CN1974881A - Prepn process of cubic monocrystalline magnesia particle with tetragonal and hexagonal burrow-shaped mesopores - Google Patents
Prepn process of cubic monocrystalline magnesia particle with tetragonal and hexagonal burrow-shaped mesopores Download PDFInfo
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- CN1974881A CN1974881A CN 200610114433 CN200610114433A CN1974881A CN 1974881 A CN1974881 A CN 1974881A CN 200610114433 CN200610114433 CN 200610114433 CN 200610114433 A CN200610114433 A CN 200610114433A CN 1974881 A CN1974881 A CN 1974881A
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- magnesium oxide
- tetragonal
- hexagonal
- room temperature
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- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 239000000395 magnesium oxide Substances 0.000 title claims abstract description 53
- 239000002245 particle Substances 0.000 title claims abstract description 31
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 238000000034 method Methods 0.000 title description 13
- 239000004094 surface-active agent Substances 0.000 claims abstract description 12
- 239000000843 powder Substances 0.000 claims abstract description 11
- 238000002360 preparation method Methods 0.000 claims abstract description 11
- 239000008367 deionised water Substances 0.000 claims abstract description 10
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000010335 hydrothermal treatment Methods 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 4
- 238000001914 filtration Methods 0.000 claims abstract description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 43
- 239000013078 crystal Substances 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 17
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 6
- 238000003825 pressing Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 230000001788 irregular Effects 0.000 claims description 3
- 229920000428 triblock copolymer Polymers 0.000 claims description 3
- 239000011148 porous material Substances 0.000 abstract description 18
- 238000005516 engineering process Methods 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 4
- 239000007787 solid Substances 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 abstract 2
- 239000000654 additive Substances 0.000 abstract 1
- 230000000996 additive effect Effects 0.000 abstract 1
- 239000003973 paint Substances 0.000 abstract 1
- 239000002887 superconductor Substances 0.000 abstract 1
- 238000009826 distribution Methods 0.000 description 7
- 238000001027 hydrothermal synthesis Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 5
- 238000002159 adsorption--desorption isotherm Methods 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- 238000001106 transmission high energy electron diffraction data Methods 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002003 electron diffraction Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 239000007783 nanoporous material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
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- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The preparation process of cubic onocrystalline magnesia particle with tetragonal and hexagonal burrow-shaped mesopores belongs to the field of solid mesopore material preparing technology. The preparation process includes the following steps: dissolving surfactant in deionized water and adding magnesia powder through stirring at room temperature; hydrothermal treatment in a self-pressurizing kettle; suction filtering, washing and drying to obtain white powder; and final igniting at 400-550 deg.c in a muffle for 3 hr to obtain the magnesia particle product. The produced magnesia particle has regular mesopore structure, specific surface area of 101-145 sq m/g, and average pore size of 3.7-6.8 nm. The produced magnesia particle is suitable for use as catalyst and catalyst carrier, as well as additive for heat resisting material, paint and superconductor.
Description
Technical Field
The invention relates to a preparation technology of a solid mesoporous material, in particular to a process for converting non-porous magnesium oxide with irregular surface morphology into magnesium oxide particles with a wormhole-shaped mesoporous cubic single crystal structure with tetragonal and hexagonal surface morphology by using a hydrothermal method.
Background
Because of its good thermal stability and high surface reactivity, magnesium oxide becomes an important object for surface structure and catalysis research, and is widely used in the fields of ceramics, enamel, catalysis, textile, medicine, etc. In recent years, the rapid rise of the nanometer preparation technology and the regular pore material synthesis technology brings new opportunities for preparing nanometer particles with specific morphologies and specific structures. The nano porous material has the advantages of small particle size, high specific surface area, uniform particle size and pore size distribution, ordered porearrangement, scale effect and pore size effect, so that the material has different characteristics from the conventional large particle size material. Therefore, establishing a set of process for preparing the nano or mesoporous magnesium oxide particles has important significance.
