| Abstract |
Selective conversion of alcohols into energy and oxidation products is a target of primary importance for the development of new sustainable energy resources (potentially without CO2 emission) and useful chemicals. Organometallic (immobilized) transition metal complexes can be used as anode electro-catalyst in direct alcohol fuel cells, where the free energy of alcohols is converted into electrical energy. Similar systems selectively convert alcohols into useful oxidation products. Recently, the clean decomposition of MeOH/water mixtures into H2 and CO2 was demonstrated, liberating the full hydrogen content of methanol (~12 weight%). All of these interesting energy conversion reactions operate via well-defined complexes with special 'non-innocent' ligands, but the exact reaction mechanisms have remained elusive. Given the high relevance of these processes we here propose to evaluate the reaction mechanism of these systems with detailed density functional theory (DFT) calculations. The proposal specifically focusses on understanding the special role of the 'cooperative' and 'redox non-innocent' ligands. |
