Isotopic Effect on Electrochemical CO2 Reduction Activity and Selectivity in H2O- and D2O-based Electrolytes over Palladium
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The origin of ubiquitous nucleosynthetic isotope anomalies in meteorites may represent spatial and/or temporal heterogeneity in the sources that supplied material to the nascent solar nebula, or enhancement by chemical processing. For elements beyond the Fe peak, deficits in s-process isotopes have been reported in some (e.g., Mo, Ru, W) but not all refractory elements studied (e.g., Os) that, among the iron meteorites, are most pronounced in IVB iron meteorites. Palladium is a non-refractory element in the same mass region as Mo and Ru. In this study, we report the first precise Pd isotopic abundances from IVB irons to test the mechanisms proposed for the origin of isotope anomalies. First, this study determined the existence of a cosmogenic neutron dosimeter from the reaction {sup 103}Rh(n, β{sup −}){sup 104}Pd in the form of excess {sup 104}Pd, correlated with excess {sup 192}Pt, in IVB irons. Second, all IVB irons show a deficit of the s-process only isotope {sup 104}Pd (ε {sup 104}Pd = −0.48 ± 0.24), an excess of the r-only isotope {sup 110}Pd (ε{sup 110}Pd = +0.46 ± 0.12), and no resolvable anomaly in the p-process {sup 102}Pd (ε {sup 102}Pd = +1 ± 1). The magnitude of the Pd isotope anomaly is about half that predicted from a uniform depletion of the s-process yields from the correlated isotope anomalies of refractory Mo and Ru. The discrepancy is best understood as the result of nebular processing of the less refractory Pd, implying that all the observed nucleosynthetic anomalies in meteorites are likely to be isotopic relicts. The Mo–Ru–Pd isotope systematics do not support enhanced rates of the {sup 22}Ne(α,n){sup 25}Mg neutron source for the solar system s-process.
Ru, Mo and Pd are very useful indicators for the identification of nucleosynthetic components. We have developed techniques for Pd isotopes, in an effort to check the extent of isotopic effects in this mass region and for a Pt-group element which is less refractory than Ru. Stable Pd isotopes are produced by the process only (102Pd), the s-process only (104Pd), the process only (Pd-110) and by both the r- and s-processes (Pd-105, Pd-106, Pd-108). Kelly and Wasserburg reported a hint of a shift in 102Pd (approx. 25(epsilon)u; 1(epsilon)u (triple bonds) 0.01%) in Santa Clara. Earlier searches for Mo and Ru isotopic anomalies were either positive or negative.
Abstract not provided.
This report summarizes computational model development and simulations results for a series of isotope exchange dynamics experiments including long and thin isothermal beds similar to the Foltz and Melius beds and a larger non-isothermal experiment on the NENG7 test bed. The multiphysics 2D axi-symmetric model simulates the temperature and pressure dependent exchange reaction kinetics, pressure and isotope dependent stoichiometry, heat generation from the reaction, reacting gas flow through porous media, and non-uniformities in the bed permeability. The new model is now able to replicate the curved reaction front and asymmetry of the exit gas mass fractions over time. The improved understanding of the exchange process and its dependence on the non-uniform bed properties and temperatures in these larger systems is critical to the future design of such systems.
Abstract not provided.
Currently, thirty-eight palladium, thirty-eight antimony, thirty-nine tellurium, thirty-eight iodine, and forty xenon isotopes have been observed and the discovery of these isotopes is described here. For each isotope a brief synopsis of the first refereed publication, including the production and identification method, is presented.
By leveraging the large isotope effect in the palladium hydrogen isotope system, the Thermal Cycling Absorption Process (TCAP) provides an efficient and advantageous means to separate protium, deuterium, and tritium. To meet increased future tritium processing demands, such as those needed for fusion power plants, current designs of the separation columns need to be adapted and optimized using the progress made in understanding hydrogen isotope science. One key to this optimization lies in understanding the baseline performance for currently employed separation packing materials. Pd/k and molecular sieves, as commonly used for the separation of hydrogen isotopes, are herein evaluated to establish a baseline for their separation efficiency. Van Deemter plots are formulated, and the influence of each parameter is evaluated to determine areas for improvement.
Density functional theory calculations are performed to study the interaction between hydrogen isotopes, vacancy, and antisite defects in Pd and V. Various defect configurations and defect-defect distances are systematically explored. Binding energies and migration energy barriers are calculated and tabulated. The study provides atomistic data for subsequent mesoscale simulations of tritium, vacancy, and antisite diffusion. In Pd, a strong binding is found between a vacancy and tritium (0.16 eV). This tritium binding increases the thermal concentration of vacancies by a factor of ~10 at 500 ?C. The increase in vacancy concentration enhances V antisite diffusion in Pd by a factor of ~6 at 500 ?C. The influence of tritium is even stronger in V, with a tritium and vacancy binding energy of 0.38 eV. Such a strong binding increases the thermal concentration of vacancies by a factor of ~300 at 500 ?C. The increase in vacancy concentration enhances Pd antisite diffusion in V by a factor of ~640 at 500 ?C. Vanadium and Pd exhibit a strong driving force to intermix with a formation energy of -1.57 eV for V antisite in Pd and -1.05 eV for Pd antisite in V. The results suggest vanadium diffusion into Pd is energetically stronger than the reverse. Zero-point-energy corrections are taken into account and calculations for hydrogen and tritium are presented.
