Metal–organic framework (MOF) thin films are highly desirable because the unique characteristics of MOFs could then be incorporated into micro-electronic devices, sensors, and membranes. We have recently developed a new thin film growth method for highly oriented Cu3(BTC)2(HKUST-1) under vacuum without the use of solvents. Using a layer-by-layer (LBL) growth technique, we sequentially deposited H3BTC employing a chemical vapor deposition process and Cu using a physical vapor deposition process, which yields a 20 nm thick HKUST-1 film for each growth cycle. With this growth method, it is easy to control the quantity of deposited Cu, so in this study we deposit extra Cu atoms into the HKUST-1 structure in order to observe their catalytic activity. By depositing 4 ML and 8 ML Cu during the growth cycles, which are more than the optimized amount needed (1 ML Cu) for one growth cycle of the HKUST-1 thin film, we can incorporate 4-6 nm and 8-10 nm Cu nanoparticles in the HKUST-1 structure respectively (as confirmed by TEM measurements). These Cu nanoparticle-incorporated HKUST-1 thin films show catalytic activity for the methanol oxidation under vacuum. In particular, the 4 ML Cu-HKUST-1 film (5 growth cycles) selectively oxidizes methanol molecules to formaldehyde, but the 8 ML Cu-HKUST-1 film (5 growth cycles) more strongly oxidizes the methanol to generate not only formaldehyde, but also CO2by forming formate species. In this study, we investigate how to control the Cu nanoparticle size in the vacuum grown HKUST-1 thin film and how it affects to the catalytic activity under vacuum.

Copper controlled vacuum deposition of HKUST-1 thin films and their use as heterogeneous catalysts

Macromolecular Chemistry: The Second Century

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ACS Spring 2020 National Meeting & Expo

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.