CN102019419A - Mesoporous-macroporous Au-nano particle with adjustable wall thickness as well as preparation method and application thereof - Google Patents
Mesoporous-macroporous Au-nano particle with adjustable wall thickness as well as preparation method and application thereof Download PDFInfo
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- CN102019419A CN102019419A CN 201010551150 CN201010551150A CN102019419A CN 102019419 A CN102019419 A CN 102019419A CN 201010551150 CN201010551150 CN 201010551150 CN 201010551150 A CN201010551150 A CN 201010551150A CN 102019419 A CN102019419 A CN 102019419A
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Abstract
The invention discloses a mesoporous-macroporous Au-nano particle with adjustable wall thickness as well as a preparation method and an application thereof. 0.005-0.05M of soluble quaternary phosphonium salt aqueous solution is poured into an inorganic salt aqueous solution of 0.5mM-30mM of Au, stirring is carried out for 2-10 minutes violently at the meantime, and the color of the solution is changed into deep yellow from pale yellow; and a proper hydroboron aqueous solution of 0.1-2.0M, which is prepared just now, is added rapidly, and stirring is carried out for 5-15 minutes violently, the generated multiple bubbles can be viewed, the color of the solution is changed to be colorless, and black solid particles are generated at the meantime, namely the black solid particles are mesoporous-macroporous Au-nano particles. The mesoporous-macroporous Au-nano particle has ideal effect on the application of SERS (surface enhanced Raman scattering) detection, as an antibody or an antigen and DNA or RNA can be riveted on the surface of the Au particle, the mesoporous-macroporous Au-nano material has great potential application in the trace biomolecule detection field.
Description
Technical field
The present invention relates to the adjustable middle macropore golden nanometer particle of a kind of wall thickness, and this nanometer particle process method and in the application in surface-enhanced Raman field, belongs to the metal material technical field.
Background technology
In recent years, nanostructured gold because have that high electricity is led, high thermal conductance, unique optical property, and also show the character of brilliance in fields such as analysiss, catalysis, and more and more cause the extensive concern of scientists.Research more has nanowires of gold, gold nanorods, contains nucleocapsid structure, golden dendroid, golden network structure, golden polyhedron and golden sponge body structure of gold or the like in the middle of this.And middle macropore golden nanometer particle since its compare with the non-porous nano particle have high-specific surface area, low-density and cavity structure, the more important thing is that it has distinct plasma properties, and have very high researching value.Early-stage Study shows, the plasma peak that contains the spherical gold nanoshell of dielectric core can be regulated at an easy rate and cover 600 to 1200nm scope, and for color of spherical gold, also is unusual difficulty even make it to surpass 20nm.
Mainly contain two class methods now and be used for synthesizing middle macropore golden nanometer particle.First kind is at first to cover the skim gold at silica bead or polymer emulsion particle surface, then optionally removes the colloid template and promptly obtains; Second kind is by gold ion and other metal generation displacement reactions, and the metal nanoparticle for preparing is in advance generated middle macropore golden nanometer particle as sacrificing template.Thick very heterogeneity of the product shell that the former obtains and spherical shell breakage are very serious, and the golden shell that the latter generates is more complete, smooth surface and do not have hole, but must at first control synthetic metal nanoparticle template, and the difficult control of particle shell wall thickness.
Raman spectrum and infrared spectrum complement one another, and the structural information of organic molecule can be provided, so be considered to a powerful analysis tool.But its major defect is a poor sensitivity, and particularly at the adsorbing species that detects the substrate surface monolayer, intensity generally will be lower than the instrument detecting limit and can't observe.Based on this limitation, SERS (SERS) arises at the historic moment, and it has overcome the shortcoming of common Raman technology muting sensitivity, can provide that architectural feature is strong, the information of molecular level, is widely used in biochemistry detects.By the approach at the bottom of the modification precious metal-based, SERS is used to strengthen the sensitiveness of extremely rare solute Raman scattering more and more, such as the nano particle and the metal film that use coarse electrode, gathering.In various noble metals, the modification of gold is very effective for strengthening Raman scattering.Up to now, great majority research all concentrates on the dimensional effect of solid atresia golden nanometer particle and contains the application of golden nucleocapsid structure in SERS, as for middle macropore golden nanometer particle and micro-structural thereof the influence that strengthens Raman scattering is not also had report.
Summary of the invention
The purpose of this invention is to provide a kind of middle macropore golden nanometer particle easy, that wall thickness is adjustable for preparing.
Another object of the present invention provide above-mentioned in the preparation method of macropore golden nanometer particle, and in the application in surface-enhanced Raman field.
Purpose of the present invention can be achieved through the following technical solutions.
