CN113774407B - Synthesis method of graphite alkyne - Google Patents
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- CN113774407B CN113774407B CN202110937445.2A CN202110937445A CN113774407B CN 113774407 B CN113774407 B CN 113774407B CN 202110937445 A CN202110937445 A CN 202110937445A CN 113774407 B CN113774407 B CN 113774407B
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- -1 graphite alkyne Chemical class 0.000 title claims abstract description 96
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 86
- 239000010439 graphite Substances 0.000 title claims abstract description 86
- 238000001308 synthesis method Methods 0.000 title description 7
- 238000000034 method Methods 0.000 claims abstract description 64
- 239000002243 precursor Substances 0.000 claims abstract description 33
- 239000003792 electrolyte Substances 0.000 claims abstract description 32
- 238000011282 treatment Methods 0.000 claims abstract description 18
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000011889 copper foil Substances 0.000 claims abstract description 13
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 12
- 239000000758 substrate Substances 0.000 claims abstract description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 21
- 230000015572 biosynthetic process Effects 0.000 claims description 15
- 238000003786 synthesis reaction Methods 0.000 claims description 14
- 238000002484 cyclic voltammetry Methods 0.000 claims description 13
- 150000004985 diamines Chemical class 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 10
- 150000003751 zinc Chemical class 0.000 claims description 10
- 238000010408 sweeping Methods 0.000 claims description 8
- 238000010189 synthetic method Methods 0.000 claims description 5
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 4
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004246 zinc acetate Substances 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 8
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 24
- 238000010521 absorption reaction Methods 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 19
- 239000000243 solution Substances 0.000 description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 14
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 14
- VXFRCHRNRILBMZ-UHFFFAOYSA-N 1,2,3,4,5,6-hexaethynylbenzene Chemical compound C#CC1=C(C#C)C(C#C)=C(C#C)C(C#C)=C1C#C VXFRCHRNRILBMZ-UHFFFAOYSA-N 0.000 description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- 125000003118 aryl group Chemical group 0.000 description 10
- 150000001721 carbon Chemical group 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 10
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 238000001069 Raman spectroscopy Methods 0.000 description 8
- 238000001237 Raman spectrum Methods 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 229910052697 platinum Inorganic materials 0.000 description 7
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 6
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- LLCSWKVOHICRDD-UHFFFAOYSA-N buta-1,3-diyne Chemical group C#CC#C LLCSWKVOHICRDD-UHFFFAOYSA-N 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 230000029058 respiratory gaseous exchange Effects 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- 229910052725 zinc Inorganic materials 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 229910021607 Silver chloride Inorganic materials 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 239000012300 argon atmosphere Substances 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 4
- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 238000010511 deprotection reaction Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000006506 Hay coupling reaction Methods 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 150000001345 alkine derivatives Chemical class 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000003487 electrochemical reaction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000002120 nanofilm Substances 0.000 description 2
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 238000004506 ultrasonic cleaning Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 1
- JPESOWAMJACNJV-UHFFFAOYSA-N 1,3,5-tris(prop-1-ynyl)benzene Chemical compound CC#CC1=CC(C#CC)=CC(C#CC)=C1 JPESOWAMJACNJV-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000003477 Sonogashira cross-coupling reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- 238000000861 blow drying Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910021387 carbon allotrope Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- NCWQJOGVLLNWEO-UHFFFAOYSA-N methylsilicon Chemical compound [Si]C NCWQJOGVLLNWEO-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000006239 protecting group Chemical group 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Images
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/135—Carbon
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/50—Processes
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Carbon And Carbon Compounds (AREA)
- Electrolytic Production Of Metals (AREA)
Abstract
The invention relates to a method for synthesizing graphite alkyne, which comprises the steps of taking a copper foil or a copper-carrying substrate as a working electrode, and carrying out electrochemical treatment on electrolyte containing a graphite alkyne precursor and electrolyte so as to generate graphite alkyne. The method for synthesizing the graphite alkyne has the advantages of multiple synthesizing means, simple and time-saving synthesizing process, reduces the use of organic reagents, is more environment-friendly, economical and efficient, and is easy to industrialize.
Description
Technical Field
The invention belongs to the technical field of carbon materials, and particularly relates to a method for synthesizing graphite alkyne.
Technical Field
Graphite alkyne is a novel carbon allotrope and is formed by conjugated connection of benzene ring and diyne. The porous polymer has a uniformly distributed pore structure, a large conjugated system and a unique two-dimensional planar network structure, so that the porous polymer has wide application prospects in the fields of electrochemistry, photoelectrochemistry, catalysis and the like. Li Yuliang et al successfully prepared a graphite alkyne film on the surface of a copper foil by using a glass-Hay coupling reaction for the first time in 2010; according to the method, hexaethynyl benzene is selected as a monomer molecule, copper foil is simultaneously used as a reaction substrate and a catalyst donor, pyridine is used as an organic base ligand and a reaction solvent, and the graphite alkyne film (chem. Commun.2010,46, 3256-3258) is prepared by reacting at 60 ℃ for 72 hours in a nitrogen atmosphere. After that, various synthetic methods of graphite alkyne have been developed on the basis of the work. Zhang Jin et al prepared a graphitic alkyne nanowall structure on the surface of copper sheets by controlling the active site formation process using a modified glass-Hay coupling reaction at 50 ℃ for 12h under argon atmosphere (j.am. Chem. Soc.2015,137, 7596-7599). Hiroshi Nishihara et al propose a method of synthesizing a graphite alkyne at a liquid/liquid interface and a gas/liquid interface, but this method is difficult to synthesize a graphite alkyne film in a large area (j.am. Chem. Soc.2017,139,8, 3145-3152). Li Yuliang et al synthesized graphite alkynes by the "explosion method" and heated hexaethynyl benzene in the air at 120℃to cause a coupling reaction in the gas phase (chem. Commun.,2017,53,8074-8077). Patent CN201010102048.5 discloses a method for preparing a graphite alkyne film, which takes a copper sheet or a copper-coated material as a substrate, and hexaalkynyl benzene undergoes a coupling reaction under the catalysis of copper to prepare the graphite alkyne film; the reaction temperature is 50-80 ℃ and the reaction time is 2-4 days. Patent CN201110075103.0 discloses a graphite alkyne nano film and a preparation method thereof, wherein a container containing graphite alkyne powder and a substrate with a zinc oxide nano rod array growing on the surface are placed in a tubular reactor, heated to 570-630 ℃, and argon is introduced into the tubular reactor for reaction, so that the graphite alkyne nano film is obtained. Patent 201510350744.0 discloses a preparation method of graphite alkyne, wherein 1,3, 5-tripropynylbenzene as a reaction substrate and a catalyst are added into a reaction vessel under the protection of nitrogen or argon, a solvent is added for dissolution, the reaction is carried out by heating, and the reaction by-products are removed by vacuumizing for many times; the reaction temperature is 40-110 ℃, and the reaction time is 24-192 h. Patent 2017190092207. X discloses a beta-graphite alkyne and a synthesis method thereof, wherein 3- (dibromo-methyl alkenyl) -1, 4-pentadiene is used as a reaction monomer, and under the action of a catalyst and a solvent, the beta-graphite alkyne is obtained by performing Sonogashira coupling reaction at 60-150 ℃ under the protection of inert gas; the reaction time was at least 2 days.
In summary, many methods for synthesizing the graphite alkyne have been successfully developed so far, but the existing graphite alkyne synthesis technology still has various defects, such as long reaction period, high reaction temperature, use of various organic reagents, difficulty in realizing macro preparation of the graphite alkyne, and the like.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a method for synthesizing graphite alkyne, which synthesizes graphite alkyne from a graphite alkyne precursor by an electrochemical method. The method for synthesizing the graphite alkyne has the advantages of multiple synthesis means, simple and time-saving synthesis process, reduces the use of organic reagents, is more environment-friendly, economical and efficient, and is easy to industrialize.
The first aspect of the invention provides a method for synthesizing graphite alkyne, comprising the following steps: and (3) taking a copper foil or a copper-carrying substrate as a working electrode, and carrying out electrochemical treatment on electrolyte containing a graphite alkyne precursor and electrolyte, so as to generate graphite alkyne.
According to some embodiments of the invention, the graphite alkyne precursor has a structure as shown in formula I:
wherein R is hydrogen or alkyne hydrogen protecting group.
According to some embodiments of the invention, the alkyne hydrogen protecting group is-XR 1 R 2 R 3 Wherein R is 1 、R 2 、R 3 Each independently selected from C1-C6 alkyl and cyano-substituted C1-C6 alkyl, X is silicon.
According to a preferred embodiment of the invention, in-XR 1 R 2 R 3 Wherein R is 1 、R 2 、R 3 Each independently selected from C1-C4 alkyl.
In some embodiments of the present application, at-XR 1 R 2 R 3 Wherein R is 1 、R 2 、R 3 Each independently selected from methyl, and X is silicon.
In some embodiments of the present application, the graphite alkyne precursor is hexaethynyl benzene, as shown in formula II:
in other embodiments of the present application, the graphite precursor is hexa [ tri (methylsilyl) ethynyl ] benzene of formula III, as shown in formula III:
according to some embodiments of the invention, the concentration of the graphite alkyne precursor in the electrolyte is from 0.01mmol/L to 1mmol/L, which may be, for example, 0.02mmol/L, 0.03mmol/L, 0.05mmol/L, 0.06mmol/L, 0.1mmol/L, 0.2mmol/L, 0.3mmol/L, 0.5mmol/L, 0.6mmol/L, 0.8mmol/L or any value in between. According to a preferred embodiment of the invention, the concentration of the graphite alkyne precursor in the electrolyte is from 0.02mmol/L to 0.8mmol/L.
According to some preferred embodiments of the invention, the electrolyte comprises a zinc salt. According to a preferred embodiment of the present invention, the zinc salt comprises at least one of zinc chloride, zinc nitrate and zinc acetate.
According to some embodiments of the invention, the concentration of the zinc salt in the electrolyte is 0.05 to 2mol/L, which may be, for example, 0.08mmol/L, 0.1mmol/L, 0.2mmol/L, 0.5mmol/L, 0.8mmol/L, 1.0mmol/L, 1.2mmol/L, 1.5mmol/L, 1.8mmol/L or any value therebetween. According to a preferred embodiment of the invention, the concentration of the zinc salt in the electrolyte is between 0.1mol/L and 1mol/L.
According to some embodiments of the invention, the electrolyte further comprises an organic solvent. According to a preferred embodiment of the present invention, the organic solvent comprises dimethyl sulfoxide.
According to some embodiments of the invention, the electrolyte does not include a diamine.
According to other embodiments of the invention, the electrolyte further comprises a diamine. According to a preferred embodiment of the invention, the diamine comprises N, N' -tetramethyl ethylenediamine.
According to some embodiments of the invention, the diamine concentration is 0.01mol/L to 0.1mol/L, which may be, for example, 0.02mol/L, 0.03mol/L, 0.04mol/L, 0.05mol/L, 0.06mol/L, 0.07mol/L, 0.08mol/L, 0.09mol/L, or any value therebetween. According to a preferred embodiment of the invention, the diamine has a concentration of 0.03mol/L to 0.07mol/L.
According to some embodiments of the invention, the electrochemical treatment is at a temperature of 20 ℃ to 70 ℃, which may be, for example, 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃ and any value therebetween. According to a preferred embodiment of the invention, the temperature of the electrochemical treatment is between 30 ℃ and 60 ℃.
According to some embodiments of the invention, the electrochemical treatment time is 0.1h-12h, e.g. 0.2h, 0.5h, 1h, 3h, 5h, 6h, 8h, 10h and any value in between. According to a preferred embodiment of the invention, the electrochemical treatment time is between 0.2h and 5h.
According to some specific embodiments of the invention, the synthesis of the graphite alkyne is carried out under an air atmosphere or an inert gas atmosphere, for example under argon in the absence of light.
According to some embodiments of the invention, the electrochemical treatment comprises:
a) Cyclic voltammetry: the potential window is 0 to 2.5V, the cycle number is 2 to 15, and the sweeping speed is 2mV/s to 10mV/s; or B) potentiostatic method: the initial potential is 0.4V to 0.8V.
According to some specific embodiments of the invention, the method comprises the steps of:
m1: mixing a graphite alkyne precursor shown in a formula I (wherein R is an alkynyl protecting group) with an organic solvent to obtain a precursor solution, wherein the organic solvent is preferably tetrahydrofuran;
m2: mixing the precursor solution with an organic solvent containing electrolyte to obtain an electrolyte;
m3: and (3) taking a copper foil or a copper-carrying substrate as a working electrode, taking a platinum sheet electrode as a counter electrode, carrying out electrochemical treatment on the electrolyte, and carrying out electrochemical reaction by adopting a cyclic voltammetry or a potentiostatic method to obtain the graphite alkyne.
According to some specific embodiments of the invention, in step M2, the concentration of the graphite alkyne precursor in the electrolyte is from 0.2mmol/L to 0.6mmol/L.
According to some specific embodiments of the invention, in step M3, the cyclic voltammetry conditions include: the potential window is 0 to 2.5V, the cycle number is 2 to 15, and the sweeping speed is 2mV/s to 10mV/s. In some embodiments of the invention, the potential window may be controlled to be 0 to 2.5V when the concentration of the zinc salt is 0.05mol/L to 0.2 mol/L. In other embodiments of the present invention, the potential window may be controlled to be 0 to 0.8V when the concentration of the zinc salt is 0.8mol/L to 1.2 mol/L.
According to some specific embodiments of the invention, in step M3, the potentiostatic method conditions include: the initial potential is 0.4V to 0.8V.
According to other embodiments of the invention, the electrochemical treatment comprises:
d) Cyclic voltammetry: the potential window is 0 to 0.6V, the cycle number is 20 to 180, the sweeping speed is 2 to 10mV/s,
e) Potentiostatic method: the initial potential is 0.5V to 0.8V; or (b)
F) Constant current method: the current is 0.0001A to 0.001A.
According to some specific embodiments of the invention, the method for synthesizing graphite alkyne comprises the following steps:
n1: mixing a graphite alkyne precursor (R is hydrogen) shown in a formula I with an organic solvent to obtain a precursor solution, wherein the organic solvent is preferably dimethyl sulfoxide;
n2: mixing the precursor solution with an organic solvent containing electrolyte to obtain an electrolyte;
and N3: the method comprises the steps of using a copper foil or a copper-carrying substrate as a working electrode, using a platinum sheet electrode as a counter electrode, using an Ag/AgCl electrode as a reference electrode, carrying out electrochemical treatment on the electrolyte, and carrying out electrochemical reaction by adopting a cyclic voltammetry or a potentiostatic method or a galvanostatic method to obtain the graphite alkyne.
According to some specific embodiments of the invention, in step N3, the cyclic voltammetry conditions include: the potential window is 0 to 0.6V, the cycle number is 20 to 180, and the sweeping speed is 2mV/s to 10mV/s.
According to some embodiments of the invention, in step N3, the precursor solution is added dropwise at a rate of 0.062mmol/L to 0.62mmol/L for a period of 0 to 3 hours (e.g. 0.5 to 2.5 hours) when cyclic voltammetry is used.
According to some specific embodiments of the invention, in step N3, the potentiostatic method conditions include: the initial potential is 0.5V to 0.8V.
According to some embodiments of the invention, in step N3, the precursor solution is added dropwise at a rate of 0.031mmol/L to 0.31mmol/L for a period of 0 to 3 hours (e.g., 0.5 to 2.5 hours) when using the potentiostatic method.
According to some specific embodiments of the invention, in step N3, the conditions of the constant current method include: the current is 0.0001A to 0.001A.
According to some embodiments of the invention, in step N3, the precursor solution is added dropwise at a rate of 0.031mmol/L to 0.31mmol/L for a period of 0 to 3 hours (e.g., 0.5 to 2.5 hours) when using the constant current method.
According to some embodiments of the invention, in step N3, when the potentiostatic method or the galvanostatic method is used, diamine is further included in the electrolyte.
According to some embodiments of the invention, the working electrode is pre-treated prior to use, the pre-treatment comprising ultrasonic cleaning with acetone, ethanol, hydrochloric acid (1 mol/L-2 mol/L) and water, followed by drying with nitrogen.
In a second aspect, the present invention provides a graphite alkyne obtained by the synthesis process according to the first aspect.
Compared with the existing graphite alkyne synthesis method, the invention has the following obvious characteristics:
(1) Compared with the current common solution phase coupling reaction, the electrochemical synthesis method obviously shortens the reaction time, and can be shortened from 1-4 days to within a few hours;
(2) The electrochemical synthesis method can directly adopt hexa [ tri (methyl silicon-based) ethynyl ] benzene as a precursor molecule, and does not need any pretreatment and complex separation steps after reaction;
(3) The electrochemical synthesis method of the invention can avoid using pyridine.
Drawings
FIG. 1 is a schematic representation of a process for the synthesis of a graphite alkyne in accordance with the present invention.
Fig. 2 is an SEM image of a graphite alkyne synthesized in accordance with example 1 of the present invention.
FIG. 3 is a Raman spectrum of a graphite alkyne synthesized in example 1 according to the present invention.
Fig. 4 is an XPS diagram of a graphite alkyne synthesized in accordance with example 1 of the present invention.
Fig. 5 is an SEM image of a graphite alkyne synthesized in accordance with example 2 of the present invention.
Fig. 6 is a raman spectrum of a medium graphite alkyne synthesized in accordance with example 2 of the present invention.
Fig. 7 is an SEM image of a graphite alkyne synthesized in accordance with example 3 of the present invention.
FIG. 8 is a Raman spectrum of a graphite alkyne synthesized in example 3 according to the present invention.
Fig. 9 is an XPS diagram of a graphite alkyne synthesized in accordance with example 3 of the present invention.
Fig. 10 is an SEM image of a graphite alkyne synthesized in accordance with example 4 of the present invention.
Fig. 11 is a raman spectrum of a graphite alkyne synthesized in accordance with example 4 of the present invention.
Fig. 12 is an SEM image of a graphite alkyne synthesized in accordance with example 5 of the present invention.
Fig. 13 is a raman spectrum of a graphite alkyne synthesized in accordance with example 5 of the present invention.
Detailed Description
The following detailed description of the invention, taken in conjunction with the examples and the accompanying drawings, is intended to illustrate, but not to limit, the invention.
The reagents or apparatus used, not designated the manufacturer, are all commercially available conventional products.
Except copper foil or copper-carrying substrate (sequentially ultrasonic cleaning with acetone, ethanol, 1mol/L hydrochloric acid and distilled water for 5min each, and blow-drying with nitrogen), the solvents and medicines used are not subjected to other treatments unless specified.
Example 1
In this example, hexa [ tri (silyl) ethynyl ] benzene was used as a precursor to synthesize a graphite alkyne using cyclic voltammetry. The method comprises the following steps:
8mg of hexa (tri (silyl) ethynyl) benzene was dissolved in 15mL of tetrahydrofuran, and the monomer solution was added to 15mL of a 0.1mol/L zinc salt/dimethyl sulfoxide solution to prepare an electrolyte. The temperature of the system is kept at 50 ℃, copper foil and platinum sheet are respectively used as a working electrode and a counter electrode, the potential window is set to 0-1V, the sweeping speed is set to 5mV/s, and the cycle number is set to 10, so that the graphite alkyne can be prepared. After the reaction, the working electrode was rinsed with acetone and hot N, N-dimethylformamide in sequence, and dried with nitrogen.
FIGS. 2-4 are SEM, raman and XPS images of a cyclic voltammetry synthesized graphite alkyne, respectively. Raman spectroscopy is an important means of confirming the structure of the alkyne in graphites. As can be seen from FIG. 3, 1410.8cm -1 、1567.5cm -1 、1911.3cm -1 、2174.3cm -1 There appears a Raman absorption peak of 1410.8cm -1 The absorption peak at the position can be attributed to sp in the aromatic ring 2 Breathing vibration mode of hybridized carbon atom, 1567.5cm -1 The absorption peak at the position is formed by sp in the aromatic ring 2 Stretching vibration of the hybridized carbon atom (E 2g Mode) of production, 1911.3cm -1 And 2174.3cm -1 The absorption peak at this point comes from the stretching vibration of the conjugated diacetylene. As can be seen from FIG. 4, sp and sp 2 The area ratio of the spectral peak to the peak of the hybridized carbon atoms is 2:1, which indicates that benzene rings in the prepared graphite alkyne are connected through diacetylenic bonds. Thus, with hexa [ tri (methylsilyl) ethynyl ]]Benzene is a precursor molecule, and can be synthesized into graphite alkyne through cyclic voltammetry.
Example 2
In this example, hexa [ tri (methylsilyl) ethynyl ] benzene was used as a precursor, and a potentiostatic method was used to synthesize the graphite alkyne. The method comprises the following steps:
8mg of hexa (tri (silyl) ethynyl) benzene was dissolved in 15mL of tetrahydrofuran, and the monomer solution was added to 15mL of 1mol/L zinc salt/dimethyl sulfoxide solution to prepare an electrolyte. And under the voltage of 0.6V at 50 ℃, copper foil and platinum sheet are respectively used as a working electrode and a counter electrode, and the graphite alkyne is prepared after 1600s of reaction. After the reaction, the working electrode was rinsed with acetone and hot N, N-dimethylformamide in sequence, and dried with nitrogen.
Fig. 5 and 6 are SEM images and raman spectra of the synthesized graphite alkyne by potentiostatic method, respectively. As can be seen from FIG. 6, 1372.5cm -1 、1536.9cm -1 、1913.2cm -1 、2171.5cm -1 There appears a Raman absorption peak of 1372.5cm -1 The absorption peak at the position can be attributed to sp in the aromatic ring 2 Breathing vibration mode of hybridized carbon atom, 1536.9cm -1 The absorption peak at the position is formed by sp in the aromatic ring 2 Stretching vibration of the hybridized carbon atom (E 2g Mode) of production, 1913.2cm -1 And 2171.5cm -1 The absorption peak at this point comes from the stretching vibration of the conjugated diacetylene. I.e. in the form of a hexa (tri (methylsilyl) ethynyl) group]Benzene is a precursor molecule, and can be synthesized into the graphite alkyne by a potentiostatic method.
Example 3
In the embodiment, hexaethynyl benzene is used as a precursor, and a cyclic voltammetry method is adopted to synthesize the graphite alkyne material. The specific method comprises the following steps:
32.95mg of hexa [ tri (silyl) ethynyl ] benzene was dissolved in tetrahydrofuran, deprotected with 1M tetrahydrofuran solution of tetrabutylammonium fluoride (TBAF) under argon atmosphere, diluted with ethyl acetate after 15min, extracted with saturated brine, and used immediately after spin-drying. The hexaethynyl benzene solid obtained by deprotection is dissolved in 50mL of dimethyl sulfoxide, and is added dropwise to 50mL of 1mol/L zinc salt/dimethyl sulfoxide solution, which is electrolyte, in 2h under argon atmosphere and in the dark. In the dropping process, the system temperature is kept at 50 ℃, copper foil, platinum sheet and Ag/AgCl electrode are respectively used as a working electrode, a counter electrode and a reference electrode, a potential window is set to be 0-0.6V, the sweeping speed is set to be 10mV/s, and the number of circulation turns is set to be 180, so that the graphite alkyne can be prepared. After the reaction, the working electrode was rinsed with acetone and hot N, N-dimethylformamide in sequence, and dried with nitrogen.
Fig. 7-9 are SEM, raman and XPS images of the sample, respectively. As can be seen from FIG. 8, 1363.6cm -1 、1561.5cm -1 、1917.4cm -1 、2171.5cm -1 There appears a Raman absorption peak of 1363.6cm -1 The absorption peak at the position can be attributed to sp in the aromatic ring 2 Breathing vibration mode of hybridized carbon atom, 1561.5cm -1 The absorption peak at the position is formed by sp in the aromatic ring 2 Stretching vibration of the hybridized carbon atom (E 2g Mode) of production, 1917.4cm -1 And 2171.5cm -1 The absorption peak at this point comes from the stretching vibration of the conjugated diacetylene. As can be seen from FIG. 9, sp and sp 2 The area ratio of the spectral peak to the peak of the hybridized carbon atoms is 2:1, which indicates that benzene rings in the prepared graphite alkyne are connected through diacetylenic bonds. Thus, hexaethynyl benzene is used as a precursor molecule and can be recycled by voltammetryAnd electrosynthesis to obtain graphite alkyne.
Example 4
In this example, hexaethynyl benzene is used as a precursor, and a potentiostatic method is used to synthesize the graphite alkyne. The method comprises the following steps:
32.72mg of hexa [ tri (silylethynyl) benzene were deprotected in the same procedure as in example 3. The hexaethynyl benzene solid obtained by deprotection is dissolved in 50mL of dimethyl sulfoxide solution, and is added dropwise to 50mL of a mixed solution of 1mol/L zinc salt/dimethyl sulfoxide and 0.5mL of N, N' -tetramethyl ethylenediamine in 2h in the absence of light under argon atmosphere, and the solution is electrolyte. In the dropping process, the system temperature is kept at 50 ℃, copper foil, platinum sheet and Ag/AgCl electrode are respectively used as a working electrode, a counter electrode and a reference electrode, and the graphite alkyne can be prepared by reacting 14400s under 0.5V. After the reaction, the working electrode was rinsed with acetone and hot N, N-dimethylformamide in sequence, and dried with nitrogen.
FIGS. 10 and 11 are SEM and Raman spectra of the synthesized graphite alkyne by potentiostatic method, respectively. As can be seen from FIG. 11, 1388.1cm -1 、1564.7cm -1 、1922.2cm -1 、2168.6cm -1 There appears a Raman absorption peak of 1388.1cm -1 The absorption peak at the position can be attributed to sp in the aromatic ring 2 Breathing vibration mode of hybridized carbon atom, 1564.7cm -1 The absorption peak at the position is formed by sp in the aromatic ring 2 Stretching vibration of the hybridized carbon atom (E 2g Mode) of production, 1922.5cm -1 And 2168.6cm -1 The absorption peak at this point comes from the stretching vibration of the conjugated diacetylene. Namely hexaethynyl benzene is used as a precursor molecule, and the graphite alkyne can be obtained through electrosynthesis by a potentiostatic method.
Example 5
In this example, hexaethynyl benzene is used as a precursor and a constant current method is used to synthesize the graphite alkyne. The method comprises the following steps:
32.77mg of hexa [ tri (silylethynyl) benzene were deprotected in the same procedure as in example 3. The hexaethynyl benzene solid obtained by deprotection is dissolved in 50mL of dimethyl sulfoxide, and is added dropwise into 50mL of a mixed solution of 1mol/L zinc salt/dimethyl sulfoxide solution and 1mL of N, N' -tetramethyl ethylenediamine in 2h in the presence of argon in a dark place, wherein the solution is electrolyte. In the dropping process, the system temperature is kept at 50 ℃, copper foil, platinum sheet and Ag/AgCl electrode are respectively used as a working electrode, a counter electrode and a reference electrode, and the graphite alkyne can be prepared by reacting for 10000 seconds under the condition of 0.001A. After the reaction, the working electrode was rinsed with acetone and hot N, N-dimethylformamide in sequence, and dried with nitrogen.
FIGS. 10 and 11 are SEM and Raman spectra of a constant current process-synthesized graphite alkyne. As can be seen from FIG. 11, 1361.7cm -1 、1548.7cm -1 、1913.2cm -1 、2168.6cm -1 There appears a Raman absorption peak of 1361.7cm -1 The absorption peak at the position can be attributed to sp in the aromatic ring 2 Breathing vibration mode of hybridized carbon atom, 1548.7cm -1 The absorption peak at the position is formed by sp in the aromatic ring 2 Stretching vibration of the hybridized carbon atom (E 2g Mode) of production, 1913.2cm -1 And 2168.6cm -1 The absorption peak at this point comes from the stretching vibration of the conjugated diacetylene. Namely hexaethynyl benzene is used as a precursor molecule, and the graphite alkyne can be obtained through electrosynthesis by a constant current method.
It should be noted that the above-described embodiments are only for explaining the present invention and do not constitute any limitation of the present invention. The invention has been described with reference to exemplary embodiments, but it is understood that the words which have been used are words of description and illustration, rather than words of limitation. Modifications may be made to the invention as defined in the appended claims, and the invention may be modified without departing from the scope and spirit of the invention. Although the invention is described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, as the invention extends to all other means and applications which perform the same function.
Claims (13)
1. A method for synthesizing graphite alkyne comprises the following steps: electrochemical treatment is carried out on electrolyte containing a graphite alkyne precursor and electrolyte by taking a copper foil or a copper-carrying substrate as a working electrode, so as to generate graphite alkyne;
the graphite alkyne precursor has a structure shown in a formula I:
wherein R is hydrogen or alkyne hydrogen protecting group,
the alkyne hydrogen protecting group is-XR 1 R 2 R 3 Wherein R is 1 、R 2 、R 3 Each independently selected from C1-C6 alkyl and cyano-substituted C1-C6 alkyl, X is silicon.
2. The method of synthesis according to claim 1, wherein the electrolyte comprises a zinc salt.
3. The method of synthesis according to claim 2, wherein the zinc salt comprises at least one of zinc chloride, zinc nitrate and zinc acetate.
4. The method of synthesis according to claim 2, wherein the electrolyte further comprises an organic solvent.
5. The method of synthesis according to claim 4, wherein the organic solvent comprises dimethyl sulfoxide.
6. The method of synthesis according to claim 5, wherein the electrolyte further comprises a diamine.
7. The method of synthesis according to claim 6, wherein the diamine comprises N, N' -tetramethyl ethylenediamine.
8. The method of synthesis according to claim 6, wherein the concentration of the graphite alkyne precursor in the electrolyte is 0.01mmol/L to 1mmol/L; and/or
The concentration of the zinc salt is 0.05mol/L to 2mol/L; and/or
The diamine concentration is 0.01mol/L to 0.1mol/L.
9. The method of synthesis according to claim 6, wherein the concentration of the graphite alkyne precursor in the electrolyte is 0.02mmol/L to 0.8mmol/L; and/or
The concentration of the zinc salt is 0.1mol/L to 1mol/L; and/or
The diamine concentration is 0.03mol/L to 0.07mol/L.
10. The synthetic method of any one of claims 1-5 wherein the electrochemical treatment is at a temperature of 20 ℃ to 70 ℃; and/or
The electrochemical treatment time is 0.1h to 12h.
11. The synthetic method of any one of claims 1-5 wherein the electrochemical treatment is at a temperature of 30 ℃ to 60 ℃; and/or
The electrochemical treatment time is 0.2h to 5h.
12. The synthetic method of any one of claims 1-5 wherein the electrochemical treatment comprises:
a) Cyclic voltammetry: the potential window is 0V to 2.5V, the cycle number is 2 to 15, and the sweeping speed is 2mV/s to 10mV/s; or alternatively
B) Potentiostatic method: the initial potential is 0.4V to 0.8V.
13. The synthetic method of any one of claims 1-5 wherein the electrochemical treatment comprises:
d) Cyclic voltammetry: the potential window is 0V to 0.6V, the cycle number is 20 to 180, the sweeping speed is 2 to 10mV/s, or
E) Potentiostatic method: the initial potential is 0.5V to 0.8V; or (b)
F) Constant current method: the current is 0.0001A to 0.001A.
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