CN112044426B - Barium titanate/potassium niobate composite piezoelectric photocatalyst, preparation method and application thereof - Google Patents

Barium titanate/potassium niobate composite piezoelectric photocatalyst, preparation method and application thereof Download PDF

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CN112044426B
CN112044426B CN202011112614.0A CN202011112614A CN112044426B CN 112044426 B CN112044426 B CN 112044426B CN 202011112614 A CN202011112614 A CN 202011112614A CN 112044426 B CN112044426 B CN 112044426B
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batio
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申国栋
张雨晗
樊威
孙润军
贺超
刘慧景
董子靖
董洁
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Xian Polytechnic University
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Abstract

The invention discloses a barium titanate/potassium niobate composite piezoelectric photocatalyst, a preparation method and application thereof, and belongs to the field of material preparation. The barium titanate/potassium niobate composite piezoelectric photocatalyst of the invention is BaTiO with a grain size of 30-50nm 3 The nanospheres are uniformly distributed on the prism-shaped KNbO 3 And the stability is better, and the piezoelectric photocatalytic activity is excellent. The preparation method of the barium titanate/potassium niobate composite piezoelectric photocatalyst has the advantages of easily available raw materials, simple preparation method process and convenient operation. The application of the barium titanate/potassium niobate composite piezoelectric photocatalyst can improve the degradation rate of organic dye based on the piezoelectric effect and the photocatalytic effect.

Description

Barium titanate/potassium niobate composite piezoelectric photocatalyst, preparation method and application thereof
Technical Field
The invention belongs to the field of material preparation, and particularly relates to a barium titanate/potassium niobate composite piezoelectric photocatalyst, and a preparation method and application thereof.
Background
In recent years, the photocatalysis technology is taken as a novel green environment treatment technology, and has a good application prospect in the aspects of solving energy and environmental problems and the like. The traditional photocatalyst has low photocatalytic activity due to low utilization rate of sunlight and high recombination rate of photo-induced electron hole pairs. Piezoelectric photocatalysis means that when a piezoelectric body is subjected to external mechanical force, a material deforms, and the polarization state changes, so that a built-in electric field is formed in the material, the electric field can effectively promote effective separation of photogenerated charges, but a static built-in electric field is easy to saturate free carriers due to electrostatic shielding, and the separation efficiency of polarization on the carriers is reduced. Therefore, the key problem in the development of the field is to improve the strength of the built-in electric field by using the piezoelectric effect and ensure the continuous regeneration of the built-in electric field to promote the separation of photogenerated carriers in the photocatalytic reaction process.
KNbO 3 As a typical piezoelectric material, has a high piezoelectric constant (d) 33 And =80 pC/N), under the conditions of periodic ultrasonic vibration and illumination, the material generates micro deformation and polarization to form a piezoelectric potential, so that a recombination path of a photon-generated carrier is inhibited, and the photocatalytic performance is improved. Furthermore, the ferroelectric material BaTiO 3 When the temperature is lower than the Curie temperature, spontaneous polarization is realized, a micro electric field is established in the crystal grains, so that holes or electrons generated during illumination are attracted by the electric field to be separated, and effectively migrate to the surface of the catalyst, and the recombination rate of the electron and the hole pair in the process is reduced; simultaneous ultrasonic vibration of causing BaTiO 3 The intensity of polarized electric field in the crystal grains is weakened, thereby eliminating the saturation of the built-in electric field and promoting the continuous separation of electrons and holes. In the process of photocatalytic explanation of organic pollutants, piezoelectric materials and ferroelectric materials with spontaneous polarization have great development potential in the aspect of inhibiting the recombination of photon-generated carriers by constructing a built-in electric field.
Therefore, in order to improve the photocatalytic activity of the existing piezoelectric material, baTiO is adopted in the invention 3 With KNbO 3 In a composite mode, the BaTiO is prepared for the first time 3 /KNbO 3 The composite piezoelectric photocatalyst improves the piezoelectric photocatalytic performance of the material.
