CN114050239A - Silver nanocrystal modified mesoporous metal oxide composite material and preparation method thereof - Google Patents
Silver nanocrystal modified mesoporous metal oxide composite material and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of nano materials, and particularly relates to a silver nanocrystal modified mesoporous metal oxide composite material and a preparation method thereof. Firstly, preparing silver nanocrystals coated with oleylamine and dispersing the silver nanocrystals into an organic solvent; dissolving the amphiphilic block copolymer PEO-b-PS in an organic solvent to obtain a first transparent solution; adding an inorganic micromolecule precursor into an organic solvent to obtain a second transparent solution; uniformly mixing the two transparent solutions, and adding the dispersion liquid to obtain a colloidal solution; standing the colloidal solution at room temperature for volatilizing, drying, solidifying and grinding into powder; and calcining the powder in nitrogen atmosphere in stages, and calcining in air atmosphere to obtain the silver nanocrystal supported mesoporous metal oxide composite material. The invention effectively improves the loading capacity and uniformity of the mesoporous metal oxide, and the particle size and the mesoporous size of the loaded silver nanocrystal are controllable and uniform, thereby improving the basic performance of the mesoporous metal oxide loaded by the silver nanocrystal.
Description
Technical Field
The invention belongs to the technical field of nano materials, and particularly relates to a silver nanocrystal modified mesoporous metal oxide composite material and a preparation method thereof.
Background
The ordered mesoporous material is a novel nano material, and has an adjustable and ordered mesoporous pore structure, a high specific surface area and a large pore volume. The mesoporous metal oxide material has high specific surface area, pore volume, mutually communicated pore channels and abundant reactive sites, can effectively promote the transmission of guest molecules, has important application in aspects of macromolecular adsorption, catalytic reaction, drug storage and transportation and the like, and can be used for preparing gas sensors and the like. The resistance sensor based on the semiconductor metal oxide has the advantages of low price, simple structure, sensitive and quick response and easy mass production, thereby becoming the most important sensor in gas sensors and a research hotspot. In addition, the noble metal is loaded on the metal oxide, so that the catalytic property and the sensitization performance of the noble metal can be fully utilized, the activation energy of surface reaction is effectively reduced, the defects of a metal carrier are increased, and the concentration of adsorbed oxygen is increased, thereby further improving the performance of the gas sensor.
In the prior art, the synthesis steps of the mesoporous metal oxide composite material loaded by the noble metal are complicated, and a carrier or noble metal particles need to be prepared in advance; meanwhile, the pore structure of the carrier is uncontrollable, and the stability and the dispersibility of the noble metal particles are poor, so that the large-scale production is difficult. In addition, most of the synthesized materials have disordered mesopores, which is not favorable for mass transfer.
Disclosure of Invention
In view of the above problems in the prior art, an object of the present invention is to provide a silver nanocrystal-modified mesoporous metal oxide composite material having a high and uniform silver loading and excellent performance, and a method for preparing the same.
According to the method, through a sol-gel chemical synthesis method, an amphiphilic block copolymer is used as a structure directing agent and a pore-forming agent, inorganic micromolecules are used as a metal oxide precursor, the precursor is assembled with silver nanocrystals which are synthesized in advance, and the silver nanocrystals which are uniform in size and highly dispersed are loaded in mesoporous metal oxide through a solvent evaporation induced co-assembly (EICA) method, so that the loading capacity of the mesoporous metal oxide is improved, and the accurate regulation and control of the size of the loaded silver nanocrystals are realized.
The invention provides a preparation method of a silver nanocrystal modified mesoporous metal oxide composite material, which comprises the steps of taking an amphiphilic block copolymer (PEO-b-PS) with large molecular weight as a template and a pore-forming agent, forming micelles by the amphiphilic block copolymer in the solvent volatilization process, forming a micelle shell by the electrostatic force between a hydrophilic end (PEO) of the template and an inorganic micromolecule precursor (such as WCl 6) and the like, wrapping a hydrophobic block (PS) by hydrophobic effect to synthesize silver nanocrystals with a preset size in advance, and obtaining the ordered mesoscopic organic-inorganic composite material by a solvent volatilization induced self-assembly (EISA) method. After high-temperature heat treatment of nitrogen and air, the silver nanocrystal modified mesoporous metal oxide composite material is directly obtained.
