Electrodeposition of Fe-Complexes on Oxide Surfaces for Efficient OER Catalysis

Progress in non-covalent/self-assembled immobilization methods on (photo)electrode materials for molecular catalysts could broaden the scope of attainable systems. While covalent linkage (though considered more stable) necessitates functional groups introduced by means of often cumbersome synthetic procedures, non-covalent assemblies require sufficient propensity of the molecular unit for surface adsorption, thus set less rigorous pre-requisites. Herein, we report efficient electrodeposition (ED) of two Fe(III) complexes prepared with closely related NN'N pincer ligands yielding stable and active ad-layers for the electrocatalysis of the oxygen-evolving reaction (OER). The ED method is based on the utilization of a chloride precursor complex [(FeCl2)-Cl-III(NN'N)], which is dissolved in an organic electrolyte undergoes chloride/aqua ligand exchange upon addition of water. ED provides patchy distribution of a chloride-depleted catalyst layer on indium tin oxide (ITO) and fluorine-doped tin oxide (FTO) surfaces, which can be applied for long periods as OER electrocatalysts. Compared to drop-casting or layering of [(FeCl2)-Cl-III(NN'N)] with Nafion (a commonly used support for molecular electrocatalysts), the surface modification by ED is a material saving and efficient method to immobilize catalysts.