The Extent of Platinum-Induced Hydrogen Spillover on Cerium Dioxide.

Hydrogen spillover from metal nanoparticles to oxides is an essential process in hydrogenation catalysis and other applications such as hydrogen storage. It is important to understand how far this process is reaching over the surface of the oxide. Here, we present a combination of advanced sample fabrication of a model system and in situ X-ray photoelectron spectroscopy to disentangle local and far-reaching effects of hydrogen spillover in a platinum-ceria catalyst. At low temperatures (25-100 °C and 1 mbar H2) surface O-H formed by hydrogen spillover on the whole ceria surface extending microns away from the platinum, leading to a reduction of Ce4+ to Ce3+. This process and structures were strongly temperature dependent. At temperatures above 150 °C (at 1 mbar H2), O-H partially disappeared from the surface due to its decreasing thermodynamic stability. This resulted in a ceria reoxidation. Higher hydrogen pressures are likely to shift these transition temperatures upward due to the increasing chemical potential. The findings reveal that on a catalyst containing a structure capable to promote spillover, hydrogen can affect the whole catalyst surface and be involved in catalysis and restructuring.

Environmental control for X-ray nanotomography.

The acquisition speed and spatial resolution of X-ray nanotomography have continuously improved over the last decades. Coherent diffraction-based techniques breach the 10 nm resolution barrier frequently and thus pose stringent demands on sample positioning accuracy and stability. At the same time there is an increasing desire to accommodate in situ or operando measurements. Here, an environmental control system for X-ray nanotomography is introduced to regulate the temperature of a sample from room temperature up to 850°C in a controlled atmospheric composition. The system allows for a 360° sample rotation, permitting tomographic studies in situ or operando free of missing wedge constraints. The system is implemented and available at the flOMNI microscope at the Swiss Light Source. In addition to the environmental control system itself, the related modifications of flOMNI are described. Tomographic measurements of a nanoporous gold sample at 50°C and 600°C at a resolution of sub-20 nm demonstrate the performance of the device.

Elucidating the Humidity-Induced Degradation of Ni-Rich Layered Cathodes for Li-Ion Batteries.

Ni-rich layered oxides, in a general term of Li(NixCoyMn1-x-y)O2 (x > 0.5), are widely recognized as promising candidates for improving the specific energy and lowering the cost for next-generation Li-ion batteries. However, the high surface reactivity of these materials results in side reactions during improper storage and notable gas release when the cell is charged beyond 4.3 V vs Li+/Li0. Therefore, in this study, we embark on a comprehensive investigation on the moisture sensitivity of LiNi0.85Co0.1Mn0.05O2 by aging it in a controlled environment at a constant room-temperature relative humidity of 63% up to 1 year. We quantitatively analyze the gassing of the aged samples by online electrochemical mass spectrometry and further depict plausible reaction pathways, accounting for the origin of the gas release. Transmission electron microscopy reveals formation of an amorphous surface impurity layer of ca. 10 nm in thickness, as a result of continuous reactions with moisture and CO2 from the air. Underneath it, there is another reconstructed layer of ca. 20 nm in thickness, showing rock salt/spinel-like features. Our results provide insight into the complex interfacial degradation phenomena and future directions for the development of high-performance Ni-rich layered oxides.

Emissions of Secondary Formed ZnO Nano-Objects from the Combustion of Impregnated Wood. An Online Size-Resolved Elemental Investigation.

The release of secondary nano-objects formed during waste combustion processes is becoming a matter of concern, considering their known toxicity and the fact that the 100% efficiency of filtering systems is not always ensured. An increased cytotoxicity and genotoxicity on human peripheral blood lymphocytes is known particularly in the case of ZnO, which is often contained in paints and waterproof agents, heading to a relevant quantity present in the waste wood material. In this study, the behavior of ZnO nanoparticles during wood combustion and the effect of the reduction potential of generated carbon species on the release of secondarily formed ZnO-containing nano-objects were investigated. By hyphenating a modified scanning mobility particle sizer (SMPS) and inductively coupled mass spectrometry (ICP-MS), it was possible to obtain simultaneously size-resolved and chemical information on the emitted nanoparticles. Through the established correlation between SMPS and ICP-MS signals, Zn-containing particles were efficiently resolved from the combustion generated particles. Transmission electron microscopy (TEM) and energy-dispersive X-ray spectroscopy (EDS) on size-selected particles confirmed the SMPS and ICP-MS data. The use of electron diffraction allowed determining the structure of the crystalline materials as hexagonal ZnO. A possible mechanism of reduction of ZnO to Zn and further reformation as secondary nano-objects is proposed.

Radiochemical Determination of Long-Lived Radionuclides in Proton-Irradiated Heavy-Metal Targets: Part I-Tantalum.

In this study, distillation, precipitation, and ion-exchange methods were chosen for the separation of the long-lived ß-emitters 129I, 36Cl and the α-emitters 154Dy, 148Gd, 150Gd, and 146Sm from Ta targets irradiated with protons up to 2.6 GeV to determine their production cross sections. Measurements of 129I/127I and 36Cl/35Cl ratios were performed with accelerator mass spectrometry. After separation of the lanthanides, the molecular plating technique was applied to prepare thin samples to obtain highly resolved α-spectra. Autoradiography and focused ion beam/scanning electron microscopy techniques were used to characterize the lanthanide deposited layer. Experimental cross-section data are compared with theoretical predictions obtained with INCL++ and ABLA07 code, and a satisfactory agreement is observed.