CN112751047A - Iron-nitrogen co-doped carbon nanotube oxygen reduction catalyst, preparation method and application - Google Patents
Iron-nitrogen co-doped carbon nanotube oxygen reduction catalyst, preparation method and application Download PDFInfo
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- CN112751047A CN112751047A CN202110058411.6A CN202110058411A CN112751047A CN 112751047 A CN112751047 A CN 112751047A CN 202110058411 A CN202110058411 A CN 202110058411A CN 112751047 A CN112751047 A CN 112751047A
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- H01M4/90—Selection of catalytic material
- H01M4/9041—Metals or alloys
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- 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
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- H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
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- H—ELECTRICITY
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- 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
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- 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
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Abstract
The invention belongs to the field of nano material preparation, and provides an iron-nitrogen co-doped carbon nano tube oxygen reduction catalyst, a preparation method and application. The method adopts cheap iron oxide and cyanamide medicine rich in nitrogen and carbon as experimental raw materials, mixes the precursors according to a certain mass ratio by using a ball milling method, then carries out pyrolysis in a semi-closed environment under the atmosphere of flowing inert gas, and obtains the iron and nitrogen co-doped carbon nano tube oxygen reduction catalyst which shows high oxygen reduction catalytic activity in alkaline electrolyte after pickling, purification and drying, and the material can be applied to the fields of fuel cells and metal-air cells. Compared with the process that a large amount of organic solvent is used for uniformly mixing the ferric salt and the nitrogen-carbon precursor in the traditional synthesis process of the iron-nitrogen co-doped carbon-based catalyst and secondary pyrolysis is needed, the iron-nitrogen co-doped catalyst has the advantages that ferric oxide is used for replacing the ferric salt, materials are mixed by a simple ball milling method, and a two-step pyrolysis method in a semi-closed environment is used for realizing effective iron-nitrogen co-doping of the product, so that the waste of resources is reduced.
Description
Technical Field
The invention belongs to the field of preparation of oxygen reduction electrocatalytic materials, and relates to an iron-nitrogen co-doped carbon nanotube oxygen reduction catalyst, a preparation method and application thereof.
Background
The oxygen reduction reaction is a very critical process in electrochemical energy conversion devices such as fuel cells and metal air batteries. However, due to kinetic limitations, the oxygen reduction reaction is difficult to occur, and a proper electrocatalyst is needed to ensure the smooth progress of the process. To date, platinum-based catalysts have been considered to be the most catalytically active oxygen reduction catalysts. However, the high price, limited resources and poor stability of the platinum-based catalyst make it difficult to be an oxygen reduction catalyst that can be widely used. Therefore, the development of highly efficient non-platinum based catalysts has become a research hotspot. Among them, the iron-nitrogen-carbon system catalyst has become a key research object of scientists due to its advantages of low cost, good catalytic activity and stability, etc. At present, iron-nitrogen-carbon system catalysts are generally prepared by using iron salts, cyanamide nitrogen-containing organic matter precursors, carbon carriers (such as Vulcan XC-72, Ketjenblack, Black Pearls, and the like) and the like as raw materials, and then obtaining catalyst products by a pyrolysis method. Most of the existing process technical routes have the problems of waste of raw materials, and the process flow is not simple and efficient or even environment-friendly. Therefore, the method realizes simple and efficient preparation of the catalyst with high oxygen reduction catalytic activity and durability by developing and reasonably designing a synthetic route, selecting a new low-cost iron source and a nitrogen-carbon precursor and optimizing heat treatment conditions, and has very important significance for large-scale industrial application of fuel cells, metal-air cells and the like.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a simple and efficient preparation method of the iron-nitrogen co-doped carbon nanotube oxygen reduction catalyst, the invention adopts iron oxide with low cost and cyanamide organic precursor rich in nitrogen and carbon as raw materials, and the oxygen reduction catalyst which shows good oxygen reduction electrocatalytic activity and circulation stability in alkaline electrolyte can be prepared by simple mixing and pyrolysis, and has important significance in the fields of oxygen reduction electrocatalysis and related electrochemical devices.
The technical scheme of the invention is as follows:
a preparation method of an iron-nitrogen co-doped carbon nanotube oxygen reduction catalyst adopts iron oxide with low cost and cyanamide organic precursor rich in nitrocarbon as experimental raw materials. Comprises the following steps:
s1, uniformly mixing the iron oxide and the cyanamide medicine rich in nitrogen and carbon according to a certain mass ratio by a ball milling method to obtain precursor powder;
s2, putting the uniformly mixed precursor powder into a pyrolysis device, and pyrolyzing the sample in a semi-closed state at two steps at different temperatures in a flowing inert gas atmosphere to obtain carbonized black powder;
and S3, carrying out acid washing and purification on the black powder sample, and drying in vacuum to obtain the iron-nitrogen co-doped carbon nanotube oxygen reduction catalyst.
