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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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At least 631 records · Page 35
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Radiolytic Evaluation of 3,4,3-LI(1,2-HOPO) in Aqueous Solutions

We report the octadentate hydroxypyridinone ligand 3,4,3-LI(1,2-HOPO) (abbreviated as HOPO) has been identified as a promising candidate for both chelation and f-element separation technologies, two applications that require optimal performance in radiation environments. However, the radiation robustness of HOPO is currently unknown. Here, we employ a combination of time-resolved (electron pulse) and steady-state (alpha self-radiolysis) irradiation techniques to elucidate the basic chemistry of HOPO and its f-element complexes in aqueous radiation environments. Chemical kinetics were measured for the reaction of HOPO and its Nd(III) ion complex ([Nd III (HOPO)] - ) with key aqueous radiation-induced radical transients (eaq - , H · atom, and · OH and NO 3 · radicals). The reaction of HOPO with eaq - is believed to proceed via reduction of the hydroxypyridinone moiety, while transient adduct spectra indicate that reactions with the H · atom and · OH and NO 3 · radicals proceeded by addition to HOPO's hydroxypyridinone rings, potentially allowing for the generation of an extensive suite of addition products. Complementary steady-state 241 Am(III)-HOPO complex ([ 241 Am III (HOPO)] - ) irradiations showed the gradual release of 241 Am(III) ions with increasing alpha dose up to 100 kGy, although complete ligand destruction was not observed.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2020

Carbazole-Based Hole-Transport Materials for High-Efficiency and Stable Perovskite Solar Cells

As organic–inorganic halide perovskite solar cells (PSCs) near commercialization, stability challenges during real-world conditions, such as durability at elevated temperatures, still need to be addressed. We have previously reported that doping of triarylamine-based hole-transport layers (HTLs) with a triarylamine-based radical cation salt (EHCz-3EtCz/EH44-ox) leads to enhanced PSC stability at elevated temperatures. While it was shown the radical cation dopant did not need to be identical to the HTL matrix, little was known about dopant exchange to realize the maximum impact on device-level properties (e.g., increase in low intrinsic conductivity, mobility, hydrophobic properties, ease of synthesis, and thermal stability). In this paper, we study the impact of dopant exchange among stable, low-cost, high-glass-transition temperature (Tg), and easily synthesized triarylamine-based HTL and radical triarylamine cation salts as dopants. Using EH44-ox as dopant leads to the improved device-level power conversion efficiency (PCE) for all HTL matrices assessed. Moreover, increasing the number of ethylhexyl chains from one to two per molecule and positioning these chains at the periphery rather than the core resulted in improved hydrophobicity. PSCs based on our HTL formulations have similar power conversion efficiencies (PCE) as those of PSCs based on commercially available HTLs while demonstrating greatly improved device-level stability at elevated temperatures.

14 SOLAR ENERGY↗
DOE OSTI2020

Quaternary Charge-Transfer Complex Enables Photoenzymatic Intermolecular Hydroalkylation of Olefins

Intermolecular C–C bond-forming reactions are underdeveloped transformations in the field of biocatalysis. Here we report a photoenzymatic intermolecular hydroalkylation of olefins catalyzed by flavin-dependent ‘ene’-reductases. Radical initiation occurs via photoexcitation of a rare high-order enzyme-templated charge-transfer complex that forms between an alkene, α-chloroamide, and flavin hydroquinone. This unique mechanism ensures that radical formation only occurs when both substrates are present within the protein active site. Here, this active site can control the radical terminating hydrogen atom transfer, enabling the synthesis of enantioenriched γ-stereogenic amides. This work highlights the potential for photoenzymatic catalysis to enable new biocatalytic transformations via previously unknown electron transfer mechanisms.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Electronic and Spintronic Open-Shell Macromolecules, Quo Vadis ?

