CN101323964A - Synthetic method of load type floriform silver nanostructured material - Google Patents
Synthetic method of load type floriform silver nanostructured material Download PDFInfo
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Abstract
The invention discloses a synthesizing method of a loading flower-shaped nano silver structural material, which is characterized in that a silver plate with high purity is taken as an anode, a platinum film electrode is taken as a cathode, a silver nitrate solution with the concentration of 0.003 to 0.01 mol/L is taken as an electrolytic solution, and the volume of the electrolytic solution is 20 to 100 mL; the range of constant voltage is adjusted to be 50 to 200 mV during electrolytic deposition, and the time of the electrolytic deposition lasts for 2 to 15 minutes; the cathode of the loading nano silver structural material is repeatedly rinsed by deionized water after the reaction, and then dried in nitrogen. The synthesizing method of the loading flower-shaped nano silver structural material realizes the growth anisotropy of crystal, leads the size and the microstructure of the nano metallic structure to be controllable, does not need any addition agent and electrode surface modification, and achieves simple control of appropriate voltage and concentration of the electrolytic solution; the synthesizing method is ultra-simple, and has convenient operation, easy-separated products and high purity and well industrial application prospect.
Description
Technical field
The present invention relates to the synthetic method of nano structural material, especially be implemented in the silver nanostructured material that the matrix surface one-step synthesis has specific form and microstructure, this special silver nanostructured material has shown stronger microcell surface enhanced Raman scattering effect.
Background technology
It is the very popular topic in present nanotechnology research field that rule, orderly structure are set up in the small unit of nanoscale.By the approach of this " from bottom to top ", we not only can widen the range of application of nano-functional material, and can successfully realize the device of nano material.In recent years, because silver nanostructured material has very unique physical and chemical performance, they are such as optics, catalysis, and fields such as surface enhanced Raman scattering (SERS) and chemical-biological sensing have broad application prospects.By the silver-colored construction unit of nanoscale, the silver nanostructured extensive concern that causes people of classification that forms as establishments such as nano particle, nanometer rod, nano belt and nanometer sheet.The scholars of field of nanometer technology are devoted to effective synthetic method reasonable in design, to obtain classification silver nanostructured material with special appearance, size and microstructure.Recently, people have been developed various wet chemistry methods, and the classification of successfully having synthesized some different-shapes is silver nanostructured, as coralliform, and flakes, lobate, dendritic, propeller-like and flower-shaped etc.Yet, synthesize three-dimensional classification silver nanostructured material in a large number and remain a challenge with certain pattern and fine microstructure.And if can allow them in the matrix surface direct growth, the three-dimensional classification nanostructure of the loading type that makes is such as the SERS active matrix, and some special Application Areass such as ultraphobic water surface and nano-device have certain advantage.And this is to be difficult to realize to wet-chemical.
Studies show that electrochemical techniques are a kind of good approach at matrix surface direct growth classification nanostructure.At present, electrochemical method has been used to prepare some and has had the supported silver nanostructure of complex geometry pattern, as the nanometer plate array, the micron island, flower-shaped pattern, herring-bone form, dendroid and branch are dendritic etc., major part all is to make under the situation of existence such as template and tensio-active agent in the middle of them, perhaps is grown in the film modified electrode surface of polymer thin.Yet, use template, tensio-active agent and functional modification electrode surface to tend to have influence on the performance of product, make synthesis step become complicated, perhaps limited a large amount of synthetic of nano structural material.At present also do not have special preparation method, especially under the situation of template, additive and electrode face finish, a step is realized the synthetic and size of big area load type floriform silver nanostructured material, effective control of microstructure.
Summary of the invention
The objective of the invention is, propose a kind of synthetic method of nano structural material, realize especially easily and controlled electrochemical method.By this method, under the situation of template, tensio-active agent or electrode face finish, a step realizes that silver is at Si/SiO
2/ Pt (platinum film electrode, be called for short PFE, by making at silicon single crystal, silicon-dioxide or other slick tinsel surface plating one deck platinum film) surperficial moment nucleation, controllable growth, final form uniform distribution, three-dimensional classification floriform silver nanostructured (Flowerlike silver nanostructures, FSNs).The object of the invention also is, by the simple adjustment reaction parameter, realizes effective control of size, pattern and the microstructure of this loading type FSNs, and with its Preliminary Applications in the SERS active matrix.
