CN103506629A - Gold nanorod vertical array and preparing method thereof - Google Patents
Gold nanorod vertical array and preparing method thereof Download PDFInfo
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- CN103506629A CN103506629A CN201210206173.XA CN201210206173A CN103506629A CN 103506629 A CN103506629 A CN 103506629A CN 201210206173 A CN201210206173 A CN 201210206173A CN 103506629 A CN103506629 A CN 103506629A
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Abstract
The invention discloses a preparing method of a gold nanorod vertical array and the gold nanorod vertical array obtained through the preparing method. The preparing method comprises the steps that first, a water solution of a gold nanorod decorated by trimethyl cetyl ammonium bromide is prepared, centrifugal redissolving treatment is conducted, the concentration of the trimethyl cetyl ammonium bromide in the water solution is made to be 5-20 umol/L, and the concentration of the gold nanorod is 0.5-2nmol/L; second, the mixed liquid of monohydric alcohol with the carbon number being 1-3 and alkyl hydrosulfide with the carbon number being 9-12 is in contact with the water solution obtained in the first step; third, chloroform and/or dichloroethane are/is mixed with the mixed liquid obtained in the second step, the mixed liquid is stood, and the gold nanorod vertical array is obtained. According to the preparing method of the gold nanorod vertical array, the millimeter-graded super-large scale gold nanorod vertical array with the ordered array structure can be obtained, and the advantages that operating is easy, conditions are moderate, the structural uniform is high and the like are achieved.
Description
Technical field
The present invention relates to a kind of gold nanorods orthogonal array and preparation method thereof.
Background technology
Gold nano stick array possesses the optical characteristics that shape is relevant and the aggregating characteristic that plasma resonance coupling brings to each other, and the regular array of its periodicity is widely used in fields such as high sensitive sensor, solar cell, information storage, optoelectronic devices.
In prior art, the method for preparing gold nano stick array is mainly that after solvent evaporates is complete, remaining gold nanorods forms gold nano stick array on substrate by gold nanorods solution is dripped on substrate.But, the gold nano stick array small scale (below tens microns) that this method obtains, structure intersperses among on substrate discontinuous, cannot locate, and presents on the whole unordered state.
Summary of the invention
The object of the invention is to overcome the gold nano stick array small scale (below tens microns) obtaining by existing method, and the shortcoming that presents on the whole unordered state, a kind of preparation method of new gold nanorods orthogonal array is provided, and the gold nanorods orthogonal array obtaining by the method.Adopt method provided by the invention, not only can obtain the gold nanorods orthogonal array that grade is ultra-large and array structure is regular, but also there is all advantages of higher once of easy operating, mild condition, structure.
The present inventor is through research discovery repeatedly, the aqueous solution of the gold nanorods that trimethyl cetyl ammonium bromide is modified is processed by centrifugal redissolution, make the concentration of trimethyl cetyl ammonium bromide in the described aqueous solution and gold nanorods after specific scope, the mixed liquor of the alkyl hydrosulfide that the monohydric alcohol that is 1-3 with carbon number is 9-12 with carbon number contacts, and then after mixing with chloroform and/or dichloroethanes, by the standing gold nanorods vertical array that can obtain compound with regular structure and ultra-large (millimeter rank) on the surface of water, thereby completed the present invention.
That is, the invention provides a kind of preparation method of gold nanorods orthogonal array, wherein, the method comprises the following steps:
1) prepare the aqueous solution of the gold nanorods of trimethyl cetyl ammonium bromide modification, and process by centrifugal redissolution, making the concentration of the trimethyl cetyl ammonium bromide in the described aqueous solution is 5-20umol/L, and the concentration of gold nanorods is 0.5-2nmol/L;
2) monohydric alcohol that is 1-3 by carbon number and carbon number are the mixed liquor of the alkyl hydrosulfide of 9-12, and the described aqueous solution obtaining with step 1) contacts;
3) by chloroform and/or dichloroethanes and step 2) after the mixed liquor that obtains mixes, and standing, obtain gold nanorods orthogonal array.
The present invention also provides a kind of gold nanorods orthogonal array being prepared by said method.
