Iridium oxide is the catalytic material with the highest stability in the oxygen evolution reaction (OER) performed under acidic conditions. However, its high cost and limited availability demand that IrO2 is utilized as efficiently as possible. We report the synthesis and OER performance of highly active mesoporous IrO2 catalysts with optimized surface area, intrinsic activity, and pore accessibility. Catalytic layers with controlled pore size were obtained by soft-templating with micelles formed from amphiphilic block copolymers poly(ethylene oxide)-b-poly(butadiene)-b-poly(ethylene oxide). A systematic study on the influence of the calcination temperature and film thickness on the morphology, phase composition, accessible surface area, and OER activity reveals that the catalytic performance is controlled by at least two independent factors, that is, accessible surface area and intrinsic activity per accessible site. Catalysts with lower crystallinity show higher intrinsic activity. The catalyst surface area increases linearly with film thickness. As a result of the templated mesopores, the pore surface remains fully active and accessible even for thick IrO2 films. Even the most active multilayer catalyst does not show signs of transport limitations at current densities as high as 75 mA cm(-2) .

Efficient water electrolysis requires highly active electrodes. The activity of corresponding catalytic coatings strongly depends on material properties such as film thickness, crystallinity, electrical conductivity, and chemical surface speciation. Measuring these properties with high accuracy in vacuum-free and nondestructive methods facilitates the elucidation of structure−activity relationships in realistic environments. Here, we report a novel approach to analyze the optical and electrical properties of highly active oxygen evolution reaction (OER) catalysts via spectroscopic ellipsometry (SE). Using a series of differently calcined, mesoporous, templated iridium oxide films as an example, we assess the film thickness, porosity, electrical resistivity, electron concentration, electron mobility, and interband and intraband transition energies by modeling of the optical spectra. Independently performed analyses using scanning electron microscopy, energy-dispersive X-ray spectroscopy, ellipsometric porosimetry, X-ray reflectometry, and absorption spectroscopy indicate a high accuracy of the deduced material properties. A comparison of the derived analytical data from SE, resonant photoemission spectroscopy, X-ray absorption spectroscopy, and X-ray photoelectron spectroscopy with activity measurements of the OER suggests that the intrinsic activity of iridium oxides scales with a shift of the Ir 5d t 2g sub-level and an increase of p−d interband transition energies caused by a transition of μ 1 -OH to μ 3 -O species.

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The efficient generation of hydrogen via water electrolysis requires highly active oxygen evolution catalysts. Among the active metals, iridium oxide provides the best compromise in terms of activity and stability. The limited availability and usage in other applications demands an efficient utilization of this precious metal. Forming mixed oxides with titania promises improved Ir utilization, but often at the cost of a low catalyst surface area. Moreover, the role of Ir in establishing a sufficiently conductive mixed oxide has not been elucidated so far. We report a new approach for the synthesis of Ir/TiO mixed-oxide catalysts with defined template-controlled mesoporous structure, low crystallinity, and superior oxygen evolution reaction (OER) activity. The highly accessible pore system provides excellent Ir dispersion and avoids transport limitations. A controlled variation of the oxides Ir content reveals the importance of the catalysts electrical conductivity: at least 0.1 S m are required to avoid limitations owing to slow electron transport. For sufficiently conductive oxides a clear linear correlation between Ir surface sites and OER currents can be established, where all accessible Ir sites equally contribute to the reaction. The optimized catalysts outperform Ir/TiO materials reported in literature by about a factor of at least four.

Catalysts based on nickel oxide are some of the most active catalysts for the oxygen evolution reaction (OER) in alkaline media. However, preparing catalytic coatings with high surface area and good accessibility of the active sites remains challenging. We present a new approach for the synthesis of homogeneous and binder-free nickel oxide coatings comprising a highly accessible ordered mesopore structure. The synthesis is achieved via evaporation induced self assembly utilizing PEO-PB-PEO triblock copolymers as pore template and a chemical complex of Ni 2 + and citric acid as precursor. Excessive crystal-lization behaviour of NiO is avoided by thermal conversion of the precursor into an amorphous Ni carbonate intermediate, followed by transition of the carbonate into the metal oxide. We present a comprehensive analysis of the obtained materials in terms of morphology, crystallinity, surface area, composition, and OER activity of differently calcined catalysts. Retaining a low crystallinity and high surface area during the synthesis proofs to be the most important factor in obtaining a highly active OER catalyst.[a] M.