CN103055958A - Method for coating nano metal oxide catalyst precursor on ammonium perchlorate surface - Google Patents
Method for coating nano metal oxide catalyst precursor on ammonium perchlorate surface Download PDFInfo
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- CN103055958A CN103055958A CN2012105143125A CN201210514312A CN103055958A CN 103055958 A CN103055958 A CN 103055958A CN 2012105143125 A CN2012105143125 A CN 2012105143125A CN 201210514312 A CN201210514312 A CN 201210514312A CN 103055958 A CN103055958 A CN 103055958A
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Abstract
The invention discloses a method for coating a nano metal oxide catalyst precursor on ammonium perchlorate surface, which comprises the following steps: (1) adding a catalyst precursor into a solvent, and completely dissolving by stirring while controlling the temperature, thereby obtaining a catalyst precursor solution; (2) adding ammonium perchlorate into the catalyst precursor solution, wherein the ammonium perchlorate is insoluble in the catalyst precursor solution, and keeping stirring to uniformly disperse the ammonium perchlorate; (3) changing the temperature, reacting for some time, and stopping stirring to obtain the product; and (4) filtering the product, and drying to obtain the nano composite material. The catalyst precursor can be Co(NO3)2.6H2O, KMnO4, Cu(NO3)2.3H2O, Fe(NO3)3.9H2O or Zn(CH3COO)2.3H2O; and the solvent is ethyl acetate, ethanol or acetone. The invention solves the problem of dispersity of the nano oxide catalyst in AP (ammonium perchlorate); the method is simple and stable, and is accurate for control and simple to operate; the oxide catalyst can be generated in situ on the AP, and has obvious autocatalysis effect; and the method can be combined with a rocket propellant preparation technique to simplify the catalyst dispersion technique.
Description
Technical field
The present invention relates to surface coating technology, be specifically related to a kind of method at the surperficial clad nano metal oxide catalyst of ammonium perchlorate (AP) presoma: the supersaturation crystallisation.
Background technology
AP is a kind of important energetic material, only is improved AP thermal decomposition effect, promotes the thermal decomposition of AP, and it is fully released energy.In the numerous methods that improve AP thermal decomposition effect, come catalysis AP thermal decomposition to be considered to one of effective method by adding combustion catalyst.The Nomenclature Composition and Structure of Complexes by combustion catalyst divides, and effective kind commonly used can be summarized as following three major types: (1) metal oxide catalyst; (2) metal simple-substance catalyst; (3) ferrocene and derivative class catalyst thereof.Wherein the very high characteristic of metal simple-substance catalyst chemical activity also is its great shortcoming, and is very easily oxidized and lose original physicochemical characteristics in air, affects its result of use; And the volatile and migration in processing and storage process of ferrocene class catalyst, stability is not enough; The best combustion catalyst of practicality is metal oxide catalyst at present.
The nano-oxide catalyst is owing to having high-specific surface area and high surface energy, and its reactivity and catalytic selectivity are all far above tradition micron oxide catalyst.Yet the high activity just because of the nano-oxide catalyst, cause it very easily to reunite, and material itself is in case reunite, its catalytic performance will reduce greatly, simultaneously, after the reunion, can not fully contact between the uniformity, catalyst that in use also can affect its dispersion and the AP, its due catalytic efficiency must reduce.At present, nanocatalyst and AP's is compound, be by mechanochemical reaction (such as stirring, grinding etc.) mostly, utilize some surfactants to be prepared into the composite of catalyst and AP or prepare a kind of take the composite of AP as nuclear nano-oxide catalyst as shell.Wherein, the compound uniformity of mechanochemical reaction is limited, and there is certain potential safety hazard, surfactant method is then relatively high to the requirement of technique and activating agent kind, nano composite material makes the nano-oxide catalyst be evenly distributed in the AP surface, both fully contact, promoted catalytic effect, but it is limited to prepare at present this nano composite material method, liquid phase deposition etc. is typically arranged, the method utilizes chemical reaction that the metal oxide precipitation is coated on the AP surface, and chemical reaction can not be stablized and accurately control its process.
