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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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All sourcesNASA NTRSDOE OSTI
DOE OSTI2026

Mark-18A Target Material Recovery Program: Initial Hot Startup

The Savannah River National Laboratory (SRNL) has been tasked by the National Nuclear Security Administration to recover highly valued isotopes from irradiated Mark-18A (Mk-18A) targets. The Savannah River Site (SRS) has sixty-five Mk-18A targets available for the recovery of the high valued materials. The Mk-18A targets were manufactured with Pu-242 then irradiated under high neutron flux in K-Reactor at the SRS from 1968 to 1978. The sixty-five Mk-18A targets are currently stored in the SRS L-Area Basin and will be removed one at a time and individually transported to SRNL. Upon receipt at SRNL, the Mk-18A target material will be removed from the confinement, dissolved, chemically separated, and calcined to a stable oxide. The flowsheet is designed to recover the plutonium as well as the trivalent actinides. The original targets were manufactured with varying quantities of Pu-242, ranging from 5.2 grams to 121.5 grams. Taking a graded approach to process start up, the lowest loaded target (FT-80-03) was selected as the first target to be received and processed at SRNL. As operational experience and knowledge is gained from processing targets, higher loaded targets will be selected for processing to increase the quantities of valuable isotopes recovered. Due to dose concerns, the receipt and processing of the Mk-18A targets is performed in the SRNL Shielded Cells Facility. The targets are stored in a double J-can confinement in the L-Area Basin. A specially designed cask was procured for transport of the targets from L-Area to SRNL. Once received at SRNL, the targets are loaded into the back of Cell 7 and resized as they enter the cell. The resized targets (1/4 length) are then processed one at a time through the following processes: caustic dissolution and filtration, acidic dissolution and filtration, elutable Reillex anion exchange, diglycolamide (DGA) resin extraction, and DGA calcination. This processing results in two product streams. The first is an aqueous plutonium solution which is removed from the shielded cells and taken to a glovebox for further purification and conversion to an oxide. The second is a calcined oxide product containing the Am and Cm as well as other lanthanide fission products which is removed from the shielded cells using a bagless transfer system. Both materials are packaged for shipment to Oak Ridge National Laboratory (ORNL). This paper will discuss the operating experience, lessons learned, and results from initial process hot startup.

Armstrong, Christopher [Savannah River National La↗
DOE OSTI2022

Morphology and Dynamics in Hydroxide-Conducting Polysulfones

In alkaline zinc–manganese dioxide batteries, there is a need for selective polymeric separators that have good hydroxide ion conductivity but that prevent the transport of zincate (Zn(OH) 4 ) 2- . Here we investigate the nanoscale structure and hydroxide transport in two cationic polysulfones that are promising for these separators. We present the synthesis and characterization for a tetraethylammonium-functionalized polysulfone (TEA-PSU) and compare it to our previous work on an N-butylimidazolium-functionalized polysulfone (NBI-PSU). We perform atomistic molecular dynamics (MD) simulations of both polymers at experimentally relevant water contents. The MD simulations show that both polymers develop well phase separated nanoscale water domains that percolate through the polymer. Calculation of the total scattering intensity from the MD simulations reveal weak or nonexistent ionomer peaks at low wave vectors. The lack of an ionomer peak is due to a loss of contrast in the scattering. The small water domains in both polymers, with median diameters on the order of 0.5–0.7 nm, lead to hydroxide and water diffusion constants that are 1–2 orders of magnitude smaller than their values in bulk water. This confinement lowers the conductivity but also may explain the strong exclusion of zincate from the PSU membranes seen experimentally.

25 ENERGY STORAGE↗
DOE OSTI2020

Beyond Idealized Models of Nanoscale Metal Hydrides for Hydrogen Storage

Metal hydrides are attractive for compact, low-pressure hydrogen storage, yet a foundational understanding of factors governing their thermodynamics and kinetics is still lacking. Predictive modeling from the atomic to the microstructural scale plays a critical role in addressing these gaps, particularly for nanoscale materials, which promise improved performance but are difficult to probe. In this paper, we summarize strategies being developed within the Hydrogen Materials—Advanced Research Consortium (HyMARC) for going beyond conventional models to incorporate more complex physics, more realistic structures, and better approximation of operation conditions in simulations of nanoscale metal hydrides. We highlight four beyond-ideal factors that influence predicted performance: (1) surface anharmonic dynamics, (2) interface and surface energy penalties, (3) mechanical stress under confinement, and (4) the presence of native surface oxide. Approaches for addressing these factors are demonstrated on model materials representative of high-capacity hydrogen storage systems, and implications for understanding performance under operating conditions are discussed.

