CN114260009A - Precious metal loaded double-shell asymmetric semiconductor material and super-assembly method thereof - Google Patents
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Abstract
The invention belongs to the technical field of materials, and provides a noble metal loaded double-shell asymmetric semiconductor material and a super-assembly method thereof2And (3) a layer. Finally, calcining the obtained intermediate with the sandwich structure to remove the VPFs frame to obtain the noble metal loaded double-shell TiO with the asymmetric structure2@NM@TiO2A nano vase. The invention successfully designs and constructs the noble metal loaded double-shell asymmetric TiO by adopting a simple and flexible template-assisted interface super-assembly strategy2@NM@TiO2Semiconductor material, resulting nobleMetal-loaded double-shell asymmetric TiO2@NM@TiO2Semiconductor material is compared with pure TiO2@TiO2The semiconductor material has a wider visible light absorption range and higher photocurrent response intensity, and has wide application prospects in the fields of environment, catalysis, energy, micro-nano motors, biomedicine and the like.
Description
Technical Field
The invention belongs to the technical field of materials, and particularly relates to a noble metal loaded double-shell asymmetric semiconductor material and a super-assembly method thereof.
Background
TiO2Is a model material for photocatalytic research, has attracted extensive attention of researchers all over the world since being applied to research on photo (electro) catalytic water decomposition by japanese scientists for the first time in 1972, and is one of the most widely researched semiconductor oxides at present. Which is a typical n-type semiconductor material, TiO2Because of the advantages of no toxicity, good stability, low cost, large surface area, large pore volume, excellent photoelectric property and the like, the catalyst has wide application in various energy and environmental fields such as catalytic degradation, sterilization, disinfection, hydrogen production by photolysis of water and the like. TiO 22The photocatalytic performance of (a) depends to a large extent on the morphology of the catalyst. To date, nano TiO2The preparation of materials has made great progress. In various shapes, TiO with a multi-shell hollow structure2Semiconductor materials are more and more emphasized by people, and the main reason is that the unique multi-shell structure is beneficial to repeated refraction and scattering of light, so that the utilization rate of the light can be greatly improved, and the catalytic reaction of active centers on the surface of a catalyst is accelerated.
But pure TiO2The semiconductor material has low photocatalytic efficiency due to the defects of high photon-generated carrier recombination rate, few active sites and the like, so that a cocatalyst needs to be introduced to improve the reaction performance. Due to the advantages of low Fermi level, high stability, reduction of reaction overpotential and the like, the noble metal-based nano material is widely researched and reported as the most common and efficient cocatalyst, but the large-scale application of the noble metal-based photocatalytic material is limited by the high cost and low natural abundance of the noble metal. Based on the current situation, the method seeks for the high-efficiency loading of the multi-shell TiO by the noble metal2The method of preparing the material is a significant challenge.
Disclosure of Invention
The invention aims to solve the defects of the prior art, provide a simple and flexible template auxiliary interface super-assembly strategy and realize the precious gold with excellent performanceDouble-shell asymmetric TiO of load2@NM@TiO2The preparation of the semiconductor material fills the blank of the noble metal loaded multi-shell asymmetric oxide material.
The invention provides a super-assembly method of a noble metal loaded double-shell asymmetric semiconductor material, which is characterized by comprising the following steps: preparing a noble metal loaded carbon polymer framework VPFs @ NM by a microemulsion template method in a hydrothermal environment; step two, using the carbon polymer frame VPFs @ NM as a template, and depositing a layer of uniform amorphous TiO on the outer surface and the inner surface of the carbon polymer frame VPFs @ NM2Layer, intermediate TiO of sandwich structure2@VPFs@NM@TiO2(ii) a Step three, intermediate TiO of sandwich structure2@VPFs@NM@TiO2Calcining to remove VPFs frame to obtain noble metal loaded double-shell asymmetric semiconductor material TiO2@NM@TiO2。
The super-assembly method of the noble metal loaded double-shell asymmetric semiconductor material provided by the invention can also have the following characteristics: the specific operation of the first step is as follows: dissolving a template agent in water to form a uniform microemulsion system, adding a carbon source and a noble metal source, fully mixing and stirring, then placing the solution obtained by mixing and stirring in a reaction kettle, and reacting in an oven at 120-200 ℃ for 8-36 h to obtain the carbon polymer framework VPFs @ NM.
