CN112808283A - SrTiO3Microwave rapid preparation method of-BiOBr composite catalyst - Google Patents

SrTiO3Microwave rapid preparation method of-BiOBr composite catalyst Download PDF

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CN112808283A
CN112808283A CN202011638509.0A CN202011638509A CN112808283A CN 112808283 A CN112808283 A CN 112808283A CN 202011638509 A CN202011638509 A CN 202011638509A CN 112808283 A CN112808283 A CN 112808283A
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solution
composite catalyst
microwave
reaction
strontium titanate
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钮金芬
张紫琦
王凯
马璋腾斐
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Xian University of Technology
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Xian University of Technology
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/02Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/06Halogens; Compounds thereof
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/06Halogens; Compounds thereof
    • B01J27/138Halogens; Compounds thereof with alkaline earth metals, magnesium, beryllium, zinc, cadmium or mercury
    • B01J35/39
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/34Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • B01J37/341Irradiation 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
    • B01J37/344Irradiation 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 electromagnetic wave energy
    • B01J37/346Irradiation 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 electromagnetic wave energy of microwave energy

Abstract

The invention discloses SrTiO3-microwave rapid preparation method of BiOBr composite catalyst, comprising the following steps: adding bismuth nitrate into a mixed solvent consisting of ethylene glycol and water, putting the bismuth nitrate and the mixed solvent together on a magnetic stirrer, and stirring until the bismuth nitrate and the water are dissolved to obtain solution A; simultaneously adding potassium bromide into ethylene glycol and stirring to obtain solution B; slowly adding the solution B into the solution A, uniformly stirring, adding strontium titanate, and performing ultrasonic dispersion to obtain a mixed solution; then placing the mixed solution into a microwave reaction kettle, setting the temperature and time for reaction, and cooling the microwave reaction kettle to room temperature after the reaction is completedAnd centrifugally separating the reaction product, respectively washing the obtained solid substance by using deionized water and absolute ethyl alcohol, and drying to obtain the bismuth oxybromide/strontium titanate composite catalyst. The method shortens the preparation time of the composite catalyst, improves the photocatalytic activity of the single catalyst strontium titanate and bismuth oxybromide, and has good catalytic effect.

