CN103639418B - Method for preparing highly mono-dispersed metal nanoparticles in porous material - Google Patents
Method for preparing highly mono-dispersed metal nanoparticles in porous material Download PDFInfo
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- CN103639418B CN103639418B CN201310596561.8A CN201310596561A CN103639418B CN 103639418 B CN103639418 B CN 103639418B CN 201310596561 A CN201310596561 A CN 201310596561A CN 103639418 B CN103639418 B CN 103639418B
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Abstract
The invention provides a method for preparing highly mono-dispersed metal nanoparticles in a porous material. The method comprises the following steps of: 1) synthesizing the porous material with continuous and through three-dimension and a unified aperture; 2) dissolving a precursor of the metal nanoparticles and a reducing agent in a solvent to obtain a reaction solution for synthesizing the metal nanoparticles, mixing the porous material synthesized in the step 1) with the reaction solution for synthesizing the metal nanoparticles, and enabling the reaction solution of the metal nanoparticles to enter into holes of the porous material through capillary action; 3) using the porous material as a reactor for synthesizing the metal nanoparticles, and reducing the precursor of the metal nanoparticles to obtain the metal nanoparticles; 4) filtering, washing and drying the mixed solution obtained in the step 3) to obtain the final product. The method prepares the highly mono-dispersed metal nanoparticles, and is simple and convenient in process and short in synthesis period; the synthesized mono-dispersed metal nanoparticles show high activity when serving as a catalyst of a proton exchange membrane fuel cell.
Description
Technical field
The invention belongs to nano material and field of nanometer technology, more particularly, to one kind prepare highly single point in the porous material
The method of dispersed metallic nano-particle.
Background technology
Metal nanoparticle because have uniqueness hot, electric, magnetically and optically etc. performance is so as in the energy, environmental protection, oil
The fields such as work, biological medicine have a wide range of applications.These performances that metal nanoparticle has are all little with it
Based on yardstick.But, such metallic nanoparticle subsystem generally has very high specific surface energy it is easy to just there is group
Poly-, lead to metallic nanoparticle subsystem to lose had special performance.Therefore, how to prevent its reunion from being metal nanoparticle
One focus of architectural study.
Stabilizer is added to make generation electrostatic repulsion forces or sterically hindered repulsive force between metal nanoparticle stable to reach
Metal nanoparticle, prevent reunion from being a kind of effective method.Wherein polymer be make with the most use, be most important stabilizer
One of.However, by contrast, nano-particle is stoped to be reunited using inorganic material, the method for raising nano-particle stability has
Some irreplaceable advantages, such as high thermal stability and chemical stability.For catalytic applications, porous material is stably received
Rice metal has more advantages.Porous material has the advantageous characteristic such as uniform pore diameter, high-specific surface area and high heat stability, is suitable for
In the activity keeping nano metal and its stability of enhancing, and the good exchange being conducive to reactant and product.Additionally, it is many
Porous materials can also support the functional group with other properties using characteristics such as its homogeneous aperture and high-specific surface areas, thus
Extend the function of metal nanometer composite material.Therefore, porous material and compound greatly the extending of metal nanoparticle are received
The application of rice metal, such as high-temperature catalytic and selective catalysis reaction etc..But, metal current nano-particle and porous material
The preparation of composite of material has inevitable problem, and such as duct easily blocks, specific surface area be greatly lowered and
Nano metal is easily reunited, thus affecting its deep application.Therefore it provides a kind of by easy technique, in the porous material
Prepare there is high degree of monodispersity metal nanoparticle method be in the urgent need to.
Content of the invention
The technical problem to be solved is: provide a kind of preparation technology easy and wide adaptability in porous material
The middle method preparing height single dispersion metal nanometer particles.
