic material.
2. The material prepared by the method has the advantages of high crystallinity, thinner nanosheet and the like, can provide more reaction active sites, can adsorb more pollutants, and is beneficial to improving the photocatalytic efficiency of the catalyst. The results obtained by the activity test under visible light show that the BiOCl composite nano material prepared by the method has better stability and reusability, and has good photocatalytic activity and economy.
Drawings
FIG. 1 shows Bi prepared in examples 1-2 of the present invention2S3And an XRD spectrogram of the BiOCl catalyst.
FIG. 2 is an XRD spectrum of 0.02, 0.04, 0.06, 0.08, 0.10g of catalyst prepared in examples 3-5 of the present invention.
FIG. 3 shows Bi prepared in examples 1 to 5 of the present invention2S3BiOCl and Bi2S3SEM photograph of/BiOCl type Z heterojunction catalyst.
FIG. 4 shows Bi prepared in examples 1 to 5 of the present invention2S3BiOCl and Bi2S3The effect of the/BiOCl Z-type heterojunction catalyst on the catalytic degradation of tetracycline hydrochloride solution is shown in the figure.
FIG. 5 shows Bi prepared in examples 1 to 5 of the present invention2S3The effect of the/BiOCl Z-type heterojunction catalyst on the catalytic cycle degradation of tetracycline hydrochloride solution is shown in the figure.
FIG. 6 shows Bi prepared in examples 1 to 5 of the present invention2S3BiOCl and Bi2S3DRS spectrum of/BiOCl type Z heterojunction catalyst.
FIG. 7 shows Bi prepared in examples 1 to 5 of the present invention2S3BiOCl and Bi2S3PL profile of/BiOCl type Z heterojunction catalyst.
Detailed Description
An embodiment of the present invention is described in detail with reference to fig. 1 to 7, but the present invention is not limited in any way by the claims.
Examples of the invention Bi2S3A method for preparing a/BiOCl catalyst, said method comprising the steps of:
step 1, weighing anhydrous bismuth nitrate, and dissolving the anhydrous bismuth nitrate in deionized water to obtain a bismuth dissolved solution; weighing L-cysteine, dissolving the L-cysteine in deionized water, and completely dissolving to obtain an L-cysteine solution;
step 2, adding the L-cysteine solution into the bismuth solution, and carrying out ultrasonic treatment at normal temperature for 25min to obtain a precipitate;
step 4, weighing anhydrous bismuth nitrate, and dissolving the anhydrous bismuth nitrate in deionized water to obtain a bismuth dissolved solution; weighing potassium chloride, dissolving the potassium chloride in deionized water, and completely dissolving to obtain a potassium chloride solution;
step 5, adding a potassium chloride solution into the bismuth dissolving solution to obtain a mixed solution;
step 6, ultrasonically treating the mixed solution in the step 5 for 25min by using an ultrasonic machine at normal temperature to obtain a precipitate;
step 7, washing the precipitate obtained in the step 6 by deionized water and absolute ethyl alcohol for several times, and drying the precipitate in an electrothermal drying oven at 60 ℃ to obtain BiOCl catalyst powder;
step 8, weighing anhydrous bismuth nitrate, and dissolving the anhydrous bismuth nitrate in deionized water to obtain a bismuth dissolved solution; weighing L-cysteine, dissolving the L-cysteine in deionized water, and completely dissolving to obtain an L-cysteine solution; weighing potassium chloride, dissolving the potassium chloride in deionized water, and completely dissolving to obtain a potassium chloride solution;
step 9, respectively and simultaneously adding the potassium chloride solution and the L-cysteine solution obtained in the step 8 into a bismuth solution, and carrying out normal-temperature ultrasonic treatment for 25min by using an ultrasonic machine to obtain a ternary mixed solution;
The bismuth nitrate starting material is typically selected to contain water of crystallization, such as commercially available Bi (NO)3)3·5H2O, soluble in ethylene glycol; the chloride is soluble in ethylene glycol. The water is preferably water having less impurities such as deionized water or ultrapure water.
In step 1, 2.42535g of bismuth nitrate pentahydrate was dissolved in 300mL of deionized water, and 0.121g L-cysteine was dissolved in 25mL of deionized water.
