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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 OSTI2024

Backend Nuclear Fuel Cycle Radiation Chemistry

Given global commitments to significantly increase nuclear energy capacity, it is now more important than ever to develop efficient used nuclear fuel management strategies to improve resource utilization, energy security, and waste minimization. Here, an overview of nuclear energy, backend fuel cycle challenges, and advances in used nuclear fuel reprocessing radiation chemistry will be presented. More specifically, the use of electron pulse irradiation techniques to explore radiation-induced reaction mechanisms in actinide containing solutions and solvent systems.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2025

Electrons and Their Multiple Kinetic Fates in an Ionic Liquid

Ionic liquids (ILs) for electrochemical, nuclear, and solar energy applications operate under harsh conditions, where electrons and transient radical species can form. This communication discusses why anions such as bis(trifluoromethylsulfonyl)imide (Tf 2 N − ) are reduced at the electron-rich electrode whereas in laser photoionization or pulse radiolysis studies, where electrons are ejected from species in the bulk, we often detect long-lived electrons in cavities that interact with IL cations instead. This work argues that bulk excess electrons generated photolytically or radiolytically follow kinetically favored pathways. As such, cavity electrons may not be the most energetically favorable states, but when they form, and they do form, they are kinetically stable. Reduction reactions of anions or electron localization in cavities and subsequent reactions are all expected outcomes. Here we focus on a pyrrolidinium-based IL of the dicyanamide (N(CN) 2 − ) anion because of its large electrochemical window and very low viscosity, which are ideal for energy applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Electron Transfer Theory Elucidates the Hidden Role Played by Triethylamine and Triethanolamine during Photocatalysis

Triethylamine (TEA) and triethanolamine (TEOA) are renowned, in part, for their ability to reductively quench excited states by outer-sphere electron transfer with vast and still growing applications as sacrificial electron donors for photocatalytic systems. Upon amine oxidation, the resulting TEA •+ and TEOA •+ radical cations undergo proton transfer (or hydrogen atom transfer), resulting in the formation of a chemical reductant that has an α-carbon centered radical adjacent to the nitrogen center (TEA • and TEOA • ). In this contribution, we have electrochemically and spectroscopically characterized a set of electron acceptors which, upon accepting an electron, are a series of photocatalysts, [ReCl(R 1 R 2 -bpy)(CO) 3 ] •– , where R 1 and R 2 are electron-donating and electron-withdrawing groups in the 4,4′- and 5,5′-positions on the bipyridyl ligand. Here, we substantiated the formation of the electron donors, TE(O)A • , by spin trapping electron paramagnetic resonance spectroscopy, where TE(O)A • reacts with 2,4,6-tri-tert-butylnitrosobenzene to generate N-centered and O-centered radical adducts. Having established the chemical behaviors of the electron acceptors and donors individually, the electron transfer rate constants were determined across a 1.43 V range in driving force. The redox potential of TEA • was benchmarked to within ±80 mV on an absolute scale in V vs Fc + /Fc in CH 3 CN by using an empirical rate vs free-energy correlation, electron transfer theory, and density functional theory calculations. The equilibrium potentials for TEA • and TEOA • were determined to be −1.98 V and −1.76 V, respectively. Based on the kinetic and thermochemical analysis presented for TEA • and TEOA • , these transient radicals can be broadly considered strong homogeneous chemical reductants within the wider context of photoredox potentials. Thus, this work clarifies a frequently unnoticed secondary function for these sacrificial electron donors during photocatalysis and rationalizes the possibility of a one-photon/two-electron conversion process that is dependent on the free-energy exchange between TE(O)A • and photocatalysts.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
NASA NTRS1979

An analytical approach to evaluation of space radiation effects on materials for long-life missions

An analytical model was developed which quantifies effects on organic composite matrix materials of high energy electrons and of UV as well as interactions between the two radiations. Literature data on polyethylene were used to construct a degradation kinetics scheme corresponding to an Earth orbit at L=3. Analysis of the model showed that steady state concentrations of radicals put limits on accelerated test conditions. These conclusions were validated by an experimental study on polymethylmethacrylate using UV laser excitation. Relationships for balancing electron and UV radiations to equal acceleration factors are derived. Pulse radiolysis using an electron-beam along with time-resolved spectroscopy is shown to be able to separate primary form secondary reactions. Implications of these reactions to changes in engineering material properties are indicated. The use of mechanistic studies is discussed in the context of general test strategies for evaluating materials for space applications.