Summary of the invention
The object of the present invention is to provide a kind of new nano-oxide catalyst precursor to coat the method for AP, thereby solve the dispersion problem that brings when the nano-oxide catalyst mixes with AP, efficiently catalysis AP thermal decomposition.
A kind of method at ammonium perchlorate surface clad nano metal oxide catalyst presoma provided by the invention is characterized in that,
The catalyst precursor that the 1st step was lower than AP thermal decomposition high-temperature decomposition temperature with heat decomposition temperature be dissolved in can the solvent of catalyst-solvent presoma in, magnetic agitation, and be heated to t2 and it dissolved fully obtain the complex catalyst precursor liquid solution;
The catalyst precursor chemical formula is M
aS
b, relative molecular weight is M
CpThe chemical formula of the nano-metal-oxide catalyst that the catalyst precursor thermal decomposition produces is M
xO
y, relative molecular weight is M
Mon, establishing described solvent volume is V
Sol, the quality of described catalyst precursor is m
Cp, r is that the mass percent of nano-metal-oxide catalyst and AP is 0.1%＜r＜15%, m
APBe the quality of ammonium perchlorate, the density of solvent is ρ, T
mBe solvent fusing point, T
bBe solvent boiling point, at solvent fusing point T
mWith boiling point T
bBetween get two temperatures point t
1And t
2, T
m＜t
1＜t
2＜T
bAt t
1Under the temperature, catalyst precursor solubility in solvent is m
1, the quality m of catalyst precursor
CpSatisfy: m
Cp=[(arm
APM
Cp)/(M
MonX)+m
1V
Solρ/100];
It is m that the 2nd step added quality in the mentioned solution
APAmmonium perchlorate, to continue magnetic agitation, be cooled to t
1, continue reaction, until crystallize out no longer in the solution;
The 3rd step stopped magnetic agitation, at t
1Filter mentioned solution under the temperature, products therefrom is dry, obtain AP/ complex catalyst precursor composite material.
The present invention is a kind of new method for coating: the supersaturation crystallisation can reach the Uniform Dispersion of catalyst and the purpose of efficient catalytic AP thermal decomposition equally.The theoretical foundation of the method is that classical temperature-changes in solubility rule and heterogeneous forming core are theoretical, when the complex catalyst precursor liquid solution becomes supersaturated solution after temperature reduces, the catalyst precursor solute can be grown up at AP surface forming core, be coated on equably the AP surface, and catalyst precursor can decompose generation nano-metal-oxide catalyst in the AP thermal decomposition process, thereby reaches the effect of self-catalysis.Particularly, the present invention compares with material with prior art and has the following advantages:
1. solved the dispersion problem of nano-oxide catalyst in AP.
Practical application shows, single nano particle is easily reunited, and the actual surface area that plays catalytic action is very little.And adopt the supersaturation crystallisation catalyst precursor to be coated on the surface of AP, and make a kind of compound particle, this compound particle has good dispersiveness and very large catalytic surface amasss, and has preferably practical application effect.This directly mixes AP and nano-metal-oxide catalyst the limited problem of dispersiveness, uniformity that causes with regard to efficiently solving present employing mechanical mixing.
2. the method mild condition, precise control, stability is strong, and good reproducibility is easy and simple to handle.
The method is utilized the basic principle of temperature-changes in solubility rule and heterogeneous forming core, thereby cooling forms supersaturated solution and makes the solute crystallization, forming core is grown up, do not relate to chemical reaction in the preparation process, stability and repeatability are all fine, and the covering amount of AP surface catalyst presoma also can accurately be regulated control.The method preparation flow is short and sweet, and is simple to operation.
3. self-catalysis successful.
Rarely have at present report by the method for adding combustion catalyst the AP high-temperature decomposition temperature to be dropped to about 300 ℃, and AP/ catalyst precursor compound particle drops to 280 ℃ with the minimum pyrolytic peak temperature of AP from 397 ℃ in this research under certain test condition, and thermal discharge is from 584Jg
-1Be increased to 1592Jg
-1, catalytic effect is remarkable.
4. the method can in conjunction with propellant preparation technology, be simplified the catalyst dispersing technology.
