CN109745950B - Method for preparing micro-mesoporous carbon cathode material by modifying metal organic framework with amino acid and application - Google Patents
Method for preparing micro-mesoporous carbon cathode material by modifying metal organic framework with amino acid and application Download PDFInfo
- Publication number
- CN109745950B CN109745950B CN201910190942.3A CN201910190942A CN109745950B CN 109745950 B CN109745950 B CN 109745950B CN 201910190942 A CN201910190942 A CN 201910190942A CN 109745950 B CN109745950 B CN 109745950B
- Authority
- CN
- China
- Prior art keywords
- organic framework
- amino acid
- metal organic
- micro
- temperature
- 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.)
- Active
Links
Images
Classifications
-
- 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 method for preparing a micro-mesoporous carbon anode material by modifying a metal organic framework with amino acid and application thereof. The method comprises the steps of synthesizing an amino acid modified metal organic framework material, pretreating the metal organic framework material, performing carbonization reaction and the like, and directly performing high-temperature carbonization treatment on the synthesized metal organic framework material after washing and drying treatment to obtain the nitrogen-doped porous carbon material with rich micro-mesoporous structure. Compared with a pure metal organic framework based carbon material, the carbon electrode material obtained by the method has higher specific surface area, wider pore size distribution and larger pore volume, and has higher activity for electrocatalytic oxygen reduction reaction. Meanwhile, the preparation method is simple and easy to control, mild in condition, easy to obtain raw materials and good in application prospect.
Description
Technical Field
The invention relates to a preparation method of a porous carbon material, in particular to a method for preparing a micro-mesoporous carbon anode material by modifying a metal organic framework with amino acid and application thereof.
Background
Fuel cells are environmentally friendly because they can directly convert chemical energy into electrical energy while maintaining high energy conversion efficiency when operating, and are considered to be one of the most promising green clean energy sources. The key problem of the fuel cell technology lies in the development of a high-efficiency electrocatalyst for the oxygen reduction reaction of the anode, and the porous carbon material becomes a research hotspot in the field of anode materials of fuel cells due to the characteristics of high specific surface area, excellent physical and chemical stability, high activity and the like.
The porous carbon material can be prepared by different carbon precursors, and comprises a metal organic framework material, a micromolecular organic matter, a biomass material and the like, wherein the metal organic framework material draws wide attention due to the characteristics of high specific surface area, adjustable and regular pore channel structure. For example, chinese invention CN105217600A discloses a method for preparing a porous carbon material using a metal organic framework as a template, the porous carbon material is prepared by heating the metal organic framework material with microwaves, and the obtained carbon material has a high specific surface area, uniform pore size distribution and high application value. The porous carbon material prepared by using the organic porous framework material as the raw material in the invention CN102730665A in China has a long-range ordered structure, a high specific surface area and high thermal stability.
However, the porous carbon material prepared by using the metal organic framework as a precursor is almost all micropores, and a small amount of stacked pores among the particles exist, which is not favorable for the adsorption and diffusion of oxygen during the oxygen reduction reaction. With the further research of the metal organic framework derived porous carbon material, researchers begin to focus on the aspect of regulating and controlling the pore diameter structure of the porous carbon material, mainly enlarge the pore diameter size of the metal organic framework based porous carbon material to obtain the hierarchical porous carbon material or improve the hierarchical porous carbon material from the raw material for preparing the metal organic framework, but the research usually relates to the use of activators such as KOH, NaOH and the like. KOH, etc., which is a pore-forming agent for a porous carbon material, can surely increase the pore volume and pore size of the carbon material, but usually forms a large number of new micropores, and although the specific surface area of the porous carbon material can be increased greatly, it does not have much actual effect on the effective expansion of the pore size. The invention 201610141478.5, China, discloses a method for rapidly preparing a metal organic framework material by taking amino acid as a ligand, which comprises the steps of dissolving the amino acid in deionized water containing NaOH, adding 3-10% of ethylamine derivative as a catalyst by volume fraction, slowly dropwise adding 0.5mol/L of metal salt solution under the stirring action, continuing to react for 1-5h after the dropwise addition is finished, filtering, washing with water and washing with alcohol for a plurality of times, and drying at 80 ℃ for at least 24h to obtain the metal organic framework material. The invention directly takes amino acid as ligand to synthesize metal organic framework material, has mild synthesis condition and high yield, but still relates to the use of NaOH with higher concentration in the process, simultaneously needs to use catalyst ethylamine derivative, and has larger dosage of amino acid used as ligand. In addition, the purpose is to improve the specific surface area of the metal organic framework material so as to improve the liquid phase adsorption performance of the metal organic framework, and no related research is carried out on the carbonization of the metal organic framework material constructed by the amino acid ligand to prepare the carbon material. Therefore, there is a need to develop a new method for adjusting the pore size of the metal organic framework derived carbon material to meet more demands.
