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At least 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

A critical review of molybdenum sequestration mechanisms under euxinic conditions: Implications for the precision of molybdenum paleoredox proxies

The observed difference in molybdenum (Mo) mobility and isotopic fractionation under oxic versus euxinic (i.e., anoxic and sulfidic) aqueous conditions provides a sound operational basis for the use of Mo geochemical signatures in ancient sedimentary records to infer palaeoceanographic redox conditions. While Mo is known to exist predominantly as molybdate (MoO 4 2– ) in oxic waters and convert into thiomolybdate species (MoO x S 4-x 2– ) under euxinic conditions, the pathways that lead to Mo sequestration are highly debated. As mechanistic understanding of Mo sequestration is crucial for accurately reconstructing the chemistry of ancient oceans and constraining the timing and intensity of oxygenation events through Earth's history using Mo paleoproxies, we have closely examined the current proposed mechanisms for Mo sequestration across a wide range of euxinic conditions. Through compilation and comparison of such information, we aim to provide an integrated view of Mo sequestration processes, to identify the current controversies as well as the roots of such controversies, and importantly, to propose avenues for future research. Here, sequestration of Mo may occur through complexation with organic matter (OM), reactions with oxyhydroxide and sulfide mineral surfaces, incorporation into iron sulfide crystal structures, formation of Mo-sulfide, and cellular assimilation. However, several major questions remains unresolved, including whether OM complexation plays a significant role in overall sedimentary Mo accumulation, whether the reduction of Mo(VI) occurs during interaction with Fe-S clusters/precipitates and/or with OM, whether microbial enzymatic reduction of Mo(VI) is important in Mo sequestration, whether synergistic effects exist between the biological and abiotic processes in Mo sequestration, and whether differences in reactivity among the various thiomolybdate intermediate species and tetrathiomolybdate influence the Mo sequestration process. At the end of the review, the reliability of Mo paleoproxies is discussed and reevaluated.

58 GEOSCIENCES↗
DOE OSTI2023

Molybdenum-99 from Molten Salt Reactor as a Source of Technetium-99m for Nuclear Medicine: Past, Current, and Future of Molybdenum-99

Technitium-99m ( 99m Tc), a widely used radioisotope, is used in tens of millions of medical diagnostic procedures annually. However, it is hard to store and must be immediately used upon production due to its short half-life (i.e., 6 h); thus, it is currently produced from 99 Mo, which itself is a result of 235 U fission. The majority of 99 Mo supplies to U.S. patients are currently provided by foreign producers and produced using highly enriched uranium (HEU). In order to minimize the proliferation risks of HEU-based medical isotope production, the U.S. Department of Energy’s National Nuclear Security Administration has funded a program to accelerate the development of technologies to produce 99 Mo without the use of HEU. Today, the global supply of 99 Mo depends on a limited number of nuclear reactors, and production has been interrupted unexpectedly since 2009 due to the fleet’s advanced age. Herein, alternative options for 99 Mo production are discussed, and one potential option is to obtain 99m Tc from molten salt reactors (MSRs). A MSR is a nuclear fission reactor that can operate at or close to atmospheric pressure with liquid fuel, which allows for producing isotopes in a timely manner. In this paper, the past and current production of 99 Mo via nuclear reactors is described, and the future of 99 Mo production by MSRs is discussed. The behavior and chemical properties of molybdenum in fluoride salts in MSRs and the possible extraction methods are also examined in addition to the limitation of current studies.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗
DOE OSTI2022

Modulating Chemical Environments of Metal–Organic Framework-Supported Molybdenum(VI) Catalysts for Insights into the Structure–Activity Relationship in Cyclohexene Epoxidation

Solid supports are crucial in heterogeneous catalysis due to their profound effects on catalytic activity and selectivity. However, elucidating the specific effects arising from such supports remains challenging. We selected a series of metal–organic frameworks (MOFs) with 8-connected Zr 6 nodes as supports to deposit molybdenum(VI) onto to study the effects of pore environment and topology on the resulting Mo-supported catalysts. As characterized by X-ray absorption spectroscopy (XAS) and single-crystal X-ray diffraction (SCXRD), we modulated the chemical environments of the deposited Mo species. For Mo-NU-1000, the Mo species monodentately bound to the Zr 6 nodes were anchored in the microporous c-pore, but for Mo-NU-1008 they were bound in the mesopore of Mo-NU-1008. Both monodentate and bidentate modes were found in the mesopore of Mo-NU-1200. Cyclohexene epoxidation with H 2 O 2 was probed to evaluate the support effect on catalytic activity and to unveil the resulting structure–activity relationships. SCXRD and XAS studies demonstrated the atomically precise structural differences of the Mo binding motifs over the course of cyclohexene epoxidation. No apparent structural change was observed for Mo-NU-1000, whereas the monodentate mode of Mo species in Mo-NU-1008 and the monodentate and bidentate Mo species in Mo-NU-1200 evolved to a new bidentate mode bound between two adjacent oxygen atoms from the Zr 6 node. This work demonstrates the great advantage of using MOF supports for constructing heterogeneous catalysts with modulated chemical environments of an active species and elucidating structure–activity relationships in the resulting reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Design of Experiments Involving Molybdenum in SNL SPRF/CX Facility

