CN112225255A - Noble metal-loaded ordered double-mesoporous metal oxide composite material and preparation method thereof - Google Patents
Noble metal-loaded ordered double-mesoporous metal oxide composite material and preparation method thereof Download PDFInfo
- Publication number
- CN112225255A CN112225255A CN202011015498.0A CN202011015498A CN112225255A CN 112225255 A CN112225255 A CN 112225255A CN 202011015498 A CN202011015498 A CN 202011015498A CN 112225255 A CN112225255 A CN 112225255A
- Authority
- CN
- China
- Prior art keywords
- composite material
- mesoporous
- metal oxide
- noble metal
- loaded
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G41/00—Compounds of tungsten
- C01G41/02—Oxides; Hydroxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G19/00—Compounds of tin
- C01G19/02—Oxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G33/00—Compounds of niobium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/14—Pore volume
Abstract
The invention belongs to the technical field of nano porous materials, and particularly relates to a noble metal-loaded ordered double-mesoporous metal oxide composite material and a preparation method thereof. The invention takes an amphiphilic block copolymer as a structure directing agent, and utilizes the interaction of hydroxyl and sulfydryl contained in a sulfydryl-containing phenolic resin prepolymer with a metal oxide precursor and a noble metal precursor respectively to fix the precursor at the hydrophilic end of the block copolymer; performing solvent volatilization induced co-assembly to enable the block copolymer and the precursor compound to form an ordered mesostructure; and removing organic components through calcination to obtain the ordered double mesoporous metal oxide composite material with the highly uniform noble metal nano particles loaded. The composite material has a double mesoporous structure and a high specific surface area, mesoporous channels are orderly arranged and are uniformly loaded with noble metal nano particles. The method is simple, has strong universality and easily obtained raw materials, is suitable for amplified production, and has good application prospect in the fields of catalysis, sensing and the like.
Description
Technical Field
The invention belongs to the technical field of nano porous materials, and particularly relates to a preparation method of a noble metal-loaded ordered double-mesoporous metal oxide composite material.
Background
In recent years, metal oxide composite materials loaded with noble metals have been widely used in the fields of energy conversion, catalysis, sensing and the like by virtue of unique physicochemical characteristics and synergistic effects thereof, and have received extensive attention from researchers (s.linear, p.christopher, d.b. ingram, nat.mater.2011,10,911; c.clavero, nat.photonics 2014,8, 95; a.a.herzing, c.j.kiely, a.f.carley, p.landon, g.j.huttings, Science 2008,321,1331; w.koo, s.choi, s.kim, j.jang, h.l.teller, i.kim, j.am.chem.sac.2016, 138, 13431).
The loading of the noble metal into the metal oxide with the mesoporous structure is an effective way for improving the performance of the noble metal/metal oxide composite material. On one hand, the mesoporous pore canal of the metal oxide can play a role of nano confinement, prevent the migration and agglomeration inactivation of noble metal nano particles, and improve the stability of the composite material; on the other hand, the abundant mesoporous channels improve the specific surface area of the material, are beneficial to the transmission and diffusion of guest molecules in the material, and can improve the performance of the noble metal/metal oxide composite material in catalysis, sensing and other applications which depend on surface interface reaction strongly. At present, the synthesis of the mesoporous metal oxide loaded with noble metal usually adopts an impregnation method or a coprecipitation method, and the steps are complicated. In the traditional impregnation method, the resistance of a metal precursor entering a porous carrier is large, and noble metal species are easily adsorbed at the entrance of a pore channel, so that the phenomenon of uneven load occurs; the coprecipitation method has difficulty in controlling the pore structure and size, and the surface ligands of the surface-modified noble metal nanoparticles are difficult to remove. Meanwhile, the currently reported mesoporous metal oxide composite material loaded with noble metal generally has a single mesoporous structure, small pore channel window size, low utilization efficiency inside the material, and influences further improvement of the performance (c.y.ma, z.mu, j.j.li, y.g.jin, j.cheng, g.q.lu, z.p.hao, s.z.qiao, j.am.chem.soc.2010,132,2608, b.liu, c.kuo, j.chen, z.luo, s.thanneeru, w.li, w.song, s.biswas, s.chel.suib, j.he, angew.em.in.ed.2015, 54,9061, s.kim, s.ch, j.cheng, n.cheim, kim, h.helle.i, anger.i.75, wag.10, wang.j.qio, j.m, j.sw, s.sou.75, j.k.k, h.h.l.hell.i.i.i.i.i.75, anger.75, anger, wa, wang.j.42, wang.j.j.j.j.j.j.j.j.j.chen, fao.
Different from the previously reported synthesis method of the mesoporous metal oxide loaded with noble metal, the invention adopts a novel one-pot co-assembly method, namely, the principle of auxiliary co-assembly of a prepolymer of phenolic resin containing sulfhydryl groups is utilized, amphiphilic block copolymer is used as a structure directing agent and a template agent, and the solvent volatilization induced co-assembly and calcination treatment are carried out to synthesize the ordered double mesoporous metal oxide which is uniformly loaded with noble metal, has high specific surface area and large window size. In the process, the hydroxyl of the thiol-containing phenolic resin prepolymer enhances the interaction of the metal oxide precursor and the hydrophilic block through the hydrogen bond effect, and the thiol of the thiol-containing phenolic resin prepolymer enhances the interaction of the noble metal precursor and the hydrophilic block through the coordination effect, so that multi-component co-assembly is realized. After being roasted in inert atmosphere, the thiol-containing phenolic resin prepolymer is carbonized in situ to form a hard template with secondary pores, and the noble metal precursor is reduced in situ in the pore canal, so that the uniform loading of the noble metal nanoparticles is realized. After carbon residue is removed in the air atmosphere, the size of a pore channel window and the connectivity of the pore channel are improved by creating secondary pores, and the surface of the noble metal confined in the pore channel is fully exposed. The method disclosed by the invention has the characteristics of simplicity in operation, wide raw material source, easiness in regulation and control of components and pore channel structures and strong universality, and is suitable for large-scale production.
Disclosure of Invention
The invention aims to provide a simple and controllable ordered double-mesoporous metal oxide composite material which is easy to repeat and strong in universality and uniformly loads noble metal and a preparation method thereof.
The invention proposesA preparation method of a noble metal-loaded ordered double-mesoporous metal oxide composite material comprises the steps of taking an amphiphilic block copolymer as a structure directing agent, and fixing various precursors at the hydrophilic end of the block copolymer by utilizing the principle that hydroxyl and sulfydryl contained in a sulfydryl-containing phenolic resin prepolymer can respectively react with a metal oxide precursor and a noble metal precursor; performing solvent volatilization induced co-assembly to form an ordered mesostructure by the block copolymer and the precursor compound; and removing organic components in the composite material by calcining to obtain the ordered double mesoporous metal oxide composite material with the highly uniform noble metal nano particles loaded. The specific surface area of the synthesized composite material is 50m2/g-110m2Per g, pore volume of 0.05cm3/g-0.3cm3The noble metal particle size is 2-10 nm.
