CN107570171B - Preparation method of cobaltosic oxide supported nano gold catalyst, product and application thereof - Google Patents
Preparation method of cobaltosic oxide supported nano gold catalyst, product and application thereof Download PDFInfo
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- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 239000003054 catalyst Substances 0.000 title claims abstract description 49
- 239000010931 gold Substances 0.000 title claims abstract description 33
- 229910052737 gold Inorganic materials 0.000 title claims abstract description 26
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000000243 solution Substances 0.000 claims abstract description 35
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002244 precipitate Substances 0.000 claims abstract description 18
- 239000006185 dispersion Substances 0.000 claims abstract description 15
- 239000007864 aqueous solution Substances 0.000 claims abstract description 12
- 239000007788 liquid Substances 0.000 claims abstract description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000001301 oxygen Substances 0.000 claims abstract description 7
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims abstract description 6
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 6
- 239000002253 acid Substances 0.000 claims abstract description 6
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 6
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 230000003197 catalytic effect Effects 0.000 claims description 9
- 239000012855 volatile organic compound Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 5
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 4
- 230000008030 elimination Effects 0.000 claims description 3
- 238000003379 elimination reaction Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 9
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 5
- 239000002105 nanoparticle Substances 0.000 abstract description 4
- 238000007254 oxidation reaction Methods 0.000 abstract description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 10
- 238000007084 catalytic combustion reaction Methods 0.000 description 5
- 229910000510 noble metal Inorganic materials 0.000 description 5
- 239000001294 propane Substances 0.000 description 5
- 229910002451 CoOx Inorganic materials 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000000593 microemulsion method Methods 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- RCFVMJKOEJFGTM-UHFFFAOYSA-N cerium zirconium Chemical compound [Zr].[Ce] RCFVMJKOEJFGTM-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 239000004530 micro-emulsion Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E20/00—Combustion technologies with mitigation potential
- Y02E20/34—Indirect CO2mitigation, i.e. by acting on non CO2directly related matters of the process, e.g. pre-heating or heat recovery
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Abstract
The invention provides a cobaltosic oxide supported nano gold catalyst, a preparation method and application thereof, wherein a cyclohexane solution of oleylamine is dripped into Co (NO)3)2Obtaining a solution A from the aqueous solution; adding cetyl trimethyl ammonium bromide and n-butyl alcohol into water, adding a chloroauric acid solution to form a solution B, and dropwise adding the solution A into the solution B to obtain a dispersion liquid; reacting NaBH4And dropwise adding the aqueous solution into the dispersion liquid, and simultaneously introducing high-purity oxygen to wash, dry and roast the obtained precipitate to obtain the required catalyst. The invention utilizes the method of complexation-oxidation to synthesize the novel cobaltosic oxide supported nano gold catalyst in one step, realizes the uniform dispersion of gold nano particles, greatly reduces the cost of the catalyst on the basis of ensuring the activity, and has wider market application prospect.
Description
Technical Field
The invention relates to a cobaltosic oxide supported nano gold catalyst, a preparation method and application thereof, in particular to a preparation method and application of a supported gold catalyst for catalytic elimination of volatile organic compounds.
Background
With the higher control requirement of the national environmental protection laws and regulations on the discharge of the VOCs atmospheric pollutants, in recent years, great attention is paid to the treatment of waste gas containing volatile organic compounds. Various technologies have been developed for the exhaust emission of VOCs, including thermal destruction, adsorption, and catalytic oxidation. Thermal destruction requires high operating temperatures and high equipment investment, energy consumption and costs, and therefore may not be the most effective. In some cases, the removal of VOCs from exhaust emissions by adsorption with an adsorbent such as activated carbon is an alternative method. However, this method does not destroy the contaminants but merely enriches them, easily causing secondary pollution. In addition, the adsorption efficiency can be affected by the type and concentration of volatile organic compounds in the exhaust emissions. Catalytic oxidation is an efficient and economical way to destroy volatile organic compounds in exhaust emissions. The d electron orbit of the noble metal is not filled, reactants are easily adsorbed on the surface, an intermediate active compound is favorably formed, and the catalyst has high catalytic activity, comprehensive excellent characteristics of oxidation resistance, corrosion resistance and the like and good application effect. Transition metal oxides are often used as catalysts for catalytic combustion due to their low cost and relatively stable structure.
