CN100509150C - Mesoporous material containing fiber-like nano silver and preparing method thereof - Google Patents
Mesoporous material containing fiber-like nano silver and preparing method thereof Download PDFInfo
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- CN100509150C CN100509150C CNB2006100078459A CN200610007845A CN100509150C CN 100509150 C CN100509150 C CN 100509150C CN B2006100078459 A CNB2006100078459 A CN B2006100078459A CN 200610007845 A CN200610007845 A CN 200610007845A CN 100509150 C CN100509150 C CN 100509150C
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Abstract
This invention relates to a mesoporous material containing fibrous nm silver and preparation method. The material characteristics consist in that nm fibrous silver in the mesoporous distribution channels, 2-8nm in diameter, the length of 100nm- 1um. Preparation method feature is the that first mesoporous materials in an atmosphere of ammonia, handing in 700-1200degree centigrade conditions, have a nitrogen mesoporous material with nitrogen content of1-25%. The above nitride mesoporous materials impregnated in the 0.001-1mol/L AgNO3 solution, after stirring 10-80h remove excessive AgNO3 and drying in air under 120deg.C, the final reduction can be obtained the mesoporous materials containing silver nm-fibrous by adding the reducing agent. Preparation materials of this invention can be applied to prepara catalyst or other functional materials.
Description
Technical field
The present invention relates to a kind of mesoporous material that contains fiber-like nano silver.
The invention still further relates to the preparation method of above-mentioned mesoporous material.
Background technology
Silver is hot, electric good conductor, also has good ductility and chemical stability simultaneously.And when the size of ag material reaches nanometer range, its performance will have new characteristics, show unique light, electricity, antibiotic and catalytic performance.Along with the integrated and quantization of photoelectric component, fiber-like nano silver also has wide application prospect at catalytic field and field such as antibiotic simultaneously because the conduction and the heat conductivility of its excellence comes into one's own.
The preparation fiber-like nano silver mainly adopts template and liquid phase reactor method both at home and abroad at present.Wherein the liquid phase reactor method is one of method of widespread usage, as Chinese patent " synthetic method of monocrystal silver nanofiber " (publication number: CN1424163A), Chinese patent " preparation method of 1-dimention nano ag material " (publication number: CN1493421A).But the growth of fiber-like nano silver is wayward in the liquid phase reactor method, and diameter distributes and do not concentrate.And the restriction of utilizing template to pass through template can be controlled the diameter of fiber-like nano silver effectively, can access the fiber-like nano silver of diameter homogeneous, and silver-colored fiber can be grown along the duct simultaneously, can prepare long nanofiber.Material as template has CNT (Jeremy Sloan, etal, Chem.Commun., 1999,699,700), silica (S.Bhattacharyya and S.K.Saha, Appl.Phys.Lett., 2000,77,3770), polymer (Byung Hee Hong, et al, Science, 2001,294,348) etc.
Mesoporous material has bigger aperture and regular pore passage structure, helps the diffusion of macromolecular substances in the duct, is a kind of outstanding carrier material, has obtained paying close attention to widely.Mesoporous material is commonly used to carrying metal, particularly nano metal.Some researchers have reported the method for synthetic metal nano fiber in the mesoporous material, as document (L.M.Worboys, P.P.Edwards and P.A.AndersonChem.Commn.2002,2894), (M.H.Huang, A.Choudrey and P.YangChem.Commn.2000,1063), (P.V.Adhyapaka, P.Karandikarb, K.Vijayamohananb, A.A.Athawalec and A.J.Chandwadkar Mater.Lett.58 (2004) 1168).This template can be synthesized the silver-colored nanofiber of diameter homogeneous effectively, but can't avoid a large amount of silver to assemble at the outer surface of carrier with the form of particle.And utilize organic solvent can increase the inlet of fiber-like nano silver in the duct, but still have distribution of particles at outer surface.
Summary of the invention
The object of the present invention is to provide a kind of mesoporous material that contains fiber-like nano silver.
Another purpose of the present invention is to provide the preparation method of above-mentioned mesoporous material.
For achieving the above object, the mesoporous material that contains fiber-like nano silver provided by the invention, its fiber-like nano silver are distributed in the duct of mesoporous material, and the aperture of diameter and mesoporous material is suitable, and length is 100nm～1 μ m; After the described mesoporous material that contains fiber-like nano silver can be flooded in silver salt solution by mesoporous material, get through reduction again.
