CN106853523B - A kind of preparation method of the racemosus shape gold and silver composite nano materials with Surface enhanced Raman scattering characteristic - Google Patents
A kind of preparation method of the racemosus shape gold and silver composite nano materials with Surface enhanced Raman scattering characteristic Download PDFInfo
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Abstract
The present invention provides a kind of preparation method of racemosus shape gold and silver composite nano materials with Surface enhanced Raman scattering characteristic.Preparation step of the present invention is as follows: silver nitrate, polysorbate80 being dissolved in deionized water, ultrasonic disperse；Gold target is added and obtains Ag@Au duplex metal nano granule through laser irradiation, centrifugation, drying；By obtained Ag@Au duplex metal nano granule ultrasonic disperse in deionized water, aqueous solution of chloraurate and aqueous ascorbic acid is added, in room temperature reaction 2-3min, obtains racemosus shape Ag@Au composite nano materials dispersion liquid initially；Obtained dispersion liquid is mixed with the ethanol solution of silver nitrate, through laser irradiation, centrifugation, washing, drying to get racemosus shape gold and silver composite nano materials.Preparation method of the present invention is simple, controllable, environmentally protective, at low cost, and gained composite nano materials size is smaller (~50nm), has excellent performance in terms of Surface enhanced Raman scattering.
Description
Technical field
The present invention relates to a kind of racemosus shape gold and silver (Ag@Au) composite nano materials with Surface enhanced Raman scattering characteristic
Preparation method, belong to the preparation and application field of novel nano-material.
Background technique
Shaggy Ag, Au noble metal nanometer material due near infrared light region have unique local surface etc. from
Sub-resonance mode can be formed about powerful electromagnetic field by light excitation in precious metal surface, therefore have to load substance
Significant Surface enhanced Raman scattering (SERS) effect, to realize biomolecule micro-analysis and competent cell it is fine
Detection exerts far reaching influence in the special dimensions such as tumour cell diagnosis and photo-thermal therapy.It is effective in turn to construct novel nano structure
Surface roughness is improved, is the deciding factor for significantly improving probe molecule SERS performance, not only there is pole to basic scientific research
The most important link that its important meaning, even more propulsion probe molecule make a breakthrough in biomedicine field.
Compared to nanoshells or the structures such as hollow and porous, racemosus shape configuration is for example flower-shaped, sea urchin shape, dandelion shape,
Starfish shape etc. has prong pattern more outstanding, and possesses great surface roughness.Especially with other configuration phases
Than enriching intensive elongated dendritic morphology under ambient light excitation, more unrivaled powerful electromagnetic field can be generated, being subsequent
The SERS effect of further investigation cellular elements provides ideal nano-carrier.
Researcher is main using classical chemical synthesising technology, including seed mediated growth method, hydro-thermal method, polyol reduction method etc.
Realize the regulation preparation of the single metal nano material of racemosus shape Ag or Au.Currently, the experimental results show single Au
Or Ag nanometers of dendritic materials are 10 to the SERS enhancement factor of the probe molecule of load6-109(Nanoscale,2014,6,8891–
8899；RSC Adv., 2016,6,29669-29673；J.Phys.D:Appl.Phys., 2009,42,175403).If can
Controlledly synthesis goes out racemosus shape Ag Au bimetal nano material, not only can use the significant coarse configuration of dendritic surface, Er Qieshuan
Between metal there is unique synergistic effect can also generate additional Electromagnetic enhancement effect, will further increase and be supported on
The probe molecule SERS performance of nano-material surface.The research work of only a few is related to the dendritic material of Ag@Au composite nano
The synthesis of (RSC.Adv.2014,4,3929-3933), the dendritic scantling of Ag@Au composite nano prepared in the prior art
It is larger, at 500 nanometers or more, the reinforcing effect of probe molecule is not been significantly enhanced.Synergistic effect between bimetallic
Only it is decreased within 100nm in scantling, can just embodies excellent SERS characteristic.However, being mainly used for the Ag of SERS
With Au due to extremely similar lattice structure, by complicated chemical synthesis process, alloy nanoparticle, racemosus often will form
Shape structure is less.In addition, researcher changes it is also recognized that even if in the racemosus shape nano material preparation process of single metal
Learning synthetic technology, there is also certain deficiencies, including inevitably largely use toxic, harmful chemicals reaction reagent and band
There are the activating agent, stabilizer, curing agent etc. of phenyl ring or halogen.Even across later period stringent complicated purification process, nano material
Still carry toxic residuals, it is difficult to detect to obtain reality to the SERS of trace active molecule in the fields of biomedicine and the like
Matter is deeply promoted.
