CN100549244C - A kind of rectangle bimetallic nano rod with gold nucleus and palladium shell and preparation method thereof - Google Patents
A kind of rectangle bimetallic nano rod with gold nucleus and palladium shell and preparation method thereof Download PDFInfo
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- CN100549244C CN100549244C CN 200610112504 CN200610112504A CN100549244C CN 100549244 C CN100549244 C CN 100549244C CN 200610112504 CN200610112504 CN 200610112504 CN 200610112504 A CN200610112504 A CN 200610112504A CN 100549244 C CN100549244 C CN 100549244C
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Abstract
The invention provides rectangle bimetallic nano rod monocrystalline of a kind of gold nucleus and palladium shell structure and preparation method thereof, the rectangle bimetallic nano rod monocrystalline of described gold nucleus and palladium shell structure comprises: a cylindric gold nanorods kernel, and be coated on the rectangle palladium shell of described cylindric gold nanorods kernel outside surface; The diameter of described cylindric gold nanorods kernel is 10～15nm, and length is 45～55nm; The length of described rectangle palladium shell is 50～62nm, and wide is 14～24nm, and height is 14～24nm; Bimetal nano rod geometry of the present invention is determined, crystal face is determined, therefore be a good model research system, preparation method provided by the invention is simple, flexibly, environmental protection, Green Chemistry and less energy-consumption, and the gold nucleus and palladium shell structure bimetallic nano rod that obtains has the adjustable characteristics of high yield, narrow size distribution, Stability Analysis of Structures and optical property.
Description
Technical field
The present invention relates to a kind of monocrystalline gold nucleus and palladium shell structure bimetallic nano rod and preparation method thereof, this method has realized that by the control reaction process rectangle palladium shell structure is epitaxially grown in columned golden nuclear structure.
Background technology
For metal nanoparticle, size, composition, crystallinity, shape and structure are to its character, and especially optical property has remarkable influence.Since middle nineteen nineties, the synthetic of shape control begins to cause extensive concern because in many cases, and it is than the easier finely regulating of obtaining material character of other Several Factors.For example, existing research work shows that the effective spectral range of the peak position at metal surface plasma resonance body peak and number and surperficial enhanced Raman scattering can regulate and control by the shape of control metal Nano structure.Therefore a synthetic importance that has become in the metal nanoparticle research of shape control has some synthetic methods and occurs.In these synthetic methods, a kind of being called as " the synthetic growth method of seed " obtained to pay close attention to comparatively widely.It (is example: C.J.Murphy with the gold that this method can be briefly described as follows, T.K.Sau, A.M.Gole, C.J.Orendorff, J.X.Gao, L.F.Gou, S.E.Hunyadi, T.Li, J.Phys.Chem.B 2005,109,13857-13870.): at first in the aqueous solution, reduce golden salt and obtain the spherical gold grain of a few nanometer sizes, be referred to as crystal seed with strong reductant; The aqueous solution with golden salt, structure directing agent (as cetyl trimethylammonium bromide) and weak reductant (as xitix) mixes with certain proportion afterwards, is referred to as growth solution; At last, add an amount of little gold nano grain as nucleation centre in growth solution, the gold nano structure of different shape will form.This reaction is at air, carries out under the aqueous solution and the room temperature condition, and also nontoxicity of used chemical reagent, therefore can be described as a kind of easy, green chemical synthesis method flexibly.From the angle that saves energy and protect environment now, be expected to obtain to use widely.The gold and silver nano particle that can synthesize different shape at present with this growth method.But in general, the pattern of controlling metal nanoparticle with the synthetic growth method of seed still is a newer research direction, and mostly what obtained is some empirical laws, and the concrete mechanism of reaction is not clear.At present, in the synthetic growth method of seed, seed all is the spherical metal particle of several nanometers basically, and crystal seed does not have particular geometric shapes.In the metal Nano structure of different shape, the research of bar-shaped metallic particles has obtained to pay close attention to more.Synthesizing gold nanorods with the synthetic growth method of seed is that the research group that is at first led by American university Murphy puts forward, but the productive rate of gold nanorods is not high, the research group of EL-Sayed is further improved this method afterwards, and the productive rate that makes gold nanorods is up to more than 90%.Therefore we can say that in the synthetic growth of seed the synthetic of gold nanorods is the most sophisticated.
Although the synthetic growth method of seed is obtaining remarkable progress aspect the shape control, the success of this method only limits to two kinds of metals of gold and silver at present.Therefore the expansion to other metal needs.Palladium is a kind of good catalyzer, can carry out multiple catalyzed reaction on its surface.But the peak position of the surface plasma body resonant vibration peak of spherical palladium nano-particles (electronics moves along the collective oscillation of long axis direction) is positioned at the UV spectrum wave band, and this makes and utilizes its optical property very difficult.The researchist of the U.S. has synthesized the palladium nano-particles of trilateral, sexangle and the square of tens nanometer sizes recently, the peak position of finding their surface plasma body resonant vibration peak can move on to the visible spectrum wave band, and this makes and utilizes optical property to become possibility at the visible spectrum wave band.For example, to studies show that of above-mentioned several shape palladium nano-particles, they will be that another is expected the system in surface plasma and the acquisition application of surperficial enhanced Raman scattering (Surface Enhanced Raman Scattering is hereinafter to be referred as SERS) aspect.
Preparing in the research of golden palladium nucleocapsid structure as template with gold nanorods, have to the surface growth (J.H.Song of the spherical palladium particle of several nanoscales at present round gold nanorods, F.Kim, D.Kim, P.D.Yang, Chem.Eur.J.2005,11,910-916.), the preparation of epitaxially grown rectangular palladium nanometer rod yet there are no report.
Summary of the invention:
The purpose of this invention is to provide a kind of rectangle gold nucleus and palladium shell structure bimetallic nano rod;
Another object of the present invention provides a kind of method for preparing above-mentioned rectangle gold nucleus and palladium shell structure bimetallic nano rod.
