CN103506629B - A kind of gold nanorods orthogonal array and preparation method thereof - Google Patents
A kind of gold nanorods orthogonal array and preparation method thereof Download PDFInfo
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Abstract
The preparation method that the invention discloses a kind of gold nanorods orthogonal array and the gold nanorods orthogonal array obtained by the method.The method comprises: the aqueous solution 1) preparing the gold nanorods that trimethyl cetyl ammonium bromide is modified, and by centrifugal redissolution process, the concentration making 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) mixed liquor of to be the monohydric alcohol of 1-3 and carbon number by carbon number the be alkyl hydrosulfide of 9-12, contacts with the described aqueous solution that step 1) obtains; 3) by chloroform and/or dichloroethanes and step 2) after the mixed liquor that obtains mixes, and leave standstill, obtain gold nanorods orthogonal array.Adopt method provided by the invention, the ultra-large and gold nanorods orthogonal array that array structure is regular of grade can not only be obtained, but also have and be easy to operation, mild condition, structure uniformity advantages of higher.
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 possess optical characteristics that shape is correlated with and to each other plasma resonance to be coupled the aggregating characteristic brought, its periodically regular array be widely used in fields such as high sensitive sensor, solar cell, information storage, optoelectronic devices.
In prior art, prepare the method for gold nano stick array mainly by being dripped on substrate by gold nanorods solution, after solvent volatilization completely, remaining gold nanorods forms gold nano stick array 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 unordered state on the whole.
Summary of the invention
The object of the invention is to overcome the gold nano stick array small scale (below tens microns) obtained by existing method, and present the shortcoming of unordered state on the whole, a kind of preparation method of new gold nanorods orthogonal array is provided, and by gold nanorods orthogonal array that the method obtains.Adopt method provided by the invention, the ultra-large and gold nanorods orthogonal array that array structure is regular of grade can not only be obtained, but also have and be easy to operation, mild condition, structure uniformity advantages of higher.
The present inventor is through studying discovery repeatedly, the aqueous solution of the gold nanorods modified by trimethyl cetyl ammonium bromide is by centrifugal redissolution process, make the concentration of trimethyl cetyl ammonium bromide in the described aqueous solution and gold nanorods after specific scope, the mixed liquor that the monohydric alcohol and the carbon number that are 1-3 with carbon number are the alkyl hydrosulfide of 9-12 contacts, and then after mixing with chloroform and/or dichloroethanes, compound with regular structure can be obtained on the surface of water and the gold nanorods vertical array of ultra-large (millimeter rank) by leaving standstill, thus complete 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 that trimethyl cetyl ammonium bromide is modified, and by centrifugal redissolution process, the concentration making 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) mixed liquor of to be the monohydric alcohol of 1-3 and carbon number by carbon number the be alkyl hydrosulfide of 9-12, contacts with the described aqueous solution that step 1) obtains;
3) by chloroform and/or dichloroethanes and step 2) after the mixed liquor that obtains mixes, and leave standstill, obtain gold nanorods orthogonal array.
The present invention also provides a kind of gold nanorods orthogonal array prepared by said method.
According to the preparation method of gold nanorods orthogonal array provided by the invention, the ultra-large and gold nanorods orthogonal array that array structure is regular of grade can not only be obtained, but also have and be easy to operation, mild condition, structure uniformity advantages of higher.
In addition, the gold nano stick array obtained due to the present invention has the large and advantage of compound with regular structure of scale, is with a wide range of applications in fields such as photoelectric device, sensor, information storages.Especially there is uniform two-dimensional structure, be particularly suitable for preparing thin-film device as solar cell and the device with two-dimensional functional material compounds such as Graphenes.Further, very large potentiality are also possessed realizing trace quantitative detection field by surface-enhanced Raman effects.
Accompanying drawing explanation
Fig. 1 is the electron scanning micrograph (top view photograph) of the gold nanorods orthogonal array that embodiment 1 obtains;
Fig. 2 is the electron scanning micrograph (side-looking photo) of the gold nanorods orthogonal array that embodiment 1 obtains;
Fig. 3 a is the X-ray powder diffraction figure of the gold nanorods orthogonal array obtained by embodiment 1, Fig. 3 b is draw to compose from the AuXRD powder diffraction of XRD powder diffraction standard P DF card base.
