CN106112003B - A kind of preparation method and application of size and the adjustable noble metal nano particles of pattern - Google Patents
A kind of preparation method and application of size and the adjustable noble metal nano particles of pattern Download PDFInfo
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Abstract
The invention discloses a kind of sizes and the preparation method and application of the adjustable noble metal nano particles of pattern.Using acetone, tetrahydrofuran, ethyl alcohol organic solvent miscible with water, in organic solvent/water mixed system, by adjusting the species of organic solvent and ratio with aqueous solvent, the nano-particle of different sizes and pattern is prepared for.Synthetic operation step provided by the invention is simple and easy to control, and chemical reaction is quick, is not required to add additional surfactant, preparation method is environmentally protective.Noble metal nano particles prepared by the present invention have stronger surface-enhanced Raman effects, 4 nitrobenzene benzenethiols are used as probe molecule, the intensity of its scattered signal and the species of nano-particle, grain size and pattern are closely related, use it for the minimal detectable concentration for endangering additive malachite green molecule respectively up to 10‑9 mol·dm‑3And 10‑11 mol·dm‑3, important meaning is respectively provided in scientific research and practical application.
Description
Technical field
The present invention relates to a kind of preparation methods of noble metal nano particles, belong to crystal growth and detection technique field.
Background technology
For metal nanoparticle there are quantum size effect, it is only different from macroparticle that special electronic structure determines that it has
Special physicochemical properties.So far, had largely on metal nanoparticle in the necks such as catalysis, biology, optics, medicine
The application report in domain.In numerous metals, be related to that the research contents of gold, silver nano-particle is more, and achievement is enriched, including synthesis,
Modification, assembling, photoelectric property and application in every respect.It is worth noting that in Surface enhanced Raman spectroscopy (SERS) field,
The gold, silver nano-particle of a large amount of different-shapes, size and assembling mode reported in succession, accelerates that SERS is resonable to refer to application side
The development in face.Meanwhile scientist SERS has also encouraged nanometer expert preparing to further enhancing the craving of scattered signal intensity
Increasingly seek to break through in method.
In general, the preparation method of nanostructured is broadly divided into (top-down) and from bottom to top (Bottom- from top to down
Up) two kinds.Method from top to down, i.e., by some instruments by the metal of bulk, continuous Ground Split is levigate to become smaller, until particle
Size reaches nanoscale.However, the preparation method not only needs instrument and equipment costly, at the same particle size and
There is also many restrictions for the control aspect of pattern.From bottom to top, i.e., it is gradual since atom or molecule by chemical reduction method
Accumulation forms cluster (cluster), further accumulates, and until size is within nanometer range, and stops accumulating.With gold nano
Exemplified by particle, this synthetic method from bottom to top has been invented early in 1857 by faraday.That more famous is Turkevich-
Frens methods are initiated respectively by Turkevich in nineteen fifty-one, and are improved in 1973 by Frens.This method is the water in boiling
Using sodium citrate as protective agent and reducing agent in solution, gold chloride is reduced, forms gold nanoparticle (referring to document：Frens
G. Nat. Phys. Sci., 1973, 241, 20.).Similar method can be used for the synthesis of Nano silver grain, Lee
Deng at first by sodium citrate be used as reduction synthesis Nano silver grain, be referred to as Lee-Meisel methods (referring to document：Lee P. C.,
Meisel D., J. Phys. Chem. 1982, 86, 3391.)。
Except Turkevich-Frens methods, a kind of method that synthesis gold nanoparticle is controlled based on mercaptan is named as
Brust-Schiffrin methods are also widely used and conduct in-depth research (referring to document：Perala, S. R. K.,
Kumar, S., Langmuir, 2013, 29, 9863).However, the nano-particle of this method synthesis is smaller, it is generally several to receive
Rice, it is difficult to be applied in SERS fields.In addition, also high polymer, biomolecule etc. are introduced reaction system by researcher, make
For additive, stabilizer or reducing agent synthesizing nano-particle.And above-mentioned research mostly concentrates on body of the water as solvent
It is carried out in system.Xia etc. has developed reduces the different gold, silver nanometer of a large amount of patterns of precious metal salt synthesis with polyol process at high temperature
Particle, and the systematicness of method and versatility are very good (referring to document：Wiley, B., Sun, Y. G.Langmuir,
2005, 21, 8077).Synthetic method used in Xia, experiment carry out in organic solvent (ethylene glycol).Certainly, except with
The nucleation of previous step synthetic method, i.e. nano-particle and growth occur simultaneously, another method is known as seed mediated growth method, i.e., with one
The particle (being typically small particle) of footwork synthesis is used as seed, regrows, can separate nucleation and growth in growth-promoting media,
To be more accurately controlled reaction process, the different size of particle and pattern are obtained.