The invention provides a preparation method of a noble metal-loaded ordered double-mesoporous metal oxide composite material, which comprises the following specific steps:
(1) first, a mercapto group-containing phenol resin prepolymer is prepared. Heating p-hydroxyphenylthiophenol at 40-50 deg.C for melting, adding 10-30 wt.% NaOH aqueous solution, and adjusting pH to 9-11; stirring at 40-50 deg.C for 10-30min, adding 35-40 wt.% formaldehyde water solution, and stirring at 70-80 deg.C for 1-3 h; naturally cooling to room temperature, adjusting pH to 6-8 with 1-3mol/L hydrochloric acid water solution, heating in 40-50 deg.C water bath, vacuum rotary evaporating to remove water, and dispersing in volatile solvent; wherein the molar ratio of the p-hydroxyphenylthiophenol to the formaldehyde is 1: (2-3);
(2) secondly, dissolving the amphiphilic block copolymer in a volatile solvent, adding a mercapto-containing phenolic resin prepolymer and a noble metal precursor, and fully stirring to obtain a solution A; adding the metal oxide precursor into ethanol or a mixed system of the ethanol and a metal ion hydrolysis inhibitor, and uniformly stirring to obtain a solution B; adding the solution B into the solution A, and fully stirring for 15-180min (preferably 30-120min) to obtain a transparent mixed solution; in the synthesis process, the mass ratio of the block copolymer to the volatile solvent is 1: (30-200), wherein the mass ratio of the block copolymer to the metal oxide precursor is 1: (1-7), wherein the mass ratio of the metal oxide precursor to the prepolymer of the mercapto-containing phenolic resin is 1: (0.1-0.5), wherein the mass ratio of the metal oxide precursor to the ethanol is 1: (0.5-5), the mass of the added noble metal precursor is not more than that of the added prepolymer of the phenolic resin containing the mercapto group, and the mass of the added metal ion hydrolysis inhibitor is not more than 2 times of that of the added metal oxide precursor;
(3) then spreading the transparent mixed solution on a substrate in a film spreading, spin coating or lifting mode for volatilization or directly volatilizing in an open mode at the temperature of 20-35 ℃ for 2-24 h; then placing the sample at 40-70 ℃ for 8-48h (preferably 20-30h), further completely volatilizing the solvent, and transferring the sample to 100-150 ℃ for baking for 6-48h (preferably 20-30h) to solidify;
(4) finally, scraping the cured sample from the substrate, grinding the cured sample into powder, heating the powder to 350-600 ℃ at the speed of 1-5 ℃/min in an inert gas atmosphere, and calcining the powder for 2-4h to obtain the noble metal-loaded mesoporous metal oxide/carbon composite material; heating the obtained noble metal-loaded mesoporous metal oxide/carbon composite material to 400-600 ℃ at the speed of 5-10 ℃/min in the air atmosphere, calcining for 0.5-5h, and removing carbon in the material to obtain the noble metal-loaded double mesoporous metal oxide composite material.
In the step (1), the used volatile solvent is one or more of tetrahydrofuran, chloroform, dichloromethane and dioxane; the metal ion hydrolysis inhibitor is one or more of acetylacetone, concentrated hydrochloric acid and glacial acetic acid.
In the step (2), the number average molecular weight of the amphiphilic block copolymer is 60000, the hydrophilic block is a block which can interact with a metal oxide precursor through electrostatic interaction, hydrogen bond interaction or other acting forces, such as polyoxyethylene, poly- (2-vinylpyridine) or poly- (4-vinylpyridine), and the number average molecular weight is 10000; the hydrophobic blocks used were: polymers having hydrophobic properties such as polyoxypropylene, polystyrene or derivatives thereof, polyisoprene or derivatives thereof, or polymethylmethacrylate or derivatives thereof, or copolymers of two or more of these polymers, having number average molecular weights of between 4000 and 50000.
According to the invention, the molecular weight and the hydrophilic-hydrophobic chain segment ratio of the used amphiphilic block copolymer have a larger adjusting space, and the aperture and the pore wall thickness can be adjusted by changing the molecular weight and the hydrophilic-hydrophobic end chain segment ratio of the block copolymer.
In the step (4), the metal oxide of the synthesized noble metal-supported ordered double-mesoporous metal oxide composite material can be one or more of tungsten oxide, titanium oxide, tin oxide, niobium oxide and other metal oxides. The source of the metal oxide precursor needed by the synthesis is wide, WCl6，NbCl5，TiCl4Or SnCl4And one or more of metal chloride salts or metal alkoxides such as tetra-n-butyl titanate and tetra-n-butyl stannate can be used for synthesizing the ordered double mesoporous metal oxide composite material loaded with the noble metal.
In the step (4), the precious metal of the synthesized ordered double mesoporous metal oxide composite material loaded with precious metal can be one or an alloy of gold, platinum, palladium, rhodium and other precious metals. The source of the noble metal precursor required for synthesis is wide, and one or more noble metal compounds such as chloroauric acid, chloroplatinic acid, platinum acetylacetonate, palladium acetylacetonate and the like which can be dissolved in one solvent or a plurality of mixed solvents of tetrahydrofuran, chloroform, dichloromethane and dioxane can be used for synthesizing the noble metal-loaded ordered double mesoporous metal oxide composite material.
In the invention, the method for synthesizing the double-mesoporous metal oxide loaded with noble metal by using the thiol-containing phenolic resin prepolymer for auxiliary co-assembly has universality. The mercapto-containing phenolic resin prepolymer can generate hydrogen bond action with a metal oxide precursor through hydroxyl and generate coordination action with a noble metal precursor through mercapto, so that the action of various precursors and block copolymers is enhanced. Any method for synthesizing mesoporous metal oxide by adopting solvent volatilization to induce self-assembly can be applicable. The synthesis can be carried out by film-coating, spin-coating, dip-coating or direct open-evaporation.
In the invention, the method for synthesizing the noble metal-loaded mesoporous metal oxide by removing carbon residue through inert atmosphere carbonization reduction and air atmosphere calcination has universality. Hydrophobic block and mercapto-containing phenolic resin prepolymer are converted into amorphous carbon in situ in inert atmosphere calcination to serve as rigid support of metal oxide, noble metal precursor is reduced to form noble metal nano particles, and the growth and migration of the noble metal particles are prevented by the limited domain effect of the pore channel. And removing residual carbon in the air to obtain the double mesoporous metal oxide composite material loaded with the surface bare noble metal nano particles.
In the invention, the synthesized ordered double-mesoporous metal oxide material loading noble metal has the pore canal with the shape of spherical pore canal or tubular pore canal, the mesoporous material has ordered arrangement, the space group of the pore canal structure is p6mm,
P63/mmc，
one or more of the above structures are mixed. The pore size distribution of the porous material shows a bimodal distribution.
Compared with the prior art, the invention has the following beneficial technical effects:
the thiol-containing phenolic resin prepolymer is adopted to assist in synthesizing the noble metal-loaded double-mesoporous metal oxide composite material, the interaction of a metal oxide precursor and a noble metal precursor with the hydrophilic end of the block copolymer is enhanced by utilizing the hydroxyl and the thiol of the thiol-containing phenolic resin prepolymer, the one-pot co-assembly is realized, and the problem of uneven noble metal loading is solved. The high exposure of the surface of the noble metal nano particles is realized through the treatment of removing carbon residue through the inert gas atmosphere calcination and the air atmosphere calcination, meanwhile, a double mesoporous structure is created in the metal oxide carrier, the pore channels are highly communicated, the window size is large, the transmission and diffusion rates of the guest molecules are improved, and the utilization efficiency of the interior of the material is improved.