The technology of the present invention solution is: the synthetic method of load type floriform silver nanostructured material: it is characterized in that anode is high-purity silver strip, what negative electrode used is the platinum film electrode, electrolytic solution is silver nitrate solution, and concentration is 0.003-0.01mol/L, and the volume of electrolytic solution is 20-100mL; Regulating the constant voltage scope during galvanic deposit is 50-200mV, and electrodeposition time is 2-15min; Negative pole with the load silver nanostructured material after the reaction washes repeatedly with deionized water, dries in nitrogen atmosphere at last.Temperature generally gets final product in room temperature, can also be from room temperature to 40 ℃.
The invention has the beneficial effects as follows: without any need for additive, do not need the counter electrode surface to modify in advance yet, the present invention is just by simple control voltage and concentration of electrolyte, makes argent at the surperficial instantaneous nucleation of platinum film, thereby regulates the distribution density of final product at matrix surface.In addition, in silver-colored electrochemical growth process, suitable electroreduction motivating force makes and obviousization that become of the speed of growth difference on the nucleus different crystal orientations to reach the purpose of anisotropic growth, finally makes the silver nanostructured material with special appearance.This method is simple unusually, easy to operate, and product is easily separated, purity is higher.
Electrochemical deposition technique has some advantages that traditional method does not have aspect the preparation nano material: on the one hand, by changing institute's deposition material and the surface energy difference of matrix and the voltage that acts on electrode surface, electrodip process can be controlled initial one-tenth kernel normal form (instantaneous nucleation with progressively nucleation), thereby the control nanostructure is in the distribution number density of matrix surface; On the other hand, the material productive rate height of electrodip process preparation, purity is high and pollution-free; The controllability of electro-reduction reaction motivating force is good, can realize the crystal growth (isotropy or anisotropy) of different modes; Electrochemical method is very simple, cost is low and easy to operate.Electrochemical deposition can make the metal nano nano structural material fix and realize assembling at matrix surface, satisfies some special application demands.Therefore, the present invention has following advantage:
1) equipment configuration is simple, easy to operate.Only need simple two electrode systems (positive and negative electrode and electrolyzer);
2) controllability is good.Can pass through the simple adjustment reaction parameter, accurately control pattern, size and the microstructure of silver nanostructured material as the reaction times;
3) silver nanostructured material at matrix surface fixing and discontinuous some special applications that are distributed as it, as nano-electrode, nano-sensor, etc. advantageous conditions is provided;
4) this method cost is low, easily realizes having good industrial applications prospect.
Electrochemical deposition technique was applied in synthesizing of metal Nano structure morphology control, can realize of the effective control of metal Nano structure material a step, thereby be implemented in application such as some fields such as catalysis, chemical sensitisation, nano-devices in extensive synthetic and distribution density, pattern and the size of matrix surface.
The present invention had both realized the anisotropic growth of silver under the situation of no any additives and electrode face finish, had realized the adjusting of floriform silver nanostructured material in matrix surface size and microstructure again.This research idea is the breakthrough of a novelty in the synthetic field of silver nanostructured morphology control.In addition, because floriform silver nanostructured material and platinum film matrix bond are together, can drop into application easily.The inventive method also extends to the preparation of nano structural materials such as other precious metals, semi-conductor, for synthetic loaded three-dimensional classification nanostructure material provides a new approach; In addition, it provides a kind of new thinking for the novel nano preparation of devices.
Description of drawings
Fig. 1 is the reaction unit synoptic diagram of the synthetic load type floriform silver nanostructured material of the present invention.
(a)-(d) is the SEM picture (reaction conditions is respectively: silver nitrate concentration is 3mM, and voltage is 80mV, and depositing time is 10min) of the representative floriform silver nanostructured different amplification that makes among Fig. 2.
Fig. 3 is the XRD figure spectrum of product correspondence and the XPS collection of illustrative plates (illustration) of Ag 3d.The diffraction peak that is produced by the platinum film diffraction is labeled as " ◆ ".XPS electronic spectrum data are benchmark with the C1s peak of 284.6eV all.