Moacanin, J.↗
DOE OSTI2026

Selective Reduction of Carbon Dioxide in Water Using [M(bpy2+)(CO)3(I)]2+ (M = Mn, Re) Electrocatalysts with Pendent Cations

Manganese(I) carbonyl complexes are promising electrocatalysts for CO2 reduction, yet their application in homogeneous aqueous media remains limited by poor solubility and selectivity. Here, we report water-soluble Mn(I) and Re(I) complexes fac-[M(bpy2+)(CO)3X]2+ (X = I or Cl), featuring bipyridine ligands functionalized with -Ph-CH2-(NMe3)+ cationic ammonium groups that integrate water solubility with secondary-sphere stabilization. In bicarbonate buffer at pH 6.8, the Mn catalyst is completely selective for CO production at a low overpotential (η = 0.3 V), operating by a protonation-first mechanism with observed rates of ~10 s−1. Pulse radiolysis reveals that the one-electron reduced Mn species undergoes dimerization in the absence of CO2 but uniquely reacts competitively with CO2 through an initial pre-equilibrium followed by fast formation of a dinuclear CO2-bridged species (ΔGo = −12.4 kcal mol−1). At a higher 0.6 V over-potential, a faster reduction-first pathway (~100 s−1) is available upon reduction of the metallo-carboxylic acid intermediate, Mn-CO2H2+; however, this regime is functionally limited by the formation of a resistive, noncatalytic film on the electrode surface. Comparison to the analo-gous water-soluble Re catalyst (kobs = 440 s−1, η = 0.6 V) highlights the distinct mechanistic ad-vantages of earth-abundant Mn in low-potential catalysis. These results demonstrate how cati-onic second-sphere design enables selective, homogeneous CO2 reduction in water while reveal-ing competing radical and electrode-mediated processes that govern catalytic performance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Ionic Liquids under Radiation and the Dimer Radical Dicyanamide Anion

Ionic liquids (ILs) used in solar, electrochemical, nuclear, or even space exploration applications will necessarily be exposed to conditions in which electron detachment may occur and transient charge-depleted radical species may form. In a recent article (J. Am. Chem. Soc. 2025, 147, 23395–23398), we studied the different possible kinetic fates of an excess electron in the popular 1-butyl-1-methylpyrrolidinium dicyanamide IL but did not address the nature of electron-deficient transient radical species these leaving electrons produce, the so-called holes. Using pulse radiolysis measurements and first-principles calculations in the bulk and gas phases to interpret these, we show that the most likely hole species in this IL is a dimer radical anion that, somewhat surprisingly, has similar spectral features to the excess electron, including a broad near-infrared absorption band.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Transient methods for understanding the properties of strongly oxidizing radicals

This review discusses the properties of strongly oxidizing radicals in organic and aqueous media and highlights the challenges in obtaining accurate values of their reduction potentials. Transient redox equilibrium methods based on the use of strong photooxidants or initiated by pulse radiolysis are shown to provide versatile approaches for decoupling electron transfer reactions from follow-up reactivity of unstable radical species, resulting in accurate values of reduction potentials of very positive couples, including some solvent radical cations. Here, we also show that correlations of reduction potentials with Hammett Σσ + p parameters, as well as gas phase ionization potentials, can be used to estimate the redox properties of unknown couples within a homologous series of compounds. The effects of ion pairing and hemicolligation on redox properties of organic and inorganic radicals are also discussed.

14 SOLAR ENERGY↗
DOE OSTI2025

Impacts of molecular architecture on the radiation-induced degradation and reaction kinetics of hydrophobic diglycolamides with the solvated electron and the dodecane radical cation

