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Method for identification of redox control parameters for corrosion mitigation in molten fluoride salts
Structural material corrosion is a significant concern for the development of molten salt-cooled reactors (MSR) and redox control was proposed to mitigate the corrosion. This study presents an efficient approach to identify the partial pressure of F 2 gas for fluorine driven corrosion, the concentration ratios of UF 4 /UF 3 and ZrF 4 /ZrF 2 , and the partial pressure ratio of HF/H 2 needed to limit metal corrosion and its subsequent dissolution in molten fluoride salts. The identification procedure is made by simply using auxiliary axes in Ellingham diagrams. This approach greatly simplifies the optimization of redox control methods in studying the material corrosion in molten salts.
Radiolytic evaluation of a new technetium redox control reagent for advanced used nuclear fuel separations
Technetium is a problematic radioisotope for used nuclear fuel (UNF) and subsequent waste management owing to its high environmental mobility and coextraction in reprocessing technologies as the pertechnetate anion (TcO 4 - ). Consequently, several strategies are under development to control the transport of this radioisotope. A proposed approach is to use diaminoguanidine (DAG) for TcO 4 - and transuranic ion redox control. Although the initial DAG molecule is ultimately consumed in the redox process, its susceptibility to radiolysis is currently unknown under envisioned UNF reprocessing conditions, which is a critical knowledge gap for evaluating its overall suitability for this role. To this end, we report the impacts of steady-state gamma irradiation on the rate of DAG radiolysis in water, aqueous 2.0 M nitric acid (HNO 3 ), and in a biphasic solvent system composed of aqueous 2.0 M HNO 3 in contact with 1.5 M N,N-di-(2-ethylhexyl)isobutyramide (DEHiBA) dissolved in n-dodecane. In addition, we report chemical kinetics for the reaction of DAG with key transients arising from electron pulse radiolysis, specifically the hydrated electron (e aq - ), hydrogen atom (H ˙ ), and hydroxyl ( ˙ OH) and nitrate (NO 3 ˙ ) radicals. The DAG molecule exhibited significant reactivity with the ˙ OH and NO 3 ˙ radicals, indicating that oxidation would be the predominant degradation pathway in radiation environments. This is consistent with its role as a reducing agent. Steady-state gamma irradiations demonstrated that DAG is readily degraded within a few hundred kilogray, the rate of which was found to increase upon going from water to HNO 3 containing solutions and solvents systems. This was attributed to a thermal reaction between DAG and the predominant HNO 3 radiolysis product, nitrous acid (HNO 2 ), k(DAG + HNO 2 ) = 5480 ± 85 M -1 s -1 . Although no evidence was found for the radiolysis of DAG altering the radiation chemistry of the contacted DEHiBA/n-dodecane phase in the investigated biphasic system, the utility of DAG as a redox control reagent will likely be limited by significant competition with its degradation by HNO 2 .
Compatibility of Type 304H Stainless Steel in Static Molten FLiBe for Inertial Confinement Fusion Reactors: Role of Impurities and Redox Control
Molten fluoride salts, such as FLiBe (LiF-BeF2), are promising candidates for tritium breeding and heat transfer in fusion reactors, but corrosion of structural materials remains a major challenge. This study investigates the corrosion behavior of austenitic stainless steel 304H in purified and NiF2-containing FLiBe at 500°C and 600°C, focusing on the effects of impurities and redox control. Exposure to purified FLiBe resulted in the concurrent depletion of Cr, Mn, and Fe, with corrosion at 500 °C dominated by the combined oxide formation and elemental dissolution, while at 600°C elemental depletion was predominant. The addition of a controlled NiF2 impurity significantly accelerated corrosion at both temperatures, demonstrating the sensitivity of 304H to the salt redox state. Beryllium additions were effective in mitigating corrosion for both baseline and NiF2-containing FLiBe; minimal depletion of Cr, Mn, and Fe occurred with Be additions as low as 2.5 mg (147 wppm), and no NiBe intermetallics formed at 5 mg (294 wppm), indicating that small Be inventories can provide substantial protection without deleterious phase formation. Thermodynamic equilibrium and coupled thermodynamic-kinetic analyses at the salt-alloy interface suggested low corrosion rates in systems with limited hydrogen fluoride (HF) generation, highlighting the importance of salt redox control. Estimates for a Be addition rate were calculated for the HYLIFE-II fusion reactor that can mitigate corrosion-induced degradation, assuming complete conversion of tritium to tritium fluoride (TF). Overall, 304H shows reasonable compatibility with FLiBe under optimized redox conditions. These results provide quantitative guidance for material selection and salt management in fusion blanket and heat exchanger systems and motivate validation under flowing, nonisothermal, and irradiated conditions.
