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At least 955 records · Page 53

Electrochemical Behavior of Cerium at an Indium Tin-Doped Oxide Electrode in Acidic Media

The redox behavior and speciation of cerium at mesoporous thin films composed of nanoparticles of indium tin-doped oxide (nITO) electrodes were characterized in pH 4.8, 0.1 M acetate buffer and both 0.1 and 1 M HNO 3 using electrochemical techniques and X-ray photoelectron spectroscopy. Anodic deposition of ceria species from Ce(III) to the nITO electrode was achieved under all solvent conditions via spontaneous condensation of electrochemically generated ceric hydroxide species. In 1 M nitric acid, the rate of CeO 2 dissolution is on the same order as CeO 2 deposition, resulting in negligible amounts of CeO 2 electrodeposited at the nITO surface. The cathodic stripping of CeO 2 from the nITO substrate deposited in 0.1 M nitric acid or pH 4.8 acetate buffer follows a 2-step process where Ce(IV)-oxide is initially reduced to an unstable Ce(III)-oxide species that rapidly undergoes acid catalyzed dissolution to yield soluble Ce(III) (aq) . These findings provide a foundation for the pH and anodic potential controlled deposition of CeO 2 thin films to ITO substrates, which can aid in the development of materials composed of ceria. As a result, they can also be used to infer likely analogous actinide redox behavior and speciation at these electrodes.

Cerium↗

Photocatalyzed electron exchange between organic chromophores and hematite nanoparticles and the role of solid-state charge transport

Understanding photocatalyzed redox interactions between Fe(III)–(oxyhydr)oxide mineral nanoparticles and adsorbed chromophoric organic matter is critical for accurately predicting bioavailable iron fluxes in the euphotic zone of natural aquatic systems, and for improving the effectiveness of nano-iron-based water purification systems. However, the electron transfer processes that underpin photoreductive dissolution at particle/organic/solution interfaces occur on ultrafast timescales and thus remain difficult to probe. In this work, we report an ultrafast transient absorption spectroscopy (TAS) study of suspensions of hematite nanoplatelets (HNPs) sensitized by adsorbed rhodamine B (RhB) dye as a function of solution media and pH. The TAS results indicate a substantially longer fluorescence lifetime of RhB adsorbed on HNPs across a wide range of pH conditions, consistent with transient photoinduced electron transfer to the oxide with recombination kinetics controlled by electron migration back to the interface via small polaron hopping. Normalization of the observed kinetics to the measured surface loading of RhB at different pH values shows that the recombination rates are insensitive to environmental variables, likely controlled instead by particle properties that determine small polaron diffusion behavior.

54 ENVIRONMENTAL SCIENCES↗

The relationship between lunar metal particles and phosphate minerals

Phosphorus is often present in lunar rocks and soils in bulk concentrations in excess of 0.5 wt % P205. The minerals apatite and whitlockite account for most of the phosphorus. However, it may also be present in metal grains. The relations between metal particles and the phosphates commonly found adjacent to these particles are investigated, taking into account studies involving three Apollo 17 rocks. It appears that phosphorus in lunar metal particles is related to the phosphate minerals by a redox reaction. The independent phosphates probably formed over much of the cooling period of the rock. While the rock was at high temperature, however, phosphorus was free to diffuse and dissolve in the metal droplets providing conditions were sufficiently reducing. If the rock was partially molten, this process would take less than 1 hr. If cooling occurred slowly under less reducing conditions, some of the phosphorus in the metal particles would be oxidized to form whitlockite.

Friel, J. J.↗

The NASA Redox Storage System Development project, 1980

The technical accomplishments pertaining to the development of Redox systems and related technology are outlined in terms of the task elements: prototype systems development, application analyses, and supporting technology. Prototype systems development provides for a major procurement to develop an industrial capability to take the current NASA Lewis technology and go on to the design, development, and commercialization of iron-chromium Redox storage systems. Application analyses provides for the definition of application concepts and technology requirements, specific definition studies, and the identification of market sectors and their penetration potential. Supporting technology includes both in house and contractual efforts that encompass implementation of technology improvements in membranes, electrodes, reactant processing, and system design. The status of all elements is discussed.