101786170 A of Chinese patent literature CN discloses the cauliflower nano of tool surface-enhanced Raman scattering activity
The preparation method of gold-silver alloy: by the silver nitrate of 0.001mol/L and 0.001mol/L sodium phytate, with volume ratio 30:1 mixing；
It is heated to boiling, temperature is maintained at 90-100 DEG C.By 1/50 amount of above-mentioned silver nitrate volume, be added 1% trisodium citrate it is molten
Liquid reacts 3 hours at 90-100 DEG C, and the nano silver cluster dispersion liquid stable by phytic acid is made；The above-mentioned dispersion liquid of 12-17m is taken respectively
In the beaker of 25ml, under stiring, after solution is heated to 45-65 DEG C, 0.01mol/L high gold chloride 1.5- is slowly added dropwise
Sample is made after stirring 25-35 minutes in 2.4mL；The stability of obtained nano particle was up to 6 months or more, signal reproducibility
Well, there are surface-enhanced Raman effects.But consuming time is long for the invention, higher cost.
105436516 A of Chinese patent literature CN discloses a kind of high photon absorbing intensity racemosus shape colloid Jenner of controllable grain size
The preparation method of rice corpuscles.First using conventional trisodium citrate reduction method, by the Au in gold chloride molecule3+It is reduced into Au0, is obtained
To spherical shape colloid gold seeds.Then colloid gold seeds are added to main component includes ultrapure water, gold chloride and citric acid three
In the growth-promoting media of the solution such as sodium, solution is heated to 50 DEG C after mixing, and revs up, while being added at one time enough hydroquinones
Solution, mixed solution temperature maintain 50 DEG C, stop heating after the reaction was continued 10min, be cooled to room temperature to obtain the final product.Inventive method tool
Have easy to operate, process is simple, is swift in response, the features such as controllability is good, repeatability is high.But what the invention was prepared is simple gold
The racemosus shape colloid of nanoparticle needs to be unfavorable for environmental protection using hydroquinone organic reagent.
It explores through a kind of preparation method of environmentally protective simplicity and obtains the lesser racemosus shape Ag@Au nano material of size
It is major issue in the urgent need to address at present.Because this Au nanometers of dendritic materials of unique Ag@can significantly improve load
Probe molecule SERS intensity, be conducive to detect extremely low concentration (< 10-10M Raman scattering of molecule signal) is expected to cure in biology
It makes substantial progress in the special dimensions such as medicine to the SERS detection of trace active molecule.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of racemosus shape with excellent surface enhancing Raman scattering characteristic
Gold and silver (Ag@Au) composite nano materials.The composite nano materials size is smaller (~50nm), as simultaneously comprising two kinds of stronger tables
Face enhances the composite nano materials of Raman scattering active noble metal (Au, Ag), to the low of organic matter 4- aminothiophenol (4-ATP)
Concentration detection shows excellent Surface enhanced Raman scattering characteristic.
The present invention also provides a kind of racemosus shape gold and silver (Ag@Au) with excellent surface enhancing Raman scattering characteristic compound to receive
The preparation method of rice material.The preparation method is easy, green, efficient, at low cost.
A kind of racemosus shape gold and silver composite nano materials with excellent surface enhancing Raman scattering characteristic, the composite Nano
Golden mass content is 60-75% in material, and silver-colored mass content is 25-40%.
Preferred according to the present invention, the composite nano materials are that nano particle is accumulated, the nano grain surface
For dendritic morphology, and each nano particle is by the elongated branch structure composition of central entity structure and central entity body structure surface,
The nanoparticle size size is 50-60nm.
Preferably, number >=20 of the elongated branch structure of the central entity body structure surface；It is further preferred that in described
The number of the elongated branch structure on heart entity structure surface is 20-30.