High-Temperature Controlled Redox Crystallization Studies
The crystallization of silicates containing redox sensitive ions (e.g., Fe, Ti, Ce) must be performed under controlled and known redox conditions in order to obtain the maximum scientific benefit from experimental study. Furthermore, many compositions crystallize dense phases which settle during ground-based experiments. This settling influences the texture and chemical evolution of the crystallizing system. The purpose of this investigation is to develop a test system in which controlled redox experiments can be performed in the microgravity environment. The system will use solid ceramic oxygen electrolyte cells for control, measurements, and production of the required redox conditions. A preliminary design for a prototype is developed, the electrolyte and furnace tested, and a tentative protocol for experiment developed. The control parameter is to be established and a laboratory prototype built.
A system for conducting igneous petrology experiments under controlled redox conditions in reduced gravity
The Space Shuttle and the planned Space Station will permit experimentation under conditions of reduced gravitational acceleration offering experimental petrologists the opportunity to study crystal growth, element distribution, and phase chemistry. In particular the confounding effects of macro and micro scale buoyancy-induced convection and crystal settling or flotation can be greatly reduced over those observed in experiments in the terrestrial laboratory. Also, for experiments in which detailed replication of the environment is important, the access to reduced gravity will permit a more complete simulation of processes that may have occurred on asteroids or in free space. A technique that was developed to control, measure, and manipulate oxygen fugacities with small quantities of gas which are recirculated over the sample. This system could be adaptable to reduced gravity space experiments requiring redox control.
A system for conducting igneous petrology experiments under controlled redox conditions in reduced gravity
The Space Shuttle and the planned Space Station will permit experimentation under conditions of reduced gravitational acceleration offering experimental petrologists the opportunity to study crystal growth, element distribution, and phase chemistry. In particular the confounding effects of macro and micro scale buoyancy-induced convection and crystal settling or floatation can be greatly reduced over those observed in experiments in the terrestrial laboratory. Also, for experiments in which detailed replication of the environment is important, the access to reduced gravity will permit a more complete simulation of processes that may have occurred on asteroids or in free space. A technique that was developed to control, measure, and manipulate oxygen fugacites with small quantities of gas which are recirculated over the sample is described. This system should be adaptable to reduced gravity space experiments requiring redox control. Experiments done conventionally and those done using this technique yield identical results done in a 1-g field.
Treatment of Spacecraft Wastewater Using a Hollow Fiber Membrane Biofilm Redox Control Reactor
The purpose of this project was to develop and evaluate design concepts for biological treatment reactors for the purification of spacecraft wastewater prior to reverse osmosis treatment. The motivating factor is that wastewater recovery represents the greatest single potential reduction in the resupply requirements for crewed space missions. Spacecraft wastewater composition was estimated from the characteristics of the three major component streams: urine/flush water, hygiene water, and atmospheric condensate. The key characteristics of composite spacecraft wastewater are a theoretical oxygen demand of 4519 mg/L, of which 65% is nitrogenous oxygen demand, in a volume of 11.5 liter/crew-day. The organic carbon to nitrogen ratio of composite wastewater is 0.86. Urine represents 93% of nitrogen and 49% of the organic carbon in the composite wastestream. Various bioreaction scenarios were evaluated to project stoichiometric oxygen demands and the ability of wastewater carbon to support denitrification. Ammonia nitrification to the nitrite oxidation state reduced the oxygen requirement and enabled wastewater carbon to provide nearly complete denitrification. A conceptual bioreactor design was established using hollow fiber membranes for bubbleless oxygen transfer in a gravity-free environment, in close spatial juxtaposition to a second interspaced hollow fiber array for supplying molecular hydrogen. Highly versatile redox control and an enhanced ability to engineer syntrophic associations are stated advantages. A prototype reactor was constructed using a microporous hollow fiber membrane module for aeration. Maintaining inlet gas pressure within 0.25 psi of the external water pressure resulted in bubble free operation with no water ingress into hollow fiber lumens. Recommendations include the design and operational testing of hollow fiber bioreactors using: 1) Partial nitrification/nitrite predenitrification; 2) Limited aeration for simultaneous nitrification/denitrification or for nitrite reduction/ammonia oxidation; 3) Hydrogenotrophic denitrification.