The SEM picture of the floriform silver nanostructured material that Fig. 4 makes for different depositing times.(a) depositing time is 2min; (b) depositing time is 5min.Wherein, C and V are respectively 3mM and 80 mV.
Fig. 5 is the SEM picture of galvanic deposit product under the different mode of deposition.Concentration of electrolyte, voltage and depositing time are respectively (a) 3mM, 50mV, 5min; (b) 3mM, 100mV, 5min; (c) 3mM, 200mV, 1min; (d) 3mM, 200mV, 2min; (e) 3mM, 500mV, 2min; (f) 30mM, 80mV, 2min.
Fig. 6 is for surveying the microcell surface enhanced Raman spectroscopy figure (data collection time is 30 seconds) that the rhodamine B be adsorbed on different silver nanostructured surfaces obtains.Curve a-c: corresponding to the floriform silver nanostructured material among Fig. 1 c, Fig. 2 a and Fig. 2 b.Curve d: the Raman collection of illustrative plates that is adsorbed on the rhodamine B on smooth platinum film surface.
Embodiment
Anode is high-purity silver strip, and it is of a size of 40mm (length) * 20mm (wide)～40mm * (length) 30mm (wide); What negative electrode adopted is the PFE electrode, and size is 10mm * 10mm～30mm * 30mm, and it is silver nanostructured to be used for electrochemical growth; Interelectrode distance is 30～40mm, and two electrodes are fixed with iron stand, and the volume of electrolytic solution is 20-100mL; Adjust silver nanostructured distribution density, pattern, size and microstructure by changing voltage, concentration of electrolyte and depositing time.
Particularly be: (1) uses acetone, ethanol and deionized water to monocrystalline silicon piece ultrasonic cleaning repeatedly successively, dries in air, carries out single face at silicon single crystal then on accurate spraying plating instrument and sprays certain thickness platinum film and make the PFE matrix; (2) silver nitrate crystal is added deionized water and be mixed with certain density electrolytic solution; (3) with No. 2000 diamond sand paper the silver strip single face is polished, use acetone, ethanol and deionized water ultrasonic cleaning then successively; (4) will fix in two electrodes insertion electrolytic solution and with iron stand, what immerse electrolytic solution is 10mm * 5mm over against area effectively, and interelectrode distance is 30～40mm; (5) beginning galvanic deposit certain hour under a constant voltage; (6) after reaction finishes, the negative electrode of load silver nanostructured material is cleaned repeatedly with deionized water, to remove the AgNO of surface attachment
3Crystal dries in flowing nitrogen then.
The preparation facilities of load type floriform silver nanostructured material: the precision DC stabilizer that comprises a voltage stabilization and current stabilization, be used for fixing the iron stand of two electrodes, electrolyzer is a rectangular plastic hopper, cell dimension is 5cm (length) * 3cm (wide) * 0.5cm (thick), two electrodes are fixed on the both sides of electrolyzer, therefore the distance between them is 30～40mm, and whole loop connects with copper conductor.
At first, (the present invention has adopted AgNO to dispose certain density silver salt electrolytic solution
3, analytical pure), and the solution of measuring certain volume is poured in the electrolyzer; Two prepared electrode are inserted electrolyzers and fix; Under constant voltage (certain voltage is set) pattern, the logical direct current reaction regular hour, form at the product that negative terminal surface just has galvanic deposit this moment; Negative pole is cleaned repeatedly with deionized water, in nitrogen atmosphere, dry at last.So just made the big area load type floriform silver nanostructured material.
Adopting electrodip process to prepare the big area load type floriform silver nanostructured material carries out in simple two electrode systems.Anode is high-purity silver strip, to silver strip be polished with No. 2000 diamond sand paper before each galvanic deposit, and use acetone successively, ethanol and washed with de-ionized water, to remove the impurity of silver electrode surface.The electrode that is used for negative electrode is Si/SiO
2/ Ti/Pt electrode or directly in the front of Si (111) matrix deposition or plate certain thickness platinum film (the platinum film electrode is called for short PFE).Before deposition or platinum plating film, with ethanol, acetone and deionized water silicon substrate is cleaned repeatedly successively, in air, dry then.
