CN103537707A - Five-twin-crystal gold-silver alloy particles, preparation method of five-twin-crystal gold-silver alloy particles, five-twin-crystal gold particles and preparation method of five-twin-crystal gold particles - Google Patents
Five-twin-crystal gold-silver alloy particles, preparation method of five-twin-crystal gold-silver alloy particles, five-twin-crystal gold particles and preparation method of five-twin-crystal gold particles Download PDFInfo
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Abstract
The invention discloses a preparation method of five-twin-crystal decanedron gold-silver alloy particles comprising chloroauric acid, silver nitrate, polyvinylpyrrolidone, water and N, N-dimethylformamide, and the five-twin-crystal decanedron gold-silver alloy particles prepared through the preparation method. The invention further discloses a preparation method of five-twin-crystal gold particles comprising chloroauric acid, the five-twin-crystal decanedron gold particles, polyvinylpyrrolidone, water and N, N-dimethylformamide, and also discloses the five-twin-crystal gold particles with the shape similar to spheroids, the pentagon dodecahedral five-twin-crystal gold particles with all crystal faces being {110} crystal faces, the pentagon-star five-twin-crystal gold particles with a part of crystal faces being {110} crystal faces, and the chamfered-decanedron five-twin-crystal gold particles with a part of crystal faces being {110} crystal faces, wherein all the five-twin-crystal gold particles are prepared through the preparation method. According to the five-twin-crystal gold-silver alloy particles, the preparation method of the five-twin-crystal gold-silver alloy particles, the five-twin-crystal gold particles and the preparation method of five-twin-crystal gold particles, the five-twin-crystal structure and the high-energy {110} crystal faces are combined for the first time, so that the five-twin-crystal gold particles have more physicochemical properties determined by shapes and forms.
Description
Technical field
The present invention relates to five heavy twin electrum particles and preparation method thereof and five heavy twin gold grains and preparation method thereof, particularly, relate to decahedron electrum particle of five heavy twins and preparation method thereof, five heavy twin gold grains of quasi-ellipsoid and preparation method thereof, all crystal face is { pentagon dodecahedral five heavy twin gold grains of 110} crystal face and preparation method thereof, part crystal face is { five heavy twin gold grains of the pentagon star of 110} crystal face and preparation method thereof, part crystal face is { rescinded angle decahedral five heavy twin gold grains of 110} crystal face and preparation method thereof.
Background technology
Gold nano grain has good optics and photoelectronics characteristic.They all have very important using value in fields such as catalysis, bio-sensings.Because the physicochemical characteristics of the gold grain difference with its pattern and size changes, therefore, the size of gold nano grain and the research of morphological control method have become the forward position focus of noble metal nanometer material and association area research.
Generally speaking, the chemical mobility of the surface of gold nano grain is by the crystal face type decided of its exposure.Up to now, by a large amount of Study of synthesis method, people have successfully realized the control preparation of the gold nano grain that low energy bread wraps up in.For example,, by { the preparation of the monocrystalline tetrahedron of 111} type crystal face parcel and octahedron, five heavy twin decahedrons and multiple twin icosahedron gold nano grain; By { the cubic monocrystalline body of 100} type crystal face parcel and the preparation of cuboid gold nano grain.But, with { 111}, { gold nano grain of 100} type crystal face parcel is compared, by higher-energy face, { the control preparation of the gold nano grain of 110} type crystal face parcel is one always and is difficult to the target realizing, because in three kinds low index faces, { surface of 110} type crystal face can be the highest, that is: γ { 111}< γ { 100}< γ { 110}.Chad A.Mirkin research group successfully synthesized a kind of by { trigonal biyramid gold nano grain (the Michelle L.Personick of the double twin of 110} type crystal face parcel in 2011, et al.Synthesis and Isolation of{110}-Faceted Gold Bipyramids and Rhombic Dodecahedra.J.AM.CHEM.SOC.2011,133,6170 – 6173).But, about by { the five heavy twin gold nano grains wrapped up in of 110} bread are but had no precedent report.Therefore,, how by the suitable synthesis condition of design, realize by { the control preparation of the five heavy twin gold nano grains that 110} bread is wrapped up in has become following gold nano-material in the key of the field application such as high-performance catalysis and high-sensitive biosensor.
Summary of the invention
The object of the invention is in order to overcome the above-mentioned defect of prior art, decahedron electrum particle of five heavy twins and preparation method thereof is provided, by the decahedron electrum particle of five heavy twins, prepared the method for five heavy twin gold grains and the five heavy twin gold grains of the quasi-ellipsoid prepared by the method for quasi-ellipsoid, and realize and by five heavy twin gold grains of quasi-ellipsoid, control preparation and there are { five heavy twin gold nano grains of 110} crystal face.
To achieve these goals, on the one hand, the invention provides the preparation method of the decahedron electrum particle of a kind of five heavy twins, it is characterized in that, described method comprises: by gold chloride, silver nitrate, polyvinylpyrrolidone, water at N, in dinethylformamide, mix, gold chloride, silver nitrate, polyvinylpyrrolidone, water and N, the mol ratio of dinethylformamide is 1:0.5-1.5:2.9-3.7:2200-5600:12900-25900, and under stirring condition, the mixed liquor obtaining is reacted to 0.5-1.5h at 110-130 ℃.
Second aspect, the invention provides by said method prepare and the decahedron electrum particle of five heavy twins.
The third aspect, the invention provides the preparation method of a kind of five heavy twin gold grains, it is characterized in that, described method comprises: by gold chloride, the decahedron electrum particle of claimed in claim 2 five heavy twins, polyvinylpyrrolidone, water is at N, in dinethylformamide, mix, gold chloride, the decahedron electrum particle of five heavy twins, polyvinylpyrrolidone, water and N, the mass ratio of dinethylformamide is 1:0.02-0.04:290-415:175-415:2770-5600, and under stirring condition, the mixed liquor obtaining is reacted to 1-2h at 110-130 ℃.
Fourth aspect, the invention provides by said method prepare and five heavy twin gold grains of quasi-ellipsoid.
The 5th aspect, the invention provides the preparation method of a kind of five heavy twin gold grains, it is characterized in that, described method comprises: by five of gold chloride, quasi-ellipsoid claimed in claim 4, weigh twin gold grains, polyvinylpyrrolidone, water at N, in dinethylformamide, mix, five heavy twin gold grains, polyvinylpyrrolidone, water and the N of gold chloride, quasi-ellipsoid, the mass ratio of dinethylformamide is 1:0.003-0.01:290-415:29-90:2770-5600, and under stirring condition, the mixed liquor obtaining is reacted to 4-6h at 75-85 ℃.
The 6th aspect, the invention provides by method as above prepare and whole crystal faces be { the heavy twin gold grains of the pentagon of 110} crystal face dodecahedral five.
The 7th aspect, the invention provides the preparation method of a kind of five heavy twin gold grains, it is characterized in that, described method comprises: by gold chloride, five heavy twin gold grains of quasi-ellipsoid claimed in claim 4, polyvinylpyrrolidone, water is at N, in dinethylformamide, mix, gold chloride, five heavy twin gold grains of quasi-ellipsoid, polyvinylpyrrolidone, water and N, the mass ratio of dinethylformamide is 1:0.003-0.01:290-415:58-120:2770-5600, and under stirring condition, the mixed liquor obtaining is reacted to 1.5-2.5h at 110-130 ℃.
