CN101538736A - Dendritic golden nanophase material and preparation method thereof - Google Patents
Dendritic golden nanophase material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a dendritic golden nanophase material and a preparation method thereof. The gold nanophase material is dendritic, and all golden branches are formed by mutually stuck and fused golden nano particles or formed in a twin-crystal structure for growing. The preparation method comprises the following steps: pure water is added with chloroauric acid or chloraurate, ammonium formate and polyvinyl-pyrrolidone stabilizer and then transferred to a hydro-thermal reaction vessel after even ultrasonic mixing; after heating is carried out for 1-6 hours, a black mixturei is obtained after natural cooling; and the obtained product naturally subsides for 24-48 hours with ethyl alcohol or acetone or centrifugally subsides for at least 30 minutes, and after the liquid on the upper layer is removed, the product is added with absolute ethyl alcohol or acetone for dilution, and the black dendritic golden nanophase material deposition is obtained after centrifugal settling; and the ethyl alcohol or acetone washing process is repeated for 2-3 times, and finally, the black dendritic golden nanophase material coated with the polyvinyl-pyrrolidone is obtained. The dendritic golden nanophase material can be used as a commercial catalyst, a surface enhanced Raman substrate material, and the like. The method has the advantages of simple process and device and safe operation; and large-scale production can be performed by the method.
Description
Technical field
The present invention relates to have the preparation method of the noble metal nanometer material of dendritic structure, particularly relate to the dendroid gold nano-material and adopt a step hydro-thermal synthetic, directly prepare the method for dendroid gold nano-material.
Background technology
Precious metal (such as gold and silver, palladium and platinum) nano material with dendritic structure is subjected to investigator's extensive attention because of its application of inhaling aspects such as ripple in heterocatalysis, the high-sensitivity biological sensor based on surface plasma, biomarker, low energy.Branched structure can provide big specific surface area and numerous little nano level gaps.The characteristics determined of this configuration aspects superior catalysis and the electromagnetism of this kind material strengthen the property.Recently, about the existing report of dendritic gold and silver preparation of nanomaterials.For example document 1, Chen, S.H.; Wang, Z.L.; Ballato, J.; Foulger, S.H.; Carroll, D.L.J.Am.Chem.Soc., 2003,125,16186. introductions: utilize hydrochloro-auric acid to be raw material, Trimethyllaurylammonium bromide is a stablizer, by the reductive action of xitix, can prepare two branches, three and four s' gold nano grain.And for example document 2, " Sau; T.K.and Murphy; C.J.J.Am.Chem.Soc.; 2002,124,14316 " introduces: add golden nanometer particle earlier and do crystal seed in water, by adding hydrochloro-auric acid, Trimethyllaurylammonium bromide and xitix, can prepare highly branched golden nanometer particle again.In the preparation process of above-mentioned dendritic gold nano-material, Trimethyllaurylammonium bromide is considered to play a key effect.It can be grown along specific direction by induced nano particle on the particular crystal plane that optionally is adsorbed onto gold nano grain.In addition, golden institute inherent face-centred cubic structure has also determined the shape of the final state golden nanometer particle that may form.Except that gold, people such as Archer prepare dendritic silver nano-grain (Lou, X.W. there not being picture to be similar under the situation of Trimethyllaurylammonium bromide stablizer existence in the aqueous solution; Yuan, C.L.; Archer, L.A.Chem.Mater., 2006,18,3921.).The growth of this dendritic silver nano-grain does not have the selectivity of direction.Their appearance is because the kinetic factor of process of growth determines, is unsettled therefore.Finally, they can carry out the transition to spherical and plate-like silver nano-grain.More nearest, people such as Zeng utilize the small size golden nanometer particle of mercaptan parcel to be presoma, under hydrothermal condition, prepare spongiform nanometer gold net materials, and in reticulated structure, the distribution of sizes of gold grain is at 15 to 150 nanometer range (Zhang, Y.X.; Zeng, H.C.J.Phys.Chem.C 2007,111, and 6970.).This golden web frame has shown significant Raman reinforcing effect.Though, be in peak time of exploitation about the research of dendroid noble metal nanometer material,, by the control reaction parameter, controllably handle the growth of branch, also there not be the way of getting well.
Summary of the invention
One of purpose of the present invention: a kind of gold nano-material of the dendritic structure by polyvinylpyrrolidonemolecules molecules parcel is provided, and this material has good stability, and absorption contains organic molecule or amino acid, the protein molecule mcroorganism etc. of sulphur easily.Be more suitable in the basic material of making the high sensitivity biosensor.
