CN105521805B - Nanocomposite GO-MgWO4Preparation method and application - Google Patents
Nanocomposite GO-MgWO4Preparation method and application Download PDFInfo
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- CN105521805B CN105521805B CN201610031956.7A CN201610031956A CN105521805B CN 105521805 B CN105521805 B CN 105521805B CN 201610031956 A CN201610031956 A CN 201610031956A CN 105521805 B CN105521805 B CN 105521805B
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- 239000002114 nanocomposite Substances 0.000 title claims abstract description 18
- 238000000034 method Methods 0.000 title claims abstract description 10
- 229910017672 MgWO4 Inorganic materials 0.000 claims abstract description 39
- 239000003054 catalyst Substances 0.000 claims abstract description 15
- 238000002360 preparation method Methods 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 8
- 239000000725 suspension Substances 0.000 claims abstract description 5
- 239000008187 granular material Substances 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 238000001556 precipitation Methods 0.000 claims abstract description 3
- 239000013049 sediment Substances 0.000 claims abstract description 3
- 239000002105 nanoparticle Substances 0.000 claims description 10
- 230000003197 catalytic effect Effects 0.000 abstract description 11
- 239000004449 solid propellant Substances 0.000 abstract description 8
- 238000002485 combustion reaction Methods 0.000 abstract description 7
- 238000005979 thermal decomposition reaction Methods 0.000 abstract description 5
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- 238000000354 decomposition reaction Methods 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910021389 graphene Inorganic materials 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 239000003380 propellant Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- -1 Fe2O3 Chemical class 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000002905 metal composite material Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N CuO Inorganic materials [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 229910020350 Na2WO4 Inorganic materials 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- ZXOKVTWPEIAYAB-UHFFFAOYSA-N dioxido(oxo)tungsten Chemical compound [O-][W]([O-])=O ZXOKVTWPEIAYAB-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N nickel(II) oxide Inorganic materials [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
Classifications
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
-
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/30—Tungsten
-
- B01J35/61—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B23/00—Compositions characterised by non-explosive or non-thermic constituents
- C06B23/007—Ballistic modifiers, burning rate catalysts, burning rate depressing agents, e.g. for gas generating
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Abstract
The present invention relates to nanocomposite GO MgWO4Preparation method and applications.Involved preparation method includes：The MgWO for being 3~5 by pH4Nano granule suspension and GO solution mixing, precipitation, gained sediment are GO MgWO4Nanocomposite.One of involved application is GO MgWO prepared by method4The application of catalyst is thermally decomposed as energetic material RDX.It is involved using its two GO MgWO for being to provide above method preparation4The application of catalyst is thermally decomposed as energetic material HMX.Nanocomposite GO MgWO4 produced by the present invention have given full play to the synergic catalytic effect of the two, it is better than the MgWO4 and GO of one pack system to the catalytic effect of energetic material RDX, HMX thermal decomposition, it is expected to the combustion catalyst as solid propellant, realizes the quick steady-state burning of solid propellant.
Description
Technical field
The invention belongs to nanocomposite technical field, more particularly to a kind of new combustion for solid propellant is urged
Agent GO-MgWO4Preparation and use.
Background technology
Propellant is the important research field of military and space technology.Solid propellant is towards high energy, insensitiveness, low spy at present
The directions such as reference number, environmental protection are developed.RDX and HMX is the most common oxidant arrived, their thermal decomposition performance in solid propellant
Key effect is played to propellant combustion behavior：The heat decomposition temperature and apparent activation energy of the two are lower, and the igniting of propellant is stagnant
The time is shorter afterwards, and burn rate is higher[5-8].Past, researchers have been devoted to develop single metal oxide (such as
Fe2O3, CuO, NiO and Co3O4Deng) it is used as combustion catalyst.But the composite oxides of two or more different metal are done
Generation " synergistic effect " can be generated better catalytic effect by catalyst, the performance complement of different metal oxides.Both at home and abroad
There is CuFe in succession2O4、Bi2WO6Document report of the equal nano-metal composite oxides as combustion catalyst, research are found
Its effect is not only better than the catalyst of single metal oxide, and also the effect being simply mixed than two kinds of catalyst, which has, significantly carries
It is high.