Detailed description of the invention
Below the specific embodiment of the present invention is described in detail.Should be understood that, detailed description of the invention described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
Preparation method according to gold nanorods orthogonal array of the present invention comprises:
1) prepare the aqueous solution of the gold nanorods that trimethyl cetyl ammonium bromide is modified, and by centrifugal redissolution process, the concentration making 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) mixed liquor of to be the monohydric alcohol of 1-3 and carbon number by carbon number the be alkyl hydrosulfide of 9-12, contacts with the described aqueous solution that step 1) obtains;
3) by chloroform and/or dichloroethanes and step 2) after the mixed liquor that obtains mixes, and leave standstill, obtain gold nanorods orthogonal array.
According to the present invention, the described method preparing the aqueous solution of the gold nanorods that trimethyl cetyl ammonium bromide is modified can adopt the conventional method of ability to carry out.Such as 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 stirred, sodium borohydride and/or the potassium borohydride aqueous solution is added, continue to stir 3-5min, standing 2-5h obtains 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, mixing gained mixture is placed under the condition of the growth of the seed of gold nano grain to make 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.Length and the diameter ratio of nanometer rods can be regulated in this step by the silver nitrate controlling described gold nanorods growth solution.Wherein, the seed of the gold nano grain relative 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 μm of ol/L.It is 25-35 DEG C that the condition of the growth of the seed of described gold nano grain comprises temperature, 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 obtained 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 to carry out centrifugal redissolution process to the aqueous solution of the gold nanorods that the trimethyl cetyl ammonium bromide prepared is modified, the concentration making 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, the concentration making 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 ensure in subsequent step, alkyl hydrosulfide can replace the trimethyl cetyl ammonium bromide be originally adsorbed on gold nanorods smoothly, needs the concentration of the trimethyl cetyl ammonium bromide in the described aqueous solution to remain in the scope of 5-20umol/L.If when the concentration of the trimethyl cetyl ammonium bromide in the described aqueous solution is lower than 5umol/L, gold nanorods can not keep stable, and irreversible reunion can occur, thus subsequent step is caused to carry out; If when the concentration of the trimethyl cetyl ammonium bromide in the described aqueous solution is higher than 20umol/L, the stability of gold nanorods is excessively strong, the mercaptan that subsequent step is added cannot carry out enough replacements, thus causes obtaining the consistent regular array of orientation.And, in the present invention, also need the concentration of the gold nanorods in the described aqueous solution to remain in the scope into 0.5-2nmol/L, if when the concentration of the gold nanorods in the described aqueous solution is lower than 0.5nmol/L, can causes obtaining enough non-agglomerated gold nanorods and separate out at the water surface; If when the concentration of the gold nanorods in the described aqueous solution is higher than 2nmol/L, ligand modified efficiency can be caused low and regular arrangement cannot be formed after precipitation.
In the present invention, the concentration of the trimethyl cetyl ammonium bromide in the described aqueous solution refers to dissolving trimethyl cetyl ammonium bromide in aqueous and modifies the total concentration of the trimethyl cetyl ammonium bromide in gold nanorods.
According to the present invention, centrifugal redissolution process described in step 1) refers to and the described aqueous solution preparing the gold nanorods that trimethyl cetyl ammonium bromide is modified is carried out high speed centrifugation, thus make gold nanorods be deposited to the bottom of centrifuge tube, then the solution containing trimethyl cetyl ammonium bromide is separated with precipitation, then precipitation is used water-soluble solution.There is no particular limitation for the number of times processed described centrifugal redissolution, and only can make final with in the solution obtained after water-soluble solution, 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 centrifugal number of times redissolving process is 2-3 time.In addition, centrifugal when redissolving the consumption of water identical with the described volume preparing the aqueous solution of the gold nanorods that trimethyl cetyl ammonium bromide is modified.