The method is simple, has strong universality and easily obtained raw materials, is suitable for amplified production, and has good application prospect in the fields of catalysis, sensing and the like.
Drawings
Fig. 1 is a scanning electron microscope (a) and a high-resolution transmission electron microscope (B) of the palladium nanoparticle-supported ordered mesoporous metal tungsten oxide composite material prepared in example 1.
Fig. 2 is an element distribution map of the palladium nanoparticle-supported ordered double mesoporous metallic tungsten oxide composite prepared in example 1, including element W, O and Pd.
Fig. 3 is a nitrogen adsorption and desorption curve (a) obtained by nitrogen adsorption and desorption characterization of the palladium-supported nanoparticle ordered mesoporous tungsten oxide composite material prepared in example 1, and a pore size distribution (B) calculated by using adsorption branch data of the isothermal adsorption and desorption curve and a pore size distribution curve (window size) (C) calculated by using desorption branch data of the isothermal adsorption and desorption curve according to the Broekhoff de Boer (BdB) method.
Fig. 4 is a sulfur element X-ray photoelectron spectrum of the palladium nanoparticle-supported ordered double mesoporous metal tungsten oxide composite material prepared in example 1.
Detailed Description
Example 1: synthesis of palladium nanoparticle supported ordered double-mesoporous tungsten oxide composite material
(1) First, a mercapto group-containing phenol resin prepolymer is prepared. P-hydroxybenzothiophenol is melted at 45 ℃ under heating, 20 wt.% aqueous NaOH is added, and the pH is adjusted to 10. After stirring at 45 ℃ for 15min, 37 wt.% aqueous formaldehyde solution was added and stirred at 70 ℃ for 2 h. Naturally cooling to room temperature, adjusting pH to 7 with 2mol/L hydrochloric acid aqueous solution, vacuum rotary evaporating to remove water under 45 deg.C water bath heating, and dispersing in tetrahydrofuran for use. Wherein the molar ratio of the p-hydroxyphenylthiophenol to the formaldehyde is 1: 2.4;
(2) amphiphilic block copolymer polyethylene oxide-b-Polystyrene (PEO)114-b-PS183，Mn24000), adding a mercapto-containing phenolic resin prepolymer and palladium acetylacetonate, and fully stirring to obtain a solution A; adding tungsten chloride intoAdding the mixture into a mixed system of ethanol and acetylacetone, and uniformly stirring to obtain a solution B. Adding the solution B into the solution A, and fully stirring for 120min to obtain a transparent mixed solution. During the synthesis, the block copolymer PEO114-b-PS183The mass ratio of the tetrahydrofuran to the tetrahydrofuran is 1: 50, Block copolymer PEO114-b-PS183The mass ratio of the tungsten chloride to the tungsten chloride is 1: 4, the mass ratio of the tungsten chloride to the prepolymer of the phenolic resin containing the mercapto group is 1: 0.2, the mass ratio of the tungsten chloride to the ethanol is 1: 2.5, the mass of the added palladium acetylacetonate is 8.4 wt% of the mass of the prepolymer of the phenolic resin containing sulfydryl, and the mass of the added acetylacetone is 100 wt% of the mass of the tungsten chloride;
(3) then pouring the transparent mixed solution into a culture dish with the diameter of 15cm, volatilizing the solution at 25 ℃ for 24 hours, placing the culture dish in 40 ℃ for 24 hours, further completely volatilizing the solvent, and baking the sample at 100 ℃ for 24 hours to solidify the sample;
(4) and finally, scraping the solidified sample from a culture dish, grinding the sample into powder, heating the powder to 350 ℃ at a speed of 1 ℃/min in the nitrogen atmosphere, calcining the powder for 2 hours, and heating the powder to 500 ℃ at a speed of 5 ℃/min, and calcining the powder for 1 hour to obtain the palladium nanoparticle-loaded mesoporous tungsten oxide/carbon composite material. And (3) heating the obtained palladium nanoparticle-loaded mesoporous tungsten oxide/carbon composite material to 400 ℃ at the speed of 5 ℃/min in the air atmosphere, calcining for 0.5h to remove carbon, and obtaining the palladium nanoparticle-loaded bi-mesoporous tungsten oxide composite material.
The test characterization and experimental results of the palladium nanoparticle-supported ordered double mesoporous metal tungsten oxide composite material prepared in example 1 are shown in the attached drawings 1-4.
Referring to fig. 1, fig. 1 is an electron microscope representation of the palladium nanoparticle-supported ordered double mesoporous metal tungsten oxide composite material, which is a scanning electron microscope image (a) and a high resolution transmission electron microscope image (B). Scanning electron microscope images show that the palladium-loaded nanoparticle ordered double-mesoporous metal tungsten oxide composite material synthesized by the method has a mesoporous structure, and mesopores are arranged in a face-centered cubic manner. The high-resolution transmission electron microscope picture shows that the palladium nano-particles with the particle size of 1-2 nanometers are loaded on the wall of the highly crystallized tungsten oxide pore.
Referring to fig. 2, fig. 2 is an element distribution map of the supported palladium nanoparticle ordered double mesoporous metallic tungsten oxide composite prepared in example 1, including element W, O and Pd. W, O, Pd elements are almost completely overlapped as seen from the element distribution map, indicating that the Pd nanoparticles are highly uniformly distributed in the tungsten oxide skeleton.
Referring to fig. 3, fig. 3 is a nitrogen adsorption and desorption curve (a) obtained by nitrogen adsorption and desorption characterization of the palladium nanoparticle-supported ordered mesoporous tungsten oxide composite prepared in example 1 and a pore size distribution (B) calculated using isotherm adsorption branch data and a pore size distribution curve (window size) (C) calculated using isotherm desorption branch data according to the Broekhoff de Boer (BdB) method. The isothermal adsorption and desorption curve shows an IV-type curve, and the material is proved to have uniform mesopores. The pore size distribution calculated by utilizing the adsorption branch data of the isothermal adsorption-desorption curve shows bimodal distribution, and is obviously distributed at about 3 nanometers and 10 nanometers, which shows that the synthesized palladium-loaded nanoparticle ordered double-mesoporous metal tungsten oxide composite material has a double-mesoporous structure. The pore size distribution curve calculated by utilizing the desorption branch data of the isothermal adsorption and desorption curve is usually the window size of the material, and the window size of the synthesized palladium-loaded nanoparticle ordered double mesoporous metal tungsten oxide composite material is larger than 4 nanometers, has a large window size and high pore channel connectivity.
Referring to fig. 4, fig. 4 is a sulfur element X-ray photoelectron spectrum of the palladium nanoparticle-supported ordered mesoporous tungsten oxide composite prepared in example 1. It can be seen from the figure that the characteristic peak of the sulfur element is completely undetectable, which indicates that the mercapto group as the coordinating group is completely removed, and further indicates that the palladium particle surface of the supported palladium nanoparticle ordered double mesoporous metal tungsten oxide composite material has no ligand chelate and is fully exposed.
