CN109698075B - Multi-core single-shell structure Au @ mSiO2Composite microsphere, preparation method and application - Google Patents
Multi-core single-shell structure Au @ mSiO2Composite microsphere, preparation method and application Download PDFInfo
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- CN109698075B CN109698075B CN201810714733.XA CN201810714733A CN109698075B CN 109698075 B CN109698075 B CN 109698075B CN 201810714733 A CN201810714733 A CN 201810714733A CN 109698075 B CN109698075 B CN 109698075B
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- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
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Abstract
The invention relates to a multi-core single-shell structure Au @ mSiO2The preparation method comprises the steps of dissolving CTAB and sodium oleate in water, mixing uniformly, and adding AgNO3Standing, and adding HAuCl4Stirring the solution for reaction for 30-90 minutes to obtain a mixed solution a; slowly adding hydrochloric acid into the mixed solution a to continue stirring and reacting, and then adding an ascorbic acid solution to obtain a mixed solution b; step three, HAuCl is added4Adding the solution into aqueous solution of CTAB, mixing uniformly, and then adding NaBH4Soaking for 30-60min to obtain a mixed solution c; step four, adding the mixed solution b into the mixed solution c, standing, and centrifugally washing to obtain octahedral Au nanoparticles; adding Au particles into a CTAB solution, performing ultrasonic dispersion uniformly, and performing oil bath at constant temperature to obtain a mixed solution d; and step six, uniformly mixing TEOS and cyclohexane, dropwise adding into the mixed solution d, raising the temperature in an oil bath, carrying out magnetic stirring reaction, and carrying out centrifugal washing to obtain the product. The method is simple and has high efficiency.
Description
Technical Field
The invention belongs to the field of solar cells, and particularly relates to a multi-core single-shell Au @ mSiO2Composite microspheres, a preparation method and application thereof by using an encapsulation method.
Background
Today, energy problems are highlighted, and people pay attention to how to utilize sustainable and pollution-free solar energy. In recent years, the research on solar cells has gradually become increasingly popular, especially with new types of dye solar cells. However, as the research progresses, researchers have found that the properties of sensitized dye molecules are key factors affecting the generation and injection of electrons, and as a photosensitizer, a dye must have a strong absorption band as wide as possible in the visible light region to enhance the absorption of visible light. The dye absorption spectrum should match the solar spectrum as closely as possible. However, the absorption range of dyes is limited, and researchers have looked to the surface plasmon effect of gold nanoparticles in order to increase the absorption of light by the dye molecules.
As is known, the gold nanoparticles have an absorption peak in the visible light range at about 520nm, and have a surface plasmon effect, so that the absorption of the dye to light can be enhanced. Researchers have therefore placed gold nanoparticles on dye-sensitized solar cells. But bare gold particles are attached to the TiO2The surface of the nano-particles is easy to form a recombination center of electrons, so that the electrons are not easy to be conducted to an external circuit, the photoelectric conversion efficiency is reduced, and meanwhile, the surface of the nano-particles is long-timeThe gold nanoparticles may also be corroded by the electrolyte solution.
Disclosure of Invention
The invention aims to provide a multi-core single-shell structure Au @ mSiO2Composite microspheres, a preparation method and application of the composite microspheres by a packaging method.
In order to realize the technical problem, the technical scheme adopted by the invention is to prepare the Au @ mSiO with the multi-core-single-shell structure by a packaging method2The composite microsphere is characterized by comprising the following steps:
step one, dissolving CTAB and sodium oleate in water, mixing uniformly, and adding AgNO3Standing, and adding HAuCl4Stirring the solution for reaction for 30-90 minutes to obtain a mixed solution a;
step two, slowly adding hydrochloric acid into the mixed solution a obtained in the step one to continue stirring and reacting, and then adding an ascorbic acid solution to obtain a mixed solution b;
step three, HAuCl is added4Adding the solution into aqueous solution of CTAB, mixing uniformly, and then adding NaBH4Soaking for 30-60min to obtain a mixed solution c;
step four, adding the mixed solution b in the step two into the mixed solution c in the step three, standing, and centrifugally washing to obtain Au nano-particles;
step five, adding the Au particles prepared in the step four into a CTAB solution, performing ultrasonic dispersion uniformly, and performing oil bath at constant temperature to obtain a mixed solution d;
step six, uniformly mixing TEOS and cyclohexane, then dropwise adding the mixture into the mixed solution d obtained in the step five, raising the temperature of an oil bath, carrying out magnetic stirring reaction, and carrying out centrifugal washing to obtain the multi-core single-shell Au @ mSiO2Composite microspheres
Preferably, in the first step, the mass ratio of CTAB to sodium oleate is 10: 1-2: 1, the concentration of the sodium oleate in the mixed solution a in the first step is 2.5g/L-10 g/L; AgNO3The mass ratio of the sodium oleate to the sodium oleate is (0.01-0.1) to 1; HAuCl in the step one4The concentration of the solution is 0.5 to 2 mM.
