CN102310201B - Surface phosphonic acid functionalized Au nano particle preparing method - Google Patents
Surface phosphonic acid functionalized Au nano particle preparing method Download PDFInfo
- Publication number
- CN102310201B CN102310201B CN 201110306591 CN201110306591A CN102310201B CN 102310201 B CN102310201 B CN 102310201B CN 201110306591 CN201110306591 CN 201110306591 CN 201110306591 A CN201110306591 A CN 201110306591A CN 102310201 B CN102310201 B CN 102310201B
- Authority
- CN
- China
- Prior art keywords
- aunps
- phosphonic acid
- haucl
- solution
- acid functionalized
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Abstract
The invention discloses a surface phosphonic acid functionalized Au nano particle (AuNPs) preparing method. Olefin organic phosphonic acid is used as a reducing agent to be added into a HAuCl4 water solution and heated at the temperature of 80-120 DEG C under a stirring condition for reaction, and surface phosphonated spherical Au nano particles with uniform size and regular shapes are obtained. The surfaces of the prepared AuNPs are wrapped by oxidization products of the reduction agent and then are decorated with phosphonic acid base groups, so the colloid stability of AuNPs is effectively improved, the phenomenon of agglomeration is avoided, and the phosphonic acid functionalized AuNPs with good monodispersity and uniform particle size are prepared. The preparing method disclosed by the invention has a clear and reliable mechanism and is simple and feasible, and the obtained AuNPs have excellent colloid stability in water and wide application prospects in the material science and biomedicine fields of nano devices, fuel batteries, bio-mimetic enzyme sensors and the like.
Description
Technical field
The present invention relates to a kind of preparation method of functionalization golden nanometer particle, relate in particular to a kind of golden nanometer particle preparation method of finishing phosphonyl group.
Background technology
Golden nanometer particle (AuNPs) namely refers to the molecule of gold, and its diameter has high electron density, dielectric property and catalytic action at 1～100 nm, can be combined with multiple large biological molecule, and not affect its biologically active.By HAuCl
4Can prepare easily the nm of gold of various different-grain diameters by reducing process, its color takes on a red color to purple according to diameter.AuNPs has caused the various fields researchers' such as optics, biology, catalysis, sensor and medical treatment interest owing to its unique physics, chemical property.The AuNPs of stably dispersing has very high using value at biological field in the aqueous solution.
A lot of different methods that prepare AuNPs are arranged at present, and wherein the wet chemistry reducing process is a kind of very traditional and universal method for the preparation of the stable AuNPs of aqueous dispersion.Because AuNPs is very easy to reunite and sedimentation in aqueous environment, so thereby usually can cover its surface with some protective agents reaches stable purpose.The polymer that contains corresponding functional group as mercaptan, hydrogen phosphide, amine, carboxylate, biomolecule and some has been widely used in stablizes AuNPs, mainly is based on the hydrophily of electrostatic repulsion strong between the functional group of dissociating or functional group's oneself height.Than-NH
2With-the COOH group ,-PO
3H
2Because the binary acid of himself essence have wider pH response range, thereby so that there is electrostatic repulsion in the AuNPs of phosphonic acids in very wide pH scope.Therefore, all show outstanding colloidal stability in the aqueous solution of the AuNPs of phosphonic acid functionalized in very wide pH scope.
The present invention is intended to utilize chemical preparation functionalization AuNPs, make AuNPs finishing phosphonyl group, by the Coulomb repulsion between the phosphonyl group and the outstanding hydrophily of phosphonyl group self, the colloidal stability of Effective Raise AuNPs in the aqueous solution prepared the AuNPs of the phosphonic acid functionalized of monodispersed, uniform particle diameter.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of golden nanometer particle (AuNPs) of surface phosphonic acid functionalized, AuNPs easily reunites in the aqueous solution to overcome, the defective of sedimentation, can make single AuNPs of dispersion of the regular surface phosphonic acid functionalized of uniform particle diameter, shape, to satisfy the requirement of relevant field development.
The technical solution adopted in the present invention is as follows:
A kind of preparation method of golden nanometer particle of surface phosphonic acid functionalized is characterized in that, a certain amount of olefines organic phospho acid reducing agent is joined HAuCl
4In the aqueous solution, 80 ~ 120 ℃ add thermal response under the stirring condition, obtain the golden nanometer particle of surface phosphonic acid.
The inventive method utilizes the olefines organic phospho acid as reducing agent, adopts " one kettle way " with HAuCl
4Be reduced into uniform particle diameter, the regular monodisperse spherical AuNPs of shape.In the preparation process, because the oxidation product of reducing agent is coated on the AuNPs surface, thereby modify phosphonyl group on the AuNPs surface.