Concentration with the Silver Nitrate electrolytic solution of deionized water preparation is 0.003-0.01mol/L, and the volume of electrolytic solution is 20-100mL; Regulating constant total voltage during galvanic deposit is 50-200mV, and electrolysis time is 2-15min.
1. synthesizer
As shown in Figure 1, this reaction unit is made of simple two electrode systems (power supply, electrode, electrolyzer).Power supply be one can voltage stabilization and current stabilization precision DC stabilizer (model SB118, Shanghai forward Electronics Equipment Co., Ltd); Electrolyzer is rectangular plastic channel; Electrolytic solution 3 is certain density AgNO
3Solution; The anodic electrode is rectangular high-purity silver strip 1, and what negative electrode 2 adopted is that (below the insertion liquid level is 1/2 of whole PFE electrode over against area effectively to a foursquare PFE electrode, and interelectrode distance is that 30～40mm), two electrodes are fixed with iron stand; Whole loop adopts lead to connect.
2. the preparation of load type floriform silver nanostructured material
(1) uses acetone, ethanol and deionized water that Si (111) sheet is cleaned repeatedly successively, in air, dry.On accurate plated film instrument, deposit certain thickness platinum film then;
(2) (the present invention has adopted AgNO to take by weighing a certain amount of silver salt
3, analytical pure), add deionized water and be mixed with solution, the solution that takes out certain volume is as electrolytic solution;
(4) with No. 2000 diamond sand paper silver electrode is polished, use acetone, ethanol and deionized water ultrasonic cleaning successively, to remove surface impurity.With fixing in two electrodes insertion electrolytic solution and with iron stand, be 1/2 of PFE electrode over against area, interelectrode distance is the inner width of electrolyzer.With copper conductor whole loop is connected.
(5) setting power mode is constant voltage (a constant magnitude of voltage), begins galvanic deposit then;
(6) after reaction finishes,,, in nitrogen atmosphere, dry then to remove the AgNO3 crystal of surface attachment with the cleaning repeatedly in the deionized water of the PFE electrode of load product.
3. the principal element of single dispersion of influence and equally distributed floriform silver nanostructured formation has three aspects:
(1) voltage: under constant voltage galvanic deposit pattern, voltage is the motivating force of impelling reaction to carry out.When voltage is too big, on the one hand, the speed that the silver ions in the electrolytic solution is reduced will be too fast, and Ag (0) adatom will be too fast in the sedimentary speed of electrode surface, the speed of growth difference in each crystal orientation of nucleus is just very little, so just is difficult to grow into have the silver nanostructured of regular morphology.On the other hand, silver for progressively becoming kernel normal form, has new galactic nucleus to generate in the nucleation on platinum film surface in the process that galactic nucleus is grown up again like this, finally causes the nanocrystalline size of silver inhomogeneous, and can't form distribution more uniformly on golden film surface.Therefore, suitable voltage is the key that forms single dispersion and equally distributed floriform silver nanostructured material.
(2) concentration of silver ions: the quantity of silver ions can have influence on nucleation and the speed of growth of silver at electrode surface in the electrolytic solution of unit volume.Therefore, suitable concentration of silver ions also is very crucial.
(3) depositing time: along with the prolongation of electrodeposition time, the pattern of product, size and microstructure can change gradually.In electrodeposition process, what at first form is the small-particle of irregular pattern; With these particles is the center, and silver-colored adatom constantly deposits on its surface, and some silver-colored small shredss form on the particulate surface gradually; Then, along with the continuation prolongation of time, these small shredss are grown up gradually, simultaneously secondary, three grades even multistage also progressively formation of silver strip.
