Nanostructure-dependent indentation fracture toughness of metal-organic framework monoliths

Monolithic metal-organic frameworks (MOFs) represent a promising solution for the industrial implementation of this emerging class of multifunctional materials, due to their structural stability. When compared to MOF powders, monoliths exhibit other intriguing properties like hierarchical porosity, that significantly improves volumetric adsorption capacity. The mechanical characterization of MOF monoliths plays a pivotal role in their industrial expansion, but so far, several key aspects remain unclear. In particular, the fracture behavior of MOF monoliths has not been explored. In this work, we studied the initiation and propagation of cracks in four prototypical MOF monoliths, namely ZIF-8, HKUST-1, MIL-68 and MOF-808. We observed that shear faults inside the contact area represent the main failure mechanism of MOF monoliths and are the source of radial cracks. MIL-68 and MOF-808 showed a remarkably high resistance to cracking, which can be ascribed to their consolidated nanostructure.