CN106853984B - A kind of preparation method of the nano oxygen cadmium of special appearance - Google Patents
A kind of preparation method of the nano oxygen cadmium of special appearance Download PDFInfo
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- CN106853984B CN106853984B CN201710107759.3A CN201710107759A CN106853984B CN 106853984 B CN106853984 B CN 106853984B CN 201710107759 A CN201710107759 A CN 201710107759A CN 106853984 B CN106853984 B CN 106853984B
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- CXKCTMHTOKXKQT-UHFFFAOYSA-N cadmium oxide Chemical compound [Cd]=O CXKCTMHTOKXKQT-UHFFFAOYSA-N 0.000 title claims abstract description 102
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims abstract description 72
- CFEAAQFZALKQPA-UHFFFAOYSA-N cadmium(2+);oxygen(2-) Chemical compound [O-2].[Cd+2] CFEAAQFZALKQPA-UHFFFAOYSA-N 0.000 claims abstract description 53
- GDDNTTHUKVNJRA-UHFFFAOYSA-N 3-bromo-3,3-difluoroprop-1-ene Chemical group FC(F)(Br)C=C GDDNTTHUKVNJRA-UHFFFAOYSA-N 0.000 claims abstract description 43
- PLLZRTNVEXYBNA-UHFFFAOYSA-L cadmium hydroxide Chemical compound [OH-].[OH-].[Cd+2] PLLZRTNVEXYBNA-UHFFFAOYSA-L 0.000 claims abstract description 23
- 239000000843 powder Substances 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- AMULVJPCIVLXGR-UHFFFAOYSA-N cadmium(2+) ethanol dinitrate Chemical compound C(C)O.[N+](=O)([O-])[O-].[Cd+2].[N+](=O)([O-])[O-] AMULVJPCIVLXGR-UHFFFAOYSA-N 0.000 claims abstract description 8
- XIEPJMXMMWZAAV-UHFFFAOYSA-N cadmium nitrate Inorganic materials [Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XIEPJMXMMWZAAV-UHFFFAOYSA-N 0.000 claims description 19
- NMHMNPHRMNGLLB-UHFFFAOYSA-N phloretic acid Chemical compound OC(=O)CCC1=CC=C(O)C=C1 NMHMNPHRMNGLLB-UHFFFAOYSA-N 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- HUKFCVYEXPZJJZ-UHFFFAOYSA-N cadmium;hydrate Chemical compound O.[Cd] HUKFCVYEXPZJJZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 238000013019 agitation Methods 0.000 claims description 3
- 239000011148 porous material Substances 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 35
- 238000000354 decomposition reaction Methods 0.000 abstract description 27
- 238000000034 method Methods 0.000 abstract description 20
- 239000000243 solution Substances 0.000 description 17
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 238000012360 testing method Methods 0.000 description 10
- 238000004458 analytical method Methods 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 229910052793 cadmium Inorganic materials 0.000 description 6
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 5
- 238000010835 comparative analysis Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000004455 differential thermal analysis Methods 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 238000002411 thermogravimetry Methods 0.000 description 4
- YKYOUMDCQGMQQO-UHFFFAOYSA-L Cadmium chloride Inorganic materials Cl[Cd]Cl YKYOUMDCQGMQQO-UHFFFAOYSA-L 0.000 description 3
- 101000957678 Mus musculus Cytochrome P450 7B1 Proteins 0.000 description 3
- 241000209094 Oryza Species 0.000 description 3
- 235000007164 Oryza sativa Nutrition 0.000 description 3
- 101000957679 Rattus norvegicus 25-hydroxycholesterol 7-alpha-hydroxylase Proteins 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 235000009566 rice Nutrition 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- KHPLPBHMTCTCHA-UHFFFAOYSA-N ammonium chlorate Chemical compound N.OCl(=O)=O KHPLPBHMTCTCHA-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000003837 high-temperature calcination Methods 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 239000003380 propellant Substances 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 241000168486 Causus Species 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 229910000369 cadmium(II) sulfate Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910001914 chlorine tetroxide Inorganic materials 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000005909 ethyl alcohol group Chemical group 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000004449 solid propellant Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001149 thermolysis Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G11/00—Compounds of cadmium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/26—Chromium
-
- B01J35/50—
-
- B01J35/60—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/88—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by thermal analysis data, e.g. TGA, DTA, DSC
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
- C01P2004/24—Nanoplates, i.e. plate-like particles with a thickness from 1-100 nanometer
Abstract
The present invention relates to a kind of preparation methods of the nano oxygen cadmium of special appearance.This method includes:Lithium hydroxide solution is added dropwise in cadmium nitrate ethanol solution, mixed liquor obtained reacts 10~12h at 180~200 DEG C, and products therefrom is washed, dry, obtains cadmium hydroxide presoma;By cadmium hydroxide presoma baking inphases obtained, nano oxygen cadmium powder is obtained;Gained nano oxygen cadmium is the hexagon cadmium oxide nanometer plate of porous structure.Nano oxygen cadmium powder purity produced by the present invention is high, catalytic performance is high, is used as the catalyst of Performance for Decomposition of Ammonium Perchlorate.Preparation method of the present invention is simple, at low cost, is suitable for commercial Application.
