Galvanic Restructuring of Exsolved Nanoparticles for Plasmonic and Electrocatalytic Energy Conversion.

There is a growing need to control and tune nanoparticles (NPs) to increase their stability and effectiveness, especially for photo- and electrochemical energy conversion applications. Exsolved particles are well anchored and can be re-shaped without changing their initial location and structural arrangement. However, this usually involves lengthy treatments and use of toxic gases. Here, the galvanic replacement/deposition method is used, which is simpler, safer, and leads to a wealth of new hybrid nanostructures with a higher degree of tailorability. The produced NiAu bimetallic nanostructures supported on SrTiO3 display exceptional activity in plasmon-assisted photoelectrochemical (PEC) water oxidation reactions. In situ scanning transmission electron microscopy is used to visualize the structural evolution of the plasmonic bimetallic structures, while theoretical simulations provide mechanistic insight and correlate the surface plasmon resonance effects with structural features and enhanced PEC performance. The versatility of this concept in shifting catalytic modes to the hydrogen evolution reaction is demonstrated by preparing hybrid NiPt bimetallic NPs of low Pt loadings on highly reduced SrTiO3 supports. This powerful methodology enables the design of supported bimetallic nanomaterials with tunable morphology and catalytic functionalities through minimal engineering.

Double Perovskite Cobaltites Integrated in a Monolithic and Noble Metal-Free Photoelectrochemical Device for Efficient Water Splitting.

Water photoelectrolysis has the potential to produce renewable hydrogen fuel, therefore addressing the intermittent nature of sunlight. Herein, a monolithic, photovoltaic (PV)-assisted water electrolysis device of minimal engineering and of low (in the µg range) noble-metal-free catalysts loading is presented for unassisted water splitting in alkaline media. An efficient double perovskite cobaltite catalyst, originally developed for high-temperature proton-conducting ceramic electrolyzers, possesses high activity for the oxygen evolution reaction in alkaline media at room temperatures too. Ba1-xGd1-yLax+yCo2O6-δ (BGLC) is combined with a NiMo cathode, and a solar-to-hydrogen efficiency of 6.6% in 1.0 M NaOH, under 1 sun simulated illumination for 71 h, is demonstrated. This work highlights how readily available earth-abundant materials and established PV methods can achieve high performance and stable and monolithic photoelectrolysis devices with potential for full-scale applications.

Single-step approach to sensitized luminescence through bulk-embedded organics in crystalline fluorides.

Luminescent materials enable warm white LEDs, molecular tagging, enhanced optoelectronics and can improve energy harvesting. With the recent development of multi-step processes like down- and upconversion and the difficulty in sensitizing these, it is clear that optimizing all properties simultaneously is not possible within a single material class. In this work, we have utilized the layer-by-layer approach of atomic layer deposition to combine broad absorption from an aromatic molecule with the high emission yields of crystalline multi-layer lanthanide fluorides in a single-step nanocomposite process. This approach results in complete energy transfer from the organic molecule while providing inorganic fluoride-like lanthanide luminescence. Sm3+ is easily quenched by organic sensitizers, but in our case we obtain strong fluoride-like Sm3+ emission sensitized by strong UV absorption of terephthalic acid. This design allows combinations of otherwise incompatible species, both with respect to normally incompatible synthesis requirements and in controlling energy transfer and quenching routes.

First complex oxide superconductor by atomic layer deposition.

We here report on atomic layer deposition (ALD) of the superconducting complex oxide La2-xSrxCuO4-y and provide details of the structural and electrical properties of such films. This is the first report on a complex oxide thin film with superconducting properties that has been deposited by atomic layer deposition.

Band gap maps beyond the delocalization limit: correlation between optical band gaps and plasmon energies at the nanoscale.

Recent progresses in nanoscale semiconductor technology have heightened the need for measurements of band gaps with high spatial resolution. Band gap mapping can be performed through a combination of probe-corrected scanning transmission electron microscopy (STEM) and monochromated electron energy-loss spectroscopy (EELS), but are rare owing to the complexity of the experiments and the data analysis. Furthermore, although this method is far superior in terms of spatial resolution to any other techniques, it is still fundamentally resolution-limited due to inelastic delocalization of the EELS signal. In this work we have established a quantitative correlation between optical band gaps and plasmon energies using the Zn1-xCd x O/ZnO system as an example, thereby side-stepping the fundamental resolution limits of band gap measurements, and providing a simple and convenient approach to achieve band gap maps with unprecedented spatial resolution.