CN113797910B - Defect-containing nano microspherical perovskite catalyst and preparation method and application thereof - Google Patents

Defect-containing nano microspherical perovskite catalyst and preparation method and application thereof Download PDF

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CN113797910B
CN113797910B CN202010549633.3A CN202010549633A CN113797910B CN 113797910 B CN113797910 B CN 113797910B CN 202010549633 A CN202010549633 A CN 202010549633A CN 113797910 B CN113797910 B CN 113797910B
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赵进才
热沙来提·海里里
盛桦
陈春城
籍宏伟
马万红
章宇超
车延科
宋文静
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Institute of Chemistry CAS
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Abstract

The invention provides a nano microspherical perovskite catalyst containing defects, and a preparation method and application thereof. The microsphere nano structure can realize repeated absorption, reflection and refraction of light, so that the full utilization of sunlight is realized. Compared with two-dimensional materials (such as a nano sheet structure), the microsphere nano structure disclosed by the invention not only can be transmitted at the edge, but also can be transmitted at the surface, so that the surface interface reaction is enhanced, and the separation and transmission of photo-generated charges are facilitated. The method introduces defects by utilizing the reduction and induction actions of titanium trichloride and ascorbic acid in solvothermal reaction, expands and increases the absorption of the catalyst to visible light, and can become active reaction sites at the same time, thereby further promoting the removal efficiency of photocatalytic NO.

Description

Defect-containing nano microspherical perovskite catalyst and preparation method and application thereof
Technical Field
The invention belongs to the technical field of photocatalysis of environmental functional nano materials, and particularly relates to a nano microsphere perovskite catalyst containing defects, 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 the main component of NO/NO 2 NO is the main component (more than 90%). The existing NO treatment methods such as a source control method have the defects of high equipment requirement, high cost, easiness in generating highly toxic byproducts and the like. How to effectively convert NO into non-toxic nitrate or nitrogen and other products, and reducing the harm of NO is still a challenging research in the field of air pollution control at present.
Research has shown that semiconductor material-based photocatalytic technology can convert low concentrations of air pollutants such as NO (ppb level) to HNO 3 、HNO 2 、NO 2 And N 2 And the like, thereby reducing the concentration of NO. At present, the research of the semiconductor photocatalytic material for NO removal has a certain progress, however, due to the large equivalent band gap, some materials can only be excited under the irradiation of ultraviolet light, and the visible light can not be fully utilized; whereas catalysts with visible light response have good light absorption due to the supportThe composition of the fluid is fast, the quantum efficiency is still not ideal, and the structure stability is poor.
The surface structure is an important factor affecting the physical and chemical properties of the solid material, the main place where the photocatalytic reaction occurs is also the catalyst surface, and is a typical surface interface catalytic process, the first step of which is the effective excitation of the catalyst material and the generation of photo-generated electrons and holes, and the roles of these active species in the pollutant treatment process, surface interface properties, electronic properties, chemical composition, structure and crystal form, surface state and disposal route of pollutants are closely related to the microstructure of the catalyst. At present, the regulation and control of the microstructure is mainly realized by means of modifying the surface of the catalyst, morphology, crystal face, surface defects and the like.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a nano microsphere perovskite catalyst containing defects, and a preparation method and application thereof, and belongs to the technical field of photocatalysis of typical environmental functional nano materials. The synthesis process of the nano microsphere perovskite catalyst containing the defects is simple, the yield and the purity are high, the reaction condition is easy to regulate and control, and the perovskite catalyst with excellent microstructure and good visible light response is realized by utilizing a simple alkaline reagent and a structure inducer in a system with water and an organic solvent.
The nanometer microspherical perovskite catalyst containing the defects has different surface defects, so that the nanometer microspherical perovskite catalyst shows stronger visible light correspondence, and therefore, the invention also relates to application of potential atmospheric pollutant Nitric Oxide (NO) photocatalysis removal, the prepared catalyst can realize rapid conversion of nitrogen monoxide under irradiation of visible light with emission wavelength lambda of more than or equal to 420nm, 55% removal rate can be realized in a short period of 30min, and the nanometer microspherical perovskite catalyst is a potential visible light driving 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 developing environmental functional materials and positively promoting the aspects of treating low-concentration and high-toxicity potential pollutants in the atmosphere.