08 HYDROGEN↗
DOE OSTI2020

Stabilizing Single-Atom Iron Electrocatalysts for Oxygen Reduction via Ceria Confining and Trapping

Atomically dispersed Fe-N-C materials recently hold great interest in costly Pt substitution for the cathodic oxygen reduction reaction of fuel cells. However, the heat treatment involved in the materials preparation excites Fe aggregating into low activity of nanosized species rather than high activity of single-atom Fe sites. Herein we proposed a new "ceria-assisted" strategy to preferentially generate the active single-atom Fe sites in Fe-N-C materials, which involves oxidative polymerization of pyrrole, Ce 3+ and Fe 3+ adsorption, and subsequent heat treatment. Owing to its spatial confinement and strong trapping for Fe atoms, ceria can effectively suppress agglomeration of isolated Fe atoms and stabilize the Fe atoms by bonding to O in the lattice during the heat treatment, leading to a high content of atomically dispersed Fe (4.6 wt.%). Accordingly, the final catalyst showed ultrahigh ORR activity with a half-wave potential of 0.915 V and kinetic current density of 7.15 mA cm -2 at 0.9 V. When it was as assembled an anion exchange membrane fuel cell, a large maximum power density of 496 mW cm -2 was achieved.

25 ENERGY STORAGE↗
DOE OSTI2024

Impact of Confinement and Zwitterionic Ligand Chemistry on Ion–Ion Selectivity of Functionalized Nanopores

Membranes incorporating zwitterionic chemistries have recently emerged as promising candidates for facilitating challenging ion–ion separations. Transport of ions in such membranes predominantly occurs in hydrated nanopores lined with zwitterionic monomers. Here, to shed light on the physics of ion–ion selectivity underlying such materials, we conducted molecular dynamics simulations of sodium halide transport in model nanopores grafted with sulfobetaine methacrylate molecules. Our results reveal that in both functionalized and unfunctionalized nanopores smaller ions prefer to reside near the pore center, while the larger ions tend to reside near the pore walls. An enhancement in the selective transport of larger anions is observed within the unfunctionalized nanopores relative to that in salt-in-water solutions. Upon functionalization of the nanopores with zwitterions (ZIs), the disparities in the anionic distribution profiles within the pores coupled with differences in the anion-ZI interactions result in a slowdown of larger anions relative to smaller anions. Increasing the ZI grafting density exacerbates these effects, further promoting the selective transport of smaller anions. Our results suggest that selectivity toward large anions can be realized by using nanoporous membranes with ZI content that is high enough to facilitate ion/water partitioning into the pores while preserving the characteristic tendency of the unfunctionalized pores to facilitate faster transport of the larger anions. On the other hand, selectivity toward smaller anions can be achieved by targeting ZI content within the pores that is high enough to significantly slow down the transport of large anions but not high enough to hinder the partitioning of ions/water molecules into the pore due to steric effects.

anions↗
DOE OSTI2022

Ion Correlations and Partial Ionicities in the Lamellar Phases of Block Copolymeric Ionic Liquids

Recently, significant interest has arisen on the impact of dynamical ion correlations on the conductivity and transport properties of polymeric electrolyte materials. It has been hypothesized that confining ion motion to narrow channels may reduce such ion correlations and enhance the resulting ionic conductivity. Motivated by such considerations, in this study we used a multiscale simulation framework to study the dynamical ion correlations in the microphase-separated lamella phase of block copolymeric ionic liquids and compare with the corresponding results for homopolymeric systems. We probed the influence of ion correlations through the partial ionicity, Δ, which quantifies the ratio of true conductivity to the ideal, Nernst–Einstein conductivity for the anion-related contributions. Consistent with our original hypothesis, our results demonstrate that the partial ionicity relating to the mobile anions is much larger in the lamella phases of block copolymers compared to that in homopolymers. Analysis of the distinct conductivity contributions demonstrates that such results arise as a result of an intricate compensation among the nonideal dynamical correlations relating to anions in lamella phases. Overall, our results suggest that self-assembled phases of block copolymers may provide an avenue to tune the dynamical ion correlations in polymer electrolyte systems.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Elucidating the geometric and electronic structure of a fully sulfided analog of an Anderson polyoxomolybdate cluster

