CN101992081B - Method for preparing composite metal oxide with graded porous structure - Google Patents
Method for preparing composite metal oxide with graded porous structure Download PDFInfo
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- CN101992081B CN101992081B CN2010102707678A CN201010270767A CN101992081B CN 101992081 B CN101992081 B CN 101992081B CN 2010102707678 A CN2010102707678 A CN 2010102707678A CN 201010270767 A CN201010270767 A CN 201010270767A CN 101992081 B CN101992081 B CN 101992081B
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- metal oxide
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- metal salt
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Abstract
The invention provides a method for preparing a composite metal oxide with a graded porous structure. The method comprises the following steps of: pouring a bivalent metal salt and a trivalent metal salt into a container filled with a mixed solvent of ethylene glycol and water, placing the container into a closed container filled with thick aqueous ammonia after dissolution, and reacting the volatilized aqueous ammonia and the metal salts on the surface of the solution layer by layer at room temperature to generate hydrotalcite sol; and pouring out the transparent solution of the upper layer, transferring the rest sol into a crucible, insulating and ageing the sol for 12 hours at the temperature of between 80 and 180 DEG C, directly performing suction filtration on the aged sol under reduced pressure, drying the obtained filter cakes in an oven, finally putting the dried gel product into the crucible, roasting the gel product for 5 hours at the temperature of between 300 and 500 DEG C, and cooling the roasted product to room temperature to obtain the graded porous composite metal oxide. The hydrotalcite sol with three-dimensional spatial network structure is formed by adopting a gas-liquid interface reaction method, and the hydrotalcite sol is dried and roasted to prepare the composite metal oxide with the graded porous structure.
Description
Technical field
That the present invention relates to is a kind of preparation method of composite metal oxide of loose structure.
Background technology
Porous material is with its unique pore structure and excellent specific surface performance, in catalysis, absorption with the field such as separate and be with a wide range of applications.The porous material that contains the graded structure of specific micropore, mesoporous or macropore, because the compound advantage of multiple size hole, thereby caused increasing researcher's concern.Up to the present, graduate porous material such as TiO
2, ZrO
2, CeO
2And composite metal oxide, normally applying template synthesizes, and template commonly used has polyethylene micelle, block copolymer, ionic surfactant etc.Yet these template lack intrinsic complexity and hierarchy usually; Thereby be difficult to obtain the pore structure and the pattern of many sizes; And need loaded down with trivial details and complicated post-processing step to remove organic formwork, and these steps can cause new environmental pollution and energy waste.Therefore many researchers begin to adopt complicated natural biological template such as butterfly's wing, shell, wooden bacterium to wait and construct the porous inorganic material (S.A.Davis with hierarchy; H.M.Patel, E.L.Mayes, N.H.Mendelson; G.Franco; S.Mann, Chem.Mater.10,2516 (1998); B.Zhang, S.A.Davis, N.H.Mendelson, S.Mann, Chem.Commun.9,781 (2000); Y.Zheng, X.Gao, L.Jiang, Soft Matter.3,178 (2007)).
Composite metal oxide in the porous material is widely used in the catalyst that improves environment, the carrier of adsorbent and biomaterial etc. because of it has excellent loose structure and high heat stability performance.Though mixed-metal oxides (M.Sadakane, T.Asanuma, J.Kubo, W.Ueda, Chem.Mater.17,3546 (2005) of adopting glue crystal template method can prepare the ordered big hole structure; E.G é raud, V.Pr é vot, J.Ghanbaja, F.Leroux, Chem.Mater.18,238 (2006)), but the method for synthetic graduate porous composite metal oxide is rarely found.With the hydrotalcite is presoma, can obtain composite metal oxide at suitable roasting temperature, and the product outward appearance presents sheet, unordered, network structure, so porous and have bigger specific area, has good stable property simultaneously again.Reported that recently a kind of the use has the classifying porous composite metal oxide with biological appearance (Y.Zhao, M.Wei, J.Lu, Z.L.Wang, X.Duan, ACS Nano.3,4009 (2009)) that the ciliary beanpod of specific cast is that biological template is synthetic.And the shortcoming of biological template is to be difficult to guarantee that meticulous mechanics of biological tissue is not destroyed in course of reaction.