Preferably, the concentration of the hydrochloric acid in the step two is 3 mol/L-12 mol/L, and the ascorbic acid is mixed with the hydrochloric acid in the step oneHAuCl of4The mass ratio of the substances is (0.275-14.2): 1.
Preferably, the concentration of CTAB in the third step is 0.2-1M, and HAuCl4The concentration of the solution is 0.5-1 mM, and HAuCl4The volume ratio of the CTAB solution to the CTAB solution is 1: 1-1: 4; NaBH4The concentration of (A) is 0.01-0.1M, and the NaBH is4With HAuCl4The volume ratio of (1-2): 5.
Preferably, the mixed solution b in the fourth step is added into the mixed solution c and then stands for 12-24 hours.
Preferably, in the fifth step, 0.01-0.15 g of Au nanoparticles is taken, the concentration of CTAB solution is 0.2-1M, and the constant temperature is 50-80 ℃.
Preferably, the volume ratio of TEOS to cyclohexane in the sixth step is 1: 10-1: 40, the temperature of the temperature-raising oil bath is 70-100 ℃, and the magnetic stirring reaction time is 12-30 hours.
The invention also comprises a method for preparing the multi-core single-shell structure Au @ mSiO by using a packaging method2The composite microsphere is characterized by being prepared by the preparation method.
Further, the multi-core-single-shell structure Au @ mSiO2The particle size of the composite microsphere is 50nm-300nm, and the Au @ mSiO2Mesoporous SiO film with core formed by multiple Au nano-particles2An outer shell is formed around the exterior of the core.
Specifically, the multi-core single-shell structure Au @ mSiO2The diameter of the core single Au nano-particle of the composite microsphere is 15-60nm, and the mesoporous SiO2The thickness of (A) is 28nm-60 nm.
The invention also comprises a composite microsphere applied to the dye-sensitized solar cell, and the composite microsphere adopts the multi-core-single-shell structure Au @ mSiO2And (3) compounding the microspheres.
Has the advantages that:
1. the invention designs and prepares the multi-core-single-shell structure Au @ mSiO by a packaging method2Nano particles, Au nano particles as core, mesoporous as shell layer, SiO2The coating effectively improves the agglomeration phenomenon of the nano Au nanoparticles applied to the dye-sensitized solar cell.
2. According to the invention, experimental parameters are accurately designed, and a packaging method enables a plurality of Au nanoparticles to form a core, so that the existence of gold nanoparticles in a plurality of core structures can greatly exert the surface plasma effect of the Au nanoparticles and enhance the absorption of the dye to light.
3. According to the invention, a layer of silicon dioxide film is formed on the surface of the gold nano-particle, and the silicon dioxide is an inert object and is not conductive. After the gold nanoparticles and the silicon dioxide are assembled, the absorption peak value in a visible light range is widened, and the absorption of sunlight is facilitated, so that the absorption of the dye in the visible light range is enhanced, and meanwhile, electrons can be rapidly conducted out.
4. The invention prepares SiO with mesoporous pore canals2The shell layer is beneficial to the transmission of the broad-spectrum electrons in the solar cell and improves the performance of the dye-sensitized solar cell.