The invention provides a preparation method of a silver nanocrystal modified mesoporous metal oxide composite material, which comprises the following specific steps:
step A, dissolving silver nitrate and oleylamine in a predetermined ratio in a first organic solvent, uniformly mixing by ultrasonic, adding ascorbic acid in a predetermined ratio, and stirring for 1-2 hours in a dark place; and adding ethanol into the stirred solution for settling, centrifuging to obtain a precipitate, washing and drying the precipitate to obtain the solid particles with the surface covered with the oleylamine silver nanocrystals.
The step is a process for preparing silver nanocrystals, and the obtained silver nanocrystal solid particles have high crystallinity, uniform particle size of 5-10 nm, and can be conveniently regulated and controlled according to the feeding concentration and reaction time of silver nitrate; meanwhile, the surface of the silver nanocrystalline solid particle is coated with oleylamine. The silver nitrate accounts for 1-2 wt% of the mass of the solution, the oleylamine accounts for 45-50 wt% of the mass of the solution, and the ascorbic acid accounts for 2-4 wt% of the mass of the solution. The first organic solvent comprises nonpolar organic reagents such as toluene, cyclohexane, n-hexane, benzene and the like.
And B, dispersing the silver nanocrystals into a second organic solvent to obtain a silver nanocrystal dispersion.
In this step, the concentration of the silver nanocrystals in the obtained dispersion is 0.05-1.5 wt.%. The second organic solvent includes: nonpolar solvents such as cyclohexane, toluene, and n-hexane, or mixed solvents thereof.
Step C, dissolving an amphiphilic block copolymer PEO-b-PS with large molecular weight in a third organic solvent, and fully stirring to obtain a first transparent solution; adding an inorganic micromolecule precursor and a hydrolysis inhibitor into tetrahydrofuran THF or absolute ethyl alcohol EtOH to obtain a second transparent solution; and C, uniformly mixing the first transparent solution and the second transparent solution, adding the silver nanocrystalline dispersion liquid obtained in the step B in a preset proportion, and fully stirring to obtain a transparent colloidal solution.
In this step, the third organic solvent includes one or more of tetrahydrofuran, toluene, chloroform, and dimethylformamide.
The molecular weight of a PEO block of the amphiphilic block copolymer is 2000-5000 g/mol, and the molecular weight of a PS block of the amphiphilic block copolymer is 10000-30000 g/mol; the molecular weight of the amphiphilic block copolymer is controlled by controlling the activity or adjusting the time, temperature, charge ratio and the like of free radical polymerization reaction, and the size of the mesoporous diameter can be adjusted by the size of the molecular weight. The PEO-b-PS concentration in the first clear solution is 0.5-2 wt.%.
The inorganic micromolecule precursor is one or more of tungsten chloride, tetrabutyl titanate, aluminum acetylacetonate and zirconium acetylacetonate; the inorganic micromolecule precursor is a commercialized reagent, and is convenient and easy to obtain. When the inorganic micromolecule precursor is a component, a metal oxide is obtained, and the silver nanocrystal is loaded in the mesoporous metal oxide; when the inorganic micromolecule precursor is two or more than two, two or more than two metal oxides are obtained, and the silver nanocrystals are loaded in the composite mesoporous metal oxide. Different inorganic micromolecules are used as metal oxide precursors to synthesize WO modified by silver nanocrystals in reaction3、TiO2、Al2O3、ZrO2An isomesoporous metal oxide or a composite mesoporous metal oxide. The concentration of the inorganic micromolecule precursor in the second transparent solution is 2-10 wt.%. The hydrolysis inhibitor is one or more of acetylacetone, hydrochloric acid, acetic acid and dilute nitric acid, and the hydrolysis rate of tetrabutyl titanate is controlled by the hydrolysis inhibitor to obtain porous non-porousAn organic oxide.