The super-assembly method of the noble metal loaded double-shell asymmetric semiconductor material provided by the invention can also have the following characteristics: wherein the carbon polymer framework VPFs @ NM is in a bottle-shaped open structure and is rich in hydrophilic functional groups.
The super-assembly method of the noble metal loaded double-shell asymmetric semiconductor material provided by the invention can also have the following characteristics: wherein the carbon source is any one or more of ribose, arabinose or phenolic resin; the template agent is formed by self-assembling a triblock copolymer and an organic sodium salt according to a molar ratio of 1: 2-32; the noble metal source is one or more of chloroauric acid, chloroplatinic acid, chloroiridic acid and chlororhodic acid.
The super-assembly method of the noble metal loaded double-shell asymmetric semiconductor material provided by the invention can also have the following characteristics: wherein the triblock copolymer is PEO20-PPO70-PEO20Or EO106-PO70-EO106The organic sodium salt is any one of sodium oleate, sodium stearate or sodium laurate, and the mass ratio of the noble metal source to the carbon source is 1: 1000-4000.
The super-assembly method of the noble metal loaded double-shell asymmetric semiconductor material provided by the invention can also have the following characteristics: wherein, the specific operation of the step two is as follows: dispersing the carbon polymer framework VPFs @ NM obtained in the step one in an ethanol solution, adding ammonia water and a titanium source, placing the mixture in an oil bath kettle at the temperature of 30-80 ℃ for reaction for 12-30 h, and obtaining an intermediate TiO of a sandwich structure2@VPFs@NM@TiO2。
The super-assembly method of the noble metal loaded double-shell asymmetric semiconductor material provided by the invention can also have the following characteristics: wherein, the specific operation of the third step is as follows: the intermediate TiO with the sandwich structure obtained in the second step2@VPFs@NM@TiO2Placing the mixture in a tubular furnace, heating the mixture from room temperature to 400-700 ℃ at a heating rate of 1-10 ℃/min in the air atmosphere, calcining the mixture, and keeping the temperature for 2-6 h to remove the VPFs frame to obtain the noble metal loaded double-shell asymmetric semiconductor material TiO2@NM@TiO2。
The invention also provides a noble metal loaded double-shell asymmetric semiconductor material which has the characteristics and is prepared by a super-assembly method of the noble metal loaded double-shell asymmetric semiconductor material.
The noble metal loaded double-shell asymmetric semiconductor material provided by the invention can also have the following characteristics: wherein the noble metal loaded double-shell asymmetric semiconductor material has a bottle-shaped structure with continuous double shells, the length of the bottle-shaped structure is 300nm-1 μm, and the double shells are double-layer TiO2Layer of, constituting TiO2TiO in the layer2The crystal structure of the noble metal particle is anatase type, and the noble metal particle grows between double shell layers。
The noble metal loaded double-shell asymmetric semiconductor material provided by the invention can also have the following characteristics: wherein, the thickness of the inner wall and the outer wall of the bottle-shaped structure is 20nm-120nm, and the length of the bottle neck is 100nm-500 nm.