Disclosure of Invention
The invention aims to overcome the defects of weak built-in electric field intensity, low photocatalytic activity and the like of the conventional piezoelectric material, and provides a barium titanate/potassium niobate composite piezoelectric photocatalyst, a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:
BaTiO 3 /KNbO 3 Composite piezoelectric photocatalyst BaTiO with grain size of 30-50nm 3 The nanospheres are uniformly distributed on the prism-shaped KNbO 3 The above.
Further, in the BaTiO 3 /KNbO 3 In the composite piezoelectric photocatalyst, baTiO 3 With KNbO 3 The molar ratio of (9.
BaTiO 3 /KNbO 3 The preparation method of the composite piezoelectric photocatalyst comprises the following steps:
1) Preparation of nano-spherical BaTiO 3 Powder, preparation of prismatic KNbO 3 Powder;
2) With said BaTiO 3 Powder and KNbO 3 The powder is used as raw material to prepare BaTiO by hydrothermal method 3 /KNbO 3 A composite piezoelectric photocatalyst.
Further, preparing nano spherical BaTiO in the step 1) 3 The specific operation of the powder is as follows:
in BaCl 2 ·2H 2 Dropwise adding TiCl into the O solution 4 Stirring the solution until the solution is transparent;
then adding NaOH mineralizer, uniformly mixing, transferring the mixed solution into a hydrothermal reaction kettle, and carrying out hydrothermal reaction for 12 hours at the temperature of 140-180 ℃;
after the reaction is finished, washing and drying to obtain BaTiO 3 And (3) powder.
Further, in the mixed solution, baCl 2 ·2H 2 The concentration of O is 0.1 to 0.5mol/L, tiCl 4 The concentration is 0.5-0.8 mol/L, and the concentration of NaOH is 3-6 mol/L.
Further, preparing the prism-shaped KNbO in the step 1) 3 The specific operation of the powder is as follows:
adding Nb into KOH solution 2 O 5 Uniformly mixing the powder to obtain a reaction solution, transferring the reaction solution into a hydrothermal reaction kettle, and carrying out hydrothermal reaction for 12 hours at the temperature of 140-180 ℃;
washing and drying after the reaction is finished to obtain KNbO 3 And (3) powder.
Further, the KOH concentration in the reaction solution is 13 to 15mol/L, nb 2 O 5 The concentration is 3-5 mm/mol.
Further, baTiO is prepared in step 2) 3 /KNbO 3 Composite piezoelectric elementThe photocatalyst comprises the following specific steps:
201 The KNbO 3 Powder of the BaTiO compound 3 Dissolving the powder and sodium dodecyl sulfate in water, and stirring until the solution is clear and transparent;
the addition amount of the sodium dodecyl sulfate is KNbO 3 1% of the powder mass;
202 Transferring the clear and transparent solution to a hydrothermal reaction kettle, and carrying out hydrothermal reaction for 12h at 140-180 ℃;
203 ) washing and drying after the reaction to obtain BaTiO 3 /KNbO 3 A composite piezoelectric photocatalyst.
Further, baTiO 3 With KNbO 3 The molar ratio of (9.
BaTiO of the invention 3 /KNbO 3 The application of the composite piezoelectric photocatalyst is based on the synergistic degradation of organic dye by piezoelectric effect and photocatalytic effect.
