CN113797910A - Defect-containing nano microspheric perovskite catalyst and preparation method and application thereof - Google Patents
Defect-containing nano microspheric perovskite catalyst and preparation method and application thereof Download PDFInfo
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- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 18
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- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 claims abstract description 10
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
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- B82—NANOTECHNOLOGY
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Abstract
The invention provides a defect-containing nano microspherical perovskite catalyst and a preparation method and application thereof. The microspherical nano structure can realize multiple absorption, reflection and refraction of light, thereby realizing the full utilization of sunlight. Compared with a two-dimensional material (such as a nano-sheet structure), the microspherical nano structure can be transmitted on the edge and the surface, so that the surface interface reaction is enhanced, and the separation and transmission of photogenerated charges are facilitated. The method introduces defects by utilizing the reduction and induction effects of titanium trichloride and ascorbic acid in a solvothermal reaction, expands and increases the absorption of a catalyst to visible light, and can also become an active reaction site to further promote the removal efficiency of photocatalytic NO.
Description
Technical Field
The invention belongs to the technical field of environmental function nano material photocatalysis, and particularly relates to a defect-containing nano microspherical perovskite catalyst and a preparation method and application thereof.
Background
Nitrogen Oxides (NO)x) Is an important precursor of secondary aerosol, can cause severe environmental effects such as acid rain, global climate change and the like, and has NO/NO as a main component2Mainly (at least 90%) NO. The existing NO treatment methods such as a source control method and the like have the defects of high equipment requirement and cost, easy generation of highly toxic byproducts and the like. How to effectively convert NO into products such as nontoxic nitrate or nitrogen and the like and reduce the harm of NO still remains a challenging research in the field of air pollution control at present.
Research has shown that semiconductor-material-dominated photocatalytic technology can convert low concentrations of air pollutants, such as NO (ppb levels), to HNO3、HNO2、NO2And N2Etc., thereby reducing the concentration of NO. At present, research on the application of semiconductor photocatalytic materials in NO removal is advanced to a certain extent, however, some materials can only be excited under ultraviolet irradiation due to large equal band gaps, and visible light cannot be fully utilized; although the catalyst with visible light response has good light absorption, the quantum efficiency is still not ideal due to fast carrier recombination, and meanwhile, the problems of poor structural stability and the like exist.
The surface structure is an important factor influencing the physical and chemical properties of a solid material, the main place where the photocatalytic reaction occurs is also the surface of a catalyst, and the photocatalytic reaction is a typical surface-interface catalytic process, the first step of the photocatalytic reaction is the effective excitation of the catalyst material and the generation of photo-generated electrons and holes, and the action, the surface-interface properties, the electronic properties, the chemical composition, the structure and the crystal form of active species in the pollutant treatment process, the surface state and the pollutant disposal path are all closely related to the microstructure of the catalyst. At present, the regulation and control of the microstructure are mainly realized by means of modifying, morphology, crystal face, surface defect and the like of the surface of the catalyst.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a defect-containing nano microspherical perovskite catalyst, a preparation method and application thereof, and belongs to the technical field of typical environmental functional nano material photocatalysis. The defect-containing nano microspherical perovskite catalyst has the advantages of simple synthesis process, high yield and purity and easily-regulated reaction conditions, and the perovskite catalyst with excellent microstructure and good visible light response is realized in a system in which water and an organic solvent exist by using a simple alkaline reagent and a structure inducer.
The defect-containing nano microspherical perovskite catalyst has different surface defects, so that stronger visible light response is shown, and the application of the photocatalyst removal of nitrogen monoxide (NO) which is a potential atmospheric pollutant is also related, the prepared catalyst can realize the rapid conversion of nitric oxide under the irradiation of visible light with the emission wavelength lambda of more than or equal to 420nm, can realize the removal rate of 55 percent within 30min, and is a potential visible light driven catalyst. The catalyst disclosed by the invention is simple to prepare, has a good microstructure and high-end photocatalytic activity, and has important significance in actively promoting development of environmental functional materials and treatment of low-concentration and high-toxicity potential pollutants in the atmosphere and the like.
The purpose of the invention is realized by the following technical scheme:
a defect-containing nano microspherical perovskite catalyst has a chemical composition of strontium titanate SrTiO3The catalyst has a microsphere structure, the diameter of the microsphere is 50-500nm, and the surface of the catalyst contains oxygen vacancies.
