Heterogenized Molecular Catalysts: Vibrational Sum-Frequency Spectroscopic, Electrochemical, and Theoretical Investigations

ConspectusRhenium and manganese bipyridyl tricarbonyl complexes have attracted intense interest for their promising applications in photocatalytic and electrocatalytic CO2 reduction in both homogeneous and heterogenized systems. To date, there have been extensive studies on immobilizing Re catalysts on solid surfaces for higher catalytic efficiency, reduced catalyst loading, and convenient product separation. However, in order for the heterogenized molecular catalysts to achieve the combination of the best aspects of homogeneous and heterogeneous catalysts, it is essential to understand the fundamental physicochemical properties of such heterogeneous systems, such as surface-bound structures of Re/Mn catalysts, substrate–adsorbate interactions, and photoinduced or electric-field-induced effects on Re/Mn catalysts. For example, the surface may act to (un)block substrates, (un)trap charges, (de)stabilize particular intermediates (and thus affect scaling relations), and shift potentials in different directio...