CN111545225A - Heterostructure photocatalyst for enhancing visible light response and preparation method thereof - Google Patents
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 230000004298 light response Effects 0.000 title claims description 14
- 230000002708 enhancing effect Effects 0.000 title claims description 5
- 239000000243 solution Substances 0.000 claims abstract description 51
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 35
- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical compound Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000008367 deionised water Substances 0.000 claims abstract description 30
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 30
- 239000002244 precipitate Substances 0.000 claims abstract description 27
- 238000003756 stirring Methods 0.000 claims abstract description 24
- 239000000725 suspension Substances 0.000 claims abstract description 22
- 238000005406 washing Methods 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 14
- 238000000926 separation method Methods 0.000 claims abstract description 14
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 13
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 8
- 230000032683 aging Effects 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 238000007865 diluting Methods 0.000 claims abstract description 7
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims abstract description 7
- 239000011259 mixed solution Substances 0.000 claims abstract description 7
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- 239000000047 product Substances 0.000 claims description 16
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- -1 polytetrafluoroethylene Polymers 0.000 claims description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 6
- 229910001220 stainless steel Inorganic materials 0.000 claims description 6
- 239000010935 stainless steel Substances 0.000 claims description 6
- 230000001699 photocatalysis Effects 0.000 abstract description 12
- 238000000034 method Methods 0.000 abstract description 10
- 239000011575 calcium Substances 0.000 abstract description 8
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 abstract description 4
- 229940043267 rhodamine b Drugs 0.000 abstract description 4
- 239000002131 composite material Substances 0.000 abstract description 3
- ZHJGWYRLJUCMRT-UHFFFAOYSA-N 5-[6-[(4-methylpiperazin-1-yl)methyl]benzimidazol-1-yl]-3-[1-[2-(trifluoromethyl)phenyl]ethoxy]thiophene-2-carboxamide Chemical compound C=1C=CC=C(C(F)(F)F)C=1C(C)OC(=C(S1)C(N)=O)C=C1N(C1=C2)C=NC1=CC=C2CN1CCN(C)CC1 ZHJGWYRLJUCMRT-UHFFFAOYSA-N 0.000 abstract description 2
- 230000032900 absorption of visible light Effects 0.000 abstract description 2
- 230000015556 catabolic process Effects 0.000 abstract description 2
- 238000006731 degradation reaction Methods 0.000 abstract description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 abstract 2
- 229910052791 calcium Inorganic materials 0.000 abstract 2
- PRXPKDJOWUKXRS-UHFFFAOYSA-N barium(2+) dinitrate pentahydrate Chemical compound O.O.O.O.O.[N+](=O)([O-])[O-].[Ba+2].[N+](=O)([O-])[O-] PRXPKDJOWUKXRS-UHFFFAOYSA-N 0.000 abstract 1
- 238000001556 precipitation Methods 0.000 description 10
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- 239000004065 semiconductor Substances 0.000 description 5
- 238000004448 titration Methods 0.000 description 5
- 238000011160 research Methods 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 239000000969 carrier Substances 0.000 description 3
- 230000031700 light absorption Effects 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
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- 238000012986 modification Methods 0.000 description 2
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- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 1
- 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 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 1
- 229940012189 methyl orange Drugs 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/138—Halogens; Compounds thereof with alkaline earth metals, magnesium, beryllium, zinc, cadmium or mercury
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G29/00—Compounds of bismuth
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
Abstract