According to the preparation method of gold nanorods orthogonal array provided by the invention, not only can obtain the gold nanorods orthogonal array that grade is ultra-large and array structure is regular, but also there is all advantages of higher once of easy operating, mild condition, structure.
In addition, the gold nano stick array obtaining due to the present invention has advantages of scale greatly and compound with regular structure, in fields such as photoelectric device, sensor, information storages, is with a wide range of applications.Especially there is uniform two-dimensional structure, be particularly suitable for preparing thin-film device as solar cell and the device compound with two-dimentional functional materials such as Graphenes.And, also possess very large potentiality realizing trace quantitative detection field by surface-enhanced Raman effects.
Accompanying drawing explanation
Fig. 1 is the electron scanning micrograph (overlooking photo) of the gold nanorods orthogonal array that obtains of embodiment 1;
Fig. 2 is the electron scanning micrograph (side-looking photo) of the gold nanorods orthogonal array that obtains of embodiment 1;
The X-ray powder diffraction figure that Fig. 3 a is the gold nanorods orthogonal array that obtained by embodiment 1, Fig. 3 b is the AuXRD powder crystal diffraction spectra of drawing from XRD powder crystal diffraction standard P DF card base.
The specific embodiment
Below the specific embodiment of the present invention is elaborated.Should be understood that, the specific embodiment described herein only, for description and interpretation the present invention, is not limited to the present invention.
According to the preparation method of gold nanorods orthogonal array of the present invention, comprise:
1) prepare the aqueous solution of the gold nanorods of trimethyl cetyl ammonium bromide modification, and process by centrifugal redissolution, making the concentration of the trimethyl cetyl ammonium bromide in the described aqueous solution is 5-20umol/L, and the concentration of gold nanorods is 0.5-2nmol/L;
2) monohydric alcohol that is 1-3 by carbon number and carbon number are the mixed liquor of the alkyl hydrosulfide of 9-12, and the described aqueous solution obtaining with step 1) contacts;
3) by chloroform and/or dichloroethanes and step 2) after the mixed liquor that obtains mixes, and standing, obtain gold nanorods orthogonal array.
According to the present invention, the described method of preparing the aqueous solution of the gold nanorods that trimethyl cetyl ammonium bromide modifies can adopt the conventional method of ability to carry out.For example can adopt seed mediated growth method to prepare, the steps include: that (1) by adding the tetra chlorauric acid aqueous solution in the softex kw aqueous solution, then under the condition stirring, add sodium borohydride and/or the potassium borohydride aqueous solution, continue to stir 3-5min, standing 2-5h makes the seed solution of gold nano grain, wherein, the mol ratio of softex kw, sodium borohydride and/or potassium borohydride and tetra chlorauric acid is 295-305:2.2-2.5:1.(2) seed solution of gold nano grain is mixed with gold nanorods growth solution, will mix gained mixture and be placed under the condition of growth of seed of gold nano grain so that the seed growth of described gold nano grain obtain gold nanorods.Described gold nanorods growth solution contains trimethyl cetyl ammonium bromide, ascorbic acid, tetra chlorauric acid and silver nitrate.In this step, can regulate by controlling the silver nitrate of described gold nanorods growth solution length and the diameter ratio of nanometer rods.Wherein, the seed of the gold nano grain with respect to every mole, the addition of described trimethyl cetyl ammonium bromide, ascorbic acid, tetra chlorauric acid and silver nitrate can be 125000-208334mol, 920-1334mol, 831-835mol and 33-250mol.
In addition, in the seed solution of described gold nano grain, the concentration of the seed of gold nano grain is preferably 0.2-0.3mmol/L.In described mixture, the concentration of described silver nitrate is preferably 30-50 μ mol/L.The condition of the growth of the seed of described gold nano grain comprises that temperature is 25-35 ℃, and the time is 12-16h.
