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Molecular Mixed‐Metal Manganese Oxido Cubanes as Precursors to Heterogeneous Oxygen Evolution Catalysts
Author(s) -
Suseno Sandy,
McCrory Charles C. L.,
Tran Rosalie,
Gul Sheraz,
Yano Junko,
Agapie Theodor
Publication year - 2015
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201501104
Subject(s) - oxygen evolution , catalysis , oxide , metal , chemistry , inorganic chemistry , manganese , moiety , cubane , electrocatalyst , oxygen , materials science , crystallography , electrochemistry , crystal structure , electrode , stereochemistry , organic chemistry
Well‐defined mixed‐metal [CoMn 3 O 4 ] and [NiMn 3 O 4 ] 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 analyzed 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 NiMn 3 ratio. XAS studies provided structural insights indicating that the electrocatalysts are different from the molecular precursors, but that the original NiMn 3 O 4 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 undergo structural changes upon electrolysis, but they do not convert into the same material. The observed structural motifs in these heterogeneous electrocatalysts are reminiscent of the biological oxygen‐evolving complex in Photosystem II, including the MMn 3 O 4 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.