The catalytic activity of transition metal sulfide (TMS) clusters in small molecule activation, redox transformations, and charge transfer has inspired the design of novel TMS-based materials for energy-related catalysis and chemical applications. Polyoxometalates (POMs), known for their structural diversity, can in principle be transformed into TMS clusters; however, fully sulfided analogs are rarely isolated, likely due to the strong tendency of uncapped TMS clusters to agglomerate. Here, we report the geometric and electronic structure of a capping ligand-free fully sulfided analog of heptamolybdate Anderson POM [Mo VI 7 O 24 ] 6− , synthesized through the sulfidation of a nanoconfined POM secured within a porous Zr-metal organic framework (NU-1000). A combined computational and experimental analysis indicates that the sulfided counterpart of the Anderson POM is geometrically and electronically more sophisticated than the parent POM. Comparison of experimental pair distribution function (PDF) data with computational simulations confirms that, unlike the oxygen-only [Mo VI 7 O 24 ] 6− cluster, the [Mo IV 7 (μ 3 -S) 6 (μ 2 -SH) 6 (S 2 ) 6 ] 2− polythiometalate (PTM) exhibits diverse sulfur anions (S 2− , HS − , S 2 2− ). DFT calculations indicate that H 2 S acts as a reducing agent, and together with terminal disulfide (S 2 2− ) ligands in the PTM structure, facilitates the complete reduction of all seven Mo VI centers in the parent POM to Mo IV . These findings are supported by X-ray photoelectron spectroscopy (XPS), which confirms exclusive Mo IV , and elemental analysis, which shows quantitative sulfur incorporation. Difference envelope density (DED) mapping further reveals that the PTM clusters are spatially confined within the MOF pores, preventing agglomeration and preserving molecular integrity.

Rabbani, S. M. Gulam [The Ohio State University, C↗
DOE OSTI2026

Deciphering competing elementary steps to correlate electrocatalyst chemical state with activity

The overpotential in multielectron transfer heterogeneous electrocatalysis fundamentally arises from thermodynamic and kinetic disparities among elementary steps; however, deciphering coupled and competing steps has long remained a challenge. Here, we establish an electrochemical deconvolution paradigm based on key processes in electrocatalytic reactions, such as charge accumulation, electron/proton transfer, and intermediate evolution, to resolve competing elementary steps. Taking the oxygen evolution reaction as a prototypical reaction, we design a model catalyst featuring a precise isolated cation-anion vacancy pair and track the previously elusive electrochemical behavior of lattice oxygen by disentangling interference from adsorbed oxygen intermediates. Mechanistically, the lattice oxygen oxidation pathway originates from the spontaneous, nonelectrochemical deprotonation of replenished water molecules coordinated to unsaturated cation sites. Alternating current techniques further reveal that although lattice oxygen oxidation requires a higher potential than metal oxidation, it exhibits faster kinetics, providing insight into its superior catalytic activity. These findings establish a direct experimental correlation between the initial chemical state and the catalytic activity and prove surface-confined lattice oxygen cycling. Furthermore, expanding conventional potential-current analysis into a multidimensional framework enables disentanglement of thermodynamic and kinetic contributions of key elementary steps, thereby guiding the rational optimization of various complex multielectron transfer reactions.

OER↗
DOE OSTI2023

High-entropy halide perovskite single crystals stabilized by mild chemistry

High entropy materials are excellent candidates for a range of functional materials but traditionally require high-temperature synthetic procedures over 1000°C and complex processing techniques such as hot rolling to form. One route to address the extreme synthetic requirements for high entropy materials should involve designing crystal structures with ionic bonding networks and low cohesive energies. Here, we develop room-temperature (20°C) and low temperature (80°C) solution synthesis procedures for a new class of metal-halide perovskite high entropy semiconductor (HES) single crystals. Due to the soft, ionic lattice nature of the class of metal-halide perovskites, these HES single crystals are designed on the cubic Cs 2 MCl 6 (M = Zr 4+ , Sn 4+ , Te 4+ , Hf 4+ , Re 4+ , Os 4+ , Ir 4+ , or Pt 4+ ) vacancy-ordered double perovskite structure from the self-assembly of stabilized complexes in multielement inks, namely free Cs + cations and five or six different isolated [MCl6] 2- anionic octahedral molecules well-mixed in strong hydrochloric acid. The resulting single-phase single crystals span two HES families of five- and six-elements occupying the M-site as a random alloy in near-equimolar ratios, with the overall Cs 2 MCl 6 crystal structure and stoichiometry maintained. In conclusion, the incorporation of various [MCl 6 ] 2- octahedral molecular orbitals disordered across the high entropy five- and six-element Cs 2 MCl 6 single crystals produces complex vibrational and electronic structures with energy transfer interactions between the confined exciton states of the five or six different isolated octahedral molecules.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Hole-Trapping-Induced Stabilization of Ni 4+ in SrNiO 3 /LaFeO 3 Superlattices