Disclosure of Invention
The invention aims to provide a method for preparing a micro-mesoporous carbon cathode material by using an amino acid modified metal organic framework and application thereof, wherein water is used as a solvent in the preparation process of a precursor metal organic framework, an acid-base solution is not involved, the obtained material has a specific form of micro-mesopores, the problems of single pore diameter and poor adjustability of a metal organic framework-based porous carbon material are solved, and the obtained micro-mesoporous carbon material is applied to a fuel cell and shows excellent electrochemical performance.
The technical scheme of the invention is as follows:
a method for preparing a micro-mesoporous carbon anode material by modifying a metal organic framework with amino acid comprises the following steps:
(1) synthesizing an amino acid modified metal organic framework, namely adding amino acid in the process of synthesizing the metal organic framework by taking metal salt and organic ligand as raw materials to regulate the crystal growth process, namely adding the amino acid in the process of synthesizing the metal organic framework by taking the metal salt and the organic ligand as raw materials, wherein the molar ratio of the metal salt to the organic ligand is 1: 2-8, and the molar ratio of the amino acid to the metal salt is 1: 2-5 to obtain the amino acid modified metal organic framework material;
(2) pretreating the metal organic framework material, namely filtering and washing the amino acid modified metal organic framework material obtained in the step (1), and then performing vacuum drying treatment to obtain a carbonized precursor;
(3) and (3) performing carbonization reaction, namely raising the temperature of the carbonized precursor obtained in the step (2) from room temperature to the carbonization temperature under nitrogen flow to perform high-temperature carbonization treatment, and then reducing the temperature to room temperature under the protection of nitrogen to obtain the micro mesoporous carbon cathode material.
Further, in the step (1), the metal salt is one or more than two of zinc acetate dihydrate, zinc nitrate hexahydrate, zinc acetate and zinc chloride; the organic ligand is one or more than two of 2-methylimidazole, 2-nitroimidazole and imidazole-2-formaldehyde.
Further, in the step (1), the amino acid is one or more than two of aspartic acid, alanine and tyrosine; the synthesis temperature is 5-30 ℃ and the synthesis time is 12-48 h.
Further, in the step (3), the flow rate of nitrogen is 20-80 ml/min; the temperature of the high-temperature carbonization is 600-.
The micro-mesoporous carbon anode material obtained by the method is applied to a fuel cell and shows excellent electrochemical performance.
According to the invention, an effective pore size adjusting mode of the metal organic framework derived carbon is adopted, amino acid is introduced into the synthesis process of the metal organic framework material, the amino acid influences the shape and structure of a precursor, so that the pore structure of the porous carbon material obtained by carbonizing the metal organic framework material is changed, the pore size is increased, and meanwhile, the porous carbon material rich in nitrogen is obtained, the obtained material has a specific micro-mesoporous shape, and the material has a more excellent effect when being applied to a fuel cell anode material.
The invention has the beneficial effects that:
1. the metal organic framework material obtained by the invention has the advantages of high specific surface area, developed pores, good stability, easily obtained raw materials, simple synthetic method, easy repetition and hopeful large-scale production.
2. The invention takes water as solvent, does not relate to the use of activating agents such as KOH, NaOH and the like, not only can improve the environmental protection of the process, but also can not obstruct the effective expansion of the aperture.
3. Due to the microporous characteristic of the metal organic framework and the definite imprinting of the precursor of the metal organic framework on the fine structure of the porous carbon material, the porous carbon material obtained by carbonization has a large number of micropores and a plurality of open pore channels, which is beneficial to charge transfer and electrolyte transportation.
4. The modification of amino acid changes the appearance and structural characteristics of a precursor metal organic framework material, further influences the pore structure of a porous carbon material obtained by pyrolyzing the metal organic framework, increases the pore size distribution range of the porous carbon material, generates a large number of mesopores, has high mesoporous rate, and is beneficial to the adsorption and diffusion of oxygen during the catalytic oxygen reduction reaction.
5. The obtained material is applied to a fuel cell, shows excellent electrochemical performance, and can adjust the pore structure of the obtained porous carbon material by adjusting the dosage and the type of amino acid, the carbonization temperature and the like, so as to obtain the micro-mesoporous carbon material with adjustable pore diameter and high mesoporous rate, thereby having good commercial application prospect.