Described olefines organic phospho acid is styryl phosphonic acids, vinylphosphonic acid, propylene phosphonic acids or isopropylene and phosphonic acid sodium.
Described HAuCl
4The pH of the aqueous solution is 3 ~ 12.
Described HAuCl
4With the molar ratio of olefines organic phospho acid be 1:0.5 ~ 7.
The described reaction time is 10 ~ 120 min, preferred 10 min～20 min.
The preparation method of the golden nanometer particle of surface phosphonic acid functionalized of the present invention utilizes the olefines organic phospho acid as reducing agent, with HAuCl
4Be reduced into big or small homogeneous, the regular spherical AuNPs of shape.Prepared AuNPs finishing phosphonyl group, by the Coulomb repulsion between the phosphonyl group and the outstanding hydrophily of phosphonyl group self, effectively raise the colloidal stability of AuNPs, avoided the appearance of agglomeration, prepared that monodispersity is good, the AuNPs of the phosphonic acid functionalized of uniform particle diameter.The inventive method preparation process mechanism is clear and definite, reliable, and the preparation method is simple, and the product that obtains shows as outstanding colloidal stability in water.The AuNPs of the surface phosphonic acid functionalized that the inventive method makes has high electron density, dielectric property and catalytic action, can be combined with multiple large biological molecule, and do not affect its biologically active, can be applied to the Disciplinary Frontiers such as structure of bioelectrochemistry, electro-catalysis, ZrP material and Biomimetic membranes, and have broad application prospects in the material science such as nano-device, fuel cell, biosimulation enzyme sensor and biomedicine field.
Describe the present invention below in conjunction with specific embodiment.Protection scope of the present invention is not limited with the specific embodiment, but is limited by claim.
Description of drawings
Fig. 1 is HAuCl
4With the ratio of the amount of substance of isopropylene and phosphonic acid sodium be the variation relation figure of the ultraviolet absorptivity of the AuNPs for preparing under the condition of 1:3 with the reaction time.
As can be seen from Figure 1, at HAuCl
4With front 3 min of isopropylene and phosphonic acid sodium reaction, the ultraviolet absorptivity of the AuNPs of generation increases rapidly along with the increase in reaction time, and isopropylene and phosphonic acid sodium reduction HAuCl is described
4Reaction very fast.After the reaction time arrived 10 min, the ultraviolet absorptivity of AuNPs was along with the increase in reaction time remains unchanged substantially, and this shows that reaction carried out substantially fully.Reduction to a certain degree occurs in the ultraviolet absorptivity of AuNPs on the contrary after 20 min, and the AuNPs of generation under the condition that continues heating a small amount of reunion may occur.So recommendations for selection HAuCl
4With the reaction time of isopropylene and phosphonic acid sodium be 10 min～20 min.
Fig. 2 a to Fig. 2 d is HAuCl
4Be respectively 1:0.5 (a), 1:1 (b), 1:2 (c), 1:3 (d) with the ratio of the amount of substance of isopropylene and phosphonic acid sodium, the reaction time is the TEM collection of illustrative plates of the AuNPs for preparing under the 10 min reaction conditions.
From figure, obviously see, utilize isopropylene and phosphonic acid sodium as reducing agent, with HAuCl
4Big or small homogeneous, the regular spherical AuNPs of shape have been reduced into.This is to coat because the AuNPs surface is reduced the oxidation product of agent, make its finishing phosphonyl group, by the Coulomb repulsion between the phosphonyl group and the outstanding hydrophily of phosphonyl group self, effectively raise the monodispersity of AuNPs, avoided the appearance of agglomeration.And along with HAuCl
4Constantly increase with the ratio of the amount of substance of isopropylene and phosphonic acid sodium, the large variation of rear change that diminishes has first occured in the particle diameter of AuNPs.As seen from the figure, HAuCl
4With the ratio of the amount of substance of isopropylene and phosphonic acid sodium be that the particle diameter of the AuNPs for preparing under the 1:1 condition is minimum.
Fig. 3 is HAuCl
4Be respectively 1:0.5 (a), 1:1 (b), 1:2 (c), 1:3 (d) with the ratio of the amount of substance of isopropylene and phosphonic acid sodium, the reaction time is the UV-vis collection of illustrative plates of the AuNPs for preparing under the 10 min reaction conditions.