Technical scheme of the present invention is as follows:
The rectangle bimetallic nano rod monocrystalline of gold nucleus and palladium shell structure provided by the invention comprises;
One cylindric gold nanorods kernel, and be coated on the rectangle palladium shell of described cylindric gold nanorods kernel outside surface; The diameter of described cylindric gold nanorods kernel is 10～15nm, and length is 45～55nm; The length of described rectangle palladium shell is 50～62nm, and wide is 14～24nm, and height is 14～24nm.
The preparation method of the rectangle bimetallic nano rod monocrystalline of gold nucleus and palladium shell structure provided by the invention, its step comprises:
1. preparation Jin Jing plants solution;
2. prepare gold nanorods solution; It is characterized in that, further comprising the steps of:
3. purifying gold nanorods solution
The gold nanorods solution of step 2 preparation through centrifugation, obtain purifying gold nanorods solution, and wherein the concentration of gold is adjusted into 0.1mM-0.44mM;
4. the rectangle bimetallic nano rod monocrystalline for preparing the gold nucleus and palladium shell structure:
With concentration is the cetyl trimethylammonium bromide (C of 0.03-0.6M
19H
42N
+Br
-, hereinafter to be referred as CTAB) aqueous solution and concentration be 0.1M xitix (hereinafter to be referred as AA) aqueous solution evenly after, add the purifying gold nanorods solution that step 3 obtains and also shake up, adding concentration at last again is 2mM tetrachloro-palladium acid (H
2PdCl
4) aqueous solution makes mixing solutions; The mole proportioning of the cetyl trimethylammonium bromide in the described mixing solutions, xitix, purifying gold nanorods and tetrachloro-palladium acid is=55-800: 2-100: 1-0.33: 1;
The above-mentioned mixing solutions that mixes inserted in 30 ℃ the water bath with thermostatic control and to carry out water-bath in 12 hours, carry out centrifugation again, obtain the rectangle bimetallic nano rod monocrystalline of gold nucleus and palladium shell structure.
The method that the described Jin Jing of preparation plants solution is: to concentration is that to add concentration in the cetyl trimethylammonium bromide aqueous solution of 0.1M be the tetra chlorauric acid (HAuCl of 10mM
4) aqueous solution; Adding concentration again in above-mentioned mixing solutions then under stirring condition is the sodium borohydride aqueous solution of 0.01M, make first mixing solutions, the mol ratio that the described cetyl trimethylammonium bromide aqueous solution, the tetra chlorauric acid aqueous solution and the sodium borohydride aqueous solution in described first mixing solutions is mixed=0.75: 0.0025: 0.006; Continue to stir described first mixing solutions and left standstill after 2 minutes 2 hours, obtain containing the Jin Jing that Jin Jing plants and plant solution, the concentration that described Jin Jing plants GOLD FROM PLATING SOLUTION is 0.25mM.
The described method for preparing gold nanorods solution is: adding the tetra chlorauric acid aqueous solution and the concentration that concentration is 10mM respectively in concentration is the cetyl trimethylammonium bromide aqueous solution of 0.1M is the silver nitrate aqueous solution of 10mM, mixing back adding concentration is the aqueous ascorbic acid of 0.1M, and then be that the Jin Jing of 0.25mM plants solution to the gold concentration that wherein adds step (1) preparation, make second mixed solution; Again described second mixing solutions is inserted in 30 ℃ of following waters bath with thermostatic control water-bath 12 hours, and obtained containing the gold nanorods solution of gold nanorods;
The cetyl trimethylammonium bromide aqueous solution in described second mixed solution, the tetra chlorauric acid aqueous solution, silver nitrate aqueous solution, aqueous ascorbic acid and Jin Jing plant the mol ratio that solution is mixed=5: 0.025: 0.005: 0.0275: 0.000015.
The concentration of the described CTAB aqueous solution is preferably 0.1-0.3M.
The advantage of bimetallic nano rod with gold nucleus and palladium shell of the present invention and preparation method thereof is:
1, the rectangle gold nucleus and palladium shell structure bimetallic nano rod of method preparation of the present invention is compared with pure palladium nano-particles, its surface plasma body resonant vibration peak (SPR, electronics moves along the collective oscillation of long axis direction) peak position can realize by the thickness of simple adjustment palladium shell, and its SPR peak position moves to the visible spectrum wave band by the UV spectrum wave band, and optical property is significantly improved; In addition, because the bimetal nano rod geometry of preparation is determined, crystal face is determined, is a good model research system therefore.
2, simple, the flexible and environmental protection (Green Chemistry, less energy-consumption) of the preparation method of rectangle gold nucleus and palladium shell structure bimetallic nano rod, and the gold nucleus and palladium shell structure bimetallic nano rod that obtains has the adjustable characteristics of high yield, narrow size distribution, Stability Analysis of Structures and optical property.
3, in the synthetic growth method of seed, seed all is the spherical metal particle of several nanometers basically, and crystal seed does not have particular geometric shapes.At this, we expand to the gold nanorods with geometry in particular with " crystal seed ", have further widened the scope of this method.From the angle of " crystal seed ", have and common used some different characteristics of " crystal seed " as " crystal seed " with gold nanorods: used usually activity of crystal seed is shorter, and ageing will lose activity after several hours; And our used crystal seed, the active shelf time is very long.In addition, reaction product also reduces the dependency of reaction conditions, thereby has improved the repeatability of reaction product greatly.
4, study carefully the character of himself, palladium is not a highly active SERS medium, and gold is highly active SERS medium.Therefore palladium is attached to gold go up can " by " a part of golden SERS activity, thereby improve the SERS activity of palladium.Therefore prepare bimetallic nano rod and can significantly improve the SPR feature of palladium, and then improve its SERS character with gold nucleus and palladium shell structure.
Description of drawings
Fig. 1 a is the scanning electron microscope and the images of transmissive electron microscope of columned gold nanorods; Fig. 1 b is the scanning electron microscope and the images of transmissive electron microscope of rectangular parallelepiped gold palladium nuclear shell structure nano rod.
