Press Release: The 1996 Nobel Prize in Chemistry

KUNGL. VETENSKAPSAKADEMIEN
THE ROYAL SWEDISH ACADEMY OF SCIENCES
9 October 1996

The Royal Swedish Academy of Sciences has decided to award the 1996
Nobel Prize in Chemistry to

Professor Robert F. Curl, Jr., Rice University, Houston, USA,

Professor Sir Harold W. Kroto, University of Sussex, Brighton, U.K., and
Professor Richard E. Smalley, Rice University, Houston, USA,

for their discovery of fullerenes.

R.F. Curl H.W. Kroto R.E. Smalley

C60 survives surface collisions
with velocities up to 25000 km/h.
Up to 10 electrons can be
removed before the cage
disintegrates.

Inside C60 there is a

perfect vacuum. Thus it
can be filled with all
elements and many small
molecules.
1922 discovered by Mary Lea Heger ~ 600 lines
PAHs and carbon clusters expected
No agreement with laboratory measurements or theoretical
calculations until July 2015
 Ion yield (arb. units)

Cluster size (n)

O. Hahn, F. Strassmann, J. Mattauch, H. Ewald, Naturwiss. 30 (1942) 541

H. Hintenberger and E. Dörnenburg, Z. Naturforschg. 14a (1959) 765

O. Hahn, F. Straßmann, J. Mattauch and H. Ewald, Naturwiss. 36 (1942) 541

H. Hintenberger and E. Dörenburg, Z. Naturforschg. 14a (1959) 765

D.E.H. Jones (Pseudonym Daedalus), New Scientist 32 (1966) 245

E. Osawa, Kagaku (Kyoto) 25 (1970) 854

D.A. Bochvar and E.G. Gal'pern, Proc. Acad. Sci. USSR 209 (1973) 239

E.A. Rohlfing, D.M. Cox and A. Kaldor, J. Chem. Phys. 81 (1984) 3322

H.W. Kroto, J.R. Heath, S.C. O'Brien, R.F. Curl and R.E. Smalley, Nature
318 (1985) 162

W. Krätschmer, K. Fostiropoulos and R.D. Huffman, Nature 347 (1990) 354

E.A. Rohlfing, M.D. Cox and A. Kaldor, J. Chem. Phys. 81 (1984) 3322
H.W. Kroto, J.R. Heath, S.C. O'Brien, R.F. Curl and R.E.
Smalley, Nature 318 (1985) 162
W. Krätschmer, K. Fostiropoulos and R.D. Huffman, Nature 347 (1990) 354
 Graphite
Diamond

Buckminster Fullerene C60

Strictly speaking only fullerenes are made exclusively from carbon.

 Diamonds are not rare (135 million carats are mined per year)
Diamonds have not always been a symbol of eternal love (3-months salary
rule)
Mining destroys the environment and working conditions are ghastly
A diamond loses up to 50% of its value as soon as you buy it from the
jeweler
CVD formed diamonds have down to ppb range defects while natural
diamonds contain up to 0.3% nitrogen (gives them a yellowish color)
Synthesized diamonds cost as little as 15 cents/carat
The Cullinan is the largest natural diamond (3100 carats, 620 g) and the
Great Star of Africa (530 carats) is the largest clear cut diamond – optical
windows for high-power lasers can reach more than 1000 carats
The environmental impact of a mined diamond is about seven times more
than that of a grown diamond

https://www.feedough.com/diamond-marketing-de-beers/
Diamant

Lonsdaleite

Q-carbon

Narayan/Bhaumik, APL 2015

DOI: 10.1063/1.4936595
Linear acetylenic carbon

Amorphous carbon

Chaoite
= Vertices - Edges + Faces

Cube: 8 - 12 + 6 = 2
Tetrahedron: 4 - 6 + 4 =2
Cube: 8 - 12 + 6 = 2
Octahedron: 6 - 12 + 8 = 2
Dodecahedron: 20 - 30 + 12 = 2
Icosahedron: 12 - 30 + 20 = 2
Truncated icosahedron: 60 - 90 + 32 = 2
Sphere: 2 - 1 + 1 =2
Torus: 1 - 2 + 1 =0
Prezel: 4 - 10 + 2 =-4

Any closed polyhedron has an Euler number of 2

Fullerenes consist only of hexagons and pentagons

from the Euler number we can deduce the following:

H:=number of hexagons
• the number of pentagons
P:=number of pentagons
is 12
• any number of hexagons is possible
a hexagon has 6 vertices, 6 edges and 1 face
• a pentagon
the smallest
has 5fullerene
vertices, 5isedges
the pentagon
and 1 facededecahedron
each vertex is shared by 3 faces
• each
each hexagon
edge is sharedincreases
be 2 facesV (number of C atoms) by 2
• only even numbered fullerenes exist
E=(6H+5P)/2 V=(6H+5P)/3 F=H+P
2=V-E+F=[2(6H+5P)-3(6H+5P)+6(H+P)]/6
12=P
 V=2H+20
In all of the fullerenes synthesized so far, each pentagon is
surrounded by hexagonal rings. Indeed, this has been proposed
as a criterion for fullerene stability-the 'isolated-pentagon rule'-on
the basis that adjacent pentagons are expected to be chemically
reactive.