Source record↗

Stabilizing Reversible Oxygen Redox Chemistry in Layered Oxides for Sodium‐Ion Batteries

Abstract Triggering oxygen‐related activity is demonstrated as a promising strategy to effectively boost energy density of layered cathodes for sodium‐ion batteries. However, irreversible lattice oxygen loss will induce detrimental structure distortion, resulting in voltage decay and cycle degradation. Herein, a layered structure P2‐type Na 0.66 Li 0.22 Ru 0.78 O 2 cathode is designed, delivering reversible oxygen‐related and Ru‐based redox chemistry simultaneously. Benefiting from the combination of strong Ru 4d‐O 2p covalency and stable Li location within the transition metal layer, reversible anionic/cationic redox chemistry is achieved successfully, which is proved by systematic bulk/surface analysis by in/ex situ spectroscopy (operando Raman and hard X‐ray absorption spectroscopy, etc.). Moreover, the robust structure and reversible phase transition evolution revealed by operando X‐ray diffraction further establish a high degree reversible (de)intercalation processes (≈150 mAh g −1 , reversible capacity) and long‐term cycling (average capacity drop of 0.018%, 500 cycles).

Cao, Xin↗

Analysis of the thermal-mechanical redox stability of Nb 2 TiO 7 and Nb 1.33 Ti 0.67 O 4 for SOFC application

Nb 2 TiO 7 and Nb 1.33 Ti 0.67 O 4 was reported as a potential anode materials for Solid Oxide Fuel Cells (SOFCs) based on their stable reversible phase transformation and high electronic conductivity. A high-temperature redox dilatometry test was developed to monitor the linear expansion or contraction of Nb 2 TiO 7 and Nb 1.33 Ti 0.67 O 4 synthesized through a solid-state route. XRD analysis confirmed the phase purity. It was found that Nb 2 TiO 7 contracts linearly up to 0.006% in a reducing atmosphere and this contraction is reversible in nature whereas Nb 1.33 Ti 0.67 O 4 expands linearly up to 1.9% in an oxidizing atmosphere which is irreversible in nature at 800 °C. In addition, the electrical conductivity of the materials was analyzed in redox atmospheres. At 800 °C, Nb 2 TiO 7 showed an electrical conductivity of 1.35 S/cm in forming gas (5%H 2 /95%N 2 ) which increases to 85 S/cm upon the reduction of Nb 2 TiO 7 to Nb 1.33 Ti 0.67 O 4 .Here this study emphasizes the importance of high-temperature redox dilatometry in the development of SOFC electrode materials.

36 MATERIALS SCIENCE↗

Roadmap for Deployment of Modularized Hydrothermal Liquefaction: Understanding the Impacts of Industry Learning, Optimal Plant Scale, and Delivery Costs on Biofuel Pricing

Hydrothermal liquefaction (HTL) is a promising technology for converting abundant organic wastes into fuels. Previous techno-economic analyses (TEAs) of HTL have been used to estimate the minimum fuel selling price (MFSP) of biofuel products, but these analyses often assume a bespoke plant design where each plant operates under unique process conditions and neglect transportation costs. However, transportation costs must be included in realistic TEAs, and further, a mass-produced fixed-scale modular plant design approach may be more effective than case-by-case plant design, provided that there is sufficient market capacity to benefit from modularization. This study estimates fuel price behavior in the presence of transportation costs and benefits stemming from modular plant design. This analysis indicates that a modular process capable of handling 60 dry tons per day (DTPD) is optimal, resulting in a ~25% reduction in MFSP (from $4.70/GGE, fully upgraded) at complete market feedstock utilization compared with case-by-case design. The associated cost reductions are attributable to learning benefits and modularization. Several HTL deployment “roadmaps” are then explored, with each roadmap consisting of different periods of case-by-case design followed by adoption of a modularized approach. A period of nonmodular industry growth up to market saturation of ~7% followed by implementation of modular plant design strikes a balance between the investment risk and learned cost reductions associated with modular plant design. However, if bespoke plants built during this period of nonmodular growth saturate more than 23% of available feedstock, learned cost reductions are significantly diminished. Here, this study points to the potential benefits of modularized and decentralized waste-to-energy processes when the modularization follows an optimal deployment strategy.

