CN103962545A - Method for processing nanorods - Google Patents
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- CN103962545A CN103962545A CN201310035477.9A CN201310035477A CN103962545A CN 103962545 A CN103962545 A CN 103962545A CN 201310035477 A CN201310035477 A CN 201310035477A CN 103962545 A CN103962545 A CN 103962545A
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Abstract
The invention discloses a method for processing nanorods. The method comprises the following step: enabling the nanorods to be in contact with regulation and control reagents under the existence of solvents, wherein the regulation and control reagents contain surface-active agents and soluble copper salt. Through the technical scheme, various nanorods are processed by the method, so that the nanorods of which the profiles are more uniform are obtained, or the nanorods are etched; the operation is simple, the repeatability is high, the reaction conditions are mild, the used reagents are cheap and nontoxic, and the method has potential application value. The method provided by the invention is also especially beneficial to the control on the etching efficiency by controlling the conditions such as the dosage of different surface-active agents, the dosage of acid, the dosage of the soluble copper salt, and the temperature of contact.
Description
Technical field
The present invention relates to a kind of processing method of nanometer rods, particularly, relate to a kind of processing method that can improve nanometer rods pattern.
Background technology
At present, the method that is widely used most synthetic gold nanorods is the growing method (Seed-mediated Growth) of the seed modulation of people's propositions such as Murphy, namely by regulating correlated response parameter if reactant concentration, seed concentration, kinds of surfactants etc. are to obtain the gold nanorods of different-shape and size.It is spherical (Carbo-Argibay that common the method starts the synthetic gold nanorods head obtaining from gold seeds, E., B.Rodriguez-Gonzalez, et al. (2010). " The crystalline structure of goldnanorods revisited:evidence for higher-index lateral facets. " Angew Chem Int EdEngl 49 (49): 9397-9400.), can be because certain deviation can not ensure nose shape uniformity for different operating personnel or the synthetic gold nanorods shape of different batches.In the time that in gold nanorods growth-promoting media, each reagent concentration changes, can change synthetic gold nanorods nose shape: while raising such as reductant concentration, the synthetic dog-bone gold nanorods of meeting (Gou, L.and C.J.Murphy (2005). " Fine-Tuningthe Shape of Gold Nanorods. " Chem.Mater17 (14): 3668-3672.).Also can affect the shape of final gold nanorods head by add other reaction reagents in gold nanorods growth-promoting media: such as the quick phase of growing at gold nanorods adds Na
2s, can make gold nanorods form rest on dumbbell shaped structure (Zweifel, D.A.and A.Wei (2005). " Sulfide-arrested growth of gold nanorods. " Chemistry of Materials17 (16): 4256-4261.).After gold nanorods is synthetic, can gold nanorods nose shape be changed to some extent by the regrowth process in later stage.In regrowth process, can be by regulating pH value and surfactant softex kw (CTAB) concentration in regrowth liquid, obtaining head is spherical dumbbell shaped or cube gold nanorods (Sohn, K., F.Kim, et al. (2009). " Construction of Evolutionary Tree for Morphological Engineering ofNanoparticles. " Acs Nano3 (8): 2191-2198.), in regrowth liquid, add PVP and DMF can make gold nanorods head become pointed (Carbo-Argibay from spherical, E., B.Rodriguez-Gonzalez, et al. (2007). " Chemical sharpening of gold nanorods:therod-to-octahedron transition. " Angew Chem Int Ed Engl46 (47): 8983-8987.)., synthetic gold nanorods, do not carry out complicated regrowth process, and only gold nanorods head is reinvented to conversion for starting from gold kind, not yet report at present.
