CN115385326A - Preparation method of nickel and nitrogen co-doped gamma-graphite monoalkyne carbon material - Google Patents
Preparation method of nickel and nitrogen co-doped gamma-graphite monoalkyne carbon material Download PDFInfo
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- 239000010439 graphite Substances 0.000 title claims abstract description 55
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 23
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 23
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- 238000002360 preparation method Methods 0.000 title claims abstract description 9
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- CLZWAWBPWVRRGI-UHFFFAOYSA-N tert-butyl 2-[2-[2-[2-[bis[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]amino]-5-bromophenoxy]ethoxy]-4-methyl-n-[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]anilino]acetate Chemical compound CC1=CC=C(N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)C(OCCOC=2C(=CC=C(Br)C=2)N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)=C1 CLZWAWBPWVRRGI-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
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- 238000003756 stirring Methods 0.000 claims description 3
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- 239000011425 bamboo Substances 0.000 abstract description 3
- 238000002474 experimental method Methods 0.000 abstract description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 abstract description 3
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- 239000001301 oxygen Substances 0.000 description 14
- 229910052760 oxygen Inorganic materials 0.000 description 14
- 239000000446 fuel Substances 0.000 description 8
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- 238000003917 TEM image Methods 0.000 description 6
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- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 238000002484 cyclic voltammetry Methods 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
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- 238000012360 testing method Methods 0.000 description 4
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
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- 229910021387 carbon allotrope Inorganic materials 0.000 description 2
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
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- 239000010411 electrocatalyst Substances 0.000 description 2
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- 239000004215 Carbon black (E152) Substances 0.000 description 1
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- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
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- 238000009826 distribution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
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- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
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- 229910052726 zirconium Inorganic materials 0.000 description 1
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
-
- 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
-
- 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
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Abstract
The invention discloses a novel bamboo joint-shaped carbon material of nickel and nitrogen co-doped graphite monoalkyne, which is prepared by taking gamma-graphite monoalkyne as a precursor, melamine as a nitrogen source and nickel sulfate hexahydrate as a nickel source and utilizing a high-temperature reduction technology. The composite catalyst prepared by the method has a unique bamboo joint structure, and the doped N atoms can improve the conductivity of the gamma-type graphite monoalkyne and improve the dynamic performance of the gamma-type graphite monoalkyne in catalysis; the nickel metal is uniformly loaded on the surface of the graphite alkyne, so that the electron diffusion rate is increased; the stability and durability of the material can be greatly improved. The method has simple technology and easy experiment operation, and greatly reduces the preparation cost and difficulty. The prepared product is used for electrocatalytic reduction of O 2 The catalyst material has application prospect in the field.
Description
Technical Field
The invention belongs to the technical field of carbon materials, and particularly relates to a preparation method of a nickel and nitrogen co-doped gamma-type graphite single alkyne carbon material.
Background
In recent years, fuel cells that generate electricity with high efficiency using clean renewable fuels (hydrogen, methanol) have been receiving increasing attention due to the increasing global environmental problems caused by burning fossil fuels. The fuel cell is an electrochemical power generation device without passing through a Carlo cycle, converts chemical energy into electric energy directly in an isothermal electrochemical mode without passing through a heat engine process, and has the advantages of high energy conversion efficiency, no noise and low pollution. Among many factors, the oxygen reduction reaction at the cathode is a fundamental problem. It is well known that the slow kinetics of the oxygen reduction reaction at the cathode have been limiting to the overall performance of the fuel cell and have been a major obstacle to the commercial use of fuel cells. The development of an economical and efficient electrocatalyst is the key to the problem.
The novel carbon allotrope is divided into graphite single alkyne, graphite double alkyne and the like according to the number of alkyne bonds among six-membered carbocyclic rings, has an orderly-distributed pore channel structure, riches adjustable electronic structures and unique semiconductor transport properties, and has important application prospects in the field of energy storage and conversion. However, experiments and theoretical researches on the synthesis of gamma-type graphite monoalkyne by a mechanochemical method show that the oxygen permeation energy barrier is large in the electrocatalytic oxygen reduction process, and the method is not suitable for application in the field of oxygen reduction catalysis.