The size of nano-particle has significant impact to its optical property.55 common nm Au have one bright at 520 nm
Aobvious absworption peak, if the size of nano-particle is more than or less than 55 nm, red shift or blue shift can be occurred by absorbing peak position.Work as nanometer
Particle size is less than 10 nm, which can generally disappear.In addition, the pattern of nano-particle also have to its optical property it is important
It influences.If spherical nano-particle is only able to detect a peak on extinction spectra, there are two peak, sheets for rodlike nano-particle
Can detect three even four peaks.In SERS fields, the size of nano-particle, which has the scattering strength of probe molecule, to be shown
The influence of work, the particle of general 10 below nm is substantially without enhancement effect.In addition, the aggregation between the pattern and particle of particle
Mode and aggregation extent etc. generate final SERS signal intensity important influence.
Therefore, in order to regulate and control the heterogeneity of particle, to obtain suitable application in every field, different sizes are synthesized
And the nano-particle of pattern is its top priority.Most commonly seen method, that is, regulate and control size Turkevich-Fens methods and
Regulate and control the polyol process of pattern.Turkevich-Fens methods adjust particle by adjusting the additional proportion of sodium citrate and gold chloride
Size, and polyol process by add different auxiliary agents and control reaction parameters obtain different-shape nano junction
Structure.However, these classical having some limitations property of method.Such as：Two methods are required to be reacted at high temperature, it is necessary to take
Reflux condensate device is built, therefore operating process is complicated；Entire reaction is from heating, being reacted to cooling, and time-consuming for process；Polyol process
In additional auxiliary agent, the reagent especially adsorbed by force may influence the subsequent modification of particle or application.Therefore, development is a kind of often
Temperature reacts, is easy to operate, being swift in response, " green " synthetic method without Additional auxiliaries is particularly important.
The content of the invention
The present invention in view of the deficienciess of the prior art, provide a kind of synthesis technology is simple, be swift in response, it is environmentally protective and
The preparation method of size and the adjustable noble metal nano particles of pattern.
Realize that the technical solution of the object of the invention is to provide a kind of size and the system of the adjustable noble metal nano particles of pattern
Preparation Method.By volume, in every 10 parts of reaction systems, including gold chloride or 1 part of silver nitrate aqueous solution, organic solvent 1~7
Part, 7~1 parts of pure water, 1 part of aqueous ascorbic acid；Wherein, organic solvent is controlled：Water is mutually 1~7: 9~3；In room temperature, play
Under strong stirring condition, reactant is mixed, 10~50 minutes is stood after reaction, then through eccentric cleaning, preserves, obtain in aqueous solution
To the adjustable gold of a kind of size and pattern or Nano silver grain；
The organic solvent is one kind in acetone, tetrahydrofuran or ethyl alcohol, selects different organic solvent and organic
Solvent and the volume ratio of water phase, regulate and control the size and pattern of noble metal nano particles, and regulation and control method is as follows：
（1）Using acetone as organic solvent, aqueous solution of chloraurate is added in, regulates and controls the volume ratio of acetone and water from 1:9~7:3 by
Gradually rise, obtain that average-size gradually increases from the nm of 65 nm~400, pattern is spherical gold nanoparticle；
（2）Using tetrahydrofuran as organic solvent, aqueous solution of chloraurate is added in, regulates and controls the volume ratio of tetrahydrofuran and water from 1:
9~7:3 are gradually increasing, and obtain that average-size gradually increases from the nm of 25 nm~330, pattern is spherical gold nanoparticle；
（3）Using ethyl alcohol as organic solvent, aqueous solution of chloraurate is added in, regulates and controls the volume ratio of ethyl alcohol and water from 1:9~7:3 by
Gradually rise, obtain that average-size gradually increases from the nm of 66 nm~930, pattern is spherical or flower-shaped gold nanoparticle；
（4）Using acetone as organic solvent, silver nitrate aqueous solution is added in, regulates and controls the volume ratio of acetone and water from 1:9~7:3 by
Gradually rise, the Nano silver grain pattern respectively obtained successively is spherical, flower-shaped and irregular aggregate structure；
（5）Using tetrahydrofuran as organic solvent, silver nitrate aqueous solution is added in, regulates and controls the volume ratio of tetrahydrofuran and water from 1:
9~7:3 are gradually increasing, obtain average-size be gradually reduced from 1.3 μm~0.4 μm, pattern be flower-shaped Nano silver grain；When
The volume ratio of tetrahydrofuran and water is 7:When 3 and more than, be irregular structure；
（6）Using ethyl alcohol as organic solvent, silver nitrate aqueous solution is added in, regulates and controls the volume ratio of ethyl alcohol and water from 1:9~7:3 by
Gradually rise, obtain average-size be gradually reduced from 1.3 μm~0.7 μm, pattern be flower-shaped Nano silver grain, when ethyl alcohol and water
Volume ratio be 7:3 and it is above when, be irregular structure.
