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An original method of experimental modeling depth distribution of radionuclides in sphere thick targets irradiated by protons in 4(pi)-geometry on JINR (Dubna) synchrocyclotron is described. Some results are presented.
The EUCLID (Experiments Underpinned by Computational Learning for Improvements in Nuclear Data) project created a library of sensitivities for nine different integral responses with respect to nuclear data. These integral responses were obtained from measurements at LLNL (Lawrence Livermore National Laboratory) pulsed spheres, critical and sub-critical assemblies. At the same time, covariances for ENDF/B-VIII.0 were processed at LANL (Los Alamos National Laboratory). The combination of these data allow us to study the impact of nuclear-data covariances on various integral responses, either by forward-propagating covariances via sensitivities, or by using nuclear data, integral responses, and sensitivities for adjustment. Here, we will present: the impact of 1 H, 9 Be, 12 C, 27 Al, 56 Fe, 235,238 U, and 239,240 Pu ENDF/B-VIII.0 covariances on simulated bounds of the following integral responses: LLNL pulsed-spheres neutron-leakage spectra, the effective neutron multiplication factor, reaction rates, and reactivity coefficients of ICSBEP critical assemblies. Also, adjustment results with the same nuclear-data covariances and responses will be discussed.
This report documents evaluations of the neutron-induced 239 Pu and 235 U average prompt neutron multiplicities, $\overline{v}_p$, using the CGMF model developed at LANL. These evaluations are not updates of existing ENDF/B-VIII.0 nuclear data, but were both re-done from "scratch". That is, all experimental data were extracted from EXFOR, re-normalized to the newest nuclear data representing monitor observables, and detailed uncertainties were estimated from information in EXFOR as well as from templates of expected measurement uncertainties. We also included experimental data that were not yet available for ENDF/B-VIII.0, for instance, the data of Marini et al. for 239 Pu(n,f) $\overline{v}_p$ or the data of Khoklov et al. for 235 U(n,f) $\overline{v}_p$. Finally, we include the CGMF model; it computes $\overline{v}_p$ based on model parameters that at the same time calculate fission fragments as a function of mass, Y (A), the average total kinetic energy as a function of incident-neutron energy, $\langle TKE \rangle$(E inc ), etc. Such a detailed fission model that ties together many fission quantities has not been used to date for any $\overline{v}_p$ evaluation in ENDF/B. Here, we show that we can get evaluated 235 U(n,f) and 239 Pu $\overline{v}_p$ that not only correspond well to experimental $\overline{v}_p$, but that the associated evaluated model parameters also yield parameterizations of Y (A), $\langle TKE \rangle$(E inc ), etc., that correspond well to their respective experimental data. The new evaluated 239 Pu(n,f) $\overline{v}_p$ was also combined into a 239 Pu test file with the newest nuclear data for the 239 Pu prompt-fission neutron spectrum and fission cross sections. This new 239 Pu file performed reasonably well in predicting PU-MET-FAST assemblies, reaction rates in Jezebel and Flattop and three LLNL pulsed spheres. Due to that, the new 239 Pu(n,f) $\overline{v}_p$ evaluation presented here is being considered for ENDF/B-VIII.1. Hence, we can show here that CGMF is able to produce ENDF/B quality $\overline{v}_p$ nuclear data.
Reactions of 1,3,5-trimethyl-triazacyclohexane (Me 3 tach) with common rare-earth metal iodide, chloride, and triflate salts were examined to determine the capacity of this inexpensive chelate to provide alternative precursors for THF-free reactions. The reaction of LaI 3 (THF) 4 and CeI 3 (THF) 4 with 1,3,5-trimethyl-triazacyclohexane in THF generated toluene soluble (Me 3 tach) 2 LnI 3 , 1-Ln , in which the Ln center has a tri-capped trigonal prismatic geometry with two eclipsed Me 3 tach rings. Reaction with NdI 3 (THF) 3.5 forms the analogous 1-Nd , but a different structure with one outer sphere iodide, [(Me 3 tach) 2 NdI 2 ][I], 2-Nd , is also accessible and has a structure reminiscent of bent metallocenes. The reaction of LaCl 3 and Me 3 tach forms the less soluble (Me 3 tach) 2 LaCl 3 , which has a structure analogous to 1-Ln with eclipsed Me 3 tach rings. The mono-ring yttrium complex, (Me 3 tach)YCl 3 (THF) 2 , could be isolated from the reaction of YCl 3 with Me 3 tach. Reactions of La(OTf) 3 with Me 3 tach were sensitive to the presence of residual proton sources as exemplified by the isolation of {[(Me 3 tach)La(μ-OH)(μ-OTf)] 2 (μ-OTf) 2 } 2 , 5-La , and [HMe 3 tach][(Me 3 tach) 2 La-(OTf) 4 ], 6-La . SmI 2 reacts with Me 3 tach to produce the Sm( II ) complex, (Me 3 tach) 2 SmI 2 (THF), 7-Sm , but 2-Sm can also form in this reaction. Complexes of the larger 1,4,7-trimethyltriazacyclononane (Me 3 tacn) ligand, namely (Me 3 tacn)LaI 3 (THF), (Me 3 tacn)YCl 3 , and (Me 3 tacn)SmI 2 (THF) were synthesized for comparison. Several examples of the protonated ligands with simple counteranions, [HMe 3 tach][X] (X = Cl, Br, I) and [HMe 3 tacn][OTf], were identified in the course of these studies.