Drawings
In order that the manner in which the present invention is made will be more readily understood, a more particular description of the invention, briefly summarized above, may be had by reference to the embodiments thereof which are illustrated in the appended drawings,
FIG. 1 is a diagram of the preparation of a multi-core single-shell Au @ mSiO by the encapsulation method of example 12Transmission electron microscopy of composite microspheres;
FIG. 2 is a diagram of the preparation of Au @ mSiO of a multi-core single-shell structure by the encapsulation method in example 12XRD pattern of composite microspheres;
FIG. 3 is the preparation of Au @ mSiO of multi-core-single-shell structure by the encapsulation method in example 12EDAX map of composite microspheres;
FIG. 4 is a diagram of the preparation of Au @ mSiO of a multi-core single-shell structure by the encapsulation method in example 22Transmission electron microscopy of composite microspheres;
FIG. 5 is a diagram of example 3 encapsulation process for preparing Au @ mSiO with multi-core-single-shell structure2Transmission electron microscopy of composite microspheres;
FIG. 6 is a diagram of example 4 encapsulation process for preparing Au @ mSiO with multi-core-single-shell structure2Transmission electron microscopy of composite microspheres;
FIG. 7 is a diagram of example 5 encapsulation process for preparing Au @ mSiO with multi-core-single-shell structure2Transmission electron microscopy images of composite microspheres.
Detailed Description
In order to facilitate an understanding of the invention, the invention will be described more fully and in detail below with reference to the accompanying drawings and preferred embodiments, but the scope of the invention is not limited to the specific embodiments below.
Example 1
Method for preparing multi-core single-shell structure Au @ mSiO by packaging method2A composite microsphere comprising the steps of:
step one, dissolving CTAB and sodium oleate in water, mixing uniformly, and adding AgNO3Standing, and adding HAuCl4Stirring the solution for reaction for 30-90 minutes to obtain a mixed solution a;
step two, slowly adding hydrochloric acid into the mixed solution a obtained in the step one to continue stirring and reacting, and then adding an ascorbic acid solution to obtain a mixed solution b;
step three, HAuCl is added4Adding the solution into aqueous solution of CTAB, mixing uniformly, and then adding NaBH4Soaking for 30-60min to obtain a mixed solution c;
step four, adding the mixed solution b in the step two into the mixed solution c in the step three, standing, and centrifugally washing to obtain Au nano-particles;
step five, adding the Au particles prepared in the step four into a CTAB solution, performing ultrasonic dispersion uniformly, and performing oil bath at constant temperature to obtain a mixed solution d;
step six, uniformly mixing TEOS and cyclohexane, then dropwise adding the mixture into the mixed solution d obtained in the step five, raising the temperature of an oil bath, carrying out magnetic stirring reaction, and carrying out centrifugal washing to obtain the multi-core single-shell Au @ mSiO2And (3) compounding the microspheres.
Specifically, in this embodiment, a multi-core single-shell structure Au @ mSiO is prepared by a packaging method2A method of compounding microspheres comprising the steps of:
step one, dissolving 7g CTAB and 1g sodium oleate in 200ml water, mixing and stirring uniformly, and adding 15mg AgNO3Standing for 20min, and adding 200ml HAuCl with concentration of 1mM4Stirring the solution for reaction for 30 minutes to obtain a mixed solution a;
step two, slowly adding 5ml of hydrochloric acid with the concentration of 12M into the mixed solution a in the step one, continuously stirring for reaction, and then adding 20mg of ascorbic acid solution to obtain a mixed solution b;
step three, 5ml of 0.5mM HAuCl4Adding the solution into 0.5MCTAB aqueous solution, mixing well, adding 1ml NaBH with concentration of 0.01M4Soaking for 30min to obtain a mixed solution c;
step four, adding the mixed solution b in the step two into the mixed solution c in the step three, standing for 24 hours, and centrifugally washing to obtain Au nano particles;
step five, adding 0.05g of Au particles prepared in the step four into a CTAB solution with the concentration of 0.2M, performing ultrasonic dispersion uniformly, and performing oil bath at a constant temperature of 60 ℃ to obtain a mixed solution d;
step six, uniformly mixing 0.5ml of TEOS and 8ml of cyclohexane, then dropwise adding the mixture into the mixed solution d obtained in the step five, carrying out oil bath at the temperature of 100 ℃, carrying out magnetic stirring reaction for 24 hours, and carrying out centrifugal washing to obtain the multi-core single-shell Au @ mSiO2And (3) compounding the microspheres.