Fig. 2 a-Fig. 2 c is the high-resolution-ration transmission electric-lens image of rectangular parallelepiped gold palladium nuclear shell structure nano rod under the different amplification.The figure that insert in the upper right corner among Fig. 2 b and Fig. 2 c then is and the corresponding Fourier transform pattern of high resolution lattice image.
Fig. 3 a is the golden palladium nuclear shell structure nano rod scanning electron microscope image of not purified gold nanorods formulations prepared from solutions; Fig. 3 b is the golden palladium nuclear shell structure nano rod scanning electron microscope image of purified gold nanorods formulations prepared from solutions.
Fig. 4 a is the ultraviolet/visible absorption spectra of the golden palladium nuclear shell structure nano rod under the different growth times with Fig. 4 b; Fig. 4 c is the absorption peak corresponding with the palladium ion variation with growth time.
Fig. 5 a is purified gold nanorods scanning electron microscope image; Fig. 5 b-Fig. 5 f is the golden palladium nuclear shell structure nano rod scanning electron microscope image for preparing under the CTAB of different concns, and the scale of scanning electron microscope image is 60nm; Fig. 5 g is the ultraviolet/visible absorption spectra of sample shown in Fig. 5 a-Fig. 5 f.
Fig. 6 a is purified gold nanorods scanning electron microscope image; Fig. 6 b-Fig. 6 f is the scanning electron microscope image of the golden palladium nuclear shell structure nano rod for preparing under the different AA consumptions, and the scale of scanning electron microscope image is 60nm; Fig. 6 g is the ultraviolet/visible absorption spectra of sample shown in Fig. 6 a-Fig. 6 f.
Fig. 7 a is purified gold nanorods scanning electron microscope image; Fig. 7 b-Fig. 7 f is the scanning electron microscope image of the golden palladium nuclear shell structure nano rod for preparing under the different palladium ion consumptions, and the scale of scanning electron microscope image is 60nm; Fig. 7 g is the ultraviolet/visible absorption spectra of sample shown in Fig. 7 a-Fig. 7 f.
Fig. 8 a is purified gold nanorods scanning electron microscope image; Fig. 8 b-Fig. 8 f is the scanning electron microscope image of the golden palladium nuclear shell structure nano rod that obtains of different gold nanorods prepared at concentrations, and the scale of scanning electron microscope image is 60nm; Fig. 8 g is the ultraviolet/visible absorption spectra of sample shown in Fig. 8 a-Fig. 8 f.
Fig. 9 a is that not purified golden palladium nuclear shell structure nano rod solution ultraviolet/visible absorption spectra is at room temperature with the variation of digestion time; Fig. 9 b is at room temperature with the variation of digestion time through the golden palladium nuclear shell structure nano rod solution ultraviolet/visible absorption spectra of centrifugal treating.
Figure 10 a and Figure 10 c are respectively the purified gold nanorods scanning electron microscope images of ageing 1 day and 20 days; Figure 10 b is the golden palladium nuclear shell structure nano rod scanning electron microscope image with the preparation of 1 day gold nanorods of ageing: Figure 10 d is that the scale of scanning electron microscope image is 60nm with the golden palladium nuclear shell structure nano rod scanning electron microscope image of 20 days gold nanorods of ageing preparation.
Figure 11 a is purified gold nanorods scanning and images of transmissive electron microscope; Figure 11 b-Figure 11 f is the scanning and the images of transmissive electron microscope of the golden palladium nuclear shell structure nano rod for preparing under the different palladium ion concentration, and the scale of scanning electron microscope image is 90nm; Figure 11 g is the ultraviolet/visible absorption spectra of sample shown in Figure 11 a-Figure 11 f; Figure 11 h is the X-ray energy spectrum analysis (EDX) of sample shown in Figure 11 f.
Embodiment
The present invention will be further explained and explanation below in conjunction with specific embodiment.
At first dispose following various solution:
0.1M cetyl trimethylammonium bromide (C
19H
42N
+Br
-, hereinafter to be referred as CTAB) and the aqueous solution: take by weighing 3.64g cetyl trimethylammonium bromide (analytical pure) and be dissolved in the 100mL deionized water.Should place 30 ℃ of waters bath with thermostatic control that it is dissolved fully before use.
0.1M xitix (AA) aqueous solution: take by weighing 0.176g xitix (analytical pure) and be dissolved in the 10mL deionized water, before use preparation temporarily.
10mM tetra chlorauric acid (HAuCl
43H
2O) aqueous solution: take by weighing 0.393g tetra chlorauric acid (analytical pure, homemade) and be dissolved in the 100mL deionized water.
10mM Silver Nitrate (AgNO
3) aqueous solution: take by weighing 0.425g Silver Nitrate (analytical pure) and be dissolved in the 250mL deionized water.Keep in Dark Place.
2mM H
2PdCl
4The aqueous solution: take by weighing 0.035g palladium chloride (analytical pure) and be dissolved in the 2mL 0.2M hydrochloric acid, be diluted to 100mL then.
The rectangle bimetallic nano rod monocrystalline for preparing the gold nucleus and palladium shell structure then as follows:
1. the preparation of Jin Jing's kind:
To 7.5mL concentration is that adding 250 μ L concentration are the HAuCl of 10mM in the 0.1M CTAB aqueous solution
4The aqueous solution arrives 9.4mL with volume dilution after mixing, and adding 0.6mL concentration under the condition of magnetic agitation is the sodium borohydride (NaBH of 0.01M
4, analytical pure) and the aqueous solution (temporarily prepare before the use and place frozen water), stir and stop after two minutes, left standstill 2 hours, obtain containing the Jin Jing that Jin Jing plants and plant solution, the concentration that described Jin Jing plants GOLD FROM PLATING SOLUTION is 0.25mM.
