CN109778214B - Method for rapidly and selectively filling nano particles into carbon nano tube cavity - Google Patents
Method for rapidly and selectively filling nano particles into carbon nano tube cavity Download PDFInfo
- Publication number
- CN109778214B CN109778214B CN201711130179.2A CN201711130179A CN109778214B CN 109778214 B CN109778214 B CN 109778214B CN 201711130179 A CN201711130179 A CN 201711130179A CN 109778214 B CN109778214 B CN 109778214B
- Authority
- CN
- China
- Prior art keywords
- carbon
- nano
- particles
- electrolytic cell
- filling
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Abstract
The invention relates to the field of carbon nano tube composite structures, in particular to a method for quickly and selectively filling nano particles into a hollow tube cavity of a carbon nano tube driven by electric field force. Assembling the anodic aluminum oxide sheet deposited with the thin-layer carbon on an electrolytic cell device, injecting an electrolyte solution of elements to be filled into an electrolytic cell, inserting electrodes, applying direct-current voltage between the two electrodes to rapidly fill the electrolyte into the anodic aluminum oxide nanometer pore channel coated by the carbon layer, taking out the anodic aluminum oxide sheet, performing heat treatment, and finally removing an anodic aluminum oxide sheet template to obtain the carbon nanometer tube composite structure filled with the nanometer particles. The nano particles are selectively filled in the carbon nano tube cavities with openings at two ends and are uniformly distributed. The method has a rapid filling process, and only needs 0.5 second to 5 minutes; the filling amount is accurate and controllable, and the carbon nano tube cavity can be filled up to the highest content. The problems that the existing process for filling the nano particles in the carbon nano tubes is complex, long in time consumption, difficult to fill in a large amount and the like are effectively solved.
Description
Technical Field
The invention relates to the field of carbon nano tube composite structures, in particular to a method for quickly and selectively filling nano particles into a hollow tube cavity of a carbon nano tube driven by electric field force.
Background
The hollow tube cavity of the carbon nano tube is a typical one-dimensional confinement space, and due to the special electronic structure and confinement effect of the carbon nano tube, the substances in the carbon nano tube are obviously different from macroscopic materials in the aspects of crystallinity, magnetism, electrical properties, chemical catalytic activity and the like. The novel nano structure formed by compounding the carbon nano tube and the nano particles in the carbon nano tube has the advantages of two single materials, has large specific surface area, abundant pore structures and good structural stability, shows excellent conductivity, electrochemical catalytic activity and the like, has great potential to be applied as a catalytic material or an electrode material and the like, and can control the preparation of the nano particle filled carbon nano tube composite structure, which is the basis of related foundation and application research.
Currently, there are physical adsorption methods (literature, Kumiko Ajima, Masako Yudasaka, Tatsuya Murakami, Alan Meigne, Kiyotaka Shiba, Sumio Ijima, Molecular pharmaceuticals.2 (6): 475) 480(2005)), wet (solution) methods (literature, Hongkun Zhang, Huaihe Song, Xiaohong Chen, Jisheng Zhou, J.Phys.Chem.C (116): 22774) 22779(2012)), and vapor phase filling methods (literature, Nanrun Thamauranaukup, Heing A).
Luisa Ruiz-Gonzalez, Pedr M.F.J.Costa, Jermey Sloan, Angus Kirkland, Malcolm L.H.Green, Chemi.Commun. (15): 1686-. Each method has its scope of application, but also has problems such as: the nano particles are difficult to be selectively filled into the carbon nano tube cavity by 100 percent, the filling process has long time consumption, low filling efficiency, uncontrollable filling process, single filling species and the like. Most of the work requires cutting and opening of carbon nanotubes in an oxidizing acid solution (reference 1, Pan XL, Fan ZL, Cheng W, Ding YJ, Luo HY, Bao XH. Nature Materials 6:507 (2007); reference 2, Zhang J, Muller JO, ZHENG WQ, Wang D, Su DS, Schlogl R. Nano Letters 8:2738(2008)), and the uniformity of the obtained composite material is poor.