Regulation and control method（4）In, when the volume ratio of acetone and water is 1:When 9, the spherical silver that average diameter is 360 nm is obtained
Nano-particle；When the volume ratio of acetone and water is 3:7~5:When 5, the flower that average-size falls to 220 nm from 380 nm is obtained
Shape Nano silver grain；When the volume ratio of acetone and water is 7:When 3 and more than, be irregular aggregate structure.
Technical solution of the present invention further includes size and the adjustable noble metal nano grain of pattern that the method for being prepared as described above obtains
The application of son, one is it is 10 to malachite green concentration that obtained gold nanoparticle, which is used for,-9~10-7 mol·dm-3It is water-soluble
Liquid carries out Surface enhanced Raman spectroscopy detection；The second is it is 10 to malachite green concentration that obtained Nano silver grain, which is used for,-11~
10-9 mol·dm-3Aqueous solution carry out Surface enhanced Raman spectroscopy detection.
The present invention forms hybrid reaction system by selecting common organic solvent miscible with water, with aqueous solution, provides
It is a kind of it is easy to operate at normal temperatures, be swift in response and can regulate and control gold, silver nano-particles size and the preparation method of pattern.In view of
Influence of the size and pattern of nano-particle to SERS properties, is selected in different solvents system most using 4- nitro thiophenols
Optimize SERS substrates, to endangering the minimal detectable concentration of additive malachite green molecule respectively up to 10-9 mol·dm-3And 10-11 mol·dm-3。
The present invention provides a kind of synthesis technology is simple, the environment-friendly preparation method thereof that is swift in response and is not required to heating, for closing
Into grain size and the adjustable gold, silver nano-particle of pattern.The method is by selecting common organic solvent, determining with acetone, tetrahydrochysene
Furans, ethyl alcohol and water composition mixed system, select certain mixed proportion, using common gold chloride and silver nitrate as oxidant
The Jin Heyin of high-valence state is provided, it is anti-by redox in organic solvent/water mixed system using ascorbic acid as reducing agent
The gold, silver nano-particle of different sizes and pattern should be obtained.After tested, a series of gold, silver nano-particles obtained by the method
It is respectively provided with good SERS enhancement effects.Using 4- nitro thiophenols as probe molecule, same in the mixed solvent SERS letters are selected
Number most strong substrate.It with the SERS substrates of the optimization, is detected respectively to endangering additive malachite green, gold, silver nanometer
Particle can obtain relatively low detectable concentration, and solid experiment base is provided fast, easily to prepare highly sensitive SERS substrates.
Compared with prior art, the present invention it has the following advantages that：
1st, reaction carries out at normal temperatures and pressures, mild condition, and there is no need to the complexity such as heat, pressurize, expensive device, drops
Low production cost.
2nd, the reagent that reaction uses is common organic solvent, cheap, is remarkably improved mass and prepares SERS
The feasibility of substrate.
3rd, it is swift in response, takes short.Under the organic-inorganic solvent mixture proportions of part, time of completion is reacted in " second grade ",
The most slow time is also no more than " minute grade ".
4th, the nano-particle of synthesis can provide excellent without the surfactant that adsorbs by force is additionally added for the molecule of less strongly adsorbed
Good SERS substrates.
