CN104117349A - Method utilizing atomized ethanol assisted penetration high-temperature pyrolysis to prepare carbon nanotube array/transition metal oxide coaxial structural material - Google Patents
Method utilizing atomized ethanol assisted penetration high-temperature pyrolysis to prepare carbon nanotube array/transition metal oxide coaxial structural material Download PDFInfo
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- CN104117349A CN104117349A CN201410335797.0A CN201410335797A CN104117349A CN 104117349 A CN104117349 A CN 104117349A CN 201410335797 A CN201410335797 A CN 201410335797A CN 104117349 A CN104117349 A CN 104117349A
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- Y02E60/30—Hydrogen technology
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Abstract
The invention discloses a method utilizing atomized ethanol assisted penetration high-temperature pyrolysis to prepare a carbon nanotube array/transition metal oxide coaxial structural material. Different composite structures can be obtained by reasonably controlling the concentration of catalyst in raw materials, the pyrolysis time, the species of the oxide precursor, and the pyrolysis time and pyrolysis temperature of ethanol solution. The metal oxide is evenly covered on the surface of the carbon nanotube array. The density and diameter of the coaxial structure and the coating thickness of the oxide are adjustable, the stable coating layer of the composite structure can tolerate overgrowth and cannot be peeled off basically, and thus the coaxial structural can exert excellent electrochemical properties.
Description
Technical field
The present invention relates to nano materials research field, particularly a kind of method of preparing carbon nano pipe array/transition metal oxide coaxial configuration material by the auxiliary infiltration of atomization ethanol high temperature pyrolysis.
Background technology
Along with social development, utilization the having a strong impact on environment of the growing and fossil fuel of global energy consumption, fuel cell is as a kind of energy conversion device of clean and effective, have advantages of that energy conversion efficiency is high, environmental protection, noise be low, safe and reliable, renewable to a certain extent, thereby receive much concern.It is eelctro-catalyst and with high costs that classical fuel cell adopts metal platinum, and one-tenths such as platinosis and poor durability is to be to restrict the business-like Main Bottleneck of fuel cell.
Transition metal oxide (MOs), because of its environment friendly, safety, chemical property that cost is low and good, is widely used in the research of many energy fields, as the catalyst in hydrogen reduction, and the electrode material of lithium ion battery and ultracapacitor.But its poor electric conductivity has limited its practical application at electrochemical apparatus.For this reason, by itself and material with carbon element as carbon black, CNT, compound its electric conductivity of improving such as Graphene.Wherein the employing of common CNT can improve the performance of MOs really, but improves limited.The carbon nano pipe array (VACNTs) of material with carbon element nanostructured, the especially vertical alignment of 3D structure, has good one dimension electron channel and suitable tube pitch, can ensure the transmission of efficient ion and intermediate product.For by well compound to carbon nano pipe array (VACNTs) and transition metal oxide (MOs), three practical problems need to solve: in (1) VACNTs, carbon nanotube density is higher, limited space between pipe, be unfavorable for the embedding of MOs, (2) the intrinsic hydrophobicity of CNTs be unfavorable for the aqueous solution enter (3) VACNTs between the pipe of CNT growth and compound be two processes of separating, the transfer recombination process of VACNTs may destroy the oldered array of VACNTs.
In recent years, some researchers adopt electrochemical deposition, ald, and microwave ancillary technique is by compound to VACNTs and MOs, as the electrode material of ultracapacitor and lithium ion battery, the chemical property of doing well, but do not solve three above-mentioned problems completely, especially obtain the three-dimensional structure of the VACNTs of high-quality compound MOs, make the three-dimensional composite material based on VACNTs not show the performance of expection.
Summary of the invention
The object of the invention is the shortcoming and defect existing in order to overcome prior art, assist infiltration high temperature pyrolysis to prepare the method for carbon nano pipe array/transition metal oxide coaxial configuration material and provide a kind of by atomization ethanol, the application is by the high temperature pyrolytic cracking (HTP) of the auxiliary infiltration of ethanol of atomization, preparation original position on CVD method grow the VACNTs obtaining is evenly coated MOs(MnO2 etc.) three-dimensional structure material, and first by this structure as the cathod catalyst of fuel cell, show good performance compared with business platinum/carbon (20w%) catalyst.