The surface chemistries of three particulate samples collected from the lower stratosphere have been determined using a Scanning Auger Microprobe (SAM). These samples are typical of the most abundant natural and anthropogenic particles observed within the stratosphere in the greater-than-2-micron diameter size fraction. Succsessive sputtering and analysis below the first few adsorbed monolayers of all particles shows the presence of a thin (less than 150A) sulfur layer. These sulfur regions probably formed by surface reaction of sulfur-rich aerosols with each particle within the stratosphere. Settling rate calculations show that a typical sphere (10-micron diameter) may reside within the aerosol layer for 20 days and thus provide a qualitative guide to surface sulfur reaction rates.
An experimental investigation was conducted to obtain detailed effects of the RCS jet flow direct impingement on the orbiter during on-orbit flight of the space shuttle vehicle. RCS flow was simulated by blowing a jet of cold air from nozzles attached to the model sting support system near the fuselage base. Thrust was obtained by setting the nozzle plenum pressure. Three RCS on-orbit flight conditions were simulated. Six component force data were measured on the complete model.
The rate of charge transfer within a discrete donor–acceptor (D/A) pair is well-described by semi-classical electron transfer theory, but the effects of multiple equivalent redox sites remain less understood. We report a series of ground-state intramolecular proton-coupled electron transfer (PCET) complexes designed to isolate the effects of donor number, N, while holding geometry, coupling, and driving forces constant. The [Ru(L) 3−N (OH) N ] 2+ complexes incorporate one, two, or three identical phenolic electron donors linked to Ru through rigid phenanthroline bridges (OH = 2,4-di-tert-butyl-6-(1-methyl-1H-imidazo[4,5-f][1,10]phenanthrolin-2-yl)phenol). Upon flash photolysis and oxidative quenching with methyl viologen (MV 2+ ), the transient Ru(III) oxidizes an appended phenol by PCET with the hydrogen-bonded imidazole nitrogen atom functioning as the base. The rate increased by 3.4-fold and 5.7-fold (1.7-fold and 1.9-fold after statistical correction) for two- and three-donor complexes compared to the single-donor system. The supra-statistical acceleration is attributed to a reduced effective outer sphere reorganization energy (λ m ) modeled by a partially shared solvent reaction coordinate, in which a subset of solvent dipoles is already oriented to stabilize charge from any donor. The final phenoxyl radical state is localized due to the transfer of a proton, and the recombination reaction with the viologen radical is not accelerated. These results demonstrate the effects of solvent dynamics on intramolecular PCET rates, offering a new strategy for the design of synthetic charge transfer systems.
Clay minerals retain or adsorb metal ions in the Earth’s critical zone. Rocks, sediments and soils rich in clay minerals can concentrate rare earth elements (REEs) in ion adsorption-type deposits (IADs) and are similarly effective at metallic contaminant remediation. However, the molecular-scale chemical and physical mechanisms of metal ion retention remain only partly understood. Here, we describe the nature, location and energy requirements of metal retention at clay mineral surfaces. Retention originates mainly from electrostatic interactions during cation exchange at low pH and chemical bonding in surface complexation and precipitation at neutral and high pH. Surface complexation can induce surface redox reactions and precipitation mechanisms including neoformation of clay mineral layered structures. In IADs, outer-sphere adsorption is the major retention mechanism of REE ions. By contrast, the use of clay minerals in pollution control relies on various mechanisms that can coexist, including cation exchange, surface complexation and nucleation growth. To more effectively leverage clay mineral–metal interactions in resource recovery and contaminant remediation, complex mechanisms such as surface precipitation and redox reactions must be better understood; for instance, by utilizing advances in quantum mechanical calculations, close combination between synchrotron and simulation techniques, and upscaling of molecular-level information in macroscopic thermokinetic predictive models.