The middle macropore golden nanometer particle that a kind of wall thickness is adjustable is polycrystalline structure, and spherical particle, shell external diameter are 40-100nm, and average grain diameter is 60-80nm, and the spherical shell wall thickness is 10-20nm, and it is the aperture of 8-30nm that there are many diameters on the spherical shell surface.
The preparation method of the middle macropore golden nanometer particle that above-mentioned wall thickness is adjustable, concrete steps are as follows:
At a certain temperature, the 0.005-0.05M solubility quaternary alkylphosphonium salt aqueous solution is poured in the inorganic salt solution of 0.5mM-30mM gold, while vigorous stirring 2-10min, solution colour is gradually by the light yellow buff that becomes, the boron hydride aqueous solution that adds the 0.1-2.0M of proper amount of fresh preparation subsequently fast, vigorous stirring 5-15min, can observe a large amount of bubbles generates, it is colourless that solution colour gradually becomes, there is the black solid particle to generate simultaneously, the promptly middle macropore golden nanometer particle of the black solid product that obtains.Through centrifugal, filtration and standby with the deionized water cyclic washing.
Temperature of reaction system is preferably 298K-333K.
Quaternary alkylphosphonium salt is (10-50) with the mol ratio of the inorganic salts of gold: 1, preferred (20-30): 1.
Preferred tetrabutyl phosphonium bromide phosphorus of solubility quaternary alkylphosphonium salt or tetrabutyl phosphorus chloride.
Preferred gold chloride (the HAuCl of inorganic salts of gold
4) or gold trichloride (AuCl
3).
The preferred 3-5min of described mixing time.
Boron hydride is (4-10) with the mol ratio of the inorganic salts of gold: 1.
The preferred sodium borohydride of boron hydride, potassium borohydride or both mixtures.
In of the present invention the macropore golden nanometer particle prepare easy, structural integrity, good stability, particle diameter is evenly distributed, spherical shell wall thickness homogeneous and can regulating, the shell surface presents vesicular texture.
The middle macropore golden nanometer particle of prepared different wall is used for the SERS detection as substrate, rhodamine 6G is as Raman microprobe, the result shows that its SERS signal peak than the atresia golden nanometer particle of similar particle diameter has very big enhancing, increase along with wall thickness, peak intensity strengthens, and the highest peak signal increases about 40 times than golden nanometer particle.
The preparation present situation of macropore gold in the present invention is directed at present, prepare with a kind of very easy method that particle diameter is even, wall thickness is adjustable, the middle macropore golden nanometer particle of porous surface, and in using, the SERS detection obtained desirable effect, because this excellent biological compatibility that antibody or antigen and DNA or RNA can riveting decide in the gold particle surface, make this in the large hole nano material in detection trace biomolecular field huge application potential is arranged.
Description of drawings
Fig. 1 is that the ultraviolet-visible of the atresia golden nanometer particle of the middle macropore golden nanometer particle of different wall and similar particle diameter absorbs collection of illustrative plates;
Fig. 2 is the TEM photo of the middle macropore golden nanometer particle of different wall;
Fig. 3 is the FESEM photo of middle macropore golden nanometer particle;
The SERS spectrogram that Fig. 4 is rhodamine 6G (R6G) Molecular Adsorption on the atresia golden nanometer particle of the middle macropore golden nanometer particle of different wall and similar particle diameter.
The specific embodiment
The following examples will give further instruction to the present invention, and its protection domain is not limited.
Embodiment 1-3 is for preparing the method for nano material of the present invention, and embodiment 4 is control experiment.
Embodiment 1
Under 298K, with the tetrabutyl phosphonium bromide phosphorus (Bu of 20mL (10mM)
4PBr) aqueous solution is poured the gold chloride (HAuCl of 2.0mL (5.0mM) into
4) in the aqueous solution, vigorous stirring 3min simultaneously, solution colour adds the KBH of 0.10mL (0.50M) subsequently fast gradually by the light yellow buff that becomes
4The aqueous solution, vigorous stirring 5min can observe a large amount of bubbles and generate, and it is colourless that solution colour gradually becomes, and has the black solid particle to generate simultaneously, and the black solid product that obtains is through centrifugal, filtration and standby with the deionized water cyclic washing.
The UV, visible light absorption collection of illustrative plates of sample is seen a curve among Fig. 1, and TEM figure sees a curve among Fig. 2, and wall thickness is 10nm, and FESEM figure sees Fig. 3.
