CN105645375A - Method for direct growth of porous carbon nanotubes on nano-porous copper - Google Patents
Method for direct growth of porous carbon nanotubes on nano-porous copper Download PDFInfo
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- CN105645375A CN105645375A CN201510967418.4A CN201510967418A CN105645375A CN 105645375 A CN105645375 A CN 105645375A CN 201510967418 A CN201510967418 A CN 201510967418A CN 105645375 A CN105645375 A CN 105645375A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 41
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 41
- 239000010949 copper Substances 0.000 title claims abstract description 41
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 21
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000007789 gas Substances 0.000 claims abstract description 27
- 229910052786 argon Inorganic materials 0.000 claims abstract description 24
- 239000008367 deionised water Substances 0.000 claims abstract description 18
- 239000012018 catalyst precursor Substances 0.000 claims abstract description 17
- 239000001257 hydrogen Substances 0.000 claims abstract description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 17
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims abstract description 16
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims abstract description 16
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 10
- 239000000956 alloy Substances 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 9
- 239000010453 quartz Substances 0.000 claims abstract description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000000137 annealing Methods 0.000 claims abstract description 8
- 239000012298 atmosphere Substances 0.000 claims description 9
- 238000001291 vacuum drying Methods 0.000 claims description 9
- 238000005275 alloying Methods 0.000 claims description 7
- 230000007797 corrosion Effects 0.000 claims description 7
- 238000005260 corrosion Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 238000010792 warming Methods 0.000 claims description 7
- 238000007605 air drying Methods 0.000 claims description 4
- 230000009467 reduction Effects 0.000 claims description 2
- 239000012300 argon atmosphere Substances 0.000 abstract description 7
- 238000001816 cooling Methods 0.000 abstract description 5
- 150000002431 hydrogen Chemical class 0.000 abstract description 5
- 238000002360 preparation method Methods 0.000 abstract description 4
- 238000010438 heat treatment Methods 0.000 abstract 2
- 238000005530 etching Methods 0.000 abstract 1
- 238000005229 chemical vapour deposition Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000007935 neutral effect Effects 0.000 description 5
- 238000000643 oven drying Methods 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000002109 single walled nanotube Substances 0.000 description 2
- 239000011232 storage material Substances 0.000 description 2
- 238000001241 arc-discharge method Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002048 multi walled nanotube Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
-
- B01J35/60—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Abstract
The present invention relates to a method for direct growth of porous carbon nanotubes on the nano-porous copper. The method comprises the steps of: (1) preparation of a nano-porous copper catalyst precursor: rinsing a Cu30Mn70 alloy strip with thickness of 20-50 mum with deionized water, drying, placing the alloy strip in dilute hydrochloric acid solution with concentration of 0.001-0.02 mol/L for dealloying etching and taking out the sample until no bubble overflow; rinsing with deionized water; then placing the alloy strip in a vacuum oven and drying at room temperature; (2) preparation of a porous carbon nanotube: placing the nano-porous copper catalyst precursor into a quartz ark, placing the quartz ark in a constant-temperature area of a tube furnace, and heating to 600-800 DEG C in argon atmosphere with flow of 50-100 sccm under a heating rate of 2-10 DEG C/min; introducing hydrogen with flow of 50-100 sccm, reducing and annealing for 0.5-2 h; closing the hydrogen, introducing a mixed gas of acetylene and argon in the volume ratio of 1:(10-30) for growing for 0.2-1 h; cooling to 200-300 DEG C in an argon atmosphere with flow of 50-100 sccm at a cooling rate of 2-10 DEG C/min; and cooling to room temperature with the furnace and taking out the finished product.
Description
Technical field
The invention belongs to the technical field of carbon nanomaterial, particularly relate to a kind of method of direct growth porous carbon nanotube on nano porous copper.