2. the preparation of gold nanorods:
To 50mL concentration is that to add 2.5mL concentration in the CTAB aqueous solution of 0.1M be the HAuCl of 10mM
4The aqueous solution and 300 μ L concentration are the AgNO of 10mM
3The aqueous solution after mixing, adds the AA aqueous solution of 275 μ L concentration 0.1M again, and the mixing solutions that obtains is become colorless by orange, adds the crystal seed of 60 μ L then, puts into 30 ℃ of waters bath with thermostatic control after mixing.Solution began to occur color after 20 minutes, through 12 hours, finally become brown, illustrated to have formed gold nanorods.
3. the purifying of gold nanorods:
Earlier the gold nanorods for preparing was left standstill in 30 ℃ water bath with thermostatic control 24 hours, change under the condition of (rpm) centrifugal twice at per minute 12000 then, each 10 minutes, having removed unreacted monovalence gold ion and unnecessary CTAB like this, is 0.1mM with the gold nanorods solution dilution after centrifugal to concentration with deionized water at last.
4. the formation of palladium shell structure:
Get a above-mentioned gold nanorods solution 4mL after centrifugal and put into test tube, the AA aqueous solution of the CTAB aqueous solution of 2mL concentration 0.1M and 22 μ L concentration 0.1M is joined in the 4mL gold nanorods solution after even shake up, add the H of 550 μ L 2mM at last
2PdCl
4The aqueous solution.Put into 30 ℃ water bath with thermostatic control after mixing, solution has shown the formation of palladium layer shell structure by the light brown grey that become after several hours.After 12 hours, reaction soln was left the heart 10 minutes at per minute 12000.Remove supernatant liquor, precipitate with deionized water is diluted to original volume, centrifugal under similarity condition again.2 to 4 times like this, nanometer rod is separated with reaction system, thereby obtain the rectangle bimetallic nano rod monocrystalline of gold nucleus and palladium shell structure.
Fig. 1 a is the scanning electron microscope image and the low voltage images of transmissive electron microscope of columned gold nanorods, and the mean diameter of gold nanorods is that 15nm, mean length are 49nm; Fig. 1 b is the scanning electron microscope image and the low voltage images of transmissive electron microscope of the rectangular parallelepiped gold palladium nucleocapsid structure bimetallic nano rod of present embodiment preparation, and the mean diameter of golden palladium nuclear shell structure nano rod is that 24nm, mean length are 58nm.
Fig. 2 a-Fig. 2 c is the high-resolution-ration transmission electric-lens image of rectangular parallelepiped gold palladium nucleocapsid structure bimetallic nano rod.Wherein Fig. 2 a is low magnification image, can know that the gold of seeing the inside is examined and the palladium shell structure of outside; Fig. 2 b and Fig. 2 c are the high-amplification-factor images, can see lattice image.Among Fig. 2 b, when electron beam when [100] direction incident, can see that the palladium atom is＜002〉distribution on the lattice plane; Corresponding Fourier transform pattern also only demonstrates＜002〉face diffraction spot; Among Fig. 2 c, when electron beam when [110] direction incident, can see simultaneously that the palladium atom is＜002〉and＜distribution on 111〉lattice plane; Corresponding Fourier transform pattern also demonstrates simultaneously＜and 002〉and＜111〉face diffraction spot.
Embodiment 2-3: the purifying of gold nanorods is to the influence of growth palladium shell structure
Adjusting the concentration that step 2 among the embodiment 1 obtains gold nanorods solution is 0.1mM, get the above-mentioned gold nanorods solution of 4mL and put into test tube, in 2mL concentration is that to add 22 μ L concentration in the CTAB aqueous solution of 0.1M be the AA aqueous solution of 0.1M, then above-mentioned mixing solutions is joined in the above-mentioned test tube that gold nanorods solution is housed and shake up, adding 125 μ L concentration at last is the H of 2mM
2PdCl
4The aqueous solution is put into 30 ℃ water bath with thermostatic control after mixing, centrifugal reaction soln is 2 to 4 times after 12 hours, obtains the bimetallic nano rod of gold nucleus and palladium shell structure, and its pattern is shown in Fig. 3 a.
Get the purifying gold nanorods liquor capacity that step 3 obtains among the 4mL embodiment 1 and put into test tube, in 2mL concentration is that to add 22 μ L concentration in the CTAB aqueous solution of 0.1M be the AA aqueous solution of 0.1M, then above-mentioned mixing solutions is joined in the above-mentioned test tube that gold nanorods solution is housed and shake up, adding 125 μ L concentration at last is the H of 2mM
2PdCl
4The aqueous solution is put into 30 ℃ water bath with thermostatic control after mixing, centrifugal reaction soln is 2 to 4 times after 12 hours, obtains the rectangular parallelepiped bimetallic nano rod of gold nucleus and palladium shell structure, and its pattern is shown in Fig. 3 b.
In preparation during gold nanorods, in order to control the pattern of nanometer rod, the consumption of reductive agent AA is far below the dosage ratio, so also has a large amount of unreacted monovalence gold ion (Au in the growth solution
+).If under the condition that exists the monovalence gold ion, adding palladium ion reduces, made the gold nanorods pattern that (because the gold nanorods pattern is very strong to the dependency of reductant concentration) take place significantly to change owing to the monovalence gold ion preferentially reduces, (see Fig. 3 a) thereby can cause the pattern of the palladium shell that generates thereafter to be difficult to control.Based on this, when growth palladium shell, at first the monovalence gold ion is separated from gold nanorods solution by centrifugation method, the original pattern of gold nanorods is preserved like this, and the palladium shell structure of growth is very regular rectangle (seeing Fig. 3 b).Therefore, the purifying of gold nanorods is to obtain a most key step of intact palladium shell structure.
Embodiment 4: the growth kinetics of palladium shell.
Get the purifying gold nanorods solution that step 3 obtains among the 4mL embodiment 1 and put into test tube, in 2mL concentration is that to add 22 μ L concentration in the CTAB aqueous solution of 0.1M be the AA aqueous solution of 0.1M, then above-mentioned mixing solutions is joined in the above-mentioned test tube that gold nanorods solution is housed and shake up, adding 550 μ L concentration at last is the H of 2mM
2PdCl
4The aqueous solution is put into 30 ℃ water bath with thermostatic control after mixing, then by measuring ultraviolet-visible absorption spectroscopy, thus the process of growth of monitoring palladium shell.
