Stabilization of Reactive Chemical Species and Fundamental Studies of Small-Molecule Reactivity in Metal-Organic Frameworks

  • Harris, Thomas David (PD/PI)

Project: Research project

Project Details


This proposal seeks to synthesize microporous, supramolecular architectures, or metal-organic frameworks (MOFs), and employ them to (1) stabilize and study reactive chemical species, such as terminal metal oxo and nitrido functionalities, and (2) carry out and study stoichiometric and catalytic activation of small inorganic and organic molecules, such as dioxygen and dinitrogen. MOFs are synthesized through solution-based coordination chemistry routes often associated with molecular chemistry, enabling myriad chemical tunability of structure and function. Moreover, MOFs exhibit crystalline structures that allow us to know the exact composition of each catalytic site at the atomic level, through characterization techniques such as X-ray and neutron diffraction, various forms of spectroscopy, and SQUID magnetometry. In addition, the rigid structure of a MOF provides a surface upon which to anchor reactive chemical species, precluding their participation in side reactions often encountered in molecular catalysts, such as bimolecular condensation and hydrogen atom abstraction. Additionally, the solid-state composition of the MOF will enable gas-phase reactions to be conducted in the absence of solvent, thereby eliminating the possibility of side reactions with solvent molecules. A key feature of this approach is that reactive chemical species will be stabilized without sacrificing their inherent reactivity. This work sets out to answer fundamental scientific questions that will translate to applications in Army Soldier protection. Our ability to establish structure-function relationships that govern interactions between MOF surfaces and small-molecule substrates in microscopic detail will inform the design of future materials with programmable responses to dangerous chemical species. In particular, our work will focus on the formation of strong solid-state oxidants from ubiquitous small molecules such as dioxygen and dinitrogen. From these studies, we will gain unprecedented insight into oxidation chemistry that occurs on MOF surfaces, which will be of use in areas such as the selective oxidative decomposition of chemical warfare agents, such as mustard gases and VX gas nerve agents, into inactive chemical forms.
Effective start/end date4/15/144/14/22


  • U.S. Army RDECOM Acquisition Center, Research Triangle Park Contracting Division (W911NF-14-1-0168/P00010)


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