The invention also provides a preparation method of the defect-containing nano microspherical perovskite catalyst, which comprises the following steps:
mixing a strontium source, a titanium source, an alkali source and a structure inducer, and carrying out solvothermal reaction to prepare the defect-containing nano microspherical perovskite catalyst strontium titanate SrTiO3。
According to the invention, the method comprises the following steps:
(1) respectively mixing a strontium source, an alkali source, a titanium source and a structure inducer in an aqueous solution, stirring, and then adding an organic solvent for stirring again;
(2) carrying out solvothermal reaction on the mixed system in the step (1) to prepare the defect-containing nano microspherical perovskite catalyst strontium titanate SrTiO3。
According to the invention, the step (1) specifically comprises the following steps:
(1-1) dissolving a strontium source in water, adding an alkali source, and stirring;
(1-2) adding a titanium source, and continuing stirring;
(1-3) adding a structure inducer, and continuously stirring;
(1-4) adding the organic solvent, and stirring again.
According to the invention, in the step (1), the strontium source, the alkali source and the titanium source are preferably subjected to grinding treatment before mixing, and the grinding treatment time is 10-50 min.
According to the invention, in the step (1), the strontium source is selected from strontium carbonate, strontium nitrate and strontium chloride; for example selected from strontium chloride. The titanium source is selected from titanium trichloride. The alkali source is selected from sodium hydroxide, potassium hydroxide and lithium hydroxide; for example selected from sodium hydroxide.
Wherein, the alkali source can be prepared into a solution for adding in advance.
According to the invention, in the step (1), the strontium source and the titanium source are added in a molar ratio which satisfies the strontium titanate SrTiO3I.e. the molar ratio of the strontium source and the titanium source is 1: 1.
According to the invention, in the step (1), the molar ratio of the strontium source to the alkali source is 1: 1.
According to the invention, in step (1), the molar mass (mmol: g) ratio of the strontium source and the structure-inducing agent is 1:0.5-5, such as 1: 0.5-2.
According to the present invention, in step (1), the molar ratio by volume (mmol/mL) of the strontium source and water may be 1-5:30, such as 1: 6.
According to the invention, in step (1), the volume ratio of water to organic solvent may be 15-30:1, such as 15: 1.
According to the invention, in step (1), the structure-inducing agent is selected from ascorbic acid and the organic solvent is selected from methanol, ethanol, isopropanol, etc., for example from methanol.
According to the invention, in the step (2), the temperature of the solvothermal reaction is 120-180 ℃, and the time of the solvothermal reaction is 12-36 h.
According to the invention, the method also comprises a post-treatment step, wherein the post-treatment step comprises washing for 5-6 times by using secondary distilled water and centrifuging, collecting a centrifugal product and drying.
Illustratively, the preparation method of the catalyst comprises the following steps:
accurately weighing strontium chloride in an agate mortar, and grinding the strontium chloride into powder;
accurately weighing sodium hydroxide in an agate mortar, and grinding the sodium hydroxide into powder;
slowly adding strontium chloride powder and sodium hydroxide powder into distilled water successively and stirring;
under the condition of stirring, slowly dripping titanium trichloride into the reaction for continuous stirring;
under the condition of stirring, slowly dripping ascorbic acid into the reaction, and continuously stirring;
then gradually adding methanol into the solution and stirring again;
and carrying out solvothermal reaction to obtain the defect-containing nano microspherical perovskite catalyst.
The invention also provides the defect-containing nano microspherical perovskite catalyst prepared by the method.
The invention also provides the defect-containing nano micro-spherical perovskite catalyst for removing nitrogen monoxide through photocatalysis.
The invention has the beneficial effects that:
the invention provides a defect-containing nano microspherical perovskite catalyst, a preparation method and application thereof, and the defect-containing nano microspherical perovskite catalyst has the following advantages:
1. the method is characterized in that the shape of the catalyst is regulated and controlled by adjusting the adding amount of the organic solvent in the solvothermal reaction, so that a uniform microspherical nano structure is obtained. The microspherical nano structure can realize multiple absorption, reflection and refraction of light, thereby realizing the full utilization of sunlight. Compared with a two-dimensional material (such as a nanosheet structure), the microspherical nanostructure disclosed by the invention can be transmitted not only at the edge but also on the surface, so that the surface interface reaction is enhanced, and the separation and transmission of photo-generated charges are facilitated.
