Browsing by Subject "H-2"

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  • IAEA DLW Database Grp; Speakman, John R.; Yamada, Yosuke; Sagayama, Hiroyuki; Pietiläinen, Kirsi H. (2021)
    The doubly labeled water (DLW) method measures total energy expenditure (TEE) in free-living subjects. Several equations are used to convert isotopic data into TEE. Using the International Atomic Energy Agency (IAEA) DLW database (5,756 measurements of adults and children), we show considerable variability is introduced by different equations. The estimated rCO(2) is sensitive to the dilution space ratio (DSR) of the two isotopes. Based on performance in validation studies, we propose a new equation based on a new estimate of the mean DSR. The DSR is lower at low body masses (
  • Bowden, Mark E.; Ginovska, Bojana; Jones, Martin Owen; Karkamkar, Abhijeet J.; Ramirez-Cuesta, Anibal J.; Daemen, Luke L.; Schenter, Gregory K.; Miller, Seth A.; Repo, Timo; Chernichenko, Konstantin; Leick, Noemi; Martinez, Madison B.; Autrey, Tom (2020)
    We report the heterolysis of molecular hydrogen under ambient conditions by the crystalline frustrated Lewis pair (FLP) 1-{2-[bis (pentafluorophenyOboryl] phenyl -2, 2,6,6-tetrame-thylpiperidine (KCAT). The gas-solid reaction provides an approach to prepare the solvent-free, polycrystalline ion pair KCATH2 through a single crystal to single crystal transformation. The crystal lattice of KCATH2 increases in size relative to the parent KCAT by approximately 2%. Microscopy was used to follow the transformation of the highly colored red/orange KCAT to the colorless KCATH2 over a period of 2 h at 300 K under a flow of H-2 gas. There is no evidence of crystal decrepitation during hydrogen uptake. Inelastic neutron scattering employed over a temperature range from 4-200 K did not provide evidence for the formation of polarized H-2 in a precursor complex within the crystal at low temperatures and high pressures. However, at 300 K, the INS spectrum of KCAT transformed to the INS spectrum of KCATH2. Calculations suggest that the driving force is more favorable in the solid state compared to the solution or gas phase, but the addition of H-2 into the KCAT crystal is unfavorable. Ab Initio methods were used to calculate the INS spectra of KCAT, KCATH2, and a possible precursor complex of H-2 in the pocket between the B and N of crystalline KCAT. Ex-situ NMR showed that the transformation from KCAT to KCATH2 is quantitative and our results suggest that the hydrogen heterolysis process occurs via H-2 diffusion into the FLP crystal with a rate-limiting movement of H-2 from inactive positions to reactive sites.
  • Nordlund, Kai; Hori, Masaki; Sundholm, Dage (2022)
    We simulate the deceleration and transmission of antiprotons with keV-scale kinetic energies through polymer foils using a molecular dynamics approach, which includes a model of nuclear stopping based on the attractive interaction potentials between antiprotons and target atoms calculated by quantum chemical methods. Antiprotons scatter into larger angles with higher cross sections than protons. This causes a significant fraction of antiprotons to annihilate in the foil instead of emerging with energies of a few keV, especially when coatings of materials with high atomic number are applied to the surfaces. The simulation results are in good agreement with data from two experiments that involved pulsed antiproton beams with incident energies between 63 keV and 122 keV that traverse polymer foils with thicknesses of approximate to 1.3 mu m and 1.8 mu m. The 25-nm-thick layers of Ag on the latter foil reduced the transmission of antiprotons. The results will be utilized to design the degrader foils in laser spectroscopy experiments of antiprotonic helium atoms and experiments involving Penning traps that are carried out at the ELENA facility of CERN.
  • Antoniassi, Rodolfo M.; Machado, Arthur P.; Paiva, Ana Rita N.; Queiroz, Carla M. S.; Vaz, Jorge M.; Spinace, Estevam; Silva, Julio Cesar M.; Carmine, Eduardo; Camargo, Pedro H. C.; Torresi, Roberto M. (2021)
    Active Pt-based catalysts at low temperature towards the preferential oxidation of carbon monoxide in hydrogen-rich stream reaction (CO-PROX) are of great importance for H-2-fueled fuel cells, but still remain a challenge. Herein, we propose a simple approach to synthesize a highly active Pt20Fe/CeO2 catalyst employing the borohydride reduction process. Transmission electronic microscopy revealed monodispersed 2.8 nm-Pt nanoparticles on CeO2, and the role of Fe species on the activity is discussed. The excellent CO conversion of 99.6% and CO2 selectivity of 92.3% carried out at ambient temperature meet the CO-PROX requirements for an adequate supply of hydrogen in fuel cell device. (C) 2021 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
  • Zakharov, Danila O.; Chernichenko, Konstantin; Sorochkina, Kristina; Repo, Timo; Zhivonitko, Vladimir V. (2022)
    Parahydrogen-induced polarization is a nuclear spin hyperpolarization technique that can provide strongly enhanced NMR signals for catalytic hydrogenation reaction products and intermediates. Among other matters, this can be employed to study the mechanisms of the corresponding chemical transformations. Commonly, noble metal complexes are used for reactions with parahydrogen. Herein, we present a PHIP study of metal-free imine hydrogenations catalyzed by the ansa-aminoborane catalyst QCAT. We discuss the reaction mechanism by showing the pairwise nature of the initial hydrogen activation step that leads to the formation of the negative net nuclear spin polarization of N-H hydrogen in the QCAT-H-2 intermediate, enabling the further transfer of parahydrogen-originating protons to the imine substrate with the accumulation of hyperpolarized amine products. Parahydrogen-induced polarization also demonstrates the reversibility of the catalytic cycle.
  • Birchall, Nicholas; Feil, Christoph M.; Gediga, Michael; Nieger, Martin; Gudat, Dietrich (2020)
    The reversible reaction of H(2)with a bis-phosphenium complex of chromium provides a rare example of 3d transition metal/phosphenium cooperativity. Photolysis induces the activation of H(2)and yields a spectroscopically detectable phosphenium-stabilized (sigma-H-2)-complex, readily showing exchange with gaseous H(2)and D-2. Further reaction of this complex affords a phosphine-functionalized metal hydride, representing a unique example of reversible H(2)cleavage across a 3d MP bond. The same species is also accessibleviastepwise H+/H(-)transfer to the bis-phosphenium complex, and releases H(2)upon heating or irradiation. Dihydrogen transfer from the H-2-complex to styrene is exploited to demonstrate the first example of promoting hydrogenation with a phosphenium complex.