Compared with the prior art, the invention has the following beneficial effects:
the barium titanate/potassium niobate composite piezoelectric photocatalyst of the invention is BaTiO with the grain diameter of 30-50nm 3 The nanospheres are uniformly distributed on the prismatic KNbO 3 Surface, baTiO 3 The nanosphere is uniformly coated with KNbO 3 The morphology of the photocatalyst promotes the separation of photon-generated carriers, reduces the recombination of the photon-generated carriers and further improves the photocatalytic performance from the following two aspects. On the one hand, band structure matched BaTiO 3 With KNbO 3 BaTiO with obvious size difference and easy formation of typical type II heterojunction 3 At KNbO 3 The uniform dispersion of the surface can not only effectively increase the area of a composite interface, but also ensure that the two materials obtain good combination fastness, and the generation of a large number of heterojunctions improves the generation of photon-generated carriers in BaTiO 3 /KNbO 3 The interface migration improves the photocatalytic performance of the composite material by promoting the separation of photon-generated carriers and reducing the recombination of the photon-generated carriers; on the other hand, structural defects formed on a composite interface of the traditional heterojunction material can become the center of secondary recombination of partial photon-generated carriers, and the improvement degree of the photocatalytic performance of the heterojunction is further weakened. BaTiO 2 3 And KNbO 3 The barium titanate/potassium niobate composite piezoelectric electro-optic catalytic material formed by the method can inhibit the secondary recombination of photon-generated carriers by utilizing a built-in electric field generated under the action of ultrasonic cavitation, and provides strong and long-term internal driving force for the separation and migration of the carriers. Thus, baTiO 3 Nanosphere uniformly coated KNbO 3 The prism composite structure has the advantages of good stability, excellent piezoelectric photocatalysis performance and the like.
Further, baTiO 3 With KNbO 3 When the molar ratio of (9.
The preparation method of the barium titanate/potassium niobate composite piezoelectric photocatalyst has the advantages of easily available raw materials, simple preparation method process and convenient operation.
The application of the barium titanate/potassium niobate composite piezoelectric photocatalyst can improve the degradation rate of organic dye based on the piezoelectric effect and the photocatalytic effect.
Drawings
FIG. 1 shows BaTiO of example 4 3 、KNbO 3 、BaTiO 3 /KNbO 3 XRD pattern of the composite photocatalyst;
FIG. 2 shows BaTiO of example 4 3 、KNbO 3 、BaTiO 3 /KNbO 3 SEM and EDS pictures of the composite photocatalyst;
FIG. 3 is BaTiO of example 4 3 、KNbO 3 、BaTiO 3 /KNbO 3 PFM picture of the composite photocatalyst;
FIG. 4 shows BaTiO of example 4 3 、KNbO 3 、BaTiO 3 /KNbO 3 The composite photocatalyst degrades a dye effect graph under a piezoelectric effect;
FIG. 5 shows BaTiO of example 4 3 、KNbO 3 、BaTiO 3 /KNbO 3 The composite photocatalyst is a dye degradation effect graph under the piezoelectric photocatalysis effect.
Detailed Description
In order to make the technical solutions of the present invention better understood, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, shall fall within the protection scope of the present invention.
It should be noted that the terms "first," "second," and the like in the description and claims of the present invention and in the drawings described above are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used is interchangeable under appropriate circumstances such that the embodiments of the invention described herein are capable of operation in other sequences than those illustrated or described herein. Moreover, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed, but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
The invention is described in further detail below with reference to the accompanying drawings:
example 1
1) Preparation of BaTiO 3 Powder and KNbO 3 Powder body
With 0.3mol/L of BaCl 2 ·2H 2 O is taken as precursor solution, and TiCl with the concentration of 0.6mol/L is added dropwise under the condition of continuous stirring 4 The solution was stirred until clear. Then adding 4mol/L NaOH mineralizer, stirring uniformly, quickly transferring the mixed solution into a hydrothermal reaction kettle, and carrying out hydrothermal reaction for 12h at 180 ℃. Naturally cooling the furnace to room temperature, taking out the reactant, neutralizing the reactant to be neutral by using acetic acid, washing the reactant for a plurality of times by using deionized water and alcohol, and drying the reactant to finally obtain BaTiO 3 And (3) powder.