In microemulsion systems, the dispersed phases are present in sizes smaller than 100 nm, separated from each other to form microreactors. The nano particle catalyst prepared by the microemulsion method has the advantages of small particle size, large specific surface area, narrow distribution, easy control, high catalytic activity, good selectivity, good thermal stability and the like. Although the cobaltosic oxide has good catalytic activity as a catalytic combustion catalyst for hydrocarbon pollutants, the cobaltosic oxide still has the problem of poor thermal stability in the use process. It is easily sintered at high temperature and even converted into inert CoO, thus greatly reducing its catalytic activity. Patent (CN 105817229 a) reports that the anti-sintering performance of cobaltosic oxide can be improved by using a cerium-zirconium solid solution to support cobalt oxide, however, when the catalyst is baked at 500 ℃, the conversion rates of the cobalt oxide can reach 10%, 50% and 90% at 210 ℃, 266 ℃ and 350 ℃, respectively, and the conversion rates of the cobaltosic oxide-supported nano-gold catalyst can reach 10%, 50% and 90% at 200 ℃, 220 ℃ and 260 ℃, respectively, so that the performance of the catalyst can be further improved, which indicates that the method plays a certain role in the high-temperature stability of cobaltosic oxide, and has a very important significance in developing and applying the catalyst.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to: provides a preparation method of cobaltosic oxide supported nano gold catalyst.
The invention further aims to provide a cobaltosic oxide-supported nanogold catalyst product obtained by the preparation method.
Yet another object of the present invention is to: provides the application of the cobaltosic oxide supported nano gold catalyst.
The purpose of the invention is realized by the following scheme: a preparation method of cobaltosic oxide supported nano gold catalyst comprises the following steps:
(1) 100ml of oleylamine in cyclohexane solution was added dropwise to 300ml of 0.1mol/L Co (NO)3)2Stirring the aqueous solution at a high speed for 2 hours to obtain a solution A;
(2) adding a proper amount of cetyl trimethyl ammonium bromide and n-butyl alcohol into 300mL of water, stirring at a high speed for 1h, adding 1mL of 0.01mol/L chloroauric acid solution, stirring at a high speed for 2h to form a uniformly dispersed solution B, dropwise adding the solution A into the solution B, and stirring at a high speed for 3h to obtain a dispersion liquid;
(3) adding 0.05mol/L NaBH4And dropwise adding the aqueous solution into the dispersion liquid, simultaneously introducing 20ml/min of high-purity oxygen to ensure an oxygen-enriched environment, wherein the reaction temperature is 40 ℃, washing the obtained precipitate, drying in a drying oven at 100 ℃ for 12h, and placing in a muffle furnace, wherein the roasting temperature is 300-500 ℃, and the roasting time is 2h, so as to obtain the required catalyst.
The invention utilizes a complexing-oxidizing method to synthesize a novel cobaltosic oxide supported nano gold catalyst in one step, realizes the uniform dispersion of gold nanoparticles, supports noble metal nanoparticles by a transition metal oxide, improves the atom utilization rate of noble metal and effectively reduces the dosage of the noble metal through the interaction of the noble metal and a carrier, and improves the high-temperature stability of the catalyst. The method greatly reduces the cost of the catalyst on the basis of ensuring the activity, so that the method has wider market application prospect.
The invention provides a cobaltosic oxide supported nano gold catalyst obtained by the preparation method. The Au/CoOx supported catalyst effectively reduces the ignition temperature of propane combustion, propane can be completely combusted at 270 ℃, and the working temperature of the Au/CoOx supported catalyst is suitable for heat accumulating type catalytic combustion equipment.
The invention also provides application of the cobaltosic oxide supported nano gold catalyst in catalytic elimination of volatile organic compounds.
The invention has the advantages that: the novel cobaltosic oxide supported nano-gold catalyst is synthesized in one step by using a microemulsion method, the uniform dispersion of gold nanoparticles is realized, and the catalyst has the characteristics of good activity and high-temperature stability and simple preparation method. The cobaltosic oxide supported nano gold catalyst product obtained by the method effectively reduces the ignition temperature of propane combustion, and is suitable for heat accumulating type catalytic combustion equipment.
