Defect Creation in Surface-Mounted Metal-Organic Framework Thin Films

Defect engineering is a strategy for tailoring the properties of metal-organic frameworks (MOFs). Plenty of efforts have been devoted to study the defect chemistry and structures of bulk MOFs; however, the reported example of a defect-engineered surface-mounted MOF (SURMOF) thin film is rare. In this work, defects were incorporated in SURMOF thin films by using defect-generating linkers and taking advantage of the liquid-phase stepwise epitaxial layer-by-layer growth (LBL). Two methods based on the LBL, named mixing method and alternating method, are proposed for incorporating defects in the prototypical SURMOF HKUST-1 by partially substituting the parent H₃btc (benzene-1,3,5-tricarboxylic acid) linker with a set of defect-generating linkers H₂ip (isophthalic acid), H₂OH-ip (5-hydroxyisophthalic acid), and H₂pydc (3,5-pyridinedicarboxylic acid). The crystallinity and phase purity of the obtained "defected" SURMOFs were confirmed by X-ray diffraction, infrared reflection absorption spectroscopy, and Raman spectroscopy. The incorporation of the defect-generating linkers and the types of induced defects were characterized by ultraviolet-visible spectroscopy, time-of-flight secondary ion mass spectrometry, methanol adsorption, scanning electron microscopy, and ¹H nuclear magnetic resonance spectroscopy (after digestion of the samples). These two methods provide avenues for controlling the defect formation in MOF thin films.