CN101642710B

CN101642710B - Cu2O-Bi2O3/carbon nano-tube composite powder and preparation method thereof

Info

Publication number: CN101642710B
Application number: CN2008101427776A
Authority: CN
Inventors: 洪伟良; 赵凤起; 张金霞; 刘剑洪; 仪建华; 高茵
Original assignee: Shenzhen University
Current assignee: Shenzhen University
Priority date: 2008-08-04
Filing date: 2008-08-04
Publication date: 2011-06-01
Anticipated expiration: 2028-08-04
Also published as: CN101642710A

Abstract

The invention provides a Cu2O-Bi2O3/carbon nano-tube composite powder and a preparation method thereof. The components of the Cu2O-Bi2O3/carbon nano-tube composite powder are Cu2O, Bi2O3 and multi-walled carbon nano-tubes (MWCNT), wherein the mixture ratio by weight of the components is: 40 to 60 percent of Cu2O-Bi2O3 (wherein Cu2O accounts for 20 to 40 percent, and Bi2O3 accounts for 20 to 40 percent), the particle size of the Cu2O-Bi2O3 is 10 to 20 nm, and 40 to 60 percent of MWCNT. The preparation method comprises the steps of purifying the multi-walled carbon nano-tubes, performing oxidation modification on the surfaces of the multi-walled carbon nano-tubes, adding the multi-walled carbon nano-tubes to stoichiometric bismuth salt and copper salt solutions, ultrasonically dispersing, stirring, standing, performing alkalization deposition, washing, filtering, burning, performing other processes and obtaining the composite powder. The Cu2O-Bi2O3/carbon nano-tube composite powder as a combustion catalyst has excellent catalytic effect on the combustion of double-base or modified double-base propellants, is free from toxicity and pollution, and is an environment-friendly combustion catalyst.

Description

A kind of Cu 2O-Bi 2O 3/ carbon nano-tube composite powder and preparation method thereof

Technical field

That the present invention relates to is a kind of Cu ₂O-Bi ₂O ₃/ carbon nano-tube composite powder and preparation method thereof.Cu ₂O-Bi ₂O ₃/ carbon nano-tube composite powder can be used as the environmentally friendly combustion catalyst of solid propellant.

Technical background

Double base propellant and modified double base propellant are the used class high-energy fuel of rocket and guided missile, need add combustion catalyst during actual the use and improve its combustibility.Development along with missilery, development low signature, environmentally friendly high-performance propellant are the important development directions, correspondingly need to develop nontoxic or hypotoxicity, pollution-free, novel burningrate catalyst efficiently, satisfy the needs of development novel solid propellant.

CNT is owing to have huge specific area and cavity structure, and there is fault of construction again in its surface and edge, makes it have unique catalytic performance and adsorption property, is a kind of special catalyst, is again a kind of good catalyst carrier.As catalyst carrier, can be prepared into environmentally friendly composite catalyst with avirulence or hypotoxicity metallic compound and CNT are compound.CNT plays dual parts catalyst and carrier, catalyst with the nanoparticle form high degree of dispersion on the tube wall of CNT, CNT can stop the mutual reunion between metal oxide nanoparticles as " carbon skeleton ", can give full play to the efficient catalytic effect of nano particle.Because CNT is made up of carbon, can not produce toxic and harmful after the burning, therefore can not pollute environment, the metal oxide of load simultaneously again can with the catalytic performance " complementation " of CNT, the catalytic action of promotion metal oxide.

Bismuth is a kind of nontoxic element, and copper is a kind of low toxicity element, and they are that the burning of propellant all has catalytic action preferably to double-basis.With Bi ₂O ₃And Cu ₂O is compound on nanoscale, and their catalytic performance can " complementation ", produces strong " cooperative effect ", can significantly improve its catalytic effect, and can be by changing Bi ₂O ₃And Cu ₂The ratio of O is optimized catalytic performance.Therefore, exploitation Cu ₂O-Bi ₂O ₃The compound burningrate catalyst of/carbon nanotube loaded type can be solid propellant environmentally friendly efficient burning catalyst is provided.

Summary of the invention

The objective of the invention is at the problems referred to above, a kind of Cu that is used as the combustion catalyst of double-basis or modified double base propellant is provided ₂O-Bi ₂O ₃/ carbon nano-tube composite powder.

Another object of the present invention provides Cu ₂O-Bi ₂O ₃The preparation method of/carbon nano-tube composite powder.

