CN1594071A - Method for preparing one dimensional nanomaterial of transitional metal-oxide - Google Patents
Method for preparing one dimensional nanomaterial of transitional metal-oxide Download PDFInfo
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- CN1594071A CN1594071A CN 200410025737 CN200410025737A CN1594071A CN 1594071 A CN1594071 A CN 1594071A CN 200410025737 CN200410025737 CN 200410025737 CN 200410025737 A CN200410025737 A CN 200410025737A CN 1594071 A CN1594071 A CN 1594071A
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Abstract
The invention provides a method for preparing one dimensional nano material of transitional metal-oxide, wherein a silicon oxide type mesoporous solid is used as hard formwork, the method consists of, steeping the mesoporous material in aqueous solution of transition metal salts, making the solvent alloy positive ions and related countering negative ions enter the pore passages of the mesoporous material, letting ammonia gas into the solution to form sediment in the pore passages with the form of hydroxides, proceeding filtration, drying, scouring, heat treatment and silicon dissolution.
Description
Technical field
The present invention is a kind of preparation method of transition metal oxide nano-material.
Background technology
Nanosecond science and technology from eighties of last century develop rapidly the latter stage eighties, and emerging melt front line science and hi-tech in the comprehensive cross discipline of one, it goes to study the characteristic and the interaction of material from nanoscale.Nano material has small size, complex configuration, high integration and characteristics such as strong interaction, high surface area, has tempting application prospect, makes nanotechnology be described as three big pillars of 21 century high-tech industry with information technology, biotechnology.
The preparation of nano material is the core subdiscipline of the richest originality and vitality in the nanosecond science and technology field, because nano material has at least one dimension to be in the nanoscale scope in three-dimensional space, nano material roughly can be divided into the nanometer powder of zero dimension, the unidimensional nanofiber, the nanometer film of two dimension, three-dimensional nano block and nano composite material etc., therefore the control of appearance of nano material is the key issue of nano material preparation, a series of physics have been developed at present, chemical process is as microemulsion method, chemical Vapor deposition process, the hot method of solvent (water), template synthesis method etc. all successfully is applied to the morphology control of nano material.
In existing numerous methods, template is one of the most effective synthesizing mean, and based on the notion of template, template can be divided into soft template and hard template again.Soft template mainly comprises the liquid crystal, micelle, microemulsion, LB film and the diblock that contain oleophylic and hydrophilic radical simultaneously, triblock copolymer etc., under the effect of the water oil phase of certain proportioning and tensio-active agent, select conditions suitable and certain sol-gel to assemble, formation has the nano material of certain pattern after removing template, because soft template method is subjected to multiple factor affecting, often be difficult to expect the product pattern; Hard template then is meant the template with certain rigid structure, as molecular sieve, porous activated carbon, porous alumina, polycarbonate membrane, carbon nanotube, silicon type mesoporous material etc., they often have the space size that higher thermostability and homogeneous are determined, can control and expect the size and the pattern of nano material effectively.Utilize hard template method to prepare metal, nonmetal (G.D.Stucky etc., Chem.Mater.2000,12,2068), oxide compound (M.Froba etc., Chem.Mater.1999,11,2858), sulfide (F.Gao etc., Nano.Lett.2001,1,743) and polymkeric substance (S.W.Haggata etc., J.Mater.Chem.1996,7,1969) nano wire, rod, pipe etc.In numerous hard template, being most widely used of silicon type mesoporous solid, this is because the aperture (K.S.W.Sing etc., Pure Appl.Chem.1985,57,603) in the 2-50nm scope of mesoporous solid at first is fit to the control of nanoscale; The second, the synthetic development of mesoporous solid material is rapid, and new mesoporous solid emerges in an endless stream, various apertures are adjustable, the mesoporous material of duct arranging rule is successfully synthetic in succession, as the M41S series of Mobil company exploitation (C.T.Kresge etc., Nature 1992,359,710; J.S.Beck etc., US Patent:5 057 296,1991; 5,098 684,1992; 5 108 725,1992; 5 145 816,1992; 5 156 829,1992; 5 183561,1993; 5 264 203,1993; 5 334 368,1994; 5 370 785,1994), and Pinnavaia research group in 1994 (Nature 1994,368, and 321; Science 1995,167, and 865; Angew.Chem.Int.Ed.1997,36,516) synthetic has six side's aerosil mesoporous solids (HMS and MSU) of honeycomb structure structure, (Science 1998 for G.D.Stucky in 1998 and co-worker thereof, 279,548) synthetic long-range order, aperture big (can reach 50nm), wall thicker (typical wall thickness is 9nm) and SBA-15 with high thermal stability and hydrothermal stability, these all are that silicon type mesoporous material is laid a good foundation as hard mould agent; The 3rd, the duct internal surface of silica-type mesoporous solid has abundant slightly acidic silicon hydroxyl, can interact with multiple precursor, but this interaction is more weak, often make that the charge capacity of precursor is low, easily by wash-out, make the productive rate of monodimension nanometer material not high, yardstick is uneven, kind is few.