In propellant preparation technology, the series of temperature change procedure of heat temperature raising and cooling is arranged, in this process, can use the supersaturation crystallisation that catalyst precursor is coated on the AP surface, thereby simplify the catalyst dispersing technology.
Description of drawings
Fig. 1 is supersaturation crystallisation schematic diagram;
A among Fig. 2～1st, pure AP, AP: Co (NO
3)
2=100: 4, AP: Zn (CH
3COO)
2=100: 4, AP: Fe (NO
3)
3=100: 4, AP: Cu (NO
3)
2=100: 4 and AP: KMnO
4=100: 4 compound particle covered effect field emission scanning electron microscope results;
Fig. 3 is AP/Co (NO
3)
2The Raman scattering result of compound particle;
(a), (b) are pure AP among Fig. 4, AP: Co (NO
3)
2=100: 4, AP: Zn (CH
3COO)
2=100: 4, AP: Fe (NO
3)
3=100: 4, AP: Cu (NO
3)
2=100: 4 and AP: KMnO
4The TG-DTA analysis result of=100: 4 compound particle self-catalysis effects;
(a), (b) are pure AP among Fig. 5, AP/Co (NO
3)
2The TG-DTA analysis result of different covering amount compound particle self-catalysis effects;
Fig. 6 is Co (NO
3)
2The differential scanning calorimetry analysis result of thermal decomposition;
A～d is the X-ray diffraction analysis result who generates nano-metal-oxide after the inorganic salts thermal decomposition that coats of composite material surface among Fig. 7.
The specific embodiment
The objective of the invention is to reach by following measure.
According to the basic principle of temperature-changes in solubility rule and heterogeneous forming core, adopt the supersaturation crystallisation to prepare AP/ complex catalyst precursor composite material, its preparation process is followed successively by heating, dissolving, stirring, cooling, filtration, drying.The experimentation schematic diagram of this method as shown in Figure 1.In the present invention, the selection of catalyst precursor and solvent is very crucial.For catalyst precursor, require its heat decomposition temperature to be lower than 410 ℃ of AP thermal decomposition high-temperature decomposition temperatures, thereby before the AP thermal decomposition, form the nano-metal-oxide catalyst, alternative presoma has: Co (NO
3)
26H
2O, KMnO
4, Cu (NO
3)
23H
2O, Fe (NO
3)
39H
2O and Zn (CH
3COO)
2Etc., but be not limited to these, as long as the slaine that can meet the demands is all passable.And for selected solvent AP is insoluble to wherein, but this solvent can dissolve corresponding catalyst precursor, and alternative solvent has: ethyl acetate, ethanol and acetone etc., but be not limited to these, as long as the solvent that can meet the demands is all passable.
Preparation method provided by the invention comprises the steps:
(1) preparing quality is m
APAmmonium perchlorate (AP, Ammonium Perchlorate) for the preparation of, m
APBe arbitrary value; Catalyst precursor (catalyst precursor) chemical formula is M
aS
b, quality is m
Cp, relative molecular weight is M
CpThe chemical formula of the nano-metal-oxide catalyst (metal oxide nanocatalyst) that catalyst precursor thermal decomposition (before the AP thermal decomposition) produces is M
xO
y, relative molecular weight is M
Mon, the mass percent of nano-metal-oxide catalyst and AP is r (0.1%＜r＜15%, its preferred mass percent is 2%-6%); Solvent volume is V
Sol, density is ρ, at solvent fusing point (T
m) and boiling point (T
b) between get two temperatures point t
1And t
2, T
m＜t
1＜t
2＜T
b(t
1Be preferably room temperature), at t
1Under the temperature, catalyst precursor solubility in solvent is m
1, at t
2Under the temperature, solubility is m
2, require (m
2-m
1) V
Solρ/100＞(arm
APM
Cp)/(M
MonX);
(2) be m with quality
Cp=[(arm
APM
Cp)/(M
MonX)+m
1V
Solρ/100] catalyst precursor to be dissolved in volume be V
SolIn the solvent, magnetic agitation, rotating speed is 100r/min-1800r/min, its preferred rotating speed is 400r/min-800r/min, and is heated to t
2It is dissolved fully obtain the complex catalyst precursor liquid solution;
(3) adding quality in the mentioned solution is m
APAmmonium perchlorate, keeping rotating speed is the magnetic agitation of 100r/min-1800r/min, is cooled to t with the speed of 10K/min-50K/min
1, continue reaction, until crystallize out no longer in the solution; Reaction time is preferably 5min-30min.
