CN110911702B - Two-dimensional iron-nitrogen co-doped carbon-based composite material and preparation method and application thereof - Google Patents
Two-dimensional iron-nitrogen co-doped carbon-based composite material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a two-dimensional iron-nitrogen co-doped carbon-based composite material which is prepared by synthesizing a metal organic framework in a water phase and then pyrolyzing the metal organic framework serving as a precursor. The invention also discloses a preparation method of the two-dimensional iron-nitrogen co-doped carbon-based composite material and application of the two-dimensional iron-nitrogen co-doped carbon-based composite material as an electrocatalyst in a cathode oxygen reduction reaction of a fuel cell. The iron-nitrogen co-doped carbon-based composite material prepared by the invention is a composite structure with a two-dimensional flaky nano structure as a substrate and a carbon nano tube growing on the substrate, and the iron-nitrogen co-doped carbon-based catalyst with a unique structure has good oxygen reduction electrocatalytic performance.
Description
Technical Field
The invention relates to a two-dimensional iron-nitrogen co-doped carbon-based composite material, a preparation method of the composite material and application of the composite material as an electrocatalyst in a cathode oxygen reduction reaction of a fuel cell, and belongs to the technical field of nano materials.
Background
The problems of energy shortage and environmental pollution caused by fossil fuel combustion are becoming more and more acute, and the traditional fossil energy cannot meet the requirement of rapid development of the current human society. Both energy and environmental pressures have prompted the continual search for new types of energy and new ways of storing and converting energy. Among the many types of energy storage and conversion, electrochemical energy conversion and storage technologies (mainly including metal air batteries, fuel cells, supercapacitors, etc.) have been recognized as one of the most feasible and effective energy conversion and storage means. Fuel cells are widely concerned by people because of their advantages of high energy conversion efficiency, environmental friendliness, high reliability, and the like. However, in proton exchange membrane fuel cells using hydrogen as fuel, the kinetics of the cathodic Oxygen Reduction Reaction (ORR) relative to the anodic hydrogen oxidation reaction is slow and highly dependent on the rare and expensive Pt-based noble metal catalyst, which has severely hindered the large-scale commercial application of hydrogen-powered fuel cells.
The design and development of low-cost, high-performance ORR (oxygen reduction reaction) electrocatalysts are the focus of research in the field of fuel cell technology. In order to break through the resource barrier of noble metal Pt and reduce the cost of fuel cells, the development of non-noble metal catalysts is widely concerned by people. Among them, iron nitrogen doped carbon based catalysts are the most promising candidates due to their remarkable ORR activity.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to solve the technical problem of providing a two-dimensional iron-nitrogen co-doped carbon-based composite material which has good oxygen reduction electrocatalytic performance.
The invention also aims to solve the technical problem of providing the preparation method of the two-dimensional iron-nitrogen co-doped carbon-based composite material, which is simple in process, low in cost and suitable for large-scale production.
The invention finally aims to solve the technical problem of providing the application of the two-dimensional iron-nitrogen co-doped carbon-based composite material as an electrocatalyst in the cathode oxygen reduction reaction of a fuel cell.
The invention content is as follows: the technical means adopted by the invention are as follows:
the two-dimensional iron-nitrogen co-doped carbon-based composite material is prepared by synthesizing a metal organic framework in a water phase and then pyrolyzing the metal organic framework serving as a precursor.
The metal organic framework catalyzes the generation of the carbon nano tube in the pyrolysis process, the appearance of the composite material obtained after pyrolysis takes a two-dimensional flaky nano structure as a substrate, and the carbon nano tube grows on the substrate.
The preparation method of the two-dimensional iron-nitrogen co-doped carbon-based composite material comprises the following specific steps: respectively dissolving an iron precursor, a chelating agent, zinc nitrate and 2-methylimidazole in water, reacting the mixed material at room temperature for 2-4 h, and centrifuging after reaction; and heating the centrifuged intermediate product to 600-900 ℃ at a heating rate of 2-5 ℃/min in an inert atmosphere, and preserving heat for 1-3 h to obtain the two-dimensional iron-nitrogen co-doped carbon-based composite material.
When the metal organic framework precursor of the two-dimensional iron-nitrogen co-doped carbon-based composite material is prepared, dissolving an iron precursor and a chelating agent in water, performing ultrasonic treatment at normal temperature for 30-60 min until the iron precursor and the chelating agent are uniformly dissolved, adding zinc nitrate into the iron precursor solution, and stirring at normal temperature for 1-2 h to promote the homogenization of the product; and finally, adding the iron precursor solution into the prepared 2-methylimidazole solution, and synthesizing the metal organic framework in a water phase.