The invention discloses a CaBi2O4A/BiOCl heterojunction composite photocatalyst and a preparation method thereof belong to the technical field of photocatalytic materials. The method comprises the following steps: dissolving calcium nitrate tetrahydrate in deionized water, dissolving barium nitrate pentahydrate in dilute nitric acid, and mixing the two solutions uniformly. And then, dropwise adding the diluted ammonia water and the mixed solution into deionized water at the same time, and continuously stirring until the pH value is 6-8 to obtain a white turbid liquid. Stirring and aging the obtained precipitate suspension for 30min, performing solid-liquid separation by using a centrifuge to obtain white precipitate, washing and diluting the white precipitate, placing the white precipitate in a reaction kettle, heating the white precipitate at 180-260 ℃ for 6h, and cooling and drying the white precipitate to obtain the calcium bismuthate. Roasting calcium bismuthate for 4 hours, and adding absolute ethyl alcohol and deionized water for ultrasonic treatment. Adding hydrochloric acid with required volume according to different mole fractions, stirring, filtering, washing and drying to obtain a series of CaBi with different BiOCl contents2O4/BiOCl heterojunctionA photocatalyst. The method is characterized by low preparation temperature, simple process and capability of preparing CaBi2O4the/BiOCl heterojunction photocatalyst enhances the absorption of visible light, and the degradation performance of the photocatalyst on rhodamine B is obviously superior to that of CaBi2O4。
Description
Technical Field
The invention relates to the technical field of preparation of novel photocatalysts, in particular to a method for synthesizing CaBi by taking calcium nitrate tetrahydrate, bismuth nitrate pentahydrate, ammonia water, dilute nitric acid and deionized water as raw materials2O4A method for preparing a BiOCl heterojunction composite photocatalyst.
Background
The semiconductor photocatalysis technology is used for degrading organic pollutants, and people pay more and more attention to energy conservation and high efficiency. Wherein, TiO2The method has the advantages of no toxicity, low price, easy obtainment, good thermal stability and the like, thereby arousing great interest in the early research of heterogeneous photocatalysis. But TiO 22The forbidden band width is large, and the utilization rate of visible light is low; in addition, TiO2The high recombination rate of photogenerated carriers also results in a decrease in its photocatalytic efficiency. These inherent drawbacks limit their application in the field of photocatalysis.
In the course of research on novel photocatalytic materials, Bi-based compounds have received attention because of their special layered structure and appropriate size of forbidden band width. BiOCl is an indirect band gap semiconductor, has a highly anisotropic layered structure, and is very beneficial to the separation of photon-generated carriers; meanwhile, the photocatalyst has the advantages of no toxicity, low cost and the like, so that the photocatalyst attracts attention in the field of photocatalysis in recent years. Researches find that the activity of BiOCl for degrading methyl orange under ultraviolet light is even better than that of TiO2. BiOCl is a wide bandgap semiconductor material, and the generated holes have strong oxidation capability due to the high valence band potential. However, the larger forbidden band width of BiOCl also limits the utilization of visible light, and constructing a heterojunction type photocatalyst by compounding the BiOCl with a narrow forbidden band semiconductor is a good method for improving the photocatalytic efficiency of the heterojunction type photocatalyst. Therefore, the search for good narrow bandgap semiconductors becomes the main research direction of the BiOCl photocatalytic material at present.
Disclosure of Invention
In view of the above technical problems in the prior art, it is an object of the present invention to provide a method for enhancing visible light responseCaBi2O4The preparation method of the/BiOCl heterojunction composite photocatalyst comprises the step of mixing CaBi2O4A heterostructure photocatalyst is constructed with BiOCl to improve the absorption of visible light and greatly enhance the utilization of solar energy; on the other hand, CaBi2O4The heterojunction formed after the heterojunction is compounded with BiOCl can promote the separation of photon-generated carriers and improve the photocatalytic efficiency. The problem of thereby the wide influence of BiOCl forbidden band is to visible light absorption among the prior art is solved.
In order to achieve the purpose, the technical scheme adopted by the invention for solving the technical problem is as follows: a preparation method of a heterostructure photocatalyst for enhancing visible light response comprises the following steps:
(1) weighing a certain amount of Ca (NO) according to a stoichiometric ratio3)2·4H2O and Bi (NO)3)3·5H2O, first Ca (NO)3)2·4H2Dissolving O in deionized water to obtain transparent solution, and dissolving Bi (NO)3)3·5H2O is dissolved in the freshly prepared dilute nitric acid solution.
