CN110902649B - Method for preparing iron-nitrogen-carbon catalyst by using template - Google Patents

Method for preparing iron-nitrogen-carbon catalyst by using template Download PDF

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CN110902649B
CN110902649B CN201911219961.0A CN201911219961A CN110902649B CN 110902649 B CN110902649 B CN 110902649B CN 201911219961 A CN201911219961 A CN 201911219961A CN 110902649 B CN110902649 B CN 110902649B
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nitrogen
iron
precursor
melamine
template
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CN110902649A (en
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盛赵旻
李俊
甘祖忠
黄欢
牛睿梁
韩志伟
王格
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Shanghai Institute of 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
    • H01M4/96—Carbon-based electrodes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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 provides a method for preparing an iron-nitrogen-carbon catalyst by a template, wherein the catalyst is obtained by heating and carbonizing a nitrogen-rich iron coordination polymer precursor and then removing a sacrificial template; the method mainly comprises the following steps: selecting melamine as a nitrogen source, dissolving the melamine in deionized water, heating and stirring, adding formaldehyde and ferric salt, regulating and controlling the solution to be acidic, and carrying out in-situ polymerization to obtain a nitrogen-rich iron coordination polymer precursor; drying the precursor, uniformly mixing the precursor with a sacrificial template, putting the precursor into a quartz tube, putting the quartz tube into a tube furnace, introducing nitrogen for protection, and carbonizing at high temperature to obtain catalyst particles; collecting particles, removing the sacrificial template, performing ultrasonic treatment, filtering, and washing with deionized water; and drying the catalyst to obtain the nitrogen-rich iron-nitrogen-carbon catalyst with high specific surface area. The preparation method of the catalyst is simple, easy to operate, easy to obtain raw materials, green and environment-friendly, high in catalytic activity of oxygen reduction of the product, good in stability, capable of being used in the field of fuel cell cathode catalysts, and suitable for industrial production.