Redox-controlled reorganization and flavin strain within the ribonucleotide reductase R2b–NrdI complex monitored by serial femtosecond crystallography
Redox reactions are central to biochemistry and are both controlled by and induce protein structural changes. Here, we describe structural rearrangements and crosstalk within the Bacillus cereus ribonucleotide reductase R2b–NrdI complex, a di-metal carboxylate-flavoprotein system, as part of the mechanism generating the essential catalytic free radical of the enzyme. Femtosecond crystallography at an X-ray free electron laser was utilized to obtain structures at room temperature in defined redox states without suffering photoreduction. Together with density functional theory calculations, we show that the flavin is under steric strain in the R2b–NrdI protein complex, likely tuning its redox properties to promote superoxide generation. Moreover, a binding site in close vicinity to the expected flavin O 2 interaction site is observed to be controlled by the redox state of the flavin and linked to the channel proposed to funnel the produced superoxide species from NrdI to the di-manganese site in protein R2b. These specific features are coupled to further structural changes around the R2b–NrdI interaction surface. The mechanistic implications for the control of reactive oxygen species and radical generation in protein R2b are discussed
Shifting mineral and redox controls on carbon cycling in seasonally flooded mineral soils
Although wetland soils represent a relatively small portion of the terrestrial landscape, they account for an estimated 20%–30% of the global soil carbon (C) reservoir. C stored in wetland soils that experience seasonal flooding is likely the most vulnerable to increased severity and duration of droughts in response to climate change. Redox conditions, plant root dynamics, and the abundance of protective mineral phases are well-established controls on soil C persistence, but their relative influence in seasonally flooded mineral soils is largely unknown. To address this knowledge gap, we assessed the relative importance of environmental (temperature, soil moisture, and redox potential) and biogeochemical (mineral composition and root biomass) factors in controlling CO 2 efflux, C quantity, and organic matter composition along replicated upland–lowland transitions in seasonally flooded mineral soils. Specifically, we contrasted mineral soils under temperature deciduous forests in lowland positions that undergo seasonal flooding with adjacent upland soils that do not, considering both surface (A) and subsurface (B and C) horizons. We found the lowland soils had lower total annual CO 2 efflux than the upland soils, with monthly CO 2 efflux in lowlands most strongly correlated with redox potential (E h ). Lower CO 2 efflux as compared to the uplands corresponded to greater C content and abundance of lignin-rich, higher-molecular-weight, chemically reduced organic compounds in the lowland surface soils (A horizons). In contrast, subsurface soils in the lowland position (C g horizons) showed lower C content than the upland positions (C horizons), coinciding with lower abundance of root biomass and oxalate-extractable Fe (Fe o , a proxy for protective Fe phases). Our linear mixed-effects model showed that Fe o served as the strongest measured predictor of C content in upland soils, yet Fe o had no predictive power in lowland soils. Instead, our model showed that E h and oxalate-extractable Al (Al o , a proxy of protective Al phases) became significantly stronger predictors in the lowland soils. Combined, our results suggest that low redox potentials are the primary cause for C accumulation in seasonally flooded surface soils, likely due to selective preservation of organic compounds under anaerobic conditions. In seasonally flooded subsurface soils, however, C accumulation is limited due to lower C inputs through root biomass and the removal of reactive Fe phases under reducing conditions. Our findings demonstrate that C accrual in seasonally flooded mineral soil is primarily due to low redox potential in the surface soil and that the lack of protective metal phases leaves these C stocks highly vulnerable to climate change.
Interface‐Controlled Redox Chemistry in Aqueous Mn 2 ⁺/MnO₂ Batteries
Manganese dioxide (MnO 2 ) deposition/dissolution (Mn 2+ /MnO 2 ) chemistry, involving a two-electron-transfer process, holds promise for safe and eco-friendly large-scale energy storage. However, challenges like electrode/electrolyte interface environment fluctuations (H + and H 2 O activity), irreversible Mn degradation, and limited understanding of degradation mechanisms hinder the reversibility of the Mn 2+ /MnO 2 conversion. This study demonstrates a vanadyl/pervanadyl (VO 2+ /VO 2 + ) redox-mediated interface designed for high-energy Mn 2+ /MnO 2 batteries. Unlike flow systems, this work uncovers, for the first time, the mechanism of a static redox-mediated interface in regulating interfacial H + and H 2 O activities. Significantly, the VO 2+ /VO 2 + chemical redox mediation targets Mn 3+ intermediates, suppressing their hydrolysis and enabling 100% Mn 2+ /MnO 2 conversion. The redox-mediated interface enhances the Mn redox electron transfer process, achieving a stable ≈95% coulombic efficiency and ultrahigh capacity of 100 mAh cm −2 with an areal energy density of 111 mWh cm −2 , outperforming flow systems. The electrode also exhibits an average specific capacity of 593 mAh g −1 , approaching the theoretical limit of 616 mAh g −1 , and a specific energy density of 721 Wh kg −1 at high MnO 2 loadings (50–150 mg cm −2 ). Furthermore, the findings highlight the critical role of interfacial redox mediation in regulating H + and H 2 O activities and underscore the significance of interface dynamics.