Example 2: synthesis of gold nanoparticle-loaded ordered double-mesoporous titanium oxide composite material
(1) First, a mercapto group-containing phenol resin prepolymer is prepared. P-hydroxybenzothiophenol is melted at 45 ℃ under heating, 20 wt.% aqueous NaOH is added, and the pH is adjusted to 10. After stirring at 45 ℃ for 15min, 37 wt.% aqueous formaldehyde solution was added and stirred at 70 ℃ for 2 h. Naturally cooling to room temperature, adjusting pH to 7 with 2mol/L hydrochloric acid aqueous solution, vacuum rotary evaporating to remove water under 45 deg.C water bath heating, and dispersing in tetrahydrofuran for use. Wherein the molar ratio of the p-hydroxyphenylthiophenol to the formaldehyde is 1: 2.4;
(2) amphiphilic block copolymer polyethylene oxide-b-Polystyrene (PEO)114-b-PS183，Mn24000), adding a mercapto-containing phenolic resin prepolymer and chloroauric acid tetrahydrate, and fully stirring to obtain a solution A; adding tetrabutyl titanate into a mixed system of ethanol, concentrated hydrochloric acid and glacial acetic acid, and uniformly stirring to obtain a solution B. Adding the solution B into the solution A, and fully stirring for 30min to obtain a transparent mixed solution. During the synthesis, the block copolymer PEO114-b-PS183The mass ratio of the tetrahydrofuran to the tetrahydrofuran is 1: 50, Block copolymer PEO114-b-PS183The mass ratio of the titanium dioxide to the tetrabutyl titanate is 1: 3, the mass ratio of the tetra-n-butyl titanate to the prepolymer of the phenolic resin containing mercapto groups is 1: 0.3, the mass ratio of the tetrabutyl titanate to the ethanol is 1: 3, the mass of the added chloroauric acid is 3.8 wt% of the mass of the prepolymer of the mercapto-containing phenolic resin, the mass of the added concentrated hydrochloric acid is 50 wt% of the mass of the tetrabutyl titanate, and the mass of the added glacial acetic acid is 50 wt% of the mass of the tetrabutyl titanate;
(3) then pouring the transparent mixed solution into a culture dish with the diameter of 15cm, volatilizing for 24h at 25 ℃, placing the culture dish into a culture dish with the temperature of 40 ℃ for 24h, further completely volatilizing the solvent, and baking the sample at 100 ℃ for 24h to solidify the sample;
(4) and finally, scraping the solidified sample from a culture dish, grinding the sample into powder, heating the powder to 450 ℃ at a speed of 1 ℃/min in a nitrogen atmosphere, and calcining the powder for 2 hours to obtain the gold nanoparticle-loaded mesoporous titanium oxide/carbon composite material. And (3) heating the obtained gold nanoparticle-loaded mesoporous titanium oxide/carbon composite material to 450 ℃ at the speed of 5 ℃/min in the air atmosphere, calcining for 1h to remove carbon, and obtaining the gold nanoparticle-loaded double mesoporous titanium oxide composite material.
Example 3: synthesis of platinum nano-particle loaded ordered double-mesoporous titanium oxide composite material
(1) First, a mercapto group-containing phenol resin prepolymer is prepared. P-hydroxybenzothiophenol is melted under heating at 50 ℃,10 wt.% aqueous NaOH is added, and the pH is adjusted to 9. After stirring at 50 ℃ for 10min, 35 wt.% aqueous formaldehyde was added and stirred at 70 ℃ for 3 h. Naturally cooling to room temperature, adjusting pH to 8 with 1mol/L hydrochloric acid aqueous solution, vacuum rotary evaporating to remove water under heating in water bath at 40 deg.C, and dispersing in tetrahydrofuran for use. Wherein the molar ratio of the p-hydroxyphenylthiophenol to the formaldehyde is 1: 2;
(2) amphiphilic triblock copolymer polyoxyethylene-polyoxypropylene-polyoxyethylene (PEO-PPO-PEO, EO)106-PO70-EO106Pluronic F127) is dissolved in tetrahydrofuran, added with a mercapto-containing phenolic resin prepolymer and chloroplatinic acid hexahydrate, and fully stirred to obtain a solution A; adding tetrabutyl titanate into a mixed system of ethanol, concentrated hydrochloric acid and glacial acetic acid, and uniformly stirring to obtain a solution B. Adding the solution B into the solution A, and fully stirring for 15min to obtain a transparent mixed solution. In the above synthesis, block copolymer EO106-PO70-EO106The mass ratio of the tetrahydrofuran to the tetrahydrofuran is 1: 60, Block copolymer EO106-PO70-EO106The mass ratio of the titanium dioxide to the tetrabutyl titanate is 1: 2.3, the mass ratio of the tetrabutyl titanate to the prepolymer of the phenolic resin containing mercapto groups is 1: 0.25, the mass ratio of the tetrabutyl titanate to the ethanol is 1: 3, adding chloroplatinic acid in an amount of 11.2 wt.% based on the mass of the mercapto-containing phenolic resin prepolymer, adding concentrated hydrochloric acid in an amount of 70 wt.% based on the mass of tetra-n-butyl titanate, and adding glacial acetic acid in an amount of 70 wt.% based on the mass of tetra-n-butyl titanate;
(3) then, dropwise adding the transparent mixed solution on a silicon wafer, carrying out spin coating, volatilizing for 24h at 20 ℃, then placing the silicon wafer in 40 ℃ for 20h to further completely volatilize the solvent, and then transferring the sample to 100 ℃ for baking for 48h to solidify the sample;
(4) and finally, scraping the cured sample from the silicon wafer, grinding the sample into powder, heating the powder to 450 ℃ at a speed of 3 ℃/min in an argon gas atmosphere, and calcining the powder for 4 hours to obtain the mesoporous titanium oxide/carbon composite material loaded with the platinum nano particles. And (3) heating the obtained platinum nanoparticle-loaded mesoporous titanium oxide/carbon composite material to 450 ℃ at the speed of 8 ℃/min in the air atmosphere, calcining for 3h to remove carbon, and obtaining the platinum nanoparticle-loaded bi-mesoporous titanium oxide composite material.