For achieving the above object, technical scheme of the present invention comprises the following steps:
(1) xylene solution of the ferrocene of at high temperature pyrolysis atomization, obtains carbon nano pipe array;
(2) nitrogen buffer gas, the ethanolic solution of the presoma of transition metal oxide is penetrated between the prepared carbon nano pipe array of step (1) by atomizer, and under protective atmosphere, carry out chemical vapour deposition (CVD), make the presoma high temperature pyrolysis of transition metal oxide become transition metal oxide, this transition metal oxide is coated on carbon nano-pipe array and lists;
(3), after the time of chemical vapour deposition reaction expection in step (2), insulation 0.5-6h, naturally cools to room temperature, obtains the coaxial configuration of three-dimensional carbon nano pipe array/transition metal oxide.
Further arranging is that the horizontal pipe furnace that is added with quartz plate is preheating to 50-1000 DEG C by described step (1), and the xylene solution of the ferrocene preparing is in advance passed into horizontal pipe furnace by atomizer, obtains growing in the carbon nano pipe array on quartz plate.
Further arrange is that the pyrolysis temperature of described step (2) is 300-1000 DEG C.
Further arranging is that described step (2) repeats at least one times before in step (3) again.
Further arrange be the transition metal oxide precursor body of described step (3) be can generation gas-phase reaction generation manganese oxide under high temperature material: manganese acetate or manganese acetylacetonate; Can generation gas-phase reaction under high temperature generate the material of titanium oxide: tetrabutyl titanate, isopropyl titanate, titanium acetylacetone or butyl titanate or titanium tetrachloride; Can generation gas-phase reaction under high temperature generate the material of cobalt oxide: cobalt acetate or linoleic acid cobalt soap; Can generation gas-phase reaction under high temperature generate the material of nickel oxide: butter of tin, tin acetate or oleic acid nickel soap; Can generation gas-phase reaction under high temperature generate the material of zinc oxide: zinc acetylacetonate, zinc chloride or zinc acetate; Can generation gas-phase reaction under high temperature generate the material of iron oxide: iron chloride, thiocyanation iron, ferric acetyl acetonade or ferrocene.
Further arranging is the coaxial configuration of carbon nano pipe array/transition metal oxide of obtaining in described step (4), transition metal oxide nano uniform particles is coated, coaxial configuration carbon nano pipe array height 10 ~ 1500 μ m, external diameter 10 ~ 100nm, tube pitch 45 ~ 430nm, the coated thickness of oxide is 0.1-300 μ m, and compound has retained the three-dimensional structure of the carbon nano pipe array that growth obtains.
Argon gas, nitrogen or the helium of the protective atmosphere that is described step (3) are further set.
Said method has the following advantages: 1, on quartz plate the VACNTs that obtains of growth at whole experimentation without transfer, ensure complete three-dimensional structure: 2, combine the auxiliary infiltration of ethanol and atomization, make MOs on VACNTs evenly, the degree of depth is compound, the thickness of having realized first MOs coated on the larger VACNTs of thickness reaches hundred micron orders, and can reach hundreds of micron; 3, this simple method can be pervasive for being compound in VACNTs as MOs such as manganese oxide.The VACNTs compound of these high-quality three-dimensional structures has huge using value in production capacity and energy storage and photoelectric field.
At this, on the one hand, the invention provides the ingenious method of the coaxial composites of nano particle such as a kind of carbon nano pipe array/transition metal oxide, this material comprises the carbon nano pipe array growing on quartz plate, and is evenly distributed on the nano particle such as carbon nano pipe array outer surface the manganese dioxide compound with it obtaining.Load capacity when spray time is 1 ~ 100min can reach 0.1 ~ 48% respectively.The xylene solution concentration range of the corresponding ferrocene using is 0.8 ~ 45g/L, carbon nano pipe array height 10 ~ 1500 μ m that obtain, external diameter 10 ~ 100nm, tube pitch 45 ~ 430nm.
