CN101708554A - Method for synthesizing gold hollow shell layer nano structural material by wet chemical method - Google Patents
Method for synthesizing gold hollow shell layer nano structural material by wet chemical method Download PDFInfo
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Abstract
The invention discloses a method for synthesizing a gold hollow shell layer nano structural material by a wet chemical method, which comprises the following steps: firstly, preparing a high-purity germanium dioxide nano square by a micro emulsion method; secondly, modifying the surface of the high-purity germanium dioxide nano square by using aminopropyl trimethoxy silane, and then reacting the high-purity germanium dioxide nano square with chlorauric acid to generate a germanium dioxide nano composite material of which the surface has gold particles; and finally, heating and reacting the nano composite material in a mixed aqueous solution of potassium carbonate and the chlorauric acid, and then performing centrifugal purification and separation on the mixture to obtain a gold hollow shell layer structure. The nano material prepared by the method has the advantages of controllable appearance, high purity, good performance and the like, and has very good repeatability. The method is a high-efficiency method and can accurately control the synthesis of the gold hollow shell layer nano material. The method can be applied in the fields of medicaments, sensing, optical detection, catalysis and the like.
Description
Technical field
The present invention relates to preparation method of nano material, especially relate to a kind of method of synthesizing gold hollow shell layer nano structural material by wet chemical.
Background technology
Nano material and nanostructured be the most dynamic in the current new material research field, the future economy and social development are had the very research object of material impact, also be the most active in the nanosecond science and technology, the important component part of approaching application.When the size of nano particle dropped to certain value, electron energy level was by the quasi-continuous discrete energy level that changes near the metallic Fermi surface; And the Nano semiconductor particulate exists the highest discontinuous molecular orbital energy level that is occupied and the minimum molecular orbital energy level that is not occupied, and makes the phenomenon that energy gap broadens, and is called as the quantum size effect of nano material.In nano particle, be in a series of special natures that The Wave Behavior of Electrons in the discrete quantized level has brought nano particle, as high optical nonlinearity, special catalysis and photocatalysis property etc.Size and optical wavelength when nano particle, de Broglie wavelength, the coherence length of superconducting state or with the magnetic field penetration degree of depth quite or more hour, crystal periodic boundary condition is with destroyed, near the particle surface layer of amorphous nano particulate atomic density reduces, and causes characteristics such as sound, light, electricity, magnetic, thermodynamics to occur and the distinct phenomenon of block materials.
Gold is very important a kind of in the precious metal material, just begins to be studied from faraday's epoch.On tradition was used, nm of gold by extensive studies and application, again because gold utensil has good biocompatibility, thereby became the emphasis in the biomedical research as catalysis material, colouring agent in recent years.Nm of gold has very strong plasma resonance phenomenon, and different patterns is being controlled the skew of plasma resonance absorbing wavelength, and the spectral absorption peak of the gold grain about for example monodispersed 10nm and is covered in the SiO of 100nm near 520nm
2The absworption peak of the golden shell of the 10nm of outer surface of ball can reach more than the 900nm.There is strong response to have meaning aspect the important biomedical near infrared band to light absorption, because at this wavelength frequency range people in-vivo tissue, blood the decling phase contrast visible light of light is much smaller, so prepare the emphasis that golden shell layer nano structural becomes people's research.Existing at present research is by direct-reduction process, and finishing reducing process, template etc. have prepared SiO
2/ gold goal forming core shell structure, Fe
2O
3/ golden cuneiform nucleus shell structure, gold square hollow porous cage or the like specifically can list of references: Langmuir, and 18 (2002), 4915; Nano lett., 6 (2006), 827; Chem.Soc.Rev., 35 (2006), 1084 etc.Above method all can prepare the material with golden shell layer nano structural, but reaction condition relative complex all, the reaction time is long, and output is also relatively low.Simultaneously according to the knowledge of the applicant, the golden shell nano material of reporting is not up to now also prepared common traits such as large scale, square, hollow-core construction, surface are complete.
Summary of the invention
The method that the purpose of this invention is to provide a kind of synthesizing gold hollow shell layer nano structural material by wet chemical adopts template to prepare hollow shell layer, has the nano material of strong near infrared band response.