In the present invention, to described centrifugal condition, there is no particular limitation, as long as gold nanorods can be made fully to 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 DEG C, and the time of contact can be 2-10min; Under preferable case, the temperature of contact is 20-35 DEG C, 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 carbon number can be made to be the monohydric alcohol of 1-3 and carbon number be the mixed liquor of the alkyl hydrosulfide of 9-12, the described aqueous solution obtained with step 1) evenly.
According to the present invention, step 2) in, the mixed liquor of to be the monohydric alcohol of 1-3 and carbon number by carbon number the be alkyl hydrosulfide of 9-12, the mode carrying out contacting with the described aqueous solution that step 1) obtains is preferably: the mixed liquor of to be the monohydric alcohol of 1-3 and carbon number by carbon number the be alkyl hydrosulfide of 9-12 drips or joins in batches in the described aqueous solution that step 1) obtains.When the mixed liquor of to be the monohydric alcohol of 1-3 and carbon number by carbon number the be alkyl hydrosulfide of 9-12 joins in the described aqueous solution that step 1) obtains in batches, preferably a point 2-3 criticizes and adds, often criticize the amount added can be the same or different, but preferably identical.When the mixed liquor of to be the monohydric alcohol of 1-3 and carbon number by carbon number the be alkyl hydrosulfide of 9-12 is added drop-wise in the described aqueous solution that step 1) obtains, 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 dripping solution are suitably selected.Relative to the reactor of 10 milliliters, the volume of the described aqueous solution that described step 1) obtains is below 0.6 times of volume of reactor with the volume sum of dropping solution, and 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 described carbon number to be the monohydric alcohol of 1-3 and carbon number the be alkyl hydrosulfide of 9-12 can change in wide scope.Generally, described carbon number is the monohydric alcohol of 1-3 is that the mixed volume of the alkyl hydrosulfide of 9-12 is than being 1-9:1 with carbon number; Under preferable case, described carbon number is the monohydric alcohol of 1-3 is that the mixed volume of the alkyl hydrosulfide of 9-12 is than being 2-8:1 with carbon number.
In the present invention, the volume of the described aqueous solution that the consumption of described carbon number to be the alkyl hydrosulfide of 9-12 and described carbon number the be monohydric alcohol of 1-3 can obtain according to step 1) is suitably selected.Generally, described carbon number is the volume ratio of the described aqueous solution that the alkyl hydrosulfide of 9-12 and described step 1) obtain can be 0.01-0.02:1, and described carbon number is the volume ratio of the described aqueous solution that the monohydric alcohol of 1-3 obtains with described step 1) can be 0.04-0.08:1; Under preferable case, described carbon number is the volume ratio of the described aqueous solution that the alkyl hydrosulfide of 9-12 and described step 1) obtain is 0.015-0.02:1; Described carbon number is the volume ratio of the described aqueous solution that the monohydric alcohol of 1-3 and described step 1) obtain is 0.05-0.07:1.In the present invention, need to be that the volume ratio of the described aqueous solution that the alkyl hydrosulfide of 9-12 and described step 1) obtain remains in the scope of 0.01-0.02:1 by described carbon number, if described carbon number be the described aqueous solution that the alkyl hydrosulfide of 9-12 and described step 1) obtain volume ratio lower than 0.01 time, can cannot form regular array after gold nanorods is separated out; If described carbon number be the described aqueous solution that the alkyl hydrosulfide of 9-12 and described step 1) obtain volume ratio higher than 0.02 time, reactant liquor can form emulsion thus cause obtaining gold nanorods orthogonal array.And, in the present invention, also need to be that the volume ratio of the described aqueous solution that the monohydric alcohol of 1-3 and described step 1) obtain remains in the scope of 0.04-0.08:1 by described carbon number, if described carbon number be the described aqueous solution that the monohydric alcohol of 1-3 and described step 1) obtain volume ratio lower than 0.04 time, gold nanorods will be difficult to separate out to water surface; If described carbon number be the described aqueous solution that the monohydric alcohol of 1-3 and described step 1) obtain volume ratio higher than 0.8 time, irreversible reunion can be caused.