According to the present invention, in the aqueous solution of the gold nanorods that the trimethyl cetyl ammonium bromide obtaining by said method is modified, the concentration of trimethyl cetyl ammonium bromide is generally 0.05-0.2mol/L, outside scope of the presently claimed invention, therefore, need in the present invention the aqueous solution of the gold nanorods of the trimethyl cetyl ammonium bromide modification to preparing to carry out centrifugal redissolution processing, making the concentration of the trimethyl cetyl ammonium bromide in the described aqueous solution is 5-20umol/L, and the concentration of gold nanorods is 0.5-2nmol/L; In preferred situation, making the concentration of the trimethyl cetyl ammonium bromide in the described aqueous solution is 10-15umol/L, and the concentration of gold nanorods is 1-1.5nmol/L.In the present invention, in order to guarantee in subsequent step, alkyl hydrosulfide can replace the trimethyl cetyl ammonium bromide being originally adsorbed on gold nanorods smoothly, the concentration of the trimethyl cetyl ammonium bromide in the described aqueous solution need to be remained in the scope of 5-20umol/L.If the concentration of the trimethyl cetyl ammonium bromide in the described aqueous solution is during lower than 5umol/L, it is stable that gold nanorods can not keep, and irreversible reunion can occur, thereby cause subsequent step to carry out; If the concentration of the trimethyl cetyl ammonium bromide in the described aqueous solution is during higher than 20umol/L, the stability of gold nanorods is excessively strong, makes the mercaptan that subsequent step adds cannot carry out enough replacements, thereby causes cannot obtaining being orientated consistent regular array.And, in the present invention, the concentration of the gold nanorods in the described aqueous solution also needs the concentration of the gold nanorods in the described aqueous solution to remain in the scope into 0.5-2nmol/L, if during lower than 0.5nmol/L, can cause obtaining enough non-reunion gold nanorods and separate out at the water surface; If the concentration of the gold nanorods in the described aqueous solution during higher than 2nmol/L, can cause ligand modified efficiency low and cannot form regular arrangement after separating out.
In the present invention, the concentration of the trimethyl cetyl ammonium bromide in the described aqueous solution refers to the trimethyl cetyl ammonium bromide being dissolved in the aqueous solution and modifies in the total concentration of the trimethyl cetyl ammonium bromide of gold nanorods.
According to the present invention, centrifugal redissolution processing described in step 1) refers to carries out high speed centrifugation by the described aqueous solution of preparing the gold nanorods of trimethyl cetyl ammonium bromide modification, thereby make gold nanorods be deposited to the bottom of centrifuge tube, then the solution that contains trimethyl cetyl ammonium bromide and precipitation are carried out separatedly, then will precipitate water and dissolve.There is no particular limitation for the number of times that described centrifugal redissolution is processed, and in the solution that only can make to obtain after final water dissolving, the concentration of described trimethyl cetyl ammonium bromide is 5-20umol/L, and the concentration of gold nanorods is 0.5-2nmol/L.Under preferable case, the number of times that centrifugal redissolution is processed is 2-3 time.In addition, the consumption of water is identical with the volume of the aqueous solution of the described gold nanorods of preparing the modification of trimethyl cetyl ammonium bromide during centrifugal redissolve.
In the present invention, to described centrifugal condition, there is no particular limitation, as long as can make gold nanorods fully precipitate and can again disperse.Under preferable case, above-mentioned centrifugal speed is 10000-15000rpm/min; The above-mentioned centrifugal time is 3-6 minute.
According to the present invention, step 2) in, the temperature of contact can be 15-40 ℃, the time of contact can be 2-10min; Under preferable case, the temperature of contact is 20-35 ℃, and the time of contact is 3-5min.Preferred described contact is under agitation carried out, to the speed of described stirring, there is no particular limitation, as long as can make carbon number is the monohydric alcohol of 1-3 and the mixed liquor of the alkyl hydrosulfide that carbon number is 9-12, the described aqueous solution obtaining with step 1) evenly.