Background technology
Since beginning, carbon nanotube always with characteristics such as the structure of its uniqueness, excellent thermodynamics and electricity at electron stored energy device, there is the application prospect of great potential the aspects such as hydrogen storage material, especially the crystalline structure of its uniqueness is suitable as catalyst cupport material very much, is thus more subject to the extensive concern of scientific circles. Carbon nanotube is according to the difference of the Sheet Graphite number of plies, Dan Bi and Duo Bi can be divided into, Single Walled Carbon Nanotube can regard that individual layer flake graphite is curling and becomes structure to have good symmetry and unicity as, and multi-walled carbon nano-tubes can be regarded as the Single Walled Carbon Nanotube suit of different diameter and becomes, interlamellar spacing 0.34nm. Flat carbon nanotube, bamboo-like carbon nano tubes, spiral carbon nanotubes, Y type carbon nanotube etc. can be divided into again according to microscopic appearance difference, but there is no the relevant report of porous carbon nanotube at present, wherein, the caliber 30-100nm of porous carbon nanotube and the interior hollow of pipe, tube wall is uniformly distributed 2-10nm hole, this kind of structure makes it have bigger specific surface area and graphite face, also have better degree of graphitization in addition, in electrochemical energy storage materials and device and biosensor etc., therefore have potential application prospect.
At present, the method having been reported middle synthesizing carbon nanotubes mainly contains arc discharge method, laser evaporation method, chemical Vapor deposition process, pyrolysis carborization and solvent-thermal method etc. Wherein, chemical Vapor deposition process utilizes the carbon-source gas such as methane, acetylene, ethanol to go out carbon atom through catalyst cracking under high temperature or low-temperature plasma, and on catalyst matrix, continuous deposition growing goes out the structure of carbon nanotube then. It is all the metallic compound of the transition metal such as supported copper, iron, cobalt, nickel, vanadium on inorganic or metallic matrix that carbon nanotube prepared by chemical Vapor deposition process known at present is gone up substantially, grows as catalyzer through certain process afterwards again. Although various processing method all achieves very big progress, but still there is complicated operation and the lower deficiency of output, and be easily mixed with more by product in product, so the carbon nanotube of a large amount of high purity of even preparation is still a problem important and urgently to be resolved hurrily.
Do not find to have at present only with nano porous copper as template and catalyzer through retrieval, utilize report paper or the patent report of a large amount of porous carbon nanotube of chemical vapour deposition (CVD) method one-step synthesis yet.There is unique surface tissue and make it have the specific surface area more much bigger than general carbon nanotube, and there is the thermotolerance of carbon nanotube own, chemical stability, electric heating conductivity height, the excellent properties such as thermal expansivity is low, density is low, thus certainly exist utilization prospect greatly in fields such as electrode materials, sensor and energy storage devices.
Summary of the invention
The present invention provides a kind of method of direct growth porous carbon nanotube on nano porous copper for the technical problem of existence in solution known technology, simplifies operating process, promotes controllability, promotes homogeneity and the purity of porous carbon nano tube structure.
The present invention is the technical scheme that the technical problem existed in solution known technology is taked: a kind of method of direct growth porous carbon nanotube on nano porous copper comprises the following steps, (1) prepare nano porous copper catalyst precursor, it is the Cu of 20-50 ��m by thickness30Mn70After alloy strip washed with de-ionized water, drying, is placed in the dilute hydrochloric acid solution that concentration is 0.001-0.02mol/L and carries out removal alloying corrosion, until basic bubble-free takes out sample after overflowing; By washed with de-ionized water; Put into vacuum drying oven afterwards and carry out Air drying, be i.e. obtained nano porous copper catalyst precursor; (2) porous carbon nanotube is prepared, the nano porous copper catalyst precursor that step (1) is obtained is put into quartz Noah's ark, the constant temperature district being placed in tube furnace, is under the argon gas atmosphere of 50-100sccm at flow, is warming up to 600-800 DEG C with the temperature rise rate of 2-10 DEG C/min; Lead to into hydrogen with the flow of 50-100sccm afterwards, reduction annealing 0.5-2h; Closing hydrogen afterwards and lead to and grow into the gas mixture of acetylene and argon gas, wherein the volume ratio of acetylene and argon gas is 1: (10-30), and growth time is 0.2-1h; It is under the argon gas atmosphere of 50-100sccm afterwards at flow, it is cooled to 200-300 DEG C with the rate of temperature fall of 2-10 DEG C/min; Cool to room temperature afterwards with the furnace to take out, namely obtain the porous carbon nanotube of evenly growth on nano porous copper.
Advantage and the positively effect of the present invention be: the present invention provide a kind of directly by template and catalyzer of nano porous copper (NPC), the method that catalyzed and synthesized porous carbon nanotube by chemical Vapor deposition process one step, product structure evenly, purity height and product rate big, can prepare in a large number. Compared to other method, nano porous copper is directly as template and catalyzer, and a step catalyzed reaction prepares mass good purity much higher hole carbon nanotube in a large number, and preparation process and device requirement are simple, is easy to realize and promote.