Eight aspect, the invention provides by method as above prepare and part crystal face be { five heavy twin gold grains of the pentagon star of 110} crystal face.
The 9th aspect, the invention provides the preparation method of a kind of five heavy twin gold grains, it is characterized in that, described method comprises: by gold chloride, five heavy twin gold grains of quasi-ellipsoid claimed in claim 4, polyvinylpyrrolidone, water is at N, in dinethylformamide, mix, gold chloride, five heavy twin gold grains of quasi-ellipsoid, polyvinylpyrrolidone, water and N, the mass ratio of dinethylformamide is 1:0.003-0.01:290-415:230-355:2770-5600, and under stirring condition, the mixed liquor obtaining is reacted to 1-2h at 110-130 ℃.
The tenth aspect, the invention provides by method as above prepare and part crystal face be { the heavy twin gold grains of the rescinded angle of 110} crystal face decahedral five.
Provided by the invention five weigh the decahedron electrum particle of twins, have the small size feature of uniform gold and silver distribution and nearly 5nm; Five heavy twin gold grains of quasi-ellipsoid provided by the invention, profile is round and smooth; Whole crystal face provided by the invention is { the heavy twin gold grain of pentagon dodecahedral five of 110} crystal face, { { 110} type isosceles trapezoid side forms, and its five twin-plane boundaries lay respectively at the centre of five sides for the pentagon end face of 110} type and ten by two; Part crystal face provided by the invention is { five heavy twin gold grains of the pentagon star of 110} crystal face, by two end faces and 20 sides, formed, two end face is { the pentagon crystal face of 110} type, the side of its acute angle isosceles triangle is the { crystal face of 111} type, the side of remaining obtuse angle isosceles triangle be the crystal face of 110} type, its five twin-plane boundaries lay respectively at the centre of five sides; Part crystal face provided by the invention is { the heavy twin gold grain of rescinded angle decahedral five of 110} crystal face, by ten larger { rescinded angle gores of 111} type, two { less { the isosceles triangle face of 110} type forms, and its twin-plane boundary is positioned at the centre of isosceles triangle for the pentagon end face of 110} type and ten.
The inventive method, make first five heavy twin structures and { 110} face combines compared with high energy, thereby the means that regulate gold grain physicochemical properties have been increased, especially the pentagon of preparation dodecahedral five weighs twin gold grain, all crystal faces be compared with high energy { 110} face, can be further used as the research material of catalysis; Five heavy twin electrum particles or gold grain prepared by the present invention have good monodispersity, electrum particle has high catalytic activity, can be as the catalyst of CO under low temperature, gold grain can be used as the making material of high sensitivity biology sensor, also can be used as medicine or the pharmaceutical carrier of oncotherapy; The inventive method is simple, quick, and preparation condition is loose, can extensive use.
Other features and advantages of the present invention partly in detail are described the specific embodiment subsequently.
Accompanying drawing explanation
(a) and (b) in Fig. 1 are the decahedron electrum particulate scan electron microscope image of five heavy twins of the embodiment of the present invention 1.1 making, and (c) in Fig. 1, (d), (e) are respectively its transmission electron microscope image, silver atoms atomic number Z-contrast imaging and gold atom atomic number Z-contrast imaging;
(a) and (b) in Fig. 2 are the transmission electron microscope image of five heavy twin gold grains of the quasi-ellipsoid made of the embodiment of the present invention 2.1; The structural representation that (c) in Fig. 2, (d) are respectively its side-looking, overlook;
(a) and (b) in Fig. 3 are that whole crystal faces that the embodiment of the present invention 3.1 is made are { the scanning electron microscope image of the pentagon dodecahedral five heavy twin gold grains of 110} crystal face; (a) and (b) in Fig. 6 are respectively its transmission electron microscope image and SEAD image, wherein arrow indication twin-plane boundary; Fig. 9 a, Fig. 9 b are respectively that it is overlooked, the structural representation of side-looking; (a) in Figure 10 is the High-Resolution Map of its center, side, illustration is the Fourier transformation image in arrow indication twin-plane boundary region in figure, (c) in Figure 10 is the Fourier transformation image of arrow indication twin-plane boundary upper area in (a) in Figure 10, and (d) in Figure 10 is the Fourier transformation image of arrow indication twin-plane boundary lower zone in (a) in Figure 10; (b) in Figure 10 is the full resolution pricture of its end face center, the Fourier transformation image of the central area that (e) in Figure 10 crosses for five twin-plane boundaries in (b) in Figure 10, (f) in Figure 10 be the Fourier transformation image in the region between two twin-plane boundaries, (b) middle lower left corner in Figure 10;
(a) and (b) in Fig. 4 are that the part crystal face that the embodiment of the present invention 4.1 is made is { the scanning electron microscope image of five heavy twin gold grains of the pentagon star of 110} crystal face; (a) and (b) in Fig. 7 are respectively its transmission electron microscope image and SEAD image, wherein arrow indication twin-plane boundary; Fig. 9 c, Fig. 9 d are respectively that it is overlooked, the structural representation of side-looking;
(a) and (b) in Fig. 5 are that the part crystal face that the embodiment of the present invention 5.1 is made is { the scanning electron microscope image of the rescinded angle decahedral five heavy twin gold grains of 110} crystal face; (a) and (b) in Fig. 8 are respectively its transmission electron microscope image and SEAD image, arrow indication twin-plane boundary wherein, and Fig. 9 e, Fig. 9 f are respectively that it is overlooked, the structural representation of side-looking.
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.
On the one hand, the invention provides the preparation method of the decahedron electrum particle of a kind of five heavy twins, described method comprises: by gold chloride, silver nitrate, polyvinylpyrrolidone, water at N, in dinethylformamide, mix, gold chloride, silver nitrate, polyvinylpyrrolidone, water and N, the mol ratio of dinethylformamide is 1:0.5-1.5:2.9-3.7:2200-5600:12900-25900, and under stirring condition, the mixed liquor obtaining is reacted to 0.5-1.5h at 110-130 ℃.
In the present invention, for gold chloride, silver nitrate, polyvinylpyrrolidone, water, add form and addition sequence without specific (special) requirements, as long as making the mol ratio of gold chloride, silver nitrate, polyvinylpyrrolidone, water and DMF is 1:0.5-1.5:2.9-3.7:2200-5600:12900-25900.
In the present invention, stirring can adopt the conventional various agitating devices in this area, in order to meet, stirs and temperature requirements, preferably adopts agitating heater, for example, can adopt magnetic agitation heater, and mixing speed is preferably 600-800rpm.
In the present invention, water is preferably ultra-pure water, and ultra-pure water refers to almost completely to be removed the conducting medium in water, again by water, the colloidal substance of dissociation, gas and organic matter are not all removed to the very water of low degree, resistivity is greater than 18M Ω cm, or approaches 18.3M Ω cm limiting value.In addition, in order to prevent that water and DMF evaporate reaction system under said temperature, to guarantee the mol ratio of each reaction raw materials, above-mentioned reaction is preferably carried out in closed container.
In the present invention, the number-average molecular weight of polyvinylpyrrolidone is preferably 50000-60000, lower same.
