CN113145128A - Mesoporous WO3-x-MOx-Pt composite material and preparation method thereof - Google Patents
Mesoporous WO3-x-MOx-Pt composite material and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of advanced nano materials, and particularly relates to a transition metal oxide loaded MOxMesoporous WO of (iron, cobalt or nickel) and platinum nanoparticles3‑xComposite material WO3‑x‑MOx-Pt and a process for its preparation. The invention takes amphiphilic block copolymer as a structure directing agent and takes tungsten chloride as WO3‑xPrecursor of (a), a metallocene or a derivative thereof as a transition metal oxide MOxThe precursor, organic platinum complex as Pt precursor, is volatilized by solvent to induce co-assembly to form ordered mesostructure,removing the polymer by high-temperature calcination to obtain Pt-loaded nano particles and transition metal oxide MOxMesoporous WO of nanoparticles3‑xA composite material. The composite material has rich mesoporous pore canals, high specific surface area and uniformly dispersed Pt nano particles and transition metal oxide MOxThe nano-particles have great application potential in the fields of catalysis and sensing.
Description
Technical Field
The invention belongs to the technical field of advanced nano materials, and particularly relates to mesoporous WO3-x-MOx-Pt composite material and a method for preparing the same.
Background
Transition metal oxides carrying noble metal nanoparticles are an important functional inorganic material and are widely applied in the fields of photocatalysis, electrocatalysis, thermocatalysis, gas sensing and the like. In this class of materials, the noble metal nanoparticles are usually the active catalyst component, while the metal oxide is often not just the support, but it also participates in reactions, such as in the transfer of charge carriers or redox reactions. One of the effective means for improving the performance of this kind of materials is to load other types of metal oxides. On one hand, heterojunction structures such as p-n junctions and n-n junctions are constructed by loading semiconductor metal oxides with different forbidden band widths, so that the carrier concentration can be effectively regulated and controlled, the forbidden band width of the material can be changed, and the performance of the material can be remarkably improved. If the absorption of light is regulated and controlled in photocatalysis, the separation efficiency of photo-generated charges is improved; a depletion layer is formed in gas sensing, the change range of resistance before and after contact with gas is increased, and the sensitivity is improved. (H, Khan, M.G. Rigamonti, D.C. Boffito,Applied Catalysis B: Environmental2019, 252, 77-85；W. Koo, S. Choi, S. Kim, J. Jang, H. L. Tuller, I. Kim, Journal of the American Chemical Society2016, 13813431-13437) on the other hand, if the supported transition metal oxide has strong interaction with the noble metal nanoparticles, the catalytic properties can be further controlled to act as "1 + 1->2 "in the composition. As has been shown, FeOxAnd strong interaction exists between the Pt nanoparticles, so that the catalytic oxidation performance of the Pt nanoparticles on CO can be improved, and the anti-interference capability of the Pt nanoparticles is improved. (B, Qiao, A, Wang, X, Yang, L.F. Allard, Z. Jiang, Y. Cui, J. Liu, J. Li, T. Zhang,Nature Chemistry2011, 3, 634-641；T. L. Da Silva, A. H. M. Da Silva, J. M. Assaf, Materials Research Express2018, 6, 15042）。
the impregnation method is the most common method for preparing a carrier loaded with multiple active ingredients. However, this method has a problem that the steps are complicated and a multi-step impregnation treatment is required. In addition, the method easily causes the pore channel blockage of the mesoporous carrier, and is not beneficial to maintaining the mass transfer rate of the mesoporous carrier. Achieving one-pot loading of noble metals and metal oxides on the same support is a great challenge.
The invention adopts a novel direct co-assembly method, overcomes the complexity of an impregnation method, realizes the enrichment of tungsten species in a hydrophilic region by utilizing the characteristic that an amphiphilic block copolymer and a precursor are microphase separated to form an ordered mesostructure, realizes the enrichment of hydrophobic organic platinum complexes and metallocene (iron, cobalt and nickel) or derivatives thereof in a hydrophobic region, further removes organic matters by calcination decomposition, and obtains the catalyst simultaneously loaded with Pt nano particles and MOxMesoporous WO of (M: Fe, Co, Ni) nanoparticles3-x-composite material WO3-x-MOx-Pt. The prepared material has a mesoporous structure, a large specific surface area and rich WO3-x-MOx(M: Fe, Co, Ni) -Pt interface. The method disclosed by the invention has the advantages of simplicity, rapidness, high efficiency and controllability, and has potential application value in the aspects of catalysis and sensing.