Further, in step S1, the iron oxide is one or a combination of iron sesquioxide and ferroferric oxide; the cyanamide medicine rich in nitrogen and carbon comprises melamine, dicyandiamide, urea and the like, but is not limited to any one of the melamine, dicyandiamide and urea; the mass ratio of the ferric oxide to the cyanamide medicine rich in the nitrocarbon is 1 (1-10).
Further, in step S1, when the material is mixed by ball milling, the rotation speed of the ball mill is 100-300rpm/min, and the milling time is 30-120 min.
Further, in step S2, the porcelain boat holding the pyrolysis sample in the pyrolysis device must have a non-sealing cover to ensure a semi-closed atmosphere during the pyrolysis process; the inert gas is nitrogen or argon.
Further, in step S2, the temperature rising speed in the pyrolysis process is 5-10 ℃/min, the first stage of pyrolysis is at 350-.
Further, in step S3, in the acid cleaning and purifying process, 2-6M hydrochloric acid is used to soak the black powder sample for 2-12 hours, and then a suction filtration device is used to perform a large amount of water cleaning and purification; and in the vacuum drying process, the sample after acid cleaning and purification is dried for 0.5-3h at the temperature of 80 ℃ to finally obtain the iron-nitrogen co-doped carbon nano tube oxygen reduction catalyst.
The invention synthesizes the iron-nitrogen co-doped carbon nanotube catalyst by a semi-closed two-step pyrolysis method, can be applied to the fields of fuel cells and metal-air cells, and is used for catalyzing oxygen reduction reaction. Through electrochemical tests, the Fe/N-CNTs show good oxygen reduction electrocatalytic activity and stability in an alkaline electrolyte. The invention has the following advantages:
(1) compared with the traditional preparation method of the Fe-N-C system catalyst, the method adopts the Fe oxide and the cyanamide medicine as raw materials, does not need to adopt an organic solvent for dissolving when uniformly mixing the precursor, can directly mix the uniform powder material by a ball milling method, and reduces the waste of resources.
(2) In the semi-closed stepwise pyrolysis process, the cyanamide medicine can release ammonia gas, so that the interior of the porcelain boat containing the sample is also protected by ammonia gas atmosphere, the aim of nitrogen doping can be achieved without introducing ammonia gas from the outside, and the yield of products can be improved.
(3) The raw materials of the iron oxide and the cyanamide medicine for preparing the iron-nitrogen co-doped carbon nanotube oxygen reduction catalyst have low cost, are non-toxic and harmless, and the adopted two-step pyrolysis method has simple and efficient process and can be used for industrial production.
Drawings
FIG. 1 is an X-ray diffraction pattern (XRD) of Fe/N-CNTs synthesized in example 1.
FIG. 2 is a field emission Scanning Electron Micrograph (SEM) of the Fe/N-CNTs synthesized in example 1.
FIG. 3 is a graph comparing the Linear Sweep Voltammogram (LSV) of the Fe/N-CNTs synthesized in example 1 with a commercial 20% wtPt/C catalyst in alkaline electrolyte.
FIG. 4 is a graph comparing LSV before and after cycling of the Fe/N-CNTs synthesized in example 1.
Detailed Description
The invention is further described with reference to the following figures and detailed description.
Example 1:
preparation of a Fe/N-CNTs catalyst:
(1) weighing 2gFe in turn2O3And 6g of melamine is placed in an agate ball milling tank, and the raw materials are uniformly mixed by ball milling for 30min at 300rpm/min by using a planetary ball mill to obtain uniformly mixed brown yellow precursor powder.
(2) Weighing a proper amount of brown yellow powder, placing the brown yellow powder in a clean aluminum oxide porcelain boat with a cover (in a non-sealed state), placing the porcelain boat with the sample in a tubular furnace, performing step-by-step pyrolysis in a flowing Ar atmosphere, keeping the temperature rise speed at 5 ℃/min, raising the temperature to 350 ℃ in the first stage, keeping the temperature for 30min, raising the temperature to 800 ℃ in the second stage, keeping the temperature for 120min, and finally naturally cooling to room temperature.
(3) And (3) soaking the obtained black powder in 2M hydrochloric acid for 12h, sucking the reacted liquid by using a rubber head dropper, adding a large amount of deionized water into the sample, washing and performing suction filtration by using a suction filtration device, and after the suction filtration is completed, placing the sample in a vacuum drying oven for vacuum drying at 80 ℃ for 2h to obtain a final sample Fe/N-CNTs.
