CN1320953C - Process for preparing controllable hollow nanometer gold ball based on polymeric vesicle mold plates - Google Patents
Process for preparing controllable hollow nanometer gold ball based on polymeric vesicle mold plates Download PDFInfo
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- CN1320953C CN1320953C CNB200410070474XA CN200410070474A CN1320953C CN 1320953 C CN1320953 C CN 1320953C CN B200410070474X A CNB200410070474X A CN B200410070474XA CN 200410070474 A CN200410070474 A CN 200410070474A CN 1320953 C CN1320953 C CN 1320953C
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Abstract
The present invention discloses a preparation method of controllable hollow nanometer gold balls on the basis of a polymerization type vesicle template, which comprises: nanometer sol and amidogen polymer vesicles are mixed and shaken up, and after being stood still, the mixture is centrifuged; the solution of an upper layer is removed, deionized water is added to the base solution, and the base solution is dispersed ultrasonically; the centrifugation/dispersion process is repeated, which can obtain hollow nanometer balls. Further, after the nanometer balls are added to water solutions of HAuCl4.4H2O and NH2OH. HCl under an agitating state for reacting, the process of centrifugation/dispersion is carried out once again. The hollow nanometer balls prepared on the basis of the polymerization type vesicle template of the present invention have the advantages of simple preparation, low cost, high stability, good surface coating rate controllability, etc., and can be widely applied to the fields of adsorption, catalysis, etc.
Description
Technical field
The present invention relates to a kind of preparation method of the controllable hollow nanometer gold goal based on polymeric vesicle mold.
Background technology
People know the hollow Nano gold goal owing to have light weight, specific area height, and the low grade of cost is different from the characteristics of base metal and is widely used in absorption and catalysis aspect.
Traditional method for preparing the hollow Nano gold goal is many to be template with the resin microsphere, template is carried out surface chemical modification, the functional groups that has ADSORPTION OF GOLD colloidal sol ability in the modification, and then absorption nano Au particle, and be that seed constantly increases with the nano Au particle that is adsorbed on the template, thereby make the different nano gold spherical of surface coverage, fall center resin template with method corrosions such as chemical attacks more at last, form the hollow Nano gold goal.Its typical preparation example is referring to 2003 the 15th the 3176th page of volumes (F.Caruso etc., Chem.Mater.2003, the 15th volume, 3176 pages) of " chemical material " magazine.But in the preparation process of hollow Nano gold goal that with the resin is template,, finally the template corrosion to be fallen for reaching hollow structure, so this type of preparation method is to be prerequisite to sacrifice template, cost height, preparation route complexity.
2000, A.L. lattice are graceful at 1286 pages of " advanced material " the 12nd volumes (A.L.German etc., Advanced Material 2000, the 12nd volume, 1286 pages) on reported a kind of brand-new method for preparing hollow nano-material, he is that template has prepared hollow Nano phosphoric acid calcisphere with the vesica.Because the vesicle mold of its use is non-polymeric type, only rely on intermolecular Van der Waals force to form template, so be difficult to stand the disturbance of extraneous factors such as pH value, temperature, poor stability is difficult for promoting.
Summary of the invention
The objective of the invention is to avoid that the corrosion template causes the expensive and complicated preparation process in ground in the traditional preparation process method, overcome the shortcoming of non-polymeric type vesicle mold poor stability simultaneously, a kind of preparation method of controllable hollow nanometer gold goal of the polymeric vesicle mold that forms based on covalent bond is provided, it is simple that the method has preparation, low cost and other advantages.The stability of this hollow Nano gold goal and controllability are all higher, can be widely used in fields such as absorption, catalysis and medicine coating.
The present invention based on the polymeric vesicle mold that connects of covalent bond, the poly-diacetylene bimolecular vesicle mold layer of water and amido in comprising, wherein the poly-diacetylene bimolecular vesicle mold layer of amido is CH by structure
3-(CH
2)
n-C ≡ C-C ≡ C-(CH
2)
l-CONH-(CH
2)
m-NH
2The lipoid monomer polymerization form, m=2-6 wherein, l=0-10, n=7-30, concrete synthetic method is seen 2003 the 42nd 3264 pages of volumes (I.Gill etc., Angew.Chem.Int.Ed.2003, the 42nd volume, 3264 pages) of " German applied chemistry " magazine.Interior water is wrapped in wherein by bilayer and forms the hollow vesicle mold.Have combining nano aurosol ability-NH
2Group is distributed on the inside and outside two layers of surface of vesicle mold.