The design of synthetic inorganic catalysts mimicking the first coordination spheres of enzymatic cofactors often results in lower yields and selectivity than their biological counterparts. In this study, we exploit Kohn-Sham density functional methods to compare the reaction profiles of four single iron-based catalysts for the direct oxidation of methane to methanol: two biomimetic models based on two enzymes (cytochrome P450 and taurine dioxygenase [TauD]) and two synthetic reticular frameworks (iron-BEA zeolite and tri-iron oxo-center-based metal-organic framework). Both the biomimetic and inorganic catalysts show almost zero selectivity toward methanol for methane conversions >1% at ambient temperature. Furthermore, this study highlights that iron’s first coordination shell can influence selectivity toward methanol but to a limited extent. In the absence of methanol protection strategies, high selectivity can be reached only by mimicking the reaction microenvironment of enzymes beyond the first coordination shell of iron.
Results are reported for an investigation of a new direct-simulation Monte Carlo method by which energy transfer and chemical reactions are calculated. The new method, which reduces to the variable cross-section hard sphere model as a special case, allows different viscosity-temperature exponents for each species in a gas mixture when combined with a modified Larsen-Borgnakke phenomenological model. This removes the most serious limitation of the usefulness of the model for engineering simulations. The necessary kinetic theory for the application of the new method to mixtures of monatomic or polyatomic gases is presented, including gas mixtures involving chemical reactions. Calculations are made for the relaxation of a diatomic gas mixture, a plane shock wave in a gas mixture, and a chemically reacting gas flow along the stagnation streamline in front of a hypersonic vehicle. Calculated results show that the introduction of different molecular interactions for each species in a gas mixture produces significant differences in comparison with a common molecular interaction for all species in the mixture. This effect should not be neglected for accurate DSMC simulations in an engineering context.
Within material test reactor calculations, energy dependent flux and reaction rate uncertainties are typically not quantified when performing as-run analyses to determine the neutron field experienced by the experiment. When high fidelity Monte-Carlo codes are used in such analyses, straight forward methods to calculate output uncertainties are not available, instead expert opinion is used to postulate computational uncertainties. New methods to propagate uncertainties through these high fidelity simulations are available when sufficient computational power is available. A tool is developed here for sampling any part of an MCNP input from random distributions to determine output uncertainties based on those inputs. Another tool is developed to sample nuclear data cross-section in ACE format using multi-group nuclear data covariances. The Total Monte-Carlo Method and Gesellschaft für Anlagen-und Reaktorsicherheit method (GRS) are implemented and compared to one another as well as MCNP sensitivity and uncertainty calculations. The methods were applied to the Godiva critical sphere k-eigenvalue, the UAM pin-cell benchmark energy dependent flux and reaction rates, and the Advanced Test Reactor energy dependent flux within an experimental location. Furthermore, the two methods agree well, with GRS allowing for an order of magnitude speedup for reaction rate uncertainty calculations and several orders of magnitude for eigenvalue uncertainty calculations.
The cosmogenic ³⁹Ar(t1∕2 = 268 years) isotope of argon is used for geophysical dating and tracing of underground and ocean water, as well as ice owing to its appropriate half-life and chemical inertness as a noble gas; ³⁹Ar serves also in nuclear weapon test monitoring. We measured for the first time the total cross section of the main ³⁹Ar cosmogenic production reaction in the atmosphere, namely ⁴⁰Ar(𝑛, 2𝑛)39 Ar, using 14.8 ± 0.3 MeV neutrons. The neutrons, produced by a deuterium-tritium generator, impinged on a stainless steel sphere filled with Ar gas highly enriched in the ⁴⁰Ar isotope and were monitored by a stack of fast-neutron activation foils. The reaction yield was measured by atom counting of long-lived ³⁹Ar with noble gas accelerator mass spectrometry and, independently, by decay counting relative to atmospheric argon (³⁹Ar/Ar= 8.12 × 10−16 ). A total ⁴⁰Ar(𝑛, 2𝑛)39 Ar cross section of 610 ± 100 mb was determined at 14.8 ± 0.3 MeV incident neutron energy. This result serves as a benchmark for recent theoretical calculations and evaluations, found to reproduce well the experimental total cross section. We use these energy-dependent theoretical cross sections together with experimental spectra of cosmogenic neutrons at different altitudes to calculate the global average rate of neutron-induced ³⁹Ar atmospheric production, resulting in 770 ± 240 39 Ar atoms/cm²/day. The secular equilibrium between the ³⁹Ar calculated production rate and radioactive decay rate leads to a partial isotopic abundance ³⁹Ar/Ar = (5.9 ± 1.8) × 10−16 , showing that ≈73% of atmospheric ³⁹Ar is produced by cosmogenic neutrons, the remaining part believed to be induced by muons and high-energy 𝛾 rays. The ⁴⁰Ar(𝑛, 2𝑛)³⁹Ar cross section at 14 MeV is also a key parameter for quantifying the anthropogenic contribution to atmospheric 39 Ar produced during the thermonuclear tests of the 1960s. We estimate that anthropogenic ³⁹Ar accounts for roughly 20% of the present atmospheric inventory.