Referring to Fig. 1 a-1e, can find out, by gold chloride, silver nitrate, polyvinylpyrrolidone, water at N, in dinethylformamide, mix, gold chloride, silver nitrate, polyvinylpyrrolidone, water and N, the mol ratio of dinethylformamide is 1:0.5-1.5:2.9-3.7:2200-5600:12900-25900, and under stirring condition, the mixed liquor obtaining is reacted to 0.5-1.5h at 110-130 ℃, what obtain is the decahedron electrum particle of five heavy twins, has the particle size of uniform gold and silver distribution and nearly 5nm.
Second aspect, the invention provides a kind of by method as above prepare and the decahedron electrum particle of five heavy twins.
In the present invention, the decahedron electrum particle of the five heavy twins that obtain generally exists with five forms that weigh the decahedron electrum particle colloidal sols liquid of twins, hereinafter, adopt the decahedron electrum particle of five heavy twins to prepare five heavy twin gold grains of quasi-ellipsoid, by the decahedron electrum particle colloidal sols liquid of five heavy twins directly and other materials at N, in dinethylformamide, mix, but in mass ratio, only consider the decahedron electrum particle of the heavy twin of five in sol liquid, it is the quality of gold and silver, other material in sol liquid is not all taken into account in mass ratio.
The third aspect, the invention provides the preparation method of a kind of five heavy twin gold grains, described method comprises, by the decahedron electrum particle of gold chloride, five heavy twins as above, polyvinylpyrrolidone, water at N, in dinethylformamide, mix, decahedron electrum particle, polyvinylpyrrolidone, water and the N of gold chloride, five heavy twins, the mass ratio of dinethylformamide is 1:0.02-0.04:290-415:175-415:2770-5600, and under stirring condition, the mixed liquor obtaining is reacted to 1-2h at 110-130 ℃.
In the present invention, for the decahedron electrum particle of gold chloride, five heavy twins as above, polyvinylpyrrolidone, water, add form and addition sequence without specific (special) requirements, as long as making the mass ratio of decahedron electrum particle, polyvinylpyrrolidone, water and the DMF of gold chloride, five heavy twins is 1:0.02-0.04:290-415:175-415:2770-5600.
Wherein, for the optimum condition that stirs mixing water as previously mentioned, do not repeat them here.
Referring to Fig. 2 a-2d, can find out, by the decahedron electrum particle of gold chloride, five heavy twins as above, polyvinylpyrrolidone, water at N, in dinethylformamide, mix, gold chloride, five heavy twin electrum particles, polyvinylpyrrolidone, water and N, the mass ratio of dinethylformamide is 1:0.02-0.04:290-415:175-415:2770-5600, and under stirring condition, the mixed liquor obtaining is reacted to 1-2h at 110-130 ℃, what obtain is five heavy twin gold grains of quasi-ellipsoid, and profile is round and smooth.
Fourth aspect, the invention provides a kind of by method as above prepare and five heavy twin gold grains of quasi-ellipsoid.
In the present invention, five heavy twin gold grains of the quasi-ellipsoid obtaining generally exist with the form of five heavy twin gold grain sol liquid of quasi-ellipsoid, hereinafter, five heavy twin gold grains of employing quasi-ellipsoid are prepared whole crystal faces and are { the heavy twin gold grain of pentagon dodecahedral five of 110} crystal face, part crystal face is that { five heavy twin gold grains of the pentagon star of 110} crystal face or part crystal face are { the heavy twin gold grain of rescinded angle decahedral five of 110} crystal face, by five heavy twin gold grain sol liquid of quasi-ellipsoid directly and other materials at N, in dinethylformamide, mix, but in mass ratio, only consider five heavy twin gold grains of the quasi-ellipsoid in sol liquid, it is golden quality, other material in sol liquid is not all taken into account in mass ratio.
The 5th aspect, the invention provides the preparation method of a kind of five heavy twin gold grains, described method comprises: by five of gold chloride, quasi-ellipsoid as above, weigh twin gold grains, polyvinylpyrrolidone, water at N, in dinethylformamide, mix, five heavy twin gold grains, polyvinylpyrrolidone, water and the N of gold chloride, quasi-ellipsoid, the mass ratio of dinethylformamide is 1:0.003-0.01:290-415:29-90:2770-5600, and under stirring condition, the mixed liquor obtaining is reacted to 4-6h at 75-85 ℃.
In the present invention, for five heavy twin gold grains of gold chloride, quasi-ellipsoid, polyvinylpyrrolidone, water, add form and addition sequence without specific (special) requirements, as long as making the mass ratio of five heavy twin gold grains, polyvinylpyrrolidone, water and the DMF of gold chloride, quasi-ellipsoid is 1:0.003-0.01:290-415:29-90:2770-5600.
Wherein, for the optimum condition that stirs mixing water as previously mentioned, do not repeat them here.
Referring to Fig. 3 a-3b, Fig. 6 a-6b, Fig. 9 a-9b and Figure 10 a-10f, by gold chloride, five heavy twin gold grains of quasi-ellipsoid obtained above, polyvinylpyrrolidone, N, dinethylformamide mixes in water, gold chloride, five heavy twin gold grains of quasi-ellipsoid, polyvinylpyrrolidone, water and N, the mass ratio of dinethylformamide is 1:0.003-0.01:290-415:29-90:2770-5600, and under stirring condition, the mixed liquor obtaining is reacted to 4-6h at 75-85 ℃, what obtain is that whole crystal faces are { the heavy twin gold grain of pentagon dodecahedral five of 110} crystal face, by two { the pentagon end face of 110} type and ten { 110} type isosceles trapezoid side formations, its five twin-plane boundaries lay respectively at the centre of five sides.
In the present invention, all crystal faces are that { all crystal faces that 110} crystal face refers to five heavy twin gold grains are { 110} type.
In the present invention, for the whole crystal faces that make to obtain are { the stabilized structure of the pentagon dodecahedral five heavy twin gold grains of 110} crystal face, it is cooling that described method preferably also comprises that ice bath is carried out in reaction after finishing, it is cooling that more preferably ice bath is carried out in reaction after finishing immediately, and ice bath is preferably 10-20min cool time.
The inventive method preferably also comprises after the cooling end of ice bath, gained particle is cleaned, for the method for cleaning without specific (special) requirements, can adopt the conventional the whole bag of tricks in this area, for example, the cooling fluid of cooling gained, with the centrifugal 4-6min of 9000-11000rpm, is removed after supernatant, appropriate deionized water, ultrasonic cleaning 4-6min will be added in the precipitation obtaining; Continue with the centrifugal 3-5min of 7000-9000rpm, remove after supernatant, by adding appropriate deionized water in the precipitation obtaining, repeat this step at least one times.
The 6th aspect, the invention provides a kind of by method as above prepare and whole crystal faces be { the heavy twin gold grains of the pentagon of 110} crystal face dodecahedral five.
The 7th aspect, the invention provides the preparation method of a kind of five heavy twin gold grains, described method comprises: by five of gold chloride, quasi-ellipsoid as above, weigh twin gold grains, polyvinylpyrrolidone, water at N, in dinethylformamide, mix, five heavy twin gold grains, polyvinylpyrrolidone, water and the N of gold chloride, quasi-ellipsoid, the mass ratio of dinethylformamide is 1:0.003-0.01:290-415:58-120:2770-5600, and under stirring condition, the mixed liquor obtaining is reacted to 1.5-2.5h at 110-130 ℃.