(4) stop magnetic agitation, at t
1Filter mentioned solution under the temperature, products therefrom is dry under 25 ℃-80 ℃ (its preferred temperature is 60 ℃-80 ℃) temperature in air, obtain AP/ complex catalyst precursor composite material.
Below in conjunction with accompanying drawing the specific embodiment of the present invention is described further.Need to prove at this, understand the present invention for the explanation of these embodiments for helping, but do not consist of limitation of the invention.In addition, below in each embodiment of described the present invention involved technical characterictic just can mutually not make up as long as consist of each other conflict.
Embodiment 1:
AP/Co (NO
3)
2Compound particle, m
AP=2g, r=4%, catalyst precursor are Co (NO
3)
2, m
Cp=0.7752g, solvent are ethyl acetate, and volume is V
Sol=60mL, t
1=25 ℃, t
2=60 ℃.Its preparation process is followed successively by heating, dissolving, stirring, cooling, filtration, drying.
The used AP of composite is provided by Shanghai reagent company, and average grain diameter is 135 μ m, its shape appearance figure such as accompanying drawing 2 (a), (b) shown in, the AP particle surface that coats is smoothless.
In order to adopt SEM (FESEM FEI Sirion 200) observation post to get the covered effect of powder, its shape appearance figure such as accompanying drawing 2 (c), (d) shown in, AP surface major part is wrapped by, clad is fine and close, is dendroid, and length is about several microns.For the element of analyzing the gained powder forms, compound particle is carried out EDX analyze, component has N, O, Cl, Co explanation surface particles may be the compound of Co.Composite granule is done the Raman scattering test, the results are shown in accompanying drawing 3.Analyze as can be known 933cm among the figure
-1The vibration peak at place is C1O
4 -Vibration peak, 1041cm
-1And 1058cm
-1The place is NO
3 -Vibration peak.
For studying the effect of this compound particle self-catalysis AP thermal decomposition, it is done the TG-DTA test, test condition is: nitrogen atmosphere, heating rate 10K/min, temperature range 50-350 ℃, used crucible uncovered the results are shown in accompanying drawing 4, as can be seen from the figure, AP is the endothermic process of crystal transfer about 245 ℃, changes mutually Emission in Cubic into by oblique side, is the low-temperature decomposition stage at 312 ℃, its quality approximately reduces 30%, be the pyrolytic stage at 410 ℃, AP decomposes complete substantially, and two stages all are exothermic process, latter's thermal discharge is a bit larger tham the former, and can be calculated thermal discharge is 584J/g.Than AP, compound particle still has the crystal transfer process about 245 ℃, but low-temperature decomposition stage and pyrolytic stage are merged into a catabolic phase, decomposition temperature is 308 ℃, can be calculated thermal discharge is 978J/g, obviously greater than the thermal discharge of AP, therefore, compound particle has obvious self-catalysis effect.
In order to study coating thickness to the impact of compound particle self-catalysis performance, contrast r=2%, 4% and 6% compound particle TG-DTA process, such as accompanying drawing 5, can find out, the compound particle of r=2% still exists low-temperature decomposition stage and pyrolytic stage, and only there is a catabolic phase in the compound particle of r=4% and 6%.Three's decomposition temperature is respectively 342 ℃, and 308 ℃ and 286 ℃, thermal discharge is respectively 1115J/g, 978J/g and 848J/g.Therefore, coating thickness increases, and decomposition temperature reduces, but thermal discharge also reduces, and considers to think that the compound particle self-catalysis effect of r=4% is best.