Preparing 13mol/L KOH as precursor solution, stirring and cooling to room temperature, and adding 2mm/mol Nb under stirring 2 O 5 After stirring evenly, continuing to perform ultrasonic treatment for 10min, and stirring for 10min. Then the mixture is transferred to a hydrothermal reaction kettle and reacted for 12 hours at 140 ℃. After the furnace temperature is naturally cooled to room temperature, taking out the reactant, neutralizing the reactant to be neutral by using acetic acid, washing the reactant for a plurality of times by using deionized water and alcohol, and drying the reactant to finally obtain KNbO 3 And (3) powder.
2)BaTiO 3 /KNbO 3 Preparation of composite catalyst
First, 50mL of deionized water was taken and 0.018g of KNbO was added 3 Adding the powder, stirring for 15min, and performing ultrasonic treatment for 15min. Then adding Sodium Dodecyl Sulfate (SDS) with the mass fraction of 1%, stirring for 15min, and carrying out ultrasonic treatment for 15min. 0.2097g of BaTiO was continuously added with stirring 3 Stirring was continued for 4h until the solution was clear and transparent. Then the mixture is transferred into a hydrothermal reaction kettle and reacted for 12 hours at 180 ℃. Naturally cooling the furnace to room temperature, taking out the reactant, neutralizing the reactant to be neutral by using acetic acid, washing the reactant for a plurality of times by using deionized water and alcohol, and drying the reactant to finally obtain BaTiO 3 /KNbO 3 And (3) compounding a catalyst.
Example 2
1) Preparation of BaTiO3 powder and KNbO3 powder
With 0.3mol/L of BaCl 2 ·2H 2 O is taken as precursor solution, and TiCl with the concentration of 0.6mol/L is added dropwise under the condition of continuous stirring 4 The solution was stirred until clear. Then adding a 4mol/L NaOH mineralizer, stirring uniformly, quickly transferring the mixed solution into a hydrothermal reaction kettle, and carrying out hydrothermal reaction for 12 hours at 180 ℃. After the furnace temperature is naturally cooled to room temperature, taking out the reactant, neutralizing the reactant to be neutral by using acetic acid, washing the reactant for a plurality of times by using deionized water and alcohol, and drying the reactant to finally obtain BaTiO 3 And (3) powder.
Preparing 13mol/L KOH as precursor solution, stirring and cooling to room temperature, and adding 2mm/mol Nb under stirring 2 O 5 After stirring evenly, continuing to carry out ultrasonic treatment for 10min, and stirring for 10min. It is subsequently transferred to a hydrothermal reactionThe mixture is reacted in a kettle for 12 hours at 140 ℃. After the furnace temperature is naturally cooled to room temperature, taking out the reactant, neutralizing the reactant to be neutral by using acetic acid, washing the reactant for a plurality of times by using deionized water and alcohol, and drying the reactant to finally obtain KNbO 3 And (3) powder.
2) Preparation of BaTiO 3 /KNbO 3 Composite catalyst
First, 50mL of deionized water was taken and 0.054g of KNbO was added 3 Adding into the above mixture, stirring for 15min, and performing ultrasonic treatment for 15min. Then adding Sodium Dodecyl Sulfate (SDS) with the mass fraction of 1%, stirring for 15min, and carrying out ultrasonic treatment for 15min. 0.1631g of BaTiO was added with stirring 3 Stirring was continued for 4h until the solution was clear and transparent. Then the mixture is transferred into a hydrothermal reaction kettle and reacted for 12 hours at 180 ℃. Naturally cooling the furnace to room temperature, taking out the reactant, neutralizing the reactant to be neutral by using acetic acid, washing the reactant for a plurality of times by using deionized water and alcohol, and drying the reactant to finally obtain BaTiO 3 /KNbO 3 And (3) compounding a catalyst.