Description of the drawings
Fig. 1 be the embodiment of the present invention one in the mixed system of acetone and water, by different acetone：The ratio synthesis Au of water receives
The SEM figures of rice corpuscles；
Fig. 2 is four kinds of substrates in Fig. 1 for probe molecule in the embodiment of the present invention one with 4- nitro thiophenols (PNTP)
The SERS spectrograms of upper acquisition；
Fig. 3 is with the malachite green of the substrate detection various concentration of the strongest line of Fig. 2 in the embodiment of the present invention one
SERS spectrograms；
Fig. 4 be the embodiment of the present invention one in the mixed system of tetrahydrofuran and water, by different tetrahydrofurans：The ratio of water
Synthesize the SEM figures of Au nano-particles；
Fig. 5 is four kinds of substrates in Fig. 4 for probe molecule in the embodiment of the present invention one with 4- nitro thiophenols (PNTP)
The SERS spectrograms of upper acquisition；
Fig. 6 is with the malachite green of the substrate detection various concentration of the strongest line of Fig. 5 in the embodiment of the present invention one
SERS spectrograms；
Fig. 7 be the embodiment of the present invention one in the mixed system of second alcohol and water, by different ethyl alcohol：The ratio synthesis Au of water receives
The SEM figures of rice corpuscles；
Fig. 8 is four kinds of substrates in the figure 7 for probe molecule in the embodiment of the present invention one with 4- nitro thiophenols (PNTP)
The SERS spectrograms of upper acquisition；
Fig. 9 is with the malachite green of the substrate detection various concentration of the strongest line of Fig. 8 in the embodiment of the present invention one
SERS spectrograms；
Figure 10 be the embodiment of the present invention two in the mixed system of acetone and water, by different acetone：The ratio synthesis Ag of water
The SEM figures of nano-particle；
Figure 11 is four kinds of bases in Fig. 10 for probe molecule in the embodiment of the present invention two with 4- nitro thiophenols (PNTP)
The SERS spectrograms obtained on bottom；
Figure 12 is with the malachite green of the substrate detection various concentration of the strongest line of Figure 11 in the embodiment of the present invention two
SERS spectrograms；
Figure 13 be the embodiment of the present invention two in the mixed system of tetrahydrofuran and water, by different tetrahydrofurans：The ratio of water
The SEM figures of example synthesis Ag nano-particles；
Figure 14 is four kinds of bases in fig. 13 for probe molecule in the embodiment of the present invention two with 4- nitro thiophenols (PNTP)
The SERS spectrograms obtained on bottom；
Figure 15 is with the malachite green of the substrate detection various concentration of the strongest line of Figure 14 in the embodiment of the present invention two
SERS spectrograms；
Figure 16 be the embodiment of the present invention two in the mixed system of second alcohol and water, by different ethyl alcohol：The ratio synthesis Ag of water
The SEM figures of nano-particle；
Figure 17 is four kinds of bases in figure 16 for probe molecule in the embodiment of the present invention two with 4- nitro thiophenols (PNTP)
The SERS spectrograms obtained on bottom；
Figure 18 is with the malachite green of the substrate detection various concentration of the strongest line of Figure 17 in the embodiment of the present invention two
SERS spectrograms.
Specific embodiment
Embodiment one:
First, the preparation of series A u nano-particles
1st, the preparation of precursor solution：
（1）0.33% aqueous solution of chloraurate：By 6 mL 1% (w/w) chlorauric acid solution（1g HAuCl4·4H2O is dissolved in
In 100 mL water）It is added in 12 mL water, is uniformly mixed.
（2）10 mmol·dm-3Aqueous ascorbic acid：It weighs 0.176 g ascorbic acid powder and is added to 10 mL water
In, it dissolves and is uniformly mixed.
2nd, the preparation of gold nanoparticle：
（1）Acetone/water system：
Control solvent acetone：Water phase volume ratio is respectively 1: 9、3 : 7、5 : 5、7:3, in the item being vigorously stirred
Added in successively in reaction bulb under part 0.33% aqueous solution of chloraurate, 1 mL, 1,3,5,7 mL of acetone, pure water volume be respectively 7,
5、3、1 mL、10 mmol·dm-31 mL of aqueous ascorbic acid makes the total volume in reaction bulb be kept stirring 3 for 10 mL
Stop after minute, stand 30 minutes, preserved in aqueous solution after eccentric cleaning, the Au nanoparticles in acetone/water system can be obtained
Son.
Referring to attached drawing 1, it is the present embodiment by different acetone：The SEM figures of the ratio synthesis Au nano-particles of water, scale are
600 nm；Wherein, acetone：The ratio of water, (A) figure is 1:9;(B) figure is 3:7;(C) figure is 5:5;(D) figure is 7:
3；By scheming（A）~（D）As can be seen that Au nano-particles are spherical shape, the diameter of particle gradually increases from 65~400 nm, single point
It is preferable to dissipate property.
