CN103600082A - Silver nanoparticle layer and preparation method and application thereof - Google Patents
Silver nanoparticle layer and preparation method and application thereof Download PDFInfo
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- CN103600082A CN103600082A CN201310610671.5A CN201310610671A CN103600082A CN 103600082 A CN103600082 A CN 103600082A CN 201310610671 A CN201310610671 A CN 201310610671A CN 103600082 A CN103600082 A CN 103600082A
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Abstract
The invention discloses a silver nanoparticle layer and a preparation method and application thereof. The preparation method includes the steps 1), centrifuging silver nano sol composed of silver nanoparticles and water, and collecting, sedimenting and washing the silver nano sol with water prior to subjecting the same to ultrasonic dispersion in water to obtain silver nano sol subjected to centrifuging and enriching; 2), filtering the silver nano sol subjected to the ultrasonic dispersion in the step 1) through a filter membrane, forming the silver nanoparticle layer on the filter membrane and drying the same to obtain the silver nanoparticle layer loaded on the filter membrane. A filter membrane base prepared by the method has excellent SERS (surface enhanced roman scattering) performance including uniformity, repeatability, high sensitivity and long-term stability; the preparation method is low in raw materials, simple in process, capable of effectively lowering production cost, suitable for industrialization and high in application prospect and practical value.
Description
Technical field
The present invention relates to a kind of silver nano-grain layer and preparation method thereof and application.
Background technology
The preparation of SERS (referred to as SERS) substrate is mainly divided into two kinds: physical method and chemical method.Substrate prepared by physical method can strictly be controlled the parameter of substrate as the size of base particle, shape, distribute, can well control surface strengthen uniformity and the repeatability of Raman scattering signal, but the required equipment of these class methods and technology all too complexity and high cost; Chemical method is obviously simple, and convenient, cost is low, and the substrate that conventionally prepared by these class methods has stronger strengthening the property, but the common reappearance of these class methods and homogeneity are poor.Most process is also difficult to have the advantage of these two class methods simultaneously, and most methods all cannot, guaranteeing to have the longer shelf-life under high prerequisite of strengthening the property, can reach the effect of this technology practical application of SERS.
Summary of the invention
The object of this invention is to provide a kind of silver nano-grain layer and preparation method thereof and application.
The method of preparing silver nano-grain layer provided by the invention, comprises the steps:
1) the silver nanoparticle colloidal sol being comprised of silver nano-grain and water is carried out centrifugal, ultrasonic being scattered in water again after collecting precipitation washes with water, obtains the silver nanoparticle colloidal sol after centrifugal enrichment;
2) the silver nanoparticle colloidal sol after step 1) gained centrifugal enrichment is filtered with filter membrane, on described filter membrane, form silver nano-grain layer, dry, obtain loading on the silver nano-grain layer on described filter membrane.
In the step 1) of said method, in the silver nanoparticle colloidal sol being comprised of silver nano-grain and water, the mass ratio of silver nano-grain and water is 10-100mg:200mL, is specially 50mg:200mL;
The particle diameter 20-120nm of silver nano-grain, concrete 50-100nm;
In silver nanoparticle colloidal sol after described centrifugal enrichment, the mass ratio of silver nano-grain and water is 0.1-0.5:100, is specially 0.125:100.
In centrifugation step, centrifugal rotational speed is 5000-12000rmp, is specially 12000rpm; Centrifugal force is 1816-10464g, is specially 10464g; Time is 5-20min, is specially 10min;
In described ultrasonic step, the time is 5-20 minute, is specially 10 minutes; Ultrasonic power is 30-100W, is specially 30W.
Described step 2), in, the aperture of filter membrane used is less than 3 times of described silver nano-grain particle diameter; The aperture of filter membrane used is specially 2.2 times of described silver nano-grain particle diameter.
In filtration step, filtering rate is 0.25～1ml/min, is specially 0.5ml/min;
Filtration pressure is 2-10.3bar, is specially 5.2bar;
In drying steps, temperature is 25-40 ℃, is specially 30 ℃; Time is 10-30min, is specially 15min.
In addition, the silver nano-grain layer preparing according to the method described above, and using the application in surface-enhanced raman scattering as substrate of this silver nano-grain layer, also belong to protection scope of the present invention.
The present invention utilizes a kind of simple filter method, obtained densification, homogeneous, can repetition, excellent stability, can be to a certain extent quantitatively and the surface enhanced Raman scattering substrate of practical application, solved that prior art prepares that ubiquitous sensitivity in SERS substrate is low, complicated process of preparation, cost is high, homogeneity is poor, the shelf-life is short problem.The method is to utilize filtration that the nano particle in noble metal nano colloidal sol is separated with water, the high pressure producing in filter process will be adsorbed on nano particle on filter membrane evenly, combine densely, thereby obtains repeatably surface enhanced Raman scattering substrate of uniform compact.Wherein applied filter membrane aperture and prepared nanoparticle size are extremely important, will select corresponding filter membrane to filter in the situation that selecting different size nano particle, to reach the object that forms nano-grain array on filter membrane surface.In concrete preparation technology, can select the nano particle of different size and the filter membrane of respective aperture to mate different excitation wavelengths and applied environment, to strengthen the application of SERS technology.