In order to achieve the above object, the step of the technical solution used in the present invention is as follows:
One, used raw material:
Purity is 99.99% anhydrous germanium tetrachloride GeCl
4,
Analyze pure tetrahydrofuran C
4H
8O,
Analyze pure octane C
7H
16,
Analyze pure amylalcohol C
5H
12O,
Concentration is the aqueous solution of 75% formaldehyde,
Analyze pure cetyl trimethyl ammonia bromide C
19H
42BrN,
Purity is 97% oleyl amine C
18H
37N,
Analyze pure absolute ethyl alcohol C
2H
6O,
Purity is 99% gold chloride HAuCl
43H
2O,
Purity is 98% no water sodium hydroxide NaOH,
Purity is 97% amine propyl trimethoxy silicane,
Purity is 99% Anhydrous potassium carbonate K
2CO
3, above reagent does not all pass through purification process;
Two, preparation method:
(1) anhydrous GeCl
4Be dissolved in the oxolane that to form molar concentration be the transparent solution of 0.5mol/L;
(2) with 30 parts by volume octanes, 3.6 parts by volume n-amyl alcohols and after 1 parts by volume formalin mixes, the mixed solution that obtains adds CTAB, and the quality of CTAB and the volume ratio of mixed solution are 1.25g/15mL;
(3) with 10 parts by volume octanes, 1.4 parts by volume oleyl amines and 1 parts by volume GeCl
4The mixed solution of 34.6 parts by volume that obtain with (2) step again of the mixed solution of 12.4 parts by volume that obtain after mixing of tetrahydrofuran solution mixes and adds in the container and under 78HW-3 type constant temperature magnetic agitation instrument, mix and stir the transparent microemulsion of formation;
(4) container that transparent micro emulsion is housed that (3) step was obtained places ultrasonic cleaner supersonic frequency 40KHz vibration to stop reaction after 3～5 minutes, the white opacity solution that reaction is obtained passes through 10000r/minSORVALL LEGEND-T centrifuge centrifugation 15min, obtain solid product and repeatedly disperse washing, centrifugal with absolute ethyl alcohol, obtain pure germanium dioxide square solid product, this product adds anhydrous alcohol solution and forms the germanium dioxide square ethanolic solution of 10 parts by volume in order to next step reaction usefulness.
(5) be that the ethanolic solution of 10 parts germanium dioxide square takes out 6 parts by volume with (4) volume that makes of step, then with the ethanolic solution of the germanium dioxide square of this 6 parts by volume, the amine propyl trimethoxy silicane of 4 parts by volume mixes with 190 parts by volume absolute ethyl alcohols to add and stirs in the container behind the 24h at 60 ℃ of following backflow 1h, the white opacity solution that reaction is obtained passes through 10000r/min SORVALL LEGEND-T centrifuge centrifugation 15min, obtain solid product and repeatedly disperse washing with absolute ethyl alcohol, centrifugal, obtain the germanium dioxide solid product that amine oxypropyl trimethyl silane is modified, the ethanolic solution that this product adding anhydrous alcohol solution forms the germanium dioxide of 30 parts by volume amine oxypropyl trimethyl silane modification is used in order to next step reaction.
(6) gold chloride is dissolved in the deionized water that to form mass concentration be 5% yellow transparent solution, NaOH is dissolved in to form molar concentration in the deionized water be the colourless transparent solution of 0.5mol/L.
(7) ethanolic solution of the germanium dioxide of the amine oxypropyl trimethyl silane modification that (5) step was made takes out (6) of 4 parts by volume and 1.2 parts by volume and goes on foot the aqueous solution of chloraurate that makes, 0.8 in 80 ℃ of water-baths, leave standstill 5min after the NaOH aqueous solution that (6) step of parts by volume makes adds in the container, the brownish red turbid solution that reaction is obtained passes through 2000r/min SORVALL LEGEND-T centrifuge centrifugation 15min, obtain solid product and repeatedly disperse washing with absolute ethyl alcohol, centrifugal, the germanium dioxide solid product of the brownish red surface coverage gold grain that obtains, the ethanol solution that this product adding anhydrous alcohol solution forms the germanium dioxide of 30 parts by volume surface coverage gold grains is used in order to next step reaction.
(8) K
2CO
3Pressed powder is made into the K of 250mg/L with the volumetric flask constant volume
2CO
3Behind the aqueous solution, with the K of 200 parts by volume
2CO
35% aqueous solution of chloraurate of the aqueous solution and 0.6 parts by volume mixes to add to preserve in the brown container in order to next step reaction to be used.
