Assessment of the Degradation Mechanisms of Cu Electrodes during the CO2 Reduction Reaction.

Catalyst degradation and product selectivity changes are two of the key challenges in the electrochemical reduction of CO2 on copper electrodes. Yet, these aspects are often overlooked. Here, we combine in situ X-ray spectroscopy, in situ electron microscopy, and ex situ characterization techniques to follow the long-term evolution of the catalyst morphology, electronic structure, surface composition, activity, and product selectivity of Cu nanosized crystals during the CO2 reduction reaction. We found no changes in the electronic structure of the electrode under cathodic potentiostatic control over time, nor was there any build-up of contaminants. In contrast, the electrode morphology is modified by prolonged CO2 electroreduction, which transforms the initially faceted Cu particles into a rough/rounded structure. In conjunction with these morphological changes, the current increases and the selectivity changes from value-added hydrocarbons to less valuable side reaction products, i.e., hydrogen and CO. Hence, our results suggest that the stabilization of a faceted Cu morphology is pivotal for ensuring optimal long-term performance in the selective reduction of CO2 into hydrocarbons and oxygenated products.

On the Activity/Selectivity and Phase Stability of Thermally Grown Copper Oxides during the Electrocatalytic Reduction of CO2.

Revealing the active nature of oxide-derived copper is of key importance to understand its remarkable catalytic performance during the cathodic CO2 reduction reaction (CO2RR) to produce valuable hydrocarbons. Using advanced spectroscopy, electron microscopy, and electrochemically active surface area characterization techniques, the electronic structure and the changes in the morphology/roughness of thermally oxidized copper thin films were revealed during CO2RR. For this purpose, we developed an in situ cell for X-ray spectroscopy that could be operated accurately in the presence of gases or liquids to clarify the role of the initial thermal oxide phase and its active phase during the electrocatalytic reduction of CO2. It was found that the Cu(I) species formed during the thermal treatment are readily reduced to Cu0 during the CO2RR, whereas Cu(II) species are hardly reduced. In addition, Cu(II) oxide electrode dissolution was found to yield a porous/void structure, where the lack of electrical connection between isolated islands prohibits the CO2RR. Therefore, the active/stable phase for CO2RR is metallic copper, independent of its initial phase, with a significant change in its morphology upon its reduction yielding the formation of a rougher surface with a higher number of underco-ordinated sites. Thus, the initial thermal oxidation of copper in air controls the reaction activity/selectivity because of the changes induced in the electrode surface morphology/roughness and the presence of more undercoordinated sites during the CO2RR.

Graphene-Capped Liquid Thin Films for Electrochemical Operando X-ray Spectroscopy and Scanning Electron Microscopy.

Electrochemistry is a promising building block for the global transition to a sustainable energy market. Particularly the electroreduction of CO2 and the electrolysis of water might be strategic elements for chemical energy conversion. The reactions of interest are inner-sphere reactions, which occur on the surface of the electrode, and the biased interface between the electrode surface and the electrolyte is of central importance to the reactivity of an electrode. However, a potential-dependent observation of this buried interface is challenging, which slows the development of catalyst materials. Here we describe a sample architecture using a graphene blanket that allows surface sensitive studies of biased electrochemical interfaces. At the examples of near ambient pressure X-ray photoelectron spectroscopy (NAP-XPS) and environmental scanning electron microscopy (ESEM), we show that the combination of a graphene blanket and a permeable membrane leads to the formation of a liquid thin film between them. This liquid thin film is stable against a water partial pressure below 1 mbar. These properties of the sample assembly extend the study of solid-liquid interfaces to highly surface sensitive techniques, such as electron spectroscopy/microscopy. In fact, photoelectrons with an effective attenuation length of only 10 Å can be detected, which is close to the absolute minimum possible in aqueous solutions. The in-situ cells and the sample preparation necessary to employ our method are comparatively simple. Transferring this approach to other surface sensitive measurement techniques should therefore be straightforward. We see our approach as a starting point for more studies on electrochemical interfaces and surface processes under applied potential. Such studies would be of high value for the rational design of electrocatalysts.

