CN104016413B - Preparation method of exposed [200] crystal face monocrystal square OMS-2 nano material - Google Patents
Preparation method of exposed [200] crystal face monocrystal square OMS-2 nano material Download PDFInfo
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- CN104016413B CN104016413B CN201410260220.8A CN201410260220A CN104016413B CN 104016413 B CN104016413 B CN 104016413B CN 201410260220 A CN201410260220 A CN 201410260220A CN 104016413 B CN104016413 B CN 104016413B
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Abstract
The invention discloses a preparation method of an exposed [200] crystal face monocrystal square OMS-2 nano material. The method comprises the following steps: dropwisely adding 0.02 mmol of aldehyde substance into 0.02 mmol of potassium permanganate solution according to the mole ratio of 1:1, continuing stirring for 12-24 hours after finishing the dropwise addition, carrying out vacuum filtration, washing with water, washing with anhydrous ethanol, and roasting the obtained product in a muffle furnace at 500-600 DEG C for 4-6 hours, thereby obtaining the exposed [200] crystal face monocrystal square OMS-2 nano material. The method has the advantages of simple equipment, low cost, no environmental pollution and mild reaction conditions, and can easily implement large-scale production. The prepared catalyst material has low-temperature activity for o-xylene, and can completely convert the o-xylene into CO2 and H2O at 200-230 DEG C. The material has important application values in the fields of adsorption, catalysis, molecular sieves, electrode materials and the like.
Description
Technical field
The present invention relates to a kind of manganese oxide molecular sieve class catalystic material, particularly a kind of nanometer four directions build manganese oxide molecular sieve class catalystic material exposing [200] crystal face, belong to nano material and environmental catalysis and technical field of air pollution control.
Background technology
The benzene homologues such as benzene, toluene and dimethylbenzene are widely used in the suitability for industrialized production such as medicine, chemical industry and building and ornament materials as important chemical feedstocks and good organic solvent, this kind of volatile organic matter (volatile organic compounds is called for short VOCs) serious harm environment and human health after discharge entered environment.VOCs under the effect of catalyzer, can be converted into carbonic acid gas and water by Production by Catalytic Combustion Process.Therefore, it is the promising a kind of technology of most.The development of effective catalyst is the key realizing catalyticcombustion.MnO
2there is the features such as variable valence state, abundant pore structure and excellent thermostability, more and more receive publicity in environmental catalysis field.As, Chinese patent (application number 201110071206.X), toluene complete catalysts oxidation is CO by the Mn oxide that the people such as report Ye prepare two-dimensional layered structure 190 DEG C time
2and H
2o.The people such as Wu (Y. S. Wu, Y. Lu, C. J. Song, et al., Catal. Today 2013; 201:32-9.) prepare the MnO of the nano flower-like of nanometer sheet composition
2be CO by o-Xylol complete catalysts oxidation 210 DEG C time
2and H
2o.Manganese oxide octahedral molecular sieve (OMS-2) belongs to MnO
2in α-MnO
2one of.OMS-2 is because having the mn ion (Mn of a large amount of interlayer of opening wide and pore passage structure, mixed valence
2+, Mn
3+and Mn
4+), the constructional feature such as gentle surface acidic-basic property and surface hydrophobicity and excellent effect is shown to the catalyticcombustion of benzo pollutants class VOCs.As, the people such as suib (J. Luo, Q. H. Zhang, A. M. Huang, S. L. Suib. Total oxidation of volatile organic compounds with hydrophobic cryptomelane-type octahedral molecular sieves [J].
microporous and Mesoporous Materials. 2000,35-36:209-217) be catalyzer with OMS-2, achieve the catalyzed oxidation of benzene.The catalytic activity of OMS-2 and its pattern and closely related (the C. K. King ' ondu of crystal face exposed, N. Opembe, C. H. Chen, K. Ngala, H. Huang, A. Iyer, H. F. Garc é s, S. L. Suib. Manganese Oxide Octahedral Molecular Sieves (OMS-2) Multiple Framework Substitutions:A New Route to OMS-2 Particle Size and Morphology Control [J].