At present, for regulating long wave surface plasmon resonance absworption peak (LSPR) peak value of gold nanorods solution, generally obtain by regulating the draw ratio of gold nanorods or changing its pattern.Therefore the variation of LSPR peak position can reflect the change of gold nanorods draw ratio or pattern.Normally used method is the draw ratio that regulates gold nanorods: except change the concentration (Nikoobakht of reaction reagent in gold nanorods building-up process in early stage, B.and M.A.El-Sayed (2003). " Preparation and GrowthMechanism of Gold Nanorods (NRs) Using Seed-Mediated Growth Method. " Chem.Mater 15:1957-1962.), can also process synthetic gold nanorods by the later stage, comprise anisotropy oxide etch and horizontal two kinds of methods of regrowth.Conventional lithographic method comprises heat or LASER HEATING (Link, S., C.Burda, et al. (2000). " Laser-Induced Shape Changes ofColloidal Gold Nanorods Using Femtosecond and Nanosecond Laser Pulses. " J.Phys.Chem.B 104:6152-6163.), cyanide (Jana, N.R., L.Gearheart, et al. (2002). " Anisotropic Chemical Reactivity of Gold Spheroids and Nanorods. " Langmuir18:922-927.) or trivalent gold dissolving (Rodr í guez-Fern á ndez, J., J.P é rez-Juste, et al. (2005). " Spatially-Directed Oxidation of Gold Nanoparticles by Au (III)-CTABComplexes. " The Journal of Physical Chemistry B 109 (30): 14257-14261.), other various oxidants, such as oxygen (Tsung, C.-K., X.Kou, et al. (2006). " SelectiveShortening of Single-Crystalline Gold Nanorods by Mild Oxidation. " J.AM.CHEM.SOC.128:5352-5353.), hydrogen peroxide (Ni, W., X.Kou, et al. (2008). " Tailoring Longitudinal Surface Plasmon Wavelengths, Scattering and AbsorptionCross Sections of Gold Nanorods. " Acs Nano 2 (4): 677 – 686, Bao, Z., Z.Sun, etal. (2011). " Transverse oxidation of gold nanorods assisted by selective endcapping of silver oxide. " Journal of Materials Chemistry 21 (31): 11537.), ferric ion (Zou, R., X.Guo, et al. (2009). " Selective etching of gold nanorods by ferricchloride at room temperature. " CrystEngComm 11 (2797): 2797 – 2803.) etc.The speed of etching process can embody in the variation of 400 nanometers absorption values (representing the amount of gold atom) from the variation of LSPR peak value and ultraviolet-visible spectrogram.
The etching gold nanorods of having reported at present or the method for other noble metals have some drawbacks: or not too homogeneous of pattern, or complicated operation (heat or LASER HEATING), or reagent poisonous (cyanide), or expensive (trivalent gold), or severe reaction conditions (oxygen, hydrogen peroxide).Rarely found compared with (as room temperature, low concentration solvent) method simple to operate, that agents useful for same is cheap, nontoxic under temperate condition.
Summary of the invention
The object of the present invention is to provide a kind of processing method of the 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 a kind of processing method of nanometer rods, the method is included under the existence of solvent, and 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, the present invention has realized the processing to various nanometer rods, obtained pattern more homogeneous nanometer rods or realized the etching of nanometer rods, the inventive method is simple to operate, the high and reaction condition gentleness of repeatability, agents useful for same non-toxic inexpensive, has potential using value.Method of the present invention is also particularly conducive to by the speed of the condition control etching such as consumption, the temperature of contact of the consumption of the consumption of control different surfaces activating agent, acid, soluble copper salt.
Especially, the present inventor has found the preferably transformation of copper ion to gold nanorods nose shape under acid condition first.In the preferred embodiment of the present invention, be respectively in bone-shaped, square or arrow shaped gold nanorods solution and add appropriate CTAB, copper ion and acid (selectively adding) toward nose shape, and be placed in and under the condition of 25-80 DEG C, within 0.25-20 hour, can obtain the gold nanorods that head is spherical pattern homogeneous.In addition, method of the present invention can also realize other noble metal structures as the etching of the shell in the nucleocapsid structures such as the silver nanoparticle shell taking gold nanorods as nucleus growth (Au@Ag), palladium nanoshells (Au@Pd) taking gold nanorods as nucleus growth.
Other features and advantages of the present invention are described in detail the detailed description of the invention part subsequently.