Summary of the invention
The objective of the invention is to obtain that a kind of preparation method is simple, suitability is wide, presoma is stable, productive rate is high, the uniform one dimension transition metal of nano-scale nano preparation methods.
The present invention is a hard mould agent with the silica-type mesoporous solid, hard mould agent is immersed in the aqueous solution that contains transition metal salt, it is that carrier gas feeds ammonia in the solution by strong aqua that normal temperature stirs down after 1-6 hour with nitrogen, stop ventilation after 2-6 hour, transition metal ion is deposited in the duct with the form of oxyhydroxide, after filtration, washing, after the oven dry, in 400-600 ℃ of following nitrogen atmosphere, handled 4-6 hour, make the oxyhydroxide that generates in the duct be decomposed into oxide compound, use the diluted hydrofluoric acid dissolve silica at last, after filtration, washing, after the oven dry, can obtain introducing the one dimension transition metal nano material of species, the transition metal salt concentration of aqueous solution is 1-3mol/L.
It is worthy of note because the precursor transition metal ion is deposited in the duct with precipitation forms, make precursor be easy to load, stability is high, avoids last handling process to deviate from.
In the above-mentioned preparation process, the species of introducing can be the water-soluble salts of transition metal, as Manganous chloride tetrahydrate, chromium chloride, Xiao Suangu, nickelous nitrate etc.
In the above-mentioned preparation process, be fit to multiple SiO 2 mesoporous materials, as MCM-41, SBA-15 etc.
Analyze and the detection of original position X-ray powder diffraction by differential thermal-weightlessness, the mesoporous solid that load has an oxyhydroxide precursor at a lower temperature, be that the decomposition that oxyhydroxide takes place in the 400-600 ℃ of scope generates crystalline oxide, in the duct of mesoporous solid, form monodimension nanometer material.
Oxide compound generates the back with diluted hydrofluoric acid dissolve silica hard template, can remove silicon-dioxide fully after repeatedly washing and drying, and obtains pure one dimension transition metal oxide nano-material.
The present invention feeds that the commercially available strong aqua of ammonia concn gets final product in the transition metal salt brine solution, i.e. 25-28wt%.
The hydrofluoric acid of dissolve silica of the present invention with 5-10wt% for well.
Reaction after-filtration, washing, oven dry, bake out temperature is advisable with 80-100 ℃.
The present invention is a hard template with the silica-type mesoporous solid, by chemical reaction transition metal salt is deposited in the mesopore orbit with hydroxide form, by simple thermal decomposition process and silicon dissolving, prepares the monodimension nanometer material of multiple transition metal oxide.This method adopts chemical control technology, and technology is simple, and controllability is strong, and presoma is stable, and the productive rate height is applied widely, can be used for the multiple transition metal oxide monodimension nanometer material of preparation scale homogeneous.
Description of drawings
Fig. 1 is Co
2O
3The TEM figure that is parallel to the nano material of one dimension direction.
Fig. 2 is perpendicular to the Co of one dimension direction
2O
3The TEM figure of nano material.
Fig. 3 is one dimension MnO
2The TEM figure of nano material.
Fig. 4 is one dimension Cr
2O
3The TEM figure of nano material.
Fig. 5 is one dimension Cr
2O
3The electron-diffraction diagram of nano material.
Fig. 6 is the XRD powder diagram of one dimension NiO nano material.
Fig. 7 is perpendicular to the TEM figure of the NiO nano material of one dimension direction.
Fig. 8 is the TEM figure that is parallel to the NiO nano material of one dimension direction.
Fig. 9 is the HRTEM figure of one dimension NiO nano material.
Figure 10 is the electron-diffraction diagram of one dimension NiO nano material
Embodiment
Embodiment 1:
Co
2O
3The preparation of monodimension nanometer material: the 3g Xiao Suangu is dissolved in the 10ml water, then 1.5gSBA-15 silicon type mesoporous solid is immersed in wherein, normal temperature stirred 1.5 hours down, fed ammonia 2 hours, filtered then, washed, and oven dry earlier is 2 hours under 90 ℃.550 ℃ of following roastings 5.5 hours, resulting product of roasting was removed silicon-dioxide with 10% HF, obtains Co after washing and drying then
2O
3Monodimension nanometer material (seeing Fig. 1 and Fig. 2).