NASA has conducted an investigation of PbO-B2O3 glass with a view to PbO reduction and subsequent crucible reactions as a function of temperature and oxygen partial pressure, in order to establish the optimum processing conditions for subcentimetric glass hollow spheres applicable to inertial confinement fusion targets. The results obtained support the selection of appropriate crucible materials and oxygen partial pressure-temperature combinations that avoid phase separation from PbO reduction and/or crucible reactions.
Abstract Microenvironments tailored by multifunctional secondary coordination sphere groups can enhance catalytic performance at primary metal active sites in natural systems. Here, we capture this biological concept in synthetic systems by developing a family of iron porphyrins decorated with imidazolium (im) pendants for the electrochemical CO 2 reduction reaction (CO 2 RR), which promotes multiple synergistic effects to enhance CO 2 RR and enables the disentangling of second‐sphere contributions that stem from each type of interaction. Fe‐ ortho ‐im(H) , which poises imidazolium units featuring both positive charge and hydrogen‐bond capabilities proximal to the active iron center, increases CO 2 binding affinity by 25‐fold and CO 2 RR activity by 2000‐fold relative to the parent Fe tetraphenylporphyrin ( Fe‐TPP ). Comparison with monofunctional analogs reveals that through‐space charge effects have a greater impact on catalytic CO 2 RR performance compared to hydrogen bonding in this context.
Lithium metal (LM) is a promising anode for next-generation batteries due to its high theoretical capacity and low electrode potential. Nonetheless, side reactions, volume change, and unwanted lithium dendrite growth seriously limit the practical application of LM. Herein, with the aid of a hard template approach, a novel lithiophilic CoF 2 -carbon hollow sphere (CoF 2 @C-HS) composite material is successfully prepared via a facile in-situ fluorination and etching strategy. The lithiophilic CoF 2 acts as nucleation sites to reduce nucleation overpotential as well as induces the spatial Li deposition and the formation of LiF-rich solid electrolyte interphase (SEI), and the hollow carbon matrix can enhance the electrical conductivity and offer free space for LM deposition. Theoretical simulations reveal that the synergistic effect of lithiophilic CoF 2 and hollow carbon matrix homogenizes the electric field distribution and Li + flux. Benefiting from these advantages, the CoF 2 @C-HS-modified copper substrate electrode delivers an enhanced Coulombic efficiency (CE) of 93.7% for 280 cycles at 1 mA cm –2 and 1 mA h cm –2 . The symmetrical cell using CoF 2 @C-HS can stably cycle more than 1800 h with a low voltage hysteresis of 11 mV at a current density of 0.5 mA cm –2 and an areal capacity of 0.5 mA h cm –2 . Moreover, the Li@CoF 2 @C-HS composite anode enables more than 300 stable cycles at 1 C with a capacity retention of 95% in LiFePO 4 -based full cell and 110 stable cycles at 1 C in LiNi 0.8 Co 0.1 Mn 0.1 O 2 (NCM811)-based high-voltage full cell. Finally, this work might shed a new light on designing lithiophilic hosts to spatially confine LM deposition, realizing dendrite-free LM anodes and the practical applications of LM batteries.
