CN1237494A - Preparation of metal nanometre cluster - Google Patents
Preparation of metal nanometre cluster Download PDFInfo
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- CN1237494A CN1237494A CN 98102193 CN98102193A CN1237494A CN 1237494 A CN1237494 A CN 1237494A CN 98102193 CN98102193 CN 98102193 CN 98102193 A CN98102193 A CN 98102193A CN 1237494 A CN1237494 A CN 1237494A
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- metal
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- nanometre cluster
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Abstract
The preparation method of metal nanometer cluster includes the following steps: uniformly mixing metal salt (RhCl3.3H2O or RuCl3.3H2O) or metal complex (H2PtCl6.6H2O or H2PdCl4 or HA11Cl4) and stabilizing agent (for example polyethylene pyrrolidone) in alcohol-water mixed solution, microwave irradiation and reduction so as to obtain metal nanometer cluster with uniform grain size and narrow distribution.
Description
The present invention relates to a kind of preparation method of metal cluster, particularly a kind of preparation method of metal nanometre cluster.
1992, Science257,219-223 reported spent ion exchange resin exchange Fe
2+Prepare γ-Fe
2O
3Nano microcrystalline is because γ-Fe
2O
3Crystallite is attached on the crosslinked ion exchange resin, can't obtain single γ-Fe
2O
3Crystallite.
1994, J.Mol.Catal.86,129-177 reported with chemical reduction method in the solution and prepared metal nanometre cluster, and this method produces the uniformity coefficient of precipitated metal thing and uncontrollable metallic particles in preparation process high-volume.
Nineteen ninety-five, J.Chem.Mater.7,1991-1994 have reported the CO that utilizes polymer-based bulk effect metal-organic complex to be dissolved in above-critical state
2In, infiltrate again in the macromolecule matrix, make homodisperse metal nanometre cluster by pyrolysis, but this metal nanometre cluster can not be separated from macromolecule matrix.
1997, Chinese invention patent 97119954.X disclosed a kind of method that adopts freeze-drying to prepare metal nanometre cluster, but the uniformity coefficient of the metal nanometre cluster particle that this method obtains is wayward.
The present invention has overcome in the prior art and to have produced the precipitated metal thing, and metallic particles is inhomogeneous and can not get the shortcoming of single metal nanometre cluster and a kind of methods that adopt the evengranular metal nanometre cluster of a large amount of preparations of microwave irradiation method are provided.
The method that the present invention prepares metal nanometre cluster is to carry out in the following order:
One, the preparation of metal cluster presoma:
1, preparation metal complex or metal salt solution:
Metal complex or slaine are dissolved in alcohol or water or the two mixed solvent of pure water, become metal complex or metal salt solution, its solution concentration is 10
-2Mol/L～1mol/L, described metal complex are H
2PtCl
66H
2O or H
2PdCl
4Or HAuCl
4, described slaine is RhCl
33H
2O or RuCl
33H
2O.
2, the preparation of stabiliser solution:
(1) preparation of stabilizing polymer agent solution:
Polyvinylpyrrolidone is dissolved in alcohol or water or the two mixed solvent of pure water, and the water-soluble chain link molar concentration that makes of polyvinyl alcohol is 1 * 10
-1Mol/L～50mol/L.
(2) preparation of little molecule ligand stabilizing agent:
Little molecule ligand is dissolved in alcohol or water or the two mixed solvent of pure water, and making solution concentration is 1 * 10
-1Mol/L～50mol/L.
Above-mentioned little molecule ligand can be triphenyl phosphorus or single sulfonic acid triphenyl phosphorus or trisulfonic acid triphenyl phosphorus.
(3) preparation of benzene sulfonic acid sodium salt or long chain quaternary stabilizing agent:
With 12,16, in the octadecyl benzene sulfonic acid sodium salt or eight, ten, the water-soluble or pure water mixed solvent of dodecyl quaternary ammonium salt, making solution concentration is 1 * 10
-1Mol/L～50mol/L.
With above-mentioned metal complex or salt and stabiliser solution 0.5: 1 by volume～1: 1, mix at 25 ℃, obtain the clear solution of metal nanometre cluster presoma.
Two, the preparation of metal nanometre cluster
There are two kinds of methods to prepare metal nanometre cluster.