A kind of preparation method of the racemosus shape gold and silver composite nano materials with excellent surface enhancing Raman scattering characteristic, packet
Include that steps are as follows:
(1) silver nitrate is dissolved in deionized water, is added surfactant Polysorbate 80 (T80), ultrasonic disperse obtains
Mixed liquor；Then gold target is added into mixed liquor, using the gold target in laser ablation mixed liquor, obtains colloidal solution；Colloidal solution
It is centrifuged, dried, obtain Ag@Au duplex metal nano granule；
(2) gold chloride is added in deionized water in the Ag@Au duplex metal nano granule ultrasonic disperse for obtaining step (1)
Aqueous solution and aqueous ascorbic acid, obtain reaction solution；In room temperature reaction 2-3min, racemosus shape Ag@Au composite Nano initially is obtained
Material dispersion liquid；
(3) dispersion liquid that step (2) obtains is mixed with the ethanol solution of silver nitrate, through laser irradiation, much dendritic gold
Silver-colored composite nano materials dispersion liquid, through centrifugation, washing, drying to get racemosus shape gold and silver composite nano materials.
Preferred according to the present invention, the molar concentration of silver nitrate is 0.1-0.3mol/L in step (1) mixed liquor；It is poly-
The volumetric concentration of sorbitol ester 80 is 0.2-0.6%.
Preferred according to the present invention, the mass ratio of gold target and silver nitrate in step (1) mixed liquor is 80:1-80:
3。
Preferred according to the present invention, the wavelength of laser ablation is 500-800nm, pulsewidth 10ns, frequency in the step (1)
Rate is 10Hz, power density 10-15GW/cm2；Mixed liquor liquid level spot size of laser beams is 300-400 μm.
Preferred according to the present invention, the ablation time is 10-30min in the step (1).
Preferred according to the present invention, centrifugal rotational speed is 16000-20000rpm, centrifugation time 8- in the step (1)
15min。
Preferred according to the present invention, the concentration of aqueous solution of chloraurate is 0.02-0.06mol/L in the step (2)；It is anti-bad
The concentration of hematic acid aqueous solution is 0.06-0.1mol/L.
Preferred according to the present invention, the mass concentration of Ag@Au duplex metal nano granule is in step (2) reaction solution
0.1-0.3%.
It is preferred according to the present invention, Ag@Au duplex metal nano granule in step (2) reaction solution, gold chloride and anti-bad
The mass ratio of hematic acid is 8:0.6-2:28.
Preferred according to the present invention, the molar concentration of silver nitrate is 0.5- in the ethanol solution of step (3) silver nitrate
1.5mmol/L。
Preferred according to the present invention, the volume ratio of the ethanol solution of dispersion liquid and silver nitrate in the step (3) is 4:
1-4:3。
Preferred according to the present invention, irradiation wavelengths are 500-800nm in the step (3), pulsewidth 10ns, and frequency is
10Hz, power density 100-200mW/cm2；Liquid level spot size of laser beams is 300-400 μm.
Preferred according to the present invention, irradiation time is 1.5-5h in the step (3).
Preferred according to the present invention, centrifugal rotational speed is 6000-8000rpm, centrifugation time 8- in the step (3)
15min。
It has the beneficial effect that:
1. racemosus shape gold and silver (Ag Au) composite nano materials are prepared using induced with laser photochemical method in the present invention,
Preparation method is simple, controllable, environmentally protective, at low cost.
2. the general dendritic nano material prepared by the present invention racemosus shape gold and silver (Ag@Au) composite nano materials and reported
It compares, size is smaller, is 50nm or so, lesser size is more conducive to play better surface enhanced Raman scattering effect.
3. unique collaboration effect that racemosus shape gold and silver (Ag Au) composite nano materials prepared by the present invention have played Jin Heyin
It answers, can produce additional Electromagnetic enhancement effect；And prepared racemosus shape scantling is smaller, rough surface, more can
The synergistic effect of gold and silver is played, to show excellent SERS characteristic.
4. composite nano materials are as a kind of high-performance substrate for racemosus shape gold and silver (Ag@Au) prepared by the present invention, on surface
Excellent performance is shown in terms of enhancing Raman scattering, 10 are reached for probe molecule detection limit-14Mol/L, enhancement factor can
To reach 1011.Particularly with probe molecule 4-ATP, excellent Surface enhanced Raman scattering effect is shown, in biomedical table
Face, which enhances Raman scattering analysis aspect, has important application value.
