CN113145128B - Mesoporous WO 3-x -MO x -Pt composite material and preparation method thereof - Google Patents

Mesoporous WO 3-x -MO x -Pt composite material and preparation method thereof Download PDF

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CN113145128B
CN113145128B CN202110163289.9A CN202110163289A CN113145128B CN 113145128 B CN113145128 B CN 113145128B CN 202110163289 A CN202110163289 A CN 202110163289A CN 113145128 B CN113145128 B CN 113145128B
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邓勇辉
马俊豪
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Zhuhai Fudan Innovation Research Institute
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Abstract

The invention belongs to the technical field of advanced nano materials, and particularly relates to a transition Metal Oxide (MO) loaded on a substrate x Mesoporous WO of (iron, cobalt or nickel) and platinum nanoparticles 3‑x Composite material WO 3‑x ‑MO x -Pt and a process for its preparation. The invention takes amphiphilic block copolymer as a structure directing agent and takes tungsten chloride as WO 3‑x Precursor of (a), a metallocene or a derivative thereof as a transition metal oxide MO x Precursor, organic platinum complex as Pt precursor, solvent volatilization inducing co-assembling to form ordered mesostructure, high temperature calcining to eliminate polymer and obtain nanometer Pt particle and transition metal oxide supported MO x Mesoporous WO of nanoparticles 3‑x A composite material. The composite material has rich mesoporous pore canals, high specific surface area and uniformly dispersed Pt nano particles and transition metal oxide MO x The nano particles have great application potential in the fields of catalysis and sensing.