1, above-mentioned precursor solution is placed directly in the microwave field, under the microwave irradiation of certain frequency (2450MHz) and power (300-750W), reduction obtain black (Pt, Pd, Ru, Rh) or the solution of (Au) rosy metal nanometre cluster.This solution can and then obtain pressed powder with the method for precipitating reagents such as decompression distillation or acetone precipitations.
2, above-mentioned precursor solution is added a certain amount of NaOH in advance, be placed on then in the microwave field, under the microwave irradiation of certain frequency (2450MHz) and power (300-750W), reduction obtains the (Pt of black, Pd, Ru, Rh) or the solution of (Au) rosy metal nanometre cluster.This solution can and then obtain pressed powder with the method for precipitating reagents such as decompression distillation or acetone precipitations.
The metal cluster grain diameter of the present invention's preparation is even, and relative standard deviation is 0.17, is significantly less than present additive method.In this metal cluster water soluble, alcohol, nitrobenzene, nitromethane, nitroethane, chloroform, the dichloroethanes equal solvent, help catalyst as chemical reaction etc.
Metal nanometre cluster preparation method of the present invention, the employing inorganic metal compound is a raw material, does not need Co 2 supercritical fluid or organo-metallic compound as (COD) PtMe
2(COD) Ag (Hfacac), wherein, COD=1,5-cyclo-octadiene, Hfacac=[CF
3C (O) CHC (O) CF
3]
-As raw material, so method is simple, and cost is low.
Observe by transmission electron microscope (TEM), the average grain diameter of Pt metal cluster is 2.9nm, standard deviation=0.57nm, and relative standard deviation is 0.15.
Change the ratio of PVP chain link molal quantity and Pt molal quantity, can obtain the metal nanometre cluster of different-grain diameter, see Table 1.
| PVP chain link molal quantity/Pt molal quantity | Average grain diameter (nm) | Standard deviation (nm) | Relative standard deviation |
| ????100∶1 | ????2.9 | ????0.57 | ????0.15 |
| ?????50∶1 | ????3.0 | ????0.56 | ????0.16 |
| ?????20∶1 | ????3.4 | ????0.50 | ????0.17 |
| ?????10∶1 | ????3.8 | ????0.47 | ????0.16 |
When adding NaOH in advance in above-mentioned precursor solution, the particle diameter of metal nanometre cluster diminishes, and relative standard deviation is constant.When PVP chain link molal quantity and Pt molal quantity ratio are 50: 1, change the ratio of NaOH molal quantity and Pt molal quantity, can obtain the metal nanometre cluster of different-grain diameter, see Table 2.
| NaOH molal quantity/Pt molal quantity | Average grain diameter (nm) | Standard deviation (nm) | Relative standard deviation |
| ?????0 | ????3.0 | ????0.56 | ????0.16 |
| ????2∶1 | ????3.0 | ????0.49 | ????0.16 |
| ????4∶1 | ????2.6 | ????0.48 | ????0.18 |
| ????6∶1 | ????1.9 | ????0.33 | ????0.17 |
| ????8∶1 | ????2.0 | ????0.32 | ????0.16 |
| ???10∶1 | ????2.1 | ????0.40 | ????0.19 |
Embodiment 1,
12.9mg chloroplatinic acid (H
2PtCl
66H
2O) be dissolved in the 10ml ethylene glycol, polyvinylpyrrolidone (PVP) 0.139g is dissolved in the 14ml ethylene glycol, mixes, and adds the NaOH aqueous solution of 1ml0.2M then, orange-yellow clear solution, at 2450MHz, 30 seconds of 750W microwave irradiation.Color is black by xanthochromia, obtains nano platinum and belongs to bunch.This metal cluster can get off to become solid with acetone precipitation.This ferrous metal bunch water soluble, methyl alcohol, nitrobenzene, chloroform equal solvent.
Average grain diameter: 2.0nm; Standard deviation: 0.32nm; Relative standard deviation: 0.16 embodiment 2,
In 50ml distilled water, dissolve in 24.5mg chlorine palladium acid (H
2PdCl
4), add polyvinyl alcohol (PVA) 0.44g subsequently, dissolving evenly, orange-yellow clear solution, at 2450MHz, 40 seconds of 300W microwave irradiation.Color is black by xanthochromia, obtains nanometer palladium metal bunch.