Wherein the iron precursor is ferric chloride or ferric nitrate. Since the metal organic framework precursor is prepared in the aqueous phase, the raw materials are all selected to be water soluble.
Wherein the chelating agent is glucose or fructose, and the chelating agent has the following functions: thermolysis of metal complexes formed by chelators with iron precursors to produce metallic Fe or FeCxCatalyzing the generation of carbon nanotubes; the protective layer is formed to prevent the shape collapse of the two-dimensional metal organic framework in the high-temperature reaction process.
Wherein the mixing molar ratio of the iron precursor to the chelating agent is 1: 22-30, and the mixing molar ratio of the iron precursor to the zinc nitrate is 1: 4-6.
Wherein the mixing molar ratio of the iron precursor, the chelating agent, the zinc nitrate and the 2-methylimidazole is 1: 22: 4: 32-1: 30:6: 36.
The two-dimensional iron-nitrogen co-doped carbon-based composite material is applied to the cathode oxygen reduction reaction of a fuel cell as an electrocatalyst.
The composite material is a two-dimensional sheet-shaped nano structure, the two-dimensional sheet-shaped structure has a smaller diffusion barrier, and the structure provides favorable conditions for the interaction between an active center and a reactant.
Has the advantages that: the iron-nitrogen co-doped carbon-based composite material prepared by the method is a two-dimensional sheet-shaped nano structure, and the structure can provide a good oxygen and electrolyte diffusion channel to promote a catalytic reaction process and ensure that the composite material has good oxygen reduction performance; in addition, the two-dimensional nano flaky substrate-supported carbon nanotube composite structure obtained after pyrolysis has the characteristics of high specific surface area, high active sites and the like, and the carbon nanotube has good conductivity and can cooperate with a catalyst to perform oxygen reduction electrocatalytic reaction; finally, the preparation method has simple process and low cost, and is suitable for large-scale production.
Drawings
FIG. 1 is a scanning electron microscope image of a two-dimensional iron-nitrogen co-doped carbon-based composite material prepared in example 1;
FIG. 2 is a transmission electron microscope image of the two-dimensional iron-nitrogen co-doped carbon-based composite material prepared in example 1;
FIG. 3 is a transmission energy spectrum of the two-dimensional iron-nitrogen co-doped carbon-based composite material prepared in example 1;
fig. 4 is a graph of oxygen reduction performance of the two-dimensional iron-nitrogen co-doped carbon-based composite material prepared in example 1 and a commercial Pt/C catalyst.
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples.
Example 1
The preparation method of the two-dimensional iron-nitrogen co-doped carbon-based composite material comprises the following steps:
(1) dissolving ferric nitrate and glucose in 40mL of water at room temperature, and performing ultrasonic treatment for 30min to completely dissolve the ferric nitrate and the glucose to obtain a mixed solution A; in the mixed solution A, the concentration of ferric nitrate is 0.0125mol/L, and the concentration of glucose is 0.28 mol/L;
(2) adding 590mg of zinc nitrate into the mixed solution A, and stirring for 1h at room temperature until the zinc nitrate is completely dissolved to obtain a mixed solution B;
(3) under the condition of room temperature, 1.3g of 2-methylimidazole is dissolved in 40mL of water and is stirred uniformly by magnetic force to obtain a 2-methylimidazole solution;
(4) adding the mixed solution B obtained in the step (2) into the 2-methylimidazole solution obtained in the step (3), and magnetically stirring at room temperature for reaction for 4 hours;
(5) centrifuging and washing the reaction solution reacted in the step (4) for three times by deionized water, removing supernatant, taking out precipitate, and drying the precipitate at 60 ℃;
(6) and (3) heating the intermediate product dried in the step (5) to 900 ℃ at a heating rate of 3 ℃/min in an argon or nitrogen atmosphere, preserving heat for 3 hours, and cooling to room temperature after the reaction is finished to obtain the two-dimensional iron-nitrogen co-doped carbon-based composite material.
Fig. 1 is a scanning electron microscope image of the two-dimensional iron-nitrogen co-doped carbon-based composite material prepared in example 1, and the magnification of the scanning electron microscope image is 10000.
Fig. 2 is a transmission electron microscope image of the two-dimensional iron-nitrogen co-doped carbon-based composite material prepared in example 1, wherein the magnification is 150000.
Fig. 3 is a transmission energy spectrum of the two-dimensional iron-nitrogen co-doped carbon-based composite material prepared in example 1, wherein red represents C element, blue represents N element, and green represents Fe element. The magnification of fig. 3 is 1800000.