Description
Technical field
The present invention relates to a kind of preparation methods of the nano oxygen cadmium of the special appearance of high catalytic performance, belong to nano material
Technical field.
Background technology
Cadmium oxide (CdO) is a kind of typical n-type semiconductor, and the difference of band gap is derived from the vacancy of cadmium and oxygen, and
There is close relationship with preparation process.Cadmium oxide is widely used in optoelectronic areas, for example, solar cell, phototransistor,
Photodiode, transparent electrode, gas sensor etc..Meanwhile cadmium oxide also is used as the thermal decomposition catalyst of ammonium perchlorate.It is high
Ammonium chlorate (AP), molecular formula NH4ClO4, colourless or white orthogonal or acicular crystal.Have a hygroscopicity, heat resolve, by causus or
Clashing can set off an explosion, and belong to strong oxidizer, be commonly used for propellant.The decomposition temperature of ammonium perchlorate and decomposition rate etc.
There are substantial connections for parameter and the combustibility of rocket solid propellant.Therefore, the gold that pattern is different, microstructure is special is prepared
Belong to oxide-based nanomaterial, it is always focus of people's attention therefrom to filter out the catalyst with excellent properties.
In recent years, the nanometer cadmium hydroxide Cd (OH) of different-shape is prepared using different methods2, by roasting dehydration,
The research for obtaining nanometer CdO has document report.Wherein, the research of six side's CdO nanometer plates with anisotropic structure causes
The great interest of people.For example, Liu Junbo etc. utilizes hydro-thermal method, by cadmium nitrate Cd (NO3)2Solution is mixed with potassium hydroxide KOH solution
It closes, suitable mineralizer NaNO is added3, 12h, synthesis hexagon Cd (OH) are reacted in 200-250 DEG C of baking oven2Nanometer plate.It is not added with
Mineralizer NaNO3, then without hexagon Cd (OH)2Generation.Refering to《Jilin University's journal (Edition)》, 2009,47 (3):605-
608.The report that hexagon CdO is not prepared in text, also without catalytic performance test.
Shi Weidong etc. utilize hydro-thermal method, by CdCl2Solution is mixed with NaOH solution, is placed in reaction kettle, in 140
DEG C reaction 12h, it is washed, dry, hexagon Cd (OH) is made2Nanometer plate obtains hexagon CdO using 350 DEG C of roasting 3h
Nanometer plate.Hexagon Cd (OH) prepared by this method2Nanometer plate, surface is smooth, and the length of side is 45 ± 5nm, and thickness is about 20nm,
Wherein there is the Cd (OH) of not full-grown hexagon2.Above-mentioned hexagon Cd (OH)2Nanometer plate is by 350 DEG C of roasting 3h, all
It is converted into CdO.Nanometer CdO at this time maintains hexagon nanometer plate pattern, and surface is smooth, but the length of side reduces, while having one
A little CdO nanometer plate structure collapses, pattern are damaged.The hexagon nanometer CdO prepared in text does not carry out catalytic property test.Referring to
Crystal Growth&Design,2006,6(4):915-918。
CN 102432061A, which are disclosed, prepares Cd (OH) in a kind of simple dicyandiamide solution2With the side of CdO hexagonal nano disks
Method, using solvent-thermal method, respectively with CdCl2、Cd(NO3)2、Cd(CH3CH2COO)2、CdSO4It is cadmium source and NaOH in water and second two
It is fully reacted in the mixed solution of alcohol;Then 4h being reacted under certain temperature (160~200 DEG C) in drying box, to obtain brownish red molten
Liquid;It is dried in vacuo at 60 DEG C, obtains Cd (OH)2Brown-red powder.For 24 hours in 220 DEG C of high-temperature calcinations, CdO white powders are made,
Microscopic appearance is the nanometer plate of hexagon.CdO nanometers of panel surface obtained is smooth, the length of side be 100nm~2 μm, thickness be 50~
100nm, but size is not uniform enough, pattern is also not regular enough.Equally, also without the testing research of associated catalytic performance.
