CN102581301A - Method for preparing multi-metal nanoparticles by one-step coreduction - Google Patents
Method for preparing multi-metal nanoparticles by one-step coreduction Download PDFInfo
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- CN102581301A CN102581301A CN201210090839XA CN201210090839A CN102581301A CN 102581301 A CN102581301 A CN 102581301A CN 201210090839X A CN201210090839X A CN 201210090839XA CN 201210090839 A CN201210090839 A CN 201210090839A CN 102581301 A CN102581301 A CN 102581301A
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Abstract
The invention belongs to the technical field of preparation of metal nanoparticles, and relates to a method for preparing multi-metal nanoparticles by one-step coreduction through citrate, particularly to the method for preparing the multi-metal nanoparticles with different sizes and morphologies by heating and boiling a mixed solution of a variety of metal ions and adding a citrate solution into the mixed solution rapidly, or heating and boiling the citrate solution and adding the mixed solution of a variety of metal ions into the citrate solution rapidly. The method can be used for preparing the multi-metal nanoparticles with high-efficiency catalytic activity easily and rapidly on a large scale. The gold source is HAuCl4.4H2O or HAuBr4.H2O, the palladium source is K2PdCl6 or K2PdCl4, the silver source is AgNO3 or AgF, the platinum source is K2PtCl6 or H2PtCl6.6H2O, and the citrate is sodium citrate, potassium citrate or ammonium citrate.
Description
Technical field
The invention belongs to the metal nanoparticle preparing technical field; Be specifically related to a kind of method for preparing the multi-element metal nano particle through one step of citrate coreduction; Particularly relate to a kind of with multiple metallic ion mixed liquor heated and boiled to wherein adding citrate solution fast; Or with the citrate solution heated and boiled to wherein adding metallic ion mixed liquor fast, thereby prepare the method for multi-element metal nano particle.
Background technology
Multi-element metal nano particle with high catalytic activity can be used as new catalyst and is widely used in many chemical reactions; Like the reaction of suzuki coupling reaction, acetylene hydrogenation, vinyl acetate is synthetic, hydrogen peroxide is synthetic, carbon monoxide oxidation etc., therefore becomes the focus that numerous researchers pay close attention to.Along with people's is to the increase day by day of multi-element metal nano-particle catalyst demand, and increasing synthetic method is developed.The method for preparing at present the multi-element metal nano particle is mainly: a kind of metal nanoparticle with synthetic in advance is a seed, second kind of metal shell of epitaxial growth, synthetic in regular turn the third metal shell.The shortcoming of this method is to need at first synthetic a kind of metal nanoparticle in the preparation process, and separating behind this metal nanoparticle of purifying with it be further reduction second metal ion species of seed, formation metal shell.Synthetic method is through multistep reaction, and experiment condition is harsh complicated, can not large-scale production, and make its application receive very big restriction.
Developing efficient, energy-conservation synthetic method is the problem that the researcher needs solution badly.Through the directly synthetic multi-element metal nano particle of step coreduction reaction; This preparation method has not only simplified complicated experimental procedure; Be easy to mass preparation; And the metal nanoparticle that obtains is because the active surface area that has unique electronic structure and obviously increase has higher catalytic activity, thereby expanded the catalytic applications of multi-element metal nano particle in the number of chemical reaction.
Summary of the invention
The object of the invention just provides a kind of simple method for preparing the multi-element metal nano particle fast; Be about to multiple metallic ion mixed liquor heated and boiled to wherein adding citrate solution fast; Or with the citrate solution heated and boiled to wherein adding metallic ion mixed liquor fast, thereby preparation multi-element metal nano particle.
The present invention adopts a step coreduction method in the aqueous solution, to prepare the multi-element metal nano particle, in preparation process, do not need the multistep reduction and separate purification step, so experimental implementation is simply quick, and have good experimental repeatability.The method of the invention can be used for preparing multiple multi-element metal nano particles such as Au/Pd, Pd/Pt, Au/Pd/Pt, Au/Pt, Au/Ag, Ag/Pd, Ag/Pt.
Above-mentioned experimental technique is raw materials used to be source metal and citrate, and source metal is the mixing in two or three in Jin Yuan, palladium source, Yin Yuan, the platinum source; Wherein, golden source can be HAuCl
44H
2O, HAuBr
4H
2O etc.; The palladium source can be K
2PdCl
6, K
2PdCl
4Deng; The silver source can be AgNO
3, AgF etc.; The platinum source can be K
2PtCl
6, H
2PtCl
66H
2O etc.; Citrate can be natrium citricum, potassium citrate, ammonium citrate etc.
