Heme-Containing Metal-Organic Frameworks for the Oxidative Degradation of Chemical Warfare Agents

Abstract

The objective of this effort is to synthesize and study heme-containing metal-organic framework (MOF) materials for the oxidative degradation of small molecules. This STIR effort will explore the proof-of-concept of using heme-containing MOFs to oxidatively degrade small molecules including chemical warfare agents and simulants. Both solution- and gas-phase studies will be carried out with simulants including dimethylmethylphosphonate, diethylemthylthiphosphonate, and diethyl-3-(dimethylamino)propylphosphonate. Solution-phase experiments will be aimed at understanding the reactive intermediates. Oxo- and peroxo- intermediates will be generated by a variety of reagents. The resulting complexes will be characterized by Mossbauer, EPR, diffuse reflectance UV-Vis, and IR. Degradation reactions will be carried out with the heme-based MOF scaffolds and a variety of reagent combinations (reductant, acid, O2, or H2O2), and will be monitored by NMR, GC, and other analytical techniques to determine chemoselectivity as well as turnover and efficiency of the catalyst. Gas-phase studies will be carried out, and similar to the solution-phase studies, initial investigations will focus on the generation and characterization of high valent oxo- or peroxo-intermediates. Degradation studies will be carried out, and pressures of reagents will be varied. Green reagents such as O2 and H2 will be explored.

Document Details

Document Type
DoD Grant Award
Publication Date
Jan 12, 2017
Source ID
W911NF1510119

Entities

People

  • Thomas Harris

Organizations

  • Army Contracting Command
  • Northwestern University
  • United States Army

Tags

Fields of Study

  • Chemistry

Readers

  • Analytical Chemistry
  • Nanoscale Plasmonic Nanotechnology
  • Organic Chemistry