Example 4: synthesis of gold nanoparticle-loaded ordered double-mesoporous tungsten oxide composite material
(1) First, a mercapto group-containing phenol resin prepolymer is prepared. P-hydroxybenzothiophenol was melted under heating at 40 ℃, and 30 wt.% NaOH aqueous solution was added to adjust pH to 11. After stirring at 40 ℃ for 30min, 40 wt.% aqueous formaldehyde solution was added and stirred at 80 ℃ for 1 h. Naturally cooling to room temperature, adjusting pH to 6 with 3mol/L hydrochloric acid aqueous solution, vacuum rotary evaporating to remove water under heating in water bath at 50 deg.C, and dispersing in chloroform for use. Wherein the molar ratio of the p-hydroxyphenylthiophenol to the formaldehyde is 1: 3;
(2) amphiphilic block copolymer polyethylene oxide-b-Polystyrene (PEO)46-b-PS77，Mn10000) is dissolved in chloroform, and a mercapto-containing phenolic resin prepolymer and chloroauric acid tetrahydrate are added and fully stirred to obtain a solution A; adding tungsten chloride into a mixed system of ethanol and acetylacetone, and uniformly stirring to obtain a solution B. Adding the solution B into the solution A, and fully stirring for 60min to obtain a transparent mixed solution. During the synthesis, the block copolymer PEO46-b-PS77The mass ratio of the chloroform to the chloroform is 1: 30 Block copolymer PEO46-b-PS77The mass ratio of the tungsten chloride to the tungsten chloride is 1: 1, the mass ratio of tungsten chloride to a prepolymer of phenolic resin containing sulfhydryl groups is 1: 0.1, the mass ratio of the tungsten chloride to the ethanol is 1: 0.5, the mass of the added chloroauric acid is 100 wt.% of the prepolymer of the mercapto-containing phenolic resin, and the mass of the added acetylacetone is 200 wt.% of the mass of the tungsten chloride;
(3) then, immersing the quartz plate in the transparent mixed solution, slowly pulling, volatilizing for 2h at 20 ℃, placing the quartz plate in 40 ℃ for 48h, further completely volatilizing the solvent, and baking the sample at 150 ℃ for 6h to solidify;
(4) and finally, scraping the cured sample from a quartz plate, grinding the sample into powder, heating the powder to 350 ℃ at a speed of 1 ℃/min in the nitrogen atmosphere, calcining the powder for 2h, and heating the powder to 500 ℃ at a speed of 5 ℃/min, and calcining the powder for 1h to obtain the gold nanoparticle-loaded mesoporous tungsten oxide/carbon composite material. And (3) heating the obtained gold nanoparticle-loaded mesoporous tungsten oxide/carbon composite material to 400 ℃ at the speed of 10 ℃/min in the air atmosphere, calcining for 0.5h to remove carbon, and obtaining the gold nanoparticle-loaded bi-mesoporous tungsten oxide composite material.
Example 5: synthesis of platinum nanoparticle-loaded ordered double-mesoporous tungsten oxide composite material
(1) First, a mercapto group-containing phenol resin prepolymer is prepared. P-hydroxybenzothiophenol is melted at 45 ℃ under heating, 20 wt.% aqueous NaOH is added, and the pH is adjusted to 10. After stirring at 45 ℃ for 15min, 37 wt.% formaldehyde solution was added and stirred at 75 ℃ for 1.5 h. Naturally cooling to room temperature, adjusting pH to 7 with 2mol/L hydrochloric acid aqueous solution, vacuum rotary evaporating to remove water under 45 deg.C water bath heating, and dispersing in tetrahydrofuran for use. Wherein the molar ratio of the p-hydroxyphenylthiophenol to the formaldehyde is 1: 2.4;
(2) amphiphilic block copolymer polyethylene oxide-b-Polystyrene (PEO)227-b-PS481，Mn60000), adding a mercapto-containing phenolic resin prepolymer and chloroplatinic acid hexahydrate, and fully stirring to obtain a solution A; adding tungsten chloride into a mixed system of ethanol and concentrated hydrochloric acid, and uniformly stirring to obtain a solution B. Adding the solution B into the solution A, and fully stirring for 180min to obtain a transparent mixed solution. During the synthesis, the block copolymer PEO227-b-PS481The mass ratio of the dichloromethane to the dichloromethane is 1: 200, Block copolymer PEO227-b-PS481The mass ratio of the tungsten chloride to the tungsten chloride is 1: 7, the mass ratio of the tungsten chloride to the prepolymer of the phenolic resin containing the mercapto group is 1: 0.5, the mass ratio of the tungsten chloride to the ethanol is 1: 5, adding 7 wt.% of chloroauric acid based on the mass of the prepolymer of the phenolic resin containing sulfydryl, and adding 200 wt.% of concentrated hydrochloric acid based on the mass of tungsten chloride;
(3) then, pouring the transparent mixed solution into a culture dish with the diameter of 15cm, volatilizing the solution at 35 ℃ for 24 hours, then placing the solution in a culture dish with the temperature of 60 ℃ for 36 hours to further completely volatilize the solvent, and then baking the sample at 120 ℃ for 36 hours to solidify the sample;
(4) and finally, scraping the solidified sample from a culture dish, grinding the sample into powder, heating the powder to 350 ℃ at a speed of 2 ℃/min in an argon gas atmosphere, calcining the powder for 3 hours, and heating the powder to 600-1 h at a speed of 5 ℃/min to obtain the platinum nanoparticle-loaded mesoporous tungsten oxide/carbon composite material. And (3) heating the obtained platinum nanoparticle-loaded mesoporous tungsten oxide/carbon composite material to 400 ℃ at the speed of 5 ℃/min in the air atmosphere, calcining for 5h to remove carbon, and obtaining the platinum nanoparticle-loaded double mesoporous tungsten oxide composite material.
Example 6: synthesis of gold nanoparticle-loaded ordered double-mesoporous niobium oxide composite material
(1) First, a mercapto group-containing phenol resin prepolymer is prepared. P-hydroxybenzothiophenol is melted at 45 ℃ under heating, 20 wt.% aqueous NaOH is added, and the pH is adjusted to 10. After stirring at 45 ℃ for 15min, 37 wt.% aqueous formaldehyde solution was added and stirred at 70 ℃ for 2 h. Naturally cooling to room temperature, adjusting pH to 7 with 2mol/L hydrochloric acid water solution, vacuum rotary evaporating to remove water under 45 deg.C water bath heating, and dispersing in 1, 4-dioxane for use. Wherein the molar ratio of the p-hydroxyphenylthiophenol to the formaldehyde is 1: 2.4;
(2) amphiphilic block copolymer polyethylene oxide-b-polymethyl methacrylate (PEO)114-b-PMMA248，Mn30000) is dissolved in 1, 4-dioxane, added with a mercapto-containing phenolic resin prepolymer and chloroauric acid tetrahydrate, and fully stirred to obtain a solution A; adding niobium chloride into ethanol, and uniformly stirring to obtain a solution B. Adding the solution B into the solution A, and fully stirring for 120min to obtain a transparent mixed solution. During the synthesis, the block copolymer PEO114-b-PMMA248The mass ratio of the mixed solution to 1, 4-dioxane is 1: 100, block copolymer PEO114-b-PMMA248The mass ratio of the niobium chloride to the niobium chloride is 1: 5, the mass ratio of the niobium chloride to the prepolymer of the phenolic resin containing the mercapto group is 1: 0.2, the mass ratio of the niobium chloride to the ethanol is 1: 3, adding chloroauric acid with the mass of 50 wt% of the prepolymer of the mercapto-containing phenolic resin;
(3) then, pouring the transparent mixed solution into a culture dish with the diameter of 15cm, volatilizing the solution at the temperature of 30 ℃ for 20 hours, placing the culture dish in the temperature of 70 ℃ for 8 hours, further completely volatilizing the solvent, and baking the sample at the temperature of 100 ℃ for 48 hours to solidify the sample;
(4) and finally, scraping the solidified sample from a culture dish, grinding the sample into powder, heating the powder to 500 ℃ at a speed of 1 ℃/min in a nitrogen atmosphere, and calcining the powder for 3 hours to obtain the gold nanoparticle-loaded mesoporous niobium oxide/carbon composite material. And (3) heating the obtained gold nanoparticle-loaded mesoporous niobium oxide/carbon composite material to 400 ℃ at the speed of 5 ℃/min in the air atmosphere, calcining for 1h to remove carbon, and obtaining the gold nanoparticle-loaded double-mesoporous niobium oxide composite material.