Due to the existence of sp hybridized carbon atoms, compared with other carbon allotropes such as carbon nano tubes and graphene, the graphdiyne has completely different structures and performances, and previous researches prove that hetero atoms are introduced into the carbon material, so that the charge distribution can be further regulated and controlled, and the doping position can be used as an active site of a reduction reaction, so that the performances of the carbon material in the electrocatalytic reduction reaction, such as the oxygen reduction reaction in a fuel cell and the carbon dioxide reduction reaction in the synthesis of carbon-based fuel, are improved. Nitrogen-doped carbon materials (including activated carbon, carbon nanotubes and graphene) have received a great deal of attention as metal-free electrocatalysts for oxygen reduction reactions. They show a surprising catalytic activity in electrocatalytic oxygen reduction reactions, which is significantly improved over the corresponding non-nitrogen doped carbon material, approaching or even exceeding that of commercial platinum/carbon (Pt/C). Professor Dai Liming, university of Dayton, USA, reports a nitrogen-doped carbon nanotube array as a high-efficiency oxygen reduction catalyst (Science, 2009, 323, 760-763). Professor Dai Hongjie at the university of standard ford in the united states reports nitrogen-doped graphene loaded with cobaltosic oxide as a high-activity oxygen reduction catalyst (Nature Material,2011, 10, 780-786). However, the prior art has not reported about the preparation of the oxygen reduction catalyst material based on nickel and nitrogen co-doped graphite monoalkyne.
Because acetylene bonds are arranged among benzene rings in a graphite alkyne network, the graphite alkyne has an aperture advantage in a network frame, which obviously helps the graphite alkyne to absorb oxygen in air, and a nitrogen-rich carbon material has good catalytic capability on oxygen reducibility. Compared with the existing iron and nitrogen co-doped graphite diyne material, the composite catalyst prepared by the method has a unique bamboo joint shape in structure, and the stability and durability of the material can be greatly improved; and the technology is simple, the experiment is easy to operate, and the preparation cost and difficulty are greatly reduced.
Disclosure of Invention
The invention mainly aims at the problem that gamma-type graphite monoalkyne is not suitable for catalyzing fuel cells, and provides a synthesis method of nickel and nitrogen co-doped graphite monoalkyne, which is simple in process, low in raw material cost, easy to obtain and low in equipment requirement.
The technical scheme of the invention is as follows: the preparation method and the application of the nickel and nitrogen codoped gamma graphite monoalkyne are characterized by comprising the following specific preparation steps:
(1) Adding calcium carbide and hexahalobenzene into a ball milling tank, and preparing gamma-type graphite monoalkyne by using a ball milling method;
(2) Dispersing graphite monoene and melamine in absolute ethyl alcohol, and carrying out ultrasonic treatment to obtain a suspension;
(3) Adding nickel sulfate hexahydrate into the suspension, and stirring under Ar condition;
(4) Vacuum drying the solution;
(5) And (3) adopting a high-temperature reduction technology, and putting the gamma-type graphite single alkyne sample prepared in the step (4) into a vacuum tube furnace device for high-temperature treatment in a vacuum state.
And after the reaction is finished, carrying out structural characterization and electrochemical performance test on the sample.
In the invention, hexabromobenzene is selected as the hexahalobenzene.
In the invention, the graphite alkyne sample is gamma-type graphite monoalkyne prepared by a ball milling method, ball milling beads adopt zirconium beads with the small size of 2-5mm, the ball milling time is 12-18h, and the ball milling rotating speed is 600-800rpm.
In the invention, ultrasonic treatment is carried out for 30min.
In the present invention, the reaction was stirred under Ar for 24h.
In the invention, the vacuum drying time of the solution is 12h.
In the invention, the high-temperature treatment temperature is 900 ℃ and the time is 1h.
According to the invention, the high-temperature reduction technology is utilized to prepare the nickel-nitrogen co-doped gamma-type graphite mono-alkyne, the structure of the composite material can be regulated and controlled by adjusting the mass ratio of the nickel source to the carbon source and the high-temperature treatment time, the nickel-nitrogen co-doping of the gamma-type graphite mono-alkyne is realized, and the nitrogen-doped graphite mono-alkyne coated nickel bamboo-shaped novel carbon material is formed. The synthesized nickel-nitrogen co-doped graphite monoalkyne is used as a novel non-noble metal catalyst, and a small amount of nickel precursor is used for replacing a platinum-based catalyst. The synthesized composite catalyst has good catalytic performance.
Compared with the prior art, the invention has the beneficial effects that: the invention provides a novel method for synthesizing in-situ doped graphite monoalkyne by using calcium carbide and polyhalogenated hydrocarbon as raw materials and utilizing a mechanochemical principle. The method has the advantages of cheap and easily obtained reaction raw materials, mild reaction conditions, simple reaction equipment, simple and convenient reaction process and no need of complex post-treatment. The synthesized nickel and nitrogen co-doped graphite monoalkyne composite material further proves that the co-doping of non-noble metal elements and nitrogen elements changes the structure of the graphite monoalkyne and improves the catalytic performance, and has important and wide application prospects in the fields of energy, catalysis, environmental protection and the like.
The salient features and significant improvements of the present invention can be seen from the following examples, but are not limited thereto.
Drawings
(1) FIG. 1 is a schematic diagram of the structure of gamma-type graphitic monoalkyne;
(2) FIG. 2 is a Transmission Electron Micrograph (TEM) of examples 1-3;
(3) FIG. 3 is a Scanning Electron Micrograph (SEM) of examples 1-3;
(4) FIG. 4 is a full spectrum of X-ray photoelectron spectroscopy of examples 1-3;
(5) Fig. 5 is an electrochemical Cyclic Voltammogram (CV) of untreated gamma-type graphitic monoalkyne;
(6) FIG. 6 is the electrochemical cyclic voltammograms of examples 1-3;
Detailed Description
The following describes in detail a method for preparing a modified graphite monoalkyne material by using a tubular furnace high-temperature reduction treatment device, according to the present invention, with reference to specific examples. It should be understood that the specific examples are intended only to illustrate and describe the present invention and are not intended to limit the scope of the present invention. Any modifications and variations of the present invention can be made without departing from the purpose and scope of the present invention.
In the embodiment, a tube furnace high-temperature treatment device developed by medium-ring technology limited is adopted.
Example 1:
firstly, putting calcium carbide and hexabromobenzene into a ball milling tank, and preparing gamma graphite monoalkyne by adopting a ball milling technology. TEM and SEM representation is carried out on the prepared gamma-type graphite monoalkyne, catalyst ink is prepared, and the initial catalytic activity of the catalyst is tested.
And secondly, dispersing the gamma-type graphite monoalkyne and the melamine prepared by the ball mill in absolute ethyl alcohol, and carrying out ultrasonic treatment for 30min.
In a third step, 5mg of nickel sulfate hexahydrate are added to the suspension and stirred under Ar for 24h.
Fourthly, drying the solution in vacuum for 12 hours.
Fifthly, pretreating the mixture for 30min, heating to 900 ℃ under Ar flow, and keeping for 1h.
And sixthly, co-doping the obtained nickel and nitrogen with the gamma-type graphite single alkyne powder.
The structural schematic diagram of pyridine N-doped gamma-type graphite monoalkyne is shown in FIG. 1. Sp on gamma-type graphite mono-alkyne benzene ring 2 The hybridized carbon atoms are partially substituted by nitrogen atoms to form larger pores at the substitution positions, and sp 2 The molar ratio of hybridized carbon to sp hybridized carbon atoms increases.
The TEM (figure 2) of the nickel and nitrogen co-doped graphite monoalkyne shows that a special bamboo-shaped structure is generated.
Scanning Electron Microscope (SEM) test results (fig. 3) indicate that a large amount of pore structures exist on the surface of the formed nickel and nitrogen co-doped graphite monoalkyne.
X-ray photoelectron spectroscopy C spectrum (FIG. 4) shows the presence of sp between carbon elements in the sample 2 And sp hybridization, demonstrating the built-in alkynyl structure.
Example 2:
firstly, putting calcium carbide and hexabromobenzene into a ball milling tank, and preparing gamma graphite monoalkyne by adopting a ball milling technology. And performing TEM and SEM characterization on the prepared gamma-type graphite monoalkyne, preparing catalyst ink, and testing the initial catalytic activity of the catalyst.
And secondly, dispersing the gamma-type graphite monoalkyne and the melamine prepared by the ball mill in absolute ethyl alcohol, and carrying out ultrasonic treatment for 30min.
In a third step, 6mg of nickel sulfate hexahydrate are added to the suspension and stirred under Ar for 24h.
Fourthly, drying the solution in vacuum for 12 hours.
Fifthly, pretreating the mixture for 30min, heating to 900 ℃ under Ar flow, and keeping for 1h.
And sixthly, co-doping the obtained nickel and nitrogen with the gamma-type graphite single alkyne powder.
The Scanning Electron Microscope (SEM) test results (fig. 3) show that the formed nickel and nitrogen co-doped graphite monoalkyne surface has a large amount of pore structures, which are consistent with the samples obtained in example 1.
Example 3:
firstly, putting calcium carbide and hexabromobenzene into a ball milling tank, and preparing gamma graphite monoalkyne by adopting a ball milling technology. And (3) performing TEM spectrum and SEM characterization on the prepared gamma-type graphite monoalkyne, preparing catalyst ink, and testing the initial catalytic activity of the catalyst.
And secondly, dispersing the gamma-type graphite monoalkyne and the melamine prepared by the ball mill in absolute ethyl alcohol, and carrying out ultrasonic treatment for 30min.
In the third step, 7mg of nickel sulfate hexahydrate was added to the suspension and stirred under Ar for 24h.
Fourthly, drying the solution in vacuum for 12 hours.
Fifthly, pretreating the mixture for 30min, heating to 900 ℃ under Ar flow, and keeping for 1h.
And sixthly, co-doping the obtained nickel and nitrogen with the gamma-type graphite single alkyne powder.
Dispersing the obtained nickel and nitrogen co-doped gamma-type graphite mono-alkyne powder in an ethanol solution of Nafion, ultrasonically preparing uniformly dispersed catalyst ink, dripping the uniformly dispersed catalyst ink on a clean glassy carbon electrode, naturally airing, carrying out an electrochemical performance test, and carrying out doping treatment to obtain the CV peak position of 412 (figure 5) to 717mV (figure 6). The result shows that the nickel and nitrogen doped gamma-type graphite monoalkyne can obviously improve the structural characteristics and reduce the oxygen permeability barrier, and the nitrogen atoms have strong electronegativity and an electron-withdrawing effect, so that adjacent carbon atoms are positively charged and are easy to attract electrons, and the catalytic reaction is promoted to be carried out.
Claims (5)
1. A preparation method of a nickel and nitrogen co-doped gamma-graphite single alkyne carbon material comprises the following steps:
(1) Adding calcium carbide and hexabromobenzene into a ball milling tank, and preparing gamma-type graphite monoalkyne by using a ball milling method;
(2) Dissolving a mixed sample of gamma graphite monoacyne, melamine and nickel sulfate hexahydrate in absolute ethyl alcohol, and stirring for 24 hours at room temperature for full mixing;
(3) Drying the mixed sample;
(4) Putting the sample into a tubular furnace device by adopting a high-temperature reduction technology; the system is in a vacuum state; the obtained sample is the nickel and nitrogen co-doped graphite monoalkyne.
2. The method of claim 1, wherein: the modified graphite alkyne is gamma type graphite monoalkyne prepared by a ball milling method.
3. The method of claim 1, wherein: the stirring system is in a vacuum state.
4. The production method according to claim 1, characterized in that: the drying device is an oven, and the parameters are 60 ℃ and 24h.
5. The production method according to claim 1, characterized in that: ar is introduced in the reaction, the temperature is 900 ℃, the treatment time is 1h, and the gas flow rate is 5sccm.
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| CN115124026A (en) * | 2022-06-28 | 2022-09-30 | 天津工业大学 | Bamboo-like gamma-type graphite monoalkyne material and preparation method thereof |
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| CN109626368A (en) * | 2019-01-10 | 2019-04-16 | 复旦大学 | A kind of N doped gamma type graphite list alkynes carbon material and its preparation method and application |
| CN111384409A (en) * | 2020-02-25 | 2020-07-07 | 南京师范大学 | Nitrogen-doped graphite alkyne-riveted transition metal monoatomic catalyst and preparation method and application thereof |
| CN115133045A (en) * | 2022-06-28 | 2022-09-30 | 天津工业大学 | Preparation method of iron and nitrogen co-doped gamma-graphite single alkyne carbon material |
| CN115124026A (en) * | 2022-06-28 | 2022-09-30 | 天津工业大学 | Bamboo-like gamma-type graphite monoalkyne material and preparation method thereof |
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