2. The method introduces defects by utilizing the reduction and induction effects of titanium trichloride and ascorbic acid in a solvothermal reaction, expands and increases the absorption of a catalyst to visible light, and can also become an active reaction site to further promote the removal efficiency of photocatalytic NO.
3. Because the defect-containing nano microsphere perovskite catalyst has an excellent microscopic surface structure, namely a microspherical nano structure and effectively constructed defect sites, the surface interface synergistic effect induced by the surface structure can be well utilized, the expansion of photoresponse and the enhancement of surface interface reaction can be realized, the chemical adsorption of NO can be promoted, and the reaction kinetics of a system can be optimized, so that the NO conversion quantum efficiency can be improved. The defect-containing nano microspherical perovskite catalyst provided by the invention shows high-end photocatalytic activity under the irradiation of visible light, and the oxidation removal rate of potential atmospheric pollutants nitric oxide can reach 55%.
Drawings
FIG. 1 is a scanning electron micrograph of a catalyst according to example 1 of the present invention;
FIG. 2 is a powder diffraction pattern of the catalyst of example 1 of the present invention;
FIG. 3 is a surface defect distribution diagram of the catalyst of example 1 of the present invention;
FIG. 4 is a UV-VIS diffuse reflectance absorption spectrum of the catalyst of example 1 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to specific examples. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
The experimental methods used in the following examples are all conventional methods unless otherwise specified; reagents, materials and the like used in the following examples are commercially available unless otherwise specified.
Comparative example 1
a. Accurately weighing 5.0mmol of strontium chloride, and grinding in a mortar for about 20 min; putting weighed 5.0mmol of sodium hydroxide into another mortar, and grinding respectively;
b. preparing a container containing 30mL of distilled water, adding the strontium chloride powder ground in the step a step by step into the container, stirring the mixture, adding the ground sodium hydroxide powder into the container, and continuing stirring the mixture to observe the formation of a white turbid liquid; slowly dripping 3.0mL of titanium trichloride into the suspension, and continuously stirring for about 30 min; then, 2.0mL of methanol is added in sequence, and stirring is continued for about 80 min;
c. the solution was transferred to a hydrothermal kettle and placed in an oven at 180 deg.CHeating for 12h, cooling to room temperature at the speed of 2 ℃/min after the reaction is finished, washing, drying and grinding the sample to obtain the catalyst strontium titanate SrTiO3。
Example 1
a. Accurately weighing 5.0mmol of strontium chloride, and grinding in a mortar for about 20 min; putting weighed 5.0mmol of sodium hydroxide into another mortar, and grinding respectively;
b. preparing a container containing 30mL of distilled water, adding the strontium chloride powder ground in the step a step by step into the container, stirring the mixture, adding the ground sodium hydroxide powder into the container, and continuing stirring the mixture to observe the formation of a white turbid liquid; slowly dripping 3.0mL of titanium trichloride into the suspension, and continuously stirring for about 30 min; then adding 0.5g of ascorbic acid as a structure inducer and 2.0mL of methanol in sequence, and continuing stirring for about 80 min;
c. transferring the solution into a hydrothermal kettle, placing the hydrothermal kettle into an oven, heating the hydrothermal kettle at 180 ℃ for 12h, cooling the hydrothermal kettle to room temperature at the speed of 2 ℃/min after the reaction is finished, washing, drying and grinding the sample to obtain the nano microspherical perovskite catalyst strontium titanate SrTiO3。
Example 2
a. Accurately weighing 5.0mmol of strontium chloride, and grinding in a mortar for about 20 min; putting weighed 5.0mmol of sodium hydroxide into another mortar, and grinding respectively;
b. preparing a container containing 30mL of distilled water, adding the strontium chloride powder ground in the step a step by step into the container, stirring the mixture, adding the ground sodium hydroxide powder into the container, and continuing stirring the mixture to observe the formation of a white turbid liquid; slowly dripping 3.0mL of titanium trichloride into the suspension, and continuously stirring for about 30 min; then adding 1.0g of ascorbic acid as a structure inducer and 2.0mL of methanol in sequence, and continuing stirring for about 80 min;
c. transferring the solution into a hydrothermal kettle, placing the hydrothermal kettle into an oven, heating the hydrothermal kettle at 180 ℃ for 12h, cooling the hydrothermal kettle to room temperature at the speed of 2 ℃/min after the reaction is finished, washing, drying and grinding the sample to obtain the nano microspherical perovskite catalyst strontium titanate SrTiO3。
