Leveraging metal node-linker self-assembly to access functional anisotropy of zirconium-based MOF-on-MOF epitaxial heterostructure thin films

Abstract

Chemically robust, functional porous materials are imperative for designing novel membranes for chemical separation and heterogeneous catalysts. Among the array of potential materials, zirconium (Zr)-based metal–organic frameworks (MOFs) have garnered considerable attention, and have been investigated for applications related to gas separation and storage, and catalysis. However, a significant challenge with Zr-MOFs lies in their processibility, particularly in achieving homogenous thin films and controlling functional anisotropy. The recent developments in MOF thin film fabrication methodologies do not yield a solution to achieve mild reaction condition growth of Zr-MOF thin films with epitaxial MOF-on-MOF geometry (i.e. functional anisotropy). In the current work, we have devised a straightforward methodology under room temperature conditions, which enables epitaxial, oriented MOF-on-MOF thin film growth. This achievement is accomplished through a stepwise self-assembly approach involving Zr nodes and linkers on a functionalized substrate. This de novo developed strategy of functionality design is demonstrated for UiO-66 (University of Oslo) type Zr-MOFs. We have demonstrated the precise placement of chemical functionalities within the thin film structure, allowing for controlled chemical diffusion and regulation of diffusion selectivity.