MgWO4As a kind of simplest wolframite metal composite oxide, there is good chemical stability, due to it
Potential catalytic applications value, is favored by more and more researchers in recent years.Especially Mg as lightweight element,
Molecular weight very little is used to be easy to decompose discharge when the combustion catalyst of solid propellant, and avoiding being deposited on influences to push away in engine
Into the burning of agent, hence it is evident that improve ballistic performance.The design of inventor's experimental group synthesizes MgWO4Nano particle, however, due to nanometer
The minimum size of particle and relatively high surface energy, the problem of being inevitably present reunion in actual use, to make
Its catalytic performance substantially reduces.Therefore how to disperse these nano materials, it is big as one to give full play to its excellent catalytic performance
Problem.
Invention content
An object of the present invention is to provide above-mentioned nanocomposite GO-MgWO4Preparation method.
The present invention preparation method include：The nanometer MgWO for being 3~5 by pH4Nano granule suspension is mixed with GO solution
Even, precipitation, gained sediment GO-MgWO4Nanocomposite.
Further, MgWO in preparation method of the invention4Mass ratio with GO is 9:1.
Further, MgWO4The grain size of nano particle is 20~30nm.
The second object of the present invention is to provide the GO-MgWO of above method preparation4It is urged as energetic material RDX thermal decompositions
The application of agent.
The third object of the present invention is to provide the GO-MgWO of above method preparation4It is urged as energetic material HMX thermal decompositions
The application of agent.
Compared with prior art, advantages of the present invention and good effect are as follows：
(1) nanocomposite GO-MgWO obtained above4In, the MgWO of about 20nm4Uniform load is in GO superthin layer tables
Face greatly inhibits the reunion of nano-particle, increases specific surface area, has given full play to the synergic catalytic effect of the two.
(2) synthetic method of the present invention is simple, effectively, and it is good to environment, be easy to industrialized production；The present invention synthesizes to obtain
GO-MgWO4It is a kind of new catalyst, is better than the MgWO of one pack system to the catalytic effect of energetic material RDX, HMX thermal decomposition4
And GO, it is expected to the combustion catalyst as solid propellant, realizes the quick steady-state burning of solid propellant.
Description of the drawings
Fig. 1 is the MgWO of embodiment 14And GO-MgWO4XRD curve graphs；
Fig. 2 is the MgWO of embodiment 14(a) and GO-MgWO4(b) SEM figures；
Fig. 3 is the MgWO of embodiment 14And GO-MgWO4FT-IR curve graphs；
Fig. 4 is the DSC curve figure that RDX in the presence of different catalysts of embodiment 2 is thermally decomposed；
Fig. 5 is the DSC curve figure that HMX in the presence of different catalysts of embodiment 3 is thermally decomposed.
Specific implementation mode
Graphene oxide (Graphene Oxide, abbreviation GO) is an analog derivative of graphene, structure and graphene phase
Together, but in two-dimentional basal plane and a large amount of functional group of marginal existence, such as carboxyl, hydroxyl, epoxy group, the hydroxyl and phenolic on surface
Carboxylic group so that its is negatively charged, thus is easier to through non-covalent bond and Nanocomposites；On the other hand, two-dimentional GO is thin
Layer has elasticity, ductility and specific surface well, is particularly suitable for load nano particle, to inhibit the group of nano-particle
It is poly-；Moreover, the very ultra thin conductor layers structure of GO is very beneficial for electronics and the transmission of substance passes through.It can be seen that preparing GO loads
Nanocomposite can greatly improve the original catalytic activity of nano-particle.
GO is negatively charged in the preparation method of the present invention, MgWO4Insoluble in soda acid, H is introduced+Make MgWO4It is positively charged, due to quiet
Electric power acts on, and electronegative GO is carried on positively charged MgWO4Surface forms nanocomposite GO-MgWO4。
It is the specific embodiment that inventor provides below, to be further explained explanation to technical scheme of the present invention.
Embodiment 1：
(1) by 1.2mmol Na2WO4·2H2O and 1.2mmol Mg (NO3)2·6H2O is dissolved in respectively in 40 mL ethylene glycol,
After being vigorously stirred uniformly, it is 9 to adjust solution ph with 0.5mol/L NaOH, and then mixed liquor is transferred in polytetrafluoroethylene (PTFE)
In the autoclave of lining, for 24 hours, precipitated product washs through ethyl alcohol, is dried to obtain MgWO 250 DEG C of hydro-thermal reactions4Nano particle；
(2) by GO ultrasonic disperses in deionized water, a concentration of 1mg mL-1；
(3) 0.27g MgWO are taken4MgWO4The grain size of nano particle is 20~30nm.
