Abstract : The valorization of CO2 via photo- or electrocatalytic reduction constitutes a promising approach toward the sustainable production of fuels or value-added chemicals using intermittent renewable energy sources. For this purpose, molecular catalysts are generally studied independently with respect to the photo- or the electrochemical application, although a unifying approach would be much more effective with respect to the mechanistic understanding and the catalyst optimization. In this context, we present a combined photo- and electrocatalytic study of three Mn diimine catalysts, which demonstrates the synergistic interplay between the two methods. The photochemical part of our study involves the development of a catalytic system containing a heteroleptic Cu photosensitizer and the sacrificial BIH reagent. The system shows exclusive selectivity for CO generation and renders turnover numbers which are among the highest reported thus far within the group of fully earth-abundant photocatalytic systems. The electrochemical part of our investigations complements the mechanistic understanding of the photochemical process and demonstrates that in the present case the sacrificial reagent, the photosensitizer, and the irradiation source can be replaced by the electrode and a weak Brønsted acid.