C60 is the smallest fullerene that fulfills the IPR

C70 is the next larger one
For both exists only one isomeric IPR form.
Larger fullerenes exhibit several IPR isomers:
C78 : 4, C80 : 7, C82 : 9, C88 : 35

Petrie et al. Nature 365 (1993) 426

Fowler et al. The Fullerenes (eds. H. Kroto et al.) Pergamon Press, Oxford (1993) 97
 Laser vaporization and supersonic expansion
Neutral, negatively and
Arc discharge in inert atmosphere
positively charged
Fullerene synthesis in combustion
clusters
Yield: are produced.
up to 14% of the
soot 90% C60, ~10% C70
Fullerenes naturally formed

In sooting flames (69 Torr, 25% He, C/O ratio 0.989 up to 20% of
the soot mass are fullerenes. The ratio of C70/C60 can be tuned
from 0.26 - 8.8 (compared to 0.02 - 0.18 for arc discharge).
Kroto et al., Nature 318 (1985) 162
von Helden
Howard et al., J.
et al. US-patent Chem. Phys
5,273,729 97 (1993) 8182
(1993);
Nature 352
Smalley (1991)
et al. 139 5,227,038 (1993)
US-patent
Becker et al. Science 265 (1994) 642
J. Cami et al. Science 329 (2010) 1180-1182
 HeC60+

E.K. Campbell et al. Nature 523 (2015) 322

G.A.H. Walker et al. APJL 812 (2015) L8

HPLC of solvated fullerenes;
benzene, toluene, ...

1992: 1g pure C60: 3000$

Nov.
Price2023: 1g 99.8
for the large %C
scale 60 :
production of fullerenes is189$
defined
1g the
by the costs for 99.99% sublimed
electricity C60 :be expected
and can 330$
to be a
few dollars per1gkilogram.
99.0% C70 : 395$
1g 99.0% C84: 201400 $

1g gold (13.11.2023): 62.35 $

http://www.mercorp.com/mercorp/fullbro.pdf
http://www.sesres.com/default.htm
Entwicklung des Goldpreis in $/Unze (31.103 g) inflationsbereinigt
 Can C60 in Olive Oil Double Your Life Span?

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Oil Extra Virgin, Cert. Organic
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Does C60 Expand the Lifespan of Humans?

https://vitalityc60.com/can-taking-c60-infused-olive-oil-increase-your-lifespan/
111 times cited
478 times cited
Rohlfing et al. J. Chem. Phys. 81 (1984) 3322

Kroto et al., Nature 318 (1985) 162

O´Brien et al. J. Chem. Phys. 88 (1988) 220

>19 eV of excitation necessary

shrink-wrapping to C32+

unusually high stability of C60+

 8
C44+ C K +
7 C48+ C50K+ 50 56

C52K+
6 C46 + 48

C46K+
5 C42 +
52 54

C44K+
4
3

Ion signal (arb units)

2
1
0
500 550 600 650

C60+ C64+

C54Cs+
6 C56+
5 C58+

C52Cs+
C50Cs+
4
Cet
Heath +al. J. Am. Chem. Soc. 107 (1985) 7779

+
3 54

C48Cs
2
C62+
1
0
650 700 750
Weiss et al. J. Am. Chem. Soc. 110 (1988) 4464
Mass per charge (Thomson)
During the arc discharge about one C60 in one million
molecules is filled with a helium atom
Helium filled C60 in meteor craters:
3
He ratio not from earth
Becker et al. Science 272 (1996) 249