(9) ethanolic solution of the germanium dioxide of the surface coverage gold grain that (7) step was made takes out (8) of 4 parts by volume and 4～16 parts by volume and goes on foot the K that makes
2CO
3/ gold chloride mixed aqueous solution leaves standstill 5min after mixing in the adding container in 80 ℃ of water-baths, the brownish red turbid solution that reaction is obtained passes through 10000r/min SORVALLLEGEND-T centrifuge centrifugation 15min, obtain solid product and repeatedly disperse washing, centrifugal, repeat the brownish red gold hollow shell layer nano structural material that obtains after 3 times with absolute ethyl alcohol.
The beneficial effect that the present invention has is:
1) reaction is the liquid phase participation and prepares material by chemical reaction, and the preparation method is simple, can repeat preparation, the productive rate height.
2) this preparation process is only being carried out in the mixed solution of ethanolic solution or alcohol-water, and raw material is simple, the product purity height.
3) the gold hollow shell layer nano material for preparing reaches more than the 900nm the absorbing wavelength of light, and near infrared spectrum is had very big response, can be applied to fields such as medicine, sensing, optical detection, catalysis.
Description of drawings
Fig. 1 is the transmission electron microscope photo of the germanium dioxide square nano structural material of embodiment 1 preparation.
Fig. 2 is the XRD phenogram of the germanium dioxide square nano structural material of embodiment 1 preparation.
Fig. 3 is the transmission electron microscope photo that the surface of embodiment 1 preparation coats the germanium dioxide nano material of gold grain.
Fig. 4 is the transmission electron microscope photo of the gold hollow shell layer nano structural material of embodiment 1 preparation.
Fig. 5 is the stereoscan photograph of the gold hollow shell layer nano structural material of embodiment 1 preparation.
Fig. 6 is the X-ray energy spectrum figure of the gold hollow shell layer nano structural material of embodiment 1 preparation.
Fig. 7 is the abosrption spectrogram of the gold hollow shell layer nano structural material of embodiment 1 preparation.
The specific embodiment
Embodiment 1:
Step according to technical scheme is carried out.At first, with the anhydrous GeCl of 5g
4Be dissolved in the 44mL oxolane that to form molar concentration be the transparent solution of 0.5mol/L.0.5mol/L GeCl with the mixed solution of 15mL octane, 1.8mL amylalcohol, 0.5mL formalin and four kinds of materials of 1.25g CTAB and 5ml octane, 0.7mL oleyl amine, 0.5mL
4The mixed solution of three kinds of materials of tetrahydrofuran solution mix to add beaker and under 78HW-3 type constant temperature magnetic agitation instrument, mix to stir and form transparent microemulsion; The beaker that transparent micro emulsion is housed that obtains places the ultrasonic cleaner sonic oscillation to stop reaction after 3 minutes, the white opacity solution that reaction is obtained passes through 10000r/min centrifugation 15min, obtain solid product and disperse washing once more with absolute ethyl alcohol, centrifugal once more, repeat the pure white germanium dioxide solid product that obtains after 3 times, this product is with 5mL ethanol dissolving bottling.Secondly, the ethanolic solution that takes out the 3mL germanium dioxide mixes with 2mL amine propyl trimethoxy silicane and 95mL ethanol in the adding conical flask behind the stirring 24h at 60 ℃ of following backflow 1h, the white opacity solution that reaction is obtained passes through 10000r/min centrifuge centrifugation 15min, obtain solid product and disperse washing once more with absolute ethyl alcohol, centrifugal once more, repeat the germanium dioxide solid product of the amine oxypropyl trimethyl silane modified that obtains after 3 times, this product is with 15mL ethanol dissolving bottling.Once more, it is that the 1mol/L NaOH aqueous solution of 5% aqueous solution of chloraurate and 0.2mL adds in the conical flask and then leaves standstill 5min in 80 ℃ of water-baths that the ethanolic solution of the germanium dioxide of the amine oxypropyl trimethyl silane modified that obtains is before taken out 2mL and 0.3mL mass fraction, the brownish red turbid solution that reaction is obtained passes through 2000r/min centrifugation 15min, obtain solid product and disperse washing once more with absolute ethyl alcohol, centrifugal once more, repeat the germanium dioxide solid product of the brownish red surface coverage gold grain that obtains after 3 times, this product is with 15mL ethanol dissolving bottling.At last, use 25mg K
2CO
3Pressed powder be made into the K of 250mg/L with 100mL volumetric flask constant volume
2CO
3Behind the aqueous solution, mix with 5% aqueous solution of chloraurate of 0.3mL and to add in the brown jar, with the ethanolic solution and the 8mL K of the germanium dioxide of 2mL surface coverage gold grain
2CO