Example 3
a. Accurately weighing 5.0mmol of strontium chloride, and grinding in a mortar for about 20 min; putting weighed 5.0mmol of sodium hydroxide into another mortar, and grinding respectively;
b. preparing a container containing 30mL of distilled water, adding the strontium chloride powder ground in the step a step by step into the container, stirring the mixture, adding the ground sodium hydroxide powder into the container, and continuing stirring the mixture to observe the formation of a white turbid liquid; slowly dripping 3.0mL of titanium trichloride into the suspension, and continuously stirring for about 30 min; then adding 1.5g of ascorbic acid as a structure inducer and 2.0mL of methanol in sequence, and continuing stirring for about 80 min;
c. transferring the solution into a hydrothermal kettle, placing the hydrothermal kettle into an oven, heating the hydrothermal kettle at 180 ℃ for 12h, cooling the hydrothermal kettle to room temperature at the speed of 2 ℃/min after the reaction is finished, washing, drying and grinding the sample to obtain the nano microspherical perovskite catalyst strontium titanate SrTiO3。
Test example 1
The catalyst prepared in example 1 was used in nitric oxide removal applications, and the specific operation was carried out as follows:
1. accurately weighing 50.0mg of the catalyst prepared in the example 1 into a culture dish with the diameter of 6.0cm, adding deionized water, performing ultrasonic treatment to obtain uniform and stable suspension, and drying in an oven at 60 ℃; placing the dried sample and container in a reactor under dark condition, sealing, vacuumizing, and introducing NO standard gas (13.0 × 10)-6) And 99.9999% high purity air to control the NO concentration at 500 ppb; then, shading the sample in the reactor for 30min to ensure that the surface of the sample fully absorbs NO gas, waiting for the establishment of adsorption-desorption balance, and keeping the temperature at 25 ℃ in the whole process;
2. after the system is balanced, irradiating the balance system established in the step 1 with visible light (xenon lamp, lambda is more than or equal to 420nm) from the upper part, reading a group of NO and NO from the NOx analyzer every 1min, wherein the distance between the system and the outlet of the xenon lamp is 15cm2And NOx is richDegree change data;
3. taking out reacted powder sample, weighing, adding distilled water, performing ultrasonic treatment for 80min to disperse uniformly, filtering with 0.45 μ L microporous filter membrane, collecting supernatant, testing ion chromatography, and analyzing oxidation product nitric acid (NO) after NO photocatalytic oxidation3 —) And calculating the corresponding conversion.
The results of the removal rate of NO by the catalyst obtained in example 1 were as follows:
| illumination time (min) | NO removal Rate (%) |
| 1 | 0.67194 |
| 2 | 0.37103 |
| 3 | 0.21242 |
| 4 | 0.11896 |
| 5 | 0.08689 |
| 6 | 0 |
| 7 | 0.04068 |
| 8 | 0.03674 |
| 9 | 0.34975 |
| 10 | 3.82814 |
| 11 | 18.93195 |
| 12 | 20.39244 |
| 13 | 24.46457 |
| 14 | 26.78496 |
| 15 | 28.29578 |
| 16 | 29.04033 |
| 17 | 28.83928 |
| 18 | 28.53793 |
| 19 | 27.87168 |
| 20 | 27.44539 |
| 21 | 26.88002 |
| 22 | 26.41145 |
| 23 | 26.17017 |
| 24 | 25.97218 |
| 25 | 25.54225 |
| 26 | 25.16786 |
| 27 | 25.2147 |
| 28 | 25.3341 |
| 29 | 25.4163 |
| 30 | 25.6095 |
Test example 2
The catalyst prepared in example 2 was used in nitric oxide removal applications, and the specific operation was carried out as follows:
1. 50.0mg of the catalyst prepared in example 2 was accurately weighed in a 6.0cm diameter petri dish, deionized water was added, and then sonication was performed to obtain homogeneous solutionDetermining the suspension, and drying in an oven at 60 ℃; placing the dried sample and container in a reactor under dark condition, sealing, vacuumizing, and introducing NO standard gas (13.0 × 10)-6) And 99.9999% high purity air to control the NO concentration at 500 ppb; then, shading the sample in the reactor for 30min to ensure that the surface of the sample fully absorbs NO gas, waiting for the establishment of adsorption-desorption balance, and keeping the temperature at 25 ℃ in the whole process;
2. after the system is balanced, irradiating the balance system established in the step 1 with visible light (xenon lamp, lambda is more than or equal to 420nm) from the upper part, reading a group of NO and NO from the NOx analyzer every 1min, wherein the distance between the system and the outlet of the xenon lamp is 15cm2And NOx concentration variation data;
3. taking out reacted powder sample, weighing, adding distilled water, performing ultrasonic treatment for 80min to disperse uniformly, filtering with 0.45 μ L microporous filter membrane, collecting supernatant, testing ion chromatography, and analyzing oxidation product nitric acid (NO) after NO photocatalytic oxidation3 —) And calculating the corresponding conversion.
