Porous Materials -Metal-Organic Frameworks
Transcript of Porous Materials -Metal-Organic Frameworks
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Porous Materials -Metal-Organic Frameworks
2012 Nanocamp NCMN, UNL
Dr. Jian Zhang & Jacob Johnson
Department of Chemistry
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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
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Chemistry is the Central Science
Chemistry
Medicine
Environmental Sciences
Astronomy
Biology
Geology
Physics Materials Science
Pharmaceutical
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What does a chemist do?
• Chemists make compounds and materials
– Synthetic chemistry
• Measure properties of materials
– Analytical chemistry
• Model chemical reactions and materials structures
– Theoretical and computational
chemistry
Penicillin
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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
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The Zhang’s Group Research
Metal-organic Frameworks Covalent-organic Frameworks Porous polymer networks
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Porous Materials in Nature
Sandstones
Sea Sponge
Butterfly Wings
Egg Shells Snow
Coral Soil Bone Lungs
Lemons
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Artificial Porous Materials
Insulation
Cake
Concrete
Bread Ceramics
Chalk Brick Paper
Sponges
Clothing
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Pore Type (size)
Micropores (< 2 nm) Mesopores (2-50 nm) Macropores (< 50 nm)
Surface of a chicken egg shell Carbon membrane Monolithic column
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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
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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
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Activated Carbons
Rice Husk Nut Shells
Coconut Fiber Biomass
Made from a variety of materials:
Organic, non-ordered structure
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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
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Metal Organic Frameworks MOFs
– Synthetic materials
– Also called coordination polymers
– Similar materials without metals are called COFs… covalent coordination polymers
– Still a very active research area
Inorganic-Organic Hybrid, ordered structure
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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
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Metal Organic Frameworks MOFs
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Breathable MOFs
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• 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 (biomass, hydro, wind, solar, and geothermal)
Fossil fuels (coal ,natural gas, etc.)
Nuclear Energy
Hydrogen storage
Hydrogen Storage in Nano-Porous Materials
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• 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
Hydrogen storage
Hydrogen Storage in Nano-Porous Materials
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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)
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MOFs as hydrogen storage materials
~ 3% wt @ 77 K, 1 atm
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CO2 Sequestration
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MOFs as CO2 storage materials
38.5 wt% @ 273 K, 1 atm
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MOF Construction
Organic Linkers Metal Nodes
Mn2+
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109.5° 90° 90°
120°
Tetrahedral Octahedral Trigonal Bipyrimidal
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