CN107011504A - One class is rich in the two-dimentional carbon-rich material preparation method and applications of carbonyl, thioketones and selenone functional group - Google Patents
One class is rich in the two-dimentional carbon-rich material preparation method and applications of carbonyl, thioketones and selenone functional group Download PDFInfo
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Abstract
Carbonyl is rich in the invention discloses a class（C=O bond）, thioketones（Carbon sulphur double bond）And selenone（Carbon selenium double bond）The two-dimentional carbon-rich material preparation method and applications of functional group, category materials application field.Such material is made up of conjugation hexatomic ring and acetylene bond containing carbonyl, thioketones and selenone functional group, the 1 of above-mentioned conjugation hexatomic ring, 4 are replaced by carbonyl, thioketones or selenone functional group, 2,3,5,6 are connected with acetylene bond, there are two acetylene bonds between adjacent hexatomic ring, constitute the two dimensional surface skeleton structure of height conjugation.Its preparation method is mainly comprised the steps of：The materials such as the 1,4-benzoquinone using four alkynyl substituteds carry out the coupling reaction of alkynes, so as to obtain the rich carbon two-dimensional material with height conjugated structure as polymeric precursors in dioxane solution.Due to the introducing of carbonyl, carbon sulphur double bond and carbon selenium double bond, ion transmission channel and the energy storage active site position of two-dimentional carbon-rich material are effectively raised, it is had a good application prospect in energy storage device field.
Description
Technical field
The invention belongs to materials application research field, and in particular to be rich in carbonyl, thioketones and selenone function to one kind is new
Two-dimentional carbon-rich material of group and preparation method thereof.
Background technology
Carbon is a kind of very common element, and it is widely present among the earth's crust, atmosphere and life entity in a variety of forms.
Over nearly 20 years, scientists are directed to developing the new carbon allotrope of new method synthesis always and explore its new performance,
Successively it is found that the new carbon allotrope such as fullerene, CNT and graphene, and the forward position studied as International Academic
And focus, form the independent studies field of interdisciplinary science.In recent years, because Two-dimensional Carbon and carbon-rich material have larger ratio table
The advantage such as area, good thermal conductivity and electrical conductivity, excellent chemical stability, causes the extensive concern of people, and in energy
The fields such as source storage, catalysis, biology sensor achieve gratifying achievement（F. Bonaccorso, L. Colombo, G.
Yu, M. Stoller, V. Tozzini, A. C. Ferrari, R. S. Ruoff, V. Pellegrini,Science2015, 347, 1246501.）.2010, chemistry Suo Liyuliang seminar of the Chinese Academy of Sciences took in terms of graphite alkene research
Obtained important breakthrough.They occur coupling reaction using six alkynyl benzene under the catalytic action of copper sheet, successfully on copper sheet surface
Upper pass through has been chemically synthesized large area graphite alkene（graphdiyne）Film（G. Li, Y. Li, H. Liu, Y.
Guo, Y. Li, D. Zhu, Chem. Commun.2010, 46, 3256.）.As the new two-dimentional carbon material of a class,
Graphite alkene has larger two-dimension plane structure, and the electrical conductivity of its film reaches 10 at room temperature-3~10-4S/m, is a class
Can excellent organic semiconducting materials, such recent material is in lithium ion battery, a variety of semiconductor devices such as perovskite battery
It is widely used in part.In addition, with comprising only sp2The graphene of carbon is compared, and graphite alkene is both to contain sp2Carbon, and contain sp carbon
The full carbon skeleton material of one class high conjugation（A. T. Balaban, C. C. Rentia and E. Ciupitu,Rev. Roum. Chim.,1968, 13, 231.）, with more macromolecular surface aperture and more electrochemistry and photochemical reaction site, make it
Also there is fabulous application prospect in terms of energy storage, catalysis（Li Yongjun, Li Yuliang,Macromolecule journal, 2015,2, 147.）.It is worth
One is mentioned that, due to the introducing of acetylene bond, carry out high-temperature process to such material or Heteroatom doping also have more reactions and
Doping site, so that its physical and chemical performance can be adjusted and optimize in a wider context.For example, nitrogen, boron, fluorine,
The miscellaneous element doping such as sulphur, oxygen can be very good to improve the electrochemical properties of such material, so that obtain higher, more stable specific volume
Amount（S. Zhang, H. Du, J. He, C. Huang, H. Liu, G. Cui, Y. Li,ACS Appl. Mater. Interfaces2016, 8, 8467.）.Above-mentioned all multielements can form different functional groups in several ways, wherein
Ion transmission channel and the energy storage active site position of material can be effectively improved by the introducing of polarity heteroatoms double bond functional group.