ZnO@TiO2 Core Shell Nanorod Arrays with Tailored Structural, Electrical, and Optical Properties for Photovoltaic Application.

ZnO has prominent electron transport and optical properties, beneficial for photovoltaic application, but its surface is prone to the formation of defects. To overcome this problem, we deposited nanostructured TiO2 thin film on ZnO nanorods to form a stable shell. ZnO nanorods synthesized by wet-chemistry are single crystals. Three different procedures for deposition of TiO2 were applied. The influence of preparation methods and parameters on the structure, morphology, electrical and optical properties were studied. Nanostructured TiO2 shells show different morphologies dependent on deposition methods: (1) separated nanoparticles (by pulsed laser deposition (PLD) in Ar), (2) a layer with nonhomogeneous thickness (by PLD in vacuum or DC reactive magnetron sputtering), and (3) a homogenous thin layer along the nanorods (by chemical deposition). Based on the structural study, we chose the preparation parameters to obtain an anatase structure of the TiO2 shell. Impedance spectroscopy shows pure electron conductivity that was considerably better in all the ZnO@TiO2 than in bare ZnO nanorods or TiO2 layers. The best conductivity among the studied samples and the lowest activation energy was observed for the sample with a chemically deposited TiO2 shell. Higher transparency in the visible part of spectrum was achieved for the sample with a homogenous TiO2 layer along the nanorods, then in the samples with a layer of varying thickness.

Suitability of low density materials for 3D printing of physical breast phantoms.

Breast physical phantoms are a basic tool for the assessment and verification of performance standards in daily clinical practice of x-ray breast imaging modalities. They are also invaluable in testing and evaluation of new x-ray breast modalities to be potentially established, e.g. breast computed tomography, dual-energy breast CT and phase-contrast mammography and tomography. Nowadays, there is a lack or there are only a limited number of breast physical phantoms available for this purpose. The aim of this study is to explore a range of 3D printing materials such as resins, PLA, ABS, Nylon etc, to determine their attenuation and refractive properties, and to finally compare them to the properties of the breast tissues: adipose, glandular and skin. To achieve this goal, step-wedge phantoms were computationally modeled and then manufactured using stereolithographic and fused-deposition modeling technologies. X-ray images of the phantoms were acquired, using monochromatic beam at ID17, ESRF, Grenoble for three energies-30 keV, 45 keV and 60 keV. Experimental data were further processed to obtain the linear attenuation coefficients of these materials. Comparison with theoretical data for the linear attenuation coefficients and the refractive indexes for breast tissues was performed. From the studied materials, most of the resins, Nylon, Hybrid, PET-G show absorption properties close to the glandular tissue, while ABS shows absorption characteristics close to these of the adipose tissue. For phase-contrast imaging, it turns out that the ABS combined with resin-based materials to represent the adipose and glandular tissues, respectively may be a good combination for manufacturing of a phantom suitable for these studies. These results can be used for the design and the construction of a new physical anthropomorphic phantom of the breast with improved anatomical and radiological characteristics dedicated for advanced mammography imaging techniques implemented at higher photon energies.

Determinants of personal health record use: a large population study at Cleveland Clinic.

While research in other domains leads us to expect that some patients will be more predisposed to technology adoption than others, the factors that indicate propensity for use are not clear. In this study, researchers extracted the demographic and usage information of 63,295 people who had registered to use eCleveland Clinic MyChart. Of those, 12,101 had never logged onto the system and were termed registered never users. Registered users are more likely to be Caucasian and married than registered never users. The only predictors of degree of PHR use among the registered users are number of diagnoses from the EMR problem list and the number of clinical encounters. Hence, Cleveland Clinic's PHR portal appears to be most useful to patients who are sicker and greater consumers of healthcare.