Non-covalent ligand-oxide interaction promotes oxygen evolution.

Strategies to generate high-valence metal species capable of oxidizing water often employ composition and coordination tuning of oxide-based catalysts, where strong covalent interactions with metal sites are crucial. However, it remains unexplored whether a relatively weak “non-bonding” interaction between ligands and oxides can mediate the electronic states of metal sites in oxides. Here we present an unusual non-covalent phenanthroline-CoO₂ interaction that substantially elevates the population of Co⁴⁺ sites for improved water oxidation. We find that phenanthroline only coordinates with Co²⁺ forming soluble Co(phenanthroline)₂(OH)₂ complex in alkaline electrolytes, which can be deposited as amorphous CoO_xH_y film containing non-bonding phenanthroline upon oxidation of Co²⁺ to Co^3+/4+. This in situ deposited catalyst demonstrates a low overpotential of 216 mV at 10 mA cm⁻² and sustainable activity over 1600 h with Faradaic efficiency above 97%. Density functional theory calculations reveal that the presence of phenanthroline can stabilize CoO₂ through the non-covalent interaction and generate polaron-like electronic states at the Co-Co center.If and how non-bonding ligands mediate the electronic states of metal sites is interesting yet remains to be explored. Here the authors show that a non-covalent phenanthroline can promote the population of Co⁴⁺ and induce polaron-like Co sites for improved water oxidation. [ABSTRACT FROM AUTHOR]