Open-shell macromolecules (i.e., polymers containing radical sites either along their backbones or at the pendant sites of repeat units) have attracted significant attention owing to their intriguing chemical and physical (e.g., redox, optoelectronic, and magnetic) properties, and they have been proposed and/or implemented in a wide range of potential applications (e.g., energy storage devices, electronic systems, and spintronic modules). These successes span multiple disciplines that range from advanced macromolecular chemistry through nanoscale structural characterization and on to next-generation solid-state physics and the associated devices. In turn, this has allowed different scientific communities to expand the palette of radical-containing polymers relatively quickly. However, critical gaps remain on many fronts, especially regarding the elucidation of key structure–property–function relationships that govern the underlying electrochemical, optoelectronic, and spin phenomena in these materials systems. Here, we highlight vital developments in the history of open-shell macromolecules to explain the current state of the art in the field. Moreover, we provide a critical review of the successes and bring forward open opportunities that, if solved, could propel this class of materials in a meaningful manner. Finally, we provide an outlook to address where it seems most likely that open-shell macromolecules will go in the coming years. Furthermore, our considered view is that the future of radical-containing polymers is extremely bright and the addition of talented researchers with diverse skills to the field will allow these materials and their end-use devices to have a positive impact on the global science and technology enterprise in a relatively rapid manner.

36 MATERIALS SCIENCE↗
DOE OSTI2023

OH Roaming and Beyond in the Unimolecular Decay of the Methyl-Ethyl-Substituted Criegee Intermediate: Observations and Predictions

Alkene ozonolysis generates short-lived Criegee intermediates that are a significant source of hydroxyl (OH) radicals. Here this study demonstrates that roaming of the separating OH radicals can yield alternate hydroxycarbonyl products, thereby reducing the OH yield. Specifically, hydroxybutanone has been detected as a stable product arising from roaming in the unimolecular decay of the methyl-ethyl-substituted Criegee intermediate (MECI) under thermal flow cell conditions. The dynamical features of this novel multistage dissociation plus a roaming unimolecular decay process have also been examined with ab initio kinetics calculations. Experimentally, hydroxybutanone isomers are distinguished from the isomeric MECI by their higher ionization threshold and distinctive photoionization spectra. Moreover, the exponential rise of the hydroxybutanone kinetic time profile matches that for the unimolecular decay of MECI. A weaker methyl vinyl ketone (MVK) photoionization signal is also attributed to OH roaming. Complementary multireference electronic structure calculations have been utilized to map the unimolecular decay pathways for MECI, starting with 1,4 H atom transfer from a methyl or methylene group to the terminal oxygen, followed by roaming of the separating OH and butanonyl radicals in the long-range region of the potential. Roaming via reorientation and the addition of OH to the vinyl group of butanonyl is shown to yield hydroxybutanone, and subsequent C–O elongation and H-transfer can lead to MVK. A comprehensive theoretical kinetic analysis has been conducted to evaluate rate constants and branching yields (ca. 10–11%) for thermal unimolecular decay of MECI to conventional and roaming products under laboratory and atmospheric conditions, consistent with the estimated experimental yield (ca. 7%).

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

Mechanistic Investigation of the Ce(III) Chloride Photoredox Catalysis System: Understanding the Role of Alcohols as Additives

Photocatalytic C–H activation is an emerging area of research. While cerium chloride photocatalysts have been extensively studied, the role of alcohol additives in these systems remains a subject of ongoing discussion. It was demonstrated that the photocatalyst [NEt 4 ] 2 [Ce IV Cl 6 ] ( 1 ) produces •Cl and added alcohols exhibit zero-order kinetics. Prior studies by other researchers suggested that 1 and alcohols lead to cerium alkoxide [Ce–OR] and alkoxy radical intermediates. Here, to understand these seemingly divergent mechanistic proposals, an expanded investigation comparing cerium(IV) catalyst 1 and cerium(III) complex [NEt 4 ] 3 [Ce III Cl 6 ] ( 2 ), which exhibit markedly different reactivity and C–H selectivity, is disclosed. Our findings reveal that alcohol additives accelerate the conversion of cerium(III) to cerium(IV) catalysts, forming key intermediates such as [NEt 4 ] 2 [Ce III Cl 5 (HOCH 3 )] ( 5 ) and [NEt 4 ] 2 [Ce IV Cl 5 (OCH 3 )] ( 6 ), driven by excited-state di-tert-butyl azodicarboxylate under blue light irradiation. The active complex 6 releases the •OCH 3 radical, in sharp contrast to •Cl radicals initiated by cerium(IV) photoredox catalyst 1 . These different reactivity and selectivity profiles can be understood in the context of complex 5 generation and in situ formation of base to afford complex 6 . Experimental validation shows enhanced selectivity toward C–H bonds with different reactivity with catalyst 1 and methanol upon the addition of base and decreased selectivity with catalyst 2 and methanol upon the addition of acid. These findings unify the previously contrasting observations of cerium halide/alkoxide photocatalytic systems and provide a comprehensive understanding on the essential role of base/acid and alcohol in selectivity and reactivity.

