Surface anchored metal-organic frameworks (SurMOFs) represent a class of extremely porous, crystalline materials with high surface area that consist of both metal ions and organic ligands.  Layer-by-layer solution-phase epitaxy has been studied extensively for the HKUST-1 system, consisting of Cu and trimesic acid (TMA), deposited on a SAM-coated Au substrate. We have extended our investigations beyond this method to study additional means of fabricating SurMOFs via co-deposition, drop-casting, and seeded deposition.  By varying temperature, time and deposition method, design rules to tailor SurMOFs with a desired thickness, roughness, and grain size were investigated.  In addition to studies investigating film growth mechanisms, ammonia adsorption capabilities of these films have been examined and compared to bulk powder.  The HKUST-1 system can contain ligands coordinated to the axial positions of the copper-carboxylic acid paddlewheel structure. We have interrogated how different paddlewheel adsorbates alter the ammonia gas interaction with the framework, affecting the morphology and crystal structure.  Fourier-transform infrared spectroscopy, scanning electron microscopy, energy dispersive x-ray spectroscopy, scanning probe microscopy, and powder x-ray diffraction were used to characterize samples before and after ammonia exposure, tracking uptake of ammonia, as well as monitoring changes in both surface morphology and crystal structure.  Specifically, systematic studies have compared three variations of the HKUST-1system: bulk powder, drop-casted film, and surMOF.  The size of these structures span from millimeter crystals (bulk powders) to micrometer grains (drop-cast films) and nanometer crystallites (surMOFs) elucidating what effects are inherent to the MOF system or fabrication method as opposed to being substrate-induced or size-dependent.<br/>

Exploring fabrication and gas adsorption for HKUST-1 thin films and powders

254th National Meeting (2017)

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