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The development of non-precious metal-based electrodes that actively and stably support the oxygen evolution reaction (OER) in water electrolysis systems remains a challenge, especially at low pH levels. The recently published study has conclusively shown that the addition of haematite to H2 SO4 is a highly effective method of significantly reducing oxygen evolution overpotential and extending anode life. The far superior result is achieved by concentrating oxygen evolution centres on the oxide particles rather than on the electrode. However, unsatisfactory Faradaic efficiencies of the OER and hydrogen evolution reaction (HER) parts as well as the required high haematite load impede applicability and upscaling of this process. Here it is shown that the same performance is achieved with three times less metal oxide powder if NiO/H2 SO4 suspensions are used along with stainless steel anodes. The reason for the enormous improvement in OER performance by adding NiO to the electrolyte is the weakening of the intramolecular O─H bond in the water molecules, which is under the direct influence of the nickel oxide suspended in the electrolyte. The manipulation of bonds in water molecules to increase the tendency of the water to split is a ground-breaking development, as shown in this first example.
For a good reason, water splitting is the most pioneering energy storage technology. However, particularly water electrolysis still has a shadow existence compared to currently used methods for mass production of hydrogen. All known materials currently exploited as anodes for electrocatalytically initiated water-splitting suffer from high overpotentials and substantial mass loss during long term operation in acidic media. Low electrode stability affects operating and maintenance costs and together with high overpotentials directly lowers the overall efficiency of electrocatalytically driven splitting of water. In circumventing these problems, scientists and engineers are currently modifying electrode materials. We chose a completely different path and modified the electrolyte. An electrolysis set up, that consists of a Ni42 stainless steel anode and of hematite which is suspended in high concentration in sulfuric acid and acts as the electrolyte, exhibits oxygen evolution electrocatalysis at extremely low potential (1.26 V vs. RHE; 0.5 M H2SO4, j = 30 mA cm−2). If implemented in a suitable electrolyzer, an ultralow cell voltage of 1.6 V and an almost quantitative charge to oxygen + hydrogen conversion rate can be achieved. Remarkably, the negligible mass loss of the anode which consists exclusively of non-platinum group metals (non-PGM) during 100 h of operation. Experiments aimed at clarifying the mechanism suggest that Fe2O3 is converted to a Fe(II)/Fe(III) oxide species on the cathode which is then reconverted to Fe2O3 upon release of molecular oxygen when touching the anode. As a result, the oxygen-evolving centers are likely to be on the oxide particles rather than on the electrode. This proposed mechanism would explain the low potential of the OER electrode (+1.26 V vs. RHE at j = 30 mA cm−2) that could not be explained convincingly by an assumed direct oxidation of water molecules.