3/ gold chloride mixed aqueous solution leaves standstill 5min after mixing in the adding conical flask in 80 ℃ of water-baths, the brownish red turbid solution that reaction is obtained passes through 10000r/min centrifugation 15min, obtain solid product and disperse washing once more with absolute ethyl alcohol, centrifugal once more, repeat the brownish red gold hollow shell layer nano structural material that obtains after 3 times.The transmissioning electric mirror test sample is that the pressed powder taking-up that will obtain after the drying is dispersed in the absolute ethyl alcohol on a small quantity again, draws two with liquid-transfering gun and drops in the clean copper mesh surface that is coated with one deck carbon film.The sem test sample then be with sample drop on the silicon chip and stick on the aluminium base sample platform, Fig. 1 has provided the stereoscan photograph according to the germanium dioxide nano structural material of embodiment 1 preparation.Fig. 2 has provided the XRD phenogram according to the germanium dioxide nano structural material of embodiment 1 preparation.The germanium dioxide that as can be seen from Figure 1 prepares is the square shape substantially entirely, helps last golden shell and presents square hollow shell layer structure.As can be seen from Figure 2 the germanium dioxide product is very pure, does not contain any impurity.Fig. 3 has provided the transmission electron microscope photo that coats the germanium dioxide nano material of gold grain according to the surface of embodiment 1 preparation.The as can be seen from Figure 3 general 10nm of the gold grain left and right sides outer surface that covers the germanium dioxide square of uniform size.Fig. 4 has provided the transmission electron microscope photo according to the gold hollow shell layer nano structural material of embodiment 1 preparation.As can be seen from Figure 4 significantly square shape, the length of side are 300nm, and shell thickness is the gold hollow shell layer structure of 50nm.Fig. 5 has provided the stereoscan photograph according to the gold hollow shell layer nano structural material of embodiment 1 preparation.As can be seen from Figure 5 the hollow shell layer of square shape gold can well be arranged in together.Fig. 6 has provided the X-ray energy spectrum figure according to the gold hollow shell layer nano structural material of embodiment 1 preparation.As can be seen from Figure 6 product is gold fully, and does not have germanium dioxide remnants.Fig. 7 has provided the abosrption spectrogram according to the gold hollow shell layer nano structural material of embodiment 1 preparation.As can be seen from Figure 7 the absworption peak of gold hollow shell layer has surpassed the scope that instrument can be tested at 900nm, wants to have embodied extraordinary performance about red shift 400nm than the discrete particles absworption peak 520nm of common gold.
Embodiment 2:
Step according to technical scheme is carried out.At first, with the anhydrous GeCl of 5g
4Be dissolved in the 44mL oxolane that to form molar concentration be the transparent solution of 0.5mol/L.0.5mol/L GeCl with the mixed solution of 15mL octane, 1.8mL amylalcohol, 0.5mL formalin and four kinds of materials of 1.25g CTAB and 5ml octane, 0.7mL oleyl amine, 0.5mL
4The mixed solution of three kinds of materials of tetrahydrofuran solution mix to add beaker and under 78HW-3 type constant temperature magnetic agitation instrument, mix to stir and form transparent microemulsion; The beaker that transparent micro emulsion is housed that obtains places the ultrasonic cleaner sonic oscillation to stop reaction after 4 minutes, the white opacity solution that reaction is obtained passes through 10000r/min centrifugation 15min, obtain solid product and disperse washing once more with absolute ethyl alcohol, centrifugal once more, repeat the pure white germanium dioxide solid product that obtains after 3 times, this product is with 5mL ethanol dissolving bottling.Secondly, the ethanolic solution that takes out the 3mL germanium dioxide mixes with 2mL amine propyl trimethoxy silicane and 95mL ethanol in the adding conical flask behind the stirring 24h at 60 ℃ of following backflow 1h, the white opacity solution that reaction is obtained passes through 10000r/min centrifuge centrifugation 15min, obtain solid product and disperse washing once more with absolute ethyl alcohol, centrifugal once more, repeat the germanium dioxide solid product of the amine oxypropyl trimethyl silane modified that obtains after 3 times, this product is with 15mL ethanol dissolving bottling.Once more, it is that the 1mol/L NaOH aqueous solution of 5% aqueous solution of chloraurate and 0.2mL adds in the conical flask and then leaves standstill 5min in 80 ℃ of water-baths that the ethanolic solution of the germanium dioxide of the amine oxypropyl trimethyl silane modified that obtains is before taken out 2mL and 0.3mL mass fraction, the brownish red turbid solution that reaction is obtained passes through 2000r/min centrifugation 15min, obtain solid product and disperse washing once more with absolute ethyl alcohol, centrifugal once more, repeat the germanium dioxide solid product of the brownish red surface coverage gold grain that obtains after 3 times, this product is with 15mL ethanol dissolving bottling.At last, use 25mg K
2CO
3Pressed powder be made into the K of 250mg/L with 100mL volumetric flask constant volume
2CO
3Behind the aqueous solution, mix with 5% aqueous solution of chloraurate of 0.3mL and to add in the brown jar, with the ethanolic solution and the 8mL K of the germanium dioxide of 2mL surface coverage gold grain
2CO
3/ gold chloride mixed aqueous solution leaves standstill 5min after mixing in the adding conical flask in 80 ℃ of water-baths, the brownish red turbid solution that reaction is obtained passes through 10000r/min centrifugation 15min, obtain solid product and disperse washing once more with absolute ethyl alcohol, centrifugal once more, repeat the brownish red product that obtains after 3 times.Product is that square shape, the length of side are 400nm, and shell thickness is the gold hollow shell layer structure of 50nm.
