Reactive Electrophilic OI- 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 OI- species, which are identified by characteristic near-edge X-ray absorption fine structure (NEXAFS) features. A prototypical titration reaction with CO as a probe molecule shows that these OI- species are highly susceptible to nucleophilic attack at room temperature. Similarly to the preactivated oxygen involved in the biological OER in photosystem II, the electrophilic OI- species evidenced in the iridium(III/IV) oxohydroxides are suggested to be precursors to species involved in the O-O bond formation during the electrocatalytic OER. The CO titration also highlights a link between the OER performance and the surface/subsurface mobility of the OI- species. Thus, the superior electrocatalytic properties of the iridium (III/IV) oxohydroxides are explained by their ability to accommodate preactivated electrophilic OI- species that can migrate within the lattice.

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 IrOx films and crystalline IrO2 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. The best compound achieved a lifetime 33 times longer than the best commercial Ir benchmark. Thus, the reported efficient synthesis of an Ir oxohydroxide phase with superior intrinsic OER performance constitutes a major step towards the targeted design of cost-efficient Ir based OER electrocatalysts for acidic media.

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 IrIII/IV oxohydroxide. To identify chemical and structural features responsible for the high activity and exceptional stability under acidic OER conditions with loadings as low as 20 µgIr cm-2 , we used stepwise thermal treatment to gradually alter the XRD-amorphous Ir phase by dehydroxylation and crystallization of IrO2 . This resulted in dramatic depletion of OER performance, indicating that the outstanding electrocatalytic properties of the MW-produced IrIII/IV oxohydroxide are prominently linked to the nature of the produced Ir phase. This finding is in contrast with the often reported stable but poor OER performance of crystalline IrO2 -based compounds produced through more classical calcination routes. Our investigation demonstrates the immense potential of Ir oxohydroxide-based OER electrocatalysts for stable high-current water electrolysis under acidic conditions.