CN103962545B - A kind of processing method of nanometer rods - Google Patents
A kind of processing method of nanometer rods Download PDFInfo
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- CN103962545B CN103962545B CN201310035477.9A CN201310035477A CN103962545B CN 103962545 B CN103962545 B CN 103962545B CN 201310035477 A CN201310035477 A CN 201310035477A CN 103962545 B CN103962545 B CN 103962545B
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Abstract
The invention discloses the processing method of a kind of nanometer rods, the method includes in the presence of the solvent, nanometer rods is contacted with regulation and control reagent, and described regulation and control reagent contains surfactant and soluble copper salt. Pass through technique scheme, present invention achieves the process to various nanometer rods, namely obtain the more homogeneous nanometer rods of pattern or achieve the etching of nanometer rods, height simple to operate, repeated and reaction condition are gentle, agents useful for same non-toxic inexpensive, has potential using value. The method of the present invention is also particularly conducive to the conditions such as the temperature of the consumption by controlling different surfaces activating agent, the consumption of acid, the consumption of soluble copper salt, contact and controls the speed of etching.
Description
Technical field
The present invention relates to the processing method of a kind of nanometer rods, in particular it relates to a kind of processing method that can improve nanometer rods pattern.
Background technology
At present, the method widely using most synthesis gold nanorods is the growing method (Seed-mediatedGrowth) of Murphy et al. the seed proposed modulation, namely by regulating the correlated response parameter such as gold nanorods to obtain different-shape and size such as reactant concentration, seed concentration, kinds of surfactants. Usual the method is spherical (Carbo-Argibay from the gold nanorods head that gold seeds starts to be synthetically derived, E., B.Rodriguez-Gonzalez, etal. (2010). " Thecrystallinestructureofgoldnanorodsrevisited:evidencef orhigher-indexlateralfacets. " AngewChemIntEdEngl49 (49): 9397-9400.), the gold nanorods shape synthesized for different operator or different batches can because of certain deviation, it is impossible to ensure nose shape concordance. When in gold nanorods growth-promoting media, each reagent concentration changes, synthesis gold nanorods nose shape can be changed: when such as reductant concentration improves, can synthesize dog-bone gold nanorods (Gou, L.andC.J.Murphy (2005). " Fine-TuningtheShapeofGoldNanorods. " Chem.Mater17 (14): 3668-3672.). Also the shape of final gold nanorods head can be affected: such as grow addition of quick phase Na at gold nanorods by adding other reaction reagents in gold nanorods growth-promoting media2S, can make gold nanorods formed rest on dumbbell structure (Zweifel, D.A.andA.Wei (2005). " Sulfide-arrestedgrowthofgoldnanorods. " ChemistryofMaterials17 (16): 4256-4261.).After gold nanorods synthesizes, it is possible to make gold nanorods nose shape change by the regrowth process in later stage. in such as regrowth process, can pass through to regulate pH value and surfactant cetyl trimethylammonium bromide (CTAB) concentration in regrowth liquid, obtaining head is spherical dumbbell shaped or cube gold nanorods (Sohn, K., F.Kim, etal. (2009). " ConstructionofEvolutionaryTreeforMorphologicalEngineerin gofNanoparticles. " AcsNano3 (8): 2191-2198.), adding PVP and DMF in regrowth liquid can so that gold nanorods head becomes pointed (Carbo-Argibay from spherical, E., B.Rodriguez-Gonzalez, etal. (2007). " Chemicalsharpeningofgoldnanorods:therod-to-octahedrontra nsition. " AngewChemIntEdEngl46 (47): 8983-8987.). after starting to synthesize gold nanorods from gold kind, do not carry out the regrowth process of complexity, and only gold nanorods head is reinvented conversion, not yet report at present.