Description

Mesoporous WO 3-x -MO x -Pt composite material and preparation method thereof
Technical Field
The invention belongs to the technical field of advanced nano materials, and particularly relates to mesoporous WO 3-x -MO x -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. In one aspect, disabling by load differentiationThe semiconductor metal oxide with the bandwidth constructs heterojunction structures such as p-n junctions, n-n junctions and the like, can effectively regulate and control carrier concentration, change the forbidden bandwidth of materials and obviously improve the performance of the materials. For example, the absorption of light is regulated and controlled in photocatalysis, and 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 a strong interaction with the noble metal nanoparticles, its catalytic properties can be further regulated to play the role of "1+1>2 "in the composition. As has been shown, feO x 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 problems 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 MO x Mesoporous WO of (M: fe, co, ni) nanoparticles 3-x -composite material WO 3-x -MO x -Pt. The prepared material has a mesoporous structure, a large specific surface area and rich WO 3-x -MO x (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 repeatedly x Mesoporous WO of (iron, cobalt or nickel) and platinum nanoparticles 3-x (as mesoporous WO) 3-x -MO x -Pt) composite material and a method for the production thereof.
The mesoporous WO provided by the invention 3-x -MO x -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 WO 3-x A precursor of (A), a metallocene (iron, cobalt or nickel) or a derivative thereof as a metal oxide MO x Precursor and hydrophobic organic platinum complex are used as Pt precursor, according to the solvent volatilization induced co-assembly (EICA) principle, in the solvent volatilization process, the block copolymer and the precursor are microphase separated to form an ordered mesostructure, tungsten species are enriched in a hydrophilic area, metallocene or metallocene derivative of iron, cobalt and nickel and hydrophobic organic platinum complex are enriched in a hydrophobic area, and after the polymer is removed by high-temperature calcination, the Pt-loaded nano particles and MO are prepared x Mesoporous WO of (M: fe, co, ni) nanoparticles 3-x A composite material. The composite material has rich mesoporous pore canals, high specific surface area and uniformly dispersed Pt nano particles and MO x (M: fe, co, or Ni) nanoparticles. The specific surface area of the synthesized composite material is 50m 2 /g-200 m 2 Per g, pore volume of 0.01cm 3 /g-0.4 cm 3 The pore size of the mesopores is 2nm-30nm, and the size of the Pt noble metal particles is 2nm-10nm.
The mesoporous WO provided by the invention 3-x -MO x Method for preparing-Pt composite materialThe method comprises the following steps:
(1) Firstly, dissolving an amphiphilic block copolymer serving as a structure directing agent in a volatile solvent, sequentially adding hydrochloric acid and tetraethoxysilane, 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 30-180min; 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 weight ratio 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 12-36h, then placing at 40-80 ℃ for 24-48) h, further completely volatilizing the solvent, placing the sample at 80-120 ℃ for 12-48h, and solidifying;
(3) Finally, scraping the solidified sample, grinding the sample into powder, heating the powder to 300-400 ℃ at a heating rate of 1-5 ℃/min in an inert gas atmosphere, and keeping the temperature at 2-4h; then heating to 500-900 ℃ and keeping for 1-3h; taking out the sample, heating to 300-500 deg.C at 5-10 deg.C/min in air atmosphere, calcining for 30-180min to obtain mesoporous WO 3-x -MO x -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 5000-70000, the hydrophilic block is a block which can react with a tungsten precursor, such as polyethylene oxide, poly- (2-vinylpyridine) or poly- (4-vinylpyridine), and the number average molecular weight is 1000-10000; the hydrophobic block is a polymer with hydrophobic property 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 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 WO 3-x -MO x The (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
Figure DEST_PATH_IMAGE001
m，Im
Figure 16705DEST_PATH_IMAGE001
m，Pm
Figure 527321DEST_PATH_IMAGE001
n，Pm
Figure 307058DEST_PATH_IMAGE001
m，Fd
Figure 171108DEST_PATH_IMAGE001
m，P6 3 /mmc，Ia
Figure 985481DEST_PATH_IMAGE001
dOne or more of themThe hybrid structure of (1); the specific surface area is 50m 2 /g-200 m 2 Per g, pore volume of 0.01cm 3 /g-0.4 cm 3 The pore size of the mesopores is 2nm-30nm, and the size of the Pt noble metal particles is 2nm-10nm.
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 MO x The nano-particles have great application prospect in the fields of catalysis and sensing.
Drawings
FIG. 1 shows mesoporous WO prepared in example 1 3-x -FeO x Transmission electron micrographs of Pt composite.
Detailed Description
Example 1:
(1) First, 0.05 g amphiphilic block copolymer polyethylene oxide-blockPolystyrene (PEO) 109 -b-PS 229 ) Dissolving the compound serving as a structure directing agent in a 2.5 g tetrahydrofuran solvent, sequentially adding 0.4 mg hydrochloric acid and 0.042 g tetraethoxysilane, and fully stirring to obtain a solution A; sequentially adding 0.2 g acetylacetone and 0.2 g anhydrous tungsten hexachloride into 0.4 g anhydrous ethanol, and fully stirring to obtain a solution B; mixing A and B to obtain a solution C, sequentially adding 2 mg (1,5-cyclooctadiene) dimethyl platinum (II) and 2.2 mg ferrocene into the solution C, and stirring the obtained mixed solution for 120 min;
(2) Then, the mixed solution is poured into a culture dish, 24 h volatilizes at 25 ℃, 24 h is placed in 70 ℃ to further completely volatilize the solvent, and finally 24 h is placed in 100 ℃ to be solidified;
(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 of the sample at 2 h at 350 ℃, and then heating the sample to 800 ℃ and keeping the temperature at 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 WO 3-x -FeO x -a Pt composite.
Example 2:
(1) First, 0.025 g amphiphilic block copolymer polyethylene oxide-blockPolystyrene (PEO) 23 -b-PS 39 ) Dissolving the compound serving as a structure directing agent in a 5 g tetrahydrofuran solvent, sequentially adding 0.004 g of 1 mol/L hydrochloric acid solution and 0.002 g tetraethoxysilane, and fully stirring to obtain a solution A; sequentially adding 0.1 g acetylacetone and 0.1 g anhydrous tungsten hexachloride into 0.2 g anhydrous ethanol, and fully stirring to obtain a solution B; mixing A and B to obtain a solution C, sequentially adding 0.2 mg (1,5-cyclooctadiene) dimethyl platinum (II) and 0.15 mg (dimethyl aminomethyl) ferrocene into the solution C, and stirring the obtained mixed solution for 30 min;
(2) Then, the silicon chip is immersed in the mixed solution, pulled, volatilized at 25 ℃ for 12 h, then placed in 40 ℃ for 24 h to further completely volatilize the solvent, and finally placed in 80 ℃ for 12 h to be solidified;
(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 of the sample at 2 h at the temperature of 300 ℃, and then heating the sample to 500 ℃ and keeping the temperature at 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 WO 3-x -FeO x -a Pt composite.
Example 3:
(1) First, 0.3 g amphiphilic block copolymer polyethylene oxide-blockPolymethyl methacrylate (PEO) 227 -b-PMMA 599 ) Dissolving the compound serving as a structure directing agent in 10g chloroform solvent, sequentially adding 0.08 g of 37% concentrated hydrochloric acid and 0.6 g tetraethoxysilane, and fully stirring to obtain a solution A; sequentially adding 3.6 g acetylacetone and 1.2 g anhydrous tungsten hexachloride into 4.8 g anhydrous ethanol, and fully stirring to obtain a solution B; mixing A and B to obtain a solution C, sequentially adding 0.24 g (trimethyl) methylcyclopentadiene platinum (IV) and 2.8 g cobaltocene into the solution C, and stirring the obtained mixed solution for 180min;
(2) Then, the mixed solution is dripped on a silicon wafer to carry out spin coating volatilization, 36h is volatilized at 35 ℃, 48h is placed in 80 ℃ to further completely volatilize the solvent, and finally 48h is placed in 120 ℃ to be solidified;
(3) Finally, scraping the solidified sample, grinding the sample into powder, heating the powder at a rate of 5 ℃/min in an argon atmosphere, and keeping the temperature at 400 ℃ before4h, then heating to 900 ℃ and keeping 3h; then the sample is heated to 500 ℃ at a speed of 10 ℃/min in the air atmosphere and calcined for 180min to obtain the mesoporous WO 3-x -CoO x -a Pt composite.
Example 4:
(1) First, 0.3 g poly- (2-vinylpyridine) -blockPolystyrene-blockPolyisoprene (P2 VP) 47 -b-PS 389 -PI 289 ) And 0.3 g poly- (4-vinylpyridine) -blockPolystyrene (P4 VP) 50 -b-PS 389 ) An amphiphilic block copolymer as a structure directing agent is dissolved in a mixed solvent of 10g dioxane and 10g dichloromethane (20 g volatile solvent in total), 0.2 g of 3 mol/L hydrochloric acid and 0.8 g tetraethoxysilane are sequentially added, and the mixture is fully stirred to obtain a solution A; sequentially adding 2 g acetylacetone and 2 g anhydrous tungsten hexachloride into 4 g anhydrous ethanol, and fully stirring to obtain a solution B; mixing A and B to obtain a solution C, sequentially adding 0.2 g (trimethyl) methylcyclopentadiene platinum (IV) and 0.2 g (1,5-cyclooctadiene) dimethyl platinum (II), 1.1 g nickelocene and 1.1 g (dimethylaminomethyl) ferrocene into the solution C, and stirring the obtained mixed solution for 180min;
(2) Then, the mixed solution is poured into a culture dish for membrane spreading and volatilization, 18 h is volatilized at 30 ℃, 36h is placed in 50 ℃ for further complete solvent volatilization, and finally 36h is placed in 100 ℃ for solidification;
(3) Finally, scraping the cured sample, grinding the sample into powder, placing the powder in a helium gas atmosphere at the temperature rise rate of 3 ℃/min, keeping the temperature at 3h at 350 ℃, and then heating the powder to 700 ℃ and keeping the temperature at 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 WO 3-x -FeO x /NiO x -a Pt composite.

