MOF for energy appl

MOF for energy appl - Metal-Organic Framework Materials for...

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Metal-Organic Framework Materials for Energy Applications • U.S. Dept. of Energy • AFOSR • Northwestern NSEC • DTRA O O O O O O O O O O O O [O] [O] [O] [O] Notre Dame, November, 2010
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Acknowledgments • Avi Shultz • Dr. Andy Nelson • Prof. SonBinh Nguyen • Prof. Randall Snurr
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Acknowledgments • Research Prof. Omar Farha
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• Hydrogen storage • Chemical catalysis • Carbon dioxide capture and storage • Gas separations • Light harvesting and energy conversion Metal-Organic Framework Materials for Energy Applications
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• Solvothermal synthesis simple, scalable materials assembly • Broad channel and pore size tunability • Complete uniformity of channels • Amenable to experimental structural characterization Why Metal-Organic Frameworks? • Amenable to detailed explanative and predictive computational characterization • Enormous internal surface areas: up to 5,200 m 2 /g (e.g. Matzger)
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Materials Challenges Purification Retaining porosity Controlling catenation
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b) Catenated versus non-catenated: a) Paddlewheel from cubic Problem: MOFs Are Often Obtained as Solid-state Mixtures Acc. Chem, Res. 2010 , 43 , 1053-1176 N N O O N N Zn R R O HO OH O + Zn(NO 3 ) 2 6H 2 O 70 o C, 5 days + unknown + Zn(NO 3 ) 2 DMF/70 ° C +
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Solution: Density based separation using high-density solvents Zn(NO 3 ) 2 6H 2 O 70 o C, 5 days + unknown Process of separation yellow white + Zn(NO 3 ) 2 DMF/70 ° C +
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35 Solution: Density based separation
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Differences in porosity and surface area 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 25 125 225 325 425 525 Temperature (°C) Weight Fraction 0 10 20 30 40 50 60 70 80 90 100 0.00 0.20 0.40 0.60 0.80 1.00 Pressure (atm) CO 2 Volume (cc/g) Vs.
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Materials Challenges Purity Retaining porosity Controlling catenation
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Case Study: Preventing Collapse of Cubic “TClPDl” MOF BET Surface Area: Conventional evacuation 22 m 2 /g completely “collapsed” Supercritical CO 2 evacuation 490 m 2 /g highly porous N N O O O O Cl Cl O OH HO O Cl Cl Nitrogen adsorption isotherms 490 m 2 /g 22 m 2 /g
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Other Examples with Supercritical CO 2
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Materials Challenges Purity Retaining porosity Controlling catenation
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