At present, for regulating long wave surface plasmon resonance absworption peak (LSPR) peak value of gold nanorods solution, typically via regulating the draw ratio of gold nanorods or changing its pattern and obtain. Therefore the change of LSPR peak position can reflect the change of gold nanorods draw ratio or pattern. Commonly used approach is the draw ratio regulating gold nanorods: except changing the concentration (Nikoobakht of reaction reagent in early stage gold nanorods building-up process, B.andM.A.El-Sayed (2003). " PreparationandGrowthMechanismofGoldNanorods (NRs) UsingSeed-MediatedGrowthMethod. " Chem.Mater15:1957-1962.), by the later stage, synthetic gold nanorods can also be processed, including anisotropic oxide etching and horizontal two kinds of methods of regrowth. Conventional lithographic method includes heat or LASER HEATING (Link, S., C.Burda, etal. (2000). " Laser-InducedShapeChangesofColloidalGoldNanorodsUsingFem tosecondandNanosecondLaserPulses. " J.Phys.Chem.B104:6152-6163.); Cyanide (Jana, N.R., L.Gearheart, etal. (2002). " AnisotropicChemicalReactivityofGoldSpheroidsandNanorods. " Langmuir18:922-927.) or trivalent gold dissolving (Rodr í guez-Fern á ndez, J., J.P é rez-Juste, etal. (2005). " Spatially-DirectedOxidationofGoldNanoparticlesbyAu (III)-CTABComplexes. " TheJournalofPhysicalChemistryB109 (30): 14257-14261.); Other various oxidants, such as oxygen (Tsung, C.-K., X.Kou, etal. (2006). " SelectiveShorteningofSingle-CrystallineGoldNanorodsbyMil dOxidation. " J.AM.CHEM.SOC.128:5352-5353.), hydrogen peroxide (Ni, W., X.Kou, etal. (2008). " TailoringLongitudinalSurfacePlasmonWavelengths, ScatteringandAbsorptionCrossSectionsofGoldNanorods. " AcsNano2 (4): 677 686; Bao, Z., Z.Sun, etal. (2011). " Transverseoxidationofgoldnanorodsassistedbyselectiveendc appingofsilveroxide. " JournalofMaterialsChemistry21 (31): 11537.), ferric ion (Zou, R., X.Guo, etal. (2009). " Selectiveetchingofgoldnanorodsbyferricchlorideatroomtemp erature. " CrystEngComm11 (2797): 2,797 2803.) etc.The speed of etching process can embody from the change of LSPR peak value and ultraviolet-visible spectrogram in the change of 400 nanometers absorption values (representing the amount of gold atom).
The etching gold nanorods reported at present or the method for other noble metals have some drawbacks: or pattern is less homogeneous, or complicated operation (heat or LASER HEATING), or reagent poisonous (cyanide), or expensive (trivalent gold), or severe reaction conditions (oxygen, hydrogen peroxide). Under relatively temperate condition, (such as room temperature, low concentration solvent), method simple to operate, that agents useful for same is cheap, nontoxic is rarely found.
Summary of the invention
It is an object of the invention to provide the processing method of a kind of nanometer rods that can improve nanometer rods pattern, simple to operate and agents useful for same non-toxic inexpensive.
To achieve these goals, the invention provides the processing method of a kind of nanometer rods, the method includes in the presence of the solvent, nanometer rods is contacted with regulation and control reagent, and described regulation and control reagent contains surfactant and soluble copper salt.
Pass through technique scheme, present invention achieves the process to various nanometer rods, obtain the more homogeneous nanometer rods of pattern or achieve the etching of nanometer rods, the inventive method height simple to operate, repeated and reaction condition are gentle, agents useful for same non-toxic inexpensive, has potential using value. The method of the present invention is also particularly conducive to the conditions such as the temperature of the consumption by controlling different surfaces activating agent, the consumption of acid, the consumption of soluble copper salt, contact and controls the speed of etching.
Especially, the present inventor is found that preferably the copper ion transformation to gold nanorods nose shape in acid condition first. In a preferred embodiment of the invention, in nose shape respectively bone-shaped, square or arrow shaped gold nanorods solution, add appropriate CTAB, copper ion and acid (selectively adding), the gold nanorods that pattern that head is spherical is homogeneous within when being placed in 25-80 DEG C 0.25-20 hour, can be obtained. It addition, the method for the present invention can also realize to other noble metal structures as be nucleus growth with gold nanorods silver nanoparticle shell (AuAg), with the etching of the shell in the nucleocapsid structure such as palladium nanoshells (AuPd) that gold nanorods is nucleus growth.
Other features and advantages of the present invention will be described in detail in detailed description of the invention part subsequently.