Utilize the method gained surface enhanced Raman scattering substrate to have splendid repeatability, its relative standard deviation reaches 10%; Signal homogeneity reaches 9%; Enhancer can reach 10 simultaneously
8the order of magnitude, can reach 10 respectively to the detectability of rhodamine 6G and melamine
-14m and 10
-8the M order of magnitude; The shelf-life of prepared substrate is extremely long, can reach two months.In preparation method provided by the invention, raw material is inexpensive, technique is simple, effectively reduces product cost, is suitable for industrialization, has very high application prospect and practical value.
Accompanying drawing explanation
Fig. 1 is the FE-SEM figure of the filter membrane substrate of embodiment 1 preparation.
Fig. 2 is the Raman mapping figure of the filter membrane substrate of embodiment 1 preparation.
Fig. 3 is the SERS figure of the filter membrane substrate of embodiment 1 preparation to rhodamine 6G detectability.
Fig. 4 is the SERS figure of the filter membrane substrate of embodiment 1 preparation to melamine detectability.
Fig. 5 is the SERS figure of different time in the filter membrane substrate three months of embodiment 1 preparation.
Fig. 6 is the XPS figure of different time in the filter membrane substrate three months of embodiment 1 preparation.
The specific embodiment
Below in conjunction with specific embodiment, the present invention is further elaborated, but the present invention is not limited to following examples.Described method is conventional method if no special instructions.Described raw material all can obtain from open commercial sources if no special instructions.
Following embodiment silver nanoparticle colloidal sol used is all prepared as follows and obtains:
Getting weak reductant glucose and the 200mg protective agent PVP that 100mg has aldehyde radical is dissolved in 150mL deionized water, ultrasonic it is dissolved completely, through the membrane filtration in 450nm aperture, process after twice, after adding the 1MNaOH aqueous solution 180 μ L to be 9 to the pH value of system under stirring at room state, add again Jin Jing's kind that 200 μ L particle diameters are 5nm (concentration that Jin Jing plants is 65 μ g/mL), the drop rate of 0.5mL/min of take again adds the silver ammino solution 50mL that concentration is 1mg/mL, at 20 ℃, carry out the silver-colored ammonia react of planting based on Jin Jing, after 100 minutes, react complete, obtain the colloidal sol that contains particle diameter 100nm silver nano-grain, wherein, the mass ratio of silver nano-grain and water is 1.25mg:5mL.
1) the silver nanoparticle colloidal sol that the silver nano-grain 1.25mg that is 100nm by 5mL by particle diameter and water 5mL form is centrifugal 10min under 12000rmp, the centrifugal force condition that is 10464g at rotating speed, the supernatant that contains unreacted surfactant to remove upper strata, collecting precipitation is scattered in 1mL deionized water with ultrasonic 10min under the condition that is 30W at power again after deionized water washing 2 times, obtain the silver nanoparticle colloidal sol after centrifugal enrichment, the mass ratio of silver nano-grain and water is 0.125:100;
2) the silver nanoparticle colloidal sol after step 1) gained centrifugal enrichment is packed in the syringe of 5mL capacity, with the filter membrane in 0.22 μ m aperture, filter, filtering rate is 0.5mL/min, filtration pressure is 5.2bar, after filtration, on filter membrane, form silver nano-grain layer, by being attached to film on miillpore filter and being placed on dry 15min in the baking oven of 30 ℃, obtain loading on the silver nano-grain layer (being also filter membrane substrate) on filter membrane.
The morphology characterization of this silver nano-grain layer carries out (voltage 10kV) on German LEO-1530 type field emission scanning electron microscope (FE-SEM), and its FE-SEM image as shown in Figure 1.
As shown in Figure 1, after through filtration, the hole on filter membrane is covered by the silver nano-grain of size homogeneous.The color of filter membrane also becomes the bright silver with metallic luster from white.Filtering under the high pressure produce, thereby nearly all silver nano-grain has all got lodged in and in the hole of filter membrane itself, has formed one deck densification, homogeneous, silver nano-grain array repeatably.This nano-array has not only been realized the repeatability of preparation condition, due to its three-dimensional fine and close array structure, has formed more " focus " in same area simultaneously, and this excellent SERS that has guaranteed this substrate strengthens the property.