As can be seen from fig. 1, the two-dimensional iron-nitrogen co-doped carbon-based composite material prepared in example 1 is a composite structure in which a two-dimensional nano sheet-shaped substrate supports a carbon nanotube. The transmission electron microscope image of fig. 2 further verifies the composite structural feature of the composite material in fig. 1, which is a two-dimensional nano sheet substrate carrying carbon nanotubes. The transmission spectrum of fig. 3 shows that the final product of example 1 is a two-dimensional iron-nitrogen co-doped carbon-based composite material, i.e., the two-dimensional nanosheet-shaped substrate is a carbon-based substrate with Fe and N doped therein.
Electrochemical performance tests are performed on the two-dimensional iron-nitrogen co-doped carbon-based composite material prepared in example 1, fig. 4 is a corresponding oxygen reduction performance curve diagram, and as can be seen from fig. 4, the two-dimensional iron-nitrogen co-doped carbon-based composite material prepared in example 1 and the initial potential (E) of a commercial Pt/C catalyst are shownonset) 1V vs. reversible hydrogen electrode and 0.99V vs. reversible hydrogen electrode, half-wave potential (E)1/2) The two-dimensional iron-nitrogen co-doped carbon-based composite material obtained in example 1 has better oxygen reduction catalytic performance than a commercial Pt/C catalyst, which indicates that the two-dimensional iron-nitrogen co-doped carbon-based composite material of the present invention has excellent oxygen reduction catalytic performance.
Example 2
The preparation method of the two-dimensional iron-nitrogen co-doped carbon-based composite material comprises the following steps:
(1) dissolving ferric nitrate and glucose in 40mL of water at room temperature, and performing ultrasonic treatment for 30min to completely dissolve the ferric nitrate and the glucose to obtain a mixed solution A; in the mixed solution A, the concentration of ferric nitrate is 0.025mol/L, and the concentration of glucose is 0.28 mol/L;
(2) adding 885mg of zinc nitrate into the mixed solution A, and stirring for 1h at room temperature until the zinc nitrate is completely dissolved to obtain a mixed solution B;
(3) under the condition of room temperature, 1.46g of 2-methylimidazole is dissolved in 40mL of water and is stirred uniformly by magnetic force to obtain a 2-methylimidazole solution;
(4) adding the mixed solution B obtained in the step (2) into the 2-methylimidazole solution obtained in the step (3), and magnetically stirring at room temperature for reaction for 4 hours;
(5) centrifuging and washing the reaction solution reacted in the step (4) for three times by deionized water, removing supernatant, taking out precipitate, and drying the precipitate at 60 ℃;
(6) and (3) heating the intermediate product dried in the step (5) to 900 ℃ at a heating rate of 3 ℃/min in an argon or nitrogen atmosphere, preserving heat for 3 hours, and cooling to room temperature after the reaction is finished to obtain the two-dimensional iron-nitrogen co-doped carbon-based composite material.
The results obtained in this example are similar to those of example 1.
Example 3
The preparation method of the two-dimensional iron-nitrogen co-doped carbon-based composite material comprises the following steps:
(1) dissolving ferric nitrate and glucose in 40mL of water at room temperature, and performing ultrasonic treatment for 30min to completely dissolve the ferric nitrate and the glucose to obtain a mixed solution A; in the mixed solution A, the concentration of ferric nitrate is 0.0125mol/L, and the concentration of glucose is 0.28 mol/L:
(2) adding 590mg of zinc nitrate into the mixed solution A, and performing ultrasonic treatment at room temperature for 1h until the zinc nitrate is completely dissolved to obtain a mixed solution B;
(3) dissolving 2-methylimidazole 1.3g in 40mL of water at room temperature, and uniformly stirring by magnetic force to obtain a 2-methylimidazole solution;
(4) adding the mixed solution B obtained in the step (2) into the 2-methylimidazole solution obtained in the step (3), and magnetically stirring at room temperature for reaction for 3 hours;
(5) centrifuging and washing the reaction solution reacted in the step (4) for three times by deionized water, removing supernatant, taking out precipitate, and drying the precipitate at 60 ℃;
(6) and (3) heating the intermediate product dried in the step (5) to 800 ℃ at a heating rate of 3 ℃/min in an argon or nitrogen atmosphere, preserving heat for 3 hours, and cooling to room temperature after the reaction is finished to obtain the two-dimensional iron-nitrogen co-doped carbon-based composite material.
The results obtained in this example are similar to those of example 1.
Example 4
The preparation method of the two-dimensional iron-nitrogen co-doped carbon-based composite material comprises the following steps:
(1) dissolving ferric nitrate and glucose in 40mL of water at room temperature, and performing ultrasonic treatment for 30min to completely dissolve the ferric nitrate and the glucose to obtain a mixed solution A; in the mixed solution A, the concentration of ferric nitrate is 0.0125mol/L, and the concentration of glucose is 0.28 mol/L;
(2) adding 590mg of zinc nitrate into the mixed solution A, and performing ultrasonic treatment at room temperature for 1h until the zinc nitrate is completely dissolved to obtain a mixed solution B;
(3) under the condition of room temperature, 1.3g of 2-methylimidazole is dissolved in 40mL of water and is stirred uniformly by magnetic force to obtain a 2-methylimidazole solution;
(4) adding the mixed solution B obtained in the step (2) into the 2-methylimidazole solution obtained in the step (3), and magnetically stirring at room temperature for reaction for 3 hours;
(5) centrifuging and washing the reaction solution reacted in the step (4) for three times by deionized water, removing supernatant, taking out precipitate, and drying the precipitate at 60 ℃;
(6) and (3) heating the intermediate product dried in the step (5) to 800 ℃ at a heating rate of 3 ℃/min in an argon or nitrogen atmosphere, preserving heat for 3 hours, and cooling to room temperature after the reaction is finished to obtain the two-dimensional iron-nitrogen co-doped carbon-based composite material.
Example 5
The preparation method of the two-dimensional iron-nitrogen co-doped carbon-based composite material comprises the following steps:
(1) dissolving ferric nitrate and glucose in 40mL of water at room temperature, and performing ultrasonic treatment for 30min to completely dissolve the ferric nitrate and the glucose to obtain a mixed solution A; in the mixed solution A, the concentration of ferric nitrate is 0.0125mol/L, the concentration of glucose is 0.32 moI/L:
(2) adding 590mg of zinc nitrate into the mixed solution A, and performing ultrasonic treatment at room temperature for 1h until the zinc nitrate is completely dissolved to obtain a mixed solution B;
(3) under the condition of room temperature, 1.3g of 2-methylimidazole is dissolved in 40mL of water and is stirred uniformly by magnetic force to obtain a 2-methylimidazole solution;
(4) adding the mixed solution B obtained in the step (2) into the 2-methylimidazole solution obtained in the step (3), and magnetically stirring at room temperature for reaction for 3 hours;
(5) centrifuging and washing the reaction solution reacted in the step (4) for three times by deionized water, removing supernatant, taking out precipitate, and drying the precipitate at 60 ℃;
(6) and (3) heating the intermediate product dried in the step (5) to 900 ℃ at a heating rate of 3 ℃/min in an argon or nitrogen atmosphere, preserving heat for 3 hours, and cooling to room temperature after the reaction is finished to obtain the two-dimensional iron-nitrogen co-doped carbon-based composite material.
The results obtained in this example are similar to those of example 1.
Claims (6)
1. Two-dimensional iron and nitrogen co-doped carbon-based composite material is characterized in that: the composite material is prepared by firstly synthesizing a metal organic framework in a water phase, wherein the metal organic framework is an iron-based complex metal organic framework, and then pyrolyzing the metal organic framework serving as a precursor; the composite material takes a two-dimensional sheet nanostructure as a substrate, the substrate is a carbon-based substrate, Fe and N are doped in the carbon-based substrate, and carbon nanotubes grow on the substrate;
the two-dimensional iron-nitrogen co-doped carbon-based composite material is prepared by the following method: respectively dissolving an iron precursor, a chelating agent, zinc nitrate and 2-methylimidazole in water, reacting the mixed material at room temperature for 2-4 h, and obtaining a metal organic framework after reaction; and heating the obtained metal organic framework to 600-900 ℃ at a heating rate of 2-5 ℃/min in an inert atmosphere, and preserving heat for 1-3 h to obtain the two-dimensional iron-nitrogen co-doped carbon-based composite material.
2. The preparation method of the two-dimensional iron-nitrogen co-doped carbon-based composite material according to claim 1, characterized in that: the iron precursor is ferric chloride or ferric nitrate.
3. The preparation method of the two-dimensional iron-nitrogen co-doped carbon-based composite material according to claim 1, characterized in that: the chelating agent is glucose or fructose.
4. The preparation method of the two-dimensional iron-nitrogen co-doped carbon-based composite material according to claim 1, characterized in that: the mixing molar ratio of the iron precursor to the chelating agent is 1: 22-30, and the mixing molar ratio of the iron precursor to the zinc nitrate is 1: 4-6.
5. The preparation method of the two-dimensional iron-nitrogen co-doped carbon-based composite material according to claim 1, characterized in that: the mixing molar ratio of the iron precursor to the chelating agent to the zinc nitrate to the 2-methylimidazole is 1: 22: 4: 32-1: 30:6: 36.
6. The application of the two-dimensional iron and nitrogen co-doped carbon-based composite material as an electrocatalyst in a cathode oxygen reduction reaction of a fuel cell.
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