Disclosure of Invention
The invention aims to provide a simple and controllable transition metal oxide MO loaded easily and repeatedlyxMesoporous WO of (iron, cobalt or nickel) and platinum nanoparticles3-x(as mesoporous WO)3-x-MOx-Pt) composite material and a method for the production thereof.
The mesoporous WO provided by the invention3-x-MOx-Pt composite material, M being Fe, Co or Ni, x being 0<x<3; the preparation method comprises the following steps: amphiphilic block copolymer is used as a structure directing agent, and tungsten chloride is used as WO3-xA precursor of (A), a metallocene (iron, cobalt or nickel) or a derivative thereof as a metal oxide MOxPrecursor, hydrophobic organo platinumThe coordination compound is used as a Pt precursor, and by utilizing the principle of solvent volatilization induced co-assembly (EICA), in the solvent volatilization process, the block copolymer and the precursor are subjected to microphase separation to form an ordered mesostructure, tungsten species are enriched in a hydrophilic region, metallocene or metallocene derivative of iron, cobalt and nickel and a hydrophobic organic platinum coordination compound are enriched in a hydrophobic region, and after the polymer is removed by high-temperature calcination, the Pt-loaded nano-particles and MO are preparedxMesoporous WO of (M: Fe, Co, Ni) nanoparticles3-xA composite material. The composite material has rich mesoporous pore canals, high specific surface area and uniformly dispersed Pt nano particles and MOx(M: Fe, Co, or Ni) nanoparticles. The specific surface of the synthesized composite material is 50 m2/g-200 m2Per g, pore volume of 0.01 cm3/g-0.4 cm3The pore size of the mesopores is 2 nm-30 nm, and the particle size of the Pt noble metal is 2 nm-10 nm.
The mesoporous WO provided by the invention3-x-MOxThe preparation method of the-Pt composite material comprises the following specific steps:
(1) firstly, dissolving an amphiphilic block copolymer serving as a structure directing agent in a volatile solvent, sequentially adding hydrochloric acid and ethyl orthosilicate, and fully stirring to obtain a solution A; sequentially adding acetylacetone and anhydrous tungsten hexachloride into anhydrous ethanol, and fully stirring to obtain a solution B; mixing the solution A and the solution B to obtain a solution C, sequentially adding a hydrophobic organic platinum complex and a metallocene (iron, cobalt or nickel) or a derivative thereof into the solution C to obtain a mixed solution, and stirring for 30-180 min; in the mixed solution C, the content of the template agent is 0.5-4% of the mass of the volatile solvent, the content of the tungsten chloride is 2-12% of the mass of the volatile solvent, and the content of the tungsten chloride: ethyl orthosilicate: the mass ratio of the hydrochloric acid is 1: (0.01-0.5): (0.0005-0.025), tungsten chloride: ethanol: the mass ratio of the acetylacetone is 1: (1-4): (0.5-3), the content of the hydrophobic organic platinum complex is 0.1-20% of the mass of the tungsten chloride, and the molar ratio of the hydrophobic organic platinum complex to the metallocene or the derivative thereof is 1: (1-20); the metal element of the metallocene or the derivative thereof is selected from iron, cobalt and nickel;
(2) then transferring the mixed solution to the surface of a substrate by a pulling, spin coating or film spreading method for volatilization, volatilizing at 25-35 ℃ for 12-36 h, then placing at 40-80 ℃ for 24-48) h, further completely volatilizing the solvent, placing the sample at 80-120 ℃ for 12-48 h, and solidifying;
(3) finally, scraping the solidified sample, grinding the sample into powder, heating the powder to 400 ℃ at the heating rate of 1-5 ℃/min in the inert gas atmosphere, and keeping the temperature for 2-4 h; then heating to 900 ℃ at 500 ℃ and keeping for 1-3 h; taking out the sample, heating to 300-500 ℃ at a speed of 5-10 ℃/min in the air atmosphere, calcining for 30-180 min to obtain the mesoporous WO3-x-MOx-a Pt composite; x is 0<x<3; m is Fe, Co or Ni.
In step (1) of the present invention:
the number average molecular weight of the used amphiphilic block copolymer is 5000-; the hydrophobic block is a polymer with hydrophobic properties such as polystyrene and derivatives thereof, polyisoprene and derivatives thereof or polymethyl methacrylate and derivatives thereof, or a copolymer of two or more of the polymers, and the number average molecular weight is between 4000-60000;
the solvent is one or more of tetrahydrofuran, chloroform, dichloromethane and dioxane;
the hydrophobic organic platinum complex is one or more of water-insoluble organic platinum complexes such as (1, 5-cyclooctadiene) dimethyl platinum (II), (trimethyl) methyl cyclopentadienyl platinum (IV) and the like;
the used metallocene (iron, cobalt or nickel) or its derivative is one or more of hydrophobic organic compounds such as ferrocene, cobaltocene, nickelocene or (dimethyl aminomethyl) ferrocene.