Specifically, step of the present invention is following:
Source metal is dissolved in 10~1000mL deionized water, and the concentration of source metal is 5 * 10
-5~5 * 10
-3Mol/L, the mol ratio between two kinds of source metal is that 1: 0.25~4, the three kinds mol ratios between the source metal are 1: 0.25~4: 0.25~4, reaction system is stirred and is heated to 100 ℃ make the solution boiling, obtains the sepia clear solution; In above-mentioned reaction system, adding concentration again is that 1~5wt%, volume are the citrate solution of 0.24~120mL; Keep the solution fluidized state after 10~20 minutes, stop heating and continue to stir cool to room temperature, thereby obtain the multi-element metal nano particle of different-shape, different size.
Be that 1~5wt%, volume are that the citrate of 0.24~120mL is dissolved in 10~1000mL deionized water perhaps, reaction system stirred and be heated to 100 ℃ make the solution boiling, obtain colourless transparent solution concentration; In above-mentioned reaction system, add source metal again, the concentration of source metal is 5 * 10
-5~5 * 10
-3Mol/L; Mol ratio between two kinds of source metal is 1: 0.25~4; Mol ratio between three kinds of source metal is 1: 0.25~4: 0.25~4; Keep the solution fluidized state after 10~20 minutes, stop heating and continue to stir cool to room temperature, thereby obtain the multi-element metal nano particle of different-shape, different size.
Description of drawings
Fig. 1: the transmission electron microscope photo of Au/Pd bielement nano particle;
Fig. 2: the transmission electron microscope photo of Au/Pd bielement nano particle;
Fig. 3: the transmission electron microscope photo of Au/Pd bielement nano particle;
Fig. 4: the transmission electron microscope photo of Au/Pd bielement nano particle;
Fig. 5: the transmission electron microscope photo of Pd/Pt bielement nano particle;
Fig. 6: the transmission electron microscope photo of Au/Pd/Pt ternary nano particle;
Fig. 7: the transmission electron microscope photo of Au/Pt bielement nano particle;
Fig. 8: the transmission electron microscope photo of Au/Pd bielement nano particle.
The specific embodiment
Below in conjunction with embodiment the present invention is done further elaboration, rather than will limit the invention with this.
Embodiment 1
With 0.0648mL concentration is the HAuCl of 0.04g/mL
4Solution and 0.0625mL concentration are the H of 0.04g/mL
2PdCl
6Solution is dissolved in the 50mL deionized water, and this moment, the total concentration of metal ion was 2.5 * 10
-4Mol/L, HAuCl
4With H
2PdCl
6Between mol ratio be 1: 1, reaction system stirs and is heated to 100 ℃ and makes the solution boiling, obtains the sepia clear solution.In reaction system, adding 1mL concentration then is the sodium citrate solution of 2wt%.Keep the solution fluidized state after 10 minutes, stop heating and continue stirring cool to room temperature, as shown in Figure 1, obtaining average grain diameter is the spherical Au/Pd binary metal nano particle of class of 34.4nm.
Embodiment 2
With 0.0648mL concentration is the HAuCl of 0.04g/mL
4Solution and 0.0625mL concentration are the H of 0.04g/mL
2PdCl
6Solution is dissolved in the 50mL deionized water, and this moment, the total concentration of metal ion was 2.5 * 10
-4Mol/L, HAuCl
4With H
2PdCl
6Between mol ratio be 1: 1, reaction system stirs and is heated to 100 ℃ and makes the solution boiling, obtains the sepia clear solution.In reaction system, adding 3mL concentration then is the sodium citrate solution of 2wt%.Keep the solution fluidized state after 10 minutes, stop heating and continue stirring cool to room temperature, as shown in Figure 2, obtaining average grain diameter is the flower-shaped Au/Pd binary metal nano particle of 28.6nm.
Embodiment 3
With 0.0648mL concentration is the HAuCl of 0.04g/mL
4Solution and 0.0625mL concentration are the H of 0.04g/mL
2PdCl
6Solution is dissolved in the 50mL deionized water, and this moment, the total concentration of metal ion was 2.5 * 10
-4Mol/L, HAuCl
4With H
2PdCl
6Between mol ratio be 1: 1, reaction system stirs and is heated to 100 ℃ and makes the solution boiling, obtains the sepia clear solution.In reaction system, adding 4mL concentration then is the sodium citrate solution of 2wt%.Keep the solution fluidized state after 10 minutes, stop heating and stir cool to room temperature, as shown in Figure 3, obtain dendritic Au/Pd binary metal nano particle.