What make among the present invention is floriform silver nanostructured relatively unique, mainly is to be intersected by many nano silver slices to constitute, and the outside surface of these silver strips is lower { the 111} series face of surface energy.Therefore, Yin anisotropic growth is to form the floriform silver nanostructured essential factor that this Nano silver piece constitutes.In the forming process, owing to the crystalline speed of growth is directly proportional with surface energy, so the speed of growth in each crystal orientation has certain difference.For argent, the pass between three low index face surface energy sizes is that { { { 111} shows that the slowest crystal orientation of the speed of growth is＜111〉direction to 100}＞γ to 110}＞γ to γ.Under a suitable voltage drove, the speed of growth difference in each crystal orientation was obviously changed gradually, thereby made＜110〉and＜100〉direction the speed of growth is greater than＜111〉direction.Therefore, meticulous controlled in order to realize floriform silver nanostructured size and microstructure, the optimization of preparation condition mainly comprises following three aspects:
(1) voltage: under the constant situation of other condition, change voltage respectively, and the product that different voltages are generated has down carried out sem analysis.The result shows, total voltage numerical value is between 50-100mV the time, and reaction can evenly be carried out lentamente, forms beautiful floriform silver nanostructured easily.
(2) concentration of silver ions: studies show that the concentration of electrolytic solution is 0.003-0.01mol/L, can obtain single dispersion, equally distributed silver nanostructured material.
(3) reaction times: under proper condition, the product that the differential responses time is generated has carried out sem analysis.The result shows that under the certain reaction condition, silver nanostructured pattern changes along with the variation in reaction times, and along with certain variation has taken place for the prolongation of time floriform silver nanostructured diameter and microstructure.When depositing time is controlled at 2min-15min, can make the floriform silver nanostructured material of different diameter, different microstructure (size of Nano silver piece and distribution density).
Load type floriform silver nanostructured material synthesizes example:
Be exemplified below: (total voltage (V), concentration of silver ions (C) and depositing time (t) are respectively 3mM, 80mV and 10min) under suitable condition made silver nanostructured material on negative electrode PFE surface.Adopt scanning electron microscope analysis (SEM) that product direct (not needing metal spraying) is observed, the result as shown in Figure 2.(Fig. 2 a) shows the SEM picture of low power, is distributed in the platinum film matrix surface to a large amount of uniform particles, and product has been realized large-area distribution.Fig. 2 b shows that particle has flower-shaped pattern, and diameter is between 9-11 μ m.More the SEM picture of high-amplification-factor (Fig. 2 c) has disclosed the detailed form of flower-like nanostructure, can see, flower-like nanostructure is formed by the nanometer sheet structure of two dimension, intersects mutually between the nanometer sheet.This floriform silver nanostructured very particular structure that has yet there are no the someone and reported.All nanometer sheet all have slick surface, outward extending corrugated edge and homogeneous thickness.Fig. 2 d amplifies for the part of the centre portions of the flower showed among Fig. 2 c, can be clear that the about 50nm of the thickness of nanometer sheet.
Corresponding XRD test result shows that product is the silver-colored crystal of FCC structure.As shown in Figure 3, (111) face is much bigger with the diffracted intensity ratio (4.7) of a diffracted intensity odds ratio standard block money crystal face of (200) face, this explanation silver carries out with anisotropic growth pattern under this experiment condition, therefore final floriform silver nanostructured outer surface with minimum surface can { 111} series face is main crystal face.Degree of purity of production and chemical composition are approved really to obtain by further x-ray photoelectron power spectrum (XPS) test.The illustration in Fig. 2 upper right corner is the silver-colored 3d spectrogram of the XPS spectrum figure of product.As can be seen, Ag3d
5/2And 3d
3/2Paired bimodal respectively with 368.0 and 374.1eV corresponding in conjunction with the subject of knowledge and the object of knowledge, kinetic force is approximately 510.7eV, these values and simple substance silver Ag
0The standard value unanimity.The XPS test result has hinted the prepared silver nanostructured clean surface that has, and this may be owing to the reason that does not add any additives in the reaction.
