CN112058301A - Preparation method of pyrrole-derived monoatomic iron-based nitrogen-carbon material for oxygen reduction - Google Patents

Preparation method of pyrrole-derived monoatomic iron-based nitrogen-carbon material for oxygen reduction Download PDF

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CN112058301A
CN112058301A CN202011093433.8A CN202011093433A CN112058301A CN 112058301 A CN112058301 A CN 112058301A CN 202011093433 A CN202011093433 A CN 202011093433A CN 112058301 A CN112058301 A CN 112058301A
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iron
carbon material
oxygen reduction
zinc
solution
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曹传宝
姚秀云
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Beijing Institute of Technology BIT
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Beijing Institute of Technology BIT
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
    • B01J35/33—
    • B01J35/394—

Abstract

The invention relates to a general preparation method of a monoatomic iron-based nitrogen-carbon material and application of the monoatomic iron-based nitrogen-carbon material as an oxygen reduction reaction catalyst material. Firstly, dissolving an iron source compound and a zinc source compound in a hydrophilic solution, adding a pyrrole monomer, violently stirring for a certain time to form a uniformly mixed solution, centrifugally washing a product for several times by deionized water and ethylene glycol after the solution is finished, and calcining the dried product to obtain a final product. The invention has the advantages that: the method has the advantages of simple operation, low cost, mild reaction conditions, uniform product size and appearance, good dispersibility and no occurrence of agglomeration of metal particles, and the whole reaction is carried out at normal temperature and normal pressure without an additional pickling process. The catalyst used for the oxygen reduction reaction has high conductivity, abundant active sites and excellent electrocatalytic activity, and is an ideal catalytic material for the oxygen reduction reaction with wide commercial application prospect.