Drawings
FIG. 1 is a high resolution scanning electron micrograph of the Au/CoOx supported catalyst of example 1.
Detailed Description
The following examples are given to illustrate the invention in more detail with reference to the accompanying drawings, but the invention is not limited thereto. All catalyst activity evaluations for the catalytic combustion of propane were carried out in a fixed-bed microreactor (8 mm internal diameter quartz, 250mm long), with a catalyst dosage of 100mg and a temperature automatically controlled using a K-type thermocouple. The standard steel cylinder gas is mixed with air through a gas distribution system and enters a reactor for combustion. The flow rate was controlled by a mass flow meter, the concentration of propane was 0.1vol%, and the amount of exhaust gas treated per gram of catalyst per hour was 30L. The main reaction products are carbon dioxide and water.
Example 1
A preparation method of a cobaltosic oxide supported nano gold catalyst is characterized by comprising the following steps:
(1) 100ml of oleylamine in cyclohexane solution was added dropwise to 300ml of 0.1mol/L Co (NO)3)2Stirring the aqueous solution at a high speed for 2 hours to obtain a solution A;
(2) adding a proper amount of cetyl trimethyl ammonium bromide and n-butyl alcohol into 300mL of water, stirring at a high speed for 1h, adding 1mL of 0.01mol/L chloroauric acid solution, stirring at a high speed for 2h to form uniformly dispersed solution B, dropwise adding the solution A into the solution B, and stirring at a high speed for 3h to obtain a dispersion liquid;
(3) adding 0.05mol/L NaBH4And (3) dropwise adding the aqueous solution into the dispersion, introducing 20ml/min pure oxygen to ensure an oxygen-enriched environment at the same time, controlling the reaction temperature to be 40 ℃, washing the obtained precipitate, drying the precipitate in a 100 ℃ oven for 12 hours, placing the dried precipitate in a muffle furnace, and roasting the dried precipitate at 300 ℃ for 2 hours to obtain the required cobaltosic oxide-loaded nano gold catalyst. The catalyst was named Au/CoOx-300. A high resolution scanning electron micrograph of the Au/CoOx supported catalyst is shown in FIG. 1.
T in Table 1 below10%、T50%、T90%The reaction temperatures required for the conversions to 10%, 50%, 90%, respectively:
example 2
A preparation method of a cobaltosic oxide supported nano gold catalyst is characterized by comprising the following steps:
(1) 100ml of oleylamine in cyclohexane solution was added dropwise to 300ml of 0.1mol/L Co (NO)3)2Stirring the aqueous solution at a high speed for 2 hours to obtain a solution A;
(2) adding a proper amount of cetyl trimethyl ammonium bromide and n-butyl alcohol into 300mL of water, stirring at a high speed for 1h, adding 1mL of 0.01mol/L chloroauric acid solution, stirring at a high speed for 2h to form uniformly dispersed solution B, dropwise adding the solution A into the solution B, and stirring at a high speed for 3h to obtain a dispersion liquid;
(3) adding 0.05mol/L NaBH4And (3) dropwise adding the aqueous solution into the dispersion, introducing 20ml/min pure oxygen to ensure an oxygen-enriched environment at the same time, controlling the reaction temperature to be 40 ℃, washing the obtained precipitate, drying the precipitate in a 100 ℃ oven for 12 hours, placing the dried precipitate in a muffle furnace, and roasting the dried precipitate at 400 ℃ for 2 hours to obtain the required cobaltosic oxide-loaded nano gold catalyst. The catalyst was named Au/CoOx-400.
