Fig. 4. Mn-OEC catalysis and self-assembly.

A Proposed OER catalytic cycle for Mn-OECs, as determined from spectroscopic analysis and electrochemical kinetics studies at different pHs. B Proposed mechanism for the generation of Mn-OEC films. The protons (H⁺) that appear in the electrochemical rate laws for OER and catalyst deposition/regeneration are highlighted in red. Owing to the disproportionation reaction involving two manganese complexes, an inverse fourth-order proton dependence is observed, enabling self-healing to be preserved at pH > –0.5. DISP and TLS denote disproportionation and turnover-limiting step, respectively.