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

Mechanistic Studies of Oxidative Degradation in Diamine-Appended Metal–Organic Frameworks Exhibiting Cooperative CO 2 Capture

Understanding the impact of O 2 during a carbon capture process is vital for designing robust, cost-effective materials for carrying it out. However, mechanistic studies of the O 2 -induced degradation of materials are not easily undertaken owing to the complex sequential reaction pathways that arise. Here, we report comprehensive mechanistic investigations of the O 2 -induced degradation of diamine-appended metal−organic frameworks (MOFs) exhibiting cooperative CO 2 adsorption. Oxygen exposure experiments were performed on seven different diamine-appended MOFs, including e-2−Mg 2 (dobpdc) (e-2 = N-ethylethylenediamine, dobpdc 4− = 4,4′-dioxidobiphenyl-3,3′-dicarboxylate), under various temperatures and O 2 pressures. These experiments show that diamine degradation inhibits CO 2 chemisorption and that the degradation rate is significantly influenced by the diamine structure. In contrast, the parent frameworks remain essentially intact upon O 2 exposure. Detailed characterization of O 2 -exposed e-2−Mg 2 (dobpdc) revealed the formation of various degradation products, including acetaldehyde, carbon dioxide, water, ethylamine, and other aldehyde- and imine-containing species. Together, these observations suggest that diamine degradation occurs via C−N bond cleavage through pathways involving C-centered radicals. Furthermore, computational evaluation of the initiation and propagation pathways for amine degradation in diamine-appended MOFs indicates that (i) degradation is likely initiated by OH • , (ii) carbon-centered radicals generated via radical transfer reactions react with O 2 , leading to amine degradation, and (iii) the ratelimiting step of the degradation reactions likely involves O−O bond cleavage. Overall, these mechanistic insights could inform strategies for mitigating O 2 -induced amine degradation in next-generation carbon capture technologies.

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

Electrochemically Initiated Depolymerization of Poly(Methyl Methacrylate)

Efficient depolymerization of polymers with all-carbon backbones under mild conditions would be valuable in chemically recycling commodity plastics. Poly(methyl methacrylate) (PMMA) is a commodity thermoplastic that is currently depolymerized under temperatures in excess of 400 °C. Herein, we lower the temperatures needed to achieve depolymerization of PMMA by performing radical generation and depropagation with orthogonal stimuli. This first demonstration of electrochemically initiated PMMA depolymerization relies on reduction of phthalimide esters that, upon subsequent decarboxylation, generate polymer-centered radicals. These radicals then spontaneously unzip the polymer back to its monomeric constituents at temperatures as low as 105 °C. We studied the mechanism and efficiency of this transformation as a function of phthalimide ester placement, incorporation density, and polymer molecular weight. We found that chain-end activation is effective for modest molecular weights but suffers diminished efficiency at higher degrees of polymerization. In contrast, pendent-group activation is more effective for depolymerizing higher molecular weight species. Integrating higher molar amounts of phthalimide ester pendants leads to more effective depolymerization, with >95% depolymerization in copolymers with 5 mol% phthalimide ester incorporation. We leveraged this understanding to create a custom electro-distillation apparatus that allowed us to simultaneously electrochemically depolymerize PMMA and directly distill methyl methacrylate in >22% yield, which could ultimately be repolymerized. These findings establish electrochemistry as a versatile and orthogonal stimulus for vinyl polymer depolymerization and provide a foundation for closed-loop electrochemical recycling of widely used plastics.