The Fe/N-CNTs prepared in example 1 of the present invention and a sample were subjected to electrochemical tests, and the comparative sample was a 20% Pt/C catalyst from Johnson Matthey. The electrochemical test method is as follows: mixing 4mg of catalyst sample with 20 mu L of Nafion dispersion liquid with the mass fraction of 5% and 480 mu L of absolute ethyl alcohol, carrying out ultrasonic treatment for 2h to prepare uniformly mixed slurry, sucking 5 mu L of slurry by using a liquid transfer gun, coating the slurry on a glassy carbon electrode with the diameter of 4mm, and naturally drying the glassy carbon electrode at room temperature. The dried sample can be used for testing the oxygen reduction electrocatalysis performance in a three-electrode electrochemical test system by utilizing a rotary disc electrode device and an electrochemical workstation, the three-electrode system is characterized in that the sample coated on a glassy carbon electrode is taken as a research electrode, a Pt wire is taken as a counter electrode, Ag/AgCl is taken as a reference electrode, and an electrolyte is 0.1M KOH solution saturated by oxygen. When testing linear sweep voltammograms, the rotating disk electrode was selected at 1600rpm and the sweep rate was 10 mV/s. When the stability of the catalyst is tested, after 5000 circles of cyclic test is carried out by adopting a cyclic voltammetry method, a linear sweep voltammetry curve is tested, and the quality of the stability of the catalyst is judged through the loss of a half-wave potential.
The XRD pattern of Fe/N-CNT is shown in figure 1, and it can be seen that the main composition phases of the sample are graphite, Fe3C and FeN0.0324. FIG. 2 is an SEM image of a Fe/N-CNTs catalyst sample, and it can be seen that the sample is in a carbon nanotube shape. FIG. 3 is a comparison of LSV of the Fe/N-CNTs catalyst prepared in example 1 and a commercial 20% Pt/C catalyst in an alkaline electrolyte, wherein the half-wave potential of the Fe/N-CNTs catalyst prepared in the present invention is 0.84V higher than the half-wave potential of the commercial 20% Pt/C catalyst is 0.81V, which shows that the catalyst prepared in the present invention has high oxygen reduction electrocatalytic activity. FIG. 4 is a LSV comparison graph before and after 5000 CV cycles of the Fe/N-CNTs oxygen reduction electrocatalyst synthesized in example 1, and it can be seen from the graph that the half-wave potential of the Fe/N-CNTs oxygen reduction electrocatalyst prepared by the present invention loses 18mV after multiple cycles, and has good cycle stability.
In conclusion, after the iron oxide and the cyanamide organic precursor rich in nitrocarbon are uniformly mixed by ball milling, the iron-nitrogen co-doped carbon-based high-performance oxygen reduction electrocatalyst with the carbon nanotube morphology can be obtained by pyrolysis step by step in a semi-closed state.
Claims (8)
1. The preparation method of the iron-nitrogen co-doped carbon nanotube oxygen reduction catalyst is characterized by comprising the following steps of:
s1, uniformly mixing the iron oxide and the cyanamide medicine rich in nitrogen and carbon according to a certain mass ratio by a ball milling method to obtain precursor powder;
s2, putting the uniformly mixed precursor powder into a pyrolysis device, and pyrolyzing the sample in a semi-closed state at two steps at different temperatures in a flowing inert gas atmosphere to obtain carbonized black powder;
and S3, carrying out acid washing and purification on the black powder sample, and drying in vacuum to obtain the iron-nitrogen co-doped carbon nanotube oxygen reduction catalyst.
2. The preparation method according to claim 1, wherein in step S1, the iron oxide is one of ferric oxide and ferroferric oxide; the cyanamide medicine rich in nitrogen and carbon is one or the combination of more than two of melamine, dicyandiamide and urea; the mass ratio of the iron oxide to the cyanamide medicine rich in nitrocarbon is 1 (1-10).
3. The method as claimed in claim 1, wherein in step S1, when the material is mixed by ball milling, the rotation speed of the ball mill is 100-300rpm/min, and the milling time is 30-120 min.
4. The method of claim 1, wherein in step S2, the porcelain boat holding the pyrolysis sample in the pyrolysis device must have a non-sealing cover to ensure a semi-closed atmosphere during the pyrolysis process; the inert gas is nitrogen or argon.
5. The method as claimed in claim 1, wherein in step S2, the temperature rising rate in the pyrolysis process is 5-10 ℃/min, the first stage of pyrolysis is 350-400 ℃ for 30min, and the second stage of pyrolysis is 700-900 ℃ for 1-3h, and the black powder is obtained after cooling to room temperature.