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The Q values for double-electron capture in {sup 102}Pd, {sup 106}Cd, and {sup 144}Sm have been measured by Penning-trap mass spectrometry. The results exclude at present all three nuclides from the list of suitable candidates for a search for resonant neutrinoless double-electron capture.
Here we report measurements of the isotope shift of the mass 104, 105, 106, 108, and 110 stable palladium isotopes for transitions from the metastable state $4d^9(^2D_{5/2})5s$, $^2[5/2]_3 → 4d^9(^2D_{5/2})5p, ^2[7/2]^o_4$ at 340 nm, and $4d^9(^2D_{5/2})5_s, ^2[5/2]_3 → 4d^9(^2D_{5/2})5p, ^2[3/2]^o_2$ at 363 nm. For 105 Pd , we determine the hyperfine structure of both transitions. The measurements were performed by saturation absorption spectroscopy in a custom-built hollow cathode lamp and will serve as a reference for collinear laser spectroscopy of short-lived neutron-rich palladium isotopes. We also report on the observation of a population inversion for the 363-nm transition under certain discharge conditions.
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<p style="text-align: justify;">Poster presented at American Institute of Chemical Engineers (AIChE) Annual Conference in Orlando Florida, November 2019Objective: Evaluate the separation of hydrogen isotopes (protium/deuterium) as a function of various process conditions and with various membrane materials in a membrane reactor</p><p style="text-align: justify;"><br></p><p style="text-align: justify;"><br></p>
Shell-model calculations using realistic interactions reveal that the ground and low-lying yrast states of the N=Z nucleus {sub 46}{sup 92}Pd are mainly built upon isoscalar neutron-proton pairs, each carrying the maximum angular momentum J=9 allowed by the shell 0g{sub 9/2}, which is dominant in this nuclear region. This structure is different from that found in the ground and low-lying yrast states of all other even-even nuclei studied so far. The low-lying spectrum of excited states generated by such correlated neutron-proton pairs has two distinctive features: (i) the levels are almost equidistant at low energies and (ii) the transition probability I{yields}I-2 is approximately constant and strongly selective. This unique mode is shown to replace normal isovector pairing as the dominant coupling scheme in N=Z nuclei approaching the doubly magic nucleus {sup 100}Sn.
Purpose: We report the long-term results of a prospective, Phase II study of long-term androgen deprivation (AD), pelvic radiotherapy (EBRT), permanent transperineal prostate brachytherapy boost (PB), and adjuvant docetaxel in patients with high-risk prostate cancer. Methods and Materials: Eligibility included biopsy-proven prostate adenocarcinoma with the following: prostate-specific antigen (PSA) > 20 ng/ml; or Gleason score of 7 and a PSA >10 ng/ml; or any Gleason score of 8 to 10; or stage T2b to T3 irrespective of Gleason score or PSA. Treatment consisted of 45 Gy of pelvic EBRT, followed 1 month later by PB with either iodine-125 or Pd-103. One month after PB, patients received three cycles of docetaxel chemotherapy (35 mg/m{sup 2} per week, Days 1, 8, and 15 every 28 days). All patients received 2 years of AD. Biochemical failure was defined as per the Phoenix definition (PSA nadir + 2). Results: From August 2000 to March 2004, 42 patients were enrolled. The median overall and active follow-ups were 5.6 years (range, 0.9-7.8 years) and 6.3 years (range, 4-7.8 years), respectively. Grade 2 and 3 acute genitourinary (GU) and gastrointestinal (GI) toxicities were 50.0% and 14.2%, respectively, with no Grade 4 toxicities noted. Grade 3 and 4 acute hematologic toxicities were 19% and 2.4%, respectively. Of the patients, 85.7% were able to complete the planned multimodality treatment. The 5- and 7-year actuarial freedom from biochemical failures rates were 89.6% and 86.5%, and corresponding rates for disease-free survival were 76.2% and 70.4%, respectively. The 5- and 7-year actuarial overall survival rates were 83.3% and 80.1%, respectively. The 5- and 7-year actuarial rates of late Grade 2 GI/GU toxicity (no Grade 3-5) was 7.7%. Conclusions: The trimodality approach of using 2 years of AD, external radiation, brachytherapy, and upfront docetaxel in high-risk prostate cancer is well tolerated, produces encouraging long-term results, and should be validated in a multi-institutional setting.