CN102528021A - Method for preparing precious metal/organic functional small molecule core-shell structure nano particles - Google Patents
Method for preparing precious metal/organic functional small molecule core-shell structure nano particles Download PDFInfo
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- CN102528021A CN102528021A CN2011104428147A CN201110442814A CN102528021A CN 102528021 A CN102528021 A CN 102528021A CN 2011104428147 A CN2011104428147 A CN 2011104428147A CN 201110442814 A CN201110442814 A CN 201110442814A CN 102528021 A CN102528021 A CN 102528021A
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Abstract
The invention relates to a method for preparing precious metal/organic functional small molecule core-shell structure nano particles. The method comprises the following steps that: the cationic radical solution of organic molecules is prepared through a silver perchlorate (AgClO4) and iodine (I2) oxidation method or a ferric chloride (FeCl3) oxidation method; after precious metal nano particles are prepared, the cationic radical solution of the organic molecules is dripped to precious metal nano-particle suspension; and organic molecular cations have displacement reaction with the precious metal nano particles, and the precious metal/organic functional small molecule core-shell structure nano particles are obtained. The method is simple and easy, the shell thicknesses of the nano particles can be regulated only by controlling the amount of the added cationic radical solution of the organic molecules, different shell thicknesses reflect different optical properties, so that good materials and methods are provided for the development of optics in biological application.
Description
Technical field
The present invention relates to a kind of method for preparing noble metal/organic functions small molecular core shell structural nano particle.
Background technology
Nuclear shell type nano meter particle is the one type of multifunctional novel type material that receives much concern in recent years; Through the bare nucleus particle is coated; Can improve the stable and dispersed of nuclear particle greatly, change or strengthen their original character, for the many-sided potential application of exploitation nano material provides excellent opportunity.Noble metal/organic core-shell nano particle is as nuclear or the formed core-shell material of shell (wherein noble metal mainly comprises Pt, Pd, Ag, Au and alloy thereof etc.) with noble metal; Can change its character through regulating nucleocapsid size and chemical composition, realize controlledly synthesis nano particle character.Because after noble metal group bunch or the colloidal nanoization; Show a lot of new optics and physics character; Make the noble metal core-shell material be with a wide range of applications, as loose look (SERS) research and as the sensitization mark etc. as catalyst, biological and chemical sensing, surface-enhanced Raman in material science and molectronics and based on the fluorescence engineering science field of surperficial enhancement effect.
At present, the preparation method of noble metal/functional material core-shell nano mainly is through two kinds of approach: (1) will be examined with shell through the couplant chemical bond and be connected; (2), be covered with the material alternating packets of different electric charges through LBL technology.The advantage of second method is that layer is accomplished through charge effect with the effect of interlayer, and relative first method is not high to material requirements, and deficiency is that the rapid effect of multistep can make some beads do not coated, and the active force between the static a little less than.And said method only is applicable to that selected shell material is inorganic, metal oxide (SiO
2, TiO
2Deng) and a few system such as macromolecular material.
Therefore, be necessary to provide a kind of easy and simple to handle, be applicable to the noble metal/organic molecule nanometer particle process method of large-scale production.
Summary of the invention
The purpose of this invention is to provide a kind of method of utilizing the liquid phase in-situ reaction to prepare noble metal/organic molecule core-shell nano.
The method for preparing noble metal/organic molecule core-shell nano provided by the present invention specifically may further comprise the steps:
1) organic molecule is dissolved in the saturated solution that obtains organic molecule in the organic solvent; Oxidant is dissolved in the saturated solution that obtains oxidant in the organic solvent; Under the inert gas shielding condition, the saturated solution of organic molecule and the saturated solution of oxidant are mixed with the chemical dosage ratio of oxidant reaction according to organic molecule, obtain the radical cation solution of organic molecule;
2) under sealing black out and stirring condition; Radical cation solution reaction 5-30min with the organic molecule of preparing in noble metal nano particles and the step 1); The concentration of the radical cation solution of control organic molecule is 0.1-10mM; Washing, centrifugal, obtain noble metal/organic molecule core-shell structure nanometer particle.
Organic molecule described in the step 1) is selected from metalloporphyrin (Porphyran), metal phthalocyanine (Metal Phthalocyanine), polycyclic aromatic hydrocarbon.
Oxidant described in the step 1) is the mixture of silver perchlorate and iodine.
Organic solvent described in the step 1) is acetonitrile or carrene.
Inert gas described in the step 1) is argon gas or nitrogen.