According to the present invention, step 2) in, the monohydric alcohol that is 1-3 by carbon number and carbon number are the mixed liquor of the alkyl hydrosulfide of 9-12, and the mode that the described aqueous solution obtaining with step 1) contacts is preferably: the mixed liquor of the alkyl hydrosulfide that the monohydric alcohol that is 1-3 by carbon number and carbon number are 9-12 drips or joins in batches in the described aqueous solution that step 1) obtains.The monohydric alcohol that is 1-3 by carbon number and carbon number are that the mixed liquor of the alkyl hydrosulfide of 9-12 while joining in the described aqueous solution that step 1) obtains in batches, preferably a minute 2-3 criticizes and adds, every batch of amount adding can be the same or different, but is preferably identical.The monohydric alcohol that is 1-3 by carbon number and carbon number are the mixed liquor of the alkyl hydrosulfide of 9-12 while being added drop-wise in the described aqueous solution that step 1) obtains, and the volume of the described aqueous solution that its rate of addition can obtain according to the volume of reactor, step 1) and the volume that drips solution are suitably selected.With respect to the reactor of 10 milliliters, 0.6 times that the volume of the described aqueous solution that described step 1) obtains and the volume sum that drips solution are reactor below volume, rate of addition is 1-2000 mul/min; More preferably rate of addition be 5-500 mul/min reactor volume/minute.
According to the present invention, the mixed proportion of the alkyl hydrosulfide that the monohydric alcohol that described carbon number is 1-3 and carbon number are 9-12 can change in wide scope.Generally, the monohydric alcohol that described carbon number is 1-3 is 1-9:1 with the mixed volume ratio of the alkyl hydrosulfide that carbon number is 9-12; Under preferable case, the monohydric alcohol that described carbon number is 1-3 is 2-8:1 with the mixed volume ratio of the alkyl hydrosulfide that carbon number is 9-12.
The volume of the described aqueous solution that the consumption of the monohydric alcohol that the alkyl hydrosulfide that in the present invention, described carbon number is 9-12 and described carbon number are 1-3 can obtain according to step 1) is suitably selected.Generally, described carbon number is that the alkyl hydrosulfide of 9-12 and the volume ratio of the described aqueous solution that described step 1) obtains can be 0.01-0.02:1, and the volume ratio of the described aqueous solution that the monohydric alcohol that described carbon number is 1-3 and described step 1) obtain can be 0.04-0.08:1; Under preferable case, the volume ratio of the described aqueous solution that the alkyl hydrosulfide that described carbon number is 9-12 and described step 1) obtain is 0.015-0.02:1; Described carbon number is that the monohydric alcohol of 1-3 and the volume ratio of the described aqueous solution that described step 1) obtains are 0.05-0.07:1.In the present invention, the volume ratio of the described aqueous solution that the alkyl hydrosulfide that need to be 9-12 by described carbon number and described step 1) obtain remains in the scope of 0.01-0.02:1, if the volume ratio of the described aqueous solution that the alkyl hydrosulfide that described carbon number is 9-12 and described step 1) obtain, lower than 0.01 o'clock, can cannot form regular array after gold nanorods is separated out; If the volume ratio of the described aqueous solution that the alkyl hydrosulfide that described carbon number is 9-12 and described step 1) obtain, higher than 0.02 o'clock, causes obtaining gold nanorods orthogonal array thereby reactant liquor can form emulsion.And, in the present invention, the volume ratio of the described aqueous solution that the monohydric alcohol that also to need described carbon number be 1-3 and described step 1) obtain remains in the scope of 0.04-0.08:1, if the volume ratio of the described aqueous solution that the monohydric alcohol that described carbon number is 1-3 and described step 1) obtain was lower than 0.04 o'clock, gold nanorods will be difficult to separate out to water surface; If the volume ratio of the described aqueous solution that the monohydric alcohol that described carbon number is 1-3 and described step 1) obtain, higher than 0.8 o'clock, can cause irreversible reunion.
In the present invention, step 2) in, the monohydric alcohol that described carbon number is 1-3 is selected from one or more in methyl alcohol, ethanol and propyl alcohol; Be preferably ethanol.Described carbon number is that the alkyl hydrosulfide of 9-12 is one or more in nonyl mercaptan, decyl mercaptan, undecyl mercaptan and lauryl mercaptan; Be preferably undecyl mercaptan and/or lauryl mercaptan.
According to the present invention, step 3) comprises: by chloroform and/or dichloroethanes and step 2) mixed liquor that the obtains steps A of mixing; And by mixed solution left standstill, obtain the step B of gold nanorods orthogonal array.