6. The preparation method according to claim 1, wherein in step S3, the acid cleaning and purifying process comprises soaking a black powder sample in 2-6M hydrochloric acid for 2-12h, and then washing and purifying with a suction filtration device; and in the vacuum drying process, the sample after acid cleaning and purification is dried for 0.5-3h at the temperature of 80 ℃ to finally obtain the iron-nitrogen co-doped carbon nano tube oxygen reduction catalyst.
7. An iron-nitrogen co-doped carbon nanotube oxygen reduction catalyst, which is characterized by being prepared by the preparation method of any one of claims 1 to 6.
8. The application of the iron-nitrogen co-doped carbon nanotube oxygen reduction catalyst prepared by the preparation method of any one of claims 1 to 6 is characterized in that the iron-nitrogen co-doped carbon nanotube oxygen reduction catalyst is applied to the fields of fuel cells and metal-air cells and used for catalyzing oxygen reduction reaction.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113813984A (en) * | 2021-10-21 | 2021-12-21 | 东北农业大学 | Preparation method and application of N/Fe co-doped nanotube catalytic material |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102416337A (en) * | 2011-08-29 | 2012-04-18 | 重庆大学 | Method for preparing nitrogen-doped carbon nanotube fuel cell catalyst |
| CN102974380A (en) * | 2012-11-13 | 2013-03-20 | 中国科学院长春应用化学研究所 | Iron and nitrogen doped carbon black catalyst and preparation method thereof |
| CN105271229A (en) * | 2015-10-10 | 2016-01-27 | 华南理工大学 | Method for in-situ preparation of iron carbide filled doped carbon nanotube |
| CN108543545A (en) * | 2018-04-26 | 2018-09-18 | 大连理工大学 | A kind of tri- doped carbon nanometer pipe cladded type FeNi@NCNT catalyst of Fe, Ni, N, preparation method and applications |
| CN109817933A (en) * | 2019-01-29 | 2019-05-28 | 陕西科技大学 | A kind of carbon-based compound cyanamide iron material and preparation method thereof and use its sodium-ion battery as negative electrode material |
| CN109888318A (en) * | 2019-02-13 | 2019-06-14 | 上海交通大学 | A kind of preparation method and application of the nitrogen co-doped C-base composte material of metal- |
| CN110783582A (en) * | 2019-11-06 | 2020-02-11 | 浙江理工大学 | Nitrogen-doped carbon nanotube-loaded nitrogen-doped carbon-coated iron-cobalt alloy dual-function catalyst and preparation method and application thereof |
| CN111250008A (en) * | 2020-02-08 | 2020-06-09 | 浙江师范大学 | Method for synthesizing hollow sphere nano material formed by wrapping CoFe alloy in N and P co-doped carbon assembly by solvent-free thermal decomposition method |
-
2021
- 2021-01-16 CN CN202110058411.6A patent/CN112751047A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102416337A (en) * | 2011-08-29 | 2012-04-18 | 重庆大学 | Method for preparing nitrogen-doped carbon nanotube fuel cell catalyst |
| CN102974380A (en) * | 2012-11-13 | 2013-03-20 | 中国科学院长春应用化学研究所 | Iron and nitrogen doped carbon black catalyst and preparation method thereof |
| CN105271229A (en) * | 2015-10-10 | 2016-01-27 | 华南理工大学 | Method for in-situ preparation of iron carbide filled doped carbon nanotube |
| CN108543545A (en) * | 2018-04-26 | 2018-09-18 | 大连理工大学 | A kind of tri- doped carbon nanometer pipe cladded type FeNi@NCNT catalyst of Fe, Ni, N, preparation method and applications |
| CN109817933A (en) * | 2019-01-29 | 2019-05-28 | 陕西科技大学 | A kind of carbon-based compound cyanamide iron material and preparation method thereof and use its sodium-ion battery as negative electrode material |
| CN109888318A (en) * | 2019-02-13 | 2019-06-14 | 上海交通大学 | A kind of preparation method and application of the nitrogen co-doped C-base composte material of metal- |
| CN110783582A (en) * | 2019-11-06 | 2020-02-11 | 浙江理工大学 | Nitrogen-doped carbon nanotube-loaded nitrogen-doped carbon-coated iron-cobalt alloy dual-function catalyst and preparation method and application thereof |
| CN111250008A (en) * | 2020-02-08 | 2020-06-09 | 浙江师范大学 | Method for synthesizing hollow sphere nano material formed by wrapping CoFe alloy in N and P co-doped carbon assembly by solvent-free thermal decomposition method |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113813984A (en) * | 2021-10-21 | 2021-12-21 | 东北农业大学 | Preparation method and application of N/Fe co-doped nanotube catalytic material |
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Application publication date: 20210504 |