09 BIOMASS FUELS↗

Glass-contact refractory of the nuclear waste vitrification melters in the United States: a review of corrosion data and melter life

The performance of the refractory lining in glass melters used for nuclear waste vitrification is critical to the melter reliability for long-term continuous operation. Monofrax® K-3, a high Cr 2 O 3 fused cast refractory material, has been widely used to build the liners of nuclear waste glass melters in the United States. Corrosion behaviour of Monofrax® K-3 refractory has been evaluated based on crucible-scale testing, inspection of the refractory components following scaled melter testing, and inspections of the Defense Waste Processing Facility (DWPF) melter refractory after service. The literature generally consists of empirical models based on short-term testing to describe refractory corrosion dependence on glass composition. Corrosion data from tests with longer testing times, at various temperatures, in the presence of molten salts, and with different redox reactions in the plenum atmosphere exist, may be insufficient to provide accurate refractory service life estimates. Additionally, the corrosion data collected under actual and scaled melter operating conditions are limited. Recommendations to achieve more direct correlation between the laboratory refractory corrosion data predictions and the observed melter service life are discussed to allow for more accurate predictions of the useful life of melter refractory linings.

Jin, Tongan↗

Abiotic manganese oxide formation induced by light and copper-driven Fenton chemistry

Redox-active transition metals such as manganese (Mn) and copper (Cu) frequently coexist in surface water systems, where their interactions can significantly influence contaminant fate and water quality. It is widely known that the oxidation of Mn 2+ (aq) to Mn(IV) oxide solids is driven mainly by biotic processes in which Cu 2+ serves as an inhibitor of Mn oxidation. However, Cu 2+ can also trigger Fenton reactions to produce reactive oxygen species (ROS) capable of promoting the abiotic Mn oxidation (i.e., without the involvement of biological organisms), through an alternative natural pathway that remains overlooked in water. In this study, we found that the abiotic oxidation of Mn 2+ can be facilitated by the co-existence of sunlight and Cu 2+ . By contrasting Cu 2+ with other divalent cations, such as Ca 2+ , Mg 2+ , and Zn 2+ , this investigation highlights the distinct role of Cu 2+ in promoting Mn oxidation. Moreover, the study elucidated how light induces ROS to trigger Cu-driven photo-Fenton reactions and identified the roles of ROS in Mn oxidation. Chemical-Fenton reactions (i.e., the interaction between Cu and H 2 O 2 in the absence of light) were also examined for their contribution to the Cu-driven Mn photo-oxidation, supporting the involvement of Fenton chemistry in Mn oxidation. By elucidating the novel photochemical mechanism of Mn oxide formation, our findings advance the understanding of heavy metal interactions in aqueous environments and highlight the intricate roles of Cu 2+ in affecting elemental cycling and the evaluation of heavy metal contamination in water resources. This discovery also underscores the critical contribution of co-existing Fenton-active metals in forming Mn oxide solids.

Abiotic Mn oxidation↗

Co-sputtering of lithium vanadium oxide thin films with variable lithium content to enable advanced solid-state batteries

Advanced solid-state batteries most likely will entail aggressive structures or architectures with constraints that typically limit processing temperatures. Considering this, we have identified the importance of providing lithiated electrode materials at a modest processing temperature. Here we describe a pathway to meet this by the development of a co-sputtering process using lithium oxide and vanadium oxide targets which enables the growth of lithiated vanadium oxide (LVO) thin films for application in solid-state batteries. Analysis of the structure and film composition of samples deposited with different co-sputtering rate ratios and post-annealing shows that multiple phases of Li x V 2 O 5 likely coexist (i.e. α-, ε-, δ-, and γ-V 2 O 5 ), and that this is unchanged after electrochemical cycling. The co-sputtering process can tune the lithium content up to a highly lithiated state of at least Li 2 V 2 O 5 . Electrochemical half-cells showed a significant amount of lithium available on the first charge (delithiation of LVO). LVO samples post-annealed at 300 °C showed typical redox peaks for Li x V 2 O 5 for both one and two lithium insertion reactions, which were highly reversible in most cases. A thin-film solid-state battery prototype using LVO as a cathode had 20% of the expected capacity, although the coulombic efficiency is near 100% at a fast rate (22C). As a result, this co-sputtering technique represents an opportunity for low temperature synthesis of pre-lithiated cathodes for thin film batteries, and introduces a broader methodology of depositing metal oxides with different alkali metal contents.

