Marvin T. Schmidt Research Professor Kenneth S. Suslik, School of Chemical Sciences, University of Illinois at Urbana-Champaign, USA

The Mechanochemistry of Metal-Organic Frameworks and of Crystals
When Jan 28, 2019
from 02:00 PM to 03:00 PM
Where LR1, Thom Building
Contact Name
Contact Phone +44 (0) 1865 273030
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We do not yet understand, at a molecular level, how things break. What happens to macroscopic solids (crystalline or not) as stresses are applied and how those stresses create breakage of chemical bond breakage and weaker inter-molecular interactions remain remarkably mysterious.  Mechanochemistry (i.e., the chemical consequences of grinding, milling and breakage of bulk materials) is an area with a long (but not well-known) history that is currently undergoing vigorous renaissance and rapid expansion of interest for chemists, physicists, theoreticians and industrial researchers.

 

As an example, the practical applications of metal−organic framework (MOF) materials require an in-depth understanding of their mechanical properties. We have investigated the mechanical properties and energy absorption behavior of single crystals of four isostructural UiO-type MOFs under uniaxial compression. In situ nanocompression experiments were used to measure the mechanical behavior of individual MOF nanocrystals under compression within a transmission electron microscope. The plasticity and endothermicity during deformation of MOFs shows a surprising potential for absorption and dissipation of mechanical shock. At compressive stress below 2 GPa, only small amounts of energy are absorbed by the compression of these MOFs. As the stress is increased, however, the energy absorption is substantially enhanced. Above 2 GPa, the energy absorption typically reaches 3−4 kJ/g; for comparison, the energy release in the explosion of TNT is 4 kJ/g. Gram for gram, MOFs can absorb as much energy as a high explosive can release.  The storage of this energy comes from compression-induced endothermic coordination bond breakage in these MOF, demonstrated by FTIR and EXAFS that confirm loss of bonding between the bridging carboxylates and the Zr6O4 clusters. The use of MOFs for shock wave energy dissipation and the physical and chemical consequences of shocks on MOFs will also be discussed.

 

 

 

    Zeiger, B. W.; Suslick, K. S. “Sonofragmentation of Molecular Crystals”  J. Am. Chem. Soc. 2011, 133, 14530-14533.

 

    You, S.; Chen, M.-W.; Dlott, D. D.; Suslick, K. S. “Ultrasonic hammer produces hot spots in solids”
Nature Commun. 2015, 6, 6581-1-7. 

 

    Kim, H. N.; Suslick, K. S. “Sonofragmentation of Ionic Crystals” Chem. Eur. J., 2017, 23, 2778-2782.

 

    Su, Z.; Shaw, W. L.; Miao, Y.-R.; You, S.; Dlott, D. D.; Suslick, K. S. “Shock Wave Chemistry in a Metal–Organic Framework” J. Am. Chem. Soc.2017139, 4619–4622. 

 

    Miao, Y.-R.; Zu, Z.; Suslick, K. S.  “Energy Storage during Compression of Metal–Organic Frameworks”
J. Am. Chem. Soc.2017139, 4667–4670.

 

    Miao, Y.-R.; Suslick, K. S. “Mechanochemical Reactions of MOFs” Adv. Inorg. Chem. 2018, 71, 403-434

 

    Su, Z.; Miao, Y.-R.; Zhang, G.; Miller, J. T.; Suslick, K. S. “Bond breakage under pressure in a metal organic framework” Chem. Sci. 2017, 23, 2778-2782.

 

 

 

 

·         Zeiger, B. W.; Suslick, K. S. “Sonofragmentation of Molecular Crystals”  J. Am. Chem. Soc. 2011, 133, 14530-14533.

·         You, S.; Chen, M.-W.; Dlott, D. D.; Suslick, K. S. “Ultrasonic hammer produces hot spots in solids”
Nature Commun. 2015, 6, 6581-1-7. 

·         Kim, H. N.; Suslick, K. S. “Sonofragmentation of Ionic Crystals” Chem. Eur. J., 2017, 23, 2778-2782.

·         Su, Z.; Shaw, W. L.; Miao, Y.-R.; You, S.; Dlott, D. D.; Suslick, K. S. “Shock Wave Chemistry in a Metal–Organic Framework” J. Am. Chem. Soc.2017139, 4619–4622. 

·         Miao, Y.-R.; Zu, Z.; Suslick, K. S.  “Energy Storage during Compression of Metal–Organic Frameworks”
J. Am. Chem. Soc.2017139, 4667–4670.

·         Miao, Y.-R.; Suslick, K. S. “Mechanochemical Reactions of MOFs” Adv. Inorg. Chem. 2018, 71, 403-434

·         Su, Z.; Miao, Y.-R.; Zhang, G.; Miller, J. T.; Suslick, K. S. “Bond breakage under pressure in a metal organic framework” Chem. Sci. 2017, 23, 2778-2782.


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