Can see from the UV-vis collection of illustrative plates of the AuNPs of different proportion preparation, be all to can be observed the characteristic absorption peak that comes from AuNPs about 520 nm at wavelength.And work as HAuCl
4When increasing to 1:1 with the ratio of the amount of substance of isopropylene and phosphonic acid sodium from 1:0.5, the blue shift of 3 nm has occured in the UV absorption wavelength, shows that the particle diameter of AuNPs has reduced.And work as HAuCl
4When continuing to increase with the ratio of the amount of substance of isopropylene and phosphonic acid sodium, red shift has to a certain degree but occured in the UV absorption wavelength, and particle diameter of this explanation AuNPs is increasing gradually.
The specific embodiment
Embodiment 1
Get the HAuCl of 325 uL, 0.0971 M
4Join and get HAuCl in the three-neck flask that fills 25 mL distilled water
4The aqueous solution, pH is 12 with NaOH solution regulator solution.In 120 ℃ of oil bath devices, constantly stir, reflux heating is to boiling, then add fast 158 uL, 0.1 M isopropylene and phosphonic acid sodium solution, continue reflux heating and stir 10 ~ 20 min, solution is by the colourless peony that becomes, stopped heating when no longer changing to color obtains the AuNPs of the phosphonic acids of dispersion stabilization.
Embodiment 2
Get the HAuCl of 325 uL, 0.0971 M
4Join and get HAuCl in the three-neck flask that fills 25 mL distilled water
4The aqueous solution, pH is 12 with NaOH solution regulator solution.In 120 ℃ of oil bath devices, constantly stir, reflux heating is to boiling, then add fast 316 uL, 0.1 M isopropylene and phosphonic acid sodium solution, continue reflux heating and stir 10 ~ 20 min, solution is by the colourless peony that becomes, stopped heating when no longer changing to color obtains the AuNPs of the phosphonic acids of dispersion stabilization.
Embodiment 3
Get the HAuCl of 325 uL, 0.0971 M
4Join and get HAuCl in the three-neck flask that fills 25 mL distilled water
4The aqueous solution, pH is 12 with NaOH solution regulator solution.In 120 ℃ of oil bath devices, constantly stir, reflux heating is to boiling, then add fast 632 uL, 0.1 M isopropylene and phosphonic acid sodium solution, continue reflux heating and stir 10 ~ 20 min, solution is by the colourless peony that becomes, stopped heating when no longer changing to color obtains the AuNPs of the phosphonic acids of dispersion stabilization.
Embodiment 4
Get the HAuCl of 325 uL, 0.0971 M
4Join and get HAuCl in the three-neck flask that fills 25 mL distilled water
4The aqueous solution, pH is 12 with NaOH solution regulator solution.In 120 ℃ of oil bath devices, constantly stir, reflux heating is to boiling, then add fast 947 uL, 0.1 M isopropylene and phosphonic acid sodium solution, continue reflux heating and stir 10 ~ 20 min, solution is by the colourless peony that becomes, stopped heating when no longer changing to color obtains the AuNPs of the phosphonic acids of dispersion stabilization.
Get the HAuCl of 325 uL, 0.0971 M
4Join and get HAuCl in the three-neck flask that fills 25 mL distilled water
4The aqueous solution, pH is 3 with NaOH solution regulator solution.In 120 ℃ of oil bath devices, constantly stir, reflux heating is to boiling, then add fast 158 uL, 0.1 M styryl phosphonic acids solution, continue reflux heating and stir 10 ~ 20 min, solution is by the colourless peony that becomes, stopped heating when no longer changing to color obtains the AuNPs of the phosphonic acids of dispersion stabilization.
Embodiment 6
Get the HAuCl of 325 uL, 0.0971 M
4Join and get HAuCl in the three-neck flask that fills 25 mL distilled water
4The aqueous solution, pH is 6 with NaOH solution regulator solution.In 100 ℃ of oil bath devices, constantly stir, reflux heating is to boiling, then add fast 316 uL, 0.1 M styryl phosphonic acids solution, continue reflux heating and stir 10 ~ 20 min, solution is by the colourless peony that becomes, stopped heating when no longer changing to color obtains the AuNPs of the phosphonic acids of dispersion stabilization.
Embodiment 7
Get the HAuCl of 325 uL, 0.0971 M
4Join and get HAuCl in the three-neck flask that fills 25 mL distilled water
4The aqueous solution, pH is 9 with NaOH solution regulator solution.Constantly stir in 100 ℃ of oil bath devices, then reflux heating adds 632 uL, 0.1 M styryl phosphonic acids solution fast to boiling, continuing reflux heating stirs, solution is by the colourless peony that becomes, and stopped heating when no longer changing to color obtains the AuNPs of the phosphonic acids of dispersion stabilization.