During hexagon CdO nanometer plates are prepared disclosed in the prior art, some need adds mineralizer;When some need is long
Between high-temperature calcination;The hexagon Cd (OH) of some preparations2Nanometer plate thinner thickness is converted into CdO nanometers of hexagon in roasting
When disk, lead to the structure collapses of product, pattern is damaged, and then influences its chemical property.Therefore, there is an urgent need for seek a kind of easy system
The standby method to hexagon CdO nanometer plate of the Performance for Decomposition of Ammonium Perchlorate with preferable catalytic performance.The present invention is proposed thus.
Invention content
In view of the deficiencies of the prior art, the present invention provides a kind of receiving for special appearance for Catalytic Performance for Decomposition of Ammonium Perchlorate
The preparation method of rice cadmium oxide.The method of the present invention has successfully synthesized pattern rule, the hexagon CdO nanometer plates of porous structure
Powder body material, and prove that the thermal decomposition to ammonium perchlorate has preferable catalytic performance through experimental test.
Technical scheme is as follows:
A kind of preparation method of the special appearance nano oxygen cadmium of high catalytic performance, including steps are as follows:
(1) cadmium nitrate is dissolved in absolute ethyl alcohol, forms cadmium nitrate ethanol solution;Lithium hydroxide is dissolved in redistilled water
In, form lithium hydroxide solution;Under agitation, lithium hydroxide solution is added dropwise in cadmium nitrate ethanol solution, is formed
Uniform mixed liquor continues 30~90min of stirring;
(2) mixed liquor made from step (1) is placed in reaction kettle, 10~12h is reacted at 180~200 DEG C;Gained produces
Object is washed, dry, obtains cadmium hydroxide presoma;
(3) cadmium hydroxide presoma made from step (2) is placed in Muffle furnace, successively 160~220 DEG C, 280~
Baking inphases at a temperature of 340 DEG C obtain nano oxygen cadmium;Gained nano oxygen cadmium is the hexagon CdO nanometer plates of porous structure.
According to the present invention, the hexagon CdO nanometer plates of the porous structure of the nano oxygen cadmium assemble shape by small cubes
At the length of side of the small cubes is 230~260nm, length of side 500nm~1 μm of the hexagon nanometer plate, thickness 230
~270nm.
According to currently preferred, the cadmium nitrate described in step (1) is four water cadmium nitrates.
According to currently preferred, in step (1), molar ratio=1 of cadmium nitrate and lithium hydroxide:2.3~2.7;Into one
Step is preferred, molar ratio=1 of the cadmium nitrate and lithium hydroxide:2.5;The amount ratio of cadmium nitrate and lithium hydroxide can be to product shape
Looks bring great influence.
, according to the invention it is preferred to, the continuation mixing time described in step (1) is 50~70min, further preferably
, continuation mixing time is 60min.
According to currently preferred, the washing described in step (2) is to be washed successively with redistilled water, absolute ethyl alcohol.
According to currently preferred, the drying temperature described in step (2) is 80~90 DEG C, and drying time is 20~38h;
It is further preferred that drying temperature is 85 DEG C, dry 30h.
According to currently preferred, the baking inphases described in step (3) are 180~220 DEG C of 1~1.5h of roasting, then
280-320 DEG C of 2~2.5h of roasting;Further preferred 80-100 DEG C of baking inphases temperature difference is preferred.Most preferably, point
Section is roasted to 200 DEG C of roasting 1h, then 300 DEG C of roasting 2h.The mode of the calcination temperature and two-stage roasting is also to prepare pattern
The key factor of rule, porous hexagon cadmium oxide nanometer plate.
