Chemistry of Graphene and Its Technological Applications

LOH KIAN PING DEPARTMENT OF CHEMISTRY NATIONAL U OF SINGAPORE

In celebration of ULSAN CHEMISTRY DAY

The Uniqueness of Carbon

ONE OF THE MOST FLEXIBLE ELEMENTS

Organic chemistry derives its richness from this chemical flexibility of carbon -Carbon allotropes: Diamond, Graphite, Fullerene, Carbon nanotube, and now GRAPHENE

Carbon materials
Wrapping (10,0) SWNT (zigzag)(Animation)

The origin of many forms of carbon

2010 Nobel Prize in Physics: Graphene

uAndre Geim in New Scientist. Graphene is stronger and stiffer than diamond, yet can be stretched by a quarter of its length, like rubber. Its surface area is the largest known for its weight.

Geim and his colleague (and former postdoctoral assistant) Konstantin Novoselov first produced graphene in 2004 by repeatedly peeling away graphite strips with adhesive tape to isolate a single atomic plane.

Large heat and electrical conduction in Carbon materials help solve the problem of energy waste

C*: 1s2, 2s1, 2px1, 2py1, 2pz1

The Manchester team in 2008 created a 1-nanometer graphene transistor, only one atom thick and 10 atoms across -smaller than the smallest possible silicon transistor -represent the absolute physical limit of Moores Law governing the shrinking size and growing speed of computer processors

2008

Superior Mechanical Properties

Super-elastic

Stretchable Electronics

Super-friction

Future electronics

Super-conductive

SKKU, Nature 2009, 457, 706.

Carbon
Doping of Si

Silicon
Dangling bonds at Si (110)

sp2 hybridization:120o

sp3 hybridization: 109o

Si-SiO2 interface engineering

CARBON VERSUS SILICON

CARBON 1. CAN BE SCALED DOWN TO ATOMIC SCALE: GRAPHENE 2. STRONG BONDS, HIGHLY DIRECTIONAL 3. GOOD THERMAL CONDUCTOR (diamond, graphene) 4. RESISTANT TO IMPURITIES SILICON 1. SCALABILITY AN ISSUE at length scale below 30 nm 2. NOT AS STRONG AS CARBON 3. NOT AS GOOD A THERMAL CONDUCTOR THERMAL WASTE 4. IMPURITY INCOPORATION easy, OXIDIZED EASILY

The Uniquenes of Graphene

ULTRATHIN SHEETS WHICH CAN MEDIATE MULTIPLE INTERCATIONS

Doping and functionalization of graphene

Approaches: 1. covalent bonding; 2. p-p stacking; 3. adsorbing graphane
B or N-doped
Graphane & fluorographene

H or K-doped Biomolecules-adsorbed F4-TCNQ-doped

Small molecules on graphene

How scientists make graphene?

Mechanical Exfoliation (2004) Epitaxial graphene on SiC

GTech, IBM, NRL, HRL, NUS,

Chemical Vapor Deposition

SKKU, MIT, Austin,

How to D. I. Y. Graphene?

DIY Graphene: 1. Attach a graphite flake to about six inches (15 cm) of plastic sticky tape with tweezers 2. Fold the tape right next to the flake so that you sandwich it between the tape's sticky sides 3. Press down gingerly to get a good seal and then peel the tape apart slowly enough so that the graphite cleaves smoothly in two 4. Repeat the above steps 2 and 3 for many rounds until the duplicate flakes looks shinier, which means the peeling has exposed an atom-smooth layer 5. Transfer the sample onto SiO2/Si substrate for checking under optical microscopy and device fabrication

Chemical Vapor Deposition Growth of Graphene on Copper Catalyst

Five steps occur during generic CVD processes:
Reactants pumped through reactor. Reactants diffuse across boundary layer to surface. Reactants adsorb on surface (adatoms). Surface reactions; pos. formation of islands or clusters. Pos. surface diffusion of adatoms. Diffusion of by-products away from surface.

Science 324, 2009, 1312

large-area single-layer graphene fabricated by a roll-to-roll process and transferred onto a flexible transparent substrate

Nature Nanotechnology 5, 2010, 574

Applications of large-area graphene

Touch-screen panel

Solar cell

The Chemists way: how graphite can be exfoliated to produce graphene oxide

Angew. Chem. Int. Ed. 2010, 49, 227

Summary of several structural models of Graphene Oxide

A Lerf., et al., J. Phys. Chem. B,1998, 102, 44774482.

