Porous Materials

-Metal-Organic Frameworks
2012 Nanocamp
NCMN, UNL

Dr. Jian Zhang & Jacob Johnson

Department of Chemistry
 What does a chemist do?
• Chemists observe and
study
• Chemists study the
composition,
assembly, properties,
and reactivity of
matter (atoms,
molecules, materials)
• Chemistry is
considered as the
central science
Chemistry is the Central Science
Medicine Biology Pharmaceutical

Geology Astronomy

Chemistry

Environmental
Physics Materials Science Sciences
 What does a chemist do?
• Chemists make compounds and materials
– Synthetic chemistry

• Measure properties of materials Penicillin

– Analytical chemistry

• Model chemical reactions and materials

structures
– Theoretical and computational
chemistry
What does it take to become a chemist?
• Strong interest in science
• Strong academic performance
• 4+ years of college
• Graduate degree (2-4 years)
– Hundreds of graduate schools in the US
• Diverse and rewarding career
– Creativity is important
– Worldwide industry
– Work on important global problems
• Energy
• Pollution
• Disease
 The Zhang’s Group Research

Metal-organic Frameworks Covalent-organic Frameworks Porous polymer networks

 Lungs Bone Coral Soil

Porous Materials in
Nature
Sandstones Butterfly Wings

Snow Sea Sponge Egg Shells Lemons

 Paper Clothing Chalk Brick

Artificial Porous
Materials
Insulation Concrete

Ceramics Cake Bread Sponges

 Pore Type (size)
Micropores (< 2 nm) Mesopores (2-50 nm) Macropores (< 50 nm)

Surface of a chicken egg shell Carbon membrane Monolithic column

 Microporous Materials
• A microporous material is a material containing
pores with diameters less than 2 nm
• Activated Carbons
• Zeolites
• Metal-organic frameworks
• Covalent organic frameworks
• Microporous polymer
 Applications
– Microporous materials
• Activated carbons
– The small size of their pores gives them great surface area… they can
adsorb a large amount of gas directly on to their surface. Popular
support for some catalyst metals (especially palladium and platinum).
ρ~ 2g/cm3
• Zeolites
– The narrow size distribution of their pores makes them very useful
for gas separation. Also used as catalysts because of acid sites in the
pores. ρ~ 4g/cm3

• Metal organic frameworks

– Their huge surface area and pore volume makes them potentially
useful for gas sequestration/storage. ρ< 0.5g/cm3
 Activated Carbons
Made from a variety of materials:

Rice Husk Nut Shells

Coconut Fiber Biomass

Organic, non-ordered structure

 Zeolites
– Micropores are part of their crystal structure:
• Most are synthetic
• Alumino-silicates
• Silicalite = no aluminum
• Cation can be H+, Na+, Ca2+, NH4+, etc
• Pore shape needs to be incorporated into pore size
calculation for accurate results
• Some adsorbates are better than others

Inorganic, ordered structure

 Metal Organic Frameworks
MOFs
Inorganic-Organic Hybrid, ordered structure

– Synthetic materials
– Also called coordination polymers
– Similar materials without metals are called COFs…
covalent coordination polymers
– Still a very active research area
Metal Organic Frameworks
MOFs

Zn4O tetrahedra (blue) are joined by

organic linkers (O, red, C, black), giving an
extended 3D cubic framework with inter-
connected pores of 11.2 Å aperture
width and 18.5Å pore (yellow sphere)
diameter
Metal Organic Frameworks
MOFs
Breathable MOFs
 Hydrogen Storage in Nano-Porous
Materials
Hydrogen storage
• Petroleum dependence → U.S. imports 55% of its oil
expected to grow to 68% in 2025

• Hydrogen as energy carrier → clean, efficient, and can be derived from

domestic resources

Renewable Fossil fuels Nuclear Energy

(biomass, hydro, wind, solar, and geothermal) (coal ,natural gas, etc.)
 Hydrogen Storage in Nano-Porous
Materials
Hydrogen storage

• Hydrogen storage is a critical enabling technology for the

acceptance of hydrogen powered vehicles

• Storing sufficient hydrogen on board to meet consumers

requirements (eg. driving range, cost, safety, and performance)
is a crucial technical parameter

• No approach currently exists that meets technical requirement.

(driving range > 300 miles)

• U.S. DoE → develop on board storage systems achieving 6 and 9

wt% for 2010 and 2015
 Current Challenges with H2 Storage
Options
Compressed Hydrogen
-High pressure (500-700 atm),
-Expensive storage container

Liquid Hydrogen
-Expensive cooling system required
-High energy cost to liquefy H2

Complex and Metal Hydrides

-Poor reversibility
-Require high temperature
and pressure (>100 ˚C
and >100 atm)
MOFs as hydrogen storage materials

~ 3% wt @ 77 K, 1 atm
CO2 Sequestration
MOFs as CO2 storage materials

38.5 wt% @ 273 K, 1 atm

 MOF Construction
Mn2+

Organic Linkers Metal Nodes

 120°

109.5° 90° 90°

Tetrahedral Octahedral Trigonal Bipyrimidal