Creating new functionality in materials containing transition metals is predicated on our ability to control the associated charge states. For a given metal, forming lower oxidation states is typically easier than generating higher values, and there is an upper limit on valence that is not exceeded under normal conditions. Here we demonstrate that we can exceed the normal upper limit of 3+ for Ni and Fe via synthesis of (SrNiO 3 )m/(LaFeO 3 )n superlattices by tuning n and m. The Goldschmidt tolerance constraints are lifted and SrNi 4+ O 3 with holes on adjacent O anions can be stabilized as a perovskite at the single unit cell level (m = 1). Spectroscopy reveals that the n = 1 superlattice contains Ni 3+ and Fe 4+ , whereas Ni 4+ and Fe 3+ are observed in the n = 5 superlattice. Here, our results show that the B-site cation valences can be tuned by controlling the magnitude of the FeO6 octahedral rotations which in turn drive the energy balance between Ni 3+ /Fe 4+ and Ni 4+ /Fe 3+ , thus controlling emergent electrical properties such as the band alignment and resulting hole confinement. We suggest that this approach may be generally useful for synthesizing novel, metastable layered structures with new functionalities.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Self-generated electrokinetic flows from active-charged boundary patterns

We develop a hydrodynamic description of self-generated electrolyte flow in capillaries whose bounding walls feature nonuniform distributions of charge nonuniform active ionic fluxes. The hydrodynamic velocity arising in such a system has components that are forbidden by symmetry in the absence of charge and fluxes. However, when these two boundary mechanisms are simultaneously present, they can lead to a symmetry broken state where steady flows with both unidirectional and circulatory components emerge. We show that these flow states arise when modulated boundary patterns of charge and fluxes are offset by a flux-charge phase difference, which is associated with the separation between sites of their peak densities on the wall. Mismatch in diffusivity of cationic and anionic species can modify the flow states and becomes an enhancing factor when fluxes of both ion species are being produced together at the same site. We demonstrate that this mechanism can be realized with a microfluidic generator that is powered by enzyme-coated patches that catalyze reactants in the solution to produce fluxes of ions. The local ionic elevation or depletion, which disrupts a nonuniform double layer, promotes self-induced gradients yielding persistent body forces to generate bulk fluid motion. Our work quantifies a boundary-driven mechanism behind self-sustained electrolyte flow in confined environments that exists without any external bulk-imposed fields or gradients. It provides a theoretical framework for understanding the combined effect of active and charged boundaries that are relevant in biological or soft matter systems, and can be utilized in electrofluidic and iontronic applications.

active matter↗
DOE OSTI2024

Mark-18A Cold Runs

The Savannah River National Laboratory (SRNL) is tasked by the National Nuclear Security Administration (NNSA) to recover highly valued isotopes from irradiated Mark-18A (Mk-18A) targets. The Savannah River Site (SRS) has sixty-five Mk-18A targets available for the recovery of the high valued materials. The sixty-five Mk-18A targets are currently stored in the L-Area Basin and will be removed one at a time and individually transported to SRNL. Upon receipt at SRNL, the Mk-18A target material will be removed from the confinement, dissolved, chemically separated, and calcined to a stable oxide. The flowsheet is designed to recover the plutonium as well as the trivalent actinides. The remaining unrecovered material will be discarded to the high activity drain (HAD) system in SRNL. A specially designed cask was procured for transport of the targets from L-Area to SRNL. Once received at SRNL, the targets will be loaded into the back of Cell 7 and resized as they enter the cell. The resized targets (1/4 lengths) will then be processed one at a time through the following processes: caustic dissolution and filtration; acidic dissolution and filtration, Reillex anion exchange, diglycolamide (DGA) cation exchange; and DGA calcination. This processing will result in two product streams. The first is an aqueous plutonium solution which will be removed from the shielded cells and taken to a glovebox for further purification and conversion to an oxide. The second is a calcined oxide containing the Am and Cm as well as other lanthanide fission products which will be removed from the shielded cells using a bagless transfer system. Both materials will be packaged for shipment to Oak Ridge National Laboratory (ORNL). All equipment to carry out this process was designed, procured or fabricated, and installed in a mock-up facility (716-4A) at SRS to allow for simulation testing in a non-radioactive area. This equipment was then dismantled and transferred from 716-4A to 773-A and installed in the SRNL Shielded Cells. After installation in the shielded cells facility testing was performed using water followed by surrogates and cold chemicals. Issues were identified during these evaluations, including equipment issues as well as technical challenges. Many of the issues were rectified during performance of the cold runs, and the remaining have a resolution identified. Table ES-1 provides a summary of all issues identified during the cold run operations, as well as the status and identified resolutions to outstanding issues.

