Chemistry and

Nanomaterials
Carl C. Wamser
Portland State University
Nanomaterials Course - June 27,
2006

Nanoscale = billionths (10-9)

6 billion people
8000 mile diameter

10 billion components
8 inch diameter

Effects of Nanoscale
Structural differences:

Nanoscale Carbon

Bulk Carbon

C60 (Buckeyball)
Smalley, Curl, Kroto
1996 Nobel Prize
Graphite

Diamond
Carbon Nanotubes
Sumio Iijima - 1991

Instrumentation / Imaging
Quantum
Corral
48 Fe atoms
positioned by
the STM
used to
image them

http://www.nano.gov/html/facts/home_facts.html

Dimensional Issues
length scale:

nm

ONAMI

mm

Chemistry

molecules polymers supramolecular

assemblies

Biology

amino
acids

Electronics

proteins

cells/tissues organisms

semitransistors integrated
conductors
circuits

computers

Chemistry Issues

Structure / Dynamics / Synthesis

Structure-Function Correlations
Self-Assembled Systems
Applications:
Materials
Biological
Environmental

Organic LEDs
Structure-Function Correlations (emission wavelengths)

Quantum Effects
Band gap depends on particle size
(number of atoms in the particle)

4 nm

2 nm

Fluorescence of cadmium selenide nanoparticles

Chemical Bonding
Forces used to assemble structure:
Ionic
Metallic
Covalent
H-bonding
Metal-ligand
Van der Waals
- stacking

Ionic Bonding
Molecular beaker
epitaxy
Layer-by-layer
growth of
polyelectrolytes
Tom Mallouk
Penn State U

http://www.mapr.ucl.ac.be/~jonas/Home_page_AJ/Research/ESA/ESA.html

Ionic / Electrostatic Effects

A molecular
elevator
Responsive to
acid/base
J. D. Badjic, et al.,
Accts. Chem. Res.,
in press.
J.F. Stoddart, UCLA

Ionic / Electrostatic Effects

Conformational Molecular Rectifiers, A. Troisi and M. A. Ratner,

Nano Lett., 4(4), 591-595 (2004).

Metallic Bonding
Nanoscale gold has different properties than bulk gold, including:
appearance, solubility, and melting point.

Gold Statue

Gold nanoparticles

thiol stabilized gold nanoparticle

melting point: 1337 K

Jim Hutchison, U. Oregon

http://darkwing.uoregon.edu/~hutchlab

gold nanoparticles (2 nm) in solution

melting point: 650 K

Covalent Bonding - Carbon

Single-walled
carbon nanotubes:
armchair - metallic
zigzag - semiconducting
chiral - semiconducting
multi-walled - metallic

Covalent Bonding - Carbon

Carbon nanotubes coated with diamond nanocrystals

M. L. Terranova, et al., Chem. Mater., 17(12) pp 3214 - 3220

Hydrogen Bonding

DNA
Double
Helix

http://www.haveland.com/ graphics/dna-3d.jpg

- Stacking - Liquid Crystals

Charge-Trapping Memory Device

Liu, C-Y.; Bard, A.J.; Acc. Chem. Res.

(1999), 32, 235-234.

Self-Assembled Monolayer
10 nm

Monolayer of
DDB on
graphite
(didodecylbenzene)

http://www.nanoscience.com/education/gallery/DDB_ani.htm

Van der Waals Interactions

SAMMS
Self-Assembled
Monolayers on
Mesoporous
Supports

QuickTime and a
TIFF (LZW) decompressor
are needed to see this picture.

Glen Fryxell, PNNL

http://samms.pnl.gov/

Polyporphyrin Interfacial Film (thin)

Polyporphyrin Interfacial Film (thick)

Photosynthetic Reaction Center

( 1988 Nobel Prize )

http://www.mpibp-frankfurt.mpg.de/~michael.hutter/rcenter.html

Resources
Nanochemistry references and websites:
Handbook of Nanotechnology, B. Bhushan, ed. (2004)
Molecular Nanotechnology, D. E. Newton, ed. (2002)
Integrated Chemical Systems, A. J. Bard (1994)
Engines of Creation, K. Eric Drexler (1986)
( http://www.foresight.org/EOC/ )
Theres Plenty of Room at the Bottom, Richard Feynman (1959)
( http://www.zyvex.com/nanotech/feynman.html )
National Nanotechnology Initiative ( http://www.nano.gov/ )
Nano Letters - ACS Journal ( http://pubs.acs.org/journals/nalefd/ )
Materials Today - British journal ( http://www.materialstoday.com )