Action and Effect of the invention
According to the noble metal loaded double-shell asymmetric semiconductor material and the super-assembly preparation method thereof, firstly, a noble metal loaded bottle-shaped open carbon polymer framework (VPFs @ NM) is prepared by a micro-emulsion template method in a hydrothermal environment, and then the VPFs @ NM containing rich hydrophilic functional groups is taken as a template, and uniform amorphous TiO is deposited on the outer surface and the inner surface of the VPFs @ NM2And (3) a layer. Finally, the obtained intermediate with the sandwich structure is calcined to remove the VPFs frame, and the noble metal loaded double-shell TiO with the unique asymmetric structure can be obtained2@NM@TiO2A nano vase. The invention successfully designs and constructs the noble metal loaded double-shell asymmetric TiO by adopting a simple and flexible template-assisted interface super-assembly strategy2@NM@TiO2Semiconductor material, resulting noble metal-loaded double-shelled asymmetric TiO2@NM@TiO2Semiconductor material is compared with pure TiO2@TiO2The semiconductor material has a higher visible light absorption range and higher photocurrent response intensity.
The invention has the following beneficial effects:
1) the invention relates to precious metal loaded double-shell asymmetric TiO constructed by a super-assembly method2@NM@TiO2The semiconductor material has the advantages of uniform size, small noble metal particle size, high dispersity, large specific surface area and multistage mesoporous structure, so that the transmission and separation efficiency of the photo-generated carriers of the material is remarkably improved. The photocurrent is pure double-shell TiO2@TiO2150-300% of the nano bottle.
2) The preparation method of the invention requires extremely low consumption of noble metal source, thus greatly reducing the preparation cost.
3) The preparation method provided by the invention is suitable for more noble metal sources, and can be combined according to application requirements, so that the application potential of the semiconductor material is greatly improved.
4) The method is a preparation method developed based on a super-assembly strategy, is simple to operate, has mild and easily-controlled reaction conditions, and has great industrial potential.
Drawings
FIG. 1 shows a double-shell asymmetric TiO compound in example 1 of the present invention2@Pt@TiO2Transmission electron microscope photos of the semiconductor material under different multiples;
FIG. 2 shows TiO in example 2 of the present invention2@Au@TiO2Transmission electron microscope photos under different multiples;
FIG. 3 is a double shell asymmetric TiO embodiment of the present invention2@Pt@TiO2、TiO2@Au@TiO2And TiO2@TiO2A solid ultraviolet contrast spectrum of the semiconductor material;
FIG. 4 is a double shell asymmetric TiO embodiment of the present invention2@Pt@TiO2、TiO2@Au@TiO2And TiO2@TiO2The photocurrent performance of the semiconductor material is compared with the spectrum.
Detailed Description
In order to make the technical means, the creation characteristics, the achievement purposes and the effects of the invention easy to understand, the following describes a noble metal loaded double-shell asymmetric semiconductor material and a super-assembly method thereof in detail with reference to the embodiments and the attached drawings.
The methods in the examples of the present invention are conventional methods unless otherwise specified, and the starting materials in the examples of the present invention are commercially available from public sources unless otherwise specified.
The invention relates to a super-assembly method of a noble metal loaded double-shell asymmetric semiconductor material, which specifically comprises the following steps:
step one, preparing a carbon polymer framework VPFs @ NM loaded with noble metal by a microemulsion template method in a hydrothermal environment. The specific operation is as follows:
dissolving a template agent in water to form a uniform microemulsion system, adding a carbon source and a noble metal source, fully mixing and stirring, then placing the solution obtained by mixing and stirring in a reaction kettle, and reacting in an oven at 120-200 ℃ for 8-36 h to obtain the carbon polymer framework VPFs @ NM.