Detailed description of the invention
Fig. 1 is TEM of the Ag@Au duplex metal nano granule that is prepared of 1 step of embodiment (1) under different amplification
Map.
Fig. 2 is the initial racemosus shape Ag@Au composite nano materials that are prepared of 1 step of embodiment (2) in different amplifications
TEM map under multiple.
Fig. 3 is the elemental analysis for the initial racemosus shape Ag@Au composite nano materials that 1 step of embodiment (2) is prepared
Map.
Fig. 4 is TEM figure of the racemosus shape gold and silver composite nano materials that are prepared of embodiment 1 under different amplification
Spectrum.
Fig. 5 is the elemental analysis map for the racemosus shape gold and silver composite nano materials that embodiment 1 is prepared.
Fig. 6 is the racemosus shape gold and silver composite nano materials a that embodiment 1 is prepared and is prepared in step (2) first
The X-ray diffraction spectrum comparison diagram of the racemosus shape Ag@Au composite nano materials b of beginning.
Fig. 7 be in racemosus shape Ag@Au composite nano materials dispersion liquid initial in test example 1 solution absorption peak with gold chloride
The uv-visible absorption spectrum figure of additional amount variation.
Fig. 8 is uv-visible absorption spectrum figure obtained in test example 2.
Fig. 9 be in test example 3 sample to 10-10The reinforcing effect test chart of mol/L 4-ATP Raman spectrum.
Figure 10 is that the racemosus shape gold and silver composite nano materials that in test example 3 prepared by embodiment 1 do substrate to various concentration
The reinforcing effect test chart of 4-ATP Raman spectrum.
Figure 11 is that the racemosus shape gold and silver composite nano materials that in test example 3 prepared by embodiment 1 do substrate to 10-10mol/L
The reinforcing effect reperformance test figure of 4-ATP Raman spectrum.
Figure 12 is the SEM spectrum for the racemosus shape gold and silver composite nano materials substrate that in test example 3 prepared by embodiment 1.
Specific embodiment
The present invention is described further combined with specific embodiments below, but not limited to this.
Experimental method described in following embodiments is unless otherwise specified conventional method simultaneously；The reagent and material
Material, unless otherwise specified, commercially obtains.
Gold target used is high-purity gold target in embodiment, and purity 99.99% is closed vertical green wood by Beijing and provided.
By high-purity gold target (99.99%), sonic oscillation cleans 5min in deionized water, through 45 DEG C of drying for standby.
In embodiment the ethanol solution of the silver nitrate of 1mmol/L the preparation method is as follows: weigh 3.4mg silver nitrate, be added
20mL ethyl alcohol, ultrasonic vibration 5min to silver nitrate are completely dissolved, and can be prepared by the ethanol solution of the silver nitrate of 1mmol/L.
Embodiment 1
A kind of racemosus shape gold and silver composite nano materials with excellent surface enhancing Raman scattering characteristic, the composite Nano
Golden mass content is 66% in material, and silver-colored mass content is 34%；The composite nano materials be nano particle accumulate and
At the nano grain surface is dendritic morphology, and each nano particle is by central entity structure and central entity structure table
The elongated branch structure composition in face, the nano particle average-size size are 50nm.
The preparation method of the above-mentioned racemosus shape gold and silver composite nano materials with excellent surface enhancing Raman scattering characteristic, packet
Include that steps are as follows:
(1) at room temperature, 0.34g silver nitrate, 40 μ L T80 are dissolved in 10mL deionized water, ultrasonic disperse
5min obtains mixed liquor；27.2g gold target is added, utilizes wavelength 532nm, pulsewidth 10ns, frequency 10Hz, laser power density 12GW/
cm2Nd-YAG laser to gold target ablation 20min in mixed liquor, the average spot size of mixed liquor liquid level laser beam is 350 μ
M obtains colloidal solution；After irradiation, colloidal solution is centrifuged 10min through 18000rpm revolving speed, takes precipitating, in 45 DEG C of dry 12h,
Obtain Ag@Au duplex metal nano granule；In gained Ag@Au duplex metal nano granule, the quality that the mass content of Ag is 8%, Au contains
Amount is 92%.
