CN102398901B - Method for high-efficiency purification of single-wall carbon nanotubes prepared by chemical vapor deposition - Google Patents
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- 239000002109 single walled nanotube Substances 0.000 title claims abstract description 108
- 238000000034 method Methods 0.000 title claims abstract description 71
- 238000000746 purification Methods 0.000 title claims abstract description 36
- 238000005229 chemical vapour deposition Methods 0.000 title claims abstract description 33
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 26
- 230000003647 oxidation Effects 0.000 claims abstract description 24
- 229910003481 amorphous carbon Inorganic materials 0.000 claims abstract description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- 238000004455 differential thermal analysis Methods 0.000 claims abstract description 12
- 238000002474 experimental method Methods 0.000 claims abstract description 12
- 238000002411 thermogravimetry Methods 0.000 claims abstract description 10
- 239000008367 deionised water Substances 0.000 claims abstract description 9
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 7
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 7
- 239000002245 particle Substances 0.000 claims abstract description 5
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 3
- 238000001035 drying Methods 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000002360 preparation method Methods 0.000 claims description 18
- 230000001590 oxidative effect Effects 0.000 claims description 9
- 238000004445 quantitative analysis Methods 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 239000008187 granular material Substances 0.000 claims description 5
- 230000036760 body temperature Effects 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract 2
- 238000004140 cleaning Methods 0.000 abstract 1
- 239000002048 multi walled nanotube Substances 0.000 abstract 1
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 239000012159 carrier gas Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000012141 concentrate Substances 0.000 description 3
- 238000005137 deposition process Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
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Abstract
The invention relates to the field of single-wall carbon nanotubes, and specifically, relates to a method for high-efficiency purification of single-wall carbon nanotubes prepared by chemical vapor deposition. The method has high efficiency, is simple and is suitable for industrialization. The method comprises the following steps of uniformly placing single-wall carbon nanotubes prepared by chemical vapor deposition in a horizontal heating furnace, carrying out oxidation in an air atmosphere at an amorphous carbon rapid oxidation temperature for 5 to 20 hours, immersing the oxidized single-wall carbon nanotubes in a hydrochloric acid solution to remove catalyst particles, cleaning the single-wall carbon nanotubes treated by the previous step by deionized water multiple times, and drying to obtain a purified single-wall carbon nanotube sample. The method is simple, is suitable for large-scale industrialized production and purification of single-wall carbon nanotubes or multi-wall carbon nanotubes prepared by chemical vapor deposition, and has important industrial application prospects. The method can determine a sample oxidation temperature through a thermogravimetric/differential thermal analysis experiment and thus solving the problem that because carbon nanotubes prepared by the existing chemical vapor deposition under different conditions and carbon nanotubes which have different production batch numbers and are prepared under the same conditions are different in inoxidizability, purification purity and a yield cannot be controlled accurately.
Description
Technical field
The present invention relates to the Single Walled Carbon Nanotube field, be specially efficient, simple, the capable of being industrialized method of purification of the Single Walled Carbon Nanotube of chemical Vapor deposition process preparation.
Background technology
Single Walled Carbon Nanotube because its particular structure has unusual physics-chem characteristic and excellent electricity and mechanical property, has had broad application prospects in nanoelectronic element, an emission and prepare composite since 1993 are found.All these tempting application prospects are that acquisition with high-purity, a large amount of, cheap Single Walled Carbon Nanotube is prerequisite.In three kinds of methods of traditional preparation process Single Walled Carbon Nanotube (chemical Vapor deposition process, arc process, laser evaporation method), but chemical Vapor deposition process is simple because of it, a large amount of, cheap and characteristics such as mass-producing obtain people's favor.Yet the purity of the Single Walled Carbon Nanotube of chemical Vapor deposition process preparation at present is also lower, and the method for therefore seeking the Single Walled Carbon Nanotube that the chemical vapor deposition method of a kind of simple, efficient, capable of being industrialized purification is equipped with becomes the bottleneck of restriction Single Walled Carbon Nanotube industrial applications.
Be found beginning from Single Walled Carbon Nanotube, the Purification of Single Walled Carbon Nanotube is one of main direction of studying of scientific workers always, especially the Purification of the Single Walled Carbon Nanotube of chemical Vapor deposition process preparation.The method of the Single Walled Carbon Nanotube that the chemical vapor deposition method of existing purification is equipped with mainly is divided into the method (document 1 of chemical method, physics method and physics and chemofacies combination, Chiang IW, Brinson BE, Huang AY, Willis PA, Bronikowski MJ, Margrave JL, et al.J Phys Chem B105 (35): 8297-301 (2001); Document 2, Hou PX, Bai S, Yang QH, Liu C, Cheng HM.Carbon 40 (1): 81-5 (2002)).Chemical method is simple because of purification process, the purification amount big and but characteristics such as mass-producing are subjected to people's attention, and the subject matter of this method is: in the process of removing impurity such as amorphous carbon, the intrinsic structure of carbon nanotube is also destroyed.In addition, because that chemical Vapor deposition process prepares in the process of Single Walled Carbon Nanotube contingent condition is very many, so quality, the purity of the Single Walled Carbon Nanotube produced of different condition and different batches are all different.And at present many chemical purification methods of report only are applicable to the Single Walled Carbon Nanotube that each investigator studies respectively, and the sample of different condition or different batches is difficult to realize guarantee when purifying back single wall carbon nano pipe purity and productive rate.
Summary of the invention
The object of the present invention is to provide the method for the Single Walled Carbon Nanotube that the chemical vapor deposition method of a kind of pervasive, efficient purification is equipped with, do not destroy the intrinsic structure of Single Walled Carbon Nanotube, solved at present in the method for purification to the Single Walled Carbon Nanotube of different condition and the preparation of different batches chemical Vapor deposition process, purification productive rate and purity such as can't guarantee simultaneously at problem.
In addition, the present invention has also solved the bottleneck problem that the industrial applications of present restriction Single Walled Carbon Nanotube runs into.
Technical scheme of the present invention is:
The method of the Single Walled Carbon Nanotube that the chemical vapor deposition method of a kind of efficient purification is equipped with, the Single Walled Carbon Nanotube of chemical Vapor deposition process preparation is evenly placed in the horizontal process furnace, under air atmosphere and the quick oxidizing temperature of amorphous carbon, carry out long-time (5-20h) oxidation; Sample after the oxidation is soaked in the hydrochloric acid soln removes granules of catalyst and repeatedly clean with deionized water.After the drying, can obtain pure Single Walled Carbon Nanotube sample.
The present invention is pervasive, the purify method of the Single Walled Carbon Nanotube that chemical vapor deposition method is equipped with efficiently, under the prerequisite of not destroying Single Walled Carbon Nanotube intrinsic structure, can realize simultaneously to Single Walled Carbon Nanotube the purification productive rate (>90wt%) and purity (>98wt%) accurate control.
Among the present invention, the oxidizing temperature of amorphous carbon is determined by the thermogravimetric curve of this batch sample, and is specific as follows:
With the Single Walled Carbon Nanotube of a small amount of different condition or different batches preparation (~3mg) carry out thermogravimetric/differential thermal analysis experiment earlier, the quick oxidizing temperature (being generally 270-400 ℃) of amorphous carbon can be analyzed from this empirical curve surely grandly, and the content of amorphous carbon, carbon nanotube and metal catalyst can be analyzed quantitatively.A large amount of this kind Single Walled Carbon Nanotube samples evenly are positioned in the horizontal process furnace, concentrate under the temperature of oxidation at the amorphous carbon that thermogravimetric/the differential thermal analysis experiment is determined, long-time oxidation (5-20h), after treating the furnace body temperature cool to room temperature, sample is taken out, place hydrochloric acid soln to soak and remove catalyst particle, clean repeatedly, until hydrochloric acid soln no longer till the variable color, and with washed with de-ionized water repeatedly, be 7 until pH; Vacuum-drying can obtain purity>98wt% at last, the Single Walled Carbon Nanotube sample of productive rate>90wt% (only calculating the productive rate of Single Walled Carbon Nanotube).
The temperature of described hydrochloric acid soln is 60-100 ℃, and concentration is 15-35wt%.
The purity of the described back Single Walled Carbon Nanotube of purifying is according to thermogravimetric/differential thermal curve quantitative Analysis, and the intrinsic structure of carbon nanotube whether destroy also be to obtain (the oxidation peak invariant position of Single Walled Carbon Nanotube before and after purifying) according to thermogravimetric/differential thermal curve is qualitative.
The weight ratio of Single Walled Carbon Nanotube before and after described productive rate refers to purify calculates according to following formula:
{ (the weight * of the back Single Walled Carbon Nanotube sample of purifying (after the purification that quantitatively obtains according to thermogravimetric/differential thermal curve in the sample weight percent of Single Walled Carbon Nanotube) }/(the weight * of original Single Walled Carbon Nanotube sample (weight percent of Single Walled Carbon Nanotube in the primary sample that quantitatively obtains according to thermogravimetric/differential thermal curve) }.(formula 1)
How many described concrete oxidization times is determined according to the content of amorphous carbon in the primary sample.
Among the present invention, the specification of Single Walled Carbon Nanotube (diameter, length, purity, oxidation resistance temperature etc.) is unrestricted, but is only limited to the Single Walled Carbon Nanotube of chemical Vapor deposition process preparation.
Advantage of the present invention is:
1, the inventive method is with Single Walled Carbon Nanotube low temperature, long-time oxidation in air of chemical Vapor deposition process preparation, in impurity such as efficient removal amorphous carbon and catalyst particle, the intrinsic structure of not broken ring Single Walled Carbon Nanotube, purity and the productive rate of the Single Walled Carbon Nanotube sample of different condition and different batches can accurately be controlled.
2, the inventive method is applicable to the Single Walled Carbon Nanotube sample of all chemical Vapor deposition process preparations, and can guarantee purity and the productive rate of carbon nanotube simultaneously.
3, but the inventive method has simply, low consumption, is easy to enlarge, can repeats characteristics such as industrialization.
Description of drawings
Fig. 1. the differential thermogravimetric curve before and after the Single Walled Carbon Nanotube sample of chemical Vapor deposition process preparation of the present invention is purified; Wherein, (a) for before purifying; (b) for after purifying.
Fig. 2. the stereoscan photograph before and after Single Walled Carbon Nanotube sample of the present invention is purified; Wherein, a is for before purifying; B is for after purifying.
Embodiment
Below by embodiment in detail the present invention is described in detail.
Embodiment 1.
Get and utilize floating catalytic agent vapour deposition process (1000 ℃ of temperature of reaction, be catalyzer with the ferrocene, 200ml/min hydrogen is carrier gas, 4ml/min methane is carbon source) preparation Single Walled Carbon Nanotube sample 3mg, in the present embodiment, the specification of Single Walled Carbon Nanotube is as follows: diameter Distribution is 0.8-3.0nm, and purity is: 30wt%, oxidation resistance temperature is: 460 ℃.
Carry out thermogravimetric/differential thermal analysis experiment under air atmosphere, the thermogravimetric/differential thermal curve that obtains is shown in Fig. 1 (a).Be 350~370 ℃ according to the qualitative concentrated oxidizing temperature that draws amorphous carbon of this thermogravimetric curve, wherein the weight percent of amorphous carbon, granules of catalyst and Single Walled Carbon Nanotube is respectively 5%, 65% and 30%.It is 22mm that above-mentioned Single Walled Carbon Nanotube sample 20mg is evenly placed internal diameter, and flat-temperature zone length is in the horizontal heating furnace tube of 4cm, feeds the air of 100ml/min, at 370 ℃ of following oxidation 10h.After treating the sample cool to room temperature, take out and be soaked in the hydrochloric acid soln (concentration is 35wt%) at 60 ℃ and clean repeatedly down, until hydrochloric acid soln no longer till the variable color.Be 7 with this sample of washed with de-ionized water until pH, at 120 ℃ of this sample of following vacuum-drying 5h, weighing is taken out in the cooling back, and this example weight is 5.43mg.Get the Single Walled Carbon Nanotube sample 3mg after the purification, carry out thermogravimetric/differential thermal analysis experiment under air atmosphere, the thermogravimetric/differential thermal curve that obtains is shown in Fig. 1 (b).The purity that goes out Single Walled Carbon Nanotube from this curve quantitative Analysis is 99wt%, the productive rate that can calculate Single Walled Carbon Nanotube according to formula 1 is 90.5wt%, and the oxidation peak of Single Walled Carbon Nanotube is for being 460 ℃ among Fig. 1, the intrinsic structure of this proof Single Walled Carbon Nanotube does not change before and after purifying, and stereoscan photograph (Fig. 2) has also proved the high efficiency of this purification process simultaneously.
Embodiment 2.
Get floating catalytic agent vapour deposition process (1100 ℃ of the temperature of reaction of utilizing embodiment 1, be catalyzer with the ferrocene, 200ml/min hydrogen is carrier gas, 4ml/min methane is carbon source) preparation Single Walled Carbon Nanotube sample 1g, evenly placing internal diameter is 45mm, flat-temperature zone length is in the horizontal heating furnace tube of 10cm, feeds the air of 1000ml/min, at 370 ℃ of following oxidation 20h.After treating the sample cool to room temperature, take out and be soaked in the hydrochloric acid soln (concentration is 20wt%) at 80 ℃ and clean repeatedly down, until hydrochloric acid soln no longer till the variable color.Be 7 with this sample of washed with de-ionized water until pH, at 120 ℃ of this sample of following vacuum-drying 5h, weighing is taken out in the cooling back, and this example weight is 0.28g.Get the Single Walled Carbon Nanotube sample 3mg after the purification, carry out thermogravimetric/differential thermal analysis experiment under air atmosphere, the purity that goes out Single Walled Carbon Nanotube from this curve quantitative Analysis is 98wt%, and the productive rate that can calculate Single Walled Carbon Nanotube according to formula 1 is 91wt%.
Embodiment 3.
With the Single Walled Carbon Nanotube 3mg that the Hipco method of buying prepares, in the present embodiment, the specification of Single Walled Carbon Nanotube is as follows: diameter Distribution is at 0.6-1.3nm, and purity is: 95wt%, oxidation resistance temperature is: 500 ℃.
Under air atmosphere, carry out thermogravimetric/differential thermal analysis experiment, draw amorphous carbon to concentrate the temperature of oxidation be 350 ℃ according to this thermogravimetric curve is qualitative, wherein the weight percent of amorphous carbon and Single Walled Carbon Nanotube is respectively 2%, 95%, and all the other account for 3% for granules of catalyst.It is 22mm that above-mentioned Single Walled Carbon Nanotube sample 50mg is evenly placed internal diameter, and flat-temperature zone length is in the horizontal heating furnace tube of 4cm, feeds the air of 100ml/min, at 325 ℃ of following oxidation 10h.After treating the sample cool to room temperature, take out and be soaked in the hydrochloric acid soln (concentration is 35wt%) at 90 ℃ and clean repeatedly down, until hydrochloric acid soln no longer till the variable color.Be 7 with this sample of washed with de-ionized water until pH, at 120 ℃ of this sample of following vacuum-drying 5h, weighing is taken out in the cooling back, and this example weight is 46.25mg.Get the Single Walled Carbon Nanotube sample 3mg after the purification, carry out thermogravimetric/differential thermal analysis experiment under air atmosphere, the purity that goes out Single Walled Carbon Nanotube from this curve quantitative Analysis is 99.5wt%, and the productive rate that can calculate Single Walled Carbon Nanotube according to formula 1 is 97wt%.
Embodiment 4.
Get and utilize floating catalytic agent vapour deposition process (1100 ℃ of temperature of reaction, be catalyzer and carbon source with the ferrocene, 200ml/min hydrogen is carrier gas) preparation Single Walled Carbon Nanotube 3mg, in the present embodiment, the specification of Single Walled Carbon Nanotube is as follows: diameter Distribution is 0.7-3.5nm, purity is: 35wt%, oxidation resistance temperature is: 600 ℃.
Under air atmosphere, carry out thermogravimetric/differential thermal analysis experiment, draw amorphous carbon to concentrate the temperature of oxidation be 390 ℃ according to this thermogravimetric curve is qualitative, wherein the weight percent of amorphous carbon and Single Walled Carbon Nanotube is respectively 5wt% and 27wt%, and all the other are granules of catalyst.It is 22mm that above-mentioned Single Walled Carbon Nanotube sample 50mg is evenly placed internal diameter, and flat-temperature zone length is 4cm, horizontal heating furnace tube in, feed the air of 100ml/min, at 370 ℃ of following oxidation 10h.After treating the sample cool to room temperature, take out and be soaked in the hydrochloric acid soln (concentration is 35wt%) at 80 ℃ and clean repeatedly down, until hydrochloric acid soln no longer till the variable color.Be 7 with this sample of washed with de-ionized water until pH, at 120 ℃ of this sample of following vacuum-drying 5h, weighing is taken out in the cooling back, and this example weight is 12.25mg.Get the Single Walled Carbon Nanotube sample 3mg after the purification, carry out thermogravimetric/differential thermal analysis experiment under air atmosphere, the purity that goes out Single Walled Carbon Nanotube from this curve quantitative Analysis is 99wt%, and the productive rate that can calculate Single Walled Carbon Nanotube according to formula 1 is 90wt%.
Embodiment result shows, the present invention can determine chemical Vapor deposition process in cleansing temp and the time of the Single Walled Carbon Nanotube sample of different condition/batch preparation qualitatively by thermogravimetric/differential thermal curve, and this method is applicable to the Single Walled Carbon Nanotube sample of all chemical Vapor deposition process preparations; This method of purification is not destroyed the intrinsic structure of Single Walled Carbon Nanotube when removing impurity such as amorphous carbon and catalyst particle; The purity that this method of purification can guarantee to purify simultaneously (>98wt%) and the productive rate of Single Walled Carbon Nanotube (>90wt%); But and characteristics such as this method of purification has simply, a large amount of, low-cost industrialization.
Claims (7)
1. the method for the Single Walled Carbon Nanotube that is equipped with of the efficient chemical vapor deposition method of purifying, it is characterized in that: the Single Walled Carbon Nanotube of chemical Vapor deposition process preparation is evenly placed in the horizontal process furnace, under air atmosphere and the quick oxidizing temperature of amorphous carbon, carry out the 5-20h oxidation; Sample after the oxidation is soaked in the hydrochloric acid soln removes granules of catalyst and repeatedly clean with deionized water; After the drying, can obtain pure Single Walled Carbon Nanotube sample;
The quick oxidizing temperature of amorphous carbon is determined by the thermogravimetric curve of this batch sample, be specially: the Single Walled Carbon Nanotube of different condition or different batches preparation is carried out thermogravimetric/differential thermal analysis experiment earlier, go out the quick oxidizing temperature of amorphous carbon from this empirical curve qualitatively analyze, and can analyze the content of amorphous carbon, carbon nanotube and metal catalyst quantitatively;
The quick oxidizing temperature of described amorphous carbon is 270~400 ℃.
2. the method for the Single Walled Carbon Nanotube that is equipped with according to the chemical vapor deposition method of the described efficient purification of claim 1, it is characterized in that: under the prerequisite of not destroying Single Walled Carbon Nanotube intrinsic structure, realize simultaneously the purification productive rate of Single Walled Carbon Nanotube and the accurate control of purity; Wherein, the purification productive rate>90wt% of Single Walled Carbon Nanotube, the purity>98wt% of Single Walled Carbon Nanotube.
3. the method for the Single Walled Carbon Nanotube that is equipped with according to the chemical vapor deposition method of the described efficient purification of claim 1, it is characterized in that, the Single Walled Carbon Nanotube sample evenly is positioned in the horizontal process furnace, under the quick oxidizing temperature of amorphous carbon that thermogravimetric/the differential thermal analysis experiment is determined, carry out the 5-20h oxidation, after treating the furnace body temperature cool to room temperature, sample is taken out, place hydrochloric acid soln to soak and remove catalyst particle, clean repeatedly, until hydrochloric acid soln no longer till the variable color, and with washed with de-ionized water repeatedly, be 7 until pH; After the vacuum-drying, obtain the Single Walled Carbon Nanotube sample of purity>98wt%, productive rate>90wt%.
4. the method for the Single Walled Carbon Nanotube that is equipped with according to claim 2 or the chemical vapor deposition method of 3 described efficient purifications is characterized in that, the weight ratio of Single Walled Carbon Nanotube before and after productive rate refers to purify calculates according to following formula:
{ (the weight * of the back Single Walled Carbon Nanotube sample of purifying (after the purification that quantitatively obtains according to thermogravimetric/differential thermal curve in the sample weight percent of Single Walled Carbon Nanotube) }/(the weight * of original Single Walled Carbon Nanotube sample (weight percent of Single Walled Carbon Nanotube in the primary sample that quantitatively obtains according to thermogravimetric/differential thermal curve) }.
5. the method for the Single Walled Carbon Nanotube that is equipped with according to claim 2 or the chemical vapor deposition method of 3 described efficient purifications, it is characterized in that, the purity of the back Single Walled Carbon Nanotube of purifying is according to thermogravimetric/differential thermal curve quantitative Analysis, whether the intrinsic structure of the back Single Walled Carbon Nanotube of purifying is destroyed also is to obtain according to thermogravimetric/differential thermal curve is qualitative, the oxidation peak invariant position of Single Walled Carbon Nanotube before and after purifying, then the intrinsic structure does not change before and after purifying.
6. the method for the Single Walled Carbon Nanotube that is equipped with according to claim 1 or the chemical vapor deposition method of 3 described efficient purifications is characterized in that the temperature of hydrochloric acid soln is 60-100 ℃, and concentration is 15-35wt%.
7. the method for the Single Walled Carbon Nanotube that is equipped with according to claim 1 or the chemical vapor deposition method of 3 described efficient purifications is characterized in that, concrete oxidization time is determined according to the content of amorphous carbon in the thermogravimetric curve.
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Effective date of registration: 20221208 Address after: 110000 Room 606, No. 39-1, Chuangxin Second Road, China (Liaoning) pilot Free Trade Zone, Hunnan District, Shenyang City, Liaoning Province Patentee after: WeCarbon Nanotechnology (Shenyang) Co.,Ltd. Address before: 110016 No. 72, Wenhua Road, Shenhe District, Liaoning, Shenyang Patentee before: INSTITUTE OF METAL RESEARCH CHINESE ACADEMY OF SCIENCES |
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