Step two, using the carbon polymer frame VPFs @ NM as a template, and depositing a layer of uniform amorphous TiO on the outer surface and the inner surface of the carbon polymer frame VPFs @ NM2Layer, intermediate TiO of sandwich structure2@VPFs@NM@TiO2. The specific operation is as follows:
dispersing the carbon polymer framework VPFs @ NM obtained in the step one in an ethanol solution, adding ammonia water and a titanium source, placing the mixture in an oil bath kettle at the temperature of 30-80 ℃ for reaction for 12-30 h, and obtaining an intermediate TiO of a sandwich structure2@VPFs@NM@TiO2。
Step three, intermediate TiO of sandwich structure2@VPFs@NM@TiO2Calcining to remove VPFs frame to obtain noble metal loaded double-shell asymmetric semiconductor material TiO2@NM@TiO2. The specific operation is as follows:
the intermediate TiO with the sandwich structure obtained in the second step2@VPFs@NM@TiO2Placing the mixture in a tubular furnace, heating the mixture from room temperature to 400-700 ℃ at a heating rate of 1-10 ℃/min in the air atmosphere, calcining the mixture, and keeping the temperature for 2-6 h to remove the VPFs frame to obtain the noble metal loaded double-shell asymmetric semiconductor material TiO2@NM@TiO2。
The carbon polymer framework VPFs @ NM is a bottle-like open structure rich in hydrophilic functional groups.
The carbon source is any one or more of ribose, arabinose or phenolic resin. The titanium source was tetrabutyl titanate (TBOT). The template agent is formed by self-assembling a triblock copolymer and an organic sodium salt according to the molar ratio of 1: 2-32.
The noble metal source is one or more of chloroauric acid, chloroplatinic acid, chloroiridic acid and chlororhodic acid. In the following examples, only chloroauric acid and chloroplatinic acid are described as examples, and other noble metal sources can achieve the same technical effects as chloroauric acid and chloroplatinic acid.
Three-embedded typeThe segmented copolymer is PEO20-PPO70-PEO20Or EO106-PO70-EO106The organic sodium salt is any one of sodium oleate, sodium stearate or sodium laurate, and the mass ratio of the noble metal source to the carbon source is 1: 1000-4000.
The prepared noble metal loaded double-shell asymmetric semiconductor material has a bottle-shaped structure with continuous double shells, the length (namely the length from a bottle opening to a bottle bottom) is 300nm-1 mu m, and the double shells are double-layer TiO2Layer of, constituting TiO2TiO in the layer2The crystal structure of the noble metal particle is anatase type, and the noble metal particle grows between double shell layers. The thickness of the inner wall and the outer wall of the bottle-shaped structure is 20nm-120nm, and the length of the bottle neck is 100nm-500 nm.
< example 1>
This example is for double shell asymmetric TiO2@Pt@TiO2The preparation and structure of the semiconductor material are described in detail. Double-shell asymmetric TiO2@Pt@TiO2The assembling method of the semiconductor material specifically comprises the following steps:
the method comprises the following steps: pt-supported carbon polymer frameworks (VPFs @ Pt) were prepared by a microemulsion template method in a hydrothermal environment. The specific process is as follows:
0.12mmol SO and 0.0075mmol P123 were first stirred in 40mL-100mL deionized water until it became a clear solution. Then slowly adding 1-5.00 g of ribose, 1-100 mg of phenolic resin and 1-5 mg of chloroplatinic acid, and stirring at room temperature for 0.5-2 h. Subsequently, the resulting solution was transferred to an autoclave (100mL) and subjected to hydrothermal treatment at 120 ℃ to 200 ℃ for 8h to 36 h. And finally, cooling the high-pressure kettle to room temperature, collecting precipitates through centrifugation, washing the precipitates three times by using deionized water, and drying the precipitates in a 60 ℃ drying oven to obtain VPFs @ Pt, wherein the VPFs @ Pt contains rich hydrophilic functional groups.
Step two: VPFs @ Pt containing abundant hydrophilic functional groups is used as a template, and amorphous TiO which is uniform grows on the outer surface and the inner surface of the VPFs @ Pt2And (3) a layer. The specific process is as follows:
first 10mg-100mg VPFs @ Pt was dispersed in 100ml ethanol, followed by NH3·H2O (0.30ml, 28 wt.%) was addedAdding the suspension into a suspension, performing ultrasonic treatment for 5-30 min, quickly adding 0.4-2 mL of TBOT, heating to reflux reaction at 25-80 ℃ for 12-30 h, performing centrifugal separation, washing with ethanol and deionized water for three times, and freeze-drying to obtain the product with TiO2@VPFs@Pt@TiO2Sandwich structured brown powder.