（2）Tetrahydrofuran/aqueous systems：
Control tetrahydrofuran：Water phase volume ratio is respectively 1: 9、3 : 7、5 : 5、7:3, in the condition being vigorously stirred
Under added in successively in reaction bulb 0.33% chlorauric acid solution, 1 mL, 1,3,5,7 mL of tetrahydrofuran, pure water volume be respectively 7,
5、3、1 mL、10 mmol·dm-31 mL of ascorbic acid solution makes the total volume in reaction bulb be kept stirring 3 points for 10 mL
Stop after clock, stand 30 minutes, preserved in aqueous solution after eccentric cleaning, the Au nanometers in tetrahydrofuran/aqueous systems can be obtained
Particle.Its particle diameter gradually increases from 25~330 nm, and referring to attached drawing 4, it is the present embodiment in tetrahydrofuran and water
In mixed system, by different tetrahydrofurans：The ratio (A) 1 of water:9; (B) 3:7; (C) 5:5; (D) 7:3 synthesis Au receive
The SEM figures of rice corpuscles, scale are 300 nm；Fig. 4（A）~（D）In as it can be seen that pattern for spherical shape.
（3）Ethanol/water system：
Control ethyl alcohol：Water phase volume ratio is respectively 1: 9、3 : 7、5 : 5、7:3, under conditions of being vigorously stirred according to
It is secondary added in reaction bulb 0.33% chlorauric acid solution, 1 mL, 1,3,5,7 mL of ethyl alcohol, pure water volume be respectively 7,5,3,1 mL,
10 mmol·dm-31 mL of ascorbic acid solution makes the total volume in reaction bulb stop for 10 mL after being kept stirring 3 minutes,
30 minutes are stood, is preserved in aqueous solution after eccentric cleaning, the Au nano-particles in ethanol/water system can be obtained.Its particle is straight
Footpath gradually increases from 66 ~ 930 nm, referring to attached drawing 7, it be the present embodiment in the mixed system of second alcohol and water, by different second
Alcohol：The ratio (A) 1 of water:9; (B) 3:7; (C) 5:5; (D) 7:The SEM figures of 3 synthesis Au nano-particles, scale 400
nm；By scheming（A）~（D）As it can be seen that the pattern of the particle obtained developed by spherical shape it is flower-shaped.
2nd, the SERS substrates of optimal Au are determined using 4- nitro thiophenols：
Prepare 1 mmoldm-34- nitro thiophenols ethanol solution, using the molecule as probe molecule.By all systems
After the Au nano-particle eccentric cleanings of middle synthesis, it is added dropwise to respectively on clean silicon chip, vacuum is drained, and SERS substrates are made.It will
This substrate is separately immersed in 1 mmoldm-34- nitro thiophenols ethanol solution in, 8 it is small when after take out, alcohol flushing, nitrogen
After air-blowing is done, SERS detections are carried out.When SERS is tested, every substrate takes acquisition SERS signal at 10 at random, by the signal of acquisition
Intensity is averaged.It is for probe molecule, in Fig. 1 in the present embodiment with 4- nitro thiophenols (PNTP) referring to attached drawing 2,5 and 8, Fig. 2
Four kinds of substrates on the SERS spectrograms that obtain, wherein, (a) is using A as substrate;(b) using B as substrate;(c) using C as substrate;
(d) using D as substrate；Fig. 5 is four kinds of substrates in Fig. 4 for probe molecule in the present embodiment with 4- nitro thiophenols (PNTP)
The SERS spectrograms of upper acquisition, wherein, (a) is using A as substrate;(b) using B as substrate;(c) using C as substrate;(d) using D as
Substrate；Fig. 8 is to be obtained with 4- nitro thiophenols (PNTP) for probe molecule in four kinds of substrates in the figure 7 in the present embodiment
SERS spectrograms, wherein, (a) is using A as substrate;(b) using B as substrate;(c) using C as substrate;(d) using D as substrate.Through
Comparison finds that the substrate that SERS signal optimizes is respectively acetone：Water phase volume ratio is 1：9, tetrahydrofuran：Water phase volume ratio is
3：7 and ethyl alcohol：Water phase volume ratio is 3：7 prepared Au nano-particles.As shown in Figure 2, spectral line a has most strong
SERS signal, about 1100 cps.Therefore, in acetone/water system, the spherical Au nano-particles of 65 nm is in the systems
Optimal SERS substrates.Similarly, the optimal SERS substrates in tetrahydrofuran/aqueous systems, ethanol/water system are 58 nm respectively
Au spheroidal particles and 240 nm Au nano flower-like structures.