The present invention by solving the technical scheme that above-mentioned technical problem is taken is:
A kind of method preparing height single dispersion metal nanometer particles in the porous material, it comprises the steps:
1) three-dimensional continuous insertion, the porous material of uniform pore are synthesized；
2) metal nanoparticle predecessor and reducing agent are dissolved in solvent, obtain synthesizing the reaction of metal nanoparticle
Solution, takes the porous material of step 1) synthesis to mix with the reaction solution of described synthesis metal nanoparticle, metal nanoparticle
Reaction solution wick themselves in the duct of porous material；
3) using porous material as the reactor of synthesis metal nanoparticle, obtained by reducing metal Precursor of Nano Particles
To metal nanoparticle；
4) mixed solution that step 3) obtains is filtered, washing, after being dried, obtain final product.
In such scheme, described porous material includes mesoporous or large pore material.
In such scheme, described porous material is silica, titanium oxide, zirconium oxide, di-iron trioxide or aluminum oxide porous
Material.
In such scheme, described step 2) in metal nanoparticle predecessor be acetylacetone,2,4-pentanedione platinum and palladium acetylacetonate
Mixture.
In such scheme, described step 2) in reducing agent be polyvinylpyrrolidone.
In such scheme, described step 2) in solvent be BDO.
The invention has the benefit that the invention provides a kind of prepare in the porous material there is high degree of monodispersity
The method of metal nanoparticle.Synthesis has three-dimensional continuous insertion, the porous material of uniform pore first, is then made by capillary
With introducing the predecessor of synthesis metal nanoparticle, finally fabricated in situ metal nanoparticle in the porous material, thus reach
Preparation has the purpose of high degree of monodispersity metal nanoparticle.The maximum innovation of the present invention is by using larger molten of viscosity
Agent BDO as preparing metal nanoparticle reactant liquor, thus having prepared the metallic nanoparticle of high degree of monodispersity
Son, it is to avoid traditional Porous materials carrying metal nano-particle is easily reunited, blocking duct and lead to deactivated problem, improve
The stability of metal nanoparticle.The method that this preparation method supports than other metal nanoparticles, has process simplicity, closes
Become the advantage of cycle is short.And, the monodispersity metal nanoparticle of present invention synthesis is urged as Proton Exchange Membrane Fuel Cells
Agent illustrates high activity.
Brief description
Fig. 1 is the stereoscan photograph of embodiment 1 gained porous oxidation silicon materials mcf.
Fig. 2 is the transmission electron microscope of embodiment 1 gained bimetal nano particles porous oxidation silicon composite (ptpd mcf)
Photo: a) low resolution photo, b) high-resolution photo.
Fig. 3 is that the x-ray of embodiment 1 gained bimetal nano particles porous oxidation silicon composite (ptpd mcf) is spread out
Penetrate spectrogram.
Fig. 4 is that embodiment 1 gained bimetal nano particles porous oxidation silicon composite (ptpd mcf), bimetallic are received
The electrochemical surface area contrast of rice corpuscles ptpd and conventional two-dimensional mesoporous carrying bimetallic nano-particle (ptpd@mcm-41)
Figure.
Fig. 5 is that embodiment 1 gained bimetal nano particles porous oxidation silicon composite (ptpd mcf), bimetallic are received
Rice corpuscles ptpd and the mass activity comparison diagram of conventional two-dimensional mesoporous carrying bimetallic nano-particle (ptpd@mcm-41).
Fig. 6 is the transmission electron microscope photo of comparative example 1 gained bimetal nano particles and porous oxidation silicon composite.
Fig. 7 is the transmission electron microscope photo of comparative example 2 gained bimetal nano particles and porous oxidation silicon composite.
Specific embodiment
The invention will be further described with reference to the accompanying drawings and examples, and it is right that certainly following embodiments should not be construed as
The restriction of the present invention.
