Final technical report. Bimetallic complexes as methanol oxidation catalysts

Our work on the electrocatalyzed oxidation of methanol was initially motivated by the interest in methanol as an anodic reactant in fuel cells. The literature on electrochemical oxidation of alcohols can be roughly grouped into two sets: fuel cell studies and inorganic chemistry studies. Work on fuel cells primarily focuses on surface-catalyzed oxidation at bulk metal anodes, usually Pt or Pt/Ru alloys. In the surface science/electrochemistry approach to these studies, single molecule catalysts are generally not considered. In contrast, the inorganic community investigates the electrooxidation of alcohols in homogeneous systems. Ruthenium complexes have been the most common catalysts in these studies. The alcohol substrates are typically either secondary alcohols (e.g., isopropanol) such that the reaction stops after 2 e{sup -} oxidation to the aldehyde and 4 e{sup -} oxidation to the carboxylic acid can be observed. Methanol, which can also undergo 6 e{sup -} oxidation to CO{sub 2}, rarely appears in the homogeneous catalysis studies. Surface studies have shown that two types of metal centers with different functions result in more effective catalysts than a single metal; however, application of this concept to homogeneous systems has not been demonstrated. The major thrust of the work is to apply this insight from the surface studies to homogeneous catalysis. Even though homogeneous systems would not be appropriate models for active sites on Pt/Ru anodes, it is possible that heterobimetallic catalysts could also utilize two metal centers for different roles. Starting from that perspective, this work involves the preparation and investigation of heterobinuclear catalysts for the electrochemical oxidation of methanol