In the present invention, step 2) in, described carbon number be the monohydric alcohol of 1-3 be selected from methyl alcohol, ethanol and propyl alcohol one or more; Be preferably ethanol.Described carbon number to be the alkyl hydrosulfide of 9-12 be in nonyl mercaptan, decylthiol, undecyl mercaptan and lauryl mercaptan one or more; 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 obtains carries out the steps A that mixes; 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, at temperature is 15-40 DEG C, mix 8-40min can meet above-mentioned requirements; In preferred situation, at temperature is 20-35 DEG C, mix 10-30min.Preferred described mixing is undertaken by stirring, and to the speed of described stirring, there is no particular limitation, as long as the gold in mixed liquor can be impelled to separate out.
In described step B, the time left standstill can be 5-48h; Be preferably 10-24h.
In addition, in step 3), the consumption of described chloroform and dichloroethanes can according to described rapid 2) volume of mixed liquor that obtains suitably selects.Under preferable case, the cumulative volume of described chloroform and dichloroethanes and described step 2) volume ratio of 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 mixed liquor that obtains is 0.9-1.1:1.
It is to be noted: when only by the one in chloroform and dichloroethanes and step 2) mixed liquor that obtains is when mixing, the cumulative volume of described chloroform and dichloroethanes refers to used chloroform or the volume of dichloroethanes, when to use chloroform and dichloroethanes simultaneously, the cumulative volume of described chloroform and dichloroethanes refers to the total volume of the volume of chloroform and the volume of dichloroethanes.
Present invention also offers a kind of gold nanorods orthogonal array 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 of gold nanorods is long 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 of gold nanorods is long 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%, is preferably more than 90%.The ratio of described vertical orientated gold nanorods refers to the ratio of vertical orientated gold nanorods and all gold nanorods in described gold nanorods orthogonal array.
Below will be described 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 SEM (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 used 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 stirred, sodium borohydride and/or the potassium borohydride aqueous solution is added, continue to stir 5min, standing 5h obtains 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, the concentration of gold is 0.3mmol/L) being mixed with gold nanorods growth solution, being placed in mixing gained mixture under the condition of the growth of the seed of gold nano grain to make 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.Wherein, the gold relative to 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 μm of ol/L; The temperature of the growth of the seed of described gold nano grain is 30 DEG C, time is 4h, the concentration obtaining trimethyl cetyl ammonium bromide is 0.1mol/L, and the concentration of gold nanorods is the aqueous solution of the gold nanorods of the trimethyl cetyl ammonium bromide modification of 1-2nmol/L.
In following examples, the ratio of described vertical orientated gold nanorods refers to the ratio of vertical orientated gold nanorods and all gold nanorods in described gold nanorods orthogonal array.In gold nanorods, the crystal face perpendicular to long axis direction is (200) crystal face, calculates the ratio of vertical orientated gold nanorods in overall by the relative intensity of XRD determining (200) crystallographic plane diffraction peak.
Embodiment 1
1) concentration of getting the aqueous solution 1mL(trimethyl cetyl ammonium bromide of the gold nanorods that trimethyl cetyl ammonium bromide is modified is 0.1mol/L, the concentration of gold nanorods is 1nmol/L), with the centrifugation of 12000rpm/min after 4 minutes in table model high speed centrifuge, isolate precipitation, then the abundant dissolution precipitation of the water of 1mL is used, again with identical condition carry out centrifugal after, with the water dissolution precipitation of 1mL, the concentration obtaining trimethyl cetyl ammonium bromide is 10umol/L, and the concentration of gold nanorods is the aqueous solution of 1nmol/L.
2) temperature be 25 DEG C, under mixing speed is the condition of 700rpm/min, the aqueous solution obtained in the step 1) of 1mL is joined in the vial of 10mL, and instill 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 leave standstill after 12 hours, water surface obtains 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.