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

Photochemical Tungsten–Carbon Bond Cleavage in Bicyclic Tungstacyclopentanes

W(NCPh 3 )(OSiPh 3 ) 2 (C7H 12 ) (1) and W(NAd)(OSiPh 3 ) 2 (C 7 H 12 ) (2) undergo photochemical α-hydrogen abstraction to form alkylidenes. Transient absorption studies suggest that fast W–C homolysis precedes thermal α-hydrogen abstraction. Radical trapping experiments in the presence of 5,5-dimethyl-1-pyrroline-N-oxide (DMPO) support formation of an alkyl radical in these reactions. DFT calculations of models of 1 and 2 are also consistent with formation of W(V)-alkyl-radical intermediates that ultimately abstract an α-hydrogen to form the alkylidene. This article provides evidence for W–C bond cleavage in reac-tions that convert catalytically inactive d 0 tungstacyclopentanes into metathesis-active alkylidenes.

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

Ultrafast Proton-Coupled Electron Transfer Reactions at Unit Quantum Yield

Proton-coupled electron transfer (PCET) reactions mediate essential biological energy-conversion processes, yet dynamical experiments that distinguish concerted electron/proton motion from sequential electron-transfer/proton-transfer pathways are unprecedented on ultrafast time scales. Here we report a tightly coupled donor–spacer–acceptor assembly, NDI-Sp-PhOH/BI, that enables direct interrogation of light-triggered and ultrafast PCET dynamics. Photoexcitation of the naphthalene diimide chromophore drives charge separation forming NDI radical anion and benzimidazolium phenoxy radical (PhO●/BIH+) products with a 440 fs time constant, followed by thermal charge recombination on a 5 ps time scale. Transient visible/near-infrared and mid-infrared spectroscopies independently track electron and proton motion and reveal coincident formation and decay of the charge-separated PCET products, excluding detectable phenol radical cation or phenoxide intermediates expected for sequential electron transfer-proton transfer (ET-PT) pathways. Surface-hopping quasiclassical trajectory simulations demonstrate rapid proton relocation coupled to evolution from locally excited to charge-transfer states, congruent with a concerted mechanism. These combined spectroscopic and computational results establish NDI-Sp-PhOH/BI as an archetype for ultrafast, concerted PCET occurring with unit quantum yield; further, because this platform provides distinct electronic and vibrational spectroscopic handles in its ground, electronically excited, and charge-separated states, it provides new opportunities to characterize mechanistic crossover in biomimetic PCET systems.

10 SYNTHETIC FUELS↗
DOE OSTI2020

Diversion of Catalytic C–N Bond Formation to Catalytic Oxidation of NH 3 through Modification of the Hydrogen Atom Abstractor

We report that (TMP)Ru(NH 3 ) 2 (TMP = tetramesitylporphryin) is a molecular catalyst for oxidation of ammonia to dinitrogen. An aryloxy radical, tri-tert-butylphenoxyl (ArO•) abstracts H atoms from a bound ammonia ligand of (TMP)Ru(NH 3 ) 2 , leading to the discovery of a new catalytic C-N coupling to the para position of ArO•, forming 4-amino-2,4,6-tri-tert-butylcyclohexa-2,5-dien-1-one. Modification of the aryloxy radical to contain a trityl group at the para position, 2,6-di-tert-butyl-4-tritylphenoxyl radical, prevents C-N coupling and diverts the reaction to catalytic oxidation of ammonia to give N 2 . We achieve 125(±5) turnovers at 22 °C for oxidation of NH 3 , the highest reported to date for a molecular catalyst.

