(757d) Design of Stratified Hybrid Metal Organic Frameworks for Chemical Detection and Destruction

There is a pressing need for materials capable of rapidly detecting and destroying chemical warfare agents. Stratified metal-organic frameworks (MOFs) containing plasmonic nanoparticles may be able to meet this need. Stratified MOFs consist of layered materials having different functional groups in each layer, the purpose of which is to provide a gradient of functional groups to direct transport of target analytes to the center of the MOF. We seek to develop a detailed understanding of the fundamental properties of sorption, transport, photodetection, and photocatalytic degradation of target chemical species in stratified hybrid MOF-nanoparticle systems. The first step to achieve this is to design, synthesize, and evaluate MOFs to identify promising functional groups to produce differential binding of analytes. We use quantum mechanical methods to identify functional groups for binding target species, Monte Carlo methods to perform fluid adsorption isotherms in candidate MOFs, and ab initio molecular dynamics to sample configurations and determine optimal binding sites in MOFs. In addition, we synthesize robust Zr-based MOFs with the identified functional groups, measure isotherms of target molecules to compare with calculations, and use temperature programmed desorption to measure loading and binding energies of target molecules in MOFs.