With PdCl
4 2-After the aqueous solution joins reaction system, owing to exist a large amount of CTAB, PdCl in the solution
4 2-At first with CTAB on Br
-Ion generation ligand exchange forms PdBr
4 2-PdBr
4 2-Two absorption bands (250nm and 340nm) are arranged in the UV spectrum district, therefore can come monitoring reaction course by the variation of monitoring them.From the variation of uv-vis spectra, the process of growth of palladium shell structure can be divided into two stages: the rapid reaction stage, (about 3 hours, Fig. 4 a) and the slow reaction stage (about 16 hours, Fig. 4 b).In the rapid reaction stage, be accompanied by PdBr
4 2-The rapid decline that absorbs, long wave band (400-700nm) is equivalent to the then corresponding increase of absorption of zeroth order palladium, shows from PdBr
4 2-Be reduced the zeroth order palladium, rectangular palladium layer shell forms in the time of 3 hours.From the X-ray analysis of energy dispersion as can be known, palladium/gold is than being 1.4.At slow reaction stage, PdBr
4 2-Absorption continue to descend (but becoming slow), and the absorption of long wave band also begins slow decline, palladium layer shell continues to grow up.In the time of 9 hours, palladium/gold is than becoming 1.9.Detailed growth kinetics process can find out from Fig. 4 c, 250nm and 340nm be absorbed in 3 hours before descend rapidly; Between 3 hours to 12 hours, then slowly descend.Can draw reaction from the pattern of palladium layer shell and EDX composition analysis can stop after 12 hours.
Embodiment 5-9:CTAB concentration is to the influence of growth palladium shell structure
Get the purifying gold nanorods solution that step 3 obtains among the 4mL embodiment 1 and put into test tube, in 2mL concentration is that to add 22 μ L concentration in the CTAB aqueous solution of 0.03M be the AA aqueous solution of 0.1M, then above-mentioned mixing solutions is joined in the above-mentioned test tube that gold nanorods solution is housed and shake up, adding 125 μ L concentration at last is the H of 2mM
2PdCl
4The aqueous solution is put into 30 ℃ water bath with thermostatic control after mixing, centrifugal reaction soln is 2 to 4 times after 12 hours, and the SEM image of the bimetallic nano rod of the gold nucleus and palladium shell structure that obtains is seen Fig. 5 b.
Concentration except that CTAB in the present embodiment becomes the 0.1M, and all the other steps are identical with embodiment 5, and the SEM image of the bimetallic nano rod of the gold nucleus and palladium shell structure that obtains is seen Fig. 5 c.
Concentration except that CTAB in the present embodiment becomes the 0.21M, and all the other steps are identical with embodiment 5, and the SEM image of the bimetallic nano rod of the gold nucleus and palladium shell structure that obtains is seen Fig. 5 d.
Concentration except that CTAB in the present embodiment becomes the 0.3M, and all the other steps are identical with embodiment 5, and the SEM image of the bimetallic nano rod of the gold nucleus and palladium shell structure that obtains is seen Fig. 5 e.
Concentration except that CTAB in the present embodiment becomes the 0.6M, and all the other steps are identical with embodiment 5, and the SEM image of the bimetallic nano rod of the gold nucleus and palladium shell structure that obtains is seen Fig. 5 f.
Shown in Fig. 5 g, from the variation of uv-vis spectra, CTAB concentration is adjusted the influence of the long wave plasma body absorption band of gold nanorods similar between 0.03M-0.6M: intensity significantly reduces, and peak width is significantly widened, and peak position is red shift or blue shift slightly.CTAB concentration is bigger to the pattern influence of the palladium layer shell of generation, and when CTAB concentration was lower than 0.1M or is higher than 0.3M, the rectangle palladium layer shell of generation be rule (Fig. 5 b and Fig. 5 f) not really; CTAB concentration is between 0.1M-0.3M the time, and the rectangle palladium layer shell of generation be rule (Fig. 5 c, Fig. 5 d and Fig. 5 e) then.
Embodiment 10-14:AA concentration is to the influence of growth palladium shell structure
Get the purifying gold nanorods solution that step 3 obtains among the 4mL embodiment 1 and put into test tube, in 2mL concentration is to add the AA aqueous solution that 2.5 μ L concentration are 0.1M (AA with palladium ion according to dosage than) in the CTAB aqueous solution of 0.1M, then above-mentioned mixing solutions is joined in the above-mentioned test tube that gold nanorods solution is housed and shake up, adding 125 μ L concentration at last is the H of 2mM
2PdCl
4The aqueous solution is put into 30 ℃ water bath with thermostatic control after mixing, centrifugal reaction soln is 2 to 4 times after 12 hours, and the SEM image of the bimetallic nano rod of the gold nucleus and palladium shell structure that obtains is seen Fig. 6 b.
Embodiment 11
Volume except that AA in the present embodiment becomes the 5 μ L (excessive 2 times of AA), and all the other steps are identical with embodiment 10, and the SEM image of the bimetallic nano rod of the gold nucleus and palladium shell structure that obtains is seen Fig. 6 c.
Embodiment 12
Volume except that AA in the present embodiment becomes the 25 μ L (excessive 10 times of AA), and all the other steps are identical with embodiment 10, and the SEM image of the bimetallic nano rod of the gold nucleus and palladium shell structure that obtains is seen Fig. 6 d.
Embodiment 13
Volume except that step 4AA in the present embodiment becomes the 125 μ L (excessive 50 times of AA), and all the other steps are identical with embodiment 10, and the SEM image of the bimetallic nano rod of the gold nucleus and palladium shell structure that obtains is seen Fig. 6 e.
Embodiment 14
Volume except that AA in the present embodiment becomes the 250 μ L (excessive 100 times of AA), and all the other steps are identical with embodiment 10, and the SEM image of the bimetallic nano rod of the gold nucleus and palladium shell structure that obtains is seen 6f.