Characterization test: example 1 encapsulation method for preparing Au @ mSiO with multi-core single-shell structure2The transmission electron microscope image of the composite microsphere is shown in FIG. 1, and from FIG. 1, the multi-core-single-shell structure Au @ mSiO2The overall size of the composite microsphere is about 230nm, the central core part of the composite microsphere consists of a plurality of Au nano particles with the size of 15-30 nm, and the shell layer is provided with a layer of film-shaped mesoporous SiO2Material, and in this example, the crust layer SiO2Is about 28nm, the scanning graph can clearly see Au @ mSiO2The composite microsphere has a multi-core-single-shell structure. Example 1 encapsulation method for preparing Au @ mSiO with multi-core single-shell structure2The XRD of the nano-microsphere is shown in figure 2, and as can be seen from figure 2, the obvious characteristic peak marked in the figure is completely matched with the characteristic peak of Au, and obvious SiO appears between 20 and 30 DEG2The characteristic peak proves that the multi-core single-shell structure Au @ mSiO is successfully prepared by the packaging method2And (3) compounding the microspheres. Example 1 preparation of the Multi-core Single-Shell Au @ mSiO2The EDAX pattern of the composite microspheres is shown in FIG. 3, from which it can be seen that the spectrumObvious Au, O and Si elements exist, and no other elements exist. Au @ mSiO of the invention2The method for enabling the gold nanoparticles to be in an insulating state in the solar cell without interfering with the surface plasma effect of the gold nanoparticles by the composite microspheres is characterized in that a layer of silicon dioxide film is formed on the surfaces of the gold nanoparticles, and the silicon dioxide is an inert object and is not conductive. The absorption peak value is widened in the visible light range, which is beneficial to the absorption of sunlight, thereby enhancing the absorption of the dye in the visible light range and simultaneously leading electrons to be rapidly conducted out. The existence of a plurality of gold nano particles can greatly exert the surface plasma effect of the gold nano particles and enhance the absorption of the dye to light.
Example 2
Method for preparing multi-core single-shell structure Au @ mSiO by packaging method2A composite microsphere comprising the steps of:
step one, dissolving 7g CTAB and 1g sodium oleate in 200ml water, mixing and stirring uniformly, and adding 10mg AgNO3Standing for 20min, and adding 200ml HAuCl with concentration of 1mM4Stirring the solution for reaction for 30-90 minutes to obtain a mixed solution a, wherein AgNO3 is used as a reducing agent in the step;
step two, slowly adding 5ml of hydrochloric acid with the concentration of 12M into the mixed solution a in the step one, continuously stirring for reaction, and then adding 20mg of ascorbic acid solution to obtain a mixed solution b;
step three, 5ml of 0.5mM HAuCl4Adding the solution into 5ML 0.5MCTAB aqueous solution, mixing well, adding 1ML NaBH with concentration of 0.05M4Soaking for 30-60min to obtain a mixed solution c;
step four, adding the mixed solution b in the step two into the mixed solution c in the step three, standing for 24 hours, and centrifugally washing to obtain Au nano particles;
step five, adding 0.05g of Au particles prepared in the step four into a CTAB solution with the concentration of 0.2M, performing ultrasonic dispersion uniformly, and performing oil bath at a constant temperature of 60 ℃ to obtain a mixed solution d;
step six, 0.2ml of TEOS and 5ml of cyclohexane are uniformly mixed and then are dripped into the mixed solution d in the step five, oil bath is carried out at the temperature of 100 ℃, and magnetic stirring is carried out reverselyThe reaction time is 24 hours, and the multi-core single-shell structure Au @ mSiO is obtained after centrifugal washing2And (3) compounding the microspheres.
FIG. 4 shows the multi-core single-shell Au @ mSiO prepared in this example2Transmission electron microscopy of the composite microspheres, from which it can be seen that Au @ mSiO2The overall size of the composite microsphere is about 310nm, the central core part of the composite microsphere consists of a plurality of Au nano-particles with the size of 31-51 nm, gap channels are arranged among the Au nano-particles of the core part, and the shell layer is a layer of film-shaped mesoporous SiO2Material, outer shell SiO2Is 45-60nm, the scanning can clearly see Au @ mSiO2The nano-microsphere presents a multi-core-single-shell structure.
