433890 Dihydropteridine/Pteridine As a 2H+/2e- Redox Mediator for the Catalytic Reduction of CO2 to Methanol Via Hydride-Proton Transfer

Wednesday, November 11, 2015: 3:36 PM
250E (Salt Palace Convention Center)
Charles B. Musgrave, Department of Chemical and Biological Engineering, University of Colorado, Boulder, CO, Chern-Hooi Lim, Chemical and Biological Engineering, University of Colorado Boulder, Boulder, CO, Aaron Holder, Department of Chemistry and Biochemistry, University of Colorado, Boulder, CO, James T. Hynes, Chemistry, Ecole Normale Supérieure, Paris, France and Yu-Ching Kuo, University of Colorado at Boulder, Boulder, CO

The development of renewable energy technologies has been the focus of tremendous recent effort. One particularly desirable approach involves using solar energy to power the production of “solar fuels” by either splitting H2O or reducing CO2. These technologies would form the basis of either a hydrogen or, for example, methanol economy. In either case, the discovery of capable redox catalysts lies at the heart of both of these visions and remains as a grand challenge.

Dyer and coworkers have recently reported the use of a pteridine electrocatalyst, 6,7-dimethyl-4-hydroxy-2-mercaptopteridine (PTE), to catalyze the reduction of CO2 to CH3OH with a Faradaic efficiency of 10-23% and at low overpotentials; intermediate 2e-(formic acid) and 4e- (formaldehyde) products are also observed. In this contribution, we use computational chemistry to discover that species 3 is the most stable tautomer of PTE and that it undergoes a concerted 2H+/2e- transfer to dominantly form 3a (Scheme 1). We predict that PTE's ability to catalyze the reduction of CO2 originates from a dearomatization-aromatization process of the 3/3a redox couple, in which 3a acts as a regenerable organo-hydride that reduces CO2 to CH3OH via three successive hydride and proton transfer (HTPT) steps (Scheme 1).

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See more of this Session: Novel Approaches to CO2 Utilization
See more of this Group/Topical: Topical Conference: Advances in Fossil Energy R&D