In addition, the inventor uses the anodic alumina deposited with a carbon layer as a template in the earlier stage, and selectively fills silicon particles, iron oxide and other nanoparticles into the hollow carbon nanotube cavity by respectively adopting a chemical vapor deposition method and a liquid phase immersion method (Chinese patent application 1, Houpeng, well-known scenery, Lishi Sheng, Liu Chang, Cheng Ming, a method for selectively filling iron oxide particles into the hollow carbon nanotube cavity, patent number ZL 200810229969.0; Chinese patent application 2, Liu Chang, well-known scenery, Houpeng Xiang, Cheng Ming, a carbon nanotube composite filled with silicon nanoparticles and a preparation method and application thereof, patent number ZL 201210566788.3); the two methods still have the defects of complex filling process, long filling time, limited filling material types, difficult achievement of high filling rate (the maximum filling rate is 70 percent by weight) and the like.
The key problems to be solved at present are as follows: how to develop an economic, rapid and effective filling method to realize controllable filling without limitation on the types and filling amounts of nano particles in the carbon nano tubes.
Disclosure of Invention
The invention aims to provide a method for quickly and selectively filling nano particles into a hollow cavity of a carbon nano tube driven by electric field force, which solves the problems of complex filling process, time-consuming filling process, poor controllability, difficult large-scale filling and the like.
The technical scheme of the invention is as follows:
a method for filling nano particles into a carbon nano tube cavity rapidly and selectively comprises the steps of assembling an anodic aluminum oxide sheet deposited with thin-layer carbon on an electrolytic cell device, dividing an electrolytic cell main body of the electrolytic cell device into two independent electrolytic cells through a combined body, respectively inserting an electrode into each electrolytic cell, injecting an electrolyte solution needing elements to be filled into each electrolytic cell, applying 1-50V direct-current voltage between the two electrodes, filling nano particles for 0.5 second to 5 minutes, taking down the anodic aluminum oxide sheet, performing heat treatment, and removing the anodic aluminum oxide sheet to obtain a carbon nano tube composite structure filled with the nano particles; wherein the anodic aluminum oxide sheet is provided with a through nanometer pore canal with the pore diameter of 20-100 nm.
The method for filling nano particles into the carbon nano tube cavity rapidly and selectively comprises the following steps that an electrolytic cell device comprises an electrolytic cell main body and a combination body, the electrolytic cell main body is provided with an electrode I, an electrode II, a sealing rubber strip I and a sealing rubber strip II, the combination body is provided with an organic glass sheet I, a rubber sealing gasket II, an organic glass sheet II and an anodic oxidation aluminum sheet, and the specific structure is as follows:
the recess of assembly top-down inserted electrolysis trough main part, and two electrolytic bath are separated into by organic glass piece I, the sealed I of rubber packing, anodic oxidation aluminum sheet, the sealed II of rubber packing, the assembly of organic glass piece II: the device comprises an electrolytic cell I and an electrolytic cell II, wherein a sealing rubber strip I is arranged at the matching position of a combination body and the electrolytic cell I, a sealing rubber strip II is arranged at the matching position of the combination body and the electrolytic cell II, an electrode I is inserted in the electrolytic cell I, and an electrode II is inserted in the electrolytic cell II; after assembly, a nanoparticle-filled device is formed;
carbon-layer coated anodic oxidation aluminum sheet presss from both sides at the rubber packing pad I of center trompil, the middle of rubber packing pad II, carbon-layer coated anodic oxidation aluminum sheet and rubber packing pad I, the shape of rubber packing pad II center trompil, the size is the same, carbon-layer coated anodic oxidation aluminum sheet covers rubber packing pad I completely, the center trompil of rubber packing pad II, organic glass piece I, II centre grippings of organic glass piece are in rubber packing pad I, II outsides of rubber packing pad, one side symmetry that organic glass piece II and rubber packing pad II correspond sets up the fixed pin, rubber packing pad I, set up the pilot hole that corresponds with the fixed pin on rubber packing pad II and the organic glass piece I, rubber packing pad II, organic glass piece II passes through fixed.
The method for rapidly and selectively filling the nano particles into the carbon nano tube cavity comprises the following steps of: the electrode I and the electrode II are inert electrodes, and when the electrodes are electrified, the electrodes have a conductive effect and do not react with the electrolyte.