Drawings
FIG. 1 is a high-resolution transmission electron micrograph of A-Z-1000 obtained in example 1;
FIG. 2 is a nitrogen adsorption isotherm and pore size distribution plot of A-Z-1000 obtained in example 1;
FIG. 3 is a plot of cyclic voltammetry of A-Z-1000 obtained in example 1 applied to a fuel cell anode;
FIG. 4 is a polarization diagram of A-Z-1000 obtained in example 1 applied to a positive electrode of a fuel cell;
FIG. 5 is a nitrogen adsorption isotherm and pore size distribution plot of Z-1000 in comparative example 1;
FIG. 6 is a cyclic voltammogram of Z-1000 applied to a fuel cell positive electrode in comparative example 1;
FIG. 7 is a polarization diagram of comparative example 1 in which Z-1000 is applied to a positive electrode of a fuel cell;
Detailed Description
The present invention will be described in detail with reference to examples, but the present invention is not limited thereto. The invention can be implemented in a number of different ways, as defined and covered by the claims.
Example 1
A method for preparing a micro-mesoporous carbon anode material by modifying a metal organic framework with amino acid specifically comprises the following steps:
the synthesis of the amino acid modified metal organic framework specifically comprises the following steps: taking a 250ml round-bottom flask, adding 100ml of deionized water, 2.63g of 2-methylimidazole and 0.355g of aspartic acid into the flask, stirring to dissolve, then taking a 200ml beaker, adding 100ml of deionized water into the beaker to dissolve 1.760g of zinc acetate dihydrate, adding the solution in the beaker into the round-bottom flask after the solution is clear, stirring for 0.5h, and standing at room temperature for 24 h;
the pretreatment of the metal organic framework material specifically comprises the following steps: centrifuging and collecting the reacted powdery crystals, then repeatedly cleaning the powdery crystals for three times by using absolute ethyl alcohol, and then carrying out vacuum drying for 12 hours at the temperature of 80 ℃;
the carbonization reaction specifically comprises the following steps: weighing 1g of dry metal organic framework material, placing the material in a tubular furnace, carrying out constant temperature treatment for 4h at 1000 ℃ in a nitrogen atmosphere, wherein the heating rate is 4 ℃/min, and the obtained micro-mesoporous carbon anode material is marked as A-Z-1000; the micro-mesoporous carbon cathode material (A-Z-1000) obtained in the embodiment is applied to a fuel cell, and the electrochemical performance of the micro-mesoporous carbon cathode material is tested in 0.1mol/L KOH electrolyte saturated by oxygen, and the operating voltage is 0-1V.
The detailed performance of the a-Z-1000 obtained by adopting the technical scheme of the embodiment is shown in fig. 1-4, and specifically:
as can be seen from FIG. 1, the high resolution TEM image shows that the A-Z-1000 sample has abundant microporous structure and a small amount of graphitized regions.
As can be seen from FIG. 2, the adsorption capacity of the sample rises rapidly when the relative pressure is lower than 0.02, which indicates that the sample has a rich microporous structure; when the pressure is in the range of 0.02-0.45, the separation of the adsorption curve and the desorption curve shows that the porous carbon material contains rich small-size mesopores; the pore size distribution curve in fig. 2 confirms that the pore size distribution is widened, all the pore sizes are concentrated in small-sized mesopore and micropore regions, and the micro-mesoporous structure of the amino acid modified metal organic framework derived porous carbon material is proved.
As can be seen from fig. 3 and 4: n given separately from FIG. 32And O2Cyclic voltammograms in saturated 0.1mol/L KOH solutions are seen at O2In a saturated 0.1mol/L KOH solution, a curve shows a remarkable reduction peak compared with N2The cyclic voltammetry curve in the saturated 0.1mol/L KOH solution shows that A-Z-1000 has good catalytic activity on the oxygen reduction reaction; it can be seen from the polarization curves at different scanning speeds in fig. 7 that as the scanning speed increases, the measured current density also increases, because the contact area between the electrode and oxygen increases, the mass transfer of oxygen in the electrode material is accelerated, and the current density generated by the reaction is further increased, and meanwhile, the nearly overlapped curves in the polarization area also indicate that a-Z-1000 has good stability as the electrode material.