In described steps A, described mixing can impel the gold in mixed liquor fully to separate out, and generally, in temperature, is at 15-40 ℃, to mix 8-40min can meet above-mentioned requirements; In preferred situation, in temperature, be to mix 10-30min at 20-35 ℃.Preferred described mixing is undertaken by stirring, and to the speed of described stirring, there is no particular limitation, as long as can impel the gold in mixed liquor to separate out.
In described step B, the standing time can be 5-48h; Be preferably 10-24h.
In addition, in step 3), the consumption of described chloroform and dichloroethanes can be according to described rapid 2) volume of the mixed liquor that obtains suitably selects.Under preferable case, the cumulative volume of described chloroform and dichloroethanes and described step 2) volume ratio of the mixed liquor that obtains is 0.8-1.2:1; More preferably the cumulative volume of described chloroform and dichloroethanes and described step 2) volume ratio of the mixed liquor that obtains is 0.9-1.1:1.
It is to be noted: when only by a kind of and step 2 in chloroform and dichloroethanes) mixed liquor that obtains is when mix, the cumulative volume of described chloroform and dichloroethanes refers to used chloroform or the volume of dichloroethanes, when using chloroform and dichloroethanes, the cumulative volume of described chloroform and dichloroethanes refers to the total volume of the volume of chloroform and the volume of dichloroethanes simultaneously.
The present invention also provides a kind of gold nanorods orthogonal array being prepared by said method.
According to the present invention, in described gold nanorods orthogonal array, the diameter of gold nanorods is 12-25 nanometer, and the rod length of gold nanorods is 45-80 nanometer, and interrod spacing is 1-3 nanometer; Under preferable case, in described gold nanorods orthogonal array, the diameter of gold nanorods is 16-19 nanometer, and the rod length of gold nanorods is 60-70 nanometer, and interrod spacing is 1.5-2 nanometer.
In addition, in described gold nanorods orthogonal array, the ratio of vertical orientated gold nanorods is more than 85%, to be preferably more than 90%.The ratio of described vertical orientated gold nanorods refers to the ratio of gold nanorods vertical orientated in described gold nanorods orthogonal array and all gold nanorods.
Below will describe the present invention by embodiment, but the present invention is not limited to following embodiment.
Centrifugal employing table model high speed centrifuge (XiangYi H-1650) in following examples; Scanning transmission electron microscope photo adopts cold field emission scanning electron microscope (Hitachi S4800) to obtain; Fig. 3 a adopts X-ray diffractometer (D/MAX-TTRIII (CBO)) to obtain.
In following examples, the aqueous solution of the gold nanorods that the trimethyl cetyl ammonium bromide using is modified adopts seed mediated growth method to obtain: (1) by adding the tetra chlorauric acid aqueous solution in the softex kw aqueous solution, then under the condition stirring, add sodium borohydride and/or the potassium borohydride aqueous solution, continue to stir 5min, standing 5h makes the seed solution of gold nano grain, wherein, the mol ratio of softex kw, sodium borohydride and/or potassium borohydride and tetra chlorauric acid is 400:2.4:1.(2) seed solution of gold nano grain (in the seed solution of described gold nano grain gold concentration be 0.3mmol/L) is mixed with gold nanorods growth solution, mixing gained mixture is placed under the condition of growth of seed of gold nano grain so that the seed growth of described gold nano grain obtains gold nanorods.Described gold nanorods growth solution contains trimethyl cetyl ammonium bromide, ascorbic acid, tetra chlorauric acid and silver nitrate.Wherein, with respect to the gold of every mole, the addition of described trimethyl cetyl ammonium bromide, ascorbic acid, tetra chlorauric acid and silver nitrate can be 35000mol, 200mol, 200mol and 7-35mol; In described mixture, the concentration of described silver nitrate is 20-100 μ mol/L; The temperature of the growth of the seed of described gold nano grain is 30 ℃, time is 4h, the concentration that obtains trimethyl cetyl ammonium bromide is 0.1mol/L, the aqueous solution of the gold nanorods that the trimethyl cetyl ammonium bromide that the concentration of gold nanorods is 1-2nmol/L is modified.
