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At least 163 records · Page 9

Introduction to (Photo)electrocatalysis For Renewable Energy

Humanity is facing a significant and growing energy demand, necessitating a new energy paradigm built on clean and abundant renewable energy.1 Within this context, electrocatalysis and (photo)electrocatalysis hold great promise for enabling renewable energies such as solar and wind power to overcome the transient nature of their energy output.2-6 Developing catalysts that operate efficiently and selectively, and that are also robust, has been the focus of much research. This special issue brings together the latest advances in the fundamental and applied science addressing the synthesis, characterization, mechanisms, and performance of (photo)electrocatalysts for energy storage and conversion of small molecules into useful specialty and commodity chemicals and fuels. The electrocatalysts and (photo)electrocatalysts highlighted in this issue include metalloenzymes, homogeneous and supported molecular catalysts, and diverse heterogeneous nanoparticulate and thin film systems. The reports span across basic and applied studies and encompass both experimental and theoretical investigations.

Dey, Abhishek↗

Studying single nanocrystals under high pressure using an x-ray nanoprobe

In this report, we demonstrate the feasibility of applying a 250-nm focused x-ray beam to study a single crystalline NbSe{sub 3} nanobelt under high-pressure conditions in a diamond anvil cell. With such a small probe, we not only resolved the distribution and morphology of each individual nanobelt in the x-ray fluorescence maps but also obtained the diffraction patterns from individual crystalline nanobelts with thicknesses of less than 50 nm. Single crystalline diffraction measurements on NbSe{sub 3} nanobelts were performed at pressures up to 20 GPa.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Pressure-induced densification in GeO{sub 2} glass: A transmission x-ray microscopy study

Nanoscale transmission x-ray microscopy measurements have been performed to determine the effect of pressure (P) on the volume (V) change in GeO{sub 2} glass up to 38.5 GPa. The P-V data show a continuous increase upon compression, indicating that the density-driven structural transformation is a gradual process. Over the pressure range studied, a transition is observed at approximately 10–13 GPa, where the material displays distinct compression behaviors. The pressure-induced densification that involves the coordination number change has been discussed. Using this newly developed high-pressure imaging technique with tens of nanometer resolution, we have provided a direct and unequivocal way for measuring density of amorphous materials to much higher pressures with accuracy rivaling x-ray diffraction of crystalline solids.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Ring-polymer molecular dynamics: Rate coefficient calculations for energetically symmetric (near thermoneutral) insertion reactions (X + H{sub 2}) → HX + H(X = C({sup 1}D), S({sup 1}D))

Following our previous study of prototypical insertion reactions of energetically asymmetric type with the RPMD (Ring-Polymer Molecular Dynamics) method [Y. Li, Y. Suleimanov, and H. Guo, J. Phys. Chem. Lett. 5, 700 (2014)], we extend it to two other prototypical insertion reactions with much less exothermicity (near thermoneutral), namely, X + H{sub 2} → HX + H where X = C({sup 1}D), S({sup 1}D), in order to assess the accuracy of this method for calculating thermal rate coefficients for this class of reactions. For both chemical reactions, RPMD displays remarkable accuracy and agreement with the previous quantum dynamic results that make it encouraging for the future application of the RPMD to other barrier-less, complex-forming reactions involving polyatomic reactants with any exothermicity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Pressure tuning the lattice and optical response of silver sulfide

Binary transition metal chalcogenides have attracted increasing attention for their unique structural and electronic properties. High pressure is a powerful tool for tuning the lattice and electronic structure of transition metal chalcogenides away from their pristine states. In this work, we systematically studied the in situ structural and optical behavior of silver sulfide (Ag{sub 2}S) under pressure by synchrotron X-ray diffraction and infrared spectroscopy measurements in a diamond anvil cell. Upon compression, Ag{sub 2}S undergoes structural symmetrization accompanied by a series of structural transitions while the crystallographic inequivalence of the two Ag sites is maintained. Electronically, pressure effectively tunes the ambient semiconducting Ag{sub 2}S into a metal at ∼22 GPa. Drude model analysis shows that the optical conductivity evolves significantly, reaching the highest value of 100 Ω{sup −1} cm{sup −1} at ∼40 GPa. Our results highlight the structural and electronic tunability of silver chalcogenides as a function of pressure and suggest the potential of Ag{sub 2}S as a platform for developing optical and opto-electronic applications.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

High-pressure behavior of A 2 B 2 O 7 pyrochlore (A=Eu, Dy; B=Ti, Zr)

In situ high-pressure X-ray diffraction and Raman spectroscopy were used to determine the influence of composition on the high-pressure behavior of A 2 B 2 O 7 pyrochlore (A=Eu, Dy; B=Ti, Zr) up to ~50GPa. Based on X-ray diffraction results, all compositions transformed to the high-pressure cotunnite structure. The B-site cation species had a larger effect on the transition pressure than the A-site cation species, with the onset of the phase transformation occurring at ~41 GPa for B=Ti and ~16 GPa B=Zr. However, the A-site cation affected the kinetics of the phase transformation, with the transformation for compositions with the smaller ionic radii, i.e., A=Dy, proceeding faster than those with a larger ionic radii, i.e., A=Eu. These results were consistent with previous work in which the radius-ratio of the A- and B-site cations determined the energetics of disordering, and compositions with more similarly sized A- and B-site cations had a lower defect formation energy. Raman spectra revealed differences in the degree of short-range order of the different compositions. Due to the large phase fraction of cotunnite at high pressure for B=Zr compositions, Raman modes for cotunnite could be observed, with more modes recorded for A=Eu than A=Dy. These additional modes are attributed to increased short-to-medium range ordering in the initially pyrochlore structured Eu 2 Zr 2 O 7 as compared with the initially defect-fluorite structured Dy 2 Zr 2 O 7 .