Preferably: step (1) is 2-5 time by deionized water wash number.
Preferably: the time carrying out Air drying in step (1) in vacuum drying oven is 2-4h.
Accompanying drawing explanation
Fig. 1 is the porous carbon nanotube preparating mechanism figure of the present invention;
Fig. 2 is the SEM figure of the nano porous metal copper persursor material obtained by embodiment one, and scale is 300nm;
Fig. 3 is the SEM figure of the porous carbon nanotube obtained by embodiment one, and scale is 1um;
Fig. 4 is the SEM figure of the porous carbon nanotube obtained by embodiment one, and scale is 200nm;
Fig. 5 is the SEM figure of the porous carbon nanotube obtained by embodiment two, and scale is 500nm.
Embodiment
For summary of the invention, the Characteristic of the present invention can be understood further, hereby lift following examples and it be described in detail as follows:
Embodiment one
By the Cu that length to be 20mm, width be 5mm, thickness are 30 ��m30Mn70Alloy strip is with, after deionized water cleaning-drying, being placed in the dilute hydrochloric acid solution that concentration is 0.02mol/L and carry out removal alloying corrosion, until taking-up sample when substantially not having bubble to overflow;
With deionized water wash to neutral, wash number is 3 times, afterwards sample is put into vacuum drying oven drying at room temperature 3h, obtains nano porous copper (NPC) presoma, and microtexture is as shown in Figure 2;
The nano porous copper catalyst precursor obtained is put into quartz boat, is placed in the constant temperature district of tube furnace, under flow is 100sccm argon atmosphere, is warming up to 630 DEG C with 10 DEG C/min;
Lead to into hydrogen reducing annealing 0.5h with 100sccm flow velocity afterwards;
Stop leading to into hydrogen afterwards, then to lead to into flow be that the acetylene of 10sccm and the argon gas gas mixture of 200sccm carry out catalytic growth 1h;
Reaction closes acetylene after terminating, and argon flow amount reduces to 100sccm, cools to 300 DEG C with the speed of 10 DEG C/min under the atmosphere of argon gas shielded;
Cooling to room temperature afterwards with the furnace, obtain the porous carbon nanotube of evenly growth, microtexture is as shown in Figures 3 and 4.
Observed the porous carbon nano pipe purity height of the present invention by sem analysis, the carbon output of 220% can be reached through 1h growth. Being 20-50nm by the caliber of high power sem analysis porous carbon nanotube, porous nano aperture is 5-10nm.
Embodiment two
By the Cu that length to be 20mm, width be 5mm, thickness are 30 ��m30Mn70Alloy strip is with, after deionized water cleaning-drying, being placed in the dilute hydrochloric acid solution that concentration is 0.02mol/L and carry out removal alloying corrosion, until taking-up sample when substantially not having bubble to overflow;
With deionized water wash to neutral, wash number is 5 times, afterwards sample is put into vacuum drying oven drying at room temperature 3h, obtains nano porous copper catalyst precursor (NPC);
The nano porous copper catalyst precursor obtained is put into quartz boat, is placed in the constant temperature district of tube furnace, under flow is 100sccm argon atmosphere, is warming up to 630 DEG C with 10 DEG C/min;
Lead to into hydrogen reducing annealing 0.5h with 100sccm flow velocity afterwards;
Stopping afterwards leading to into hydrogen, leading to into flow is that the acetylene of 20sccm and the argon gas gas mixture of 200sccm carry out catalytic growth 1h;
Reaction closes acetylene after terminating, and argon flow amount reduces to 100sccm, cools to 300 DEG C with the speed of 10 DEG C/min under the atmosphere of argon gas shielded;
Cooling to room temperature afterwards with the furnace, obtain the porous carbon nanotube of evenly growth, microtexture is as shown in Figure 5.