On the other hand, the present invention adopts carrying transition metal oxide in position, the VACNTs cubical array structural damage of having avoided the transfer of VACNTs and having caused, and perfectly realized the uniform load on VACNTs of the transition metal oxides such as manganese dioxide.Diameter 10 ~ the 100nm of compound, and closely compound between VACNTs and transition metal oxide.According to the conclusion of the report before us and nearest relevant report, between the transition metal oxides such as VACNTs and manganese dioxide, be compounded with closely the cooperative effect being beneficial between high efficiency of transmission and the material of realizing electronics.
To sum up, the present invention proposes the one auxiliary infiltration of atomization ethanol cleverly high temperature pyrolytic cracking (HTP), has obtained MnO on the high-quality VACNTs obtaining in pyrolysis by the simple and easy process of three steps
2deng the even coated composites of transition metal oxide original position, coaxial configuration diameter, the coated thickness of transition metal oxide is adjustable, and composite construction is stable, clad can bear ultrasound destruction and substantially peel off, separates, for its good electrocatalysis characteristic provides material and architecture basics.
Below in conjunction with specification drawings and specific embodiments, the present invention is described further.
Brief description of the drawings
Fig. 1 prepares the schematic diagram of VACNTs and the coated transition metal oxide of original position;
The stereoscan photograph of Fig. 2 VACNTs-MnO2 compound;
The stereoscan photograph of Fig. 3 VACNTs-ZnO compound;
Fig. 4 VACNTs-TiO
2the stereoscan photograph of compound;
The voltammetry resolution chart of the VACNTs-MnO2 compound that the pure VACNTs of Fig. 5 and different nebulisation time obtain.
Detailed description of the invention
Below by embodiment, the present invention is specifically described; only be used to further illustrate the present invention; can not be interpreted as limiting the scope of the present invention, the technician in this field can make some nonessential improvement and adjustment to the present invention according to the content of foregoing invention.
embodiment 1
1) preparation of quartz plate growth substrate
Get the rectangle quartz plate of big or small 1 cm × 2 cm, put into H
2sO
4: H
2o
2ultrasonic certain hour in mixed solution (volume ratio is selected as required), and then with ethanol cleaning, ultrasonic a few minutes, be finally immersed in high purity water stand-by.Cleaned quartz plate is dried up stand-by with high pure nitrogen.
2) CNT/Mn oxide (MnO
2-CNTs) preparation of composite
A. prepare certain density ferrocene and xylene solution, be poured into respiration bottle, and be placed in atomizer.
B. quartz plate is placed in quartz ampoule, allows its furnace temperature district in tube furnace, connect experimental provision, open nitrogen cylinder, after atomization situation good in the sealing of confirming gas circuit and atomizer is normal, tube furnace is warming up to set temperature.
C. confirming after temperature stabilization, to open atomising device, switch three-way valve, makes to carry the device respiration bottle of flowing through, and brings pre-reaction material into reaction tube.
D. after reaction finishes, switch three-way valve, allows reactor directly under the protection of nitrogen, be cooled to room temperature.
E. prepare as required the ethanolic solution of certain density manganese acetate (or compound of other manganese), adopt secondary spray pyrolysis, reaction temperature is 550 DEG C of left and right, the flow of nitrogen is under the condition of 450 mL/min left and right, react certain hour, can prepare the coaxial composite of three groups of carbon nanotube/manganese oxides.
3) electro-chemical test
(a) glass-carbon electrode polish, polishing.After each polishing, first wash away surface contaminants, more repeatedly wash electrode with redistilled water, finally use respectively redistilled water, absolute ethyl alcohol, redistilled water supersound washing electrode, dry for subsequent use.
(b) the coaxial composite of the above-mentioned carbon nanotube/manganese oxide preparing is transferred on glass-carbon electrode, then the Nafion solution of getting certain volume drops in electrode surface, naturally dry.
(c) cyclic voltammetry curve of measurement catalyst in three-electrode system (glass-carbon electrode is as working electrode, and saturated Ag|AgCl electrode is as reference electrode, and platinum plate electrode is as auxiliary electrode).Test potassium hydroxide solution that electrolyte solution used is 0.1 ~ 0.5M and the methanol solution of 3 M.