T in Table 2 below10%、T50%、T90%The reaction temperatures required for the conversions to 10%, 50%, 90%, respectively:
example 3
A preparation method of a cobaltosic oxide supported nano gold catalyst is characterized by comprising the following steps:
(1) 100ml of oleylamine in cyclohexane solution was added dropwise to 300ml of 0.1mol/L Co (NO)3)2Stirring the aqueous solution at a high speed for 2 hours to obtain a solution A;
(2) adding a proper amount of cetyl trimethyl ammonium bromide and n-butyl alcohol into 300mL of water, stirring at a high speed for 1h, adding 1mL of 0.01mol/L chloroauric acid solution, stirring at a high speed for 2h to form uniformly dispersed solution B, dropwise adding the solution A into the solution B, and stirring at a high speed for 3h to obtain a dispersion liquid;
(3) adding 0.05mol/L NaBH4And (3) dropwise adding the aqueous solution into the dispersion, introducing 20ml/min pure oxygen to ensure an oxygen-enriched environment at the same time, controlling the reaction temperature to be 40 ℃, washing the obtained precipitate, drying the precipitate in a 100 ℃ oven for 12 hours, placing the dried precipitate in a muffle furnace, and roasting the dried precipitate at 500 ℃ for 2 hours to obtain the required cobaltosic oxide-loaded nano gold catalyst. The catalyst was named Au/CoOx-500.
T in Table 3 below10%、T50%、T90%The reaction temperatures required for the conversions to 10%, 50%, 90%, respectively:
the calcination temperature is increased, and the reaction temperature required for the conversion to 10%, 50% or 90% is also increased.
Claims (3)
1. A preparation method of a cobaltosic oxide supported nano gold catalyst is characterized by comprising the following steps:
(1) dissolving 100ml oleylamine in cyclohexane300ml of 0.1mol/L Co (NO) is dropwise added3)2Stirring the aqueous solution at a high speed for 2 hours to obtain a solution A;
(2) adding a proper amount of cetyl trimethyl ammonium bromide and n-butyl alcohol into 300mL of water, stirring at a high speed for 1h, adding 1mL of 0.01mol/L chloroauric acid solution, stirring at a high speed for 2h to form uniformly dispersed solution B, dropwise adding the solution A into the solution B, and stirring at a high speed for 3h to obtain a dispersion liquid;
(3) adding 0.05mol/L NaBH4And dropwise adding the aqueous solution into the dispersion liquid, introducing pure oxygen of 20ml/min to ensure an oxygen-enriched environment at the same time, controlling the reaction temperature to be 40 ℃, washing the obtained precipitate, drying the precipitate in a drying oven at 100 ℃ for 12 hours, placing the dried precipitate in a muffle furnace, and roasting the dried precipitate at the temperature of 300 ℃ and 500 ℃ for 2 hours to obtain the required cobaltosic oxide-loaded nano gold catalyst.
2. A tricobalt tetraoxide-supported nanogold catalyst obtained by the production method according to claim 1.
3. The use of the cobaltosic oxide-supported nanogold catalyst according to claim 2 for catalytic elimination of volatile organic compounds.
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Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103990461A (en) * | 2014-05-16 | 2014-08-20 | 上海纳米技术及应用国家工程研究中心有限公司 | Propane full-catalytic oxidation agent of cobaltosic oxide as well as preparation method and application of oxidation agent |
CN105772027A (en) * | 2016-04-28 | 2016-07-20 | 中国科学院上海高等研究院 | Supported cobaltosic oxide catalyst and preparation method and application thereof |
CN106552630A (en) * | 2016-10-26 | 2017-04-05 | 上海纳米技术及应用国家工程研究中心有限公司 | A kind of spherical CoOXBase catalyst and preparation method and application |
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Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
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CN103990461A (en) * | 2014-05-16 | 2014-08-20 | 上海纳米技术及应用国家工程研究中心有限公司 | Propane full-catalytic oxidation agent of cobaltosic oxide as well as preparation method and application of oxidation agent |
CN105772027A (en) * | 2016-04-28 | 2016-07-20 | 中国科学院上海高等研究院 | Supported cobaltosic oxide catalyst and preparation method and application thereof |
CN106552630A (en) * | 2016-10-26 | 2017-04-05 | 上海纳米技术及应用国家工程研究中心有限公司 | A kind of spherical CoOXBase catalyst and preparation method and application |
Non-Patent Citations (1)
Title |
---|
Fe/Au核壳复合纳米粒子的制备及表征;端木云 等;《东南大学学报(自然科学版)》;20040531;第34卷(第3期);前言部分、第1.2节 * |
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