Optimal Au bases SERS substrates are to endangering the detection of additive molecule malachite green：
Using malachite green as harm additive molecule to be detected, a series of malachite green aqueous solution of concentration is prepared, point
The gold nanoparticle that SERS signal optimizes is not added drop-wise on clean silicon chip, vacuum is drained, and SERS substrates are made.By substrate
Be separately immersed in the malachite green aqueous solution of various various concentrations, 8 it is small when after take out, water rinse, nitrogen drying after, carry out
SERS is detected.Its result referring to attached drawing 3,6 and 9, Fig. 3 be in the present embodiment it is different dense with the detection of the substrate of the strongest line of Fig. 2
The SERS spectrograms of the malachite green of degree, wherein, (a) 10-5 mol·dm-3; (b) 10-6 mol·dm-3; (c) 10-7
mol·dm-3; (d) 10-8 mol·dm-3; (e) 10-9 mol·dm-3；Fig. 6 is with the most strong spectrum of Fig. 5 in the present embodiment
The SERS spectrograms of the malachite green of the substrate detection various concentration of line, wherein, (a) 10-5 mol·dm-3; (b) 10-6 mol·
dm-3; (c) 10-7 mol·dm-3; (d) 10-8 mol·dm-3；Fig. 9 is with the base of the strongest line of Fig. 8 in the present embodiment
The SERS spectrograms of the malachite green of bottom detection various concentration, wherein, (a) 10-5 mol·dm-3; (b) 10-6 mol·dm-3;
(c) 10-7 mol·dm-3; (d) 10-8 mol·dm-3; (e) 10-9 mol·dm-3; (f) 10-10 mol·dm-3；By
Figure understands that three of the above Au nano-particles can detect that the minimum concentration of malachite green is respectively 10-8、10-7With 10-9 mol·
dm-3。
Embodiment two:
First, the preparation of series A g nano-particles
1st, the preparation of precursor solution：
（1）10 mmol·dm-3Silver nitrate aqueous solution:Weigh 85 mg AgNO3Powder is added in 50 mL water, dissolving
And it is uniformly mixed.
（2）10 mmol·dm-3Aqueous ascorbic acid：It weighs 0.176 g ascorbic acid powder and is added to 10 mL water
In, it dissolves and is uniformly mixed.
2nd, the preparation of Nano silver grain：
（1）Acetone/water system：
Control solvent acetone：The volume ratio of water phase is respectively 1: 9、3 : 7、5 : 5、7:3, in the item being vigorously stirred
Add in 10 mmoldm under part in reaction bulb successively-31 mL of silver nitrate aqueous solution, 1,3,5,7 mL of acetone, pure water volume integral
It Wei not 7,5,3,1 mL, 10 mmoldm-31 mL of aqueous ascorbic acid makes the total volume in reaction bulb be kept for 10 mL
Stirring stops after 3 minutes, stands 30 minutes, is preserved in aqueous solution after eccentric cleaning, the Ag that can be obtained in acetone/water system receives
Rice corpuscles.Referring to attached drawing 10, it be the present embodiment in the mixed system of acetone and water, by different acetone：The ratio (A) of water
1:9; (B) 3:7; (C) 5:5; (D) 7:The SEM figures of 3 synthesis Ag nano-particles, scale are 500 nm；Silver nanoparticle in A figures
Particle is preferably spherical for monodispersity, and average diameter is 360 nm, and B figures are then flower-like structure.With the increasing of acetone addition
More, average-size is begun to decline, such as Figure 10（C）Shown, diameter is reduced to 220 nm, and D figures are then irregular aggregate structure.
（2）Tetrahydrofuran/aqueous systems：
Control solvents tetrahydrofurane：The volume ratio of water phase is respectively 1: 9、3 : 7、5 : 5、7:3, acutely stirring
Add in 10 mmoldm under conditions of mixing in reaction bulb successively-31 mL of silver nitrate aqueous solution, 1,3,5,7 mL of tetrahydrofuran,
Pure water volume is respectively 7,5,3,1 mL, 10 mmoldm-31 mL of aqueous ascorbic acid, makes the total volume in reaction bulb be
10 mL stop after being kept stirring 3 minutes, stand 30 minutes, preserved in aqueous solution after eccentric cleaning, can obtain tetrahydrofuran/
Ag nano-particles in aqueous systems.Referring to attached drawing 13, it be the present embodiment in the mixed system of tetrahydrofuran and water, by difference
Tetrahydrofuran：The ratio (A) 1 of water:9; (B) 3:7; (C) 5:5; (D) 7:The SEM figures of 3 synthesis Ag nano-particles, scale
For 1 μm；（A）~（D）It is shown in figure, Nano silver grain is flower-like structure, and average diameter is reduced to 0.4 μm by 1.3 μm, D figures
It is then irregular structure.