Description

Preparation method of pyrrole-derived monoatomic iron-based nitrogen-carbon material for oxygen reduction
Technical Field
The invention belongs to the field of monoatomic materials, and particularly relates to preparation of an iron monoatomic material based on pyrrole polymerization.
Background
With the continuous development of human society, the traditional fossil energy is gradually exhausted due to overuse, so that the problem of environmental pollution is also gradually serious, and people gradually realize the importance of developing sustainable new energy and efficient energy conversion technology. Among these new devices, fuel cells and rechargeable metal-air cells are two ways of receiving much attention, but the price of noble metal catalysts is high, and large-scale popularization and application have not been realized. Therefore, the development of an economical and efficient oxygen reduction catalyst becomes a key point for promoting the practicability and scale of fuel cells and metal-air cells.
The non-noble metal catalyst not only can reduce the cost of the catalyst, but also can keep higher stability. In actual fuel cell testing, the nitrogen-doped carbon material demonstrated superior catalytic activity and stability over Pt-based catalysts. On the basis, the surface of the nitrogen-containing carbon material is doped with metal single atoms (M-NC), so that the catalytic activity of the material can be further improved, for example, the active site is MN4The catalyst of (1). Among them, Fe-NC exhibits excellent catalytic performance in electrocatalytic oxygen reduction (angelw. chem. int. ed, 50(2011) 11765-.
The monatomic catalyst is a new star which is completely open at the head corner in the field of catalysis in recent years, and has the advantages of high atom utilization rate, uniform active site distribution, adjustable electronic structure and very high electrocatalytic activity and selectivity. However, the preparation of monoatomic dispersions of metal species remains a significant challenge due to the tendency of the metal species to migrate and agglomerate at the atomic level.
It is now common internationally to disperse metal atoms with the aid of templates or substrates, such as silica templates, graphene substrates and metal-organic framework structures. But finally, most require an acid washing step to remove the template, thereby reducing the catalytic activity of the material. The pyrrole polymerization mode is selected, so that iron atoms are polymerized onto polypyrrole in situ in the pyrrole polymerization process, and the monatomic iron-based nitrogen-carbon material is obtained through simple calcination.
Disclosure of Invention
The invention aims to synthesize a monatomic iron-based nitrogen-carbon material with high stability and high catalytic performance, thereby solving the problems of easy agglomeration of metal atoms, low current density, poor stability and complex preparation process existing in the existing catalyst.
In order to achieve the purpose, the invention adopts the following technical scheme:
adding an iron source compound and a zinc source compound into the hydrophilic solution to obtain a metal organic solution with a certain concentration;
adding a polymer monomer into the mixed system in the step 1;
stirring the mixed system in the step 2 for reaction for a certain time to obtain a reaction product, and washing and drying the product to obtain a polymer containing metal;
and (4) calcining the product obtained in the step (3) at a certain temperature for a certain time, and naturally cooling to room temperature to obtain the monatomic iron-based nitrogen-carbon material.
Further, the hydrophilic solution in step 1 includes one or more mixed solutions of deionized water, methanol, ethanol, ethylene glycol, glycerol, dimethylformamide, pyridine, piperidine, tetrahydrofuran, and the like.
Further, the iron source compound in step 1 includes one or more mixed salts of ferric nitrate, ferrous nitrate, ferric chloride, ferrous oxalate, ferric sulfate, ferrous sulfate, and the like.
Further, the zinc source compound in step 1 includes one or more mixed salts of zinc nitrate, zinc chloride, zinc oxalate, zinc sulfate, etc.
Further, the concentration of the metal organic solution in the step 1 is 0.01-10 mol/L.
Further, the polymer monomer in step 2 comprises one or more of pyrrole, aniline, p-phenylenediamine, m-phenylenediamine, o-phenylenediamine and the like.
Further, the reaction time in the step 3 is 1-24 h.
Further, the medium used for washing the product in the step 3 is deionized water and absolute ethyl alcohol; the solid-liquid separation mode in the washing process comprises suction filtration, filter pressing or centrifugation and the like.
Further, the calcining temperature in the step 4 is 600-1000 ℃, and the calcining time is 0.5-3 hours.
Further, the monatomic iron-based nitrogen-carbon material in the step 4 is used as an oxygen reduction reaction catalytic material and shows excellent electrochemical performance.
Compared with the prior art, the invention has at least the following outstanding advantages:
the monoatomic iron-based nitrogen-carbon material prepared by the simple in-situ polymerization method has the advantages of simple operation, low cost, mild reaction conditions, no need of an additional pickling process when the whole reaction is carried out at normal temperature and normal pressure, no agglomeration of large metal particles, uniform size, shape and good dispersibility of the product. Can be used as a good catalyst for oxygen reduction, and has higher half-wave potential and limiting current density in alkaline electrolyte.
Drawings
FIG. 1 is a TEM spectrum of the monatomic iron-based nitrogen-carbon material prepared in example 1;