In the step, after the dispersion liquid is added into the mixed solution, the silver nanocrystals in the dispersion liquid can be automatically assembled with the PS section through hydrophobic effect due to the fact that the surface of the silver nanocrystals is covered with the oleylamine, so that ordered accumulation of micelles is prevented from being damaged, and meanwhile, the silver nanocrystals can be directly and uniformly loaded in mesoporous channels.
And D, transferring the colloidal solution into a culture dish, standing and volatilizing for 12 hours at room temperature, drying the culture dish in an oven at the temperature of 40-60 ℃ for 12-24 hours, transferring the culture dish into an oven at the temperature of 80-100 ℃ for curing for 12-24 hours to obtain an organic-inorganic composite membrane, scraping the composite membrane from the culture dish and grinding the composite membrane into powder.
And E, placing the obtained powder in a tubular furnace, heating to 300-350 ℃ at a speed of 1-2 ℃/min in a nitrogen atmosphere, calcining for 2-4 h, and continuing heating to 500-600 ℃ at a speed of 1-5 ℃/min, calcining for 1-2h, so as to obtain the silver nanocrystal loaded mesoporous metal oxide-carbon composite material.
In the step, a method of low-temperature carbonization in nitrogen atmosphere is applied to separate sp from PS block2The hybridized carbon atoms and carbon in oleylamine are converted into amorphous carbon in situ, and when calcined in air, amorphous carbon residue is used as a rigid support on one hand, so that a mesoporous structure is kept in the high-temperature calcination crystallization process of the metal oxide, on the other hand, the growth and migration of silver nanocrystals can be prevented, silver is prevented from being oxidized by using the amorphous carbon residue as a sacrificial agent, and the particle size of the silver nanocrystals is limited to 5-10 nm.
And F, placing the obtained silver nanocrystal loaded mesoporous metal oxide-carbon composite material in a muffle furnace, heating to 450-600 ℃ at the speed of 2-5 ℃/min in the air atmosphere, and calcining for 1-2h to obtain the silver nanocrystal loaded mesoporous metal oxide.
The invention also provides the silver nanocrystal modified mesoporous metal oxide composite material prepared by the preparation method, the composite material takes the mesoporous metal oxide as a matrix, silver nanocrystals are uniformly loaded in a mesoporous structure, the pore size of mesopores is 30-40 nm, and the particle size of the silver nanocrystals is 5-10 nm.
Wherein the mesoporous metal is oxidizedThe substance comprises WO3、TiO2、Al2O3、ZrO2One or more of the above components are compounded.
According to the technical scheme, the silver nanocrystal modified mesoporous metal oxide composite material and the preparation method provided by the embodiment of the invention synthesize Ag/WO (silver/WO) by controlling the type of the inorganic micromolecular precursor3、Ag/TiO2、Ag/Al2O3、Ag/ZrO2And the like, and various silver nanocrystalline modified mesoporous metal oxide composite materials. The aperture size of the mesopores of the synthesized composite material is 30-40 nm, the particle size of the silver nanocrystals is 5-10 nm, the aperture size of the mesopores in the composite material is controlled by controlling the molecular weight of the block copolymer, the particle size of the silver nanocrystals in the composite material is controlled by controlling the size of the silver nanocrystals synthesized in advance and the proportion of oleylamine, the loading capacity and uniformity of silver in the mesoporous metal oxide are effectively improved, the particle size of the loaded silver nanocrystals is controllable and uniform, the stability of the silver noble metal load is effectively improved, the impact of the noble metal load on the stability of the mesoporous framework is greatly reduced, and the catalytic performance of the mesoporous metal oxide loaded by the silver nanocrystals is improved.
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In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
FIG. 1 shows Ag/WO mesoporous tungsten trioxide supported by silver nanocrystals in example 1 of the present invention3Transmission electron microscopy images of;
FIG. 2 shows Ag/TiO mesoporous TiO 2 loaded with Ag nanocrystals according to example 2 of the present invention2Transmission electron microscopy images of;
FIG. 3 shows Ag nanocrystals loaded with mesoporous alumina Ag/Al in example 3 of the present invention2O3Transmission electron microscopy images of;
FIG. 4 shows an embodiment of the present inventionSilver nanocrystal loaded mesoporous zirconia Ag/ZrO provided in example 42Transmission electron micrograph (D).