（3）Ethanol/water system：
Control etoh solvent：Water phase volume ratio is respectively 1: 9、3 : 7、5 : 5、7:3, in the item being vigorously stirred
Add in 10 mmoldm under part in reaction bulb successively-31 mL of silver nitrate aqueous solution, 1,3,5,7 mL of ethyl alcohol, pure water volume integral
It Wei not 7,5,3,1 mL, 10 mmoldm-31 mL of aqueous ascorbic acid makes the total volume in reaction bulb be kept for 10 mL
Stirring stops after 3 minutes, stands 30 minutes, is preserved in aqueous solution after eccentric cleaning, the Ag that can be obtained in ethanol/water system receives
Rice corpuscles.Referring to attached drawing 16, be the present embodiment in the mixed system of second alcohol and water, by different ethyl alcohol：The ratio (A) 1 of water:
9; (B) 3:7; (C) 5:5; (D) 7:The SEM figures of 3 synthesis Ag nano-particles, scale are 1 μm；Wherein, in A, B, C figure
Nano silver grain is flower-like structure, and average diameter is respectively 1.3 μm, and 0.8 μm, 0.7 μm, D figures are then irregular structure.
2nd, optimal Ag bases SERS substrates are determined using 4- nitro thiophenols：
Prepare 1 mmoldm-34- nitro thiophenols ethanol solution, using the molecule as probe molecule.By Ag nanoparticles
After sub- eccentric cleaning, it is added drop-wise to respectively on clean silicon chip, vacuum is drained, and SERS substrates are made.This substrate is separately immersed in 1
mmol·dm-34- nitro thiophenols ethanol solution in, 8 it is small when after take out, alcohol flushing, nitrogen drying after, carry out SERS
Detection.When SERS is tested, every substrate takes acquisition SERS signal at 10 at random, and the signal strength of acquisition is averaged.By comparing,
It was found that the substrate that SERS signal optimizes is respectively acetone：Water phase volume ratio is 1：9, tetrahydrofuran：Water phase volume ratio is 7：3,
And ethyl alcohol：Water phase volume ratio is 1：9 Ag nano-particles.Referring to attached drawing 11,14 and 17；Figure 11 is with 4- nitre in the present embodiment
Base benzenethiol (PNTP) is probe molecule, the SERS spectrograms obtained in four kinds of substrates in Fig. 10, wherein, (a) is using A as base
Bottom;(b) using B as substrate;(c) using C as substrate;(d) using D as substrate；Figure 14 is with 4- nitrobenzene sulphur in the present embodiment
Phenol (PNTP) is probe molecule, the SERS spectrograms obtained in four kinds of substrates in fig. 13, wherein, (a) is using A as substrate;
(b) using B as substrate;(c) using C as substrate;(d) using D as substrate；Figure 17 is with 4- nitro thiophenols in the present embodiment
(PNTP) it is probe molecule, the SERS spectrograms obtained in four kinds of substrates in figure 16, wherein, (a) is using A as substrate; (b)
Using B as substrate;(c) using C as substrate;(d) using D as substrate.As seen from the figure, signal can be observed most in every group of spectroscopic data
A strong spectral line.In Figure 11, spectral line a has most strong SERS signal, about 1600 cps, therefore, in acetone/water system
In, the spherical Ag nano-particles of 360 nm are the optimal SERS substrates in the system.Similarly, in tetrahydrofuran/aqueous systems, second
Optimal SERS substrates in alcohol/aqueous systems are the Ag nano flower-like structures of Ag irregular granules and a diameter of 1.3 μm respectively.