The preparation method of a kind of controllable hollow nanometer gold goal based on polymeric vesicle mold of the present invention is characterized in that with concentration be 1 * 10
16-1 * 10
17Individual/L, diameter is that nano gold sol and the concentration of 1-10nm is that the poly-diacetylene vesica solution of amido of 1-10mM mixes, the volume ratio of the poly-diacetylene vesica solution of nano gold sol and amido is preferably (10-40) for (1-100): 1[: 1], left standstill 1-24 hour after mixed system shaken up, centrifugal under the rotating speed of 10000-15000 rev/min (being preferably 10000-12000 rev/min) then, after removing upper solution, liquid at the bottom of adding deionized water and the ultrasonic dispersion in end liquid, repeat above-mentioned centrifugal/dispersion process 2-4 time, obtain the aurosol clad ratio and be the hollow Nano gold goal about 20-30%.
Further this nano gold spherical can be joined under stirring and contain weight portion 0.01-0.1%HAuCl
44H
2O and 0.1-1mM NH
2Reaction is 10-30 minute in the aqueous solution of OHHCl, with reacted solution repeat above-mentioned centrifugal/dispersion process 2-4 time, the clad ratio that obtains nano Au particle is the hollow Nano gold goal about 30-90%.
Hollow Nano gold goal based on the polymeric vesicle mold preparation of the present invention has advantages such as preparation is simple, cost is low, stability is high, the surface coating rate controllability is good, can be widely used in fields such as absorption, catalysis.
Description of drawings:
Fig. 1. based on preparation method's schematic diagram of the controllable hollow nanometer gold goal of polymeric vesicle mold
Fig. 2. surface coating rate is the TEM photo of 25% left and right sides hollow Nano gold goal
Fig. 3. surface coating rate is the TEM photo of 50% left and right sides hollow Nano gold goal
Fig. 4. surface coating rate is the TEM photo of 90% left and right sides hollow Nano gold goal
Fig. 5. the ultraviolet-visible spectrum of hollow Nano gold goal: new preparation (solid line), deposit 20 days (dotted line)
Fig. 6. the ultraviolet-visible spectrum of nano gold sol: new preparation (solid line), deposit 20 days (dotted line)
The specific embodiment
Below in conjunction with embodiment in detail the present invention is described in detail.
Embodiment 1
(1) the class alicyclic monomer is synthetic: according to 2003 the 42nd 3264 pages of volumes (I.Gill etc., Angew.Chem.Int.Ed.2003, the 42nd volume, 3264 pages) of document " German applied chemistry " magazine, 10mL, the C of 2.4mM
6H
11N=C=NC
6H
11Dichloromethane solution join 10mL, 10 of 2.45mM, 12-pentacosyl diacetylenic acid [CH
3-(CH
2)
n-C ≡ C-C ≡ C-(CH
2)
l-COOH is l=8 wherein, n=11] dichloromethane solution in, place the darkroom at room temperature to stir (300 rev/mins) reaction 1 hour mixed solution, then mixed solution is joined 10mL in 20 minutes dropping time, continue to stir (300 rev/mins) reaction 1 hour in the dichloromethane solution of the ethylenediamine of 4mM.Reacted solution is diluted and filtration with the 20mL benzinum, filtrate is steamed to dry with Rotary Evaporators, (Kieselgel 60 with silicagel column for dried product, solvent is that volume ratio is 5: 1 a chloroform-methanol) purifying, obtain class alicyclic monomer 10,12-pentacosyl diacetylenic acid 2 '-amino-ethyl acid amides [CH
3-(CH
2)
n-C ≡ C-C ≡ C-(CH
2)
l-CONH-(CH
2)
m-NH
2M=2 wherein, l=8, n=11].