Two of purpose of the present invention: overcome the prepared dendroid gold nano-material stability of existing preparation method, the weakness of poor controllability; Thereby a kind of synergy of utilizing ammonium formiate and two kinds of coating agents of polyvinylpyrrolidone is provided, synthesizes, directly prepare the method for dendroid gold nano-material by a step hydro-thermal.This method technology is simple, and the branch number of golden branch can be regulated and control by the concentration that changes ammonium formiate, and promptly this method is controllably handled the growth of branch.
The object of the present invention is achieved like this:
Dendroid gold nano-material provided by the invention, it is characterized in that: each gold branch of described dendroid gold nano-material is to form by mutual bonding fusion of gold nano grain or the growth of formation twin structure, have nano level gap between the gold branch, whole dendroid gold nano body structure surface is by polyvinylpyrrolidonemolecules molecules parcel (seeing Fig. 1 a, Fig. 1 b); Wherein the size of dendroid gold nano-material is in the 100-500 nanometer range.
The information of dendroid gold nano-material pattern provided by the invention and configuration aspects can pass through scanning electronic microscope (SEM) and transmission electron microscope (TEM) characterizes acquisition.When carrying out the scanning electronic microscope sign, specimen preparation is in n-Si (100) substrate.When carrying out the transmission electron microscope sign, specimen preparation is on the copper mesh that carbon film covers.Can obtain the information of product crystalline structure aspect by X-ray powder diffraction (XRD).X-ray photoelectron power spectrum (XPS) characterizes the information that can obtain golden panel surface composition and the chemical state aspect of obtaining.
The method of the gold nano-material of preparation dendritic structure provided by the invention is characterized in that, may further comprise the steps:
1) reaction system is selected: concentration is 0.01M hydrochloro-auric acid (HuAuCl43H2O) or chlor(o)aurate (MAuCl4XH2O), concentration is 0.1M-0.5M ammonium formiate (Ammonium Formate), concentration is 0.1M polyvinylpyrrolidone (PVP) coating agent, 10-1000mL pure water, for example ion exchanged water;
2) configuration reactant mixing solutions: in concentration is in the 10-1000mL aqueous solution of 0.01M hydrochloro-auric acid or chlor(o)aurate, and adding concentration is 0.1M polyvinylpyrrolidone (PVP), stirs rapidly, and thorough mixing is even;
3) in step 2) in the reactant mixing solutions of configuration, add 0.1M-1M ammonium formiate (Ammonium Formate) again, stir it is dissolved fully;
4) solution that step 3) is obtained shifts in the polytetrafluoroethylcontainer container, is sealed in the metal high pressure autoclave.Whole autoclave is put into heating unit, and heating is 1-6 hour under 100-120 ℃ of condition, after the question response still naturally cools to room temperature, takes out polytetrafluoroethylcontainer container, obtains to have the colloidal sol of black precipitate; Clean repeatedly at least 3 times with 100mL pure water and 100mL ethanol, centrifugation, drying obtain atrament dendroid gold nano-material.
In above-mentioned technical scheme, in described step (3),, can regulate and control the size of gold branch by the selection of ammonium formiate concentration.For example, is ammonium formiate/polyvinylpyrrolidone mol ratio less than 3/1 the time when selecting ammonium formiate concentration less than 0.3M, the gold nano structure of few branch is formed (seeing Fig. 2 a, Fig. 2 b), when ammonium formiate concentration is ammonium formiate/polyvinylpyrrolidone mol ratio greater than 3/1 the time greater than 0.3M, highly branched gold nano structure is formed.Ammonium formiate had both been served as reductive agent in reaction, also serve as coating agent simultaneously.The collaborative regulating effect of it and two kinds of coating agents of polyvinylpyrrolidone has caused the formation of dendritic gold nano-material.
In above-mentioned technical scheme, be at least 30 minutes in described step (4) the described centrifugal settling time.
In above-mentioned technical scheme, described chlor(o)aurate comprises: potassium chloraurate, sodium chloraurate etc.