Detailed Description
The technical problems, aspects and advantages of the invention will be explained in detail below with reference to exemplary embodiments. The following exemplary embodiments are merely illustrative of the present invention and are not to be construed as limiting the invention. It will be understood by those skilled in the art that, unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the prior art and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.
Example 1:
the embodiment provides a silver nanocrystal modified mesoporous tungsten oxide composite material and a preparation method thereof.
The preparation method comprises the following steps:
step A, dissolving 85 mg of silver nitrate and 4.05 g of oleylamine in 5 ml of toluene solution, carrying out ultrasonic homogenization, adding 175 mg of ascorbic acid, and stirring for 1 hour in a dark place; adding 80 ml of ethanol into the stirred solution for sedimentation, centrifuging to obtain a precipitate, and washing and drying the precipitate to obtain a silver nanocrystal solid;
b, dispersing the silver nanocrystal solid into 10 ml of cyclohexane solution to obtain a dispersion liquid for later use;
step C, amphiphilic block copolymer (PEO-b-PS) 75 mg dissolved in 5 ml THF and stirred well to give a first clear solution; 300 mg WCl6And 300. mu.L of acetylacetone was added to 1 ml of EtOH to obtain a second transparent solution; uniformly mixing the first transparent solution and the second transparent solution, adding a proper amount of pre-synthesized silver nanocrystal dispersion, and fully stirring to obtain a transparent colloidal solution; the molecular weight of the amphiphilic block copolymer PEO segment in the embodiment is 2000g/mol, and the molecular weight of the PS block is 10000 g/mol;
step D, transferring the colloidal solution into a culture dish, standing and volatilizing for 12 hours at room temperature, transferring the culture dish into a 40 ℃ oven for drying for 12 hours, transferring the culture dish into a 100 ℃ oven for curing for 12 hours to obtain an organic-inorganic composite membrane, scraping the membrane from the culture dish and grinding the membrane into powder;
step E, placing the obtained powder in a tube furnace, heating to 350 ℃ at a speed of 1 ℃/min in a nitrogen atmosphere, calcining for 3h, continuing heating to 500 ℃ at a speed of 5 ℃/min, and calcining for 1 h to obtain the silver nanocrystal loaded mesoporous tungsten oxide-carbon composite material;
step F, placing the obtained silver nanocrystal loaded mesoporous metal oxide-carbon composite material in a muffle furnace, heating to 450 ℃ at the speed of 2 ℃/min in the air atmosphere, and calcining for 1 h to obtain the silver nanocrystal loaded mesoporous tungsten oxide composite material Ag/WO3。
Referring to FIG. 1, the resulting Ag/WO3The mesoporous tungsten oxide is used as a substrate of the composite material, silver nanocrystals are uniformly loaded in a mesoporous structure, the aperture size of the mesoporous is 35nm, and the particle size of the silver nanocrystals is 7 nm.
Example 2:
the embodiment provides a silver nanocrystal modified mesoporous titanium oxide composite material and a preparation method thereof.