Step 2) noble metal nano particles described in is selected from a kind of in silver (Ag), platinum (Pt), palladium (Pd), the Dor (Ag-Au).Routine techniques is adopted in the preparation of noble metal nano particles, is about to precious metal salt and is dissolved in the solution that obtains slaine in inorganic or the organic solvent; Reducing agent is dissolved in the solution that obtains reducing agent in the organic or inorganic solvent; Under the condition of heated and stirred, precious metal salt solution and reductant solution are pressed slaine mixes with the stoichiometric proportion of reducing agent reaction, add the surfactant reaction, the size of particle and pattern can be controlled through the input amount and the reaction time of adjusting raw material.With washing with alcohol, centrifugal, dry, and be scattered in the acetonitrile solution for use again after reaction is accomplished.
The present invention has following beneficial effect:
Operation is simple for preparation method provided by the present invention, can prepare noble metal/organic core shell structure nano particle in enormous quantities.The concentration of the radical cation solution of kind, size that can be through the control noble metal nano particles, pattern, organic molecule and reaction time etc.; Reach control, and can carry out following process as required and improve performance like means such as assemblings to noble metal/organic core shell structure nano particle pattern.Method provided by the present invention is that fields such as catalysis, chemical sensitisation, biomarker provide wide application prospect.
Description of drawings
Fig. 1 is the sample 1 of embodiment 1 preparation
#Transmission electron microscope (TEM) image.
Fig. 2 is the sample 1 of embodiment 1 preparation
#X-ray diffraction (XRD) image.
Fig. 3 is the sample 2 of embodiment 2 preparations
#Transmission electron microscope (TEM) image.
Fig. 4 is the sample 2 of embodiment 2 preparations
#X-ray diffraction (XRD) image.
Fig. 5 is the sample 3 of embodiment 3 preparations
#Transmission electron microscope (TEM) image.
Fig. 6 is the sample 3 of embodiment 3 preparations
#X-ray diffraction (XRD) image.
Fig. 7 is the sample 4 of embodiment 4 preparations
#Transmission electron microscope (TEM) image.
Fig. 8 is the sample 4 of embodiment 4 preparations
#X-ray diffraction (XRD) image.
Fig. 9 is the sample 5 of embodiment 5 preparations
#Transmission electron microscope (TEM) image.
Figure 10 is the sample 5 of embodiment 5 preparations
#X-ray diffraction (XRD) image.
Below in conjunction with the accompanying drawing and the specific embodiment the present invention is described further, but protection scope of the present invention is not limited only to following embodiment.
The specific embodiment
Embodiment 1
1) 486mg (0.72mmol) tetraphenyl zinc protoporphyrin (ZnTPP) is dissolved in the 10ml carrene; With 102mg (0.40mmol) I
2Be dissolved in the 10ml carrene; With 166mg (0.80mmol) AgClO
4Be dissolved in the 1.5ml acetonitrile; Feeding under the condition of nitrogen gas, I
2Dichloromethane solution and AgClO
4Acetonitrile solution add in the dichloromethane solution of ZnTPP, the gained deposition with being dissolved in the acetonitrile after petroleum ether and the drying, is obtained the radical cation solution of the ZnTPP of 1mmol/L;
Reaction equation is: ZnTPP+1/2I
2+ AgClO
4→ AgI+ZnTPP
+ClO
4 -
2) under the condition of sealing black out and magnetic agitation; The radical cation solution of 2ml 1mmol/L ZnTPP is added in the acetonitrile suspension of 1ml 5mmol/L Ag nano particle successively; Behind the reaction 5min; The centrifugal deposition that obtains is scattered in the acetonitrile solution again, obtains the AgZnTPP core-shell structure nanometer particle of different shell thicknesses.
Reaction equation is: ZnTPP
++ Ag → ZnTPP+Ag
+
Gained AgZnTPP core-shell structure nanometer particle (numbering 1
#) transmission electron microscope image be shown among Fig. 1, XRD figure looks like to be shown among Fig. 2, and is three oblique monocrystalline.Visible by figure, the noble metal/organic matter core-shell structure nanometer particle that adopts preparation method of the present invention to obtain is big or small homogeneous, and good dispersion, organic matter be growth in situ on noble metal optionally.
Referring to Fig. 1,2.
Embodiment 2
1) 729mg (1.07mmol) tetraphenyl zinc protoporphyrin (ZnTPP) is dissolved in the 15ml carrene; With 152mg (0.60mmol) I
2Be dissolved in the 10ml carrene; With 249mg (1.20mmol) AgClO
4Be dissolved in the 2.25ml acetonitrile; Feeding under the condition of nitrogen gas, I
2Dichloromethane solution and AgClO
4Acetonitrile solution add in the dichloromethane solution of ZnTPP, the gained deposition with being dissolved in the acetonitrile after petroleum ether and the drying, is obtained the radical cation solution of the ZnTPP of 5mmol/L;
Reaction equation is: ZnTPP+1/2I
2+ AgClO
4→ AgI+ZnTPP
+ClO
4 -
2) under the condition of sealing black out and magnetic agitation; The radical cation solution of 2ml 5mmol/L ZnTPP is added in the acetonitrile suspension of 1ml 5mmol/L Pd nano particle successively; Behind the reaction 15min; The centrifugal deposition that obtains is scattered in the acetonitrile solution again, obtains the PtZnTPP core-shell structure nanometer particle of different shell thicknesses.