This report is part of the collaboration with the Nuclear Criticality Safety Program and constitutes the “CED-2 report” of the experiments proposed in the SPRF/CX facility of SANDIA National Laboratories to contribute to the validation of Molybdenum in thermal energy spectrum. It supplements the study carried out in the CED-1 report by providing a more precise design of the proposed experiments and presents a complete evaluation of the experimental uncertainties. In the CED-1 report, corresponding to the preliminary design of the experiments, IRSN identified several promising configurations that could be implemented in the SPRF/CX facility of SNL. They use metallic molybdenum either in the form of foils between the UO 2 pellets inside BUCCX rods, or in the form of sleeves surrounding 7uPCX rods. In this CED-2 report, a new design using molybdenum sleeves surrounding BUCCX rods is also analyzed and the experimental uncertainties of all the proposed configurations are estimated. Given the constraints to carry out the experiments and the costs associated with the manufacturing of the foils, the experiments using molybdenum foils are discarded. Similarly, the design using molybdenum sleeves around BUCCX rods leads to significant manufacturing costs which could certainly be partially offset by use of existing grids but which would lead to slightly lower values of the integral sensitivities to the cross sections of molybdenum. Consequently, the design using molybdenum sleeves around 7uPCX rods is favored insofar as it presents higher $k_{eff}$ sensitivities to the molybdenum cross sections and that there is still possibility to reduce the number of sleeves to reduce the cost of experiments. Regarding feedback on nuclear data in support of criticality safety assessment, one of the advantages of the work described here is that the proposed experiments are not correlated with the MIRTE and FP experiments using molybdenum. In addition, they lead to higher sensitivity values in the thermal energy range than the existing experiments and partly “cover” the first resonance of the 95 Mo, which is a real advantage for improving knowledge on molybdenum cross sections.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2020

Determination of the N–H Bond Dissociation Free Energy in a Pyridine(diimine)molybdenum Complex Prepared by Proton-Coupled Electron Transfer

The pyridine(diimine) molybdenum bis(imido) complex, ( iPr PDI)Mo(=NTol) 2 (Tol = 4-methylphenyl) was synthesized by addition of two equivalents of 4-methylphenylazide to a corresponding molybdenum benzene derivative, ( iPr PDI)Mo(η 6 -C 6 H 6 ) ( iPr PDI = 2,6-(2,6-iPr 2 C 6 H 3 N=CMe) 2 C 5 H 3 N). Protonation of ( iPr PDI)Mo(=NTol) 2 with 2,6-lutinidum triflate yielded a cationic molybdenum amido complex, [( iPr PDI)Mo(NHTol)(=NTol)][OTf], which was further transformed into the neutral molybdenum amido complex, ( iPr PDI)Mo(NHTol)(=NTol) by reduction with zinc powder. A series of spectroscopic, synthetic and pK a determination studies along with electrochemical measurements by the protonation-reduction pathway were used to establish an N–H bond dissociation free energy (BDFE) between 65-69 kcal/mol for the molybdenum imido-amido compound, ( iPr PDI)Mo(NHTol)(=NTol). Full molecule DFT studies provided a computed value of 61 kcal/mol. By contrast, reduction of ( iPr PDI)Mo(=NTol) 2 with KC 8 afforded the corresponding anionic molybdenum complex, K[( iPr PDI)Mo(=NTol) 2 ] that has a potassium cation intercalated with the pyridine and the tolyl groups. Protonation of K[( iPr PDI)Mo(=NTol) 2 ] with the weak amidinium acids [TBD(H)][BArF 24 ] (TBD = triazabicyclodecene, BArF 24 = B[3,5-(CF 3 ) 2 C 6 H 3 ] 4 ) also produced the neutral molybdenum amido complex, ( iPr PDI)Mo(NHTol)(=NTol). Measurement of the pKa and oxidation potential of K[( iPr PDI)Mo(=NTol) 2 ] provided a range of 69-73 kcal/mol for the N–H BDFE of ( iPr PDI)Mo(NHTol)(=NTol), in good agreement with the protonation-reduction route and completing the square scheme. The similar pK a and redox potentials obtained from each pathway demonstrate that both sequences are energetically feasible for PCET events. This study on the determination of N–H BDFE of the molybdenum amido complex renders fundamental insight into the N 2 reduction cycle by proton-coupled electron transfer.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Molybdenum Sleeve Experiments in Fully-Reflected Water-Moderated Triangular-Pitched U(6.90)O 2 Fuel Rod Lattices (1.55 cm Pitch)