The preparation method comprises the following steps:
step A, 85 mg of silver nitrate and 4.05 g of oleylamine were dissolved in 5 ml of toluene solution and homogenized by ultrasound, then 175 mg of ascorbic acid was added and stirred for 1 hour in the dark. Adding 80 ml of ethanol into the stirred solution for sedimentation, centrifuging and washing to obtain a silver nanocrystalline solid;
b, dispersing the silver nanocrystals into 10 ml of n-hexane solution to obtain a dispersion liquid for later use;
step C, amphiphilic block copolymer (PEO-b-PS) 75 mg dissolved in 5 mL chloroform and stirred well to obtain a first clear solution; adding 600 mu L of tetrabutyl titanate into 1 ml of THF, and then adding 75 mu L of hydrochloric acid and glacial acetic acid respectively to obtain a second transparent solution; uniformly mixing the first transparent solution and the second transparent solution, and adding a proper amount of the mixtureFully stirring the pre-synthesized silver nanocrystal dispersion liquid to obtain a transparent colloidal solution; the molecular weight of the amphiphilic block copolymer PEO segment is 5000g/mol, and the molecular weight of the PS block is 20000 g/mol;
step D, transferring the colloidal solution into a culture dish, standing and volatilizing for 12 hours at room temperature, transferring the culture dish into a 60 ℃ drying oven for drying for 12 hours, transferring the culture dish into a 80 ℃ drying oven for curing for 24 hours to obtain an organic-inorganic composite membrane, scraping the membrane from the culture dish and grinding the membrane into powder;
step E, placing the obtained powder sample in a tubular furnace, heating to 350 ℃ at a speed of 1 ℃/min in a nitrogen atmosphere, and calcining for 2h to obtain the silver nanocrystal loaded mesoporous titanium dioxide-carbon composite material;
and F, placing the obtained silver nanocrystal loaded mesoporous titanium dioxide-carbon composite material in a muffle furnace, heating to 450 ℃ at the speed of 2 ℃/min in the air atmosphere, and calcining for 1 h to obtain the silver nanocrystal loaded mesoporous titanium dioxide composite material.
Referring to FIG. 2, the resulting Ag/TiO2The composite material takes mesoporous titanium dioxide as a substrate, silver nanocrystals are uniformly loaded in a mesoporous structure, the aperture size of mesopores is 30nm, and the particle size of the silver nanocrystals is 5 nm.
Example 3:
the embodiment provides a silver nanocrystal modified mesoporous alumina composite material and a preparation method thereof.
The preparation method comprises the following steps:
step A, 85 mg of silver nitrate and 4.05 g of oleylamine were dissolved in 5 ml of toluene solution and homogenized by ultrasound, then 175 mg of ascorbic acid was added and stirred for 1 hour in the dark. Adding 80 ml of ethanol into the stirred solution for sedimentation, centrifuging and washing to obtain a silver nanocrystalline solid;
b, dispersing the silver nanocrystals into 10 ml of toluene solution to obtain a dispersion liquid for later use;
step C, amphiphilic block copolymer (PEO-b-PS) 75 mg dissolved in 5 mL dimethylformamide, stirred well to obtain a first clear solution; 375 mg of aluminum acetylacetonate are added to 3 ml of THFAdding 150 mu L of concentrated nitric acid to obtain a second transparent solution; uniformly mixing the first transparent solution and the second transparent solution, adding a proper amount of pre-synthesized silver nanocrystal dispersion, and fully stirring to obtain a transparent colloidal solution; the molecular weight of the amphiphilic block copolymer PEO segment is 3000g/mol, and the molecular weight of the PS block is 15000 g/mol;
step D, transferring the solution into a culture dish, standing and volatilizing for 24 hours at room temperature, transferring the culture dish into a 50 ℃ oven for drying for 18 hours, transferring the culture dish into a 90 ℃ oven for curing for 18 hours to obtain an organic-inorganic composite membrane, scraping the membrane from the culture dish and grinding the membrane into powder;
step E, placing the obtained powder sample in a tubular furnace, heating to 350 ℃ at a speed of 1 ℃/min in a nitrogen atmosphere, and calcining for 3h to obtain the silver nanocrystal loaded mesoporous alumina-carbon composite material;
and F, placing the obtained silver nanocrystal loaded mesoporous alumina-carbon composite material in a muffle furnace, heating to 600 ℃ at the speed of 5 ℃/min in the air atmosphere, and calcining for 2h to obtain the silver nanocrystal loaded mesoporous alumina composite material.
Referring to FIG. 3, the resulting Ag/Al2O3The composite material takes mesoporous alumina as a matrix, silver nanocrystals are uniformly loaded in a mesoporous structure, the pore size of mesopores is 40nm, and the particle size of the silver nanocrystals is 10 nm.
Example 4:
the embodiment provides a silver nanocrystal modified mesoporous zirconium dioxide composite material and a preparation method thereof.