Reaction equation is: 2ZnTPP
++ Pd → 2ZnTPP+Pd
2+
Gained PdZnTPP core-shell structure nanometer particle (numbering 2
#) transmission electron microscope image be shown in 4, XRD figure looks like to be shown among Fig. 5, and is three oblique monocrystalline.Visible by figure, the noble metal/organic matter core-shell structure nanometer particle that adopts preparation method of the present invention to obtain is big or small homogeneous, and good dispersion, organic matter be growth in situ on noble metal optionally.
Referring to Fig. 3,4.
Embodiment 3
1) 972mg (1.43mmol) tetraphenyl zinc protoporphyrin (ZnTPP) is dissolved in the 20ml carrene; With 203mg (0.80mmol) I
2Be dissolved in the 10ml carrene; With 332mg (1.60mmol) AgClO
4Be dissolved in the 3ml acetonitrile; Feeding under the condition of nitrogen gas, I
2Dichloromethane solution and AgClO
4Acetonitrile solution add in the dichloromethane solution of ZnTPP, the gained deposition with being dissolved in the acetonitrile after petroleum ether and the drying, is obtained the radical cation solution of the ZnTPP of 10mmol/L;
Reaction equation is: ZnTPP+1/2I
2+ AgClO
4→ AgI+ZnTPP
+ClO
4 -
2) under the condition of sealing black out and magnetic agitation; The radical cation solution of 1ml 10mM ZnTPP is added in the acetonitrile suspension of 1ml 5mM Au-Ag duplex metal nano granule successively; Behind the reaction 30min; The centrifugal deposition that obtains is scattered in the acetonitrile solution again, obtains the PdZnTPP core-shell structure nanometer particle of different shell thicknesses.
Reaction equation is: ZnTPP
++ Ag → ZnTPP+Ag
+
Gained PtZnTPP core-shell structure nanometer particle (numbering 3
#) transmission electron microscope image be shown in 6, XRD figure looks like to be shown among Fig. 7, and is three oblique monocrystalline.Visible by figure, as to adopt preparation method of the present invention to obtain noble metal/organic matter core-shell structure nanometer particle size homogeneous, good dispersion, organic matter be growth in situ on noble metal optionally.
Referring to Fig. 5,6.
Embodiment 4
1) (0.10mmol) perylene (Perylene) is dissolved in the 10ml carrene with 25mg; With 102mg (0.40mmol) I
2Be dissolved in the 5ml carrene; With 166mg (0.80mmol) AgClO
4Be dissolved in the 1.5ml acetonitrile; Feeding under the condition of nitrogen gas, I
2Dichloromethane solution and AgClO
4Acetonitrile solution add stirring reaction 0.5h in the dichloromethane solution of Perylene; With the gained precipitation and centrifugal separation, with after washed with dichloromethane and the drying; Carefully dropwise add acetonitrile and cross the top; Container closure left standstill 16 hours, got the radical cation solution that the superiors' clear liquid is Perylene, was 0.1mmol/L through softex kw (CTAB) measured in solution concentration;
Reaction equation is: Pe+1/2I
2+ AgClO
4→ AgI+Pe
+ClO
4 -
2) under the condition of sealing black out and magnetic agitation; The radical cation solution of 3ml 0.1mmol/L Pe is added in the acetonitrile suspension of 1ml 5mM Ag nano particle successively; Behind the reaction 5min; The centrifugal deposition that obtains is scattered in the acetonitrile solution again, obtains the AgPe core-shell structure nanometer particle of different shell thicknesses.
Reaction equation is: Pe
++ Ag → Pe+Ag
+
Gained AgPe core-shell structure nanometer particle (numbering 4
#) transmission electron microscope image be shown among Fig. 8, XRD figure looks like to be shown among Fig. 9, and is three oblique monocrystalline.Visible by figure, the noble metal/organic matter core-shell structure nanometer particle that adopts preparation method of the present invention to obtain is big or small homogeneous, and good dispersion, organic matter be growth in situ on noble metal optionally.
Referring to Fig. 7,8.
