【別紙5】

発光性ナノグラフェン材料

広島大学

大学院先進理工系科学研究科
教授 灰野 岳晴
令和２年１０月１日

1

Carbon Allotropes

Graphene2Graphene

using scotch-tape

HOPGgraphene
Geim, A. K. et al., Science, 2004, 306, 666–669.

Yi, M.; Shen, Z. et al., J. Mater. Chem., 2015, 3, 11700–111715.

3Graphene
Atomic thickness
0.345 nm (3.45 Å)High surface area
> 2,500 m2 g–1

Transparent to light97.7 %

Young’s modulus~130 G Pa

2
sp bonded carbon “polymer”

Zero bandgap
ThermalHigh carrier
conductivity
mobilities>5000 W m–1 K–1>150,000 cm2 V–1s–1High-Frequency Transistors
Capacitors
Transparent electrodes
Sensors4

Oxidative Cutting of Graphite

Oxidation cutting
H2SO4, HNO3

carbon fiber

Oxidation cutting
NaNO3, KMnO4

Ajayan, P. M., Zhu, J.-J. et al., Nano Lett. 2012, 12, 844–849.
H2SO4

Graphite powder
2.15 g W. S. et al., J. Am. Chem. Soc. 1958, 80, 1339.
Hummers,

GQD-1
0.62 gSekiya, R.; Uemura, Y.; Murakami, H.; Haino, T., Angew. Chem. Int. Ed. 2014, 53, 5619–5623.
Sekiya, R.; Uemura, Y.; Naito, H.; Naka, K.; Haino, T., Chem. Eur. J. 2016, 22, 8198-8206.

5

XPS Spectra of GQDs

GQD-1
C sp2
C-O
C sp2

C-O

CO2H

C=O
CO2H

Binding Energy / eV
Shouwu Guo, et al. Chem. Commun.,
2010, 46, 1112–1114.

6

Synthesis of GQD-2

1) (COCl)2, cat. DMF
reflux, 3 days
2)
DMF, Et3N, DMAP
100 oC, 3 days

Sekiya, R.; Uemura, Y.; Murakami, H.; Haino, T., Angew. Chem. Int. Ed. 2014, 53, 5619–5623.

7

Structure of Graphene Edgearmchairzigzag

Sekiya, R.; Uemura, Y.; Murakami, H.; Haino, T., Angew. Chem. Int. Ed. 2014, 53, 5619–5623.

8Edge Structure of GQD

ArmchairZigzag

GQD-1
GQD-2Sekiya, R.; Uemura, Y.; Murakami, H.; Haino, T., Angew. Chem. Int. Ed. 2014, 53, 5619–5623.

9

Thermal Gravimetric Analysis of GQD
60-70 substituents at the periphery
6000

5500
TG / ug5093 ug

50004827 ug
4500
50100

150200250300

Temperature / ºC
Sekiya, R.; Uemura, Y.; Murakami, H.; Haino, T., Angew. Chem. Int. Ed. 2014, 53, 5619–5623.

10Huisgen Cycloaddition Reaction[CuIBr(PPh3)3], CHCl3

R=Sekiya, R.; Uemura, Y.; Murakami, H.; Haino, T., Angew. Chem. Int. Ed. 2014, 53, 5619–5623.

11

TEM Images of GQD functionalized with 3rd Generation Dendron

Sekiya, R.; Uemura, Y.; Murakami, H.; Haino, T., Angew. Chem. Int. Ed. 2014, 53, 5619–5623.

12

Atomic Force Microscopic Images of GQDs

Size of GQDs = ca. 20 nm

100 nm

100 nm

Sekiya, R.; Uemura, Y.; Murakami, H.; Haino, T., Angew. Chem. Int. Ed. 2014, 53, 5619–5623.

13

Morphologies of Dendronized GQDs

R=R=R=Sekiya, R.; Uemura, Y.; Murakami, H.; Haino, T., Angew. Chem. Int. Ed. 2014, 53, 5619–5623.

14

Optimized Structure of GQD with Fréchet’s Dendritic
Wedges.

MacroModel v. 9.1, OPLS2005 force field

15

Photophysical Properties of GQDs

Sekiya, R.; Uemura, Y.; Murakami, H.; Haino, T., Angew. Chem. Int. Ed. 2014, 53, 5619–5623.

16

Photophysical Properties of Dendronized GQDs

1st Generation

2nd Generation

3rd Generation

R=Sekiya, R.; Uemura, Y.; Murakami, H.; Haino, T., Angew. Chem. Int. Ed. 2014, 53, 5619–5623.

17

White-Light-Emission from Dendronized GQDs

360 nm

380 nm

1st2nd3rd360 nm

360 nm

360 nmDendronizedSekiya, R.; Uemura, Y.; Murakami, H.; Haino, T., Angew. Chem. Int. Ed. 2014, 53, 5619–5623.GQDs
GQD-218

CIE 1931 Color Space

0.8

1st generation
360 nm, x = 0.336, y = 0.394

0.6

380 nm, x = 0.240, y = 0.265

360 nm, x = 0.223, y = 0.214

2nd generation

Y 0.4

360 nm, x = 0.340, y = 0.392

0.2

3rd generation
0.00.0360 nm, x = 0.324, y = 0.383

0.2X0.40.6

Sekiya, R.; Uemura, Y.; Murakami, H.; Haino, T., Angew. Chem. Int. Ed. 2014, 53, 5619–5623.