The invention aims at realizing the following technical scheme:
a nano microspherical perovskite catalyst containing defects has the chemical composition of strontium titanate SrTiO 3 The 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 microsphere perovskite catalyst, which comprises the following steps:
mixing a strontium source, a titanium source, an alkali source and a structure inducer, and performing solvothermal reaction to prepare the strontium titanate SrTiO serving as the nano microsphere perovskite catalyst containing the defects 3 。
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 into the 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 strontium titanate SrTiO serving as the nano microsphere perovskite catalyst containing defects 3 。
According to the invention, in the step (1), the method 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 an 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 being mixed, wherein the grinding treatment time is 10-50min.
According to the invention, in step (1), said 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; for example selected from sodium hydroxide.
Wherein the alkali source can also be pre-configured as a solution for addition.
According to the invention, in the step (1), the adding mole ratio of the strontium source and the titanium source satisfies the condition of strontium titanate SrTiO 3 I.e. the molar ratio of strontium source to titanium source is 1:1.
According to the invention, in 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 to the structure-inducing agent is from 1:0.5 to 5, such as from 1:0.5 to 2.
According to the invention, in step (1), the molar ratio volume ratio (mmol/mL) of strontium source to 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 12-36h.
According to the invention, the method further comprises a post-treatment step, wherein the post-treatment is to wash for 5-6 times with secondary distilled water, centrifuge, collect the centrifugate and dry.
Illustratively, the method of preparing the catalyst comprises 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 to powder;
sequentially and slowly adding strontium chloride powder and sodium hydroxide powder into distilled water and stirring;
slowly dripping titanium trichloride into the reaction under stirring, and continuing stirring;
slowly dripping ascorbic acid into the reaction under stirring, and continuing stirring;
then gradually adding methanol into the solution to stir again;
and carrying out solvothermal reaction to obtain the nano microsphere perovskite catalyst containing the defects.
The invention also provides the nano microsphere perovskite catalyst containing the defects, which is prepared by the method.
The invention also provides the defect-containing nano microspherical perovskite catalyst for removing nitrogen monoxide through photocatalysis.
The invention has the beneficial effects that:
the invention provides a nanometer microspherical perovskite catalyst containing defects, a preparation method and application thereof, and the nanometer microspherical perovskite catalyst has the following advantages:
1. the method is characterized in that the morphology of the catalyst is regulated and controlled by regulating the addition amount of an organic solvent in the solvothermal reaction, and a uniform microspherical nano structure is obtained. The microsphere nano structure can realize multiple absorption, reflection and refraction of light, so as to realize full utilization of sunlight. Compared with a two-dimensional material (such as a nano sheet structure), the microsphere nano structure disclosed by the invention not only can be transmitted at the edge, but also can be transmitted at 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 actions of titanium trichloride and ascorbic acid in solvothermal reaction, expands and increases the absorption of the catalyst to visible light, and can become active reaction sites at the same time to further promote the removal efficiency of photocatalytic NO.
3. Because the nano microsphere perovskite catalyst containing the defects has excellent microscopic surface structures, namely the microsphere nano structures and defect sites with effective structures, the surface interface synergistic effect induced by the surface structures can be well utilized, the development of light response and the enhancement of surface interface reaction can be realized, the chemical absorption of NO can be promoted, and the system reaction dynamics can be optimized so as to improve the NO conversion quantum efficiency. The nano microsphere perovskite catalyst containing the defects has high-end photocatalytic activity under irradiation of visible light, and the oxidation removal rate of nitrogen monoxide, which is a potential atmospheric pollutant, can reach 55%.
Drawings
FIG. 1 is a scanning electron microscope image 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 graph showing the surface defect distribution of the catalyst of example 1 of the present invention;
FIG. 4 is a graph showing the ultraviolet-visible 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 illustrative only and are not to be construed as limiting the scope of the invention. All techniques implemented based on the above description of the invention are intended to be included within the scope of the invention.
The experimental methods used in the following examples are all conventional methods unless otherwise specified; the reagents, materials, etc. used in the examples described below are commercially available unless otherwise specified.
