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DOE OSTI2021

Photodriven Elimination of Chlorine From Germanium and Platinum in a Dinuclear Pt II →Ge IV Complex

Searching for a connection between the two-electron redox behavior of Group-14 elements and their possible use as platforms for the photoreductive elimination of chlorine, we have studied the photochemistry of [(o-(Ph 2 P)C 6 H 4 ) 2 Ge IV Cl 2 ]Pt II Cl 2 and [(o-(Ph 2 P)C 6 H 4 ) 2 ClGe III ]Pt III Cl 3 , two newly isolated isomeric complexes. These studies show that, in the presence of a chlorine trap, both isomers convert cleanly into the platinum germyl complex [(o-(Ph 2 P)C 6 H 4 ) 2 ClGe III ]Pt I Cl with quantum yields of 1.7 % and 3.2 % for the Ge IV –Pt II and Ge III –Pt III isomers, respectively. Conversion of the Ge IV –Pt II isomer into the platinum germyl complex is a rare example of a light-induced transition-metal/main-group-element bond-forming process. Additionally, transient-absorption-spectroscopy studies carried out on the Ge III –Pt III isomer point to a ligand arene–Cl. charge-transfer complex as an intermediate.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2022

Chemical Grafting of Highly Dispersed VO x /CeO 2 for Increased Catalytic Activity in Methanol Oxidative Dehydrogenation

Vanadia supported on well-defned ceria nanocubes are synthesized at various loadings using a liquid-phase chemical grafting technique and are compared to those prepared using traditional incipient wetness impregnation. Raman and IR characterization reveal that, as vanadia loading is increased to near monolayer coverage, vanadia deposited using grafting shows greatly enhanced dispersion (i.e., improved VO x monomer/dimer distribution). Methanol is used as a probe molecule to explore the redox behavior of the catalysts. IR and temperature programmed desorption of methanol show increased CO 2 formation occurs on the bare ceria support and increasing the dispersion of vanadia promotes dehydrogenation to formaldehyde due to the inhibited oxygen vacancy formation on VO x /CeO 2 . Hydrogen temperature programmed reduction demonstrates that the catalyst reducibility and formation of surface oxygen vacancy are directly related to the degree of vanadia oligomerization. In conclusion, the samples prepared using grafting exhibit superior catalytic performance for methanol oxidative dehydrogenation to formaldehyde compared to the impregnated samples, due to the presence of highly dispersed VO x species (i.e., monomers and dimers).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2026

Impact of europium and samarium on growth and metabolism of two anaerobic wastewater microorganisms: Sporacetigenium mesophilum and Clostridium sporogenes

Increases in environmental fluxes of rare earth elements (REEs) stemming from increased demand for these technology critical elements may affect microbial ecosystem functions important for pollutant degradation and nutrient cycling. Here, this study investigates the responses of Sporacetigenium mesophilum and Clostridium sporogenes, two anaerobic fermenters, to varying concentrations of two REE, namely europium and samarium. Eu and Sm are adjacent lanthanides but differ significantly in their redox behavior. We tested Eu and Sm concentrations ranging from < 1 to 600 µM. Despite the close phylogenetic relatedness of the two bacteria, we observed species-specific as well as REE-specific and incubation time-dependent sensitivities. S. mesophilum exhibited pronounced inhibition of hydrogen production and growth with exposure to ≥ 60 µM of Eu, but with 6 µM Eu, a hormetic effect was observed—hydrogen production was enhanced relative to the control. With Sm, the only impact observed on S. mesophilum was inhibition at the highest concentration (600 µM) tested. For C. sporogenes, growth inhibition was observed only at 600 µM Eu or Sm, and no hormesis was observed with either REE. This study offers both significant benefits and novelty by addressing the emerging environmental concern of REE pollution, particularly the effects of Eu and Sm on anaerobic microorganisms relevant to wastewater treatment. It provides valuable insights into REE impacts under anaerobic conditions, which are essential for understanding potential disruptions to organic matter degradation and nutrient cycling processes.

