The photochemical reduction of CO2 to deep reduction products, such as methanol, represents a net six electron process and is difficult to reconcile with the one photon-one electron stoichiometry of photochemical excitations, unless the process can be broken down into sequential one-electron steps. Bocarsly and co-workers have shown that pyridine is a functional electrocatalyst for the CO2 to methanol process, albeit with some dependence on the electrode material suggesting an active role in the reduction mechanism by the metallic surface.1 We recently demonstrated that a homogeneous mixture of [Ru(phen)3]Cl2/pyridine/ascorbate yields formate and to a lesser extent methanol upon visible light irradiation.2 This paper will present our recent studies in this area in which we constructed a Ru chromophore-pyridine unimolecular catalyst in an effort to improve performance. We have also expanded our studies to additional Ru-based chromophores. The successes, limitations, and future directions of this research will be presented. References 1. Cole, EB; Lakkaraju, PS; Rampulla, DM; Morris, AJ; Abelev, E; Bocarsly, AB. J Am Chem Soc. 2010 132(33), 11539-51. 2. Boston, DJ; Xu, C.; Armstrong, DW; MacDonnell, FM J. Am. Chem. Soc., 2013, 135 (44), 16252–16255. Boston, DJ; Pachon, YMF; Lezna, RO; de Tacconi, NR; MacDonnell, FM Inorg. Chem. 2014 53(13), 6544-6553.

Deep photoreduction of carbon dioxide to methanol and formate by ruthenium polypydridyl chromophores with pendant pyridyl sites

249th National Meeting (2015)

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