The black sample is immersed in 1.0 * 10 earlier
-42h in the rhodamine 6G of M (R6G) aqueous solution detects with the clean SERS that is used for of deionized water then.Find out that from Fig. 4 a compare golden solid nano particle (embodiment 4), middle macropore golden nanometer particle has manifested the Raman scattering enhancement effect stronger to R6G.All characteristic peak that observes 1181,1312,1362,1503,1575 and 1643cm
-1All belong to R6G.1181cm
-1Be the C-C stretching vibration peak, 1312,1362,1503 and 1643cm
-1The SERS peak ownership at place is the C-C stretching vibration peak on the aromatic rings in the R6G molecule, 1575cm
-1Then come from the deformation vibration of oxa-anthracene nucleus and the acting in conjunction of N-H in-plane bending vibration.
Embodiment 2
Under 313K, with the tetrabutyl phosphonium bromide phosphorus (Bu of 30mL (10mM)
4PBr) aqueous solution is poured the gold chloride (HAuCl of 2.0mL (5.0mM) into
4) in the aqueous solution, vigorous stirring 4min simultaneously, solution colour adds the NaBH of 0.15mL (0.50M) subsequently fast gradually by the light yellow buff that becomes
4The aqueous solution, vigorous stirring 10min can observe a large amount of bubbles and generate, and it is colourless that solution colour gradually becomes, and has the black solid particle to generate simultaneously, and the black solid product that obtains is through centrifugal, filtration and standby with the deionized water cyclic washing.
The UV, visible light of sample absorbs collection of illustrative plates and sees b curve among Fig. 1, and TEM figure sees b curve among Fig. 2, and wall thickness is 15nm.
The SERS of sample detects with embodiment 1.Find out that from Fig. 4 b sample and golden solid nano particle (embodiment 4) that the sample of embodiment 2 is compared embodiment 1 all demonstrate the Raman scattering enhancement effect stronger to R6G (Fig. 4 b strengthens about 40 times than 4d).
Embodiment 3
Under 333K, with the tetrabutyl phosphonium bromide phosphorus (Bu of 20mL (10mM)
4PBr) aqueous solution is poured the gold chloride (HAuCl of 2.0mL (5.0mM) into
4) in the aqueous solution, vigorous stirring 5min simultaneously, solution colour adds the KBH of 0.20mL (0.50M) subsequently fast gradually by the light yellow buff that becomes
4The aqueous solution, vigorous stirring 15min can observe a large amount of bubbles and generate, and it is colourless that solution colour gradually becomes, and has the black solid particle to generate simultaneously, and the black solid product that obtains is through centrifugal, filtration and standby with the deionized water cyclic washing.
The UV, visible light of sample absorbs collection of illustrative plates and sees c curve among Fig. 1, and TEM figure sees c curve among Fig. 2, and wall thickness is 20nm.
The SERS of sample detects with embodiment 1.Find out that from Fig. 4 c sample and golden solid nano particle (embodiment 4) that the sample of embodiment 3 is compared embodiment 1 all demonstrate the Raman scattering enhancement effect stronger to R6G, and close with the sample of embodiment 2.
Embodiment 4
The natrium citricum reducing process is adopted in the preparation of atresia golden nanometer particle.Elder generation is with the gold chloride (HAuCl of 100mL (0.3 mM)
4) aqueous solution is heated to boiling, drip the citric acid three sodium solution of 1.0mL 1% then in vigorous stirring, system is cooled to room temperature after continuing the about 20min of boiling, through centrifugal, filtration, washing, obtain the solid nano particle of atresia gold that particle diameter is distributed as 30-70nm.
The UV, visible light of sample absorbs collection of illustrative plates and sees d curve among Fig. 1.
The SERS of sample detects with embodiment 1, sees d curve among Fig. 4.
The absworption peak of middle as seen from Figure 1 macropore golden nanometer particle is compared the atresia golden nanometer particle sizable red shift, measures test wavelength 400-800nm on Techcomp 8500 ultraviolet-uisible spectrophotometers.Average grain diameter is 60-80nm as seen from Figure 2, and the spherical shell wall thickness is 10-20nm, adopts Japanese JEOLTEM 2010 transmission electron microscope observations.Many diameters are arranged is the aperture of 8-30nm on the spherical shell surface as seen from Figure 3, adopts Japanese HITACHI S4800 field emission scanning electron microscope to observe.
By Fig. 4, on the burnt Raman spectrometer of micro-copolymerization (Dilor LabRam II), carry out, the He-Ne laser instrument that with the wavelength is 632.8nm is an excitation source, cooled with liquid nitrogen type CCD detector (1024 * 256pixels), Olympus 50/20 double-length focal length objective lens, 1800 lines/mm grating, the preposition slit of grating (Slit) they are 100 μ m, pinhole diaphragm aperture (hole) is 1000 μ m, the notch filter sheet.With 50 times of object lens laser is focused on 30s on the sample, amount to 3 times.Measure with 760CRT dual-beam ultraviolet specrophotometer, all spectrograms are standardized as the same time of integration.The detection of each sample is triplicate at least.