According to currently preferred, cadmium hydroxide presoma made from step (2) is hexagonal phase, and shape characteristic is surface
Smooth, regular hexagonal cadmium hydroxide nanometer plate, 400~900nm of the length of side, thickness are 210~300nm.Further preferably
, the cadmium hydroxide nanometer plate length of side of the hexagon is 500~800nm, and thickness is 230~280nm.
The cadmium hydroxide presoma is placed in Muffle furnace, by double roasting, cadmium oxide powder is made.The cadmium oxide is
Cubic phase, shape characteristic are to assemble the porous hexagon cadmium oxide nanometer plate of formation rule by small cubes.Small cubes
The length of side is 230~260nm, and length of side 500nm~1 μm for the hexagon nanometer plate being assembled into, thickness is 230~270nm.Further
Preferably, the length of side of small cubes is 250~260nm, the 700~900nm of the length of side for the hexagon nanometer plate being assembled into, and thickness is
250~260nm.
Application of the cadmium oxide nanometer plate of special appearance prepared by the present invention in terms of Catalytic Performance for Decomposition of Ammonium Perchlorate.This hair
The cadmium oxide nanometer plate of the special appearance of bright preparation is used as Performance for Decomposition of Ammonium Perchlorate catalyst.
The present invention tests the hexagon CdO nanometer plates of porous structure to height using TG-DTA analysis method (TG-DTA)
The thermal decomposition catalytic performance of ammonium chlorate, catalytic performance measurement result show the hexagon oxidation of porous structure prepared by the present invention
Cadmium nanometer plate has preferable catalytic property, can be used as the High Efficiency Thermal decomposition catalyst application of ammonium perchlorate.
The technical characterstic and excellent results of the present invention:
Present invention cadmium nitrate and lithium hydroxide generate that surface is smooth, hexagon hydrogen-oxygen of the close rule of matter through solvent thermal reaction
Cadmium presoma, the roasting then through different temperatures twice in succession obtain nano oxygen cadmium powder, and microscopic appearance is by small cube
Body assembles the porous hexagon cadmium oxide nanometer plate of formation rule.The hydrogen-oxygen of the hexagonal configuration of the close rule of matter prepared by the present invention
The characteristics of cadmium presoma is uniform in size, and thickness is thicker, so during roasting dehydration is changed into cadmium oxide, can be formed
Porous microstructure, and complete hexagonal configuration can be kept.The special microscopic appearance, which is it, has preferable catalysis
The premise of performance.
Nano oxygen cadmium prepared by the method for the present invention has the following advantages:
1, cadmium hydroxide presoma obtained is hexagonal phase, diffraction maximum and standard card (PDF#31-0228) unanimously, nothing
Other impurities exist, and purity is high.Its microscopic appearance feature is that surface is smooth, hexagon of the close rule of matter.
2, nano oxygen cadmium produced by the present invention is cubic phase, diffraction maximum and standard card (PDF#65-2908) unanimously,
Its microscopic appearance feature is to assemble the porous hexagon cadmium oxide nanometer plate of formation rule by small cubes.
3, compared with sodium hydroxide and potassium hydroxide raw material that the prior art uses, the present invention using lithium hydroxide as raw material,
Since lithium hydroxide is slightly soluble in water and ethyl alcohol, when being reacted with the ethanol solution of cadmium nitrate, a large amount of precipitations will not be generated at once, it can be with
The nucleus of fine uniform is formed, slowly aggregation growth, is conducive to the generation of uniform products;In addition, the present invention has surprisingly been found that hydrogen
The ability of lithia absorbing carbon dioxide in the synthesis process is slightly worse compared with sodium hydroxide and potassium hydroxide, therefore is easy to be made high-purity
The nano oxygen cadmium product of degree.
4, the nano oxygen cadmium powder property obtained by the present invention is stablized, and catalytic performance is good, for the low temperature of ammonium perchlorate
It decomposes, pyrolytic all has stable high catalytic performance.Especially have to the low-temperature decomposition of ammonium perchlorate unexpected
Efficient catalytic acts on, and ammonium perchlorate can be made to have stronger low-temperature decomposition effect at 280~330 DEG C.
5, preparation method of the present invention is simple, and reaction temperature is not high, low for equipment requirements, and raw material is easy to get, cheap, is suitble to
Batch production.
6, nano oxygen cadmium prepared by the method for the present invention also has anti-microbial property and air-sensitive performance in addition to as catalyst.