(2) preparation of vesicle mold: 10mL, the class alicyclic monomer 10 of 1mM, the chloroformic solution of 12-pentacosyl diacetylenic acid 2 '-amino-ethyl acid amides place the 50mL round-bottomed flask to steam to dry with Rotary Evaporators.In flask, add the 10mL deionized water, ultrasonic 30 minutes at 80 ℃ then, solution after ultrasonic is that 0.8 micron nylon leaching film filters and to obtain unpolymerized 10 with the aperture, 12-pentacosyl diacetylenic acid 2 '-amino-ethyl acid amides vesica is the vesica that the UV illumination of 256nm obtained polymerization in 2 hours then with the solution wavelength.
(3) preparation of hollow Nano gold goal: get 0.5mL, 10 of 1mM polymerization, 12-pentacosyl diacetylenic acid 2 '-amino-ethyl acid amides vesica and 10mL, concentration is 1 * 10
16Individual/L, diameter is to leave standstill 4 hours after the freshly prepd aurosol mixing of 3nm shakes up, then with mixed solution under 10000 rev/mins rotating speed centrifugal 10 minutes, remove upper solution, in end liquid, add the ultrasonic dispersion of deionized water 1mL 1 minute, repeat above-mentioned centrifugal/dispersion process 4 times, the hollow Nano gold goal that obtains is observed through transmission electron microscope (TEM), surface coating rate is about 25%, sees Fig. 2.
Embodiment 2
(1) the class alicyclic monomer is synthetic: according to 2003 the 42nd 3264 pages of volumes (I.Gill etc., Angew.Chem.Int.Ed.2003, the 42nd volume, 3264 pages) of document " German applied chemistry " magazine, 10mL, the C of 2.4mM
6H
11N=C=NC
6H
11Dichloromethane solution join 10mL, 10 of 2.45mM, 12-tricosyl diacetylenic acid [CH
3-(CH
2)
n-C ≡ C-C ≡ C-(CH
2)
l-COOH is l=8 wherein, n=9] dichloromethane solution in, place the darkroom at room temperature to stir (300 rev/mins) reaction 1 hour mixed solution, then mixed solution is joined 10mL in 20 minutes dropping time, continue to stir (300 rev/mins) reaction 1 hour in the dichloromethane solution of the ethylenediamine of 4mM.Reacted solution is diluted and filtration with the 20mL benzinum, filtrate is steamed to dry with Rotary Evaporators, (Kieselgel 60 with silicagel column for dried product, solvent is that volume ratio is 5: 1 a chloroform-methanol) purifying, obtain class alicyclic monomer 10,12-tricosyl diacetylenic acid 2 '-amino-ethyl acid amides [CH
3-(CH
2)
n-C ≡ C-C ≡ C-(CH
2)
l-CONH-(CH
2)
m-NH
2M=2 wherein, l=8, n=9].
(2) preparation of vesicle mold: 10mL, the class alicyclic monomer 10 of 1mM, the chloroformic solution of 12-tricosyl diacetylenic acid 2 '-amino-ethyl acid amides place the 50mL round-bottomed flask to steam to dry with Rotary Evaporators.In flask, add the 10mL deionized water, ultrasonic 30 minutes at 80 ℃ then, solution after ultrasonic is that 0.8 micron nylon leaching film filters and to obtain unpolymerized 10 with the aperture, 12-tricosyl diacetylenic acid 2 '-amino-ethyl acid amides vesica is the vesica that the UV illumination of 256nm obtained polymerization in 4 hours then with the solution wavelength.
(3) preparation of hollow Nano gold goal: get 5mL, 10 of 1mM polymerization, 12-tricosyl diacetylenic acid 2 '-amino-ethyl acid amides vesica and 20mL, concentration is 1 * 10
17Individual/L, diameter is that the freshly prepd aurosol of 5nm mixes and left standstill 1 hour after shaking up, and with mixed solution under 12000 rev/mins rotating speed centrifugal 20 minutes, removes upper solution then, in end liquid, add the ultrasonic dispersion of 2mL deionized water 1 minute, repeat above-mentioned centrifugal/dispersion process 4 times.The hollow Nano gold goal that obtains is joined volume under stirring be that 20mL contains weight portion 0.01%HAuCl
44H
2O and 0.4mMNH
2In the aqueous solution of OHHCl, reacted 10 minutes, with reacted solution repeat above-mentioned centrifugal/dispersion process 2 times, the hollow Nano gold goal that obtains is observed through transmission electron microscope (TEM), surface coating rate is about 50%, sees Fig. 3.
