CN100419132C - 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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- CN100419132C CN100419132C CNB2006101144335A CN200610114433A CN100419132C CN 100419132 C CN100419132 C CN 100419132C CN B2006101144335 A CNB2006101144335 A CN B2006101144335A CN 200610114433 A CN200610114433 A CN 200610114433A CN 100419132 C CN100419132 C CN 100419132C
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- magnesium oxide
- burrow
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- magnesia particle
- room temperature
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- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 239000000395 magnesium oxide Substances 0.000 title claims abstract description 52
- 239000002245 particle Substances 0.000 title claims abstract description 27
- 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 abstract 2
- 238000000034 method Methods 0.000 title description 12
- 238000002360 preparation method Methods 0.000 claims abstract description 12
- 239000008367 deionised water Substances 0.000 claims abstract description 11
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 11
- 239000000843 powder Substances 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 6
- 238000010335 hydrothermal treatment Methods 0.000 claims abstract description 5
- 238000003756 stirring 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 28
- 239000013078 crystal Substances 0.000 claims description 17
- 239000013543 active substance Substances 0.000 claims description 10
- 238000001354 calcination Methods 0.000 claims description 10
- 238000012876 topography Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 7
- 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
- 238000000967 suction filtration Methods 0.000 claims description 5
- 230000001788 irregular Effects 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 229920000428 triblock copolymer Polymers 0.000 claims description 3
- 239000011148 porous material Substances 0.000 abstract description 16
- 239000000463 material Substances 0.000 abstract description 4
- 239000007787 solid Substances 0.000 abstract description 3
- 239000004094 surface-active agent 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
- 238000001914 filtration Methods 0.000 abstract 1
- 239000003973 paint Substances 0.000 abstract 1
- 239000002887 superconductor Substances 0.000 abstract 1
- 238000005406 washing Methods 0.000 abstract 1
- 238000009826 distribution Methods 0.000 description 7
- 238000001027 hydrothermal synthesis Methods 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000011799 hole material Substances 0.000 description 4
- 238000002336 sorption--desorption measurement Methods 0.000 description 4
- 206010013786 Dry skin Diseases 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 238000001106 transmission high energy electron diffraction data Methods 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 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
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000007783 nanoporous material Substances 0.000 description 1
- 238000004098 selected area electron diffraction Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
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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 present invention relates to a kind of solid mesoporous material technology of preparing, be specifically related to a kind of technology of utilizing hydrothermal method the atresia magnesium oxide of irregular surface pattern to be converted into four directions and the magnesia particle of the burrow-shaped mesopores cube single crystal structure of six side's surface topographies.
Background technology
Because magnesium oxide has thermostability and higher surface reaction preferably, makes its important object that becomes surface tissue and catalyticing research, is widely used in fields such as pottery, enamel, catalysis, weaving, medical science.In recent years, the rapid emergence of nanometer technology of preparing and regular hole material synthesis technology has brought new opportunity for preparation specific morphology and ad hoc structure nanoparticle.Nano-porous materials has that particle diameter is little, specific surface area is high, particle diameter even aperture distribution, hole are arranged orderly scale effect and cell size effect, makes this type of bill of material reveal and the conventional different characteristic of particle diameter material greatly.Therefore, it is significant to set up the technology of a cover preparation nanometer or mesoporous magnesia particle.
The preparation method of porous magnesia particle grew up in nearest 2 years, but they mostly are hard template method, and preparation technology is loaded down with trivial details, the cost height.For example, (J.Am.Chem.Soc. such as Roggenbuck, 2005,127 (4): 1096-1097) the synthesising mesoporous SBA-15 of elder generation, make meso-porous carbon material (CMK-3) with SBA-15 as hard template then, be that hard template is decomposed into magnesium oxide through 300 with the magnesium nitrate in the CMK-3 hole again with CMK-3, then in air atmosphere, remove the carbon elimination template again in 750 ℃ of calcinations, thereby make the mesoporous magnesia particle, mean pore size is 7nm, and specific surface area is 280m
2/ g.(Chem.Mater. such as Li, 2004,16:5676-5681) utilize yellow soda ash catalysis formaldehyde and pyrocatechol condensation reaction to make the mesoporous carbon gel earlier, make hard template with this mesoporous carbon gel again and after 800 ℃ of calcinations, make mesoporous magnesia, mean pore size is 5.8～15.2nm, and specific surface area is 130m
2/ g.
Hydrothermal synthesis method is a kind of method that comparatively effectively prepares cellular solid.Yu etc. (J.Phys.Chem.B, 2004,108:64-70) with magnesium oxide be raw material, make mesoporous magnesia particle with two kinds of pore size distributions by hydrothermal treatment consists and after 450 ℃ of calcinations, specific surface area is 97m
2/ g, mean pore size is respectively 3.5nm and 35nm.The operation of Hydrothermal Preparation mesoporous magnesia is easier, and cost is lower, but the specific surface area of gained target product is less, simultaneously the pore size distribution broad.
