CN111232955A - Based on CoNxSpiral nitrogen-doped carbon nano tube and preparation and application thereof - Google Patents

Based on CoNxSpiral nitrogen-doped carbon nano tube and preparation and application thereof Download PDF

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CN111232955A
CN111232955A CN202010041026.6A CN202010041026A CN111232955A CN 111232955 A CN111232955 A CN 111232955A CN 202010041026 A CN202010041026 A CN 202010041026A CN 111232955 A CN111232955 A CN 111232955A
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con
nitrogen
doped carbon
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carbon nanotube
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赵振路
高存源
沙琦琦
怀杰
王建荣
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University of Jinan
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/158—Carbon nanotubes
    • C01B32/16—Preparation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8825—Methods for deposition of the catalytic active composition
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
    • H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/96—Carbon-based electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Abstract

The invention provides a method based on CoNxThe spiral-wound nitrogen-doped carbon nanotube and the preparation method thereof. The product is obtained by adopting a secondary pyrolysis method, the preparation process is simple, and the industrial realization is easy. The prepared carbon nano-tube has uniform diameter, CoNxThe base nanoparticles are uniformly distributed on the carbon nanotubes, are efficient oxygen reduction reaction catalysts, have higher half-slope potential and limiting current density compared with 20% commercial Pt/C, and more importantly, have good methanol tolerance and stability. The catalyst has important significance in electrochemical energy conversion equipment such as fuel cells, metal-air cells and the like.

Description

Based on CoNxSpiral nitrogen-doped carbon nano tube and preparation and application thereof
Technical Field
The invention belongs to the technical field of material chemistry, and particularly relates to a CoN-based materialxThe spiral winding nitrogen-doped carbon nanotubeAnd applications thereof.
Background
The fuel cell, the metal-air battery and other clean and efficient energy conversion devices convert chemical energy into electric energy in an electrochemical mode, are not limited by Carnot cycle, reduce unnecessary energy loss and improve the energy conversion efficiency. Therefore, extensive research has been conducted. It still faces a series of scientific and technical challenges, the most critical being the slow kinetics of the oxygen reduction reaction at the cathode. Therefore, a high efficiency oxygen reduction catalyst is needed to increase the reaction rate and realize the practical application of the energy conversion device. At present, the most important catalyst for oxygen reduction is a platinum-based catalyst, but the platinum-based catalyst is widely applied on a large scale due to a series of problems of high price, scarce resources, poor methanol tolerance, poor stability and the like. To reduce the reliance on noble metal catalysts, it is of current interest to investigate low or no platinum. Currently, non-noble metal catalysts are rapidly developed, and particularly, the combination of transition metals and carbon nanotubes shows excellent electrocatalytic activity, but still have many disadvantages.
The oxygen reduction reaction is the key of electrochemical energy conversion equipment such as fuel cells, metal-air cells and the like, the reaction process is complex, and various intermediate oxygen-containing species such as O can be generated2 -、OH-、HO2 -And H2O2And the like. And the ORR process is very different in alkaline, acidic or non-aqueous aprotic electrolytes.
In alkaline electrolytes, the oxygen reduction reaction involves four elementary reactions:
(i)O2+2H2O+4e−→4OH−，E𝑖=0.4V vs RHE (1)
(ii)O2+2H2O+2e−→HO2 −+OH−，E𝑖𝑖=−0.065V vs RHE (2)
(iii)HO2 −+H2O+2e−→3OH−，E𝑖𝑖𝑖=0.867 V vs RHE (3)
(iv)HO2 −→OH−+1/2O2(4)
reaction (1) is a direct four-electron transfer pathway, i.e. O2Direct generation of OH by four-electron transfer process−. Reaction (2) is a two-electron transfer pathway, in which HO is produced2 −HO generated2 −OH formation by another two-electron transfer process−However, in this process, disproportionation reaction occurs to form O2。
In an acidic electrolyte, the oxygen reduction reaction also involves four elementary reactions:
(i)O2+4H++4e−→2H2O，E𝑖=1.229 V vs RHE (1)
(ii)O2+2H++2e−→H2O2，E𝑖𝑖=0.670 V vs RHE (2)
(iii)H2O2+2H++2e−→H2O，E𝑖𝑖𝑖=1.770 V vs RHE (3)
(iv)H2O2→H2O+1/2O2(4)
reaction (1) is a direct four-electron transfer pathway, i.e. O2Direct generation of H by four electron transfer process2And O. Reaction (2) is a two-electron transfer pathway, in which H is produced2O2H produced by2O2Generation of H by another two-electron transfer process2O or by this process2。
In summary, the four-electron pathway is more efficient from an energy conversion perspective, but a highly active catalyst is required to match it, and therefore, an excellent ORR electrocatalyst should satisfy the four-electron pathway. Currently, platinum-based noble metal catalysts are the best oxygen reduction catalysts, but their high price prevents their large-scale use, and thus there is a need to improve the catalytic efficiency of oxygen reduction electrocatalysts to reduce or eliminate the dependence on noble metals. With electrocatalysts for oxygen reduction in corrosive environmentsPoor stability under operating conditions and easy poisoning. The results of the United states department of energy survey showed that the fuel cell vehicle used 0.4 mg/m of cathode2Even more platinum, and the stability of these catalysts still does not meet the requirements of industrialization. Therefore, how to reduce the cost and improve the durability of the catalyst by reducing the amount of platinum or not using platinum while improving the catalytic performance is an important issue of electrocatalytic research at present. In recent years, with the development of material science and nanotechnology, significant progress has been made in the research of low-platinum or platinum-free oxygen reduction catalysts with reasonable design and excellent performance, wherein the most important research directions are low-content noble metal catalysts, non-noble metal heteroatom catalysts and metal-heteroatom-free doped carbon-based catalysts.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a CoNx-based spiral-wound nitrogen-doped carbon nanotube which has excellent oxygen reduction activity, better starting potential and higher current density, better methanol tolerance and higher stability.
In order to achieve the purpose, the invention adopts the following technical scheme.
Based on CoNxThe preparation method of the spiral nitrogen-doped carbon nano tube comprises the following steps:
(1) calcining ZIF-67 at 350 ℃ for 1.5 hours, calcining at 800 ℃ for 3.5 hours, and cooling to obtain black powder;
(2) and (3) mixing the black powder obtained in the step (2) with melamine, and sequentially calcining at 520 ℃ for 2 hours, 540 ℃ for 2 hours and 800 ℃ for 2 hours to obtain the spiral nitrogen-doped carbon nanotube.
In the step (1) and the step (2), the temperature rising speed is 3 ℃/min; the cooling rate is 5 ℃/min from 800 ℃ to 500 ℃, and the temperature is naturally cooled below 500 ℃.
In the step (2), the addition amount of melamine is 2 times of the mass of ZIF-67.
Preferably, the ZIF-67 is prepared by the following method:
mixing Co (NO)3）2·6H2O andCTAB is dissolved in water, then 2-methylimidazole is dissolved in water, the two solutions are mixed and stirred for 30 minutes, the mixture is placed at room temperature for 24 hours to obtain a purple solution, and then the purple solution is centrifuged, washed and dried.
The Co (NO)3）2·6H2O, CTAB, 2-methylimidazole and water in a molar ratio of 66: 1: 3686: 333333.
the centrifugation speed was 8000rpm and the centrifugation time was 15 minutes.
The washing step is ethanol washing for 3 times.
The spiral nitrogen-doped carbon nanotube obtained by the preparation method is in a spiral structure similar to a spring, the diameter of the tube is about 50nm, and the CoN is wrapped at the tip of the tubexNanoparticles of CoN homogeneously dispersed on the surface of the tubexAnd (3) nanoparticles.
Based on CoNxThe helical nitrogen-doped carbon nanotubes of (a) can be used as oxygen reduction catalysts.
The distribution of the transition metal nanoparticles on the nitrogen-doped carbon nanotube can influence the oxygen reduction activity of the carbon nanotube, and compared with the transition metal-based nanoparticles loaded on the outer surface of the nitrogen-doped carbon nanotube, the transition metal-based nanoparticles wrapped in the nitrogen-doped carbon nanotube can induce host-guest electron interaction, so that the local work function of the carbon nanotube is improved, and the outer surface of the carbon layer has higher oxygen reduction reaction activity; meanwhile, the weakening of the Ostwald effect in the oxygen reduction process can greatly improve the stability of the Ostwald effect. According to the invention, the pyrolyzed ZIF-67 and melamine are mixed and pyrolyzed for the second time, and the pyrolyzed melamine derivative and transition metal interact at 520 ℃ and 540 ℃ to form transition metal nano particles. After heating to 800 ℃, the formed transition-based metal nanoparticles facilitate the formation of nitrogen-doped carbon nanotubes. By means of pyrolysis, the catalyst with cobalt transition metal nanoparticles embedded in the nanotubes is a high-efficiency oxygen reduction reaction electrocatalyst and has the synergistic effect of doped carbon nanotubes and transition active sites.
The invention has the following advantages:
the invention adoptsThe method of secondary pyrolysis synthesizes the catalyst based on CoNxThe spiral-wound nitrogen-doped carbon nanotube has simple preparation process and is easy to realize industrially. The prepared carbon nano-tube has uniform diameter, CoNxThe base nanoparticles are uniformly distributed on the carbon nanotubes, are efficient oxygen reduction reaction catalysts, have higher half-slope potential and limiting current density compared with 20% commercial Pt/C, and more importantly, have good methanol tolerance and stability. The catalyst has important significance in electrochemical energy conversion equipment such as fuel cells, metal-air cells and the like.
Drawings
FIG. 1 is a micrograph of ZIF-67 and CoNx-based helically coiled nitrogen-doped carbon nanotubes;
FIG. 2 is based on CoNxA transmission electron microscope image and an element mapping image of the spirally wound nitrogen-doped carbon nanotube;
FIG. 3 is based on CoNxThe X-ray diffraction pattern of the spiral-wound nitrogen-doped carbon nano tube and the X-ray electron energy spectrogram of different constituent elements;
FIG. 4 is based on CoNxElectrochemical oxygen reduction test pictures of the spiral wound nitrogen doped carbon nanotubes and 20% commercial Pt/C of (a);
FIG. 5 is based on CoNxThe cyclic voltammograms of the spiral wound nitrogen doped carbon nanotubes and 20% commercial Pt/C under different conditions.
Detailed Description
The present invention will be further described with reference to the following examples and drawings, but the present invention is not limited to the following examples.
Example 1 CoN-basedxPreparation of the spiral-wound nitrogen-doped carbon nanotube
(1) 0.58g of cobalt nitrate hexahydrate (Co (NO) was weighed out on an electronic balance3)2·6H2O) and 0.01g cetyltrimethylammonium bromide (CTAB) were placed in a clean beaker and 20mL of deionized water was pipetted into the beaker for dissolution. And taking another clean beaker, weighing 9.08g of 2-methylimidazole into the clean beaker by using an electronic balance, and transferring 140mL of deionized water by using a liquid transfer gun to add into the beaker for dissolving. Dissolving the two solutionsMixing the solutions, stirring for 30 min, standing at room temperature for 24 hr, centrifuging to collect purple solid, and drying at 80 deg.C under Scanning Electron Microscope (SEM) as shown in FIG. 1- (a);
(2) putting the dried ZIF-67 into a clean ceramic boat, and calcining in a tube furnace: firstly, heating to 350 ℃ at 3 ℃/min, calcining for 1.5 hours, and then heating to 800 ℃ at 3 ℃/min, calcining for 2 hours; cooling to obtain black powder;
(3) uniformly mixing black powder and 2g of melamine, putting the mixture into a clean ceramic boat, putting the boat into a tube furnace, heating the mixture to 520 ℃, 540 ℃, and 800 ℃ at the speed of 3 ℃/min, calcining the mixture for 2 hours respectively, cooling the mixture to 500 ℃ at the speed of 5 ℃/min, and then naturally cooling the mixture to room temperature from 500 ℃ to obtain the CoN-based materialxThe nitrogen-doped carbon nanotube is spirally wound.
Example 2 CoN-basedxThe composition and appearance of the spiral-wound nitrogen-doped carbon nanotube
CoN-based obtained in example 1xThe scanning electron microscope of the spiral wound nitrogen-doped carbon nanotube is shown in FIG. 1- (b), the transmission electron microscope is shown in FIG. 1- (c-e), and the high resolution transmission electron microscope is shown in FIG. 1- (f). Scanning electron microscope images (FIGS. 1 a-b) show CoN-basedxAfter successful preparation of ZIF-67 (fig. 1 a), after adding melamine and performing secondary calcination, spiral carbon nanotubes with a diameter of about 50nm were synthesized, and transmission electron microscopy images (fig. 1 c-e) showed the presence of a small amount of a layered carbon shell surrounding the carbon nanotubes based on CoNxEspecially at the tip and inside of the carbon nanotubes, and furthermore, high resolution transmission electron microscopy images (fig. 1 f) show a lattice distance of about 0.24 nm.
Intercepting a section of the CoN-based data obtained in example 1xThe obtained transmission electron microscope and the element mapping of the section are respectively shown in fig. 2- (a) and 2- (b). Based on CoN according to element mappingxNot only at the tip or inside of the carbon nanotube, but also uniformly dispersed on the surface of the carbon nanotube, may result in higher activity of ORR. It has also been found that nitrogen atomsThe elements are uniformly distributed throughout the structure, which indicates that abundant N heteroatoms can be uniformly doped into the carbon material under pyrolysis.
CoN-based obtained in example 1xThe X-ray diffraction pattern, C1 s orbital high resolution X-ray electron energy spectrum, N1 s orbital high resolution X-ray electron energy spectrum and cobalt 2p orbital high resolution X-ray electron energy spectrum of the spirally wound nitrogen-doped carbon nanotube are respectively shown in FIGS. 3 (a-d). Further research on the CoN-based photoelectron spectroscopy by X-ray diffraction and high-resolution X-rayxThe spiral-wound nitrogen-doped carbon nanotube has a composition and a structure. As shown in fig. 3a, two diffraction peaks at about 26.4 ° and 44.2 ° belong to the C (002) plane and the Co (111) plane. FIG. 3 (b-d) shows the X-ray photoelectron spectrum of the sample, further illustrating the detailed composition. In the high resolution spectrum of C1 s (fig. 3 b), two peaks 284.5 eV and 285.6 eV, respectively, can be observed, which are designated as C-C, C = N bonds. The broader peaks at 286eV and 289eV are N-sp 3C and C-O. The X-ray electron spectrum of N1 s (FIG. 3 c) shows four peaks 398.5 eV, 400.8 eV, 401.8eV and 403.9 eV, corresponding to pyridine nitrogen, pyrrole nitrogen, graphite nitrogen and nitrogen oxide, respectively. The Co 2p spectrum shows two distinct bands at 794.7 eV and 779.2 eV, which readily distribute to Co 2p respectively1/2And Co 2p3/2(FIG. 3 d). And Co 2p3/2Peak indications based on CoNxThe spiral-wound nitrogen-doped carbon nanotube contains 778.4 eV of metal Co0And 780.4 eV of Co2+. The metal Co is from Co2+Reduction of (2). The Co-Nx moiety with a highly active ORR can be generated by Co from decomposed organic ligands during pyrolysis2+And a combination of N atoms. Also consistent with the results of the EDS mapping is that the distribution of N and Co at the CNTs is essentially the same. In short, based on CoNxSubstantially facilitates the growth of carbon nanotubes.
Example 3 CoN-basedxElectrochemical performance of the spiral-wound nitrogen-doped carbon nanotube
CoN-based prepared in example 1xThe spiral winding nitrogen-doped carbon nanotubeCommercially available 20% Pt/C was measured for electrochemical performance at a three electrode electrochemical workstation and the results are shown in FIG. 4, where (a) is the cyclic voltammetry test (black and red curves representing sweep rates of 50 mV/s in 0.1M KOH solution saturated with nitrogen and oxygen), (b) is the linear sweep voltammogram at different rotational speeds, (C) is the electron transfer profile at different potentials from the K-L equation from (b) and (d) is Pt/C and CoN-basedxThe oxygen reduction polarization curves of the spiral wound nitrogen doped carbon nanotube catalyst of (1600 rpm) are compared. As can be seen from cyclic voltammetry test FIG. 4 (a), based on CoNxThe spiral-wound nitrogen-doped carbon nanotube catalyst has an obvious oxygen reduction peak in an oxygen saturated environment, which indicates that the catalyst has oxygen reduction catalytic activity. As can be seen from the linear sweep voltammograms at different sweep rates, the catalyst has higher oxygen reduction activity (FIG. 4b), and the initial voltage at 1600 rpm is 1.02eV, and the half slope voltage is 0.92 eV. Notably, its oxygen reduction catalytic activity is higher than some previously reported transition metal and nitrogen doped carbon materials. The Koutecky-Levich (K-L) curves at the corresponding potentials show an approximately parallel linear relationship (FIG. 4c), with electron transfer numbers (n) at values of 3.82-3.97, indicating the presence of a complete four electron transfer path. In contrast to the linear voltammogram (1600 rpm) for 20% of commercial Pt/C measured under the same conditions, based on CoNxThe spiral-wound nitrogen-doped carbon nanotube catalyst has higher half-slope potential and higher extreme diffusion current density than commercial Pt/C.
Determination of CoN-based prepared in example 1xThe methanol tolerance and stability of the spiral wound nitrogen doped carbon nanotube, commercially available Pt/C of (1) are shown in FIG. 5, in which FIG. 5 (a) is based on CoNxCyclic voltammetry curves (scan rate 50mV s) of spiral wound nitrogen doped carbon nanotubes in 0.5M methanol and 0.1M potassium hydroxide solution without methanol-1) FIG. (b) is a cyclic voltammogram of 20% commercial Pt/C in methanol and 0.1M potassium hydroxide solution without methanol (scan rate 50mV s)-1) Graph (c) shows the rotation speed at 1600rmp under 0.6VThe timing current response diagram of (a). Comparing FIG. 5 (a) and FIG. 5 (b), it can be seen that after adding methanol, it is based on CoNxThe cyclic voltammogram of the spiral wound nitrogen-doped carbon nanotubes varied little, whereas that of 20% commercial Pt/C varied greatly, showing that the CoN-based curvexThe spiral-wound nitrogen-doped carbon nanotube has better methanol tolerance in alkaline solution. In addition, by testing CoN-based samples under the same conditionsxThe long-term stability of the spiral-wound nitrogen-doped carbon nanotubes and 20% commercial Pt/C (FIG. 5 (C)), based on CoN, can be foundxThe spiral wound nitrogen doped carbon nanotube lost only 1.4% under the test of long-term stability, while the 20% commercial Pt/C lost 64.4%, and through the above test, it proved that the CoN-based carbon nanotubexThe stability of the spiral wound nitrogen doped carbon nanotube is far better than that of 20% commercial Pt/C.

Claims (8)

1. Based on CoNxThe preparation method of the spiral nitrogen-doped carbon nano tube is characterized by comprising the following steps:
(1) calcining ZIF-67 at 350 ℃ for 1.5 hours, calcining at 800 ℃ for 3.5 hours, and cooling to obtain black powder;
(2) and (3) mixing the black powder obtained in the step (2) with melamine, and sequentially calcining at 520 ℃ for 2 hours, 540 ℃ for 2 hours and 800 ℃ for 2 hours to obtain the spiral nitrogen-doped carbon nanotube.
2. The production method according to claim 1, wherein in the step (1) and the step (2), the temperature rising rate is 3 ℃/min; the cooling rate is 5 ℃/min from 800 ℃ to 500 ℃, and the temperature is naturally cooled below 500 ℃.
3. The production method according to claim 1, wherein in the step (2), the melamine is added in an amount of 2 times the mass of the ZIF-67.
4. The preparation method according to claim 1, wherein the ZIF-67 is prepared by the following method:
mixing Co (NO)3）2·6H2Dissolving O and CTAB in water, dissolving 2-methylimidazole in water, mixing the two solutions, stirring for 30 minutes, standing at room temperature for 24 hours to obtain a purple solution, centrifuging, washing and drying.
5. The method of claim 4, wherein the Co (NO) is3）2·6H2O, CTAB, 2-methylimidazole and water in a molar ratio of 66: 1: 3686: 333333.
6. the method according to claim 4, wherein the centrifugation speed is 8000rpm and the centrifugation time is 15 minutes; the washing step is ethanol washing for 3 times.
7. A helical N-doped carbon nanotube obtained by the method of any one of claims 1 to 6, wherein the shape is a spring-like helical structure, the diameter of the tube is about 50nm, and the tip of the tube is wrapped with CoNxNanoparticles of CoN homogeneously dispersed on the surface of the tubexAnd (3) nanoparticles.
8. CoN-based according to claim 7xThe spiral nitrogen-doped carbon nanotube as an oxygen reduction catalyst.
CN202010041026.6A 2020-01-15 2020-01-15 Based on CoNxSpiral nitrogen-doped carbon nano tube and preparation and application thereof Withdrawn CN111232955A (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108923051A (en) * 2018-07-06 2018-11-30 郑州大学 A kind of nitrogen-doped carbon nanometer pipe composite catalyst of package metals cobalt nano-particle and its application
CN110048128A (en) * 2019-04-19 2019-07-23 江苏师范大学 A kind of nitrogen-doped carbon nanometer pipe oxygen reduction electro-catalyst and preparation method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108923051A (en) * 2018-07-06 2018-11-30 郑州大学 A kind of nitrogen-doped carbon nanometer pipe composite catalyst of package metals cobalt nano-particle and its application
CN110048128A (en) * 2019-04-19 2019-07-23 江苏师范大学 A kind of nitrogen-doped carbon nanometer pipe oxygen reduction electro-catalyst and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
ZHENLU ZHAO ET AL.: "Pyrolysis derived helically nitrogen-doped carbon nanotubes with uniform cobalt for high performance oxygen reduction", 《APPLIED SURFACE SCIENCE》 *

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Application publication date: 20200605