Accompanying drawing explanation
Accompanying drawing is used to provide a further understanding of the present invention, and constitutes the part of description, is used for explaining the present invention, but is not intended that limitation of the present invention together with detailed description below. In the accompanying drawings:
Fig. 1 is (A) and the images of transmissive electron microscope of (B) after processing before bone-shaped gold nanorods solution being processed in the present invention, and ultraviolet-visible absorption spectroscopy changes over figure (C); And difference CTAB (D), sulphuric acid (E), Cu2+(F) concentration and temperature (G) LSPR peak value in this process change over trendgram;
Fig. 2 be bone-shaped gold nanorods in different condition: CTAB (A), sulphuric acid (B), Cu2+(C) the ultraviolet-visible absorption spectroscopy figure of concentration and temperature (D) final state;
Fig. 3 be the inventive method to tack (a, b) and arrow shaped (c, d) gold nanorods head process before (a, c) (b, ultraviolet-visible absorption spectroscopy figure (A) d) and transmission electron microscope picture (B, C and after processing, D, E). The wherein line a-d in B-E corresponding A;
When Fig. 4 is to be absent from/exist copper ion, gold nanorods solution ultraviolet-visible absorption spectroscopy figure in the process of hydrogen peroxide etching gold nanorods: (A) only adds acid and copper ion, (B) it is only add acid and hydrogen peroxide, (C) acid adding, copper ion and hydrogen peroxide while, (D) in, a, b, c correspond to A, B, C medium ultraviolet visible absorption spectra at the change curve of 450 nanometers absorption values (with initial point value for zero point.The absorption value of 400 nanometers can be affected in the solution, so selecting 450 nanometers absorption values to substitute) owing to adding the ion that gold atom is etched to after hydrogen peroxide;
When Fig. 5 is to be absent from/exist copper ion, gold nanorods solution ultraviolet-visible absorption spectroscopy figure in the process of ferric ion etching gold nanorods: (A) only adds acid and copper ion, (B) it is only add acid and ferric ion, (C) acid adding, copper ion and ferric ion while, (D) in, a, b, c correspond to A, B, C medium ultraviolet visible absorption spectra is at 400 nanometers absorption value change curves (with initial point value for zero point);
When Fig. 6 is for being absent from/exist copper ion, hydrogen peroxide (A) and ferric ion (B) etch in the process of gold nanorods gold nanorods solution ultraviolet-visible absorption spectroscopy figure (with peak position for X-axis, half-peak breadth (FWHM) is figure by Y-axis), a () is only add acid and copper ion, b () is only add acid and hydrogen peroxide or ferric ion, (c) be acid adding, copper ion and hydrogen peroxide or ferric ion simultaneously;
Fig. 7 be in the present invention when processing different AuAg nucleocapsid structure, the images of transmissive electron microscope of (B) (C) afterwards before adding the ultraviolet-visible spectrogram (A) after copper ion and acid reaction and adding copper and acid, wherein, (A) in, AuNRs is original gold nanorods, a is for being not added with any reagent, b is an acid adding, and c is for only to add copper ion, and d is acid adding and copper ion;
Fig. 8 be in the present invention when processing different AuPd nucleocapsid structure, the images of transmissive electron microscope of (B) (C) afterwards before adding the ultraviolet-visible spectrogram (A) after copper ion and acid reaction and adding copper and acid, wherein, (A) in, AuNRs is original gold nanorods, a is for being not added with any reagent, b is an acid adding, and c is for only to add copper ion, and d is acid adding and copper ion.
Detailed description of the invention
Hereinafter the specific embodiment of the present invention is described in detail. It should be appreciated that detailed description of the invention described herein is merely to illustrate and explains the present invention, it is not limited to the present invention.
The processing method of nanometer rods provided by the invention includes in the presence of the solvent, nanometer rods is contacted with regulation and control reagent, and described regulation and control reagent contains surfactant and soluble copper salt.
Wherein, described solvent can be various solvent commonly used in the art, for instance water, it is preferable that deionized water.
According to the present invention, the nanometer rods relative to every mole, the consumption of surfactant is preferably 4 × 107-4×108Mol, more preferably 1.5 × 108-2.5×108Mol. Described surfactant can be selected for surfactant commonly used in the art, it is preferable that in situation, and described surfactant is cetyl trimethylammonium bromide.
