In situ Neutron Diffraction Studies of CO2 Photoreduction over MOF-catalysts

The photocatalytic reduction of CO2 to liquid C2+ products is an important but extremely challenging target owing to difficulties in the formation of C–C bonds. Metal–organic frameworks (MOFs) show porous structures and tuneable band-gap and thus emerge as promising photocatalysts. We have prepared a series of Ce-MOF catalysts [Ce-UiO-66-R (R= -NH2, -NO2, -COOH, -Br, -H)] for CO2 photoreduction. Importantly, Ce(IV)-UiO-66-NH2 shows an unprecedented catalytic performance for the reduction of CO2 to acetic acid (1.4 mmol gcat-1 h-1, selectivity >99.9%), which surpasses all state-of-the-art catalysts (unpublished). This proposal aims to test a newly developed sample environment coupling neutron powder diffraction (NPD) and photocatalysis at WISH to evaluate the formation of intermediates of the hydrogenation and C-C coupling as well as any structural changes during the reaction, which will afford key insights into the catalytic mechanism, the first of its kind in NPD studies.