In step 4, 2.42535g of bismuth nitrate pentahydrate was dissolved in 300mL of deionized water, and 0.7455g of potassium chloride was dissolved in 25mL of deionized water.
In the step 8, 2.42535g of bismuth nitrate pentahydrate is dissolved in 300mL of deionized water, 0.7455g of potassium chloride is dissolved in 25mL of deionized water, and the L-cysteine is dissolved in 25mL of deionized water, and the addition amounts of the L-cysteine are respectively 0.02g, 0.04g, 0.06g, 0.08g and 0.10 g.
Example 1
2.42535g of bismuth nitrate pentahydrate is weighed and dissolved in 300mL of deionized water, 0.121g L-cysteine is weighed and dissolved in 25mL of deionized water until all the bismuth nitrate pentahydrate is dissolved; adding the dissolved L-cysteine solution into nitre pentahydrateIn bismuth acid solution; performing ultrasonic treatment for 25min at normal temperature by using an ultrasonic machine; washing the obtained precipitate with deionized water and absolute ethyl alcohol for several times; putting the sample into an electrothermal blowing drying oven, wherein the drying temperature is 60 ℃; sample Bi obtained by drying2S3(ii) a 2.42535g of bismuth nitrate pentahydrate is weighed and dissolved in 300mL of deionized water, 0.7455g of potassium chloride is weighed and dissolved in 25mL of deionized water until all the potassium nitrate pentahydrate is dissolved; adding a potassium chloride solution into a bismuth nitrate pentahydrate solution; performing ultrasonic treatment for 25min at normal temperature by using an ultrasonic machine to obtain a precipitate; washing the precipitate with deionized water and absolute ethyl alcohol for several times, and drying the sample in an electrothermal blowing drying oven at 60 ℃ to obtain BiOCl; 2.42535g of bismuth nitrate pentahydrate, 0.7455g of potassium chloride and 0.02g L-cysteine are weighed; dissolving bismuth nitrate pentahydrate in 300mL of deionized water, and respectively dissolving potassium chloride and L-cysteine in 25mL of deionized water; respectively and simultaneously adding a potassium chloride solution and an L-cysteine solution into the bismuth nitrate pentahydrate solution, and performing ultrasound for 25min at normal temperature by using an ultrasonic machine; washing with deionized water and anhydrous ethanol for several times, drying the sample in an electrothermal blowing drying oven at 60 deg.C to obtain Bi2S3a/BiOCl type Z heterojunction catalyst powder, about 0.02 g.
Example 2
2.42535g of bismuth nitrate pentahydrate is weighed and dissolved in 300mL of deionized water, 0.121g L-cysteine is weighed and dissolved in 25mL of deionized water until all the bismuth nitrate pentahydrate is dissolved; adding the dissolved L-cysteine solution into a bismuth nitrate pentahydrate solution; performing ultrasonic treatment for 25min at normal temperature by using an ultrasonic machine; washing the obtained precipitate with deionized water and absolute ethyl alcohol for several times; putting the sample into an electrothermal blowing drying oven, wherein the drying temperature is 60 ℃; sample Bi obtained by drying2S3(ii) a 2.42535g of bismuth nitrate pentahydrate is weighed and dissolved in 300mL of deionized water, 0.7455g of potassium chloride is weighed and dissolved in 25mL of deionized water until all the potassium nitrate pentahydrate is dissolved; adding a potassium chloride solution into a bismuth nitrate pentahydrate solution; performing ultrasonic treatment for 25min at normal temperature by using an ultrasonic machine to obtain a precipitate; washing the precipitate with deionized water and absolute ethyl alcohol for several times, and drying the sample in an electrothermal blowing drying oven at 60 ℃ to obtain BiOCl; 2.42535g of bismuth nitrate pentahydrate, 0.7455g of potassium chloride and 0.04g L-cysteine are weighed; nitric acid pentahydrateDissolving bismuth in 300mL of deionized water, and respectively dissolving potassium chloride and L-cysteine in 25mL of deionized water; respectively and simultaneously adding a potassium chloride solution and an L-cysteine solution into the bismuth nitrate pentahydrate solution, and performing ultrasound for 25min at normal temperature by using an ultrasonic machine; washing with deionized water and anhydrous ethanol for several times, drying the sample in an electrothermal blowing drying oven at 60 deg.C to obtain Bi2S3a/BiOCl type Z heterojunction catalyst powder, about 0.04 g.