The preparating mechanism of the gold nano-material of preparation dendritic structure provided by the invention is:
Utilize two kinds of surfaces of polyvinylpyrrolidone and ammonium formiate parcel reagent, regulate and control the growth of gold branch in the dynamic (dynamical) difference of gold nuclear interfacial adsorption by it.Polyvinylpyrrolidone is a kind of polymer of the parents' of having characteristic.Pyridine ring possess hydrophilic property and Polyethylene Chain has hydrophobicity.Pyridine ring with water-wet behavior can be adsorbed in the surface of golden nanometer particle with gold surface generation interaction.Can control its coverage by the concentration of control polyvinylpyrrolidone in solution, so as to the pattern and the size of control golden nanometer particle on the golden nanometer particle surface.But, the then cladodification growth degree of uncontrollable golden nanometer particle of polyvinylpyrrolidone is only arranged.Therefore, the ammonium formiate molecule not only plays reductive agent, and can be used to control the cladodification degree of gold nano grain.Its action principle is: the ammonium formiate molecule has the similar polar functional group of polyvinylpyrrolidonemolecules molecules.Nucleation stage at gold nano grain, the existence of a large amount of ammonium formiate molecules can make it be adsorbed in gold nuclear surface rapidly, and its little molecular weight and fast diffusibility can allow it promptly from gold nano grain surface desorption (by temperature of reaction decision), the naked gold part that ammonium formiate molecule desorption is exposed then can be grown fast.This process is easy to bring out the generation of twin-plane boundary, the perhaps adhesion of adjacent gold nano grain (seeing Fig. 3 a, Fig. 3 b, Fig. 3 c, Fig. 3 d) (seeing also embodiment 1).Thereby, build fractal growth path, cause the generation of dendroid gold nano structure.Attention: polyvinylpyrrolidonemolecules molecules must exist, and could generate discrete dendroid nm gold particles.Otherwise, will form the aggregate (seeing Fig. 4 a, Fig. 4 b) of gold grain.Simultaneously, the concentration of ammonium formiate molecule also is the vital condition that ensures that dendroid nanometer gold material forms.When the concentration of ammonium formiate molecule is hanged down, can not form the gold nano structure of height cladodification.
The invention has the advantages that:
1. the size of the dendroid gold nano structure of the polyvinylpyrrolidone parcel of the present invention's preparation is in the 100-500 nanometer range.The gold nano-material of this kind dendritic structure is black, can be used for surface plasmon sensor material, surface reinforced Raman active base material and sun power absorbing material.
2. the dendritic gold nano-material of this kind can be used as commercial catalysts and car tail gas purificant material
3. the dendritic gold nano-material of this kind can be directly as the medicine of oncotherapy or as effective pharmaceutical carrier.
4. preparation method of the present invention adopts wet chemical preparation method, relates generally to a step hydrothermal reduction method.Utilize pure water to be solvent, ammonium formiate is a reductive agent, polyvinylpyrrolidone and ammonium formiate are reduced to a large amount of gold nano-materials with dendritic structure as stablizer or coating agent with hydrochloro-auric acid or chlor(o)aurate, can obtain this dendroid nanometer gold precipitation by the centrifugation technology.Ammonium formiate had both been served as reductive agent in reaction, also served as coating agent simultaneously.The collaborative regulating effect of it and two kinds of coating agents of polyvinylpyrrolidone has caused the formation of dendritic gold nano-material.In preparation method's of the present invention step (3),, can regulate and control the size of gold branch by the selection of ammonium formiate concentration.For example, is ammonium formiate/polyvinylpyrrolidone mol ratio less than 3/1 the time when selecting ammonium formiate concentration less than 0.3M, the gold nano structure of few branch is formed (seeing Fig. 2 a, Fig. 2 b), when ammonium formiate concentration is ammonium formiate/polyvinylpyrrolidone mol ratio greater than 3/1 the time greater than 0.3M, highly branched gold nano structure is formed.Ammonium formiate had both been served as reductive agent in reaction, also serve as coating agent simultaneously.The collaborative regulating effect of it and two kinds of coating agents of polyvinylpyrrolidone has caused the formation of dendritic gold nano-material.
5. simple, the safety of the equipment of this method and technology, versatility, workable; By the amplification of corresponding proportion, and use large-scale hydro-thermal device, can carry out large-scale production.
Describe the present invention below in conjunction with the drawings and specific embodiments, but not as a limitation of the invention.
Description of drawings
Fig. 1 a, Fig. 1 b are respectively two transmission electron micrograph of a kind of dendroid gold nano structure of the inventive method preparation
Fig. 2 a, Fig. 2 b, Fig. 2 c, Fig. 2 d are respectively three transmission electron micrograph and the selected area electron diffraction picture of gold nano structure of a kind of few branch of the inventive method preparation
Fig. 3 a, Fig. 3 b, Fig. 3 c, Fig. 3 d are respectively four high resolution transmission electron microscopy pictures of a branch in the dendroid gold nano structure of the inventive method preparation, and wherein Fig. 3 c, Fig. 3 d have shown two kinds of dendroid gold nano-materials the interface is promptly clearly: twin-plane boundary and particle adhere to the interface
Fig. 4 a, Fig. 4 b be not for when having polyvinylpyrrolidonemolecules molecules to exist, two scanning electron microscope diagram sheets of the aggregates of nanoparticles that forms by chemical reaction
Fig. 5 a, Fig. 5 b, Fig. 5 c, Fig. 5 d are respectively three transmission electron micrograph and the selected area electron diffraction picture of dendroid gold nano-material of the initial cladodification of the inventive method preparation
Embodiment
Present embodiment prepares highly branched dendroid gold nano-material, its size range is in the 100-500 nanometer, as Fig. 1 a and Fig. 1 b is the transmission electron micrograph of prepared dendritic gold nano structure, each gold branch of described as can be seen dendroid gold nano-material is to form by mutual bonding fusion of gold nano grain or formation twin structure growth (seeing Fig. 3 a, Fig. 3 b, Fig. 3 c, Fig. 3 d), have nano level gap between the gold branch, and this dendroid gold nano body structure surface is wrapped up by polyvinylpyrrolidonemacromolecule macromolecule.
Concrete preparation method may further comprise the steps:
(1) reaction system is selected hydrochloro-auric acid (HuAuCl43H2O) or chlor(o)aurate (MAuCl4XH2O), and chlor(o)aurate is for example selected potassium chloraurate for use; Ammonium formiate (AmmoniumFormate) and stablizer polyvinylpyrrolidone (PVP), the three is a reactant, deionized water is a solvent; Wherein hydrochloro-auric acid or potassium chloraurate 0.18mmol, polyvinylpyrrolidone 0.2 gram, ammonium formiate 0.57 gram, deionized water 18ml;
(2) at first prepare the aqueous solution of hydrochloro-auric acid (HuAuCl43H2O) or chlor(o)aurate (MAuCl4XH2O): in 18ml, concentration are the aqueous solution of 0.01M hydrochloro-auric acid or potassium chloraurate, add 0.2 gram polyvinylpyrrolidone (0.1M), stir, after thorough mixing is even, add 0.57 gram ammonium formiate (Ammonium Formate) again (0.5M), stir once more, it is dissolved fully, obtain mixing solutions;
(3) then, with above-mentioned steps 2) mixing solutions that obtains shifts in the polytetrafluoroethylcontainer container of 25ml into, and be sealed in the metal high pressure autoclave, subsequently, whole autoclave is put into heating unit, under 120 ℃ of conditions the heating 5 hours, treat that the entire reaction still naturally cools to room temperature after, take out polytetrafluoroethylcontainer container, obtain to have the colloidal sol of black precipitate;
(4) clean repeatedly with pure water and ethanol after, centrifugation, drying obtain black dendroid gold nano-material.
Embodiment 2
The dendroid gold nano structure of the few branch of present embodiment preparation, its size range is in the 100-200 nanometer, as Fig. 2 a and Fig. 2 b is the transmission electron micrograph of prepared dendritic gold nano structure, each gold branch of described as can be seen dendroid gold nano-material is to form by the mutual bonding formation twin structure growth of gold nano grain (seeing Fig. 2 c, Fig. 2 d), have nano level gap between the gold branch, and this dendroid gold nano body structure surface is wrapped up by polyvinylpyrrolidonemacromolecule macromolecule.
