CN115133045A - Preparation method of iron and nitrogen co-doped gamma-graphite single alkyne carbon material - Google Patents
Preparation method of iron and nitrogen co-doped gamma-graphite single alkyne carbon material Download PDFInfo
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 64
- 239000010439 graphite Substances 0.000 title claims abstract description 64
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 32
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 239000003575 carbonaceous material Substances 0.000 title abstract description 9
- 150000001345 alkine derivatives Chemical class 0.000 title description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 66
- 238000000034 method Methods 0.000 claims abstract description 25
- 230000009467 reduction Effects 0.000 claims abstract description 14
- 238000005516 engineering process Methods 0.000 claims abstract description 12
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 7
- 229940044631 ferric chloride hexahydrate Drugs 0.000 claims abstract description 7
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims abstract description 7
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000002243 precursor Substances 0.000 claims abstract description 4
- -1 graphite alkyne Chemical class 0.000 claims abstract 2
- 238000000498 ball milling Methods 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000005997 Calcium carbide Substances 0.000 claims description 5
- CAYGQBVSOZLICD-UHFFFAOYSA-N hexabromobenzene Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1Br CAYGQBVSOZLICD-UHFFFAOYSA-N 0.000 claims description 5
- 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 5
- 230000004048 modification Effects 0.000 claims description 2
- 238000012986 modification Methods 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims 2
- 239000003054 catalyst Substances 0.000 abstract description 19
- 239000000463 material Substances 0.000 abstract description 11
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- 239000002131 composite material Substances 0.000 abstract description 4
- 238000002474 experimental method Methods 0.000 abstract description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 abstract description 4
- 235000017166 Bambusa arundinacea Nutrition 0.000 abstract description 3
- 235000017491 Bambusa tulda Nutrition 0.000 abstract description 3
- 241001330002 Bambuseae Species 0.000 abstract description 3
- 235000015334 Phyllostachys viridis Nutrition 0.000 abstract description 3
- 239000011425 bamboo Substances 0.000 abstract description 3
- 238000009792 diffusion process Methods 0.000 abstract 1
- 238000006722 reduction reaction Methods 0.000 description 15
- 239000000446 fuel Substances 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 230000003197 catalytic effect Effects 0.000 description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
- 238000001878 scanning electron micrograph Methods 0.000 description 7
- 238000001237 Raman spectrum Methods 0.000 description 6
- 229910052697 platinum Inorganic materials 0.000 description 5
- 239000000725 suspension Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000009210 therapy by ultrasound Methods 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 239000012692 Fe precursor Substances 0.000 description 1
- 208000021251 Methanol poisoning Diseases 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- YYXHRUSBEPGBCD-UHFFFAOYSA-N azanylidyneiron Chemical compound [N].[Fe] YYXHRUSBEPGBCD-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000002837 carbocyclic group Chemical group 0.000 description 1
- 229910021387 carbon allotrope Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 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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- 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
- H01M4/88—Processes of manufacture
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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
- H01M4/90—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
- H01M4/9041—Metals or alloys
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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
- H01M4/90—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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- 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 bamboo-like novel carbon material with iron and nitrogen codoped graphite monoalkyne, which is prepared by taking gamma-graphite monoalkyne as a precursor, melamine as a nitrogen source and ferric chloride hexahydrate as an iron 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; iron metal is uniformly distributed in 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 an iron and nitrogen co-doped gamma graphite single alkyne carbon material.
Background
Fuel cells have been a hot spot in the field of energy research because of their superior performance and no environmental pollution. The fuel cell has the following characteristics: the energy conversion efficiency is high; it directly converts the chemical energy of fuel into electric energy, and does not pass through the combustion process, so that it is not limited by Carnot cycle. The fuel-electric energy conversion efficiency of the fuel cell system is 45-60%, and the efficiency of thermal power generation and nuclear power generation is about 30-40%. However, since it employs noble metal platinum nanoparticles as an electrode catalytic material, the development of fuel cells is greatly restricted. At present, the method is only applied to high-tech fields such as aerospace and aviation. The cost of platinum materials in fuel cells accounts for about 40% of the overall fuel cell cost. Platinum catalysts are used primarily in fuel cells for catalyzing the electrochemical reduction of oxygen at the cell cathode. Moreover, the platinum catalyst has another major disadvantage of poor resistance to methanol poisoning, thereby greatly reducing the use efficiency of the battery. Therefore, the development of cheap oxygen reduction catalytic materials with high oxygen reduction catalytic activity, methanol interference resistance and high stability is a hot problem of research in various countries;
in 2010, Leyuliang researchers and the like in the chemical institute of Chinese academy of sciences use hexaalkynyl benzene as a precursor to generate a coupling reaction under the catalytic action of a copper sheet, and successfully synthesize a large-area graphite diyne film on the surface of the copper sheet by a chemical method. However, the prior art has not reported about the preparation of the oxygen reduction catalyst material based on iron and nitrogen co-doped graphite monoalkyne;
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 prospect 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. Previous researches prove that the introduction of an N source and an Fe source into the carbon material can further regulate and control charge distribution, and the doping position can be used as an active site of a reduction reaction, so that the performance 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 carbon-based fuel synthesis, is improved.