Embodiment 3
(1) the class alicyclic monomer is synthetic: according to 2003 the 42nd 3264 pages of volumes (I.Gill etc., Angew.Chem.Int.Ed.2003, the 42nd volume, 3264 pages) of document " German applied chemistry " magazine, 10mL, the C of 2.4mM
6H
11N=C=NC
6H
11Dichloromethane solution join 10mL, 2 of 2.45mM, 4-tricosyl diacetylenic acid [CH
3-(CH
2)
n-C ≡ C-C ≡ C-(CH
2)
l-COOH is l=0 wherein, n=17] dichloromethane solution in, place the darkroom at room temperature to stir (300 rev/mins) reaction 1 hour mixed solution, then mixed solution is joined 10mL in 20 minutes dropping time, continue to stir (300 rev/mins) reaction 1 hour in the dichloromethane solution of the hexamethylene diamine of 4 mM.Reacted solution is diluted and filtration with the 20mL benzinum, filtrate is steamed to dry with Rotary Evaporators, (Kieselgel 60 with silicagel column for dried product, solvent is that volume ratio is 5: 1 a chloroform-methanol) purifying, obtain class alicyclic monomer 2,4-tricosyl diacetylenic acid 2 '-amino hexyl acid amides [CH
3-(CH
2)
n-C ≡ C-C ≡ C-(CH
2)
l-CONH-(CH
2)
m-NH
2M=6 wherein, l=0, n=17].
(2) preparation of vesicle mold: 5mL, the class alicyclic monomer 2 of 3mM, the chloroformic solution of 4-tricosyl diacetylenic acid 2 '-amino hexyl acid amides place the 50mL round-bottomed flask to steam to dry with Rotary Evaporators.In flask, add the 10mL deionized water, ultrasonic 30 minutes at 75 ℃ then, solution after ultrasonic is that 0.8 micron nylon leaching film filters and to obtain unpolymerized 2 with the aperture, 4-tricosyl diacetylenic acid 2 '-amino hexyl acid amides vesica is the vesica that the UV illumination of 256nm obtained polymerization in 4 hours then with the solution wavelength.
(3) preparation of hollow Nano gold goal: use 1mL, 2 of 3mM polymerization, 4-tricosyl diacetylenic acid 2 '-amino hexyl acid amides vesica and 30mL, concentration is 1 * 10
17Individual/L, diameter is that the freshly prepd aurosol of 10nm mixes and left standstill 10 hours after shaking up, and with mixed solution under 10000 rev/mins rotating speed centrifugal 30 minutes, removes upper solution then, in end liquid, add the ultrasonic dispersion of 1mL deionized water 1 minute, repeat above-mentioned centrifugal/dispersion process 4 times.The hollow Nano gold goal that obtains is joined volume under stirring be that 100mL contains weight portion 0.1%HAuCl
44H
2O and 1mMNH
2In the aqueous solution of OHHCl, reacted 10 minutes, with reacted solution repeat above-mentioned centrifugal/dispersion process 2 times, the hollow Nano gold goal that obtains is observed through transmission electron microscope (TEM), surface coating rate is about 90%, sees Fig. 4.
Embodiment 4
The control experiment of hollow Nano gold goal stability:
(1) deionized water solution of getting freshly prepd embodiment 1 hollow core nano gold spherical carries out the ultraviolet-visible light analysis of spectrum, then this solution is placed refrigerator under 4 ℃, to deposit 20 days, and the solution after depositing carried out the ultraviolet-visible light analysis of spectrum, see Fig. 5,540nm place absworption peak is represented the absorption of gold particle on the nano gold spherical, as seen through 20 days, the absworption peak at 540nm place did not almost change.
(2) deionized water solution of getting the aurosol of the freshly prepd embodiment of being used for 1 carries out the ultraviolet-visible light analysis of spectrum, then this solution is placed refrigerator under 4 ℃, to deposit 20 days, and the solution after depositing carried out the ultraviolet-visible light analysis of spectrum, see Fig. 6,520nm place absworption peak is represented the absorption of nano Au particle in the solution, as seen through 20 days, the have an appointment red shift of 10nm of the absworption peak at 520nm place.
Claims (4)
1. the preparation method based on the controllable hollow nanometer gold goal of polymeric vesicle mold is characterized in that with concentration be 1 * 10
16-1 * 10
17Individual/L, diameter is that nano gold sol and the concentration of 1-10nm is that the poly-diacetylene vesica solution of amido of 1-10mM mixes, the volume ratio of the poly-diacetylene vesica solution of nano gold sol and amido is (1-100): 1, left standstill 1-24 hour after mixed system shaken up, centrifugal under 10000-15000 rev/min rotating speed then, after removing upper solution, in end liquid, add liquid at the bottom of deionized water and the ultrasonic dispersion, repeat above-mentioned centrifugal/dispersion process can obtain the hollow Nano gold goal 2-4 time.
2. according to the preparation method of claim 1, it is characterized in that further this nano gold spherical being joined under stirring containing weight portion 0.01-0.1%HAuCl
44H
2O and 0.1-1mMNH
2Reaction is 10-30 minute in the aqueous solution of OHHCl, with reacted solution repeat above-mentioned centrifugal/dispersion process gets final product for 2-4 time.
3. according to the preparation method of claim 1 or 2, it is characterized in that the volume ratio of the poly-diacetylene vesica solution of described nano gold sol and amido is (10-40): 1.
4. according to the preparation method of claim 1 or 2, it is characterized in that described rotating speed is 10000-12000 rev/min.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100427200C (en) * | 2006-03-23 | 2008-10-22 | 中国科学院化学研究所 | Polymerization type hollow vesicle and polymerization type hollow vesicle/nanometer metal hollow ball |
| CN102079505B (en) * | 2009-12-01 | 2013-09-04 | 中国科学院合肥物质科学研究院 | Ordered structure array of two-dimensional hollow balls and preparing method thereof |
| CN102126703B (en) * | 2010-01-15 | 2013-05-08 | 中国科学院合肥物质科学研究院 | Two-dimensional multi-shell hollow sphere ordered structure array and preparation method thereof |
| CN101758243B (en) * | 2010-01-28 | 2011-08-17 | 中国科学院长春应用化学研究所 | Preparation method of hollow gold nanometer cage |
| CN102674236A (en) * | 2011-03-10 | 2012-09-19 | 中国科学院合肥物质科学研究院 | Gold micro-nano composite structure array and preparation method thereof |
| CN110639441A (en) * | 2019-09-26 | 2020-01-03 | 京东方科技集团股份有限公司 | Preparation method of vesicle, hollow nano structure and preparation method of hollow nano structure |
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| US6479146B1 (en) * | 1998-03-19 | 2002-11-12 | Max-Planck-Gesellschaft Zur Forderung Der Wissenschaften, E.V. | Fabrication of multilayer-coated particles and hollow shells via electrostatic self-assembly of nanocomposite multilayers on decomposable colloidal templates |
| CN1143817C (en) * | 2001-11-28 | 2004-03-31 | 中国科学院长春应用化学研究所 | Method for preparing silver-golden core-shell nano granule 2D collector |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6479146B1 (en) * | 1998-03-19 | 2002-11-12 | Max-Planck-Gesellschaft Zur Forderung Der Wissenschaften, E.V. | Fabrication of multilayer-coated particles and hollow shells via electrostatic self-assembly of nanocomposite multilayers on decomposable colloidal templates |
| CN1143817C (en) * | 2001-11-28 | 2004-03-31 | 中国科学院长春应用化学研究所 | Method for preparing silver-golden core-shell nano granule 2D collector |
Non-Patent Citations (1)
| Title |
|---|
| 油酸囊泡层状液晶作为模板电化学合成银纳米颗粒 郑龙珍 金乐红 吴守国，分析科学学报，第19卷第5期 2003 * |
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