Step three, the obtained TiO2@VPFs@Pt@TiO2The intermediate of the sandwich structure is subjected to a calcination treatment to remove the VPFs framework. The specific process is as follows:
adding TiO into the mixture2@VPFs@Pt@TiO2Placing the powder in a tube furnace, calcining for 2-6 h at 450-600 ℃ in air atmosphere at the heating rate of 1-10 ℃/min to remove VPFs and improve the crystallinity to obtain the double-shell asymmetric TiO2@Pt@TiO2A semiconductor material.
FIGS. 1(a-d) are TiO prepared in example 12@Pt@TiO2Transmission Electron Microscopy (TEM) pictures. As can be seen from the electron micrograph of FIG. 1, the synthesized TiO2@Pt@TiO2The intermediate material has uniform size, is a uniform double-shell asymmetric bottle-shaped structure, has a bottle body diameter of about 400-500 nm, and has Pt particles supported on TiO2The size of Pt particles on the inner wall between the two shells is about 2nm-4 nm.
FIG. 3 is the solid state ultraviolet spectrum (DRS) of the material with the light gray line for the double shell asymmetric TiO prepared in example 12@Pt@TiO2DRS spectra of semiconductor materials, from which it can be seen that the materials compare to pure TiO2@TiO2A material having a broader visible light absorption range.
FIG. 4 is a photo-electric flow chart of the material with light gray line for the double-shell asymmetric TiO prepared in example 12@Pt@TiO2The photoelectric flow spectrum of the semiconductor material can be seen as that the photocurrent response value of the material is pure TiO2@TiO23 times the material.
< example 2>
This example is for double shell asymmetric TiO2@Au@TiO2The preparation and structure of the semiconductor material are described in detail. Double-shell asymmetric TiO2@Au@TiO2The assembling method of the semiconductor material specifically comprises the following steps:
step one, preparing an Au-loaded carbon polymer framework (VPFs @ Au) by a microemulsion template method in a hydrothermal environment. The specific process is as follows:
0.12mmol SO and 0.0075mmol P123 were first stirred in 40mL-100mL deionized water until it became a clear solution. Then slowly adding 1-5.00 g of ribose, 1-100 mg of phenolic resin and 1-5 mg of chloroauric acid, and stirring at room temperature for 0.5-2 h. Subsequently, the resulting solution was transferred to an autoclave (100mL) and subjected to hydrothermal treatment at 120 ℃ to 200 ℃ for 8h to 36 h. And finally, cooling the high-pressure kettle to room temperature, collecting precipitates through centrifugation, washing the precipitates three times by using deionized water, and drying the precipitates in a 60 ℃ drying oven to obtain VPFs @ Pt which contains rich hydrophilic functional groups.
Step two, taking VPFs @ Au containing abundant hydrophilic functional groups as a template, and growing uniform amorphous TiO on the outer surface and the inner surface of the VPFs @ Au2And (3) a layer. The specific process is as follows:
first 10mg-100mg VPFs @ Au were dispersed in 100ml ethanol, followed by NH3·H2Adding O (0.30mL, 28 wt%) into the suspension, performing ultrasonic treatment for 5min-30min, rapidly adding 0.4mL-2mL TBOT, heating to reflux reaction at 25-80 deg.C for 12h-30h, centrifuging, washing with ethanol and deionized water for three times, and lyophilizing to obtain the final product with TiO2@VPFs@Au@TiO2Sandwich structured brown powder.
Step three, the obtained TiO2@VPFs@Au@TiO2The intermediate of the sandwich structure is subjected to a calcination treatment to remove the VPFs framework. The specific process is as follows:
adding TiO into the mixture2@VPFs@Au@TiO2Placing the powder in a tube furnace, calcining for 2-6 h at 400-600 ℃ in air atmosphere at the heating rate of 1-10 ℃/min to remove VPFs and improve the crystallinity to obtain the double-shell asymmetric TiO2@Au@TiO2A semiconductor material.
