CN113003614B - Cobalt oxide-hydroxylation single-walled carbon nanotube composite material and preparation and application thereof - Google Patents
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Abstract
The invention belongs to the technical field of composite materials. A cobalt oxide-hydroxylation single-wall carbon nanotube composite material is prepared by carrying out ultrasonic self-assembly on cobalt oxide nano particles with uniform particle size and good crystal form and hydroxylation single-wall carbon nanotubes with reticular distribution structures, so that the agglomeration phenomenon of the cobalt oxide is weakened, and the conductivity of the cobalt oxide nano particles is improved; the distance between the hydroxylated carbon oxide nanotubes is increased, the bonding action between hydroxyl components on the hydroxylated carbon oxide nanotubes is weakened, more active sites are exposed, and the hydroxyl components can also show different selectivities to dopamine and other interferent molecules through different electrostatic acting forces. The prepared composite material has large specific surface area, high catalytic activity, good conductivity and multiple active catalytic sites, and can be stably and uniformly dispersed in aqueous solution. The composite material is used as an electrochemical sensing material, and the prepared modified electrode has a large number of active sites and excellent conductivity, has excellent catalytic performance and selectivity to dopamine, and can be applied to electrochemical detection of dopamine.
Description
Technical Field
The invention belongs to the technical field of composite materials, and particularly relates to a cobalt oxide-hydroxylated single-walled carbon nanotube composite material, and preparation and application thereof.
Background
Dopamine (DA) is an important catechol neurotransmitter in the human central system and plays an important role in controlling human activities such as emotion, cognition, behavior, and memory. Disorders of dopamine concentration in the brain can cause schizophrenia, parkinson's disease, huntington's syndrome, and HIV infection. DA concentration in human body can be used as pathological index of the above diseases, and its equilibrium concentration is 10.0 nmol L in normal human body -1 -1.0 μmol L -1 The content of the extract in the Parkinson's disease patient can be as low as 1.0 nmol L -1 Therefore, the detection technology with high sensitivity and accurate result is selected to have important practical significance. Because the electrochemical technology has the advantages of instant detection, convenience, high sensitivity, simple operation and the like, the electrochemical technology has been widely applied to concentration detection of DA, but Uric Acid (UA) and Ascorbic Acid (AA) coexisting with the DA can influence the detection result in an oxidation potential window of DA, so that the construction of an electrochemical sensing platform with high sensitivity and high selectivity is still a challenge at present.
Cobalt oxide (Co) 3 O 4 ) As one of the transition metal oxides, due to its high theoretical capacity, crystallinity of nano-scale, large specific surface area and chemical stability, has been widely used in the fields of supercapacitors, lithium ion batteries, catalysts, solar energy converters, electrochemical sensing, and the like; co (Co) 3 O 4 Crystal structure with spinel type and Co with magnetism 2+ Distributed in tetrahedral sites, other than magnetic Co 3+ Distributed in octahedral sites, where a large number of unoccupied tetrahedral and octahedral interstitial sites are available for ion migration, such that Co 3 O 4 Has excellent catalytic activity. However, low electrical conductivity limits its application in the electrochemical field, and at present, combining it with conductive materials (metal nanoparticles, metal oxides, carbon nanomaterials, etc.) is a major solution to improve its conductivityIn the scheme, the metal nano ions and the metal oxides have the defects of high price, easy aggregation and the like, and the prepared composite material has poor stability, so the carbon nano material is selected as a modified substrate in the invention.
Carbon nanotubes are considered to be an excellent electrochemical sensing material due to their high electrical conductivity, efficient catalytic activity and less surface contamination; carbon nanotubes are classified into single-walled carbon nanotubes (SWCNTs) and multi-walled carbon nanotubes (MWCNTs), and single-walled carbon nanotubes have better electronic characteristics than multi-walled carbon nanotubes. For a network of freely aligned SWCNTs, when used for electrode surface modification, it is equivalent to a thin conductive layer with abundant internal connection points, which is advantageous for fast electron transfer, high sensitivity and low detection limit. However, SWCNTs have very poor dispersibility in water, are easy to agglomerate, cannot form a uniform electrode modification layer, and in order to solve the problem, hydrophilic groups (-OH) are introduced into the surface of the SWCNTs to form the hydroxylated single-walled carbon nanotubes (SWCNTs-OH) with good dispersibility and stability, thereby providing convenience for the application of the SWCNTs in the field of electrochemical sensing. In addition, the surface oxygen-containing functional group can generate attraction action on dopamine molecules through hydrogen bonds and electrostatic attraction, and generate electrostatic repulsion on interferents AA and UA, so that the constructed electrochemical sensing material has excellent selectivity.
Researchers are constantly striving to develop composite materials with high sensitivity, high selectivity, pollution resistance and good stability for electrode modification, but the composite materials still face serious challenges, and the development of composite materials with excellent electrochemical performance is of great practical significance.
Disclosure of Invention
The invention aims to solve the technical problem of providing a cobalt oxide-hydroxylation single-walled carbon nanotube composite material, which has good stability and selectivity, and the cobalt oxide/hydroxylation single-walled carbon nanotube modified electrode prepared by the composite material can be applied to electrochemical detection of dopamine.
The technical scheme of the invention is as follows:
a cobalt oxide-hydroxylation single-wall carbon nanotube composite material is prepared by ultrasonic assembly of cobalt oxide nano particles and hydroxylation single-wall nanotubes.
Furthermore, the cobalt oxide nano particles are prepared by a hydrothermal method.
Further, the preparation method of the cobalt oxide nanoparticle comprises the following steps: mixing cobalt nitrate hexahydrate solution with ammonia water, wherein the molar ratio of the cobalt nitrate hexahydrate solution to the ammonia water is 1:2-1:40, stirring for 0.5-4h, transferring to a reaction kettle, performing hydrothermal reaction at 100-180 ℃ for 1-12h, cooling, collecting a product, washing with ultrapure water, and drying at 50-60 ℃ for 10-15 h.
Further, the preparation method of the hydroxylation single-wall nanotube comprises the following steps: adding single-wall carbon nano tubes into 30% hydrogen peroxide aqueous solution, stirring and reacting at 50-100 ℃ for 1-6h, cooling, washing the reaction solution with ethanol and ultrapure water, collecting precipitate, and freeze-drying at a temperature not higher than-50 ℃ for 24-48 h.
Further, the mass ratio of the cobalt oxide nano particles to the hydroxylated single-wall nano tubes is 4:1-1:4; the ultrasonic assembly time is 1-30min, and the power is 60-180W.
The preparation method of the cobalt oxide/hydroxylated single-walled carbon nanotube modified electrode comprises the following steps of coating the cobalt oxide-hydroxylated single-walled carbon nanotube composite material on the surface of a glassy carbon electrode, and drying to obtain the electrode.
Further, on the surface of the glassy carbon electrode with the diameter of 3mm, the coating amount of the cobalt oxide-hydroxylation single-walled carbon nanotube composite material is 3-10 mu L; drying with air flow or infrared lamp for 10min-3 hr.
An application of the cobalt oxide/hydroxylation single-walled carbon nanotube modified electrode in electrochemical detection of dopamine.
Furthermore, the cobalt oxide/hydroxylated single-walled carbon nanotube modified electrode is used as a working electrode, the Ag/AgCl electrode is used as a reference electrode, the platinum wire electrode is used as an auxiliary electrode, and dopamine is detected in the electrolyte.
The invention has the following beneficial effects:
the cobalt oxide-hydroxylation single-walled carbon nanotube composite material comprises: (1) Cobalt oxide is distributed in a crosslinked hydroxylated single-walled carbon nanotube network structure, firstly, the coagulation of cobalt oxide nano particles is inhibited, the conductivity of the cobalt oxide is improved, and more catalytic sites are exposed; secondly, the distance between the hydroxylated single-walled carbon nanotubes is increased, the bonding effect between hydroxyl components on the hydroxylated single-walled carbon nanotubes is weakened, more free hydroxyl components can be obtained, and more dopamine molecules are adsorbed to an electrode modification material interface through hydrogen bonding effect; the combination of the two also enables the composite material to have a large active surface area and effective catalytic sites. The above points enable the cobalt oxide-hydroxylation single-walled carbon nanotube composite material modified electrode to exhibit extremely high electrocatalytic activity to dopamine. (2) The hydroxyl component on the surface of the hydroxylated single-walled carbon nanotube presents electronegativity in the electrolyte, and can realize the selective detection of dopamine, ascorbic acid and uric acid through different electrostatic acting forces, so that the cobalt oxide/hydroxylated single-walled carbon nanotube modified electrode presents excellent selectivity to dopamine. (3) The cobalt oxide-hydroxylation single-walled carbon nanotube composite material has good dispersibility and stability in aqueous solution, so that the detection result of the cobalt oxide/hydroxylation single-walled carbon nanotube modified electrode on dopamine is more stable and accurate. The cobalt oxide-hydroxylation single-walled carbon nanotube composite material can be widely applied to the field of electrochemical detection.
Drawings
FIG. 1 is a scanning electron microscope image of a hydroxylated single-walled carbon nanotube (A), cobalt oxide (B) and cobalt oxide-hydroxylated single-walled carbon nanotube composite (C), respectively;
FIG. 2 is an X-ray diffraction spectrum of cobalt oxide and cobalt oxide-hydroxylated single-walled carbon nanotube composites (A), and an infrared spectrum of hydroxylated single-walled carbon nanotubes (B, a) and cobalt oxide-hydroxylated single-walled carbon nanotube composites (B, B), respectively;
fig. 3 is a differential pulse voltammogram of a bare electrode (a, a), hydroxylated single-walled carbon nanotubes (a, b), cobalt oxide (a, c), and cobalt oxide-hydroxylated single-walled carbon nanotube composite (a, d) modified glassy carbon electrode versus dopamine, respectively; the method comprises the steps of (1) catalyzing differential pulse voltammograms (B) and standard curves (C) of dopamine with different concentrations by using cobalt oxide/hydroxylated single-walled carbon nanotube modified electrodes, and detecting differential pulse voltammograms (D) of dopamine with certain concentrations in the presence of interferents (ascorbic acid and uric acid) with different concentrations;
FIG. 4 shows the results of the determination of dopamine in fetal bovine serum by using the cobalt oxide/hydroxylated single-walled carbon nanotube modified electrode of the present invention.
Detailed Description
The present invention will be described in detail with reference to the following examples, which are only preferred embodiments of the present invention and are not limiting thereof.
Example 1
The preparation method of the cobalt oxide/hydroxylation single-walled carbon nanotube modified electrode comprises the following steps:
s1, preparing cobalt oxide nano particles: mixing 0.5 mmol of cobalt nitrate hexahydrate solution with 12 mmol of ammonia water, stirring at normal temperature (25 ℃) for 1 hour, then transferring to a reaction kettle, carrying out hydrothermal reaction at 140 ℃) for 6h, cooling to room temperature, collecting a product, washing with ultrapure water, and drying at 60 ℃ for 12h to obtain the cobalt oxide nano particles;
s2, preparing a hydroxylated single-walled carbon nanotube: adding SWCNTs of 200 mg into 50 mL of 30% hydrogen peroxide water solution by adopting a condensation reflux device, stirring and reacting at 100 ℃ for 4h, repeatedly washing the reaction solution with ethanol and ultrapure water, collecting reaction precipitate, and freeze-drying at-50 ℃ for 24 h to prepare the hydroxylated single-walled carbon nanotube;
s3, preparing a cobalt oxide-hydroxylation single-walled carbon nanotube composite material: mixing the cobalt oxide nano particles with hydroxylated single-walled carbon nano tubes according to the mass ratio of 2 mg to 1mg, adding 1ml of ultrapure water, and performing ultrasonic assembly for 10min with the power of 60W to obtain cobalt oxide-hydroxylated single-walled carbon nano tube composite material dispersion liquid;
s4, preparing a cobalt oxide/hydroxylation single-walled carbon nanotube modified electrode: and (3) dripping 7.0 mu L of cobalt oxide-hydroxylation single-walled carbon nanotube composite material dispersion liquid on the surface of the clean glassy carbon electrode, and airing 3h in air flow to obtain the composite material modified electrode.
Example 2
The preparation method of the cobalt oxide/hydroxylation single-walled carbon nanotube modified electrode comprises the following steps:
s1, preparing cobalt oxide nano particles: mixing 0.5 mmol of cobalt nitrate hexahydrate solution with 1 mmol of ammonia water, stirring at normal temperature (25 ℃) for 3 hours, then transferring to a reaction kettle, carrying out hydrothermal reaction at 180 ℃) for 4h, cooling to the room temperature, collecting a product, washing with ultrapure water, and drying at 60 ℃ for 12h to obtain the cobalt oxide nano particles;
s2, preparing a hydroxylated single-walled carbon nanotube: adding SWCNTs of 50 mg into 100 mL of 30% hydrogen peroxide water solution by adopting a condensation reflux device, stirring and reacting at 100 ℃ for 4h, repeatedly washing the reaction solution with ethanol and ultrapure water, collecting reaction precipitate, and freeze-drying at-50 ℃ for 24 h to prepare the hydroxylated single-walled carbon nanotube;
s3, preparing a cobalt oxide-hydroxylation single-walled carbon nanotube composite material: mixing the cobalt oxide nano particles with hydroxylated single-walled carbon nano tubes according to the mass ratio of 1mg to 1mg, adding 1ml of ultrapure water, and performing ultrasonic assembly for 30min with the power of 120W to obtain cobalt oxide-hydroxylated single-walled carbon nano tube composite material dispersion liquid;
s4, preparing a cobalt oxide/hydroxylation single-walled carbon nanotube modified electrode: and (3) dripping 8.0 mu L of cobalt oxide-hydroxylation single-walled carbon nanotube composite material dispersion liquid on the surface of the clean glassy carbon electrode, and airing in air flow for 10min to obtain the composite material modified electrode.
Example 3
The preparation method of the cobalt oxide/hydroxylation single-walled carbon nanotube modified electrode comprises the following steps:
s1, preparing cobalt oxide nano particles: mixing 0.5 mmol of cobalt nitrate hexahydrate solution with 2 mmol of ammonia water, stirring at normal temperature (25 ℃) for 2 hours, then transferring to a reaction kettle, carrying out hydrothermal reaction at 120 ℃ for 8h, cooling to room temperature, collecting a product, washing with ultrapure water, and drying at 60 ℃ for 12h to obtain the cobalt oxide nano particles;
s2, preparing a hydroxylated single-walled carbon nanotube: adding SWCNTs of 50 mg into 100 mL of 30% hydrogen peroxide water solution by adopting a condensation reflux device, stirring and reacting at 100 ℃ for 2h, repeatedly washing the reaction solution with ethanol and ultrapure water, collecting reaction precipitate, and freeze-drying at-50 ℃ for 24 h to prepare the hydroxylated single-walled carbon nanotube;
s3, preparing a cobalt oxide-hydroxylation single-walled carbon nanotube composite material: mixing the cobalt oxide nano particles with hydroxylated single-walled carbon nano tubes according to the mass ratio of 2 mg to 1mg, adding 1ml of ultrapure water, performing ultrasonic assembly for 15min, and obtaining cobalt oxide-hydroxylated single-walled carbon nano tube composite material dispersion liquid with the power of 180W;
s4, preparing a cobalt oxide/hydroxylation single-walled carbon nanotube modified electrode: and (3) dripping 9.0 mu L of cobalt oxide-hydroxylation single-walled carbon nanotube composite material dispersion liquid on the surface of the clean glassy carbon electrode, and airing 3h in air flow to obtain the composite material modified electrode.
The cobalt oxide-hydroxylation single-walled carbon nanotube composite material and the modified electrode prepared in the embodiment 1 are selected, catalytic analysis is carried out on dopamine, electrochemical characteristics are explored, and a scanning electron microscope image, an X-ray diffraction spectrogram and a Fourier infrared spectrogram are adopted to analyze the surface morphology, the crystal form and the surface modification functional groups of the material. The electrochemical detection results and the material characterization results are as follows:
as can be seen from fig. 1A, the hydroxylated single-walled carbon nanotubes exhibit an irregular winding distribution, and a 3D network structure having a large specific surface area is constructed; as can be seen from fig. 1B, the particle size of the hydrothermally synthesized cobalt oxide is relatively uniform, but a partial agglomeration phenomenon occurs; as can be seen from fig. 1C, the distribution of cobalt oxide over the hydroxylated single-walled carbon nanotubes can attenuate the aggregation phenomenon itself and increase the distance between the crosslinked hydroxylated single-walled carbon nanotubes, exposing more active catalytic sites that are masked in a tightly stacked structure.
It can be seen from fig. 2 that the synthesis of cobalt oxide and the assembly of the composite material was successful. In fig. 2A, the angles are 19.09 degrees, 31.28 degrees, 36.76 degrees and 37.8 degreesEight characteristic diffraction peaks at 9, 44.85, 55.65, 59.35 and 65.29 positions correspond to (111), (220), (311), (222), (400), (422), (511) and (440) crystal planes (JCPDS 74-2120), respectively, of spinel-type cobalt oxide. From the curve a in FIG. 2B, 3447 and 3447 cm -1 The absorption peak at this point illustrates the successful modification of the hydroxyl component on single-walled carbon nanotubes; in the b curve 665 cm -1 And 573 cm -1 The peak at which corresponds to the characteristic infrared absorption of cobalt oxide at 3624 cm -1 The peaks of (a) are characteristic absorption peaks of free hydroxyl components, which indicate that the recombination of cobalt oxide in the oxidized multi-wall carbon nano tube can increase the distance between tubes, weaken the bonding action between the hydroxyl components, expose more free hydroxyl components and further indicate the successful assembly of the cobalt oxide and the hydroxylated single-wall carbon nano tube composite material.
In fig. 3A, curve a illustrates that bare glassy carbon electrode has little catalytic activity towards dopamine; in the curve b, the hydroxylated single-walled carbon nanotube has good electron transfer characteristics and has certain catalytic capability on dopamine molecules; in the c curve, the poor conductivity of cobalt oxide makes its modified electrode have little galvanic response to dopamine; in the curve d, the current response generated by the glassy carbon electrode modified by the cobalt oxide-hydroxylation single-walled carbon nanotube composite material is 23.27,2.75 and 74.31 times of the current response generated by the bare electrode, the hydroxylation single-walled carbon nanotube and the cobalt oxide modified glassy carbon electrode respectively; the extremely high oxidation current and negative oxidation potential both indicate that the composite material has good catalytic activity on dopamine, has good conductivity and effective catalytic sites when being used for electrode surface modification, and can fully play the synergistic effect of cobalt oxide and hydroxylated single-walled carbon nanotubes. In FIGS. 3B and 3C, the concentration is 1-100. Mu. Mol L -1 In the range, the composite material modified electrode shows linear increase of catalytic current of dopamine, and the linear regression equation is thati p (μA) = 1.427 C DA (μmol L -1 ) – 0.852 (R 2 =0.997); calculating the lowest detection limit under the condition of 3 times of signal to noise ratioLOD) 0.08 mu mol L -1 . Can be obtained from FIG. 3DAs is known, ascorbic acid (0 to 250. Mu. Mol L) as an interfering substance was added to the detection system -1 ) And uric acid (0-120 mu mol L) -1 ) For 30. Mu. Mol L -1 The current response of the dopamine is not affected, so that the composite material modified electrode has higher selectivity to the dopamine.
In order to verify the application of the cobalt oxide/hydroxylation single-walled carbon nanotube modified electrode in actual detection, the dopamine content in an actual sample of fetal bovine serum is measured, and the accuracy of a detection result is verified by adopting a labeled recovery method; as shown in FIG. 4, the relative standard deviation of dopamine in the fetal bovine serum was measured [ (]RSD) And recovery rates of 3.02% -5.83% and 93.68% -105.47%, respectively.
The cobalt oxide-hydroxylation single-walled carbon nanotube prepared by the method has the advantages of large specific surface area, high catalytic activity, good conductivity, multiple active catalytic sites and capability of being stably and uniformly dispersed in aqueous solution. The cobalt oxide/hydroxylation single-walled carbon nanotube modified electrode prepared by the method can realize high-sensitivity, high-selectivity and accurate detection results when applied to electrochemical detection of dopamine.
Claims (7)
1. The cobalt oxide-hydroxylated single-walled carbon nanotube composite material is characterized by being prepared by ultrasonic assembly of cobalt oxide nano particles and hydroxylated single-walled carbon nanotubes; the mass ratio of the cobalt oxide nano particles to the hydroxylated single-walled carbon nano tubes is 4:1-1:4; the ultrasonic assembly time is 1-30min, and the power is 60-180W; the preparation method of the hydroxylation single-walled carbon nanotube comprises the following steps: adding single-wall carbon nano tubes into 30% hydrogen peroxide aqueous solution, wherein the dosage ratio of the mass of the single-wall carbon nano tubes to the volume of the hydrogen peroxide aqueous solution is 5mg to 1ml to 1mg to 2ml, stirring and reacting for 1 to 6 hours at the temperature of 50 to 100 ℃, cooling, washing the reaction solution with ethanol and ultrapure water, collecting precipitate, and freeze-drying for 24 to 48 hours at the temperature of not higher than-50 ℃.
2. The cobalt oxide-hydroxylated single-walled carbon nanotube composite of claim 1, wherein the cobalt oxide nanoparticles are prepared by a hydrothermal process.
3. The cobalt oxide-hydroxylated single-walled carbon nanotube composite according to claim 2, wherein the cobalt oxide nanoparticles are prepared by: mixing cobalt nitrate hexahydrate solution with ammonia water, wherein the molar ratio of the cobalt nitrate hexahydrate solution to the ammonia water is 1:2-1:40, stirring for 0.5-4h, transferring to a reaction kettle, performing hydrothermal reaction at 100-180 ℃ for 1-12h, cooling, collecting a product, washing with ultrapure water, and drying at 50-60 ℃ for 10-15 h.
4. The cobalt oxide/hydroxylated single-walled carbon nanotube modified electrode is characterized by being prepared by coating the cobalt oxide-hydroxylated single-walled carbon nanotube composite material according to any one of claims 1-3 on the surface of a glassy carbon electrode and drying the electrode.
5. The cobalt oxide/hydroxylated single-walled carbon nanotube modified electrode according to claim 4, wherein the coating amount of the cobalt oxide-hydroxylated single-walled carbon nanotube composite material is 3 to 10 μl on the surface of the glassy carbon electrode having a diameter of 3 mm; drying with air flow or infrared lamp for 10min-3 hr.
6. Use of the cobalt oxide/hydroxylated single-walled carbon nanotube modified electrode of claim 4 in electrochemical detection of dopamine.
7. The use according to claim 6, wherein the cobalt oxide/hydroxylated single-walled carbon nanotube modified electrode is used as a working electrode, ag/AgCl electrode is used as a reference electrode, platinum wire electrode is used as an auxiliary electrode, and dopamine is detected in an electrolyte.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106442689A (en) * | 2016-09-29 | 2017-02-22 | 青岛大学 | Preparation and application of dopamine sensors on basis of nickel oxide-carbon nano-tubes |
| CN108982609A (en) * | 2018-06-19 | 2018-12-11 | 中国科学院合肥物质科学研究院 | A kind of three-dimensional carbon cloth/ferronickel layered hydroxide cladding cobaltosic oxide nano line composite material and preparation method and application |
| CN109036860A (en) * | 2018-08-30 | 2018-12-18 | 东华理工大学 | A kind of ferroso-ferric oxide/single angle combination electrode material and preparation method thereof |
| CN110681417A (en) * | 2019-09-20 | 2020-01-14 | 太原理工大学 | Nano Co3O4Preparation method of carbon nanotube integrated air electrode catalytic material |
| CN111653798A (en) * | 2020-06-22 | 2020-09-11 | 武汉瑞科美新能源有限责任公司 | Metal-air battery cathode, preparation method and application thereof, and battery |
-
2021
- 2021-01-25 CN CN202110096815.4A patent/CN113003614B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106442689A (en) * | 2016-09-29 | 2017-02-22 | 青岛大学 | Preparation and application of dopamine sensors on basis of nickel oxide-carbon nano-tubes |
| CN108982609A (en) * | 2018-06-19 | 2018-12-11 | 中国科学院合肥物质科学研究院 | A kind of three-dimensional carbon cloth/ferronickel layered hydroxide cladding cobaltosic oxide nano line composite material and preparation method and application |
| CN109036860A (en) * | 2018-08-30 | 2018-12-18 | 东华理工大学 | A kind of ferroso-ferric oxide/single angle combination electrode material and preparation method thereof |
| CN110681417A (en) * | 2019-09-20 | 2020-01-14 | 太原理工大学 | Nano Co3O4Preparation method of carbon nanotube integrated air electrode catalytic material |
| CN111653798A (en) * | 2020-06-22 | 2020-09-11 | 武汉瑞科美新能源有限责任公司 | Metal-air battery cathode, preparation method and application thereof, and battery |
Non-Patent Citations (2)
| Title |
|---|
| Facile Self-Assembly Route to Co3O4 Nanoparticles Confined into Single-Walled Carbon Nanotube Matrix for Highly Reversible Lithium Storage;Zhiqiang Xie et al.;《Electrochimica Acta》;20170316;第613-622页 * |
| Probing the electrochemical behaviour of SWCNT–cobalt nanoparticles and their electrocatalytic activities towards the detection of nitrite at acidic and physiological pH conditions;Abolanle S. Adekunle et al.;《Electrochimica Acta》;20090314;第55卷;第4319–4327页 * |
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