Given their proposed use as trivalent actinide–lanthanide separation ligands, the role of molecular architecture on the radiation robustness of diglycolamide (DGA) molecules has been investigated. This study examined three prototypical molecules with differences in their aliphatic chain architecture: N,N,N′,N′-tetra(n-octyl)diglycolamide (TODGA), N,N,N′,N′-tetra(2-ethylhexyl)diglycolamide (T2EHDGA), and N,N′-dimethyl-N,N′-dioctyldiglycolamide (DMDODGA). Rate coefficients and activation parameters are reported for the reactivity of each DGA with the solvated electron (e solv − ) and the corresponding dodecane radical cation (RH˙ + ) over the temperature range of 10.0 to 44.1 °C. These measurements indicate that DMDODGA is the most chemically reactive with both transient radicals, which may be attributed to this molecule's more accessible backbone. Complementary gamma dose accumulation studies (≤ 600 kGy) under envisioned process conditions—50 mM DGA in n-dodecane solvent—afforded dose constants for the loss of DGA of d = (3.41 ± 0.07) × 10 −3 , (4.19 ± 0.09) × 10 −3 , and (4.65 ± 0.09) × 10 −3 kGy −1 for T2EHDGA, DMDODGA, and TODGA, respectively. These dose constants indicate that varying DGA architecture affords subtle differences in chemical reactivity, leading to varying rates of radiolytic degradation under envisioned actinide–lanthanide separation conditions. However, more ambitious DGA frameworks, such as modifying the backbone, branching of the aliphatic chains, and/or changing the size of the chain may be required for larger gains in radiolytic longevity while optimizing actinide–lanthanide selectivity.

Arrhenius parameters↗
DOE OSTI2026

Extraction, Characterization, and Stability Studies of Bistriazinyl-Derived Carboxylic Acids

Separation of An(III) and Ln(III) ions will benefit the recycling of used nuclear fuel (UNF). For this purpose, many ligands have been tested over the years, and several separation processes have been successfully demonstrated on the laboratory scale. Current research aims at the development of new ligands that are built only with carbon, hydrogen, oxygen, and nitrogen (CHON), as they can be incinerated completely without secondary waste production. Here, we tested a new class of water-soluble ligands, the bistriazinyl-octa-carboxylic acids. One member, in particular, 2,6-bis-[5,6-di(3,4-dicarboxyphenyl)-1,2,4- triazin-3-yl]-pyridine (BTPOA), was found to be suitable for the selective separation of Am(III) and Cm(III) ions from Ln(III) ions and may act as a CHON alternative to its sulfonated analogue (SO 3 -Ph-BTP). BTPOA exhibited good extraction results and a high selectivity for Am(III) over Eu(III) ions. This ligand’s complexation of metal ions was further studied using potentiometric spectroscopy, as well as time-resolved laser-induced spectroscopy with Cm(III) and Eu(III) in aqueous HClO 4 and HNO 3 media. Conditional stability constants of each formed species were determined. In the HClO 4 system, Cm(III) formed three species (1:1, 1:2, and 1:3) through the stepwise addition of a single BTPOA molecule. On the other hand, in HNO 3 , Cm(III) formed two 1:2 complexes and one 1:3 complex, while the stepwise formation of three species was observed for Eu(III). The stability constants are comparable to the values for SO 3 -Ph-BTP. The radiolytic behavior of BTPOA was also investigated using electron pulse irradiation measurements to determine absolute rate coefficients (k) under ambient temperature conditions for the reaction of BTPOA with typical UNF reprocessing radical radiolysis products the hydrated electron (e aq − , k = (1.60 ± 0.02) × 10 10 M −1 s −1 ), the hydrogen atom (H • , k = (2.17 ± 0.03) × 10 9 M −1 s −1 ), and hydroxyl ( • OH, k = (6.95 ± 0.06) × 10 9 M −1 s −1 ) and nitrate (NO 3 • , k = (0.37 ± 0.02) × 10 7 M −1 s−1) radicals. These rate coefficients indicate that the radiolytic longevity of BTPOA should increase with HNO 3 concentration, owing to the consumption of e aq − /H • , by nitrate anions, and the replacement of • OH by the less reactive NO 3 • .