60 - APPLIED LIFE SCIENCES↗

DOE OSTI2025

One-step atmospheric microplasma synthesis of an NMC-type lithium-ion battery cathode

The manufacture of battery cathode materials is the most energy-intensive step in the production of commercial lithium-ion batteries; specifically, the synthesis of the widely used transition metal oxide cathodes can require tens of hours at temperatures exceeding 700 °C. Attempts to limit the reaction time and energy required to form crystalline cathode materials often still include a heating or calcination step. This communication aims to highlight a nascent yet novel synthesis route: a one-step atmospheric microplasma process for synthesizing cathode particles in less than one second. The hollow-tube reactor employed produces crystalline particles measuring 0.1–3 μm in diameter, displays narrow XRD peaks corresponding to the 003, 104, and 101 planes, and exhibits anodic redox behavior at 3.75 V vs. lithium—characteristic of transition-metal oxide cathode materials—all without requiring an additional calcination step.

25 ENERGY STORAGE↗

DOE OSTI2026

Elucidating the role of surface species in CO oxidation catalyzed by boron nitride nanotube supported transition metal oxides

Boron nitride nanotube (BNNT) is considered a highly promising catalyst support due to its outstanding thermal stability and chemical inertness. These characteristics make BNNT an attractive alternative for high-temperature applications. However, most studies to date have focused on incorporating platinum group metals (PGMs) to achieve high activity. Although BNNT-supported PGM catalysts are highly effective, their scarcity and high cost hinder widespread use in industrial processes. In this study, BNNT-supported transition metal oxides (TMO x /BNNT; TM = Fe, Co, Ni, and Cu) catalysts were investigated, and CO oxidation was applied as a model reaction to evaluate their catalytic performance. Several characterization techniques, including SEM-EDX, TEM, SXRD, H 2 -TPR, and XPS, were employed to examine their physicochemical properties. Notably, the particle size of the metal oxides differed significantly depending on the metal type. This variation is primarily attributed to the inherent metal–support interactions and the thermodynamic stability of each oxide during synthesis. These properties also affected catalytic activity, and various parameters, such as oxygen mobility and redox behavior, played important roles in determining performance. Finally, in situ DRIFTS, CO-TPSR, reaction-order analysis, and 18 O 2 isotope-labeling experiment were used to investigate the reaction mechanism. In conclusion, the findings provide insights into the design of cost-effective BNNT-supported catalysts and highlight their potential applicability in oxidation reactions.

36 MATERIALS SCIENCE↗

DOE OSTI2026

The Use of Microelectrodes in Molten Salt Electrochemistry

Molten salts have attracted considerable interest as essential media for advanced high-temperature technologies, including molten salt reactors, thermal energy storage, high-temperature electrolysis, and pyrochemical processing. Their ability to remain stable in liquid form at elevated temperatures, combined with favorable thermophysical properties and wide electrochemical windows, makes them highly suitable for applications involving heat transfer, energy storage, and hightemperature electrochemical processing. However, despite these advantages, molten salts present challenges due to their chemically reactive nature at high-temperatures, especially in the presence of oxidizing impurities. Salt chemistry can fluctuate through interactions with impurities over time, or fuel burnup in the case of molten salt reactors, often leading to the dissolution of metal species. This dynamic environment not only results in complex redox behavior but also promotes corrosion, which is rarely uniform and frequently manifests as localized degradation driven by structural materials’ compositional differences, electrochemical imbalances, and microstructural susceptibilities.

