CN110828830A - Self-growing carbon tube composite ZIF-8 oxygen reduction electrocatalyst - Google Patents

Self-growing carbon tube composite ZIF-8 oxygen reduction electrocatalyst Download PDF

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CN110828830A
CN110828830A CN201911061986.2A CN201911061986A CN110828830A CN 110828830 A CN110828830 A CN 110828830A CN 201911061986 A CN201911061986 A CN 201911061986A CN 110828830 A CN110828830 A CN 110828830A
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zif
oxygen reduction
noble metal
reduction reaction
preparing
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朱威
马猛猛
庄仲滨
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Beijing University of Chemical Technology
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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
    • H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M12/00—Hybrid cells; Manufacture thereof
    • H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
    • 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
    • Y02E60/10—Energy storage using batteries

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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
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Abstract

The invention relates to a non-noble metal electrocatalyst for preparing a carbon tube composite ZIF-8 nano material for an oxygen reduction reaction by using a strategy of forming a carbon tube by a catalytic method. Adding a proper amount of iron source to form iron-loaded ZIF-8 in the process of synthesizing ZIF-8, then adding a part of iron source through a freeze-drying method, and finally carbonizing at high temperature to form Fe-N from a part of iron source x And the other part of the iron source catalyzes and forms a carbon tube, so that the composite catalytic material of the carbon tube and ZIF-8 is obtained by a one-step method. The method adopts a method of adding an iron source, and forms an active site and a carbon tube simultaneously in a carbonization stage. The method is simple, efficient, cheap and reliable, and the prepared catalyst has the high activity of the ZIF-based catalyst and the carbon tubeHigh stability and certain commercial value.