Example 3
2.42535g of bismuth nitrate pentahydrate is weighed and dissolved in 300mL of deionized water, 0.121g L-cysteine is weighed and dissolved in 25mL of deionized water until all the bismuth nitrate pentahydrate is dissolved; adding the dissolved L-cysteine solution into a bismuth nitrate pentahydrate solution; performing ultrasonic treatment for 25min at normal temperature by using an ultrasonic machine; washing the obtained precipitate with deionized water and absolute ethyl alcohol for several times; putting the sample into an electrothermal blowing drying oven, wherein the drying temperature is 60 ℃; sample Bi obtained by drying2S3(ii) a 2.42535g of bismuth nitrate pentahydrate is weighed and dissolved in 300mL of deionized water, 0.7455g of potassium chloride is weighed and dissolved in 25mL of deionized water until all the potassium nitrate pentahydrate is dissolved; adding a potassium chloride solution into a bismuth nitrate pentahydrate solution; performing ultrasonic treatment for 25min at normal temperature by using an ultrasonic machine to obtain a precipitate; washing the precipitate with deionized water and absolute ethyl alcohol for several times, and drying the sample in an electrothermal blowing drying oven at 60 ℃ to obtain BiOCl; 2.42535g of bismuth nitrate pentahydrate, 0.7455g of potassium chloride and 0.06g L-cysteine are weighed; dissolving bismuth nitrate pentahydrate in 300mL of deionized water, and respectively dissolving potassium chloride and L-cysteine in 25mL of deionized water; respectively and simultaneously adding a potassium chloride solution and an L-cysteine solution into the bismuth nitrate pentahydrate solution, and performing ultrasound for 25min at normal temperature by using an ultrasonic machine; washing with deionized water and anhydrous ethanol for several times, drying the sample in an electrothermal blowing drying oven at 60 deg.C to obtain Bi2S3The amount of the/BiOCl Z type heterojunction catalyst powder was 0.06 g.
Example 4
2.42535g of bismuth nitrate pentahydrate is weighed and dissolved in 300mL of deionized water, 0.121g L-cysteine is weighed and dissolved in 25mL of deionized water until all the bismuth nitrate pentahydrate is dissolved; adding the dissolved L-cysteine solution into bismuth nitrate pentahydrateIn solution; performing ultrasonic treatment for 25min at normal temperature by using an ultrasonic machine; washing the obtained precipitate with deionized water and absolute ethyl alcohol for several times; putting the sample into an electrothermal blowing drying oven, wherein the drying temperature is 60 ℃; sample Bi obtained by drying2S3(ii) a 2.42535g of bismuth nitrate pentahydrate is weighed and dissolved in 300mL of deionized water, 0.7455g of potassium chloride is weighed and dissolved in 25mL of deionized water until all the potassium nitrate pentahydrate is dissolved; adding a potassium chloride solution into a bismuth nitrate pentahydrate solution; performing ultrasonic treatment for 25min at normal temperature by using an ultrasonic machine to obtain a precipitate; washing the precipitate with deionized water and absolute ethyl alcohol for several times, and drying the sample in an electrothermal blowing drying oven at 60 ℃ to obtain BiOCl; 2.42535g of bismuth nitrate pentahydrate, 0.7455g of potassium chloride and 0.08g L-cysteine are weighed; dissolving bismuth nitrate pentahydrate in 300mL of deionized water, and respectively dissolving potassium chloride and L-cysteine in 25mL of deionized water; respectively and simultaneously adding a potassium chloride solution and an L-cysteine solution into the bismuth nitrate pentahydrate solution, and performing ultrasound for 25min at normal temperature by using an ultrasonic machine; washing with deionized water and anhydrous ethanol for several times, drying the sample in an electrothermal blowing drying oven at 60 deg.C to obtain Bi2S3The amount of the/BiOClZ type heterojunction catalyst powder was 0.08 g.