Nanometer rods relative to every mole, the consumption of soluble copper salt is preferably 1 × 105-2×106Mol, more preferably 1.5 × 105-3.5×105Mol. Wherein, as long as described soluble copper salt dissolubility in water under room temperature (25 DEG C) can realize the purpose of the present invention more than 25g/100g water, therefore, described soluble copper salt is preferably water solublity mantoquita, it is highly preferred that described soluble copper salt is one or more in copper chloride, copper sulfate and copper nitrate.
It was found by the inventors of the present invention that acid can make gold nanorods nose shape convert and noble metal structures etching is easier to occur, and speed is faster, it is thus preferred to ground, described regulation and control reagent is possibly together with acid. With pH meter, the consumption of described acid is preferably 2 × 107-4×108Mol, more preferably 3.5 × 107-4.5×107Mol. Described acid can be one or more in sulphuric acid, hydrochloric acid and nitric acid.
It was found by the inventors of the present invention that when the surfactant added, soluble copper salt and acid are in above-mentioned preferred scope, gold nanorods nose shape can be converted within a short period of time, thus improving the concordance of gold nanorods nose shape further.The etching to other noble metal structures (such as AuAg or AuPd) can also be realized better simultaneously.
In the present invention, described gold nanorods concentration in contact system is preferably 0.45-0.55nM.
According to the present invention, described nanometer rods is contacted with described regulation and control reagent and can realize the purpose of the present invention, it is preferable that in situation, the condition of described contact includes temperature and is 25-80 DEG C, and the time is 0.25-20h.
According to the present invention, described nanometer rods can be one or more in gold nanorods, AuAg nanometer rods and AuPd nanometer rods. Especially, when described nanometer rods is gold nanorods, can obtain, by the method for the present invention, the gold nanorods that nose shape is spherical (pattern is homogeneous). When described nanometer rods is AuAg nanometer rods and AuPd nanometer rods, the method for the present invention can realize the etching to nanometer rods preferably.
In the present invention, the order that nanometer rods is contacted with each regulation and control reagent has no particular limits, it is possible to be sequentially carried out, it is also possible to carry out simultaneously.
It addition, for the process (particularly etching) realizing nanometer rods better, the method for the present invention can also include adding oxidant (such as hydrogen peroxide and/or trivalent soluble ferric iron salt) in contact system. It is therefore preferred that described regulation and control reagent is possibly together with oxidant. The inventors found that, other regulation and control reagent (surfactant and/or soluble copper salt) used in oxidant and the inventive method have good synergism, using the processing speed regulating and controlling reagent containing oxidant faster, the required process time is considerably shorter.
Described oxidant can realize, for this area, the oxidant that etching routine adopts, but is preferably hydrogen peroxide and/or trivalent soluble ferric iron salt (such as ferric nitrate). It was found by the inventors of the present invention that other regulation and control reagent used in the present invention have considerably better synergism with above-mentioned preferred oxidant.
To the consumption of described oxidant also without special restriction, for instance, the nanometer rods relative to every mole, the consumption of described oxidant can be 1 × 105-2×108mol。
Hereinafter will be described the present invention by embodiment. In following example, agents useful for same is as follows: cetyl trimethylammonium bromide (Amresco), copper chloride (Chemical Reagent Co., Ltd., Sinopharm Group). According to UV-visible-near infrared absorption figure and formula " E(energy)=h(Planck's constant) frequency of v(light)=hc(the light velocity)/λ (wavelength of light) " calculate corresponding energy value, the half-peak breadth at the peak obtained is FWHM value, can react the size dispersity of gold nanorods. UV-visible-near infrared absorption is recorded when 25-35 DEG C by ultraviolet spectrophotometer (VarianCary50, the U.S.); The length of gold nanorods and diameter are by transmission electron microscope (TecnaiG220S-TWIN, U.S.) characterize and record.