36 MATERIALS SCIENCE↗

Phase transformations of Al-bearing high-entropy alloys Al x CoCrFeNi (x = 0, 0.1, 0.3, 0.75, 1.5) at high pressure

Pressure-induced structural modifications in high-entropy alloys with varying Al contents, Al x CoCrFeNi (x = 0, 0.1, 0.3, 0.75, 1.5), have been investigated at pressures up to ~50 GPa by synchrotron X-ray diffraction and, following depressurization, by transmission electron microscopy (TEM). In Al x CoCrFeNi compounds with x ≤ 0.3, all of which exhibit an initial single-phase face-centered cubic (fcc) structure, proportionality between the Al content and the critical pressure for transformation to hexagonal close-packed (hcp) phases, distinguished by a distinct planar stacking sequence, is observed. This is attributed to the structural distortion arising from the large size of Al atoms relative to those of the other constituent elements, which results in an increase in the formation energy of stacking faults and a decrease in compressibility. High-resolution TEM results demonstrate variation of the stacking sequence from ABCABC, typical of fcc materials, to ABABAB, typical of hcp materials, in CoCrFeNi following high pressure. In Al 0.75 CoCrFeNi, which exhibits an initial dual-phase structure [fcc and body-centered cubic (bcc)], the result again shows the formation of a (hcp) phase despite its higher Al content, suggesting that the bcc phase may be more amenable to pressure-induced phase modification than is the fcc phase, which is absent for lower Al contents. However, the trend of transformation inhibition by increasing the Al content is again observed, with Al 1.5 CoCrFeNi retaining its initial structure up to the highest pressure achieved. Furthermore the determination of these compositional trends in the high-pressure phase response of these materials may enable the production of new phase mixtures with precisely tuned phase proportions and potentially desirable properties.

36 MATERIALS SCIENCE↗

Replacing fish oil and astaxanthin by microalgal sources produced different metabolic responses in juvenile rainbow trout fed 2 types of practical diets

Dietary fish oil supplementation provides n-3 long-chained polyunsaturated fatty acids for supporting fish growth and metabolism and enriching fillet with eicosapentaenoic acid (EPA; 20:5n-3) and docosahexaenoic acid (DHA; c22:6n-3). Two experiments were performed as a 3 × 2 factorial arrangement of dietary treatments for 16 wk to determine effects and mechanisms of replacing 0%, 50%, and 100% fish oil with DHA-rich microalgae in combination with synthetic vs. microalgal source of astaxanthin in plant protein meal (PM)- or fishmeal (FM)- based diets for juvenile rainbow trout (Oncorhynchus mykiss). Fish (22 ± 0.26 g) were stocked at 17/tank and 3 tanks/diet. The 100% fish oil replacement impaired (P < 0.0001) growth performance, dietary protein and energy utilization, body indices, and tissue accumulation of DHA and EPA in both diet series. Here, the impairments were associated (P < 0.05) with upregulation of hepatic gene expression related to growth (ghr1and igf1) and biosynthesis of DHA and EPA (fads6 and evol5) that was more dramatic in the FM than PM diet-fed fish, and more pronounced on tissue EPA than DHA concentrations. The source of astaxanthin exerted interaction effects with the fish oil replacement on several measures including muscle total cholesterol concentrations. In conclusion, replacing fish oil by the DHA-rich microalgae produced more negative metabolic responses than the substitution of synthetic astaxanthin by the microalgal source in juvenile rainbow trout fed 2 types of practical diets.

59 BASIC BIOLOGICAL SCIENCES↗

Emergency Response Health Physics

Health physics is an important discipline with regard to understanding the effects of radiation on human health; however, there are major differences between health physics for research or occupational safety and health physics during a large-scale radiological emergency. The deployment of a U.S. Department of Energy/National Nuclear Security Administration (DOE/NNSA) monitoring and assessment team to Japan in the wake of the March 2011 accident at Fukushima Daiichi Nuclear Power Plant yielded a wealth of lessons on these difference. Critical teams (CMOC (Consequence Management Outside the Continental U.S.) and CMHT (Consequence Management Home Team) ) worked together to collect, compile, review, and analyze radiological data from Japan to support the response needs of and answer questions from the Government of Japan, the U.S. military in Japan, the U.S. Embassy and U.S. citizens in Japan, and U.S. citizens in America. This paper addresses the unique challenges presented to the health physicist or analyst of radiological data in a large-scale emergency. A key lesson learned was that public perception and the availability of technology with social media requires a diligent effort to keep the public informed of the science behind the decisions in a manner that is meaningful to them.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗

The Role of the Consequence Management Home Team in the Fukushima Daiichi Response

The Consequence Management Home Team (CMHT) is a U.S. Department of Energy/National Nuclear Security Administration asset and played an important role in the U.S. response effort to the Fukushima Daiichi accident, ranging from the early days of the response to a continued involvement in supporting late phase efforts. Each stage of their work had distinct characteristics in terms of management of incoming data streams and creation of products. The CMHT assisted a variety of response organizations with modeling; radiological operations planning; field monitoring techniques; and the analysis, interpretation, and distribution of radiological data. In the Fukushima Daiichi response, the CMHT grew to include a broader range of support than was historically planned. Through their work, the social and economic impacts of a nuclear or radiological incident were minimized. The CMHT was an integral component of the response in Japan and acted as the central point from which all of the data and products flowed.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