The SEM photo of the coaxial composite of carbon nanotube/manganese oxide that Fig. 2 is prepared through secondary spray pyrolysis as can be seen from Fig., has been coated skim MnO the surface uniform of CNTs
2particle.
Fig. 3 is pure VACNTs and MnO
2-VACNTs glass-carbon electrode is at O
2cyclic voltammetry curve in 0.1 saturated M KOH solution.By relatively finding, at O
2relatively pure VACNTs in atmosphere, enclose manganese dioxide after peak current become large, it is that reduction current has increased significantly that spike potential is shuffled, and draws thus MnO
2-CNTs has excellent electro catalytic activity to hydrogen reduction.
In above-mentioned example, utilize the CVD method of the auxiliary infiltration of atomization ethanol secondary spraying to obtain the coaxial composite of the nano particles such as carbon nano pipe array/manganese dioxide, on the VACNTs of growth, original position is evenly coated nano-manganese dioxide, retain the cubical array structure of VACNTs, and manganese dioxide is evenly coated on carbon nano pipe array surface, coaxial configuration diameter, the coated thickness of oxide is adjustable, composite construction is stable, peel off hardly, separate, compared with business Pt/C catalyst, show better stability, electro catalytic activity and good anti methanol toxication ability, for fuel cell extensive actual provides fabulous prospect basis.
embodiment 2
According to embodiment 1 technique, taking the ethanolic solution of a certain amount of tetrabutyl titanate (or compound of other titaniums) as precursor solution, it is 400 ~ 550 DEG C in pyrolysis reaction temperature, the flow of nitrogen is under 400 ~ 600 mL/min conditions, reaction certain hour makes the coaxial composite of carbon nano pipe array/titanium oxide, and the composite making is done to a series of appearance structure sign.
embodiment 3
According to embodiment 1 technique, taking the ethanolic solution of a certain amount of linoleic acid cobalt soap (or compound of other cobalts) as precursor solution, it is 400 ~ 550 DEG C in pyrolysis reaction temperature, the flow of nitrogen is under 400 ~ 600 mL/min conditions, reaction certain hour makes the coaxial composite of carbon nano pipe array/cobalt oxide, and the composite making is done to a series of appearance structure sign.
embodiment 4
According to embodiment 1 technique, taking the ethanolic solution of a certain amount of oleic acid nickel soap (or compound of other nickel) as precursor solution, it is 400 ~ 550 DEG C in pyrolysis reaction temperature, the flow of nitrogen is under 400 ~ 600 mL/min conditions, reaction certain hour makes the coaxial composite of carbon nano pipe array/nickel oxide, and the composite making is done to a series of appearance structure sign.
embodiment 5
According to embodiment 1 technique, taking the ethanolic solution of a certain amount of zinc acetate (or compound of other zinc) as precursor solution, it is 400 ~ 550 DEG C in pyrolysis reaction temperature, the flow of nitrogen is under 400 ~ 600 mL/min conditions, reaction certain hour makes carbon nano pipe array/zinc oxide composite, and the composite making is done to a series of appearance structure sign.
embodiment 6
According to embodiment 1 technique, taking the ethanolic solution of a certain amount of thiocyanation iron (or compound of other iron) as precursor solution, it is 400 ~ 550 DEG C in pyrolysis reaction temperature, the flow of nitrogen is under 400 ~ 600 mL/min conditions, reaction certain hour makes the composite of carbon nano pipe array/iron oxide, and the composite making is done to a series of appearance structure sign.
Fig. 4 and Fig. 5 have shown the different MOs(ZnO and the TiO that obtain
2) PSTM of coated three-dimensional VACNTs.As seen from the figure, have benefited from the restructuring of the nano particle of the auxiliary osmosis of atomization ethanol and pyrolytic process and arrange, in the compound obtaining, all kinds of MOs are that deep packet overlays on three-dimensional VACNTs above equably, illustrate that method of the present invention has good universality.
Industrial applicability: the coaxial composite materials novel structure of the nano particles such as the carbon nano pipe array/manganese oxide of three-dimensional of the present invention, method is simple and easy, avoid carbon pipe to shift, original position is coated, can not reduce because the ultrasonic processing in the external world does not cause material activity, Stability Analysis of Structures, compared with the Pt/C catalyst of business, show good hydrogen reduction catalytic performance, stability and durability, for the development exploration of fuel cell goes out effectively approach of a novelty.
Claims (7)
1. a method of preparing carbon nano pipe array/transition metal oxide coaxial configuration material by the auxiliary infiltration of atomization ethanol high temperature pyrolysis, is characterized in that comprising the following steps:
The xylene solution of the ferrocene of at high temperature pyrolysis atomization, obtains carbon nano pipe array;
Nitrogen buffer gas, the ethanolic solution of the presoma of transition metal oxide is penetrated between the prepared carbon nano pipe array of step (1) by atomizer, and under protective atmosphere, carry out chemical vapour deposition (CVD), make the presoma high temperature pyrolysis of transition metal oxide become transition metal oxide, this transition metal oxide is coated on carbon nano-pipe array and lists;
After the time of chemical vapour deposition reaction expection in step (2), insulation 0.5-6h, naturally cools to room temperature, obtains the coaxial configuration of three-dimensional carbon nano pipe array/transition metal oxide.
2. a kind of method of preparing carbon nano pipe array/transition metal oxide coaxial configuration material by the auxiliary infiltration of atomization ethanol high temperature pyrolysis according to claim 1, it is characterized in that: the horizontal pipe furnace that is added with quartz plate is preheating to 50-1000 DEG C by described step (1), the xylene solution of the ferrocene preparing is in advance passed into horizontal pipe furnace by atomizer, obtain growing in the carbon nano pipe array on quartz plate.
3. a kind of method of preparing carbon nano pipe array/transition metal oxide coaxial configuration material by the auxiliary infiltration of atomization ethanol high temperature pyrolysis according to claim 1, is characterized in that: the pyrolysis temperature of described step (2) is 300-1000 DEG C.
4. a kind of method of preparing carbon nano pipe array/transition metal oxide coaxial configuration material by the auxiliary infiltration of atomization ethanol high temperature pyrolysis according to claim 1, is characterized in that: described step (2) repeats at least one times before in step (3) again.
5. the method for preparing carbon nano pipe array/transition metal oxide coaxial configuration material by the auxiliary infiltration of atomization ethanol high temperature pyrolysis according to claim 1, is characterized in that the transition metal oxide precursor body of described step (2) includes:
For can generation gas-phase reaction under high temperature generating the material of manganese oxide: manganese acetate or manganese acetylacetonate;
Can generation gas-phase reaction under high temperature generate the material of titanium oxide: tetrabutyl titanate, isopropyl titanate, titanium acetylacetone or butyl titanate or titanium tetrachloride;
Can generation gas-phase reaction under high temperature generate the material of cobalt oxide: cobalt acetate or linoleic acid cobalt soap;
Can generation gas-phase reaction under high temperature generate the material of nickel oxide: butter of tin, tin acetate or oleic acid nickel soap;
Can generation gas-phase reaction under high temperature generate the material of zinc oxide: zinc acetylacetonate, zinc chloride or zinc acetate;
Can generation gas-phase reaction under high temperature generate the material of iron oxide: iron chloride, thiocyanation iron, ferric acetyl acetonade or ferrocene.
6. assisting and permeating the method that high temperature pyrolysis is prepared carbon nano pipe array/transition metal oxide coaxial configuration material by atomization ethanol according to claim 1, it is characterized in that: the coaxial configuration of the carbon nano pipe array/transition metal oxide obtaining in described step (3), transition metal oxide nano uniform particles is coated, coaxial configuration carbon nano pipe array height 10 ~ 1500 μ m, external diameter 10 ~ 100nm, tube pitch 45 ~ 430nm, the coated thickness of oxide is 0.1-300 μ m, and compound has retained the three-dimensional structure of the carbon nano pipe array that growth obtains.
According to claim 1 prepare the method for carbon nano pipe array/transition metal oxide coaxial configuration material by the auxiliary infiltration of atomization ethanol high temperature pyrolysis, it is characterized in that: argon gas, nitrogen or the helium of the protective atmosphere of described step (3).
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104555989A (en) * | 2015-01-30 | 2015-04-29 | 西安科技大学 | Method for preparing carbon nanotubes by adopting coal tar |
| CN105225843A (en) * | 2015-09-29 | 2016-01-06 | 华中科技大学 | A kind of composite nano tube and preparation method thereof and application |
| WO2017215305A1 (en) * | 2016-06-16 | 2017-12-21 | 华为技术有限公司 | Solid electrolyte material, electrolyte, lithium battery, and preparation method therefor |
| CN107768691A (en) * | 2016-08-22 | 2018-03-06 | 常州优特科新能源科技有限公司 | A kind of carbon carries the preparation method of Mn oxide air electrode VPO catalysts |
| CN110071300A (en) * | 2019-04-28 | 2019-07-30 | 三峡大学 | A kind of preparation method of transition metal/nitrogen-doped carbon fiber elctro-catalyst |
| CN112941680A (en) * | 2021-01-28 | 2021-06-11 | 华侨大学 | Preparation method of carbon nanotube fiber-loaded nano iron oxide composite material |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102125834A (en) * | 2011-01-14 | 2011-07-20 | 上海交通大学 | Titanium-based nano-composite metal oxide catalyst and preparation method thereof |
| US8187996B2 (en) * | 2005-12-22 | 2012-05-29 | Cataler Corporation | Exhaust gas-purifying catalyst |
-
2014
- 2014-07-15 CN CN201410335797.0A patent/CN104117349A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8187996B2 (en) * | 2005-12-22 | 2012-05-29 | Cataler Corporation | Exhaust gas-purifying catalyst |
| CN102125834A (en) * | 2011-01-14 | 2011-07-20 | 上海交通大学 | Titanium-based nano-composite metal oxide catalyst and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 周学梅: "碳纳米管/锰氧化物复合材料的制备及氧还原电催化特性研究", 《中国优秀硕士学位论文全文数据库 工程科技I辑》, no. 4, 15 April 2013 (2013-04-15) * |
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| CN104555989A (en) * | 2015-01-30 | 2015-04-29 | 西安科技大学 | Method for preparing carbon nanotubes by adopting coal tar |
| CN105225843A (en) * | 2015-09-29 | 2016-01-06 | 华中科技大学 | A kind of composite nano tube and preparation method thereof and application |
| CN105225843B (en) * | 2015-09-29 | 2018-01-02 | 华中科技大学 | A kind of composite nano tube and preparation method and application |
| WO2017215305A1 (en) * | 2016-06-16 | 2017-12-21 | 华为技术有限公司 | Solid electrolyte material, electrolyte, lithium battery, and preparation method therefor |
| CN107516744A (en) * | 2016-06-16 | 2017-12-26 | 华为技术有限公司 | A kind of solid electrolyte material, electrolyte, lithium battery and preparation method thereof |
| CN107516744B (en) * | 2016-06-16 | 2020-03-10 | 华为技术有限公司 | Solid electrolyte material, electrolyte, lithium battery and preparation method thereof |
| CN107768691A (en) * | 2016-08-22 | 2018-03-06 | 常州优特科新能源科技有限公司 | A kind of carbon carries the preparation method of Mn oxide air electrode VPO catalysts |
| CN110071300A (en) * | 2019-04-28 | 2019-07-30 | 三峡大学 | A kind of preparation method of transition metal/nitrogen-doped carbon fiber elctro-catalyst |
| CN110071300B (en) * | 2019-04-28 | 2021-10-01 | 三峡大学 | Preparation method of transition metal/nitrogen-doped carbon fiber electrocatalyst |
| CN112941680A (en) * | 2021-01-28 | 2021-06-11 | 华侨大学 | Preparation method of carbon nanotube fiber-loaded nano iron oxide composite material |
| CN112941680B (en) * | 2021-01-28 | 2022-09-30 | 华侨大学 | Preparation method of carbon nanotube fiber-loaded nano iron oxide composite material |
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Application publication date: 20141029 |