Comparing example 1 with comparative example 1, it can be seen that: comparative example 1 has a higher specific surface area, however, the pore size distribution is relatively narrow, and the relatively wide range of micro-mesoporous distribution makes example 1 have higher initial potential and current density under the same test conditions, which illustrates the activity of example 1 in catalyzing the oxygen reduction reaction better than comparative example 1.
Example 2
Example 2 differs from example 1 in that: the carbonization temperature is different, namely the constant temperature treatment is carried out for 4 hours at 800 ℃ in the nitrogen atmosphere in the embodiment. The specific implementation process is that a 250ml round-bottom flask is taken, 100ml deionized water, 2.63g 2-methylimidazole and 0.355g aspartic acid are added into the flask, stirring is carried out for dissolution, then a 200ml beaker is taken, 100ml deionized water is added for dissolution of 1.760g zinc acetate dihydrate, after the solution is clarified, the solution in the beaker is added into the round-bottom flask, stirring is carried out for 0.5h, and then standing is carried out for 24h at room temperature; centrifuging and collecting the reacted powdery crystals, then repeatedly cleaning the powdery crystals for three times by using absolute ethyl alcohol, and then carrying out vacuum drying for 12 hours at the temperature of 80 ℃; weighing 1g of dry metal organic framework material, placing the metal organic framework material in a tubular furnace, and carrying out constant temperature treatment at 800 ℃ for 4h under the nitrogen atmosphere, wherein the heating rate is 4 ℃/min, so as to obtain the micro mesoporous carbon cathode material with high mesoporous rate.
Comparative example 1
The difference from the embodiment 1 is that: amino acid is not added in the process of synthesizing the metal organic framework for modification. The method comprises the following steps: a250 ml round bottom flask is taken, 100ml deionized water, 2.63g 2-methylimidazole and 0.355g aspartic acid are added into the flask and stirred to dissolve, then a 200ml beaker is taken and 100ml deionized water is added to dissolve 1.760g zinc acetate dihydrate, after the solution is clarified, the solution in the beaker is added into the round bottom flask and stirred for 0.5h and then kept stand at room temperature for 24 h. The final resulting porous carbon material is labeled Z-1000.
The performance of applying Z-1000 to the anode of the fuel cell is as follows:
the nitrogen adsorption isotherm and the pore size distribution diagram of Z-1000 are shown in detail in FIG. 5, and it can be found that there is no obvious interval between the adsorption isotherm and the desorption isotherm of Z-1000, indicating the basic micropore structure of Z-1000, and meanwhile, the pore size contains a large number of micropore regions, mainly concentrated at 1.3nm, and the existence of a very small number of mesopores indicates that it has a low mesoporosity.
The cyclic voltammogram of Z-1000 and the polarization curve at 1600 rpm are shown in detail in FIGS. 6 and 7, as seen in FIG. 6 at O2In a saturated 0.1mol/L KOH solution, a cathodic reduction peak appears in the cyclic voltammetry curve of Z-1000, which shows the activity of the cyclic voltammetry curve on the catalytic oxygen reduction reaction, and a smaller cathodic peak area shows that the cyclic voltammetry curve is relatively lower than the cyclic voltammetry curve of A-Z-1000. From the polarization curve of FIG. 7, it can be seen that the initial potential of 0.81V (vs RHE) for the catalytic oxygen reduction reaction of Z-1000 is significantly less than the initial potential of 0.87V (vs RHE) for the catalytic oxygen reduction reaction of A-Z-1000, and that the higher kinetic current density also indicates the better catalytic oxygen reduction activity of A-Z-1000 due to the mesoporous structure of O2The material transfer is accelerated, and the speed of catalyzing the oxygen reduction reaction is improved.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (3)
1. A method for preparing a micro-mesoporous carbon anode material by modifying a metal organic framework with amino acid is characterized by comprising the following steps:
(1) synthesizing an amino acid modified metal organic framework, namely adding amino acid in the process of synthesizing the metal organic framework by taking metal salt and organic ligand as raw materials to regulate the crystal growth process, namely adding the amino acid in the process of synthesizing the metal organic framework by taking the metal salt and the organic ligand as raw materials, wherein the molar ratio of the metal salt to the organic ligand is 1: 2-8, and the molar ratio of the amino acid to the metal salt is 1: 2-5 to obtain the amino acid modified metal organic framework material;
(2) pretreating the metal organic framework material, namely filtering and washing the amino acid modified metal organic framework material obtained in the step (1), and then performing vacuum drying treatment to obtain a carbonized precursor;
(3) performing carbonization reaction, namely raising the temperature of the carbonized precursor obtained in the step (2) from room temperature to the carbonization temperature under nitrogen flow for high-temperature carbonization treatment, and then reducing the temperature to room temperature under the protection of nitrogen to obtain the micro mesoporous carbon cathode material;
in the step (1), the metal salt is one or more than two of zinc acetate dihydrate, zinc nitrate hexahydrate, zinc acetate and zinc chloride; the organic ligand is one or more than two of 2-methylimidazole, 2-nitroimidazole and imidazole-2-formaldehyde;
in the step (1), the amino acid is one or more than two of aspartic acid, alanine and tyrosine; the synthesis temperature is 5-30 ℃ and the synthesis time is 12-48 h.