(2) the Ag@Au duplex metal nano granule ultrasonic disperse for obtaining 0.016g step (1) adds in 4mL deionized water
Enter the aqueous solution of chloraurate of 210 μ L 0.05mol/L and the aqueous ascorbic acid of 4mL 0.08mol/L, reaction solution is obtained, in room
Temperature reaction 3min, obtains racemosus shape Ag@Au composite nano materials dispersion liquid initially；In the composite nano materials, the quality of Ag
The mass content that content is 1.2%, Au is 98.8%.
(3) dispersion liquid that 4mL step (2) obtains is mixed with the ethanol solution of the silver nitrate of 3mL 1mmol/L, utilizes wave
Long 532nm, pulsewidth 10ns, frequency 10Hz, laser power density 150mW/cm2He-Ne laser carry out laser irradiation 3h, liquid
The average spot size of face laser beam is 350 μm, much dendritic gold and silver composite nano materials dispersion liquid；By receiving after irradiation
Rice material dispersion liquid is put into centrifuge tube, is centrifuged 10 minutes, supernatant is taken out, in centrifuge tube using the revolving speed of 7000rpm
Precipitating sonic oscillation is opened, washed, dry to get racemosus shape gold and silver composite nano materials.
TEM map of the Ag@Au duplex metal nano granule that the present embodiment step (1) is prepared under different amplification
As shown in Figure 1.By Fig. 1, it can be concluded that, prepared Ag@Au duplex metal nano granule is spherical or butterfly-like mixing gold
Metal nanometer material, and average-size is 5nm.
The initial racemosus shape Ag@Au composite nano materials that the present embodiment step (2) is prepared are in different amplification
Under TEM map it is as shown in Figure 2.As shown in Figure 2, prepared initial racemosus shape Ag@Au composite nano materials are racemosus shape
Structure, average-size 40nm.
The elemental analysis map for the initial racemosus shape Ag@Au composite nano materials that the present embodiment step (2) is prepared
As shown in Figure 3.By Fig. 3 it can be concluded that the relative amount of Au will be significantly larger than the relative amount of Ag.
TEM map of the racemosus shape gold and silver composite nano materials that the present embodiment is finally prepared under different amplification
As shown in Figure 4.As shown in Figure 4, prepared racemosus shape gold and silver composite nano materials are that nano particle is accumulated, the nanometer
Particle surface is dendritic morphology, and each nano particle is by the elongated branch structure composition of internal entity structure and number > 20, institute
Stating nano particle average-size is 50nm.
The elemental analysis map for the racemosus shape gold and silver composite nano materials that the present embodiment is finally prepared is as shown in Figure 5.
As shown in Figure 5, the relative amount of Ag will be much higher than relative amount silver-colored in initial racemosus shape Ag@Au composite nano materials.
The X-ray diffraction spectrum a and the present embodiment for the racemosus shape gold and silver composite nano materials that the present embodiment is finally prepared
The X-ray diffraction spectrum b comparison diagram for the initial racemosus shape Ag@Au composite nano materials that step (2) is prepared is as shown in Figure 6.
It will be appreciated from fig. 6 that composite material prepared by the present invention is the composite nano materials of gold and silver, due to the diffraction maximum position pole of Au and Ag
Its is similar, and the X-ray diffraction image of racemosus shape gold and silver composite nano materials compares initial racemosus shape Ag Au composite nano materials
It has and is widened.In addition, the present invention mainly directly reacts Au in composite nano materials by the elemental analysis test result of Fig. 5
With the relative amount of Ag.
Embodiment 2-10
A kind of preparation method of the racemosus shape gold and silver composite nano materials with excellent surface enhancing Raman scattering characteristic, such as
Described in embodiment 1, the difference is that being separately added into 80,95,110,125,140,155,170,185,200 μ L in step (2)
The aqueous solution of chloraurate of 0.05mol/L.
Embodiment 11
A kind of preparation method of the racemosus shape gold and silver composite nano materials with excellent surface enhancing Raman scattering characteristic, such as
Described in embodiment 1, the difference is that the laser irradiation time is 1.5h in step (3).