Example 7: synthesis of gold-palladium alloy nanoparticle-loaded ordered double-mesoporous niobium oxide composite material
(1) First, a mercapto group-containing phenol resin prepolymer is prepared. P-hydroxybenzothiophenol is melted at 45 ℃ under heating, 20 wt.% aqueous NaOH is added, and the pH is adjusted to 10. After stirring at 45 ℃ for 15min, 37 wt.% aqueous formaldehyde solution was added and stirred at 70 ℃ for 2 h. Naturally cooling to room temperature, adjusting pH to 7 with 2mol/L hydrochloric acid aqueous solution, vacuum rotary evaporating to remove water under 45 deg.C water bath heating, and dispersing in tetrahydrofuran for use. Wherein the molar ratio of the p-hydroxyphenylthiophenol to the formaldehyde is 1: 2.4;
(2) amphiphilic block copolymer poly (4-vinylpyridine) -b-polystyrene (P4 VP)48-b-PS149，Mn═ 20000) is dissolved in tetrahydrofuran, added with mercapto-containing phenolic resin prepolymer, chloroauric acid tetrahydrate and palladium acetylacetonate, and fully stirred to obtain solution a; adding niobium chloride into a mixed system of ethanol and acetylacetone, and uniformly stirring to obtain a solution B. Adding the solution B into the solution A, and fully stirring for 60min to obtain a transparent mixed solution. In the above synthesis, block copolymer P4VP48-b-PS149The mass ratio of the tetrahydrofuran to the tetrahydrofuran is 1: 150, Block copolymer P4VP48-b-PS149The mass ratio of the niobium chloride to the niobium chloride is 1: 4, the mass ratio of the niobium chloride to the prepolymer of the phenolic resin containing the mercapto group is 1: 0.2, the mass ratio of the niobium chloride to the ethanol is 1: 4, the mass of the added chloroauric acid and the mass of the palladium acetylacetonate are respectively 10 wt.% and 8 wt.% of the mass of the prepolymer of the phenolic resin containing sulfhydryl groups, and the mass of the added acetylacetone is 100 wt.% of the mass of the niobium chloride;
(3) then, pouring the transparent mixed solution into a culture dish with the diameter of 15cm, volatilizing the solution at 25 ℃ for 24 hours, then placing the culture dish in a 50 ℃ solution for 24 hours to further completely volatilize the solvent, and then baking the sample at 100 ℃ for 24 hours to solidify the sample;
(4) and finally, scraping the solidified sample from a culture dish, grinding the sample into powder, heating the powder to 600 ℃ at a speed of 3 ℃/min in an argon gas atmosphere, and calcining the powder for 2 hours to obtain the gold-palladium alloy nanoparticle-loaded mesoporous niobium oxide/carbon composite material. And (3) heating the obtained gold-palladium alloy nanoparticle-loaded mesoporous niobium oxide/carbon composite material to 500 ℃ at the speed of 7 ℃/min in the air atmosphere, calcining for 1h to remove carbon, and obtaining the gold-palladium alloy nanoparticle-loaded double-mesoporous niobium oxide composite material.
Example 8: synthesis of gold nanoparticle-loaded ordered double-mesoporous titanium oxide/tungsten oxide composite material
(1) First, a mercapto group-containing phenol resin prepolymer is prepared. P-hydroxybenzothiophenol is melted at 45 ℃ under heating, 20 wt.% aqueous NaOH is added, and the pH is adjusted to 10. After stirring at 45 ℃ for 15min, 37 wt.% aqueous formaldehyde solution was added and stirred at 70 ℃ for 2 h. Naturally cooling to room temperature, adjusting pH to 7 with 2mol/L hydrochloric acid aqueous solution, vacuum rotary evaporating to remove water under 45 deg.C water bath heating, and dispersing in tetrahydrofuran for use. Wherein the molar ratio of the p-hydroxyphenylthiophenol to the formaldehyde is 1: 2.4;
(2) amphiphilic block copolymer polyethylene oxide-b-Polystyrene (PEO)114-b-PS183，Mn24000), adding a mercapto-containing phenolic resin prepolymer and chloroauric acid tetrahydrate, and fully stirring to obtain a solution A; adding tungsten chloride and tetrabutyl titanate into ethanol, and uniformly stirring to obtain a solution B. Adding the solution B into the solution A, and fully stirring for 120min to obtain a transparent mixed solution. During the synthesis, the block copolymer PEO114-b-PS183The mass ratio of the tetrahydrofuran to the tetrahydrofuran is 1: 60 Block copolymer PEO114-b-PS183: tetra-n-butyl titanate: the mass ratio of tungsten chloride is 1: 2.5: 1.25, the mass ratio of the tetrabutyl titanate to the mercapto-containing phenolic resin is 1: 0.5, the mass ratio of the tetrabutyl titanate to the ethanol is 1: 4, adding 5 wt.% of chloroauric acid based on the mass of the thiol-containing phenolic resin prepolymer;
(3) then pouring the transparent mixed solution into a culture dish with the diameter of 15cm, volatilizing the solution at the temperature of 30 ℃ for 24 hours, then placing the culture dish in a temperature of 50 ℃ for 24 hours to further completely volatilize the solvent, and then baking the sample at the temperature of 100 ℃ for 24 hours to solidify the sample;
(4) and finally, scraping the solidified sample from a culture dish, grinding the sample into powder, heating the powder to 350 ℃ at a speed of 1 ℃/min in the nitrogen atmosphere, calcining the powder for 2h, and heating the powder to 600 ℃ at a speed of 5 ℃/min, calcining the powder for 2h, thus obtaining the mesoporous titanium oxide/tungsten oxide/carbon composite material loaded with the gold nanoparticles. And (3) heating the obtained gold nanoparticle-loaded mesoporous titanium oxide/tungsten oxide/carbon composite material to 600 ℃ at a speed of 10 ℃/min in the air atmosphere, calcining for 0.5h to remove carbon, and obtaining the gold nanoparticle-loaded double mesoporous titanium oxide/tungsten oxide composite material.
The morphology and properties of the composite materials prepared in examples 2 to 8 are similar to those of the composite material prepared in example 1, and the scanning electron microscope image, the high-resolution transmission electron microscope image, the element distribution map, the nitrogen adsorption and desorption characterization, the corresponding pore size distribution and window size distribution, the X-ray photoelectron spectrum of sulfur element and the like are omitted.