From the variation of ultraviolet-visible absorption spectroscopy, the consumption degree of AA is similar to the influence of the long wave plasma body absorption band of gold nanorods: intensity significantly reduces, and peak width is significantly widened, and peak position is blue shift or basic do not move (Fig. 6 g) slightly.The excessive degree of AA is bigger to the pattern influence of the palladium layer shell of generation.AA is excessive when being lower than 10 times, and the rectangle palladium layer shell of generation be rule (Fig. 6 b and Fig. 6 c) not really.AA excessive 10-100 doubly between the time, the rectangle palladium layer shell of generation be rule (Fig. 6 d-Fig. 6 f) then; And along with the excessive degree of AA increases the obvious thickening of palladium layer shell.Corresponding EDX measurement shows that Pd/Au is respectively 0.13,0.18,0.50,0.52 and 0.54 than from Fig. 6 b to Fig. 6 f.Analyze from EDX, AA is excessive when being higher than more than 10 times, and it is comparatively thorough that reaction is carried out.
Embodiment 15-19: low palladium ion concentration is to the modulation of gold nanorods long wave plasma body absorption band
Embodiment 15
Get the purifying gold nanorods solution that step 3 obtains among the 4mL embodiment 1 and put into test tube, in 2mL concentration is that to add 5 μ L concentration in the CTAB aqueous solution of 0.1M be the AA aqueous solution of 0.1M, then above-mentioned mixing solutions is joined in the above-mentioned test tube that gold nanorods solution is housed and shake up, adding 25 μ L concentration at last is the H of 2mM
2PdCl
4The aqueous solution is put into 30 ℃ water bath with thermostatic control after mixing, centrifugal reaction soln is 2 to 4 times after 12 hours, and the SEM image of the bimetallic nano rod of the gold nucleus and palladium shell structure that obtains is shown in Fig. 7 b.
Embodiment 16
Removing last adding 50 μ L concentration in the present embodiment is the H of 2mM
2PdCl
4Outside the aqueous solution, all the other steps are identical with embodiment 15, and the SEM image of the bimetallic nano rod of the gold nucleus and palladium shell structure that obtains is shown in Fig. 7 c.
Embodiment 17
Removing last adding 75 μ L concentration in the present embodiment is the H of 2mM
2PdCl
4Outside the aqueous solution, all the other steps are identical with embodiment 15, and the SEM image of the bimetallic nano rod of the gold nucleus and palladium shell structure that obtains is shown in Fig. 7 d.
Embodiment 18
Removing last adding 100 μ L concentration in the present embodiment is the H of 2mM
2PdCl
4Outside the aqueous solution, all the other steps are identical with embodiment 15, and the SEM image of the bimetallic nano rod of the gold nucleus and palladium shell structure that obtains is shown in Fig. 7 e.
Embodiment 19
Be the H2PdCl4 aqueous solution of 2mM except that last adding 125 μ L concentration in the present embodiment, all the other steps are identical with embodiment 15, and the SEM image of the bimetallic nano rod of the gold nucleus and palladium shell structure that obtains is shown in Fig. 7 f.
When palladium ion concentration is low, can modulate gold nanorods long wave plasma body absorption band (electronics moves along the collective oscillation of long axis direction).This can find out that along with palladium ion concentration increases, the long wave plasma body absorption band of gold nanorods at first takes place small but significantly red shift from the variation of Fig. 7 g medium ultraviolet/visible absorption spectra, shows that length-to-diameter ratio increases, and illustrates the two ends of palladium ion preferential deposition at rod.After further increasing palladium ion concentration, this absorption band begins to take place blue shift again, shows that length-to-diameter ratio begins to reduce.For peak intensity and peak width, because gold nanorods and intercoupling of palladium layer shell electronic state cause the intensity of gold nanorods absorption band significantly to reduce, peak width is significantly widened.When palladium ion concentration was low, the rectangle palladium layer shell of generation be rule (Fig. 7 b) not really.
Embodiment 20-24: gold nanorods concentration is to the influence of growth palladium shell structure
Adjusting the purifying gold nanorods strength of solution that step 3 obtains among the embodiment 1 is 0.44mM, get the above-mentioned purifying gold nanorods of 4mL solution and put into test tube, in 2mL concentration is that to add 22 μ L concentration in the CTAB aqueous solution of 0.1M be the AA aqueous solution of 0.1M, then above-mentioned mixing solutions is joined in the above-mentioned test tube that gold nanorods solution is housed and shake up, adding 550 μ L concentration at last is the H of 2mM
2PdCl
4The aqueous solution is put into 30 ℃ water bath with thermostatic control after mixing, centrifugal reaction soln is 2 to 4 times after 12 hours, and the SEM image of the bimetallic nano rod of the gold nucleus and palladium shell structure that obtains is shown in Fig. 8 b.
Embodiment 21
Become the 0.25mM except that purifying gold nanorods strength of solution in the present embodiment, all the other steps are identical with embodiment 20, and the SEM image of the bimetallic nano rod of the gold nucleus and palladium shell structure that obtains is shown in Fig. 8 c.
Embodiment 22
Become the 0.17mM except that purifying gold nanorods strength of solution in the present embodiment, all the other steps are identical with embodiment 20, and the SEM image of the bimetallic nano rod of the gold nucleus and palladium shell structure that obtains is shown in Fig. 8 d.
Become the 0.13mM except that purifying gold nanorods strength of solution in the present embodiment, all the other steps are identical with embodiment 20, and the SEM image of the bimetallic nano rod of the gold nucleus and palladium shell structure that obtains is shown in Fig. 8 e.
Embodiment 24
Become the 0.1mM except that purifying gold nanorods strength of solution in the present embodiment, all the other steps are identical with embodiment 20, and the SEM image of the bimetallic nano rod of the gold nucleus and palladium shell structure that obtains is shown in Fig. 8 f.