Embodiment 3:
Step according to technical scheme is carried out.At first, with the anhydrous GeCl of 5g
4Be dissolved in the 44mL oxolane that to form molar concentration be the transparent solution of 0.5mol/L.0.5mol/L GeCl with the mixed solution of 15mL octane, 1.8mL amylalcohol, 0.5mL formalin and four kinds of materials of 1.25g CTAB and 5ml octane, 0.7mL oleyl amine, 0.5mL
4The mixed solution of three kinds of materials of tetrahydrofuran solution mix to add beaker and under 78HW-3 type constant temperature magnetic agitation instrument, mix to stir and form transparent microemulsion; The beaker that transparent micro emulsion is housed that obtains places the ultrasonic cleaner sonic oscillation to stop reaction after 5 minutes, the white opacity solution that reaction is obtained passes through 10000r/min centrifugation 15min, obtain solid product and disperse washing once more with absolute ethyl alcohol, centrifugal once more, repeat the pure white germanium dioxide solid product that obtains after 3 times, this product is with 5mL ethanol dissolving bottling.Secondly, the ethanolic solution that takes out the 3mL germanium dioxide mixes with 2mL amine propyl trimethoxy silicane and 95mL ethanol in the adding conical flask behind the stirring 24h at 60 ℃ of following backflow 1h, the white opacity solution that reaction is obtained passes through 10000r/min centrifuge centrifugation 15min, obtain solid product and disperse washing once more with absolute ethyl alcohol, centrifugal once more, repeat the germanium dioxide solid product of the amine oxypropyl trimethyl silane modified that obtains after 3 times, this product is with 15mL ethanol dissolving bottling.Once more, it is that the 1mol/L NaOH aqueous solution of 5% aqueous solution of chloraurate and 0.2mL adds in the conical flask and then leaves standstill 5min in 80 ℃ of water-baths that the ethanolic solution of the germanium dioxide of the amine oxypropyl trimethyl silane modified that obtains is before taken out 2mL and 0.3mL mass fraction, the brownish red turbid solution that reaction is obtained passes through 2000r/min centrifugation 15min, obtain solid product and disperse washing once more with absolute ethyl alcohol, centrifugal once more, repeat the germanium dioxide solid product of the brownish red surface coverage gold grain that obtains after 3 times, this product is with 15mL ethanol dissolving bottling.At last, use 25mg K
2CO
3Pressed powder be made into the K of 250mg/L with 100mL volumetric flask constant volume
2CO
3Behind the aqueous solution, mix with 5% aqueous solution of chloraurate of 0.3mL and to add in the brown jar, with the ethanolic solution and the 8mL K of the germanium dioxide of 2mL surface coverage gold grain
2CO
3/ gold chloride mixed aqueous solution leaves standstill 5min after mixing in the adding conical flask in 80 ℃ of water-baths, the brownish red turbid solution that reaction is obtained passes through 10000r/min centrifugation 15min, obtain solid product and disperse washing once more with absolute ethyl alcohol, centrifugal once more, repeat the brownish red product that obtains after 3 times.Product is that square shape, the length of side are that 600nm, shell thickness are the gold hollow shell layer structure of 50nm.