The preparation method of the porous magnesium oxide particles is developed in recent two years, but most of the porous magnesium oxide particles are prepared by a hard template method, and the preparation process is complicated and high in cost. For example, Roggenbuck et al (J.Am.chem.Soc., 2005, 127 (4): 1096-2(ii) in terms of/g. Li, etc. (chem.Mater., 2004, 16: 5676-2/g。
Water-heat sealThe method is an effective method for preparing the porous solid material. Yu et al (J.Phys.chem.B, 2004, 108: 64-70) use magnesium oxide as raw material, through hydrothermal treatment and burning at 450 deg.C, mesoporous magnesium oxide particles with two pore size distributions are obtained, the specific surface area is 97m2In terms of a/g, the average pore diameters were 3.5nm and 35nm, respectively. The hydrothermal method for preparing mesoporous magnesium oxide has the advantages of simple operation and low costThe specific surface area of the obtained target product is small, and the pore size distribution is wide.
In order to overcome the defects of the two methods and fully utilize the advantages of the hydrothermal synthesis method, the invention introduces the surfactant into the hydrothermal synthesis method, so that magnesium oxide forms magnesium hydroxide-surfactant micelles when hydrolyzed in a self-pressure kettle, and mesoporous magnesium oxide particles with more regular pore structures are obtained by high-temperature ignition.
Disclosure of Invention
The invention aims to overcome the defects of complex operation of a hard template method and poor regularity of a sample pore structure obtained by a hydrothermal method, and provides a preparation method which is simple and convenient to operate and has a regular target product (magnesium oxide) pore structure.
The invention takes magnesium oxide as raw material and surfactant triblock copolymer EO20PO70EO20(P123) or Cetyl Trimethyl Ammonium Bromide (CTAB) is used as a soft template, the raw material is hydrolyzed into magnesium hydroxide under the condition of the existence of a surfactant through a hydrothermal reaction, and finally the obtained magnesium hydroxide is burnt to obtain magnesium oxide single crystal particles with a tetragonal and hexagonal surface morphology and a wormhole-shaped mesoporous cubic crystal structure.
The invention provides a preparation method of tetragonal and hexagonal wormhole-shaped mesoporous monocrystal cubic magnesium oxide particles, which is characterized by comprising the following steps of:
1) dissolving a surfactant in deionized water, adding magnesium oxide powder, wherein the mass ratio of the surfactant to magnesium oxide is 1.25: 1-3: 1, and uniformly stirring at room temperature; the magnesium oxide powder is non-porous magnesium oxide with irregular surface morphology, and the surfactant is triblock copolymer EO20PO70EO20(ii) having a molecular weight not less than 5800 or cetyltrimethylammonium bromide;
2) transferring the mixture to a self-pressing kettle, placing the self-pressing kettle in an oven, carrying out hydrothermal treatment at 160-240 ℃ for 24-120 hours, taking out, and naturally cooling the mixture to room temperature;
3) filtering the mixture after the hydrothermal treatment, washing with deionized water, and drying to obtain white powder;
4) and putting the obtained white powder into a muffle furnace, heating from room temperature to 400-550 ℃ at the heating rate of 1 ℃/min, and burning for 3 hours at the temperature to obtain the magnesium oxide single crystal particles with the tetragonal and hexagonal surface morphology and the wormhole-shaped mesoporous cubic crystal structure.
The chemical reaction formula relevant to the invention is:
note: the surfactant is P123 or CTAB; the firing temperature is 400-550 ℃.
Subjecting the obtained product to X-ray diffractometer (XRD) and N2And (3) performing characterization by using the technologies of adsorption-desorption, Scanning Electron Microscope (SEM), Transmission Electron Microscope (TEM), Selective Area Electron Diffraction (SAED) and the like. The result shows that the magnesium oxide single crystal particles with the sample of the wormhole-shaped mesoporous cubic crystal structure with the tetragonal and hexagonal surface morphology prepared by the method have a more regular mesoporous structure and the specific surface area of 101-145 m2(ii)/g, the average pore diameter is 3.7 to 6.8 nm.
The invention adopts a simple and easy soft template method to prepare mesoporous magnesium oxide single crystal particles with various regular morphologies. The method has the advantages of low preparation cost, simple and convenient operation process, narrow pore size distribution of the target product, large specific surface area and regular particle morphology.