Description of the drawings
Fig. 1 is the x-ray diffraction pattern of the nanometer cadmium hydroxide powder and nano oxygen cadmium powder that are prepared using this method
Figure.Wherein, (a) nanometer cadmium hydroxide;(b) nano oxygen cadmium.
Fig. 2 is the stereoscan photograph of nanometer cadmium hydroxide powder prepared by embodiment 1.
Fig. 3 is the stereoscan photograph of nano oxygen cadmium powder prepared by embodiment 1.
Fig. 4 is the hot weight-differential heat figure that nano oxygen cadmium powder prepared by embodiment 1 is catalyzed the thermal decomposition of ammonium perchlorate
Spectrum.
Fig. 5 is the hot weight-differential heat collection of illustrative plates of ammonium perchlorate itself thermal decomposition.For comparative analysis.
Specific implementation mode
With reference to embodiment, the present invention will be further described, but institute's protection domain of the present invention is without being limited thereto.
The TG-DTA analysis instrument used in embodiment is that the HCT-1 type microcomputers of the permanent scientific instrument factory production in Beijing are poor
Thermobalance.
Term explanation:Differential thermal analysis (Differential Thermal Analysis) is abbreviated as DTA.Thermogravimetry
(Thermogravimetry) it is abbreviated as TG;TG-DTA analysis method is abbreviated as TG-DTA.
The preparation method of embodiment 1, a kind of special appearance nano oxygen cadmium of high catalytic performance, including steps are as follows:
(1) four water cadmium nitrates of 0.7712g (2.5mmol) are weighed to be dissolved in 50mL absolute ethyl alcohols, it is molten to form cadmium nitrate ethyl alcohol
Liquid.It weighs 0.2623g (6.25mmol) lithium hydroxide to be dissolved in 20mL redistilled waters, forms lithium hydroxide solution.
Under agitation, lithium hydroxide solution is added dropwise in cadmium nitrate ethanol solution, after being added dropwise to complete, is continued
Stir 60min.
(2) mixed liquor obtained by step (1) is placed in reaction kettle, reacts 12h at 200 DEG C.Products therefrom is successively with secondary
Distilled water, absolute ethyl alcohol washing, 85 DEG C of dry 30h obtain cadmium hydroxide presoma;Its microscopic appearance is characterized as that surface is smooth, matter
The hexagon of close rule.The length of side is 500~800nm, and thickness is 230~280nm.As shown in Figure 2.
(3) cadmium hydroxide presoma made from step (2) is placed in Muffle furnace, 200 DEG C of roasting 1h, then 300 DEG C of roastings
2h is burnt, nano oxygen cadmium powder is obtained, microscopic appearance is characterized as assembling the porous hexagon oxygen of formation rule by small cubes
Cadmium nanometer plate.The length of side of small cubes is 250~260nm, and the length of side of nanometer plate is 700~900nm, thickness is 250~
260nm.As shown in Figure 3.Hexagon cadmium oxide nanometer plate pattern is complete, even particle size distribution.
Embodiment 1 obtains nano oxygen cadmium powder, is as used for the nano oxygen cadmium catalyst of Performance for Decomposition of Ammonium Perchlorate.It urges
It is as follows to change property test experiments:
1. weighing 100mg ammonium perchlorate in mortar, the nano oxygen cadmium catalyst 4mg prepared in embodiment 1 is added, grinds
Mill is allowed to after mixing, as sample 1, is placed in progress thermogravimetric and differential thermal analysis, test in HCT-1 type microcomputer differential thermal balances and is received
The catalytic performance of rice cadmium oxide.
Note:The nano oxygen cadmium catalyst amount of addition is different, has an impact to the thermal decomposition catalytic property of ammonium perchlorate.One
As for, dosage is bigger, and catalytic performance is better.Catalytic effect of the different nano-metal-oxides to Performance for Decomposition of Ammonium Perchlorate
It is different.
2. weighing 100mg ammonium perchlorate as sample 2, it is placed in HCT-1 type microcomputer differential thermal balances and carries out thermogravimetric and differential thermal
Analysis, tests its own thermolysis property.
3. by step 1., the step 2. thermogravimetric of two samples and differential thermal collection of illustrative plates comparative analysis, nano oxygen cadmium is added in observation
After catalyst, the situation of change of the heat decomposition temperature of ammonium perchlorate and the power of exothermic peak, and then evaluate the catalysis of nano oxygen cadmium
The catalytic performance of agent.The heat decomposition temperature of ammonium perchlorate is lower, and the intensity of exothermic peak is higher, indicates the thermocatalytic of nano oxygen cadmium
Performance is better.