Embodiment 4
With 0.0648mL concentration is the HAuCl of 0.04g/mL
4Solution and 0.03125mL concentration are the H of 0.04g/mL
2PdCl
6Solution is dissolved in the 50mL deionized water, and this moment, the total concentration of metal ion was 1.875 * 10
-4Mol/L, HAuCl
4With H
2PdCl
6Between mol ratio be 1: 0.5, reaction system stirs and is heated to 100 ℃ and makes the solution boiling, obtains the sepia clear solution.In reaction system, adding 3mL concentration then is the sodium citrate solution of 2wt%.Keep the solution fluidized state after 10 minutes, stop heating and continue stirring cool to room temperature, as shown in Figure 4, obtaining average grain diameter is the flower-shaped Au/Pd binary metal nano particle of 24.8nm.
Embodiment 5
0.0625mL concentration is the H of 0.04g/mL
2PdCl
6Solution and 0.0815mL concentration are the H of 0.04g/mL
2PtCl
6Solution is dissolved in the 50mL deionized water, and this moment, the total concentration of metal ion was 2.5 * 10
-4Mol/L, H
2PdCl
6With H
2PtCl
6Between mol ratio be 1: 1, reaction system stirs and is heated to 100 ℃ and makes the solution boiling, obtains the sepia clear solution.In reaction system, adding 3mL concentration then is the sodium citrate solution of 2wt%.Keep the solution fluidized state after 10 minutes, stop heating and continue stirring cool to room temperature, as shown in Figure 5, obtaining average grain diameter is the spherical Pd/Pt binary metal nano particle of 3.2nm.
Embodiment 6
0.0648mL concentration is the HAuCl of 0.04g/mL
4Solution, 0.0625mL concentration are the H of 0.04g/mL
2PdCl
6Solution and 0.0815mL concentration are the H of 0.04g/mL
2PtCl
6Solution is dissolved in the 50mL deionized water, and this moment, the total concentration of metal ion was 3.75 * 10
-4Mol/L, HAuCl
4, H
2PdCl
6With H
2PtCl
6Between mol ratio be 1: 1: 1, reaction system stirs and is heated to 100 ℃ and makes the solution boiling, obtains the sepia clear solution.In reaction system, adding 3mL concentration then is the sodium citrate solution of 2wt%.Keep the solution fluidized state after 10 minutes, stop heating and stir cool to room temperature, as shown in Figure 6, obtaining average grain diameter is the spherical Au/Pd/Pt ternary metal nano particle of 4.8nm.
Embodiment 7
0.0648mL concentration is the HAuCl of 0.04g/mL
4Solution and 0.0815mL concentration are the H of 0.04g/mL
2PtCl
6Solution is dissolved in the 50mL deionized water, and this moment, the total concentration of metal ion was 2.5 * 10
-4Mol/L, HAuCl
4With H
2PtCl
6Between mol ratio be 1: 1, reaction system stirs and is heated to 100 ℃ and makes the solution boiling, obtains the sepia clear solution.In reaction system, adding 3mL concentration then is the sodium citrate solution of 2wt%.Keep the solution fluidized state after 10 minutes, stop heating and stir cool to room temperature, as shown in Figure 7, obtaining average grain diameter is the spherical Au/Pt binary metal nano particle of 4.0nm.
Embodiment 8
With 3mL concentration is that the sodium citrate solution of 2wt% is dissolved in the 50mL deionized water, and reaction system stirs and is heated to 100 ℃ and makes the solution boiling, obtains colourless transparent solution.In reaction system, adding 0.0648mL concentration then is the HAuCl of 0.04g/mL
4Solution and 0.0625mL concentration are the H of 0.04g/mL
2PdCl
6Solution, this moment, the total concentration of metal ion was 2.5 * 10
-4Mol/L, HAuCl
4With H
2PdCl
6Between mol ratio be 1: 1.Keep the solution fluidized state after 10 minutes, stop heating and stir cool to room temperature, as shown in Figure 8, obtaining average grain diameter is the Au/Pd binary metal nano particle of 62.3nm.