But the method reported at present is difficult to the introducing of quantitative accurate location and single kind.The present patent application is in synthetic methodology
It is upper to be chemically synthesized using a simple step, utilize the structural controllability and diversity of chemical synthesis so that for such two
The further finely regulating of dimension carbon material chemical constitution and performance is possibly realized, and contributes to the essence of rich carbon two-dimensional material structural behaviour
Fine tuning control and performance improvement, effectively widen its application in fields such as energy storage, photoelectron, catalysis and materials.
The content of the invention
The present invention seeks to a kind of open new carbon containing oxygen, carbon sulphur, the two-dimentional carbon-rich material of carbon selenium polarity double bond and its preparation
Method.
The two-dimentional carbon-rich material of carbon containing oxygen disclosed by the invention, carbon sulphur, carbon selenium polarity double bond, the structure is with 1,4-benzoquinone knot
The two dimension that the height that structure and its oxygen atom are connected with each other and constituted by two acetylene bonds by the hexatomic ring that other hetero atoms replace is conjugated
Material, this material is rich in larger and orderly molecule, ion conveying hole, and larger specific surface area and less forbidden band are wide
Degree.Because material itself has certain self-supporting, ground in energy device, electronics, catalysis and gas or liquid separation etc.
Studying carefully field has wide application space.
The two-dimentional carbon-rich material preparation method of the double bond of polarity containing heteroatoms disclosed by the invention, is mainly included the following steps that：
With trimethyl silicon substrate（TMS）Four alkynyl benzoquinones of protection etc. are reacting precursor, and tetrabutyl ammonium fluoride is used at low temperature（TBAF）It is de-
Except TMS protection groups, using the substrate of copper sheet, copper foil or arbitrary surfaces covered with Copper thin film as catalyst substrate, in dioxane, four
Methyl ethylenediamine（TMEDA）, by alkynes coupling reaction in the mixed solution that pyridine is configured according to a certain percentage, synthesis has height
Spend the rich carbon two-dimensional material film of the double bond of heteroatoms containing polarized of conjugation.
The material macro manifestations form is ultrathin flexible film, with two dimensional crystal structure and certain self-supporting energy
There is hexa-member heterocycle and acetylene bond, and its triangle, quadrangle and the hexagon duct constituted, aperture difference in power, its structure
For 0.5-0.9nm, 0.8-1.0 nm and 1.0-1.7 nm.
The material is thin by the connected two-dimension plane structure constituted of the acetylene bond of hexa-atomic aromatic ring containing hetero atom and interannular presence
Membrane material, containing the miscellaneous element such as substantial amounts of oxygen, sulphur, selenium, theoretical carbon and nitrogen atoms ratio is 7：1.
The material be using equal four alkynyls 1,4-benzoquinone as monomer, oxygen wherein in the hexa-atomic aromatic ring of 1,4-benzoquinone can also by sulphur,
The elements such as selenium, tellurium replace, and the quantity of acetylene substituent is between 2 to 4.Contain the catalysis of the substrate of copper in copper sheet or arbitrary surfaces
Under, occur coupling reaction in dioxane in the mixed solvent, obtain with acetylene bond being connected by hexa-member heterocycle on the surface of the substrate
The material film material of two dimensional surface crystal structure is constituted, the size of film can be tested by catalyst substrate area control
Room synthesizes area up to 1.0*1 .0cm2, thickness is between 0.1-20 μm.
In the synthetic method of the material, the solvent used is dioxane, and pyridine and TMEDA match somebody with somebody according to a certain percentage
The mixed solvent put.
In the synthetic method of the material, the area ratio relation of monomer and catalyst substrate is 0.002-5 mg/cm2；
The volume relationship of monomer and described mixed solvent is 0.005-2 mg/mL；Reaction temperature is 40-110oC；Reaction time is
1-9 days.
Material energy gap is 0.5-2.7 eV, and electrical conductivity is 0.002-1.09 × 10-3 S m-1.Can be directly used for or
Crushed or other forms are used for the fields such as energy device, catalysis, material and semiconductor.
Beneficial effects of the present invention：
New containing rich carbon two-dimensional material such as aerobic, sulphur, selenium and preparation method thereof the invention provides one kind, this method uses Terminal Acetylenes
The method of coupling prepares the two-dimentional carbon-rich material of high conjugation, by controlling the ratio of monomer and catalyst substrate, Ke Yihe
Into different area and the fexible film of different-thickness.Compared with current material, the present invention is by the way that carbon oxygen, carbon sulphur, carbon selenium are drawn
Enter reaction monomers, design has synthesized that miscellaneous element position is accurate, species is single, the rich carbon two-dimensional material of ratio-dependent hetero-aromatic ring, and
With less energy gap, uniform pore passage structure has widened the species of material, energy device, catalysis, material and
The fields such as semiconductor have a good application prospect.Test result indicates that：Gained ultrathin flexible film of the invention is in laboratory
Synthesis area can reach 1.0*1.0 cm2, thickness is at 0.1-20 μm, with certain self-supporting ability.Energy gap
For 1.76 eV or so, there is potential application prospect in fields such as semiconductor, electronics, catalysis and materials.
Brief description of the drawings
Fig. 1 is new heteroatoms aromatic ring in the present invention, and contains carbonyl, thioketones, selenone functional group rich carbon two-dimensional material
Chemical structural formula.
Fig. 2 is the picture in kind of the rich carbon two-dimensional material of new polarity prepared by the embodiment of the present invention 1.
Fig. 3 is the cross-sectional scans electron microscopic picture of the rich carbon two-dimensional material of new polarity prepared by the embodiment of the present invention 1.
Fig. 4 is the scanning electron microscopic picture of the rich carbon two-dimensional material of new polarity prepared by the embodiment of the present invention 1.
Fig. 5 is the transmission electron microscope picture of the rich carbon two-dimensional material of new polarity prepared by the embodiment of the present invention 1.
Fig. 6 is the high power transmission electron microscope picture of the rich carbon two-dimensional material of new polarity prepared by the embodiment of the present invention 1.
Fig. 7 is the Raman spectrum of the rich carbon two-dimensional material of new polarity prepared by the embodiment of the present invention 1.
Fig. 8 is the infrared spectrum of the rich carbon two-dimensional material of new polarity prepared by the embodiment of the present invention 1.
Fig. 9 is the multiplying power figure of the button cell prepared by application examples 1 of the present invention.
Figure 10 is cycle performance figure of the button cell under 2A/g electric currents prepared by application examples 1 of the present invention.
Figure 11 is charging and discharging curve figure of the button cell under 0.2A/g electric currents prepared by application examples 1 of the present invention.
Embodiment
It is as follows that the present invention enumerates embodiment, and the present invention is described in further detail, but embodiments of the present invention are not limited
In this.For researcher in this field, the present invention can have various modifications and variations, all spiritual and originals in the present invention
Within then, any modification, equivalent substitution or improvement for being made etc. should be included in the scope of the protection.
It is used to prepare four alkynyl monomers in following embodiments（Compound 2）By 2,3,5,6 4 bromo- 1,4 1,4-benzoquinone（Compound
1）It is made with trimethyl silicane ethyl-acetylene.The optimization compound 2 of compound 3,4 is made, and the reaction equation is as follows：
Embodiment 1,
Under cryogenic conditions, to containing 40 mg（0.108 mmol）The tetrahydrofuran of compound 2（THF）0.5 mL is added in solution
Tetrabutyl ammonium fluoride（TBAF）（1 mol/L tetrahydrofuran solutions, 0.5 mmol）, the stirring reaction 5 minutes under argon gas protection.It
Reaction solution ethyl acetate and saturated aqueous common salt afterwards is extracted three times, merges organic phase, with anhydrous sodium sulfate drying, 30 DEG C of water temperatures
Organic solvent is evaporated off in backspin, obtains（Monomeric compound）（13 mg, 79%）.Dissolved, protected in argon gas with 25 mL dioxane
Slowly it is added dropwise under shield in filling 25mL dioxane, TMEDA and pyridine mixed solution and 80 cm2The two of copper foil catalyst substrate
In mouth bottle, time for adding is 1-4 h.Reaction temperature is 60oC argon atmospheres react 3 days.Reaction can be in copper sheet after terminating
One layer of flaxen film of upper generation, through FeCl3It is new rich carbon two dimension that light yellow clear film is obtained after aqueous corrosion
Material film（8 mg, 61%）.Its chemical equation is as follows：
Grand design（Fig. 2）Show, uniform with the new rich carbon two-dimensional material film surface obtained by prepared by this method, size is about
1.0*1.0 cm2, in light/dark balance, there is certain flexibility and self-supporting ability.
Cross-sectional scans Electronic Speculum（Fig. 3）The thickness for showing the material film is about 2.77 μm.
ESEM（Fig. 4）The microscopic appearance for showing new rich carbon two-dimensional material is uniform two-dimension plane structure, surface
With fibrous nano line.
Transmission electron microscope（Fig. 5）Show that the microscopic appearance of the material film is homogeneous.
High-resolution-ration transmission electric-lens（Fig. 6）It is polycrystalline state to show the material film, and fringe spacing is about 0.831nm.
Raman spectrum（Fig. 7）Show to contain carbon-carbon single bond, aromatic rings and carbon carbon three in the molecular structure of the material film
Key.
Infrared spectrum（Fig. 8）Show also to contain hexa-atomic aromatic rings in the molecular structure of the material film, and its C=O bond.
Embodiment 2,
Under cryogenic conditions, to containing 80 mg（0.216 mmol）The tetrahydrofuran of compound 3（THF）1.0 mL are added in solution
Tetrabutyl ammonium fluoride（TBAF）（1 mol/L tetrahydrofuran solutions, 1.0 mmol）, the stirring reaction 10 minutes under argon gas protection.
Reaction solution ethyl acetate and saturated aqueous common salt afterwards is extracted three times, merges organic phase, with anhydrous sodium sulfate drying, 30 DEG C of water
Organic solvent is evaporated off in warm backspin, obtains four alkynyl monomers（Compound 5b）（25 mg, 76%）.Dissolved with 50 mL dioxane,
Slowly it is added dropwise in the mixed solution for filling 50mL dioxane, TMEDA and pyridine and 150 cm under argon gas protection2Copper foil is urged
In the two-mouth bottle of agent substrate, time for adding is 2-4 h.Reaction temperature is 60oC, argon atmosphere reacts 3 days.Reaction terminates
After one layer of flaxen film can be generated on copper sheet, through FeCl3Light yellow clear film is obtained after aqueous corrosion is
New rich carbon two-dimensional material film P2（15 mg, 57%）.
Embodiment 3,
Under cryogenic conditions, to containing 120 mg（0.324 mmol）The tetrahydrofuran of compound 4（THF）1.5 mL are added in solution
Tetrabutyl ammonium fluoride（TBAF）（1 mol/L tetrahydrofuran solutions, 1.5 mmol）, the stirring reaction 10 minutes under argon gas protection.
Reaction solution ethyl acetate and saturated aqueous common salt afterwards is extracted three times, merges organic phase, with anhydrous sodium sulfate drying, 30 DEG C of water
Organic solvent is evaporated off in warm backspin, obtains compound 5c（35 mg, 71%）.Dissolved with 50 mL dioxane, under argon gas protection
Slowly it is added dropwise in the mixed solution for filling 75mL dioxane, TMEDA and pyridine and 200 cm2Two mouthfuls of copper foil catalyst substrate
In bottle, time for adding is 2-4 h.Reaction temperature is 60oC, argon atmosphere reacts 3 days.Reaction can be on copper sheet after terminating
One layer of flaxen film is generated, through FeCl3It is the two-dimentional material of new rich carbon that light yellow clear film is obtained after aqueous corrosion
Expect film P3（20 mg, 51%）.
Embodiment 4,
Under cryogenic conditions, to containing 20 mg（0.054 mmol）The tetrahydrofuran of compound 2（THF）0.3 mL is added in solution
Tetrabutyl ammonium fluoride（TBAF）（1 mol/L tetrahydrofuran solutions, 0.3 mmol）, the stirring reaction 5 minutes under argon gas protection.It
Reaction solution ethyl acetate and saturated aqueous common salt afterwards is extracted three times, merges organic phase, with anhydrous sodium sulfate drying, 30 DEG C of water temperatures
Organic solvent is evaporated off in backspin, obtains three compound 5a（7 mg, 85%）.Dissolved with 15 mL dioxane, under argon gas protection
Slowly it is added dropwise in the mixed solution for filling 20mL dioxane, TMEDA and pyridine and 40 cm2Two mouthfuls of copper foil catalyst substrate
In bottle, time for adding is 1-4 h.Reaction temperature is 60oC, argon atmosphere reacts 3 days.Reaction can be on copper sheet after terminating
One layer of flaxen film is generated, through FeCl3It is the two-dimentional material of new rich carbon that light yellow clear film is obtained after aqueous corrosion
Expect film P4（5.2 mg, 81%）.
Embodiment 5,
Under cryogenic conditions, to containing 40 mg（0.108 mmol）The tetrahydrofuran of compound 2（THF）0.5 mL is added in solution
Tetrabutyl ammonium fluoride（TBAF）（1 mol/L tetrahydrofuran solutions, 0.5 mmol）, the stirring reaction 8 minutes under argon gas protection.It
Reaction solution ethyl acetate and saturated aqueous common salt afterwards is extracted three times, merges organic phase, with anhydrous sodium sulfate drying, 30 DEG C of water temperatures
Organic solvent is evaporated off in backspin, obtains four alkynyl monomers compound 5a（14 mg, 85%）.Dissolved with 25 mL dioxane,
Slowly it is added dropwise in the mixed solution for filling 25mL dioxane, TMEDA and pyridine and 80 cm under argon gas protection2Copper foil catalyst
In the two-mouth bottle of substrate, time for adding is 1-4 h.Reaction temperature is 60oC, argon atmosphere reacts 3 days.Energy after reaction terminates
It is enough that one layer of flaxen film is generated on copper sheet, through FeCl3Light yellow clear film is obtained after aqueous corrosion as new
Rich carbon two-dimensional material film P5（9 mg, 69%）.
Embodiment 6,
Under cryogenic conditions, to containing 40 mg（0.108 mmol）The tetrahydrofuran of compound 2（THF）0.5 mL is added in solution
Tetrabutyl ammonium fluoride（TBAF）（1 mol/L tetrahydrofuran solutions, 0.5 mmol）, the stirring reaction 8 minutes under argon gas protection.It
Reaction solution ethyl acetate and saturated aqueous common salt afterwards is extracted three times, merges organic phase, with anhydrous sodium sulfate drying, 30 DEG C of water temperatures
Organic solvent is evaporated off in backspin, obtains compound 5a（12 mg, 73%）.Dissolved with 25 mL dioxane, it is slow under argon gas protection
Slowly it is added dropwise in the mixed solution for filling 25mL dioxane, TMEDA and pyridine and 80 cm2The two-mouth bottle of copper foil catalyst substrate
In, time for adding is 1-4 h.Reaction temperature is 80oC, argon atmosphere reacts 3 days.Reaction can give birth to after terminating on copper sheet
Into one layer of flaxen film, through FeCl3It is new rich carbon two-dimensional material that light yellow clear film is obtained after aqueous corrosion
Film P6（7 mg, 53%）.
Embodiment 7,
Under cryogenic conditions, to containing 40 mg（0.108 mmol）The tetrahydrofuran of compound 2（THF）1.0 mL are added in solution
Tetrabutyl ammonium fluoride（TBAF）（1 mol/L tetrahydrofuran solutions, 1.0 mmol）, the stirring reaction 8 minutes under argon gas protection.It
Reaction solution ethyl acetate and saturated aqueous common salt afterwards is extracted three times, merges organic phase, with anhydrous sodium sulfate drying, 30 DEG C of water temperatures
Organic solvent is evaporated off in backspin, obtains compound 5（14 mg, 85%）.Dissolved with 25 mL dioxane, it is slow under argon gas protection
Slowly it is added dropwise in the mixed solution for filling 25mL dioxane, TMEDA and pyridine and 80 cm2The two-mouth bottle of copper foil catalyst substrate
In, time for adding is 1-4 h.Reaction temperature is 120oC, argon atmosphere reacts 3 days.Reaction can give birth to after terminating on copper sheet
Into one layer of flaxen film, through FeCl3It is new rich carbon two-dimensional material that light yellow clear film is obtained after aqueous corrosion
Film P7（10 mg, 76%）..
Embodiment 8,
Under cryogenic conditions, to containing 40 mg（0.108 mmol）The tetrahydrofuran of compound 2（THF）0.5 mL is added in solution
Tetrabutyl ammonium fluoride（TBAF）（1 mol/L tetrahydrofuran solutions, 0.5 mmol）, the stirring reaction 5 minutes under argon gas protection.It
Reaction solution ethyl acetate and saturated aqueous common salt afterwards is extracted three times, merges organic phase, with anhydrous sodium sulfate drying, 30 DEG C of water temperatures
Organic solvent is evaporated off in backspin, obtains compound 5a（13 mg, 79%）.Dissolved with 25 mL dioxane, under argon gas protection
Slowly it is added dropwise in the mixed solution for filling 25mL dioxane, TMEDA and pyridine and 80 cm2Two mouthfuls of copper foil catalyst substrate
In bottle, time for adding is 1-4 h.Reaction temperature is 60oC, argon atmosphere reacts 1 day.Reaction can be on copper sheet after terminating
One layer of flaxen film is generated, through FeCl3It is the two-dimentional material of new rich carbon that light yellow clear film is obtained after aqueous corrosion
Expect film P8（7 mg, 53%）.
Embodiment 9,
Under cryogenic conditions, to containing 40 mg（0.108 mmol）The tetrahydrofuran of compound 2（THF）0.5 mL is added in solution
Tetrabutyl ammonium fluoride（TBAF）（1 mol/L tetrahydrofuran solutions, 0.5 mmol）, the stirring reaction 5 minutes under argon gas protection.It
Reaction solution ethyl acetate and saturated aqueous common salt afterwards is extracted three times, merges organic phase, with anhydrous sodium sulfate drying, 30 DEG C of water temperatures
Organic solvent is evaporated off in backspin, obtains compound 5a（12 mg, 73%）.Dissolved with 25 mL dioxane, under argon gas protection
Slowly it is added dropwise in the mixed solution for filling 25mL dioxane, TMEDA and pyridine and 80 cm2Two mouthfuls of copper foil catalyst substrate
In bottle, time for adding is 1-4 h.Reaction temperature is 60oC, argon atmosphere reacts 2 days.Reaction can be on copper sheet after terminating
One layer of flaxen film is generated, through FeCl3It is the two-dimentional material of new rich carbon that light yellow clear film is obtained after aqueous corrosion
Expect film P9（6 mg, 45%）.
Embodiment 10,
Under cryogenic conditions, to containing 40 mg（0.108 mmol）The tetrahydrofuran of compound 3（THF）0.5 mL is added in solution
Tetrabutyl ammonium fluoride（TBAF）（1 mol/L tetrahydrofuran solutions, 0.5 mmol）, the stirring reaction 5 minutes under argon gas protection.It
Reaction solution ethyl acetate and saturated aqueous common salt afterwards is extracted three times, merges organic phase, with anhydrous sodium sulfate drying, 30 DEG C of water temperatures
Organic solvent is evaporated off in backspin, obtains compound 5b（14 mg, 85%）.Dissolved with 25 mL dioxane, under argon gas protection
Slowly it is added dropwise in the mixed solution for filling 25mL dioxane, TMEDA and pyridine and 80 cm2Two mouthfuls of copper foil catalyst substrate
In bottle, time for adding is 1-4 h.Reaction temperature isoC, argon atmosphere reacts 3 days.Reaction can give birth to after terminating on copper sheet
Into one layer of flaxen film, through FeCl3It is new rich carbon two-dimensional material that light yellow clear film is obtained after aqueous corrosion
Film P10（9 mg, 62%）.
Under embodiment 11, cryogenic conditions, to containing 40 mg（0.108 mmol）The tetrahydrofuran of compound 4（THF）Solution
0.5 mL tetrabutyl ammonium fluorides of middle addition（TBAF）（1 mol/L tetrahydrofuran solutions, 0.5 mmol）, stirred under argon gas protection
Reaction 5 minutes.Reaction solution ethyl acetate and saturated aqueous common salt afterwards is extracted three times, is merged organic phase, is used anhydrous sodium sulfate
Dry, 30 DEG C of water temperature backspins are evaporated off organic solvent, obtain compound 5c（14 mg, 86%）.Dissolved with 25 mL dioxane,
Slowly it is added dropwise in the mixed solution for filling 25mL dioxane, TMEDA and pyridine and 80 cm under argon gas protection2Copper foil is catalyzed
In the two-mouth bottle of agent substrate, time for adding is 1-4 h.Reaction temperature is 60oC, argon atmosphere reacts 3 days.After reaction terminates
One layer of flaxen film can be generated on copper sheet, through FeCl3It is new that light yellow clear film is obtained after aqueous corrosion
Type richness carbon two-dimensional material film P11（9 mg, 62%）.
Application examples 1
The new rich carbon two-dimensional material prepared in above-described embodiment 1 is cut into suitable size pole piece, then 120oC vacuum
Under the conditions of dry 12 hours, be directly used in the positive pole as lithium ion battery（Working electrode）, lithium piece is as negative electrode, using 1
Mol/L lithium hexafluoro phosphates（LiPF6）/（Solvent is ethylene carbonate（EC）：Dimethyl carbonate（DMC）, volume ratio is 1：1）As
Electrolyte, 2032 type button cells are assembled into the glove box full of argon gas and carry out electrochemical property test（Referring to Fig. 9-
11）.
Constant current charge-discharge result shows the electrode of new rich carbon two-dimensional material preparation 50 under Fig. 9 different current densities
Under mA/g electric current, specific capacity can reach 1100 mAh/g, while also show electrode high rate performance under different current densities
It is excellent.
Cycle performance（Figure 10）Show that electrode prepared by new rich carbon two-dimensional material circulates 700 under 2A/g high current
Circle, its capacity remains to be maintained at 750 mAh/g.The new electricity prepared containing the rich carbon two-dimensional material of C=O bond is also illustrate that simultaneously
Has outstanding stability and security.
The charging and discharging curve of first three weeks（Figure 11）Show new rich carbon two-dimensional material as flexible electrode coulombic efficiency first
More than 60%, it is preferable negative material that typical porous carbon materials discharge curve, which is presented, possesses stable chemical property.
Applicant states that the present invention illustrates the method detailed of the present invention, but not office of the invention by above-described embodiment
It is limited to above-mentioned method detailed, that is, does not mean that the present invention has to rely on above-mentioned method detailed and could implemented.Art
Researcher it will be clearly understood that any improvement in the present invention, equivalence replacement to each raw material of product of the present invention and step and
Addition, selection of concrete mode etc., within the scope of all falling within protection scope of the present invention and being open.
Claims (9)
1. two-dimentional carbon-rich material of the new carbon containing oxygen of a class, carbon sulphur and carbon selenium double bond and preparation method thereof, comprises the following steps：With 2,
Carbonyl in the benzoquinones of 3,5,6-tetrem alkynyl substituted or its structure replaces with the conjugation six of thione group or selenone substituent group
Yuan of rings are polymeric precursors, in dioxane and a small amount of pyridine and tetramethylethylenediamine（TMEDA）Mixed solution in, pass through Terminal Acetylenes
Coupling reaction prepares the rich carbon two-dimensional material film of height conjugation；Material characteristics are：Material is two with self-supporting ability
Tie up in material, its structure and there are hexa-atomic aromatic ring and two acetylene bonds, and containing one kind in carbon oxygen, carbon sulphur or carbon selenium double bond, constituted
Planar structure there are two kinds of molecule ducts of triangle and hexagon, aperture is respectively 0.5-0.9nm and 1.0-1.7
nm；Material energy gap is 0.5-2.7 eV, and electrical conductivity is 0.002-1.09 × 10-3 S m-1。
2. the rich carbon two-dimensional material as described in claim 1, it is characterised in that：The material is by containing carbon oxygen, carbon sulphur and carbon
Containing a large amount of in the connected two-dimension plane structure thin-film material constituted of acetylene bond existed between the hexa-atomic conjugation aromatic ring of selenium double bond, material
The hetero atom such as O, S, Se, theoretical carbon and hetero atom ratio is 7：1.
3. the rich carbon two-dimensional material as described in claim 1 or 2, it is characterised in that：Contain carbon with 2,3,5,6 4 alkynyl substituteds
The hexa-member heterocycle of oxygen, carbon sulphur and carbon selenium double bond is polymerized monomer, and wherein hexa-member heterocycle can be oxygen quilt in 1,4-benzoquinone and its double bond
The hexa-atomic aromatic ring of the hetero atoms such as sulphur, selenium substitution, the quantity of acetylene substituent is four.
4. by the rich carbon two-dimensional material of any described double bonds containing heteroatoms of claim 1-3, it is characterised in that：Described solvent
For the mixed solvent based on pyridine, with dioxane, ethanol, tetrahydrofuran, dichloromethane, chloroform, petroleum ether, n-hexane
Mixed solvent is used as Deng the one or more in organic solvent；Using tetramethylethylenediamine as containing n-donor ligand, wherein pyridine is mixed
Ratio is 1~50wt%, preferably 5~10wt% in bonding solvent；Tetramethylethylenediamine in the mixed solvent ratio be 1~
20wt%, preferably 1~5wt%.
5. by the rich carbon two-dimensional material of any described double bonds containing heteroatoms of claim 1-4, it is characterised in that：Described monomer
Area ratio relation with catalyst substrate is 0.002-5 mg/cm2；The volume relationship of monomer and described mixed solvent is
0.005-2 mg/mL；Reaction temperature is 25-110oC；Reaction time is 1-9 days.
6. by the rich carbon two-dimensional material of any described double bonds containing heteroatoms of claim 1-5, it is characterised in that：The material is grand
The sight form of expression is ultrathin flexible film, with two dimensional crystal structure and certain self-supporting ability.
7. by the rich carbon two-dimensional material of any described double bonds containing heteroatoms of claim 1-6, it is characterised in that：Material can be direct
For or crushed or the mixing of its other materials, it is compound or as additive be used for energy device, photoelectric device, catalysis,
The field such as material and other semiconductors.
8. the application of the heteroatoms double bond carbon-rich material as described in claim 7, it is characterised in that：The energy storage device is gold
Belong to ion battery, ultracapacitor, lithium-sulfur cell etc., wherein, material can be used directly, crushed or be mixed with other materials
Close, be combined or used as additive.
9. the metal ion battery as described in claim 8, it is characterised in that：Described metal be selected from lithium, sodium, potassium, magnesium, aluminium,
One kind in calcium, zinc, cadmium, nickel, cobalt.
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| CN108912314A (en) * | 2018-06-05 | 2018-11-30 | 中国科学院青岛生物能源与过程研究所 | Two-dimentional carbon-rich material preparation method and applications of the one kind rich in sp carbon and III, V main group trivalent heteroatom |
| CN111333061A (en) * | 2018-12-18 | 2020-06-26 | 青岛科技大学 | Preparation method of graphyne film and graphyne film |
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| CN103022496B (en) * | 2012-12-28 | 2014-12-24 | 南开大学 | Aromatic condensed ring quinones compound positive pole material for one-class lithium secondary battery |
| CN105047933A (en) * | 2015-08-31 | 2015-11-11 | 张家港智电芳华蓄电研究所有限公司 | Rechargeable quinone-manganese oxide aqueous battery |
| CN105645378A (en) * | 2015-12-31 | 2016-06-08 | 中国科学院青岛生物能源与过程研究所 | Preparation method of hetero-atom-doped graphyne |
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| US20100125038A1 (en) * | 2008-11-17 | 2010-05-20 | Southwest Research Institute | Carbon Material For Hydrogen Storage |
| CN103022496B (en) * | 2012-12-28 | 2014-12-24 | 南开大学 | Aromatic condensed ring quinones compound positive pole material for one-class lithium secondary battery |
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| CN111333061A (en) * | 2018-12-18 | 2020-06-26 | 青岛科技大学 | Preparation method of graphyne film and graphyne film |
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