In the present invention, for five heavy twin gold grains of gold chloride, quasi-ellipsoid, polyvinylpyrrolidone, water, add form and addition sequence without specific (special) requirements, as long as making the mass ratio of five heavy twin gold grains, polyvinylpyrrolidone, water and the DMF of gold chloride, quasi-ellipsoid is 1:0.003-0.01:290-415:58-120:2770-5600.
Wherein, for the optimum condition that stirs mixing water as previously mentioned, do not repeat them here.
Referring to Fig. 4 a-4b, Fig. 7 a-7b and Fig. 9 c-9d, can find out, by gold chloride, five heavy twin gold grains of quasi-ellipsoid obtained above, polyvinylpyrrolidone, N, dinethylformamide mixes in water, gold chloride, five heavy twin gold grains of quasi-ellipsoid, polyvinylpyrrolidone, water and N, the mass ratio of dinethylformamide is 1:0.003-0.01:290-415:58-120:2770-5600, and under stirring condition, the mixed liquor obtaining is reacted to 1.5-2.5h at 110-130 ℃, what obtain is that part crystal face is { five heavy twin gold grains of the pentagon star of 110} crystal face, by two end faces and 20 sides, formed, two end face is { the pentagon crystal face of 110} type, the side of its acute angle isosceles triangle is the { crystal face of 111} type, the side of remaining obtuse angle isosceles triangle is the { crystal face of 110} type, its five twin-plane boundaries lay respectively at the centre of five sides.
In the present invention, part crystal face is for { 110} crystal face refers to a part in all crystal faces of five heavy twin gold grains for { 110} type, and another part is not { 110} type.
In the present invention, for the part crystal face that makes to obtain is { the stabilized structure of five heavy twin gold grains of the pentagon star of 110} crystal face, it is cooling that described method preferably also comprises that ice bath is carried out in reaction after finishing, it is cooling that more preferably ice bath is carried out in reaction after finishing immediately, and ice bath is preferably 10-20min cool time.
The inventive method preferably also comprises after the cooling end of ice bath, and gained particle is cleaned, and the method for cleaning as previously mentioned, does not repeat them here.
Eight aspect, the invention provides a kind of by method as above prepare and part crystal face be { five heavy twin gold grains of the pentagon star of 110} crystal face.
The 9th aspect, the invention provides the preparation method of a kind of five heavy twin gold grains, described method comprises: by five of gold chloride, quasi-ellipsoid as above, weigh twin gold grains, polyvinylpyrrolidone, water at N, in dinethylformamide, mix, five heavy twin gold grains, polyvinylpyrrolidone, water and the N of gold chloride, quasi-ellipsoid, the mass ratio of dinethylformamide is 1:0.003-0.01:290-415:230-355:2770-5600, and under stirring condition, the mixed liquor obtaining is reacted to 1-2h at 110-130 ℃.
In the present invention, for five heavy twin gold grains of gold chloride, quasi-ellipsoid, polyvinylpyrrolidone, water, add form and addition sequence without specific (special) requirements, as long as making the mass ratio of five heavy twin gold grains, polyvinylpyrrolidone, water and the DMF of gold chloride, quasi-ellipsoid is 1:0.003-0.01:290-415:230-355:2770-5600.
Wherein, for the optimum condition that stirs mixing water as previously mentioned, do not repeat them here.
Referring to Fig. 5 a-5b, Fig. 8 a-8b and Fig. 9 e-9f, can find out, by gold chloride, five heavy twin gold grains of quasi-ellipsoid obtained above, polyvinylpyrrolidone, water is at N, in dinethylformamide, mix, gold chloride, five heavy twin gold grains of quasi-ellipsoid, polyvinylpyrrolidone, water and N, the mass ratio of dinethylformamide is 1:0.003-0.01:290-415:230-355:2770-5600, and under stirring condition, the mixed liquor obtaining is reacted to 1-2h at 110-130 ℃, what obtain is that part crystal face is { the heavy twin gold grain of rescinded angle decahedral five of 110} crystal face, by ten larger { the rescinded angle gore of 111} type and ten less { isosceles triangle face formations of 110} type, its twin-plane boundary is positioned at the centre of isosceles triangle.
In the present invention, for the part crystal face that makes to obtain is { the stabilized structure of the rescinded angle decahedral five heavy twin gold grains of 110} crystal face, it is cooling that described method preferably also comprises that ice bath is carried out in reaction after finishing, it is cooling that more preferably ice bath is carried out in reaction after finishing immediately, and ice bath is preferably 10-20min cool time.
The inventive method preferably also comprises after the cooling end of ice bath, and gained particle is cleaned, and the method for cleaning as previously mentioned, does not repeat them here.
The tenth aspect, the invention provides a kind of by method as above prepare and part crystal face be { the heavy twin gold grains of the rescinded angle of 110} crystal face decahedral five.
Below describe by reference to the accompanying drawings the preferred embodiment of the present invention in detail; but; the present invention is not limited to the detail in above-mentioned embodiment; within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each concrete technical characterictic described in 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.
Embodiment
The present invention is further illustrated for following embodiment, but therefore do not limit the present invention.
In the following embodiments:
DMF (DMF): be purchased from Alfa Aesar, purity is 99.5+%.
Gold chloride: be purchased from Alfa Aesar, purity is 99.9%.
Silver nitrate: be purchased from Alfa Aesar, purity is 99.9%.
Polyvinylpyrrolidone: be purchased from Sigma Aldrich, number-average molecular weight is 55000.
Water is ultra-pure water, and the resistivity purifying purchased from the electrodeionization machine in U.S. Electropure company is the ultra-pure water of 18.2 Ω cm standards.
Embodiment 1
The present embodiment is for illustrating the preparation of the decahedron electrum particle of of the present invention five heavy twins.
In the present embodiment:
The scanning electron microscope image of the product preparing, transmission electron microscope image, silver atoms atomic number Z-contrast imaging and gold atom atomic number Z-contrast imaging: by product centrifugal 20min under 50000rpm of preparation, by the centrifugal product of removing after supernatant, be scattered in 5ml ultra-pure water, getting 5 μ l drops on the copper mesh of ultrathin carbon films, employing Tecnai G2 F20 U-TWIN field transmission electron microscope (being purchased from U.S. FEI Co., lower same) is observed, imaging.The attachment function of the atomic number Z-contrast imaging (STEM-HAADF) of silver atoms atomic number Z-contrast imaging and gold atom atomic number Z-contrast imaging employing Tecnai G2 F20 U-TWIN field transmission electron microscope is observed, imaging.
The diameter of product particle: by random 50 particles being measured under transmission electron microscope.
Embodiment 1.1
By gold chloride, silver nitrate, polyvinylpyrrolidone, water at N, in dinethylformamide, mix, gold chloride, silver nitrate, polyvinylpyrrolidone, water and N, the mol ratio of dinethylformamide is 1:1:3.3:3900:19120, adopt magnetic agitation, mixing speed is 700rpm, the mixed liquor obtaining is reacted to 1h at 120 ℃, the scanning electron microscope image of the product obtaining is shown in Fig. 1 a, Fig. 1 b, transmission electron microscope image is shown in Fig. 1 c, silver atoms atomic number Z-contrast imaging is shown in Fig. 1 d, and gold atom atomic number Z-contrast imaging is shown in Fig. 1 e.The diameter of product particle is 5-6nm.
