CN108455591A - A kind of preparation method of hydrogen substitution graphite list alkynes - Google Patents
A kind of preparation method of hydrogen substitution graphite list alkynes Download PDFInfo
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- CN108455591A CN108455591A CN201810167524.8A CN201810167524A CN108455591A CN 108455591 A CN108455591 A CN 108455591A CN 201810167524 A CN201810167524 A CN 201810167524A CN 108455591 A CN108455591 A CN 108455591A
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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
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- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention belongs to field of material technology, specially a kind of preparation method of hydrogen substitution graphite list alkynes.The present invention is using trihalogenated benzene and calcium carbide as raw material, and by the mechanical ball mill of planetary ball mill, synthesis hydrogen replaces graphite list alkynes.The method of the present invention raw material is easy to get, technical maturity, process are simple, and device requirement is low；Experiment shows that hydrogen substitution graphite list alkynes material prepared by the present invention is a kind of p-type semiconductor of 2.30 eV of band gap, can be applied to photoelectrocatalysimaterial material；It produces oxygen performance with good electro-catalysis, and the initial overpotential of analysis oxygen in neutral solution is only 0.04 V, can be applied to electro-catalysis production oxygen material.
Description
Technical field
The invention belongs to field of material technology, and in particular to a kind of preparation side of carbon-rich material-hydrogen substitution graphite list alkynes
Method.
Background technology
Graphite alkene material is after graphene, another is known as the new carbon of super material, because its is unique
Two dimensional surface reticular structure and excellent electrical properties, and gather around and have wide practical use in fields such as the energy, electronics, catalysis.
Hydrogen replaces graphite list alkynes to be a kind of novel carbon-rich material proposed on the basis of graphite alkene, byspThe alkynyl of hydridization will be between phenyl ring
Position connection, formation by hydrogen on phenyl ring, phenyl ringsp 2 On hydbridized carbon atoms and alkynylspThe two dimensional surface that hydbridized carbon atoms are constituted
Web materials.Compared to graphite list alkynes, contained mesh bigger, is conducive to the migration of lewis' acid, in lithium-ion electric in structure
There is application potential in pond high current charge-discharge, electrocatalytic reaction.Deng's Welltech seminar of Dalian Chemical Physics Research Institute is in 2012
Year, with 1,3,5- tribromo-benzene and 1,3,5- tri- alkynyl benzene are raw material, by cross-coupling polymerisation, a variety of organic molten
Hydrogen substitution graphite list alkynes is successfully synthesized in agent.Shanghai University Of Electric Power Lee and Xing seminars were forerunner with three alkynyl benzene in 2017
Body, three (tert-butoxies) (2,2- dimethyl propylidyne) tungsten (VI) are that catalyst passes through alkynyl exchange reaction in argon gas atmosphere
The hydrogen substitution graphite list alkynes of 0.37 nm of interlamellar spacing is obtained, and it is 2.45 eV's of band gap to demonstrate gained samplenType semiconductor.
The present invention proposes one kind using trihalogenated benzene and calcium carbide as raw material, passes through the mechanical ball mill of planetary ball mill, synthesis
Hydrogen replaces the new method of graphite list alkynes, synthetic route schematic diagram as shown in Figure 1.In the present invention, trihalogenated benzene and calcium carbide are
Realize the raw material of commercialization；Mechanochemical reaction is being scientific research and the maturation process in industry.The present invention is to realizing that hydrogen replaces stone
The high yield of black list alkynes, inexpensively prepare it is meaningful.
Invention content
The purpose of the present invention is to provide a kind of raw materials to be easy to get, technical maturity, process are simple, the low hydrogen substitution of device requirement
Graphite list alkynes preparation method, and replace graphite list alkynes to be applied in electro-catalysis the hydrogen being prepared.
The preparation method of hydrogen substitution graphite list alkynes provided by the invention, the specific steps are：
（1）By trihalogenated benzene（C6H3X3）, calcium carbide（CaC2）It is placed in vacuum sphere ink tank with ball milling pearl；Ball grinder is sealed, to ball milling
Tank vacuumizes or is passed through inert gas；
（2）By planetary ball mill with 400 ~ 600 revs/min of rate ball milling 6 ~ 24 hours；
（3）After the completion of ball milling, sample is taken out, is washed with dust technology or acetic acid, removes unreacted calcium carbide；
（4）To step（3）Obtained sample removes unreacted trihalogenated benzene, obtains hydrogen substitution graphite list alkynes powder.
