CN100444963C - Three-dimensional cross-linked mesoporous nanometer oxide material and its prepn process - Google Patents
Three-dimensional cross-linked mesoporous nanometer oxide material and its prepn process Download PDFInfo
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- CN100444963C CN100444963C CNB2006101179809A CN200610117980A CN100444963C CN 100444963 C CN100444963 C CN 100444963C CN B2006101179809 A CNB2006101179809 A CN B2006101179809A CN 200610117980 A CN200610117980 A CN 200610117980A CN 100444963 C CN100444963 C CN 100444963C
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Abstract
The present invention relates to 3D cross-linked mesoporous nanometer oxide material and its preparation process, and features that the 3D cross-linked mesoporous nanometer oxide material is 3D cross-linked mesoporous structure formed through stacking nanometer crystal grains and has relatively high pore wall crystallizing degree, narrow pore size distribution and great specific surface area. The oxide material is prepared with hydrated inorganic salt and amine as material and non-proton polar solvent, and through a simple hydrothermal process. The preparation process of the present invention is suitable for common oxide, such as ferric oxide, yttria, ceria and indium oxide.
Description
Technical field
The invention relates to three-dimensional cross-linked mesoporous nanometer oxide material of hole wall crystallization and preparation method thereof, belong to field of nanometer material technology.
Background technology
Porous material is owing to its important application at catalytic field receives much concern.Be divided into micropore, mesoporous and large pore material according to aperture size.Since the synthesizing ordered mesoporous material of XOM in 1992, the synthetic concern that has obtained height of ordered mesoporous material.But this ordered mesoporous material has also run into the problem that is difficult to overcome in actual applications.Because it is periodically mesoporous to be one dimension, often blocked in catalytic reaction; On the contrary, those have three-dimensional cross-linked mesoporous and do not possess the hole material of periodic structure, in catalytic reaction, show higher activity on the contrary, therefore, for mesoporous catalyst, important is not the periodicity in hole, but the structure (D.R.Rolison of porous, Science 2003, vol.299, pp.1698-1701; List of references wherein).In addition, the synthetic ordered mesoporous material of template agent guiding, its hole wall usually is an amorphous or hemicrystalline, even its heat endurance of crystallization is not high yet, meso-hole structure caves in easily in as the practical application of catalyst, and these have all seriously hindered its application as porous material.Just because of this reason, in the practical application people to porous materials such as aeroge awarded higher expectation (J.L.Mohanan, Science 2005, vol.307, pp.397-400).Therefore, obtaining a kind ofly to have good pore structure and distribute, and have the new pore structure of high-crystallinity, high-specific surface area, high thermal stability and good dispersion, will be desired.The material of this new pore structure not only should have the raising of the performance that the nanometer of crystal grain brings, and will easily disperse easy recovery, and cleaning nano material and the obstacle of mesoporous material in practical application make it can really obtain practical application.
Summary of the invention
The purpose of this invention is to provide three-dimensional cross-linked mesoporous nanometer oxide material of this new hole wall crystallization and preparation method thereof.It is characterized in that: 1) oxide material that described preparation method obtained has typical meso-hole structure, and its specific area height is (between 70-350m
2Between/the g), and pore-size distribution narrow (is that the 0.4-0.8 place has precipitous decline at relative pressure); 2) the prepared oxide of described preparation method just has good degree of crystallinity without heat treatment itself; 3) oxide material that described preparation method obtained is piled up by nano-sized grains by primary particle to form intergranular three-dimensional cross-linked mesoporous structure, is three-dimensional cross-linked; 4) size of the nanocrystal of formation microballoon is little among the described preparation method, in the quantum confinement size range; 5) described preparation method generally is applicable to common oxide; 6) described preparation method's preparation technology and uncomplicated, equipment needed thereby is also very simple, and great industrial production prospects is arranged.
The present invention is a raw material with hydrated inorganic salt, primary amine and aprotic polar solvent, utilizes simple hydro-thermal method, has synthesized the mesoporous nanometer oxide material of crystallization, and its concrete processing step is:
A. with a certain amount of hydrated inorganic salt, primary amine or urea are that raw material dissolves in aprotic polar solvent, obtain clear solution;
B. then, the solution water heating kettle of packing into carries out hydro-thermal reaction;
C. react the washing of gained sediment, air dry promptly gets final products.
Described hydrated inorganic salt can be the nitrate that contains the crystallization water, oxalates, chloride, carbonate etc.;
Described primary amine can be primary amines such as ethylenediamine, tert-butylamine, even can be unusual cheap urea;
Described aprotic polar solvent can be dimethyl formamide (DMF), methyl-sulfoxide (DMSO) etc.;
The ratio of the amount of substance of described hydrated inorganic salt and primary amine or urea is 0.1～1.0;
The volume ratio of described primary amine and aprotic polar solvent is 0.01～0.10;
Described hydrothermal treatment consists temperature is 100～220 ℃;
The described hydrothermal treatment consists time is 6～24 hours, and pack into the capacity of water heating kettle of solution is 50-80%.
Resulting oxide material is used TEM respectively, nitrogen adsorption/desorption analysis, and XRD characterizes its design feature, and characterizes with the magnetic property of vibrating specimen magnetometer to its magnetic di-iron trioxide, and the result invests Fig. 1～Fig. 4 and table 1.
Description of drawings
Fig. 1 TEM figure shows the microscopic appearance of material, from high power TEM picture as can be seen the pore structure of material be three-dimensional cross-linked hole, rather than one-dimensional tunnel structure: (a) embodiment 1, and (b) embodiment 2, and (c) embodiment 3, and (d) embodiment 5;
Fig. 2 nitrogen adsorption/desorption curve map and corresponding graph of pore diameter distribution show that this material possesses typical meso-hole structure, and the desorption curve is that 0.4～0.8 place has precipitous decline at relative pressure: (a) embodiment 1, (b) embodiment 2, (c) embodiment 3, and (d) embodiment 4, and (e) embodiment 5;
The XRD figure of Fig. 3 material, show that institute's prepared material has high degree of crystallinity: (a) embodiment 5, and (b) embodiment 6;
The hysteresis curve that Fig. 4 vibrating specimen magnetometer is measured, magnetic di-iron trioxide performance excess of export paramagnetic characteristic (embodiment 3), inserting figure is the digital photograph of di-iron trioxide;
The specific embodiment
Further specify embodiment and effect with following non-limiting embodiment:
Embodiment 1
With 2.0g nine nitric hydrate iron, the 1.0mL tert-butylamine dissolves in respectively in the 60mL dimethyl formamide, continues to stir after 3 minutes, and gained solution is transferred to water heating kettle and is enclosed in 220 ℃ of processing 6 hours.The gained reactant promptly obtains product after washing drying.Fig. 1 (a) is TEM figure, shows that products obtained therefrom is that nanocrystal is piled up the three-dimensional cross-linked pore structure that forms.Fig. 2 (a) is the nitrogen adsorption/desorption curve map and the corresponding graph of pore diameter distribution of material, shows that this material possesses typical meso-hole structure.Its BET specific area is 322.9m
2/ g.
Embodiment 2
With 2.0g nine nitric hydrate iron, 1.0mL urea dissolves in respectively in the 60mL dimethyl formamide, continues to stir after 3 minutes, and gained solution is transferred to water heating kettle and is enclosed in 180 ℃ of processing 16 hours.The gained reactant promptly obtains product after washing drying.Fig. 1 (b) is TEM figure, shows that products obtained therefrom is that nanocrystal is piled up the three-dimensional cross-linked pore structure that forms.Fig. 2 (b) is the nitrogen adsorption/desorption curve map and the corresponding graph of pore diameter distribution of material, shows that this material possesses typical meso-hole structure.Its BET specific area is 229.8m
2/ g.
Embodiment 3
With 2.0g nine nitric hydrate iron, the 1.0mL ethylenediamine dissolves in respectively in the 60mL dimethyl formamide, continues to stir after 3 minutes, and gained solution is transferred to water heating kettle and is enclosed in 180 ℃ of processing 24 hours.The gained reactant promptly obtains product after washing drying.Fig. 1 (c) is TEM figure, shows that products obtained therefrom is that nanocrystal is piled up the three-dimensional cross-linked pore structure that forms.Fig. 2 (c) is the nitrogen adsorption/desorption curve map and the corresponding graph of pore diameter distribution of material, shows that this material possesses typical meso-hole structure.Its BET specific area is 306.3m
2/ g.The hysteresis curve that Fig. 4 measures for vibrating specimen magnetometer, material list reveals super paramagnetic characteristic; Inserting figure is the photo in kind of sample, and product is a fibrous powder russet.
Embodiment 4
With 2.0g nitric hydrate yttrium, the 1.0mL ethylenediamine dissolves in respectively in the 60mL dimethyl formamide, continues to stir after 3 minutes, and gained solution is transferred to water heating kettle and is enclosed in 180 ℃ of processing 12 hours.The gained reactant promptly obtains product after washing drying.Fig. 2 (d) is the nitrogen adsorption/desorption curve map and the corresponding graph of pore diameter distribution of material, shows that this material possesses typical meso-hole structure.Its BET specific area is 98.6m
2/ g.
Embodiment 5
With 2.0g six nitric hydrate ceriums, the 1.0mL ethylenediamine dissolves in respectively in the 60mL dimethyl formamide, continues to stir after 3 minutes, and gained solution is transferred to water heating kettle and is enclosed in 100 ℃ of processing 12 hours.The gained reactant promptly obtains product after washing drying.Fig. 2 (e) is the nitrogen adsorption/desorption figure and the corresponding graph of pore diameter distribution of material, shows that products obtained therefrom has typical meso-hole structure.Fig. 3 (a) is its XRD figure, shows that institute's prepared material is the cerium oxide of crystallization.Its BET specific area is 131.9m
2/ g.
Embodiment 6
With 2.0g nitric hydrate indium, the 1.0mL ethylenediamine dissolves in respectively in the 60mL methyl-sulfoxide, continues to stir after 3 minutes, and gained solution is transferred to water heating kettle and is enclosed in 180 ℃ of processing 6 hours.The gained reactant promptly obtains product after washing drying.Fig. 3 (b) is its XRD figure, shows that institute's prepared material is the indium oxide of crystallization.Its BET specific area is 76.7m
2/ g.
The specific area of table 1 three-dimensional cross-linked mesoporous nanometer oxide material of the present invention
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | |
| BET specific area m 2/g | 322.9 | 229.8 | 306.3 | 98.6 | 131.9 | 76.7 |
Claims (2)
1, the preparation method of three-dimensional cross-linked mesoporous nanometer oxide material is characterized in that processing step is:
(1) hydrated inorganic salt, primary amine or urea are dissolved in respectively in the aprotic polar solvent, obtain clear solution;
(2) then, with the clear solution water heating kettle of packing into, carry out hydro-thermal reaction;
(3) reaction gained sediment washing, air dry promptly gets final products,
Described hydrated inorganic salt is nitrate, oxalates, chloride or the carbonate that contains the crystallization water;
Described primary amine is ethylenediamine or tert-butylamine;
Described aprotic polar solvent is dimethyl formamide or methyl-sulfoxide;
Wherein, the ratio of the amount of substance of hydrated inorganic salt and primary amine or urea is 0.1～1.0;
The volume ratio of described primary amine and aprotic polar solvent is 0.01～0.10;
Described hydrothermal treatment consists temperature is 100～220 ℃;
The described hydrothermal treatment consists time is 6～24 hours.
2, by the preparation method of the described three-dimensional cross-linked mesoporous nanometer oxide material of claim 1, capacity is 50-80% in the water heating kettle to it is characterized in that clear solution packing into.
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Citations (6)
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| JP2003519074A (en) * | 1999-12-30 | 2003-06-17 | ロディア・シミ | Production of mesostructured materials from nanometer-sized particles |
| CN1431144A (en) * | 2003-01-09 | 2003-07-23 | 复旦大学 | Method for preparing nano line of oxide of transition metals and nano crystals with multi-holes in 3D |
| CN1607176A (en) * | 2003-10-15 | 2005-04-20 | 中国科学院上海硅酸盐研究所 | Water thermostable cube phase medium aperture aluminosilicate hollow ball and preparation method thereof |
| CN1792788A (en) * | 2005-12-30 | 2006-06-28 | 中国科学院上海硅酸盐研究所 | Process for preparing silicon dioxide hollow ball material with hexagonal phase penetrating mesopore orbit |
| EP1690838A1 (en) * | 2003-11-17 | 2006-08-16 | National Institute of Advanced Industrial Science and Technology | Nanocrystal oxide/glass composite mesoporous powder or thin film, process for producing the same, and utilizing the powder or thin film, various devices, secondary battery and lithium storing device |
| CN1948161A (en) * | 2006-10-19 | 2007-04-18 | 复旦大学 | Nano-crystal large poresize mesopore oxide material and its preparation method |
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003519074A (en) * | 1999-12-30 | 2003-06-17 | ロディア・シミ | Production of mesostructured materials from nanometer-sized particles |
| CN1431144A (en) * | 2003-01-09 | 2003-07-23 | 复旦大学 | Method for preparing nano line of oxide of transition metals and nano crystals with multi-holes in 3D |
| CN1607176A (en) * | 2003-10-15 | 2005-04-20 | 中国科学院上海硅酸盐研究所 | Water thermostable cube phase medium aperture aluminosilicate hollow ball and preparation method thereof |
| EP1690838A1 (en) * | 2003-11-17 | 2006-08-16 | National Institute of Advanced Industrial Science and Technology | Nanocrystal oxide/glass composite mesoporous powder or thin film, process for producing the same, and utilizing the powder or thin film, various devices, secondary battery and lithium storing device |
| CN1792788A (en) * | 2005-12-30 | 2006-06-28 | 中国科学院上海硅酸盐研究所 | Process for preparing silicon dioxide hollow ball material with hexagonal phase penetrating mesopore orbit |
| CN1948161A (en) * | 2006-10-19 | 2007-04-18 | 复旦大学 | Nano-crystal large poresize mesopore oxide material and its preparation method |
Non-Patent Citations (1)
| Title |
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| Facile and Surfactant-Free Route to NanocrystallineMesoporous Tin Oxide. Songwang Yang et al.Journal of the American Ceramic Society,Vol.89 No.5. 2006 * |
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