Embodiment 12
A kind of preparation method of the racemosus shape gold and silver composite nano materials with excellent surface enhancing Raman scattering characteristic, packet
Include that steps are as follows:
(1) at room temperature, 0.17g silver nitrate, 20 μ L T80 are dissolved in 10mL deionized water, ultrasonic disperse
5min obtains mixed liquor；4.5g gold target is added, utilizes wavelength 500nm, pulsewidth 10ns, frequency 10Hz, laser power density 10GW/
cm2Nd-YAG laser to the gold target ablation 30min in mixed liquor, the average spot size of mixed liquor liquid level laser beam is
350 μm, obtain colloidal solution；Colloidal solution is centrifuged 10min through 18000rpm revolving speed, takes precipitating, in 45 DEG C of dry 12h, obtains Ag@Au
Duplex metal nano granule；
(2) the Ag@Au duplex metal nano granule ultrasonic disperse for obtaining 0.016g step (1) obtains in 4mL deionized water
To Ag@Au duplex metal nano granule solution, aqueous solution of chloraurate and the 4mL 0.08mol/L that 210 μ L 0.05mol/L are added are anti-
Bad hematic acid aqueous solution, obtains reaction solution, in room temperature reaction 2min, obtains racemosus shape Ag@Au composite nano materials dispersion liquid initially；
(3) dispersion liquid that 4mL step (2) obtains is mixed with the ethanol solution of the silver nitrate of 3mL 1mmol/L, utilizes wave
Long 532nm, pulsewidth 10ns, frequency 10Hz, laser power density 100mW/cm2He-Ne laser carry out laser irradiation 3h, liquid
The average spot size of face laser beam is 350 μm, much dendritic gold and silver composite nano materials dispersion liquid；By receiving after irradiation
Rice material dispersion liquid is put into centrifuge tube, is centrifuged 10 minutes, supernatant is taken out, in centrifuge tube using the revolving speed of 7000rpm
Precipitating sonic oscillation is opened, washed, dry to get racemosus shape gold and silver composite nano materials.
Embodiment 13
A kind of preparation method of the racemosus shape gold and silver composite nano materials with excellent surface enhancing Raman scattering characteristic, packet
Include that steps are as follows:
(1) at room temperature, 0.51g silver nitrate, 60 μ L T80 are dissolved in 10mL deionized water, ultrasonic disperse
5min obtains mixed liquor；20.4g gold target is added, utilizes wavelength 800nm, pulsewidth 10ns, frequency 10Hz, laser power density 15GW/
cm2Nd-YAG laser to the Au target ablation 10min in mixed liquor, the average spot size of mixed liquor liquid level laser beam is
350 μm, obtain colloidal solution；Colloidal solution is centrifuged 10min through 18000rpm revolving speed, takes precipitating, in 45 DEG C of dry 12h, obtains Ag@Au
Duplex metal nano granule；
(2) the Ag@Au duplex metal nano granule ultrasonic disperse for obtaining 0.016g step (1) obtains in 4mL deionized water
To Ag@Au duplex metal nano granule solution, aqueous solution of chloraurate and the 4mL 0.08mol/L that 210 μ L 0.05mol/L are added are anti-
Bad hematic acid aqueous solution, obtains reaction solution, in room temperature reaction 2min, obtains racemosus shape Ag@Au composite nano materials dispersion liquid initially；
(3) dispersion liquid that 4mL step (2) obtains is mixed with the ethanol solution of the silver nitrate of 3mL 1mmol/L, utilizes wave
Long 532nm, pulsewidth 10ns, frequency 10Hz, laser power density 200mW/cm2He-Ne laser carry out laser irradiation 3h, liquid
The average spot size of face laser beam is 350 μm, much dendritic gold and silver composite nano materials dispersion liquid；By receiving after irradiation
Rice material dispersion liquid is put into centrifuge tube, is centrifuged 10 minutes, supernatant is taken out, in centrifuge tube using the revolving speed of 7000rpm
Precipitating sonic oscillation is opened, washed, dry to get racemosus shape gold and silver composite nano materials.
Test example 1
Influence of the gold chloride additional amount to initial racemosus shape Ag@Au composite nano materials
Test sample: the initial racemosus shape Ag@Au composite nano materials dispersion that embodiment 1-10 step (2) is prepared
Liquid.