Comparative example 1
a. Accurately weighing 5.0mmol of strontium chloride, and grinding in a mortar for about 20min; putting 5.0mmol of sodium hydroxide into another mortar, and grinding respectively;
b. in addition, preparing a container containing 30mL of distilled water, adding the ground strontium chloride powder in the step a step by step and stirring, then adding the ground sodium hydroxide powder and continuously stirring, so that the formation of a white turbid liquid can be observed; 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 80min;
c. transferring the solution into a hydrothermal kettle, heating the hydrothermal kettle in an oven at 180 ℃ for 12 hours, cooling to room temperature at a speed of 2 ℃/min after the reaction is finished, washing, drying and grinding a sample to obtain a catalyst strontium titanate SrTiO 3 。
Example 1
a. Accurately weighing 5.0mmol of strontium chloride, and grinding in a mortar for about 20min; putting 5.0mmol of sodium hydroxide into another mortar, and grinding respectively;
b. in addition, preparing a container containing 30mL of distilled water, adding the ground strontium chloride powder in the step a step by step and stirring, then adding the ground sodium hydroxide powder and continuously stirring, so that the formation of a white turbid liquid can be observed; slowly dripping 3.0mL of titanium trichloride into the suspension, and continuously stirring for about 30 min; then adding 0.5g of structure inducer ascorbic acid and 2.0mL of methanol in sequence, and continuously stirring for about 80min;
c. transferring the solution into a hydrothermal kettle, heating the hydrothermal kettle in an oven at 180 ℃ for 12 hours, cooling the reaction product to room temperature at a speed of 2 ℃/min after the reaction is finished, washing, drying and grinding a sample to obtain the nano microspherical perovskite catalyst strontium titanate SrTiO 3 。
Example 2
a. Accurately weighing 5.0mmol of strontium chloride, and grinding in a mortar for about 20min; putting 5.0mmol of sodium hydroxide into another mortar, and grinding respectively;
b. in addition, preparing a container containing 30mL of distilled water, adding the ground strontium chloride powder in the step a step by step and stirring, then adding the ground sodium hydroxide powder and continuously stirring, so that the formation of a white turbid liquid can be observed; slowly dripping 3.0mL of titanium trichloride into the suspension, and continuously stirring for about 30 min; then adding 1.0g of structure inducer ascorbic acid and 2.0mL of methanol in sequence, and continuously stirring for about 80min;
c. transferring the solution into a hydrothermal kettle, heating the hydrothermal kettle in an oven at 180 ℃ for 12 hours, cooling the reaction product to room temperature at a speed of 2 ℃/min after the reaction is finished, washing, drying and grinding a sample to obtain the nano microspherical perovskite catalyst strontium titanate SrTiO 3 。
Example 3
a. Accurately weighing 5.0mmol of strontium chloride, and grinding in a mortar for about 20min; putting 5.0mmol of sodium hydroxide into another mortar, and grinding respectively;
b. in addition, preparing a container containing 30mL of distilled water, adding the ground strontium chloride powder in the step a step by step and stirring, then adding the ground sodium hydroxide powder and continuously stirring, so that the formation of a white turbid liquid can be observed; slowly dripping 3.0mL of titanium trichloride into the suspension, and continuously stirring for about 30 min; then adding 1.5g of structure inducer ascorbic acid and 2.0mL of methanol in sequence, and continuously stirring for about 80min;
c. transferring the solution into a hydrothermal kettle, heating the hydrothermal kettle in an oven at 180 ℃ for 12 hours, cooling the reaction product to room temperature at a speed of 2 ℃/min after the reaction is finished, washing, drying and grinding a sample to obtain the nano microspherical perovskite catalyst strontium titanate SrTiO 3 。
Test example 1
The catalyst prepared in example 1 was used in nitric oxide removal applications, and the specific procedure was as follows:
1. accurately weighing 50.0mg of the catalyst prepared in the embodiment 1, putting the catalyst into a culture dish with the diameter of 6.0cm, adding deionized water, performing ultrasonic treatment to obtain uniform and stable suspension, and putting the suspension into an oven to be dried at the temperature of 60 ℃; under the condition of light-shielding, placing the dried sample and container together in a reactor, sealing and vacuumizing, at the same time introducing a certain proportion of NO standard gas (13.0X10) -6 ) And 99.9999% high purity air to control the NO concentration at 500ppb; then, the sample in the reactor is protected from light for 30min, so that the surface of the sample fully absorbs NO gas, the adsorption-desorption balance is waited to be established, and the temperature is kept at the room temperature of 25 ℃ in the whole process;
2. after the system is balanced, the balance system established in the step 1 is irradiated with visible light (xenon lamp, lambda is more than or equal to 420 nm) from the upper part, the system is 15cm away from the outlet of the xenon lamp, and a group of NO is read from the NOx analyzer every 1min 2 And NOx concentration variation data;
3. taking out the reacted powder sample, weighing, adding distilled water and ultrasonic treatment for 80min to disperse uniformly, filtering with 0.45 μl microporous membrane, collecting supernatant, testing ion chromatography, and analyzing nitric acid (NO) as oxidation product after photocatalytic oxidation of NO 3 — ) And calculate the corresponding conversion.
The removal rate of NO by the catalyst obtained in example 1 was 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 procedure was as follows:
1. accurately weighing 50.0mg of the catalyst prepared in the embodiment 2, placing the catalyst in a culture dish with the diameter of 6.0cm, adding deionized water, performing ultrasonic treatment to obtain uniform and stable suspension, and placing the suspension in an oven to be dried at the temperature of 60 ℃; under the condition of light-shielding, placing the dried sample and container together in a reactor, sealing and vacuumizing, at the same time introducing a certain proportion of NO standard gas (13.0X10) -6 ) And 99.9999% high purity air to control the NO concentration at 500ppb; then the sample in the reactor is protected from light for 30min, so that the surface of the sample is fully absorbedCollecting NO gas, waiting for the establishment of adsorption-desorption balance, and keeping the temperature at room temperature of 25 ℃ in the whole process;
2. after the system is balanced, the balance system established in the step 1 is irradiated with visible light (xenon lamp, lambda is more than or equal to 420 nm) from the upper part, the system is 15cm away from the outlet of the xenon lamp, and a group of NO is read from the NOx analyzer every 1min 2 And NOx concentration variation data;
3. taking out the reacted powder sample, weighing, adding distilled water and ultrasonic treatment for 80min to disperse uniformly, filtering with 0.45 μl microporous membrane, collecting supernatant, testing ion chromatography, and analyzing nitric acid (NO) as oxidation product after photocatalytic oxidation of NO 3 — ) And calculate the corresponding conversion.
The removal rate of NO by the catalyst obtained in example 2 was as follows:
Figure SMS_1
Figure SMS_2
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, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (8)

1. A method for preparing a defect-containing nano-microsphere perovskite catalyst, the method comprising the steps of:
(1) Respectively mixing a strontium source, an alkali source, a titanium source and a structure inducer into the 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 strontium titanate SrTiO serving as the nano microsphere perovskite catalyst containing defects 3 ；
In the step (1), the structure inducer is selected from ascorbic acid, and the organic solvent is selected from methanol, ethanol and isopropanol;
the chemical composition of the catalyst is strontium titanate SrTiO 3 The catalyst has a microsphere structure, the diameter of the microsphere is 50-500nm, and the surface of the catalyst contains oxygen vacancies;
the mol mass ratio mmol of the strontium source to the structure inducer is 1:0.5-5;
the mol ratio of the strontium source to the water is 1-5:30;
the volume ratio of the water to the organic solvent is 15-30:1;
the titanium source is selected from titanium trichloride;
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 an organic solvent, and stirring again.
2. The preparation method according to claim 1, wherein in the step (1), the strontium source, the alkali source and the titanium source are subjected to grinding treatment before mixing, and the grinding treatment time is 10-50min.
3. The process according to claim 1, wherein in step (1), the strontium source is selected from the group consisting of strontium carbonate, strontium nitrate, strontium chloride; the alkali source is selected from sodium hydroxide, potassium hydroxide and lithium hydroxide.
4. The method of claim 1, wherein in step (1), the molar ratio of the strontium source to the titanium source is 1:1;
the molar ratio of the strontium source to the alkali source is 1:1.
5. The production method according to claim 1, wherein in the step (2), theThe solvothermal reaction temperature is 120-180 DEG o And C, the solvothermal reaction time is 12-36h.
6. The preparation method of claim 1, wherein the preparation method of the catalyst comprises 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 to powder;
sequentially and slowly adding strontium chloride powder and sodium hydroxide powder into distilled water and stirring;
under the condition of stirring, slowly dripping titanium trichloride, and continuing stirring;
under the condition of stirring, slowly dripping the ascorbic acid, and continuing stirring;
then gradually adding methanol into the solution to stir again;
and carrying out solvothermal reaction to obtain the nano microsphere perovskite catalyst containing the defects.
7. A defect-containing nano-microspheroidal perovskite catalyst prepared according to the method of any one of claims 1 to 6.
8. The use of a defect-containing nano-microspheroidal perovskite catalyst according to claim 7 for photocatalytic removal of nitric oxide.
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