A Functional Hydrogenase Mimic Chemisorbed onto Fluorine‐Doped Tin Oxide Electrodes: A Strategy towards Water Splitting Devices

A diiron benzenedithiolate hydrogen‐evolving catalyst immobilized onto fluorine‐doped tin oxide (FTO) electrodes is prepared, characterized, and studied in the context of the development of water splitting devices based on molecular components. FTO was chosen as the preferred electrode material owing to its conductive properties and electrochemical stability. An FTO nanocrystalline layer is also used to greatly improve the surface area of commercially available FTO while preserving the properties of the material. Electrodes bearing a covalently anchored diiron catalyst are shown to be competent for electrocatalytic hydrogen evolution from acidic aqueous media at relatively low overpotential (500 mV) with a faradaic efficiency close to unity. Compared with bulk solution catalysts, the catalyst immobilized onto the electrode surface operates at roughly 160 mV lower overpotentials, yet with similar rates.