From the variation of the ultraviolet-visible absorption spectroscopy of Fig. 8 g, along with gold nanorods concentration reduces gradually, the long wave plasma body absorption band of gold nanorods at the 770nm place at first is attenuated and blue shift slightly; Blue shift is widened and continued to this absorption peak gradually afterwards.Show that the palladium shell thickness increases gradually along with gold nanorods concentration reduces gradually, the shared proportion of the absorption feature of palladium shell also increases gradually on the absorption spectrum.The scanning electron microscope image of Fig. 8 shows that under higher gold nanorods concentration the rectangle palladium layer shell of generation be rule not really; Under lower gold nanorods concentration, the rectangle palladium layer shell of generation is then regular.This shows to have only after palladium layer thickness of the shell reaches certain value, the rectangle palladium layer shell of ability formation rule.When gold nanorods concentration was lower than 0.17mM, the palladium shell of formation was the rectangle of rule.When the gold nanorods strength of solution was 0.13mM, the mean diameter of bimetallic nano rod was that 15nm, mean length are 57nm.When the gold nanorods strength of solution was 0.1mM, the mean diameter of bimetallic nano rod was that 19nm, mean length are 62nm.
Embodiment 25: the stability of golden palladium nuclear shell structure nano rod
Get the purifying gold nanorods solution that step 3 obtains among the 4mL embodiment 1 and put into test tube.In 2mL concentration is that to add 22 μ L concentration in the CTAB aqueous solution of 0.1M be the AA aqueous solution of 0.1M, above-mentioned mixing solutions is joined in the above-mentioned test tube that gold nanorods solution is housed to shake up then, and adding 550 μ L concentration at last is the H of 2mM
2PdCl
4The aqueous solution is put into 30 ℃ water bath with thermostatic control after mixing, after 12 hours above-mentioned reaction soln is divided into two parts, is diluted to original volume with deionized water after a centrifugal 2 to 4 times, and another part is left intact.Monitor the stability of golden palladium nuclear shell structure nano rod with ultraviolet/visible absorption spectra.If the golden palladium nuclear shell structure nano rod that will generate continues to be kept in the growth solution O that exists in the solution
2Can corrode the palladium that generates gradually, and a large amount of Br that exist of growth solution
-Ion can be stablized the palladium ion of generation, therefore quickens the corrosion of palladium.This can find out with the variation of digestion time from Fig. 9 a nanometer rod ultraviolet/visible absorption spectra.Along with the increase of storage period, PdBr
4 2-Absorption increase gradually, the corresponding absorption of palladium shell in the long wave uptake zone then reduces gradually.If carry out centrifugal, with Br excessive in the solution
-Ion removes, then the corrosion process of palladium slow down greatly (Fig. 9 b).Therefore be the stability of security deposit's palladium nuclear shell structure nano rod, after reaction is finished, carry out centrifugal.
Embodiment 26-27: the gold nanorods digestion time is to the influence of growth palladium shell structure
Embodiment 26
Get the purifying gold nanorods solution that step 3 obtains among the 4mL embodiment 1 and put into the test tube ageing 1 day.In 2mL concentration is that to add 22 μ L concentration in the CTAB aqueous solution of 0.1M be the AA aqueous solution of 0.1M, above-mentioned mixing solutions is joined in 1 day the test tube that gold nanorods solution is housed of above-mentioned ageing to shake up then, and adding 550 μ L concentration at last is the H of 2mM
2PdCl
4The aqueous solution is put into 30 ℃ water bath with thermostatic control after mixing, centrifugal reaction soln is 2 to 4 times after 12 hours, obtains the rectangle bimetallic nano rod monocrystalline of gold nucleus and palladium shell structure.The mean diameter of the golden palladium nuclear shell structure nano rod of preparation is that 14nm, mean length are 48nm, shown in Figure 10 b.
Embodiment 27
Get the purifying gold nanorods solution that step 3 obtains among the 20mL embodiment 1, place the room temperature ageing after 20 days, the mean diameter of gold nanorods becomes 12nm, mean length becomes 55nm, shown in Figure 10 c.The gold nanorods solution 4mL that gets concentration and be 0.1mM puts into test tube, in 2mL concentration is that to add 22 μ L concentration in the CTAB aqueous solution of 0.1M be the AA aqueous solution of 0.1M, then above-mentioned mixing solutions is joined in the above-mentioned test tube that gold nanorods solution is housed and shake up, adding 550 μ L concentration at last is the H of 2mM
2PdCl
4The aqueous solution is put into 30 ℃ water bath with thermostatic control after mixing, centrifugal reaction soln is 2 to 4 times after 12 hours, obtains the rectangle bimetallic nano rod monocrystalline of gold nucleus and palladium shell structure.The mean diameter of the golden palladium nuclear shell structure nano rod of preparation is that 15nm, mean length are 62nm, shown in Figure 10 d.
The process of growth of gold nanorods is made up of a rapid reaction process and a slow reaction process.The rapid reaction process continues several hours, and the long response time process continues fortnight.In the long response time process, the length-to-diameter ratio of gold nanorods descends gradually.Fresh gold nanorods (Figure 10 a) and ageing gold nanorods (Figure 10 c) all have good active, rectangle palladium shell that can formation rule.Therefore gold nanorods has and common used some different characteristics of " seed " as " seed ": used usually seed activity is shorter, and ageing will lose activity after several hours; And our used seed, the active shelf time is very long.Test shows: when the seed room temperature is kept in the growth solution 20 days, still have good active.
Implement 28-32: higher palladium ion concentration is to the influence of growth palladium shell structure
Implement 28
Get the purifying gold nanorods solution that step 3 obtains among the 4mL embodiment 1 and put into test tube, the mean diameter of gold nanorods is that 15nm, mean length are 49nm, shown in Figure 11 a.In 2mL concentration is that to add 22 μ L concentration in the CTAB aqueous solution of 0.1M be the AA aqueous solution of 0.1M, above-mentioned mixing solutions is joined in the above-mentioned test tube that gold nanorods solution is housed to shake up then, and adding 125 μ L concentration at last is the H of 2mM
2PdCl
4The aqueous solution is put into 30 ℃ water bath with thermostatic control after mixing, centrifugal reaction soln is 2 to 4 times after 12 hours, obtains the rectangle bimetallic nano rod monocrystalline of gold nucleus and palladium shell structure.The mean diameter of the golden palladium nuclear shell structure nano rod that obtains is that 18nm, mean length are 50nm, shown in Figure 11 b.
