Anode Preparation Strategies for the Electrocatalytic Oxidation of Water Based on Strong Interactions between Multiwalled Carbon Nanotubes and Cationic Acetylammonium Pyrene Moieties in Aqueous Solutions

A strategy is reported for the immobilization of iridium‐based water oxidation catalyst 3 onto fluorine‐doped tin oxide (FTO) anodes evaluated for the electrocatalytic oxidation of H₂O. The strategy is based on noncovalent π–π interactions between multiwalled carbon nanotubes (MWCNTs) and the cationic acetylammonium pyrene moiety (Pyr⁺) covalently attached to a NHC IrCp*Cl₂ catalytically active center (NHC=N‐heterocyclic carbene, Cp*=C₅Me₅). The dispersive properties of the Pyr⁺ moiety in compound 3 leads to the formation of stable MWCNT dispersions in aqueous solutions. In addition, the MWCNT/3 assembly shows activity in the Ce⁴⁺‐driven oxidation of H₂O. FTO/MWCNT/3 anodes show increased current densities when used as a working electrode for the electrocatalytic oxidation of H₂O. At higher anodic polarizations initially high current densities were achieved; however, these currents prove to be non‐sustained due to delamination and degradation of the catalytically active surface. The immobilization strategy is limited to applications below 1.4 V vs normal hydrogen electrode (NHE) as oxidation of the pyrene backbone is evident at higher potentials.