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

Enhanced production of active species and NH 3 using non-equilibrium ferroelectric barrier discharge

Non-equilibrium plasma-assisted ammonia synthesis is investigated through enhanced active species production with ferroelectric discharge. Time-resolved in-situ diagnostics of femtosecond two-photon absorption laser-induced fluorescence, coherent anti-Stokes Raman scattering, and laser absorption spectroscopy, as well as optical emission spectroscopy, were conducted to probe the key intermediate species, such as H and N radicals as well as N 2 (ν), ions, and NH 3 to achieve better understanding of non-equilibrium energy transfer and ammonia formation. The results reveal that ferroelectric discharge improved ammonia yield by four times. Results also show that ferroelectrics not only enhanced ions (N 2 + ) production, radicals (N, H) number density, but also increased the N 2 vibrational temperature. Further plasma modeling identified the couplings between elevated radical and ion production and enhanced vibrational excitation reactions, e.g., N + H 2 (ν)→NH + H, N 2 (ν)+H → NNH, N 2 + + H 2 → H + N 2 H + , and N 2 H + +e→NH + N, facilitated by ferroelectric discharge. These findings provide critical insight into the mechanism of ferroelectric plasma catalysis and highlight their potential in advancing energy-efficient chemical synthesis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

An automated liquid jet for fluorescence dosimetry and microsecond radiolytic labeling of proteins

X-ray radiolytic labeling uses broadband X-rays for in situ hydroxyl radical labeling to map protein interactions and conformation. High flux density beams are essential to overcome radical scavengers. However, conventional sample delivery environments, such as capillary flow, limit the use of a fully unattenuated focused broadband beam. An alternative is to use a liquid jet, and we have previously demonstrated that use of this form of sample delivery can increase labeling by tenfold at an unfocused X-ray source. Here we report the first use of a liquid jet for automated inline quantitative fluorescence dosage characterization and sample exposure at a high flux density microfocused synchrotron beamline. Our approach enables exposure times in single-digit microseconds while retaining a high level of side-chain labeling. This development significantly boosts the method’s overall effectiveness and efficiency, generates high-quality data, and opens up the arena for high throughput and ultrafast time-resolved in situ hydroxyl radical labeling.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2020

Role of ring-enlargement reactions in the formation of aromatic hydrocarbons

Ring-enlargement reactions can provide a fast route towards the formation of six-membered single-ring or polycyclic aromatic hydrocarbons (PAHs). To investigate the participation of the cyclopentadienyl (C 5 H 5 ) radical in ring-enlargement reactions in high-temperature environments, a mass-spectrometric study was conducted. Experimental access to the C 5 H 5 high-temperature chemistry was provided by two counterflow diffusion flames. Cyclopentene was chosen as a primary fuel given the large amount of resonantly stabilized cyclopentadienyl radicals produced by its decomposition and its high tendency to form PAHs. In a second experiment, methane was added to the fuel stream to promote methyl addition pathways and to assess the importance of ring-enlargement reactions for PAH growth. The experimental dataset includes mole fraction profiles of small intermediate hydrocarbons and of several larger species featuring up to four condensed aromatic rings. Results show that, while the addition of methane enhances the production of methylcyclopentadiene and benzene, the concentration of larger polycyclic hydrocarbons is reduced. The increase of benzene is probably attributable to the interaction between the methyl and the cyclopentadienyl radicals. However, the formation of larger aromatics seems to be dominated only by the cyclopentadienyl driven molecular-growth routes which are hampered by the addition of methane. Furthermore, in addition to the experimental work, two chemical mechanisms were tested and newly calculated reaction rates for cyclopentadiene reactions were included. In an attempt to assess the impact of cyclopentadienyl ring-enlargement chemistry on the mechanisms’ predictivity, pathways to form benzene, toluene, and ethylbenzene were investigated. Results show that the updated mechanism provides an improved agreement between the computed and measured aromatics concentrations. Nevertheless, a detailed study of the single reaction steps leading to toluene, styrene, and ethylbenzene would be certainly beneficial.