Fig. 3 a is the X-ray powder diffraction figure of the gold nanorods orthogonal array obtained by the present embodiment, Fig. 3 b is XRD powder diffraction spectrum (i.e. the X-ray powder diffraction figure of standard A u powder crystal) of Au, it draws from XRD powder diffraction standard P DF card base, card number: 00-001-1174, and by this gold nanorods orthogonal array of following formulae discovery, 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) is strong; I
111for the Relative Peak of the diffraction maximum of crystal face (111) (tilted alignment) is strong.
Embodiment 2
1) concentration of getting the aqueous solution 2mL(trimethyl cetyl ammonium bromide of the gold nanorods that trimethyl cetyl ammonium bromide is modified is 0.1mol/L, the concentration of gold nanorods is 1.2nmol/L), with the centrifugation of 12000rpm/min after 4 minutes in table model high speed centrifuge, isolate precipitation, then the abundant dissolution precipitation of the water of 2mL is used, again with identical condition carry out centrifugal after, with the water dissolution precipitation of 2mL, the concentration obtaining trimethyl cetyl ammonium bromide is 13umol/L, and the concentration of gold nanorods is the aqueous solution of 1.5nmol/L.
2) temperature be 25 DEG C, under mixing speed is the condition of 900rpm/min, the aqueous solution obtained in the step 1) of 2mL is joined in the vial of 10mL, mixed liquor (volume ratio of ethanol and lauryl mercaptan the is 80:20) 200uL of ethanol and lauryl mercaptan is added at twice, the amount at every turn added 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 leave standstill after 24 hours, water surface obtains 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.Be 90% by calculating the ratio of vertical orientated gold nanorods.
Embodiment 3
1) concentration of getting the aqueous solution 1mL(trimethyl cetyl ammonium bromide of the gold nanorods that trimethyl cetyl ammonium bromide is modified is 0.1mol/L, the concentration of gold nanorods is 1.5nmol/L), with the centrifugation of 12000rpm/min after 4 minutes in table model high speed centrifuge, isolate precipitation, then the abundant dissolution precipitation of the water of 1mL is used, again with identical condition carry out centrifugal after, with the water dissolution precipitation of 1mL, the concentration obtaining trimethyl cetyl ammonium bromide is 13umol/L, and the concentration of gold nanorods is the aqueous solution of 1.5nmol/L.
2) temperature be 25 DEG C, under mixing speed is the condition of 800rpm/min, the aqueous solution obtained in the step 1) of 1mL is joined in the vial of 10mL, mixed liquor (volume ratio of ethanol and lauryl mercaptan the is 40:10) 50uL of ethanol and lauryl mercaptan is added at twice, the amount at every turn added 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 leave standstill after 10 hours, water surface obtains 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.Be 90% by calculating the ratio of vertical orientated gold nanorods.
Embodiment 4
Carry out according to the method for embodiment 3, be 5umol/L unlike the concentration obtaining trimethyl cetyl ammonium bromide in step 1), and the concentration of gold nanorods is the aqueous solution of 2nmol/L, on water surface, similarly 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 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.Be 85% by calculating the ratio of vertical orientated gold nanorods.
Comparative example 1
Carry out according to the method for embodiment 3, be 4umol/L unlike the concentration obtaining trimethyl cetyl ammonium bromide in step 1), and the concentration of gold nanorods is the aqueous solution of 1nmol/L, but find irreversible reunion occurs in preparation process, thus cause subsequent step to carry out, fail to obtain gold nanorods orthogonal array.
Comparative example 2
Carry out according to the method for embodiment 3, be 10umol/L unlike the concentration obtaining trimethyl cetyl ammonium bromide in step 1), and the concentration of gold nanorods is the aqueous solution of 0.4nmol/L, but find that cannot obtain enough non-agglomerated gold nanorods in preparation process separates out at the water surface, and fail to obtain gold nanorods orthogonal array.
Known by embodiment 1-4, method of the present invention is adopted preparation size size to be other gold nanorods orthogonal array of grade, and in the gold nanorods orthogonal array obtained by method of the present invention, the ratio of vertical orientated gold nanorods can reach more than 85%.
