CN103170648A - Preparation method of hollow metal microspheres - Google Patents
Preparation method of hollow metal microspheres Download PDFInfo
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- CN103170648A CN103170648A CN2013101210977A CN201310121097A CN103170648A CN 103170648 A CN103170648 A CN 103170648A CN 2013101210977 A CN2013101210977 A CN 2013101210977A CN 201310121097 A CN201310121097 A CN 201310121097A CN 103170648 A CN103170648 A CN 103170648A
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Abstract
A preparation method of hollow metal microspheres relates to a composite material. The invention provides a preparation method of hollow metal microspheres which is quick, environment-friendly and simple in subsequent treatment process. The preparation method comprises the steps of preparing gold nanoparticles and titanium dioxide successively, and then functionalizing the surface of titanium dioxide, and then preparing Au/TiO2, and finally preparing the hollow metal microspheres. Titanium dioxide microspheres are used as templates, and dimension-controllable PtM metal hollow microspheres are prepared by means of the pH sensitivity of the titanium dioxide. The size of the PtM metal hollow microspheres can be controlled by regulating the size of the template titanium dioxide, and simultaneously, the thickness of the PtM metal hollow microspheres can be changed by changing the concentration of the metal precursor. Multi-layer PtM hollow microspheres are synthesized with the titanium dioxide as the templates; and therefore, the preparation method of the hollow microspheres is expanded. Besides, the technical conditions are mild and easy to control, the reaction time is short, the templates are easy to remove without use of a high temperature or a strong acid and a strong base, and the like, and simultaneously, the subsequent treatment process is simple.
Description
Technical field
The present invention relates to a kind of composite, especially relate to a kind of preparation method of hollow metal microballoon.
Background technology
Nano material with hollow structure has multiple different application because having low-density, easily recovery, saving cost and good Surface Permeability, such as catalysis, drug delivery, artificial material, light filler, insulating materials, dielectric materials, photonic crystal etc., especially aspect catalysis, have the nano material of hollow structure and show better catalytic performance than the nano material of common solid construction.At present, the metal hollow microballoon take Pt as main component obtains extensive concern with its excellent catalytic performance to methanol oxidation.
Template is that preparation PtM(M represents metal) a kind of common method of hollow microsphere.Template commonly used has silica (SiO2) at present, polystyrene (PS), cobalt (Co), silver (Ag) etc.The people such as Lu (Lu, L.H.; Capek, R.; Kornowski, A.; Gaponik, N.; Eychm ü ller, A.Selective fabrication of ordered bimetallic nanostructures with hierarchical porosity.Angew.Chem.2005,44,5997.) utilize silica to prepare the Pt/Au Bimetallic Hollow microballoon of layering porosity as template, but the method need to be gone etching with HF, dangerous and not environmental protection.The people such as Guo (Guo, S.J.; Fang, Y.X.; Dong, S.J.; Wang, E.High-Efficiency and Low-Cost Hybrid Nanomaterial as Enhancing Electrocatalyst:Spongelike Au/Pt Core/Shell Nanomaterial with Hollow Cavity.J.Phys.Chem.C.2007,111,17104.) adopt the method for dielectric displacement reaction to prepare PtAu alloy hollow microsphere with Co as template, but need to be in inert atmosphere during preparation Co template, process is complicated.The people such as Kim (Kim, Y.M.; Kim, H.J.; Kim, Y.S.; Choi, S.M.; Seo, M.H.; Kim, W.B.Shape-and composition-sensitive activity of Pt and PtAu catalysts for formic acid electrooxidation.J.Phys.Chem.C.2012,116,18093.) utilize Ag to prepare the catalyst of the controlled PtAu Bimetallic Hollow structure of pattern for template, but can generate the AgCl precipitation in this course of reaction, the quality that this makes the subsequent processes complexity and can affect product.
Summary of the invention
The object of the invention is to for the existing defective of prior art, provide fast, the preparation method of environmental protection, the simple a kind of hollow metal microballoon of subsequent processes.
The present invention includes following steps:
1) get solubility gold precursor solution and be diluted to 150mL, regulate pH between 6～7 with sodium hydroxide solution, adding concentration after being heated to seethe with excitement is the sodium citrate solution of 25.8g/L again, till magnetic agitation to solution colour becomes ruby red, gets gold nano grain;
2) the titanium precursor body is joined in ethylene glycol, add acetone after magnetic agitation, then stir, centrifugal, washing, drying gets titanium dioxide;
3) get step 2) after gained titanium dioxide and silane coupler mix and blend, centrifugal, washing, drying gets surface-functionalized titanium dioxide;
4) get the surface-functionalized titanium dioxide of step 1) gained gold nano grain and step 3) gained and mix ultrasonicly, centrifugal, washing gets Au/TiO
2
5) get step 4) gained Au/TiO
2Add successively citric acid, soluble metal presoma and vitamin C after being heated to 100 ℃, centrifugal after reaction, washing namely gets product hollow metal microballoon.
In step 1), the mass ratio of described natrium citricum and golden presoma can be 0.5～13; The particle diameter of gained gold nano grain can be 10～25nm.