1) 50mg (0.10mmol) rubrene (Rubrene) is dissolved in the 100mL carrene; With 207mg (1mmol) AgClO
4Be dissolved in the 0.5mL acetonitrile; With 100mg (0.50mmol) I
2Be made into saturated dichloromethane solution; Feeding under the condition of nitrogen gas, AgClO
4Acetonitrile solution add in the dichloromethane solution of Rubrene, then add I
2Dichloromethane solution reaction 30min, with the distillation of gained solution decompression remove desolvate after, the gained solid is dissolved in the acetonitrile again the radical cation solution of the Rubrene of preparation 0.1mmol/L;
Reaction equation is: Ru+Ag
+ClO
4 -+ 1/2I
2→ AgI+Ru
+ClO
4 -
2) under the condition of sealing black out and magnetic agitation; The radical cation solution of 5ml 0.1mmol/L Ru is added in the acetonitrile suspension of 1ml 5mmol/L Ag nano particle successively; Behind the reaction 5min; The centrifugal deposition that obtains is scattered in the acetonitrile solution again, obtains the AgRu core-shell structure nanometer particle of different shell thicknesses.
Reaction equation is: Ru
++ Ag → Ag
++ Ru
Gained AgPe core-shell structure nanometer particle (numbering 5
#) transmission electron microscope image be shown among Figure 10, XRD figure looks like to be shown among Figure 11, and is three oblique monocrystalline.Visible by figure, the noble metal/organic matter core-shell structure nanometer particle that adopts preparation method of the present invention to obtain is big or small homogeneous, and good dispersion, organic molecule be growth in situ on noble metal optionally.
Referring to Fig. 9,10.
Claims (6)
1. a method for preparing noble metal/organic functions small molecular core shell structural nano particle is characterized in that, may further comprise the steps:
1) organic molecule is dissolved in the saturated solution that obtains organic molecule in the organic solvent; Oxidant is dissolved in the saturated solution that obtains oxidant in the organic solvent; Under the inert gas shielding condition, the saturated solution of organic molecule and the saturated solution of oxidant are mixed with the chemical dosage ratio of oxidant reaction according to organic molecule, obtain the radical cation solution of organic molecule;
2) under sealing black out and stirring condition; Radical cation solution reaction 5-30min with the organic molecule of preparing in noble metal nano particles and the step 1); The concentration of the radical cation solution of control organic molecule is that the concentration of 0.1-10mmol/L, noble metal nano particles is the 1-5mmol/L washing; Centrifugal, obtain noble metal/organic molecule core-shell structure nanometer particle.
2. method according to claim 1; It is characterized in that the organic molecule described in the step 1) is selected from a kind of in metalloporphyrin Porphyran, metal phthalocyanine Metal Phthalocyanine, polycyclic aromatic hydrocarbon, Oligopoly thiophene Oligothiophene or the Oligopoly thiophene derivative.
3. method according to claim 1 is characterized in that, the oxidant described in the step 1) is the mixture or the ferric trichloride of silver perchlorate and iodine.
4. method according to claim 1 is characterized in that, the organic solvent described in the step 1) is acetonitrile or carrene.
5. method according to claim 1 is characterized in that, the inert gas described in the step 1) is argon gas or nitrogen.
6. method according to claim 1 is characterized in that step 2) described in noble metal nano particles be selected from a kind of in silver (Ag), platinum (Pt), palladium (Pd), the Dor (Ag-Au).
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW583029B (en) * | 2001-05-01 | 2004-04-11 | Chang Chun Petrochemical Co | The process for preparing noble metal nanoparticles |
| CN101024246A (en) * | 2006-02-24 | 2007-08-29 | 三星电机株式会社 | Core-shell structure metall nanoparticles and its manufacturing method |
| CN101590531A (en) * | 2009-07-13 | 2009-12-02 | 中国科学院化学研究所 | A kind of method for preparing metal/organic small molecular core/shell type one-dimensional nano-composite material |
| CN101704502A (en) * | 2009-09-11 | 2010-05-12 | 中国科学院化学研究所 | Method for preparing arrayed organic nanoparticles |
-
2011
- 2011-12-27 CN CN2011104428147A patent/CN102528021A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW583029B (en) * | 2001-05-01 | 2004-04-11 | Chang Chun Petrochemical Co | The process for preparing noble metal nanoparticles |
| CN101024246A (en) * | 2006-02-24 | 2007-08-29 | 三星电机株式会社 | Core-shell structure metall nanoparticles and its manufacturing method |
| CN101590531A (en) * | 2009-07-13 | 2009-12-02 | 中国科学院化学研究所 | A kind of method for preparing metal/organic small molecular core/shell type one-dimensional nano-composite material |
| CN101704502A (en) * | 2009-09-11 | 2010-05-12 | 中国科学院化学研究所 | Method for preparing arrayed organic nanoparticles |
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Application publication date: 20120704 |