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At least 199 records · Page 11

Boosting energy efficiency of Li-rich layered oxide cathodes by tuning oxygen redox kinetics and reversibility

In developing electrode materials for next-generation Li-ion batteries, significant efforts have been given to the energy, power density and cycling stability, with much less (if any) attention paid to the energy efficiency – arguably, the most important practical measure for large-scale applications. This is particularly true for the oxygen-redox active electrodes, such as Li 1.2 Ni 0.13 Co 0.13 Mn 0.54 O 2 , the notorious energy-inefficient cathode that has an extremely high capacity but comes with large voltage hysteresis and voltage decay. Herein, we report the rational design of an energy-efficient Li-rich layered cathode along with high energy, power density and cycling stability enabled by tuning oxygen redox activity. Specifically, the target material Li 1.12 Ni 0.22 Co 0.13 Mn 0.52 O 2 exhibits an ultrahigh energy efficiency at 1 C (90.6%), high capacity (> 200 mAh g -1 ) with 98.9% retention and less than 150 mV decay at the extended 200 cycles. Overall, through direct comparison between the material and Li 1.2 Ni 0.13 Co 0.13 Mn 0.54 O 2 , we show that the compositional change, although slightly, greatly improves the oxygen redox kinetics and reversibility, thereby boosts energy efficiency. The findings offer a strategy to narrow the gap between scientific interest and practical application of oxygen-redox chemistry.

36 MATERIALS SCIENCE↗

Oxidation rates and redox stabilization of ferrous iron in trioctahedral smectites

Iron(II)-bearing trioctahedral smectites (saponites) form during anoxic alteration of basaltic rock. They are predicted to have been widespread on the early Earth and are observed in the oceanic subsurface today. Smectite structures, including the occupancy of sites in the octahedral sheet, affect iron redox behavior but the rates and products of trioctahedral smectite oxidation have been largely unexplored to date. In this study we synthesized two Fe(II)-bearing trioctahedral smectites, one moderate (22 wt% Fe) and one high (27 wt% Fe) in iron content. We then examined the rate, extent, and products of their oxidation by dissolved oxygen, nitrite, and hydrogen peroxide. Dissolved oxygen caused partial oxidation of Fe(II) in the smectites with 14 to 43% of Fe(II) unoxidized after 20 to 30 days of exposure. The rate and extent of oxidation correlated with the dissolved oxygen concentration and the Fe(II) content of the clay. The incomplete oxidation in these experiments is consistent with the mixed-valent trioctahedral smectites observed in oxidized natural samples but contrasts with the complete reoxidation by oxygen shown by chemically- or microbially-reduced dioctahedral smectites. Oxidation of structural Fe(II) by 5 mmol L -1 nitrite was negligible for the moderate-iron smectite and yielded only ~17% oxidation after 54 days of reaction for the high-iron smectite. Hydrogen peroxide caused rapid and near-complete oxidation of both clays. Powder X-ray diffraction, variable-temperature Mössbauer spectroscopy, and extended X-ray absorption fine structure spectroscopy together detected no crystalline or short-range-ordered secondary phases and show that oxidized iron remained in the trioctahedral smectite structure. The recalcitrant Fe(II) pool in oxidized trioctahedral smectites exists in less distorted sites than Fe(II) in the initial clays. Its unreactive nature at prolonged reaction times indicates an elevated redox potential generated by the local coordination environment. Slower oxidation rates create a larger recalcitrant Fe(II) pool, suggesting kinetic competition between oxidation and a process involved in redox stabilization, such as electron exchange between octahedral iron sites or deprotonation of hydroxyl groups in the structure. The resistance to complete oxidation of trioctahedral ferrous smectites and their full retention of iron demonstrates that transitions from anoxic to oxic conditions generate mixed-valence smectites rather than a mixture of new phases. Identifying the diagenetic products of mixed-valent trioctahedral smectites may provide an indicator in the rock record of past redox cycling. In conclusion, substantial portions of structural Fe(II) in trioctahedral smectites display slow abiotic oxidation kinetics and represent potential electron donors for both microaerophilic iron oxidizing and nitrate-reducing, iron-oxidizing microorganisms in altered mafic rocks and related settings.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Antimony redox processes in the environment: A critical review of associated oxidants and reductants