Embodiment 4:
Step according to technical scheme is carried out.At first, with the anhydrous GeCl of 5g
4Be dissolved in the 44mL oxolane that to form molar concentration be the transparent solution of 0.5mol/L.0.5mol/L GeCl with the mixed solution of 15mL octane, 1.8mL amylalcohol, 0.5mL formalin and four kinds of materials of 1.25g CTAB and 5ml octane, 0.7mL oleyl amine, 0.5mL
4The mixed solution of three kinds of materials of tetrahydrofuran solution mix to add beaker and under 78HW-3 type constant temperature magnetic agitation instrument, mix to stir and form transparent microemulsion; The beaker that transparent micro emulsion is housed that obtains places the ultrasonic cleaner sonic oscillation to stop reaction after 3 minutes, the white opacity solution that reaction is obtained passes through 10000r/min centrifugation 15min, obtain solid product and disperse washing once more with absolute ethyl alcohol, centrifugal once more, repeat the pure white germanium dioxide solid product that obtains after 3 times, this product is with 5mL ethanol dissolving bottling.Secondly, the ethanolic solution that takes out the 3mL germanium dioxide mixes with 2mL amine propyl trimethoxy silicane and 95mL ethanol in the adding conical flask behind the stirring 24h at 60 ℃ of following backflow 1h, the white opacity solution that reaction is obtained passes through 10000r/min centrifuge centrifugation 15min, obtain solid product and disperse washing once more with absolute ethyl alcohol, centrifugal once more, repeat the germanium dioxide solid product of the amine oxypropyl trimethyl silane modified that obtains after 3 times, this product is with 15mL ethanol dissolving bottling.Once more, it is that the 1mol/L NaOH aqueous solution of 5% aqueous solution of chloraurate and 0.2mL adds in the conical flask and then leaves standstill 5min in 80 ℃ of water-baths that the ethanolic solution of the germanium dioxide of the amine oxypropyl trimethyl silane modified that obtains is before taken out 2mL and 0.3mL mass fraction, the brownish red turbid solution that reaction is obtained passes through 2000r/min centrifugation 15min, obtain solid product and disperse washing once more with absolute ethyl alcohol, centrifugal once more, repeat the germanium dioxide solid product of the brownish red surface coverage gold grain that obtains after 3 times, this product is with 15mL ethanol dissolving bottling.At last, use 25mg K
2CO
3Pressed powder be made into the K of 250mg/L with 100mL volumetric flask constant volume
2CO
3Behind the aqueous solution, mix with 5% aqueous solution of chloraurate of 0.3mL and to add in the brown jar, with the ethanolic solution and the 2mL K of the germanium dioxide of 2mL surface coverage gold grain
2CO
3/ gold chloride mixed aqueous solution leaves standstill 5min after mixing in the adding conical flask in 80 ℃ of water-baths, the brownish red turbid solution that reaction is obtained passes through 10000r/min centrifugation 15min, obtain solid product and disperse washing once more with absolute ethyl alcohol, centrifugal once more, repeat the brownish red product that obtains after 3 times.Product is that square shape, the length of side are that 250nm, shell thickness are the gold hollow shell layer structure of 25nm.
Embodiment 5:
Step according to technical scheme is carried out.At first, with the anhydrous GeCl of 5g
4Be dissolved in the 44mL oxolane that to form molar concentration be the transparent solution of 0.5mol/L.0.5mol/L GeCl with the mixed solution of 15mL octane, 1.8mL amylalcohol, 0.5mL formalin and four kinds of materials of 1.25g CTAB and 5ml octane, 0.7mL oleyl amine, 0.5mL
4The mixed solution of three kinds of materials of tetrahydrofuran solution mix to add beaker and under 78HW-3 type constant temperature magnetic agitation instrument, mix to stir and form transparent microemulsion; The beaker that transparent micro emulsion is housed that obtains places the ultrasonic cleaner sonic oscillation to stop reaction after 3 minutes, the white opacity solution that reaction is obtained passes through 10000r/min centrifugation 15min, obtain solid product and disperse washing once more with absolute ethyl alcohol, centrifugal once more, repeat the pure white germanium dioxide solid product that obtains after 3 times, this product is with 5mL ethanol dissolving bottling.Secondly, the ethanolic solution that