FIG. 2 is an XRD pattern of the monatomic iron-based nitrogen-carbon material prepared in example 1;
FIG. 3 is a graph showing the linear voltammetry scanning performance of the monatomic iron-based nitrogen-carbon material prepared in example 1 in a 0.1M KOH electrolyte;
FIG. 4 is a graph of the linear voltammetry scan performance of the oxygen-reducing material prepared in example 4 in a 0.1M KOH electrolyte;
FIG. 5 is a graph of the linear voltammetry sweep performance of the oxygen-reducing material prepared in example 9 in a 0.1M KOH electrolyte.
Detailed Description
For a further understanding of the invention, reference is made to the following detailed description taken in conjunction with the accompanying drawings and examples, but it is understood that the description is intended to illustrate further features and advantages of the invention, and not to limit the scope of the invention as claimed.
A general preparation method of a monoatomic iron-based nitrogen-carbon material and an application of the material as a good catalyst for oxygen reduction are disclosed, wherein the preparation steps are as follows:
(1) adding an iron source compound and a zinc source compound into the hydrophilic solution to obtain a metal organic solution with a certain concentration;
(2) adding a polymer monomer into the mixed system in the step 1;
(3) stirring the mixed system in the step 2 for reaction for a certain time to obtain a reaction product, and washing and drying the product to obtain a polymer containing metal;
(4) and (4) calcining the product obtained in the step (3) at a certain temperature for a certain time, and naturally cooling to room temperature to obtain the monatomic iron-based nitrogen-carbon material.
Example 1
(1) A clean 200mL beaker was taken and 100mL of anhydrous methanol was added to the beaker.
(2) 500mg of iron nitrate nonahydrate and 15g of zinc nitrate hexahydrate were simultaneously added to the methanol solution in step (1) to give an orange clear solution with stirring.
(3) And (3) adding 1000 mu L of pyrrole into the clear solution obtained in the step (2), and reacting for 24 hours under stirring to obtain a dark blue turbid solution.
(4) And (4) centrifugally washing the turbid solution obtained in the step (3) for a plurality of times by using ethanol and deionized water, and drying a product obtained by suction filtration and separation at 80 ℃ for 12 hours.
(5) And (4) calcining the dried product obtained in the step (4) for 3 hours at 900 ℃ under the argon atmosphere.
Example 2
(1) A clean 200mL beaker was taken and 100mL of anhydrous methanol was added to the beaker.
(2) 500mg of ferric nitrate nonahydrate was added to the methanol solution in step (1) to give an orange clear solution with stirring.
(3) And (3) adding 1000 mu L of pyrrole into the clear solution obtained in the step (2), and reacting for 24 hours under stirring to obtain a dark blue turbid solution.
(4) And (4) centrifugally washing the turbid solution obtained in the step (3) for a plurality of times by using ethanol and deionized water, and drying a product obtained by suction filtration and separation at 80 ℃ for 12 hours.
(5) And (4) calcining the dried product obtained in the step (4) for 3 hours at 900 ℃ under the argon atmosphere.
Example 3
(1) A clean 200mL beaker was taken and 100mL of anhydrous methanol was added to the beaker.
(2) 1000 mu L of pyrrole is added into the methanol solution obtained in the step 1, and the mixture reacts for 24 hours under stirring to obtain turbid liquid.
(3) And (3) centrifugally washing the turbid solution obtained in the step (2) for a plurality of times by using ethanol and deionized water, and drying a product obtained by suction filtration and separation at 80 ℃ for 12 hours.
(4) And (4) calcining the dried product obtained in the step (3) for 3h at 900 ℃ in an argon atmosphere.
Example 4
(1) A clean 200mL beaker was taken and 100mL of absolute ethanol was added to the beaker.
(2) 500mg of iron nitrate nonahydrate and 15g of zinc nitrate hexahydrate were simultaneously added to the ethanol solution of step (1) to give a clear orange solution with stirring.
(3) And (3) adding 1000 mu L of pyrrole into the clear solution obtained in the step (2), and reacting for 24 hours under stirring to obtain turbid liquid.
(4) And (4) centrifugally washing the turbid solution obtained in the step (3) for a plurality of times by using ethanol and deionized water, and drying a product obtained by suction filtration and separation at 80 ℃ for 12 hours.
(5) And (4) calcining the dried product obtained in the step (4) for 3 hours at 900 ℃ under the argon atmosphere.
Example 5
(1) A clean 200mL beaker was taken and 100mL of anhydrous methanol was added to the beaker.
(2) 500mg of ferric chloride and 15g of zinc chloride were simultaneously added to the methanol solution in step (1) to obtain a clear solution with stirring.
(3) And (3) adding 1000 mu L of pyrrole into the clear solution obtained in the step (2), and reacting for 24 hours under stirring to obtain turbid liquid.
(4) And (4) centrifugally washing the turbid solution obtained in the step (3) for a plurality of times by using ethanol and deionized water, and drying a product obtained by suction filtration and separation at 80 ℃ for 12 hours.
(5) And (4) calcining the dried product obtained in the step (4) for 3 hours at 900 ℃ under the argon atmosphere.
Example 6
(1) A clean 200mL beaker was taken and 100mL of anhydrous methanol was added to the beaker.
(2) 500mg of iron nitrate nonahydrate and 15g of zinc nitrate hexahydrate were simultaneously added to the methanol solution in step (1) to give an orange clear solution with stirring.
(3) And (3) adding 1000 mu L of p-phenylenediamine into the clear solution obtained in the step (2), and reacting for 24 hours under stirring to obtain turbid liquid.
(4) And (4) centrifugally washing the turbid solution obtained in the step (3) for a plurality of times by using ethanol and deionized water, and drying a product obtained by suction filtration and separation at 80 ℃ for 12 hours.
(5) And (4) calcining the dried product obtained in the step (4) for 3 hours at 900 ℃ under the argon atmosphere.
Example 7
(1) A clean 200mL beaker was taken and 100mL of anhydrous methanol was added to the beaker.
(2) 500mg of iron nitrate nonahydrate and 15g of zinc nitrate hexahydrate were simultaneously added to the methanol solution in step (1) to give an orange clear solution with stirring.
(3) Adding 1000 mu L of m-phenylenediamine into the clear solution obtained in the step 2, and reacting for 24 hours under stirring to obtain a turbid solution.
(4) And (4) centrifugally washing the turbid solution obtained in the step (3) for a plurality of times by using ethanol and deionized water, and drying a product obtained by suction filtration and separation at 80 ℃ for 12 hours.
(5) And (4) calcining the dried product obtained in the step (4) for 3 hours at 900 ℃ under the argon atmosphere.
Example 8
(1) A clean 200mL beaker was taken and 100mL of anhydrous methanol was added to the beaker.
(2) 500mg of iron nitrate nonahydrate and 15g of zinc nitrate hexahydrate were simultaneously added to the methanol solution in step (1) to give an orange clear solution with stirring.
(3) And (3) adding 1000 mu L of o-phenylenediamine into the clear solution obtained in the step (2), and reacting for 24 hours under stirring to obtain turbid liquid.
(4) And (4) centrifugally washing the turbid solution obtained in the step (3) for a plurality of times by using ethanol and deionized water, and drying a product obtained by suction filtration and separation at 80 ℃ for 12 hours.
(5) And (4) calcining the dried product obtained in the step (4) for 3 hours at 900 ℃ under the argon atmosphere.
Example 9
(1) A clean 200mL beaker was taken and 100mL of anhydrous methanol was added to the beaker.
(2) 15g of zinc nitrate hexahydrate was added to the methanol solution in step (1) to obtain a clear solution with stirring.
(3) And (3) adding 1000 mu L of pyrrole into the clear solution obtained in the step (2), and reacting for 24 hours under stirring to obtain turbid liquid.
(4) And (4) centrifugally washing the turbid solution obtained in the step (3) for a plurality of times by using ethanol and deionized water, and drying a product obtained by suction filtration and separation at 80 ℃ for 12 hours.
(5) And (4) calcining the dried product obtained in the step (4) for 3 hours at 900 ℃ under the argon atmosphere.
Example 10
(1) A clean 200mL beaker was taken and 100mL of deionized water was added to the beaker.
(2) 500mg of iron nitrate nonahydrate and 15g of zinc nitrate hexahydrate were simultaneously added to the solution in step (1), and a mixed solution was obtained with stirring.
(3) And (3) adding 1000 mu L of pyrrole into the mixed solution obtained in the step (2), and reacting for 24 hours under stirring to obtain turbid liquid.
(4) And (4) centrifugally washing the turbid solution obtained in the step (3) for a plurality of times by using ethanol and deionized water, and drying a product obtained by suction filtration and separation at 80 ℃ for 12 hours.
(5) And (4) calcining the dried product obtained in the step (4) for 3 hours at 900 ℃ under the argon atmosphere.
Example 11
(1) A clean 200mL beaker was taken and 100mL of isopropanol was added to the beaker.
(2) 500mg of iron nitrate nonahydrate and 15g of zinc nitrate hexahydrate were simultaneously added to the solution in step (1), and a mixed solution was obtained with stirring.
(3) And (3) adding 1000 mu L of pyrrole into the mixed solution obtained in the step (2), and reacting for 24 hours under stirring to obtain turbid liquid.
(4) And (4) centrifugally washing the turbid solution obtained in the step (3) for a plurality of times by using ethanol and deionized water, and drying a product obtained by suction filtration and separation at 80 ℃ for 12 hours.
(5) And (4) calcining the dried product obtained in the step (4) for 3 hours at 900 ℃ under the argon atmosphere.
Example 12
(1) A clean 200mL beaker was taken and 100mL of acetone solvent was added to the beaker.
(2) 500mg of iron nitrate nonahydrate and 15g of zinc nitrate hexahydrate were simultaneously added to the solution in step (1), and a mixed solution was obtained with stirring.
(3) And (3) adding 1000 mu L of pyrrole into the mixed solution obtained in the step (2), and reacting for 24 hours under stirring to obtain turbid liquid.
(4) And (4) centrifugally washing the turbid solution obtained in the step (3) for a plurality of times by using ethanol and deionized water, and drying a product obtained by suction filtration and separation at 80 ℃ for 12 hours.
(5) And (4) calcining the dried product obtained in the step (4) for 3 hours at 900 ℃ under the argon atmosphere.
Example 13
(1) A clean 200mL beaker was taken and 100mL of methanol solvent was added to the beaker.
(2) 500mg of iron nitrate nonahydrate and 15g of zinc nitrate hexahydrate were simultaneously added to the solution in step (1), and a mixed solution was obtained with stirring.
(3) And (3) adding 1000 mu L of aniline into the mixed solution obtained in the step (2), and reacting for 24 hours under stirring to obtain turbid liquid.
(4) And (4) centrifugally washing the turbid solution obtained in the step (3) for a plurality of times by using ethanol and deionized water, and drying a product obtained by suction filtration and separation at 80 ℃ for 12 hours.
(6) And (4) calcining the dried product obtained in the step (4) for 3 hours at 900 ℃ under the argon atmosphere.

Claims (10)

1. A preparation method of a pyrrole derived monoatomic iron-based nitrogen-carbon material and an application of the material as an oxygen reduction reaction electrocatalyst material are characterized by comprising the following steps: (1) adding an iron source compound and a zinc source compound into the hydrophilic solution to obtain a metal organic solution with a certain concentration; (2) adding a polymer monomer into the mixed system in the step 1; (3) stirring the mixed system in the step 2 for reaction for a certain time to obtain a reaction product, and washing and drying the product to obtain a polymer containing metal; (4) and (4) calcining the product obtained in the step (3) at a certain temperature for a certain time, and naturally cooling to room temperature to obtain the monatomic iron-based nitrogen-carbon material.
2. The method of claim 1, wherein: the hydrophilic solution comprises one or more mixed solutions of deionized water, methanol, ethanol, glycol, glycerol, dimethylformamide, pyridine, piperidine, tetrahydrofuran and the like.
3. The method of claim 1, wherein: the iron source compound comprises one or more mixed salts of ferric nitrate, ferrous nitrate, ferric chloride, ferrous oxalate, ferric sulfate, ferrous sulfate and the like.
4. The method of claim 1, wherein: the zinc source compound comprises one or more mixed salts of zinc nitrate, zinc chloride, zinc oxalate, zinc sulfate and the like.
5. The method of claim 1, wherein: the concentration of the metal organic solution is 0.01-10 mol/L.
6. The method of claim 1, wherein: the polymer monomer comprises one or more of pyrrole, aniline, p-phenylenediamine, m-phenylenediamine, o-phenylenediamine and the like.
7. The method of claim 1, wherein: the stirring reaction time is 1-24 h.
8. The method of claim 1, wherein: the medium used for washing the product is deionized water and absolute ethyl alcohol; the solid-liquid separation mode in the washing process comprises suction filtration, filter pressing or centrifugation and the like.
9. The method of claim 1, wherein: the calcination temperature is 600-1000 ℃, and the calcination time is 0.5-3 hours.
10. The method of claim 1, wherein: the monatomic iron-based nitrogen-carbon material is used as an oxygen reduction reaction electrocatalyst and shows excellent electrochemical performance.
CN202011093433.8A 2020-10-13 2020-10-13 Preparation method of pyrrole-derived monoatomic iron-based nitrogen-carbon material for oxygen reduction Pending CN112058301A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113381034A (en) * 2021-06-18 2021-09-10 河北工业大学 Preparation method and application of polypyrrole gel loaded copper-phosphorus atom composite material
CN113410479A (en) * 2021-06-17 2021-09-17 济南大学 Preparation method and application of transition metal monoatomic and nitrogen-phosphorus-doped carbon sphere

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CN106955691A (en) * 2017-04-20 2017-07-18 南京师范大学 A kind of monatomic iron catalyst of carbon nitrogen base and preparation method thereof
CN108963276A (en) * 2018-06-27 2018-12-07 中国科学技术大学 Non-precious metal catalyst and preparation method thereof for catalytic oxidation-reduction
CN110201702A (en) * 2019-06-14 2019-09-06 北京大学深圳研究生院 Carbon carries the nitrogenous compound oxygen reduction catalyst preparation method of monoatomic metal and gained catalyst
CN110289403A (en) * 2019-06-12 2019-09-27 苏州大学 A kind of Nano carbon balls and its preparation method and application containing monatomic Fe

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106955691A (en) * 2017-04-20 2017-07-18 南京师范大学 A kind of monatomic iron catalyst of carbon nitrogen base and preparation method thereof
CN108963276A (en) * 2018-06-27 2018-12-07 中国科学技术大学 Non-precious metal catalyst and preparation method thereof for catalytic oxidation-reduction
CN110289403A (en) * 2019-06-12 2019-09-27 苏州大学 A kind of Nano carbon balls and its preparation method and application containing monatomic Fe
CN110201702A (en) * 2019-06-14 2019-09-06 北京大学深圳研究生院 Carbon carries the nitrogenous compound oxygen reduction catalyst preparation method of monoatomic metal and gained catalyst

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113410479A (en) * 2021-06-17 2021-09-17 济南大学 Preparation method and application of transition metal monoatomic and nitrogen-phosphorus-doped carbon sphere
CN113381034A (en) * 2021-06-18 2021-09-10 河北工业大学 Preparation method and application of polypyrrole gel loaded copper-phosphorus atom composite material

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