CN104016413A - 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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- CN104016413A CN104016413A CN201410260220.8A CN201410260220A CN104016413A CN 104016413 A CN104016413 A CN 104016413A CN 201410260220 A CN201410260220 A CN 201410260220A CN 104016413 A CN104016413 A CN 104016413A
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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 that exposes [200] crystal face, belongs to nano material and environmental catalysis and air pollution control technique field.
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 class volatile organic matter (volatile organic compounds is called for short VOCs) serious harm environment and human health after discharge entered environment.Production by Catalytic Combustion Process can, under the effect of catalyzer, be converted into carbonic acid gas and water by VOCs.Therefore, it is a kind of technology most with development prospect.The development of effective catalyst is the key that realizes catalyticcombustion.MnO
2there is variable valence state, the abundant feature such as pore structure and good thermostability, more and more receive publicity in environmental catalysis field.As, Chinese patent (application number 201110071206.X), the Mn oxide that the people such as report Ye prepare two-dimensional layered structure is CO by toluene complete catalysts oxidation in the time of 190 DEG C
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
2in the time of 210 DEG C, be CO by o-Xylol complete catalysts oxidation
2and H
2o.Manganese oxide octahedron molecular screen (OMS-2) belongs to MnO
2in α-MnO
2one of.OMS-2 is because having the mn ion (Mn of a large amount of unlimited interlayers and pore passage structure, mixed valence
2+, Mn
3+and Mn
4+), the gentle constructional feature such as surface acid alkalescence and surface hydrophobicity and the catalyticcombustion of benzo pollutants class VOCs is shown to excellent effect.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) taking OMS-2 as catalyzer, realize the catalyzed oxidation of benzene.The catalytic activity of OMS-2 and its pattern and closely related (the C. K. King ' ondu of the crystal face exposing, 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 common pattern of OMS-2 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 and contain α-MnO that [310] and [101] crystal face coexists
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 exposed crystal face and be respectively the α-MnO of [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
4160 DEG C of reaction 24h in autoclave, obtain the α-MnO of surface for the crystalline structure of [211] and [001] intersection 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 under High Temperature High Pressure, and these methods make sample aftertreatment difficulty, and production cost is high, and environment is also had to impact to a certain degree.And, so far, about the monocrystalline four directions build OMS-2 that exposes [200] crystal face there is not yet report.And rarely has report about the research of structure activity relationship between the crystal face of OMS-2 and catalyzed oxidation VOCs activity is same.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of the monocrystalline four directions build OMS-2 nano material that exposes [200] crystal face.
The object of the present invention is achieved like this.A kind of preparation method of the monocrystalline four directions build OMS-2 nano material that exposes [200] crystal face, at ambient temperature, in 0.02mmol potassium permanganate solution, drip 0.02mmol aldehyde material, reactant molar ratio is 1:1, dropwise rear continuation and stir 12-24h, wash through suction filtration, washing, dehydrated alcohol, products obtained therefrom rises to after 400 DEG C-600 DEG C with the temperature rise rate of 1 DEG C/min in retort furnace, roasting 4-6h, obtains exposing the monocrystalline four directions build OMS-2 nano material (catalyzer) of [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 the application of this OMS-2 nano material.Be exactly specifically that this OMS-2 nano material is eliminated the application in VOCs gas at low-temperature catalytic burning.VOCs gas catalytic combustion taking o-Xylol as representative is eliminated reaction and is carried out in fixed bed quartz tube reactor, taking this OMS-2 nano material as catalyzer, passes into and is mixed with o-Xylol and simulated air (N
2/ O
2=4/1) mixed gas, wherein the concentration of o-Xylol is 400ppm, 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 gentleness, is easy to scale operation.The monocrystalline four directions build OMS-2 nano material of prepared exposure [200] crystal face of the present invention shows good low temperature active to o-Xylol.Can, in the time of 200 DEG C-230 DEG C, o-Xylol 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.
Brief description of the drawings
Fig. 1 is embodiment 1,2, the catalytic activity test data figure of the OMS-2 of 3,4,5 preparations.
Fig. 2 is embodiment 1,2, the XRD figure of the OMS-2 of 3,4,5 preparations.