(2) Mixing the two transparent solutions, and continuously stirring until the two transparent solutions are uniformly mixed. Taking a proper amount of deionized water as a base solution, and mixing the mixed solution with 3-4 mol/L ammonia water (NH)3·H2And O) dripping the two solutions into the base solution, continuously stirring to uniformly mix the precipitation reactants, controlling the dripping speed of the two solutions to keep the pH value between 6 and 8, and continuously stirring and aging the precipitation suspension obtained after the titration for 30 min.
(3) Separating the obtained suspension with a centrifuge, washing the obtained white precipitate with deionized water and anhydrous ethanol to remove NH4+And NO3-And repeating the washing for 4-6 times. Diluting the precipitate after washing and centrifugal separation to a certain concentration to obtain white precipitate suspension, then putting the suspension into a closed reaction kettle made of stainless steel and lined with white polytetrafluoroethylene for heat treatment at 160-200 ℃ for 6-8 h, and cooling and drying after the treatment to obtain CaBi2O4White powder.
(4) Preparing the mass fraction of36% hydrochloric acid, and storing in shade for later use. Accurately weighing a certain amount of CaBi2O4And (3) roasting the white powder at a certain temperature for 4 hours, adding 20mL of absolute ethyl alcohol and 10mL of primary distilled water, carrying out ultrasonic treatment for 30min, and stirring at room temperature for 30 min. Respectively according to Bi3+With Cl-The molar ratio is 1: 0.00,1: 0.25,1: 0.5,1: 0.75 addition of the desired volume (0.000, 0.065, 0.130, 0.195mL) of hydrochloric acid [ preparation of pure BiOCl requires addition of sufficient (0.26mL) hydrochloric acid]The mixture was stirred at room temperature for 1 hour. After the reaction is finished, filtering the obtained product, washing the product for a plurality of times by using absolute ethyl alcohol and deionized water in sequence, and drying the product for 6 hours at the temperature of 80 ℃ to obtain CaBi with different BiOCl contents2O4a/BiOCl heterojunction photocatalyst.
(4) 5mg/L of rhodamine B is used as an organic pollutant, and a set of equipment which is used for separating a photocatalyst from a pollutant solution and can circularly and uninterruptedly carry out photocatalytic degradation reaction is adopted. The device reactor is divided into two parts, and the upper part and the lower part are connected through frosted openings, so that the rhodamine B solution is prevented from overflowing. The light source adopts a parallel visible light source, can provide stable photon energy, and enables the photocatalyst to generate photo-generated electrons and holes. After the visible light is irradiated for 70min, the degradation rate of the photocatalyst on rhodamine B reaches about 90%.
The invention has the beneficial effects that:
the invention adopts the common hydrothermal synthesis method to prepare CaBi2O4the/BiOCl heterostructure photocatalyst has lower forbidden band width and higher visible light absorption response. The low forbidden band width reduces the transmission distance of the photoproduction electron holes, improves the separation efficiency of the photoproduction electron holes, reduces the recombination rate, improves the photon utilization rate due to high visible light absorption response, improves the electron hole pair generation rate, and greatly improves the photocatalytic activity under visible light. The catalyst prepared by the method has good stability and stable chemical property.
Drawings
FIG. 1 shows the visible light response CaBi prepared by the present invention2O4SEM scanning electron microscope image of/BiOCl heterojunction photocatalyst shows that after HCl is added,in CaBi2O4The two structures are closely overlapped, so that the structure is not only favorable for adsorbing reactants, but also favorable for effectively separating photoproduction electrons from holes, and plays a role of two-dimensional photocatalysis.
FIG. 2 shows that the prepared CaBi can respond to light2O4SEM partial enlarged view of/BiOCl heterojunction photocatalyst.
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.
Example 1
(1) White CaBi2O4And (3) preparing a powder material. Weighing 1.3573gCa (NO) in stoichiometric ratio3)2·4H2O and 5.5844gBi (NO)3)3·5H2O, first Ca (NO)3)2·4H2Dissolving O in 50mL deionized water to obtain a transparent solution, and adding Bi (NO)3)3·5H2Dissolving O in 50mL of dilute nitric acid solution, mixing the two transparent solutions in a 200mL beaker, and stirring for 30min to mix the two transparent solutions uniformly. Adding 100mL of deionized water into a 500mL beaker as a base solution, and mixing the mixed solution with 3mol/L ammonia water (NH)3·H2And O) dripping the two solutions into the base solution, continuously stirring to uniformly mix the precipitation reactants, keeping the pH of the reaction solution at about 8, and continuously stirring and aging the precipitation suspension obtained after the titration for 30 min. Then solid-liquid separation is carried out by adopting a centrifuge, and the obtained white precipitate is washed by deionized water to remove NH4+And NO3-And the washing was repeated 6 times. Diluting the precipitate after washing and centrifugal separation to 100mL to obtain white precipitate suspension; then respectively putting the suspension prepared above into two closed reaction kettles with 100mL capacity and made of stainless steel and white polytetrafluoroethylene lining for heat treatment at 180 ℃ for 6 hours, cooling and drying in an oven at 50 ℃ for 10 hours to obtain the photocatalyst CaBi2O4。
(2) Visible light response CaBi2O4Preparation of/BiOCl heterojunction photocatalyst.
Preparing hydrochloric acid with the mass fraction of 36%, and storing the hydrochloric acid in a shade place for later use. 0.76g of CaBi2O4White powder, 20mL of absolute ethanol and 10mL of distilled water were added and sonicated for 30min, and stirred at room temperature for 30 min. According to Bi3+With Cl-The molar ratio is 1: 0.25 mL of hydrochloric acid was added and the mixture was stirred at room temperature for 1 hour. After the reaction is finished, filtering the obtained product, washing the product for several times by using absolute ethyl alcohol and deionized water in sequence, and drying the product for 6 hours at 80 ℃ to finally obtain visible light response CaBi2O4a/BiOCl heterojunction photocatalyst.
Example 2
(1) White CaBi2O4And (3) preparing a powder material. Weighing 1.3566gCa (NO) in stoichiometric ratio3)2·4H2O and 5.5812gBi (NO)3)3·5H2O, first Ca (NO)3)2·4H2Dissolving O in 50mL deionized water to obtain a transparent solution, and adding Bi (NO)3)3·5H2Dissolving O in 50mL of dilute nitric acid solution, mixing the two transparent solutions in a 200mL beaker, and stirring for 30min to mix the two transparent solutions uniformly. Adding 100mL of deionized water into a 500mL beaker as a base solution, and mixing the mixed solution with 3mol/L ammonia water (NH)3·H2And O) dripping the two solutions into the base solution, continuously stirring to uniformly mix the precipitation reactants, keeping the pH of the reaction solution at about 8, and continuously stirring and aging the precipitation suspension obtained after the titration for 30 min. Then solid-liquid separation is carried out by adopting a centrifuge, and the obtained white precipitate is washed by deionized water to remove NH4+And NO3-And the washing was repeated 6 times. Diluting the precipitate after washing and centrifugal separation to 100mL to obtain white precipitate suspension; then respectively putting the suspension prepared above into two closed reaction kettles with 100mL capacity and made of stainless steel and white polytetrafluoroethylene lining for heat treatment at 180 ℃ for 6 hours, cooling and drying in an oven at 50 ℃ for 10 hours to obtain the photocatalyst CaBi2O4。
(2) Visible light response CaBi2O4Preparation of/BiOCl heterojunction photocatalyst.
