Centimeter-Scale Pillared-Layer Metal-Organic Framework Thin Films Mediated by Hydroxy Double Salt Intermediates for...

Fabrication of metal-organic framework (MOF) thin films over macroscopic surface areas is a subject of great interest for gas sensor application platforms such as optics and microelectronics. However, a direct synthesis of MOF films at ambient conditions, in particular pillared-layer MOF films due to their anisotropic structures, remains a significant challenge. Herein, we demonstrate for the first time a facile construction of dense and continuous pillared-layer MOF thin films on a centimeter scale via an aluminum-doped zinc oxide template and hydroxy double salt (HDS) intermediates at room temperature. A series of Cu(II)-based pillared MOFs with different 1,4-benzenedicarboxylic acid (bdc) ligands were explored for optimizing MOF film formation for CO₂ sensor applications. Nonpolar ligands with lower water solubility preferentially formed crystalline pillared MOF structures from HDS intermediates. A Cu₂(ndc)₂(dabco) (ndc = 1,4-naphthalene-bdc; dabco = 1,4-diazabicyclo[2.2.2]octane) MOF demonstrated the most dense and uniform film growth with micrometer thickness over one square centimeter area. This synthetic approach for growing Cu₂(ndc)₂(dabco) MOF thin films was successfully translated toward two sensing platforms: a quartz crystal microbalance and an optical fiber sensor. These Cu₂(ndc)₂(dabco) MOF-coated sensors displayed sensitivity toward CO₂ and response/recovery time on the scale of seconds, even at moderate humidity levels. This work provides a road map for producing continuous and anisotropic crystalline MOF thin films over a centimeter scale area on various substrates, which will greatly facilitate their utilization in MOF-based sensor devices, among other applications.