It has been a long-standing goal to combine the high specificity of homogeneous catalysts with facile product separability of heterogeneous catalysis. One approach involves supporting a molecular catalyst on solid surfaces. In this work, we use density functional theory (DFT) calculations to study the oxygen reduction reaction (ORR), the bottleneck reaction in cathode side of fuel cells, on 3d metal(II) porphycenes (M–Pc) supported on Au(111) surface. M–Pc are M–N<sub>4</sub> type aromatic macrocyclces like M–porphyrins (M–P) which are known ORR molecular electrocatalysts. We show that all the studied M–Pcs form strong bond to the substrate, indicating a stable structure under ORR condition. Based on thermodynamic analysis we estimate the activity of each of the 3d M–Pc both in the presence and absence of Au support. Our analysis show that, Mn–Pc, Fe–Pc, Co–Pc as the best ORR electrocatalysts with highest activities. Moreover, in many cases the Au support strongly affects the ORR activity of metal(II) porphycene electrocatalysts. We further demonstrate the role of the Au support in modifying the charge, spin and magnetic properties of the adsorbed metal complexes.

Investigating the oxygen reduction reaction on inorganic/metal interfaces

255th National Meeting (2018)

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