Description

SrTiO3Microwave rapid preparation method of-BiOBr composite catalyst
Technical Field
The invention belongs to the technical field of photocatalyst preparation, and relates to SrTiO3A microwave rapid preparation method of the BiOBr composite catalyst.
Background
Strontium titanate (SrTiO)3) As a typical perovskite structure metal oxide, the titanium dioxide-based photocatalytic material is another semiconductor photocatalytic material with larger application potential besides titanium dioxide, and is also a typical n-type semiconductor. Bismuth oxybromide (BiOBr) is a typical layered oxide and is considered to be a promising photocatalyst due to its physicochemical stability, non-toxicity and excellent photocatalytic activity. However, both of these catalysts have the problem of limited photoresponse capability, and there are a lot of literature and patents on the modification method of bismuth oxybromide and strontium titanate to improve the photoresponse capability of single catalyst and the photocatalytic capability of composite catalyst, but at present, the method relates to the heterostructure SrTiO3BiOBr composite catalyst is rarely reported, and the latest reported research paper of Photocalalytic activities of novel SrTiO3In BiOBrheteohejoint catalysts, which are synthesized by the decomposition of reactive dyes (Applied Catalysis B: Environmental, 2017, P218-232), the composite catalyst shows excellent photocatalytic activity superior to that of a single catalyst, but the preparation process needs 7 hours, the drying needs 48 hours, the preparation steps are complicated, and the completion of the process conditions is difficult to meet the requirement of industrial batch production. Currently, SrTiO3The preparation of the-BiOBr composite catalyst is not recorded and reported in related patents, so that the SrTiO which has excellent catalytic performance, simple preparation method, low preparation cost, mild conditions and easy industrialization is searched3The preparation method of the BiOBr heterojunction catalyst is of great importance.
Disclosure of Invention
The invention aims to provide SrTiO3A microwave rapid preparation method of a BiOBr composite catalyst, which solves the problems of long reaction time, low synthesis efficiency, insufficient catalytic activity and high time and economic cost in the preparation process of the prior art.
The invention adopts the technical scheme that SrTiO3The microwave rapid preparation method of the BiOBr composite catalyst is implemented according to the following steps:
adding 1 g-2 g of bismuth nitrate into 15-50ml of mixed solvent consisting of ethylene glycol and water, putting the mixture on a magnetic stirrer together, and stirring for 10-30min until the mixture is dissolved to obtain solution A; simultaneously adding 0.1-0.5 g of potassium bromide into 10-45ml of ethylene glycol and stirring to obtain solution B;
slowly adding the solution B into the solution A, uniformly stirring, adding 0.02g-0.15g of strontium titanate, and performing ultrasonic dispersion to obtain a mixed solution;
placing the mixed solution into a microwave reaction kettle for reaction, cooling the microwave reaction kettle to room temperature after the reaction is completed, and carrying out centrifugal separation on a reaction product; and (3) respectively washing the solid matters obtained by separation by using deionized water and absolute ethyl alcohol, and drying to obtain the bismuth oxybromide/strontium titanate composite catalyst.
The invention has the beneficial effect of solving the problem of the traditional SrTiO3Long preparation time of-BiOBr composite catalyst and single catalyst strontium titanate (SrTiO)3) And bismuth oxybromide (BiOBr) has low photocatalytic activity and poor catalytic effect. The method can improve the catalytic preparation efficiency of the composite catalyst, simultaneously can make up the problem of the catalytic efficiency of a single catalyst, improves the overall performance, accelerates the photocatalytic reaction rate, and prepares the SrTiO3the-BiOBr composite photocatalyst has stable chemical property and high catalytic efficiency, and is compared with single catalyst SrTiO3The catalytic activity can be improved by 2.2 times, and the preparation method is simple and safe to operate and low in cost.
Drawings
FIG. 1 is an XRD pattern of strontium titanate, bismuth oxybromide and the different ratios of bismuth oxybromide/strontium titanate photocatalyst obtained in example 5;
FIG. 2 is a graph showing the degradation rate of the bismuth oxybromide/strontium titanate photocatalyst with different combination ratios obtained in example 5 for degrading methylene blue solution as a function of time.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
