Electrocatalysis offers the potential to efficiently store electrical energy generated by solar, wind, geothermal, or nuclear energy sources in the form of fuels such as H2, alcohols, ammonia, etc. by the reduction of small abundant molecules such as water, CO2, and N2, respectively. Future technological applications will require a broad array of such catalysts that can operate under a wide range of conditions. A modular energy-based approach has been used to develop molecular electrocatalysis for CO2 reduction, formate oxidation, H2 oxidation, and H2 production.  In this approach, catalyst structures are broken down into first, second, and outer coordination spheres.  The first coordination sphere can be used to incorporate vacant sites for substrate binding and to control thermodynamic properties, such as redox potentials, hydride donor/acceptor abilities, and pKa values.  The second coordination sphere consists of functional groups in close proximity to the metal that can interact directly with substrate molecules such as H2 or CO2. The second coordination sphere can facilitate substrate binding, bond formation and cleavage, and proton movement during catalytic reactions. In enzymes the outer coordination sphere includes electron transfer pathways, proton channels, and tunnels for the transport of small molecules such as H2 and CO. Once a general structural motif has been established for electrocatalysis, a second and equally important aspect for the development of fast and efficient catalysts is the ability to avoid high-energy intermediates and thermodynamic sinks.  Progress toward simple models for predicting free energy landscapes for complete catalytic cycles will be presented for electrocatalysts for H2 production and oxidation.  These principles have been used to develop highly active catalysts for CO2 reduction to CO, formate oxidation and production, and H2 oxidation and production.

Award Address  (ACS Award in Inorganic Chemistry sponsored by Aldrich Chemical Company LLC). Studies in molecular electrocatalysis for renewable energy storage and utilization

245th National Meeting (2013)

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