Self-Assembly of Metal-Organic Frameworks into Monolithic Materials with Highly Controlled Trimodal Pore Structures.

We present a two-step template-free approach toward monolithic materials with controlled trimodal porous structures with macro-, meso-, and micropores. Our method relies on two ordering processes in discrete length scales: 1) Spontaneous formation of macroporous structures in monolithic materials by the sol-gel process through the short-range ordered self-assembly of metal-organic frameworks (MOFs), and 2) reorganization of the framework structures in a mediator solution. The Zr-terephthalate-based MOF (UiO-66-NH2 ) was adopted as a proof of concept. The self-assembly-induced phase separation process offered interconnected macropores with diameters ranging from 0.9 to 1.8 μm. The subsequent reorganization process converted the microporous structure from low crystalline framework to crystalline UiO-66. The resultant mesopore size within the skeletons was controlled in the range from 9 to 21 nm. This approach provides a novel way of designing spaces from nano- to micrometer scale in network-forming materials.