In following examples, the ratio of described vertical orientated gold nanorods refers to the ratio of gold nanorods vertical orientated in described gold nanorods orthogonal array and all gold nanorods.In gold nanorods, perpendicular to the crystal face of long axis direction, be (200) crystal face, by the relative intensity of XRD determining (200) crystal face diffraction maximum, calculate the ratio of vertical orientated gold nanorods in overall.
Embodiment 1
1) concentration of getting the aqueous solution 1mL(trimethyl cetyl ammonium bromide of the gold nanorods that trimethyl cetyl ammonium bromide modifies is 0.1mol/L, the concentration of gold nanorods is 1nmol/L), in table model high speed centrifuge with the speed of 12000rpm/min after centrifugal 4 minutes, isolate precipitation, then use the abundant dissolution precipitation of water of 1mL, again with identical condition carry out centrifugal after, water dissolution precipitation with 1mL, the concentration that obtains trimethyl cetyl ammonium bromide is 10umol/L, and the concentration of the gold nanorods aqueous solution that is 1nmol/L.
2) in temperature, be under 25 ℃, the mixing speed condition that is 700rpm/min, the aqueous solution obtaining in the step 1) of 1mL is joined in the vial of 10mL, and splash into mixed liquor (volume ratio of ethanol and undecyl mercaptan the is 50:15) 65uL of ethanol and undecyl mercaptan, continue to stir 3min; Then at the same temperature, mixing speed is changed to 300rpm/min, and add 1mL chloroform, stir after 30 minutes and stop stirring, and after standing 12 hours, on water surface, obtain gold nanorods orthogonal array (circular array, diameter is 5mm).
Known by scanning transmission electron microscope photo Fig. 1 and Fig. 2, in this gold nanorods orthogonal array, the diameter of gold nanorods is about 18 nanometers, and it is 65 nanometers that the rod of gold nanorods is about, and interrod spacing is 1.5 nanometers.
The X-ray powder diffraction figure that Fig. 3 a is the gold nanorods orthogonal array that obtained by the present embodiment, Fig. 3 b is the XRD powder crystal diffraction spectra (being the X-ray powder diffraction figure of standard A u powder crystal) of Au, it draws the card base from XRD powder crystal diffraction standard P DF, card number: 00-001-1174, and calculate in this gold nanorods orthogonal array by following formula, the ratio a of vertical orientated gold nanorods is 95%;
A=(1-I
standard/ I
sample) * 100%, wherein, I
sample=I
200/ I
111, I
200for the Relative Peak of the diffraction maximum of crystal face (200) (vertical orientated) strong; I
111for the Relative Peak of the diffraction maximum of crystal face (111) (tilted alignment) strong.
Embodiment 2
1) concentration of getting the aqueous solution 2mL(trimethyl cetyl ammonium bromide of the gold nanorods that trimethyl cetyl ammonium bromide modifies is 0.1mol/L, the concentration of gold nanorods is 1.2nmol/L), in table model high speed centrifuge with the speed of 12000rpm/min after centrifugal 4 minutes, isolate precipitation, then use the abundant dissolution precipitation of water of 2mL, again with identical condition carry out centrifugal after, water dissolution precipitation with 2mL, the concentration that obtains trimethyl cetyl ammonium bromide is 13umol/L, and the concentration of the gold nanorods aqueous solution that is 1.5nmol/L.
2) in temperature, be under 25 ℃, the mixing speed condition that is 900rpm/min, the aqueous solution obtaining in the step 1) of 2mL is joined in the vial of 10mL, the mixed liquor of ethanol and lauryl mercaptan (volume ratio of ethanol and lauryl mercaptan is 80:20) 200uL is added at twice, the amount at every turn adding is identical, and adds rear stirring 2min at every turn; Then at the same temperature, mixing speed is changed to 400rpm/min, and add 1.8mL chloroform, stir after 20 minutes and stop stirring, and after standing 24 hours, on water surface, obtain gold nanorods orthogonal array (circular array, diameter is 4mm).