Kim, Changkyu [University of Wisconsin-Madison, WI↗

DOE OSTI2021

Snapshots of Ce 70 Toroid Assembly from Solids and Solution

Crystallization at the solid–liquid interface is difficult to spectroscopically observe and therefore challenging to understand and ultimately control at the molecular level. The Ce70-torroid formulated [Ce IV 70 (OH) 36 (O) 64 (SO 4 ) 60 (H 2 O) 10 ] 4– , part of a larger emerging family of M IV 70 -materials (M = Zr, U, Ce), presents such an opportunity. We elucidated assembly mechanisms by the X-ray scattering (small-angle scattering and total scattering) of solutions and solids as well as crystallizing and identifying fragments of Ce 70 by single-crystal X-ray diffraction. Fragments show evidence for templated growth (Ce 5 , [Ce 5 (O) 3 (SO 4 ) 12 ] 10- ) and modular assembly from hexamer (Ce 6 ) building units (Ce 13 , [Ce 13 (OH) 6 (O) 12 (SO 4 ) 14 (H 2 O) 14 ] 6– and Ce 62 , [Ce 62 (OH) 30 (O) 58 (SO 4 ) 58 ] 14- ). Ce 62 , an almost complete ring, precipitates instantaneously in the presence of ammonium cations as two torqued arcs that interlock by hydrogen boding through NH 4 + , a structural motif not observed before in inorganic systems. The room temperature rapid assemblies of both Ce 70 and Ce 62 , respectively, by the addition of Li + and NH 4 + , along with ion-exchange and redox behavior, invite exploitation of this emerging material family in environmental and energy applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2021

Chemically Stable Polyarylether-Based Metallophthalocyanine Frameworks with High Carrier Mobilities for Capacitive Energy Storage

Covalent organic frameworks (COFs) with efficient charge transport and exceptional chemical stability are emerging as an import class of semiconducting materials for opto-/electronic devices and energy-related applications. However, the limited synthetic chemistry to access such materials and the lack of mechanistic understanding of carrier mobility greatly hinder their practical applications. Herein, we report the synthesis of three chemically stable polyarylether-based metallophthalocyanine COFs (PAE-PcM, M = Cu, Ni, and Co) and facile in situ growth of their thin films on various substrates (i.e., SiO 2 /Si, ITO, quartz) under solvothermal conditions. We show that PAE-PcM COFs thin films with van der Waals layered structures exhibit p -type semiconducting properties with the intrinsic mobility up to ~19.4 cm 2 V -1 s -1 and 4 orders of magnitude of increase in conductivity for PAE-PcCu film (0.2 S m -1 ) after iodine doping. Density functional theory calculations reveal that the carrier transport in the framework is anisotropic, with the out-of-plane hole transport along columnar stacked phthalocyanine more favorable. Furthermore, PAE-PcCo shows the redox behavior maximumly contributes ~88.5% of its capacitance performance, giving rise to a high surface area normalized capacitance of ~19 μF cm -2 . Overall, this work not only offers fundamental understandings of electronic properties of polyarylether-based 2D COFs but also paves the way for their energy-related applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2023

Exceptional Electron-Rich Heteroaromatic Pentacycle for Ultralow Band Gap Conjugated Polymers and Photothermal Therapy

Stable redox-active conjugated molecules with exceptional electron-donating abilities are key components for the design and synthesis of ultralow band gap conjugated polymers. While hallmark electron-rich examples such as pentacene derivatives have been thoroughly explored, their poor air stability has hampered their broad incorporation into conjugated polymers for practical applications. Herein, we describe the synthesis of the electron-rich, fused pentacyclic pyrazino[2,3-b:5,6-b’]diindolizine (PDIz) motif and detail its optical and redox behavior. The PDIz ring system exhibits a lower oxidation potential and a reduced optical band gap than the isoelectronic pentacene while retaining greater air stability in both solution and the solid state. The enhanced stability and electron density, together with readily installed solubilizing groups and polymerization handles, allow for the use of the PDIz motif in the synthesis of a series of conjugated polymers with band gaps as small as 0.71 eV. Importantly; the tunable absorbance throughout the biologically relevant near-infrared I and II regions enables the use of these PDIz-based polymers as efficient photothermal therapeutic reagents for laser ablation of cancer cells.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2021