Brief description of the drawings
Accompanying drawing is to be used to provide a further understanding of the present invention, and forms a part for description, is used from explanation the present invention, but is not construed as limiting the invention with detailed description of the invention one below.In the accompanying drawings:
Fig. 1 is (A) and the processing images of transmissive electron microscope of (B) afterwards before bone-shaped gold nanorods solution being processed in the present invention, ultraviolet-visible absorption spectroscopy temporal evolution figure (C); And different CTAB (D), sulfuric acid (E), Cu
2+(F) concentration and temperature (G) LSPR peak value temporal evolution tendency chart in this processing;
Fig. 2 is that bone-shaped gold nanorods is at different condition: CTAB (A), sulfuric acid (B), Cu
2+(C) the ultraviolet-visible absorption spectroscopy figure of concentration and temperature (D) final state;
Fig. 3 (a before to be the inventive method process tack (a, b) and arrow shaped (c, d) gold nanorods head, c) with the ultraviolet-visible absorption spectroscopy figure (A) and transmission electron microscope picture (B, the C that process rear (b, d), D, E).The wherein line a-d in B-E corresponding A;
Fig. 4 is while there is not/exist copper ion, gold nanorods solution ultraviolet-visible absorption spectroscopy figure in the process of hydrogen peroxide etching gold nanorods: (A) for only adding acid and copper ion, (B) for only adding acid and hydrogen peroxide, (C) while acid adding, copper ion and hydrogen peroxide, (D) a in, b, c corresponds to A, B, C medium ultraviolet visible absorption spectra at the change curve of 450 nanometers absorption values (taking initial point value as zero point.Owing to adding the ion that gold atom is etched to after hydrogen peroxide can affect the absorption value of 400 nanometers in solution, so select the 450 nanometers absorption values alternative);
Fig. 5 is while there is not/exist copper ion, gold nanorods solution ultraviolet-visible absorption spectroscopy figure in the process of ferric ion etching gold nanorods: (A) for only adding acid and copper ion, (B) for only adding acid and ferric ion, (C) while acid adding, copper ion and ferric ion, (D) a in, b, c corresponds to A, B, C medium ultraviolet visible absorption spectra is at 400 nanometers absorption value change curves (taking initial point value as zero point);
When not there is not/exist copper ion in Fig. 6, in the process of hydrogen peroxide (A) and ferric ion (B) etching gold nanorods, gold nanorods solution ultraviolet-visible absorption spectroscopy figure is (taking peak position as X-axis, half-peak breadth (FWHM) is figure by Y-axis), (a) for only adding acid and copper ion, (b) for only adding acid and hydrogen peroxide or ferric ion, (c) while acid adding, copper ion and hydrogen peroxide or ferric ion;
Fig. 7 be in the present invention in the time processing different Au@Ag nucleocapsid structure, add the ultraviolet-visible spectrogram (A) after copper ion and acid reaction and add copper and acid before the images of transmissive electron microscope of (C) after (B), wherein, (A) in, Au NRs is original gold nanorods, a is not for adding any reagent, b is an acid adding, and c is for only adding copper ion, and d is acid adding and copper ion;
Fig. 8 be in the present invention in the time processing different Au@Pd nucleocapsid structure, add the ultraviolet-visible spectrogram (A) after copper ion and acid reaction and add copper and acid before the images of transmissive electron microscope of (C) after (B), wherein, (A) in, Au NRs is original gold nanorods, a is not for adding any reagent, b is an acid adding, and c is for only adding copper ion, and d is acid adding and copper ion.
Detailed description of the invention
Below the specific embodiment of the present invention is elaborated.Should be understood that, detailed description of the invention described herein only, for description and interpretation the present invention, is not limited to the present invention.
The processing method of nanometer rods provided by the invention is included under the existence of solvent, and 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 the conventional solvents that use in various this areas, for example water, preferably deionized water.
According to the present invention, with respect to the nanometer rods of every mole, the consumption of surfactant is preferably 4 × 10
7-4 × 10
8mol, more preferably 1.5 × 10
8-2.5 × 10
8mol.Described surfactant can be selected the conventional surfactant in this area, and under preferable case, described surfactant is softex kw.
With respect to the nanometer rods of every mole, the consumption of soluble copper salt is preferably 1 × 10
5-2 × 10
6mol, more preferably 1.5 × 10
5-3.5 × 10
5mol.Wherein, as long as described soluble copper salt solubility in water under room temperature (25 DEG C) is greater than 25g/100g water and can realizes object of the present invention, therefore, described soluble copper salt is preferably water-soluble mantoquita, more preferably, described soluble copper salt is one or more in copper chloride, copper sulphate and copper nitrate.
The present inventor's discovery, acid can make gold nanorods nose shape transform and noble metal structures etching more easily occurs, and speed is faster, and therefore preferably, described regulation and control reagent also contains acid.With pH meter, the consumption of described acid is preferably 2 × 10
7-4 × 10
8mol, more preferably 3.5 × 10
7-4.5 × 10
7mol.Described acid can be one or more in sulfuric acid, hydrochloric acid and nitric acid.