Known by scanning transmission electron microscope photo, in this gold nanorods orthogonal array, the diameter of gold nanorods is 19 nanometers, and the rod length of gold nanorods is 70 nanometers, and interrod spacing is 1.5 nanometers; In addition, by X-ray powder diffraction figure, the diffraction maximum of crystal face (200) (vertical orientated) and the diffraction maximum of crystal face (111) (tilted alignment) only detected.By calculating the ratio of vertical orientated gold nanorods, be 90%.
Embodiment 3
1) concentration of getting the aqueous solution 1mL(trimethyl cetyl ammonium bromide of the gold nanorods that trimethyl cetyl ammonium bromide modifies is 0.1mol/L, the concentration of gold nanorods is 1.5nmol/L), in table model high speed centrifuge with the speed of 12000rpm/min after centrifugal 4 minutes, isolate precipitation, then use the abundant dissolution precipitation of water of 1mL, again with identical condition carry out centrifugal after, water dissolution precipitation with 1mL, the concentration that obtains trimethyl cetyl ammonium bromide is 13umol/L, and the concentration of the gold nanorods aqueous solution that is 1.5nmol/L.
2) in temperature, be under 25 ℃, the mixing speed condition that is 800rpm/min, the aqueous solution obtaining in the step 1) of 1mL is joined in the vial of 10mL, the mixed liquor of ethanol and lauryl mercaptan (volume ratio of ethanol and lauryl mercaptan is 40:10) 50uL is added at twice, the amount at every turn adding is identical, and adds rear stirring 2.5min at every turn; Then at the same temperature, mixing speed is changed to 400rpm/min, and add 1.1mL dichloroethanes, stir after 10 minutes and stop stirring, and after standing 10 hours, on water surface, obtain gold nanorods orthogonal array (circular array, diameter is 4mm * 4mm).
Known by scanning transmission electron microscope photo, in this gold nanorods orthogonal array, the diameter of gold nanorods is 16 nanometers, and the rod length of gold nanorods is 65 nanometers, and interrod spacing is 2 nanometers; In addition, by X-ray powder diffraction figure, the diffraction maximum of crystal face (200) (vertical orientated) and the diffraction maximum of crystal face (111) (tilted alignment) only detected.By calculating the ratio of vertical orientated gold nanorods, be 90%.
Embodiment 4
According to the method for embodiment 3, carry out, different is obtains trimethyl cetyl ammonium bromide concentration in step 1) is 5umol/L, and the aqueous solution that the concentration of gold nanorods is 2nmol/L similarly obtains gold nanorods orthogonal array (circular array, diameter is 4mm) on water surface.
Known by scanning transmission electron microscope photo, in this gold nanorods orthogonal array, the diameter of gold nanorods is 18 nanometers, and the rod length of gold nanorods is 70 nanometers, and interrod spacing is 1.3 nanometers; In addition, by X-ray powder diffraction figure, the diffraction maximum of crystal face (200) (vertical orientated) and the diffraction maximum of crystal face (111) (tilted alignment) only detected.By calculating the ratio of vertical orientated gold nanorods, be 85%.
Comparative example 1
According to the method for embodiment 3, carry out, different is obtains trimethyl cetyl ammonium bromide concentration in step 1) is 4umol/L, and the aqueous solution that the concentration of gold nanorods is 1nmol/L, but find to occur irreversible reunion in preparation process, thereby cause subsequent step to carry out, fail to obtain gold nanorods orthogonal array.
Comparative example 2
According to the method for embodiment 3, carry out, different is obtains trimethyl cetyl ammonium bromide concentration in step 1) is 10umol/L, and the aqueous solution that the concentration of gold nanorods is 0.4nmol/L, but find that in preparation process, cannot obtain enough non-reunion gold nanorods separates out at the water surface, and fail to obtain gold nanorods orthogonal array.
Known by embodiment 1-4, adopting method of the present invention can preparation size size be other gold nanorods orthogonal array of grade, and in the gold nanorods orthogonal array obtaining by method of the present invention, the ratio of vertical orientated gold nanorods can reach more than 85%.