adv. Funct. Mater. 2011,21:312-323).At present, the pattern that OMS-2 is common is particle, nano thread or rod.As, Chinese patent literature (application number CN 103331156 A.).Due to the difference of preparation condition, these nanometer rod or nano particle expose different crystal faces.As, the people such as Liu (Y. Liu, M. Zhang, J. Zhang,
et al. A simple method of fabricating large-area a-MnO2 nanowires and nanorods [J]. Journal of Solid State Chemistry, 2006,179:1757 – 1761.) utilize MnSO
4h
2o and KClO
3reaction, prepare the α-MnO coexisted containing [310] and [101] crystal face
2nano wire.The people such as Li (Y. Li, H. Q. Xie, J.F. Wang,
et al. Preparation and electrochemical performances of α-MnO
2nanorod for supercapacitor [J]. Materials Letters, 2011,65:403 – 405) utilize Mn (CH
3cOO)
2and KMnO
4reaction, and add hexadecyl trimethyl ammonium bromide (CTAB) as tensio-active agent, prepare the α-MnO of [200] crystal face
2nanometer rod.The people such as Ye (Q. Ye, J. S. Zhao, F. F. Huo,
et al. Nanosized Ag/-MnO
2catalysts highly active for the low-temperature oxidation of carbon monoxide and benzene [J]. Catalysis Today, 2011,175:603 – 609.) utilize KMnO
4and C
4h
4o
4, at room temperature react 24h, obtain the α-MnO that exposed crystal face is respectively [200] and [300]
2nano particle.The people such as Tang (N. Tang, X. K. Tian, C. Yang,
et al. Facile synthesis of α-MnO
2nanorods for high-performance alkaline batteries [J]. Journal of physics and chemistry of Solids, 2010,71:258 – 262.) utilize MnSO
4h
2o and KMnO
4in autoclave, 160 DEG C of reaction 24h, obtain the α-MnO of the crystalline structure that surface intersects for [211] and [001] after 500 DEG C of roasting 6h
2nanometer rod.In above patent or bibliographical information, the exposure of special crystal face often needs organic solvent, tensio-active agent, template or carries out at high temperature under high pressure, and these methods make sample aftertreatment difficulty, and production cost is high, also has impact to a certain degree to environment.And so far, about exposing the monocrystalline four directions build OMS-2 of [200] crystal face, there is not been reported.And rarely have report with the research of structure activity relationship is same between catalyzed oxidation VOCs activity about the crystal face of OMS-2.
Summary of the invention
The object of the present invention is to provide a kind of preparation method exposing the monocrystalline four directions build OMS-2 nano material of [200] crystal face.
The object of the present invention is achieved like this.A kind of preparation method exposing the monocrystalline four directions build OMS-2 nano material of [200] crystal face, at ambient temperature, 0.02mmol aldehyde material is dripped in 0.02mmol potassium permanganate solution, reactant molar ratio is 1:1, dropwise rear continuation and stir 12-24h, wash through suction filtration, washing, dehydrated alcohol, after products obtained therefrom rises to 400 DEG C-600 DEG C with the temperature rise rate of 1 DEG C/min in retort furnace, roasting 4-6h, obtains monocrystalline four directions build OMS-2 nano material (catalyzer) exposing [200] crystal face.
In preparation method of the present invention, aldehyde material is that propionic aldehyde, butyraldehyde-n, isobutyric aldehyde and phenyl aldehyde are wherein a kind of.
The present invention gives this OMS-2 applications to nanostructures.It is exactly specifically this OMS-2 nano material eliminates in VOCs gas application at low-temperature catalytic burning.Be that the VOCs gas catalytic combustion eliminative reaction of representative carries out in fixed bed quartz tube reactor with o-Xylol, with this OMS-2 nano material for catalyzer, pass into and be mixed with o-Xylol and simulated air (N
2/ O
2=4/1) mixed gas, wherein the concentration of o-Xylol is 400ppm, and air-flow air speed is 7200h
-1.Residual content and the CO of the gas chromatographic detection o-Xylol of two FID are housed
2growing amount.
The beneficial effect that the present invention obtains is as follows: preparation method's non-environmental-pollution of the present invention, and technique is simple, with low cost, and reaction conditions is gentle, is easy to scale operation.The monocrystalline four directions build OMS-2 nano material of exposure [200] crystal face prepared by the present invention shows good low temperature active to o-Xylol.200 DEG C-230 DEG C time, o-Xylol can be converted into CO completely
2and H
2o.Such material is because having very high specific surface area and pore capacities, abundant mesoporous, higher lattice oxygen content, good oxygen mobility and good structural stability, can also have important using value in fields such as absorption, catalysis, molecular sieve and electrode materialss.
Accompanying drawing explanation
Fig. 1 is embodiment 1, the catalytic activity test data figure of the OMS-2 of 2,3,4,5 preparations.
Fig. 2 is embodiment 1, the XRD figure of the OMS-2 of 2,3,4,5 preparations.
Fig. 3, Fig. 4 are embodiments 1, the stereoscan photograph of the OMS-2 of 2,3,4,5 preparations.
Fig. 5, Fig. 6 are transmission electron microscope photo and the high-resolution-ration transmission electric-lens photo of OMS-2 prepared by embodiment 4.
Embodiment
Following examples are for illustration of the present invention.
Embodiment 1
(1) at ambient temperature, in the potassium permanganate solution of 0.02mmol, drip the propionic aldehyde of 0.02mmol, dropwise rear continuation and stir 24h, filter, washing, then after washing three times with dehydrated alcohol, be placed in retort furnace and rise to 400 DEG C with the temperature rise rate of 1 DEG C/min, calcination 6h, obtains MnO
2-propyl-400 catalyzer.