Incorporation of He and Ne by fast C60+

Weiske et al. J. Phys. Chem. 95 (1991) 8451

pressure % of % occupancy
gas (bar) recovery C60 C70
Inflating C60 at
Ne 2620 66 0.2 0
high pressure Ar 2758 45 0.3 0.2
Saunders et al. J. Am. Chem. Kr 1689 25 0.3 0.2
Soc. 116 (1994) 2193
Xe 1241 45 0.008 0.04
S. Bloodworth and R.J. Whitby,
Comm. Chem. 5 (2022) 121
S. Bloodworth and R.J. Whitby,
Comm. Chem. 5 (2022) 121
von Helden et al., J. Chem. Phys 97 (1993) 8182
M. Kumar, Carbon Nanotube Synthesis and Growth
Mechanism. Nanotechnology and Nanomaterials » "Carbon
Nanotubes - Synthesis, Characterization, Applications“ DOI:
10.5772/19331
L.V. Radushkevich & V.M. Lukyanovich, O strukture ugleroda, obrazujuce gosja pri
termiceskom razlozenii okisi ugleroda na zeleznom kontakte. Zurn Fisic Chim 26
(1952) 88-95 – hollow graphitic carbon fibers 50 nm in diameter
L.J.E. Hofer, E. Sterling & J.T. McCartney, Structure of the carbon deposited from
carbon monoxide on iron, cobalt and nickel. J. Chem. Phys. 59 (1955) 1153–1155.
doi:10.1021/j150533a010 – growth of tubular carbon filaments 10-200 nm in
diameter
M. Hillert & N. Lange, The Structure of Graphite Filaments. Z. Kristallogr. 111 (1958)
23–34. doi:10.1524/zkri.1959.111.1-6.24 – growth of nanoscale tubular carbon
filaments from n-heptane decomposition on iron at about 1000°C
Roger Bacon, Growth, Structure, and Properties of Graphite Whiskers. J. Appl.
Phys. 31 (1960) 283. doi:10.1063/1.1735559 – concentric cylinders of rolled-up
graphene sheets formed in an arc discharge (MWCNT)
W. Bollmann & J. Spreadborough, Action of Graphite as a Lubricant. Nature 186
(1960) 29-30. doi:10.1038/186029a0 – electron microscope picture clearly shows
MWCNT
M.L. Lieberman, C.R. Hills & C.J. Miglionico, Growth of graphite filaments. Carbon 9
(1971) 633–635. doi:10.1016/0008-6223(71)90085-6 – TEM images and diffraction
data show MWCNT
A. Oberlin, M. Endo, T. Koyama, Filamentous
growth of carbon through benzene decomposition.
Journal of Crystal Growth 32 (1976) 335-349 –
hollow tubes, probably SWCNT
Arthur C. Clarke: science fiction novel “The
Fountains of Paradise” (1979) – popularizes the
idea of a space elevator using a continuous
pseudo-one dimensional diamond crystal
T. Koyama and M.T. Endo, (1983) "Method for
Manufacturing Carbon Fibers by a Vapor Phase
Process," Japanese Patent 1982-58, 966 -
continuous or floating-catalyst process
Howard G. Tennent of Hyperion Catalysis, (1987)
U.S. Patent 4 663 230 – for graphitic, hollow core
"fibrils"
S. Iijima of NEC, Helical microtubules of graphitic
carbon. Nature 354 (1991) 56–58.
doi:10.1038/354056a0 – diffraction pattern proofs
helical SWCNT and MWCNT
Al Harrington and Tom Maganas of Maganas
Industries, (1991) U.S. Patent 5 143 745 –
monomolecular thin film nanotube coatings
 W.A. de Heer, A. Châtelain and D. Ugarte; A Carbon Nanotube Field-Emission
Electron Source. Science 270 (1995) 1179. DOI: 10.1126/science.270.5239.1179 –
0.1 mA/cm-2 for voltages as low as 200V

TU-Delft

Z. Chen et al. Appl. Phys. Lett. 90 (2007)

133108; doi: 10.1063/1.2717530

S.H. Heo et al. Appl. Phys. Lett. 90 (2007)

183109; doi: 10.1063/1.2735549
C. Philip et al. Engineering Carbon Nanotubes and Nanotube Circuits Using
Electrical Breakdown. Science 292 (2001) 706–709, doi:10.1126/science.1058782. –
first report on a technique for separating semiconducting and metallic nanotubes
K. Jiang et al. Nanotechnology: Spinning continuous carbon nanotube yarns. Nature
419 (2002) 801, doi:10.1038/419801a
2002: Multi-walled nanotubes demonstrated to be fastest known oscillators (> 50
GHz)
2003: NEC announced stable fabrication technology of carbon nanotube transistors.
L.X. Zheng, et al. Ultralong single-wall carbon nanotubes. Nature Materials 3 (2004)
673–676, doi:10.1038/nmat1216 – 4cm long
2005: May - prototype of a high-definition
10-cm flat screen made using nanotubes
2005: August –Y-shaped nanotubes are
ready-made transistors;
General Electric announced the development
of an ideal CNT diode that operates at the
"theoretical limit“. A photovoltaic effect was also
observed in the nanotube diode device that
could lead to breakthroughs in solar cells,
making them more efficient and thus more
economically viable.
 M. Zhang et al. Strong, Transparent, Multifunctional, Carbon Nanotube Sheets.
Science 309 (2005) 1215, doi:10.1126/science.1115311