Example 3
Method for preparing multi-core single-shell structure Au @ mSiO by packaging method2The nano microsphere comprises the following steps:
step one, dissolving 7g CTAB and 1g sodium oleate in 200ml water, mixing and stirring uniformly, and adding 15mg AgNO3Standing for 20min, and adding 200ml of 2mM HAuCl4Stirring the solution for reaction for 30-90 minutes to obtain a mixed solution a;
step two, slowly adding 5ml of hydrochloric acid with the concentration of 12M into the mixed solution a in the step one, continuously stirring for reaction, and then adding 20mg of ascorbic acid solution to obtain a mixed solution b;
step three, 5ml of 0.5mM HAuCl4The solution was added to 5mL of 0.5MCTAB aqueous solution, mixed well, and then 1mL of 0.01M NaBH was added4Soaking for 30-60min to obtain a mixed solution c;
step four, adding the mixed solution b in the step two into the mixed solution c in the step three, standing for 24 hours, and centrifugally washing to obtain Au nano particles;
step five, adding 0.05g of Au particles prepared in the step four into a CTAB solution with the concentration of 0.2M, performing ultrasonic dispersion uniformly, and performing oil bath at a constant temperature of 50 ℃ to obtain a mixed solution d;
step six, 0.5ml of TEOS and 8ml of cyclohexane are uniformly mixed and then are dripped into the mixed solution d in the step five, and oil bath is carried out at the temperature of 80 DEG CMagnetically stirring for reaction for 24h, and centrifugally washing to obtain the multi-core single-shell Au @ mSiO2And (3) compounding the microspheres.
FIG. 5 shows the multi-core single-shell Au @ mSiO prepared in this example2Transmission electron microscopy of the composite microspheres, from which it can be seen that Au @ mSiO2The overall size of the composite microsphere is about 525nm, the central core part of the composite microsphere consists of a plurality of Au nano particles with the size of 32-47 nm, and the shell layer is a layer of film-shaped mesoporous SiO2Material, outer shell SiO2Is about 45nm, the scanning graph can clearly see Au @ mSiO2The nano-microsphere presents a multi-core-single-shell structure.
Example 4
Method for preparing multi-core single-shell structure Au @ mSiO by packaging method2The nano microsphere comprises the following steps:
step one, dissolving 7g CTAB and 1g sodium oleate in 200ml water, mixing and stirring uniformly, and adding 15mg AgNO3Standing for 20min, and adding 200ml HAuCl with concentration of 1mM4Stirring the solution for reaction for 30-90 minutes to obtain a mixed solution a;
step two, slowly adding 5ml of hydrochloric acid with the concentration of 12M into the mixed solution a in the step one, continuously stirring for reaction, and then adding 20mg of ascorbic acid solution to obtain a mixed solution b;
step three, 5ml of 0.5mM HAuCl4Adding the solution into 0.5MCTAB aqueous solution, mixing well, adding 1ml NaBH with concentration of 0.01M4Soaking for 30-60min to obtain a mixed solution c;
step four, adding the mixed solution b in the step two into the mixed solution c in the step three, standing for 24 hours, and centrifuging and washing to obtain octahedral Au nanoparticles;
step five, adding 0.15g of Au particles prepared in the step four into a CTAB solution with the concentration of 0.2M, performing ultrasonic dispersion uniformly, and performing oil bath at a constant temperature of 60 ℃ to obtain a mixed solution d;
step six, 0.5ml of TEOS and 8ml of cyclohexane are uniformly mixed and then are dripped into the mixed solution d in the step five, oil bath is carried out at the temperature of 100 ℃, magnetic stirring reaction is carried out for 12 hours, and centrifugal washing is carried outNamely, the multi-core-single-shell structure Au @ mSiO is prepared2And (3) compounding the microspheres.
As shown in FIG. 6, the multi-core single-shell Au @ mSiO prepared in this example is shown2Transmission electron microscopy of the composite microspheres, from which it can be seen that Au @ mSiO2The overall size of the composite microsphere is about 385nm, the central core part of the composite microsphere consists of a plurality of Au nano particles with the size of 41-51 nm, and the shell layer is a film-shaped mesoporous SiO2Material, outer shell SiO2Is about 50nm, the scanning graph can clearly see Au @ mSiO2The nano-microsphere presents a multi-core-single-shell structure.
