Electrochemical Reduction Pathways from Goethite to Green Iron in Alkaline Solution with Silicate Additive

Energy-efficient and low-temperature iron electrolysis in alkaline solutions is a low-cost and sustainable ironmaking process with zero-carbon emissions when renewable electrical sources are involved. However, its implementation is hindered by electrochemically inert Fe₃O₄ and parasitic H₂ gas formation during the electrochemical reduction process, resulting in the low energy efficiency of iron electrolysis. Here, we further explore the potential of electrochemical reduction of goethite (FeOOH) by employing a low concentration of silicate additive in an alkaline solution to mitigate Fe₃O₄ accumulation and H₂ generation. Electrochemical measurements coupled with operando X-ray diffraction and X-ray absorption spectroscopy suggested FeOOH → Fe₃O₄ → Fe-(OH)₂ → Fe reduction pathways. Interestingly, a poorly crystalline or amorphous Fe-(OH)₂ phase formed in the NaOH/silicate mixed electrolyte, possibly due to the inhibitive effect of silicate on water and ion transport, which eventually contributed to the improved reduction of Fe₃O₄, also supported by atomistic simulations. This work demonstrates the potential for silicate as a low-cost and effective electrolyte additive to improve room-temperature green iron formation via electrolysis.