Bone-shaped gold nanorods solution (concentration of gold nanorods is 0.5nM), the gold nanorods solution (concentration of gold nanorods is 0.5nM) of square head portion obtains (Gou with reference to the method for Murphy et al., L.andC.J.Murphy (2005). " Fine-TuningtheShapeofGoldNanorods. " Chem.Mater17 (14): 3668-3672.), the gold nanorods solution (concentration of gold nanorods is 0.5nM) of arrowhead-shaped head part obtains (Xiang with reference to the method for Xiang et al., Y., X.Wu, etal. (2008). " TuningtheMorphologyofGoldNanocrystalsbySwitchingtheGrowt hof{110}FacetsfromRestrictiontoPreference. " TheJournalofPhysicalChemistryC112 (9): 3203-3208.),AuAg nanometer rods solution (concentration of nanometer rods is 0.5nM) and AuPd nanometer rods solution (concentration of nanometer rods is 0.5nM) obtain (Xiang with reference to the method in Xiang et al., Y., X.Wu, etal. (2008). " GoldNanorod-SeededGrowthofSilverNanostructures:FromHomog eneousCoatingtoAnisotropicCoating. " Langmuir24 (7): 3465-3470.; Xiang, Y., X.Wu, etal. (2006). " FormationofRectangularlyShapedPd-AuBimetallicNanorods:Ev idenceforCompetingGrowthofthePdShellbetweenthe{110}and{1 00}SideFacetsofAuNanorods. " NanoLetters6 (10): 2290-2294.), after the synthesis of above sample, by 12000 turns per minute, 5 minutes, it is centrifuged and once returns the deionized water adding same volume, obtain the nanometer rods solution of purification.
Embodiment 1
Take 12000 turns per minute of the bone-shaped gold nanorods solution of 5 parts of 1mL purification, 5 minutes centrifugal more once removes supernatant, be separately added into concentration be 10,20,50,100, the cetyl trimethylammonium bromide solution 1mL of 200mM, be added thereto to sulphuric acid that 10 μ L concentration are 1M and 10 μ L concentration are the copper chloride solution of 10mM; Mix homogeneously; Put in 30 DEG C of waters bath with thermostatic control, place 49h, 49h, 27h, 10h, 5h respectively; With the above-mentioned mixed solution of ultraviolet-ray visible absorbing spectrophotometric determination ultra-violet absorption spectrum in time, measuring temperature is 30 DEG C;
The time dependent result of LSPR is as shown in figure ip, it shows that the regulation and control speed of gold nanorods nose shape is increased, with cetyl trimethylammonium bromide concentration, the trend that LSPR peak position blue shift is accelerated by the inventive method, from each condition of Fig. 2 A, uv absorption spectra is it can be seen that final state is basically identical, when cetyl trimethylammonium bromide solution concentration is less than or equal to 20mM, varying less within the 49h time, taking sample final state transmission electron microscope when cetyl trimethylammonium bromide solution concentration is 100mM to characterize, result is as shown in Figure 1B. Based on this, utilize the present invention can pass through to change cetyl trimethylammonium bromide concentration and regulate the speed of gold nanorods nose shape, reaction can be made to complete within a short period of time.
Embodiment 2
Take 12000 turns per minute of the bone-shaped gold nanorods solution of 5 parts of 1mL purification, 5 minutes centrifugal supernatant of once removing again, and add cetyl trimethylammonium bromide that 1mL concentration is 100mM and 10 μ L concentration are the copper chloride solution of 10mM; And it is separately added into sulfuric acid solution 0,5,10,50,100, the 200 μ L that concentration is 1M, mix homogeneously; Put in 30 DEG C of waters bath with thermostatic control, place 25h, 10h, 10h, 10h, 10h, 10h respectively; With the above-mentioned mixed solution of ultraviolet-ray visible absorbing spectrophotometric determination ultra-violet absorption spectrum in time, measuring temperature is 30 DEG C.
The time dependent result of LSPR is as referring to figure 1e, it shows that the regulation and control speed of gold nanorods nose shape is increased LSPR peak position blue shift with sulfuric acid concentration and first accelerates to affect less trend afterwards by the inventive method, from each condition of Fig. 2 B, uv absorption spectra is it can be seen that final state is basically identical, when anacidity, varying less within the 25h time, almost without change, taking sample final state transmission electron microscope when sulfuric acid concentration is 10mM and characterize, result is as shown in Figure 1B. Based on this, utilize the present invention can also pass through to change sulfuric acid concentration and regulate the speed of gold nanorods nose shape.