In addition, known by embodiment 3 and comparative example 1-2, in the present invention, in the aqueous solution of the gold nanorods that trimethyl cetyl ammonium bromide is modified, the concentration of trimethyl cetyl ammonium bromide and the concentration of gold nanorods, need to, in specific scope, if not in this specific scope, cannot obtain gold nanorods orthogonal array of the present invention.
More than describe 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 the above-mentioned specific embodiment, 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 (14)
1. a preparation method for gold nanorods orthogonal array, is characterized in that, the method comprises the following steps:
1) prepare the aqueous solution of the gold nanorods of trimethyl cetyl ammonium bromide modification, and process by centrifugal redissolution, making the concentration of the trimethyl cetyl ammonium bromide in the described aqueous solution is 5-20umol/L, and the concentration of gold nanorods is 0.5-2nmol/L;
2) monohydric alcohol that is 1-3 by carbon number and carbon number are the mixed liquor of the alkyl hydrosulfide of 9-12, and the described aqueous solution obtaining with step 1) contacts;
3) by chloroform and/or dichloroethanes and step 2) after the mixed liquor that obtains mixes, and standing, obtain gold nanorods orthogonal array.
2. preparation method according to claim 1, wherein, in step 1), processes by centrifugal redissolution, and making the concentration of the trimethyl cetyl ammonium bromide in the described aqueous solution is 5-20umol/L, and the concentration of gold nanorods is 0.5-2nmol/L.
3. preparation method according to claim 1, wherein, in step 1), the method for preparing the aqueous solution of the gold nanorods that trimethyl cetyl ammonium bromide modifies is seed mediated growth method.
4. preparation method according to claim 1, wherein, step 2) in, the temperature of contact is 20-35 ℃, the time of contact is 3-5min.
5., preparation method according to claim 1, wherein, step 2), the mixed volume of the alkyl hydrosulfide that the monohydric alcohol that described carbon number is 1-3 and carbon number are 9-12 is than being 1-9:1.
6. preparation method according to claim 5, wherein, step 2) in, the volume ratio of the described aqueous solution that the alkyl hydrosulfide that described carbon number is 9-12 and described step 1) obtain is 0.01-0.02:1; Described carbon number is that the monohydric alcohol of 1-3 and the volume ratio of the described aqueous solution that described step 1) obtains are 0.04-0.08:1.
7. according to the preparation method described in claim 1,5 or 6, wherein, step 2) in, the monohydric alcohol that is 1-3 by carbon number and carbon number are the mixed liquor of the alkyl hydrosulfide of 9-12, and the mode that the described aqueous solution obtaining with step 1) contacts is: the mixed liquor of the alkyl hydrosulfide that the monohydric alcohol that is 1-3 by carbon number and carbon number are 9-12 drips or joins in batches in the described aqueous solution that step 1) obtains.
8. according to the preparation method described in claim 1,5 or 6, wherein, step 2) in, the monohydric alcohol that described carbon number is 1-3 is selected from one or more in methyl alcohol, ethanol and propyl alcohol; Described carbon number is that the alkyl hydrosulfide of 9-12 is one or more in nonyl mercaptan, decyl mercaptan, undecyl mercaptan and lauryl mercaptan.
9. preparation method according to claim 1, wherein, in step 3), the cumulative volume of described chloroform and dichloroethanes and described step 2) volume ratio of the mixed liquor that obtains is 0.8-1.2:1.
10. according to the preparation method described in claim 1 or 9, wherein, in step 3), the temperature of mixing is 15-40 ℃, and the time of mixing is 8-40min.
11. according to the preparation method described in claim 1 or 9, and wherein, in step 3), the standing time is 5-48h.
12. 1 kinds of gold nanorods orthogonal array, is characterized in that, the preparation method in claim 1-11 described in any one prepares.
13. gold nanorods orthogonal array according to claim 12, wherein, in described gold nanorods orthogonal array, the diameter of gold nanorods is 12-25 nanometer, and the rod length of gold nanorods is 45-80 nanometer, and interrod spacing is 1-3 nanometer.
14. according to the gold nanorods orthogonal array described in claim 12 or 13, and wherein, in described gold nanorods orthogonal array, the ratio of vertical orientated gold nanorods is more than 85%.
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