Embodiment three
By the Cu that length to be 20mm, width be 5mm, thickness are 30 ��m30Mn70Alloy strip is with, after deionized water cleaning-drying, being placed in the dilute hydrochloric acid solution that concentration is 0.02mol/L and carry out removal alloying corrosion, until taking-up sample when substantially not having bubble to overflow;
With deionized water wash to neutral, wash number is 4 times, afterwards sample is put into vacuum drying oven drying at room temperature 3h, obtains nano porous copper catalyst precursor (NPC);
The nano porous copper catalyst precursor obtained is put into quartz boat, is placed in the constant temperature district of tube furnace, under flow is 100sccm argon atmosphere, is warming up to 650 DEG C with 10 DEG C/min;
Lead to into hydrogen reducing annealing 0.5h with 100sccm flow velocity afterwards;
Stopping afterwards leading to into hydrogen, leading to into flow is that the acetylene of 10sccm and the argon gas gas mixture of 200sccm carry out catalytic growth 1h;
Reaction closes acetylene after terminating, and argon flow amount reduces to 100sccm, cools to 300 DEG C with the speed of 10 DEG C/min under the atmosphere of argon gas shielded;
Cool to room temperature afterwards with the furnace, obtain the porous carbon nanotube of evenly growth.
Embodiment four
By the Cu that length to be 20mm, width be 5mm, thickness are 30 ��m30Mn70Alloy strip is with, after deionized water cleaning-drying, being placed in concentration is that 0.02mol/L dilute hydrochloric acid solution carries out removal alloying corrosion, until taking-up sample when substantially not having bubble to overflow;
With deionized water wash to neutral, wash number is 4 times, afterwards sample is put into vacuum drying oven drying at room temperature 3h, obtains nano porous copper catalyst precursor (NPC);
The nano porous copper catalyst precursor obtained is put into quartz boat, is placed in the constant temperature district of tube furnace, be warming up to 680 DEG C with 10 DEG C/min under the argon atmosphere of 100sccm at flow;
Lead to into hydrogen reducing annealing 0.5h with 100sccm flow velocity afterwards;
Stopping afterwards leading to into hydrogen, leading to into flow is that the acetylene of 10sccm and the argon gas gas mixture of 200sccm carry out catalytic growth 1h;
Reaction closes acetylene after terminating, and argon flow amount reduces to 100sccm, cools to 300 DEG C with the speed of 10 DEG C/min under the atmosphere of argon gas shielded;
Cool to room temperature afterwards with the furnace, obtain the porous carbon nanotube of evenly growth.
Embodiment five
By the Cu that length to be 20mm, width be 5mm, thickness are 30 ��m30Mn70Alloy strip is with, after deionized water cleaning-drying, being placed in the dilute hydrochloric acid solution that concentration is 0.02mol/L and carry out removal alloying corrosion, until taking-up sample when substantially not having bubble to overflow;
With deionized water wash to neutral, wash number is 3 times, afterwards sample is put into vacuum drying oven drying at room temperature 3h, obtains nano porous copper catalyst precursor (NPC);
The nano porous copper catalyst precursor obtained is put into quartz boat, is placed in the constant temperature district of tube furnace, be warming up to 700 DEG C with 10 DEG C/min under the argon atmosphere of 100sccm at flow;
Lead to into hydrogen reducing annealing 0.5h with 100sccm flow velocity afterwards;
Stopping afterwards leading to into hydrogen, leading to into flow is that the acetylene of 20sccm and the argon gas gas mixture of 200sccm carry out catalytic growth 1h:
Reaction closes acetylene after terminating, and argon flow amount reduces to 100sccm, cools to 300 DEG C with the speed of 10 DEG C/min under the atmosphere of argon gas shielded;
After cool to room temperature with the furnace, obtain the porous carbon nanotube of evenly growth.
The above; it is only the present invention's preferably embodiment, but protection scope of the present invention is not limited thereto, any it is familiar with those skilled in the art in the technical scope that the present invention discloses; the change that can expect easily or replacement, all should be encompassed within protection scope of the present invention. Therefore, protection scope of the present invention should be as the criterion with the protection domain of claim.