Embodiment 8
Get the HAuCl of 325 uL, 0.0971 M
4Join and get HAuCl in the three-neck flask that fills 25 mL distilled water
4The aqueous solution, pH is 12 with NaOH solution regulator solution.Constantly stir in 80 ℃ of oil bath devices, then reflux heating adds 947 uL, 0.1 M styryl phosphonic acids solution fast, continue reflux heating and stir 10 ~ 20 min, solution is by the colourless peony that becomes, and stopped heating when no longer changing to color obtains the AuNPs of the phosphonic acids of dispersion stabilization.
Embodiment 9
Get the HAuCl of 325 uL, 0.0971 M
4Join and get HAuCl in the three-neck flask that fills 25 mL distilled water
4The aqueous solution, pH is 12 with NaOH solution regulator solution.In 120 ℃ of oil bath devices, constantly stir, reflux heating is to boiling, then add fast 158 uL, 0.1 M vinylphosphonic acid solution, continue reflux heating and stir 10 ~ 20 min, solution is by the colourless peony that becomes, stopped heating when no longer changing to color obtains the AuNPs of the phosphonic acids of dispersion stabilization.
Get the HAuCl of 325 uL, 0.0971 M
4Join and get HAuCl in the three-neck flask that fills 25 mL distilled water
4The aqueous solution, pH is 12 with NaOH solution regulator solution.In 120 ℃ of oil bath devices, constantly stir, reflux heating is to boiling, then add fast 316 uL, 0.1 M vinylphosphonic acid solution, continue reflux heating and stir 10 ~ 20 min, solution is by the colourless peony that becomes, stopped heating when no longer changing to color obtains the AuNPs of the phosphonic acids of dispersion stabilization.
Embodiment 11
Get the HAuCl of 325 uL, 0.0971 M
4Join and get HAuCl in the three-neck flask that fills 25 mL distilled water
4The aqueous solution, pH is 12 with NaOH solution regulator solution.In 120 ℃ of oil bath devices, constantly stir, reflux heating is to boiling, then add fast 632 uL, 0.1 M propylene phosphonic acids solution, continue reflux heating and stir 10 ~ 20 min, solution is by the colourless peony that becomes, stopped heating when no longer changing to color obtains the AuNPs of the phosphonic acids of dispersion stabilization.
Embodiment 12
Get the HAuCl of 325 uL, 0.0971 M
4Join and get HAuCl in the three-neck flask that fills 25 mL distilled water
4The aqueous solution, pH is 12 with NaOH solution regulator solution.In 120 ℃ of oil bath devices, constantly stir, reflux heating is to boiling, then add fast 947 uL, 0.1 M propylene phosphonic acids solution, continue reflux heating and stir 10 ~ 20 min, solution is by the colourless peony that becomes, stopped heating when no longer changing to color obtains the AuNPs of the phosphonic acids of dispersion stabilization.
Claims (4)
1. the preparation method of the golden nanometer particle of a surface phosphonic acid functionalized is characterized in that, a certain amount of olefines organic phospho acid reducing agent is joined HAuCl
4In the aqueous solution, 80 ~ 120 ℃ add thermal response under the stirring condition, and the reaction time is 10 ~ 20 min, obtains the golden nanometer particle of surface phosphonic acid.
2. the preparation method of the golden nanometer particle of surface phosphonic acid functionalized according to claim 1 is characterized in that described olefines organic phospho acid is styryl phosphonic acids, vinylphosphonic acid, propylene phosphonic acids or isopropylene and phosphonic acid sodium.
3. the preparation method of the golden nanometer particle of surface phosphonic acid functionalized according to claim 1 is characterized in that, described HAuCl
4With the molar ratio of olefines organic phospho acid be 1:0.5 ~ 7.