Example 3
1) Preparation of BaTiO 3 Powder and KNbO 3 Powder body
With 0.3mol/L of BaCl 2 ·2H 2 O is taken as a precursor solution, and TiCl with the concentration of 0.6mol/L is dropwise added under the condition of continuous stirring 4 The solution was stirred until clear. Then adding a 4mol/L NaOH mineralizer, stirring uniformly, quickly transferring the mixed solution into a hydrothermal reaction kettle, and carrying out hydrothermal reaction for 12 hours at 180 ℃. After the furnace temperature is naturally cooled to room temperature, taking out the reactant, neutralizing the reactant to be neutral by using acetic acid, washing the reactant for a plurality of times by using deionized water and alcohol, and drying the reactant to finally obtain BaTiO 3 And (3) powder.
Preparing 13mol/L KOH as a precursor solution, stirring and cooling to room temperature, and adding 2mm/mol Nb in a stirring state 2 O 5 After stirring evenly, continuing to carry out ultrasonic treatment for 10min, and stirring for 10min. Then the mixture is transferred to a hydrothermal reaction kettle and reacted for 12 hours at 140 ℃. Naturally cooling the furnace to room temperature, taking out the reactant, neutralizing the reactant to be neutral by using acetic acid, washing the reactant for a plurality of times by using deionized water and alcohol, and drying the reactant to finally obtain KNbO 3 And (3) powder.
2) Preparation of BaTiO 3 /KNbO 3 Composite catalyst
First, 50mL of deionized water was charged with 0.09g of KNbO 3 Adding into the above mixture, stirring for 15min, and performing ultrasonic treatment for 15min. Then adding Sodium Dodecyl Sulfate (SDS) with the mass fraction of 1%, stirring for 15min, and carrying out ultrasonic treatment for 15min. Continuously adding 0.1165g of BaTiO under stirring 3 Stirring was continued for 4h until the solution was clear and transparent. Then the mixture is transferred to a hydrothermal reaction kettle and reacted for 12 hours at 180 ℃. After the furnace temperature is naturally cooled to room temperature, taking out the reactant, neutralizing the reactant to be neutral by using acetic acid, washing the reactant for a plurality of times by using deionized water and alcohol, and drying the reactant to finally obtain BaTiO 3 /KNbO 3 And (3) compounding a catalyst.
Example 4
1) Preparation of BaTiO 3 Powder and KNbO 3 Powder body
With 0.3mol/L of BaCl 2 ·2H 2 O is taken as precursor solution, and TiCl with the concentration of 0.6mol/L is added dropwise under the condition of continuous stirring 4 The solution was stirred until clear. Then adding 4mol/L NaOH mineralizer, stirring uniformly, quickly transferring the mixed solution into a hydrothermal reaction kettle, and carrying out hydrothermal reaction for 12h at 180 ℃. Naturally cooling the furnace to room temperature, taking out the reactant, neutralizing the reactant to be neutral by using acetic acid, washing the reactant for a plurality of times by using deionized water and alcohol, and drying the reactant to finally obtain BaTiO 3 And (3) powder.
Preparing 13mol/L KOH as precursor solution, stirring and cooling to room temperature, and adding 2mm/mol Nb under stirring 2 O 5 After stirring evenly, continuing to carry out ultrasonic treatment for 10min, and stirring for 10min. Then the mixture is transferred to a hydrothermal reaction kettle and reacted for 12 hours at 140 ℃. Naturally cooling the furnace to room temperature, taking out the reactant, neutralizing the reactant to be neutral by using acetic acid, washing the reactant for a plurality of times by using deionized water and alcohol, and drying the reactant to finally obtain KNbO 3 And (3) powder.
2) Preparation of BaTiO 3 /KNbO 3 Composite catalyst
First, 50mL of deionized water was taken and 0.126g of KNbO was added 3 Adding into the above mixture, stirring for 15min, and performing ultrasonic treatment for 15min. Adding Sodium Dodecyl Sulfate (SDS) with mass fraction of 1%, stirring for 15min, and performing ultrasonic treatment for 15min. 0.0699g of BaTiO was continuously added with stirring 3 Stirring was continued for 4h until the solution was clear and transparent. Then the mixture is transferred to a hydrothermal reaction kettle and reacted for 12 hours at 180 ℃. Naturally cooling the furnace to room temperature, taking out the reactant, neutralizing the reactant to be neutral by using acetic acid, washing the reactant for a plurality of times by using deionized water and alcohol, and drying the reactant to finally obtain BaTiO 3 /KNbO 3 And (3) compounding a catalyst.