The present inventor finds, in the time that the surfactant adding, soluble copper salt and acid are in above-mentioned preferred scope, can transform gold nanorods nose shape within a short period of time, thereby further improve the uniformity of gold nanorods nose shape.Can also realize better the etching to other noble metal structures (as Au@Ag or Au@Pd) simultaneously.
In the present invention, the concentration of described gold nanorods in contact system is preferably 0.45-0.55nM.
According to the present invention, described nanometer rods is contacted and can realize object of the present invention with described regulation and control reagent, under preferable case, the condition of described contact comprises that temperature is 25-80 DEG C, the time is 0.25-20h.
According to the present invention, described nanometer rods can be one or more in gold nanorods, Au Ag nanometer rods and Au Pd nanometer rods.Especially, in the time that described nanometer rods is gold nanorods, can obtain by method of the present invention the gold nanorods that nose shape is spherical (pattern homogeneous).In the time that described nanometer rods is Au@Ag nanometer rods and Au@Pd nanometer rods, method of the present invention can realize the etching to nanometer rods preferably.
In the present invention, nanometer rods is had no particular limits with the order that each regulation and control reagent contacts, can carry out successively, also can carry out simultaneously.
In addition, in order to realize better the processing (particularly etching) of nanometer rods, method of the present invention can also comprise in contact system adds oxidant (as hydrogen peroxide and/or trivalent soluble ferric iron salt).Therefore, preferably, described regulation and control reagent also contains oxidant.The present inventor finds, other regulation and control reagent (surfactant and/or soluble copper salt) that use in oxidant and the inventive method have good synergy, the processing speed of the regulation and control reagent that use contains oxidant is faster, and the required processing time is obviously shorter.
Described oxidant can be realized the conventional oxidant adopting of etching for this area, but is preferably hydrogen peroxide and/or trivalent soluble ferric iron salt (as ferric nitrate).The present inventor's discovery, other regulation and control reagent used in the present invention and above-mentioned preferred oxidant have obviously better synergy.
Consumption to described oxidant also has no particular limits, and for example, with respect to the nanometer rods of every mole, the consumption of described oxidant can be 1 × 10
5-2 × 10
8mol.
Below will describe the present invention by embodiment.In following examples, agents useful for same is as follows: softex kw (Amresco), copper chloride (Chemical Reagent Co., Ltd., Sinopharm Group).According to ultraviolet-visible-near-infrared absorption spectrum figure and formula " E(energy)=h(Planck's constant) v(light frequency)=hc(the light velocity)/λ (light wavelength) " calculate corresponding energy value, the half-peak breadth at the peak obtaining is FWHM value, can react the size dispersion of gold nanorods.Ultraviolet-visible-near-infrared absorption spectrum is recorded 25-35 DEG C time by ultraviolet specrophotometer (Varian Cary 50, the U.S.); The length of gold nanorods and diameter are by transmission electron microscope (Tecnai G
220S-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 people's such as Murphy method, L.and C.J.Murphy (2005). " Fine-Tuning the Shape of Gold Nanorods. " Chem.Mater17 (14): 3668-3672.), the gold nanorods solution (concentration of gold nanorods is 0.5nM) of arrow shaped head obtains (Xiang with reference to the people's such as Xiang method, Y., X.Wu, et al. (2008). " Tuning the Morphology of Gold Nanocrystals by Switching the Growth of{110}Facets from Restriction to Preference. " The Journal of Physical Chemistry C112 (9): 3203-3208.), Au@Ag nanometer rods solution (concentration of nanometer rods is 0.5nM) and Au@Pd nanometer rods solution (concentration of nanometer rods is 0.5nM) obtain (Xiang with reference to the method in the people such as Xiang, Y., X.Wu, et al. (2008). " Gold Nanorod-Seeded Growth of Silver Nanostructures:From Homogeneous Coating to Anisotropic Coating. " Langmuir 24 (7): 3465-3470., Xiang, Y., X.Wu, et al. (2006). " Formation of Rectangularly ShapedPd-Au Bimetallic Nanorods:Evidence for Competing Growth of the Pd Shellbetween the{110}and{100}Side Facets of Au Nanorods. " Nano Letters 6 (10): 2290-2294.), after above sample is synthetic, turn by per minute 12000,5 minutes, the centrifugal deionized water of adding same volume of once returning, obtains the nanometer rods solution of purifying.
