Mechanochemistry of Metal-Organic Frameworks under Pressure and Shock

CONSPECTUS: Metal-organic framework solids (MOFs) are synthetic nanoporous materials that have drawn intense efforts in synthesis and characterization of chemical properties, most notably for their ability to adsorb liquids and gases. They are constructed as node-spacer nanostructured materials: metal centers (ions or clusters) connected by organic linkers (commonly containing carboxylate or imidazolate groups) to form crystalline, extended, often highly nanoporous structures. MOFs exhibit a variety of advantages over conventional porous materials: rationally designed synthesis of desired crystal structures and crystal engineering become feasible; great synthetic versatility and ease of incorporating different chemical functionalities are realized; and the use of lightweight organic linkers allows for ultrahigh surface area and porosity previously not accessible to conventional materials (i.e., zeolites and porous carbon). As a consequence, MOFs show great promise for a rapidly expanding collection of applications such as gas storage, separations, catalysis, sensing, and drug delivery. The mechanochemistry of MOFs and their response to shock waves, which we discuss in this Account, have been only partially explored. Mechanochemistry, the connection between the mechanical and the chemical worlds, has ancient origins. Rubbing sticks together to start a fire is mechanochemistry. Only in the past decade or so, however, has mechanochemistry gained a notable focus in the chemical community. In the following discussion, we present a general introduction to the complex mechanochemical behavior of MOFs both under quasi-static compression and under shock loading created by high-speed impact. During elastic deformation, MOFs undergo reversible structural or phase transitions. Plastic deformation of MOFs can result in mechanochemistry and can permanently modify the crystal structure, the pore dimensions and configuration, and the chemical bonding. The large energies required to induce bond rearrangement during plastic deformation suggest an interesting potential of MOFs for shock wave mitigation applications. MOFs are promising materials for shock energy dissipation because of the high density of nanopores which can absorb shock energy as they collapse. We have recently developed a platform to assess shock wave energy attenuation by MOFs and other powdered materials. It uses a tabletop laser-driven flyer plate to impact MOF samples at velocities of up to 2.0 km/s. The pressure of the shock waves that break out from the MOF sample can be measured by photon Doppler velocimetry. By measuring the shock profiles of MOF layers with different thicknesses, we can determine the shock pressure attenuation by the MOF layer. We have identified the two-wave structure of shocks in MOFs caused by nanopore collapse. Electron micrographs of recovered shocked MOFs show distinct zones in the shocked material corresponding to shock powder compaction, nanopore collapse, and chemical bond destruction.