Claims (11)
1. middle macropore golden nanometer particle that wall thickness is adjustable, it is characterized in that: be polycrystalline structure, spherical particle, shell external diameter are 40-100nm, and average grain diameter is 60-80nm, and the spherical shell wall thickness is 10-20nm, it is the aperture of 8-30nm that there are many diameters on the spherical shell surface.
2. method for preparing the adjustable middle macropore golden nanometer particle of wall thickness, it is characterized in that: concrete steps are as follows:
At a certain temperature, the 0.005-0.05M solubility quaternary alkylphosphonium salt aqueous solution is poured in the inorganic salt solution of 0.5mM-30mM gold, while vigorous stirring 2-10min, solution colour is gradually by the light yellow buff that becomes, the boron hydride aqueous solution that adds the 0.1-2.0M of proper amount of fresh preparation subsequently fast, vigorous stirring 5-15min, can observe a large amount of bubbles generates, it is colourless that solution colour gradually becomes, there is the black solid particle to generate simultaneously, the promptly middle macropore golden nanometer particle of the black solid product that obtains.
3. the method for the middle macropore golden nanometer particle that preparation wall thickness according to claim 2 is adjustable is characterized in that: described temperature of reaction system is 298K-333K.
4. the method for the middle macropore golden nanometer particle that preparation wall thickness according to claim 2 is adjustable is characterized in that: quaternary alkylphosphonium salt is (10-50) with the mol ratio of the inorganic salts of gold: 1.
5. the method for the middle macropore golden nanometer particle that preparation wall thickness according to claim 4 is adjustable is characterized in that: quaternary alkylphosphonium salt is (20-30) with the mol ratio of the inorganic salts of gold: 1.
6. the method for the middle macropore golden nanometer particle that preparation wall thickness according to claim 2 is adjustable is characterized in that: described solubility quaternary alkylphosphonium salt is selected from tetrabutyl phosphonium bromide phosphorus or tetrabutyl phosphorus chloride.
7. the method for the middle macropore golden nanometer particle that preparation wall thickness according to claim 2 is adjustable is characterized in that: the inorganic salts of described gold are selected from HAuCl
4Or AuCl
3
8. the method for the middle macropore golden nanometer particle that preparation wall thickness according to claim 2 is adjustable is characterized in that: described mixing time is 3-5min.
9. the method for the middle macropore golden nanometer particle that preparation wall thickness according to claim 2 is adjustable is characterized in that: boron hydride is (4-10) with the mol ratio of the inorganic salts of gold: 1.
10. the method for the middle macropore golden nanometer particle that preparation wall thickness according to claim 2 is adjustable is characterized in that: described boron hydride is selected from sodium borohydride, potassium borohydride or both mixtures.
11. the middle macropore golden nanometer particle that preparation wall thickness according to claim 1 is adjustable is characterized in that: can be applicable to SERS and detect.
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Cited By (2)
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CN102296349A (en) * | 2011-07-06 | 2011-12-28 | 上海大学 | De-alloying preparation method of nanometer porous metal substrate with surface enhanced Raman scattering activity |
CN111515410A (en) * | 2020-04-23 | 2020-08-11 | 江南大学 | Preparation method based on gold nanoparticle chiral three-dimensional structure conformation transformation |
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CN101279256A (en) * | 2008-05-23 | 2008-10-08 | 上海师范大学 | Hollow metallic ball with mesopore structure and preparation method and application thereof |
CN101787458A (en) * | 2010-01-26 | 2010-07-28 | 南京大学 | Preparation method of nano-porous gold |
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CN1583331A (en) * | 2004-06-10 | 2005-02-23 | 复旦大学 | Preparing method for medium hole noble metal hollow microscapsule |
CN101279256A (en) * | 2008-05-23 | 2008-10-08 | 上海师范大学 | Hollow metallic ball with mesopore structure and preparation method and application thereof |
CN101787458A (en) * | 2010-01-26 | 2010-07-28 | 南京大学 | Preparation method of nano-porous gold |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102296349A (en) * | 2011-07-06 | 2011-12-28 | 上海大学 | De-alloying preparation method of nanometer porous metal substrate with surface enhanced Raman scattering activity |
CN111515410A (en) * | 2020-04-23 | 2020-08-11 | 江南大学 | Preparation method based on gold nanoparticle chiral three-dimensional structure conformation transformation |
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Application publication date: 20110420 |