Concrete preparation method may further comprise the steps:
(1) reaction system selection hydrochloro-auric acid (HuAuCl43H2O) or sodium chloraurate, ammonium formiate (Ammonium Formate) and polyvinylpyrrolidone (PVP) stablizer three are reactant, and water is a solvent; Wherein hydrochloro-auric acid or chlor(o)aurate 0.18mmol, polyvinylpyrrolidone 0.2 gram, ammonium formiate 0.34 gram, aqueous solvent 18ml;
(2) at first prepare the aqueous solution of hydrochloro-auric acid (HuAuCl43H2O) or chlor(o)aurate (MAuCl4XH2O): in the aqueous solution of 18ml, 0.01M hydrochloro-auric acid or chlor(o)aurate, add 0.2 gram polyvinylpyrrolidone (0.1M), stir, after thorough mixing is even, add 0.34 gram ammonium formiate (Ammonium Formate) again (0.3M), stir once more, it is dissolved fully, obtain mixing solutions;
(3) then, with above-mentioned steps 2) mixing solutions that obtains shifts in the polytetrafluoroethylcontainer container of 25ml into, and be sealed in the metal high pressure autoclave, subsequently, whole autoclave is put into heating unit, heating is 6 hours under 120 ℃ of conditions.After treating that the entire reaction still naturally cools to room temperature, take out polytetrafluoroethylcontainer container, obtain to have the colloidal sol of black precipitate;
(4) clean repeatedly with pure water and ethanol after, centrifugation, drying obtain black dendroid gold nano-material.
Embodiment 3
Present embodiment prepares the gold nano structure of preliminary cladodification, its size range is in the 100-200 nanometer, as Fig. 5 a and Fig. 5 b is the transmission electron micrograph of prepared dendritic gold nano structure, each gold branch of described as can be seen dendroid gold nano-material is to form by mutual bonding fusion of gold nano grain or formation twin structure growth (seeing Fig. 5 c, Fig. 5 d), have nano level gap between the gold branch, and this dendroid gold nano body structure surface is wrapped up by polyvinylpyrrolidonemacromolecule macromolecule.
Concrete preparation method may further comprise the steps:
(1) reaction system selection hydrochloro-auric acid (HuAuCl43H2O) or chlor(o)aurate (MAuCl4XH2O), ammonium formiate (Ammonium Formate) and polyvinylpyrrolidone (PVP) stablizer three are reactant, and water is a solvent; Wherein hydrochloro-auric acid or chlor(o)aurate 0.18mmol, polyvinylpyrrolidone 0.2 gram, ammonium formiate 0.11 gram, aqueous solvent 18ml;
(2) at first prepare the aqueous solution of hydrochloro-auric acid (HuAuCl43H2O) or chlor(o)aurate (MAuCl4XH2O): in the aqueous solution of 18ml, 0.01M hydrochloro-auric acid or chlor(o)aurate, add 0.2 gram polyvinylpyrrolidone (0.1M), stir, after thorough mixing is even, add 0.11 gram ammonium formiate (Ammonium Formate) again (0.1M), stir once more, it is dissolved fully, obtain mixing solutions;
(3) then, with above-mentioned steps 2) mixing solutions that obtains shifts in the polytetrafluoroethylcontainer container of 25ml into, and be sealed in the metal high pressure autoclave, subsequently, whole autoclave is put into heating unit, heating is 6 hours under 120 ℃ of conditions.After treating that the entire reaction still naturally cools to room temperature, take out polytetrafluoroethylcontainer container, obtain to have the colloidal sol of black precipitate;
(4) clean repeatedly with pure water and ethanol after, centrifugation, drying obtain black dendroid gold nano-material.
Certainly; the present invention also can have other various embodiments; under the situation that does not deviate from spirit of the present invention and essence thereof; those of ordinary skill in the art work as can make various corresponding changes and modification according to the present invention, but these corresponding changes and distortion all should belong to the protection domain of the appended claim of the present invention.
Claims (5)
1. dendroid gold nano-material, it is characterized in that: each gold branch of described dendroid gold nano-material is to form by mutual bonding fusion of gold nano grain or the growth of formation twin structure, have nano level gap between the gold branch, and whole dendroid gold nano body structure surface is wrapped up by polyvinylpyrrolidonemolecules molecules; Wherein the size of dendroid gold nano-material is in the 100-500 nanometer range.
2. the preparation method of a dendroid gold nano-material is characterized in that, may further comprise the steps:
Reaction system is selected: concentration is 0.01M hydrochloro-auric acid or chlor(o)aurate, and concentration is the 0.1M-0.5M ammonium formiate, and concentration is 0.1M polyvinylpyrrolidone coating agent, the 10-1000mL pure water;
Configuration reactant mixing solutions: adding polyvinylpyrrolidone to concentration in the 10-1000mL of 0.01M hydrochloro-auric acid or the chlor(o)aurate aqueous solution is 0.1M, stirs rapidly, and thorough mixing is even;
Get the reactant mixing solutions (10-1000mL) of step (b) configuration, and to add ammonium formiate to concentration again be 0.1M-0.5M, stir it is dissolved fully;
The solution that step (c) is obtained shifts in the polytetrafluoroethylcontainer container, be sealed in the metal high pressure autoclave, whole autoclave is put into heating unit, heating is 1-6 hour under 100-120 ℃ of condition, after the question response still naturally cools to room temperature, take out polytetrafluoroethylcontainer container, obtain to have the colloidal sol of black precipitate; Clean repeatedly at least 3 times with 100mL pure water and 100mL ethanol, centrifugation, drying obtain black dendroid gold nano-material.