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

Radiation-Induced Effects on the Extraction Properties of Hexa-n-octylnitrilo-triacetamide (HONTA) Complexes of Americium and Europium

The candidate An(III)/Ln(III) separation ligand hexa-n-octylnitrilo-triacetamide (HONTA) was irradiated under envisioned SELECT (Solvent Extraction from Liquid waste using Extractants of CHON-type for Transmutation) process conditions (n-dodecane/0.1 M HNO 3 ) using a solvent test loop in conjunction with cobalt-60 gamma irradiation. The extent of HONTA radiolysis and complimentary degradation product formation was quantified by HPLC-ESI-MS/MS. Further, the impact of HONTA radiolysis on process performance was evaluated by measuring the change in 243 Am and 154 Eu distribution ratios as a function of absorbed gamma dose. HONTA was found to decay exponentially with increasing dose, affording a dose coefficient of d = (4.48 ± 0.19) × 10 –3 kGy –1 . Multiple degradation products were detected by HPLC-ESI-MS/MS with dioctylamine being the dominant quantifiable species. Both 243 Am and 154 Eu distribution ratios exhibited an induction period of ~70 kGy for extraction (0.1 M HNO 3 ) and back-extraction (4.0 M HNO 3 ) conditions, after which both values decreased with absorbed dose. The decrease in distribution ratios was attributed to a combination of the destruction of HONTA and ingrowth of dioctylamine, which is capable of interfering in metal ion complexation. Furthermore, the loss of HONTA with absorbed gamma dose was predominantly attributed to its reaction with the n-dodecane radical cation (R˙ + ). These R˙ + reaction kinetics were measured for HONTA and its 241 Am and 154 Eu complexes using picosecond pulsed electron radiolysis techniques. All three second-order rate coefficients (k) were essentially diffusion limited in n-dodecane indicating a significant reaction pathway: k(HONTA + R˙ + ) = (7.6 ± 0.8) × 10 9 M –1 s –1 , k(Am(HONTA) 2 + R˙ + ) = (7.1 ± 0.7) × 10 10 M –1 s –1 , and k(Eu(HONTA) 2 + R˙ + ) = (9.5 ± 0.5) × 10 10 M –1 s –1 . HONTA-metal ion complexation afforded an order-of-magnitude increase in rate coefficient. Additional nanosecond time-resolved measurements showed that both direct and indirect HONTA radiolysis yielded the short-lived (< 100 ns) HONTA radical cation and a second long-lived (µs) species identified as the HONTA triplet excited state. The latter was confirmed by a series of oxygen quenching picosecond pulsed electron measurements, affording a quenching rate coefficient of k( 3 [HONTA]* + O 2 ) = 2.2 × 10 8 M –1 s –1 . Overall, both the HONTA radical cation and triplet excited state are important precursors to the suite of measured HONTA degradation products.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2020

Non-catalytic oxidative depolymerization of lignin in perfluorodecalin to produce phenolic monomers

We demonstrate for the first time non-catalytic, oxidative cracking with molecular oxygen (O 2 ) to depolymerize native lignin into oxygenated phenolic monomers. Maximum monomer yield of 10.5 wt% was achieved at 250 °C after only 10 min of reaction and included vanillin, syringaldehyde, vanillic acid, and syringic acid. High rates of oxidation are attributed to the use of perfluorodecalin as solvent. Perfluorodecalin is a perfluorocarbon (PFC), characterized by their chemical stability and exceptionally high solubility for O 2 . Monomer yields were typically five-fold higher in perfluorodecalin compared to solvents more commonly employed in lignin conversion, such as methanol, butanol, acetonitrile, and ethyl acetate. Phenolic monomer production in perfluorodecalin favors high temperatures and short reaction times to prevent further oxidation of the produced monomers. Lignin oil obtained under oxidative conditions in perfluorodecalin showed lower molecular weight and smaller polydispersity compared to other solvents. Increasing the reaction time further decreased the molecular weight, while increasing reaction time in an inert atmosphere increased the molecular weight of the lignin oil. High concentrations of O 2 in perfluorodecalin not only increased lignin depolymerization but suppressed undesirable condensation reactions. Depolymerization is likely initiated by thermally induced homolytic cleavage of ether linkages in lignin to form phenoxy and carbon-based radicals. These radicals bind with O 2 as a radical scavenger and further react to form phenolic monomeric products rather than repolymerizing to large oligomers. The PFC process was scaled from 5 mL to 250 mL without any loss of yield. Because most organic compounds are not soluble in perfluorodecalin, recycling is easily achieved via liquid–liquid separation.