Claims (8)
1. A noble metal-loaded ordered double-mesoporous metal oxide composite material and a preparation method thereof are characterized in that the preparation method comprises the following steps:
(1) firstly, preparing a sulfhydryl-containing phenolic resin prepolymer; heating p-hydroxyphenylthiophenol at 40-50 deg.C for melting, adding 10-30 wt.% NaOH aqueous solution, and adjusting pH to 9-11; stirring at 40-50 deg.C for 10-30min, adding 35-40% formaldehyde water solution, and stirring at 70-80 deg.C for 1-3 h; naturally cooling to room temperature, adjusting pH to 6-8 with 1-3mol/L hydrochloric acid water solution, heating in 40-50 deg.C water bath, vacuum rotary evaporating to remove water, and dispersing in volatile solvent; wherein the molar ratio of the p-hydroxyphenylthiophenol to the formaldehyde is 1: (2-3);
(2) secondly, dissolving the amphiphilic block copolymer in a volatile solvent, adding a mercapto-containing phenolic resin prepolymer and a noble metal precursor, and fully stirring to obtain a solution A; adding the metal oxide precursor into ethanol or a mixed system of the ethanol and a metal ion hydrolysis inhibitor, and uniformly stirring to obtain a solution B; adding the solution B into the solution A, and fully stirring for 15-180min to obtain a transparent mixed solution; wherein the mass ratio of the block copolymer to the volatile solvent is 1: (30-200), wherein the mass ratio of the block copolymer to the metal oxide precursor is 1: (1-7), wherein the mass ratio of the metal oxide precursor to the prepolymer of the mercapto-containing phenolic resin is 1: (0.1-0.5), wherein the mass ratio of the metal oxide precursor to the ethanol is 1: (0.5-5), the mass of the added noble metal precursor is not more than that of the added prepolymer of the phenolic resin containing the mercapto group, and the mass of the added metal ion hydrolysis inhibitor is not more than 2 times of that of the added metal oxide precursor;
(3) then spreading the transparent mixed solution on a substrate in a film spreading, spin coating or lifting mode for volatilization or directly volatilizing in an open mode at the temperature of 20-35 ℃ for 2-24 h; placing the mixture at 40-70 deg.C for 8-48h to further completely volatilize solvent; transferring the sample to 100-150 ℃ for baking for 6-48h to solidify;
(4) finally, scraping the solidified sample from the substrate, grinding the sample into powder, heating the powder to 350-600 ℃ at the speed of 1-5 ℃/min in the inert gas atmosphere, and calcining the powder for 2-4h to obtain the noble metal-loaded mesoporous metal oxide/carbon composite material; heating the obtained noble metal-loaded mesoporous metal oxide/carbon composite material to 400-600 ℃ at the speed of 5-10 ℃/min in the air atmosphere, calcining for 0.5-5h, and removing carbon in the material to obtain the noble metal-loaded double mesoporous metal oxide composite material.
2. The preparation method according to claim 1, wherein the volatile solvent in step (1) is one or more of tetrahydrofuran, chloroform, dichloromethane and dioxane; the metal ion hydrolysis inhibitor is one or more of acetylacetone, concentrated hydrochloric acid and glacial acetic acid.
3. The method as claimed in claim 1, wherein the amphiphilic block copolymer in step (2) has a number average molecular weight of about 5000-; the hydrophobic block is: the polymer with hydrophobic property or the copolymer of two or more polymers has the number average molecular weight of 4000-50000, and is specifically selected from polyoxypropylene, polystyrene or derivatives thereof, polyisoprene or derivatives thereof, or polymethyl methacrylate or derivatives thereof.
4. The production method according to any one of claims 1 to 3, wherein the pore size and the pore wall thickness are adjusted by changing the molecular weight and the ratio of the hydrophilic-hydrophobic end segments of the block copolymer.
5. The method according to claim 1, wherein the metal oxide in step (4) is one or more of tungsten oxide, titanium oxide, tin oxide, niobium oxide and other metal oxides.
6. The method according to claim 1, wherein the noble metal in step (4) is one or an alloy of gold, platinum, palladium, rhodium and other noble metals.
7. The preparation method according to claim 1, wherein the specific surface area of the obtained noble metal-supported ordered double mesoporous metal oxide composite material is 50m2/g-130m2Per g, pore volume of 0.05cm3/g-0.4cm3The noble metal particle size is 2-10 nm.
8. A noble metal-loaded ordered double mesoporous metal oxide composite material prepared by the preparation method of any one of claims 1 to 7, wherein the shape of the pore canal is a spherical pore canal or a tubular pore canal, the mesoporous structure of the material has an ordered arrangement, the spatial group of the pore canal structure is p6mm,
P63/mmc，
one or more of the above structures are mixed. The pore size distribution of the porous material shows a bimodal distribution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011015498.0A CN112225255B (en) | 2020-09-24 | 2020-09-24 | Noble metal-loaded ordered double-mesoporous metal oxide composite material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011015498.0A CN112225255B (en) | 2020-09-24 | 2020-09-24 | Noble metal-loaded ordered double-mesoporous metal oxide composite material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112225255A true CN112225255A (en) | 2021-01-15 |
| CN112225255B CN112225255B (en) | 2021-10-26 |
Family
ID=74107695
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011015498.0A Active CN112225255B (en) | 2020-09-24 | 2020-09-24 | Noble metal-loaded ordered double-mesoporous metal oxide composite material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112225255B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114050239A (en) * | 2021-10-28 | 2022-02-15 | 复旦大学 | Silver nanocrystal modified mesoporous metal oxide composite material and preparation method thereof |
| CN114324495A (en) * | 2021-12-08 | 2022-04-12 | 复旦大学 | Nano sensing material for methane detection, preparation method thereof and methane sensor |
| CN115000433A (en) * | 2021-03-01 | 2022-09-02 | 中国科学院广州能源研究所 | Preparation method and application of nitrogen-doped ordered porous noble metal nano material based on self-assembly |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101134567A (en) * | 2007-07-26 | 2008-03-05 | 复旦大学 | High-stability large aperture ordered meso-porous carbon material and preparation method thereof |
| CN103115912A (en) * | 2013-01-23 | 2013-05-22 | 中国科学院合肥物质科学研究院 | Surface enhanced raman spectrum printing test paper for field test and preparation method thereof |
| CN105129856A (en) * | 2015-09-14 | 2015-12-09 | 复旦大学 | Resol-assisted synthetic large aperture ordered mesopore metallic oxide material and preparation method of material |
| CN105236468A (en) * | 2015-09-12 | 2016-01-13 | 复旦大学 | Alumina-doped mesoporous zinc oxide material having uniform pore channels, and preparation method thereof |
| KR20160098545A (en) * | 2015-02-09 | 2016-08-19 | 포항공과대학교 산학협력단 | Titanium-niobium mesoporous oxide and manufacturing mehtod thereof |
