Reactive Electrophilic O Species Evidenced in High-Performance Iridium Oxohydroxide Water Oxidation Electrocatalysts.

Although quasi-amorphous iridium oxohydroxides have been identified repeatedly as superior electrocatalysts for the oxygen evolution reaction (OER), an exact description of the performance-relevant species has remained a challenge. In this context, we report the characterization of hydrothermally prepared iridium(III/IV) oxohydroxides that exhibit exceptional OER performances. Holes in the O 2p states of the iridium(III/IV) oxohydroxides result in reactive O species, which are identified by characteristic near-edge X-ray absorption fine structure (NEXAFS) features.

Identifying Key Structural Features of IrO Water Splitting Catalysts.

Hydrogen production by electrocatalytic water splitting will play a key role in the realization of a sustainable energy supply. Owing to their relatively high stability and activity, iridium (hydr)oxides have been identified as the most promising catalysts for the oxidation of water. Comprehensive spectroscopic and theoretical studies on the basis of rutile IrO have provided insight about the electronic structure of the active X-ray amorphous phase.

High-Performance Supported Iridium Oxohydroxide Water Oxidation Electrocatalysts.

The synthesis of a highly active and yet stable electrocatalyst for the anodic oxygen evolution reaction (OER) remains a major challenge for acidic water splitting on an industrial scale. To address this challenge, we obtained an outstanding high-performance OER catalyst by loading Ir on conductive antimony-doped tin oxide (ATO)-nanoparticles by a microwave (MW)-assisted hydrothermal route. The obtained Ir phase was identified by using XRD as amorphous (XRD-amorphous), highly hydrated Ir oxohydroxide.

Microwave-Assisted Synthesis of Stable and Highly Active Ir Oxohydroxides for Electrochemical Oxidation of Water.

Water splitting for hydrogen production in acidic media has been limited by the poor stability of the anodic electrocatalyst devoted to the oxygen evolution reaction (OER). To help circumvent this problem we have synthesized a class of novel Ir oxohydroxides by rapid microwave-asisted hydrothermal synthesis, which bridges the gap between electrodeposited amorphous IrO films and crystalline IrO electrocatalysts prepared by calcination routes. For electrode loadings two orders of magnitude below current standards, the synthesized compounds present an unrivalled combination of high activity and stability under commercially relevant OER conditions in comparison to reported benchmarks, without need for pretreatment.

Reactive oxygen species in iridium-based OER catalysts.

Tremendous effort has been devoted towards elucidating the fundamental reasons for the higher activity of hydrated amorphous Ir oxyhydroxides (IrO ) in the oxygen evolution reaction (OER) in comparison with their crystalline counterpart, rutile-type IrO, by focusing on the metal oxidation state. Here we demonstrate that, through an analogy to photosystem II, the nature of this reactive species is not solely a property of the metal but is intimately tied to the electronic structure of oxygen. We use a combination of synchrotron-based X-ray photoemission and absorption spectroscopies, calculations, and microcalorimetry to show that holes in the O 2p states in amorphous IrO give rise to a weakly bound oxygen that is extremely susceptible to nucleophilic attack, reacting stoichiometrically with CO already at room temperature.

Microwave-hydrothermal synthesis and characterization of nanostructured copper substituted ZnM2O4 (M = Al, Ga) spinels as precursors for thermally stable Cu catalysts.

Nanostructured Cu(x)Zn(1-x)Al(2)O(4) with a Cu:Zn ratio of ¼:¾ has been prepared by a microwave-assisted hydrothermal synthesis at 150 °C and used as a precursor for Cu/ZnO/Al(2)O(3)-based catalysts. The spinel nanoparticles exhibit an average size of approximately 5 nm and a high specific surface area (above 250 m(2) g(-1)). Cu nanoparticles of an average size of 3.