Embodiment 3
Take 12000 turns per minute of the bone-shaped gold nanorods solution of 5 parts of 1mL purification, 5 minutes centrifugal supernatant of once removing again, and add cetyl trimethylammonium bromide that 1mL concentration is 100mM and 10 μ L concentration are the sulfuric acid solution of 1M; And it is separately added into copper chloride solution 0,5,10,50, the 100 μ L that concentration is 10mM, mix homogeneously; Put in 30 DEG C of waters bath with thermostatic control, place more than 25h, 10h, 10h, 7h, 7h respectively; With the above-mentioned mixed solution of ultraviolet-ray visible absorbing spectrophotometric determination ultra-violet absorption spectrum in time, measuring temperature is 30 DEG C.
The time dependent result of LSPR is as shown in fig. 1f, it shows that the regulation and control speed of gold nanorods nose shape is increased, with copper chloride concentration, the trend that LSPR peak position blue shift is accelerated by the inventive method, from each condition of Fig. 2 C, uv absorption spectra is it can be seen that final state is basically identical, when without copper, varying less within the 25h time, almost without change, taking sample final state transmission electron microscope when copper solution concentration is 100 μMs and characterize, result is as shown in Figure 1B. Based on this, utilize the present invention can also pass through to change copper chloride concentration and regulate the speed of gold nanorods nose shape.
Embodiment 4
Take 12000 turns per minute of the bone-shaped gold nanorods solution of 5 parts of 1mL purification, 5 minutes centrifugal supernatant of once removing again, and add the cetyl trimethylammonium bromide that 1mL concentration is 100mM and the sulfuric acid solution that 10 μ L concentration are 1M and 10 μ L concentration are the copper chloride solution of 10mM; And mix homogeneously puts in water-bath; Bath temperature respectively 30 DEG C, 40 DEG C, 50 DEG C, 60 DEG C, 80 DEG C, places 10h, 3h, 100min, 50min, 12min respectively.
The time dependent result of LSPR is as shown in fig. 1f, it shows that the regulation and control speed of gold nanorods nose shape is raised, with temperature, the trend that LSPR peak position blue shift is accelerated by the inventive method, from each condition of Fig. 2 D, uv absorption spectra is it can be seen that final state is basically identical, taking sample final state transmission electron microscope when 30 DEG C to characterize, result is as shown in Figure 1B. Based on this, utilize the present invention can also pass through to change reaction temperature and regulate the speed of gold nanorods nose shape.
As known from the above, the transforming agent affecting gold nanorods nose shape includes CTAB, acidity, copper ion and temperature, and solvent strength increases and reaction temperature raises the conversion rate that can accelerate nose shape. From transmission electron microscope picture it can be seen that green bone head gold nanorods converts the gold nanorods obtaining spherical head shape through above method. We select to carry out above reaction in relatively mild condition, therefore select the bath temperature close to room temperature to react, to sum up, optimal conditions is: cetyl trimethylammonium bromide is 100mM, the concentration 10mM of sulfuric acid solution, and the concentration of copper chloride solution is 100 μMs, 30 DEG C of water-baths, place about 10h.
It can also be seen that the absorption value in 400 nanometers decreases in time from Fig. 1 C ultraviolet-visible absorption spectroscopy figure, illustrate that gold nanorods has the phenomenon being etched, and under normal circumstances, gold nanorods is more stable, only by oxygen eremacausis in storage, therefore this phenomenon illustrates that the addition of copper ion and acid accelerates the process that gold nanorods is etched by oxygen.
Embodiment 5
Take each 1mL of gold nanorods solution square, arrowhead-shaped head part, 12000 turns per minute, 5 minutes centrifugal more once removes supernatant, and each adding 1mL concentration is the cetyl trimethylammonium bromide of 100mM, and 10 μ L concentration are the sulphuric acid of 1M and 10 μ L concentration are the copper chloride solution of 10mM;And mix homogeneously; Put into about 10h in 30 DEG C of waters bath with thermostatic control; In described mixed solution, the mol ratio of cetyl trimethylammonium bromide, sulphuric acid, copper chloride and gold nanorods is 1:0.1:0.001:0.000000005;
Fig. 3 is (a, c) afterwards (b, ultraviolet-visible absorption spectroscopy figure (A) d) and transmission electron microscope picture (B, C, D, E) before the gold nanorods head of different head shape in embodiment 5 converts. LSPR peak position blue shift after converting from ultraviolet-visible absorption spectroscopy figure, illustrates that gold nanorods nose shape or draw ratio change, by transmission electron microscope picture it can be seen that the gold nanorods of the different head shape of former synthesis has been converted into spherical by the method for the present invention.