The preparation method comprises the following steps:
step A, 85 mg of silver nitrate and 4.05 g of oleylamine were dissolved in 5 ml of toluene solution and homogenized by ultrasound, then 175 mg of ascorbic acid was added and stirred for 1 hour in the dark. Adding 80 ml of ethanol into the stirred solution for sedimentation, centrifuging and washing to obtain a silver nanocrystalline solid;
step B, dispersing the silver nanocrystals into 10 ml of cyclohexane solution to obtain a dispersion solution for later use;
step C, amphiphilic block copolymer (PEO-b-PS) 75 mg dissolved in 5 mL of formazanBenzene, and fully stirring to obtain a first transparent solution; adding 375 mg of zirconium acetylacetonate into 3 ml of THF, then adding 150 μ L of concentrated nitric acid to obtain a second transparent solution; uniformly mixing the first transparent solution and the second transparent solution, adding a proper amount of pre-synthesized silver nanocrystal dispersion, and fully stirring to obtain a transparent colloidal solution; the molecular weight of the amphiphilic block copolymer PEO segment is 4000g/mol, and the molecular weight of the PS block is 18000 g/mol;
step D, transferring the colloidal solution into a culture dish, standing and volatilizing for 24 hours at room temperature, transferring the culture dish into a 40 ℃ oven for drying for 24 hours, transferring the culture dish into a 100 ℃ oven for curing for 12 hours to obtain an organic-inorganic composite membrane, scraping the membrane from the culture dish and grinding the membrane into powder;
step E, placing the obtained powder sample in a tubular furnace, heating to 350 ℃ at a speed of 1 ℃/min in a nitrogen atmosphere, and calcining for 3h to obtain the silver nanocrystal loaded mesoporous zirconia-carbon composite material;
and F, placing the obtained silver nanocrystal loaded mesoporous zirconia-carbon composite material in a muffle furnace, heating to 600 ℃ at the speed of 5 ℃/min in the air atmosphere, and calcining for 2h to obtain the silver nanocrystal loaded mesoporous zirconia composite material.
Referring to FIG. 4, the resulting Ag/Al2O3The mesoporous zirconium dioxide is used as a matrix of the composite material, silver nanocrystals are uniformly loaded in a mesoporous structure, the aperture size of the mesoporous structure is 38nm, and the particle size of the silver nanocrystals is 6 nm.
While the foregoing is directed to the preferred embodiment of the present invention, it is understood that the invention is not limited to the exemplary embodiments disclosed, but is made merely for the purpose of providing those skilled in the relevant art with a comprehensive understanding of the specific details of the invention. It will be apparent to those skilled in the art that various modifications and adaptations of the present invention can be made without departing from the principles of the invention and the scope of the invention is to be determined by the claims.
Claims (10)
1. A preparation method of a silver nanocrystal modified mesoporous metal oxide composite material is characterized in that an amphiphilic block copolymer is used as a structure directing agent and a pore-forming agent through a sol-gel chemical synthesis method, inorganic micromolecules are used as a metal oxide precursor, the amphiphilic block copolymer and a pre-synthesized silver nanocrystal are assembled, and the silver nanocrystal with uniform size and high dispersion is loaded in the mesoporous metal oxide through a solvent volatilization induction co-assembly method, so that the loading capacity of the mesoporous metal oxide is improved, and the accurate regulation and control of the size of the loaded silver nanocrystal is realized; the method comprises the following specific steps:
step A, dissolving silver nitrate and oleylamine in a predetermined ratio in a first organic solvent, uniformly mixing by ultrasonic waves, adding ascorbic acid in a predetermined ratio, and uniformly stirring in a dark place; adding ethanol into the stirred solution for sedimentation, centrifuging to obtain a precipitate, washing and drying the precipitate to obtain solid particles with the surface covered with the oleylamine silver nanocrystal;
b, dispersing the silver nanocrystals into a second organic solvent to obtain a silver nanocrystal dispersion liquid;
step C, dissolving an amphiphilic block copolymer PEO-b-PS with large molecular weight in a third organic solvent, and fully stirring to obtain a first transparent solution; adding an inorganic small-molecule precursor and a hydrolysis inhibitor into tetrahydrofuran THF or ethanol EtOH to obtain a second transparent solution; uniformly mixing the first transparent solution and the second transparent solution, adding the silver nanocrystalline dispersion liquid in a preset proportion, and fully stirring to obtain a transparent colloidal solution;
step D, transferring the transparent colloidal solution into a culture dish, standing and volatilizing for 12 hours at room temperature, drying the culture dish in an oven at 40-60 ℃ for 12-24 hours, transferring the culture dish into an oven at 80-100 ℃ for curing for 12-24 hours to obtain an organic-inorganic composite membrane, scraping the composite membrane from the culture dish and grinding the composite membrane into powder;
step E, placing the obtained powder in a tubular furnace, heating to 300-350 ℃ at a heating rate of 1-2 ℃/min in a nitrogen atmosphere, calcining for 2-4 h, and continuing heating to 500-600 ℃ at a heating rate of 1-5 ℃/min, calcining for 1-2h to obtain the silver nanocrystal supported mesoporous metal oxide-carbon composite material;
and F, heating the obtained silver nanocrystal loaded mesoporous metal oxide-carbon composite material to 450-600 ℃ at a heating rate of 2-5 ℃/min in the air atmosphere, and calcining for 1-2h to obtain the silver nanocrystal loaded mesoporous metal oxide.