Embodiment 1:
The present embodiment provides a kind of height single dispersing bimetal nano particles porous oxidation silicon composite (ptpd mcf)
Preparation, specifically comprise the following steps that
(1) three-dimensional continuous insertion, the synthesis of the porous oxidation silicon materials mcf of uniform pore:
At ambient temperature 1.5～2.5g p123 and 1.5～2.5g mesitylene being added concentration is 1.2～2.0m, body
Amass as, in the hydrochloric acid solution of 50～100ml, mixing；Then mixed solution is warming up to 35～45 DEG C, after 1～2 hour,
Add tetraethyl orthosilicate in mixed solution, stir 15～25 hours under the conditions of continuing 35～45 DEG C；Then solution is loaded reaction
Kettle is aging 20～30 hours at 110～130 DEG C；Finally the product obtaining filtered, wash, air drying, then in air
Under the conditions of 500～600 DEG C of roastings obtained porous material mcf more than 5 hours.
(2) by 0.1～1.0g(1) the middle porous material mcf synthesizing, the acetylacetone,2,4-pentanedione platinum of 0.02～0.10mmol, 0.02
The palladium acetylacetonate of～0.10mmol and 0.5～2.0mmol polyvinylpyrrolidone are dissolved in the 1,4- that volume is 20～30ml
In butanediol；
(3) under conditions of having protective atmosphere (nitrogen or argon gas), the mixed solution in (2) is heated to 210～220
DEG C, it is incubated 30～60 minutes, then naturally cool to room temperature；
(4) mixed solution in (3) is filtered, washed with acetone, after being dried, obtain final products.
As shown in figure 1, the porous silica silicon materials mcf preparing has the structure of continuous insertion, uniform pore, its
Aperture is about 25nm.As shown in Figure 2 a, in the bimetal nano particles porous oxidation silicon composite (ptpd mcf) of preparation
In, the particle diameter of bimetal nano particles ptpd is about 5nm, has the dispersiveness of height in the porous material, and each
Bimetal nano particles correspond to a hole, by high-resolution-ration transmission electric-lens photo (Fig. 2 b) and x-ray diffraction collection of illustrative plates (Fig. 3)
As can be seen that metal nanoparticle ptpd has good degree of crystallinity.Fig. 4 can be seen that bimetal nano manufactured in the present embodiment
The electrochemical surface area of particle porous oxidation silicon composite (ptpd mcf) is bimetal nano particles ptpd and biography respectively
2.5 and 1.6 times of system 2 D mesopore carrying bimetallic nano-particle (ptpd@mcm-41).Fig. 5 can be seen that the present embodiment system
The mass activity of standby bimetal nano particles porous oxidation silicon composite (ptpd mcf) is bimetal nano particles respectively
Ptpd and 1.9 and 1.4 times of conventional two-dimensional mesoporous carrying bimetallic nano-particle (ptpd@mcm-41).It follows that the present invention
The monodispersity metal nanoparticle of synthesis illustrates high activity as catalyst of fuel batter with proton exchange film.
Comparative example 1
This comparative example 1 is same as Example 1, and difference is step 2) in by mcf, acetylacetone,2,4-pentanedione platinum, acetylacetone,2,4-pentanedione
Palladium and polyvinylpyrrolidone are dissolved in ethylene glycol.As shown in fig. 6, in the case that other conditions are completely the same, with viscosity
Relatively low ethylene glycol is that the ptpd bimetallic generating in the system of solvent there occurs reunion, therefore deduces that, larger viscosity
Solvent is conducive to synthesizing the metal nanoparticle of high dispersive in the porous material.
Comparative example 2
This comparative example 1 is same as Example 1, and difference is step 2) in by mcf, na2pdcl4、k2ptcl4, anti-bad
Hematic acid and polyvinylpyrrolidone are dissolved in deionized water.As shown in fig. 7, with the lower deionized water of viscosity as solvent
The ptpd bimetallic synthesizing there occurs even more serious reunion, and the solvent further demonstrating larger viscosity is conducive in porous
The metal nanoparticle of high dispersive is synthesized in material.