Embodiment 1
The bone-shaped gold nanorods solution per minute 12000 of getting 5 parts of 1mL purifying turns, 5 minutes centrifugal supernatants of once removing again, add respectively that concentration is 10,20,50,100, the softex kw solution 1mL of 200mM, add the copper chloride solution that sulfuric acid that 10 μ L concentration are 1M and 10 μ L concentration are 10mM wherein; Mix; Put into 30 DEG C of waters bath with thermostatic control, place respectively 49h, 49h, 27h, 10h, 5h; 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. 1 D, it shows that the inventive method increases with softex kw concentration the trend that LSPR peak position blue shift is accelerated to the regulation and control speed of gold nanorods nose shape, from the each condition of Fig. 2 A, uv absorption spectra can see that final state is basically identical, in the time that softex kw solution concentration is less than or equal to 20mM, reach in the 49h time change very little, get softex kw solution concentration while being 100mM sample final state transmission electron microscope characterize, result is as shown in Figure 1B.Based on this, utilize the present invention can be by changing the speed of softex kw concentration adjustment gold nanorods nose shape, can make to react and complete within a short period of time.
Embodiment 2
The bone-shaped gold nanorods solution per minute 12000 of getting 5 parts of 1mL purifying turns, and 5 minutes centrifugal more once removes supernatant, and to add 1mL concentration be the softex kw of 100mM and the copper chloride solution that 10 μ L concentration are 10mM; And to add respectively concentration be sulfuric acid solution 0,5,10,50,100, the 200 μ L of 1M, mix; Put into 30 DEG C of waters bath with thermostatic control, place respectively 25h, 10h, 10h, 10h, 10h, 10h; 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. 1 E, it shows that the inventive method increases LSPR peak position blue shift on the regulation and control speed of gold nanorods nose shape with sulfuric acid concentration and first accelerates the less trend of rear impact, from the each condition of Fig. 2 B, uv absorption spectra can see that final state is basically identical, in the time of anacidity, reach in the 25h time change very little, almost unchanged, when getting sulfuric acid concentration and being 10mM, sample final state transmission electron microscope characterizes, and result as shown in Figure 1B.Based on this, utilize the present invention also can regulate by changing sulfuric acid concentration the speed of gold nanorods nose shape.
Embodiment 3
The bone-shaped gold nanorods solution per minute 12000 of getting 5 parts of 1mL purifying turns, and 5 minutes centrifugal more once removes supernatant, and to add 1mL concentration be the softex kw of 100mM and the sulfuric acid solution that 10 μ L concentration are 1M; And to add respectively concentration be copper chloride solution 0,5,10,50, the 100 μ L of 10mM, mix; Put into 30 DEG C of waters bath with thermostatic control, place respectively that 25h is above, 10h, 10h, 7h, 7h; 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. 1 F, it shows that the inventive method increases with copper chloride concentration the trend that LSPR peak position blue shift is accelerated to the regulation and control speed of gold nanorods nose shape, from the each condition of Fig. 2 C, uv absorption spectra can see that final state is basically identical, when without copper, reach in the 25h time change very little, almost unchanged, get copper solution concentration while being 100 μ M sample final state transmission electron microscope characterize, result is as shown in Figure 1B.Based on this, utilize the present invention also can pass through to change the speed of copper chloride concentration adjustment gold nanorods nose shape.
Embodiment 4
The bone-shaped gold nanorods solution per minute 12000 of getting 5 parts of 1mL purifying turns, 5 minutes centrifugal more once removes supernatant, and to add 1mL concentration be the copper chloride solution that the softex kw of 100mM and sulfuric acid solution that 10 μ L concentration are 1M and 10 μ L concentration are 10mM; And mix and put in water-bath; Bath temperature is respectively 30 DEG C, 40 DEG C, 50 DEG C, 60 DEG C, 80 DEG C, places respectively 10h, 3h, 100min, 50min, 12min.
The time dependent result of LSPR is as shown in Fig. 1 F, it shows the trend that the inventive method is accelerated with temperature rising LSPR peak position blue shift the regulation and control speed of gold nanorods nose shape, from the each condition of Fig. 2 D, uv absorption spectra can see that final state is basically identical, while getting 30 DEG C, sample final state characterizes with transmission electron microscope, and result as shown in Figure 1B.Based on this, utilize the present invention can also regulate by changing reaction temperature the speed of gold nanorods nose shape.