19

Cyclic Voltammetry–––e–e–＋

R=
R=
R=0.0

R=
–2.0

–1.5

–1.0

–0.5

0.0

Potential / V
Solvents = chlorobenzene + acetonitrile (1:1, v/v), supporting Electrolyte = n-Bu4N PF6, scan rate = 0.05 Vs–1.
All starting potentials are 0.0 V and are relative to the Ag/Ag+ reference electrode20

Reduction Potentials of GQDs
GQD-1: R =2: R =
3: R =
Model-1–4

4: R =

R

E1,red / V

E2,red / V

E2,red / V b ELUMO / eV EHOMO / eV Eg / eVEg, opt / eV

GQD-1 –0.74
GQD-2 –0.60
GQD-3 –0.74
GQD-4 –0.75

–1.32
–1.55
–1.36
–1.33

0.30
0.11
0.26
0.29

2.00
2.07
2.10
2.00

Model-1 –1.62––

Model-2 –1.66––

Model-3 –1.61––

Model-4 –1.64–––3.91
–4.05
–3.91
–3.90

–6.01
–6.04
–5.95
–5.97

2.10
1.99
2.04
2.07

a 0.6 mg mL–1 of the organic solution was used in each analysis. The measurements were carried out under N atmosphere.
2b E2,red = E2,red (GQD-X) – E1,red (Model-1) .

c Determined by photoemission yield spectroscopy.

21Plausible Edge Structures

FGFG

22

Benzimidazole Derivatives

NH2
H2N

△H2N

dicarboxylic acid anhydrides

diamines

P. Anzenbacher Jr, et al., Org. Lett. 2011, 18, 4882-4885
P. Anzenbacher Jr, et al., Chem. Eur. J. 2014, 20, 11835-1184623

Edge Functionalization

1) (COCl)2, DMF
2)

DMAP, TEA, DMF

Yamato, K.; Sekiya, R.; Suzuki, K.; Haino, T., Angew. Chem. Int. Ed. 2019, 58, 9022-9026.

24

Edge Functionalization
1) (COCl)2, DMF
2)

DMAP, TEA, DMF

Band gap: 2.20 eVBand gap: 1.27 eV
LUMO -4.04 eV

800300500700
Wavelength / nm

1000

90025

Edge Functionalization
1) (COCl)2, DMF
2)

GQD-1b243 mg

Graphene Oxide
84 mg
DMAP, TEA, DMF

Band gap: 2.20 eVBand gap: 0.96 eV
LUMO -4.40 eV

800300500700
Wavelength / nm

1200

900
26

Chiral Nanograohenes with Twisted π-Surface

Nishitani, S.; Sekiya, R.; Haino, T., Angew. Chem. Int. Ed., 2020, 59, 669-673. (Hot Paper)

27

Chiral Nanograohenes with Twisted π-Surface(R)-, (S)30
3Δε / L mol–1 cm–1

X=H00

CD / mdeg–30–3300

500
Wavelength / nm

700

Nishitani, S.; Sekiya, R.; Haino, T., Angew. Chem. Int. Ed., 2020, 59, 669-673. (Hot Paper)
28

Chiral Nanograohenes with Twisted π-Surface(R)-, (S)1.5

CD / mdeg

X = Br0–1.5300500
Wavelength / nm

700

Nishitani, S.; Sekiya, R.; Haino, T., Angew. Chem. Int. Ed., 2020, 59, 669-673. (Hot Paper)
29

Chiral Nanograohenes with Twisted π-Surface＋−30

Estimation of Edge Structure(P)-twist
Nanographene Sheet(M)-twist+1.34 kJ mol–1
Gaussian 09, M06-2X / 6-31G(d,p)
Nishitani, S.; Sekiya, R.; Haino, T., Angew. Chem. Int. Ed., 2020, 59, 669-673. (Hot Paper)

31

Graphene Supramolecular Polymer

Uemura, Y.; Sekiya, R.; Yamato, K.; Haino, T., Angew. Chem. Int. Ed. 2018, 57, 4960–4964.

32

Gelation of Networked Graphene

UPy＝Bn＝UPy = 0 %UPy = 8 %UPy = 13 %UPy = 19 %2.7 g L-1

2.0 g L-1

solvent: 1-decanol
C: 4.0 mg mL-1
T: 20 °C
33

Gelation of Networked Graphene

UPy = 19 %
UPy＝
Bn＝

[inhibitor] / mM:

0.0

0.12

0.25

0.32

0.49solvent: 1-decanol
C: 20 mg mL-1
34

本技術に関する知的財産権• 発明の名称 ：グラフェン構造体• 出願番号 ：特願2014-235842
：広島大学
• 出願人
：灰野 岳晴，関谷 亮
• 発明者

35

産学連携の経歴• 2016年- 積水化学工業株式会社と共同研究実施• 2007年-2008年 JST A-STEP事業に採択36

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e-mail ykondok@hiroshima-u.ac.jp37