Drawings
For further understanding of the present invention, the following examples are given to describe the magnesium oxide single crystal particles with wormhole-like mesoporous cubic crystal structure with tetragonal and hexagonal surface morphology obtained by the present invention, and the accompanying drawings are given, wherein:
FIG. 1 is an SEM photograph of a magnesium oxide feedstock.
FIG. 2 is an XRD spectrum of a mesoporous magnesia sample, wherein curve (a) is the magnesia raw material; (b) is mesoporous magnesia example 1; (c) is mesoporous magnesia example 2; (d) is mesoporous magnesia example 3.
Fig. 3(a) and (b) are SEM and TEM photographs of the mesoporous magnesium oxide example 1 sample, respectively, and the inset in fig. 3(b) is the SAED pattern of the sample. FIG. 3(c) shows N in this sample2The adsorption-desorption isotherm, and the inset in fig. 3(c) is the pore size distribution curve.
Fig. 4(a) and (b) are SEM and TEM photographs of the mesoporous magnesium oxide example 2 sample, respectively, and the inset in fig. 4(b) is the SAED pattern of the sample. FIG. 4(c) shows N in this sample2The adsorption-desorption isotherm, and the inset in fig. 4(c) is the pore size distribution curve.
Fig. 5(a) and (b) are SEM and TEM photographs of the mesoporous magnesium oxide example 3 sample, respectively, and the inset in fig. 5(b) is the SAED pattern of the sample. FIG. 5(c) shows N in this sample2The adsorption-desorption isotherm, and the inset in fig. 5(c) is the pore size distribution curve.
Detailed Description
Example 1: 0.025mol of P123 was dissolved in 60mL of deionized water, 0.02mol of magnesium oxide was added, and the mixture was stirred at room temperature for 24 hours. And transferring the mixture into a self-pressure kettle, putting the self-pressure kettle into an oven, carrying out hydrothermal treatment at 160 ℃ for 24 hours, taking out the self-pressure kettle, naturally cooling to room temperature, carrying out suction filtration and deionized water washing, and drying at 80 ℃ for 12 hours. Then putting the obtained sample into a muffle furnace, raising the temperature to 400 ℃ at the speed of 1 ℃/min, and firing at the constant temperature of 400 ℃ for 3 hours to obtain magnesium oxide single crystal particles with the tetragonal and hexagonal surface morphology and the wormhole-shaped mesoporous cubic crystal structure, wherein the magnesium oxide single crystal particles mainly have the tetragonal morphology and the specific surface area of 101m2In terms of/g, the mean pore diameter is 3.7 nm.
Example 2: 0.06mol of P123 was dissolved in 60mL of deionized water0.02mol of a magnesium oxide raw material was added to the solution, and the mixture was stirred at room temperature for 24 hours. And transferring the mixture into a self-pressure kettle, putting the self-pressure kettle into an oven, carrying out hydrothermal treatment at 240 ℃ for 120 hours, taking out the mixture, naturally cooling the mixture to room temperature, carrying out suction filtration and deionized water washing, and drying the mixture at 80 ℃ for 12 hours. Then putting the obtained sample into a muffle furnace, raising the temperature by program (1 ℃/min) to 450 ℃, and burning the sample at the constant temperature of 450 ℃ for 3 hours to obtain magnesium oxide single crystal particles with a wormhole-shaped mesoporous cubic crystal structure with the tetragonal and hexagonal surface morphology, wherein the magnesium oxide single crystal particles mainly have the tetragonal morphology and the specific surface area of145m2In terms of/g, the mean pore diameter is 6.8 nm.
Example 3: 0.04mol of CTAB was dissolved in 60mL of deionized water, and 0.02mol of magnesium oxide powder was added thereto, followed by stirring at room temperature for 24 hours. And transferring the mixture into a self-pressing kettle, placing the self-pressing kettle into an oven, carrying out hydrothermal treatment at 160 ℃ for 72 hours, taking out the mixture, naturally cooling the mixture to room temperature, carrying out suction filtration and deionized water washing, and drying the mixture at 80 ℃ for 12 hours. Then putting the obtained sample into a muffle furnace, raising the temperature by a program (1 ℃/min) to 550 ℃, and burning the sample at the constant temperature for 3 hours to obtain magnesium oxide single crystal particles with a wormhole-shaped mesoporous cubic crystal structure with the square and hexagonal surface appearances, wherein the magnesium oxide single crystal particles mainly have the hexagonal appearance and the specific surface area of 136m2In terms of/g, the mean pore diameter is 4.1 nm.
Claims (1)
1. A preparation method of tetragonal and hexagonal wormhole mesoporous single crystal cubic magnesium oxide particles is characterized by comprising the following steps:
1) dissolving a surfactant in deionized water, adding magnesium oxide powder, wherein the mass ratio of the surfactant to magnesium oxide is 1.25: 1-3: 1, and uniformly stirring at room temperature; the magnesium oxide powder is non-porous magnesium oxide with irregular surface morphology, and the surfactant is triblock copolymer EO20PO70EO20(ii) having a molecular weight not less than 5800 or cetyltrimethylammonium bromide;
2) transferring the mixture to a self-pressing kettle, placing the self-pressing kettle in an oven, carrying out hydrothermal treatment at 160-240 ℃ for 24-120 hours, taking out, and naturally cooling the mixture to room temperature;
3) filtering the mixture after the hydrothermal treatment, washing with deionized water, and drying to obtain white powder;
4) and putting the obtained white powder into a muffle furnace, heating from room temperature to 400-550 ℃ at the heating rate of 1 ℃/min, and burning for 3 hours at the temperature to obtain the magnesium oxide single crystal particles with the tetragonal and hexagonal surface morphology and the wormhole-shaped mesoporous cubic crystal structure.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006101144335A CN100419132C (en) | 2006-11-10 | 2006-11-10 | Prepn process of cubic monocrystalline magnesia particle with tetragonal and hexagonal burrow-shaped mesopores |
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|---|---|---|---|
| CNB2006101144335A CN100419132C (en) | 2006-11-10 | 2006-11-10 | Prepn process of cubic monocrystalline magnesia particle with tetragonal and hexagonal burrow-shaped mesopores |
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| CN100419132C CN100419132C (en) | 2008-09-17 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101219799B (en) * | 2007-10-11 | 2010-07-14 | 北京工业大学 | Method for producing foramen magnum-mesoporous magnesia by using dual mould plate agent |
| CN101734691B (en) * | 2009-12-11 | 2011-12-14 | 北京工业大学 | Method for preparing porous magnesium oxide with fatty amine solvent by means of hot method |
| CN104307462A (en) * | 2014-10-11 | 2015-01-28 | 哈尔滨工程大学 | Method for preparing mesoporous magnesium oxide through one-step boiling |
| CN104445296A (en) * | 2014-11-25 | 2015-03-25 | 重庆文理学院 | Synthesis method of spherical MgO nano particle |
-
2006
- 2006-11-10 CN CNB2006101144335A patent/CN100419132C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101219799B (en) * | 2007-10-11 | 2010-07-14 | 北京工业大学 | Method for producing foramen magnum-mesoporous magnesia by using dual mould plate agent |
| CN101734691B (en) * | 2009-12-11 | 2011-12-14 | 北京工业大学 | Method for preparing porous magnesium oxide with fatty amine solvent by means of hot method |
| CN104307462A (en) * | 2014-10-11 | 2015-01-28 | 哈尔滨工程大学 | Method for preparing mesoporous magnesium oxide through one-step boiling |
| CN104307462B (en) * | 2014-10-11 | 2016-06-29 | 哈尔滨工程大学 | The method that one step water-boiling method prepares mesoporous magnesia |
| CN104445296A (en) * | 2014-11-25 | 2015-03-25 | 重庆文理学院 | Synthesis method of spherical MgO nano particle |
| CN104445296B (en) * | 2014-11-25 | 2016-02-10 | 重庆文理学院 | A kind of synthetic method of spherical MgO nano particle |
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| CN100419132C (en) | 2008-09-17 |
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Granted publication date: 20080917 Termination date: 20121110 |