Referring to FIG. 1, FIG. 1 is BaTiO of example 4 3 、KNbO 3 、BaTiO 3 /KNbO 3 XRD pattern of the composite piezoelectric photocatalyst, as can be seen from FIG. 1, baTiO is compared with the unmixed sample 3 /KNbO 3 No new diffraction peak was generated after mixing, and all samples had BaTiO 3 And KNbO 3 The characteristic peak of the compound indicates that the BaTiO is successfully prepared 3 /KNbO 3 A composite photocatalyst. And following KNbO 3 The proportion is increased, the characteristic peaks of the XRD pattern at the positions of 21.98 degrees, 31.36 degrees, 38.64 degrees, 44.92 degrees, 50.58 degrees and 55.86 degrees are slightly changed to high angles, and BaTiO 3 Characteristic peak gradually towards KNbO 3 The characteristic peaks are transited, the characteristic peaks corresponding to the crystal faces are continuously enhanced, and the gradual change characteristics consistent with the component change are shown.
Referring to FIG. 2, FIG. 2 shows BaTiO of example 4 3 、KNbO 3 、BaTiO 3 /KNbO 3 Scanning Electron Microscope (SEM) of the composite piezoelectric photocatalyst, the appearance of the prepared material can be observed from the SEM picture of FIG. 2, and FIG. 2 (a) is nano spherical BaTiO 3 Powder, nanosphere with particle size of 30-50nm, and prism-shaped KNbO in FIG. 2 (c) 3 Powder, FIG. 2 (e) is a nano-spherical BaTiO 3 Growing on prismatic KNbO 3 From the above, it can be seen that the nanospheres are uniformly distributed without significant agglomeration. FIG. 2 (b), (d) and (f) are BaTiO, respectively 3 、KNbO 3 、BaTiO 3 /KNbO 3 EDS diagram of (B), detection shows BaTiO 3 The molar ratio of the Ba to the Ti is 19.25 3 The atomic ratio of Ba to Ti (1; KNbO 3 The molar ratio of the medium K to the Nb is 21.64 and is 20.07, and the ratio is close to KNbO 3 The atomic ratio of medium K and Nb (1; composite piezoelectric lightCatalyst BaTiO 3 /KNbO 3 In the above-mentioned sample, ba, ti, K, nb and O can be detected. EDS energy spectrum test proves that (b) and (d) are pure-phase BaTiO respectively 3 And KNbO 3 (f) is BaTiO 3 /KNbO 3 The result of the composite piezoelectric photocatalyst of (3) is consistent with XRD analysis.
Referring to FIG. 3, FIG. 3 is BaTiO of example 4 3 、KNbO 3 、BaTiO 3 /KNbO 3 The piezoelectricity of the material can be characterized through a Piezoelectric Force Microscope (PFM) graph of the composite piezoelectric photocatalyst, and the pure BaTiO is proved 3 、KNbO 3 And a composite piezoelectric photocatalyst BaTiO 3 /KNbO 3 The microscopic piezoelectric effect of (2). FIGS. 3 (a), (d) and (g) show BaTiO, respectively 3 、KNbO 3 And composite BaTiO 3 /KNbO 3 Showing the surface structure of different materials, consistent with SEM image analysis. However, unlike topographic images, piezoelectric image-representing materials have excellent piezoelectric properties. FIGS. 3 (b), (e) and (h) show BaTiO, respectively 3 、KNbO 3 And composite BaTiO 3 /KNbO 3 The amplitude diagrams of (a) and (c), (f) and (i) respectively represent BaTiO 3 、KNbO 3 And composite BaTiO 3/ KNbO 3 The phase diagram of (2) can more clearly observe areas of different brightness through a piezoelectric image, because of weak piezoelectric BaTiO 3 And a strong voltage KNbO 3 Is caused by the phase distribution of (a). In addition, the phase diagram shows that the piezoelectric domain has a good correlation with the phase, but does not show morphology, further confirming the piezoelectric effect of the material.