In the invention, the prepared mesoporous WO3-x-MOxThe (M: Fe, Co, Ni) -Pt composite material has a pore channel in the shape of a spherical pore channel or a tubular pore channel, mesoporous pores of the material are orderly arranged, and the pore channel structure is in a space groupp6mm，Fm 
m，Im 
m，Pm 
n， Pm 
m，Fd 
m，P6 3 /mmc，Ia 
dOne or more of the structures are mixed; its specific surface area is 50 m2/g-200 m2Per g, pore volume of 0.01 cm3/g-0.4 cm3The pore size of the mesopores is 2 nm-30 nm, and the particle size of the Pt noble metal is 2 nm-10 nm.
The composite material prepared by the invention has rich mesoporous pore canals, high specific surface area and uniformly dispersed Pt nano particles and transition metal oxide MOxThe nano-particles have great application prospect in the fields of catalysis and sensing.
Drawings
FIG. 1 shows mesoporous WO prepared in example 13-x-FeOxTransmission electron micrographs of Pt composite.
Detailed Description
Example 1:
(1) first, 0.05 g of an amphiphilic block copolymer polyethylene oxide-blockPolystyrene (PEO)109-b-PS229) Dissolving the compound serving as a structure directing agent in 2.5 g of tetrahydrofuran solvent, sequentially adding 0.4 mg of hydrochloric acid and 0.042 g of tetraethoxysilane, and fully stirring to obtain a solution A; in 0.4 g of absolute ethanolSequentially adding 0.2 g of acetylacetone and 0.2 g of anhydrous tungsten hexachloride, and fully stirring to obtain a solution B; mixing A and B to obtain a solution C, sequentially adding 2 mg of (1, 5-cyclooctadiene) dimethyl platinum (II) and 2.2 mg of ferrocene into the solution C, and stirring the obtained mixed solution for 120 min;
(2) then, pouring the mixed solution into a culture dish, volatilizing at 25 ℃ for 24 h, then placing at 70 ℃ for 24 h to further completely volatilize the solvent, and finally placing at 100 ℃ for 24 h to solidify;
(3) finally, scraping the cured sample, grinding the sample into powder, heating the sample at a heating rate of 1 ℃/min in a nitrogen atmosphere for 2 h at the temperature of 350 ℃, and heating the sample to 800 ℃ for 2 h; then heating the sample to 350 ℃ at the speed of 5 ℃/min in the air atmosphere and calcining for 75 min to obtain the mesoporous WO3-x-FeOx-a Pt composite.
Example 2:
(1) first, 0.025 g of an amphiphilic block copolymer polyethylene oxide-blockPolystyrene (PEO)23-b-PS39) Dissolving the compound serving as a structure directing agent in 5 g of tetrahydrofuran solvent, sequentially adding 0.004 g of 1 mol/L hydrochloric acid solution and 0.002 g of ethyl orthosilicate, and fully stirring to obtain a solution A; sequentially adding 0.1 g of acetylacetone and 0.1 g of anhydrous tungsten hexachloride into 0.2 g of anhydrous ethanol, and fully stirring to obtain a solution B; mixing A and B to obtain a solution C, sequentially adding 0.2 mg of (1, 5-cyclooctadiene) dimethyl platinum (II) and 0.15 mg of (dimethyl aminomethyl) ferrocene into the solution C, and stirring the obtained mixed solution for 30 min;
(2) then, immersing the silicon wafer into the mixed solution, pulling, volatilizing at 25 ℃ for 12 h, then placing in 40 ℃ for 24 h to further completely volatilize the solvent, and finally placing in 80 ℃ for 12 h to solidify;
(3) finally, scraping the cured sample, grinding the sample into powder, heating the sample at the speed of 1 ℃/min in the nitrogen atmosphere, keeping the temperature for 2 h at the speed of 300 ℃, and then heating the sample to 500 ℃ and keeping the temperature for 1 h; then heating the sample to 300 ℃ at the speed of 5 ℃/min in the air atmosphere and calcining for 30 min to obtain the mesoporous WO3-x-FeOx-a Pt composite.