TEMPO allegro: liquid catholyte redoxmers for nonaqueous redox flow batteries

Redoxmers are organic active molecules storing energy in redox flow batteries (RFBs). Liquid redoxmers represent an extreme scenario where maximum concentration may be achieved by minimizing supporting solvents, thus maximizing the energy density of RFBs. Herein, a series of (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO)-based high potential (catholyte) liquid redoxmers, TEMPO-EG1, TEMPO-EG2, and TEMPO-EG3, were developed by incorporating polyethylene glycol (PEG) chains. Such modifications not only afford dramatic physical changes from solid to liquid and full miscibility in acetonitrile, but also impact the redox behavior. DFT calculations indicate that the incorporated PEG chains impact the charge distribution, which may account for the electrochemical changes. Importantly, compared to our previous liquid catholytes, the new redoxmers exhibit lower viscosity, which is desired for enhancing high concentration cycling performance. Furthermore, by using a hybrid flow cell, TEMPO-EG1 demonstrated more than 70% capacity retention over 100 cycles at 0.1 M and 66% capacity retention at 0.5 M, affording excellent cyclability at various concentrations. The study exemplifies how molecular engineering tuned the rheological properties of redoxmers, such as viscosity, to improve the high concentration cycling performance of RFBs, which may represent a promising avenue for a high energy density and low-cost flow battery system.

25 ENERGY STORAGE↗

DOE OSTI2025

The electrode–electrolyte interface of Cu via modulation excitation X-ray absorption spectroscopy

The development and application of modulation excitation X-ray absorption spectroscopy with sub-second resolution and better than 0.02% detection sensitivity unveils the kinetics of the anodic oxidation of Cu in bicarbonate electrolytes. Accessing the electrode–electrolyte interface under operating conditions and capturing time-resolved kinetics remain challenging in electrochemical studies. Copper's interfacial oxidation dynamics remain unclear despite extensive research. Modulation excitation X-ray absorption spectroscopy (ME-XAS) was used to probe Cu in 100 mM KHCO 3 with sub-second sensitivity, revealing that hydroxide forms 30 ± 10 ms before the appearance of Cu 2 O at positive potentials (0 to 0.5 V vs. RHE) near open-circuit conditions. From −0.4 to 0.8 V vs. RHE, hydroxide coverage reaches 49%, accompanied by a balanced presence of Cu( i ) and Cu( ii ) oxides. These insights into Cu interfacial redox behavior under intermittent renewable energy operation—relevant to CO 2 electrolyzer durability—enhance our fundamental understanding of electrochemical interfaces.

Garcia-Esparza, Angel T↗

DOE OSTI2025

Structural and electronic changes in L⁢i 2 ⁢Ru⁢O 3 induced by lithium intercalation

Despite extensive research on oxide battery cathodes that transcend classical cationic redox activity, the detailed interplay between structural transformations and electronic redox processes remains insufficiently understood. We report a detailed study of the sequential structural and electronic changes in Li 2 RuO 3 upon lithium intercalation, characterized by powder x-ray and neutron diffraction alongside Ru and O K-edge x-ray absorption spectroscopy (XAS), and guided by operando synchrotron x-ray diffraction. During delithiation, Li 2 RuO 3 evolves from a well-defined monoclinic state to a complex trigonal phase via multiple intermediate structures, marked by significant changes in Ru-O bond distances that closely track the transition from a classical cationic redox to an unconventional process centered at oxygen states. Armed with high-quality atomic structural descriptions, computational models of the O K-edge XAS closely reproduce the experimentally observed spectral shifts. Lastly, we relate observations of electrochemical hysteresis with concurrent changes in the pathways of structural and electronic transitions. In conclusion, our results not only clarify the mechanisms underpinning voltage hysteresis in a model for lattice oxygen redox but also underscore the importance of structural fidelity in modeling redox behavior when this type of complex reactivity is present.