Diaz Gomez, Laura [Forschungszentrum Juelich (Germ↗
DOE OSTI2025

Quantitative Determination of Electronic Effects in Free Radicals through Open-Shell Hammett Substituent Constants

Hammett substituent constants (σ), which quantify the electronic effects of functional groups, are widely used for predicting the properties of organic compounds and investigating reaction mechanisms. While these values have been obtained for a wide range of closed-shell substituents, measurements of analogous values for open-shell substituents are rare due to challenges associated with their short lifetimes. Here, in this report, we developed a combined experimental and computational approach for quantifying the electronic properties of open-shell substituents based on changes in nitrile vibrational frequencies (ν(C≡N)). By coupling pulse radiolysis and time-resolved infrared spectroscopy (PR-TRIR), we measured ν(C≡N) IR bands of 30 para - and meta -substituted benzonitriles bearing C-, N-, and S-centered radicals. A linear scaling relationship was obtained between these experimental values and values obtained from DFT calculations. Using these computed values, two different Hammett constants, σ m , and σ p + , were determined for a series of C-, N-, O-, S-, Si-, and B-centered radicals. The differences between σm and σp+ values enable the separate evaluation of inductive and resonance effects in these open-shell substituents. The results suggest that there are three classes of radicals: one is electron withdrawing (σ m , σ p + > 0), one is electron donating (σm, σp+ < 0), and one is inductively withdrawing but resonance donating (σ m > 0, σ p + < 0). Our study represents a general approach to the analysis of the electronic properties of open-shell species and has potential applications in a wide range of molecular processes involving free radical intermediates.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1982

Pulsed radiolysis of model aromatic polymers and epoxy based matrix materials

Models of primary processes leading to deactivation of energy deposited by a pulse of high energy electrons were derived for epoxy matrix materials and polyl-vinyl naphthalene. The basic conclusion is that recombination of initially formed charged states is complete within 1 nanosecond, and subsequent degradation chemistry is controlled by the reactivity of these excited states. Excited states in both systems form complexes with ground state molecules. These excimers or exciplexes have their characteristics emissive and absorptive properties and may decay to form separated pairs of ground state molecules, cross over to the triplet manifold or emit fluorescence. ESR studies and chemical analyses subsequent to pulse radiolysis were performed in order to estimate bond cleavage probabilities and net reaction rates. The energy deactivation models which were proposed to interpret these data have led to the development of radiation stabilization criteria for these systems.

Gupta, A.↗
DOE OSTI2026

Effects of Dimethylamino Functional Group Substitution on the Physical, Structural and Radiolytic Properties of Pyridinium Ionic Liquids

A diverse range of 4-dimethylaminopyridinium (DMAP) bis(trifluoromethylsulfonyl)-amide ionic liquids with specific functionalities (alkyl, alkoxy, hydroxyalkyl and benzyl) were designed, characterized and compared with their pyridinium analogs in terms of their physical and radiolytic properties. The influence of the dimethylamino group on ionic liquid structure was investigated by X-ray diffraction and molecular dynamics simulations. The influence of the electron-donating ability of the dimethylamino-substituted cation is evident in the differences in the electronic density of states between the DMAP and pyridinium ILs. This leads to substantial changes in the radical transients observed in pulse radiolysis of the neat ILs. It was found that the DMAP salts were higher melting, more viscous and less conducting than their pyridinium analogs. However, the DMAP salts exhibited higher thermal stabilities and could therefore be useful for high-temperature applications.

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

Evidence for Photoinduced Polaron Generation in a High Persistence Length Low Bandgap Conjugated Polymer in Solution

Using ultrafast time-resolved infrared (TRIR) spectroscopy, we studied the solution-phase excited-state structural evolution of an indacenodithiophene-co-benzothiadiazole polymer (C8-IDTBT). Following band gap excitation, the TRIR spectra reveal vibrational features that develop within 10 ps and decay over 4 ns. Using pulse radiolysis measurements, charge-modulation spectroscopy, and quantum-chemical calculations, the IR features are assigned to polaron pairs. Interestingly, these features appear on an evolving broad mid-IR electronic absorption background, with kinetics correlating with the formation and decay of the cationradical vibrational bands. A three-state kinetic model successfully reproduces the spectral evolution, revealing that the polaron and exciton populations exist in dynamic equilibrium on picosecond time scales, with time constants for exciton dissociation in the range of 3− 5 ps and polaron-to-exciton reformation between 20 and 100 ps, while both species decay to the ground state on much slower nanosecond time scales (∼1 ns), yielding a remarkably high polaron-generation efficiency, higher than 50%. These findings provide fundamental insights into intramolecular charge photogeneration mechanisms in conjugated polymers, demonstrating efficient bound-polaron formation in isolated polymer chains.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Assessment of Hydroxyl Radical Reactivity in Sulfur-Containing Amino Acid Models Under Acidic pH