According to the method for rapidly and selectively filling the nano particles into the carbon nano tube cavity, the same or different electrolyte solutions are adopted in the two electrolytic baths, and when different electrolyte solutions are contained in the two electrolytic baths, two electrolytes and the direction of an electric field are selected according to needs, so that the nano particles are directly and rapidly synthesized in the carbon nano tube hollow tube cavity.
According to the method for rapidly and selectively filling the nano particles into the carbon nano tube cavity, the anode aluminum oxide sheet coated by the carbon layer is replaced by other sheet-shaped and through hole materials with similar structures, so that the nano particles can be rapidly filled in various nano tube or porous material nano pore channels.
The method for rapidly and selectively filling the nano particles into the carbon nano tube cavity has the heat treatment condition determined according to the required particle structure, the atmosphere is one or more than two mixed gases of air, argon, nitrogen and hydrogen, and the temperature is 50-1000 ℃.
According to the method for rapidly and selectively filling the nano particles into the carbon nano tube cavity, the content of the nano particles in the carbon nano tube is accurately regulated and controlled by the concentration of the electrolyte solution and the voltage application time, and the content of the nano particles is accurately controllable within the range of 0.5-95 wt%.
According to the method for rapidly and selectively filling the nano particles into the carbon nano tube cavity, the nano particles show different appearances along with the content change, exist in a particle form when the content is low, and fill the carbon nano tube cavity to form the nano rod when the content is high.
According to the method for rapidly and selectively filling the nano particles into the carbon nano tube cavity, when the content of the nano particles is less than 75wt%, the nano particles exist in a particle form.
According to the method for rapidly and selectively filling the nano particles into the carbon nano tube cavity, due to the physical isolation effect of the anodic aluminum oxide on the outer wall of the carbon nano tube, 100% of the nano particles are filled in the hollow tube cavity of the carbon nano tube.
The design idea of the invention is as follows:
in order to realize high-content and controllable filling of nano particles in a hollow tube cavity of the carbon nano tube, positive and negative ions in electrolyte can only move in opposite directions through an anodic alumina pore passage coated by a carbon layer under the drive of electric field force by designing an electrolytic cell structure, the positive and negative ions are combined in the nano pore passage, and water-insoluble substances directly generate the nano particles; the water-soluble substance forms a high-concentration salt solution in the nano-pore, the high-concentration salt solution is uniformly filled in the nano-pore, and the uniformly filled nano-particles can be obtained through later-stage heat treatment.
The invention has the advantages and beneficial effects that:
1. the invention provides a method for rapidly and controllably filling nano particles in a hollow cavity of a carbon nano tube, wherein the nano particles are selectively filled in the hollow cavity of the carbon nano tube, the filling process only needs 0.5 second-5 minutes, the aging is greatly improved, and the technical problem that the filling process of other methods usually needs hours to days and consumes long time is solved.
2. The invention provides a controllable filling method of various nano particles in a hollow tube cavity of a carbon nano tube, which greatly enriches the carbon nano tube composite material with the structure.
3. The invention provides a filling method with controllable nano particle content, which can realize controllable filling of nano particles with the content of 0.5-95 wt% and unlimited types only by short-time direct current charging in an electrolytic cell. The nano particles filled by the method are uniform in distribution and accurate and controllable in content, and the types and the filling amount of the nano particles are not limited. The filling amount is accurately controlled by the conditions such as electrolyte concentration, voltage application time and the like, and the filling method has remarkable advantages particularly in the aspect of large-amount filling and can fill the hollow tube cavity of the carbon nano tube.
4. The method has simple process, does not need expensive equipment in the filling process, and is an economic, simple and efficient method for filling the nano particles in the carbon nano tubes.
5. The carbon nano tube filled with the nano particles prepared by the method can be used as a nano reactor for in-situ research, and can be used as an electrochemical energy storage material or a catalytic material and the like.
Drawings
FIG. 1 is a schematic view of an electrolytic cell apparatus used in the present invention; wherein, (a), (b), (c) are the front view, left side view, top view of the electrolytic cell body assembled with electrode and sealing rubber strip; (d) the (e) and (f) are respectively an exploded view, a front view and a left view of the combined body of the organic glass sheet and the rubber sealing gasket; (g) is a left view of the device after the combination body is assembled with the main body of the electrolytic bath. In the figure, 1 an electrolytic cell main body; 2, an electrode I; 3, an electrode II; 4, sealing the rubber strip I; 5, sealing the rubber strip II; 6, an organic glass sheet I; 7, a rubber sealing gasket I; 8, a rubber sealing gasket II; 9 organic glass sheet II; 10 anodizing an aluminum sheet; 11, assembling holes; 12 a fixing pin; 13 assembly; 14 grooves; a, an electrolytic cell I; b, an electrolytic cell II.