Li, Haifeng [Univ. of Illinois, Chicago, IL (Unite↗

DOE OSTI2020

Mechanism of Electrochemical Oxidation of Nitroxide Radicals in Ethaline Deep Eutectic Solvent

Deep eutectic solvents (DESs) are emerging as promising electrolytes for electrochemical energy storage applications. Electroactive nitroxide-radical-containing organics can be dissolved in DESs to facilitate redox reactions; however, mechanistic know-how of their charge transfer kinetics at the electrode surface is rather limited. Here, we investigate the mechanism underlying the electrochemical oxidation of 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) and 4-hydroxy-2,2,6,6-tetramethyl-piperidine-1-oxyl (4-hydroxy-TEMPO). Using polarization measurements on a platinum rotating disk electrode and micro-electrode, we show that the anodic charge transfer coefficient (a) for one-electron transfer oxidations of TEMPO and4-hydroxy-TEMPO approaches 0.9 in DES as well as in aqueous electrolytes, i.e., a significant deviation fromα≈0.5 expected for symmetric redox behavior. To explain this observation, a two-step oxidation mechanism is proposed wherein the nitroxide-containing species undergo fast charge transfer at an electrode surface followed by slow rate-limiting desorption of the adsorbed oxidized species. Numerical simulations are reported to characterize how the proposed two-step mechanism manifests intransient cyclic voltammetry behavior of the 4-hydroxy-TEMPO oxidation reaction, and good agreement with experiments is noted.

25 ENERGY STORAGE↗

DOE OSTI2022

The Influence of Cr-Additives on the Polarization Resistance of Praseodymium-Doped Ceria Cathodes for Solid Oxide Fuel Cells

While Cr poisoning of the oxygen reduction reaction (ORR) at SOFC cathodes is widely agreed to involve deactivation of oxygen exchange sites, the degradation mechanism remains ambiguous. Here, we selected an alternative cathode material Pr 0.1 Ce 0.9 O 2− δ , free of Sr segregation, to systematically investigate the effect of Cr-induced degradation in ORR. We expand on our previous studies in which the acidity/basicity of binary additives was found to be a strong indicator of the rate of oxygen surface exchange, by electrochemically investigating the ORR activity of the PCO cathode by impedance spectroscopy. Serial infiltration with acidic Cr-based oxides was found to degrade ORR activity as reflected in a 20-fold increase in area specific resistance (ASR) without corresponding changes in activation energy, with the opposite trend obtained with Ca-based oxides. Detected changes in total capacitance, attributed to changes in surface capacitance, also suggest depressed/enhanced PCO surface redox behavior with Cr/Ca-based infiltrants. Taken together, these results point to a more universal source of ORR poisoning/activation, based on acidity/basicity, rather than physical blocking of active sites. With this improved understanding, one can expect progress to be made in the coming years in optimizing means for protecting catalytic surfaces from degradation and/or improving their performance.

25 ENERGY STORAGE↗

DOE OSTI2025

Electrochemical Recovery of Iron from Spent Pickle Liquor by Chloride-Based Molten Salt Electrolysis

Spent pickle liquor (SPL) is a waste stream generated in the steel industry that presents both a disposal challenge and a potential resource for metal recovery. This study investigates the electrochemical extraction of high-purity iron metal from SPL using chloride-based molten salt electrolysis (CMSE). Electrochemical characterization of diluted SPL confirmed Fe 2+ as the dominant species. Thermal dehydration of SPL under inert atmosphere yielded FeCl 2 -rich solids, which were directly employed as feedstock for electrolysis in LiCl–KCl eutectic melts at 500 °C. Cyclic voltammetry of FeCl 2 in this melt revealed well-defined Fe 2+ /Fe 0 redox behavior within the electrochemical stability window of the supporting electrolyte. High coulombic efficiency (>85%) electrodeposition was achieved demonstrating that iron metal can be produced from dehydrated SPL by CMSE. The electrodeposited iron exhibited >98 wt% purity, which was further enhanced to 99.9 wt% via arc melting. The resulting iron powder was ferromagnetic, and its size distribution was found to be suitable for powder metallurgy applications. This work demonstrates a scalable, energy-efficient pathway for valorizing SPL into high-purity iron metal, advancing circular economy strategies in the steel industry.