In addition, by embodiment 3 and comparative example 1-2 known, 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 in specific scope, if not in this specific scope, then 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 characteristic described in above-mentioned detailed description of the invention, in reconcilable situation, can be combined by any suitable mode, in order to avoid unnecessary repetition, the present invention illustrates no longer separately to various possible combination.
In addition, also can be combined between various different embodiment of the present invention, 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) aqueous solution of the gold nanorods that trimethyl cetyl ammonium bromide is modified is prepared, and by centrifugal redissolution process, the concentration making 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) mixed liquor of to be the monohydric alcohol of 1-3 and carbon number by carbon number the be alkyl hydrosulfide of 9-12, with step 1) the described aqueous solution that obtains contacts;
3) by chloroform and/or dichloroethanes and step 2) after the mixed liquor that obtains mixes, and leave standstill, obtain gold nanorods orthogonal array.
2. preparation method according to claim 1, wherein, step 1) in, by centrifugal redissolution process, the concentration making 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.
3. preparation method according to claim 1, wherein, step 1) in, the method preparing the aqueous solution of the gold nanorods that trimethyl cetyl ammonium bromide is modified is seed mediated growth method.
4. preparation method according to claim 1, wherein, step 2) in, the temperature of contact is 20-35 DEG C, and the time of contact is 3-5min.
5. preparation method according to claim 1, wherein, step 2) in, described carbon number is the monohydric alcohol of 1-3 is that the mixed volume of the alkyl hydrosulfide of 9-12 is than being 1-9:1 with carbon number.
6. preparation method according to claim 5, wherein, step 2) in, described carbon number is the alkyl hydrosulfide of 9-12 and described step 1) volume ratio of the described aqueous solution that obtains is 0.01-0.02:1; Described carbon number is the monohydric alcohol of 1-3 and described step 1) volume ratio of the described aqueous solution that obtains is 0.04-0.08:1.
7. the preparation method according to claim 1,5 or 6, wherein, step 2) in, the mixed liquor of to be the monohydric alcohol of 1-3 and carbon number by carbon number the be alkyl hydrosulfide of 9-12, with step 1) the described aqueous solution that the obtains mode carrying out contacting is: the mixed liquor of to be the monohydric alcohol of 1-3 and carbon number by carbon number the be alkyl hydrosulfide of 9-12 drips or joins step 1 in batches) in the described aqueous solution that obtains.
8. the preparation method according to claim 1,5 or 6, wherein, step 2) in, described carbon number be the monohydric alcohol of 1-3 be selected from methyl alcohol, ethanol and propyl alcohol one or more; Described carbon number to be the alkyl hydrosulfide of 9-12 be in nonyl mercaptan, decylthiol, undecyl mercaptan and lauryl mercaptan one or more.
9. preparation method according to claim 1, wherein, step 3) in, the cumulative volume of described chloroform and dichloroethanes and described step 2) volume ratio of mixed liquor that obtains is 0.8-1.2:1.
10. the preparation method according to claim 1 or 9, wherein, step 3) in, the temperature of mixing is 15-40 DEG C, and the time of mixing is 8-40min.
11. preparation methods according to claim 1 or 9, wherein, step 3) in, the time left standstill is 5-48h.
12. 1 kinds of gold nanorods orthogonal array, is characterized in that, are prepared by the preparation method in claim 1-11 described in any one.
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 of gold nanorods is long is 45-80 nanometer, and interrod spacing is 1-3 nanometer.
14. gold nanorods orthogonal array according to claim 12 or 13, wherein, in described gold nanorods orthogonal array, the ratio of vertical orientated gold nanorods is more than 85%.
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| CN104713833B (en) * | 2015-02-04 | 2018-04-27 | 国家纳米科学中心 | A kind of method for amplifying the response of gold nanorods assembly phasmon circular dichroism |
| CN104999071B (en) * | 2015-06-24 | 2017-04-05 | 深圳先进技术研究院 | A kind of gold nano stick array and its preparation method and application |
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