FIGS. 2(a-d) are TiO prepared in example 22@Au@TiO2Transmission Electron Microscopy (TEM) pictures. As can be seen from the electron micrograph of FIG. 2, the resultantOf TiO 22@Au@TiO2The intermediate material has uniform size, is a uniform double-shell asymmetric bottle-shaped structure, has a bottle body diameter of about 400-500 nm, and Au particles are loaded on TiO2The Au particle size on the inner wall between the double shells is about 6nm-12 nm.
FIG. 3 is the solid state ultraviolet spectrum (DRS) of the material with dark grey lines for the double shell asymmetric TiO prepared in example 22@Au@TiO2DRS spectra of semiconductor materials, from which it can be seen that the materials compare to pure TiO2@TiO2A material having a broader visible light absorption range and having a distinct surface plasmon resonance absorption peak.
FIG. 4 is a photo-electric flow chart of the material with dark gray line of the double-shell asymmetric TiO prepared in example 22@Au@TiO2The photoelectric flow spectrum of the semiconductor material can be seen as that the photocurrent response value of the material is pure TiO2@TiO21.5 times of the material.
Effects and effects of the embodiments
TiO according to embodiments of the present invention2@Pt@TiO2、TiO2@Au@TiO2The material and the super-assembly preparation method thereof successfully design and construct the noble metal loaded double-shell asymmetric TiO by adopting a simple and flexible template-assisted interface super-assembly strategy2@NM@TiO2Semiconductor material, wherein NM is Pt and Au noble metal respectively. Preparing a noble metal loaded asymmetric bottle-shaped open carbon polymer frame (VPFs @ NM) by a microemulsion template method, and depositing uniform amorphous TiO on the outer surface and the inner surface of the VPFs @ NM by taking organic titanium as a titanium source, the VPFs @ NM frame as a template, ammonia water as a catalyst2And (3) a layer. Finally, removing the VPFs frame by roasting to obtain the noble metal loaded double-shell layer asymmetric TiO2@NM@TiO2A semiconductor material. The prepared semiconductor material is a double-shell bottle-shaped structure with uniform size, the specific surface area is large, the aperture distribution range is wide, and the light absorption range can be expanded to visible light, so that the photoelectric conversion efficiency of the material is remarkably improved. Purer TiO2@TiO2The semiconductor material has higher visible light absorptionRange, with higher photocurrent response intensity.
The embodiment of the invention has the advantages that:
1) noble metal loaded double-shell asymmetric TiO constructed by super-assembly method2@NM@TiO2The semiconductor material has the advantages of uniform size, small noble metal particle size, high dispersity, large specific surface area and multistage mesoporous structure, so that the transmission and separation efficiency of the photo-generated carriers of the material is remarkably improved. The photocurrent is pure double-shell TiO2@TiO2150-300% of the nano bottle.
2) The preparation method has the advantages of low consumption of noble metal source and greatly reduced preparation cost.
3) The variety of the applicable noble metal sources is more, and the noble metal sources can be combined according to the application requirements, so that the application potential of the semiconductor material is greatly improved.
4) The preparation method developed based on the super-assembly strategy is simple to operate, mild and easily controlled in reaction conditions, and has great industrial potential.
In conclusion, the preparation method is simple, raw materials are easy to obtain, reaction conditions are mild and easy to control, the method is suitable for large-scale production, and the method has a great application prospect in the fields of environment, catalysis, energy, micro-nano motors, biomedicine and the like.
The above embodiments are preferred examples of the present invention, and are not intended to limit the scope of the present invention.