The SERS signal homogeneity of this embodiment gained filter membrane substrate is evaluated:
With rhodamine 6G (R6G), as probe molecule, by 100 μ L concentration, be 1 * 10
-5the R6G solution of mol/l joins in 900 μ l silver nanoparticle colloidal sols, uses membrane filtration, then use Raman spectrum (Horiba JY HR800 Raman spectrometer) to investigate the SERS performance of this silver nano-grain layer substrate after mix and blend 1h.Raman spectrum light source adopts 514nm argon ion laser, and power is 0.05mW, and camera lens is 50 times of telephoto lenses.
Table 1 repeats ten batches for the substrate of silver nano-grain layer under identical preparation and test condition, and test gained R6G is at 614cm
-1raman peak area contrast.
The R6G of table 1, the substrate of silver nano-grain metafiltration film is at 614cm
-1raman peak area contrast
| Batch | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 |
| Peak area | 25693 | 31430 | 28271 | 27990 | 31665 | 28165 | 24647 | 27477 | 22876 | 24533 |
As seen from table, the repeatable relative standard deviation of ten different batches filter membranes substrate is approximately 10%.Illustrate that filter membrane substrate has very excellent SERS test repeatability.
Fig. 2 is that the R6G that measures of filter membrane substrate is at 614cm
-1the Raman face scanning mapping image at place, is of a size of 50 * 50 μ m
2, step-length is 2 μ m, the little figure in Fig. 2 is the normal distribution of SERS intensity.
As seen from the figure, in whole scanning area, SERS signal intensity is minimum.According to Gauss curve fitting, the relative standard deviation of SERS intensity has reached 9%.The scanning of Raman face is a kind of mode of stricter check substrate homogeneity, and this homogeneous that filter membrane substrate excellence has also been described is strengthened the property.
The R6G detectability mensuration figure of Fig. 3 for carrying out in filter membrane substrate.Being respectively concentration is from top to bottom 1 * 10
-6, 1 * 10
-8, 1 * 10
-10, 1 * 10
-12,, 1 * 10
-13, 5 * 10
-14the R6G of M, and blank filter membrane substrate.
As seen from the figure, compare 5 * 10 with the Raman spectrogram of blank filter membrane
-14in the Raman spectrogram of M, can be positioned at 613,1363 by the clear R6G of seeing, 1509,1572 and 1650cm
-1raman peaks.This has illustrated that this three-dimensional fine and close filter membrane substrate has extraordinary strengthening the property, and can improve the sensitivity that SERS detects well.
Fig. 4 is melamine detectability mensuration figure in filter membrane substrate.Being respectively concentration is from top to bottom 1 * 10
-3, 1 * 10
-4, 1 * 10
-5, 1 * 10
-6, 1 * 10
-7, 1 * 10
-8the Melamine of M, and blank filter membrane substrate.
As seen from the figure, compare 1 * 10 with the Raman spectrogram of blank filter membrane
-8in the Raman spectrogram of M, can clearly see that melamine is positioned at 686cm
-1raman peaks.This explanation filter membrane substrate, except the sensitivity to conventional probe molecule has had in SERS detects, also has extraordinary universality to the material in practical application.
Fig. 5 be filter membrane substrate different time sections in three months measure 10
-6the R6G Raman spectrum of M.
As seen from the figure, filter membrane has kept very high SERS performance within the time of the first two months, is respectively the Raman spectrum of the R6G that same filter membrane substrate gathered at the 1st, 5,10,20,30,45,60 days from top to bottom.In time of the first two months substrate in intensity almost without any variation.After two months, obviously reducing appears in the SERS intensity of filter membrane, but still has SERS activity.This explanation filter membrane is very low to the susceptibility of time, has than excellent shelf-life all at the bottom of existing most of money base.
Fig. 6 is the XPS spectrum figure of the different time corresponding with filter membrane substrate in Fig. 5.Be respectively fresh filter membrane substrate and placed the XPS contrast of the filter membrane substrate after 80 days.
As seen from the figure, the silver element valence state of filter membrane substrate surface has occurred very significantly to change, and this variation that has proved substrate SERS performance is caused by the oxidation of silver surface.
Claims (8)
1. a method of preparing silver nano-grain layer, comprises the steps:
1) the silver nanoparticle colloidal sol being comprised of silver nano-grain and water is carried out centrifugal, ultrasonic being scattered in water again after collecting precipitation washes with water, obtains the silver nanoparticle colloidal sol after centrifugal enrichment;
2) the silver nanoparticle colloidal sol after step 1) gained centrifugal enrichment is filtered with filter membrane, on described filter membrane, form silver nano-grain layer, dry, obtain loading on the silver nano-grain layer on described filter membrane.