Test method: test sample is placed in 4mL cuvette, using UV-1800, Shimadzu it is carried out it is ultraviolet-
Visible absorption spectra test, test results are shown in figure 7.Wherein, A-J curve respectively represents the first of the preparation of embodiment 2-10 and 1
The uv-visible absorption spectra of the racemosus shape Ag@Au composite nano materials dispersion liquid of beginning.
Fig. 7 is solution absorption peak in the initial racemosus shape Ag@Au composite nano materials dispersion liquid of embodiment 1-10 preparation
The uv-visible absorption spectrum figure changed with gold chloride additional amount.As shown in Figure 7, be added gold chloride content it is further
It improving, the degree that the initial racemosus shape Ag Au composite nano materials of preparation absorb peak position red shift is incrementally increasing (A-J),
The size of dendritic morphology is being further elongated in the composite nano material formed；Absorption peak strength, which steps up, to be shown to synthesize
The yield of nano material further increases.
Test example 2
Influence of the irradiation time to racemosus shape gold and silver composite nano materials
Test sample: initial racemosus shape Ag@Au composite nano materials dispersion liquid that 1 step of embodiment (2) obtains is implemented
The racemosus shape gold and silver composite nano materials dispersion liquid that example 1 and embodiment 11 obtain.
Test method: test sample is placed in 4mL cuvette, using UV-1800, Shimadzu it is carried out it is ultraviolet-
Visible absorption spectra test, test results are shown in figure 8.Wherein, curve a, b, c is respectively initial racemosus shape Ag@Au compound
Racemosus shape gold and silver composite nano materials dispersion liquid that nano material dispersion liquid, embodiment 11 are prepared, embodiment 1 are prepared
Racemosus shape gold and silver composite nano materials dispersion liquid uv-visible absorption spectra.
As shown in Figure 8, with the laser irradiation time lengthen, absorption spectra situation of change be a → b → c, i.e., absorption peak position by
Blue shift is walked, characterization racemosus shape gold and silver composite nano materials gradually form, and yield gradually increases.
Test example 3
Surface enhanced Raman scattering performance test to organic matter 4-ATP
Test sample: the initial racemosus shape Ag@Au composite nano materials being prepared in 1 step of embodiment (2) are implemented
Racemosus shape gold and silver composite nano materials prepared by example 1.
Test method: (1) dispersing 0.048g test sample in 0.5mL deionized water, takes the above-mentioned dispersant liquid drop of 30uL
It is added on the silicon wafer cleaned through RCA technique, then keeps 12h under room temperature environment, to guarantee substrate adiabatic drying.It will be above-mentioned
The substrate that preparation is completed is completely submerged in 10 respectively-10mol/L、10-11mol/L、10-12mol/L、10-13mol/L、10-14mol/L
4-ATP ethanol solution in 1h, then thoroughly cleaned using ethyl alcohol, be finally dried using nitrogen and tested for SERS.
(2) as a comparison, clean silicon wafer is made into substrate, is completely submerged in 1h in the 4-ATP ethanol solution of 1mol/L, then
It is thoroughly cleaned using ethyl alcohol, is finally dried using nitrogen and is tested for SERS.
(3) sample after being completely dried uses 800 spectrometer of LabRAM HR to carry out using 633nm as excitation wavelength to it
Raman spectrum test.
In Raman spectrum test process, the time of integration remains 10s, and same test result needs to be repeated several times, to guarantee
The reproducibility of test result, acquired results are as shown in Figures 9 and 10.
In Fig. 9, curve a, b, c are respectively racemosus shape gold and silver composite nano materials substrate and 4-ATP, initial racemosus shape
The Raman spectrum of Ag@Au composite nano materials substrate and 4-ATP, simple 4-ATP.As shown in Figure 9, for 10-10Mol/L is lower
The 4-ATP of concentration, by calculating, the enhancement factor of composite material prepared by the present invention can achieve 1011, racemosus shape gold and silver is compound
The reinforcing effect of nano material is substantially better than initial racemosus shape Ag@Au composite nano materials composite nano materials.
In Figure 10, curve a, b, c, d are respectively drawing of the racemosus shape gold and silver composite nano materials substrate to various concentration 4-ATP
Graceful spectrum reinforcing effect test chart.As shown in Figure 10, racemosus shape gold and silver composite nano materials prepared by the present invention are to low concentration
4-ATP also show stronger Raman reinforcing effect.