The above-mentioned preparation method who contains the mesoporous material of fiber-like nano silver provided by the invention, key step is:
A) nitrogen treatment of mesoporous material: mesoporous material is in containing the atmosphere of ammonia, and nitrogenize 1-80 hours (being preferably 10-30 hours) under 700-1200 ℃ of conditions obtains the mesoporous material of nitrogenize; The atmosphere composition that contains ammonia is by volume: inert gas/ammonia=0-99 (nitrogen content preferably is controlled at 1-25%, and preferred nitrogen content is 5-15%);
B) dipping: the nitrogenize mesoporous material of step a impregnated in the silver salt solution that concentration is 0.001-1mol/L that (preferred concentration is 0.01-0.1mol/L), stirs 100-120 ℃ of oven dry 10-80 hours;
C) reduction: adding reducing agent in the product of step b, is argent with silver ion reduction, obtains containing the mesoporous material of fiber-like nano silver; Described reducing agent is for making the material of silver in the normal temperature reduction, as NaBH
4Or/and formaldehyde.
Mesoporous material involved in the present invention is meant the class material with pore passage structure, and pore passage structure can be regular, and as the meso-porous molecular sieve material of types such as SBA-15 or MCM-41, but the present invention is not limited in these materials.Its of mesoporous material should contain silicon or silica in forming, normally silica or based on the material of silica.
Characteristics of the present invention are mesoporous material to be contacted with ammonia carry out nitrogenize, promptly under uniform temperature and time conditions the mesoporous material surface-the OH key and-the O-key is partly or entirely by-NH
2Key and-the NH-key replaces.This process needs hot conditions usually and needs the regular hour, and concrete condition is relevant with the The Nomenclature Composition and Structure of Complexes of used initial mesoporous material, and is also relevant with the concentration of ammonia.
Characteristics of the present invention also are to utilize the mesopore molecular sieve of above-mentioned nitrogenize, with its with filter after silver salt solution contacts certain hour, washing, oven dry, contacting the silver ion reduction in the mesoporous material duct with reducing agent then is argent, obtains containing the mesoporous material of fiber-like nano silver.The solvent of silver salt solution can be a water, also can be organic solvent.
Description of drawings
Fig. 1 and Fig. 2 are the transmission electron microscope photo of the embodiment of the invention two;
Fig. 3 is the X-ray diffracting spectrum of embodiments of the invention three; And
Fig. 4 is the transmission electron microscope photo of Comparative Examples one.
The specific embodiment
By the following examples the present invention is specifically described in detail, but the present invention is not limited to these embodiment.
Embodiment one: be the mesoporous material that preparing carriers contains fiber-like nano silver with SBA-15
A. get SBA-15 sample 1000mg, put into quartz tube furnace and purged 30 minutes with nitrogen earlier, flow velocity is 80ml/min, feeds ammonia then, and flow velocity is 100ml/min, is warmed up to 1000 ℃ simultaneously, keeps 20 hours.In nitrogen atmosphere, be cooled to room temperature then.Obtain nitrogenize product S BA-15N1, its nitrogen content is 10%.
B. get the nitrogenize sample SBA-15N1 that makes among the above-mentioned a of 100mg, put into little crucible, in crucible, add liquor argenti nitratis ophthalmicus, continue to stir 20h, then sample is taken out filtration, washing, oven dry.
C. in the sample of oven dry, add excessive N aBH
4The aqueous solution is argent with silver ion reduction, obtains end product Ag-SBA-15N1 after the drying.
Embodiment two
Utilize transmission electron microscope (TEM) to observe the sample Ag-SBA-15N1 that obtains among the embodiment one, as seen have nanofiber in the mesoporous molecular sieve duct, diameter is the 7-8 nanometer, and is suitable with the aperture of mesoporous material, and length is 100nm～1 μ m.Under the same visual field, silver-colored nanofiber all is distributed in the nano pore of SBA-15, and does not almost have particle aggregation (referring to Fig. 1 and Fig. 2) in outer surface.
Embodiment three
With the sample Ag-SBA-15N1 X-ray diffraction analysis (XRD) that obtains among the embodiment one, low-angle diffraction maximum is clear distinct, shows that the Ag-SBA-15N1 sample has kept the regular pore passage structure (referring to Fig. 3) of mesoporous material.
Embodiment four: be the mesoporous material that preparing carriers contains nano-Ag particles with SBA-15
A. get SBA-15 sample 1000mg, put into quartz tube furnace and purged 30 minutes with nitrogen earlier, flow velocity is 80ml/min, feeds ammonia then, and flow velocity is 15ml/min, is warmed up to 1000 ℃ simultaneously, keeps 40 hours.In nitrogen atmosphere, be cooled to room temperature then.Obtain the mesoporous material SBA-15 N2 of nitrogenize, its nitrogen content is 15%.