Materials science↗

DOE OSTI2021

Electrical, structural and thermomechanical properties of doped-LaCrO3 ceramics for high temperature electronics and sensing applications.

Many important electrical and sensor applications require stable conductors under working temperatures up to 1500oC various redox environments. Common high temperature conductors such as nitrides and carbides are not stable under oxidizing atmospheres, for this reason low redox behavior materials would be more attractive. In this work, further dopant studies of the LaCrO3 system were completed in order to control the electronic and ionic conductivity, as well as the relative chemical and microstructural stability. Neodymium and Niobium dopants were initially studied to control the p-type, and potentially n-type conductive mechanisms, respectively, but other dopants strategies were also investigated. The electrical conductivity and Seebeck coefficient were characterized up to 1500oC under varying oxygen partial pressures. The phase and microstructural evolution of each material was also investigated for these compositions by XRD and SEM. The materials showing the best electrical and thermomechanical performance were included within thick films sensors and were tested.

20 FOSSIL-FUELED POWER PLANTS↗

DOE OSTI2025

Review of Layered Transition Metal Oxide Materials for Cathodes in Sodium-Ion Batteries

The growing interest in sodium-ion batteries (SIBs) is driven by scarcity and the rising costs of lithium, coupled with the urgent need for scalable and sustainable energy storage solutions. Among various cathode materials, layered transition metal oxides have emerged as promising candidates due to their structural similarity to lithium-ion battery (LIB) counterparts and their potential to deliver high energy density at reduced costs. However, significant challenges remain, including limited capacity at high charge/discharge rates and structural instability during extended cycling. Addressing these issues is critical for advancing SIB technology toward industrial applications, particularly for large-scale energy storage systems. This review provides a comprehensive analysis of layered sodium transition metal oxides, focusing on their structural properties, electrochemical performance, and degradation mechanisms. Special attention is given to the intrinsic and extrinsic factors contributing to their instability, such as structural phase transitions, and cationic/anionic redox behavior. Additionally, recent advancements in material design strategies, including doping, surface modifications, and composite formation, are discussed to highlight the progress toward enhancing the stability and performance of these materials. This work aims to bridge the knowledge gaps and inspire further innovations in the development of high-performance cathodes for sodium-ion batteries.

Ahangari, Mehdi (ORCID:0000000345803969)↗

NASA NTRS2002

Wholly Aromatic Ether-imides. Potential Materials for n-Type Semiconductors

We report on the synthesis and characterization of a novel series low-molar-mass ether-imide rod-shaped model compounds. All ether-imides were obtained by terminating the appropriate rigid core dianhydride, i.e. pyromellitic dianhydride (PMDA), 1,4,5,8-naphthalenetetracarboxylic dianhydride (NDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA), and 3,3,4,4'-oxydiphthalic dianhydride (ODPA) with three flexible aryl-ether tails of different chain length. The mono-functional aryl-ether amines, i.e. 4-(3-phenoxy-phenoxy)-phenylamine (2) and 4-(3-phenoxy-3-phenoxy-phenoxy)-phenylamine (4), were synthesized using standard fluoro-displacement and Ullmann condensation techniques. The corresponding ether-imide model compounds were obtained in high yields using a one-step solution imidization procedure. Increasing the number of meta-substituted aryl-ether units reduces the melt transition temperatures and at the same time it increases the solubility of the model compounds. Most model compounds are crystalline solids and form isotropic melts upon heating. 2,7-Bis-(-4-phenoxy-phenyl)-benzo[Imn][3,8]phenanthroline1,3,6,8-tetraone (NDA-n0), however, displays a smectic A (SA) when cooled from the isotropic phase, followed by what appears to be either a highly ordered smectic phase or a, columnar phase. This is the first example, known to date, in which a mesophase is detected in a wholly aromatic ether-imide compound. For all compounds we present spectroscopic data and X-ray diffraction data. Cyclic voltammetry was used to determine the redox behavior and pertinent energy levels of the model compounds.

Dingemans, Theo J.↗