The environmental behavior of antimony (Sb) has recently received greater attention due to the increasing global use of Sb in a range of industrial applications. Although present at trace levels in most natural systems, elevated Sb concentrations in aquatic and terrestrial environments may result from anthropogenic activities. The mobility and toxicity of Sb largely depend on its speciation, which is dependent to a large extent on its oxidation state. To a certain extent, our understanding of the environmental behavior of Sb has been informed by studies of the environmental behavior of arsenic (As), as Sb and As have somewhat similar chemical properties. However, recently it has become evident that the speciation of Sb and As, especially in the context of redox reactions, may be fundamentally different. Therefore, it is crucial to study the biogeochemical processes impacting Sb redox transformations to understand the behavior of Sb in natural and engineered environments. Currently, there is a growing body of literature involving the speciation, mobility, toxicity, and remediation of Sb, and several reviews on these general topics are available; however, a comprehensive review focused on Sb environmental redox chemistry is lacking. Herein, we provide a review of research conducted within the past two decades examining the redox chemistry of Sb in aquatic and terrestrial environments and identifies knowledge gaps that need to be addressed to develop a better understanding of Sb biogeochemistry for improved management of Sb in natural and engineered systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Redox-stable symmetrical solid oxide fuel cells with exceptionally high performance enabled by electrode/electrolyte diffuse interface

Here, in this study, we report a high performance and redox-stable symmetrical solid oxide fuel cell (SOFC) based on (Ba 0.5 Sr 0.5 ) (Mo 0.1 Fe 0.9 )O 3-δ (BSMF) electrode and La 0.8 Sr 0.2 Ga 0.8 Mg 0.2 O 3-δ (LSGM) electrolyte. BSMF is able to operate both as anode and cathode. Excellent electrocatalytic activity has been achieved on BSMF towards hydrogen oxidation and oxygen reduction. Due to its closely matched lattice parameter to LSGM electrolyte, a unique diffuse interface is formed between BSMF and LSGM. Compared to a clean interface, e.g. BSMF/gadolinium doped ceria interface, this diffuse interface promotes the performance of BSMF electrode 1–1.8 times in 600–800 °C. Polarization resistance of the BSMF/LSGM specimen is as low as 0.047 and 0.007 Ωcm 2 in humidified H 2 and in air at 800 °C, respectively. On the BSMF/LSGM/BSMF symmetrical cell, a maximum power density of 2.28 W/cm 2 is achieved at 800 °C, the highest among with redox-stable ceramic electrodes to the best of our knowledge. Redox stability of this cell is confirmed. The role of anode and cathode is reversed back and forth in different operation modes. No apparent degradation is observed through 4 cycles within a 110 h operation period. These findings demonstrate that (Ba 0.5 Sr 0.5 ) (M o0.1 Fe 0.9 )O 3-δ coupled with LSGM electrolyte is an excellent choice to build a high performance, redox-stable SOFC.

25 ENERGY STORAGE↗

Reversible dual anionic-redox chemistry in NaCrSSe with fast charging capability

Utilizing the anionic redox reaction opens new approaches for the development of new cathode materials with extra capacities. Although, it suffers from several obstacles such as voltage hysteresis and sluggish kinetics. In this paper, a new layered chalcogenide-based on dual anionic-redox reaction is reported. The newly designed layered NaCrSSe exhibits the capacity of almost all Na + intercalation/deintercalation (137 mAh/g -1 at 50 mA/g), and a unique charge/discharge feature with a small polarization of 0.15 V and high energy efficiency of ~92% in initial cycles. Furthermore, a superior high-rate charge capacity of 115.5mAh/g -1 (83.7% retention) was achieved at 27.8 C (4000 mA/g -1 ). Systematic characterization studies on structure evolution and DFT calculation show the charge compensation of S and Se anions during cycling. Overall, these results will enrich the anion redox chemistry and provide valuable information for developing new anion-redox based cathode materials with high capacity and fast kinetics.

25 ENERGY STORAGE↗

Oxygen redox chemistry: A new approach to high energy density world

Sodium-ion batteries (SIBs) have been considered as promising candidates for large scale energy storage systems due to the great abundance of sodium resources. For sodium layered transition metal oxide cathode materials, oxygen redox can increase the energy density by enabling extra capacity and delivering high voltage. Here we provide a comprehensive overview of oxygen redox in SIBs from the perspectives of mechanism, challenges, and solutions. The previous studies on voltage hysteresis, capacity decay and oxygen release induced by oxygen redox as well as the effectiveness of different strategies including superlattice engineering, elemental substitution, and surface modification on the electrochemical performances of cathode materials with oxygen redox are comprehensively summarized with typical examples. Finally, the remaining challenges and the future research direction are discussed.

