Molecular Mixed–Metal Manganese Oxido Cubanes as Precursors to Heterogeneous Oxygen Evolution Catalysts

摘要

Well-defined mixed–metal [CoMn3O4] and [NiMn3O4] cubane complexes were synthesized and used as precursors for heterogeneous oxygen evolution reaction (OER) electrocatalysts. The discrete clusters were dropcasted onto glassy carbon (GC) and indium-tin oxide (ITO) electrodes, and the OER activities of the resulting films were evaluated. The catalytic surfaces were analysed by various techniques to gain insight into the structure-function relationships of the electrocatalysts’ heterometallic composition. Depending on preparation conditions, the Co-Mn-oxide was found to change metal composition during catalysis, while the Ni-Mn-oxides maintained the NiMn3 ratio. XAS studies provided structural insights indicating that the electrocatalysts are different from the molecular precursors, but that the original NiMn3O4 cubane-like geometry was maintained in the absence of thermal treatment (>2-Ni). In contrast, the thermally generated >3-Ni develops an oxide-like extended structure. Both >2-Ni and >3-Ni show structural changes upon electrolysis, but they do not convert to the same material. The observed structural motifs in these heterogeneous electrocatalysts are reminiscent of the biological Oxygen Evolving Complex in Photosystem II, including the MMn3O4 cubane moiety. The reported studies demonstrate the use of discrete heterometallic-oxide clusters as precursors for heterogeneous water oxidation catalysts of novel composition and the distinct behavior of two sets of mixed-metal oxides.