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

Curium(iii) radiation-induced reaction kinetics in aqueous media

Insight into the effects of radiolytic processes on the actinides is critical for advancing our understanding of their solution chemistry because the behaviour of these elements cannot be easily separated from the influence of their inherent radiation field. However, minimal information exists on the radiation-induced redox behaviour of curium (Cm), a key trivalent transuranic element present in used nuclear fuel and frequently used as an alpha radiation source. Here we present a kinetic study on the aqueous redox reactions of Cm(III) with radicals generated through the radiolysis of aqueous media. In particular, we probe reaction kinetics in nitric acid solutions that are used as the aqueous phase component of used nuclear fuel reprocessing solvent systems. Second-order rate coefficients (k) were measured for the reaction of Cm(III) with the hydrated electron (e aq - , k = (1.25 ± 0.03) × 10 10 M -1 s -1 ), hydrogen atom (H˙, k = (5.16 ± 0.37) × 10 8 M -1 s -1 ), hydroxyl radical (˙OH, k = (1.69 ± 0.24) × 10 9 M -1 s -1 ), and nitrate radical (NO 3 ˙, k = (4.83 ± 0.09) × 10 7 M -1 s -1 ). Furthermore, the first-ever Cm(II) absorption spectrum (300–700 nm) is also reported. These kinetic data dispel the status quo notion of Cm(III) possessing little to no redox chemistry in aqueous solution, and suggest that the resulting Cm(II) and Cm(IV) transients could exist in irradiated aqueous solutions and be available to undergo subsequent redox chemistry with other solutes.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2025

Ultrafast pre-solvated dodecane hole capture and subsequent damage of used nuclear fuel extraction ligands DEHBA, DEH i BA, HONTA, CMPO, HEH[EHP] and TBP

Here, two classes of used nuclear fuel (UNF) extraction ligands, amide (DEHBA, DEH i BA, HONTA) and organophosphorus (CMPO, HEH[EHP], TBP), were selected to study radiation induced damage at picosecond to nanosecond timescale using electron pulse radiolysis in n-dodecane (DD) and supported by quantum chemical calculations. Spectra after radiolysis of 200 mM extraction ligands were recorded in DD/0.3 M DCM. Absorption peaks at 365, 365, 400 and 387 nm in case of DEHBA, DEH i BA, HONTA and CMPO respectively are assigned to triplet excited states. Additional absorption peaks at 420, 460 and 600 nm of DEHBA, DEH i BA and HONTA respectively were identified as due to ligand radical cations. A concentration dependent absorption peak at 600 nm in the case of CMPO was observed and assigned due to a combination of CMPO˙ + , (CMPO) 2 ˙ + and possibly a radical degradation product of CMPO. Weak absorption peaks at 650 and 550 nm in case of HEH[EHP] and TBP were observed and tentatively assigned to their radical cations. A two-component DD˙ + decay in the presence of ligands was observed due to different ligand oxidation mechanisms: ultrafast capture of pre-solvated DD holes and diffusive capture of solvated DD holes. At high extraction ligand concentrations (>100 mM), the majority of DD holes were captured via the ultrafast pre-solvated pathway in <10 ps with C 37 values of 389, 401, 270, 374, 458 and 340 mM for DEHBA, DEHiBA, HONTA, CMPO, HEH[EHP] and TBP respectively. Following ultrafast capture, the remainder of DD holes became solvated and were captured with k = (2.32 ± 0.13), (1.78 ± 0.12), (1.38 ± 0.2), (0.98 ± 0.081), (1.09 ± 0.08) and (1.77 ± 0.046) × 10 10 for DEHBA, DEH i BA, HONTA, CMPO, HEH[EHP] and TBP respectively. Subsequent hole transfer from the extraction ligands˙ + to the low IP solute tri-p-tolylamine (TTA) showed only 4–16% hole transfer, most likely indicating ligand˙ + degradation in 0.9–4.6 ns.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