07 ISOTOPE AND RADIATION SOURCES↗
DOE OSTI2023

Reversible Phase Transformation of Colloidal 2D Lead Halide Perovskite Platelets under Photoirradiation

The photostability of lead halide perovskites is an important criterion for their utilization in light harvesting applications. Colloidal two-dimensional mixed halide perovskites offer a convenient approach to probe photoinduced transformations using spectroscopy tools. We employed suspensions of colloidal 2D methylammonium lead halide perovskite platelets with butylammonium and octylammonium as organic spacer cations. Upon irradiation of the mixed halide perovskite (BAOAMAPb 2 (Br 3.5 I 3.5 )) colloidal platelet suspension, we observe a phase transformation, as seen from the formation of bromide rich domains (BAOAMAPb 2 Br 7 ) and an iodide complex (PbI 3 – ). Unlike in the case of 3D mixed halide films, we did not observe the formation of iodide rich domains as part of the photoinduced phase segregation process. Instead, we observed the dissociation of the BAOAMAPb 2 I 7 to form an iodide complex, PbI 3 – . Interestingly, this photoinduced phase transformation was reversible, as the products which were confined in the colloidal core restored the original mixed halide phase upon storage in dark. The spectroscopic measurements that characterize excited states of different colloidal methylammonium lead halide perovskites and kinetics of photoinduced transformation and their dark recovery are presented. Furthermore, these new phototransformations of colloidal perovskite platelets provide new insights into the processes that dictate their overall photostability.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Potential-induced wetting and dewetting in pH-responsive block copolymer membranes for mass transport control

Wetting and dewetting behavior in channel-confined hydrophobic volumes is used in biological membranes to effect selective ion/molecular transport. Artificial biomimetic hydrophobic nanopores have been devised utilizing wetting and dewetting, however, tunable mass transport control utilizing multiple transport modes is required for applications such as controllable release/transport, water separation/purification and energy conversion. Here, we investigate the potential-induced wetting and dewetting behavior in a pH-responsive membrane composed of a polystyrene-b-poly(4-vinylpyridine) (PS-b-P4VP) block copolymer (BCP) when fabricated as a hierarchically-organized sandwich structure on a nanopore electrode array (NEA), i.e. BCP@NEA. At pH < pK a (P4VP) (pK a ~ 4.8), the BCP acts as an anion-exchange membrane due to the hydrophilic, protonated P4VP cylindrical nanodomains, but at pH > pK a (P4VP), the P4VP domains exhibit charge-neutral, hydrophobic and collapsed structures, blocking mass transport via the hydrophobic membrane. However, when originally prepared in a dewetted condition, mass transport in the BCP membrane may be switched on if sufficiently negative potentials are applied to the BCP@NEA architecture. When the hydrophobic BCP membrane is introduced on top of 2-electrode-embedded nanopore arrays, electrolyte solution in the nanopores is introduced, then isolated, by exploiting the potential-induced wetting and dewetting transitions in the BCP membrane. The potential-induced wetting/dewetting transition and the effect on cyclic voltammetry in the BCP@NEA structures is characterized as a function of the potential, pH and ionic strength. Additionally chronoamperometry and redox cycling experiments are used to further characterize the potential response. The multi-modal mass transport system proposed in this work will be useful for ultrasensitive sensing and single-molecule studies, which require long-time monitoring to explore reaction dynamics as well as molecular heterogeneity in nanoconfined volumes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Interfacial Adhesion Mechanism of Anionic Polyelectrolyte Brushes Induced by Oppositely Charged Macromolecular Counterions