2. method according to claim 1, is characterized in that: in described step 1), in the silver nanoparticle colloidal sol being comprised of silver nano-grain and water, the mass ratio of silver nano-grain and water is 10-100mg:200mL, is specially 50mg:200mL;
The particle diameter of silver nano-grain is 20-120nm, is specially 50-100nm;
In silver nanoparticle colloidal sol after described centrifugal enrichment, the mass ratio of silver nano-grain and water is 0.1-0.5:100, is specially 0.125:100.
3. method according to claim 1 and 2, is characterized in that: in described step 1) centrifugation step, centrifugal rotational speed is 5000-12000rmp, is specially 12000rmp;
Centrifugal force is 1816-10464g, is specially 10464g; Time is 5-20min, is specially 10min;
In described ultrasonic step, the time is 5-20 minute, is specially 10 minutes;
Ultrasonic power is 30-100W, is specially 30W.
4. according to the arbitrary described method of claim 1-3, it is characterized in that: described step 2), the aperture of filter membrane used is less than 3 times of described silver nano-grain particle diameter; The aperture of filter membrane used is specially 2.2 times of described silver nano-grain particle diameter.
5. according to the arbitrary described method of claim 1-4, it is characterized in that: described step 2), in filtration step, filtering rate is 0.25～1ml/min, is specially 0.5ml/min;
Filtration pressure is 2-10.3bar, is specially 5.2bar.
6. according to the arbitrary described method of claim 1-5, it is characterized in that: described step 2), in drying steps, temperature is 25-40 ℃, be specially 30 ℃; Time is 10-30min, is specially 15min.
7. the silver nano-grain layer that the arbitrary described method of claim 1-6 prepares.
8. using silver nano-grain layer application in surface-enhanced raman scattering as substrate described in claim 7.
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Cited By (7)
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| CN105022103A (en) * | 2015-07-06 | 2015-11-04 | 上海大学 | Preparation method for silver nano film for magnetofluid distorting lens |
| CN105710386A (en) * | 2016-02-25 | 2016-06-29 | 天津工业大学 | One-dimension silver chain nano-structure, self-assembly preparation method and SERS application |
| CN106770171A (en) * | 2016-12-29 | 2017-05-31 | 中国科学院城市环境研究所 | The preparation method of Raman spectrum base and sample |
| CN107064101A (en) * | 2017-03-15 | 2017-08-18 | 东南大学 | A kind of enhancing Raman substrate and its preparation and application for detecting streptomycete mycelia |
| CN109187489A (en) * | 2018-10-19 | 2019-01-11 | 福建师范大学 | A kind of preparation and application of bimolecular identification dopamine surface-enhanced Raman sensor |
| CN113324969A (en) * | 2021-04-06 | 2021-08-31 | 金陵科技学院 | Metal/carbon nanotube composite filter membrane, and manufacturing method and application thereof |
| CN113834804A (en) * | 2021-09-23 | 2021-12-24 | 中国农业大学 | Construction method and application of flexible surface enhanced Raman substrate |
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Cited By (10)
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| CN105022103A (en) * | 2015-07-06 | 2015-11-04 | 上海大学 | Preparation method for silver nano film for magnetofluid distorting lens |
| CN105710386A (en) * | 2016-02-25 | 2016-06-29 | 天津工业大学 | One-dimension silver chain nano-structure, self-assembly preparation method and SERS application |
| CN105710386B (en) * | 2016-02-25 | 2018-04-03 | 天津工业大学 | One-dimensional silver-colored chain nanostructured, self-assembly preparation method thereof and SERS applications |
| CN106770171A (en) * | 2016-12-29 | 2017-05-31 | 中国科学院城市环境研究所 | The preparation method of Raman spectrum base and sample |
| CN107064101A (en) * | 2017-03-15 | 2017-08-18 | 东南大学 | A kind of enhancing Raman substrate and its preparation and application for detecting streptomycete mycelia |
| CN107064101B (en) * | 2017-03-15 | 2020-03-31 | 东南大学 | Enhanced Raman substrate for detecting streptomyces hyphae and preparation and use methods thereof |
| CN109187489A (en) * | 2018-10-19 | 2019-01-11 | 福建师范大学 | A kind of preparation and application of bimolecular identification dopamine surface-enhanced Raman sensor |
| CN109187489B (en) * | 2018-10-19 | 2021-01-05 | 福建师范大学 | Preparation and application of bimolecular recognition dopamine surface-enhanced Raman sensor |
| CN113324969A (en) * | 2021-04-06 | 2021-08-31 | 金陵科技学院 | Metal/carbon nanotube composite filter membrane, and manufacturing method and application thereof |
| CN113834804A (en) * | 2021-09-23 | 2021-12-24 | 中国农业大学 | Construction method and application of flexible surface enhanced Raman substrate |
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