Tandem bulk oxygen diffusion and surface reactions in reducible metal oxides control redox cycle dynamics
The interplay between bulk oxygen diffusion and surface reactions in reducible metal oxides is key in heterogeneous catalysts, but direct measurements of oxygen mobility, transient kinetics, and in situ spectroscopies have been lacking. Here, we reveal complex dynamic behavior of ceria-zirconia by H 2 using transient kinetics via mass spectrometry and in situ Raman and near-ambient pressure x-ray photoelectron spectroscopies. Molecular dynamics simulations with a machine learning potential delineate competitive oxygen diffusion mechanisms, with an optimal mobility at intermediate reductions. We expose a compensation between vacancy availability and lattice distortion at intermediate to high reductions and Frenkel defects at low reductions, underscoring a potential deficiency of 16 O/ 18 O exchange experiments in deducing oxygen mobility. Vacancies in proximity require electron localization on Ce atoms further away. The continuous replenishment of surface oxygen results in a varying reduction rate, with H 2 dissociation being the rate-limiting step. Multiscale transient simulations, consistent with experiments, indicate catalysts of potentially spatially varying oxidation states. The approach is broadly applicable to reducible oxide materials.
Active Redox Control of Molten Salts For Fusion Blankets
Commonwealth Fusion Systems (CFS) is working to risk-retire aspects of technologies related to Fusion Energy System (FES) blanket technology. CFS is actively investigating the molten salt LiF-BeF 2 (FLiBe), a novel blanket material, for fusion energy machines.
Electrochemical corrosion under controlled redox conditions
A method for predicting corrosion rates of a material during service conditions is provided, the method having the steps of determining a first phase composition of the material; exposing the material to service conditions chemical environment; applying an electrical potential to the exposed material to represent the solution redox; identifying ranges of the applied potential that correspond to different corrosion behaviors of the material; quantifying current and surface electrical properties during corrosion; and determining a second phase composition of the material to identify corroded phases. Also provided is a method for determining radionuclide source terms, the method having the steps of supplying a multiphase metallic waste containing the radionuclides; immersing the waste in a solution representing repository chemistry conditions; and oxidizing the immersed waste for a period of time and at particular imposed voltages representing solution redox values to establish a steady current representing corrosion rate of the waste.
Linker Redox Mediated Control of Morphology and Properties in Semiconducting Iron-Semiquinoid Coordi
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Redox Gating for Colossal Carrier Modulation and Unique Phase Control
Redox gating, a novel approach distinct from conventional electrolyte gating, combines reversible redox functionalities with common ionic electrolyte moieties to engineer charge transport, enabling power-efficient electronic phase control. This study achieves a colossal sheet carrier density modulation beyond 10 16 cm -2 , sustainable over thousands of cycles, all within the sub-volt regime for functional oxide thin films. The key advantage of this method lies in the controlled injection of a large quantity of carriers from the electrolyte into the channel material without the deleterious effects associated with traditional electrolyte gating processes such as the production of ionic defects or intercalated species. The redox gating approach offers a simple and practical means of decoupling electrical and structural phase transitions, enabling the isostructural metal-insulator transition and improved device endurance. The versatility of redox gating extends across multiple materials, irrespective of their crystallinity, crystallographic orientation, or carrier type (n- or p-type). This inclusivity encompasses functional heterostructures and low-dimensional quantum materials composed of sustainable elements, highlighting the broad applicability and potential of the technique in electronic devices.
Electronic control of redox reactions inside Escherichia coli using a genetic module
Microorganisms regulate the redox state of different biomolecules to precisely control biological processes. These processes can be modulated by electrochemically coupling intracellular biomolecules to an external electrode, but current approaches afford only limited control and specificity. Here we describe specific electrochemical control of the reduction of intracellular biomolecules in Escherichia coli through introduction of a heterologous electron transfer pathway. E . coli expressing cymAmtrCAB from Shewanella oneidensis MR-1 consumed electrons directly from a cathode when fumarate or nitrate, both intracellular electron acceptors, were present. The fumarate-triggered current consumption occurred only when fumarate reductase was present, indicating all the electrons passed through this enzyme. Moreover, CymAMtrCAB-expressing E . coli used current to stoichiometrically reduce nitrate. Thus, our work introduces a modular genetic tool to reduce a specific intracellular redox molecule with an electrode, opening the possibility of electronically controlling biological processes such as biosynthesis and growth in any microorganism.