Claims (10)
1. A super-assembly method of a noble metal loaded double-shell asymmetric semiconductor material is characterized by comprising the following steps:
preparing a noble metal loaded carbon polymer framework VPFs @ NM by a microemulsion template method in a hydrothermal environment;
step two, with the carbon polymer frame VPFs @ NM as a template, depositing a layer of uniform amorphous TiO on the outer surface and the inner surface of the carbon polymer frame VPFs @ NM2Layer, intermediate TiO of sandwich structure2@VPFs@NM@TiO2；
Step three, preparing the intermediate TiO of the sandwich structure2@VPFs@NM@TiO2Calcining to remove VPFs frame to obtain noble metal loaded double-shell asymmetric semiconductor material TiO2@NM@TiO2。
2. The method of super-assembling a noble metal supported double-shell asymmetric semiconductor material as claimed in claim 1, wherein:
the specific operation of the first step is as follows: dissolving a template agent in water to form a uniform microemulsion system, adding a carbon source and a noble metal source, fully mixing and stirring, then placing the solution obtained by mixing and stirring in a reaction kettle, and reacting in an oven at 120-200 ℃ for 8-36 h to obtain the carbon polymer framework VPFs @ NM.
3. The method of super-assembling a noble metal supported double-shell asymmetric semiconductor material as claimed in claim 2, wherein:
wherein the carbon polymer framework VPFs @ NM is in a bottle-shaped open structure and is rich in hydrophilic functional groups.
4. The method of super-assembling a noble metal supported double-shell asymmetric semiconductor material as claimed in claim 2, wherein:
wherein the carbon source is any one or more of ribose, arabinose or phenolic resin;
the template agent is formed by self-assembling a triblock copolymer and an organic sodium salt according to a molar ratio of 1: 2-32;
the noble metal source is any one or more of chloroauric acid, chloroplatinic acid, chloroiridic acid and chlororhodic acid.
5. The method of super-assembling a noble metal supported double-shell asymmetric semiconductor material as claimed in claim 4, wherein:
wherein the triblock copolymer is PEO20-PPO70-PEO20Or EO106-PO70-EO106，
The organic sodium salt is any one of sodium oleate, sodium stearate or sodium laurate,
the mass ratio of the noble metal source to the carbon source is 1: 1000-4000.
6. The method of super-assembling a noble metal supported double-shell asymmetric semiconductor material as claimed in claim 1, wherein:
wherein, the specific operation of the step two is as follows: dispersing the carbon polymer framework VPFs @ NM obtained in the step one in an ethanol solution, adding ammonia water and a titanium source, placing the mixture in an oil bath kettle at the temperature of 30-80 ℃ for reaction for 12-30 h, and obtaining the intermediate TiO of the sandwich structure2@VPFs@NM@TiO2。
7. The method of super-assembling a noble metal supported double-shell asymmetric semiconductor material as claimed in claim 1, wherein:
wherein, the specific operation of the third step is as follows: the intermediate TiO with the sandwich structure obtained in the second step2@VPFs@NM@TiO2Placing the mixture in a tubular furnace, heating the mixture from room temperature to 400-700 ℃ at a heating rate of 1-10 ℃/min in the air atmosphere, calcining the mixture, and keeping the temperature for 2-6 h to remove the VPFs frame to obtain the noble metal loaded double-shell asymmetric semiconductor material TiO2@NM@TiO2。
8. A noble metal-loaded double-shell asymmetric semiconductor material, which is prepared by the super-assembly method of the noble metal-loaded double-shell asymmetric semiconductor material as claimed in any one of claims 1 to 7.
9. The noble metal-supported double-shell asymmetric semiconductor material of claim 8, wherein:
wherein the noble metal-loaded double-shell asymmetric semiconductor material has a bottle-shaped structure with continuous double shells, the length of the bottle-shaped structure is 300nm-1 mu m, and the double shells are double-layer TiO2Layer of the said TiO2In the layerOf TiO 22The crystal structure of (A) is anatase type, and the noble metal particles grow between the double shell layers.
10. The noble metal-supported double-shell asymmetric semiconductor material of claim 9, wherein:
wherein, the thickness of the inner wall and the outer wall of the bottle-shaped structure is 20nm-120nm, and the length of the bottle neck is 100nm-500 nm.
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