The invention provides a kind of Cu ₂O-Bi ₂O ₃/ carbon nano-tube composite powder, its component is: Cu ₂O, Bi ₂O ₃And multi-walled carbon nano-tubes, various components contents are counted by weight percentage and are Cu ₂O:20～40%, Bi ₂O ₃: 20～40%, multi-walled carbon nano-tubes: 40～60%.

Described Cu ₂O-Bi ₂O ₃In/the carbon nano-tube composite powder: the diameter of used multi-walled carbon nano-tubes is 60～90nm, and length is 500～3000nm, loads on the Cu of carbon nano tube surface ₂O-Bi ₂O ₃The particle diameter of compound particle is 10～20nm.

Cu of the present invention ₂O-Bi ₂O ₃The preparation method of/carbon nano-tube composite powder, several steps in the following order carries out: the effective hydrochloric acid of (1) multi-wall carbon nano-tube soaks and carried out purifying in 12～20 hours; (2) purified effective 1 volume red fuming nitric acid (RFNA) of multi-wall carbon nano-tube and the composite nitration mixture of the 3 volume concentrated sulfuric acids were 60～90 ℃ of following oxidations 1～2 hour; (3) a certain proportion of soluble bismuth salt and soluble copper salt are dissolved in the distilled water and add an amount of rare nitric acid be mixed with transparent mixed solution; (4) in the mixed solution of bismuth salt and mantoquita, add the multi-walled carbon nano-tubes of a certain proportion of purified and oxidation, stir and add ultrasonic dispersion 30 minutes; (5) at room temperature stir 4～6 hours, left standstill then 4～5 hours; (6) under agitation splash into 2.5wt% ammoniacal liquor, left standstill 4～6 hours then pH value to 7.5～8.5 of regulator solution; (7) suction filtration, washing, drying; (8) under nitrogen protection, calcined 2 hours, and can make Cu for 300～450 ℃ ₂O-Bi ₂O ₃/ carbon nano-tube composite powder.Described used soluble bismuth salt is: bismuth nitrate; Soluble copper salt is: copper nitrate, Schweinfurt green.

Cu of the present invention ₂O-Bi ₂O ₃/ carbon nano-tube composite powder has good catalytic effect as combustion catalyst to the burning of double-basis or modified double base propellant, and is nontoxic, pollution-free.

Description of drawings

The Cu of Fig. 1 for obtaining behind the case study on implementation 1 ₂O-Bi ₂O ₃The X-ray diffractogram of/CNT, a is the X-ray diffraction result of CNT after the preliminary treatment among the figure; B is Cu among the figure ₂O-Bi ₂O ₃The X-ray diffraction result of/carbon nano-tube composite powder contrasts with the PDF card: loaded article is mainly bismuth oxide (PDF card 65-1209) and cuprous oxide (PDF card 65-3288).

The Cu of Fig. 2 for obtaining behind the case study on implementation 1 ₂O-Bi ₂O ₃The transmission electron microscope photo of/CNT as can be seen, loads on the nanometer Cu of carbon nano tube surface from transmission electron microscope photo ₂O-Bi ₂O ₃Be spheroidal particle, the about 16nm of average grain diameter.

The Cu of Fig. 3 for obtaining behind the case study on implementation 1 ₂O-Bi ₂O ₃The EDS energy spectrogram of/carbon nano-tube composite powder, EDS composes four kinds of elements such as existing C, O, Bi, Cu, illustrates that product only contains C, O, four kinds of elements of Bi, Cu.

The specific embodiment

Cu of the present invention ₂O-Bi ₂O ₃The concrete preparation method of/carbon nano-tube composite powder combustion catalyst is provided in detail by following examples.

Embodiment 1

(1) multi-walled carbon nano-tubes that takes by weighing 0.400g places round-bottomed flask, add nitration mixture (red fuming nitric acid (RFNA): the concentrated sulfuric acid=1: 3), constant temperature refluxed 1 hour under 70 ℃ of temperature, cooling, washing is filtered, and is dry, grind.