Claims (6)

1. Mesoporous WO 3-x -MO x Preparation 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 tetraethoxysilane, 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 30-180min; 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 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 its derivative is iron, cobalt or nickel;
wherein, tungsten species are enriched in a hydrophilic region, and metallocene or metallocene derivative of iron, cobalt and nickel and hydrophobic organic platinum complex are enriched in a hydrophobic region;
(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 12-36h, then placing at 40-80 ℃ for 24-48h, further completely volatilizing the solvent, placing the sample at 80-120 ℃ for 12-48h, and solidifying;
(3) Finally, scraping the solidified sample, grinding the sample into powder, heating to 300-400 ℃ at a heating rate of 1-5 ℃/min in an inert gas atmosphere, and keeping the temperature for 2-4h; then heating to 500-900 ℃ and keeping for 1-3h; taking out the sample, heating to 300-500 ℃ at the speed of 5-10 ℃/min in the air atmosphere, calcining for 30-180min to obtain mesoporous WO 3-x -MO x -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 pore canal or a tubular pore canal, the mesoporous of the material has ordered arrangement, the space group of the pore canal structure is p6mm,
Figure FDA0003903557270000011
P6 3 /mmc，
Figure FDA0003903557270000012
one or more of the structures are mixed; its specific surface area is 50m 2 /g-200m 2 Per g, pore volume of 0.01cm 3 /g-0.4cm 3 The pore diameter of the mesopores is 2nm-30nm, and the particle size of the Pt noble metal is 2nm-10nm.
2. The method according to claim 1, wherein the amphiphilic block copolymer used in step (1) has a number average molecular weight of 5000 to 70000, the hydrophilic block is polyethylene oxide, poly- (2-vinylpyridine) or poly- (4-vinylpyridine), and the number average molecular weight is 1000 to 10000; the hydrophobic block is polystyrene and its derivatives, polyisoprene and its derivatives or polymethyl methacrylate or its derivatives, or copolymer of two or more polymers, and has number average molecular weight of 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 of any one of claims 1 to 5 3-x -MO x -Pt composite material, M being Fe, co or Ni, x being 0<x<3; the shape of the pore canal is a spherical pore canal or a tubular pore canalThe pore canal, the mesoporous of the material are orderly arranged, the space group of the pore canal structure is p6mm,
Figure FDA0003903557270000022
P6 3 /mmc，
Figure FDA0003903557270000021
one or more of the structures are mixed; the specific surface area of the powder is 50m 2 /g-200m 2 Per g, pore volume of 0.01cm 3 /g-0.4cm 3 The pore diameter of the mesopores is 2nm-30nm, and the particle size of the Pt noble metal is 2nm-10nm.
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