25 ENERGY STORAGE↗

Soil and groundwater environmental sensor data, Wax Lake Delta, Louisiana, March 2023 - March 2024

This study evaluates how environmental parameters that integrate biogeochemical processes vary with water table fluctuations in the freshwater Wax Lake Delta (WLD) in Louisiana, U.S.A. This data package contains seven *.csv files and one Excel file that compiles all the data from the individual .csv files. This dataset reports high frequency (15-min) observations of water level, soil redox potential, specific conductance, and pH made for one year along elevation transects located on the older, proximal (OT) and younger, distal (YT) ends of a deltaic island. Water depth relative to the ground surface (cm; HOBO U20L-04; error ± 0.4 cm), water pH and temperature (HOBO MX2501), and specific conductance and temperature (HOBO U24-001) sensors were installed in March 2023. Water depth was corrected for barometric pressure recorded by a separate logger secured to a platform above the highest water level. Soil redox probes (SWAP ORP-40-4-B) were also installed in March 2023. Each probe had four Pt sensors (2 mm width) placed at 10 cm, 20 cm, 30 cm, and 40 cm below the ground surface. Redox data were referenced to an external Ag0/AgCl (3M KCl) reference probe placed in saturated ground and recorded on CR1000X dataloggers (Campbell Scientific) powered by solar panels. A second reference probe was positioned near the primary reference probe for backup and data correction. The tops of the soil redox probes and soil moisture probes were flush with the soil surface so that sensors are reported at their indicated depths below ground surface. Here, we report data collected between 15 March 2023 to 15 March 2024 for all sensors, with some differences due to exact dates of sensor placement or data gaps associated with sensor malfunction. For example, water depth at OT4 was not recorded between March to November 2023. Data flags indicate whether a value is valid (1) or was excluded from data analysis in the associated manuscript (-1).

EARTH SCIENCE > LAND SURFACE > SOILS↗

Monolayer-enriched production of Au-decorated WS 2 Nanosheets via Defect Engineering

Layered transition metal dichalcogenides (TMDs) represent a diverse, emerging source of two-dimensional (2D) nanostructures with broad application in optoelectronics and energy. Chemical functionalization has evolved into a powerful tool to tailor properties of these 2D TMDs; however, functionalization strategies have been largely limited to the metallic 1T-polytype. The work herein illustrates that 2H-semiconducting liquid-exfoliated tungsten disulfide (WS 2 ) undergoes a spontaneous redox reaction with gold (III) chloride (AuCl 3 ). Au nanoparticles (NPs) predominantly nucleate at nanosheet edges with tuneable NP size and density. AuCl 3 is preferentially reduced on multi-layer WS 2 and resulting large Au aggregates are easily separated from the colloidal dispersion by simple centrifugation. This process may be exploited to enrich the dispersions in laterally large, monolayer nanosheets. It is proposed that thiol groups at edges and defects sides reduce the AuCl 3 to Au 0 and are in turn oxidized to disulfides. Optical emission, i.e. photoluminescence, of the monolayers remained pristine, while the electrocatalytic activity towards the hydrogen evolution reaction is significantly improved. Taken together, these improvements in functionalization, fabrication, and catalytic activity represent an important advance in the study of these emerging 2D nanostructures.

36 MATERIALS SCIENCE↗

Clouding of pyroxene and plagioclase in eucrites - Implications for post-crystallization processing

The clouding of pyroxene and plagioclase in the basaltic eucrites ALHA 77302, Juvinas, Pasamonte, and Stannern, is caused by finely disseminated inclusions. This clouding is interpreted to be the result of exsolution of minor components which became incompatible and crystallized on microfractures and other nucleation sites during postbrecciation metamorphism. The phases found in clouding require reduction of silicate FeO to metallic Fe in both pyroxene and plagioclase and possible redox of Cr(2+) to Cr(3+) in pyroxene. The assemblage of coexisting phases that make up clouding record conditions of T approximately equal to 900 C and f(O2) of 10 to the -16th to 10 to the -18th during slow cooling. Thus, clouding can be a useful indicator of postcrystallization conditions.