Average grain diameter: 4.8nm; Standard deviation: 1.20nm; Relative standard deviation: 0.25 embodiment 3,
With 0.13g chloroplatinic acid (H
2PtCl
66H
2O) be dissolved in the 15ml methyl alcohol, polyvinylpyrrolidone (PVP) 1.39g is dissolved in the 15ml methyl alcohol, mixes, add the 15ml0.1MNaOH methanol solution again and obtain orange-yellow clear solution, at 2450MHz, 350W microwave irradiation 10 minutes, color is black by xanthochromia, and Pt (IV) is converted into Pt (0).Under vacuum, boil off methyl alcohol and obtain black solid, water soluble, methyl alcohol, nitrobenzene, chloroform equal solvent.
Average grain diameter: 1.03nm; Standard deviation: 0.24nm; Relative standard deviation: 0.23 embodiment 4,
0.10g gold chloride (HAuCl
4) be dissolved in the 15ml methyl alcohol, polyvinylpyrrolidone (PVP) 3.27g is dissolved in the 15ml methyl alcohol, mixes, add the 10ml0.2MNaOH methanol solution again and obtain orange-yellow clear solution, at 2450MHz, 30 seconds of 300W microwave irradiation, solution is purple black by xanthochromia, and Au (III) is converted into Au (0).Pressure reducing and steaming methyl alcohol obtains the aubergine solid, water soluble, methyl alcohol, nitrobenzene, chloroform equal solvent.
Average grain diameter: 7.6nm; Standard deviation: 1.45nm; Relative standard deviation: 0.19 embodiment 5,
0.26g chloroplatinic acid (H
2PtCl
66H
2O) be dissolved in the 15ml methyl alcohol, polyvinylpyrrolidone (PVP) 2.78 g are dissolved in the 15ml methyl alcohol, mix, add the 15ml0.2MNaOH methanol solution again and obtain orange-yellow clear solution, at 2450MHz, 330W microwave irradiation 20 minutes, solution is black by xanthochromia, and Pt (IV) is converted into Pt (0).
Average grain diameter: 2.03nm; Standard deviation: 0.37nm; Relative standard deviation: 0.18 embodiment 6,
4mg chloroplatinic acid (H
2PtCl
66H
2O) be dissolved in the 10ml methyl alcohol, neopelex 1.5g is dissolved in the 50ml water, mixes, and obtains orange-yellow clear solution, at 2450MHz, and 450W microwave irradiation 40 minutes, solution is black by xanthochromia, and Pt (IV) is converted into Pt (0).
Average grain diameter: 4.1nm; Standard deviation: 0.98nm; Relative standard deviation: 0.24 embodiment 7,
12.9mg ruthenium trichloride (RuCl
33H
2O) be dissolved in the 10ml ethylene glycol, polyvinylpyrrolidone (PVP) 0.55g is dissolved in the 14ml ethylene glycol, mix, orange-yellow clear solution, at 2450MHz, 30 seconds of 750W microwave irradiation.Color is black by brown stain, obtains nanometer ruthenium metal cluster.This metal cluster can get off to become solid with acetone precipitation.This ferrous metal bunch water soluble, methyl alcohol, nitrobenzene, chloroform equal solvent.
Average grain diameter: 3.5nm; Standard deviation: 0.63nm; Relative standard deviation: 0.18 embodiment 8,
26mg rhodium chloride (RhCl
33H
2O) be dissolved in the 10ml ethylene glycol, polyvinylpyrrolidone (PVP) 0.55g is dissolved in the 14ml ethylene glycol, mix, orange-yellow clear solution, at 2450MHz, 30 seconds of 750W microwave irradiation.Color is black by red stain, obtains nanometer rhodium metal bunch.
Average grain diameter: 3.0nm; Standard deviation: 0.54nm; Relative standard deviation: 0.18
Claims (8)
1, a kind of preparation method of metal nanometre cluster is characterized in that described method, and step is carried out in the following order:
(1) preparation metal cluster presoma
With concentration is 10
-2The solution of the metal complex of mol/L～1mol/L or metal salt solution and stabilizing agent is 0.5: 1～1: 1 by volume, mixes at 25 ℃ and obtains the metal cluster precursor solution,
(2) with above-mentioned precursor solution directly at 2450MHz, under the microwave condition irradiation of 300-750W, or above-mentioned precursor solution added the solution that makes metal nanometre cluster behind the NaOH again under above-mentioned microwave condition irradiation in advance,
(3) this solution can obtain pressed powder with the method for precipitating reagents such as decompression distillation or acetone precipitation.