Referring to FIG. 4, FIG. 4 is BaTiO prepared in example 4 3 、KNbO 3 、0.3BaTiO 3 /0.7KNbO 3 Dye degradation effect diagram of the composite piezoelectric photocatalyst under the condition of ultrasonic vibration or not. As can be seen from FIG. 4, the degradation of the dye in the presence of ultrasonic vibration was significantly higher than that in the absence of ultrasonic vibration, the dye degradation effect was not significant in the absence of ultrasonic vibration, and 0.3BaTiO 3 /0.7KNbO 3 The composite piezoelectric photocatalyst has the best degradation effect.
Referring to FIG. 5, FIG. 5 is a graph of example 4Prepared BaTiO 3 、KNbO 3 、BaTiO 3 /KNbO 3 The dye degradation effect of the composite piezoelectric photocatalyst under the combined action of ultrasonic vibration and photocatalysis is shown. As can be seen from fig. 5, the degradation of the dye in the presence of ultrasonic vibration was significantly higher than that in the absence of ultrasonic vibration, and the dye degradation effect was not significant in the absence of ultrasonic vibration. In addition, the efficient degradation of the dye is due to the synergistic effect of light compared to fig. 4. From FIG. 5, 0.3BaTiO can also be obtained 3 /0.7KNbO 3 The degradation effect of the composite piezoelectric photocatalyst is far higher than that of other two single piezoelectric materials BaTiO 3 、KNbO 3 。
Example 5
1) Preparation of BaTiO 3 Powder and KNbO 3 Powder body
With 0.3mol/L of BaCl 2 ·2H 2 O is taken as precursor solution, and TiCl with the concentration of 0.6mol/L is added dropwise under the condition of continuous stirring 4 The solution was stirred until clear. Then adding a 4mol/L NaOH mineralizer, stirring uniformly, quickly transferring the mixed solution into a hydrothermal reaction kettle, and carrying out hydrothermal reaction for 12 hours at 180 ℃. Naturally cooling the furnace to room temperature, taking out the reactant, neutralizing the reactant to be neutral by using acetic acid, washing the reactant for a plurality of times by using deionized water and alcohol, and drying the reactant to finally obtain BaTiO 3 And (3) powder.
Preparing 13mol/L KOH as precursor solution, stirring and cooling to room temperature, and adding 2mm/mol Nb under stirring 2 O 5 After stirring evenly, continuing to perform ultrasonic treatment for 10min, and stirring for 10min. Then the mixture is transferred to a hydrothermal reaction kettle and reacted for 12 hours at 140 ℃. Naturally cooling the furnace to room temperature, taking out the reactant, neutralizing the reactant to be neutral by using acetic acid, washing the reactant for a plurality of times by using deionized water and alcohol, and drying the reactant to finally obtain KNbO 3 And (3) powder.
2) Preparation of BaTiO 3 /KNbO 3 Composite catalyst
First, 50mL of deionized water was taken and 0.162g of KNbO was added 3 Adding into the above mixture, stirring for 15min, and performing ultrasonic treatment for 15min. Then adding Sodium Dodecyl Sulfate (SDS) with the mass fraction of 1%, stirring for 15min, and carrying out ultrasonic treatment for 15min. Continuously adding the mixture under stirring0.0233g of BaTiO 3 Stirring was continued for 4h until the solution was clear and transparent. Then the mixture is transferred to a hydrothermal reaction kettle and reacted for 12 hours at 180 ℃. Naturally cooling the furnace to room temperature, taking out the reactant, neutralizing the reactant to be neutral by using acetic acid, washing the reactant for a plurality of times by using deionized water and alcohol, and drying the reactant to finally obtain BaTiO 3 /KNbO 3 And (3) compounding a catalyst.