SrTiO of the invention3The microwave rapid preparation method of the BiOBr composite catalyst is implemented according to the following steps:
adding 1 g-2 g of bismuth nitrate into 15-50ml of mixed solvent consisting of ethylene glycol and water, putting the mixture on a magnetic stirrer together, and stirring for 10-30min until the mixture is dissolved to obtain solution A; simultaneously adding 0.1-0.5 g of potassium bromide into 10-45ml of ethylene glycol and stirring to obtain solution B;
slowly adding the solution B into the solution A, uniformly stirring, adding 0.02g-0.15g of strontium titanate, and performing ultrasonic dispersion to obtain a mixed solution;
placing the mixed solution into a microwave reaction kettle for reaction, cooling the microwave reaction kettle to room temperature after the reaction is completed, and carrying out centrifugal separation on a reaction product; and (3) respectively washing the solid matters obtained by separation by using deionized water and absolute ethyl alcohol, and drying to obtain the bismuth oxybromide/strontium titanate composite catalyst.
The ratio of ethylene glycol to water in the mixed solvent is 10: 1-1: 10.
the speed of adding the solution B into the solution A is 0.10-0.20 mL/min.
The microwave reaction temperature is 140-200 ℃, and the reaction time is 30-60 min.
The drying temperature is 60-80 ℃, and the drying time is 8-10 h.
Example 1
Dissolving 2g of bismuth nitrate into 35mL of mixed solution of ethylene glycol and water (the mixing ratio of the two is 2:3), and stirring the solution on a magnetic stirrer for 30min (the stirring speed is 180r/min) to obtain solution A; simultaneously, 0.3 of potassium bromide is added into 25mL of ethylene glycol and stirred for 30min (the stirring speed is 180r/min) to obtain a solution B. Slowly adding the solution B (the adding speed of the solution B is 0.20mL/min) into the solution A, stirring for 20min (the stirring speed is 300r/min), adding 0.1g of strontium titanate, and ultrasonically dispersing for 25min (the oscillation frequency is 100 hz). Moving the mixed solution into a microwave reaction kettle, carrying out microwave solvothermal reaction at 175 ℃ for 45min, cooling the microwave reaction kettle to room temperature after the reaction is completed, and carrying out centrifugal separation on a reaction product; and (3) washing the obtained solid substance with deionized water for 3 times, then washing with absolute ethyl alcohol for 3 times, and drying with a drying box at the drying temperature of 70 ℃ for 8 hours to obtain a 5% bismuth oxybromide/strontium titanate composite catalyst sample.
Example 2
Dissolving 1.8g of bismuth nitrate into 50mL of mixed solution of ethylene glycol and water (the mixing ratio of the two is 1:3), and stirring the solution on a magnetic stirrer for 10min (the stirring speed is 150r/min) to obtain solution A; simultaneously, 0.2g of potassium bromide is added into 45mL of ethylene glycol and stirred for 30min (the stirring speed is 180r/min), and liquid B is obtained. Slowly adding the solution B (the adding speed of the solution B is 0.14mL/min) into the solution A, stirring for 30min (the stirring speed is 250r/min), adding 0.15g of strontium titanate, and dispersing for 20min (the oscillation frequency is 60 hz). And moving the mixed solution into a microwave reaction kettle, carrying out microwave solvothermal reaction at the temperature of 200 ℃ for 30min, and cooling the microwave reaction kettle to room temperature after the reaction is completed. And (3) washing the obtained solid substance with deionized water for 3 times, then washing with absolute ethyl alcohol for 3 times, and drying with a drying box at the drying temperature of 60 ℃ for 10 hours to obtain a 5% bismuth oxybromide/strontium titanate composite catalyst sample.
Example 3
Dissolving 1g of bismuth nitrate into 15mL of mixed solution of ethylene glycol and water (the mixing ratio of the two is 4:3), and stirring the solution on a magnetic stirrer for 20min (the stirring speed is 180r/min) to obtain solution A; simultaneously, 0.1g of potassium bromide is added into 10mL of ethylene glycol and stirred for 30min (the stirring speed is 180r/min) to obtain a solution B. Slowly adding the solution B (the adding speed of the solution B is 0.12mL/min) into the solution A, stirring for 30min (the stirring speed is 300r/min), adding 0.03g of strontium titanate, and ultrasonically dispersing for 30min (the oscillation frequency is 80 hz). And moving the mixed solution into a microwave reaction kettle, carrying out microwave solvothermal reaction for 60min at the temperature of 160 ℃, and cooling the microwave reaction kettle to room temperature after the reaction is completed. And (3) washing the obtained solid substance with deionized water for 3 times, then washing with absolute ethyl alcohol for 3 times, and drying with a drying box at the drying temperature of 60 ℃ for 10 hours to obtain a 5% bismuth oxybromide/strontium titanate composite catalyst sample.