Example 5
Method for preparing multi-core single-shell structure Au @ mSiO by packaging method2The nano microsphere comprises the following steps:
step one, dissolving 7g CTAB and 1g sodium oleate in 200ml water, mixing and stirring uniformly, and adding 15mg AgNO3Standing for 20min, and adding 200ml of 2mM HAuCl4Stirring the solution for reaction for 30-90 minutes to obtain a mixed solution a;
step two, slowly adding 5ml of hydrochloric acid with the concentration of 6M into the mixed solution a in the step one, continuously stirring for reaction, and then adding 20mg of ascorbic acid solution to obtain a mixed solution b;
step three, 5ml of 0.5mM HAuCl4Adding the solution into 0.5MCTAB aqueous solution, mixing well, adding 1ml NaBH with concentration of 0.01M4Soaking for 30-60min to obtain a mixed solution c;
step four, adding the mixed solution b in the step two into the mixed solution c in the step three, standing for 24 hours, and centrifugally washing to obtain Au nano particles;
step five, adding 0.01g of Au particles prepared in the step four into a CTAB solution with the concentration of 0.2M, performing ultrasonic dispersion uniformly, and performing oil bath at a constant temperature of 60 ℃ to obtain a mixed solution d;
step six, uniformly mixing 0.5ml of TEOS and 8ml of cyclohexane, dropwise adding the mixture into the mixed solution d obtained in the step five, performing oil bath at the temperature of 100 ℃, performing magnetic stirring reaction for 24 hours, and performing centrifugal washing to obtain Au @ mSiO2Composite micro-meterA ball.
FIG. 7 shows the multi-core single-shell Au @ mSiO prepared in this example2Transmission electron microscopy of the composite microspheres from which the Au @ mSiO2The overall size of the composite microsphere is about 170nm, the central core part of the composite microsphere consists of a plurality of Au nano particles with the size of about 60nm, and the shell layer is a layer of film-shaped mesoporous SiO2Material, outer shell SiO2Is about 35nm, the scanning graph can clearly see Au @ mSiO2The nanospheres exhibited a multi-core-single shell structure, and the number of Au nanoparticles in one shell was reduced relative to examples 1-4.
Example 6
Method for preparing multi-core single-shell structure Au @ mSiO by packaging method2The nano microsphere comprises the following steps:
step one, dissolving 10g CTAB and 1g sodium oleate in 200ml water, mixing and stirring uniformly, and adding 100mg AgNO3Standing for 20min, and adding 200ml HAuCl with concentration of 0.5mM4Stirring the solution for reaction for 90 minutes to obtain a mixed solution a;
step two, slowly adding 5ml of hydrochloric acid with the concentration of 3M into the mixed solution a in the step one, continuously stirring for reaction, and then adding 0.25g of ascorbic acid solution to obtain a mixed solution b;
step three, 5ml of 0.5mM HAuCl4The solution was added to 5mL of 0.2MCTAB aqueous solution, mixed well, and then 1mL of 0.01M NaBH was added4Soaking for 30-60min to obtain a mixed solution c;
step four, adding the mixed solution b in the step two into the mixed solution c in the step three, standing for 24 hours, and centrifugally washing to obtain Au nano particles;
step five, adding 0.01g of Au particles prepared in the step four into a CTAB solution with the concentration of 0.2M, performing ultrasonic dispersion uniformly, and performing oil bath at a constant temperature of 50 ℃ to obtain a mixed solution d;
step six, uniformly mixing 1ml of TEOS and 10ml of cyclohexane, dropwise adding the mixture into the mixed solution d obtained in the step five, carrying out oil bath at the temperature of 70 ℃, carrying out magnetic stirring reaction for 12 hours, and carrying out centrifugal washing to obtain Au @ mSiO2And (3) compounding the microspheres.
Example 7
Method for preparing multi-core single-shell structure Au @ mSiO by packaging method2The nano microsphere comprises the following steps:
step one, dissolving 2g CTAB and 1g sodium oleate in 200ml water, mixing and stirring uniformly, and adding 10mg AgNO3Standing for 20min, and adding 200ml of 2mM HAuCl4Stirring the solution for reaction for 90 minutes to obtain a mixed solution a;
step two, slowly adding 5ml of hydrochloric acid with the concentration of 12M into the mixed solution a in the step one, continuously stirring for reaction, and then adding 20.5mg of ascorbic acid solution to obtain a mixed solution b;
step three, 5ml of 1mM HAuCl4The solution was added to 20mL of 1MCTAB in water, mixed well and then 2mL of 0.1M NaBH was added4Soaking for 60min to obtain a mixed solution c;
step four, adding the mixed solution b in the step two into the mixed solution c in the step three, standing for 12 hours, and centrifugally washing to obtain Au nano particles;
step five, adding 0.15g of Au particles prepared in the step four into a CTAB solution with the concentration of 1M, performing ultrasonic dispersion uniformly, and performing oil bath at a constant temperature of 80 ℃ to obtain a mixed solution d;
step six, uniformly mixing 1ml of TEOS and 40ml of cyclohexane, dropwise adding the mixture into the mixed solution d obtained in the step five, carrying out oil bath at the temperature of 100 ℃, carrying out magnetic stirring reaction for 30 hours, and carrying out centrifugal washing to obtain Au @ mSiO2And (3) compounding the microspheres.