Embodiment 1.2
By gold chloride, silver nitrate, polyvinylpyrrolidone, N, dinethylformamide mixes in water, gold chloride, silver nitrate, polyvinylpyrrolidone, N, the mol ratio of dinethylformamide and water is 1:0.5:3.7:2200:25900, adopt magnetic agitation, mixing speed is 800rpm, the mixed liquor obtaining is reacted to 1.5h at 110 ℃, the scanning electron microscope image of the product obtaining, transmission electron microscope image, silver atoms atomic number Z-contrast imaging, gold atom atomic number Z-contrast imaging are similar with embodiment 1.1 respectively, attached not shown.The diameter of product particle is 5-6nm.
Embodiment 1.3
By gold chloride, silver nitrate, polyvinylpyrrolidone, N, dinethylformamide mixes in water, gold chloride, silver nitrate, polyvinylpyrrolidone, N, the mol ratio of dinethylformamide and water is 1:1.5:2.9:5600:12900, adopt magnetic agitation, mixing speed is 600rpm, the mixed liquor obtaining is reacted to 0.5h at 130 ℃, the scanning electron microscope image of the product obtaining, transmission electron microscope image, silver atoms atomic number Z-contrast imaging, gold atom atomic number Z-contrast imaging are similar with embodiment 1.1 respectively, attached not shown.The diameter of product particle is 5-6nm.
Embodiment 2
The present embodiment is for illustrating the preparation of five heavy twin gold grains of quasi-ellipsoid of the present invention.
In the present embodiment:
The decahedron electrum particle of five heavy twins is the decahedron electrum particle of the five heavy twins that prepare of embodiment 1.1.
The transmission electron microscope image of the product preparing: by product centrifugal 30min under 15000rpm of preparation, after removing supernatant, add suitable quantity of water, repeat above-mentioned centrifugation step totally three times, the centrifugal product of removing after supernatant is scattered in 5ml ultra-pure water again, get 5 μ l and drop on the copper mesh of ultrathin carbon films, employing Tecnai G2 F20 U-TWIN field transmission electron microscope is observed, imaging.
The diameter of product particle: by random 50 particles being measured under transmission electron microscope.
Embodiment 2.1
By gold chloride, the decahedron electrum particle of five heavy twins, polyvinylpyrrolidone, water is at N, in dinethylformamide, mix, gold chloride, the decahedron electrum particle of five heavy twins, polyvinylpyrrolidone, water and N, the mass ratio of dinethylformamide is 1:0.03:353:295:4168, adopt magnetic agitation, mixing speed is 700rpm, the mixed liquor obtaining is reacted to 1.5h at 120 ℃, the transmission electron microscope image of the product obtaining is shown in Fig. 2 a, Fig. 2 b, the side-looking of drawing according to transmission electron microscope image, the structural representation of overlooking is shown in respectively Fig. 2 c, Fig. 2 d.The diameter of product particle is 18-20nm.
Embodiment 2.2
By the decahedron electrum particle of gold chloride, five heavy twins, polyvinylpyrrolidone, water at N, in dinethylformamide, mix, decahedron electrum particle, polyvinylpyrrolidone, water and the N of gold chloride, five heavy twins, the mass ratio of dinethylformamide is 1:0.02:415:175:5600, adopt magnetic agitation, mixing speed is 800rpm, the mixed liquor obtaining is reacted to 2h at 110 ℃, the transmission electron microscope image of the product obtaining, axially and laterally the structural representation of observation is similar with embodiment 2.1 respectively, attached not shown.The diameter of product particle is 18-20nm.
Embodiment 2.3
By the decahedron electrum particle of gold chloride, five heavy twins, polyvinylpyrrolidone, water at N, in dinethylformamide, mix, decahedron electrum particle, polyvinylpyrrolidone, water and the N of gold chloride, five heavy twins, the mass ratio of dinethylformamide is 1:0.04:290:415:2770, adopt magnetic agitation, mixing speed is 600rpm, the mixed liquor obtaining is reacted to 1h at 130 ℃, the transmission electron microscope image of the product obtaining, axially and laterally the structural representation of observation is similar with embodiment 2.1 respectively, attached not shown.The diameter of product particle is 18-20nm.
Embodiment 3
The present embodiment is used for illustrating that whole crystal face of the present invention is the { preparation of the pentagon dodecahedral five heavy twin gold grains of 110} crystal face.
In the present embodiment:
Five heavy twin gold grains of quasi-ellipsoid are five heavy twin gold grains of the quasi-ellipsoid for preparing of embodiment 2.1.
The scanning electron microscope image of the product preparing: get the product obtaining after whole eccentric cleaning and add in 1ml ultra-pure water, fully mix, getting the mixed mixed liquor of 10 μ l drops on the silicon chip of a 5mm * 5mm, in the insulating box of 60 degree, after placing 1h, take out, the cold field emission scanning electron microscope of employing hitach S-4800 (being purchased from hitach company, lower same) is observed, imaging.
The transmission electron microscope image of the product preparing and SEAD image: get above-mentioned same mixed liquor 5 μ l, drop on the copper mesh of ultrathin carbon films, employing Tecnai G2 F20 U-TWIN field transmission electron microscope is observed, imaging.
The size of product particle: by random 50 particles being measured under SEM.
Embodiment 3.1
By gold chloride, five heavy twin gold grains of quasi-ellipsoid, polyvinylpyrrolidone, water is at N, in dinethylformamide, mix, gold chloride, five heavy twin gold grains of quasi-ellipsoid, polyvinylpyrrolidone, water and N, the mass ratio of dinethylformamide is 1:0.007:353:59:4168, adopt magnetic agitation, mixing speed is 700rpm, the mixed liquor obtaining is reacted to 5h at 80 ℃, the cooling 15min of ice bath immediately after reaction finishes, by the cooling fluid of cooling gained with the centrifugal 5min of 10000rpm, remove after supernatant, appropriate deionized water will be added in the precipitation obtaining, ultrasonic cleaning 5min, continue with the centrifugal 4min of 8000rpm, remove after supernatant, by adding appropriate deionized water in the precipitation obtaining, repeat this step once.The scanning electron microscope image of the product obtaining is shown in Fig. 3 a, Fig. 3 b, and transmission electron microscope image is shown in Fig. 6 a, and SEAD image is shown in Fig. 6 b, according to transmission electron microscope image, draw overlook, the structural representation of side-looking is shown in respectively Fig. 9 a, Fig. 9 b.The thickness of product particle is 80-90nm, incline is long is 50-60nm, side is long is 110-120nm, the side of end face is long for 60-70nm(is as shown in Fig. 9 b, particle is highly its thickness along the page longitudinally, and the side that the length of side of upper and lower two horizontal planes is its end face is long, the length of side of by-level face for its side long, connect upper and lower two horizontal planes and by-level face rib length for its incline long, lower with).