Example 5
2.42535g of bismuth nitrate pentahydrate is weighed and dissolved in 300mL of deionized water, 0.121g L-cysteine is weighed and dissolved in 25mL of deionized water until all the bismuth nitrate pentahydrate is dissolved; adding the dissolved L-cysteine solution into a bismuth nitrate pentahydrate solution; performing ultrasonic treatment for 25min at normal temperature by using an ultrasonic machine; washing the obtained precipitate with deionized water and absolute ethyl alcohol for several times; putting the sample into an electrothermal blowing drying oven, wherein the drying temperature is 60 ℃; sample Bi obtained by drying2S3(ii) a 2.42535g of bismuth nitrate pentahydrate is weighed and dissolved in 300mL of deionized water, 0.7455g of potassium chloride is weighed and dissolved in 25mL of deionized water until all the potassium nitrate pentahydrate is dissolved; adding a potassium chloride solution into a bismuth nitrate pentahydrate solution; performing ultrasonic treatment for 25min at normal temperature by using an ultrasonic machine to obtain a precipitate; washing the precipitate with deionized water and absolute ethyl alcohol for several times, and drying the sample in an electrothermal blowing drying oven at 60 ℃ to obtain BiOCl; 2.42535g of bismuth nitrate pentahydrate, 0.7455g of potassium chloride and 0.10g L-cysteine are weighed; adding bismuth nitrate pentahydrateDissolving in 300mL of deionized water, and respectively dissolving potassium chloride and L-cysteine in 25mL of deionized water; respectively and simultaneously adding a potassium chloride solution and an L-cysteine solution into the bismuth nitrate pentahydrate solution, and performing ultrasound for 25min at normal temperature by using an ultrasonic machine; washing with deionized water and anhydrous ethanol for several times, drying the sample in an electrothermal blowing drying oven at 60 deg.C to obtain Bi2S3The amount of the/BiOCl Z type heterojunction catalyst powder was 0.10 g.
FIG. 1 shows Bi prepared in examples 1-2 of the present invention2S3And an XRD spectrogram of the BiOCl catalyst. FIG. 2 is an XRD spectrum of 0.02, 0.04, 0.06, 0.08, 0.10g of catalyst prepared in examples 3-5 of the present invention. From the figure, it can be seen that the diffraction peak positions of the samples synthesized by adding different L-cysteine are basically consistent with those of the standard card (JCPDS: 82-0485 or JCPDS: 75-1306), no other non-consistent diffraction peak exists, and the synthesized samples have BiOCl and Bi2S3In the presence of BiOCl/Bi as sample2S3A composite material.
FIG. 3 is a Scanning Electron Micrograph (SEM) of catalysts prepared according to examples 1-5 of the present invention. Is composed of flaky nano-sheets which are arranged in an overlapped mode in an irregular shape. BiOCl is a flaky nano-sheet, the overlapping degree of the nano-sheets is smaller than that of other samples, and more like spreading, so that the contact area of the photocatalyst and a reactant is not larger than that of a composite sample, and the photocatalytic performance is poor. And Bi2S3The nano-particles are composed of porous blocky nano-sheets, and have large thickness, small specific surface area and poor activity performance.
The effect of the method for treating wastewater containing antibiotics by using the catalyst prepared in the embodiment of the invention is carried out according to the following experiment: the tetracycline hydrochloride is taken as an example to study the degradation effect of the catalytic material on pollutants in a water environment when the catalytic material is used for catalyzing and treating wastewater containing antibiotics:
example 6
An LED lamp (the current intensity is 0.9A) is used as a light source, the light source irradiates upwards from the bottom of quartz glass of the reactor, and the whole reaction process is ensured to be carried out under the constant temperature condition of 25-35 ℃ through heat dissipation of a fan. Weighing 25mg of the catalyst prepared in the embodiment 1 of the invention, putting the catalyst into 50ml of prepared tetracycline hydrochloride solution, carrying out ultrasonic treatment for 5min until the solution is uniformly mixed, putting the solution into a visible light reaction system reactor, keeping the reaction temperature at room temperature, carrying out magnetic stirring for 60min under a dark condition, and then transferring 1ml of the solution to be used as a dark adsorption sample.