25 ENERGY STORAGE↗

Access to Ru(IV)–Ru(V) and Ru(V)–Ru(VI) Redox in Layered Li 7 RuO 6 via Intercalation Reactions

The push to increase the capacity of oxides to store charge as Li-ion battery cathodes has challenged our knowledge of the boundaries of redox chemistry and its relationship to the atomic structure. Layered phases with Ru are now classical models in the quest for refined theories. Current understanding dictates that the highest formal state that can be reached in them is Ru(V), after which activity centered at the oxide anions is triggered. Yet, this picture is challenged by this investigation of the intercalation chemistry of Li 7 RuO 6 . Coupling structural and spectroscopic analysis with computational simulations, we show that Li 7 RuO 6 is capable of highly reversible lithiation to Li 8 RuO 6 through the Ru(V)/Ru(IV) redox couple. Further, Li 7 RuO 6 can also undergo anodic Li deintercalation, showing clear evidence of the reversible formation of Ru(VI) with octahedral coordination, an unusual state that is not accessible in other layered oxides. The results highlight the versatility of the Ru-O bond to undergo distinct redox transitions depending on the specific layered arrangements. They enrich our understanding of redox chemistry in solids while underscoring the need for descriptions of charge compensation that reflect the nuance of covalent interactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Molecular Nature of Mineral-Organic Associations within Redox-Active Mountainous Floodplain Sediments

Floodplains are critical terrestrial-aquatic interfaces that act as hotspots of organic carbon (OC) cycling, regulating ecosystem carbon storage as well as export to riverine systems. Within floodplain sediments, regular flooding and textural gradients interact to create dynamic redox conditions. While anaerobic protection of OC upon burial is a well-recognized carbon storage mechanism in redox-active floodplain sediments, the impact of protective mineral-organic associations is relatively unknown. Here we determined the quantitative importance and chemical composition of mineral-organic associations along well-defined redox gradients emerging from textural variations and depth within meander sediments of the subalpine East River watershed (Gothic, CO). Here we characterized mineral-organic associations using a combination of sequential extractions, physical fractionation, and high-resolution mass spectrometry. Across the meander, we found that mineral-associated OC constitutes a significant fraction of total OC, and that extractable iron (Fe) and aluminum (Al) phases as well as high-density isolates were strongly correlated with total OC content, suggesting that mineral-organic associations are quantitatively important for floodplain sediment OC protection. Our mass spectrometry results showed OC associated with increasingly ordered Fe and Al phases are relatively enriched in low-molecular weight, oxidized, aromatic compounds. Surprisingly, however, total OC content showed weak or no correlation with indicators of anaerobic protection, such as relatively bioavailable OC pools (water-extractable and particulate OC) or the molecular weight and oxidation state of OC. Overall, this work highlights that protection of OC bound to reactive mineral phases-in addition to anaerobic protection-can play a quantitatively important role in controlling soil carbon storage in redox-active floodplain sediments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Modulating Surface Anionic Redox Chemistry toward Highly Stable Li-Rich Cathodes with Negligible Oxygen Loss

Low initial Coulombic efficiency and severe capacity/voltage fading during cycling caused by serious irreversible oxygen release, especially in the initial cycle, and resultantly induced unstable electrode/electrolyte interfacial chemistry, largely prohibit the commercial application of high-capacity Li-rich layered oxide cathodes (LLOs). Here, in this work, a dual reductive gas interface cotreatment strategy is applied to regulate the lattice oxygen redox activity and reversibility with a multiple defective structure design including Li/O/TM (TM = transition metal) vacancies and the intrinsic TM doping as well as a full-surface protective layer, which can suppress the irreversible TM migration and then undesirable phase transformation, resisting the corrosion of electrolyte during cycling effectively. Importantly, the introduced reversible SO 3 2- /SO 4 2- redox couple that provides extra capacity compensation could alleviate the distortion of oxygen-central octahedral structure and structural collapse caused by immoderate oxygen oxidation. Thus, the lattice oxygen redox chemistry is optimized, with negligible oxygen loss during the initial cycle. And the designed AS-LLO cathode with greatly enhanced structure stability shows high-capacity retentions of 99.2% at 0.3C after 100 cycles and 82.4% even after 1000 cycles at 5C. This work provides a guideline for manipulating the oxygen redox chemistry to achieve long-lifespan Li-rich layered oxide cathodes for high-energy-density lithium batteries.