Further research experiment shows, the deposition parameter in the electrochemical deposition process has played very crucial effect to floriform silver nanostructured formation.Fig. 4 is concentration of electrolyte and voltage certain (C and V are respectively 3mM and 80mV), the product that is obtained during different depositing time.When depositing time was 2min, shown in Fig. 4 a, prepared silver nanostructured form was still for significantly flower-shaped, the about 5.5 μ m of their mean diameter.From the illustration in the upper right corner as can be seen, floriform silver nanostructuredly be made of several cross one another nanometer sheet, each nanometer sheet all has outward extending corrugated edge.When depositing time was increased to 5min, floriform silver nanostructured increasing diameter was added to 7.5 μ m (seeing Fig. 4 b).And the density of single floriform silver nanostructured middle nanometer sheet also increases to some extent.When depositing time further was increased to 10 minutes, shown in Fig. 2 c of front, the mean diameter of " flower " was increased to about 10 μ m.What is interesting is that the density of the Nano silver piece in single " flower " also further increases, it is compact more that nanostructure inside also becomes.Therefore, the size of the density of Nano silver piece and " flower " can control effectively by changing depositing time.Yet, can find that along with the increase of depositing time, the floriform silver nanostructured number density of matrix surface does not have variation clearly basically, this may be owing to the instantaneous nucleation of electrochemical deposition process initial stage silver on the platinum film surface.This experimental phenomena is different from the electrochemical growth of flower-shaped gold nano structure on conductive glass (ITO) surface.Report in the document that when the ITO surface electrochemistry was grown flower-shaped gold nano structure, the gold nano structure can increase along with the increase of depositing time in the number density of matrix surface.Yet at present we are not clear for the concrete reason of this difference, require further study.
Except that depositing time, applied voltage (V) may also be the deciding factor of a silver nanostructured final pattern of control.Under the constant situation of concentration of electrolyte and depositing time, promptly C and t are respectively 3mM and 2min, when applied voltage is lower than 20mV, almost do not have flower-shaped silver nano-grain to form.When deposition voltage is 50mV, flower-shaped silver nanostructured can formation, but the granule number density of nanostructure is lower, shown in Fig. 5 a.As can be seen, floriform silver nanostructured diameter with 5.5-7 μ m, petal have high density and little size.When voltage further is increased to 100mV, asymmetric floriform silver nanostructured formation.Shown in Fig. 5 b, wherein several petals have grown up to the flap of large-size in the flower-like structure, and other petal looks like little " bud " because poor growth does not also have enough time to form.When voltage is increased to 200mV, with voltage be that product under the 50mV condition compares, we can find that the granule number density of product obviously increases under the high voltage condition, as Fig. 5 c and 5d.In addition, be 200mV at voltage, when depositing time was increased to 2min by 1min, silver nanostructured structure by shred (Fig. 5 c) changed the nanostructure (Fig. 5 d) that looks like the bud shape into.Yet when response voltage further increased to 500mV, product was polyhedral particle, and shown in Fig. 5 e, the particulate diameter is approximately 850nm.We can be clearly seen that comparison diagram 5a and 5e, and silver-colored particle in the number density of PFE matrix surface comparatively obvious variation has taken place.
Above result shows that higher deposition voltage helps forming high silver-colored granule number density, but is unfavorable for the classification nanostructure formation of (as flower-shaped).In electrodeposition process, the nucleation energy of nucleus depends on the overvoltage of negative electrode.A big negative electrode overvoltage will be lowered into nuclear energy, and the number density of nucleon will increase like this.Therefore, high magnitude of voltage can cause Ag
+High rate of reduction or high Ag
0The concentration of adatom, result will promote silver in the nucleation of matrix surface and cause particle high-density and relative undersized silver nanostructured formation, shown in Fig. 4 e.On the other hand, too low deposition voltage (10mV) will cause the silver can not be at the platinum film surface nucleation for instance.In addition, concentration of electrolyte also is a very important factor of the floriform silver nanostructured formation of influence.Fig. 4 f is that deposition voltage and depositing time remain unchanged under the situation of (being respectively 80mV and 2min) the SEM picture of product when concentration of electrolyte is 30mM.Can be clear that under such reaction conditions, to have only the polyhedron silver particle of large size (the about 10 μ m of diameter) to form, and flower-shaped silver nanostructured not acquisition, silver-colored particle sparsely is dispersed in the surface of matrix.