Example 4
Dissolving 1.2g of bismuth nitrate into 20mL of mixed solution of ethylene glycol and water (the mixing ratio of the two is 7:3), and stirring the solution on a magnetic stirrer for 30min to obtain solution A; simultaneously, 0.2g of potassium bromide is added into 10mL of ethylene glycol and stirred for 30min to obtain a solution B. Slowly adding the solution B (the adding speed of the solution B is 0.10mL/min) into the solution A, stirring for 25min (the stirring speed is 350r/min), adding 0.02g of strontium titanate, and ultrasonically dispersing for 15min (the oscillation frequency is 40 hz). And moving the mixed solution into a microwave reaction kettle, carrying out microwave solvothermal reaction for 50min at the temperature of 150 ℃, and cooling the microwave reaction kettle to room temperature after the reaction is completed. And (3) washing the obtained solid substance with deionized water for 3 times, then washing with absolute ethyl alcohol for 3 times, and drying with a drying box at the drying temperature of 80 ℃ for 6 hours to obtain a 5% bismuth oxybromide/strontium titanate composite catalyst sample.
Example 5
Dissolving 1.7g of bismuth nitrate into 20mL of mixed solution of ethylene glycol and water (the mixing ratio of the two is 2:1), and stirring the solution on a magnetic stirrer for 25min (the stirring speed is 180r/min) to obtain solution A; simultaneously, 0.5g of potassium bromide is added into 20mL of ethylene glycol and stirred for 25min (the stirring speed is 180r/min), and liquid B is obtained. Slowly adding the solution B (the adding speed of the solution B is 0.20mL/min) into the solution A, stirring for 25min (the stirring speed is 250r/min), adding 0.05g of strontium titanate, and ultrasonically dispersing for 15min (the oscillation frequency is 120 hz). And then moving the mixed solution into a microwave reaction kettle, carrying out microwave solvothermal reaction at the temperature of 180 ℃ for 55min, and cooling the microwave reaction kettle to room temperature after the reaction is completed. And (3) washing the obtained solid substance with deionized water for 3 times, then washing with absolute ethyl alcohol for 3 times, and drying with a drying box at the drying temperature of 60 ℃ for 10 hours to obtain a 5% bismuth oxybromide/strontium titanate composite catalyst sample.
Bismuth oxybromide/strontium titanate samples were prepared at 5%, 10%, 30%, 50% and 70% by mass, respectively, by varying the amount of strontium titanate added.
FIG. 1 shows strontium titanate, bismuth oxybromide and SrTiO obtained in example 5 in different proportions3-XRD pattern of BiOBr photocatalyst. As can be seen from FIG. 1, SrTiO prepared by the method of the present invention3The crystal forms of the two monomers exist in the crystal form of the catalyst of BiOBr, and the successful compounding of the two monomers is proved。
Single strontium titanate, bismuth oxybromide and SrTiO with different compounding ratios obtained in example 53And (3) weighing 0.05g of BiOBr photocatalyst, degrading 50mL of 10mg/L methylene blue solution under the condition that a 150W xenon lamp is used as a light source (the wavelength range is 380-820 nm), calculating according to the change of the absorbance of the dye before and after illumination to obtain the degradation percentage, and comparing the results as shown in figure 2.
As can be seen from FIG. 2, under the xenon lamp irradiation condition, the bismuth oxybromide/strontium titanate photocatalysts with different composite ratios prepared by the method of the invention have higher catalytic effects than the single strontium titanate and bismuth oxybromide photocatalysts; when a xenon lamp is used as a light source and is degraded for 50min, the degradation rate of the bismuth oxybromide/strontium titanate photocatalyst prepared by the method in different composite proportions for degrading methylene blue can reach more than 90 percent, wherein 30 percent of the bismuth oxybromide/strontium titanate photocatalyst can reach 100 percent, and the degradation rate of the monomer strontium titanate is only 45 percent. SrTiO prepared by the method of the invention3The BiOBr catalyst has better degradation effect than the monomer catalyst, so that the SrTiO prepared by the method of the invention3The BiOBr composite catalyst can effectively reduce the preparation time of the catalyst, and the prepared composite catalyst can effectively improve the catalytic efficiency of the catalyst.