Embodiment 3.2
By gold chloride, five heavy twin gold grains of quasi-ellipsoid, polyvinylpyrrolidone, water is at N, in dinethylformamide, mix, gold chloride, five heavy twin gold grains of quasi-ellipsoid, polyvinylpyrrolidone, water and N, the mass ratio of dinethylformamide is 1:0.003:415:29:5600, adopt magnetic agitation, mixing speed is 800rpm, the mixed liquor obtaining is reacted to 6h at 75 ℃, the cooling 10min of ice bath immediately after reaction finishes, by the cooling fluid of cooling gained with the centrifugal 6min of 9000rpm, remove after supernatant, appropriate deionized water will be added in the precipitation obtaining, ultrasonic cleaning 4min, continue with the centrifugal 5min of 7000rpm, remove after supernatant, by adding appropriate deionized water in the precipitation obtaining, repeat this step once.The scanning electron microscope diagram of the product obtaining, transmission electron microscope image, SEAD image, overlook with the structural representation of side-looking similar with embodiment 3.1 respectively, attached not shown.The thickness of product particle is 80-90nm, and incline is long is 50-60nm, and side is long is 110-120nm, and the side length of end face is 60-70nm.
Embodiment 3.3
By gold chloride, five heavy twin gold grains of quasi-ellipsoid, polyvinylpyrrolidone, water is at N, in dinethylformamide, mix, gold chloride, five heavy twin gold grains of quasi-ellipsoid, polyvinylpyrrolidone, water and N, the mass ratio of dinethylformamide is 1:0.01:290:90:2770, adopt magnetic agitation, mixing speed is 600rpm, the mixed liquor obtaining is reacted to 4h at 85 ℃, the cooling 20min of ice bath immediately after reaction finishes, by the cooling fluid of cooling gained with the centrifugal 4min of 11000rpm, remove after supernatant, appropriate deionized water will be added in the precipitation obtaining, ultrasonic cleaning 6min, continue with the centrifugal 3min of 9000rpm, remove after supernatant, by adding appropriate deionized water in the precipitation obtaining, repeat this step once.The scanning electron microscope diagram of the product obtaining, transmission electron microscope image, SEAD image, overlook with the structural representation of side-looking similar with embodiment 3.1 respectively, attached not shown.The thickness of product particle is 80-90nm, and incline is long is 50-60nm, and side is long is 110-120nm, and the side length of end face is 60-70nm.
Embodiment 4
The present embodiment is used for illustrating that part crystal face of the present invention is for { the preparation of five heavy twin gold grains of the pentagon star of 110} crystal face.
In the present embodiment:
Five heavy twin gold grains of quasi-ellipsoid are five heavy twin gold grains of the quasi-ellipsoid for preparing of embodiment 2.1.
The scanning electron microscope image of the product preparing: get the product obtaining after whole eccentric cleaning and add in 1ml ultra-pure water, fully mix, getting the mixed mixed liquor of 10 μ l drops on the silicon chip of a 5mm * 5mm, in the insulating box of 60 degree, after placing 1h, take out, the cold field emission scanning electron microscope of employing hitach S-4800 is observed, imaging.
The transmission electron microscope image of the product preparing and SEAD image: get above-mentioned same mixed liquor 5 μ l, drop on the copper mesh of ultrathin carbon films, employing Tecnai G2 F20 U-TWIN field transmission electron microscope is observed, imaging.
The size of product particle: by random 50 particles being measured under SEM.
Embodiment 4.1
By gold chloride, five heavy twin gold grains of quasi-ellipsoid, polyvinylpyrrolidone, water is at N, in dinethylformamide, mix, gold chloride, five heavy twin gold grains of quasi-ellipsoid, polyvinylpyrrolidone, water and N, the mass ratio of dinethylformamide is 1:0.007:353:89:4168, adopt magnetic agitation, mixing speed is 700rpm, the mixed liquor obtaining is reacted to 2h at 120 ℃, the cooling 15min of ice bath immediately after reaction finishes, by the cooling fluid of cooling gained with the centrifugal 5min of 10000rpm, remove after supernatant, appropriate deionized water will be added in the precipitation obtaining, ultrasonic cleaning 5min, continue with the centrifugal 4min of 8000rpm, remove after supernatant, by adding appropriate deionized water in the precipitation obtaining, repeat this step once.The scanning electron microscope image of the product obtaining is shown in Fig. 4 a, Fig. 4 b, and transmission electron microscope image is shown in Fig. 7 a, and SEAD image is shown in Fig. 7 b, according to transmission electron microscope image, draw overlook, the structural representation of side-looking is shown in respectively Fig. 9 c, Fig. 9 d.The thickness of product particle is 70-80nm, incline is long is 55-65nm, side is long is 105-115nm, the side of end face is long for 55-65nm(is as shown in Fig. 9 d, particle is highly its thickness along the page longitudinally, and the side that the length of side of upper and lower two horizontal planes is its end face is long, the length of side of by-level face for its side long, connect upper and lower two horizontal planes and by-level face rib length for its incline long, lower with).
Embodiment 4.2
By gold chloride, five heavy twin gold grains of quasi-ellipsoid, polyvinylpyrrolidone, water is at N, in dinethylformamide, mix, gold chloride, five heavy twin gold grains of quasi-ellipsoid, polyvinylpyrrolidone, water and N, the mass ratio of dinethylformamide is 1:0.003:415:58:5600, adopt magnetic agitation, mixing speed is 800rpm, the mixed liquor obtaining is reacted to 2.5h at 110 ℃, the cooling 10min of ice bath immediately after reaction finishes, by the cooling fluid of cooling gained with the centrifugal 6min of 9000rpm, remove after supernatant, appropriate deionized water will be added in the precipitation obtaining, ultrasonic cleaning 4min, continue with the centrifugal 5min of 7000rpm, remove after supernatant, by adding appropriate deionized water in the precipitation obtaining, repeat this step once.The scanning electron microscope diagram of the product obtaining, transmission electron microscope image, SEAD image, overlook with the structural representation of side-looking similar with embodiment 4.1 respectively, attached not shown.The thickness of product particle is 70-80nm, and incline is long is 55-65nm, and side is long is 105-115nm, and the side length of end face is 55-65nm.
Embodiment 4.3
By gold chloride, five heavy twin gold grains of quasi-ellipsoid, polyvinylpyrrolidone, water is at N, in dinethylformamide, mix, gold chloride, five heavy twin gold grains of quasi-ellipsoid, polyvinylpyrrolidone, water and N, the mass ratio of dinethylformamide is 1:0.01:290:120:2770, adopt magnetic agitation, mixing speed is 600rpm, the mixed liquor obtaining is reacted to 1.5h at 130 ℃, the cooling 20min of ice bath immediately after reaction finishes, by the cooling fluid of cooling gained with the centrifugal 4min of 11000rpm, remove after supernatant, appropriate deionized water will be added in the precipitation obtaining, ultrasonic cleaning 6min, continue with the centrifugal 3min of 9000rpm, remove after supernatant, by adding appropriate deionized water in the precipitation obtaining, repeat this step once.The scanning electron microscope diagram of the product obtaining, transmission electron microscope image, SEAD image, overlook with the structural representation of side-looking similar with embodiment 4.1 respectively, attached not shown.The thickness of product particle is 70-80nm, and incline is long is 55-65nm, and side is long is 105-115nm, and the side length of end face is 55-65nm.
The present embodiment is used for illustrating that part crystal face of the present invention is for { the preparation of the rescinded angle decahedral five heavy twin gold grains of 110} crystal face.
In the present embodiment:
Five heavy twin gold grains of quasi-ellipsoid are five heavy twin gold grains of the quasi-ellipsoid for preparing of embodiment 2.1.