Embodiment 6
Take three test tubes, each add 12000 turns per minute of 1mL gold nanorods solution, within 5 minutes, it is centrifuged after once removing supernatant again and adds the cetyl trimethylammonium bromide that isopyknic concentration is 100mM, add cetyl trimethylammonium bromide solution that 2.0mL concentration is 100mM and 15 μ L concentration are the sulphuric acid of 1M, three test tubes are separately added into 30 μ L concentration to be again the hydrogenperoxide steam generator of 1M, 9 μ L concentration be the copper chloride solution of 10mM, 30 μ L concentration are the hydrogenperoxide steam generator of 1M and 9 μ L concentration are the copper chloride solution of 10mM; Then by above-mentioned each solution mix homogeneously, put in 30 DEG C of waters bath with thermostatic control. The mol ratio respectively 1:0.05:0.0003:0.1:0.00000000167 of the cetyl trimethylammonium bromide of mixed solution, sulphuric acid, copper chloride, hydrogen peroxide and gold nanorods in described 3rd test tube;
Take three test tubes, each add 12000 turns per minute of 1mL gold nanorods solution, 5 minutes more centrifugal once remove supernatant after add cetyl trimethylammonium bromide that equal-volume concentration is 100mM and 10 μ L concentration are the sulphuric acid of 1M, three test tubes are separately added into 10 μ L concentration to be again the iron nitrate solution of 100mM, 10 μ L concentration are the copper chloride solution of 100mM, 10 μ L concentration are the copper chloride solution of 100mM and 10 μ L concentration are the iron nitrate solution of 100mM; Then by above-mentioned solution mix homogeneously, put in 30 DEG C of waters bath with thermostatic control; The mol ratio respectively 1:0.1:0.01:0.01:0.000000005 of the cetyl trimethylammonium bromide of mixed solution, sulphuric acid, copper chloride, ferric nitrate and gold nanorods in described 3rd test tube.
When Fig. 4 and Fig. 5 is for being absent from or there is copper ion, gold nanorods solution uv absorption spectra in the process of hydrogen peroxide and ferric ion etching gold nanorods. when only adding acid and copper ion (A), gold nanorods is had certain corrasion, and the corrasion of gold nanorods is substantially accelerated by (C) than (B) when only adding hydrogen peroxide or ferric ion when adding hydrogen peroxide or ferric ion simultaneously, therefore the addition of acid and copper ion is greatly accelerated hydrogen peroxide or the process of ferric ion etching gold nanorods, it can be seen that add after copper ion bigger than the changing value sum of simple (A) and (B) from (D), illustrate that this process is accelerated, can be seen that gold nanorods solution changes the characteristic peak (i.e. shortwave surface plasmon resonance absworption peak and long wave surface plasmon resonance absworption peak) also keeping gold nanorods etching process from UV-visible-near infrared absorption figure. as seen from Figure 6, when obtaining different gold nanorods by etching process, in same peak position, add acid less with half-peak breadth after copper ion or almost with only add when hydrogen peroxide or ferric ion etch consistent, therefore the size dispersity of gold nanorods is not deteriorated, it might even be possible to obtain a degree of improvement. as known from the above, the inventive method is for existing conventional gold nanorods etching agent (oxygen, hydrogen peroxide, ferric ion), the addition of acid and copper ion can work in coordination with its effect of auxiliary well, and can improve the size dispersity of gold nanorods to a certain extent.