The hot weight-differential heat collection of illustrative plates of sample 1 is as shown in Figure 4;The hot weight-differential heat collection of illustrative plates of sample 2 is as shown in Figure 5;
According to DTA differential thermals collection of illustrative plates (Fig. 4 and Fig. 5) comparative analysis of two above sample it is found that two samples are at 245 DEG C
Nearby there is an endothermic peak, be assigned as turn brilliant process that pure ammonium perchlorate is changed into cubic crystal by rhomboidal crystal, addition is received
Rice cadmium oxide catalyst does not influence this crystalline transformation process, and this point is consistent with the result by references that early period is reported.It is added
After nano oxygen cadmium, original ammonium perchlorate is respectively reduced in 317 DEG C of low-temperature decomposition temperature and 415 DEG C of high-temperature decomposition temperature
To 304 DEG C and 385 DEG C, i.e. hexagon cadmium oxide nanometer plate has obviously the low and high temperature thermal decomposition process of ammonium perchlorate
Catalytic action so that the low-temperature decomposition temperature of ammonium perchlorate reduces 13 DEG C, and high-temperature decomposition temperature then reduces 30 DEG C;And high chlorine
The Exotherm amount of sour ammonium significantly increases, and high temperature exothermic amount reduces, and illustrates hexagon cadmium oxide nanometer plate to ammonium perchlorate
The catalytic efficiency of low temperature thermal decomposition is particularly evident, presents its very excellent catalytic performance, this characteristic is conducive to it solid
It preferably plays a role in body propellant.It follows that hexagon cadmium oxide nanometer plate prepared by the present embodiment 1 is with excellent
The catalytic effect of low-temperature decomposition ammonium perchlorate.
According to TG thermogravimetrics collection of illustrative plates (Fig. 4 and Fig. 5) comparative analysis of two above sample it is found that pure ammonium perchlorate 300~
345 DEG C of shallower weightlessness corresponds to the weaker low-temperature decomposition of ammonium perchlorate;345~425 DEG C it is obvious quickly
Weightlessness corresponds to the stronger pyrolytic of ammonium perchlorate.And after adding hexagon cadmium oxide nanometer plate, ammonium perchlorate is 280
~330 DEG C of obvious rapid weight loss corresponds to the stronger low-temperature decomposition of ammonium perchlorate;It is shallower at 330~410 DEG C
Weightlessness, correspond to ammonium perchlorate weaker pyrolytic.This also absolutely proves hexagon cadmium oxide nanometer plate to perchloric acid
The low-temperature decomposition of ammonium has obviously catalytic action.It is consistent with DTA differential thermal pattern analysis results.
Embodiment 2, method as described in Example 1 prepare hexagon cadmium oxide nanometer plate, and sequence of steps is constant, four weighed
The mass conservation of water cadmium nitrate is still tetra- water cadmium nitrates (2.5mmol) of 0.7712g.Institute the difference is that,
In step (1), the lithium hydroxide weighed is 0.2413g (5.75mmol).The molar ratio of cadmium nitrate and lithium hydroxide
=1:2.3;After lithium hydroxide solution is added dropwise in cadmium nitrate ethanol solution, continuation mixing time is 50min.
In step (2), product drying condition is 80 DEG C of dry 36h.
In step (3), the roasting condition of cadmium hydroxide presoma is:180 DEG C of roasting 1h, then roast 2h for 320 DEG C.
Hexagon cadmium oxide nanometer plate obtained.The length of side of small cubes is 230~260nm, and the length of side of nanometer plate is 500
~750nm, thickness are 230~250nm.Hexagon cadmium oxide nanometer plate pattern is complete.
Catalytic property test result discovery is carried out with TG-DTA analysis method (TG-DTA), hexagon made from embodiment 2
Cadmium oxide nanometer plate has apparent catalytic action to the low and high temperature thermal decomposition process of ammonium perchlorate.It can make the low temperature of ammonium perchlorate
Decomposition temperature and high-temperature decomposition temperature reduce 10 DEG C and 23 DEG C respectively.Equally, to the Exotherm catalytic effect of ammonium perchlorate
It is substantially better than high temperature exothermic.