Description

Self-growing carbon tube composite ZIF-8 oxygen reduction electrocatalyst
Technical Field
The invention relates to a method for preparing a carbon tube by a catalytic method, which can obtain a carbon tube and ZIF-8 composite nano material in one step without adding an exogenous carbon tube. Part of the iron source forms Fe-N in the high-temperature carbonization process x -C active sites, the other part of the iron source is agglomerated to form iron nanoparticles, and the iron nanoparticles catalyze the carbon source to grow into carbon nanotubes at high temperature. One-step method for simultaneously preparing carbon tube and catalytic active site to obtain ZIF-8-based Fe-N x High-efficiency oxygen reduction catalyst compounded by-C and carbon tube in zinc airThe battery field has wide application prospect.
Background
Zinc-air batteries are considered to be one of the most promising energy storage and conversion devices due to their high conversion, environmental friendliness, and little emission of nitrogen oxides and sulfides. Zinc is a cheap metal resource, has abundant reserves on the earth, has the advantages of no toxicity, negative electrode potential and the like, and is always an anode widely applied to chemical power sources. The industrial production is started as early as 90 s in the 19 th century, and the anode material of the zinc-manganese battery which is still widely used globally at present is zinc. The zinc or zinc alloy is used as the anode of the fuel cell, and the cathode adopts air, so that the zinc-air cell is assembled. Zinc air cells are an energy conversion technology that is intermediate between fuel cells and conventional batteries. It has the design features of conventional cells with metallic zinc as the cathode, on the other hand, they are like fuel cells, with a porous anode structure that requires oxygen from the ambient air as a reactant. Theoretically, with oxygen in the air as the cathode, the positive electrode capacity is nearly infinite and outside the cell, the space inside the cell can be filled with more anode material. Thus, zinc-air cells are the highest specific energy among zinc-type cells, up to 1086 Wh kg-1 (including oxygen), and the cathode material is from air, with zero cost.
At present, the cathode oxygen reduction electrocatalysis of the zinc-air battery is mainly made of noble metals such as Pt and the like and alloys thereof. Although the oxygen reduction catalytic performance of the noble metal Pt catalyst is high, the noble metal Pt catalyst is expensive, scarce in resources and poor in stability, and the commercial development and application of the noble metal Pt catalyst are limited. Researches show that the functionalized carbon material can catalyze the oxygen reduction reaction, and carbon tubes and ZIF-8-based Fe-N are prepared by a catalytic method x the-C composite material catalyst not only has high-efficiency oxygen reduction catalytic performance, but also has low raw material cost and simple and high-efficiency method. Since carbon tubes serve as supports and are very suitable for exhibiting good stability in a device such as a zinc-air battery, a carbon material catalyst doped with non-noble metal atoms is an important research direction for oxygen reduction catalysts.
Disclosure of Invention
The technical problem solved by the invention is as follows: the composite material of the carbon tube and the ZIF-8 is synthesized in one step in the carbonization process only depending on proper iron salt amount without adding an exogenous carbon tube, and simultaneously has ZIF-8-based Fe-N x High activity of C, and stability conferred by carbon tubes. Low cost, simplicity and high efficiency. The problems of low catalytic performance, poor stability, high cost and difficulty in large-scale popularization of the zinc-air battery cathode catalyst are solved.
The invention is realized by the following modes:
step 1) dimethylimidazole, zinc nitrate hexahydrate and ferric salt are directly used for synthesizing uniformly distributed ZIF-8, and then a part of ferric salt and ZIF-8 are uniformly mixed by a freeze-drying method. Weighing a certain amount of dimethyl imidazole, uniformly stirring to disperse the dimethyl imidazole in a solvent to be named as A, weighing a certain amount of zinc nitrate hexahydrate, adding a certain amount of ferric salt, and uniformly stirring to disperse the zinc nitrate hexahydrate in the solvent to be named as B. Mixing A and B, reacting for a period of time at a certain temperature, washing with a solvent, and carrying out suction filtration to obtain a precipitate, thereby obtaining the ZIF with uniformly distributed iron, nitrogen and carbon. And then, uniformly mixing a part of iron source with ZIF-8 by a freeze-drying method to obtain ZIF-8+ Fe.
And 2) transferring the uniformly mixed ZIF-8+ Fe into a porcelain boat, putting the porcelain boat into a tubular furnace, calcining the porcelain boat in an inert atmosphere at a certain temperature for a certain time, naturally cooling the porcelain boat to room temperature, and further pickling the porcelain boat to obtain the non-noble metal electrocatalyst for the oxygen reduction reaction.
Further preferred is
The ferric salt in the step 1) can be one of ferric nitrate nonahydrate, ferric chloride hexahydrate, ammonium ferrous sulfate hexahydrate, ferrous sulfate, ferric sulfate, ferrous chloride tetrahydrate, ferrous acetate tetrahydrate, anhydrous ferrous chloride and anhydrous ferric chloride.
The molar ratio of the zinc nitrate hexahydrate to the dimethyl imidazole in the step 1) is 1 (3-8), and the preferred ratio is 1 (4-6).
The inert gas introduced into the high-temperature tube furnace in the step 2) can be argon or nitrogen, and the gas flow is 50-120ml/min.