FIG. 2 is an electron micrograph of nickel nanoparticle-filled carbon nanotubes prepared in example 1; wherein, (a) is a scanning electron micrograph; (b) is a transmission electron microscope photograph.
FIG. 3 is an electron micrograph of iron oxide nanoparticle-filled carbon nanotubes prepared in example 2; wherein, (a) is a scanning electron micrograph; (b) is a transmission electron microscope photograph.
FIG. 4 is an electron micrograph of silver chloride nanorod-filled carbon nanotubes prepared in example 4; wherein, (a) is a scanning electron micrograph; (b) is a transmission electron microscope photograph.
Detailed Description
As shown in figure 1, the electrolysis trough device includes electrolysis trough main part 1 and assembly 13, and electrolysis trough main part 1 sets up electrode I2, electrode II 3, sealing rubber strip I4, sealing rubber strip II 5, and assembly 13 sets up organic glass piece I6, rubber seal pad I7, rubber seal pad II 8, organic glass piece II 9, anodic oxidation aluminum sheet 10, and concrete structure is as follows:
the combination body 13 is inserted into the groove 14 of the electrolytic bath main body 1 from top to bottom, the electrolytic bath main body 1 is divided into two electrolytic cells by the combination body 13 of an organic glass sheet I6, a rubber sealing gasket I7, an anodic oxidation aluminum sheet 10, a rubber sealing gasket II 8 and an organic glass sheet II 9: electrolytic bath IA, electrolytic bath IIB, assembly 13 sets up sealing rubber strip I4 with electrolytic bath IA cooperation department, and assembly 13 sets up sealing rubber strip II 5 with electrolytic bath IIB cooperation department, and cartridge electrode I2 (inert electrode) in the electrolytic bath IA, cartridge electrode II 3 (inert electrode) in the electrolytic bath IIB. The assembled electrolytic cell device is used as a filling device of nano particles.
The carbon layer coated anodic aluminum oxide sheet 10 is clamped between the rubber sealing gasket I7 with a central hole, the rubber sealing gasket II 8 is arranged in the middle, the carbon layer coated anodic aluminum oxide sheet 10 is identical to the rubber sealing gasket I7, the shape and the size of the central hole of the rubber sealing gasket II 8 are identical, the carbon layer coated anodic aluminum oxide sheet 10 completely covers the rubber sealing gasket I7, the central hole of the rubber sealing gasket II 8, the organic glass sheet I6, the organic glass sheet II 9 is clamped between the rubber sealing gasket I7 and the outer side of the rubber sealing gasket II 8, the fixing pins 12 are symmetrically arranged on one side of the organic glass sheet II 9 corresponding to the rubber sealing gasket II 8, the rubber sealing gasket I7, the rubber sealing gasket II 8 and the organic glass sheet I6 are provided with the assembling holes 11 corresponding to the fixing pins 12, the organic glass sheet I6, the rubber sealing gasket I7, the rubber sealing, forming a combined product 13.
In the specific implementation process, the method for quickly and selectively filling the nano particles into the hollow cavity of the carbon nano tube driven by electric field force comprises the steps of assembling an anodic aluminum oxide sheet coated by a carbon layer on an electrolytic cell device, injecting an electrolyte solution of elements to be filled and inserting electrodes, applying 1-50V direct current voltage between the two electrodes for 0.5 second to 5 minutes, then taking the anodic aluminum oxide sheet down, treating at a certain atmosphere and temperature, and finally removing an anodic aluminum oxide sheet template to obtain a carbon nano tube composite structure filled with the nano particles, wherein the nano particles are uniformly distributed, and the content of the nano particles is accurately controllable within the range of 0.5-95 wt%.