https://www.youtube.com/watch?v=IPM8OR6W6WE
o 2006: Floyd Landis wins Tour de France on a CNT enhanced bike

frame weighs less than 1kg

 A carbon nanotube is based on a
two-dimensional graphene sheet.
The chiral vector is defined on the
hexagonal lattice as
Ch = nâ1 + mâ2, where â1 and â2 are
A‘ unit vectors, and n and m are
integers. The chiral angle, q, is
A measured relative to the direction
defined by â1. This diagram has
q been constructed for (n, m) = (4, 2),
and the unit cell of this nanotube is
bounded by OAA'O'. To form the
O‘ nanotube, imagine that this cell is
rolled up so that O meets O' and A
O meets A', and the two ends can be
capped with half of a fullerene
â1 molecule. Different types of carbon
â2 nanotubes have different values of n
and m.
Zigzag nanotubes correspond to (n, 0) or (0, m) and have a chiral angle of 0°,
armchair nanotubes have (n, n) and a chiral angle of 30°, while chiral nanotubes
have general (n, m) values and a chiral angle of between 0° and 30°. According
the theory, nanotubes can either be metallic (green circles) or semiconducting
(blue circles).

(0,0) (1,0) (2,0) (3,0) (4,0) (5,0) (6,0) (7,0) (8,0) (9,0) (10,0) (11,0) zigzag
(1,1) (2,1) (3,1) (4,1) (5,1) (6,1) (7,1) (8,1) (9,1) (10,1)

(2,2) (3,2) (4,2) (5,2) (6,2) (7,2) (8,2) (9,2) (10,2)

(3,3) (4,3) (5,3) (6,3) (7,3) (8,3) (9,3)

(4,4) (5,4) (6,4) (7,4) (8,4) (9,4)

(5,5) (6,5) (7,5) (8,5)

(6,6) (7,6) (8,6)

â1 (7,7)
armchair
â2
Preis für SWNT:
Oktober 2016
577€/g
Weltraumlift

und vieles mehr…

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Wasserstoffspeicher
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Global market for CNT is 4.55G$ in 2018 and will reach 9.84G$ in 2023.

World wide production 2021 of fullerenes: 3.2t/a

nanotubes: 1700t/a
nano-TiO2: >10000t/a
nano-SiOx: >20000t/a

Cnano alone produces 2000 t CNT per year

(http://www.cnanotechnology.com/en)
Press Release: The 2010 Nobel Prize in Physics

KUNGL. VETENSKAPSAKADEMIEN
THE ROYAL SWEDISH ACADEMY OF SCIENCES
5 October 2010

The Royal Swedish Academy of Sciences has decided to award Nobel

Prize in Physics for 2010 to

Andre Geim, University of Manchester, UK,

Konstantin Novoselov, University of Manchester, UK,

“for groundbreaking experiments regarding the two-dimensional material graphene”

A. Geim K. Novoselov
A live frog is magnetically levitated, an experiment that earned Sir Andre Geim
from the University of Nijmegen and Sir Michael Berry from University of Bristol
the 2000 Ig Nobel Prize in physics. Geim went on to win the Nobel Prize in
Physics in 2010 for his work on graphene.
 - Electronic properties
- Thermal properties
- Mechanical properties
- Optical properties
- Relativistic charge carriers
- Anomalous quantum Hall effect
 Electrical Conductivity
Material Notes
(S·m-1)
Graphene ~ 108
Silver 63.0 × 106 Best electrical conductor of any known metal
Commonly used in electrical wire applications due to
Copper 59.6 × 106
very good conductivity and price compared to silver.

Referred to as 100% IACS or International Annealed

Copper Standard. The unit for expressing the conduc-
Annealed Copper 58.0 × 106 tivity of nonmagnetic materials by testing using the
eddy-current method. Generally used for temper and
alloy verification of aluminium.