Form the process of nano-metal-oxide catalyst for the thermal decomposition of Study of Catalyst presoma, to presoma Co (NO
3)
2Do the DSC test, the results are shown in accompanying drawing 6, can find out Co (NO
3)
2About 74 ℃, begin to decompose, an obvious endothermic peak is arranged herein, complicated process is residual on the compound particle and ethyl acetate that can't eliminate causes between 100 ℃-220 ℃, is nano-metal-oxide CATALYST Co 230 ℃ and 260 ℃ of endothermic processes of locating
3O
4Forming process.Product after decomposing is done the XRD test, the results are shown in accompanying drawing 7 (a), the result shows, product is the nano-metal-oxide CATALYST Co
3O
4(JCPDS 09-0418).Its thermal decomposition equation is 3Co (NO
3)
2→ Co
3O
4+ 6NO
2+ O
2230 ℃ of heat decomposition temperatures.
Embodiment 2:
AP/Co (NO
3)
2Compound particle, m
AP=2g, r=0.1%, catalyst precursor are Co (NO
3)
2, m
Cp=0.4924g, solvent are ethyl acetate, and volume is V
Sol=60mL, t
1=25 ℃, t
2=60 ℃.Its preparation process is followed successively by heating, dissolving, stirring, cooling, filtration, drying.
Embodiment 3:
AP/Co (NO
3)
2Compound particle, m
AP=2g, r=15%, catalyst precursor are Co (NO
3)
2, m
Cp=1.5766g, solvent are ethyl acetate, and volume is V
Sol=60mL, t
1=25 ℃, t
2=60 ℃.Its preparation process is followed successively by heating, dissolving, stirring, cooling, filtration, drying.
Embodiment 4:
AP/Zn (CH
3COO)
2Compound particle, m
AP=2g, r=4%, catalyst precursor are Zn (CH
3COO)
2, m
Cp=0.1564g, solvent are ethyl acetate, and volume is V
Sol=60mL, t
1=25 ℃, t
2=60 ℃.Its preparation process is followed successively by heating, dissolving, stirring, cooling, filtration, drying.Its shape appearance figure such as accompanying drawing 2 (e), (f) shown in, clad is fine and close, particle size is several microns.Its TG-DTA such as accompanying drawing 4, decomposition temperature are 336 ℃, and thermal discharge is 1592J/g.Zn (CH
3COO)
2Thermal decomposition product XRD such as accompanying drawing 7 (b) are ZnO (JCPDS 16336-1451).Its thermal decomposition equation is Zn (CH
3COO)
2→ ZnO+4CO
2+ 3H
2O.Heat decomposition temperature is 242-370 ℃.
Embodiment 5:
AP/Zn (CH
3COO)
2Compound particle, m
AP=2g, r=0.1%, catalyst precursor are Zn (CH
3COO)
2, m
Cp=0.0302g, solvent are ethyl acetate, and volume is V
Sol=60mL, t
1=25 ℃, t
2=60 ℃.Its preparation process is followed successively by heating, dissolving, stirring, cooling, filtration, drying.Embodiment 6:
AP/Zn (CH
3COO)
2Compound particle, m
AP=2g, r=15%, catalyst precursor are Zn (CH
3COO)
2, m
Cp=0.5137g, solvent are ethyl acetate, and volume is V
Sol=60mL, t
1=25 ℃, t
2=60 ℃.Its preparation process is followed successively by heating, dissolving, stirring, cooling, filtration, drying.
Embodiment 7:
AP/Fe (NO
3)
3Compound particle, m
AP=2g, r=4%, catalyst precursor are Fe (NO
3)
3, m
Cp=9.2863g, solvent are ethanol, and volume is V
Sol=60mL, t
1=25 ℃, t
2=60 ℃.Its preparation process is followed successively by heating, dissolving, stirring, cooling, filtration, drying.Its shape appearance figure such as accompanying drawing 2 (g), (h) shown in, the clad even compact, particle size only has tens nanometers.Its TG-DTA such as accompanying drawing 4, its decomposition temperature are 280 ℃, and thermal discharge is 838J/g.Fe (NO
3)
3Thermal decomposition product XRD such as accompanying drawing 7 (c) are Fe
2O
3(JCPDS 33-0664).Its thermal decomposition equation is 4Fe (NO
3)
3→ 2Fe
2O
3+ 12NO
2+ 3O
2Heat decomposition temperature is 250-400 ℃.