2. The method for preparing the micro-mesoporous carbon cathode material by using the amino acid modified metal-organic framework as claimed in claim 1, wherein the method comprises the following steps: in the step (3), the flow rate of nitrogen is 20-80 ml/min; the temperature of the high-temperature carbonization is 600-.
3. The application of the amino acid modified metal organic framework obtained by the method of claim 1 or 2 in preparing a micro mesoporous carbon anode material in a fuel cell.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910190942.3A CN109745950B (en) | 2019-03-13 | 2019-03-13 | Method for preparing micro-mesoporous carbon cathode material by modifying metal organic framework with amino acid and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910190942.3A CN109745950B (en) | 2019-03-13 | 2019-03-13 | Method for preparing micro-mesoporous carbon cathode material by modifying metal organic framework with amino acid and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109745950A CN109745950A (en) | 2019-05-14 |
| CN109745950B true CN109745950B (en) | 2021-09-07 |
Family
ID=66408687
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910190942.3A Active CN109745950B (en) | 2019-03-13 | 2019-03-13 | Method for preparing micro-mesoporous carbon cathode material by modifying metal organic framework with amino acid and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109745950B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110479220A (en) * | 2019-08-23 | 2019-11-22 | 河南师范大学 | The method of molecularly imprinted polymer separating and enriching trace sulfamethoxazole pollutant based on supported ion liquid metal organic framework |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7267811B2 (en) * | 2003-11-26 | 2007-09-11 | Cabot Corporation | Fuel reformer catalyst and absorbent materials |
| CN104307482A (en) * | 2014-10-14 | 2015-01-28 | 中国科学院宁波材料技术与工程研究所 | Functionalized ZIF type metal organic framework (MOF) porous material as well as preparation method and application of material |
| CN105037404A (en) * | 2015-07-31 | 2015-11-11 | 四川大学 | Method for preparing metal organic framework material based on discharge plasma in liquid phase |
| CN105289614A (en) * | 2015-03-06 | 2016-02-03 | 深圳市国创新能源研究院 | Preparation method of nickel-carbon base catalyst material for hydrogen production |
| CN105693750A (en) * | 2016-03-01 | 2016-06-22 | 青岛大学 | Rapid preparation method of environment-friendly metal-organic framework material |
| CN105977483A (en) * | 2016-05-17 | 2016-09-28 | 中国石油大学(华东) | Carbon-based nanocomposite material for electrode |
| CN106006634A (en) * | 2016-05-13 | 2016-10-12 | 大连理工大学 | Method for one-step synthesis of nitrogen-doped microporous carbon from amino acid-zinc complex |
| CN106299367A (en) * | 2015-06-29 | 2017-01-04 | 北京化工大学 | A kind of negative electrode of power lithium-ion battery porous carbon material and preparation method thereof |
| CN107331877A (en) * | 2017-08-03 | 2017-11-07 | 重庆大学 | A kind of preparation method of three-dimensional carbon skeleton embedding nano platinum base alloy catalyst |
-
2019
- 2019-03-13 CN CN201910190942.3A patent/CN109745950B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7267811B2 (en) * | 2003-11-26 | 2007-09-11 | Cabot Corporation | Fuel reformer catalyst and absorbent materials |
| CN104307482A (en) * | 2014-10-14 | 2015-01-28 | 中国科学院宁波材料技术与工程研究所 | Functionalized ZIF type metal organic framework (MOF) porous material as well as preparation method and application of material |
| CN105289614A (en) * | 2015-03-06 | 2016-02-03 | 深圳市国创新能源研究院 | Preparation method of nickel-carbon base catalyst material for hydrogen production |
| CN106299367A (en) * | 2015-06-29 | 2017-01-04 | 北京化工大学 | A kind of negative electrode of power lithium-ion battery porous carbon material and preparation method thereof |
| CN105037404A (en) * | 2015-07-31 | 2015-11-11 | 四川大学 | Method for preparing metal organic framework material based on discharge plasma in liquid phase |
| CN105693750A (en) * | 2016-03-01 | 2016-06-22 | 青岛大学 | Rapid preparation method of environment-friendly metal-organic framework material |
| CN106006634A (en) * | 2016-05-13 | 2016-10-12 | 大连理工大学 | Method for one-step synthesis of nitrogen-doped microporous carbon from amino acid-zinc complex |