Embodiment 3, method as described in Example 1 prepare hexagon cadmium oxide nanometer plate, and sequence of steps is constant, four weighed
The mass conservation of water cadmium nitrate, institute the difference is that:
In step (1), the lithium hydroxide weighed is 0.2832g (6.75mmol);The molar ratio of cadmium nitrate and lithium hydroxide
=1:2.7.After lithium hydroxide solution is added dropwise in cadmium nitrate ethanol solution, continue to stir 70min.
In step (2), product drying condition is 90 DEG C and dries for 24 hours.
In step (3), the roasting condition of cadmium hydroxide presoma is:220 DEG C of roasting 70min, then 320 DEG C of roastings
100min.Hexagon cadmium oxide nanometer plate obtained.The length of side of small cubes is 240~260nm, and the length of side of nanometer plate is
800nm~900nm, thickness are 250~270nm.Hexagon cadmium oxide nanometer plate pattern is complete.
Catalytic property test result discovery is carried out with TG-DTA analysis method (TG-DTA), hexagon made from embodiment 3
Cadmium oxide nanometer plate also has apparent catalytic action to the low and high temperature thermal decomposition process of ammonium perchlorate.It can make the low of ammonium perchlorate
Warm decomposition temperature and high-temperature decomposition temperature reduce 11 DEG C and 25 DEG C respectively.Equally, the Exotherm of ammonium perchlorate is catalyzed and is imitated
Fruit is substantially better than high temperature exothermic.
Embodiment 4, method as described in Example 1 prepare hexagon cadmium oxide nanometer plate, institute the difference is that:
In step (3), the roasting condition of cadmium hydroxide presoma is:220 DEG C of roasting 1h, then roast 2h for 280 DEG C.
Hexagon cadmium oxide nanometer plate obtained.The length of side of small cubes is 250~260nm, and the length of side of nanometer plate is
800nm~1 μm, thickness are 240~270nm.Pattern is intact but has minute quantity side damaged.
Catalytic property test result discovery is carried out with TG-DTA analysis method (TG-DTA), hexagon made from embodiment 4
Cadmium oxide nanometer plate also has apparent catalytic action to the low and high temperature thermal decomposition process of ammonium perchlorate.It can make the low of ammonium perchlorate
Warm decomposition temperature and high-temperature decomposition temperature reduce 9 DEG C and 24 DEG C respectively.Equally, to the Exotherm catalytic effect of ammonium perchlorate
It is substantially better than high temperature exothermic.
Claims (11)
1. one kind being used as the preparation method of the special appearance nano oxygen cadmium of 280 ~ 330 DEG C of thermal decomposition catalyst of ammonium perchlorate, packet
Include that steps are as follows:
(1)Cadmium nitrate is dissolved in absolute ethyl alcohol, cadmium nitrate ethanol solution is formed;Lithium hydroxide is dissolved in redistilled water,
Form lithium hydroxide solution;Under agitation, lithium hydroxide solution is added dropwise in cadmium nitrate ethanol solution, is formed uniform
Mixed liquor, continue 30 ~ 90min of stirring;Molar ratio=1 of the cadmium nitrate and lithium hydroxide: 2.3~2.7;
(2)By step(1)Mixed liquor obtained is placed in reaction kettle, and 10 ~ 12h is reacted at 180 ~ 200 DEG C;Products therefrom is through washing
It washs, dry, obtain cadmium hydroxide presoma;Cadmium hydroxide presoma obtained be hexagonal phase, shape characteristic be surface it is smooth,
The cadmium hydroxide nanometer plate of regular hexagonal, 400 ~ 900 nm of the length of side, thickness are 210 ~ 300 nm;
(3)By step(2)Cadmium hydroxide presoma obtained is placed in Muffle furnace, successively in 160 ~ 220 DEG C, 280 ~ 340 DEG C of temperature
The lower baking inphases of degree, obtain nano oxygen cadmium;Gained nano oxygen cadmium is the hexagon CdO nanometer plates of porous structure;
The hexagon CdO nanometer plates of the porous structure of the nano oxygen cadmium are assembled by small cubes to be formed, the small cubes
The length of side be 230 ~ 260 nm, 500 nm ~ 1 μm of the length of side of the hexagon nanometer plate, thickness be 230 ~ 270 nm.