The results of the removal rate of NO by the catalyst obtained in example 2 were as follows:
the embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A defect-containing nano microspherical perovskite catalyst has a chemical composition of strontium titanate SrTiO3The catalyst has a microsphere structure, the diameter of the microsphere is 50-500nm, and the surface of the catalyst contains oxygen vacancies.
2. A method of preparing a defect-containing nano-microspheroidal perovskite catalyst as claimed in claim 1, said method comprising the steps of:
mixing a strontium source, a titanium source, an alkali source and a structure inducer, and performing solvothermal reaction to prepare the defect-containing nano microspherical perovskite catalyst strontium titanate SrTiO3。
3. The method of manufacturing according to claim 2, wherein the method comprises the steps of:
(1) respectively mixing a strontium source, an alkali source, a titanium source and a structure inducer in an aqueous solution, stirring, and then adding an organic solvent for stirring again;
(2) carrying out solvothermal reaction on the mixed system obtained in the step (1) to prepare the defect-containing nano microspherical perovskite catalyst strontium titanate SrTiO3。
4. The preparation method according to claim 3, wherein the step (1) specifically comprises the following steps:
(1-1) dissolving a strontium source in water, adding an alkali source, and stirring;
(1-2) adding a titanium source, and continuing stirring;
(1-3) adding a structure inducer, and continuously stirring;
(1-4) adding the organic solvent, and stirring again.
5. The preparation method according to claim 3 or 4, wherein in the step (1), the strontium source, the alkali source and the titanium source are preferably subjected to grinding treatment before mixing, and the grinding treatment time is 10-50 min;
preferably, in step (1), the strontium source is selected from strontium carbonate, strontium nitrate, strontium chloride; for example selected from strontium chloride; the titanium source is selected from titanium trichloride; the alkali source is selected from sodium hydroxide, potassium hydroxide and lithium hydroxide.
6. The production method according to any one of claims 3 to 5, wherein in the step (1), the molar ratio of the strontium source to the titanium source is 1: 1;
the mol ratio of the strontium source to the alkali source is 1: 1;
the molar mass (mmol: g) ratio of the strontium source to the structure inducer is 1: 0.5-5;
the mol ratio of the strontium source to the water (mmol/mL) is 1-5: 30;
the volume ratio of the water to the organic solvent is 15-30: 1;
preferably, in step (1), the structure inducer is selected from ascorbic acid, and the organic solvent is selected from methanol, ethanol, and isopropanol.
7. The preparation method according to any one of claims 3 to 6, wherein, in the step (2), the temperature of the solvothermal reaction is 120-180 ℃, and the time of the solvothermal reaction is 12-36 h.
8. The production method according to any one of claims 3 to 7, wherein the catalyst is produced by a method comprising the steps of:
accurately weighing strontium chloride in an agate mortar, and grinding the strontium chloride into powder;
accurately weighing sodium hydroxide in an agate mortar, and grinding the sodium hydroxide into powder;
slowly adding strontium chloride powder and sodium hydroxide powder into distilled water successively and stirring;
under the condition of stirring, slowly dripping titanium trichloride into the reaction for continuous stirring;
under the condition of stirring, slowly dripping ascorbic acid into the reaction, and continuously stirring;
then gradually adding methanol into the solution and stirring again;
and carrying out solvothermal reaction to obtain the defect-containing nano microspherical perovskite catalyst.
9. A defect-containing nanospherical perovskite catalyst prepared by the method of any one of claims 2 to 8.
10. Use of the defect-containing nanospherical perovskite catalyst as claimed in claim 1 or 9 for photocatalytic removal of nitric oxide.
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