Example 3:
(1) first, 0.3 g of an amphiphilic block copolymer polyethylene oxide-blockPolymethyl methacrylate (PEO)227-b-PMMA599) Dissolving the compound serving as a structure directing agent in 10g of chloroform solvent, sequentially adding 0.08 g of 37% concentrated hydrochloric acid and 0.6 g of ethyl orthosilicate, and fully stirring to obtain a solution A; sequentially adding 3.6 g of acetylacetone and 1.2 g of anhydrous tungsten hexachloride into 4.8 g of anhydrous ethanol, and fully stirring to obtain a solution B; mixing A and B to obtain a solution C, sequentially adding 0.24 g of (trimethyl) methyl cyclopentadienyl platinum (IV) and 2.8 g of cobaltocene into the solution C, and stirring the obtained mixed solution for 180 min;
(2) then, the mixed solution is dripped on a silicon wafer to be subjected to spin coating volatilization, the volatilization is carried out for 36 h at 35 ℃, then the mixed solution is placed in 80 ℃ for 48h to further completely volatilize the solvent, and finally the mixed solution is placed in 120 ℃ for 48h to be solidified;
(3) finally, scraping the cured sample, grinding the sample into powder, heating the sample at the rate of 5 ℃/min in the argon atmosphere, keeping the temperature for 4 h at the temperature of 400 ℃, and then heating the sample to 900 ℃ and keeping the temperature for 3 h; then heating the sample to 500 ℃ at the speed of 10 ℃/min in the air atmosphere and calcining for 180 min to obtain the mesoporous WO3-x-CoOx-a Pt composite.
Example 4:
(1) first, 0.3 g of poly- (2-vinylpyridine) -blockPolystyrene-blockPolyisoprene (P2 VP)47-b-PS389-PI289) And 0.3 g of poly- (4-vinylpyridine) -blockPolystyrene (P4 VP)50-b-PS389) Dissolving an amphiphilic block copolymer serving as a structure directing agent into a mixed solvent of 10g of dioxane and 10g of dichloromethane (20 g of volatile solvent in total), sequentially adding 0.2 g of 3 mol/L hydrochloric acid and 0.8 g of tetraethoxysilane, and fully stirring to obtain a solution A; sequentially adding 2 g of acetylacetone and 2 g of anhydrous tungsten hexachloride into 4 g of anhydrous ethanol, and fully stirring to obtain a solution B; mixing A and B to obtain a solution C, adding 0.2 g of (trimethyl) methyl cyclopentadienyl platinum (IV), 0.2 g of (1, 5-cyclooctadiene) dimethyl platinum (II), 1.1 g of nickelocene and 1.1 g of (dimethylaminomethyl) ferrocene in sequence into the solution C, and stirring the obtained mixed solution for 180 min;
(2) then, pouring the mixed solution into a culture dish, spreading a film to volatilize, volatilizing at 30 ℃ for 18 h, then placing at 50 ℃ for 36 h to further completely volatilize the solvent, and finally placing at 100 ℃ for 36 h to solidify;
(3) finally, scraping the cured sample, grinding the sample into powder, heating the powder at the temperature of 350 ℃ for 3h in the helium gas atmosphere at the heating rate of 3 ℃/min, and then heating the powder to 700 ℃ for 2 h; then heating the sample to 400 ℃ at the speed of 8 ℃/min in the air atmosphere and calcining for 90 min to obtain the mesoporous WO3-x-FeOx/NiOx-a Pt composite.