In order to overcome the shortcoming of above two kinds of methods, and make full use of the advantage of hydrothermal synthesis method, the present invention introduces tensio-active agent in hydrothermal synthesis method, make magnesium oxide form magnesium hydroxide-surfactant micelle when being hydrolyzed in the still pressing certainly, obtain the more regular mesoporous magnesia particle of pore structure through high temperature sintering.
Summary of the invention
The objective of the invention is to overcome hard template method complicated operation and the relatively poor shortcoming of hydrothermal method gained sample well compound with regular structure degree, a kind of easy and simple to handle, more regular preparation method of target product (magnesium oxide) pore structure is provided.
The present invention is raw material with magnesium oxide, with tensio-active agent triblock copolymer EO
20PO
70EO
20(P123) or cetyl trimethylammonium bromide (CTAB) as soft template, make raw material under the condition that tensio-active agent exists, be hydrolyzed to magnesium hydroxide by hydro-thermal reaction, obtain the magnesium oxide single-crystal particle of the burrow-shaped mesopores cubic crystal structure of four directions and six side's surface topographies at last by calcination gained magnesium hydroxide.
The invention provides the preparation method of a kind of four directions and hexagonal burrow-shaped mesopores cubic monocrystalline magnesia particle, it is characterized in that, may further comprise the steps:
1). tensio-active agent is dissolved in the deionized water, adds magnesium oxide powder, tensio-active agent is 1.25: 1～3: 1 with magnesium oxide amount of substance ratio, stirs under the room temperature; Used magnesium oxide powder is the atresia magnesium oxide of irregular surface pattern, and tensio-active agent is triblock copolymer EO
20PO
70EO
20, its molecular weight is not less than 5800 or cetyl trimethylammonium bromide;
2). said mixture is transferred to from pressing still and place baking oven, and in 160～240 ℃ of hydro-thermals 24～120 hours, it naturally cooled to room temperature to take out relief;
3). with the mixture suction filtration after the hydrothermal treatment consists, with obtaining white powder after deionized water wash, the drying;
4). the gained white powder is put into retort furnace, rise to 400～550 ℃ and calcination 3 hours under this temperature from room temperature, obtain the magnesium oxide single-crystal particle of four directions and the burrow-shaped mesopores cubic crystal structure of six side's surface topographies with the temperature rise rate of 1 ℃/min.
The chemical equation relevant with the present invention is:
Annotate: tensio-active agent is P123 or CTAB; Calcination temperature is 400～550 ℃.
With products therefrom X-ray diffractometer (XRD), N
2Adsorption-desorption, scanning electronic microscope (SEM), transmission electron microscope (TEM) and selected area electron diffraction technology such as (SAED) characterize.The result shows that adopting the obtained sample of present method is the magnesium oxide single-crystal particle of the burrow-shaped mesopores cubic crystal structure of four directions and six side's surface topographies, has comparatively regular meso-hole structure, and specific surface area is 101～145m
2/ g, mean pore size is 3.7～6.8nm.
The present invention has adopted a kind of simple soft template method to prepare the mesoporous magnesia monocrystal particle of multiple regular pattern.Present method preparation cost is low, and operating process is easy, and the target product pore size distribution is narrow, and specific surface area is big, and particle morphology is regular.
Description of drawings
For further understanding the present invention, elaborate with embodiment below, and provide the magnesium oxide single-crystal particle that accompanying drawing is described the burrow-shaped mesopores cubic crystal structure of four directions that the present invention obtains and six side's surface topographies, wherein:
Fig. 1 is the SEM photo of raw materials of magnesium oxide.
Fig. 2 is the XRD spectra of mesoporous magnesia sample, and wherein curve (a) is a raw materials of magnesium oxide; (b) be mesoporous magnesia embodiment 1; (c) be mesoporous magnesia embodiment 2; (d) be mesoporous magnesia embodiment 3.
Fig. 3 (a) and (b) are respectively the SEM and the TEM photo of mesoporous magnesia embodiment 1 sample, and the illustration among Fig. 3 (b) is the SAED pattern of this sample.Fig. 3 (c) is the N of this sample
2The adsorption-desorption thermoisopleth, the illustration among Fig. 3 (c) is a pore size distribution curve.
Fig. 4 (a) and (b) are respectively the SEM and the TEM photo of mesoporous magnesia embodiment 2 samples, and the illustration among Fig. 4 (b) is the SAED pattern of this sample.Fig. 4 (c) is the N of this sample
2The adsorption-desorption thermoisopleth, the illustration among Fig. 4 (c) is a pore size distribution curve.