After the dark adsorption is finished, turning on a light source, and stirring for 30min under the irradiation of visible light at the rotating speed of 500 r/min. During the whole reaction, 1mL of solution sample was withdrawn at 5min intervals. And (3) placing the obtained solution sample into a centrifuge for high-speed centrifugation for 5min, taking supernatant, detecting absorbance by using an ultraviolet-visible spectrophotometry, and observing the change of TC-HCl concentration along with time.
FIG. 4 is a graph of the effect of degradation, which is discussed in two aspects: 1. degrading tetracycline hydrochloride solution with the catalyst of the present invention by light; 2. the catalyst of the present invention degrades tetracycline hydrochloride solution under a single condition. From this it can be found that the catalyst has good degradation properties. The removal rate is about 80% in 30 min. Therefore, the photocatalytic reaction fully exerts respective maximum degradation capability, and has good contrast effect on other pollutants in the degradation wastewater. The method is simple, green and environment-friendly, and economic feasibility of the method is improved.
FIG. 5 shows Bi produced2S3The effect of the/BiOCl Z-type heterojunction catalyst on the catalytic cycle degradation of tetracycline hydrochloride solution is shown in the figure. It can be seen that the sample recycled has good photocatalytic performance, the degradation effect is very stable and reaches 80%, and the stability of the sample is ensured.
FIG. 6 is a solid diffuse reflectance luminescence spectrum of an example of the present invention. The light absorption edge of the catalyst of the invention is gradually reduced and the forbidden band width is gradually increased along with the increase of the addition amount of the L-cysteine.
FIG. 7 is a solid state photoluminescence spectrum of an example of the invention. The catalyst of the invention can respond to visible light from the spectrum, thereby providing an advantage in application and better application in industry.
While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. It will be appreciated by those skilled in the art that the present invention may be modified or substituted equally as well to achieve the same technical result; as long as the use requirements are met, the method is within the protection scope of the invention.
Claims (10)
1. A method for synthesizing a Z-type heterojunction catalytic material by an ultrasonic-assisted method is characterized by comprising the following steps: the preparation method comprises the following steps:
step 1, weighing pentahydrate bismuth nitrate, and dissolving the pentahydrate bismuth nitrate in deionized water to obtain a bismuth dissolved solution; weighing L-cysteine, dissolving the L-cysteine in deionized water, and completely dissolving to obtain an L-cysteine solution;
step 2, adding the L-cysteine solution obtained in the step 1 into a bismuth solution, and carrying out normal-temperature ultrasonic treatment for 25min to obtain a precipitate;
step 3, washing the precipitate in the step 2 by deionized water and absolute ethyl alcohol for several times, and drying the precipitate in an electrothermal drying oven at 60 ℃ to obtain Bi2S3Catalyst powder;
step 4, weighing bismuth nitrate pentahydrate, and dissolving the bismuth nitrate pentahydrate into deionized water to obtain a bismuth dissolved solution; weighing potassium chloride, dissolving the potassium chloride in deionized water, and completely dissolving to obtain a potassium chloride solution;
step 5, adding a potassium chloride solution into the bismuth dissolving solution to obtain a mixed solution;
step 6, carrying out ultrasonic treatment on the mixed solution for 25min by adopting an ultrasonic machine at normal temperature to obtain a precipitate;
step 7, washing the precipitate obtained in the step 6 by deionized water and absolute ethyl alcohol for several times, and drying the precipitate in an electrothermal drying oven at 60 ℃ to obtain BiOCl catalyst powder;
step 8, weighing bismuth nitrate pentahydrate, and dissolving the bismuth nitrate pentahydrate into deionized water to obtain a bismuth dissolved solution; weighing L-cysteine, dissolving the L-cysteine in deionized water, and completely dissolving to obtain an L-cysteine solution; weighing potassium chloride, dissolving the potassium chloride in deionized water, and completely dissolving to obtain a potassium chloride solution;
step 9, respectively and simultaneously adding the potassium chloride solution and the L-cysteine solution into the bismuth solution, and carrying out normal-temperature ultrasound for 25min by using an ultrasonic machine to obtain a ternary mixed solution;
step 10, washing the mixture for several times by using deionized water and absolute ethyl alcohol, and drying the washed mixture in an electrothermal blowing drying oven at 60 ℃ to obtain Bi2S3the/BiOCl Z type heterojunction catalyst powder.