It should be noted that it will be understood by those within the art that, technical scheme can be carried out
Modification or equivalent, the objective without deviating from technical solution of the present invention and scope, the right that it all should be covered in the present invention will
Ask in the middle of scope.
Claims (5)
1. a kind of method preparing height single dispersion metal nanometer particles in the porous material is it is characterised in that it is by walking as follows
Rapid composition:
1) three-dimensional continuous insertion, the porous material of uniform pore are synthesized；
2) metal nanoparticle predecessor and reducing agent are dissolved in BDO solvent, obtain synthesizing metal nanoparticle
Reaction solution, take step 1) synthesis porous material with described synthesize metal nanoparticle reaction solution mix, metal is received
The reaction solution of rice corpuscles wicks themselves in the duct of porous material；
3) using porous material as the reactor of synthesis metal nanoparticle, by 210 DEG C -220 DEG C reduction gold of high temperature system
Belong to Precursor of Nano Particles and obtain metal nanoparticle；
4) mixed solution that step 3) obtains is filtered, washing, after being dried, obtain final product.
2. preparation method as claimed in claim 1 is it is characterised in that described porous material includes mesoporous or large pore material.
3. preparation method as claimed in claim 1 is it is characterised in that described porous material is silica, titanium oxide, oxidation
Zirconium, di-iron trioxide or aluminum oxide porous material.
4. preparation method as claimed in claim 1 is it is characterised in that described step 2) in metal nanoparticle predecessor be
Acetylacetone,2,4-pentanedione platinum and the mixture of palladium acetylacetonate.
5. preparation method as claimed in claim 1 is it is characterised in that described step 2) in reducing agent be polyvinylpyrrolidine
Ketone.
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| CN104259480B (en) * | 2014-10-11 | 2016-03-09 | 武汉理工大学 | A kind of cellular glass microballoon SERS substrate embedding silver nano-grain and preparation method thereof |
| US10259999B2 (en) * | 2016-08-18 | 2019-04-16 | AhuraTech LLC | Method for storing and releasing nanoparticles |
| US10035193B2 (en) * | 2016-08-18 | 2018-07-31 | AhuraTech LLC | Method for synthesizing particles in the presence of a solid phase |
| CN108246350A (en) * | 2018-01-10 | 2018-07-06 | 武汉理工大学 | A kind of mesoporous molecular sieve catalyst material and its in-situ preparation method for coating noble metal |
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| CN101618352A (en) * | 2008-06-30 | 2010-01-06 | 比亚迪股份有限公司 | Preparation method of supported metal catalyst |
| CN102205420A (en) * | 2010-03-31 | 2011-10-05 | 中国科学院福建物质结构研究所 | Preparation method of water-phase noble metal nano particles |
| CN102962059A (en) * | 2011-09-01 | 2013-03-13 | 中国科学院福建物质结构研究所 | Method for preparing noble bimetal nano catalyst granules |
| CN103240088A (en) * | 2013-05-07 | 2013-08-14 | 中国石油大学(北京) | Catalyst for macro-porous oxide supported core-shell structure nanoparticles and preparation method of catalyst |
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| CN101857217B (en) * | 2009-04-07 | 2013-03-20 | 清华大学 | Carbon nano tube metal composite and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101618352A (en) * | 2008-06-30 | 2010-01-06 | 比亚迪股份有限公司 | Preparation method of supported metal catalyst |
| CN102205420A (en) * | 2010-03-31 | 2011-10-05 | 中国科学院福建物质结构研究所 | Preparation method of water-phase noble metal nano particles |
| CN102962059A (en) * | 2011-09-01 | 2013-03-13 | 中国科学院福建物质结构研究所 | Method for preparing noble bimetal nano catalyst granules |
| CN103240088A (en) * | 2013-05-07 | 2013-08-14 | 中国石油大学(北京) | Catalyst for macro-porous oxide supported core-shell structure nanoparticles and preparation method of catalyst |
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