Embodiment 8:
AP/Fe (NO
3)
3Compound particle, m
AP=2g, r=0.1%, catalyst precursor are Fe (NO
3)
3, m
Cp=9.0488g, solvent are ethanol, and volume is V
Sol=60mL, t
1=25 ℃, t
2=60 ℃.Its preparation process is followed successively by heating, dissolving, stirring, cooling, filtration, drying.
Embodiment 9:
AP/Fe (NO
3)
3Compound particle, m
AP=2g, r=15%, catalyst precursor are Fe (NO
3)
3, m
Cp=9.9481g, solvent are ethanol, and volume is V
Sol=60mL, t
1=25 ℃, t
2=60 ℃.Its preparation process is followed successively by heating, dissolving, stirring, cooling, filtration, drying.
Embodiment 10:
AP/Cu (NO
3)
2Compound particle, m
AP=2g, r=4%, catalyst precursor are Cu (NO
3)
2, m
Cp=12.0683g, solvent are ethanol, and volume is V
Sol=60mL, t
1=25 ℃, t
2=60 ℃.Its preparation process is followed successively by heating, dissolving, stirring, cooling, filtration, drying.Its shape appearance figure such as accompanying drawing 2 (i), (j) shown in, clad is inhomogeneous, particle size distribution is wide, in the hundreds of nanometer between several microns.Its TG-DTA such as accompanying drawing 4, decomposition temperature are 331 ℃, and thermal discharge is 1241J/g.Cu (NO
3)
2Thermal decomposition product XRD such as accompanying drawing 7 (d) are CuO (JCPDS 72-0629).Its thermal decomposition equation is 2Cu (NO
3)
2→ 2CuO+4NO2+O2.Heat decomposition temperature is 350 ℃.
Embodiment 11:
AP/Cu (NO
3)
2Compound particle, m
AP=2g, r=0.1%, catalyst precursor are Cu (NO
3)
2, m
Cp=11.3641g, solvent are ethanol, and volume is V
Sol=60mL, t
1=25 ℃, t
2=60 ℃.Its preparation process is followed successively by heating, dissolving, stirring, cooling, filtration, drying.
Embodiment 12:
AP/Cu (NO
3)
2Compound particle, m
AP=2g, r=15%, catalyst precursor are Cu (NO
3)
2, m
Cp=14.0566g, solvent are ethanol, and volume is V
Sol=60mL, t
1=25 ℃, t
2=60 ℃.Its preparation process is followed successively by heating, dissolving, stirring, cooling, filtration, drying.
Embodiment 13:
AP/KMnO
4Compound particle, m
AP=2g, r=4%, catalyst precursor are KMnO
4, m
Cp=0.2465g, solvent are acetone, and volume is V
Sol=60mL, t
1=25 ℃, t
2=50 ℃.Its preparation process is followed successively by heating, dissolving, stirring, cooling, filtration, drying.Its shape appearance figure such as accompanying drawing 2 (k), (l) shown in, clad is fine and close, particle is fluid shape, size is about several microns.Its TG-DTA such as accompanying drawing 4, decomposition temperature are 305 ℃, and thermal discharge is 806J/g.Its thermal decomposition equation is 2KMnO4 → K2MnO4+MnO2+O2.Heat decomposition temperature is 240 ℃.
Embodiment 14:
AP/KMnO
4Compound particle, m
AP=2g, r=0.1%, catalyst precursor are KMnO
4, m
Cp=0.0768g, solvent are acetone, and volume is V
Sol=60mL, t
1=25 ℃, t
2=50 ℃.Its preparation process is followed successively by heating, dissolving, stirring, cooling, filtration, drying.
Embodiment 15:
AP/KMnO
4Compound particle, m
AP=2g, r=15%, catalyst precursor are KMnO
4, m
Cp=0.7499g, solvent are acetone, and volume is V
Sol=60mL, t
1=25 ℃, t
2=50 ℃.Its preparation process is followed successively by heating, dissolving, stirring, cooling, filtration, drying.