After the two electrolytic cells are filled with electrolyte, the front and back surfaces of the anodic aluminum oxide sheet coated by the sheet carbon layer are contacted with the electrolyte, but the electrolyte cannot enter the nanometer pore canal due to the action of interfacial tension. Under the drive of an external electric field, positive ions and negative ions which belong to two electrolytic cells enter a nanometer pore canal of the anodic aluminum oxide sheet coated by the carbon layer along with the solution, nanometer particles (such as silver chloride particles) or high-concentration salt solution (such as ferric nitrate solution) which are insoluble in the water solution are separated out in the nanometer pore canal, and the external electric field drives the positive ions and the negative ions to move in (and only in) the nanometer pore canal of the anodic aluminum oxide sheet coated by the carbon layer. The carbon layer coated aluminum anode oxide sheet can be replaced by other similar structural materials, the similar structural materials refer to materials or composite materials which have regularly arranged through nanometer channels with uniform size, are macroscopically sheet-shaped or film-shaped, and the channel direction is vertical to the surface of the sheet-shaped or film-shaped materials.
The anodic aluminum oxide sheet coated by the carbon layer is not used as an electrode, does not participate in an external electric field driven electrochemical oxidation-reduction reaction, and is different from electrochemical deposition. The carbon layer coated anodic aluminum oxide sheet has a through nano-pore channel with the aperture of 20-100 nm, and the thickness is not limited.
In addition, the filling device can be in different shapes and forms, but the technical means that the electrolyte solution is driven by the electric field force to overcome the interfacial tension of the material to enter the nano-pore channel, which is not departed from the technical scope protected by the invention, belongs to the technical scope protected by the invention.
The invention is further illustrated by the following examples:
example 1
As shown in fig. 1, the carbon layer coated anodized aluminum sheet 10 is assembled on the electrolytic cell device, the anodized aluminum sheet 10 is sandwiched by the rubber sealing gasket i 7 and the rubber sealing gasket ii 8 and completely covers the rubber sealing gasket i 7 and the rectangular hole in the center of the rubber sealing gasket ii 8, the organic glass sheet i 6 and the organic glass sheet ii 9 are clamped outside the rubber sealing gasket i 7 and the rubber sealing gasket ii 8, and the organic glass sheet i 6, the rubber sealing gasket i 7, the anodized aluminum sheet 10, the rubber sealing gasket ii 8 and the organic glass sheet ii 9 are sequentially assembled together to form a combined body 13, as shown in fig. 1(d) and fig. 1 (e). The assembly 13 is then inserted into the recess 14 of the cell body 1 from top to bottom, the assembled filling device being shown in figure 1 (f). At this moment, the electrolytic bath main body 1 is separated into two electrolytic cells by the organic glass sheet I6, the rubber sealing gasket I7, the anodic oxidation aluminum sheet 10, the rubber sealing gasket II 8 and the organic glass sheet II 9 assembly 13: the electrolytic cell IA and the electrolytic cell IIB are shown in a figure 1 (c). Respectively injecting 0.25 mol/L nickel nitrate solution into an electrolytic cell IA and an electrolytic cell IIB, applying 10V direct current voltage for 0.5s between an electrode I2 and an electrode II 3, treating the anode aluminum oxide sheet 10 coated by the lower carbon layer under the mixed gas of hydrogen gas and argon gas (the volume ratio is 1/3) for 2 hours at 350 ℃, soaking the anode aluminum oxide sheet in 5 mol/L sodium hydroxide solution for 40 hours at 30 ℃, and removing the anode aluminum oxide sheet template to obtain the nickel nano particle uniformly-filled carbon nano tube composite material. As shown in FIGS. 2(a) - (b), the nano particles in the hollow cavity are elementary nickel, the mass content is 8%, the diameter distribution is 1-5 nm, and the nano particles are intensively distributed at 1-2 nm.
Example 2
The carbon-coated anodized aluminum sheet 10 was assembled into an electrolytic cell assembly in the same manner as in example 1. Respectively injecting 0.4 mol/L ferric nitrate solution into an electrolytic cell IA and an electrolytic cell IIB, applying 20V direct current voltage for 25s between an electrode I2 and an electrode II 3, taking down an anodic aluminum oxide sheet 10 coated by a carbon layer, drying at 80 ℃, heating to 400 ℃ under the protection of nitrogen, carrying out constant temperature treatment for 5 hours, finally placing in 5 mol/L sodium hydroxide solution, carrying out treatment at 25 ℃ for 36 hours, and removing an anodic aluminum oxide sheet template to obtain the composite material of the iron oxide nano particles filled with the carbon nano tubes. As shown in fig. 3(a) - (b), the nano particles in the hollow cavity are iron oxide, the mass content is 20%, the diameter of the iron oxide nano particles is 10-25 nm, and the iron oxide nano particles are centrally distributed at 15-20 nm.