The method of removal unreacted trihalogenated benzene is, with hot benzene washing sample, to replace stone with 40 ~ 90 DEG C of drying to get to hydrogen
Black list alkynes powder.Or sample is placed in tube furnace, it in an inert atmosphere, is annealed with 300 ~ 600 DEG C, obtains hydrogen substitution graphite
Single alkynes powder.
In the present invention, trihalogenated benzene can be trichloro-benzenes, three triiodo-benzenes.
In the present invention, the control of ball material mass ratio is 25:1~75:1.
In the present invention, the molar ratio control of trihalogenated benzene and calcium carbide is 1:3~1:24.
In the present invention, liquid buffer can not be added.
In the present invention, the inert atmosphere is nitrogen or argon gas.
Experiment shows that hydrogen substitution graphite list alkynes material prepared by the present invention is served as reasonsspHydridization carbon,sp 2 Hydridization carbon and hydrogen composition
Two-dimensional material, structure is consistent with theory expectation.
Experiment shows that hydrogen substitution graphite list alkynes material prepared by the present invention is a kind of p-type semiconductor of 2.30 eV of band gap,
It can be applied to photoelectrocatalysimaterial material.
Experiment shows that there is hydrogen substitution graphite list alkynes material prepared by the present invention good electro-catalysis to produce oxygen performance,
The initial overpotential of analysis oxygen in neutral solution is only 0.04 V, can be applied to electro-catalysis production oxygen material.
Hydrogen replaces graphite list alkynes to be a kind of planar Web materials newly proposed on the basis of graphite list alkynes, in high current
Possess advantage in the electrochemical reaction of density, possesses widely in energy fields such as electro-catalysis, lithium ion battery, sodium-ion batteries
Application prospect.Currently, the preparation method of hydrogen substitution graphite list alkynes needs under the auxiliary of catalyst, group is carried out in organic solvent
It exchanges, the reaction time is long, reaction condition needs are stringent controls.Therefore, by mechanochemical reaction it is this have a large capacity and a wide range, technology maturation
Preparation method prepare hydrogen substitution graphite list alkynes production with application two aspect have good foreground.
Compared with prior art, the present invention has following outstanding feature：
（1）The present invention relates to preparation methods compared with prior art, and raw material is cheap and easy to get；
（2）The present invention relates to preparation methods compared with prior art, simplifies technological process；
（3）The present invention relates to preparation methods compared with prior art, and required support technology is ripe.
Present invention substantive distinguishing features outstanding and marked improvement can be emerged from from following embodiment, but are not limited to
This.
Description of the drawings
Fig. 1 is the preparation process schematic diagram that mechanochemical reaction synthesizes that hydrogen replaces graphite alkene.
Fig. 2 is the Raman spectrum that mechanochemical reaction synthesizes that hydrogen replaces graphite alkene.Wherein, a：Embodiment 1, b：Embodiment 2, c：
Embodiment 3.
Fig. 3 is the nuclear magnetic resonance spectroscopy of the hydrogen substitution graphite alkene in embodiment 1.
Fig. 4 is the transmission electron microscopy picture of the hydrogen substitution graphite alkene in embodiment 1.
Fig. 5 is the open circuit voltage curve of the hydrogen substitution graphite alkene in embodiment 1.
Fig. 6 is the UV-vis DRS absorption spectrum of the hydrogen substitution graphite alkene in embodiment 1.
Fig. 7 is the linear sweep voltammetry curve of the hydrogen substitution graphite alkene in embodiment 1.
Fig. 8 is the X-ray diffraction spectrum that mechanochemical reaction synthesizes that hydrogen replaces graphite alkene.Wherein, a：Embodiment 1, b：Embodiment
2, c：Embodiment 3.
Specific implementation mode
The specific implementation of the present invention is described further below in conjunction with example and attached drawing, but the implementation and protection of the present invention
It is without being limited thereto.
Embodiment 1
With 1:20 ball material mass ratio, according to 1:9 molar ratio weighs tribromo-benzene and calcium carbide, is placed in vacuum sphere ink tank.It is close
Blocking grinding jar, vacuumizes ball grinder.Pass through planetary ball mill ball milling 12 hours with 600 revs/min of rate.Take out ball milling
The sample of completion washs removal calcium bromide and unreacted calcium carbide using dust technology, and removal unreacted three is washed using hot benzene
Bromobenzene obtains hydrogen substitution graphite alkene powder after dry.
The Raman spectrum of sample such as Fig. 2（a）It is shown, 1576 centimetres-1'sGPeak and 1341 centimetres-1'sDPeak is on phenyl ringsp 2 The characteristic peak of hydbridized carbon atoms, 1981,2096 and 2241 centimetres-1The peaks Y bespThe characteristic peak of hydbridized carbon atoms, illustrates sample
Carbon in product there is onlysp 2 Hydridization andspHydridization two states.Nuclear magnetic resonance spectroscopy（Fig. 3）Illustrate, there is only one kind in sample
The hydrogen of chemical environment, and without connection hydrogen on the adjacent carbon atom of the connected carbon atom of the hydrogen.The Raman spectrum and nuclear-magnetism of sample are total
It is consistent with the hydrogen substitution structural formula of graphite list alkynes that the hydrogen that shakes composes provided information.The transmission electron microscopy picture of sample（Fig. 4）In can be with
See and contain a large amount of lamella in sample, lamella size illustrates that sample is two-dimensional slice material from tens nanometers to hundreds of nanometers.
For the conduction type of study sample, to having carried out open circuit potential test, electrolyte is by Na2SO4（Support electrolysis
Matter, 0.5 mol/L）, absolute methanol（Electronics capturing agent, 3.5 mol/Ls）And disodium ethylene diamine tetraacetate（Hole trapping agents,
0.008 mol/L）；Light source is xenon lamp.As shown in figure 5, the lighting change open circuit potential of sample electrode, illustrates that sample is half
Conductor material.Open circuit potential rises when illumination, and open circuit potential declines when dark-state, withpThe rule of type semiconductor is consistent.Sample
Band gap passes through UV-vis DRS absorption spectromtry.As shown in fig. 6, the band gap of sample is 2.30 electron-volts.
The electrocatalysis characteristic of sample is tested in neutral conditions, electrolyte Na2SO4（0.5 mol/L）Solution.Such as Fig. 7
Shown, the oxygen take-off potential of being analysed in neutral solution of sample electrode is 1.27 V（Relative to reversible hydrogen electrode）, there is only 0.04
The overpotential of V has good application potential in terms of as oxygen-separating catalyst.
Embodiment 2
With 1:50 ball material mass ratio, according to 1:12 molar ratio weighs trichloro-benzenes and calcium carbide, is placed in vacuum sphere ink tank.It is close
Blocking grinding jar is filled with nitrogen to ball grinder.Pass through planetary ball mill ball milling 6 hours with 500 revs/min of rate.Take out ball
The sample completed is ground, removal calcium bromide and unreacted calcium carbide are washed using acetic acid, removal unreacted three is washed using hot benzene
Bromobenzene obtains hydrogen substitution graphite alkene powder after dry.
The Raman spectrum of sample such as Fig. 2（b）It is shown, 1576 centimetres-1'sGPeak and 1341 centimetres-1'sDPeak is on phenyl ringsp 2 The characteristic peak of hydbridized carbon atoms, 1981,2096 and 2241 centimetres-1The peaks Y bespThe characteristic peak of hydbridized carbon atoms, with implementation
1 gained sample of example is consistent.Sample X-ray diffraction spectrum（Fig. 8（b））With 1 sample of embodiment（Fig. 8（a））Also consistent.
Embodiment 3
With 1:75 ball material mass ratio, according to 1:24 molar ratio weighs tribromo-benzene and calcium carbide, is placed in vacuum sphere ink tank.It is close
Blocking grinding jar, vacuumizes ball grinder.Pass through planetary ball mill ball milling 24 hours with 400 revs/min of rate.Take out ball milling
The sample of completion washs removal calcium bromide and unreacted calcium carbide using acetic acid, then sample is placed in tube furnace, in nitrogen
Atmosphere is annealed with 300 DEG C, and hydrogen substitution graphite alkene powder is obtained after cooling.
The Raman spectrum of sample such as Fig. 2（c）It is shown, 1576 centimetres-1'sGPeak and 1341 centimetres-1'sDPeak is on phenyl ringsp 2 The characteristic peak of hydbridized carbon atoms, 1981,2096 and 2241 centimetres-1The peaks Y bespThe characteristic peak of hydbridized carbon atoms, with implementation
1 gained sample of example is consistent.Sample X-ray diffraction spectrum（Fig. 8（c））With 1 sample of embodiment（Fig. 8（a））Also consistent.
Claims (6)
1. a kind of preparation method of hydrogen substitution graphite list alkynes, which is characterized in that the specific steps are：
（1）Trihalogenated benzene, calcium carbide and ball milling pearl are placed in vacuum sphere ink tank；Ball grinder is sealed, ball grinder is vacuumized or is led to
Enter inert gas；
（2）By planetary ball mill with 400 ~ 600 revs/min of rate ball milling 6 ~ 24 hours；
（3）After the completion of ball milling, sample is taken out, is washed with dust technology or acetic acid, removes unreacted calcium carbide；
（4）To step（3）Obtained sample removes unreacted trihalogenated benzene, obtains hydrogen substitution graphite list alkynes powder；
The method of removal unreacted trihalogenated benzene is, with hot benzene washing sample, to replace graphite list with 40 ~ 90 DEG C of drying to get to hydrogen
Alkynes powder；Or sample is placed in tube furnace, it in an inert atmosphere, is annealed with 300 ~ 600 DEG C, obtains hydrogen substitution graphite list alkynes
Powder.
2. the preparation method of hydrogen substitution graphite list alkynes according to claim 1, which is characterized in that the trihalogenated benzene is three
Chlorobenzene or three triiodo-benzenes.
3. the preparation method of hydrogen according to claim 1 substitution graphite list alkynes, which is characterized in that trihalogenated benzene and calcium carbide
Molar ratio control is 1:3~1:24.
4. the preparation method of hydrogen substitution graphite list alkynes according to claim 1, which is characterized in that ball material quality when ball milling
It is 25 than control:1~75:1.
5. the preparation method of hydrogen according to claim 1 substitution graphite list alkynes, which is characterized in that the inert atmosphere is
Nitrogen or argon gas.
6. the hydrogen that the preparation method as described in one of claim 1-5 obtains replaces graphite list alkynes answering as photoelectrocatalysimaterial material
With.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110371946A (en) * | 2019-08-12 | 2019-10-25 | 安徽工业大学 | A kind of naphthalyne carbon material, preparation method and application |
| CN112786880A (en) * | 2021-01-17 | 2021-05-11 | 复旦大学 | Diamond-shaped hole graphite monoalkyne derivative and preparation method and application thereof |
| CN113651311A (en) * | 2021-07-16 | 2021-11-16 | 西安理工大学 | Alkynyl carbon material, preparation method thereof and composite electrode |
| CN114906839A (en) * | 2022-05-31 | 2022-08-16 | 南方科技大学 | Preparation method of graphdiyne |
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| KR20150091577A (en) * | 2014-02-03 | 2015-08-12 | 건국대학교 산학협력단 | Graphdiyne-based semiconductor materials using hydrogenation or halogenation |
| CN105948015A (en) * | 2016-04-27 | 2016-09-21 | 北京化工大学 | Method for synthesizing carbyne nano-material from calcium carbide and polyhalohydrocarbon as raw materials through ball-milling |
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| KR20150091577A (en) * | 2014-02-03 | 2015-08-12 | 건국대학교 산학협력단 | Graphdiyne-based semiconductor materials using hydrogenation or halogenation |
| CN105948015A (en) * | 2016-04-27 | 2016-09-21 | 北京化工大学 | Method for synthesizing carbyne nano-material from calcium carbide and polyhalohydrocarbon as raw materials through ball-milling |
Non-Patent Citations (2)
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| HE XIUJIE等: "The roles of electrons in the electronic structures and optical properties of graphyne", 《CHINESE SCIENCE BULLETIN》 * |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110371946A (en) * | 2019-08-12 | 2019-10-25 | 安徽工业大学 | A kind of naphthalyne carbon material, preparation method and application |
| CN112786880A (en) * | 2021-01-17 | 2021-05-11 | 复旦大学 | Diamond-shaped hole graphite monoalkyne derivative and preparation method and application thereof |
| CN112786880B (en) * | 2021-01-17 | 2022-06-21 | 复旦大学 | Diamond-shaped hole graphite monoalkyne derivative and preparation method and application thereof |
| CN113651311A (en) * | 2021-07-16 | 2021-11-16 | 西安理工大学 | Alkynyl carbon material, preparation method thereof and composite electrode |
| CN114906839A (en) * | 2022-05-31 | 2022-08-16 | 南方科技大学 | Preparation method of graphdiyne |
| CN114906839B (en) * | 2022-05-31 | 2023-12-12 | 南方科技大学 | Preparation method of graphite alkyne |
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