3. by the described method for preparing dendroid gold nano structure of claim 2, it is characterized in that, in described step b), also comprise and adopt ultrasonic mixing.
4. by the described method for preparing dendroid gold nano structure of claim 2, it is characterized in that the centrifugal settling time was at least 30 minutes in described step (d).
5. by the described method for preparing dendroid gold nano structure of claim 2, it is characterized in that described chlor(o)aurate comprises: potassium chloraurate or sodium chloraurate.
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Cited By (8)
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| CN101775647A (en) * | 2010-02-10 | 2010-07-14 | 中国科学院长春应用化学研究所 | Gold nano-crystal and preparation method thereof |
| CN102837005A (en) * | 2012-09-27 | 2012-12-26 | 江南大学 | Method for preparing size-controlled gold nanostars with surface Raman enhanced activity |
| CN102990082A (en) * | 2012-12-17 | 2013-03-27 | 桂林理工大学 | Method for preparing fluorescence nano gold sol by using PVP (Poly Vinyl Pyrrolidone) through reduction modification under hydrothermal condition |
| CN103933583A (en) * | 2014-04-14 | 2014-07-23 | 上海交通大学 | Preparation method and application of hand-shaped gold nanoclusters for inhibiting MGC-803 cells |
| CN104028776A (en) * | 2014-06-20 | 2014-09-10 | 清华大学深圳研究生院 | Metal particles with three-dimensional dendritic crystal structures and preparation method for metal particles |
| CN105537611A (en) * | 2015-12-11 | 2016-05-04 | 中国科学院深圳先进技术研究院 | Coralline platinum-copper alloy nano-particle and preparing method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101775647A (en) * | 2010-02-10 | 2010-07-14 | 中国科学院长春应用化学研究所 | Gold nano-crystal and preparation method thereof |
| CN101775647B (en) * | 2010-02-10 | 2012-06-20 | 中国科学院长春应用化学研究所 | Gold nano-crystal and preparation method thereof |
| CN102837005A (en) * | 2012-09-27 | 2012-12-26 | 江南大学 | Method for preparing size-controlled gold nanostars with surface Raman enhanced activity |
| CN102990082A (en) * | 2012-12-17 | 2013-03-27 | 桂林理工大学 | Method for preparing fluorescence nano gold sol by using PVP (Poly Vinyl Pyrrolidone) through reduction modification under hydrothermal condition |
| CN103933583A (en) * | 2014-04-14 | 2014-07-23 | 上海交通大学 | Preparation method and application of hand-shaped gold nanoclusters for inhibiting MGC-803 cells |
| CN103933583B (en) * | 2014-04-14 | 2016-08-17 | 上海交通大学 | Preparation of chiral gold nanocluster of suppression MGC-803 cell and application thereof |
| CN104028776A (en) * | 2014-06-20 | 2014-09-10 | 清华大学深圳研究生院 | Metal particles with three-dimensional dendritic crystal structures and preparation method for metal particles |
| CN105537611A (en) * | 2015-12-11 | 2016-05-04 | 中国科学院深圳先进技术研究院 | Coralline platinum-copper alloy nano-particle and preparing method thereof |
| CN110695368A (en) * | 2018-07-10 | 2020-01-17 | 吉林大学 | Eight-fork gold nano-particle, preparation method, application and intermediate thereof |
| CN110695368B (en) * | 2018-07-10 | 2022-01-07 | 吉林大学 | Eight-fork gold nano-particle, preparation method, application and intermediate thereof |
| CN115055672A (en) * | 2022-06-15 | 2022-09-16 | 安徽理工大学 | Method for preparing coral-shaped gold nano/carbon nano tube composite material |
| CN115055672B (en) * | 2022-06-15 | 2023-10-24 | 安徽理工大学 | Method for preparing coral-shaped gold nano/carbon nano tube composite material |
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