Example 3
The carbon-coated anodized aluminum sheet was assembled into an electrolytic cell assembly in the same manner as in example 1. Respectively injecting 0.01 mol/L silver nitrate solution and 0.01 mol/L hydrochloric acid solution into an electrolytic cell IA and an electrolytic cell IIB, applying 30V direct current voltage for 1 minute between the two electrodes by taking an electrode I2 as an anode and an electrode II 3 as a cathode, taking the anode aluminum oxide sheet coated by the carbon layer, and treating in hydrofluoric acid at 25 ℃ for 32 hours to remove the anode aluminum oxide, thereby obtaining the silver chloride nanoparticle filled carbon nanotube composite material. The nano particles in the hollow cavity are silver chloride, the mass content of the nano particles is 35 percent, the diameter of the silver chloride nano particles is 15 to 30 nanometers, and the silver chloride nano particles are intensively distributed at 25 to 30 nanometers.
Example 4
The carbon-coated anodized aluminum sheet was assembled into an electrolytic cell assembly in the same manner as in example 1. Respectively injecting 0.05 mol/L silver nitrate solution and 0.05 mol/L hydrochloric acid solution into an electrolytic cell IA and an electrolytic cell IIB, applying 15V direct current voltage between the two electrodes for 5 minutes by taking an electrode I2 as an anode and an electrode II 3 as a cathode, taking the anodic aluminum oxide sheet coated by the carbon layer, and treating in hydrofluoric acid at 25 ℃ for 48 hours to remove the anodic aluminum oxide, thereby obtaining the silver chloride nanorod filled carbon nanotube composite material. As shown in FIGS. 4(a) - (b), the hollow cavity is filled with silver chloride nanorods, the mass content of which is 92%.
The embodiment result shows that the electric field force-driven method for rapidly and controllably filling the hollow cavity of the carbon nano tube is provided, positive ions and negative ions in a solution can only move towards opposite directions through the anode alumina nano pore channel under the drive of the electric field force by adopting the novel electrolytic tank device, so that the controllable filling of substances of different types and different forms (nano particles or nano rods) in the hollow cavity of the carbon nano tube is realized, and the method has important significance for promoting the base and application research of filling the carbon nano tube by the nano particles/nano rods in the fields of electrochemical catalytic materials, energy storage materials and in-situ nano reactors.
Claims (9)
1. A method for rapidly and selectively filling nano particles into a carbon nano tube cavity is characterized in that an anodic aluminum oxide sheet deposited with thin-layer carbon is assembled on an electrolytic cell device, an electrolytic cell main body of the electrolytic cell device is divided into two independent electrolytic cells through a combination body, an electrode is respectively inserted into each electrolytic cell, an electrolyte solution needing elements to be filled is injected into each electrolytic cell, 1-50V direct current voltage is applied between the two electrodes, nano particles are filled for 0.5 second to 5 minutes, the anodic aluminum oxide sheet is taken down and subjected to heat treatment, and then the anodic aluminum oxide sheet is removed, so that a carbon nano tube composite structure filled with the nano particles is obtained; wherein the anodic aluminum oxide sheet is provided with a through nano-pore channel with the pore diameter of 20-100 nm;
the electrolysis trough device includes electrolysis trough main part and assembly, and the electrolysis trough main part sets up electrode I, electrode II, sealing rubber strip I, sealing rubber strip II, and the assembly sets up organic glass piece I, rubber seal pad II, organic glass piece II, anodic oxidation aluminum sheet, and concrete structure is as follows:
the recess of assembly top-down inserted electrolysis trough main part, and two electrolytic bath are separated into by organic glass piece I, the sealed I of rubber packing, anodic oxidation aluminum sheet, the sealed II of rubber packing, the assembly of organic glass piece II: the device comprises an electrolytic cell I and an electrolytic cell II, wherein a sealing rubber strip I is arranged at the matching position of a combination body and the electrolytic cell I, a sealing rubber strip II is arranged at the matching position of the combination body and the electrolytic cell II, an electrode I is inserted in the electrolytic cell I, and an electrode II is inserted in the electrolytic cell II; after assembly, a nanoparticle-filled device is formed;
carbon-layer coated anodic oxidation aluminum sheet presss from both sides at the rubber packing pad I of center trompil, the middle of rubber packing pad II, carbon-layer coated anodic oxidation aluminum sheet and rubber packing pad I, the shape of rubber packing pad II center trompil, the size is the same, carbon-layer coated anodic oxidation aluminum sheet covers rubber packing pad I completely, the center trompil of rubber packing pad II, organic glass piece I, II centre grippings of organic glass piece are in rubber packing pad I, II outsides of rubber packing pad, one side symmetry that organic glass piece II and rubber packing pad II correspond sets up the fixed pin, rubber packing pad I, set up the pilot hole that corresponds with the fixed pin on rubber packing pad II and the organic glass piece I, rubber packing pad II, organic glass piece II passes through fixed.