2. the preparation method of special appearance nano oxygen cadmium as described in claim 1, which is characterized in that nano oxygen cadmium it is more
The hexagon CdO nanometer plates of pore structure are assembled by small cubes to be formed, and the length of side of the small cubes is 250 ~ 260 nm, assembling
At hexagon nanometer plate 700 ~ 900 nm of the length of side, thickness be 250 ~ 260 nm.
3. the preparation method of special appearance nano oxygen cadmium as described in claim 1, it is characterised in that step(1)Described in
Cadmium nitrate is four water cadmium nitrates.
4. the preparation method of special appearance nano oxygen cadmium as described in claim 1, it is characterised in that step(1)In, it is described
Molar ratio=1 of cadmium nitrate and lithium hydroxide: 2.5.
5. the preparation method of special appearance nano oxygen cadmium as described in claim 1, it is characterised in that step(1)Described in
Continuation mixing time is 50 ~ 70min.
6. the preparation method of special appearance nano oxygen cadmium as described in claim 1, it is characterised in that step(2)Described in
Washing is to be washed successively with redistilled water, absolute ethyl alcohol.
7. the preparation method of special appearance nano oxygen cadmium as described in claim 1, it is characterised in that step(2)Described in
Drying temperature is 80 ~ 90 DEG C, and drying time is 20 ~ 38h.
8. the preparation method of special appearance nano oxygen cadmium as described in claim 1, it is characterised in that step(3)Described in
Baking inphases are 180 ~ 220 DEG C of 1 ~ 1.5h of roasting, then 280-320 DEG C of 2 ~ 2.5h of roasting.
9. the preparation method of special appearance nano oxygen cadmium as described in claim 1, it is characterised in that step(3)In, it is described
Baking inphases be 200 DEG C roasting 1h, then 300 DEG C roasting 2h.
10. the preparation method of special appearance nano oxygen cadmium as described in claim 1, it is characterised in that step(2)It is obtained
The cadmium hydroxide nanometer plate length of side of hexagon is 500 ~ 800 nm, and thickness is 230 ~ 280 nm.
11. the preparation method of special appearance nano oxygen cadmium as described in claim 1, it is characterised in that step(3)It is obtained
Cadmium oxide powder is cubic phase.
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1546382A (en) * | 2003-12-10 | 2004-11-17 | 山东师范大学 | Method for synthesizing cadmium hydroxide single-crystal nanowire |
CN102432061A (en) * | 2011-09-29 | 2012-05-02 | 新疆大学 | Method for preparing Cd(OH)2 and CdO hexagonal nanoplates in simple solvent system |
CN104386737A (en) * | 2014-11-20 | 2015-03-04 | 中南大学 | Method for preparing cadmium oxide by using cadmium-containing smoke dust generated by zinc smelting |
CN105709714A (en) * | 2014-12-03 | 2016-06-29 | 青岛清泉生物科技有限公司 | Graphene-loaded TiO2 / CaO double-layer composite nanomaterial preparation method |
CN105777087A (en) * | 2009-06-03 | 2016-07-20 | 法商圣高拜欧洲实验及研究中心 | Alumina and zirconia based sintered product |
-
2017
- 2017-02-27 CN CN201710107759.3A patent/CN106853984B/en active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1546382A (en) * | 2003-12-10 | 2004-11-17 | 山东师范大学 | Method for synthesizing cadmium hydroxide single-crystal nanowire |
CN105777087A (en) * | 2009-06-03 | 2016-07-20 | 法商圣高拜欧洲实验及研究中心 | Alumina and zirconia based sintered product |
CN102432061A (en) * | 2011-09-29 | 2012-05-02 | 新疆大学 | Method for preparing Cd(OH)2 and CdO hexagonal nanoplates in simple solvent system |
CN104386737A (en) * | 2014-11-20 | 2015-03-04 | 中南大学 | Method for preparing cadmium oxide by using cadmium-containing smoke dust generated by zinc smelting |
CN105709714A (en) * | 2014-12-03 | 2016-06-29 | 青岛清泉生物科技有限公司 | Graphene-loaded TiO2 / CaO double-layer composite nanomaterial preparation method |
Non-Patent Citations (1)
Title |
---|
"Hexagonal Nanodisks of Cadmium Hydroxide and Oxide with Nanoporous Structure";Weidong Shi, et al.;《Crystal Growth & Design》;20060314;第6卷(第4期);915-918 * |
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