25 ENERGY STORAGE↗

A redox-reversible A/B-site co-doped BaFeO 3 electrode for direct hydrocarbon solid oxide fuel cells

Solid oxide fuel cells (SOFCs) can directly convert the chemical energy in fuel to electrical energy with fuel flexibility; however, the conventional nickel-based anodes face great challenges due to coking upon direct oxidation of hydrocarbon fuels and redox instability. Thus, developing new anode materials which can provide high coking resistance as well as redox stability is crucial. In this work, Ba 0.6 La 0.4 Fe 0.8 Mo 0.1 Ni 0.1 O 3-δ (BLFMN) has been synthesized in air using a sol–gel combustion method, resulting in a dual phase consisting of a cubic BLFMN main phase and scheelite BaMoO 4 (BMO 4 ) secondary phase. By heat-treating the BLFMN dual phase in H 2 at 800 °C for 5 h, a metallic nanoparticle-decorated BLFMN triple phase compound comprising cubic BLFMN, cubic BaMoO 3 (BMO 3 ) and in situ exsolved FeNi 3 alloy was obtained. BLFMN was subsequently investigated as an electrode material for La 0.8 Sr 0.2 Ga 0.83 Mg 0.17 O 3-δ (LSGM) electrolyte (300 μm) supported SOFCs. Symmetrical cells using BLFMN as electrodes with the cell configuration of BLFMN//LSGM//BLFMN showed excellent redox reversibility and a peak power density (PPD) of 1.32 W cm -2 at 850 °C when using H 2 as fuel. Single cell with the cell configuration of BLFMN//LSGM//LSCF (La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3-δ ) reached PPD of 1.61 and 0.41 W cm -2 at 850 °C when operating with H 2 and CH 4 fuel, respectively. Moreover, the single cell exhibit excellent stability (over 300 h) upon direct oxidation of hydrocarbon fuels of CH 4 and C 3 H 8 . This study indicates that BLFMN is a promising redox reversible and coking resistant anode for SOFCs.

08 HYDROGEN↗

Oscillatory redox behavior in oxides: Cyclic surface reconstruction and reactivity modulation via the Mars–van Krevelen mechanism

The breaking of translational symmetry at oxide surfaces gives rise to coordinatively unsaturated cations/anions and surface restructuring—key factors that govern surface reactivity. Using direct in situ environmental transmission electron microscopy (TEM) observations along with atomistic modeling, we report oscillatory redox behavior in CuO under H 2 , where cyclic surface reconstruction and reactivity modulation occur via the Mars–van Krevelen (MvK) mechanism. We observe self-switching between oxygen-rich and oxygen-deficient surface reconstructions, alternately activating and deactivating the surface for H 2 O formation. During periods of chemical inactivity, the oxygen-deficient surface undergoes slow reoxidation via lattice oxygen diffusing from subsurface and bulk reservoirs, restoring the active oxygen-rich surface termination. The inherent disparity in chemical activity among undercoordinated surface ions, along with sluggish subsurface-to-surface oxygen replenishment, drives this oscillatory redox cycle, modulating H2-induced loss of lattice oxygen at the surface and its delayed replenishment from the subsurface. This creates spatiotemporally separated redox steps at the oxide surface. The phenomena and atomistic insights presented here have significant implications for manipulating the surface reactivity of oxides by tuning the separation of these redox steps.

36 MATERIALS SCIENCE↗

Chlamydomonas as a model for reactive oxygen species signaling and thiol redox regulation in the green lineage

While the maintenance of redox balance is important for all organisms, the energy balance in the chloroplast is particularly tightly linked to the overall cellular redox status in photosynthetic organisms. Excess light can cause overreduction of the photosynthetic electron transport chain, which, when unchecked, results in the generation of reactive oxygen species (ROS) that can oxidize cellular components including nucleic acids, proteins, and lipids (Li et al., 2009). A photosynthetic cell possesses multiple layers of defense against oxidative stress, such as antioxidant enzymes (Foyer and Noctor, 2005) and alternative electron transfer pathways (Alric and Johnson, 2017). At the same time, ROS can function as important signals that mediate responses to biotic and abiotic stresses (Apel and Hirt, 2004). Reversibly oxidizable small molecules and proteins can serve as ROS sinks and signals and are re-reduced by multiple mechanisms. For example, the ascorbate–glutathione (GSH) cycle is central in controlling ROS levels and regenerating/reducing oxidized cellular redox agents (Figure 1A; reviewed by Foyer and Noctor, 2011). The functions of many proteins can be regulated by the redox state of cysteine residues, such as the formation or reduction of disulfides by thioredoxins (TRX) (Buchanan, 1991) and glutaredoxins (Michelet et al., 2013b; Figure 1, B and C).