2. The method for preparing a silver nanocrystal modified mesoporous metal oxide composite material according to claim 1, wherein silver nitrate accounts for 1-2wt.% of the mass of the solvent, oleylamine accounts for 45-50wt.% of the mass of the solvent, and ascorbic acid accounts for 2-4wt.% of the mass of the solvent in the step a; the concentration of the silver nanocrystals in the dispersion of step B is 0.05-1.5 wt.%.
3. The method for preparing a silver nanocrystal-modified mesoporous metal oxide composite material according to claim 1, wherein the first organic solvent is selected from the group consisting of nonpolar organic reagents toluene, cyclohexane, n-hexane, benzene; the second organic solvent is selected from nonpolar solvents such as cyclohexane, toluene and n-hexane; the third organic solvent is selected from tetrahydrofuran, toluene, chloroform and dimethylformamide.
4. The method for preparing the silver nanocrystal-modified mesoporous metal oxide composite material according to claim 1, wherein in the step C, the molecular weight of the PEO block of the amphiphilic block copolymer is 2000-5000 g/mol, and the molecular weight of the PS block of the amphiphilic block copolymer is 10000-30000 g/mol.
5. The method of claim 1, wherein the activity of the amphiphilic block copolymer is controlled or the time, temperature and feeding ratio of the free radical polymerization reaction are adjusted to control the molecular weight of the amphiphilic block copolymer, and the pore size of the mesopores can be adjusted according to the molecular weight.
6. The method for preparing a silver nanocrystal-modified mesoporous metal oxide composite material according to claim 1, wherein the PEO-b-PS concentration in the first transparent solution is 0.5 to 2 wt.%; the concentration of the inorganic micromolecule precursor in the second transparent solution is 2-10 wt.%.
7. The method for preparing the silver nanocrystal-modified mesoporous metal oxide composite material according to claim 1, wherein the inorganic small molecule precursor is one or more of tungsten chloride, tetrabutyl titanate, aluminum acetylacetonate and zirconium acetylacetonate, and the hydrolysis inhibitor is one or more of acetylacetone, hydrochloric acid, acetic acid and dilute nitric acid.
8. The method for preparing a silver nanocrystal-modified mesoporous metal oxide composite material according to claim 1, wherein the silver nanocrystals loaded into the mesoporous metal oxide in step F have a particle size of 5 to 10 nm.
9. The method for preparing a silver nanocrystal-modified mesoporous metal oxide composite material according to claim 1, wherein the mesoporous metal oxide is selected from WO3、TiO2、Al2O3、ZrO2One kind of (1).
10. A silver nanocrystal-modified mesoporous metal oxide composite material prepared according to any one of claims 1 to 9, wherein the composite material comprises a mesoporous metal oxide as a matrix, silver nanocrystals are uniformly loaded in a mesoporous structure, the pore size of the mesopores is 30 to 40nm, and the particle size of the silver nanocrystals is 5 to 10 nm.
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