In step 2) in, the addition of described ethylene glycol can be 10mL; The time of described magnetic agitation can be 8h; The addition of described acetone can be 50mL, and the water content of acetone can be 3%～5%; The described time of stirring again can be 1h; The particle diameter of prepared titanium dioxide is between 200～1500nm.
In step 3), described silane coupler can be selected from the amino trimethoxy silane of 4-(APTMS) etc.; The mass ratio of silane coupler and titanium dioxide can be 25～100.
In step 4), the content of described gold nano grain is preferably excessive.
In step 5), described Au/TiO
2Can be settled to 30mL; The mass concentration of described citric acid can be 19.2g/L, and described ascorbic mass concentration can be 17.6g/L.
The present invention utilizes the controlled PtM metal hollow microballoon of pH sensitiveness preparation size of titanium dioxide take titanium dioxide microballoon sphere as template.Can control the size of PtM hollow microsphere by the size of adjusting template titanium dioxide, the concentration that changes simultaneously metal precursor can change the thickness of PtM hollow microsphere.
Advantage of the present invention is: time PtM hollow microsphere take titanium dioxide as the template synthesizing multilayer first, the preparation method who has widened the preparation hollow microsphere.Process conditions of the present invention are gentle and be easy to control, and the reaction time is short, and template is easily removed and be need not to use high temperature or strong acid and strong base etc., and subsequent processes is simple simultaneously.
Description of drawings
Fig. 1 is the Au/TiO of embodiment 1 gained
2The SEM picture of sample.In Fig. 1, scale is 200nm.
Fig. 2 is the Au/TiO of embodiment 2 gained
2The SEM picture of sample.In Fig. 2, scale is 200nm.
Fig. 3 is the SEM picture of the PtAu hollow microsphere of embodiment 3 gained.In Fig. 3, scale is 500nm.
Fig. 4 is the SEM picture of the PtAu hollow microsphere of embodiment 4 gained.In Fig. 4, scale is 500nm.
Fig. 5 is the SEM picture of the PtAu hollow microsphere of embodiment 5 gained.In Fig. 5, scale is 500nm.
Fig. 6 is the SEM picture of the PdAu hollow microsphere of embodiment 6 gained.In Fig. 6, scale is 200nm.
Fig. 7 is the SEM picture of the PtPdAu hollow microsphere of embodiment 7 gained.In Fig. 7, scale is 200nm.
The specific embodiment
The present invention is further illustrated in connection with accompanying drawing for following examples.
Embodiment 1
(1) getting the 1mL mass concentration is that the chlorauric acid solution of 13.6g/L is diluted to 150mL, regulates pH between 6～7 with NaOH (40g/L) solution.This solution is heated to add 1.4mL natrium citricum (25.8g/L) solution after boiling, till magnetic agitation to solution colour becomes ruby red, namely gets gold nano grain.
(2) with 125mg tetra-n-butyl titanate (Ti (OC
4H
9)
4) join in 10mL ethylene glycol, at room temperature adding rapidly 50mL acetone (containing 150 μ L ultra-pure waters) after magnetic agitation 8h, the room temperature lower magnetic force stirs 1h, and centrifugal, washing, drying get titanium dioxide.
(3) get at room temperature mix and blend 12h of 10mg titanium dioxide and 250 μ L silane couplers (APTMS), centrifugal, washing, drying get surface-functionalized titanium dioxide.
(4) get the 120mL gold nano grain and mix ultrasonic 2h with surface-functionalized titanium dioxide, after centrifugal, washing, products therefrom is scattered in the 4mL ultra-pure water again, gets Au/TiO
2
The Au/TiO of embodiment 1 gained
2The SEM picture of sample is referring to Fig. 1.
Embodiment 2
The difference of the present embodiment and embodiment 1 is: silane coupler used is 1000 μ L, and remaining is identical with embodiment 1.The Au/TiO of embodiment 2 gained
2The SEM picture of sample is seen Fig. 2.
Embodiment 3
The step of front is identical with embodiment 1.Get 1mL Au/TiO
2Be settled to 30mL, add successively 3mL citric acid (19.2g/L), 0.3mL chloroplatinic acid (13.8g/L) and 1.0mL vitamin C (17.6g/L) after this solution is heated to 100 ℃, then continue reaction 0.5h, centrifugal, washing namely gets the PtAu hollow microsphere for several times.The SEM picture of the PtAu hollow microsphere of embodiment 3 gained is referring to Fig. 3.
Embodiment 4
The difference of the present embodiment and embodiment 3 is: tetra-n-butyl titanate quality used is 250mg, and remaining is identical with embodiment 3.The SEM picture of the PtAu hollow microsphere of embodiment 4 gained is referring to Fig. 4.
Embodiment 5
The difference of the present embodiment and embodiment 3 is: tetra-n-butyl titanate quality used is 2g, and remaining is identical with embodiment 3.The SEM picture of the PtAu hollow microsphere of embodiment 5 gained is referring to Fig. 5.
Embodiment 6
The difference of the present embodiment and embodiment 3 is: metal precursor used is palladium bichloride (13.7g/L), and volume is 0.2mL, and remaining is identical with embodiment 3, obtains the PdAu hollow microsphere.The SEM picture of the PdAu hollow microsphere of embodiment 6 gained is referring to Fig. 6.
Embodiment 7
The step of front is identical with embodiment 1.Get 1mL Au/TiO
2Be settled to 30mL, after being heated to 100 ℃, this solution adds successively 3mL citric acid (19.2g/L), 0.2mL palladium bichloride (13.7g/L) and 1.0mL vitamin C (17.6g/L), continue to be cooled to 80 ℃ after reaction 0.5h, then add 0.1mL chloroplatinic acid (13.8g/L), centrifugal after continuation reaction 24h, washing namely gets the PtPdAu hollow microsphere for several times.The SEM picture of the PtPdAu hollow microsphere of embodiment 7 gained is referring to Fig. 7.
Claims (10)
1. the preparation method of a hollow metal microballoon is characterized in that comprising the following steps:
1) get solubility gold precursor solution and be diluted to 150mL, regulate pH between 6～7 with sodium hydroxide solution, adding concentration after being heated to seethe with excitement is the sodium citrate solution of 25.8g/L again, till magnetic agitation to solution colour becomes ruby red, gets gold nano grain;
2) the titanium precursor body is joined in ethylene glycol, add acetone after magnetic agitation, then stir, centrifugal, washing, drying gets titanium dioxide;
3) get step 2) after gained titanium dioxide and silane coupler mix and blend, centrifugal, washing, drying gets surface-functionalized titanium dioxide;
4) get the surface-functionalized titanium dioxide of step 1) gained gold nano grain and step 3) gained and mix ultrasonicly, centrifugal, washing gets Au/TiO
2
5) get step 4) gained Au/TiO
2Add successively citric acid, soluble metal presoma and vitamin C after being heated to 100 ℃, centrifugal after reaction, washing namely gets product hollow metal microballoon.
2. a kind of preparation method of hollow metal microballoon as claimed in claim 1, is characterized in that in step 1), and the mass ratio of described natrium citricum and golden presoma is 0.5～13; The particle diameter of gained gold nano grain is 10～25nm.
3. a kind of preparation method of hollow metal microballoon as claimed in claim 1, is characterized in that in step 2) in, the addition of described ethylene glycol is 10mL.
4. a kind of preparation method of hollow metal microballoon as claimed in claim 1, is characterized in that in step 2) in, the time of described magnetic agitation is 8h.
5. a kind of preparation method of hollow metal microballoon as claimed in claim 1, is characterized in that in step 2) in, the addition of described acetone is 50mL, the water content of acetone can be 3%～5%.
6. a kind of preparation method of hollow metal microballoon as claimed in claim 1, is characterized in that in step 2) in, the described time of stirring again is 1h; The particle diameter of prepared titanium dioxide is between 200～1500nm.
7. a kind of preparation method of hollow metal microballoon as claimed in claim 1, is characterized in that in step 3), and described silane coupler is selected from the amino trimethoxy silane of 4-.
8. a kind of preparation method of hollow metal microballoon as claimed in claim 1, is characterized in that in step 3), and the mass ratio of described silane coupler and titanium dioxide is 25～100.
9. a kind of preparation method of hollow metal microballoon as claimed in claim 1, is characterized in that in step 4), and the content of described gold nano grain is excessive.
10. a kind of preparation method of hollow metal microballoon as claimed in claim 1, is characterized in that in step 5) described Au/TiO
2Be settled to 30mL; The mass concentration of described citric acid is 19.2g/L, and described ascorbic mass concentration is 17.6g/L.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105537617A (en) * | 2015-12-28 | 2016-05-04 | 重庆文理学院 | Method for preparing hollow PtPd nano material with cuprous oxide as template |
| CN107671280A (en) * | 2017-09-26 | 2018-02-09 | 铱格斯曼航空科技集团有限公司 | A kind of york shell structure Cs oNi@TiO2Nanoparticle and preparation method thereof |
| CN111640924A (en) * | 2020-06-05 | 2020-09-08 | 新昌县华发机械股份有限公司 | Shell-core structure porous carbon-TiO2Positive electrode material of lithium-sulfur battery and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105537617A (en) * | 2015-12-28 | 2016-05-04 | 重庆文理学院 | Method for preparing hollow PtPd nano material with cuprous oxide as template |
| CN107671280A (en) * | 2017-09-26 | 2018-02-09 | 铱格斯曼航空科技集团有限公司 | A kind of york shell structure Cs oNi@TiO2Nanoparticle and preparation method thereof |
| CN107671280B (en) * | 2017-09-26 | 2019-11-08 | 承德中宇众航新材料有限公司 | A kind of york-shell structure C oNi@TiO2Nanosphere and preparation method thereof |
| CN111640924A (en) * | 2020-06-05 | 2020-09-08 | 新昌县华发机械股份有限公司 | Shell-core structure porous carbon-TiO2Positive electrode material of lithium-sulfur battery and preparation method thereof |
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