Oxygen electrochemistry plays a key role in renewable energy technologies such as fuel cells and electrolyzers, but the slow kinetics of the oxygen evolution reaction (OER) limit the performance and commercialization of such devices. Here we report an iridium oxide/strontium iridium oxide (IrOx/SrIrO3) catalyst formed during electrochemical testing by strontium leaching from surface layers of thin films of SrIrO3 This catalyst has demonstrated specific activity at 10 milliamps per square centimeter of oxide catalyst (OER current normalized to catalyst surface area), with only 270 to 290 millivolts of overpotential for 30 hours of continuous testing in acidic electrolyte. Density functional theory calculations suggest the formation of highly active surface layers during strontium leaching with IrO3 or anatase IrO2 motifs. The IrOx/SrIrO3 catalyst outperforms known IrOx and ruthenium oxide (RuOx) systems, the only other OER catalysts that have reasonable activity in acidic electrolyte.

A highly active and stable IrOx/SrIrO3 catalyst for the oxygen evolution reaction

Since the first reports in the late 1970s on transition metal complexes contain- ing pincer-type ligands—named after the particular coordination mode of these ligands—these systems have at- tracted increasing interest owing to the unusual properties of the metal centers imparted by the pincer ligand. Typical- ly, such a ligand comprises an anionic aryl ring which is ortho,ortho-disubsti- tuted with heteroatom substituents, for example, CH2NR2 ,C H 2PR2 or CH2SR, which generally coordinate to the met- al center, and therefore support the MC s bond. This commonly results in a terdentate and meridional coordina- tion mode consisting of two metalla- cycles which share the MC bond. Detailed studies of the formation and the properties of a large variety of pincers containing platinum group metal complexes have provided direct access to both a fundamental under- standing of a variety of reactions in organometallic chemistry and to a range of new applications of these complexes. The discovery of alkane dehydrogenation catalysts, the mecha- nistic elucidation of fundamental transformations (for example, CC bond activation), the construction of the first metallodendrimers for sustain- able homogeneous catalysis, and the engineering of crystalline switches for materials processing represent only a few of the many highlights which have emanated from these numerous inves- tigations. This review discusses the synthetic methodologies that are cur- rently available for the preparation of platinum group metal complexes con- taining pincer ligands and especially emphasizes different applications that have been realized in materials science such as the development and engineer- ing of sensors, switches, and catalysts.

Platinum Group Organometallics Based on “Pincer” Complexes: Sensors, Switches, and Catalysts

The electronic reconstruction at the interface between two insulating oxides can give rise to a highly conductive interface. Here we show how, in analogy to this remarkable interfaceinduced conductivity, magnetism can be induced at the interface between the otherwise non-magnetic insulating perovskites SrTiO3 and LaAlO3. A large negative magnetoresistance of the interface is found, together with a logarithmic temperature dependence of the sheet resistance.At lowtemperatures, the sheet resistance reveals magnetic hysteresis.Magnetic ordering is a key issue in solid-state science and its underlying mechanisms are still the subject of intense research. In particular, the interplay between localized magnetic moments and the spin of itinerant conduction electrons in a solid gives rise to intriguingmany-body effects such as Ruderman–Kittel–Kasuya–Yosida interactions3, the Kondo effect4 and carrier-induced ferromagnetism in diluted magnetic semiconductors5. The conducting oxide interface now provides a versatile system to induce and manipulate magnetic moments in otherwise non-magnetic materials.

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Magnetic effects at the interface between non-magnetic oxides

Dendrimers in Supramolecular Chemistry: From Molecular Recognition to Self-Assembly.

New Self-Assembled Structural Motifs in Coordination Chemistry.

In recent years, well-defined and nearly perfect single crystal surfaces of oxide perovskites have become increasingly important. A single terminated surface is a prerequisite for reproducible thin film growth and fundamental growth studies. In this work, atomic and lateral force microscopy have been used to display different terminations of SrTiO3. We observe hydroxylation of the topmost SrO layer after immersion of SrTiO3 in water, which is used to enhance the etch-selectivity of SrO relative to TiO2 in a buffered HF solution. We reproducibly obtain perfect and single terminated surfaces, irrespective of the initial state of polished surfaces and the pH value of the HF solution. This approach to the problem might be used for a variety of multi-component oxide single crystals. True two-dimensional reflection high-energy electron diffraction intensity oscillations are observed during homo epitaxial growth using pulsed laser deposition on these surfaces.

Quasi-ideal strontium titanate crystal surfaces through formation of stontium hydroxide

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Large self-assembled organopalladium spheres

In order to study the homoepitaxial growth of SrTiO3, several techniques have been used to obtain atomically flat surfaces. Here, the effect of annealing in an oxygen environment and etching in a buffered HF solution on the surface morphology is studied by atomic force microscopy and reflection high-energy electron diffraction. We will show the effect of these substrate treatments on the initial growth of SrTiO3.

Influence of the surface treatment on the homoepitaixial growth of SrTiO3

Atomic force microscopic studies on the growth of self-assembled monolayer on SrTiO3 surfaces

The formation of monolayers from mixed solutions of alkylsiloxane molecules on the surface of SrTiO3 has been studied. The monolayers were formed by self-assembly from dilute n-hexadecane solutions of two binary mixtures of long- and short-chain alkyltrichlorosilanes. These films have been studied by atomic and lateral force microscopy and wettability measurements. One mixture showed evidence of phase segregation on the vicinal surface of a SrTiO3 (001) crystal. The long-chain molecules are found to preferably adsorb at or migrate toward the step ledge, probably to increase their van der Waals interaction and minimize the surface free energy.

B.L. Kropman

Papers

Quasi-ideal strontium titanate crystal surfaces through formation of stontium hydroxide

Large self-assembled organopalladium spheres

Influence of the surface treatment on the homoepitaixial growth of SrTiO3

Atomic force microscopic studies on the growth of self-assembled monolayer on SrTiO3 surfaces

Binary mixtures of self-assembled monolayers on SrTiO3: Experimental evidence for phase segregation