(1) Catalysis of the electrochemical reduction of carbon dioxide, and the photochemical "splitting" of carbon dioxide.

(2) "Ultrafast" electron transfer dynamics in inorganic mixed valence complexes.

Catalysis of the electrochemical reduction of carbon dioxide. The goal of these studies is to utilize CO2, an abundant greenhouse gas, for the ultimate manufacture of energy dense liquid fuels. These efforts have concentrated on CO2 activation and reduction of CO2 by chemical, photochemical, and electrochemical means, and the development of catalysts for transforming CO2 to organic products. Catalysts which can manage multiple proton coupled electron transfers (PCETs) to CO2 to form liquid fuels such as methanol are being developed. We are employing semiconductor devices with appropriate band energies to photochemically "split" CO2 to CO and O2.

A class of inorganic charge transfer complexes with electronic structures that can be tuned from completely delocalized to tightly localized is under investigation. At the delocaization limit, rates of intramolecular electron transfer in these systems can be so fast that coalescence of infrared spectral features occurs in a manner reminiscent of dynamic NMR, but on a picosecond (vs. millisecond for NMR) time scale. The dynamics probed by this simple IR method track solvent dipolar response, and can be developed as "reporters" of local dynamics. We expect that the fundamental knowledge gained can be applied to the rational design of "electronically wired" metal complexes and "molecular devices".

Image Gallery

• Persistence of the three-state description of mixed valency at the localized-to-delocalized transition. S. D. Glover and C. P. Kubiak, J. Am. Chem. Soc., 2011, 133, 8721-8731


• Electrocatalytic Oxidation of Formate by [Ni(PR2NR2)2(CH3CN)]2+ Complexes. J. Schoeffel, B. R. Galan, A. M. Appel, J. C. Linehan, J. A. S. Roberts, C. Seu, M. L. Helm, U. J. Kilgore, J. Y. Yang, D. DuBois, C. P. Kubiak., J. Am. Chem. Soc., 2011, 133, 1276712779.


• Kinetics and Limiting Current Densities of Homogeneous and Heterogeneous Electrocatalysts. A. J. Sathrum and C. P. Kubiak, J. Phys. Chem. Lett., 2011, 2, 2372-2379


• Re(bipy-tBu)(CO)3Cl - improved catalytic activity for reduction of carbon dioxide. IR-Spectroelectrochemical and mechanistic studies. J. M. Smieja, C. P. Kubiak, Inorg. Chem., 2010, 49, 9283-9289


• Photo-reduction of CO2 on p-type silicon using Re(bipy-But)(CO)3Cl: Photovoltages exceeding 600 mV for the selective reduction of CO2 to CO. B. Kumar, J. M. Smieja, C. P. Kubiak, J. Phys. Chem. C, 2010, 114, 14220-14223


• Mixed Valency Across Hydrogen Bonds. J. C. Goeltz, C. P. Kubiak, J. Am. Chem. Soc., 2010, 132, 17390-17392


• Inter- or Intra-molecular electron transfer: Well cross that bridge when we come to it. S. D. Glover, J. C. Goeltz, B. J. Lear, C. P. Kubiak, Coord. Chem. Rev., 2010, 254, 331-345


• Electrocatalytic and homogeneous approaches to conversion of CO2 to liquid fuels. E. E. Benson, C. P. Kubiak, A. J. Sathrum, J. M. Smieja, Chem. Soc. Rev., 2009, 38, 89-99.


• Solvent dynamical control of ultrafast ground state electron transfer: Implications for class II-III mixed valency. B. J. Lear, S. D. Glover, J. C. Salsman, C. H. Londergan, C. P. Kubiak, J. Am. Chem. Soc., 2007, 129, 12772-12779.