(2) catalyst activity evaluation
O-Xylol concentration is 400ppm, and air-flow air speed is 7200h
-1.The two FID of gas-chromatography detects o-Xylol and reaction product CO
2content.With this OMS-2 nano material for the temperature of the complete catalytic combustion elimination o-Xylol of catalyzer (o-Xylol 100% transforms) is 210 DEG C, when 167 DEG C, the transformation efficiency of o-Xylol reaches 50%, when temperature is in the scope of 150 DEG C ~ 210 DEG C, o-xylene conversion straight line raises until reach 100%, in the catalytic combustion elimination reaction of o-Xylol, o-Xylol changes into CO completely
2and H
2o.
Embodiment 2
(1) at ambient temperature, the butyraldehyde-n of 0.02mmol is dripped in the potassium permanganate solution of 0.02mmol, reactant molar ratio is 1:1, dropwise rear continuation and stir 24h, filter, washing, three times are washed again with dehydrated alcohol, be placed in retort furnace and rise to 450 DEG C with the temperature rise rate of 1 DEG C/min, calcination 6h, obtains MnO
2-positive fourth-400 catalyzer.
(2) catalyst activity evaluation
Method is with embodiment 1.
Embodiment 3
(1) at ambient temperature, the isobutyric aldehyde of 0.02mmol is dripped in the potassium permanganate solution of 0.02mmol, reactant molar ratio is 1:1, dropwise rear continuation and stir 24h, filter, washing, three times are washed again with dehydrated alcohol, be placed in retort furnace and rise to 500 DEG C with the temperature rise rate of 1 DEG C/min, calcination 6h, obtains MnO
2-isobutyl-400 catalyzer.
(2) catalyst activity evaluation
Method is with embodiment 1.
Embodiment 4
(1) at ambient temperature, the phenyl aldehyde of 0.02mmol is dripped in the potassium permanganate solution of 0.02mmol, reactant molar ratio is 1:1, dropwise rear continuation and stir 24h, filter, washing, three times are washed again with dehydrated alcohol, be placed in retort furnace and rise to 500 DEG C with the temperature rise rate of 1 DEG C/min, calcination 6h, obtains MnO
2-benzene first-500 catalyzer.
(2) catalyst activity evaluation
Method is with embodiment 1.
Embodiment 5
(1) at ambient temperature, the phenyl aldehyde of 0.02mmol is dripped in the potassium permanganate solution of 0.02mmol, reactant molar ratio is 1:1, dropwise rear continuation and stir 24h, filter, washing, three times are washed again with dehydrated alcohol, be placed in retort furnace and rise to 600 DEG C with the temperature rise rate of 1 DEG C/min, calcination 6h, obtains MnO
2-benzene first-600 catalyzer.
(2) catalyst activity evaluation
Method is with embodiment 1.
Claims (1)
1. the preparation method of the monocrystalline four directions build OMS-2 nano material of exposure [200] crystal face, it is characterized in that: at ambient temperature, 0.02mmol aldehyde material is dripped in 0.02mmol potassium permanganate solution, described aldehyde material is propionic aldehyde, butyraldehyde-n, one in isobutyric aldehyde and phenyl aldehyde, reactant molar ratio is 1:1, dropwise rear continuation and stir 12-24h, suction filtration, washing, dehydrated alcohol is washed, products obtained therefrom rises to 400 DEG C-600 DEG C with the temperature rise rate of 1 DEG C/min in retort furnace, roasting 4-6h, obtain the monocrystalline four directions build OMS-2 nano material exposing [200] crystal face.
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| CN110385125A (en) * | 2019-08-26 | 2019-10-29 | 河北师范大学 | A kind of potassium doping MnO2Catalyst and preparation method thereof |
| CN110743537B (en) * | 2019-11-21 | 2021-06-08 | 中国科学院兰州化学物理研究所 | OMS-2 catalytic material and preparation method and application thereof |
| CN114643054B (en) * | 2022-04-22 | 2024-05-28 | 北京清新环境技术股份有限公司 | Sandwich structure manganese catalyst and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101927179A (en) * | 2010-07-09 | 2010-12-29 | 北京工业大学 | OMS-2 catalyst used in elimination of benzene series at low temperature and preparation and application |
| CN102476831A (en) * | 2010-11-30 | 2012-05-30 | 中国科学院大连化学物理研究所 | Method for synthesizing OMS-2 manganese oxide octahedral molecular sieve |
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| GB0011684D0 (en) * | 2000-05-15 | 2000-07-05 | Eveready Battery Inc | Porous manganese dioxide and method of preparation thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101927179A (en) * | 2010-07-09 | 2010-12-29 | 北京工业大学 | OMS-2 catalyst used in elimination of benzene series at low temperature and preparation and application |
| CN102476831A (en) * | 2010-11-30 | 2012-05-30 | 中国科学院大连化学物理研究所 | Method for synthesizing OMS-2 manganese oxide octahedral molecular sieve |
Non-Patent Citations (1)
| Title |
|---|
| Nanosized Ag/α-MnO2 catalysts highly active for the low-temperature oxidation of carbon monoxide and benzene;Qing Ye et al.;《Catalysis Today》;20110510;第175卷;第604页左栏第2段、右栏第2段及第605页左栏第2段 * |
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