Methionine residues in proteins and peptides are frequently oxidized by losing one electron. The presence of nearby amide groups is crucial for this process, enabling methionine to participate in long-range electron transfer. Hydroxyl radical (HO•) plays an important role being generated in aerobic organisms by cellular metabolisms as well as by exogenous sources such as ionizing radiations. The reaction of HO• with methionine mainly affords the one-electron oxidation of the thioether moiety through two consecutive steps (HO• addition to the sulfur followed by HO− elimination). We recently investigated the reaction of HO• with model peptides mimicking methionine and its cysteine-methylated counterpart, i.e., CH3C(O)NHCHXC(O)NHCH3, where X = CH2CH2SCH3 or CH2SCH3 at pH 7. The reaction mechanism varied depending on the distance between the sulfur atom and the peptide backbone, but, for a better understanding of various suggested equilibria, the analysis of the flux of protons is required. We extended the previous study to the present work at pH 4 using pulse radiolysis techniques with conductivity and optical detection of transient species, as well as analysis of final products by LC-MS and high-resolution MS/MS following γ-radiolysis. Comparing all the data provided a better understanding of how the presence of nearby amide groups influences the one-electron oxidation mechanism.

Biochemistry & Molecular Biology↗
DOE OSTI2026

Radiation Effects in Used Next Generation Nuclear Fuel Reprocessing Strategies

Given global commitments to significantly increase nuclear energy capacity, it is now more important than ever to develop efficient used nuclear fuel (UNF) management strategies to encourage widespread adoption of closed fuel cycles. To achieve this ambitious goal, a comprehensive understanding of radiation effects is essential for these next generation technologies, as radiolysis often limits longevity and performance. Here, we present new findings on: (i) the radiation robustness and performance of advanced sulfur chloride-based chlorination processes in the presence of nuclear materials (Fig. 1A); and (ii) the impacts of voloxidized uranium and rhenium complexation on monoamide-based UNF direct dissolution strategies (Fig 1B). These studies employed a combination of time-resolved electron pulse and dose accumulation gamma and electron beam irradiation techniques.

38 - RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCL↗
DOE OSTI2025

Unravelling the radiation-induced redox chemistry of plutonium ions in aqueous solution

Plutonium plays a critical role in nuclear fuel cycle technologies, but our understanding of its fundamental radiation-induced redox chemistry is limited. Changes in oxidation states affect the speciation and transport of plutonium ions in solution. For example, solvent extraction techniques used to separate and recover plutonium from used nuclear fuel rely on the selective formation, maintenance, and complexation of specific plutonium oxidation states. However, radiolytically generated radicals, ions, and molecules can drive the oxidation state distribution of plutonium ions far from equilibrium, ultimately changing the physical and chemical properties of the bulk system. These radiation-induced processes are inevitable due to the ionizing radiation fields generated by the radioactive decay of plutonium and its daughter nuclides. Therefore, mechanistically understanding how plutonium's various oxidation states respond to ionizing radiation is essential for predicting its behavior in solution. Here, we present significant advances in our understanding of radiation-induced plutonium redox chemistry by using time-resolved (electron pulse) and dose accumulation (alpha and gamma) irradiation techniques, along with quantitative multiscale modeling methods.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2026

Impact of Nd ions on the chemical kinetic behavior of radiolytic transients in molten LiCl-KCl-NdCl3 salt mixtures

Pyrochemical reprocessing technologies can be used to recover valuable materials from used nuclear fuel (UNF), such as uranium. However, other critical materials, such as fission product neodymium, are challenging to recover from molten chloride eutectic mixtures (LiCl-KCl) due to the presence of multivalent states (Nd2+/Nd3+), disproportionation reactions, and re-dissolution in the molten chloride salt. Understanding, predicting, and controlling these processes is further complicated by the presence of ionizing radiation fields, for which little is known on the interaction of neodymium ions with the radiolytic transients (es– and Cl2.–) in molten LiCl-KCl salt mixtures. Here, chemical kinetics, from integrated electron pulse irradiation and transient absorption spectroscopy, are presented for the reaction of Nd3+ ions with es– and Cl2.– as a function of temperature (400–600 ?).

36 - MATERIALS SCIENCE↗