Claims (6)
1. utilize a step coreduction to prepare the method for multi-element metal nano particle, its step is following:
(1) source metal is dissolved in 10~1000mL deionized water, the concentration of source metal is 5 * 10
-5~5 * 10
-3Mol/L stirs and is heated to 100 ℃ with reaction system and makes the solution boiling, obtains the sepia clear solution; Source metal is the mixing in two or three in Jin Yuan, palladium source, Yin Yuan, the platinum source;
(2) in above-mentioned reaction system, adding concentration again is that 1~5wt%, volume are the citrate solution of 0.24~120mL; Keep the solution fluidized state after 10~20 minutes, stop heating and continue to stir cool to room temperature, thereby obtain the multi-element metal nano particle of different-shape, different size.
2. utilize a step coreduction to prepare the method for multi-element metal nano particle, its step is following:
(1) is that 1~5wt%, volume are that the citrate of 0.24~120mL is dissolved in 10~1000mL deionized water with concentration, reaction system stirred and be heated to 100 ℃ make the solution boiling, obtain colourless transparent solution;
(2) in above-mentioned reaction system, add source metal again, the concentration of source metal is 5 * 10
-5~5 * 10
-3Mol/L, source metal is the mixing in two or three in Jin Yuan, palladium source, Yin Yuan, the platinum source; Keep the solution fluidized state after 10~20 minutes, stop heating and continue to stir cool to room temperature, thereby obtain the multi-element metal nano particle of different-shape, different size.
3. according to claim 1 or claim 2 the step coreduction that utilizes prepares the method for multi-element metal nano particle, and it is characterized in that: Jin Yuan is HAuCl
44H
2O or HAuBr
4H
2O; The palladium source is K
2PdCl
6Or K
2PdCl
4The silver source is AgNO
3Or AgF; The platinum source is K
2PtCl
6Or H
2PtCl
66H
2O.
4. according to claim 1 or claim 2 the step coreduction that utilizes prepares the method for multi-element metal nano particle, and it is characterized in that: citrate is natrium citricum, potassium citrate or ammonium citrate.
5. according to claim 1 or claim 2 the step coreduction that utilizes prepares the method for multi-element metal nano particle, it is characterized in that: the mol ratio between two kinds of source metal is 1: 0.25~4.
6. according to claim 1 or claim 2 the step coreduction that utilizes prepares the method for multi-element metal nano particle, it is characterized in that: the mol ratio between three kinds of source metal is 1: 0.25~4: 0.25~4.
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Cited By (10)
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CN102806358A (en) * | 2012-08-30 | 2012-12-05 | 山东大学 | Synthesis method of water-soluble monodisperse spherical silver nanocrystals |
CN103394085A (en) * | 2013-08-19 | 2013-11-20 | 吉林大学 | Polymer-coated gold nanoparticle chain compound, preparation method and applications thereof |
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CN102806358A (en) * | 2012-08-30 | 2012-12-05 | 山东大学 | Synthesis method of water-soluble monodisperse spherical silver nanocrystals |
CN103394085A (en) * | 2013-08-19 | 2013-11-20 | 吉林大学 | Polymer-coated gold nanoparticle chain compound, preparation method and applications thereof |
CN103864971B (en) * | 2013-10-12 | 2016-08-10 | 牡丹江师范学院 | A kind of synthetic method of nucleocapsid structure high polymer brush |
CN103864971A (en) * | 2013-10-12 | 2014-06-18 | 牡丹江师范学院 | Synthetic method of novel core-shell structure polymer brush |
CN103638926A (en) * | 2013-12-02 | 2014-03-19 | 上海师范大学 | Preparation method of super-stable silver-platinum nanoparticles |
CN103638926B (en) * | 2013-12-02 | 2016-04-06 | 上海师范大学 | A kind of preparation method of overstable silver-nano platinum particle |
CN104551009A (en) * | 2015-01-16 | 2015-04-29 | 吉林大学 | Preparation method of two-dimensional fractal silver nanoparticles in alcohol-water system |
CN105170995A (en) * | 2015-09-21 | 2015-12-23 | 陕西师范大学 | Method for wrapping gold-silver alloy nanometer particles through silicon dioxide |
CN105710385A (en) * | 2016-01-27 | 2016-06-29 | 南通大学 | Preparation method for porous hollow gold-silver nano-alloy particles |
CN106112006A (en) * | 2016-07-22 | 2016-11-16 | 国家纳米科学中心 | A kind of golden nanometer particle aqueous solution and its preparation method and application |
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Application publication date: 20120718 |