Embodiment 29
Removing last adding 225 μ L concentration in the present embodiment is the H of 2mM
2PdCl
4Outside the aqueous solution, all the other steps are identical with embodiment 28.The mean diameter of the golden palladium nuclear shell structure nano rod that obtains is that 20nm, mean length are 53nm, shown in Figure 11 c.
Removing last adding 325 μ L concentration in the present embodiment is the H of 2mM
2PdCl
4Outside the aqueous solution, all the other steps are identical with embodiment 28.The mean diameter of the golden palladium nuclear shell structure nano rod that obtains is that 21nm, mean length are 54nm, shown in Figure 11 d.
Embodiment 31
Removing last adding 425 μ L concentration in the present embodiment is the H of 2mM
2PdCl
4Outside the aqueous solution, all the other steps are identical with embodiment 28.The mean diameter of the golden palladium nuclear shell structure nano rod that obtains is that 23nm, mean length are 56nm, shown in Figure 11 e.
Embodiment 32
Removing last adding 550 μ L concentration in the present embodiment is the H of 2mM
2PdCl
4Outside the aqueous solution, all the other steps are identical with embodiment 28.The mean diameter of the golden palladium nuclear shell structure nano rod that obtains is that 24nm, mean length are 58nm, shown in Figure 11 f.
Existence golden, palladium that the X-ray energy spectrum of Figure 11 h (EDX) composition analysis has proved.Variation from ultraviolet/visible absorption spectra of Figure 11 g, also the situation with low palladium ion concentration forms contrast, when higher palladium ion concentration, whole absorption spectrum mainly is presented as the absorption of palladium layer shell, absorption begins to increase gradually from 700nm, forms a wide acromion that does not have structure at 550nm.This acromion belongs to the long wave plasma body absorption band of golden palladium nuclear shell structure nano rod, but has reacted the absorption feature of palladium shell more.Therefore along with the increase gradually of palladium shell thickness, the absorption of this wave band also increases gradually.
Claims (3)
1. the rectangle bimetallic nano rod monocrystalline of a gold nucleus and palladium shell structure comprises:
One cylindric gold nanorods kernel, and be coated on the rectangle palladium shell of described cylindric gold nanorods kernel outside surface; The diameter of described cylindric gold nanorods kernel is 10～15nm, and length is 45～55nm; The length of described rectangle palladium shell is 50～62nm, and wide is 14～24nm, and height is 14～24nm.
2. method for preparing the rectangle bimetallic nano rod monocrystalline of the described gold nucleus and palladium shell structure of claim 1, its step comprises:
(1) preparation Jin Jing plants solution; Wherein, be that to add concentration in the cetyl trimethylammonium bromide aqueous solution of 0.1M be the tetra chlorauric acid aqueous solution of 10mM to concentration; Adding concentration again in above-mentioned mixing solutions then under stirring condition is the sodium borohydride aqueous solution of 0.01M, make first mixing solutions, the mol ratio that the described cetyl trimethylammonium bromide aqueous solution, the tetra chlorauric acid aqueous solution and the sodium borohydride aqueous solution in described first mixing solutions is mixed=0.75: 0.0025: 0.006; Continue to stir described first mixing solutions and left standstill after 2 minutes 2 hours, obtain containing the Jin Jing that Jin Jing plants and plant solution, the concentration that described Jin Jing plants GOLD FROM PLATING SOLUTION is 0.25mM;
(2) preparation gold nanorods solution; Wherein, adding the tetra chlorauric acid aqueous solution and the concentration that concentration is 10mM respectively in concentration is the cetyl trimethylammonium bromide aqueous solution of 0.1M is the silver nitrate aqueous solution of 10mM, mixing back adding concentration is the aqueous ascorbic acid of 0.1M, and then be that the Jin Jing of 0.25mM plants solution to the gold concentration that wherein adds step (1) preparation, make second mixed solution; Again described second mixing solutions is inserted in 30 ℃ of following waters bath with thermostatic control water-bath 12 hours, and obtained containing the gold nanorods solution of gold nanorods;
The cetyl trimethylammonium bromide aqueous solution in described second mixed solution, the tetra chlorauric acid aqueous solution, silver nitrate aqueous solution, aqueous ascorbic acid and Jin Jing plant the mol ratio that solution is mixed=5: 0.025: 0.005: 0.0275: 0.000015;
(3) purifying gold nanorods solution
The gold nanorods solution of step (2) preparation through centrifugation, is obtained purifying gold nanorods solution, and its concentration is adjusted into 0.1mM-0.44mM;
(4) the rectangle bimetallic nano rod monocrystalline of preparation gold nucleus and palladium shell structure:
With concentration is after the cetyl trimethylammonium bromide aqueous solution of 0.03-0.6M and aqueous ascorbic acid that concentration is 0.1M mix, the purifying gold nanorods solution that adding step 3 obtains also shakes up, and adding concentration at last again is that the 2mM tetrachloro-palladium acid aqueous solution makes mixing solutions; The mole proportioning of the cetyl trimethylammonium bromide in the described mixing solutions, xitix, purifying gold nanorods and tetrachloro-palladium acid is=55-800: 2-100: 1-0.33: 1;
The above-mentioned mixing solutions that mixes inserted in 30 ℃ the water bath with thermostatic control and to carry out water-bath in 12 hours, carry out centrifugation again, obtain the rectangle bimetallic nano rod monocrystalline of gold nucleus and palladium shell structure.
3. press the method for the rectangle bimetallic nano rod monocrystalline of the described preparation gold nucleus and palladium of claim 2 shell structure, in described step (4), the concentration of the described cetyl trimethylammonium bromide aqueous solution is 0.1-0.3M.
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