4. the preparation method of the golden nanometer particle of surface phosphonic acid functionalized according to claim 1 is characterized in that, described HAuCl
4The pH scope of the aqueous solution is 3 ~ 12.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110306591 CN102310201B (en) | 2011-10-11 | 2011-10-11 | Surface phosphonic acid functionalized Au nano particle preparing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110306591 CN102310201B (en) | 2011-10-11 | 2011-10-11 | Surface phosphonic acid functionalized Au nano particle preparing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102310201A CN102310201A (en) | 2012-01-11 |
| CN102310201B true CN102310201B (en) | 2013-01-02 |
Family
ID=45423987
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201110306591 Expired - Fee Related CN102310201B (en) | 2011-10-11 | 2011-10-11 | Surface phosphonic acid functionalized Au nano particle preparing method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102310201B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104127875A (en) * | 2014-03-11 | 2014-11-05 | 常州碳宇纳米科技有限公司 | Gene carrier of small size gold nanoparticle vesicle structure and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005015846A (en) * | 2003-06-26 | 2005-01-20 | National Institute Of Advanced Industrial & Technology | Surface modified gold nanoparticle and its production method |
| KR20090087591A (en) * | 2008-02-13 | 2009-08-18 | 성균관대학교산학협력단 | Surface modification method of gold nano particle, and stabilization method of gold nano particles by surface modification |
| CN101987364A (en) * | 2010-09-14 | 2011-03-23 | 江南大学 | Method for preparing functional gold nanoparticles with high stability |
| CN102000833A (en) * | 2010-12-14 | 2011-04-06 | 天津大学 | Submicron Au particles and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8558117B2 (en) * | 2010-02-13 | 2013-10-15 | Aculon, Inc. | Electroconductive inks made with metallic nanoparticles |
-
2011
- 2011-10-11 CN CN 201110306591 patent/CN102310201B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005015846A (en) * | 2003-06-26 | 2005-01-20 | National Institute Of Advanced Industrial & Technology | Surface modified gold nanoparticle and its production method |
| KR20090087591A (en) * | 2008-02-13 | 2009-08-18 | 성균관대학교산학협력단 | Surface modification method of gold nano particle, and stabilization method of gold nano particles by surface modification |
| CN101987364A (en) * | 2010-09-14 | 2011-03-23 | 江南大学 | Method for preparing functional gold nanoparticles with high stability |
| CN102000833A (en) * | 2010-12-14 | 2011-04-06 | 天津大学 | Submicron Au particles and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102310201A (en) | 2012-01-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wang et al. | Facile preparation of self-assembled black phosphorus-dye composite films for chemical gas sensors and surface-enhanced Raman scattering performances | |
| Wu et al. | Janus nanoarchitectures: From structural design to catalytic applications | |
| Liao et al. | Facile preparation of uniform nanocomposite spheres with loading silver nanoparticles on polystyrene-methyl acrylic acid spheres for catalytic reduction of 4-nitrophenol | |
| Iqbal et al. | Silver nanoparticles stabilized in polymer hydrogels for catalytic degradation of azo dyes | |
| Duan et al. | Research advances in the synthesis, application, assembly, and calculation of Janus materials | |
| Huang et al. | Photochemically controlled synthesis of anisotropic Au nanostructures: platelet-like Au nanorods and six-star Au nanoparticles | |
| Xi et al. | Amphiphilic graphene quantum dots as a new class of surfactants | |
| Yuan et al. | Polyethylenimine-bridged graphene oxide–gold film on glassy carbon electrode and its electrocatalytic activity toward nitrite and hydrogen peroxide | |
| CN101458242B (en) | Nanogold Colloid for responding heavy metal ion and method for making same | |
| CN107068319B (en) | A kind of preparation method of hydrophobic magnetic composite material | |
| Zhu et al. | Facile and green fabrication of small, mono-disperse and size-controlled noble metal nanoparticles embedded in water-stable polyvinyl alcohol nanofibers: High sensitive, flexible and reliable materials for biosensors | |
| Luty-Błocho et al. | The synthesis of platinum nanoparticles and their deposition on the active carbon fibers in one microreactor cycle | |
| CN105486733B (en) | A kind of Preparation method and use of Openworks shape bismuthyl iodide/azepine graphene quantum dot microballoon | |
| Sun et al. | Sensitive electrochemical immunoassay for chlorpyrifos by using flake-like Fe3O4 modified carbon nanotubes as the enhanced multienzyme label | |
| Wu et al. | Synthesis of Ag nanoparticles-decorated poly (m-phenylenediamine) hollow spheres and the application for hydrogen peroxide detection | |
| CN1810422A (en) | Prepn process of nanometer silver sol | |
| Kudaibergenov et al. | Polymer protected and gel immobilized gold and silver nanoparticles in catalysis | |
| CN102151527B (en) | Preparation method of monodisperse silicon oxide magnetic microspheres used for DNA purification and protein separation | |
| CN108031475A (en) | A kind of preparation method of gold load ferric oxide nano photochemical catalyst | |
| Chen et al. | Preparation and applications of freestanding Janus nanosheets | |
| CN103769583A (en) | Preparation method of gold nanoparticle modified by graphene quantum dots | |
| CN107383405A (en) | A kind of compound proton exchange membrane and preparation method thereof | |
| CN105312051A (en) | Nano gold-mesoporous silica composite nanotube, preparation and applications thereof | |
| CN102924751A (en) | Preparation method for nanocarbon fluid | |
| Bamoharram | Role of polyoxometalates as green compounds in recent developments of nanoscience |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20130102 Termination date: 20171011 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |