CN113054209A - Directly-grown carbon nanotube-based non-noble metal fuel cell catalyst and preparation method thereof - Google Patents

Directly-grown carbon nanotube-based non-noble metal fuel cell catalyst and preparation method thereof Download PDF

Info

Publication number
CN113054209A
CN113054209A CN202110293632.1A CN202110293632A CN113054209A CN 113054209 A CN113054209 A CN 113054209A CN 202110293632 A CN202110293632 A CN 202110293632A CN 113054209 A CN113054209 A CN 113054209A
Authority
CN
China
Prior art keywords
noble metal
carbon nanotube
fuel cell
catalyst
cell catalyst
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202110293632.1A
Other languages
Chinese (zh)
Inventor
魏春光
梁燕
王静霞
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shenzhen Hanshu Technology New Energy Co ltd
Original Assignee
Shenzhen Hanshu Technology New Energy Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shenzhen Hanshu Technology New Energy Co ltd filed Critical Shenzhen Hanshu Technology New Energy Co ltd
Priority to CN202110293632.1A priority Critical patent/CN113054209A/en
Publication of CN113054209A publication Critical patent/CN113054209A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • 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
    • H01M4/9041—Metals or alloys
    • 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
    • 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
    • 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 discloses a catalyst for a directly-grown carbon nanotube-based non-noble metal fuel cell and a preparation method thereof, wherein the catalyst is formed by uniformly doping a non-noble metal element and a nitrogen element in the tube wall of a carbon nanotube, the non-noble metal element is a transition metal element and at least comprises an iron element and also can simultaneously comprise at least one of a manganese element, a cobalt element and a nickel element, and the preparation method is characterized in that the growth of the carbon nanotube and the co-doping of Fe-N active sites of the non-noble metal are synchronously realized by combining two sections of heat treatment with ammonia gas atmosphere heat treatment, so that the catalyst with good crystallinity, high graphitization degree and high active site density is obtained, the catalyst has excellent catalytic activity and stability, and meanwhile, the preparation process is simple, the synthesis raw materials are rich and cheap, and the requirements of. In addition, by adding non-noble metal element types, the multi-element non-noble metal catalyst containing non-noble metal Fe can be obtained to meet different application requirements.

Description

Directly-grown carbon nanotube-based non-noble metal fuel cell catalyst and preparation method thereof
Technical Field
The invention belongs to the technical field of fuel cells, and particularly relates to a directly-grown carbon nanotube-based non-noble metal fuel cell catalyst and a preparation method thereof.
Background
In order to solve the problems of continuously-intensified chemical and petrochemical resource exhaustion, environmental deterioration and the like, clean, renewable, low-cost and high-performance green power sources and energy storage technologies become global focus of attention, and energy storage is achievedThe battery is used as an energy conversion device for directly converting chemical energy of substances into electric energy, has the advantages of high energy conversion efficiency, environmental friendliness, quick start at room temperature and the like, and shows excellent application prospects. Among the key raw materials of the fuel cell, the electrode catalyst plays a key role in accelerating electrode reaction and improving energy conversion efficiency, while the traditional commercial fuel cell uses a catalyst based on noble metal platinum, which is expensive and deficient in resources, and limits the commercialization process of the fuel cell, so that the development of low-platinum or non-noble metal catalysts is one of the key tasks. Wherein non-noble transition metals (e.g., Fe, etc.) and nitrogen co-doped carbon-based non-noble metal catalysts (e.g., Fe-N-C catalysts) are most competitive in fuel cell electrocatalytic activity. The active site of such a catalyst is generally considered to be Fe-N formed by bonding a single atom of Fe and several adjacent N atom ligandsxAnd the chelating structure is embedded in the graphene plane and is covalently bonded with the peripheral C atoms. The catalyst has low price, flexible synthesis method and strong operability, and the oxygen reduction electrocatalytic activity under the acidic condition obtains important progress.
However, most of the carbon materials used in the current carbon-based non-noble metal catalysts are amorphous carbon with relatively poor crystallinity, such as activated carbon, carbon black and the like, and the carbon-based non-noble metal catalysts have the advantages of high specific surface area and high density of single-atom catalytic active sites. However, it is easily corroded under strong acid and high potential oxidizing conditions of the fuel cell, and has poor stability, which is the biggest obstacle to the commercial application of the fuel cell. In contrast, the carbon nanotube is used as a one-dimensional carbon nanomaterial, has high graphitization degree, is easy to stack to form a three-dimensional conductive network, and has good corrosion resistance, so that the prepared carbon nanotube-based non-noble metal catalyst is expected to remarkably improve the stability of the catalyst in a fuel cell.
At present, the method for preparing the carbon nanotube-based non-noble metal catalyst mainly adopts a carbon nanotube (such as a carbon nanotube prepared by a chemical vapor deposition method) which grows well in the early stage, and then functional groups or defects are formed on the surface of the carbon nanotube by chemical oxidation or other methods, so that the carbon nanotube-based non-noble metal catalyst is combined with a non-noble metal and a nitrogen source and then is subjected to heat treatment at high temperature to obtain the carbon nanotube-supported non-noble metal catalyst. Chinese patent CN101890365A discloses a non-noble metal as oxygen reduction catalyst and a preparation method thereof, which utilizes multi-wall carbon nano-tubes to mix with transition metal salt and organic matter, and then carries out high-temperature heat treatment to prepare the non-noble metal catalyst with the coordination of the metal salt and the organic matter in the carbon nano-tubes and the tube walls. However, because the degree of graphitization of the surface of the carbon nanotube is high, it is very difficult to directly load a uniform non-noble metal on the surface of the carbon nanotube, and it is difficult to form a large number of high-density monatomic active sites, resulting in low catalytic activity, and thus the performance requirements of commercial fuel cells cannot be met.
Huang Ren (ACS Catalysis, 2017, 7, 6485) and the like provide a method for directly growing transition metal and nitrogen element doped carbon nanotubes in one step, adenosine is used as a carbon source, ferric chloride is used as an iron source, hydrothermal polymerization is carried out in an N-N, 2-methyl formamide solvent for 12 hours, then treatment is carried out at high temperature (800 ℃) and in an argon atmosphere, a Fe-N co-doped carbon nanotube is directly grown, and synchronous doping of non-noble transition metal and nitrogen element is realized in the growth process of the carbon nanotubes. However, the method adopts organic substances such as adenosine as carbon sources, so that the price is high, long-time hydrothermal polymerization is needed in the preparation process, the process is complicated, the production cost is high, and the method is not favorable for large-scale production. In addition, the obtained Fe-N doped carbon nano tube has poor shape, very uneven tube diameter and thickness and poor crystallinity.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a directly-grown carbon nanotube-based non-noble metal fuel cell catalyst and a preparation method thereof, which take solid organic nitrogenous resin as a carbon source, synchronously realize the growth of the carbon nanotube and the co-doping of non-noble metal Fe-N active sites under the solid-phase catalysis condition, obtain the catalyst with good crystallinity, high graphitization degree and high density active sites, have excellent catalytic activity and stability, simple preparation process, rich synthetic raw material sources and low cost, and are beneficial to the application of the catalyst in commercial fuel cells. In addition, by adding non-noble metal element types, the multi-element non-noble metal catalyst containing non-noble metal Fe can be obtained to meet different application requirements.
In order to achieve the purpose, the invention adopts the following technical scheme:
a catalyst for the directly grown carbon nanotube-based non-noble metal fuel cell is composed of the non-noble metal elements and nitrogen elements uniformly doped in the wall of carbon nanotube, wherein the non-noble metal elements are transition metal elements and at least contain iron element, and can also contain at least one of manganese element, cobalt element and nickel element.
A preparation method of a carbon nanotube-based non-noble metal fuel cell catalyst comprises the following steps:
(1) mixing and impregnating solid organic nitrogenous resin and non-noble metal salt solution, and drying the mixed solution to obtain a composite precursor;
(2) placing the composite precursor in a protective atmosphere, and carrying out heat treatment at the temperature of 450-600 ℃ for 0.5-5h, wherein the process is a carbon fixation process, so as to retain a carbonaceous structure in the composite precursor and provide an adequate carbon source for the subsequent growth of the carbon nanotube;
(3) continuously heating to 850-1100 ℃, treating for 0.5-5h, converting the protective atmosphere into an ammonia gas atmosphere, and directly growing the carbonaceous structure into a non-noble metal and nitrogen-doped carbon nanotube by catalysis under the condition that the non-noble metal composite precursor and ammonia gas coexist;
(4) and after the ammonia gas atmosphere treatment is finished, converting the ammonia gas atmosphere into a protective atmosphere, and naturally cooling to room temperature.
Furthermore, the mole ratio of the elements in the carbon nano tube is that the carbon element is more than 80%, the nitrogen element is less than 10%, and the non-noble metal element is less than 10%.
Furthermore, the solid organic nitrogen-containing resin is porous sponge-shaped and is at least one of melamine formaldehyde resin and melamine phenolic resin, and the sponge-shaped porous solid organic nitrogen-containing resin is used as a solid carbon source for growing the Fe-N doped carbon nano tube, and the porous structure of the sponge-shaped solid organic nitrogen-containing resin is also beneficial to the diffusion of reaction gas ammonia in the growth process of the carbon nano tube.
Further, the non-noble metal salt at least comprises iron salt, and also can simultaneously comprise at least one of manganese salt, cobalt salt and nickel salt. The ferric salt is at least one of ferric chloride hexahydrate, ferrous chloride, ferric sulfate, ferric nitrate, ferric acetylacetonate, ferric acetate and ferric oxalate.
Further, the ammonia gas atmosphere treatment temperature is 850-1100 ℃, the ammonia gas atmosphere treatment time is related to the gas flow, and the ammonia gas atmosphere treatment time is 10-60min under the gas flow of 1-15L/min.
Further, the protective atmosphere is argon or nitrogen.
Furthermore, at least one end of the carbon nano tube is of an open structure.
Compared with the prior art, the invention has at least the following beneficial effects:
(1) aiming at a nitrogen-containing carbon source of solid organic nitrogen-containing resin, the invention designs two stages of heat treatment processes, firstly, carbon fixation is carried out under protective atmosphere, the retention of a carbon structure in a precursor is realized to the maximum extent, a sufficient carbon source is provided for the subsequent growth of the carbon nano tube, then, the retained carbon structure is effectively etched through ammonia gas atmosphere treatment, the carbon nano tube has considerable growth speed, and meanwhile, the tube structure, the graphitization degree and the active site structure are effectively regulated and controlled, and the carbon nano tube with higher graphitization degree is obtained.
(2) The carbon nano tube grows through the solid organic nitrogenous resin, the surface of the carbon nano tube is provided with a large amount of ligand N elements, Fe can be anchored, and agglomeration is avoided, so that a high-density Fe-N active site is obtained, and excellent oxygen reduction catalytic performance is shown. Meanwhile, the growth of the carbon nano tube can be further catalyzed through uniform anchoring of Fe, the high graphitization degree of the carbon nano tube is kept, and the obtained Fe-N doped carbon nano tube has excellent and complete shape and uniform tube diameter thickness.
(3) The carbon nanotube-based non-noble metal catalyst obtained by the preparation method provided by the invention has the advantages of good crystallinity, high density active sites and high graphitization degree, shows excellent oxygen reduction performance under different pH conditions, and especially shows extremely high stability under an alkaline condition.
(4) The invention has the advantages of rich raw material sources, low cost, simple preparation process and easy large-scale production, and meets the performance and cost requirements of the commercial application of the fuel cell catalyst.
(5) The invention can also obtain the multi-element non-noble metal catalyst containing non-noble metal Fe by adding non-noble metal element types so as to meet different application requirements.
Drawings
Fig. 1 is a Transmission Electron Microscope (TEM) image of a catalyst prepared in example 1 of the present invention, fig. 1 (a) is a TEM image at a low magnification, and fig. 1 (b) is a TEM image at a high magnification.
FIG. 2 is a scanning transmission electron microscopy-electron energy loss spectroscopy (STEM-EELS) plot of the catalyst prepared in example 1 of the present invention.
FIG. 3 is a graph showing the cycle stability test of the catalyst prepared in example 1 of the present invention under alkaline conditions.
FIG. 4 is a graph showing Cyclic Voltammetry (CV) measurements under acidic conditions for the catalyst prepared in example 1 of the present invention.
Fig. 5 is a CV test chart under alkaline conditions of the catalysts prepared in example 1, example 2 and comparative example 1 of the present invention and the catalyst of comparative example 2.
Detailed Description
The present invention and its advantageous effects will be described in detail below with reference to specific embodiments, but the embodiments of the present invention are not limited thereto.
Example 1
The preparation method of the carbon nanotube-based non-noble metal fuel cell catalyst comprises the following steps:
(1) the melamine formaldehyde resin is used as a nitrogen-containing carbon source and is impregnated into FeCl3Adsorbing the solution until the solution is saturated, and drying to obtain a composite precursor;
(2) placing the composite precursor in a furnace filled with argon, and carrying out heat treatment for 2h at 550 ℃;
(3) continuing to heat to 900 ℃, and after the treatment is carried out for 2 hours, converting the argon atmosphere into an ammonia atmosphere, wherein the gas flow is 10L/min, and the treatment time is 15 min;
(4) and after the ammonia gas atmosphere treatment is finished, converting the ammonia gas atmosphere into a protective atmosphere, and naturally cooling to room temperature.
Example 2
The difference from example 1 is: and (3) introducing ammonia gas atmosphere for 0min, namely under the argon gas atmosphere, treating at 900 ℃ for 2h, and then directly naturally cooling to room temperature instead of converting the argon gas atmosphere into the ammonia gas atmosphere.
The other steps are the same as in example 1 and are not repeated here.
Comparative example 1
The difference from example 1 is: carbon nano tubes and melamine are adopted as a carbon source and a nitrogen source, namely the carbon nano tubes and the melamine are added into FeCl3And fully mixing the solution and drying to obtain a composite precursor.
The other steps are the same as in example 1 and are not repeated here.
Comparative example 2
A commercial Pt/C electrode was provided as comparative example 2.
The catalysts prepared in example 1, example 2 and comparative example 1 were uniformly dispersed with Nafion in a solvent to prepare dispersions, and then the dispersions were dropped on a working electrode and dried to prepare electrodes, which were respectively subjected to an alkaline condition of 0.1M KOH and 0.1M HClO4Under acidic conditions.
As shown in fig. 1, which is a TEM image of the carbon nanotube non-noble metal catalyst prepared in example 1, it can be seen that the prepared catalyst has a tube diameter of less than 200nm, a lattice spacing of 0.35nm, belongs to (002 crystal plane) of C element, and the catalyst prepared in example 1 has a high graphitization degree as seen from the lattice fringes.
The results in fig. 2 show that the carbon nanotube non-noble metal catalyst prepared in example 1 contains C, N, Fe elements, N, Fe is active sites of the catalyst, and the active sites are uniformly distributed on the carbon nanotube substrate, which indicates that the catalyst prepared in example 1 has more and uniformly distributed active sites.
As shown in fig. 3, the carbon nanotube-based non-noble metal fuel cell catalyst prepared in example 1 has extremely high stability under the alkaline test condition, and compared with the 10000 th cycle and the 1 st cycle, the catalytic performance is almost consistent, the loss of the half slope potential is less than 5mV, and the catalyst shows excellent stability.
As shown in fig. 4, the initial potential of the electrode made of the catalyst of example 1 under acidic conditions is 0.883V, and the half-wave potential is 0.768V, which reaches the average activity level of the non-noble metal catalyst of the fuel cell under acidic test conditions reported so far.
As shown in FIG. 5, the half-wave potential of the electrode made of the catalyst of example 1 was 0.942V, and the half-wave potentials of example 2, comparative example 1 and comparative example 2 were 0.689V, 0.807V and 0.883V, respectively, under alkaline conditions, i.e., the half-wave potential of example 1 was shifted up by 253mV, 135mV and 59mV, respectively, as compared to example 2, comparative example 1 and comparative example 2, indicating that the carbon nanotube-based non-noble metal fuel cell catalyst prepared in example 1 has more excellent redox performance, while the limiting current density was close to 6mA/cm2And is not much different from comparative example 2.
Variations and modifications to the above-described embodiments may also occur to those skilled in the art, which fall within the scope of the invention as disclosed and taught herein. Therefore, the present invention is not limited to the above-mentioned embodiments, and any obvious improvement, replacement or modification made by those skilled in the art based on the present invention is within the protection scope of the present invention. Furthermore, although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation.

Claims (7)

1. The utility model provides a carbon nanotube base non-noble metal fuel cell catalyst of direct growth constitutes by non-noble metal element and nitrogen element are evenly doped in the carbon nanotube pipe wall, non-noble metal element is transition metal element, contains iron element at least, still can include at least one of manganese element, cobalt element, nickel element simultaneously, wherein, the preparation method of carbon nanotube base non-noble metal fuel cell catalyst includes the following step:
s1, mixing and impregnating the solid organic nitrogenous resin and the non-noble metal salt solution, and drying the mixed solution to obtain a composite precursor;
s2, placing the composite precursor in a protective atmosphere, and carrying out heat treatment at the temperature of 450-600 ℃ for 0.5-5 h;
s3, continuously heating to 850-1100 ℃, treating for 0.5-5h, and then converting the protective atmosphere into an ammonia atmosphere;
and (S4) after the ammonia gas atmosphere treatment is finished, converting the ammonia gas atmosphere into a protective atmosphere, and naturally cooling to room temperature.
2. The carbon nanotube-based non-noble metal fuel cell catalyst of claim 1, wherein the carbon nanotubes comprise > 80% elemental carbon, < 10% elemental nitrogen, and < 10% non-noble metal, on a molar basis.
3. The carbon nanotube-based non-noble metal fuel cell catalyst of claim 1, wherein the solid organic nitrogen-containing resin is porous sponge-like and is at least one of melamine formaldehyde resin and melamine phenol formaldehyde resin.
4. The carbon nanotube-based non-noble metal fuel cell catalyst of claim 1, wherein the non-noble metal salt comprises at least one of iron salt and manganese salt, cobalt salt, and nickel salt, and the iron salt is at least one of ferric chloride hexahydrate, ferrous chloride, ferric sulfate, ferric nitrate, ferric acetylacetonate, ferric acetate, and ferric oxalate.
5. The carbon nanotube-based non-noble metal fuel cell catalyst as recited in claim 1, wherein the ammonia gas atmosphere treatment temperature is 850-1100 ℃, the gas flow rate is 1-15L/min, and the treatment time is 10-60 min.
6. The carbon nanotube-based non-noble metal fuel cell catalyst of claim 1, wherein the protective atmosphere is argon or nitrogen.
7. The carbon nanotube-based non-noble metal fuel cell catalyst of claim 1, wherein at least one end of the carbon nanotube has an open structure.
CN202110293632.1A 2021-03-19 2021-03-19 Directly-grown carbon nanotube-based non-noble metal fuel cell catalyst and preparation method thereof Pending CN113054209A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110293632.1A CN113054209A (en) 2021-03-19 2021-03-19 Directly-grown carbon nanotube-based non-noble metal fuel cell catalyst and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110293632.1A CN113054209A (en) 2021-03-19 2021-03-19 Directly-grown carbon nanotube-based non-noble metal fuel cell catalyst and preparation method thereof

Publications (1)

Publication Number Publication Date
CN113054209A true CN113054209A (en) 2021-06-29

Family

ID=76513492

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110293632.1A Pending CN113054209A (en) 2021-03-19 2021-03-19 Directly-grown carbon nanotube-based non-noble metal fuel cell catalyst and preparation method thereof

Country Status (1)

Country Link
CN (1) CN113054209A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114784301A (en) * 2021-12-20 2022-07-22 华北电力大学 Non-noble metal cathode catalyst material and preparation method and application thereof
CN115084554A (en) * 2022-07-08 2022-09-20 北京亿华通科技股份有限公司 Iron-doped melamine formaldehyde gel catalyst and preparation method thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106268817A (en) * 2016-07-18 2017-01-04 华中科技大学 A kind of preparation method of non-precious metal catalyst and products thereof
CN109755591A (en) * 2018-12-20 2019-05-14 清华大学深圳研究生院 The preparation method and application of carbon nanotube base fuel battery catalyst

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106268817A (en) * 2016-07-18 2017-01-04 华中科技大学 A kind of preparation method of non-precious metal catalyst and products thereof
CN109755591A (en) * 2018-12-20 2019-05-14 清华大学深圳研究生院 The preparation method and application of carbon nanotube base fuel battery catalyst

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114784301A (en) * 2021-12-20 2022-07-22 华北电力大学 Non-noble metal cathode catalyst material and preparation method and application thereof
CN115084554A (en) * 2022-07-08 2022-09-20 北京亿华通科技股份有限公司 Iron-doped melamine formaldehyde gel catalyst and preparation method thereof

Similar Documents

Publication Publication Date Title
Feng et al. 2-Methylimidazole as a nitrogen source assisted synthesis of a nano-rod-shaped Fe/FeN@ NC catalyst with plentiful FeN active sites and enhanced ORR activity
CN107029772B (en) Non-noble metal catalyst and preparation method thereof
Ma et al. MOF-derived N-doped carbon coated CoP/carbon nanotube Pt-based catalyst for efficient methanol oxidation
CN111342066B (en) Preparation method of transition metal-nitrogen-carbon nanotube co-doped active carbon oxygen reduction catalyst
CN110756188B (en) Preparation method of three-dimensional carbon network supported FeCo bifunctional oxygen catalyst
CN113862693B (en) Preparation method and application of nitrogen-doped mesoporous carbon-loaded high-dispersion Ru nanoparticle catalyst
CN112652780B (en) Fe/Fe 3 Preparation method of C nano-particle loaded porous nitrogen-doped carbon-based oxygen reduction catalyst
CN112680741B (en) Preparation method and application of ruthenium-doped cobalt phosphide electrocatalyst
US20100167918A1 (en) Aligned carbon nanotube with electro-catalytic activity for oxygen reduction reaction
CN112968184B (en) Electrocatalyst with sandwich structure and preparation method and application thereof
CN112838225A (en) Fuel cell catalyst and preparation method and application thereof
CN112751048A (en) Iron-containing self-loading nitrogen-doped carbon nanotube oxygen reduction catalyst, preparation method and application
CN111659439A (en) Nitrogen-doped carbon nano composite material loaded with NiS/NiO heterojunction and preparation method and application thereof
CN111558387A (en) Molybdenum carbide/foamed nickel composite material, preparation method thereof and application thereof in electrocatalytic oxygen evolution
CN113054209A (en) Directly-grown carbon nanotube-based non-noble metal fuel cell catalyst and preparation method thereof
CN108649237B (en) Gel pyrolysis-based cobalt-nitrogen doped carbon composite material and preparation method and application thereof
Wu et al. A graphene-based electrocatalyst co-doped with nitrogen and cobalt for oxygen reduction reaction
Yang et al. Chlorella-derived porous heteroatom-doped carbons as robust catalysts for oxygen reduction reaction in direct glucose alkaline fuel cell
Pan et al. Carbon-encapsulated Co3V decorated Co2VO4 nanosheets for enhanced urea oxidation and hydrogen evolution reaction
CN111883785A (en) Co-N Co-doped drum-shaped porous carbon catalyst and preparation method and application thereof
Yang et al. N-self-doped porous carbon derived from animal-heart as an electrocatalyst for efficient reduction of oxygen
CN110649276A (en) Based on N2Plasma-etched three-dimensional porous nitrogen-doped carbon nanotube electrocatalyst and preparation method thereof
CN114784299A (en) Nitrogen-sulfur doped carbon material and preparation method and application thereof
CN113036165B (en) Nitrogen-sulfur doped defected carbon nano tube and preparation method thereof
CN113422078A (en) Cellular porous carbon material with iron-nitrogen active sites and preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20210629