Preparing hydrochloric acid with the mass fraction of 36%, and storing the hydrochloric acid in a shade place for later use. 0.76g of CaBi2O4White powder, 20mL of absolute ethanol and 10mL of distilled water were added and sonicated for 30min, and stirred at room temperature for 30 min. According to Bi3+With Cl-The molar ratio is 1: 0.50 mL of hydrochloric acid was added and stirred at room temperature for 1 h. After the reaction is finished, filtering the obtained product, washing the product for several times by using absolute ethyl alcohol and deionized water in sequence, and drying the product for 6 hours at 80 ℃ to finally obtain visible light response CaBi2O4a/BiOCl heterojunction photocatalyst.
Example 3
(1) White CaBi2O4And (3) preparing a powder material. Weighing 1.3530gCa (NO) in stoichiometric ratio3)2·4H2O and 5.5856gBi (NO)3)3·5H2O, first Ca (NO)3)2·4H2Dissolving O in 50mL deionized water to obtain a transparent solution, and adding Bi (NO)3)3·5H2Dissolving O in 50mL of dilute nitric acid solution, mixing the two transparent solutions in a 200mL beaker, and stirring for 30min to mix the two transparent solutions uniformly. Adding 100mL of deionized water into a 500mL beaker as a base solution, and mixing the mixed solution with 3mol/L ammonia water (NH)3·H2And O) dripping the two solutions into the base solution, continuously stirring to uniformly mix the precipitation reactants, keeping the pH of the reaction solution at about 8, and continuously stirring and aging the precipitation suspension obtained after the titration for 30 min. Then solid-liquid separation is carried out by adopting a centrifuge, and the obtained white precipitate is washed by deionized water to remove NH4+And NO3-And the washing was repeated 6 times. Diluting the precipitate after washing and centrifugal separation to 100mL to obtain white precipitate suspension; then respectively putting the suspension prepared above into two closed reaction kettles with 100mL capacity and made of stainless steel and white polytetrafluoroethylene lining for heat treatment at 180 ℃ for 6 hours, cooling, and drying in an oven at 50 ℃ for 10 hours to obtain the lightCatalyst CaBi2O4。
(2) Visible light response CaBi2O4Preparation of/BiOCl heterojunction photocatalyst.
Preparing hydrochloric acid with the mass fraction of 36%, and storing the hydrochloric acid in a shade place for later use. 0.76g of CaBi2O4White powder, 20mL of absolute ethanol and 10mL of distilled water were added and sonicated for 30min, and stirred at room temperature for 30 min. According to Bi3+With Cl-The molar ratio is 1: 0.75 mL of hydrochloric acid was added and stirred at room temperature for 1 h. After the reaction is finished, filtering the obtained product, washing the product for several times by using absolute ethyl alcohol and deionized water in sequence, and drying the product for 6 hours at 80 ℃ to finally obtain visible light response CaBi2O4a/BiOCl heterojunction photocatalyst.
Example 4
(1) White CaBi2O4And (3) preparing a powder material. Weighing 1.3560gCa (NO) in stoichiometric ratio3)2·4H2O and 5.5840gBi (NO)3)3·5H2O, first Ca (NO)3)2·4H2Dissolving O in 50mL deionized water to obtain a transparent solution, and adding Bi (NO)3)3·5H2Dissolving O in 50mL of dilute nitric acid solution, mixing the two transparent solutions in a 200mL beaker, and stirring for 30min to mix the two transparent solutions uniformly. Adding 100mL of deionized water into a 500mL beaker as a base solution, and mixing the mixed solution with 3mol/L ammonia water (NH)3·H2And O) dripping the two solutions into the base solution, continuously stirring to uniformly mix the precipitation reactants, keeping the pH of the reaction solution at about 8, and continuously stirring and aging the precipitation suspension obtained after the titration for 30 min. Then solid-liquid separation is carried out by adopting a centrifuge, and the obtained white precipitate is washed by deionized water to remove NH4+And NO3-And the washing was repeated 6 times. Diluting the precipitate after washing and centrifugal separation to 100mL to obtain white precipitate suspension; then respectively putting the suspension prepared above into two closed reaction kettles with 100mL capacity and made of stainless steel and white polytetrafluoroethylene lining for heat treatment at 180 ℃ for 6 hours, cooling and drying in an oven at 50 DEG CObtaining the photocatalyst CaBi within 10 hours2O4。
(2) And (3) preparing a BiOCl photocatalyst.
