CN109455690B - Preparation method of nitrogen atom doped carbon material - Google Patents

Preparation method of nitrogen atom doped carbon material Download PDF

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CN109455690B
CN109455690B CN201811561112.9A CN201811561112A CN109455690B CN 109455690 B CN109455690 B CN 109455690B CN 201811561112 A CN201811561112 A CN 201811561112A CN 109455690 B CN109455690 B CN 109455690B
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carbon material
nitrogen atom
nitrogen
doped carbon
pyrolysis
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CN109455690A (en
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游晗晖
吴冬霜
曹敏纳
曹荣
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Fujian Institute of Research on the Structure of Matter of CAS
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • 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
    • 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
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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
    • Y02E60/50—Fuel cells

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Abstract

The application discloses a preparation method of a nitrogen atom doped carbon material, which comprises the following steps: pyrolyzing raw materials containing a carbon source and a nitrogen atom source to obtain the nitrogen atom-doped carbon material, and simultaneously ensuring that the nitrogen atoms can enter a carbon skeleton and can be used for electrochemical oxygen reduction reaction.

Description

Preparation method of nitrogen atom doped carbon material
Technical Field
The application relates to a preparation method of a nitrogen atom doped carbon material, belonging to the field of materials.
Background
A fuel cell is an electrochemical energy conversion device that efficiently converts electrical energy to other energy. And the fuel cell only generates electricity, water and heat in the working process, does not generate other products polluting the environment, and is environment-friendly.
Compared with the anode reaction (hydrogen oxidation reaction) of the fuel cell, the cathode reaction, namely the oxygen reduction reaction, is more than 100 times slower than the hydrogen oxidation reaction, so that the method is the speed-dependent step of the whole fuel cell and greatly limits the performance of the fuel cell. Therefore, researchers have been working on oxygen reduction catalysts with high performance and long life for decades.
Among the existing oxygen reduction catalysts, the Pt-based noble metal catalyst is acknowledged to have the most excellent catalytic performance, but the high price is obviously not suitable for large-scale production and application. Much research has therefore focused on alternatives to Pt-based catalysts. Such as base metal catalysts, non-metal catalysts, and the like.
Disclosure of Invention
According to one aspect of the present application, there is provided a method for preparing a nitrogen atom-doped carbon material, which can obtain a highly efficient oxygen reduction reaction catalyst by adjusting the doping of a hetero element in the carbon material.
The non-metal electrocatalyst has the advantages of low cost, large specific surface area, excellent electrocatalytic activity and the like, and in the nitrogen-doped carbon material, the introduction of nitrogen can change the charge distribution on the surface of the carbon material and enrich the defect sites of the carbon material, thereby improving the catalytic activity of the catalyst.
In another aspect of the present application, there is provided a method for preparing the nitrogen atom-doped carbon material, including:
and pyrolyzing raw materials containing a carbon source and a nitrogen source to obtain the carbon material doped with nitrogen atoms.
Optionally, the raw material comprises at least one of cucurbituril compounds.
Optionally, the cucurbit compound is selected from at least one of a five-membered cucurbit ring, a six-membered cucurbit ring, a seven-membered cucurbit ring, an eight-membered cucurbit ring, an alkyl-substituted five-membered cucurbit ring, an alkyl-substituted six-membered cucurbit ring, an alkyl-substituted seven-membered cucurbit ring, and an alkyl-substituted eight-membered cucurbit ring.
Optionally, the cucurbituril compound is at least one of a six-membered cucurbituril and an alkyl-substituted five-membered cucurbituril.