The (non)-Kolbe oxidation of valeric acid, sourced from a hydrolysis product of cellulose, provides a sustainable synthetic route to access value-added products, such as butene. An essential mechanistic step preceding product formation involves the oxidative and decarboxylative cleavage of a C–C bond. Yet, the role of the electrode surface in mediating this oxidative step remains an open question: the electron transfer can occur either via an inner-sphere or outer-sphere mechanism. Here, we report the electrochemical, in situ spectroscopic, computational, and reactivity studies of RuO 2 -mediated oxidative decarboxylation of valeric acid to butene in aqueous electrolytes. We find that carboxylates bind to RuO 2 anode surfaces at potential values where decarboxylation products are observed. Our results are consistent with a reaction scheme where the competitive and catalytic oxygen evolution reaction (OER) is impeded by these bound carboxylate species while these species are inert toward butene formation. Our results implicate an outer-sphere electron transfer mechanism for decarboxylation where the surface chemistry of the RuO 2 electrode serves to enable higher non-Kolbe reaction selectivity by suppressing the parasitic OER. Furthermore, our findings delineate interfacial design principles for selective electrochemical systems that utilize water as the ultimate oxidant for sustainable decarboxylation.
We report Mononuclear nickel(II) and nickel(III) complexes of a bisamidate-bisalkoxide ligand, (NMe 4 ) 2 [Ni- II (HMPAB)] (1) and (NMe 4 )[Ni III (HMPAB)] (2), respectively, have been synthesized and characterized by various spectroscopic techniques including X-ray crystallography. The reaction of redox-inactive metal ions (M n+ = Ca 2+ , Mg 2+ , Zn 2+ , Y 3+ , and Sc 3+ ) with 2 resulted in 2-M n+ adducts, which was assessed by an array of spectroscopic techniques including X-ray absorption spectroscopy (XAS), electron paramagnetic resonance (EPR), and reactivity studies. The X-ray structure of Ca 2+ coordinated to Ni(III) complexes, 2Ca 2+ T, was determined and exhibited an average Ni-Ca distance of 3.1253 angstrom, close to the metal ions' covalent radius. XAS analysis of 2-Ca 2+ and 2-Y 3+ in solution further revealed an additional coordination to Ca and Y in the 2-M n+ adducts with shortened Ni-M distances of 2.15 and 2.11 Å, respectively, implying direct bonding interactions between Ni and Lewis acids (LAs). Such a short interatomic distance between Ni(III) and M is unprecedented and was not observed before. EPR analysis of 2 and 2-M n+ species, moreover, displayed rhombic signals with g av > 2.12 for all complexes, supporting the +III oxidation state of Ni. The Ni III /Ni II redox potential of 2 and 2-M n+ species was determined, and a plot of E 1/ 2 of 2-M n+ versus pK a of [M(H 2 O) n ] m+ exhibited a linear relationship, implying that the Ni III /Ni II potential of 2 can be tuned with different redox-inactive metal ions. Reactivity studies of 2 and 2-M n+ with different 4-X-2,6-ditert-butylphenol (4-XDTBP) and other phenol derivatives were performed, and based on kinetic studies, we propose the involvement of a proton-coupled electron transfer (PCET) pathway. Analysis of the reaction products after the reaction of 2 with 4-OMe-DTBP showed the formation of a Ni(II) complex (1a) where one of the alkoxide arms of the ligand is protonated. A pK a value of 24.2 was estimated for 1a. The reaction of 2-M n+ species was examined with 4-OMe-DTBP, and it was observed that the k 2 values of 2-M n+ species increase by increasing the Lewis acidity of redox-inactive metal ions. However, the obtained k 2 values for 2-M n+ species are much lower compared to the k 2 value for 2. Such a variation of PCET reactivity between 2 and 2-M n+ species may be attributed to the interactions between Ni(III) and LAs. Our findings show the significance of the secondary coordination sphere effect on the PCET reactivity of Ni(III) complexes and furnish important insights into the reaction mechanism involving high-valent nickel species, which are frequently invoked as key intermediates in Ni-mediated enzymatic reactions, solar-fuel catalysis, and biomimetic/synthetic transformation reactions.
Understanding controlling factors is important for the development of bifunctional outer-sphere C$=$C hydrogenations. In this study, a dominant view is that the polarization of C$=$C bonds is imperative for these reactions. However, the present comparative DFT study suggests that the polarization of C$=$C bonds is not the controlling factor. Instead, the “push–pull” type π-conjugative effect can decrease activation barriers and contribute to outer-sphere bifunctional C$=$C bond hydrogenations. What is more, this study shows the feasibility of the asymmetric bifunctional outer-sphere C$=$C hydrogenation.