Preparing hydrochloric acid with the mass fraction of 36%, and storing the hydrochloric acid in a shade place for later use. 0.76g of CaBi2O4White powder, 20mL of absolute ethanol and 10mL of distilled water were added and sonicated for 30min and stirred at room temperature for 30min, 0.260mL (sufficient) of hydrochloric acid was added and stirred at room temperature for 1 h. And after the reaction is finished, filtering the obtained product, washing the product for several times by using absolute ethyl alcohol and deionized water in sequence, and drying the product for 6 hours at 80 ℃ to finally obtain the pure BiOCl photocatalyst.
Although the invention has been described in detail above with reference to a general description and specific examples, it will be apparent to one skilled in the art that modifications or improvements may be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (3)
1. CaBi2O4The preparation method of the/BiOCl heterojunction photocatalyst material is characterized by comprising the following steps:
(1)CaBi2O4preparing powder material by adding Ca (NO) at a certain stoichiometric ratio3)2·4H2Dissolving O in 50mL deionized water to obtain solution A, and dissolving Bi (NO)3)3·5H2Dissolving O in 50mL of dilute nitric acid to obtain a solution B, mixing and stirring the solution A and the solution B for 30min to obtain a mixed solution C, adding the solution C and ammonia water together dropwise into 100mL of deionized water, continuously stirring to enable the pH value to be 6-8 to obtain a white precipitate suspension D, and continuously stirring and aging for 30 min; carrying out solid-liquid separation on the precipitate suspension D by using a centrifugal machine to obtain white precipitate, washing the white precipitate for 3-6 times by using deionized water, and diluting the precipitate to 100mL to obtain white precipitate suspension E; pouring the suspension E into a closed reaction kettle made of stainless steel and lined with white polytetrafluoroethylene for heat treatment at 180 ℃ for 6 hours, washing the suspension for 3-6 times by using deionized water after the treatment is finished and cooling the suspensionDrying in a drying oven at 50 deg.C for 10 hr to obtain white CaBi2O4A powder material;
(2) preparing a CaBi2O4/BiOCl heterojunction photocatalyst material for enhancing visible light response, weighing CaBi2O4 powder, adding 20mL of absolute ethyl alcohol and 10mL of deionized water, carrying out ultrasonic treatment for 30min, and stirring for 30 min; and then adding a concentrated hydrochloric acid solution, stirring for 1h at room temperature, filtering the obtained product, washing for 3-6 times by using absolute ethyl alcohol and deionized water, and drying for 6h at 80 ℃ to obtain the CaBi2O4/BiOCl heterojunction photocatalyst with enhanced visible light response.
2. The enhanced visible light response CaBi of claim 12O4The preparation method of the/BiOCl heterojunction photocatalyst is characterized by comprising the following steps: the volume of the concentrated hydrochloric acid solution and the CaBi in the step (2)2O4The mass ratio of the powder material is 0.065-0.260mL:0.76 g.
3. The enhanced visible light response CaBi of claim 12O4The preparation method of the/BiOCl heterojunction photocatalyst is characterized by comprising the following steps: the mass concentration of the concentrated hydrochloric acid solution in the step (2) is 36%.
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| CN113750984A (en) * | 2021-10-15 | 2021-12-07 | 沈阳化工大学 | Preparation method of controllable graded porous SnO2/C photocatalyst |
| CN116212966A (en) * | 2023-01-10 | 2023-06-06 | 齐齐哈尔大学 | Indirect Z-type multicomponent bismuth-based MOF heterojunction and preparation method and application thereof |
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Application publication date: 20200818 |