2. The method for rapid selective filling of nanoparticles into carbon nanotube lumens as defined in claim 1 wherein two electrodes: the electrode I and the electrode II are inert electrodes, and when the electrodes are electrified, the electrodes have a conductive effect and do not react with the electrolyte.
3. The method for rapid and selective filling of nano-particles into carbon nanotube lumens as defined in claim 1, wherein the same or different electrolyte solutions are used in the two electrolytic cells, and when different electrolyte solutions are contained in the two electrolytic cells, the two electrolyte solutions and the direction of the electric field are selected as required to achieve direct and rapid synthesis of nano-particles in the carbon nanotube hollow lumen.
4. The method for rapidly and selectively filling nano-particles into the carbon nanotube cavity according to claim 1, wherein the anodic aluminum oxide sheet coated by the carbon layer is replaced by other sheet-shaped and through-hole materials with similar structures, so as to rapidly fill nano-particles in various nano-tubes or nano-hole channels of porous materials.
5. The method for rapid and selective filling of nano particles into carbon nanotube tube according to claim 1, wherein the heat treatment conditions are determined according to the desired particle structure, the atmosphere is one or a mixture of two or more of air, argon, nitrogen and hydrogen, and the temperature is 50 to 1000 ℃.
6. The method for rapidly and selectively filling the nano particles into the carbon nano tube cavity according to claim 1, wherein the content of the nano particles in the carbon nano tube is precisely controlled by the concentration of the electrolyte solution and the voltage application time, and the content of the nano particles is precisely controllable within the range of 0.5-95 wt%.
7. The method for rapid selective filling of nanoparticles into carbon nanotube lumens as claimed in claim 1, wherein the nanoparticles exhibit different morphologies depending on the content thereof, and exist in the form of particles at a lower content, and fill the carbon nanotube lumens to form nanorods at a higher content.
8. The method for rapid selective filling of nanoparticles into carbon nanotube lumens as claimed in claim 7 wherein the nanoparticles are present in the form of particles at a nanoparticle content below 75 wt%.