takes out the 3mL germanium dioxide mixes with 2mL amine propyl trimethoxy silicane and 95mL ethanol in the adding conical flask behind the stirring 24h at 60 ℃ of following backflow 1h, the white opacity solution that reaction is obtained passes through 10000r/min centrifuge centrifugation 15min, obtain solid product and disperse washing once more with absolute ethyl alcohol, centrifugal once more, repeat the germanium dioxide solid product of the amine oxypropyl trimethyl silane modified that obtains after 3 times, this product is with 15mL ethanol dissolving bottling.Once more, it is that the 1mol/L NaOH aqueous solution of 5% aqueous solution of chloraurate and 0.2mL adds in the conical flask and then leaves standstill 5min in 80 ℃ of water-baths that the ethanolic solution of the germanium dioxide of the amine oxypropyl trimethyl silane modified that obtains is before taken out 2mL and 0.3mL mass fraction, the brownish red turbid solution that reaction is obtained passes through 2000r/min centrifugation 15min, obtain solid product and disperse washing once more with absolute ethyl alcohol, centrifugal once more, repeat the germanium dioxide solid product of the brownish red surface coverage gold grain that obtains after 3 times, this product is with 15mL ethanol dissolving bottling.At last, use 25mg K
2CO
3Pressed powder be made into the K of 250mg/L with 100mL volumetric flask constant volume
2CO
3Behind the aqueous solution, mix with 5% aqueous solution of chloraurate of 0.3mL and to add in the brown jar, with the ethanolic solution and the 4mL K of the germanium dioxide of 2mL surface coverage gold grain
2CO
3/ gold chloride mixed aqueous solution leaves standstill 5min after mixing in the adding conical flask in 80 ℃ of water-baths, the brownish red turbid solution that reaction is obtained passes through 10000r/min centrifugation 15min, obtain solid product and disperse washing once more with absolute ethyl alcohol, centrifugal once more, repeat the brownish red product that obtains after 3 times.Product is that square shape, the length of side are that 270nm, shell thickness are the gold hollow shell layer structure of 35nm.
Claims (1)
1. the method for a synthesizing gold hollow shell layer nano structural material by wet chemical is characterized in that the step of this method is as follows:
One, used raw material:
Purity is 99.99% anhydrous germanium tetrachloride GeCl
4,
Analyze pure tetrahydrofuran C
4H
8O,
Analyze pure octane C
7H
16,
Analyze pure amylalcohol C
5H
12O,
Concentration is the aqueous solution of 75% formaldehyde,
Analyze pure cetyl trimethyl ammonia bromide C
19H
42BrN,
Purity is 97% oleyl amine C
18H
37N,
Analyze pure absolute ethyl alcohol C
2H
6O,
Purity is 99% gold chloride HAuCl
43H
2O,
Purity is 98% no water sodium hydroxide NaOH,
Purity is 97% amine propyl trimethoxy silicane,
Purity is 99% Anhydrous potassium carbonate K
2CO
3, above reagent does not all pass through purification process;
Two, preparation method:
(1) anhydrous GeCl
4Be dissolved in the oxolane that to form molar concentration be the transparent solution of 0.5mol/L;
(2) with 30 parts by volume octanes, 3.6 parts by volume n-amyl alcohols and after 1 parts by volume formalin mixes, the mixed solution that obtains adds CTAB, and the quality of CTAB and the volume ratio of mixed solution are 1.25g/15mL;
(3) with 10 parts by volume octanes, 1.4 parts by volume oleyl amines and 1 parts by volume GeCl
4The mixed solution of 34.6 parts by volume that obtain with (2) step again of the mixed solution of 12.4 parts by volume that obtain after mixing of tetrahydrofuran solution mixes and adds in the container and under 78HW-3 type constant temperature magnetic agitation instrument, mix and stir the transparent microemulsion of formation;
(4) container that transparent micro emulsion is housed that (3) step was obtained places ultrasonic cleaner supersonic frequency 40KHz vibration to stop reaction after 3～5 minutes, the white opacity solution that reaction is obtained passes through 10000r/minSORVALL LEGEND-T centrifuge centrifugation 15min, obtain solid product and repeatedly disperse washing, centrifugal with absolute ethyl alcohol, obtain pure germanium dioxide square solid product, this product adds anhydrous alcohol solution and forms the germanium dioxide square ethanolic solution of 10 parts by volume in order to next step reaction usefulness.
(5) be that the ethanolic solution of 10 parts germanium dioxide square takes out 6 parts by volume with (4) volume that makes of step, then with the ethanolic solution of the germanium dioxide square of this 6 parts by volume, the amine propyl trimethoxy silicane of 4 parts by volume mixes with 190 parts by volume absolute ethyl alcohols to add and stirs in the container behind the 24h at 60 ℃ of following backflow 1h, the white opacity solution that reaction is obtained passes through 10000r/min SORVALL LEGEND-T centrifuge centrifugation 15min, obtain solid product and repeatedly disperse washing with absolute ethyl alcohol, centrifugal, obtain the germanium dioxide solid product that amine oxypropyl trimethyl silane is modified, the ethanolic solution that this product adding anhydrous alcohol solution forms the germanium dioxide of 30 parts by volume amine oxypropyl trimethyl silane modification is used in order to next step reaction;
(6) gold chloride is dissolved in the deionized water that to form mass concentration be 5% yellow transparent solution, NaOH is dissolved in to form molar concentration in the deionized water be the colourless transparent solution of 0.5mol/L;
(7) ethanolic solution of the germanium dioxide of the amine oxypropyl trimethyl silane modification that (5) step was made takes out (6) of 4 parts by volume and 1.2 parts by volume and goes on foot the aqueous solution of chloraurate that makes, 0.8 in 80 ℃ of water-baths, leave standstill 5min after the NaOH aqueous solution that (6) step of parts by volume makes adds in the container, the brownish red turbid solution that reaction is obtained passes through 2000r/min SORVALL LEGEND-T centrifuge centrifugation 15min, obtain solid product and repeatedly disperse washing with absolute ethyl alcohol, centrifugal, the germanium dioxide solid product of the brownish red surface coverage gold grain that obtains, the ethanol solution that this product adding anhydrous alcohol solution forms the germanium dioxide of 30 parts by volume surface coverage gold grains is used in order to next step reaction;
(8) K
2CO
3Pressed powder is made into the K of 250mg/L with the volumetric flask constant volume
2CO
3Behind the aqueous solution, with the K of 200 parts by volume
2CO
35% aqueous solution of chloraurate of the aqueous solution and 0.6 parts by volume mixes to add to preserve in the brown container in order to next step reaction to be used;
(9) ethanolic solution of the germanium dioxide of the surface coverage gold grain that (7) step was made takes out (8) of 4 parts by volume and 4～16 parts by volume and goes on foot the K that makes
2CO
3/ gold chloride mixed aqueous solution leaves standstill 5min after mixing in the adding container in 80 ℃ of water-baths, the brownish red turbid solution that reaction is obtained passes through 10000r/min SORVALLLEGEND-T centrifuge centrifugation 15min, obtain solid product and repeatedly disperse washing, centrifugal, repeat the brownish red gold hollow shell layer nano structural material that obtains after 3 times with absolute ethyl alcohol.
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| CN107812200A (en) * | 2017-10-21 | 2018-03-20 | 天津大学 | BSA-gadolinium ionic complex-coated hollow gold nanosheet and preparation method thereof |
| CN108288712A (en) * | 2017-12-21 | 2018-07-17 | 浙江天能能源科技股份有限公司 | A kind of lithium ion battery negative material Fe2O3Preparation method |
| CN112730381A (en) * | 2020-12-25 | 2021-04-30 | 南京航空航天大学 | Preparation method of surface-enhanced Raman scattering optical fiber probe |
| CN115365510A (en) * | 2022-08-26 | 2022-11-22 | 杭州师范大学 | Bi-metal multilayer porous hollow nano particle with Yolk-Shell structure and synthetic method thereof |
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2009
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| CN107812200A (en) * | 2017-10-21 | 2018-03-20 | 天津大学 | BSA-gadolinium ionic complex-coated hollow gold nanosheet and preparation method thereof |
| CN107812200B (en) * | 2017-10-21 | 2020-11-06 | 天津大学 | BSA-gadolinium ionic complex-coated hollow gold nanosheet and preparation method thereof |
| CN108288712A (en) * | 2017-12-21 | 2018-07-17 | 浙江天能能源科技股份有限公司 | A kind of lithium ion battery negative material Fe2O3Preparation method |
| CN112730381A (en) * | 2020-12-25 | 2021-04-30 | 南京航空航天大学 | Preparation method of surface-enhanced Raman scattering optical fiber probe |
| CN115365510A (en) * | 2022-08-26 | 2022-11-22 | 杭州师范大学 | Bi-metal multilayer porous hollow nano particle with Yolk-Shell structure and synthetic method thereof |
| CN115365510B (en) * | 2022-08-26 | 2023-06-23 | 杭州师范大学 | Bimetal multilayer porous hollow nanoparticle with Yolk-Shell structure and synthesis method thereof |
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