The above-mentioned contents are only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited thereby, and any modification made on the basis of the technical idea of the present invention falls within the protection scope of the claims of the present invention.

Claims (10)

1. BaTiO 3 /KNbO 3 The composite piezoelectric photocatalyst is characterized in that BaTiO with the grain diameter of 30-50nm 3 The nanospheres are uniformly distributed on the prism-shaped KNbO 3 The above.
2. BaTiO according to claim 1 3 /KNbO 3 The composite piezoelectric photocatalyst is characterized in that the BaTiO 3 /KNbO 3 In the composite piezoelectric photocatalyst, baTiO 3 With KNbO 3 The molar ratio of (9.
3. BaTiO 3 /KNbO 3 The preparation method of the composite piezoelectric photocatalyst is characterized by comprising the following steps of:
1) Preparation of nano-spherical BaTiO 3 Powder, preparation of prismatic KNbO 3 Powder;
2) With said BaTiO 3 Powder and KNbO 3 The powder is used as raw material to prepare BaTiO by hydrothermal method 3 /KNbO 3 A composite piezoelectric photocatalyst.
4. The method according to claim 3, wherein the nano-sized spherical BaTiO is prepared in the step 1) 3 The specific operation of the powder is as follows:
in BaCl 2 ·2H 2 In O solutionDropwise adding TiCl 4 Stirring the solution until the solution is transparent;
then adding NaOH mineralizer, uniformly mixing, transferring the mixed solution into a hydrothermal reaction kettle, and carrying out hydrothermal reaction for 12 hours at the temperature of 140-180 ℃;
washing and drying after the reaction is finished to obtain BaTiO 3 And (3) powder.
5. The method according to claim 4, wherein the BaCl is present in a mixed solution 2 ·2H 2 O concentration is 0.1-0.5 mol/L, tiCl 4 The concentration is 0.5-0.8 mol/L, and the concentration of NaOH is 3-6 mol/L.
6. The method according to claim 3, wherein the prismatic KNbO is prepared in the step 1) 3 The specific operation of the powder is as follows:
adding Nb into KOH solution 2 O 5 Uniformly mixing the powder to obtain a reaction solution, transferring the reaction solution into a hydrothermal reaction kettle, and carrying out hydrothermal reaction for 12 hours at the temperature of 140-180 ℃;
washing and drying after the reaction is finished to obtain KNbO 3 And (3) powder.
7. The process according to claim 6, wherein the KOH concentration in the reaction solution is 13 to 15mol/L, and Nb is added 2 O 5 The concentration is 3-5 mm/mol.
8. The method according to claim 3, wherein BaTiO is prepared in the step 2) 3 /KNbO 3 The composite piezoelectric photocatalyst comprises the following specific steps:
201 The KNbO 3 Powder of the BaTiO compound 3 Dissolving the powder and sodium dodecyl sulfate in water, and stirring until the solution is clear and transparent;
the addition amount of the sodium dodecyl sulfate is KNbO 3 1% of the powder mass;
202 Transferring the clear and transparent solution to a hydrothermal reaction kettle, and carrying out hydrothermal reaction for 12 hours at 140-180 ℃;
203 ) washing and drying after the reaction to obtain BaTiO 3 /KNbO 3 A composite piezoelectric photocatalyst.
9. The method according to claim 8, wherein the BaTiO is 3 With KNbO 3 The molar ratio of (9.
10. BaTiO of claim 1 3 /KNbO 3 The application of the composite piezoelectric photocatalyst is characterized in that the organic dye is degraded based on the synergy of the piezoelectric effect and the photocatalytic effect.
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