Development of molecular electrocatalysts for CO2 reduction and H2 production/oxidation

TY - JOUR

T1 - Development of molecular electrocatalysts for CO2 reduction and H2 production/oxidation

AU - Dubois, M. Rakowski

AU - DuBois, Daniel L

PY - 2009/12/21

Y1 - 2009/12/21

N2 - The conversion of solar energy to fuels in both natural and artificial photosynthesis requires components for both light-harvesting and catalysis. The light-harvesting component generates the electrochemical potentials required to drive fuel-generating reactions that would otherwise be thermodynamically uphill. This Account focuses on work from our laboratories on developing molecular electrocatalysts for CO2 reduction and for hydrogen production. A true analog of natural photosynthesis will require the ability to capture CO2 from the atmosphere and reduce it to a useful fuel. Work in our laboratories has focused on both aspects of this problem. Organic compounds such as quinones and inorganic metal complexes can serve as redox-active CO2 carriers for concentrating CO2. We have developed catalysts for CO2 reduction to form CO based on a [Pd(triphosphine)(solvent)]2+ platform. Catalytic activity requires the presence of a weakly coordinating solvent molecule that can dissociate during the catalytic cycle and provide a vacant coordination site for binding water and assisting C-O bond cleavage. Structures of [NiFe] CO dehydrogenase enzymes and the results of studies on complexes containing two [Pd(triphosphine)(solvent)]2+ units suggest that participation of a second metal in CO2 binding may also be required for achieving very active catalysts. We also describe molecular electrocatalysts for H2 production and oxidation based on [Ni(diphosphine)2]2+ complexes. Similar to palladium CO2 reduction catalysts, these species require the optimization of both first and second coordination spheres. In this case, we use structural features of the first coordination sphere to optimize the hydride acceptor ability of nickel needed to achieve heterolytic cleavage of H2. We use the second coordination sphere to incorporate pendant bases that assist in a number of important functions including H 2 binding, H2 cleavage, and the transfer of protons between nickel and solution. These pendant bases, or proton relays, are likely to be important in the design of catalysts for a wide range of fuel production and fuel utilization reactions involving multiple electron and proton transfer steps. The generation of fuels from abundant substrates such as CO2 and water remains a daunting research challenge, requiring significant advances in new inexpensive materials for light harvesting and the development of fast, stable, and efficient electrocatalysts. Although we describe progress in the development of redox-active carriers capable of concentrating CO2 and molecular electrocatalysts for CO2 reduction, hydrogen production, and hydrogen oxidation, much more remains to be done.

AB - The conversion of solar energy to fuels in both natural and artificial photosynthesis requires components for both light-harvesting and catalysis. The light-harvesting component generates the electrochemical potentials required to drive fuel-generating reactions that would otherwise be thermodynamically uphill. This Account focuses on work from our laboratories on developing molecular electrocatalysts for CO2 reduction and for hydrogen production. A true analog of natural photosynthesis will require the ability to capture CO2 from the atmosphere and reduce it to a useful fuel. Work in our laboratories has focused on both aspects of this problem. Organic compounds such as quinones and inorganic metal complexes can serve as redox-active CO2 carriers for concentrating CO2. We have developed catalysts for CO2 reduction to form CO based on a [Pd(triphosphine)(solvent)]2+ platform. Catalytic activity requires the presence of a weakly coordinating solvent molecule that can dissociate during the catalytic cycle and provide a vacant coordination site for binding water and assisting C-O bond cleavage. Structures of [NiFe] CO dehydrogenase enzymes and the results of studies on complexes containing two [Pd(triphosphine)(solvent)]2+ units suggest that participation of a second metal in CO2 binding may also be required for achieving very active catalysts. We also describe molecular electrocatalysts for H2 production and oxidation based on [Ni(diphosphine)2]2+ complexes. Similar to palladium CO2 reduction catalysts, these species require the optimization of both first and second coordination spheres. In this case, we use structural features of the first coordination sphere to optimize the hydride acceptor ability of nickel needed to achieve heterolytic cleavage of H2. We use the second coordination sphere to incorporate pendant bases that assist in a number of important functions including H 2 binding, H2 cleavage, and the transfer of protons between nickel and solution. These pendant bases, or proton relays, are likely to be important in the design of catalysts for a wide range of fuel production and fuel utilization reactions involving multiple electron and proton transfer steps. The generation of fuels from abundant substrates such as CO2 and water remains a daunting research challenge, requiring significant advances in new inexpensive materials for light harvesting and the development of fast, stable, and efficient electrocatalysts. Although we describe progress in the development of redox-active carriers capable of concentrating CO2 and molecular electrocatalysts for CO2 reduction, hydrogen production, and hydrogen oxidation, much more remains to be done.

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U2 - 10.1021/ar900110c

DO - 10.1021/ar900110c

M3 - Article

C2 - 19645445

AN - SCOPUS:72949118053

VL - 42

SP - 1974

EP - 1982

JO - Accounts of Chemical Research

JF - Accounts of Chemical Research

SN - 0001-4842

IS - 12

ER -