These floriform silver nanostructured interesting structures make that their application facet at the bottom of the SERS active group are very attractive.Fig. 6 a and 6d are respectively the organic dye rhodamine Bs (10 that is adsorbed on floriform silver nanostructured (seeing Fig. 2 c) and platinum film surface
-6Mol/L) Raman spectrogram.Can clearly be seen that (the surface-enhanced Raman signal that curve a) produces will obviously be better than slick platinum film (curve d) by FSNs.The position at most of Ramans enhancings peak is all consistent with the numerical value in the document.For the FSNs structure, stronger surface-enhanced Raman effects is relevant with their how much special patterns.As Fig. 2 d, FSNs contains a lot of gaps between nano silver slice.Under the excitation of laser beam, high local fields will produce in these gaps, therefore will produce high Raman enhancing signal to the target molecule of surveying.Dark gap help to strengthen local fields this be since two over against and adjacent Nano silver piece between have strong phasmon coupling effect, and the metallic surface phasmon is to setting forth in the Raman enhanced influence introduction in front.Depositing time also is studied the influence of SERS effect.From Fig. 6 curve a, b and c (correspond respectively to Fig. 2 c, Fig. 3 b and Fig. 3 c silver nanostructured) as can be seen, long silver nanostructured of depositing time can produce stronger SERS signal, this with the formation of their Nano silver pieces between gap density relevant.This result and flower-shaped gold nano structure and dendritic silver nanostructured RERS result are consistent.
Claims (6)
1, the synthetic method of load type floriform silver nanostructured material: it is characterized in that anode is high-purity silver strip, what negative electrode used is the platinum film electrode, and electrolytic solution is silver nitrate solution, and concentration is 0.003-0.01mol/L, and the volume of electrolytic solution is 20-100mL; Regulating the constant voltage scope during galvanic deposit is 50-200mV, and electrodeposition time is 2-15min; Negative pole with the load silver nanostructured material after the reaction washes repeatedly with deionized water, dries in nitrogen atmosphere at last.
2, by the preparation method of the described load type floriform silver nanostructured material of claim 1, it is characterized in that adopting direct supply, during galvanic deposit under constant voltage mode electrochemical reduction make.
3, by the preparation method of the described load type floriform silver nanostructured material of claim 1, it is characterized in that suitable voltage and concentration of electrolyte obtain suitable reacting driving force and depositing time is controlled the distribution density of Nano silver piece by controlling, thereby accurately control floriform silver nanostructured size and microstructure.
4, by the preparation method of claim 1 or 2 described big area load type floriform silver nanostructured materials, it is characterized in that anode is a high-purity silver strip, it is of a size of 40mm * 20mm～40mm * 30mm; What negative electrode used is the platinum film electrode, and size is 10mm * 10mm～30mm * 30mm; Interelectrode distance is 30～40mm, and two electrodes are fixed with iron stand.
5, by the preparation method of claim 1 or 2 described big area load type floriform silver nanostructured materials: it is characterized in that adopting the precision DC stabilizer of voltage stabilization and current stabilization, electrolyzer is a rectangular plastic hopper, and it is of a size of 5cm length * 3cm, and wide * 0.5cm is thick; Wherein anode is rectangular high-purity silver strip, what negative electrode adopted is the square-shaped metal sheet or the silicon chip of positive deposition or plating one deck platinum film, what the insertion liquid level of electrolyte was following is 1/2 of whole negative electrode over against area effectively, the positive and negative electrode spacing is 30～40mm, two electrodes are fixed with iron stand, and whole loop adopts lead to connect.
6, by the preparation method of the described load type floriform silver nanostructured material of claim 1, it is characterized in that using acetone, ethanol and deionized water that Si (111) sheet is cleaned repeatedly successively earlier, in air, dry, then the certain thickness platinum film of deposition on accurate coating equipment; Take by weighing a certain amount of AgNO
3, adding deionized water and be mixed with solution, the solution that takes out certain volume is as electrolytic solution; With No. 2000 diamond sand paper silver electrode is carried out single-sided polishing, use acetone, ethanol and deionized water ultrasonic cleaning successively, to remove surface impurity; To fix in two electrodes insertion electrolytic solution and with iron stand, interelectrode distance is 30～40mm, with copper conductor whole loop is connected; After reaction finishes, with the cleaning repeatedly in the deionized water of the PFE electrode of load product, to remove the AgNO of surface attachment
3Crystal dries in nitrogen atmosphere then.
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