Claims (6)
1. Mesoporous WO3-x-MOxPreparation method of-Pt composite material, wherein M is Fe, Co or Ni, and x is 0<x<3, the method is characterized by comprising the following specific steps:
(1) firstly, dissolving an amphiphilic block copolymer serving as a structure directing agent in a volatile solvent, sequentially adding hydrochloric acid and ethyl orthosilicate, and fully stirring to obtain a solution A; sequentially adding acetylacetone and anhydrous tungsten hexachloride into anhydrous ethanol, and fully stirring to obtain a solution B; mixing the solution A and the solution B to obtain a solution C, sequentially adding a hydrophobic organic platinum complex and metallocene or derivatives thereof into the solution C to obtain a mixed solution, and stirring for 30-180 min; in the mixed solution C, the content of the template agent is 0.5-4% of the mass of the volatile solvent, the content of the tungsten chloride is 2-12% of the mass of the volatile solvent, and the content of the tungsten chloride: ethyl orthosilicate: the mass ratio of the hydrochloric acid is 1: (0.01-0.5): (0.0005-0.025), tungsten chloride: ethanol: the mass ratio of the acetylacetone is 1: (1-4): (0.5-3), the content of the hydrophobic organic platinum complex is 0.1-20% of the mass of the tungsten chloride, and the molar ratio of the hydrophobic organic platinum complex to the metallocene or the derivative thereof is 1: (1-20); here, the metal element of the metallocene or the derivative thereof is iron, cobalt or nickel;
(2) then transferring the mixed solution to the surface of a substrate by a pulling, spin coating or film spreading method for volatilization, volatilizing at 25-35 ℃ for 12-36 h, then placing at 40-80 ℃ for 24-48h, further completely volatilizing the solvent, placing the sample at 80-120 ℃ for 12-48 h, and solidifying;
(3) finally, scraping the solidified sample, grinding the sample into powder, heating the powder to 400 ℃ at the heating rate of 1-5 ℃/min in the inert gas atmosphere, and keeping the temperature for 2-4 h; then heating to 900 ℃ at 500 ℃ and keeping for 1-3 h; taking out the sample, heating to 300-500 ℃ at a speed of 5-10 ℃/min in the air atmosphere, calcining for 30-180 min to obtain the mesoporous WO3-x-MOx-a Pt composite; x is 0<x<3; m is Fe, Co or Ni;
the pore canal of the composite material is in a spherical or tubular shape, the mesoporous pores of the material are orderly arranged, and the space group of the pore canal structure isp6mm，Fm 
m，Im 
m，Pm 
n，Pm 
m，Fd 
m，P6 3 /mmc，Ia 
dOne or more of the structures are mixed; its specific surface area is 50 m2/g-200 m2Per g, pore volume of 0.01 cm3/g-0.4 cm3The pore size of the mesopores is 2 nm-30 nm, and the particle size of the Pt noble metal is 2 nm-10 nm.
2. The method as claimed in claim 1, wherein the amphiphilic block copolymer used in step (1) has a number average molecular weight of 5000-; the hydrophobic block is polystyrene and derivatives thereof, polyisoprene and derivatives thereof or polymethyl methacrylate or derivatives thereof, or a copolymer of two or more of the polymers, and the number average molecular weight is 4000-60000.
3. The method according to claim 1, wherein the solvent used in step (1) is one or more selected from tetrahydrofuran, chloroform, dichloromethane and dioxane.
4. The preparation method according to claim 1, wherein the hydrophobic organic platinum complex used in step (1) is one or more of (1, 5-cyclooctadiene) dimethyl platinum (II) and (trimethyl) methyl cyclopentadienyl platinum (IV).
5. The method according to claim 1, wherein the metallocene or its derivative used in step (1) is one or more of ferrocene, cobaltocene, nickelocene or (dimethylaminomethyl) ferrocene.
6. Mesoporous WO obtained by the preparation method according to any one of claims 1 to 53-x-MOx-Pt composite material, M being Fe, Co or Ni, x being 0<x<3; the pore canal is spherical or tubular, the mesoporous material has ordered arrangement, and the pore canal has spatial groupp6mm，Fm 
m，Im 
m，Pm 
n，Pm 
m，Fd 
m，P6 3 /mmc，Ia 
dOne or more of the structures are mixed; its specific surface area is 50 m2/g-200 m2Per g, pore volume of 0.01 cm3/g-0.4 cm3The pore size of the mesopores is 2 nm-30 nm, and the particle size of the Pt noble metal is 2 nm-10 nm.
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| 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 |
| EP3363538A1 (en) * | 2017-02-20 | 2018-08-22 | Technische Universität Berlin | A method of preparing a mesoporous carbon composite material comprising metal nanoparticles and use thereof as catalyst |
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| CN110203974A (en) * | 2019-06-18 | 2019-09-06 | 复旦大学 | Order mesoporous tungsten oxide gas sensitive of p-type semiconductor doped metallic oxide and preparation method thereof |
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| EP3363538A1 (en) * | 2017-02-20 | 2018-08-22 | Technische Universität Berlin | A method of preparing a mesoporous carbon composite material comprising metal nanoparticles and use thereof as catalyst |
| 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 |
| CN109012668A (en) * | 2018-08-17 | 2018-12-18 | 西安交通大学 | CeO2The preparation method of skeleton adulteration transition metal oxide and noble metal composite-material |
| CN110143608A (en) * | 2019-04-24 | 2019-08-20 | 启东纳睿新材料科技有限公司 | Supported porous metal oxide material with high porosity and preparation method thereof |
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