Embodiment 7
Take AuAg, AuPd each 1mL of nanometer rods solution, 12000 turns per minute, 5 minutes centrifugal supernatant of once removing again, adding equal-volume concentration is the cetyl trimethylammonium bromide of 100mM, all adds sulphuric acid that 10 μ L concentration are 1M wherein and 10 μ L concentration are the copper chloride solution of 10mM;Then by above-mentioned solution mix homogeneously; Put into about 10h in 30 DEG C of waters bath with thermostatic control; In described mixed solution, the mol ratio of cetyl trimethylammonium bromide, sulphuric acid, copper chloride and AuAg or AuPd nanometer rods is 1:0.1:0.001:0.000000005;
Fig. 7 and Fig. 8 is to the images of transmissive electron microscope (B, C) before and after ultraviolet-visible absorption spectroscopy figure (A) before and after the different reagent reacting of addition in different noble metal nucleocapsid structures and addition acid and copper ion in embodiment 7. From ultraviolet-visible spectrogram it may be seen that, add acid and copper ion after the impact of ultra-violet absorption spectrum is bigger, have almost no change when only adding acid, only add during copper ion less than the change of acid adding and copper ion simultaneously, thus the addition of acid and copper ion accelerates the etching of noble metal shell effectively, also can be illustrated by transmission electron microscope picture.
From the foregoing, it will be observed that it is homogeneous to utilize the inventive method to process the pattern of nanometer rods obtained, height simple to operate, repeated and reaction condition are gentle, agents useful for same non-toxic inexpensive; The inventive method can also work in coordination with the quickening existing etching agent etching to gold nanorods, it is possible to other noble metal nanometer nuclear shell nano-structure of auxiliary etch, has bigger potential using value.
The preferred embodiment of the present invention is described in detail above in association with accompanying drawing; but; the present invention is not limited to the detail in above-mentioned embodiment; in the technology concept of the present invention; technical scheme can being carried out multiple simple variant, these simple variant belong to protection scope of the present invention.
It is further to note that, each concrete technical characteristic described in above-mentioned detailed description of the invention, in reconcilable situation, it is possible to be combined by any suitable mode, in order to avoid unnecessary repetition, various possible compound modes are no longer illustrated by the present invention separately.
Additionally, can also carry out combination in any between the various different embodiment of the present invention, as long as it is without prejudice to the thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (9)
1. the processing method of a nanometer rods, it is characterised in that the method includes in the presence of the solvent, nanometer rods is contacted with regulation and control reagent, described regulation and control reagent contains surfactant and soluble copper salt, the nanometer rods relative to every mole, and the consumption of described surfactant is 4 × 107-4×108Mol, the consumption of described soluble copper salt is 1 × 105-2×106mol。
2. processing method according to claim 1, wherein, described surfactant is cetyl trimethylammonium bromide; Described soluble copper salt is one or more in copper chloride, copper sulfate and copper nitrate.
3. processing method according to claim 1, wherein, described regulation and control reagent is possibly together with acid, and with pH meter, the consumption of described acid is 2 × 107-4×108mol。
4. processing method according to claim 3, wherein, described acid is one or more in sulphuric acid, hydrochloric acid and nitric acid.
5. processing method according to claim 1, wherein, described nanometer rods concentration in contact system is 0.45-0.55nM.
6. processing method according to claim 1, wherein, the condition of described contact includes: temperature is 25-80 DEG C, and the time is 0.25-20h.
7. the processing method according to any one in claim 1-6, wherein, described nanometer rods is one or more in gold nanorods, AuAg nanometer rods and AuPd nanometer rods.
8. processing method according to claim 7, wherein, described regulation and control reagent is possibly together with oxidant.
9. processing method according to claim 1, wherein, described solvent is water.
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| CN104964664B (en) * | 2015-07-03 | 2017-06-06 | 国家纳米科学中心 | A kind of assay method of the nano grain surface ligand layer thickness for being coated with part |
| CN105300857B (en) * | 2015-11-12 | 2017-04-05 | 国家纳米科学中心 | A kind of assay method of rod-like nano particle geometric shape |
| CN106124476A (en) * | 2016-06-21 | 2016-11-16 | 中山大学 | Based on surface enhanced raman spectroscopy and the glucose sensing approach of bi-molecular probe |
| CN113231632B (en) * | 2021-05-12 | 2023-04-18 | 厦门大学附属心血管病医院 | Gold-palladium asymmetric heterogeneous nano structure and synthesis method thereof |
| CN113798491B (en) * | 2021-09-17 | 2023-08-25 | 杭州师范大学 | Dumbbell-shaped copper-containing composite noble metal nano material and synthesis method thereof |
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