Claims (5)

1. SrTiO3-a microwave rapid preparation method of a BiOBr composite catalyst, which is characterized in that: the method comprises the following steps:
adding 1 g-2 g of bismuth nitrate into 15-50ml of mixed solvent consisting of ethylene glycol and water, putting the mixture on a magnetic stirrer together, and stirring for 10-30min until the mixture is dissolved to obtain solution A; simultaneously adding 0.1-0.5 g of potassium bromide into 10-45ml of ethylene glycol and stirring to obtain solution B;
slowly adding the solution B into the solution A, uniformly stirring, adding 0.02g-0.15g of strontium titanate, and performing ultrasonic dispersion to obtain a mixed solution;
placing the mixed solution into a microwave reaction kettle for reaction, cooling the microwave reaction kettle to room temperature after the reaction is completed, and carrying out centrifugal separation on a reaction product; and (3) respectively washing the solid matters obtained by separation by using deionized water and absolute ethyl alcohol, and drying to obtain the bismuth oxybromide/strontium titanate composite catalyst.
2. SrTiO of claim 13-a microwave rapid preparation method of a BiOBr composite catalyst, which is characterized in that: the proportion of the ethylene glycol to the water in the mixed solvent is 10: 1-1: 10.
3. SrTiO of claim 13-a microwave rapid preparation method of a BiOBr composite catalyst, which is characterized in that: the speed of adding the solution B into the solution A is 0.10-0.20 mL/min.
4. SrTiO of claim 13-a microwave rapid preparation method of a BiOBr composite catalyst, which is characterized in that: the microwave reaction temperature is 140-200 ℃, and the reaction time is 30-60 min.
5. SrTiO of claim 13-a microwave rapid preparation method of a BiOBr composite catalyst, which is characterized in that: the drying temperature is 60-80 ℃, and the drying time is 8-10 h.
CN202011638509.0A 2020-12-31 2020-12-31 SrTiO3Microwave rapid preparation method of-BiOBr composite catalyst Pending CN112808283A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113813971A (en) * 2021-10-14 2021-12-21 内蒙古农业大学 Preparation method and application of necklace-shaped bismuth oxybromide and sodium titanate heterojunction composite catalyst
CN114534764A (en) * 2022-03-01 2022-05-27 青海大学 Non-metal element doped strontium titanate catalyst and preparation method thereof
CN115318314A (en) * 2022-08-24 2022-11-11 中国科学院过程工程研究所 Strontium titanate/bismuth oxyiodide composite photocatalytic material, photocatalytic film containing same, preparation method and application
CN116020496A (en) * 2023-01-03 2023-04-28 辽宁大学 BiOI/Zn with discrete structure 2 TiO 4 Heterojunction nanofiber photocatalyst and preparation method and application thereof
CN116020496B (en) * 2023-01-03 2024-05-10 辽宁大学 BiOI/Zn with discrete structure2TiO4Heterojunction nanofiber photocatalyst and preparation method and application thereof

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CN103406155A (en) * 2013-07-19 2013-11-27 西安理工大学 One-step microwave synthesis method of metalloporphyrin-titanium dioxide composite catalyst

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CN103406155A (en) * 2013-07-19 2013-11-27 西安理工大学 One-step microwave synthesis method of metalloporphyrin-titanium dioxide composite catalyst

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Title
CHECHIA HU ET AL: ""Decoration of SrTiO3 nanofibers by BiOI for photocatalytic methyl orange degradation under visible light irradiation" *
THAMARAISELVI KANAGARAJ ET AL: "Photocatalytic activities of novel SrTiO3– BiOBr heterojunctioncatalysts towards the degradation of reactive dyes" *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113813971A (en) * 2021-10-14 2021-12-21 内蒙古农业大学 Preparation method and application of necklace-shaped bismuth oxybromide and sodium titanate heterojunction composite catalyst
CN113813971B (en) * 2021-10-14 2023-08-22 内蒙古农业大学 Preparation method and application of necklace-shaped bismuth oxybromide and sodium titanate heterojunction composite catalyst
CN114534764A (en) * 2022-03-01 2022-05-27 青海大学 Non-metal element doped strontium titanate catalyst and preparation method thereof
CN115318314A (en) * 2022-08-24 2022-11-11 中国科学院过程工程研究所 Strontium titanate/bismuth oxyiodide composite photocatalytic material, photocatalytic film containing same, preparation method and application
CN116020496A (en) * 2023-01-03 2023-04-28 辽宁大学 BiOI/Zn with discrete structure 2 TiO 4 Heterojunction nanofiber photocatalyst and preparation method and application thereof
CN116020496B (en) * 2023-01-03 2024-05-10 辽宁大学 BiOI/Zn with discrete structure2TiO4Heterojunction nanofiber photocatalyst and preparation method and application thereof

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