59 BASIC BIOLOGICAL SCIENCES↗

Effect of iron redox ratio on the structures of boroaluminosilicate glasses

Iron oxide is commonly found in natural or industrial glass compositions and can exist as ferrous (Fe 2+ ) or ferric (Fe 3+ ) species, with their ratios depending on glass composition, temperature, pressure and the redox reactions during the glass forming process. The iron redox ratio plays an important role on silicate glass structures and consequently various properties. This work aims to study the effect of iron oxide, and particularly the iron redox ratio, on the structures of borosilicate and boroaluminosilicate glasses using molecular dynamics simulations with newly developed iron potential parameters that are compatible with the borosilicate potentials. The results provide detailed cation coordination states of both iron species and the effect of redox ratio on boron coordination and other structural features. Particularly, competition for charge compensating modifier cations (such as Na + ) among the fourfold-coordinated cations such as B 3+ , Al 3+ , and Fe 3+ is investigated by calculating the cation–cation pair distribution functions and coordination preferential ratios. The results show that the trivalent ferric ions, with a shorter Fe–O bond distance and better defined first coordiation shell with mainly four-fold coordination, act as a glass former whereas the divalent ferrous ions mainly play the role of glass modifier. The ferrous/ferric ratio (Fe 2+ /Fe 3+ ) was found to affect the glass chemistry and hence glass properties by regulating the amount of four-coordinated boron, the fraction of non-briding oxygen and other features. Finally, the results are compared with available experimental data to gain insights of the complex structures and charge compensation schemes of the glass system.

36 MATERIALS SCIENCE↗

An exploratory steady–state redox model of photosynthetic linear electron transport for use in complete modelling of photosynthesis for broad applications

A photochemical model of photosynthetic electron transport (PET) is needed to integrate photophysics, photochemistry, and biochemistry to determine redox conditions of electron carriers and enzymes for plant stress assessment and mechanistically link sun-induced chlorophyll fluorescence to carbon assimilation for remotely sensing photosynthesis. Towards this goal, we derived photochemical equations governing the states and redox reactions of complexes and electron carriers along the PET chain. These equations allow the redox conditions of the mobile plastoquinone pool and the cytochrome b 6 f complex (Cyt) to be inferred with typical fluorometry. The equations agreed well with fluorometry measurements from diverse C 3 /C 4 species across environments in the relationship between the PET rate and fraction of open photosystem II reaction centres. We found the oxidation of plastoquinol by Cyt is the bottleneck of PET, and genetically improving the oxidation of plastoquinol by Cyt may enhance the efficiency of PET and photosynthesis across species. Redox reactions and photochemical and biochemical interactions are highly redundant in their complex controls of PET. Although individual reaction rate constants cannot be resolved, they appear in parameter groups which can be collectively inferred with fluorometry measurements for broad applications. The new photochemical model developed enables advances in different fronts of photosynthesis research.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Direct Recycling of End-of-Life Cathode Material Through Redox Chemistry Mediators

Lithium-ion batteries (LIBs) are ideal for electric vehicles and electronic devices because of their high-power density and outstanding cycle life. The need for recycled LIBs material is pivotal for the sustainability of the renewable energy industry. The recycling process needs to be both economically and environmentally conscious. Direct recycling is cheaper and generates the least amount of waste compared to pyrometallurgical and hydrometallurgical processes. Direct recycling explored in this work is useful for reclaiming precious minerals from the End-of-Life (EOL) LIBs material. The EOL material has varying lithium deficiency, hence, redox mediator relithiation restores the lithium content rapidly and at low cost. The redox mechanism relithiate EOL cathode material by shuttling charges very fast between lithium metal and EOL cathode material. The redox mediator is oxidized to create lithium rich solvent and reduced to relithiate EOL cathode material. However, the process is sensitive to pH changes. The redox reaction creates acidic solvent, which may cause lithium leaching. Therefore, use of lithium hydroxide (LiOH) to remove impurities on the surface of the EOL material and as a lithium source creates a basic solution to prevent lithium leaching and relithiate EOL material. This approach will potentially pave way for fast quality cathode material recovery at a low cost.

cathode material↗

Nitrogen limitation causes a seismic shift in redox state and phosphorylation of proteins implicated in carbon flux and lipidome remodeling in Rhodotorula toruloides