Abstract Polyelectrolyte brushes are widely used as model systems for investigating electrostatic interactions at soft interfaces and to achieve exceptional lubrication properties. Previous studies have primarily focused on their behavior in the presence of multivalent counterions, which induce brush collapse, ionic crosslinking, and pronounced changes in interfacial structures. However, interactions between polyelectrolyte brushes and oppositely charged macromolecular counterions, such as polycations, remain poorly understood. Here, we prepare well-defined polystyrene sulfonate (PSS) brushes fabricated via surface-initiated grafting and employ surface forces apparatus measurements to investigate their interactions with oppositely charged polycations. In contrast to multivalent ions, polycations do not induce noticeable brush collapse, but instead generate significant adhesion between symmetric PSS brush layers. This adhesion increases with both contact time and applied load, eventually reaching a steady plateau, indicating that the interaction is governed not simply by electrostatic screening but by the gradual formation of polycation-mediated bridging under confinement. Furthermore, the introduction of monovalent Na+ ions disrupts the adhesive interaction even at very low concentrations, suggesting that the bridging function of the adsorbed polycation is highly sensitive to competitive ionic screening. In comparison, measurements with trivalent counterions reveal the expected brush collapse behavior but minimal dependence of adhesion on contact time, highlighting a clear mechanistic distinction from the polymeric counterion case. Collectively, these results demonstrate that molecular size, configurational restriction, and confinement-induced rearrangement, rather than charge valency alone, govern the interaction behavior of macromolecular counterions at brush interfaces. This work provides new insight into the molecular origins of adhesion and the regulation of interfacial interactions in charged polymer brush systems.

Park, Jinwoo [Argonne National Laboratory , , , ,;↗
DOE OSTI2023

Electron Scattering from 1-Methyl-5-Nitroimidazole: Cross-Sections for Modeling Electron Transport through Potential Radiosensitizers

In this study, we present a complete set of electron scattering cross-sections from 1-Methyl-5-Nitroimidazole (1M5NI) molecules for impact energies ranging from 0.1 to 1000 eV. This information is relevant to evaluate the potential role of 1M5NI as a molecular radiosensitizers. The total electron scattering cross-sections (TCS) that we previously measured with a magnetically confined electron transmission apparatus were considered as the reference values for the present analysis. Elastic scattering cross-sections were calculated by means of two different schemes: The Schwinger multichannel (SMC) method for the lower energies (below 15 eV) and the independent atom model-based screening-corrected additivity rule with interferences (IAM-SCARI) for higher energies (above 15 eV). The latter was also applied to calculate the total ionization cross-sections, which were complemented with experimental values of the induced cationic fragmentation by electron impact. Double differential ionization cross-sections were measured with a reaction microscope multi-particle coincidence spectrometer. Using a momentum imaging spectrometer, direct measurements of the anion fragment yields and kinetic energies by the dissociative electron attachment are also presented. Cross-sections for the other inelastic channels were derived with a self-consistent procedure by sampling their values at a given energy to ensure that the sum of the cross-sections of all the scattering processes available at that energy coincides with the corresponding TCS. This cross-section data set is ready to be used for modelling electron-induced radiation damage at the molecular level to biologically relevant media containing 1M5NI as a potential radiosensitizer. Nonetheless, a proper evaluation of its radiosensitizing effects would require further radiobiological experiments.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2023

Co 2 Mo 6 S 8 Catalyzes Nearly Exclusive Electrochemical Nitrate Conversion to Ammonia with Enzyme-like Activity

Electrocatalytic nitrate to ammonia conversion is a key reaction for energy and environmental sustainability. This reaction involves complex multi electron and proton transfer steps, and is impeded by the lack of catalyst for promoting both reactivity and ammonia selectivity. Here, we demonstrate active motifs based on the Chevrel phase Co 2 Mo 6 S 8 exhibit an enzyme-like high turnover frequency of ~95.1 s –1 for nitrate electroreduction to ammonia. We reveal strong synergy of multiple binding sites on this catalyst, such that the ligand effect of Co steers H ad* toward hydrogenation other than hydrogen evolution, the ensemble effect of Co, and the spatial confinement effect that promote the full hydrogenation of NO x to ammonia without N–N coupling. The catalyst exhibits almost exclusive ammonia conversion with a Faradaic efficiency of 97.1% and ammonia yielding rate of 115.5 mmol·g cat –1 ·h –1 in neutral electrolytes. The high activity was also confirmed in electrolytes with dilute nitrate and high chloride concentrations.

36 MATERIALS SCIENCE↗