Description

Method for preparing iron-nitrogen-carbon catalyst by using template
Technical Field
The invention belongs to the field of new energy materials and electrochemistry, relates to a preparation method of a fuel cell cathode oxygen reduction catalyst, and particularly relates to a method for preparing a nitrogen-rich iron-nitrogen-carbon catalyst with a high specific surface area by a template method.
Background
The Oxygen Reduction Reaction (ORR) is a basic reaction and has a critical role in various applications such as fuel cells, metal air cells and other electrochemical energy technologies. The slow and complex kinetics of this reaction require the use of expensive platinum catalysts to avoid efficient polarization losses, resulting in a substantial increase in the cost of these energy conversion/storage devices, especially in fuel cell technology. But even the cathode oxygen reduction catalytic activity of the noble metal platinum catalyst is much lower than that of the anode oxidation reaction. The main reasons for the above-mentioned loss of polarization are the unreasonable structural optimization and the low catalytic activity of the catalyst. Therefore, the development of a non-noble metal cathode oxygen reduction catalyst with simple preparation process, wide raw materials, low cost, environmental friendliness, high catalytic performance and good stability is crucial to the practical application of the technologies (Journal of Power Sources 375(2018) 222-.
As technology has evolved, researchers have actively sought various alternative catalysts, including non-noble metals and metal-free catalysts. In non-noble metal catalysts, transition metal coordinated nitrogen nanocarbon materials (M/N-C, M ═ Fe, Co, etc.) have been found to be active and durable for ORR. Nitrogen-doped carbon materials exhibit high electrocatalytic activity towards ORR and are being developed into high performance catalysts, which should be designed to contain a high concentration of active sites. In addition to chemical composition, the structure of the catalyst also has a significant impact on catalytic activity due to the interfacial/surface reactions of the ORR. The porous structure and high specific surface area not only maximize the exposed active sites, but also promote mass transfer of reactants, intermediates and products (ACS appl. Mater. interfaces 29(2018) 335-344). Therefore, the development of a nitrogen-rich high-specific-surface-area non-noble metal catalyst with low cost and high catalytic activity is of great significance.
Through literature search, the Xing topic group (Nano Energy 49(2018) 23-30) adopts a bottom-up engineering strategy to construct three-dimensional N, P double-doped carbon nanosheets by carbonizing polymers of melamine and diphenyl hypophosphorous acid to improve the performance of a metal-free catalyst, the initial potential reaches 0.91vs. RHE, the initial potential is close to that of a commercial 20 wt.% Pt/C catalyst, and the specific surface area is as high as 1698m2g-1. Although the catalyst has large specific surface area and good catalytic performance, the preparation conditions are harsh, the process is complex, and the catalyst is not suitable for commercial production. The oxygen reduction initial potential of the catalyst needs to be further improved, and the catalyst can be further optimized from the aspects of raw material selection, preparation process, structure, catalytic sites and the like.
Disclosure of Invention
The invention aims to solve the technical problem of providing a method for synthesizing a nitrogen-rich iron-nitrogen-carbon catalyst with high specific surface area, which is applied to the cathode oxygen reduction of a fuel cell.
In order to solve the technical problem, the invention provides a method for preparing an iron-nitrogen-carbon catalyst by using a template, which is characterized by comprising the following steps of:
step 1: weighing melamine, dissolving the melamine in a deionized water solution, heating and magnetically stirring the solution uniformly, then sequentially adding formaldehyde and an iron source, and regulating and controlling the solution to have an acidic pH value of 2-6 to obtain a precursor;
step 2: drying the precursor obtained in the step (1), uniformly mixing the dried precursor with a sacrificial template, putting the mixture into a quartz tube, placing the quartz tube into a vertical tube furnace, setting the reaction temperature between 600 and 1100 ℃, increasing the temperature at a rate of 2 to 20 ℃/min, introducing nitrogen at a flow rate of 5 to 100L/h for protection, carbonizing the precursor in a high-temperature region of the tube furnace to form nanoclusters, and forming nitrogen-doped carbon-coated iron nanoparticle products from the nanoclusters after carbonization;
and step 3: and (3) placing the nitrogen-doped carbon-coated iron nanoparticles obtained in the step (2) in an acid solution, carrying out ultrasonic treatment for 6-12 h, washing with deionized water for multiple times, filtering, and drying for 6-24 h to finally obtain the iron-nitrogen-carbon catalyst.
Preferably, the mass ratio of the melamine to the formaldehyde in the step 1 is 5: 1-1: 10.
Preferably, the iron source in step 1 is ferric nitrate or ferric oxalate.
Preferably, the mass ratio of the melamine to the iron source in the step 1 is 5: 0.1-1: 0.5.
Preferably, the sacrificial template in the step 2 is calcium carbonate or magnesium oxide.
Preferably, the mass ratio of the melamine in the step 1 to the sacrificial template in the step 2 is 1: 5-10: 1.
Preferably, in the step 3, the acidic solution comprises concentrated nitric acid and concentrated hydrochloric acid, and the volume ratio of the concentrated nitric acid to the concentrated hydrochloric acid is 0: 1-1: 9.
Compared with the prior art, the invention has the beneficial effects that:
the invention adopts a simple in-situ polymerization method to synthesize a nitrogen-rich iron-coated coordination polymer precursor, uniformly mixes the precursor and a sacrificial template, utilizes the catalytic effect of the sacrificial template method and transition metal coordination nanoparticles, puts the mixture into a quartz tube, puts the quartz tube into a tube furnace, and introduces nitrogen for protection and carries out high-temperature carbonization to obtain the nitrogen-rich doped carbon-coated iron nanoparticles. Removing the sacrificial template from the obtained nano particles by acid washing, performing ultrasonic treatment, filtering, washing with deionized water, and drying the catalyst to obtain the nitrogen-rich high-specific-surface-area catalystThe iron nitrogen carbon catalyst. The specific surface area of the catalyst is 200-800 m2g-1Pore volume of 0.5-1.4 cm3g-1High nitrogen content of 5-15 wt.%, initial oxygen reduction potential of 0.87-0.95V (reference electrode reversible hydrogen electrode), and dynamic current density JkIs 3.5 to 6.5mA cm-2。
The invention provides a preparation method of a nitrogen-rich iron-nitrogen-carbon catalyst with high specific surface area, which has simple manufacturing equipment and easy operation and is convenient for large-scale industrial production. The catalyst has the advantages of easily controlled elements, porous structure and high specific surface area. The catalyst has high oxygen reduction catalytic activity, good stability, low production cost and environmental protection, can be used in the field of fuel cell cathode catalysts, and is suitable for industrial production.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Example 1
The embodiment provides a method for preparing an iron-nitrogen-carbon catalyst by using a template, which comprises the following specific steps:
step 1: weighing melamine, dissolving the melamine in a deionized water solution, heating and magnetically stirring the solution uniformly, then sequentially adding formaldehyde and an iron source at intervals of 0.5h, wherein the mass ratio of the melamine to the formaldehyde to the iron oxalate is 5:1:0.1, and regulating the solution to the acidic pH value of 2 to obtain a precursor;
step 2: drying the precursor obtained in the step 1, uniformly mixing the dried precursor with a magnesium oxide sacrificial template, wherein the mass ratio of melamine to magnesium oxide is 10:1, placing the mixture into a quartz tube, placing the quartz tube into a vertical tube furnace, setting the reaction temperature at 1100 ℃, setting the heating rate at 2 ℃/min, introducing nitrogen at the flow rate of 5L/h for protection, carbonizing the precursor in a high-temperature region of the tube furnace to form nanoclusters, and forming nitrogen-doped carbon-coated iron nanoparticle products after the carbonization of the nanoclusters;
and step 3: placing the nitrogen-doped carbon-coated iron nanoparticles obtained in the step 2 in concentrated hydrochloric acid, and performing ultrasonic treatment: the power is 300W, and the time is 12 h; and then washing with deionized water for multiple times, filtering, and drying for 24 hours to finally obtain the iron-nitrogen-carbon catalyst.
The specific surface area of the iron-nitrogen-carbon catalyst prepared in the example is 200m2g-1Pore volume of 0.5cm3g-1Nitrogen content 5 wt.%, initial potential for oxygen reduction 0.87V (reference electrode reversible hydrogen electrode), dynamic current density JkIs 3.5mA cm-2。
Example 2
The embodiment provides a method for preparing an iron-nitrogen-carbon catalyst by using a template, which comprises the following specific steps:
step 1: weighing melamine, dissolving the melamine in a deionized water solution, heating, magnetically stirring uniformly, then sequentially adding formaldehyde and an iron source at intervals of 1h, wherein the mass ratio of the melamine to the formaldehyde to the iron oxalate is 1:1:0.2, and regulating the solution until the acidic pH value is 4 to obtain a precursor;
step 2: drying the precursor obtained in the step 1, uniformly mixing the dried precursor with a magnesium oxide sacrificial template, placing the melamine and magnesium oxide sacrificial template into a quartz tube at a mass ratio of 1:5, placing the quartz tube into a vertical tube furnace, setting the reaction temperature at 600 ℃, heating up at a rate of 15 ℃/min, introducing nitrogen at a flow rate of 60L/h for protection, carbonizing the precursor in a high-temperature region of the tube furnace to form nanoclusters, and forming nitrogen-doped carbon-coated iron nanoparticle products by the nanoclusters after carbonization;
and 3, step 3: placing the nitrogen-doped iron-coated carbon nanoparticles obtained in the step 2 in an acid solution with the volume ratio of concentrated nitric acid to concentrated hydrochloric acid of 1:6, and carrying out ultrasonic treatment: the power is 300W, and the time is 9 h; and then washing with deionized water for multiple times, filtering, and drying for 12 hours to finally obtain the iron-nitrogen-carbon catalyst.
The specific surface area of the iron-nitrogen-carbon catalyst prepared in the example is 800m2g-1Pore volume of 1.4cm3g-1Nitrogen content 15 wt.%, initial potential for oxygen reduction 0.95V (reference electrode reversible hydrogen electrode), dynamic current density JkAt 6.5mA cm-2。
Example 3
The embodiment provides a method for preparing an iron-nitrogen-carbon catalyst by using a template, which comprises the following specific steps:
step 1: weighing melamine, dissolving the melamine in a deionized water solution, heating, magnetically stirring uniformly, then sequentially adding formaldehyde and an iron source at intervals of 1.5h, regulating and controlling the solution to have an acidic pH value of 6 to obtain a precursor, wherein the mass ratio of the melamine to the formaldehyde to the iron oxalate is 1:10: 0.5;
step 2: drying the precursor obtained in the step (1), uniformly mixing the dried precursor with a magnesium oxide sacrificial template, wherein the mass ratio of melamine to magnesium oxide is 10:1, placing the precursor into a quartz tube, placing the quartz tube into a vertical tube furnace, setting the reaction temperature to be 900 ℃, the heating rate to be 20 ℃/min, introducing nitrogen at the flow rate of 100L/h for protection, carbonizing the precursor in a high-temperature region of the tube furnace to form nanoclusters, and forming nitrogen-doped carbon-coated iron nanoparticle products by the nanoclusters after carbonization;
and step 3: placing the nitrogen-doped carbon-coated iron nanoparticles obtained in the step 2 in an acid solution with the volume ratio of concentrated nitric acid to concentrated hydrochloric acid being 1:9, and carrying out ultrasonic treatment: the power is 300W, and the time is 9 h; and then washing with deionized water for multiple times, filtering, and drying for 6 hours to finally obtain the iron-nitrogen-carbon catalyst.
The specific surface area of the iron-nitrogen-carbon catalyst prepared in the example is 500m2g-1Pore volume of 1cm3g-1Nitrogen content 8 wt.%, initial potential for oxygen reduction 0.91V (reference electrode reversible hydrogen electrode), dynamic current density JkIs 5mA cm-2。

Claims (3)

1. The method for preparing the iron-nitrogen-carbon catalyst by using the template is characterized by comprising the following steps of:
step 1: weighing melamine, dissolving the melamine in a deionized water solution, heating and magnetically stirring the melamine uniformly, then sequentially adding formaldehyde and an iron source, and regulating and controlling the solution until the acid pH value is 2-6 to obtain a precursor; the mass ratio of the melamine to the formaldehyde is 5: 1-1: 10; the mass ratio of the melamine to the iron source is 5: 0.1-1: 0.5;
step 2: drying the precursor obtained in the step (1), uniformly mixing the dried precursor with a sacrificial template, putting the mixture into a quartz tube, placing the quartz tube into a vertical tube furnace, setting the reaction temperature between 600 and 1100 ℃, increasing the temperature at a rate of 2 to 20 ℃/min, introducing nitrogen at a flow rate of 5 to 100L/h for protection, carbonizing the precursor in a high-temperature region of the tube furnace to form nanoclusters, and forming nitrogen-doped carbon-coated iron nanoparticle products from the nanoclusters after carbonization; the sacrificial template is calcium carbonate or magnesium oxide; the mass ratio of the melamine to the sacrificial template is 1: 5-10: 1;
and step 3: and (3) placing the nitrogen-doped carbon-coated iron nanoparticles obtained in the step (2) in an acid solution, carrying out ultrasonic treatment for 6-12 h, washing with deionized water for multiple times, filtering, and drying for 6-24 h to finally obtain the iron-nitrogen-carbon catalyst.
2. The method for preparing the iron-nitrogen-carbon catalyst by using the template as claimed in claim 1, wherein the iron source in the step 1 is ferric nitrate or ferric oxalate.
3. The method for preparing the iron-nitrogen-carbon catalyst by using the template as claimed in claim 1, wherein in the step 3, the acidic solution comprises concentrated nitric acid and concentrated hydrochloric acid, and the volume ratio of the concentrated nitric acid to the concentrated hydrochloric acid is 0: 1-1: 6.
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CN103265008A (en) * 2013-05-21 2013-08-28 大连理工大学 Nitrogen-doped porous carbon and preparation method thereof
CN109546162A (en) * 2018-10-26 2019-03-29 江苏大学 A kind of recyclable preparation method of microporous iron-nitrogen-doped carbon catalyst material

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Publication number Priority date Publication date Assignee Title
CN103265008A (en) * 2013-05-21 2013-08-28 大连理工大学 Nitrogen-doped porous carbon and preparation method thereof
CN109546162A (en) * 2018-10-26 2019-03-29 江苏大学 A kind of recyclable preparation method of microporous iron-nitrogen-doped carbon catalyst material

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