Fig. 5 (a) and (b) are respectively the SEM and the TEM photo of mesoporous magnesia embodiment 3 samples, and the illustration among Fig. 5 (b) is the SAED pattern of this sample.Fig. 5 (c) is the N of this sample
2The adsorption-desorption thermoisopleth, the illustration among Fig. 5 (c) is a pore size distribution curve.
Embodiment
Embodiment 1: 0.025mol P123 is dissolved in the 60mL deionized water, adds 0.02mol magnesium oxide, stirred 24 hours under the room temperature.Above mixture is transferred to from pressing in the still, puts into baking oven,, naturally cool to room temperature after the taking-up, behind suction filtration, deionized water wash, in 80 ℃ of dryings 12 hours in 160 ℃ of hydro-thermals 24 hours.Then the gained sample is put into retort furnace, with the speed temperature programming to 400 of 1 ℃/min ℃ and 400 ℃ of constant temperature calcinations 3 hours, obtain the magnesium oxide single-crystal particle of the burrow-shaped mesopores cubic crystal structure of four directions and six side's surface topographies, based on cubic shape pattern, specific surface area is 101m
2/ g, mean pore size is 3.7nm.
Embodiment 2: 0.06mol P123 is dissolved in the 60mL deionized water, adds the 0.02mol raw materials of magnesium oxide in solution, stirred 24 hours under the room temperature.Above mixture is transferred to from pressing in the still, puts into baking oven,, naturally cool to room temperature after the taking-up, behind suction filtration, deionized water wash, in 80 ℃ of dryings 12 hours in 240 ℃ of hydro-thermals 120 hours.Then the gained sample is put into retort furnace, temperature programming (1 ℃/min) to 450 ℃ and 450 ℃ of constant temperature calcinations 3 hours, obtain the magnesium oxide single-crystal particle of the burrow-shaped mesopores cubic crystal structure of four directions and six side's surface topographies, based on cubic shape pattern, specific surface area is 145m
2/ g, mean pore size is 6.8nm.
Embodiment 3: 0.04mol CTAB is dissolved in the 60mL deionized water, adds the 0.02mol magnesium oxide powder, stirred 24 hours under the room temperature.Above mixture is transferred to from pressing in the still and place baking oven,, naturally cools to room temperature after the taking-up, behind suction filtration, deionized water wash, in 80 ℃ of dryings 12 hours in 160 ℃ of hydrothermal treatment consists 72 hours.Then the gained sample is put into retort furnace, temperature programming (1 ℃/min) to 550 ℃ and constant temperature calcination 3 hours under this temperature, obtain the magnesium oxide single-crystal particle of the burrow-shaped mesopores cubic crystal structure of four directions and six side's surface topographies, based on six side's shape patterns, specific surface area is 136m
2/ g, mean pore size is 4.1nm.
Claims (1)
1. the preparation method of four directions and hexagonal burrow-shaped mesopores cubic monocrystalline magnesia particle is characterized in that, may further comprise the steps:
1). tensio-active agent is dissolved in the deionized water, adds magnesium oxide powder, tensio-active agent is 1.25: 1～3: 1 with magnesium oxide amount of substance ratio, stirs under the room temperature; Used magnesium oxide powder is the atresia magnesium oxide of irregular surface pattern, and tensio-active agent is triblock copolymer EO
20PO
70EO
20, its molecular weight is not less than 5800 or cetyl trimethylammonium bromide;
2). said mixture is transferred to from pressing still and place baking oven, and in 160～240 ℃ of hydro-thermals 24～120 hours, it naturally cooled to room temperature to take out relief;
3). with the mixture suction filtration after the hydrothermal treatment consists, with obtaining white powder after deionized water wash, the drying;
4). the gained white powder is put into retort furnace, rise to 400～550 ℃ and calcination 3 hours under this temperature from room temperature, obtain the magnesium oxide single-crystal particle of four directions and the burrow-shaped mesopores cubic crystal structure of six side's surface topographies with the temperature rise rate of 1 ℃/min.
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|---|---|---|---|
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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 true CN100419132C (en) | 2008-09-17 |
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Families Citing this family (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 |
| 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 |
| 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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2006
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Non-Patent Citations (2)
| Title |
|---|
| Synthesis and characterization of porous magnesiumhydroxide and oxide nanoplates. Jimmy C.Yu et al.J.Phys.Chem.B,Vol.108 . 2004 |
| Synthesis and characterization of porous magnesiumhydroxide and oxide nanoplates. Jimmy C.Yu et al.J.Phys.Chem.B,Vol.108 . 2004 * |
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