Same ultrasonic disperse 30min in deionized water；
(4) 0.1M HCl are configured, suspension in (3) is instilled, adjusts its pH=3.5；
(5) GO solution obtained in 30mL (2) is taken, H in (4) is added to+The MgWO being modified4In suspension, continue ultrasound
2h makes its mixing be uniformly dispersed；
(6) by precipitating, being filtered, washed, drying to get nanocomposite GO-MgWO4。
Fig. 1 is GO-MgWO of the present invention4XRD spectrum, the results showed that：GO-MgWO4The purer MgWO of XRD curves4
(JCPDS 27-0789) has no significant change, illustrates that the graphite linings of GO are stripped into single-layer or multi-layer superthin section, and MgWO4
It is embedded into GO thin slices.
Fig. 2 is GO-MgWO of the present invention4SEM (a, b) figure, the results showed that：MgWO4It is about 20nm particles, GO is in 2-3nm
Transparent superthin layer, MgWO4The surfaces GO are dispersed in, the reunion of nano-particle is greatly inhibited, increases specific surface area.
Fig. 3 is GO-MgWO of the present invention4IR collection of illustrative plates, the results showed that：GO-MgWO4Infrared curve graph in both occurred
1000~1800 belong to the characteristic peak of GO, and have positioned at 400~900cm-1Belong to MgWO4Characteristic peak.
Embodiment 2：
The nanocomposite GO-MgWO synthesized by 1 method of embodiment4, with RDX with 1：4 mass ratio uniformly mixes
It closes, DSC measurement is carried out under the conditions of 10 DEG C of heating rate, obtain shown in Fig. 4 as a result, pure RDX decomposition peaks temperature is respectively 242.9
DEG C, apparent thermal discharge is 797J g-1, add GO, MgWO4And GO-MgWO4Afterwards, decomposition peak's temperature of RDX reduces 17.1 respectively
DEG C, 1.7 DEG C and 23.7 DEG C；Thermal discharge is increased to 978J g respectively-1、832J g-1With 1039J g-1.Either reduce RDX's
Highest decomposition temperature, or increase apparent thermal discharge aspect, GO-MgWO4It all shows than GO, MgWO4Higher catalytic activity.
Embodiment 3：
The nanocomposite GO-MgWO synthesized by 1 method of embodiment4, with HMX with 1：4 mass ratio uniformly mixes
It closes, DSC measurement is carried out under the conditions of 10 DEG C of heating rate, obtain shown in Fig. 5 as a result, pure HMX decomposition peaks temperature is respectively 283.4
DEG C, apparent thermal discharge is 851J g-1, add GO, MgWO4And GO-MgWO4Afterwards, decomposition peak's temperature of HMX reduces 0.7 respectively
DEG C, 6.4 DEG C and 34.5 DEG C, thermal discharge is respectively 895J g-1、913J g-1With 1346J g-1.Compared to GO, MgWO4, GO-
MgWO4HMX heat decomposition temperatures are made to reduce most, apparent thermal discharge also improves maximum, and catalytic effect is most prominent.
Claims (4)
1. a kind of nanocomposite GO-MgWO4Preparation method, which is characterized in that the preparation method includes：It is 3~5 by pH
Nanometer MgWO4Nano granule suspension and GO solution mixing, precipitation, gained sediment GO-MgWO4Nanocomposite, institute
State MgWO4The grain size of nano particle is 20~30nm.
2. nanocomposite GO-MgWO as described in claim 14Preparation method, which is characterized in that MgWO4With the matter of GO
Amount is than being 9:1.
3. GO-MgWO prepared by claim 1 the method4The application of catalyst is thermally decomposed as energetic material RDX.
4. GO-MgWO prepared by claim 1 the method4The application of catalyst is thermally decomposed as energetic material HMX.
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| CN105521805B true CN105521805B (en) | 2018-09-18 |
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| CN110396033B (en) * | 2019-08-07 | 2021-07-23 | 南京理工大学 | Preparation method of nano thermite based on electrostatic spraying |
| CN113173665B (en) * | 2021-03-31 | 2022-10-04 | 沈阳化工大学 | ZnWO 4 /MgWO 4 Method for degrading organic wastewater by using composite semiconductor material |
| CN113652009B (en) * | 2021-08-17 | 2022-05-17 | 西北大学 | Preparation method and application of nitrated chitosan/GO/n-Ti composite material |
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| CN102580714A (en) * | 2012-02-09 | 2012-07-18 | 江苏大学 | Graphene oxide/silver phosphate composite visible light catalyst and preparation method thereof |
| CN103877971A (en) * | 2014-03-07 | 2014-06-25 | 中国科学院东北地理与农业生态研究所 | Efficient visible-light-induced photocatalyst and preparation method thereof |
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