The scanning electron microscope image of the product preparing: get the product that whole eccentric cleaning obtain and add in 1ml ultra-pure water, fully mix, getting the mixed mixed liquor of 10 μ l drops on the silicon chip of a 5mm * 5mm, in the insulating box of 60 degree, after placing 1h, take out, the cold field emission scanning electron microscope of employing hitach S-4800 is observed, imaging.
The transmission electron microscope image of the product preparing and SEAD image: get above-mentioned same mixed liquor 5 μ l, drop on the copper mesh of ultrathin carbon films, employing Tecnai G2 F20 U-TWIN field transmission electron microscope is observed, imaging.
The size of product particle: by random 50 particles being measured under SEM.
Embodiment 5.1
By gold chloride, five heavy twin gold grains of quasi-ellipsoid, polyvinylpyrrolidone, water is at N, in dinethylformamide, mix, gold chloride, five heavy twin gold grains of quasi-ellipsoid, polyvinylpyrrolidone, water and N, the mass ratio of dinethylformamide is 1:0.007:353:295:4168, adopt magnetic agitation, mixing speed is 700rpm, the mixed liquor obtaining is reacted to 1.5h at 120 ℃, the cooling 15min of ice bath immediately after reaction finishes, by the cooling fluid of cooling gained with the centrifugal 5min of 10000rpm, remove after supernatant, appropriate deionized water will be added in the precipitation obtaining, ultrasonic cleaning 5min, continue with the centrifugal 4min of 8000rpm, remove after supernatant, by adding appropriate deionized water in the precipitation obtaining, repeat this step once.The scanning electron microscope image of the product obtaining is shown in Fig. 5 a, Fig. 5 b, and transmission electron microscope image is shown in Fig. 8 a, and SEAD image is shown in Fig. 8 b, according to transmission electron microscope image, draw overlook, the structural representation of side-looking is shown in respectively Fig. 9 e, Fig. 9 f.The incline length of product particle is 80-90nm, the rescinded angle pentagon face length of side at axis place is 16-20nm, the rescinded angle face at twin-plane boundary place is isosceles triangle, waist is 18-20nm, base is that the pentagon of 37-42nm(Fig. 9 e center is the rescinded angle pentagon face at axis place, the isosceles triangle of Fig. 9 f center is the isosceles triangle rescinded angle face at twin-plane boundary place, all length of sides except the length of side that the rescinded angle pentagon face at axis place and the isosceles triangle rescinded angle face at twin-plane boundary place relate to are that incline is long, lower with).
Embodiment 5.2
By gold chloride, five heavy twin gold grains of quasi-ellipsoid, polyvinylpyrrolidone, water is at N, in dinethylformamide, mix, gold chloride, five heavy twin gold grains of quasi-ellipsoid, polyvinylpyrrolidone, water and N, the mass ratio of dinethylformamide is 1:0.003:415:230:5600, adopt magnetic agitation, mixing speed is 800rpm, the mixed liquor obtaining is reacted to 2h at 110 ℃, the cooling 10min of ice bath immediately after reaction finishes, by the cooling fluid of cooling gained with the centrifugal 6min of 9000rpm, remove after supernatant, appropriate deionized water will be added in the precipitation obtaining, ultrasonic cleaning 4min, continue with the centrifugal 5min of 7000rpm, remove after supernatant, by adding appropriate deionized water in the precipitation obtaining, repeat this step once.The scanning electron microscope diagram of the product obtaining, transmission electron microscope image, SEAD image, overlook with the structural representation of side-looking similar with embodiment 5.1 respectively, attached not shown.The incline length of product particle is 80-90nm, and the rescinded angle pentagon face length of side at axis place is 16-20nm, and the rescinded angle face at twin-plane boundary place is isosceles triangle, and waist is 18-20nm, and base is 37-42nm.
Embodiment 5.3
By gold chloride, five heavy twin gold grains of quasi-ellipsoid, polyvinylpyrrolidone, water is at N, in dinethylformamide, mix, gold chloride, five heavy twin gold grains of quasi-ellipsoid, polyvinylpyrrolidone, water and N, the mass ratio of dinethylformamide is 1:0.01:290:355:2770, adopt magnetic agitation, mixing speed is 600rpm, the mixed liquor obtaining is reacted to 1h at 130 ℃, the cooling 20min of ice bath immediately after reaction finishes, by the cooling fluid of cooling gained with the centrifugal 4min of 11000rpm, remove after supernatant, appropriate deionized water will be added in the precipitation obtaining, ultrasonic cleaning 6min, continue with the centrifugal 3min of 9000rpm, remove after supernatant, by adding appropriate deionized water in the precipitation obtaining, repeat this step once.The scanning electron microscope diagram of the product obtaining, transmission electron microscope image, SEAD image, overlook with the structural representation of side-looking similar with embodiment 5.1 respectively, attached not shown.The incline length of product particle is 80-90nm, and the rescinded angle pentagon face length of side at axis place is 16-20nm, and the rescinded angle face at twin-plane boundary place is isosceles triangle, and waist is 18-20nm, and base is 37-42nm.
The crystal data of the five heavy twin gold grains that obtain preparing in embodiment 3-5 by X-ray diffraction comprises: point group symmetry D5h, lattice constant is a=4.0786 dust.
Known according to the scanning electron microscope image of embodiment 1, transmission electron microscope image, silver atoms atomic number Z-contrast imaging and gold atom atomic number Z-contrast imaging, product in embodiment 1 is the decahedron electrum particle of five heavy twins, has the small size of uniform gold and silver distribution and nearly 5nm.
The five heavy twin gold grains known according to the transmission electron microscope image of embodiment 2, the product in embodiment 2 is quasi-ellipsoid, profile is round and smooth.
Known according to the transmission electron microscope full resolution pricture of embodiment 3, SEAD image, Fourier transformation, the product in embodiment 3 is that whole crystal faces are { the heavy twin gold grains of pentagon dodecahedral five of 110} crystal face.The electron beam of SEAD is parallel with the five heavy axis along <110> direction, and end face is perpendicular to five heavy axis, by known two the pentagon end faces of image K-M, it is { the crystal face of 110} type, further transmission electron microscope full resolution pricture and its corresponding Fourier transformation image can be determined this conclusion again, and can be by the structure refinement of end face five by { the 110} crystal face formation of separated five different orientations of twin-plane boundary; The High-Resolution Map of side similarly is to be verted to gained vertical with electron beam by its side, the Fourier transformation figure of high resolution picture is shown as the { diffraction pattern of 110} type, can obtain thus its ten isosceles trapezoid sides for the crystal face of 110} type, and the side that can be refined as each isosceles trapezoid by separated two different orientations of twin-plane boundary { 110} crystal face forms; The high resolution picture of transmission electron microscope image and side can observe the centre that its five twin-plane boundaries lay respectively at five sides.