2, the preparation method of a kind of metal nanometre cluster according to claim 1 is characterized in that described metal complex solution is H
2PtCl
66H
2O or H
2PdCl
4Or HAuCl
4The pure or pure water mixed solution of water.
3, the preparation method of a kind of metal nanometre cluster according to claim 1 is characterized in that described metal salt solution is RhCl
33H
2O or RuCl
33H
2Pure or the pure water mixed solution of the water of O.
4, the preparation method of a kind of metal nanometre cluster according to claim 1 is characterized in that described metal nanometre cluster is Pt, Rh, Au, Ru or Pd metal nanometre cluster.
5, the preparation method of a kind of metal nanometre cluster according to claim 1 is characterized in that described stabilizing agent is that concentration is 1 * 10
-1Pure or the pure water mixed solution of the water of mol/L～50mol/L polyvinylpyrrolidone.
6, the preparation method of a kind of metal nanometre cluster according to claim 1 is characterized in that described stabilizing agent is that concentration is 1 * 10
-1The aqueous solution of mol/L～50mol/L polyvinyl alcohol.
7, the preparation method of a kind of metal nanometre cluster according to claim 1 is characterized in that described stabilizing agent is that concentration is 1 * 10
-1Mol/L～50mol/L sodium dodecyl benzene sulfonate aqueous solution.
8, the preparation method of a kind of metal nanometre cluster according to claim 1 is characterized in that described little molecule ligand is triphenyl phosphorus or single sulfonic acid triphenyl phosphorus or trisulfonic acid triphenyl phosphorus.
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| CN98102193A CN1095411C (en) | 1998-05-29 | 1998-05-29 | Preparation of metal nanometre cluster |
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|---|---|---|---|
| CN98102193A CN1095411C (en) | 1998-05-29 | 1998-05-29 | Preparation of metal nanometre cluster |
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| CN1095411C CN1095411C (en) | 2002-12-04 |
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|---|---|---|---|---|
| WO2008134939A1 (en) * | 2007-05-08 | 2008-11-13 | Synfuels China Technology Co., Ltd. | Transition metal nano-catalyst, its preparation method and its use in fischer-tropsch synthetic reaction |
| CN102259191A (en) * | 2011-07-13 | 2011-11-30 | 大连理工大学 | Nano silver cluster for highly sensitively detecting nitro explosive compound and preparation thereof |
| CN102341165A (en) * | 2009-03-02 | 2012-02-01 | 卡罗比亚意大利（共同）股份公司 | Process for preparing stable suspensions of metal nanoparticles and the stable colloidal suspensions obtained thereby |
| CN101767018B (en) * | 2009-01-06 | 2012-06-13 | 北京大学 | Loading type Pd base metal nanometer cluster catalyst, preparing method and applications thereof |
| CN103586484A (en) * | 2013-11-25 | 2014-02-19 | 中国科学院福建物质结构研究所 | Palladium ruthenium alloy nano-particles, preparation method thereof and application thereof |
| CN105798325A (en) * | 2016-03-24 | 2016-07-27 | 贵州大学 | Sub-2nm ruthenium (Ru) nanowire network and preparation method thereof |
| CN105945301A (en) * | 2016-05-10 | 2016-09-21 | 江南大学 | Controllable synthesis method for metallic ruthenium nano particles with different particle sizes under mild condition |
| CN106512993A (en) * | 2016-08-30 | 2017-03-22 | 北京化工大学 | Preparation and hydrogenation application of palladium-ruthenium dual-metal nano-catalyst |
| CN106862583A (en) * | 2015-12-13 | 2017-06-20 | 中国科学院大连化学物理研究所 | A kind of preparation method of the controllable gold nanoclusters of atom number |
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| CN107983948A (en) * | 2016-10-27 | 2018-05-04 | 中国科学院大连化学物理研究所 | Au6With Au11Method is mutually converted between nano-cluster |
