This proposal aims to characterize by Cu k-edge XAS, HERFD-XANES, vtc-XES and RIXS to disclose the finest details on the redox chemistry of Cu sites hosted within a selection of Cu-MOFs. In particular, structural and redox behavior will be investigated during the stepwise methane to methanol reaction. These MOFs, belonging to the UiO-6X family, have been post-synthetically treated to introduce various biomimetic anchoring site, as inspired by the histidine brace coordinating Cu in some enzymes capable of performing C-H bond oxidation. With each technique, will focus on the main reaction stages (desolvation, oxidation and reactivity with CH4). Special care will be put in characterizing the oxidized state, aiming at the identification of potentially active Cu-O species. These outcomes will provide unprecedented structural details on the local environment in such Cu-MOFs at the various reaction stages.

This proposal aims to characterize by Cu k-edge XAS, HERFD-XANES, vtc-XES and RIXS to disclose the finest details on the redox chemistry of Cu sites hosted within a selection of Cu-MOFs. In particular, structural and redox behavior will be investigated during the stepwise methane to methanol reaction. These MOFs, belonging to the UiO-6X family, have been post-synthetically treated to introduce various biomimetic anchoring site, as inspired by the histidine brace coordinating Cu in some enzymes capable of performing C-H bond oxidation. With each technique, will focus on the main reaction stages (desolvation, oxidation and reactivity with CH4). Special care will be put in characterizing the oxidized state, aiming at the identification of potentially active Cu-O species. These outcomes will provide unprecedented structural details on the local environment in such Cu-MOFs at the various reaction stages.