Mixed bimetallic oxides offer great opportunities for a systematic tuning of electrocatalytic activity and stability. Here, we demonstrate the power of this strategy using well-defined thermally prepared Ir-Ni mixed oxide thin film catalysts for the electrochemical oxygen evolution reaction (OER) under highly corrosive conditions such as in acidic proton exchange membrane (PEM) electrolyzers and photoelectrochemical cells (PEC). Variation of the Ir to Ni ratio resulted in a volcano type OER activity curve with an unprecedented 20-fold improvement in Ir mass-based activity over pure Ir oxide. In situ spectroscopic probing of metal dissolution indicated that, against common views, activity and stability are not directly anticorrelated. To uncover activity and stability controlling parameters, the Ir-Ni mixed thin oxide film catalysts were characterized by a wide array of spectroscopic, microscopic, scattering, and electrochemical techniques in conjunction with DFT theoretical computations. By means of an intuitive model for the formation of the catalytically active state of the bimetallic Ir-Ni oxide surface, we identify the coverage of reactive surface hydroxyl groups as a suitable descriptor for the OER activity and relate it to controllable synthetic parameters. Overall, our study highlights a novel, highly active oxygen evolution catalyst; moreover, it provides novel important insights into the structure and performance of bimetallic oxide OER electrocatalysts in corrosive acidic environments.

Seawater is an abundant water resource on our planet and its direct electrolysis has the advantage that it would not compete with activities demanding fresh water. Oxygen selectivity is challenging when performing seawater electrolysis owing to competing chloride oxidation reactions. In this work we propose a design criterion based on thermodynamic and kinetic considerations that identifies alkaline conditions as preferable to obtain high selectivity for the oxygen evolution reaction. The criterion states that catalysts sustaining the desired operating current with an overpotential <480 mV in alkaline pH possess the best chance to achieve 100 % oxygen/hydrogen selectivity. NiFe layered double hydroxide is shown to satisfy this criterion at pH 13 in seawater-mimicking electrolyte. The catalyst was synthesized by a solvothermal method and the activity, surface redox chemistry, and stability were tested electrochemically in alkaline and near-neutral conditions (borate buffer at pH 9.2) and under both fresh seawater conditions. The Tafel slope at low current densities is not influenced by pH or presence of chloride. On the other hand, the addition of chloride ions has an influence in the temporal evolution of the nickel reduction peak and on both the activity and stability at high current densities at pH 9.2. Faradaic efficiency close to 100 % under the operating conditions predicted by our design criteria was proven using in situ electrochemical mass spectrometry.

The electrochemical stability of thermally prepared Ir oxide films is investigated using a scanning flow cell (SFC)-inductively coupled plasma mass-spectrometer (ICP-MS) setup under transient and stationary potential and/or current conditions. Time-resolved dissolution rates provide important insights into critical conditions for material breakdown and a fully quantitative in-situ assessment of the electrochemical stability during oxygen evolution reaction (OER) conditions. In particular, the results demonstrate that stability and OER activity of the IrOx catalysts strongly depend on the chemical and structural nature of Ir oxide species and their synthesis conditions. (C) 2014 The Authors. Published by Elsevier B.V

Iridium (Ir) oxide is known to be one of the best electrocatalysts for the oxygen evolution reaction (OER) in acidic media. Ir oxide-based materials are thus of great scientific interest in current research on electrochemical energy conversion. In the present study, we applied Ir metal films as model systems for electrochemical water splitting, obtained by inductive heating in a custom-made setup using two different synthesis approaches. X-ray photoelectron spectroscopy (XPS) and selected area electron diffraction (SAED) confirmed that all films were consistently metallic. The effects of reductive heating time of calcined and uncalcined Ir acetate films on OER activity were investigated using a rotating disk electrode (RDE) setup. The morphology of all films was determined by scanning electron microscopy (SEM). The films directly reduced from the acetate precursor exhibited a strong variability of their morphology and electrochemical properties depending on heating time. The additional oxidation step prior to reductive heating accelerates the final structure formation.