According to the SEAD image of embodiment 4 and Morphology Evolution analysis, product in embodiment 4 is that part crystal face is { five heavy twin gold grains of the pentagon star of 110} crystal face, two end faces and 20 sides, consisting of, is { the pentagon crystal face of 110} type by known two end face of SEAD image, by completely by { five heavy twin gold grains of the decahedra that 111} crystal face is coated develop and deduce to five heavy twin gold grains of pentagon star again to the decahedral five heavy twin gold grains of rescinded angle, the side of the acute angle isosceles triangle of five heavy twin gold grains of known pentagon star is the { crystal face of 111} type, on the other hand, five heavy twin gold grain continued growths of pentagon star, obtuse angle isosceles triangle is just expanded as isosceles trapezoid gradually, acute angle isosceles triangle fades away, finally just can be evolved into pentagon dodecahedron, simultaneously because pentagon dodecahedron side is by { 110} crystal face is coated, so can instead push away the side of the obtuse angle isosceles triangle of the five heavy twin gold grains of learning pentagon star is the { crystal face of 110} type, transmission electron microscope image can observe the centre that its five twin-plane boundaries lay respectively at five sides.
According to the SEAD image of embodiment 5 and Morphology Evolution, analyze known, product in embodiment 5 is that part crystal face is { the heavy twin gold grain of rescinded angle decahedral five of 110} crystal face, by ten larger { the rescinded angle gore of 111} type and ten less { isosceles triangle face formations of 110} type, the determination methods of five heavy twin gold grains of the judgement of its crystal face type and pentagon star is similar, do not repeat them here, transmission electron microscope image shows that its twin-plane boundary is positioned at the centre of isosceles triangle.
The inventive method, make first five heavy twin structures and compared with high energy { 110} face combines, thereby make five heavy twin gold grains there are the physicochemical properties that more pattern determines, especially the pentagon of preparation dodecahedral five weighs twin gold grain, completely by compared with high energy { 110} bread is wrapped up in, and can be further used as the research material of high-energy surface catalysis; Five heavy twin electrum particles or gold grain prepared by the present invention have good monodispersity, electrum particle has high catalytic activity, can be as the catalyst of CO under low temperature, gold grain can be used as the making material of high sensitivity biology sensor, also can be used as medicine or the pharmaceutical carrier of oncotherapy; The inventive method is simple, quick, and preparation condition is loose, can extensive use.
Claims (13)
1. the preparation method of the decahedron electrum particle of one kind five heavy twin, it is characterized in that, described method comprises: by gold chloride, silver nitrate, polyvinylpyrrolidone, water at N, in dinethylformamide, mix, gold chloride, silver nitrate, polyvinylpyrrolidone, water and N, the mol ratio of dinethylformamide is 1:0.5-1.5:2.9-3.7:2200-5600:12900-25900, and under stirring condition, the mixed liquor obtaining is reacted to 0.5-1.5h at 110-130 ℃.
One kind by method claimed in claim 1, prepared and the decahedron electrum particle of five heavy twins.
3. the preparation method of one kind five heavy twin gold grain, it is characterized in that, described method comprises: by the decahedron electrum particle of gold chloride, five heavy twins claimed in claim 2, polyvinylpyrrolidone, water at N, in dinethylformamide, mix, decahedron electrum particle, polyvinylpyrrolidone, water and the N of gold chloride, five heavy twins, the mass ratio of dinethylformamide is 1:0.02-0.04:290-415:175-415:2770-5600, and under stirring condition, the mixed liquor obtaining is reacted to 1-2h at 110-130 ℃.
4. five of a quasi-ellipsoid of being prepared by method claimed in claim 3 and obtaining weigh twin gold grains.
5. the preparation method of one kind five heavy twin gold grain, it is characterized in that, described method comprises: by five of gold chloride, quasi-ellipsoid claimed in claim 4, weigh twin gold grains, polyvinylpyrrolidone, water at N, in dinethylformamide, mix, five heavy twin gold grains, polyvinylpyrrolidone, water and the N of gold chloride, quasi-ellipsoid, the mass ratio of dinethylformamide is 1:0.003-0.01:290-415:29-90:2770-5600, and under stirring condition, the mixed liquor obtaining is reacted to 4-6h at 75-85 ℃.
6. whole crystal faces of being prepared by method claimed in claim 5 and obtaining are { the heavy twin gold grain of pentagon dodecahedral five of 110} crystal face.
7. the preparation method of one kind five heavy twin gold grain, it is characterized in that, described method comprises: by five of gold chloride, quasi-ellipsoid claimed in claim 4, weigh twin gold grains, polyvinylpyrrolidone, water at N, in dinethylformamide, mix, five heavy twin gold grains, polyvinylpyrrolidone, water and the N of gold chloride, quasi-ellipsoid, the mass ratio of dinethylformamide is 1:0.003-0.01:290-415:58-120:2770-5600, and under stirring condition, the mixed liquor obtaining is reacted to 1.5-2.5h at 110-130 ℃.
8. a part crystal face of being prepared by method claimed in claim 7 and obtaining is { five heavy twin gold grains of the pentagon star of 110} crystal face.
9. the preparation method of one kind five heavy twin gold grain, it is characterized in that, described method comprises: by five of gold chloride, quasi-ellipsoid claimed in claim 4, weigh twin gold grains, polyvinylpyrrolidone, water at N, in dinethylformamide, mix, five heavy twin gold grains, polyvinylpyrrolidone, water and the N of gold chloride, quasi-ellipsoid, the mass ratio of dinethylformamide is 1:0.003-0.01:290-415:230-355:2770-5600, and under stirring condition, the mixed liquor obtaining is reacted to 1-2h at 110-130 ℃.
10. a part crystal face of being prepared by method claimed in claim 9 and obtaining is { the heavy twin gold grain of rescinded angle decahedral five of 110} crystal face.
11. according to the method described in claim 1,3,5,7 or 9, and wherein, described water is ultra-pure water.
12. according to the method described in claim 1,3,5,7 or 9, and wherein, the number-average molecular weight of polyvinylpyrrolidone is 50000-60000.
13. according to the method described in claim 5,7 or 9, and wherein, it is cooling that described method also comprises that ice bath is carried out in reaction after finishing.
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| CN107243626A (en) * | 2017-04-05 | 2017-10-13 | 厦门稀土材料研究所 | The synthesis of Silver nanorod and based on its prepare Raman spectrum base |
| CN107243626B (en) * | 2017-04-05 | 2020-05-26 | 厦门稀土材料研究所 | Synthesis of silver nanorod and preparation of surface enhanced Raman spectrum substrate based on silver nanorod |
| CN108637269B (en) * | 2018-04-25 | 2021-06-25 | 中国科学院合肥物质科学研究院 | Gold nano double pyramid with quintuple twin crystal structure and preparation method thereof |
| CN108637269A (en) * | 2018-04-25 | 2018-10-12 | 中国科学院合肥物质科学研究院 | A kind of gold nano bipyramid and preparation method thereof with five weight twin structures |
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| CN111888342A (en) * | 2020-07-02 | 2020-11-06 | 南方医科大学南方医院 | Drug-loaded nano-composite and preparation method and application thereof |
| CN111888342B (en) * | 2020-07-02 | 2022-03-15 | 南方医科大学南方医院 | Drug-loaded nano-composite and preparation method and application thereof |
| CN112481655B (en) * | 2020-10-26 | 2021-09-21 | 杭州师范大学 | Preparation method and application of Pd-Ru-Cu alloy type icosahedral nano-catalyst |
| CN112481655A (en) * | 2020-10-26 | 2021-03-12 | 杭州师范大学 | Preparation method and application of Pd-Ru-Cu alloy type icosahedral nano-catalyst |
| CN113369492A (en) * | 2021-06-09 | 2021-09-10 | 合肥工业大学 | Quintuple twin crystal platinum nanorod and preparation method thereof |
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