Investigating the redox properties of bioinspired Cu-MOFs using combined in situ XAS and XRD

Oxygenases are known to be excellent catalysts in C-H oxidation reactions, and are therefore good inspiration when designing new catalysts. Hybrid materials, more specifically metal-organic frameworks (MOFs), have shown potential to be used as catalysts, since they are highly tunable in terms of both chemistry and structure. Thus, we have synthesized new bioinspired Zr-based MOFs, and post-synthetically incorporated new enzyme-mimicking linkers, as well as copper cations. We have experimental evidence that suggest two copper sites inside of the MOFs, but their redox properties, as well as their chemical microenvironment are yet to be understood. This proposal therefore aims at combining in-situ XAS and XRD during redox cycles containing a purging/reduction/oxidation/reaction steps, to investigate those questions. XANES and EXAFS will be used to better understand the local environment around Cu (including Cu-oxo species and/or intermediates) at the various stages of the redox cycle.