Harlow, G. E.↗

Cyanobacterial circadian regulation enhances bioproduction under subjective nighttime through rewiring of carbon partitioning dynamics, redox balance orchestration, and cell cycle modulation

Abstract Background The industrial feasibility of photosynthetic bioproduction using cyanobacterial platforms remains challenging due to insufficient yields, particularly due to competition between product formation and cellular carbon demands across different temporal phases of growth. This study investigates how circadian clock regulation impacts carbon partitioning between storage, growth, and product synthesis in Synechococcus elongatus PCC 7942, and provides insights that suggest potential strategies for enhanced bioproduction. Results After entrainment to light-dark cycles, PCC 7942 cultures transitioned to constant light revealed distinct temporal patterns in sucrose production, exhibiting three-fold higher productivity during subjective night compared to subjective day despite moderate down-regulation of genes from the photosynthetic apparatus. This enhanced productivity coincided with reduced glycogen accumulation and halted cell division at subjective night time, suggesting temporal separation of competing processes. Transcriptome analysis revealed coordinated circadian clock-driven adjustment of the cell cycle and rewiring of energy and carbon metabolism, with over 300 genes showing differential expression across four time points. The subjective night was characterized by altered expression of cell division-related genes and reduced expression of genes involved in glycogen synthesis, while showing upregulation of glycogen degradation pathways, alternative electron flow components, the pentose phosphate pathway, and oxidative decarboxylation of pyruvate. These molecular changes created favorable conditions for product formation through enhanced availability of major sucrose precursors (glucose-1-phosphate and fructose-6-phosphate) and maintained redox balance through multiple mechanisms. Conclusions Our analysis of circadian regulatory rewiring of carbon metabolism and redox balancing suggests two potential approaches that could be developed for improving cyanobacterial bioproduction: leveraging natural circadian rhythms for optimizing cultivation conditions and timing of pathway induction, and engineering strains that mimic circadian-driven metabolic shifts through controlled carbon flux redistribution and redox rebalancing. While these strategies remain to be tested, they could theoretically improve the efficiency of photosynthetic bioproduction by enabling better temporal separation between cell growth, carbon storage accumulation, and product synthesis phases.

59 BASIC BIOLOGICAL SCIENCES↗

Manganese Oxidation States in Volcanic Soils across Annual Rainfall Gradients

Manganese (Mn) exists as Mn(II), Mn(III), or Mn(IV) in soils, and the Mn oxidation state controls the roles of Mn in numerous environmental processes. However, the variations of Mn oxidation states with climate remain unknown. Here we determined the Mn oxidation states in highly weathered bulk volcanic soils (primary minerals free) across two rainfall gradients covering mean annual precipitation (MAP) of 0.25–5 m in the Hawaiian Islands. With increasing MAP, the soil redox conditions generally shifted from oxic to suboxic and to anoxic despite fluctuating at each site; concurrently, the proportions of Mn(IV) and Mn(II) decreased and increased, respectively. Mn(III) was low at both low and high MAP, but accumulated substantially, up to 80% of total Mn, in soils with prevalent suboxic conditions at intermediate MAP. Mn(III) was likely hosted in Mn(III,IV) and iron(III) oxides or complexed with organic matter, and its distribution among these hosts varied with soil redox potentials and soil pH. Soil redox conditions and rainfall-driven leaching jointly controlled exchangeable Mn(II) in soils, with its concentration peaking at intermediate MAP. The Mn redox chemistry was at disequilibrium, with the oxidation states correlating with long-term average soil redox potentials better than with soil pH. The soil redox conditions likely fluctuated between oxic and anoxic conditions more frequently at intermediate than at low and high MAP, creating biogeochemical hot spots where Mn, Fe, and other redox-sensitive elements may be actively cycled.

36 MATERIALS SCIENCE↗

In situ atomic-resolution imaging of water vapor–driven multistep oxidation dynamics in strontium cobaltite

Understanding how water vapor interacts with transition metal oxides (TMOs) is critical for tailoring material properties to improve performance and enable new technologies. Despite extensive research efforts, atomic-scale mechanisms underpinning dynamic reactions and reaction-induced phase transitions remain elusive. Here, we use in situ environmental transmission electron microscopy to investigate how water vapor oxidizes vacancy-ordered SrCoO 2.5 at moderately elevated temperatures, demonstrating that water molecules can initiate oxidation more effectively than oxygen under comparable conditions. We discover a distinct “staging” behavior during the oxidation process: A fully ordered intermediate phase, SrCoO 2.75 , forms before transitioning into a near-perovskite SrCoO 3−δ . In addition, antiphase boundaries, originating at step terraces of SrTiO 3 , alleviate strain by creating reversible nanoscale “gaps” during lattice contraction under oxidation, providing a pathway for preserving structural integrity throughout redox cycling. This work provides atomic-level guidance for engineering TMOs by leveraging water vapor to control their redox behavior and tailor functional properties.

Science & Technology - Other Topics↗