Gold is commonly used in electrical contacts because

Gold 45.2 × 106
it does not easily corrode.
Commonly used for high voltage electricity distribution
Aluminum 37.8 × 106
cables
Corresponds to an average salinity of 35 g/kg at 20
Sea water 4.8
°C.
This value range is typical of high quality drinking wa-
Drinking water 0.0005 to 0.05
ter and not an indicator of water quality
Conductivity is lowest with monoatomic gases present;
changes to 1.2 × 10-4 upon complete de-gassing, or to
Deionized water 5.5 × 10-6 7.5 × 10-5 upon equilibration to the atmosphere due to
dissolved CO2

Jet A-1 Kerosene 50 to 450 × 10-12

n-hexane 100 × 10-12
Air 0.3 to 0.8 × 10-14
Material Thermal conductivity (W m-1 K-1)
Silica Aerogel 0.004 - 0.04
Air 0.025
Wood 0.04 - 0.4
Hollow Fill Fibre Insulation Polartherm 0.042
Alcohols and oils 0.1 - 0.21
Mineral oil 0.138
Rubber 0.16
Water (liquid) 0.6
Thermal grease 0.7 - 3
Thermal epoxy 1-7
Glass 1.1
Soil 1.5
Concrete, stone 1.7
Ice 2
Sandstone 2.4
Stainless steel 12.11 ~ 45.0
Lead 35.3
237 (pure)
Aluminum
120—180 (alloys)
Gold 318
Copper 401
Silver 429
Diamond 900 - 2320
Graphene (4840±440) - (5300±480)
 Mechanical properties

Graphene is as the strongest material

ever measured, some 200 times
stronger than structural steel

A representation of a diamond tip with a two nanometer radius

indenting into a single atomic sheet of graphene (Science, 321
(5887): 385)

• Bond length is .142 nm long = very strong bond

• Strongest material ever discovered
• ultimate tensile strength 130 GPa compared to 400 MPa for structural steel
• Very light at 0.77 milligrams per square meter, paper is 1000 times heavier
• Single sheet of graphene can cover a whole football field while weighing
under 1 gram
• Also, graphene is very flexible, yet brittle (preventing structural use)
 Optical properties
- Monolayer graphene absorbs πα ≈ 2.3% of white light (97.7 %
transmittance), where α is the fine-structure constant.

Transparent electrical conductor

 Applications
• OLED Technologies

• Body Armor

• Lightweight Aircraft/vehicles

• Photovoltaics

• Superconductor/battery

• Filtration

http://www.graphenea.com/pages/graphene-uses-applications#.U1c1hFVdV8E
Catalysis
Synthesis of diamonds and super hard materials
Lubricant for ultra high vacuum C60F48
Molecular switches
Batteries
Functional polymers
Building blocks for the synthesis of highly stereo selective systems
Medicine
Materials for nonlinear optics
Novel semiconductor materials
Molecular filters and storage for gas
Super conductivity
Fuel for ion drives of space crafts
...
 Fullerenes: 40551

Nanotubes: 175357

Graphene: 103410

Solar cells: 11017+25336+17709

Batteries: 11052+51445+36412
Medicine: 8930+39091+17294
https://ppubs.uspto.gov/pubwebapp/ November 13, 2023
Carbon nanostructures in science:

# of # of Highest cited
papers citations
Fullerenes 56122
Nanotubes 310838
Diamondoids 8123
Graphene 340276
Kroto 394 43079 DOI: 10.1038/318162a0 / 13748
Smalley 438 110895 DOI: 10.1038/318162a0 / 13748
Curl 284 31788 DOI: 10.1038/318162a0 / 13748
Iijima 318 66978 DOI: 10.1038/354056a0 / 36958
Geim 402 232865 DOI: 10.1126/science.1102896 / 51757
Novoselov 475 266341 DOI: 10.1126/science.1102896 / 51757

https://www.webofscience.com/ November 13, 2023

United States Patents on fullerenes:

Self-cooling beverage and food container using fullerene nanotubes

US Patent 5,946,930; Anthony, Sept. 7, 1999

Fullerene jet fuels

US Patent 5,611,824; Stephens, Mar. 18, 1997
Self-cooling beverage and food container using fullerene
nanotubes

Abstract

The apparatus includes a container such as a metal or plastic can

containing a product and having a conventional unified bottom and side
container wall terminating in an upper sealing flange. A refrigerant
receptacle is provided including a receptacle cup having a cup wall. The
cup wall has an expandable portion sealingly connected to a top wall to
form a refrigerant receptacle chamber. A portion of the top wall is shaped
into an invertible conical reservoir for temporary storage of liquified
refrigerant. The reservoir has a small port opening at the lowest point for
transfer of liquified refrigerant into and out of the refrigerant chamber.
Several cup wall sections extend vertically above the top wall to conntect
to a sealing flange which extends laterally. The spaces between the cup
wall sections act as passageways for the product. The receptacle is filled
with a solid or powdered form of carbon molecules of Fullerene
nanotubes. A conventional beverage can lid is further provided, including
a lid panel with a lid opener mechanism and a lid lateral edge.