The above is preferred embodiment of the present invention, but the present invention should not be confined to the disclosed content of this embodiment and accompanying drawing.So everyly do not break away from the equivalence of finishing under the spirit disclosed in this invention or revise, all fall into the scope of protection of the invention.
Claims (10)
1. the method at ammonium perchlorate surface clad nano metal oxide catalyst presoma is characterized in that,
The 1st step was dissolved in the catalyst precursor that heat decomposition temperature is lower than AP thermal decomposition high-temperature decomposition temperature in the solvent of energy catalyst-solvent presoma, magnetic agitation, and be heated to t
2It is dissolved fully obtain the complex catalyst precursor liquid solution;
The catalyst precursor chemical formula is M
aS
b, relative molecular weight is M
CpThe chemical formula of the nano-metal-oxide catalyst that the catalyst precursor thermal decomposition produces is M
xO
y, relative molecular weight is M
Mon, establishing described solvent volume is V
Sol, the quality of described catalyst precursor is m
Cp, r is that the mass percent of nano-metal-oxide catalyst and AP is 0.1%＜r＜15%, m
APBe the quality of ammonium perchlorate, the density of solvent is ρ, T
mBe solvent fusing point, T
bBe solvent boiling point, at solvent fusing point T
mWith boiling point T
bBetween get two temperatures point t
1And t
2, T
m＜t
1＜t
2＜T
bAt t
1Under the temperature, catalyst precursor solubility in solvent is m
1, the quality m of catalyst precursor
CpSatisfy: m
Cp=[(arm
APM
Cp)/(M
MonX)+m
1V
Solρ/100];
It is m that the 2nd step added quality in the mentioned solution
APAmmonium perchlorate, to continue magnetic agitation, be cooled to t
1, continue reaction, until crystallize out no longer in the solution;
The 3rd step stopped magnetic agitation, at t
1Filter mentioned solution under the temperature, products therefrom is dry, obtain AP/ complex catalyst precursor composite material.
2. want 1 described a kind of method at ammonium perchlorate surface clad nano metal oxide catalyst presoma according to right, it is characterized in that, described catalyst precursor is Co (NO
3)
26H
2O, KMnO
4, Cu (NO
3)
23H
2O, Fe (NO
3)
39H
2O or Zn (CH
3COO)
2
3. want 1 described a kind of method at ammonium perchlorate surface clad nano metal oxide catalyst presoma according to right, it is characterized in that, described solvent is ethyl acetate, ethanol or acetone.
4. want 1,2 or 3 described a kind of methods at ammonium perchlorate surface clad nano metal oxide catalyst presoma according to right, it is characterized in that, in the 1st step and the 2nd step, the rotating speed of magnetic agitation is 100r/min-1800r/min.
5. want 1,2 or 3 described a kind of methods at ammonium perchlorate surface clad nano metal oxide catalyst presoma according to right, it is characterized in that, in the 1st step and the 2nd step, the rotating speed of magnetic agitation is 400r/min-800r/min.
6. want 1,2 or 3 described a kind of methods at ammonium perchlorate surface clad nano metal oxide catalyst presoma according to right, it is characterized in that, in the 2nd step, the cooling temperature is 10～50K/min.
7. want 1,2 or 3 described a kind of methods at ammonium perchlorate surface clad nano metal oxide catalyst presoma according to right, it is characterized in that, in the 2nd step, continuing the reaction time is 5～30 minutes.
8. want 1,2 or 3 described a kind of methods at ammonium perchlorate surface clad nano metal oxide catalyst presoma according to right, it is characterized in that, drying is carried out in air, and temperature is 25 ℃～80 ℃.
9. want 1,2 or 3 described a kind of methods at ammonium perchlorate surface clad nano metal oxide catalyst presoma according to right, it is characterized in that, baking temperature is 60 ℃～80 ℃.
10. want 1,2 or 3 described a kind of methods at ammonium perchlorate surface clad nano metal oxide catalyst presoma according to right, it is characterized in that, at t
2Under the temperature, solubility is m
2, then require to satisfy: (m
2-m
1) V
Solρ/100＞(arm
APM
Cp)/(M
MonX).
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Citations (5)
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