2. The method for synthesizing the Z-type heterojunction catalytic material by the ultrasonic-assisted method according to claim 1, wherein the method comprises the following steps: in step 1, 2.42535g of bismuth nitrate pentahydrate was dissolved in 300mL of deionized water, and 0.121g of L-cysteine was dissolved in 25mL of deionized water.
3. The method for synthesizing the Z-type heterojunction catalytic material by the ultrasonic-assisted method according to claim 1, wherein the method comprises the following steps: in step 4, 2.42535g of bismuth nitrate pentahydrate was dissolved in 300mL of deionized water, and 0.7455g of potassium chloride was dissolved in 25mL of deionized water.
4. The method for synthesizing the Z-type heterojunction catalytic material by the ultrasonic-assisted method according to claim 1, wherein the method comprises the following steps: in the step 8, 2.42535g of bismuth nitrate pentahydrate is dissolved in 300mL of deionized water, 0.7455g of potassium chloride is dissolved in 25mL of deionized water, and the L-cysteine is dissolved in 25mL of deionized water, and the addition amounts of the L-cysteine are respectively 0.02g, 0.04g, 0.06g, 0.08g and 0.10 g.
5. The method for synthesizing the Z-type heterojunction catalytic material by the ultrasonic-assisted method according to claim 1, wherein the method comprises the following steps: the Bi2S3the/BiOCl Z-type heterojunction catalyst is prepared by the method, and the catalyst is of a spherical structure stacked by nano sheets.
6. The method for synthesizing the Z-type heterojunction catalytic material by the ultrasonic-assisted method according to claim 1, wherein the method comprises the following steps: the catalyst can be applied to degrading organic pollutants in organic wastewater under the illumination condition.
7. The method for synthesizing the Z-type heterojunction catalytic material by the ultrasonic-assisted method according to claim 6, wherein the method comprises the following steps: the Bi2S3The application of the/BiOCl Z-type heterojunction catalyst comprises the following preparation method:
a1, preparing an organic pollutant solution with the concentration of 20mg/L in a volumetric flask with the capacity of 1L;
a2, preparing 25mg of Bi2S3the/BiOCl flake catalyst powder is put into a 50mL beaker, and the prepared 50mL organic pollutant solution with the concentration of 20mg/L is used for dissolving Bi2S3A BiOCl Z-type heterojunction catalyst powder;
a3, stirring the solution obtained in the step a2 in the dark for 60min, turning on an LED light source to irradiate and stir for 30min, and extracting 1mL of solution sample every 5 min;
a4, centrifuging and filtering the solution sample obtained in the step a3, and detecting the concentration of pollutants every 5min by using an ultraviolet-visible spectrophotometry method;
a5, carrying out 5 times of cycle performance tests on the screened catalyst with the best catalytic performance, and researching the prepared Bi2S3Stability of/BiOCl Z-type heterojunction catalyst.
8. The method for synthesizing the Z-type heterojunction catalytic material by the ultrasonic-assisted method according to claim 7, wherein the method comprises the following steps: in the a1, the organic pollutant is selected from tetracycline hydrochloride; and the concentration of the organic pollutants is 20 mg/L.
9. The method for synthesizing the Z-type heterojunction catalytic material by the ultrasonic-assisted method according to claim 7, wherein the method comprises the following steps: in a2, Bi2S3The use amount of the/BiOCl Z-type heterojunction catalyst powder is 25 mg.
10. The method for synthesizing the Z-type heterojunction catalytic material by the ultrasonic-assisted method according to claim 7, wherein the method comprises the following steps: in the a2, the use amount of the organic pollutants is 50 mL.
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| CN115636439B (en) * | 2022-11-04 | 2023-10-13 | 中国人民解放军国防科技大学 | Preparation method and application of 3-5 mu m low-emissivity flaky bismuth oxychloride filler |
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