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Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0295283B1 (en) * | 1986-12-30 | 1991-12-04 | HALLSWORTH & ASSOCIATES PTY. LIMITED | Improvements in or relating to the formation of metal alkoxides and metal powders by the use of microwave radiation |
| CN1032904C (en) * | 1993-09-09 | 1996-10-02 | 中国科学院物理研究所 | Amorphous superfine metal particles and preparing process thereof |
| CN1060702C (en) * | 1995-01-16 | 2001-01-17 | 中国科学技术大学 | Ionization radiation chemistry redox preparation method for nm metal powder |
-
1998
- 1998-05-29 CN CN98102193A patent/CN1095411C/en not_active Expired - Fee Related
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| WO2008134939A1 (en) * | 2007-05-08 | 2008-11-13 | Synfuels China Technology Co., Ltd. | Transition metal nano-catalyst, its preparation method and its use in fischer-tropsch synthetic reaction |
| AU2008247186B2 (en) * | 2007-05-08 | 2010-11-04 | Synfuels China Technology Co., Ltd. | Transition metal nano-catalyst, its preparation method and its use in fischer-tropsch synthetic reaction |
| CN101767018B (en) * | 2009-01-06 | 2012-06-13 | 北京大学 | Loading type Pd base metal nanometer cluster catalyst, preparing method and applications thereof |
| CN102341165A (en) * | 2009-03-02 | 2012-02-01 | 卡罗比亚意大利（共同）股份公司 | Process for preparing stable suspensions of metal nanoparticles and the stable colloidal suspensions obtained thereby |
| CN102259191A (en) * | 2011-07-13 | 2011-11-30 | 大连理工大学 | Nano silver cluster for highly sensitively detecting nitro explosive compound and preparation thereof |
| CN103586484B (en) * | 2013-11-25 | 2017-10-24 | 中国科学院福建物质结构研究所 | Pd-Ru alloy nano particle and its preparation and use |
| CN103586484A (en) * | 2013-11-25 | 2014-02-19 | 中国科学院福建物质结构研究所 | Palladium ruthenium alloy nano-particles, preparation method thereof and application thereof |
| CN106862583A (en) * | 2015-12-13 | 2017-06-20 | 中国科学院大连化学物理研究所 | A kind of preparation method of the controllable gold nanoclusters of atom number |
| CN105798325B (en) * | 2016-03-24 | 2018-07-06 | 贵州大学 | A kind of ruthenium (Ru) nanometer line network of Asia 2nm and preparation method thereof |
| CN105798325A (en) * | 2016-03-24 | 2016-07-27 | 贵州大学 | Sub-2nm ruthenium (Ru) nanowire network and preparation method thereof |
| CN105945301A (en) * | 2016-05-10 | 2016-09-21 | 江南大学 | Controllable synthesis method for metallic ruthenium nano particles with different particle sizes under mild condition |
| CN106512993A (en) * | 2016-08-30 | 2017-03-22 | 北京化工大学 | Preparation and hydrogenation application of palladium-ruthenium dual-metal nano-catalyst |
| CN106512993B (en) * | 2016-08-30 | 2018-11-16 | 北京化工大学 | Palladium-ruthenium bimetal nano catalyst preparation and plus hydrogen application |
| CN107983948A (en) * | 2016-10-27 | 2018-05-04 | 中国科学院大连化学物理研究所 | Au6With Au11Method is mutually converted between nano-cluster |
| CN107983948B (en) * | 2016-10-27 | 2019-09-06 | 中国科学院大连化学物理研究所 | Au6With Au11Method is mutually converted between nano-cluster |
| CN107913707A (en) * | 2017-12-11 | 2018-04-17 | 江西省汉氏贵金属有限公司 | Double bond isomerization reaction sub-nanometer palladium alumina preparation method |
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| CN111496270A (en) * | 2020-06-11 | 2020-08-07 | 华南理工大学 | Method for preparing nano metal platinum particles |
| CN111496270B (en) * | 2020-06-11 | 2022-02-15 | 华南理工大学 | Method for preparing nano metal platinum particles |
| CN112170859A (en) * | 2020-10-09 | 2021-01-05 | 深圳技术大学 | Preparation method of gold nanocluster |
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