The US Department of Energy (DOE) Nuclear Energy Research Initiative funded the design and construction of the Seven Percent Critical Experiment (7uPCX) at Sandia National Laboratories. The start-up of the experiment facility and the execution of the experiments described here were funded by the DOE Nuclear Criticality Safety Program. The 7uPCX is designed to investigate critical systems with fuel for light water reactors in the enrichment range above 5 % 235 U. The 7uPCX assembly is a water-moderated and -reflected array of aluminum-clad U(6.90 %)O 2 fuel rods. Other critical experiments performed in the 7uPCX assembly are documented in LEU-COMP-THERM-078, LEU-COMP-THERM-080, LEU-COMP-THERM-096, LEUCOMP-THERM-097, LEU-COMP-THERM-101, and LEU-COMP-THERM-102. The purpose of these experiments was to measure the effects of molybdenum in nearly-critical systems. The molybdenum was introduced into the fuel arrays as tubular sleeves that surrounded some of the fuel rods in the fuel arrays measured. Four hundred molybdenum tubes nominally 12.7 mm outside diameter, 498 mm long, with 0.762 mm wall thickness were provided for the experiments by the Institut de Radioprotection et de Sûreté Nucléaire (IRSN). Small polyethylene adapters at each end of the tubes were used to center each tube on a fuel rod in the assembly. The critical experiments were done using a set of triangular-pitched grid plates fabricated for these experiments. The grid plate set accommodated a fuel array of a total of 1261 fuel rod positions on a pitch of 0.610 in (1.5494 cm) in a series of 20 hexagonal rings surrounding the central fuel rod. The fuel used in these experiments was fabricated using unirradiated 6.90 % enriched UO 2 fuel pellets from fuel elements designed to be used in the internal nuclear superheater section of the Pathfinder boiling water reactor operated in South Dakota by the Northern States Power Company in the 1960s. The fuel elements were obtained from The Pennsylvania State University where they had been stored for many years. The fuel pellets in those fuel elements were removed from the original Incoloy cladding and reclad in 3003 aluminum tubes and end caps for use in the experiments reported here. The five critical experiments in this series were performed in August through December 2022, in the Sandia Critical Experiments (SCX) at the Sandia Pulsed Reactor Facility. Case 1 had no molybdenum sleeves, Case 2 had 208 molybdenum sleeves clustered at the center of the array, Case 3 had 397 molybdenum sleeves clustered at the center of the array, Case 4 had 175 molybdenum sleeves in the central position and in five alternating hexagonal rings, and Case 5 had 331 molybdenum sleeves in the central position and in seven alternating hexagonal rings. All five critical experiments are judged to be acceptable as benchmark experiments.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2021

Insights into the Structure–Activity Relationship in Aerobic Alcohol Oxidation over a Metal–Organic-Framework-Supported Molybdenum(VI) Catalyst

The understanding of structure–activity relationships at the atomic level has played a profound role in heterogeneous catalysis, providing valuable insights into designing suitable heterogeneous catalysts. However, uncovering the detailed roles of how such active species’ structures affect their catalytic performance remains a challenge owing to the lack of direct structural information on a specific active species. Herein, we deposited molybdenum(VI), an active species in oxidation reactions, on the Zr 6 node of a mesoporous zirconium-based metal–organic framework (MOF) NU-1200, using solvothermal deposition in MOFs (SIM). Due to the high crystallinity of the NU-1200 support, the precise structure of the resulting molybdenum catalyst, Mo-NU-1200, was characterized through single-crystal X-ray diffraction (SCXRD). Two distinct anchoring modes of the molybdenum species were observed: one mode (Mo1), displaying an octahedral geometry, coordinated to the node through one terminal oxygen atom and the other mode (Mo2) coordinated to two adjacent Zr 6 node oxygen atoms in a tetrahedral geometry. To investigate the role of base in the catalytic activity of these Mo centers, we assessed the activity of Mo-NU-1200 for the aerobic oxidation of 4-methoxybenzyl alcohol as a model reaction. The results revealed that Mo-NU-1200 exhibited remarkably higher catalytic reactivity under base-free conditions, while the presence of base inhibited the catalytic reactivity of this species. SCXRD studies revealed that the molybdenum binding motifs (structures of the supported metal on the Zr 6 node in the MOF) changed over the course of the reactions. Following the oxidation without base, both pristine coordination modes (Mo1 and Mo2) evolved into a new coordination mode (Mo3), in which the molybdenum atom coordinated to two adjacent oxygen atoms from the Zr 6 node in an octahedral geometry, while in the presence of base, the pristine Mo1 coordination mode evolved entirely into the pristine Mo2. Here, this study demonstrates the direct observation of an active species’ structural evolution from metal installation to subsequent catalytic reaction. As a result, these subtle structural changes in catalyst binding motifs led to distinct differences in catalytic activities, providing a compelling strategy for elucidating structure–activity relationships.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