| CN106986320A (en) * | 2017-03-29 | 2017-07-28 | 上海出入境检验检疫局工业品与原材料检测技术中心 | A kind of magnetic ordered mesoporous carbon composite material of metal oxide insertion and preparation method and application |
| CN108217731A (en) * | 2017-12-16 | 2018-06-29 | 复旦大学 | Order mesoporous tungsten oxide gas sensitive of noble-metal-supported of high degree of dispersion and preparation method thereof |
| KR20190014349A (en) * | 2017-08-02 | 2019-02-12 | 포항공과대학교 산학협력단 | Method for manufacturing mesoporous silica nanoparticles and silica nanoparticles manufactured by the same |
-
2020
- 2020-09-24 CN CN202011015498.0A patent/CN112225255B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101134567A (en) * | 2007-07-26 | 2008-03-05 | 复旦大学 | High-stability large aperture ordered meso-porous carbon material and preparation method thereof |
| CN103115912A (en) * | 2013-01-23 | 2013-05-22 | 中国科学院合肥物质科学研究院 | Surface enhanced raman spectrum printing test paper for field test and preparation method thereof |
| KR20160098545A (en) * | 2015-02-09 | 2016-08-19 | 포항공과대학교 산학협력단 | Titanium-niobium mesoporous oxide and manufacturing mehtod thereof |
| CN105236468A (en) * | 2015-09-12 | 2016-01-13 | 复旦大学 | Alumina-doped mesoporous zinc oxide material having uniform pore channels, and preparation method thereof |
| CN105129856A (en) * | 2015-09-14 | 2015-12-09 | 复旦大学 | Resol-assisted synthetic large aperture ordered mesopore metallic oxide material and preparation method of material |
| CN106986320A (en) * | 2017-03-29 | 2017-07-28 | 上海出入境检验检疫局工业品与原材料检测技术中心 | A kind of magnetic ordered mesoporous carbon composite material of metal oxide insertion and preparation method and application |
| KR20190014349A (en) * | 2017-08-02 | 2019-02-12 | 포항공과대학교 산학협력단 | Method for manufacturing mesoporous silica nanoparticles and silica nanoparticles manufactured by the same |
| CN108217731A (en) * | 2017-12-16 | 2018-06-29 | 复旦大学 | Order mesoporous tungsten oxide gas sensitive of noble-metal-supported of high degree of dispersion and preparation method thereof |
Non-Patent Citations (5)
| Title |
|---|
| MA JUNHAO ET AL.: ""A General and Straightforward Route to Noble Metal-Decorated Mesoporous Transition-Metal Oxides with Enhanced Gas Sensing Performance"", 《SMALL》 * |
| MA JUNHAO ET AL.: ""Pt Nanoparticles Sensitized Ordered Mesoporous WO3 Semiconductor: Gas Sensing Performance and Mechanism Study"", 《ADV.FUNCT.MATER.》 * |
| WEI LUO ET AL.: ""A Resol-Assisted Co-Assembly Approach to Crystalline Mesoporous Niobia Spheres for Electrochemical Biosensing"", 《ANGEW.CHEM.INT.ED.》 * |
| 朱丽丽: ""巯基功能化有序介孔高分子材料的制备及其应用的研究"", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
| 邹义冬 等: ""两亲性嵌段共聚物导向合成有序介孔金属氧化物半导体材料"", 《高分子学报》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115000433A (en) * | 2021-03-01 | 2022-09-02 | 中国科学院广州能源研究所 | Preparation method and application of nitrogen-doped ordered porous noble metal nano material based on self-assembly |
| CN114050239A (en) * | 2021-10-28 | 2022-02-15 | 复旦大学 | Silver nanocrystal modified mesoporous metal oxide composite material and preparation method thereof |
| CN114050239B (en) * | 2021-10-28 | 2023-09-29 | 复旦大学 | Silver nanocrystalline modified mesoporous metal oxide composite material and preparation method thereof |
| CN114324495A (en) * | 2021-12-08 | 2022-04-12 | 复旦大学 | Nano sensing material for methane detection, preparation method thereof and methane sensor |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112225255B (en) | 2021-10-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112225255B (en) | Noble metal-loaded ordered double-mesoporous metal oxide composite material and preparation method thereof | |
| KR101278939B1 (en) | Method for producing metal nanoparticles and nanoparticles obtained in this way and use thereof | |
| Bordbar et al. | Preparation of MWCNT/TiO2–Co nanocomposite electrode by electrophoretic deposition and electrochemical study of hydrogen storage | |
| CN110201696B (en) | Preparation method of porous carbon fiber supported high-dispersion precious metal nanoparticles | |
| CN106564875A (en) | Preparation method of monodisperse cobalt-nitrogen co-doped hollow carbon nano-particles | |
| Li et al. | Carbon and nitrogen co-doped bowl-like Au/TiO2 nanostructures with tunable size for enhanced visible-light-driven photocatalysis | |
| CN103801705A (en) | Method for loading nanocrystalline metal oxide or nanocrystalline metal materials by porous carbon | |
| Bu et al. | Preparation and formation mechanism of porous TiO 2 films using PEG and alcohol solvent as double-templates | |
| CN110203974B (en) | P-type semiconductor metal oxide doped ordered mesoporous tungsten oxide gas-sensitive material and preparation method thereof | |
| Li et al. | Preparation and photocatalytic activity of eccentric Au–titania core–shell nanoparticles by block copolymer templates | |
| CN111333127A (en) | Hierarchical porous honeycomb nickel oxide microsphere and preparation method thereof | |
| CN104710191A (en) | Method for growing covalent organic framework film on alpha Al2O3 ceramic surface | |
| KR20110110538A (en) | Nanostructured film on the graphene by electrochemistry | |
| CN110451561B (en) | Synthesis method of large-aperture mesoporous bimetallic oxide semiconductor gas-sensitive material | |
| Sun et al. | Controllable fabrication of platinum nanospheres with a polyoxometalate-assisted process | |
| Miao et al. | General sacrificial template method for the synthesis of cadmium chalcogenide hollow structures | |
| Wang et al. | Hollow polyphosphazene microspheres with cross-linked chemical structure: synthesis, formation mechanism and applications | |
| US8771632B2 (en) | Methods of forming metal oxide nanostructures, and nanostructures thereof | |
| Jin et al. | Reduced graphene oxide-poly-(2-(dimethylamino) ethyl methacrylate)-Pt/Ag nanoscrolls and its electrocatalytic performance for oxidation of methanol | |
| Gaynor et al. | Characterization of nanophase titania particles synthesized using in situ steric stabilization | |
| CN113617355B (en) | Functional mesoporous material embedded with nano particles and in-situ embedding assembly method and application thereof | |
| CN109261154B (en) | Graphene-like framework loaded monoatomic structural material and preparation method and application thereof | |
| CN114950484B (en) | Preparation method and application of Janus cadmium sulfide heterojunction under photocatalysis of visible light | |
| CN116889884A (en) | Preparation method and application of CS-CSS/NHC heterogeneous nanocube | |
| Yang et al. | Preparation and properties of UiO-66 based hybrid materials via surface initiated metal-free ATRP |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| EE01 | Entry into force of recordation of patent licensing contract | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 20210115 Assignee: Shanghai Ganwei Technology Co.,Ltd. Assignor: Deng Yonghui Contract record no.: X2023990000330 Denomination of invention: Ordered double mesoporous metal oxide composites loaded with noble metals and their preparation method Granted publication date: 20211026 License type: Exclusive License Record date: 20230320 |