H. He, et al., Chem. Phys. Lett.,1998, 287, 5356.

T. Szabo et al., Chem. Mater., 2006, 18, 27402749.

Fluorescence from isolated sp2 domains in graphene oxide Edge effect ? Size effect ?

Fluorescence mechanism of Graphene is different from nanodiamond

K. P. LOH et. al. Graphene Oxide as a Chemically Tunable Platform for Optoelectronics NATURE CHEMISTRY

Reduction by hydrazine
S. Stankovich, D. A. Dikin, R. D. Piner, K. A. Kohlhaas, A. Kleinhammes, Y. Jia, Y. Wu, S. T. Nguyen and R. S. Ruoff, Carbon, 2007, 45, 15581565.

hydrogen bonding of GO with water

Nano Graphene oxide can be used to deliver drugs , and can be used for cancer therapy

b a
4T1

30min

1h

6h

24h

= Cy7 = CH2CH 2O n HN OC

H 2N H O H

NH2
CH 2 O

O C N H
KB

C OH 2

O H

O NH2

NH 2

H2N H2N O H 2N
H2 O C

H2 N O O H H H O
CH 2O

HN OC

U87MG

H NH2

In vivo photothermal therapy study using intravenously injected Nanograpnene oxide

EXP by Suzhou U, CHINA

Graphene Oxide as Green Catalyst: Metal Free, Highly Selectivity, Recyclable.

graphene oxide has been found to catalyze alcohol and alkene oxidations as well as alkyne hydrations

Hydration Reaction

Oxidation Reaction

D. R. Dreyer, H.-P. Jia, C.W. Bielawski, Angew. Chem. Int. Ed. 2010, 49, 6813 6816.

The possible mechanism for the oxygen activation:

MECHANICAL PROPERTIES - IMPERMEABLE MEMBRANE

HIGHLY SENSITIVE GAS SENSORS WORLDS THINNEST BALLOON

Impermeable Atomic Membranes from Graphene Sheets Bunch, Nano Lett., 2008,8 (8): 2458-62

FOOD PACKAGING

polymer packaging plays a critical role in the preservation and distribution of perishable goods such as food and medicine. Impermeability to gases and water is important

MIX-AND-MATCH HYBRIDS Polymers have been combined with other plastics to form blends, mixed with talc and clay to give filled systems, and extruded and molded with fibers and other reinforcements to yield composite and hybrid materials.

The superiority of graphenes over carbon nanotubes as reinforcements stems from easy access to the graphitic precursor material, the cost, the scalable method, and its orientation flexibility (morphology).

Crumpled Graphene Nanosheets as Highly Effective Barrier Property Enhancers Comption Adv. Mater. 2010, 22, 47594763

GRAPHENE for BIOTECHNOLOGY -DNA SEQUENCING Harvard team: Graphene nanopores could be used as a trans-electrode to measure the electrical signal generated as single molecules of DNA were passed through the pore

Graphene nanochannel for sequencing

Pohang University of Science and Technology

Graphene nanogap for sequencing

California State University Northridge

Graphene for Energy (1)

Graphene to replace ITO for solar cell

uGreen energy Organic solar cell Dye sensitized solar cell

Graphene for Energy (2)

Specific energy density Graphene supercapacitor 2630 m2/gram 85.6 Wh/kg at room temperature and 136 Wh/kg at 80 deg C

Graphene

Graphene battery

Graphene for Environment

TiO2/graphene Composites for Photodegradation of Methyl Orange

Photocatalytic degradation of dyes over graphene-gold nanocomposites under visible light irradiation
Chem. Commun., 2010, 46, 6099

Water splitting/hydrogen evolution/Oxygen evolution catalysts

Graphene as Green Support for Photodegradation of Dye (Methylene Blue)

The graphene platform plays important roles during the photodegradation of MB in three aspects: (i) Increase catalyst adsorptivity. (ii) Extend light absorption. (iii) Suppress charge recombination.
Zhang, H.; Lv, X. J.; Li, Y. M.;Wang, Y.; Li, J. H. ACS Nano 2010, 4, 380386.

BIOREMEDIATION OF GRAPHENE OXIDE Reduction of Graphene Oxide via Bacterial Respiration

BACTERIA degrades GO, restoring it to the naturally occurring graphite mineral form

Transistor

Quantum electronics

Gas sensor

Electromechanical Resonators Mode-locked laser

Photodetector

The carbon laboratory @ NUS

http://staff.science.nus.edu.sg/~thecarbonlab/index.html