Electrochemical Hydrogen Production from Oilfield Produced Water: Physicochemical Characterization, Impedance Analysis, and Faradaic Efficiency Evaluation

The growing deployment of green hydrogen technologies is increasing pressure on freshwater resources, motivating the exploration of alternative water sources that do not compete with human consumption. In this work, the direct use of untreated produced water from the Shushufindi 78 oil well (Ecuador) as an electrolyte for the hydrogen evolution reaction (HER) was experimentally evaluated. A comprehensive physicochemical characterization combined with electrochemical techniques, electrochemical impedance spectroscopy (EIS), and gas chromatography (GC-TCD) was performed to correlate electrolyte composition with electrochemical performance. Despite the high salinity and complex composition of the electrolyte, hydrogen production was achieved without pretreatment. Quantitative GC-TCD analysis yielded 10.29 µmol of H 2 after 4 h of electrolysis under non-optimized laboratory conditions, corresponding to a faradaic efficiency of 43.8%. These results demonstrate the feasibility of direct hydrogen generation from untreated produced water under realistic operating conditions. Additional experiments conducted in a membrane separated H-type electrolyzer evaluated mixtures of produced water and KOH, the electrolyte commonly employed in alkaline water electrolysis. Hydrogen production increased significantly under alkaline conditions, with the PW 10% + KOH 90% electrolyte exhibiting the highest hydrogen yield and faradaic efficiency among the investigated systems. Electrochemical impedance spectroscopy revealed that KOH addition reduced solution resistance and improved ionic transport, while differences in interfacial behavior were observed depending on electrolyte composition. The combined electrochemical and chromatographic results demonstrate that untreated produced water can be directly utilized for hydrogen production and can also be partially integrated into alkaline electrolysis systems without compromising electrochemical performance. These findings highlight the potential of produced water as a non-conventional water resource for sustainable hydrogen generation and industrial wastewater valorization.