Since racemosus shape gold and silver composite nano materials prepared by the present invention do substrate to 10-10The increasing of M 4-ATP Raman spectrum
Potent fruit is substantially better than other base materials, in order to guarantee that its non-contingency, the present invention have carried out a large amount of repetitions and tested, gained knot
Fruit is as shown in figure 11.As shown in Figure 11, the racemosus shape gold and silver composite nano materials favorable repeatability of method of the invention preparation, surely
It is qualitative also preferable.
Claims (8)
1. a kind of preparation method of the racemosus shape gold and silver composite nano materials with Surface enhanced Raman scattering characteristic, including step
It is as follows:
(1) silver nitrate is dissolved in deionized water, is added surfactant Polysorbate 80 (T80), ultrasonic disperse must mix
Liquid；Then gold target is added into mixed liquor, using the gold target in laser ablation mixed liquor, obtains colloidal solution；Colloidal solution pass through from
The heart, drying obtain Ag@Au duplex metal nano granule；
(2) it is water-soluble that gold chloride is added in deionized water in the Ag@Au duplex metal nano granule ultrasonic disperse for obtaining step (1)
Liquid and aqueous ascorbic acid, obtain reaction solution；In room temperature reaction 2-3min, racemosus shape Ag@Au composite nano materials initially are obtained
Dispersion liquid；
(3) dispersion liquid that step (2) obtains is mixed with the ethanol solution of silver nitrate, through laser irradiation, much dendritic gold and silver is multiple
Nano material dispersion liquid is closed, through centrifugation, washing, drying to get racemosus shape gold and silver composite nano materials.
2. the system of the racemosus shape gold and silver composite nano materials according to claim 1 with Surface enhanced Raman scattering characteristic
Preparation Method, which is characterized in that the molar concentration of silver nitrate is 0.1-0.3mol/L, polysorbate in step (1) mixed liquor
The volumetric concentration of ester 80 is 0.2-0.6%, and the mass ratio of gold target and silver nitrate is 80:1-80:3.
3. the system of the racemosus shape gold and silver composite nano materials according to claim 1 with Surface enhanced Raman scattering characteristic
Preparation Method, which is characterized in that the wavelength of laser ablation is 500-800nm, pulsewidth 10ns in the step (1), and frequency is
10Hz, power density 10-15GW/cm2；Mixed liquor liquid level spot size of laser beams is 300-400 μm；The ablation time is 10-
30min。
4. the system of the racemosus shape gold and silver composite nano materials according to claim 1 with Surface enhanced Raman scattering characteristic
Preparation Method, which is characterized in that the concentration of aqueous solution of chloraurate is 0.02-0.06mol/L in the step (2)；Vitamin C sour water
The concentration of solution is 0.06-0.1mol/L.
5. the system of the racemosus shape gold and silver composite nano materials according to claim 1 with Surface enhanced Raman scattering characteristic
Preparation Method, which is characterized in that the mass concentration of Ag@Au duplex metal nano granule is 0.1- in step (2) reaction solution
0.3%；The mass ratio of Ag@Au duplex metal nano granule, gold chloride and ascorbic acid is 8:0.6- in step (2) reaction solution
2:28.
6. the system of the racemosus shape gold and silver composite nano materials according to claim 1 with Surface enhanced Raman scattering characteristic
Preparation Method, which is characterized in that the molar concentration of silver nitrate is 0.5-1.5mmol/ in the ethanol solution of step (3) silver nitrate
L。
7. the system of the racemosus shape gold and silver composite nano materials according to claim 1 with Surface enhanced Raman scattering characteristic
Preparation Method, which is characterized in that the volume ratio of the ethanol solution of dispersion liquid and silver nitrate in the step (3) is 4:1-4:3.
8. the system of the racemosus shape gold and silver composite nano materials according to claim 1 with Surface enhanced Raman scattering characteristic
Preparation Method, which is characterized in that irradiation wavelengths are 500-800nm, pulsewidth 10ns, frequency 10Hz, power in the step (3)
Density is 100-200mW/cm2；Liquid level spot size of laser beams is 300-400 μm；Irradiation time is 1.5-5h.
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