Summary of the invention
The object of the present invention is to provide a kind of synthesis path that can further widen the graduation porous structure material; Make it in catalysis; Absorption, many fields such as separation and light, electricity, magnetic have the preparation method of the composite metal oxide with graduation loose structure of potential using value.
The objective of the invention is to realize like this:
Take by weighing divalent metal salt and trivalent metal salt respectively; And be poured in the container of the mixed solvent that fills ethylene glycol and water; Dissolving back is placed on container in the closed container that fills concentrated ammonia liquor fully; At ambient temperature, the ammoniacal liquor and the slaine that evaporate successively react in solution surface, and reaction is carried out complete and generated hydrotalcite colloidal sol; Take out container, the clear solution on the upper strata of inclining will remain colloidal sol and be transferred in the crucible; Be placed in the baking oven after covering crucible cover, 80～180 ℃ are incubated ageing 12 hours, again with the direct decompress filter of the colloidal sol of ageing; Gained filter cake in baking oven dry 24 hours is positioned over the jel product that obtains after the drying in the crucible, under 300～500 ℃ the air ambient at last; Roasting is 5 hours in Muffle furnace, when waiting to reduce to room temperature, takes out product of roasting and can obtain the porous composite metal oxide of classifying.
The scope of the volume ratio of ethylene glycol and water is 9: 1～1: 1.
The weight ratio concentration of said ammoniacal liquor is 26%.
Said divalent metal salt Mg (NO
3)
2Or MgCl
2Said trivalent metal salt is Al (NO
3)
3Or AlCl
3
The mol ratio of divalent metal salt and trivalent metal salt is 2: 1.
The present invention is directed to the problem of the composite metal oxide material preparation method existence of existing graduation loose structure; Having proposed with ethylene glycol and water is mixed solvent, adopts simple gas-liquid interface reaction method to prepare hydrotalcite colloidal sol, and this method of method that obtains to have the composite metal oxide of graduation loose structure (micropore-mesopore-macropore) through the calcined hydrotalcite presoma again will further be widened the synthesis path of graduation porous structure material; Make it in catalysis; Absorption separates and light; There is potential using value in many fields such as magnetic, and support for the formation of graduation loose structure mechanism provides theoretical.
Major technique characteristic of the present invention is to adopt the gas-liquid interface reaction method; Ammoniacal liquor and slaine that utilization evaporates successively react in solution surface; Polar group hydroxyl at ethylene glycol (OH) connects colloidal particle mutually under the effect; Form the hydrotalcite gel of three-dimensional space network structure, prepare composite metal oxide through drying and roasting with graduation loose structure (micropore-mesopore-macropore)
The specific embodiment
For example the present invention is done in more detail below and describes:
In the preparation process, with the ethylene glycol and the water as solvent of 7: 3 (volume ratio).Mg (NO with 6.15g (24.0mmol)
3)
26H
2Al (the NO of O and 4.51g (12.0mmol)
3)
39H
2O is dissolved in the beaker of the mixed solvent that fills 50mL ethylene glycol and water, is placed on beaker in the closed container that fills 150mL concentrated ammonia liquor (26wt%) then.At ambient temperature, the ammoniacal liquor and the nitrate that evaporate successively react in solution surface, and reaction is carried out complete and generated hydrotalcite colloidal sol.Take out beaker, the clear solution on the upper strata of inclining will remain colloidal sol and be transferred in the crucible, be placed in the baking oven after covering crucible cover, and 150 ℃ are incubated ageings and take out after 12 hours.This moment is again with direct (the not using any solvent clean) decompress filter of the colloidal sol of ageing, gained filter cake in baking oven dry 24 hours.Be positioned over the jel product that obtains after the drying in the crucible at last, under 400 ℃ the air ambient, roasting is 5 hours in Muffle furnace, when waiting to reduce to room temperature, takes out product of roasting and can obtain the porous composite oxide of classifying.