In the step 2), the calcining process in the high-temperature tube furnace is to heat up to 150-250 ℃ at the speed of 1-10 ℃/min and preserve heat for 0.5-3.0 hours; then the temperature is raised to 800-1000 ℃ at the speed of 1-5 ℃/min, and the temperature is preserved for 0.5-3.0 hours.
THE ADVANTAGES OF THE PRESENT INVENTION
The invention utilizes the catalysis method to synthesize the carbon tube and ZIF-8 composite material for the non-noble metal electrocatalyst of the oxygen reduction reaction, the synthesis method is simple, and the prepared electrocatalyst has excellent oxygen reduction catalysis performance and good stability. Compared with the prior art, the invention has the following advantages:
1) The invention synthesizes the carbon tube by a catalytic method, and obtains the composite material of the carbon tube and ZIF-8 without adding an exogenous carbon tube. The method is simple, low in cost and easy to popularize.
2) According to the invention, proper iron salt amount is regulated and controlled twice, so that the ZIF-8-based metal-nitrogen-carbon-oxygen reduction active site with excellent performance is prepared while the carbon tube is formed through catalysis.
3) The catalyst obtained by combining the high activity of the ZIF-8 based catalyst and the high stability of the carbon tube is very suitable for being applied to components of a zinc-air battery.
Drawings
FIG. 1 is a linear scanning voltammogram of the catalyst obtained after acid washing of the carbon tube and ZIF-8 composite synthesized by the catalytic method in example 1.
FIG. 2 is a linear sweep voltammogram of the carbonless ZIF-8 based catalyst of comparative example 1.
FIG. 3 is a linear scanning voltammogram of the carbon tube and ZIF-8 composite catalyst synthesized by the catalytic method in comparative example 2.
FIG. 4 is a graph comparing the linear scanning voltammograms of the catalysts synthesized in example 1, comparative example 1, and comparative example 2.
FIG. 5 is a transmission electron microscope photograph of the catalyst obtained after acid washing the carbon tube and ZIF-8 composite synthesized by the catalytic method in example 1.
FIG. 6 shows IrO and a catalyst obtained by acid-washing a carbon tube and ZIF-8 composite synthesized by a catalytic method in example 1 2 And (5) a test result graph of the zinc-air battery is assembled in a mixed mode.
Detailed Description
Example 1
Step 1) 2-methylimidazole (0.65 g,8 mmol) was dissolved in 100 ml of methanol with stirring in flask A, and Zn (NO) was weighed 3 ) 2 · 6H 2 O (0.56 g,1.88 mmol) and FeCl 3 ·6H 2 O (8 mg,0.05 mmol) was dissolved in 100 ml of methanol under sonication for 15 minutes to form a clear solution in flask B. Beaker A and B were mixed and stirred at 60 ℃ for 12 h. The resulting product was isolated by centrifugation, followed by a third wash with DMF, two washes with methanol, and finally dried under vacuum at 70 ℃ overnight. Weighing 100 mg of the dried powder, mixing with 50 mg of ferric acetylacetonate, adding 30 ml of water, carrying out ultrasonic treatment for 2 hours, putting the mixture into a refrigerator for freezing overnight, and then putting the mixture into a freeze drying oven for drying.
Step 2) the dried samples were transferred to a ceramic boat and placed in a tube furnace. The sample was heated to 900 ℃ at a heating rate of 5 ℃/min and held at 900 ℃ for 3 hours under flowing argon, and then allowed to cool to room temperature. The resulting material was at 0.5 MH 2 SO 4 Carrying out Acid washing and normal temperature ultrasonic treatment for 12 h, then washing with water and ethanol, and carrying out vacuum drying to obtain the non-noble metal oxygen reduction electrocatalyst A-ZIF-8/CN (Acid-ZIF-8/Carbon Nanotube).
Comparative example 1
Step 1) 2-methylimidazole (0.65 g,8 mmol) was dissolved in 100 ml of methanol with stirring in flask A, and Zn (NO) was weighed 3 ) 2 · 6H 2 O (0.56 g,1.88 mmol) and FeCl 3 ·6H 2 O（8 mg，0.05 mmol) dissolved in 100 ml of methanol under ultrasound for 15 minutes to form a clear solution in flask B. Beaker A and B were mixed and stirred at 60 ℃ for 12 h. The resulting product was isolated by centrifugation, followed by a third wash with DMF, two washes with methanol, and finally dried under vacuum at 70 ℃ overnight.
Step 2) the dried samples were transferred to a ceramic boat and placed in a tube furnace. The sample was heated to 900 ℃ at a heating rate of 5 ℃/min and held at 900 ℃ for 3 hours under flowing argon, and then allowed to cool to room temperature. Obtaining the non-noble metal oxygen reduction electrocatalyst ZIF-8.
Comparative example 2
Step 1) 2-methylimidazole (0.65 g,8 mmol) was dissolved in 100 ml of methanol under stirring in flask A, and Zn (NO) was weighed 3 ) 2 · 6H 2 O (0.56 g,1.88 mmol) and FeCl 3 ·6H 2 O (8 mg,0.05 mmol) was dissolved in 100 ml of methanol under sonication for 15 minutes to form a clear solution in flask B. Beaker A and B were mixed and stirred at 60 ℃ for 12 h. The product was isolated by centrifugation, followed by a third wash with DMF, two washes with methanol, and finally dried under vacuum at 70 ℃ overnight. Weighing 100 mg of the dried powder, mixing with 50 mg of ferric acetylacetonate, adding 30 ml of water, performing ultrasonic treatment for 2 hours, freezing in a refrigerator overnight, and drying in a freeze drying oven.
Step 2) the dried samples were transferred to a ceramic boat and placed in a tube furnace. The sample was heated to 900 ℃ at a heating rate of 5 ℃/min and held at 900 ℃ for 3 hours under flowing argon, and then naturally cooled to room temperature. Obtaining the non-noble metal oxygen reduction electrocatalyst ZIF-8/CN.

Claims (10)

1. A preparation process of a self-growing carbon tube composite ZIF-8 oxygen reduction electrocatalyst comprises the following steps:
step 1) dimethyl imidazole, zinc nitrate hexahydrate and ferric salt are directly used for synthesizing evenly distributed ZIF-8, then a part of ferric salt and ZIF-8 are evenly mixed through a freeze-drying method, a certain amount of dimethyl imidazole is weighed and evenly stirred to be dispersed in a solvent to be named as A, a certain amount of zinc nitrate hexahydrate is weighed and then added into a certain amount of ferric salt, the mixture is evenly stirred to be dispersed in the solvent to be named as B, A and B are mixed at a certain temperature for reacting for a period of time, the mixture is washed by the solvent and filtered by suction to obtain sediment, ZIF with evenly distributed iron, nitrogen and carbon is obtained, then a part of iron source and ZIF-8 are evenly mixed through a freeze-drying method to obtain ZIF-8+ Fe,
and 2) transferring the uniformly mixed ZIF-8+ Fe into a porcelain boat, calcining the porcelain boat in a tubular furnace in an inert atmosphere at a certain temperature for a certain time, naturally cooling to room temperature, and further carrying out acid pickling to obtain the non-noble metal electrocatalyst for the oxygen reduction reaction.
2. The method of preparing a non-noble metal electrocatalyst for oxygen reduction reaction according to claim 1, wherein: the ferric salt in the step 1) can be one or two of ferric nitrate nonahydrate, ferric chloride hexahydrate, ammonium ferrous sulfate hexahydrate, ferrous sulfate, ferric sulfate, ferrous chloride tetrahydrate, ferrous acetate tetrahydrate, anhydrous ferrous chloride and anhydrous ferric chloride.
3. The method of preparing a non-noble metal electrocatalyst for oxygen reduction reaction according to claim 1, wherein: the molar ratio of the zinc nitrate hexahydrate and the dimethyl imidazole in the certain amount in the step 1) can be 1 (3-8).
4. The method of claim 1 for preparing a non-noble metal electrocatalyst for oxygen reduction reaction, wherein: the solvent for dispersing the dimethyl imidazole 16563in the step 1) can be one or two of methanol, ethanol, deionized water, N-dimethylformamide and N, N-dimethylacetamide.
5. The method of preparing a non-noble metal electrocatalyst for oxygen reduction reaction according to claim 1, wherein: the solvent for dispersing the zinc nitrate hexahydrate and the ferric salt in the step 1) can be one or two of methanol, ethanol, deionized water, N-dimethylformamide and N, N-dimethylacetamide.
6. The method of claim 1 for preparing a non-noble metal electrocatalyst for acidic oxygen reduction reaction, wherein: the mixing in step 1) may be 20-80 ℃ at a certain temperature.
7. The method of claim 1 for preparing a non-noble metal electrocatalyst for acidic oxygen reduction reaction, wherein: the reaction time in step 1) may be 4 to 24 hours.
8. The method of claim 1 for preparing a non-noble metal electrocatalyst for acidic oxygen reduction reaction, wherein: the solvent used in the suction filtration in the step 1) can be one or two of methanol, ethanol, deionized water, N-dimethylformamide and N, N-dimethylacetamide.
9. The method of claim 1 for preparing a non-noble metal electrocatalyst for acidic oxygen reduction reaction, wherein: the inert gas introduced into the high-temperature tube furnace in the step 2) can be argon or nitrogen, and the gas flow can be 30-120ml/min.
10. The method of claim 1 for preparing a non-noble metal electrocatalyst for acidic oxygen reduction reaction, wherein: in the step 2), the calcining process in the high-temperature tubular furnace is a calcining process, wherein the temperature is increased to 150-250 ℃ at the speed of 1-10 ℃/min, and the temperature is kept for 0.5-3.0 hours; then the temperature is raised to 800-1000 ℃ at the speed of 1-5 ℃/min, and the temperature is preserved for 0.5-3.0 hours.
CN201911061986.2A 2019-11-01 2019-11-01 Self-growing carbon tube composite ZIF-8 oxygen reduction electrocatalyst Pending CN110828830A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112103518A (en) * 2020-09-15 2020-12-18 上海理工大学 Preparation method of nitrogen-doped graphene oxide loaded carbon nanotube and Fe/ZIF8 composite material
CN112138697A (en) * 2020-09-14 2020-12-29 广州大学 Preparation method and application of manganese-nitrogen co-doped carbon nanosheet electrocatalyst
CN112521622A (en) * 2020-12-15 2021-03-19 中国环境科学研究院 Preparation method of MOFs derivatives for catalytically activating peroxymonosulfate

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112138697A (en) * 2020-09-14 2020-12-29 广州大学 Preparation method and application of manganese-nitrogen co-doped carbon nanosheet electrocatalyst
CN112138697B (en) * 2020-09-14 2022-12-20 广州大学 Preparation method and application of manganese-nitrogen co-doped carbon nanosheet electrocatalyst
CN112103518A (en) * 2020-09-15 2020-12-18 上海理工大学 Preparation method of nitrogen-doped graphene oxide loaded carbon nanotube and Fe/ZIF8 composite material
CN112103518B (en) * 2020-09-15 2022-07-29 上海理工大学 Preparation method of nitrogen-doped graphene oxide loaded carbon nanotube and Fe/ZIF8 composite material
CN112521622A (en) * 2020-12-15 2021-03-19 中国环境科学研究院 Preparation method of MOFs derivatives for catalytically activating peroxymonosulfate

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