| CN105977483A (en) * | 2016-05-17 | 2016-09-28 | 中国石油大学(华东) | Carbon-based nanocomposite material for electrode |
| CN107331877A (en) * | 2017-08-03 | 2017-11-07 | 重庆大学 | A kind of preparation method of three-dimensional carbon skeleton embedding nano platinum base alloy catalyst |
Non-Patent Citations (2)
| Title |
|---|
| "Electrostatic assembly of graphene oxide with Zinc-Glutamate metal-organic framework crystalline to synthesis nanoporous carbon with enhanced capacitive performance";Qiang Wang等;《Electrochimica Acta》;20180314;第270卷;全文 * |
| "Nitrogen-Doped Nanoporous Carbons through Direct Carbonization of a Metal-Biomolecule Framework for Supercapacitor";Jianhui Zhang等;《Chin. J. Chem.》;20161231;第34卷;全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109745950A (en) | 2019-05-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110350211B (en) | Preparation method of ZIF-8 derived N, S-codoped non-metallic carbon-based nano oxygen reduction electrocatalyst | |
| CN110752380A (en) | ZIF-8 derived hollow Fe/Cu-N-C type oxygen reduction catalyst and preparation method and application thereof | |
| US20150352522A1 (en) | Carbon material for catalyst support use | |
| CN107658474B (en) | Nitrogen-sulfur co-doped porous carbon microsphere, preparation method and application thereof, and oxygen reduction electrode | |
| CN110467182B (en) | Reaction template-based hierarchical porous carbon-based material and preparation method and application thereof | |
| CN110993975B (en) | Nitrogen-doped porous carbon non-metal catalyst, preparation method thereof and application thereof in redox reaction | |
| CN110396701B (en) | Electrode for preparing formic acid by efficiently electro-catalytically reducing carbon dioxide | |
| CN109786764B (en) | Nitrogen-sulfur double-doped non-metallic carbon-based oxygen reduction catalyst with graded holes and preparation method thereof | |
| CN110504456B (en) | Oxygen reduction electrode based on nitrogen-oxygen doped ball/sheet porous carbon material and preparation method and application thereof | |
| CN112820886B (en) | Three-dimensional hierarchical porous nonmetal carbon-based material, and preparation method and application thereof | |
| CN113881965B (en) | Metal nanoparticle supported catalyst with biomass carbon source as template and preparation method and application thereof | |
| CN110828193A (en) | Nano flower-shaped Ni-MOF material and preparation method and application thereof | |
| CN108579718B (en) | Preparation method and application of indium-doped nano porous carbon material | |
| CN112357902A (en) | Mesoporous carbon material with high specific surface area, and preparation method and application thereof | |
| CN110124714B (en) | Cu-N-C-based carbon nanosheet and preparation method and application thereof | |
| CN114284515B (en) | Ternary heterostructure FePc/Ti 3 C 2 /g-C 3 N 4 Preparation method and application of composite material | |
| CN108565469B (en) | Cobalt-nitrogen doped carbon composite material and preparation method thereof | |
| CN112853393B (en) | Ferroferric oxide catalyst for electrochemically synthesizing ammonia and preparation method and application thereof | |
| CN109775710A (en) | A kind of preparation method of nitrogen-doped porous carbon material and the application in supercapacitor | |
| CN109745950B (en) | Method for preparing micro-mesoporous carbon cathode material by modifying metal organic framework with amino acid and application | |
| CN111450842B (en) | Preparation method of micro-flower structure black lead-copper ore phase metal oxide electrocatalyst, electrocatalyst and application thereof | |
| CN113668008A (en) | Molybdenum disulfide/cobalt carbon nanotube electrocatalyst and preparation method and application thereof | |
| CN109244492A (en) | A kind of efficient two-dimentional azepine Carbon Materials and preparation method thereof and the application in energy conversion field | |
| CN110055556A (en) | Evolving hydrogen reaction catalyst and its preparation method and application | |
| CN110038612B (en) | N-doped microporous carbon sphere ORR catalytic material 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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |