CN111574465B - Soluble graphyne derivative and preparation method and application thereof - Google Patents
Soluble graphyne derivative and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of functional materials, and particularly relates to a soluble graphdiyne derivative and a preparation method and application thereof. Compared with the solubility of the graphdine in the organic solvent, the product of the invention has greatly improved solubility. For example, the product of the invention has good solubility in polar organic solvents such as dichloromethane, chlorobenzene, N-methylpyrrolidone (NMP), tetrahydrofuran and the like, and the concentration of the product in the chlorobenzene can be as high as 5mg/ml‑1The problem that the graphdiyne is difficult to disperse or dissolve in the solution is solved, and the method has great application value.
Description
Technical Field
The invention belongs to the technical field of functional materials, and particularly relates to a soluble graphdiyne derivative and a preparation method and application thereof.
Background
Graphyne (graphydine, abbreviated as "GDY"), a novel carbon allotrope formed by sp and sp2 hybridization, namely 1, 3-diyne bond, connects benzene rings in a conjugated way to form a two-dimensional planar network structure. The group of topics of li-yuelian academy was internationally obtained for the first time by Chemical synthesis (g.x.li, y.l.li, h.b.liu, y.b.guo, y.j.li, d.b.zhu, Chemical Communications 2010,46,3256), and basic and application studies of graphdine have achieved significant success in the fields of energy storage, catalysis, and semiconductor devices, and have rapidly become a new field in carbon material Research (y.j.li, l.xu, h.b.liu, y.l.li, Chemical Society Reviews 2014,43, 2572; z.y.jia, y.j.li, z.c.zuo, h.b.liu, c.s.ang, y.l.li, y.research of Chemical Research, 50, 2470). However, the application of graphene is mostly realized by in situ synthesis (c.s.huang, s.l.zhang, h.b.liu, y.g.li, g.l.cui, y.l.li, Nano Energy 2015,11,481) or ultrasonic pulverization (z.w.jin, q.zhou, y.h.chen, p.mao, Li, h.h.b.liu, j.z.wang, y.l.li, Advanced Materials 2017,28,3697), or the addition of a co-solvent (s.l.li, y.h.chen, h.b.liu, y.x.wang, l.b.liu, f.t.lv, y.l.li, s.wang, Chemistry of Materials 2017,29,6087), and the same carbon nanotube as other graphene (carbon nanotube) is a difficult to disperse in carbon Materials, and is a key element for fullerene development. Therefore, the preparation of soluble graphdiyne materials is particularly important, but no relevant research and report exists at present.
Disclosure of Invention
In order to solve the above problems, embodiments of the present invention provide a soluble graphyne derivative represented by the following formula (I),
wherein R is1Selected from the following groups, unsubstituted or optionally substituted with one, two or more Rs: c4-20Alkyl radical, C4-20An alkoxy group;
rs is selected from halogen, OH, NH2、CN、NO2、C4-20Alkyl or C4-20An alkoxy group;
n is a number of 1 or more;
wherein the content of the first and second substances,
and (b) represents a connection site.
Preferably, said R is1Is selected from C6-18A linear or branched alkyl group;
n is selected from the group consisting of 1-200.
Also preferably, the soluble graphdine derivative of formula (I) is selected from the following structures:
wherein x is 6, 12 or 18.
Embodiments of the invention also provide forA method for preparing a soluble graphdine derivative, comprising: reacting graphyne with compound N3-R1In the presence of a copper (I) catalyst, performing a Husige cycloaddition reaction to obtain the compound N3-R1In R1Has the definition as described above.
Preferably, the copper catalyst is selected from monovalent copper containing compounds, for example at least one selected from cuprous iodide, cuprous oxide, tetrakis (acetonitrile) copper (I) tetrafluoroborate.
According to an embodiment of the invention, the method further comprises a step of preparing the graphdiyne, said step comprising: and dropwise adding the pyridine solution of hexaethynylbenzene into the pyridine solution soaked with the copper sheet to react to obtain the graphyne.
According to an embodiment of the invention, hexaethynylbenzene, compound N3-the ratio of the amount of R to the amount of copper (I) catalyst specie is 1: 6-9: 0.01 to 0.05.
According to an embodiment of the invention, the reaction is carried out in an organic solvent, for example in N, N dimethylformamide, acetonitrile or the like.
According to an embodiment of the invention, the reaction is carried out in an inert gas atmosphere.
According to an embodiment of the present invention, the temperature of the reaction may be 40 to 80 ℃, preferably 50 to 60 ℃; the time is 8-120 h, preferably 48-72 h.
According to an embodiment of the invention, the method further comprises a post-treatment step comprising: and (3) after the reaction is finished, washing the product by using an alcoholic solution and an aqueous solution of hydrochloric acid, and freeze-drying after the washing is finished.
The invention also provides application of the graphdine derivative, which can be used in the fields of solar cells, energy storage, photoelectricity, optics, catalysis, separation and purification, sensing and the like.
Advantageous effects
Compared with the solubility of the graphdine in the organic solvent, the product of the invention has greatly improved solubility. For example, the product of the invention has good solubility in polar organic solvents such as dichloromethane, chlorobenzene, N-methyl pyrrolidone (NMP), tetrahydrofuran and the like, for example, in chlorobenzeneThe product concentration can be up to 5mg/ml-1The problem that the graphdiyne is difficult to disperse or dissolve in the solution is solved, and the method has great application value.
In addition, the product of the invention also has the advantages of good film forming property and the like. Finally, the product of the invention has simple reaction condition and quick reaction; the yield is high; the reaction has strong stereoselectivity; raw materials and reaction reagents are easy to obtain; the method has the advantages of being in line with the advantages of atom economy and the like, and therefore, the method has higher practicability.
Definition and description of terms
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the claimed subject matter belongs.
The term "halogen" includes F, Cl, Br or I.
The term "C4-20Alkyl is understood to preferably mean a straight-chain or branched, saturated monovalent hydrocarbon radical having from 4 to 20 carbon atoms, preferably C6-20An alkyl group. "C6-20Alkyl "is understood to preferably mean a straight-chain or branched, saturated monovalent hydrocarbon radical having 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20 carbon atoms. The alkyl radical being, for example, C6、C12Or C18A straight or branched chain saturated monovalent hydrocarbon group.
The above for the term "alkyl", e.g. "C4-20The definition of alkyl "applies equally to compounds containing" C4-20Other terms for alkyl radicals, e.g. the term "C4-20Alkoxy ".
Hereinafter 6C represents R in the product1Selected from linear alkyl groups of 6 carbons.
Hereinafter 12C represents R in the product1Is a linear alkyl group with 12C.
Hereinafter 18C denotes R in the product1Is a linear alkyl group of 18 carbons.
Drawings
FIG. 1 is a scheme showing the synthesis of soluble graphyne prepared in examples 1-3 of the present invention.
Fig. 2 is a raman spectrum of the soluble graphdine derivative prepared in examples 1 to 3 of the present invention.
FIG. 3 is a full scanning photoelectron spectrum of the graphyne and soluble graphyne (grafted 6C, 12, 18C) prepared in examples 1, 2 and 3 of the present invention.
FIG. 4 is a narrow sweep of the C1 s and N1 s photoelectron spectra of graphdine prepared according to an embodiment of the present invention.
FIG. 5 is a narrow sweep of the C1 s and N1 s photoelectron spectra of the soluble graphdine derivative (18C) prepared in example 1 of the present invention.
FIG. 6 is a narrow sweep of the C1 s and N1 s photoelectron spectra of the soluble graphdine derivative (12C) prepared in example 2 of the present invention.
FIG. 7 is a narrow sweep of the C1 s and N1 s photoelectron spectra of the soluble graphdine derivative (6C) prepared in example 3 of the present invention.
FIG. 8 is a photograph showing the soluble graphdine derivative (18C) prepared in example 1 of the present invention dissolved in various solvents (solvents used from left to right are, in order, dimethyl sulfoxide, N-dimethylformamide, N-methylpyrrolidone, tetrahydrofuran, chlorobenzene, dichloromethane, methanol, toluene, ethyl acetate, acetone, chloroform, and N-hexane).
FIG. 9 is a photograph showing that the soluble graphtylene derivative (18C) prepared in example 1 of the present invention was dissolved in chlorobenzene in a large amount.
FIG. 10 is a photograph showing the dissolution of soluble graphdine derivatives (12C, 6C) prepared in examples 2 and 3 of the present invention in chlorobenzene and tetrahydrofuran.
Fig. 11 is a scanning electron microscope picture of a flail film of the soluble graphdine derivative (18C) prepared in example 1 of the present invention after dissolving in chlorobenzene (four pictures represent the detection results of different resolution scanning electron microscopes).
Detailed Description
The technical solution of the present invention will be further described in detail with reference to specific embodiments. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
Unless otherwise indicated, the raw materials and reagents used in the following examples are all commercially available products or can be prepared by known methods.
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.
Hexaalkynylbenzenes used in the following examples can be synthesized by reference to the following references: preparation of G.X.Li, Y.L.Li, H.B.Liu, Y.B.Guo, Y.J.Li, D.B.Zhu, chem.Commun.2010,46,3256-3258. soluble graphdine
Example 1
Dissolving hexaalkynyl benzene (81.4mg, 0.366mmol) in pyridine, adding dropwise into pyridine soaked with copper sheet, reacting at 80 deg.C for one day, taking out copper sheet with graphyne, adding octadecyl azide (18C-N) dissolved therein3) (1.1g, 3.3mmol) and CuI (3.5mg, 0.018mmol) in N, N dimethylformamide at 60 ℃ for three days. And washing the hydrochloric acid with methanol and aqueous solution, and freeze-drying to obtain the soluble graphdiyne derivative (18C). The results of the product characterization are shown in FIGS. 2 and 5, and it can be seen from the results in FIGS. 2 and 5 that the diacetylene bond in the structure of the derivative after the reaction is 2172.3cm compared with that of graphyne-1Moved to 2210.2cm-1And the ratio of the D peak to the G peak is from 0.727 to 0.827; the appearance of a new chemical environment N atom in the photoelectron spectrum of the nitrogen atom in fig. 5 demonstrates the successful modification of graphdine.
The obtained 2mg of the product was dissolved in different solvents, and the dissolution results are shown in FIG. 8. As can be seen from FIG. 8, the product of the present application has good solubility in different organic solvents, and the calculated dissolution amounts from left to right are 0.4, 0.2, 0.95, 0.55, 0.85, 0.3, 0.85, 0.35, 0.5, 0.85, 0.35mg/ml respectively. The product is added to the chlorobenzene continuously, the solubility in chlorobenzene is calculated to be up to 5mg/ml-1。
Examples 2,
Dissolving hexaalkynyl benzene (81.4mg, 0.366mmol) in pyridine, adding dropwise into pyridine soaked with copper sheet, reacting at 80 deg.C for one day, taking out copper sheet with graphyne, adding octadecyl azide (12C-N) dissolved therein3) (822.492mg, 3.3mmol) and CuI (3.5mg, 0.018mmol) in N, N dimethylformamide at 60 deg.CThree days should be used. And washing the hydrochloric acid with methanol and aqueous solution, and freeze-drying to obtain the soluble graphdiyne derivative (12C). The results of the product characterization are shown in FIGS. 2 and 6, and it can be seen from the results in FIGS. 2 and 6 that the diacetylene bond in the structure of the derivative after the reaction is 2172.3cm compared with that of graphyne-1Moved to 2218.5cm-1And the ratio of the D peak to the G peak is from 0.725 to 0.864; the appearance of a new chemical environment N atom in the photoelectron spectrum of the nitrogen atom in fig. 6 demonstrates the successful modification of graphdine.
2mg of the obtained product was dissolved in chlorobenzene and tetrahydrofuran, respectively, and the result is shown as a in FIG. 10. As can be seen from a in FIG. 10, the product of the present application has good solubility in both chlorobenzene and tetrahydrofuran, calculated as 0.9, 0.85 mg/ml.
Examples 3,
Dissolving hexaalkynyl benzene (81.4mg, 0.366mmol) in pyridine, adding dropwise into pyridine soaked with copper sheet, reacting at 80 deg.C for one day, taking out copper sheet with graphyne, adding octadecyl azide (6C-N) dissolved therein3) (544.731mg, 3.3mmol) and CuI (3.5mg, 0.018mmol) in N, N dimethylformamide at 60 ℃ for three days. And washing the hydrochloric acid with methanol and aqueous solution, and freeze-drying to obtain the soluble graphdiyne derivative (6C). The results of the product characterization are shown in FIGS. 2 and 7, and it can be seen from the results in FIGS. 2 and 7 that the diacetylene bond in the structure of the derivative after the reaction is 2172.3cm compared with that of graphyne-1Moved to 2216.2cm-1And the ratio of the D peak to the G peak is from 0.727 to 0.847; the appearance of a new chemical environment N atom in the photoelectron spectrum of the nitrogen atom in fig. 7 demonstrates the successful modification of graphdine.
2mg of the obtained product was dissolved in chlorobenzene and tetrahydrofuran, respectively, and the result is shown as b in FIG. 10. As can be seen from b in FIG. 10, the product of the present application has good solubility in both chlorobenzene and tetrahydrofuran, calculated as 0.85m, 0.8 mg/ml.
The results of the film forming tests of the graphdiyne and the product of example 1 are shown in fig. 11, and it can be seen from the results of fig. 1 that the product of the present application also has improved film forming properties.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (11)
1. A soluble graphyne derivative represented by the following formula (I),
wherein R is1Selected from the following groups, unsubstituted or optionally substituted with one, two or more Rs: c4-20Alkyl radical, C4-20An alkoxy group;
rs is selected from halogen, OH, NH2、CN、NO2、C4-20Alkyl or C4-20An alkoxy group;
n is a number of 1 or more;
wherein the content of the first and second substances,
and (b) represents a connection site.
2. The soluble graphdine derivative according to claim 1, wherein in formula (I), R is1Is selected from C6-18A linear or branched alkyl group;
n is an integer from 1 to 200.
3. The soluble graphdiyne derivative according to claim 1 or 2, wherein the soluble graphdiyne derivative represented in formula (I) is selected from the following structures:
wherein x is 6, 12 or 18.
4.A process for the preparation of a soluble graphdine derivative of formula (I) according to any one of claims 1 to 3, comprising: reacting hexaethynylbenzene with compound N3-R1In the presence of a copper catalyst, performing a Husige cycloaddition reaction to obtain the compound N3-R1In R1Having the definitions set out in any one of claims 1 to 3.
5. The method of claim 4, wherein the copper catalyst is selected from monovalent copper-containing compounds.
6. The method for preparing according to claim 4 or 5, further comprising a step of preparing graphdiyne, the step comprising: and dropwise adding the pyridine solution of hexaethynylbenzene into the pyridine solution soaked with the copper sheet to react to obtain the graphyne.
7. The process according to any one of claims 4 to 5, wherein hexaethynylbenzene, Compound N3-R1The amount ratio to the copper catalyst species was 1: 6-9: 0.01 to 0.05.
8. The production method according to any one of claims 4 to 5, wherein the reaction is carried out in an inert gas atmosphere.
9. The method according to any one of claims 4 to 5, wherein the reaction temperature is 40 to 80 ℃.
10. Use of the soluble graphdine derivative of formula (I) according to any one of claims 1-2 in the fields of energy storage, photovoltaics, catalysis, separation and purification.
11. Use of the soluble graphdine derivative of formula (I) according to any one of claims 1 to 2 in the fields of solar cells, optics and sensing.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101774570A (en) * | 2010-01-27 | 2010-07-14 | 中国科学院化学研究所 | Method for preparing graphite alkyne film |
| CN102120571A (en) * | 2011-03-28 | 2011-07-13 | 中国科学院化学研究所 | Graphite alkyne nanowire and preparation method thereof |
| CN102417476A (en) * | 2011-08-30 | 2012-04-18 | 同济大学 | Synthesis method of soluble fulleropyrrolidine derivate |
| 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 |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101774570A (en) * | 2010-01-27 | 2010-07-14 | 中国科学院化学研究所 | Method for preparing graphite alkyne film |
| CN102120571A (en) * | 2011-03-28 | 2011-07-13 | 中国科学院化学研究所 | Graphite alkyne nanowire and preparation method thereof |
| CN102417476A (en) * | 2011-08-30 | 2012-04-18 | 同济大学 | Synthesis method of soluble fulleropyrrolidine derivate |
| 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 |
Non-Patent Citations (2)
| Title |
|---|
| "Architecture of graphdiyne nanoscale films";Guoxing Li等;《Chem. Commun.》;20100111;第46卷;第3256–3258页 * |
| "石墨烯的功能化修饰研究进展";杨丽龙等;《中国胶粘剂》;20160831;第25卷(第8期);第475-478页 * |
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