Embodiment 2:
MnO
2The preparation of monodimension nanometer material: 4g hydration Manganous chloride tetrahydrate is dissolved in the middle of the 10ml water, adds the submergence of 1.5gMCM-41 silicon type mesoporous solid wherein, normal temperature stirred 6 hours down, fed ammonia 3 hours, filtered then, washed, 80 ℃ of oven dry earlier 4 hours down.600 ℃ of following roastings 4 hours, resulting product of roasting was removed silicon-dioxide with the HF of 5wt%, obtains MnO after washing and drying then
2The monodimension nanometer material (see figure 3).
Embodiment 3:
Cr
2O
3The preparation of monodimension nanometer material: 4g hydration chromium chloride is dissolved in the 10ml water, and then with the submergence of 1.5g SBA-15 silicon type mesoporous solid wherein, normal temperature stirred 4 hours down, fed ammonia 6 hours, filtered then, washed, and oven dry earlier is 2 hours under 100 ℃.450 ℃ of following roastings 5.5 hours, resulting product of roasting was removed silicon-dioxide with 10% HF, obtains Cr after washing and drying then
2O
3Monodimension nanometer material (seeing Fig. 4 and Fig. 5).
Embodiment 4:
The preparation of NiO monodimension nanometer material: 3g nitric hydrate nickel is dissolved in the 10ml water, and then with the submergence of 1gSBA-15 silicon type mesoporous solid wherein, normal temperature stirred 4 hours down, fed ammonia 2 hours, filtered then, washed, and oven dry earlier is 2 hours under 100 ℃.600 ℃ of following roastings 6 hours, resulting product of roasting was removed silicon-dioxide with the HF of 5wt% then, obtained the monodimension nanometer material (seeing Fig. 6,7,8,9,10) of NiO after washing and drying.
Claims (4)
1. the preparation method of an one dimension transition metal oxide nano-material is characterized in that:
(1) with the silica-type mesoporous material as hard mould agent, the silicon mesoporous material is immersed in is dissolved with in the 1-3mol/L transition metal salt brine solution, normal temperature stirred 1-6 hour down, with nitrogen is that carrier gas feeds in the transition metal salt brine solution ammonia and stirring by strong aqua, transition metal ion is deposited in the duct with the form of oxyhydroxide, stop ventilation after 2-6 hour, after washing after filtration,, the oven dry, handled 4-6 hour down at 400-600 ℃, make the oxyhydroxide that generates in the duct be decomposed into oxide compound;
(2) use the diluted hydrofluoric acid dissolve silica, after filtering, wash, drying, promptly obtain the one dimension transition metal oxide nano-material.
2. the preparation method of one dimension transition metal oxide nano line according to claim 1 is characterized in that the ammonia concn that strong aqua is fed in the transition metal salt brine solution is 25-28wt%.
3. the preparation method of transition metal oxide nano line according to claim 1 is characterized in that the hydrofluoric acid concentration with the diluted hydrofluoric acid dissolve silica is 5-10wt%.
4. the preparation method of transition metal oxide nano line according to claim 1 is characterized in that logical ammonia after-filtration, washing, and bake out temperature is 80-100 ℃.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1320959C (en) * | 2005-04-14 | 2007-06-13 | 复旦大学 | Prepn and application of nano composite polyacid catalyst for eliminating gaseous aldehyde at normal temperature and normal pressure |
| CN101973590A (en) * | 2010-10-21 | 2011-02-16 | 北京师范大学 | Preparation method for small-size mesoporous metal oxide |
| CN102773624A (en) * | 2011-11-02 | 2012-11-14 | 兰州大学 | One-dimensional nano welding flux for micron/nanoscale welding and preparation method thereof |
| CN103407969A (en) * | 2013-07-31 | 2013-11-27 | 济南大学 | Preparation method of three-dimensionally ordered macroporous-mesoporous metal oxide or composite oxide by using gas phase permeability-precipitation technology, and obtained product |
| CN103756636A (en) * | 2013-11-25 | 2014-04-30 | 胡敏刚 | Multi-element metal oxide mesoporous material |
-
2004
- 2004-07-05 CN CN 200410025737 patent/CN1268539C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1320959C (en) * | 2005-04-14 | 2007-06-13 | 复旦大学 | Prepn and application of nano composite polyacid catalyst for eliminating gaseous aldehyde at normal temperature and normal pressure |
| CN101973590A (en) * | 2010-10-21 | 2011-02-16 | 北京师范大学 | Preparation method for small-size mesoporous metal oxide |
| CN102773624A (en) * | 2011-11-02 | 2012-11-14 | 兰州大学 | One-dimensional nano welding flux for micron/nanoscale welding and preparation method thereof |
| CN103407969A (en) * | 2013-07-31 | 2013-11-27 | 济南大学 | Preparation method of three-dimensionally ordered macroporous-mesoporous metal oxide or composite oxide by using gas phase permeability-precipitation technology, and obtained product |
| CN103756636A (en) * | 2013-11-25 | 2014-04-30 | 胡敏刚 | Multi-element metal oxide mesoporous material |
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