(2) the five water bismuth nitrates that take by weighing 0.370g add 30ml 1.0mol/L nitric acid, ultrasonic dissolution in round-bottomed flask.The nitrate trihydrate copper that takes by weighing 0.600g in round-bottomed flask, ultrasonic dissolution.Bismuth salting liquid and copper salt solution are mixed, add the multi-walled carbon nano-tubes of 0.300g through step (1) oxidation processes, ultrasonic being uniformly dispersed, at room temperature constant temperature stirred 5 hours, left standstill then 5 hours.Under agitation splashing into 1mol/L NaOH to pH value is 7.8, leaves standstill then 5 hours.Suction filtration adds ultrasonic wave to product washing 2 times and 1 time with distilled water, ethanol respectively, and 60 ℃ dry down, and 350 ℃ of calcinations are 2 hours under nitrogen protection, can make CuO-Bi ₂O ₃/ carbon nano-tube composite powder.The content that gets Bi element in the product with atomic spectroscopic analysis count by weight percentage into: 22.0%, the content of Cu element is: 22.5%; Conversion obtains containing Bi ₂O ₃For: 24.5%, contain Cu ₂O is: 25.3%.

Embodiment 2

(2) the five water bismuth nitrates that take by weighing 0.550g add 40ml 1mol/L nitric acid in round-bottomed flask, and ultrasonic dissolution becomes transparent clear solutions.The copper nitrate that takes by weighing 0.900g in round-bottomed flask, ultrasonic dissolution.Bismuth salting liquid and copper salt solution are mixed, add the multi-walled carbon nano-tubes of 0.300g through step (1) oxidation processes, ultrasonic being uniformly dispersed at room temperature stirred 5 hours, left standstill then 6 hours.Under agitation splashing into 1mol/L NaOH to pH value is 8.0, leaves standstill then 5 hours.Suction filtration adds ultrasonic wave to product washing 2 times and 1 time with distilled water, ethanol respectively, and 60 ℃ dry down, and 350 ℃ of calcinations are 2 hours under nitrogen protection, can make Cu ₂O-Bi ₂O ₃/ carbon nano-tube composite powder.The content that gets Bi element in the product with atomic spectroscopic analysis count by weight percentage into: 25.7%, the content of Cu element is: 26.3%; Conversion obtains containing Bi ₂O ₃For: 28.7%, contain Cu ₂O is: 29.6%.

Claims

1. Cu ₂O-Bi ₂O ₃/ carbon nano-tube composite powder is characterized by: Cu ₂O-Bi ₂O ₃The component of/carbon nano-tube composite powder is: Cu ₂O, Bi ₂O ₃And multi-walled carbon nano-tubes, various components contents are by mass percentage: Cu ₂O:20～40%, Bi ₂O ₃: 20～40%, multi-walled carbon nano-tubes: 40～60%.

2. Cu according to claim 1 ₂O-Bi ₂O ₃/ carbon nano-tube composite powder is characterized in that: the diameter of used multi-walled carbon nano-tubes is 60～90nm, and length is 500～3000nm, loads on the Cu of carbon nano tube surface ₂O-Bi ₂O ₃The particle diameter of compound particle is 10～20nm.

3. claim 1 or 2 described Cu ₂O-Bi ₂O ₃The preparation method of/carbon nano-tube composite powder, carry out according to the following steps: the effective hydrochloric acid of (1) multi-wall carbon nano-tube soaks and carried out purifying in 12～20 hours; (2) purified effective 1 volume red fuming nitric acid (RFNA) of multi-wall carbon nano-tube and the composite nitration mixture of the 3 volume concentrated sulfuric acids were 60～90 ℃ of following oxidations 1～2 hour; (3) a certain proportion of soluble bismuth salt and soluble copper salt are dissolved in the distilled water and add an amount of rare nitric acid be mixed with transparent mixed solution; (4) in the mixed solution of bismuth salt and mantoquita, add the multi-walled carbon nano-tubes of a certain proportion of purified and oxidation, stir and add ultrasonic dispersion 30 minutes; (5) at room temperature stir 4～6 hours, left standstill then 4～5 hours; (6) under agitation splash into 2.5wt% ammoniacal liquor, the pH value of regulator solution extremely

7.5～8.5, left standstill then 4～6 hours; (7) suction filtration, washing, drying; (8) under nitrogen protection, calcined 2 hours, and can make Cu for 300～450 ℃ ₂O-Bi ₂O ₃/ carbon nano-tube composite powder.

4. according to the described Cu of claim 3 ₂O-Bi ₂O ₃The preparation method of/carbon nano-tube composite powder is characterized in that: used soluble bismuth salt is: bismuth nitrate; Soluble copper salt is: copper nitrate, Schweinfurt green.