As known from the above, the transforming agent that affects gold nanorods nose shape comprises CTAB, acidity, copper ion and temperature, and solvent strength increases and reaction temperature raises can accelerate the conversion rate of nose shape.Can see that from transmission electron microscope picture former bone-shaped gold nanorods transforms the gold nanorods that has obtained spherical head shape through above method.We are chosen in relatively mild condition and carry out above reaction, therefore select the bath temperature that approaches room temperature to react, to sum up, optimal conditions is: softex kw is 100mM, the concentration 10mM of sulfuric acid solution, and the concentration of copper chloride solution is 100 μ M, 30 DEG C of water-baths, place about 10h.
It can also be seen that in the absorption value of 400 nanometers and decrease 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 in storage by oxygen eremacausis, therefore this phenomenon explanation copper ion and adding of acid have accelerated gold nanorods by the process of oxygen etching.
Embodiment 5
Get the each 1mL of gold nanorods solution square, arrow shaped head, per minute 12000 turn, 5 minutes centrifugal supernatants of once removing again, adding separately 1mL concentration is the softex kw of 100mM, the copper chloride solution that the sulfuric acid that 10 μ L concentration are 1M and 10 μ L concentration are 10mM; And mix; Put into 30 DEG C of about 10h of water bath with thermostatic control; In described mixed solution, the mol ratio of softex kw, sulfuric acid, copper chloride and gold nanorods is 1:0.1:0.001:0.000000005;
Fig. 3 is ultraviolet-visible absorption spectroscopy figure (A) and the transmission electron microscope picture (B, C, D, E) of (a, c) rear (b, d) before the gold nanorods head of different head shape in embodiment 5 transforms.LSPR peak position blue shift from ultraviolet-visible absorption spectroscopy figure transforms, illustrates that gold nanorods nose shape or draw ratio change, and from transmission electron microscope picture, the gold nanorods of former synthetic different head shape has been converted into spherical by method of the present invention.
Embodiment 6
Get three test tubes, add separately 1mL gold nanorods solution per minute 12000 to turn, 5 minutes centrifugal more once removes that to add isopyknic concentration after supernatant be the softex kw of 100mM, adding 2.0mL concentration is the softex kw solution of 100mM and the sulfuric acid that 15 μ L concentration are 1M again, adds respectively the copper chloride solution that hydrogenperoxide steam generator that 30 μ L concentration are 1M, copper chloride solution that 9 μ L concentration are 10mM, hydrogenperoxide steam generator that 30 μ L concentration are 1M and 9 μ L concentration are 10mM in three test tubes again; Then above-mentioned each solution is mixed, put into 30 DEG C of waters bath with thermostatic control.In described the 3rd test tube, the mol ratio of softex kw, sulfuric acid, copper chloride, hydrogen peroxide and the gold nanorods of mixed solution is respectively 1:0.05:0.0003:0.1:0.00000000167;
Get three test tubes, add separately 1mL gold nanorods solution per minute 12000 to turn, 5 minutes centrifugal more once removes that to add equal-volume concentration after supernatant be the softex kw of 100mM and the sulfuric acid that 10 μ L concentration are 1M, adds respectively the iron nitrate solution that iron nitrate solution that 10 μ L concentration are 100mM, copper chloride solution that 10 μ L concentration are 100mM, copper chloride solution that 10 μ L concentration are 100mM and 10 μ L concentration are 100mM in three test tubes again; Then above-mentioned solution is mixed, put into 30 DEG C of waters bath with thermostatic control; In described the 3rd test tube, the mol ratio of softex kw, sulfuric acid, copper chloride, ferric nitrate and the gold nanorods of mixed solution is respectively 1:0.1:0.01:0.01:0.000000005.