Claims (3)
1. the method for direct growth porous carbon nanotube on nano porous copper, is characterized in that: comprise the following steps,
(1) nano porous copper catalyst precursor is prepared
It is the Cu of 20-50 ��m by thickness30Mn70After alloy strip washed with de-ionized water, drying, is placed in the dilute hydrochloric acid solution that concentration is 0.001-0.02mol/L and carries out removal alloying corrosion, until basic bubble-free takes out sample after overflowing; By washed with de-ionized water; Put into vacuum drying oven afterwards and carry out Air drying, be i.e. obtained nano porous copper catalyst precursor;
(2) porous carbon nanotube is prepared
The nano porous copper catalyst precursor that step (1) is obtained is put into quartz Noah's ark, is placed in the constant temperature district of tube furnace, is under the argon gas atmosphere of 50-100sccm at flow, is warming up to 600-800 DEG C with the temperature rise rate of 2-10 DEG C/min; Lead to into hydrogen with the flow of 50-100sccm afterwards, reduction annealing 0.5-2h; Closing hydrogen afterwards and lead to and grow into the gas mixture of acetylene and argon gas, wherein the volume ratio of acetylene and argon gas is 1: (10-30), and growth time is 0.2-1h; It is under the argon gas atmosphere of 50-100sccm afterwards at flow, it is cooled to 200-300 DEG C with the rate of temperature fall of 2-10 DEG C/min;Cool to room temperature afterwards with the furnace to take out, namely obtain the porous carbon nanotube of evenly growth on nano porous copper.
2. the method for direct growth porous carbon nanotube on nano porous copper as claimed in claim 1, is characterized in that: be 2-5 time by deionized water wash number in step (1).
3. the method for direct growth porous carbon nanotube on nano porous copper as claimed in claim 1, is characterized in that: the time carrying out Air drying in step (1) in vacuum drying oven is 2-4h.
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| CN107502886A (en) * | 2017-07-13 | 2017-12-22 | 天津大学 | The preparation method of fabricated in situ sheet metal hydroxide/oxide composite |
| CN107630227A (en) * | 2017-08-04 | 2018-01-26 | 天津理工大学 | A kind of method that three-D nano-porous copper mesh elctro-catalyst is prepared based on metal net |
| CN107739869A (en) * | 2017-11-09 | 2018-02-27 | 天津工业大学 | Nanoporous carbon/carbon-copper composite material and preparation method thereof |
| CN108455592A (en) * | 2018-04-28 | 2018-08-28 | 福州大学 | A kind of preparation method of N doping porous charcoal/carbon mano-tube composite of inierpeneirating network structure |
| CN108746653A (en) * | 2018-05-30 | 2018-11-06 | 南通科源新材料有限公司 | A kind of method that solution combustion method prepares CNT-Cu composite granules |
| CN111589441A (en) * | 2020-04-22 | 2020-08-28 | 中国科学技术大学 | Manganese-doped tungsten oxide catalyst, and preparation method and application thereof |
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| CN112938907A (en) * | 2021-01-05 | 2021-06-11 | 湖南大学 | Universal preparation method of nano-porous two-dimensional metal compound |
| CN114210334A (en) * | 2021-10-26 | 2022-03-22 | 山东科技大学 | CO (carbon monoxide)2Copper-zinc based catalyst for preparing methyl formate by hydrogenation and preparation method thereof |
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| CN107739869A (en) * | 2017-11-09 | 2018-02-27 | 天津工业大学 | Nanoporous carbon/carbon-copper composite material and preparation method thereof |
| CN108455592A (en) * | 2018-04-28 | 2018-08-28 | 福州大学 | A kind of preparation method of N doping porous charcoal/carbon mano-tube composite of inierpeneirating network structure |
| CN108746653A (en) * | 2018-05-30 | 2018-11-06 | 南通科源新材料有限公司 | A kind of method that solution combustion method prepares CNT-Cu composite granules |
| CN111589441B (en) * | 2020-04-22 | 2021-07-06 | 中国科学技术大学 | Manganese-doped tungsten oxide catalyst, and preparation method and application thereof |
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| CN112517009B (en) * | 2020-11-03 | 2023-05-30 | 佛山科学技术学院 | Modified porous copper-nickel alloy plate and preparation method and application thereof |
| CN112938907A (en) * | 2021-01-05 | 2021-06-11 | 湖南大学 | Universal preparation method of nano-porous two-dimensional metal compound |
| CN112897508A (en) * | 2021-03-11 | 2021-06-04 | 南昌大学 | Preparation method of carbon nano pear-shaped structure material |
| CN114210334A (en) * | 2021-10-26 | 2022-03-22 | 山东科技大学 | CO (carbon monoxide)2Copper-zinc based catalyst for preparing methyl formate by hydrogenation and preparation method thereof |
| CN114210334B (en) * | 2021-10-26 | 2024-01-30 | 山东科技大学 | CO (carbon monoxide) 2 Copper-zinc-based catalyst for preparing methyl formate by hydrogenation and preparation method thereof |
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