B. get 100mg and state the nitrogenize sample SBA-15N2 that makes among a, put into little crucible, in crucible, add liquor argenti nitratis ophthalmicus then, continue to stir 60h, take out overanxious washing oven dry then.
C. the sample after oven dry adds excess formaldehyde solution, is argent with silver ion reduction, obtains end product Ag-SBA-15N2 after the drying.
D. characterize above-mentioned Ag-SBA-15N2 with embodiment two, embodiment three identical methods, confirmation can obtain fiber-like nano silver and be distributed in the mesopore orbit, and diameter is 7-8nm, and is suitable with the aperture of mesoporous material, and length is the observed result of 100nm～1 μ m.
Embodiment five: be the mesoporous material that preparing carriers contains nano-Ag particles with MCM-41
Used mesoporous material is MCM-41, and other specific implementation process obtains containing the mesoporous material of Nano Silver with embodiment one, its fiber-like nano silver is distributed in the mesopore orbit, the aperture of diameter and mesoporous material is suitable, and about 3 nanometers, length is 100nm～1 μ m.
Comparative Examples one: SBA-15 not via nitride directly supports the preparation fiber-like nano silver
A. get SBA-15 sample 100mg, put into little crucible, add liquor argenti nitratis ophthalmicus then in crucible, continue to stir 60h, sample takes out the overanxious washing oven dry in back.
B. put into excessive N aBH in the sample after oven dry
4Solution is argent with silver ion reduction, finally obtains product A g-SBA-15.
D. characterizing above-mentioned Ag-SBA-15 with embodiment two identical methods observes, can find in the duct, to be difficult to form fiber-like nano silver, and at the outer surface of the mesopore material bigger silver-colored particle that distributing, its particle diameter distributes between the hundreds of nanometer tens, is far longer than the aperture of mesopore material.(referring to Fig. 4).
Claims (5)
1. a mesoporous material that contains fiber-like nano silver is characterized in that fiber-like nano silver is distributed in the duct of the nitrogenize mesoporous material that carries out nitrogenize in containing the atmosphere of ammonia, and the aperture of diameter and nitrogenize mesoporous material is suitable, and length is 100nm～1 μ m; After the described nitrogenize mesoporous material that contains fiber-like nano silver is flooded in silver salt solution by the nitrogenize mesoporous material, get through reduction again.
2. the described preparation method who contains the mesoporous material of fiber-like nano silver of claim 1, key step is:
A) nitrogen treatment of mesoporous material: mesoporous material under the 700-1200 ℃ of condition nitrogenize 1-80 hour, obtains the mesoporous material of nitrogenize in containing the atmosphere of ammonia; The atmosphere composition that contains ammonia is by volume: inert gas/ammonia=0～99;
B) dipping: the nitrogenize mesoporous material of step a) be impregnated in the silver salt solution, stir the back oven dry;
C) reduction: adding reducing agent in the product of step b), is argent with silver ion reduction, obtains containing the mesoporous material of fiber-like nano silver; Described reducing agent is to make the material of silver in the normal temperature reduction.
3. preparation method as claimed in claim 2 is characterized in that, nitridation time is 10-30 hour.
4. preparation method as claimed in claim 2 is characterized in that, the concentration of silver salt is 0.001～1mol/L.
5. preparation method as claimed in claim 2 is characterized in that, reducing agent is one or more mixing or the boron hydride in the aldehydes.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1422719A (en) * | 2002-12-16 | 2003-06-11 | 同济大学 | Method for making silver nano wire using aerogel as template |
| WO2003048433A1 (en) * | 2001-11-29 | 2003-06-12 | Institut Für Polymerforschung Dresden E.V. | Nanowires and method for producing the same |
| CN1709791A (en) * | 2005-07-05 | 2005-12-21 | 华东理工大学 | Method for preparing silver nano line |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003048433A1 (en) * | 2001-11-29 | 2003-06-12 | Institut Für Polymerforschung Dresden E.V. | Nanowires and method for producing the same |
| CN1422719A (en) * | 2002-12-16 | 2003-06-11 | 同济大学 | Method for making silver nano wire using aerogel as template |
| CN1709791A (en) * | 2005-07-05 | 2005-12-21 | 华东理工大学 | Method for preparing silver nano line |
Non-Patent Citations (1)
| Title |
|---|
| Synthesis of silver nanowires inside mesoporous MCM-41 host. P.V. Adhyapak et al.Materials Letters,Vol.58 No.7-8. 2003 * |
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