Background: Oleaginous yeast are prodigious producers of oleochemicals, offering alternative and secure sources for applications in foodstuff, skincare, biofuels, and bioplastics. Nitrogen starvation is the primary strategy used to induce oil accumulation in oleaginous yeast as part of a global stress response. While research has demonstrated that post-translational modifications (PTMs), including phosphorylation and protein cysteine thiol oxidation (redox PTMs), are involved in signaling pathways that regulate stress responses in metazoa and algae, their role in oleaginous yeast remain understudied and unexplored. Results: Towards linking the yeast oleaginous phenotype to protein function, we integrated lipidomics, redox proteomics, and phosphoproteomics to investigate Rhodotorula toruloides under nitrogen-rich and starved conditions over time. Our lipidomics results unearthed interactions involving sphingolipids and cardiolipins with ER stress and mitophagy. Our redox and phosphoproteomics data highlighted the roles of the AMPK, TOR, and calcium signaling pathways in regulation of lipogenesis, autophagy, and oxidative stress response. As a first, we also demonstrated that lipogenic enzymes including fatty acid synthase are modified as a consequence of shifts in cellular redox states due to nutrient availability. Conclusions: We conclude that lipid accumulation is largely a consequence of carbon rerouting and autophagy governed by changes to PTMs, and not increases in the abundance of enzymes involved in central carbon metabolism and fatty acid biosynthesis. Our systems-level approach sets the stage for acquiring multidimensional data sets for protein structural modeling and predicting the functional relevance of PTMs using Artificial Intelligence/Machine Learning (AI/ML). Coupled to those bioinformatics approaches, the putative PTM switches that we delineate will enable advanced metabolic engineering strategies to decouple lipid accumulation from nitrogen limitation.

Lipid Signalling↗

Impact of Stress-Activated Positive Holes on the Redox Timing in Organisms Living at the Surface of Rocks: Unlocking Nature's Secrets

Squeezing and deforming igneous and/or high-grade metamorphic rocks activates electronic charge carriers known as positive holes, h•, that are defect electrons in the O2– sublattice. Similar to h• in semiconductors the h• in rocks affect electrical and thermal properties. They produce electrochemical reactions, localized electrical signals, and currents. In this study, we explore the effects of positive holes on the electron flow in the electron transport chain (ETC) of organisms living at the surface of rocks such as gabbro or granite. We found that positive holes, h•, disrupt the temporal coordination in vivo governed by oscillating reduction-oxidation reactions, known as the redox cycle. Positive holes affect the timing of the redox cycle by interacting with molecules in vivo, leading to the formation of superoxide anions and hydroxyl radicals. Thus, we observed that positive holes significantly impede the growth of yeast Saccharomyces cerevisiae (i.e., colony size) and delay the sprouting of broccoli and chia seeds. Additionally, positive holes were found to exert discernible impacts on plant development such as stem length and leaf size. Our findings highlight the intricate interplay between positive holes, redox timing, and biological processes, shedding light on the potentially significant role of positive holes in influencing the growth and development of organisms in tectonically stressed rock environments. Understanding these effects has implications for a broader understanding of redox biology and of how environmental factors can influence cellular development in natural settings.

Redox Timing in Organisms↗

Predicting Radiation-Induced Plutonium Redox Chemistry using Multi-scale Modeling Methods

Over the the last 70 years plutonium (Pu) has been integral in the development of several technologies that have changed the world, yet our fundamental understanding of its chemistry is still far from complete. This is a testament to this element’s unique and complex properties, such as its ability to coexist as multiple oxidation states in aqueous solution. Careful manipulation of plutonium oxidation states is essential in the study and utilization of its rich chemistry. To achieve this level of control, a comprehensive mechanistic understanding of radiation-induced plutonium redox chemistry is critical due to the unavoidable exposure of plutonium to ionizing radiation fields, both inherent and from in-process applications. For this reason, we have developed an experimentally evaluated multi-scale computer model for the prediction of gamma radiation-induced Pu(IV) redox chemistry in concentrated nitric acid solutions (1.0, 3.0, and 6.0 M). Under these acidic, aqueous solution conditions, cobalt-60 gamma irradiation afforded negligible net change in the steady-state oxidation state distribution of Pu(IV). Multi-scale calculations, which are in excellent agreement with experimental data, indicate that this observation is due to radiation-induced redox cycling between Pu(IV) and Pu(III), as achieved by the reduction of Pu(IV) by radiolytic nitrous acid and hydrogen peroxide, and the oxidation of Pu(III) by nitrate and hydroxyl radicals. These radiation-induced redox processes are augmented by plutonium’s inherent disproportionation reactions.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