Optionally, the cucurbit [6] uril compound is at least one of cucurbit [5] alkyl substituted cucurbit [6] urea.
Alternatively, the alkyl group is selected from C1～C10Alkyl group of (1).
Optionally, the alkyl is selected from C1～C4Alkyl group of (1).
Alternatively, the cucurbituril compound serves as both a carbon source and a nitrogen source.
Optionally, the temperature of the pyrolysis is 500-1100 ℃.
Alternatively, the temperature of the pyrolysis is 800 ℃.
Optionally, the upper temperature limit of the pyrolysis is selected from 600 ℃, 700 ℃, 800 ℃, 900 ℃, 1000 ℃, or 1100 ℃; the lower limit is selected from 500 deg.C, 600 deg.C, 700 deg.C, 800 deg.C, 900 deg.C or 1000 deg.C.
Optionally, the pyrolysis time is 2-4 hours.
Alternatively, the pyrolysis time is 3 hours.
Optionally, the heating rate of heating to the pyrolysis temperature is 3-8 ℃/min.
Optionally, the heating rate of the heating to the pyrolysis temperature is 5 ℃/min.
Optionally, the pyrolysis is carried out under an inert atmosphere.
Optionally, the inert atmosphere comprises at least one of nitrogen and an inert gas.
Optionally, the inert atmosphere is selected from at least one of nitrogen and inert gas.
Optionally, the pyrolysis is performed under a nitrogen atmosphere.
Optionally, the method comprises: and heating the six-membered cucurbituril to 500-1100 ℃ at a heating rate of 3-8 ℃/min in an inactive atmosphere, calcining for 2-4 hours, and cooling to obtain the nitrogen atom doped carbon material.
Optionally, the six-membered cucurbituril is used as a carbon source and a nitrogen source, and a nitrogen-doped carbon material is obtained by high-temperature calcination and used for electrochemical oxygen reduction reaction.
As a specific embodiment, the method comprises: utilizing six-membered cucurbituril in cucurbituril family (5-8-membered cucurbituril, decamethyl five-membered cucurbituril and the like), calcining at the high temperature of 800 ℃ (500-.
Optionally, the doping amount of the nitrogen atoms in the nitrogen atom-doped carbon material is 7-22%;
wherein the doping amount of the nitrogen atoms is calculated by the atomic percentage of the nitrogen atoms in the carbon material.
Optionally, the doping amount of the nitrogen atoms in the carbon material doped with nitrogen atoms is 7.62% to 21.99%.
Optionally, the nitrogen atoms are doped into the carbon skeleton of the carbon material.
Optionally, the nitrogen atom-doped carbon material is obtained by using a cucurbituril compound as a raw material.
Compared with the method for doping heteroatoms in the post-treatment, the method has the advantages that the material with high nitrogen content can be obtained more easily by directly pyrolyzing the nitrogen-containing precursor, and meanwhile, the nitrogen atoms can be ensured to enter the carbon skeleton.
Compared with other heteroatoms, the carbon material doped with nitrogen atoms can better improve the electron transmission efficiency in the reaction process.
In yet another aspect of the present application, there is provided an electrochemical oxygen reduction catalyst, characterized by comprising at least one of the nitrogen atom-doped carbon materials prepared according to any one of the above-described methods.
In the present application, "C1～C10、C1～C4"and the like" each refer to the number of carbon atoms contained in a group.
In the present application, an "alkyl group" is a group formed by losing any one hydrogen atom on the molecule of an alkane compound.
The beneficial effects that this application can produce include:
according to the method, the catalyst with oxygen reduction performance comparable to that of commercial Pt/C is obtained by adjusting the carbonization temperature and the carbonized precursor; the carbon material catalyst does not contain any metal, so that the use amount of the noble metal Pt can be effectively reduced, and the production cost is greatly reduced.
Drawings
FIG. 1 is a graph of the oxygen reduction activity of materials CB500, CB600, CB700, CB800, CB900 in one embodiment of the present application.
FIG. 2 is a graph of the number of transfer electrons in an oxygen reduction reaction for various materials in one embodiment of the present application.
Fig. 3 is a diagram illustrating hydrogen peroxide selectivity in an oxygen reduction reaction of different materials according to an embodiment of the present disclosure.
Fig. 4 is a graph comparing the oxygen reduction activity of cucurbiturils and alkyl substituted cucurbiturils in one embodiment of the present application.
FIG. 5 is an X-ray photoelectron spectrum of CB500, CB600, CB700, CB800, CB900 or CB1000 in example.
Fig. 6 and 7 are transmission electron micrographs of the CB800 in the example.
Fig. 8 and 9 are scanning electron micrographs of the CB800 in the example.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
The raw materials in the examples of the present application were all purchased commercially, unless otherwise specified.
The six-membered cucurbituril employed therein was synthesized according to the literature (CrystEngComm 9.11(2007): 973-; the decamethyl quinary cucurbituril used was synthesized according to literature (N. -Y.Shih, Diss.Abst.int.1982, B42,4071.) Pt/C20% was purchased from Alfa (Afahisata). The catalytic performance of electrochemical oxygen reduction was carried out using an electrochemical workstation from zahar, germany and a rotary apparatus from pine. The X-ray photoelectron spectrum was measured by an ESCALAB 250Xi spectrometer from Thermo Fisher. The transmission electron microscope image was obtained from a transmission electron microscope of Tecnai F20, FEI, USA, and the scanning electron microscope image was obtained from a scanning electron microscope of SU-8010, Hitachi.
According to one embodiment of the application, six-membered cucurbituril in cucurbituril family (5-8-membered cucurbituril, decamethyl five-membered cucurbituril and the like) is subjected to high-temperature calcination (500-1100 ℃) at 800 ℃ in a nitrogen atmosphere, the temperature is raised to a target temperature from room temperature by 5 ℃ and maintained below the target temperature for 3 hours, and finally, the temperature is naturally reduced to obtain the required nitrogen-doped carbon material.
EXAMPLE 1CB-800 catalyst and preparation thereof
(1) 2g of six-membered cucurbituril is uniformly dispersed in a ceramic crucible and then placed in a tubular furnace for high-temperature pyrolysis in a nitrogen atmosphere.
(2) The specific steps of the pyrolysis are that firstly, the tubular furnace is purged by nitrogen for 1h at room temperature to remove air in the tubular furnace, then the temperature in the tubular furnace is raised to 800 ℃ at the temperature rise speed of 5 ℃ per minute, the temperature is maintained below 800 ℃ for 3h, and finally the target carbon material can be obtained by naturally cooling to room temperature; labeled CB-800.
Example 2
The temperature of the pyrolysis was 500 ℃ and the rest of the procedure was the same as in example 1, the product obtained being labelled CB 500.
The temperature of the pyrolysis was 600 ℃ and the rest of the procedure was the same as in example 1, the product obtained being labelled CB 600.
The pyrolysis temperature was 700 ℃ and the rest of the procedure was the same as in example 1, the product obtained being labelled CB 700.
The temperature of the pyrolysis was 900 ℃ and the rest of the procedure was the same as in example 1, the product obtained being labelled CB 900.
The temperature of the pyrolysis was 1000 ℃ and the rest of the procedure was the same as in example 1, the product obtained being labelled CB 1000.
The temperature of the pyrolysis was 1100 ℃ and the rest of the procedure was the same as in example 1, the product obtained being labelled CB 1100.
The pyrolysis time was 2 hours, the temperature rise rate was 8 ℃/min, the rest of the procedure was the same as in example 1, and the product obtained was labeled CB 800-1.
The pyrolysis time was 4 hours, the temperature rise rate was 3 ℃/min, the rest of the procedure was the same as in example 1, and the product obtained was labeled CB 800-2.
Example 3
All the steps are the same as example 1, except that decamethyl quinary melon rings are used as precursors to obtain carbon materials by calcination, and the carbon materials are labeled as CB 5-800.
Fig. 4 is a graph of activity test of the catalysts provided in examples 3 and 1. It can be seen from the figure that the catalytic activity of the catalyst of the carbon material obtained by using the six-membered cucurbituril as a precursor is far higher than that of the carbon material obtained by calcining the decamethyl five-membered cucurbituril as a precursor.
Example 4 structural characterization of Nitrogen atom-doped carbon materials
The products of examples 1 to 3 were subjected to structural characterization.
The elemental composition of the material was accurately tested by an elemental analyzer.
Analysis by fitting of X-ray photoelectron spectroscopy. As shown in fig. 5, it can be seen that the N atoms were successfully doped (in a different manner) into the carbon skeleton.
The morphology of the obtained material was characterized in detail by transmission electron microscopy and scanning electron microscopy, as shown in fig. 6, 7, 8 and 9, from which it can be seen that the rod-like morphology of the material was maintained after carbonization.
EXAMPLE 5 catalytic Performance of electrochemical oxygen reduction
Electrocatalytic oxygen evolution reaction
Preparing an electrode: electrochemical tests were performed in a three-electrode glass cell. The working electrode was prepared by dispersing 4mg of the catalyst (samples prepared in examples 1 to 3, Pt/C20% Alfa) in 1ml of isopropanol and adding 20. mu.l of nafion ultrasound. Then, 20. mu.L of the above mixture was dropped on the surface of a glassy carbon electrode (glassy carbon electrode, diameter 5mm, area 0.196 cm)2) And drying to obtain the product, wherein the platinum mesh is used as a counter electrode, and the reference electrode is Ag/AgCl.
The content of the catalyst loaded on the glassy carbon electrode is 200 mu g/cm2。
And (3) electrochemical performance testing: firstly, N is2Performing cyclic voltammetry scanning in 0.1M KOH solution under atmosphere at a scanning speed of 100mV · s-1The scanning range is 0-1.2V, the number of scanning turns is 10, and the step is used for cleaning the surface of the catalyst and playing a certain activating role. Then at O2The polarization curve of the catalyst is tested in 0.1M KOH solution under the atmosphere to represent the oxygen reduction reaction of the catalyst, and the scanning speed is 10mV s-1The scanning range is 0-1.0V.
The conditions of the ring electrode test are that the ring disk electrode is adopted for testing (the diameter of the glass carbon disk part of the ring disk electrode is 2.8mm, and the area is 0.246 cm)2The collection efficiency of the ring disc is 0.4). The test conditions passed through the ring disk electrode were: firstly, N is2Performing cyclic voltammetry scanning in 0.1M KOH solution under atmosphere at a scanning speed of 100mV · s-1The scanning range is 0-1.2V, the number of scanning turns is 10, and the step is used for cleaning the surface of the catalyst and playing a certain activating role.
Then at O2The polarization curve is tested in 0.1M KOH solution under the atmosphere to represent the oxygen reduction reaction of the catalyst, and simultaneously, a voltage of 1.2V is applied to a ring electrode so as to oxidize hydrogen peroxide on the ring at a scanning speed of 10 mV.s-1The scanning range is 0.2-1.2V.
The reference of the selection of the scanning range is the standard hydrogen electrode.
As is typically shown in fig. 1-3.
Fig. 1 to 3 are an oxygen reduction activity diagram, an electron transfer number, and a hydrogen peroxide selectivity spectrum obtained by an electrochemical performance test and a ring electrode test of the catalyst provided in example 1 and example 2, respectively. It can be seen from the figure that the catalytic activity of the catalyst synthesized by the invention has a certain relation with temperature, and the catalyst shows the most excellent catalytic performance when the pyrolysis temperature reaches 800 ℃.
The test results for the other samples in example 2 were similar to those described above.
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.

Claims (6)

1. Use of a nitrogen atom doped carbon material as an electrochemical oxygen reduction catalyst, wherein the electrochemical oxygen reduction catalyst comprises a nitrogen atom doped carbon material;
the preparation method of the nitrogen atom doped carbon material comprises the following steps:
pyrolyzing a raw material containing a carbon source and a nitrogen source at 800 ℃ to obtain the nitrogen atom doped carbon material;
the pyrolysis time is 2-4 hours;
the raw material is six-membered cucurbituril.
2. Use according to claim 1, characterized in that the pyrolysis time is 3 hours.
3. Use according to claim 1, wherein the rate of heating to pyrolysis temperature is 3-8 ℃/min.
4. Use according to claim 1, wherein the ramp rate for ramping up to pyrolysis temperature is 5 ℃/min.
5. Use according to claim 1, characterized in that the pyrolysis is carried out under an inert atmosphere.
6. Use according to claim 5, wherein the non-reactive atmosphere comprises at least one of nitrogen, an inert gas.
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