Embodiment 2:
Other experiment condition is with embodiment 1, and changing divalent metal salt and trivalent metal salt is MgCl
26H
2O and AlCl
36H
2O.
Embodiment 3:
Other experiment condition is with embodiment 1, and the volume ratio of ethylene glycol and water is 1: 1 in the change mixed solvent.
Embodiment 4:
Other experiment condition is with embodiment 1, and the insulation ageing temperature that changes hydrotalcite is 100 ℃.
Embodiment 5:
Other experiment condition is with embodiment 1, and the sintering temperature that changes hydrotalcite precursor is 500 ℃.
Claims (5)
1. preparation method of composite metal oxide with graduation loose structure; It is characterized in that: take by weighing divalent metal salt and trivalent metal salt respectively; And be poured in the container of the mixed solvent that fills ethylene glycol and water, the dissolving back is placed on container in the closed container that fills concentrated ammonia liquor, at ambient temperature fully; The ammoniacal liquor and the slaine that evaporate successively react in solution surface, and reaction is carried out complete and generated hydrotalcite colloidal sol; Take out container, the clear solution on the upper strata of inclining will remain colloidal sol and be transferred in the crucible; Be placed on 80～180 ℃ of insulation ageings 12 hours after covering crucible cover; With the direct decompress filter of the colloidal sol of ageing, gained filtration cakes torrefaction 24 hours is positioned over the jel product that obtains after the drying in the crucible at last again; Roasting is 5 hours under 300～500 ℃ the air ambient, reduces to room temperature and obtains the graduation porous composite metal oxide; Said divalent metal salt Mg (NO
3)
2Or MgCl
2Said trivalent metal salt is Al (NO
3)
3Or AlCl
3
2. the preparation method with composite metal oxide of graduation loose structure according to claim 1, it is characterized in that: the mol ratio of divalent metal salt and trivalent metal salt is 2: 1.
3. the preparation method with composite metal oxide of graduation loose structure according to claim 1 and 2, it is characterized in that: the scope of the volume ratio of ethylene glycol and water is 9: 1～1: 1.
4. the preparation method with composite metal oxide of graduation loose structure according to claim 1 and 2, it is characterized in that: the weight ratio concentration of said ammoniacal liquor is 26%.
5. the preparation method with composite metal oxide of graduation loose structure according to claim 3, it is characterized in that: the weight ratio concentration of said ammoniacal liquor is 26%.
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|---|---|---|---|
| CN2010102707678A CN101992081B (en) | 2010-09-03 | 2010-09-03 | Method for preparing composite metal oxide with graded porous structure |
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|---|---|---|---|
| CN2010102707678A CN101992081B (en) | 2010-09-03 | 2010-09-03 | Method for preparing composite metal oxide with graded porous structure |
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| CN101992081B true CN101992081B (en) | 2012-08-22 |
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| CN103950969B (en) * | 2014-03-18 | 2016-02-10 | 清华大学 | A kind of preparation method of multistage porous metal oxide nano material |
| CN108686618B (en) * | 2018-05-30 | 2022-06-10 | 哈尔滨师范大学 | Preparation method of hierarchical porous composite metal oxide |
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| CN1315225A (en) * | 2000-03-27 | 2001-10-03 | 北京化工大学 | Compound Mg-Al oxide catalyst for alkoxylation reaction and its preparing process |
| CA2562014C (en) * | 2003-07-07 | 2014-02-11 | Instituto Mexicano Del Petroleo | Method of obtaining multimetallic oxides derived from hydrotalcite-type compounds |
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Granted publication date: 20120822 Termination date: 20180903 |