Example 8
Multi-core single-shell structure Au @ mSiO2Nanospheres, which were multi-core-single-shell Au @ mSiO prepared as described in examples 1-72The nano-microsphere can be applied to dye-sensitized solar cells, is used for transmitting broad-spectrum electrons in the solar cells, and improves the performance of the dye-sensitized solar cells.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (5)
1. Preparation of multi-core single-shell structure Au @ mSiO2A method of compounding microspheres, comprising the steps of:
step one, dissolving CTAB and sodium oleate in water, mixing uniformly, and adding AgNO3Standing, and adding HAuCl4Stirring the solution for reaction for 30-90 minutes to obtain a mixed solution a;
step two, slowly adding hydrochloric acid into the mixed solution a obtained in the step one to continue stirring and reacting, and then adding an ascorbic acid solution to obtain a mixed solution b;
step three, HAuCl is added4Adding the solution into aqueous solution of CTAB, mixing uniformly, and then adding NaBH4Soaking for 30-60min to obtain a mixed solution c;
step four, adding the mixed solution b in the step two into the mixed solution c in the step three, standing, and centrifugally washing to obtain Au nano-particles;
step five, adding the Au particles prepared in the step four into a CTAB solution, performing ultrasonic dispersion uniformly, and performing oil bath at constant temperature to obtain a mixed solution d;
step six, uniformly mixing TEOS and cyclohexane, then dropwise adding the mixture into the mixed solution d obtained in the step five, raising the temperature of an oil bath, carrying out magnetic stirring reaction, and carrying out centrifugal washing to obtain the multi-core single-shell structure Au @ mSiO2Composite microspheres of said Au @ mSiO2Mesoporous SiO film with core formed by multiple Au nano-particles2The outer part of the core is surrounded to form a shell;
in the first step, the mass ratio of CTAB to sodium oleate is 10: 1-2: 1, the concentration of the sodium oleate in the mixed solution a in the first step is 2.5g/L-10 g/L; AgNO3The mass ratio of the sodium oleate to the sodium oleate is (0.01-0.1) to 1; HAuCl in the step one4The concentration of the solution is 0.5-2 mM;
the concentration of the hydrochloric acid in the second step is 3 mol/L-12 mol/L, and the product is resistant to the damageAscorbic acid and HAuCl of step one4The mass ratio of (0.275-14.2) to 1;
the concentration of CTAB in the third step is 0.2-1M, HAuCl4The concentration of the solution is 0.5-1 mM, and HAuCl4The volume ratio of the CTAB solution to the CTAB solution is 1: 1-1: 4; NaBH4The concentration of (A) is 0.01-0.1M, and the NaBH is4With HAuCl4The volume ratio of (1-2): 5;
in the fifth step, the concentration of the CTAB solution is 0.2-1M, and the constant temperature is 50-80 ℃;
in the sixth step, the volume ratio of TEOS to cyclohexane is 1: 10-1: 40, the temperature of the temperature-raising oil bath is 70-100 ℃, and the magnetic stirring reaction time is 12-30 hours.
2. The method for preparing the multi-core single-shell structure Au @ mSiO of claim 12The method for compounding the microspheres is characterized in that the mixed solution b in the fourth step is added into the mixed solution c and then stands for 12-24 hours.
3. Multi-core single-shell structure Au @ mSiO2Composite microspheres, characterized in that they are prepared by the process of any one of claims 1-2, said Au @ mSiO2The particle size of the nano microsphere is 50nm-300nm, and the Au @ mSiO2Mesoporous SiO film with core formed by multiple Au nano-particles2An outer shell is formed around the exterior of the core.
4. The multi-core single-shell structure Au @ mSiO of claim 32Composite microspheres, wherein the Au @ mSiO2The diameter of the core single Au nano-particle of the composite microsphere is 15-60nm, and the mesoporous SiO2The thickness of (A) is 28nm-60 nm.
5. A composite microsphere applied to a dye-sensitized solar cell, which is characterized in that the multi-core-single-shell structure Au @ mSiO of claim 3 or 4 is adopted2And (3) compounding the microspheres.
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