The invention discloses a novel method for synthesizing iron and nitrogen co-doped gamma-type graphite monoalkyne by using gamma-graphite monoalkyne as a precursor, melamine as a nitrogen source and ferric chloride hexahydrate as an iron source through a high-temperature reduction technology. 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 fuel cell catalysis, and provides a synthetic method of iron and nitrogen co-doped graphite monoalkyne, which has the advantages of simple process, cheap and easily-obtained raw materials and low equipment requirement.
The technical scheme of the invention is as follows: the preparation method and the application of the iron 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 monoalkyne and melamine in ethanol, and performing ultrasonic treatment to obtain a suspension;
(3) adding ferric chloride 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 graphdiyne sample is gamma-type graphdiyne prepared by a ball milling method, ball milling beads adopt zirconium beads with small size of 2-5mm, the ball milling time is 12-18h, and the ball milling rotating speed is 600-800 rpm.
In the invention, ultrasonic treatment is carried out for 30 min.
In the present invention, the reaction was stirred under Ar for 24 h.
In the invention, the vacuum drying time of the solution is 12 h.
In the invention, the high-temperature treatment temperature is 900 ℃ and the time is 1 h.
According to the invention, the high-temperature reduction technology is utilized to prepare the iron and nitrogen codoped gamma-type graphite monoalkyne, the structure of the reaction of iron and nitrogen elements and the gamma-type graphite monoalkyne can be regulated and controlled by regulating the amount of an iron source and a nitrogen source and the high-temperature treatment time, so that the iron and nitrogen codoped gamma-type graphite monoalkyne is realized, and the novel bamboo-shaped carbon material with iron and nitrogen coated by the graphite monoalkyne is formed. The synthesized iron-nitrogen co-doped graphite monoalkyne is used as a novel non-noble metal catalyst, and a small amount of iron 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:
(1) the method is different from ball milling doping and a common hydrothermal doping method in that after reaction, post-treatment such as washing is not needed, impurities are not introduced, and the doping process is simple and efficient;
(2) the difference between the invention and other single-atom doped carbon materials (graphene, carbon nano tubes and the like) is that sp hybridized nitrogen atoms are doped at acetyl sites, and the excellent catalytic effect is shown.
(3) Compared with the monoatomic doped graphite monoalkyne, the catalyst disclosed by the invention has the difference that the iron and nitrogen codoping increases a proper amount of surface defect positions on the surface of the graphite monoalkyne, so that the improvement of the catalytic performance can be promoted;
(4) the iron and nitrogen co-doped gamma-type graphite monoalkyne prepared by the method can realize iron and nitrogen doping with different concentrations through adjusting the high-temperature reduction doping time, and can realize continuous regulation and control of the electronic structure of the gamma-type graphite monoalkyne;
(5) the method for preparing the iron and nitrogen doped gamma-type graphite monoalkyne adopts a high-temperature reduction method, requires simple equipment, is suitable for the existing industrial production, and has low cost and easy control of the preparation process. The preparation method can realize large-scale doping of the gamma-type graphite monoacyne and batch surface doping treatment of the gamma-type graphite monoacyne.
(6) Compared with the existing iron and nitrogen co-doped graphite diyne material, the composite catalyst prepared by the method has a unique bamboo joint-shaped structure, and can greatly improve the stability and durability of the material; and the technology is simple, the experiment is easy to operate, and the preparation cost and difficulty are greatly reduced.
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 structural diagram of N-doped gamma-type graphitic monoalkyne;
(2) FIG. 2 is a Raman spectrum (Raman) of examples 1-3;
(3) FIG. 3 is a Scanning Electron Micrograph (SEM) of examples 1-3;
(4) FIG. 4 is an X-ray photoelectron spectrum C spectrum of examples 1-3;
(5) FIG. 5 is an electrochemical Cyclic Voltammogram (CV) for untreated gamma graphite monoalkyne and examples 1-3;
(6) fig. 6 is an electrochemical Linear Sweep Voltammogram (LSV) of untreated gamma graphite monoalkyne and example 13;
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 included merely for purposes of explanation and description and are not intended to limit the scope of the invention. Any modification and variation of the present invention can be made without departing from the object 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. And performing Raman 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 gamma-type graphite monoalkyne and melamine prepared by a ball mill in ethanol. And (4) carrying out ultrasonic treatment for 30 min.
In a third step, 5mg of ferric chloride hexahydrate was added to the suspension and stirred under Ar for 24 h.
Fourthly, drying the solution in vacuum.
Fifthly, pretreating the mixture for 30min, heating to 900 ℃ under Ar flow, and keeping for 1 h.
And sixthly, co-doping the obtained iron and nitrogen with the gamma-type graphite monoalkyne 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 is increased over the 1: 1 ratio of gamma type graphitic monoalkyne. FIG. 2 is a Raman spectrum of a sample, which can detect sp in the sample 2 Carbon element present in both hybridized and sp hybridized states.
Scanning Electron Microscope (SEM) test results (fig. 3) indicate that a large amount of pore structures exist on the surface of the formed iron and nitrogen co-doped graphite monoalkyne.
Raman spectrum (figure 2) of the iron and nitrogen codoped graphite monoalkyne shows that three absorption peaks are 1336cm -1 、1586cm -1 、2078cm -1 。1336cm -1 The peak of (a) is the D peak, corresponding to defects and edges; 1586cm -1 The peak of (a) is a G peak, indicating that the sample has abundant aromatic ring structures; 2078cm -1 The weaker peak is due to stretching vibrations of the conjugated diyne.
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 alkynyl structure contained therein.
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 Raman 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 gamma-type graphite monoalkyne and melamine prepared by a ball mill in ethanol. And (4) carrying out ultrasonic treatment for 30 min.
In the third step, 6mg of ferric chloride hexahydrate was added to the suspension and stirred under Ar for 24 h.
Fourthly, drying the solution in vacuum.
Fifthly, pretreating the mixture for 30min, heating to 900 ℃ under Ar flow, and keeping for 1 h.
And sixthly, co-doping the obtained iron and nitrogen with the gamma-type graphite single alkyne powder.
The Scanning Electron Microscope (SEM) test results (fig. 3) show that a large amount of pore structures exist on the surface of the formed iron and nitrogen co-doped graphite monoalkyne, which is consistent with the sample obtained in example 1.
Example 3
Firstly, putting calcium carbide and hexabromobenzene into a ball milling tank, and preparing gamma-type graphite monoalkyne by adopting a ball milling technology. And performing Raman 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 gamma-type graphite monoalkyne and melamine prepared by a ball mill in ethanol. And (4) carrying out ultrasonic treatment for 30 min.
In a third step, 7mg of ferric chloride hexahydrate was added to the suspension and stirred under Ar for 24 h.
Fourthly, drying the solution in vacuum.
Fifthly, pretreating the mixture for 30min, heating to 900 ℃ under Ar flow, and keeping for 1 h.
And sixthly, co-doping the obtained iron and nitrogen with the gamma-type graphite monoalkyne powder.
Dispersing the obtained iron and nitrogen co-doped gamma-type graphite monoalkyne 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, carrying out doping treatment, and then obtaining the product with CV peak positions from 573 (figure 5a) to 719mV (figure 5b) and starting LSVThe initial potential is from 699 (FIG. 6a) to 787mV (FIG. 6b), and the limiting current density is from 3.21 (FIG. 6a) to 4.09mA/cm 2 (FIG. 6 b). The results show that the structural characteristics of the iron and nitrogen doped gamma graphite monoalkyne can be obviously improved, the oxygen permeability barrier is reduced, 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 (4)
1. In order to apply the graphite monoalkyne to the field of electrocatalysis and carry out modification treatment on gamma-type graphite monoalkyne, the technical scheme is as follows: a method for co-doping graphite monoalkyne with iron and nitrogen 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) adopting a high-temperature reduction technology; putting a mixed sample of gamma graphite monoalkyne, melamine and ferric chloride hexahydrate prepared by ball milling into a tubular furnace device; the system is in a vacuum state; and introducing Ar gas in the reaction process, wherein the temperature is 900 ℃, the treatment time is 1h, and the obtained sample is the iron 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: ar is introduced in the reaction, the temperature is 900 ℃, the treatment time is 1h, and the gas flow rate is 5 sccm.
4. The method of claim 1, wherein: and adjusting the content of precursor iron and graphite monoalkyne according to the required requirements to obtain the required sample.
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| CN115385326A (en) * | 2022-10-11 | 2022-11-25 | 天津工业大学 | Preparation method of nickel and nitrogen co-doped gamma-graphite monoalkyne carbon material |
| CN115434141A (en) * | 2022-10-11 | 2022-12-06 | 天津工业大学 | Preparation method of gamma-graphite mono-alkyne modified fiber fabric |
| CN115448286A (en) * | 2022-10-11 | 2022-12-09 | 天津工业大学 | Preparation method of cobalt and nitrogen co-doped gamma-graphite single alkyne carbon material |
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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 |
| CN113104838A (en) * | 2021-04-30 | 2021-07-13 | 天津工业大学 | Preparation method of plasma fluorine-doped modified gamma-type graphite single alkyne carbon material |
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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 |
| CN113104838A (en) * | 2021-04-30 | 2021-07-13 | 天津工业大学 | Preparation method of plasma fluorine-doped modified gamma-type graphite single alkyne carbon material |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115385326A (en) * | 2022-10-11 | 2022-11-25 | 天津工业大学 | Preparation method of nickel and nitrogen co-doped gamma-graphite monoalkyne carbon material |
| CN115434141A (en) * | 2022-10-11 | 2022-12-06 | 天津工业大学 | Preparation method of gamma-graphite mono-alkyne modified fiber fabric |
| CN115448286A (en) * | 2022-10-11 | 2022-12-09 | 天津工业大学 | Preparation method of cobalt and nitrogen co-doped gamma-graphite single alkyne carbon material |
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