9. The method for rapid selective filling of nanoparticles into carbon nanotube lumens as claimed in claim 1 wherein the nanoparticles are 100% filled in the hollow carbon nanotube lumens due to the physical isolation of the carbon nanotube outer wall by the anodized aluminum.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711130179.2A CN109778214B (en) | 2017-11-15 | 2017-11-15 | Method for rapidly and selectively filling nano particles into carbon nano tube cavity |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711130179.2A CN109778214B (en) | 2017-11-15 | 2017-11-15 | Method for rapidly and selectively filling nano particles into carbon nano tube cavity |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109778214A CN109778214A (en) | 2019-05-21 |
| CN109778214B true CN109778214B (en) | 2020-11-13 |
Family
ID=66493740
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711130179.2A Active CN109778214B (en) | 2017-11-15 | 2017-11-15 | Method for rapidly and selectively filling nano particles into carbon nano tube cavity |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109778214B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112198175A (en) * | 2020-09-17 | 2021-01-08 | 燕山大学 | Method for researching electrochemistry of liquid battery under in-situ electron microscope |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6129901A (en) * | 1997-11-18 | 2000-10-10 | Martin Moskovits | Controlled synthesis and metal-filling of aligned carbon nanotubes |
| US7438885B1 (en) * | 2003-07-16 | 2008-10-21 | University Of Central Florida Research Foundation, Inc. | Synthesis of carbon nanotubes filled with palladium nanoparticles using arc discharge in solution |
| KR100656781B1 (en) * | 2005-03-11 | 2006-12-13 | 재단법인서울대학교산학협력재단 | Method for forming electron emitter tip by copper-carbon nanotube composite electroplating |
| KR101097219B1 (en) * | 2007-10-01 | 2011-12-21 | 한국전자통신연구원 | Fabrication method of Nanocomposite and method of dye-sensitized solar cell using the same |
| CN101745434B (en) * | 2008-12-19 | 2011-08-10 | 中国科学院金属研究所 | Method for selectively filling ferric oxide particles in hollow cavity of carbon nanotube |
| CN101937732B (en) * | 2009-07-02 | 2012-02-15 | 国家纳米科学中心 | Nano cable made of magnetic material and half-metallic material and preparation method thereof |
| FR3034258B1 (en) * | 2015-03-26 | 2021-12-17 | Commissariat Energie Atomique | POROUS MEMBRANE, IN PARTICULAR ELECTROLYTE MEMBRANE OR FILTRATION MEMBRANE, ITS PREPARATION PROCESS, AND ELECTROCHEMICAL DEVICES INCLUDING IT. |
-
2017
- 2017-11-15 CN CN201711130179.2A patent/CN109778214B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN109778214A (en) | 2019-05-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Pawar et al. | Crystal facet engineering of ZnO photoanode for the higher water splitting efficiency with proton transferable nafion film | |
| CN107215867B (en) | A kind of method that serialization prepares graphene oxide microplate | |
| Ikkurthi et al. | Synthesis of nanostructured metal sulfides via a hydrothermal method and their use as an electrode material for supercapacitors | |
| WO2016058466A1 (en) | Graphene oxide prepared by electrochemically oxidizing and cutting end face of carbon-based three-dimensional material and method therefor | |
| CN103285891A (en) | Preparation method of bismuth oxide halide-titanium oxide nanotube array composite photo-catalytic membrane | |
| CN107235486B (en) | The preparation method of water-soluble graphene | |
| ZHU et al. | Cu2S on Cu foam as highly efficient electrocatalyst for reduction of CO2 to formic acid | |
| KR101760635B1 (en) | Excess microbubble hydrogen preparation device | |
| CN110316729B (en) | Method for preparing graphene based on high-concentration organic salt aqueous solution electrochemical intercalation | |
| CN105565297B (en) | Graphene quantum dot and method prepared by electrochemical oxidation cutting carbon fiber tip surface | |
| CN112239203B (en) | Electrochemical preparation method of porous graphene dispersion liquid | |
| CN108411333A (en) | A method of preparing hydrogen peroxide using the hydrophobic cathodic reduction oxygen of acetylene black | |
| CN109704314A (en) | A method of continuously preparing graphene | |
| CN108722453A (en) | A kind of phosphating sludge/carbon composite nano-material for alkaline electrocatalytic hydrogen evolution | |
| CN108840327A (en) | A kind of electrochemical method preparing nitrogen-doped graphene material | |
| CN109778214B (en) | Method for rapidly and selectively filling nano particles into carbon nano tube cavity | |
| CN112864371A (en) | Preparation method of vanadium trioxide and nitrogen-doped porous carbon composite anode material | |
| Yang et al. | A cyclic voltammetric synthesis of PbS nanoparticles | |
| CN106591871A (en) | Method for preparing graphene through electrochemical in-situ oxidation and reduction | |
| CN105600772B (en) | The graphene oxide and method of electrochemical oxidation cutting carbon system three-dimensional material end face | |
| CN113582169A (en) | Preparation method and application of graphene quantum dot with adjustable oxygen content | |
| WO2019014633A1 (en) | Boron-nitride nanotube membranes | |
| CN108277520A (en) | The preparation method of hollow cube stannous chloride film | |
| CN111320166A (en) | Method for preparing two-dimensional porous graphene oxide through one-step electrochemical process | |
| CN108033521B (en) | Load gamma MnO2Preparation method and application of active carbon particle electrode |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |