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Surface-modified carbon material, and method for producing surface-modified carbon material

外国特許コード F210010507
整理番号 K10514WO
掲載日 2021年7月30日
出願国 中華人民共和国
出願番号 201980016294
公報番号 111936417
出願日 平成31年2月28日(2019.2.28)
公報発行日 令和2年11月13日(2020.11.13)
国際出願番号 JP2019010720
国際公開番号 WO2019168206
国際出願日 平成31年2月28日(2019.2.28)
国際公開日 令和元年9月6日(2019.9.6)
優先権データ
  • 特願2018-036704 (2018.3.1) JP
  • 2019JP10720 (2019.2.28) WO
発明の名称 (英語) Surface-modified carbon material, and method for producing surface-modified carbon material
発明の概要(英語) The present invention is a surface-modified carbon material which comprises graphene having a chemical modification group added to the surface thereof, and in which one-dimensional periodicity corresponding to multiple sites for the addition of the chemical modification group can be observed in a Fourier-transformed image of a scanning probe microscopic image of the surface of the graphene. The surface-modified carbon material according to the present invention has a band gap and therefore can be used as a sensor capable of electronically controling an operation or another electronic device.
従来技術、競合技術の概要(英語) BACKGROUND ART
Documents of the prior art
Patent document
Patent document 1: international publication WO2007/118976A2
Patent document 2: japanese patent laid-open No. 2009-61725
Patent document 3: japanese patent laid-open No. 2012-247189
Non-patent document
Non-patent document 1: navarro, j.j.; leet, s.; calleja, f.; stradi, d.; black, a.; Bernardo-Gavito, r.; garnica, m.; granados, d.; vazquez de Parga, a.l.; peez, e.m.; miranda, R. organic commercial Patterning of Nanostructured graphics with Selectivity at the Atomic level, Nano level, 2016,16,355361.
Non-patent document 2: xia, z.; leonardi, f.; gobbi, m.; liu, y.; bellani, v.; liscio, a.; kovtun, a.; li, R.; feng, x.; orgiu, e.; samori, p.; treossi, e.; palermo, V.Electrochemical function of Graphene at the Nanoscale with Self-Assembling azo salts ACS Nano 2016,10,7125-7134.
Non-patent document 3: cai, j.; ruffieux, p.; jaafar, r.; bieri, m.; braun, t.; blankenburg, s.; muoth, M.; seitsonen, a.p.; saleh, m.; feng, x.; mullen, k.; fasel, R.Atomicaily precision Bottom-Up contamination of Graphene nanoribons.Nature 2010,466,470-473.
Non-patent document 4: rabe, j.p.; buchholz, S.Commmensurationbility and Mobility in Two-Dimensional Molecular Patterns on graphite, science 1991,253,424-427.
Non-patent document 5: li, B.; tahara, k.; adisojoso, j.; vanderlinden, w.; mali, k.s.; de Gendt, s.; tobe, y.; de Feyter, S.Self-Assembled Air-Stable Supermolecular Porous on graphene. ACS Nano 2013,7, 10764-.
Non-patent document 6: tahara, k.; adisojoso, j.; inukai, k.; lei, s.; noguchi, a.; li, B.; vanderlinden, w.; de Feyter, s.; tobe, Y.Harnesing by a Diacetylene Unit a Molecular Design for a Porous Two-Dimensional Network Formation at the Liquid/Solid interface, chem.Commun.2014,50,2831-2833.
Non-patent document 7: tianyuanbang, a development of a precise graphene chemical modification technology based on reactive molecule self-assembly, Japan chemical society, 95 th spring year, 2015 3 months and 27 days.
Non-patent document 8: in order to realize a graphene preparation method with excellent uniformity of a transistor operated in a terahertz band (Japanese: テラヘルツ, working at で and するトランジスタ implementation modes に to けた uniformity に れるグラフェン), three bridge Standby, Ongtian Zheng, Stantanei, Shantazai and Zhonglinlong blogs (Japanese: SEI テクニカルレビュー) No. 191 from 53 to 58.
Non-patent document 9: novoselov, k.s.; geim, A.K.; morozov, s.v.; jiang, d.; zhang, y.; dubonos, s.v.; grigiova, i.v.; firsov, A.A.electric Field Effect in atomic Thin films science 2004,306, 666-one 669.
Non-patent document 10: lian, j.x.; lherbier, a.; wang l.j.; charlier, j. -c.; beljone, d.; olivier, Y.electronic Structure and Charge Transport in nanoscripted graphene.J.Phys.chem.C 2016,120,20024-
Non-patent document 11: greenwood, j.; phan, t.h.; fujita, y.; li, Z.; ivasenko, o.; vanderlinden, w.; van Gorp, h.; frederickx, w.; lu, g.; tahara, k.; tobe, y.; uji-i H.; mertens, s.f.l.; de Feyter, S.public Modification of Graphene and Graphite Using azo Chemistry: Flexible texturing and nanomanization. ACS Nano 2015,5, 5520-.
Non-patent document 12: canado, l.g.; jorio, a.; martins Ferreira, e.h.; stavale, f.; achite, c.a.; capaz, r.b.; moutinho, m.v.o.; lombardo, a.; kulmala, t.s.; ferrari, A.C. Quantifying Defects in Graphene via Raman Spectroscopy at differential Excitation enzymes, Nano Lett.2011,11, 3190-.
特許請求の範囲(英語) [claim1]
1. A surface-modified carbon material having a plurality of chemical modification groups on at least a part of the surface of a carbon material selected from the group consisting of graphene, graphite, a glassy carbon film and a film-like pyrolytic carbon,
it is characterized in that a one-dimensional periodicity corresponding to a plurality of addition positions of the chemical modification group is observed in a Fourier transform image of a scanning probe microscope image of the surface.

[claim2]
2. The surface-modified carbon material as claimed in claim 1, wherein the pitch corresponding to the one-dimensional periodicity is 2 to 10 nm.

[claim3]
3. The surface-modified carbon material as claimed in claim 1 or 2, wherein the carbon material is graphene, and Id/Ig of G-band intensity Ig and D-band intensity Id in Raman spectrum of the surface is 0.2-5.0.

[claim4]
4. The surface-modified carbon material as claimed in claim 1 or 2, wherein the carbon material is graphite, and Id/Ig of G band intensity Ig and D band intensity Id in Raman spectrum of the surface is 0.01 to 0.11.

[claim5]
5. The surface-modified carbon material as claimed in any one of claims 1 to 4, wherein the chemical modification group is an aryl group.

[claim6]
6. The surface-modified carbon material according to claim 5, wherein the aryl group is represented by the following formula (1),
[ chemical formula 1]

In the formula (1), R1、R2And R3Each independently is alkyl, alkenyl, alkynyl, aryl, OR, COOH, SOOH, SOONH2、NO2、COOR、SiR3、H、F、Cl、Br、I、OH、NH2、NHR、NR2CN, CONHR or COH, wherein R is alkyl, alkenyl, alkynyl, aryl or halogen substituent thereof.

[claim7]
7. An organic compound-carbon material composite comprising a carbon material, a thin film and a solvent, wherein the carbon material is selected from the group consisting of graphene, graphite, a glassy carbon film and a film-like thermally decomposed carbon, the thin film is composed of a periodic assembly of an organic compound, the surface of the carbon material is covered with the thin film, the solvent is a nonpolar organic solvent or a low-polarity organic solvent, and the solvent is deposited on the thin film.

[claim8]
8. The organic compound-carbon material composite according to claim 7, wherein the thin film comprises a periodic assembly of the organic compound in which linear alkanes having 15 to 80 carbon atoms or linear alkane derivatives having 10 to 80 carbon atoms are arranged in parallel.

[claim9]
9. The organic compound-carbon material composite according to claim 7, wherein the periodic assembly of the organic compound has polygonal pores.

[claim10]
10. A method for producing a surface-modified carbon material, which comprises a step 1 of forming a thin film on the surface of a carbon material with an organic compound and a step 2 of reacting a chemical modification compound with the surface of the carbon material using the thin film as a mask,
characterized in that the organic compound is a linear alkane having 15 to 80 carbon atoms or a derivative of a linear alkane having 10 to 80 carbon atoms,
the carbon material is selected from graphene, graphite, a glassy carbon film and a film-like pyrolytic carbon,
in the step 1, the organic compound is self-assembled on the surface of the carbon material to form a thin film which is a thin film periodic assembly exhibiting one-dimensional periodicity,
in the step 2, a chemical modification compound is reacted with the surface of the carbon material at the position of the gap in the periodic assembly.

[claim11]
11. The method for producing a surface-modified carbon material as claimed in claim 10, wherein the linear alkane or the linear alkane derivative is a compound represented by the following formula (2),
[ chemical formula 2]

In the formula (2), X represents H, CH3、CF3、CH=CH2C [ identical to ] CH, aryl, F, Cl, Br, I, OH, SH, NH2COH or COOH, Y represents CH2、CF2CH ═ CH, C ≡ C, a 2-valent atomic group formed by removing 2 hydrogen atoms from an aromatic hydrocarbon, O, S, NH, CO, COO, CONH, NHCO, or NHCHX, and Z represents H, CH3Aryl, OH, SH, NH2COH, COOH, COOX, CONH, NHCOX or NHCHX, wherein n is an integer satisfying the condition that the number of carbon atoms in the formula (2) is 15 to 80 in an alkane and 10 to 80 in an alkane derivative.

[claim12]
12. The method for producing a surface-modified carbon material as claimed in claim 10 or 11, wherein the thin film is a monolayer of a layer.

[claim13]
13. The method for producing a surface-modified carbon material as claimed in any one of claims 10 to 12, wherein the chemical modification compound is a compound represented by the following formula (3),
[ chemical formula 3]

In the formula (3), R1、R2And R3Each independently is alkyl, alkenyl, alkynyl, aryl, OR, COOH, SOOH, SOONH2、NO2、COOR、SiR3、H、F、Cl、Br、I、OH、NH2NHR, CN, CONHR or COH, wherein R is alkyl, alkenyl, alkynyl or aryl, Z is halogen atom, BF4、BR4Or PF6Wherein R is4Is alkyl, alkenyl, alkynyl, aryl or halogen substituent thereof.

[claim14]
14. A method for producing a surface-modified carbon material by electrochemically reacting a chemical modification compound with a carbon material using an electrochemical cell provided with a working electrode, a counter electrode, a reference electrode, and an aqueous electrolyte solution,
wherein the working electrode is made of the carbon material selected from the group consisting of graphene, graphite, glassy carbon film and film-like pyrolytic carbon,
the electrolyte aqueous solution is an aqueous solution containing the chemical modification compound,
a liquid medium containing a compound exhibiting periodic self-assembly is disposed between the working electrode and the aqueous electrolyte solution, and the aqueous electrolyte solution and the liquid medium are immiscible with each other.

[claim15]
15. The method for producing a surface-modified carbon material as claimed in claim 14, wherein the compound exhibiting periodic self-assembly is a linear alkane having 15 to 80 carbon atoms or a linear alkane derivative having 10 to 80 carbon atoms.

[claim16]
16. The method for producing a surface-modified carbon material as claimed in claim 15, wherein the linear alkane or the linear alkane derivative is a compound represented by the following formula (2),
[ chemical formula 4]

In the formula (2), X represents H, CH3、CF3、CH=CH2C [ identical to ] CH, aryl, F, Cl, Br, I, OH, SH, NH2COH or COOH, Y represents CH2、CF2CH ═ CH, C ≡ C, a 2-valent atomic group formed by removing 2 hydrogen atoms from an aromatic hydrocarbon, O, S, NH, CO, COO, CONH, NHCO, or NHCHX, and Z represents H, CH3Aryl, OH, SH, NH2COH, COOH, COOX, CONH, NHCOX or NHCHX, wherein n is an integer satisfying the condition that the number of carbon atoms in the formula (2) is 15 to 80 in an alkane and 10 to 80 in an alkane derivative.

[claim17]
17. The method for producing a surface-modified carbon material as claimed in claim 15 or 16, wherein the concentration of the alkane or linear alkane derivative in the liquid medium is 1 μmol/L or more.

[claim18]
18. The method for producing a surface-modified carbon material according to claim 14, wherein the compound exhibiting periodic self-assembly is a dehydrobenzo [12] annulene derivative.

[claim19]
19. The method for producing a surface-modified carbon material as claimed in any one of claims 14 to 18, wherein the liquid medium is obtained by dissolving the compound exhibiting periodic self-assembly in a nonpolar organic solvent or a low-polarity organic solvent.

[claim20]
20. The method for producing a surface-modified carbon material according to claim 19, wherein the nonpolar organic solvent or the low-polarity organic solvent is a fatty acid, an alkyl-substituted benzene, an alkane having less than 20 carbon atoms, an alkanol, a dialkyl ether, a halogenated hydrocarbon, or an aromatic hydrocarbon.

[claim21]
21. The method for producing a surface-modified carbon material as claimed in any one of claims 14 to 20, wherein the concentration of the chemical modification compound in the aqueous electrolyte solution is 0.2 to 10.0 mmol/L.

[claim22]
22. The method for producing a surface-modified carbon material as claimed in any one of claims 10 to 21, wherein the chemical modification compound is a compound represented by the following formula (3),
[ chemical formula 5]

In the formula (3), R1、R2And R3Each independently is alkyl, alkenyl, alkynyl, aryl, OR, COOH, SOOH, SOONH2、NO2、COOR、SiR3、H、F、Cl、Br、I、OH、NH2NHR, CN, CONHR or COH, wherein R is alkyl, alkenyl, alkynyl or aryl, Z is halogen atom, BF4、BR4Or PF6Wherein R is4Is alkyl, alkenyl, alkynyl, aryl or halogen substituent thereof.

[claim23]
23. A surface-modified carbon material having a plurality of chemical modification groups on at least a part of the surface of a carbon material selected from the group consisting of graphene, graphite, a glassy carbon film and a film-like pyrolytic carbon,
wherein the Fourier transform image of the scanning probe microscope image of the surface has a two-dimensional periodicity corresponding to a plurality of addition positions of the chemical modification group,
the surface is provided with 5-15 nm per each region2When the area of (A) is divided, the total number of partitions of the chemical modification group and the total number of partitions are presentThe proportion is more than 70%.

[claim24]
24. The surface-modified carbon material as claimed in claim 23, wherein the ratio is 90% or more.

[claim25]
25. A field effect transistor comprising the surface-modified carbon material according to any one of claims 1 to 6, 23 or 24.

[claim26]
26. A sensor comprising the surface-modified carbon material according to any one of claims 1 to 6, 23 or 24.

[claim27]
27. A light-emitting element comprising the surface-modified carbon material according to any one of claims 1 to 6, 23, or 24.

[claim28]
28. A catalyst comprising the surface-modified carbon material according to any one of claims 1 to 6, 23 or 24.
  • 出願人(英語)
  • JAPAN SCIENCE AND TECHNOLOGY AGENCY
  • Katholieke Universiteit Leuven
  • 発明者(英語)
  • TAHARA KAZUKUNI
  • TOBE YOSHITO
  • ISHIKAWA TORU
  • KUBO YUKI
  • DE FEYTER STEVEN WILLY NICOLAS
  • HIRSCH BRANDON EDWARD
  • LI ZHI
国際特許分類(IPC)
参考情報 (研究プロジェクト等) PRESTO Molecular technology and creation of new function AREA
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