Fig. 3, Fig. 4 are embodiment 1,2, the stereoscan photograph of the OMS-2 of 3,4,5 preparations.
Fig. 5, Fig. 6 are transmission electron microscope photo and the high-resolution-ration transmission electric-lens photos of the OMS-2 for preparing of embodiment 4.
Embodiment
Following examples are used for illustrating the present invention.
Embodiment 1
(1) at ambient temperature,, to the propionic aldehyde that drips 0.02mmol in the potassium permanganate solution of 0.02mmol, dropwise rear continuation and stir 24h, filter, washing, then wash after 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 detect o-Xylol and reaction product CO
2content.Temperature taking this OMS-2 nano material as the complete catalytic combustion elimination o-Xylol of catalyzer (o-Xylol 100% transforms) is as 210 DEG C, 167 DEG C time, the transformation efficiency of o-Xylol reaches 50%, when temperature is in the scope of 150 DEG C～210 DEG C, o-Xylol transformation efficiency 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, to the butyraldehyde-n that drips 0.02mmol in the potassium permanganate solution of 0.02mmol, reactant molar ratio is 1:1, dropwise rear continuation and stir 24h, filter, washing, wash three times with dehydrated alcohol again, 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, to the isobutyric aldehyde that drips 0.02mmol in the potassium permanganate solution of 0.02mmol, reactant molar ratio is 1:1, dropwise rear continuation and stir 24h, filter, washing, wash three times with dehydrated alcohol again, 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, to the phenyl aldehyde that drips 0.02mmol in the potassium permanganate solution of 0.02mmol, reactant molar ratio is 1:1, dropwise rear continuation and stir 24h, filter, washing, wash three times with dehydrated alcohol again, 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, to the phenyl aldehyde that drips 0.02mmol in the potassium permanganate solution of 0.02mmol, reactant molar ratio is 1:1, dropwise rear continuation and stir 24h, filter, washing, wash three times with dehydrated alcohol again, 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 (2)
1. the preparation method of the monocrystalline of an exposure [200] crystal face four directions build OMS-2 nano material, it is characterized in that: at ambient temperature, in 0.02mmol potassium permanganate solution, drip 0.02mmol aldehyde material, reactant molar ratio is 1:1, dropwise rear continuation and stir 12-24h, suction filtration, washing, dehydrated alcohol are 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, obtains exposing the monocrystalline four directions build OMS-2 nano material of [200] crystal face.
2. preparation method according to claim 1, is characterized in that aldehyde material is that propionic aldehyde, butyraldehyde-n, isobutyric aldehyde and phenyl aldehyde are wherein a kind of.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110385125A (en) * | 2019-08-26 | 2019-10-29 | 河北师范大学 | A kind of potassium doping MnO2Catalyst and preparation method thereof |
| CN110743537A (en) * | 2019-11-21 | 2020-02-04 | 中国科学院兰州化学物理研究所 | OMS-2 catalytic material and preparation method and application thereof |
| CN114643054A (en) * | 2022-04-22 | 2022-06-21 | 北京清新环境技术股份有限公司 | Manganese catalyst with sandwich structure and preparation method and application thereof |
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| WO2001087775A1 (en) * | 2000-05-15 | 2001-11-22 | Eveready Battery Company Inc. | A method of preparation of porous manganese dioxide |
| 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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2014
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001087775A1 (en) * | 2000-05-15 | 2001-11-22 | Eveready Battery Company Inc. | A method of preparation of porous manganese dioxide |
| 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)
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| QING YE ET AL.: "Nanosized Ag/α-MnO2 catalysts highly active for the low-temperature oxidation of carbon monoxide and benzene", 《CATALYSIS TODAY》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110385125A (en) * | 2019-08-26 | 2019-10-29 | 河北师范大学 | A kind of potassium doping MnO2Catalyst and preparation method thereof |
| CN110743537A (en) * | 2019-11-21 | 2020-02-04 | 中国科学院兰州化学物理研究所 | OMS-2 catalytic material and preparation method and application 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 |
| CN114643054A (en) * | 2022-04-22 | 2022-06-21 | 北京清新环境技术股份有限公司 | Manganese catalyst with sandwich structure and preparation method and application thereof |
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