{Co₄O₄} Cubanes in a conducting polymer matrix as bio-inspired molecular oxygen evolution catalysts

Exploration of efficient molecular water oxidation catalysts for long-term application remains a key challenge for the conversion of renewable energy sources into fuels. Cuboidal {Co₄O₄} complexes keep attracting interest as molecular water oxidation catalysts as they combine features of both heterogeneous and homogeneous catalysis with bio-inspired motifs. However, the application of many cluster-based catalysts for the oxygen evolution reaction still requires new stabilization strategies. Drawing inspiration from the stabilizing effects of natural polymers, we introduce a conductive polymer-hybrid approach to covalently immobilize {Co₄O₄} cubane oxo clusters as oxygen evolution catalysts. Polypyrrole is applied as an efficient p-type conducting polymer that promotes hole transfer during the oxygen evolution reaction, resulting in higher turnover frequency compared to the pristine {Co₄O₄} oxo cluster and heterogeneous Co-oxide benchmarks. The asymmetric coordination of {Co₄O₄} not only mitigates catalyst decomposition pathways, but also increases the catalytic efficiency by exposing a directed cofacial dihydroxide motif during catalysis.