Optimal Ag bases SERS substrates are to endangering the detection of additive molecule malachite green：
Using malachite green as harm additive molecule to be detected, a series of malachite green aqueous solution of concentration is prepared, point
The Ag nano-particles that SERS signal optimizes are not added drop-wise on clean silicon chip, vacuum is drained, and SERS substrates are made.By this base
Bottom is separately immersed in the malachite green aqueous solution of various various concentrations, 8 it is small when after take out, water rinse, nitrogen drying after, carry out
SERS is detected.Its result is referring to attached drawing 12,15 and 18；Figure 12 is detected not with the substrate of the strongest line of Figure 11 in the present embodiment
With the SERS spectrograms of the malachite green of concentration, wherein, (a) 10-5 mol·dm-3; (b) 10-6 mol·dm-3; (c) 10-7
mol·dm-3; (d) 10-8 mol·dm-3; (e) 10-9 mol·dm-3; (f) 10-10 mol·dm-3; (g) 10-11
mol·dm-3; (h) 10-12 mol·dm-3；Figure 15 is different dense with the substrate detection of the strongest line of Figure 14 in the present embodiment
The SERS spectrograms of the malachite green of degree, wherein, (a) 10-5 mol·dm-3; (b) 10-6 mol·dm-3; (c) 10-7
mol·dm-3; (d) 10-8 mol·dm-3; (e) 10-9 mol·dm-3; (f) 10-10 mol·dm-3；Figure 18 is this reality
It applies with the SERS spectrograms of the malachite green of the substrate detection various concentration of the strongest line of Figure 17 in example, wherein, (a) 10-7
mol·dm-3; (b) 10-8 mol·dm-3; (c) 10-9 mol·dm-3; (d) 10-10 mol·dm-3.As seen from the figure, with
Upper three kinds of Ag nano-particles can detect that the minimum concentration of malachite green is respectively 10-11、10-9And 10-9 mol·dm-3。
Claims (4)
1. a kind of preparation method of size and the adjustable noble metal nano particles of pattern, it is characterised in that：By volume, every 10
In part reaction system, including gold chloride or 1 part of silver nitrate aqueous solution, 1~7 part of organic solvent, 7~1 parts of pure water, Vitamin C
1 part of aqueous acid；Wherein, organic solvent is controlled：Water is mutually 1~7: 9~3；Under room temperature, intense agitation, by reactant
Mixing, stands 10~50 minutes after reaction, then through eccentric cleaning, preserves in aqueous solution, obtain a kind of size and pattern is adjustable
Gold or Nano silver grain；
The organic solvent is one kind in acetone, tetrahydrofuran or ethyl alcohol, selects different organic solvent and organic solvent
With the volume ratio of water phase, regulate and control the size and pattern of noble metal nano particles, it is as follows to regulate and control method：
（1）Using acetone as organic solvent, aqueous solution of chloraurate is added in, regulates and controls the volume ratio of acetone and water from 1:9~7:3 gradually on
It rises, obtains that average-size gradually increases from the nm of 65 nm~400, pattern is spherical gold nanoparticle；
（2）Using tetrahydrofuran as organic solvent, aqueous solution of chloraurate is added in, regulates and controls the volume ratio of tetrahydrofuran and water from 1:9~
7:3 are gradually increasing, and obtain that average-size gradually increases from the nm of 25 nm~330, pattern is spherical gold nanoparticle；
（3）Using ethyl alcohol as organic solvent, aqueous solution of chloraurate is added in, regulates and controls the volume ratio of ethyl alcohol and water from 1:9~7:3 gradually on
It rises, obtains that average-size gradually increases from the nm of 66 nm~930, pattern is spherical or flower-shaped gold nanoparticle；
（4）Using acetone as organic solvent, silver nitrate aqueous solution is added in, regulates and controls the volume ratio of acetone and water from 1:9~7:3 gradually on
It rises, the Nano silver grain pattern respectively obtained successively is spherical, flower-shaped and irregular aggregate structure；
（5）Using tetrahydrofuran as organic solvent, silver nitrate aqueous solution is added in, regulates and controls the volume ratio of tetrahydrofuran and water from 1:9~
7:3 are gradually increasing, obtain average-size be gradually reduced from 1.3 μm~0.4 μm, pattern be flower-shaped Nano silver grain；When four
The volume ratio of hydrogen furans and water is 7:It is irregular structure when 3；
（6）Using ethyl alcohol as organic solvent, silver nitrate aqueous solution is added in, regulates and controls the volume ratio of ethyl alcohol and water from 1:9~7:3 gradually on
Rise, obtain average-size be gradually reduced from 1.3 μm~0.7 μm, pattern be flower-shaped Nano silver grain, when ethyl alcohol and the body of water
Product is than being 7:It is irregular structure when 3.
2. the preparation method of a kind of size according to claim 1 and the adjustable noble metal nano particles of pattern, feature
It is：Regulation and control method（4）In, when the volume ratio of acetone and water is 1:When 9, the spherical silver nanoparticle that average diameter is 360 nm is obtained
Particle；When the volume ratio of acetone and water is 3:7~5:When 5, the flower-shaped silver that average-size falls to 220 nm from 380 nm is obtained
Nano-particle；When the volume ratio of acetone and water is 7:It is irregular aggregate structure when 3.
3. the application of a kind of size obtained by claim 1 preparation method and the adjustable noble metal nano particles of pattern, special
Sign is：It is 10 to malachite green concentration that obtained gold nanoparticle, which is used for,-9~10-7 mol·dm-3Aqueous solution carry out table
Face enhancing Raman spectrum detection.
4. the application of a kind of size obtained by claim 1 preparation method and the adjustable noble metal nano particles of pattern, special
Sign is：It is 10 to malachite green concentration that obtained Nano silver grain, which is used for,-11~10-9 mol·dm-3Aqueous solution carry out
Surface enhanced Raman spectroscopy detects.
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