Fig. 4 and Fig. 5 when not existing or have copper ion, gold nanorods solution uv absorption spectra in the process of hydrogen peroxide and ferric ion etching gold nanorods.In the time only adding acid and copper ion (A), gold nanorods is had to certain corrasion, and (C) when only adding hydrogen peroxide or ferric ion (B) obviously accelerates the corrasion of gold nanorods while adding hydrogen peroxide or ferric ion simultaneously, therefore acid and copper ion add the process of greatly having accelerated hydrogen peroxide or ferric ion etching gold nanorods, from (D), can see add after copper ion larger with changing value sum (B) than simple (A), illustrate that this process is accelerated, can find out that from ultraviolet-visible-near-infrared absorption spectrum figure gold nanorods solution changes the characteristic peak (being shortwave surface plasmon resonance absworption peak and long wave surface plasmon resonance absworption peak) that also keeps gold nanorods etching process.As seen from Figure 6, while obtaining different gold nanorods by etching process, in same peak position, add acid less with half-peak breadth after copper ion or almost consistent when only adding hydrogen peroxide or ferric ion etching, therefore the size dispersion of gold nanorods does not have variation, even can obtain improvement to a certain extent.As known from the above, the inventive method is for existing conventional gold nanorods etching agent (oxygen, hydrogen peroxide, ferric ion), adding of acid and copper ion can be worked in coordination with auxiliary its effect well, and can improve to a certain extent the size dispersion of gold nanorods.
Embodiment 7
Get Au@Ag, the each 1mL of Au@Pd nanometer rods solution, per minute 12000 turn, 5 minutes centrifugal supernatants of once removing again, the softex kw that to add equal-volume concentration be 100mM, all adds the copper chloride solution that sulfuric acid that 10 μ L concentration are 1M and 10 μ L concentration are 10mM wherein; Then above-mentioned solution is mixed; Put into 30 DEG C of about 10h of water bath with thermostatic control; In described mixed solution, the mol ratio of softex kw, sulfuric acid, copper chloride and Au@Ag or Au@Pd nanometer rods is 1:0.1:0.001:0.000000005;
Fig. 7 and Fig. 8 are to adding different reagent reactings front and back ultraviolet-visible absorption spectroscopy figure (A) in different noble metal nucleocapsid structures and adding the images of transmissive electron microscope (B, C) before and after acid and copper ion in embodiment 7.From ultraviolet-visible spectrogram, we can see, add acid and copper ion after larger on the impact of ultra-violet absorption spectrum, while only adding acid, almost do not change, less than the variation of while acid adding and copper ion while only adding copper ion, thus acid and copper ion add the etching of effectively having accelerated noble metal shell, also can illustrate by transmission electron microscope picture.
As from the foregoing, utilize the pattern homogeneous of the nanometer rods that the inventive method processing obtains, simple to operate, the high and reaction condition gentleness of repeatability, agents useful for same non-toxic inexpensive; The inventive method can also be worked in coordination with and be accelerated the etching of existing etching agent to gold nanorods, and can other noble metal core-shell nano structures of auxiliary etch, has larger potential using value.
Below describe by reference to the accompanying drawings the preferred embodiment of the present invention in detail; but; the present invention is not limited to the detail in above-mentioned embodiment; within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each concrete technical characterictic described in above-mentioned detailed description of the invention, in reconcilable situation, can combine by any suitable mode, for fear of unnecessary repetition, the present invention is to the explanation no longer separately of various possible combinations.
In addition, between various embodiment of the present invention, also can be combined, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (10)
1. a processing method for nanometer rods, is characterized in that, the method is included under the existence of solvent, and nanometer rods is contacted with regulation and control reagent, and described regulation and control reagent contains surfactant and soluble copper salt.
2. method according to claim 1, wherein, with respect to the nanometer rods of every mole, the consumption of described surfactant is 4 × 10
7-4 × 10
8mol, the consumption of described soluble copper salt is 1 × 10
5-2 × 10
6mol.
3. method according to claim 1 and 2, wherein, described surfactant is softex kw; Described soluble copper salt is one or more in copper chloride, copper sulphate and copper nitrate.
4. method according to claim 1, wherein, described regulation and control reagent also contains acid, and with pH meter, the consumption of described acid is 2 × 10
7-4 × 10
8mol.
5. method according to claim 4, wherein, described acid is one or more in sulfuric acid, hydrochloric acid and nitric acid.
6. method according to claim 1, wherein, the concentration of described nanometer rods in contact system is 0.45-0.55nM.
7. method according to claim 1, wherein, the condition of described contact comprises: temperature is 25-80 DEG C, the time is 0.25-20h.
8. according to the method described in any one in claim 1-7, wherein, described nanometer rods is one or more in gold nanorods, Au@Ag nanometer rods and Au@Pd nanometer rods.
9. method according to claim 8, wherein, described regulation and control reagent also contains oxidant.
10. method according to claim 1, wherein, described solvent is water.
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