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At least 145 records · Page 8

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↗

Electrochemical Behaviors of Bilayer Oxygen Electrode for Reversible Solid Oxide Cells

Reducing the resistances of oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) while retaining the stability of an oxygen electrode, even in the presence of air contaminants such as Cr, H2O and CO2, is of paramount importance to the current commercial development of intermediate-temperature reversible solid oxide cells (IT-RSOCs). In this presentation, a multifunctional, coarsening-resistant, air-contaminants-tolerant and yet ORR/OER-active oxygen electrode (OE) for IT-RSOCs is described. The testing results show that new bilayer OE exhibits a much better ORR/OER activity and stability than the single-layer benchmark LSCF-GDC OE. Remarkably, the new bilayer OE also demonstrates an exceptionally high resistance to Cr-attack, a critical issue to the development of commercial meal-interconnect loaded SOFC/SOEC stacks/systems. Theoretical analysis is also presented to understand the fundamental reasons for the improved ORR/OER activity and stability observed under real-world operating conditions.

Huang, Kevin↗

Controlling Oxidation of Nb in Oxygen Abundant Environments

Modern particle accelerators depend on Superconducting Radio Frequency (SRF) cavities made from high-purity niobium (Nb) to achieve optimal performance, including high quality factors and strong accelerating gradients. However, when exposed to air, niobium naturally forms a complex oxide layer that can introduce surface imperfections and carbon contamination. This work examines an alternative oxidation strategy under oxygen-rich conditions to better regulate the oxide formation process. The ultimate objective is to improve surface uniformity and cleanliness, thereby reducing defect density and enhancing performance. We used Confocal Microscopy, Scanning Electron Microscopy (SEM), and X-Ray Photoelectron Spectroscopy (XPS) to analyze surface changes. We used standard metrics, like Arithmetic Average Roughness (Ra) and Root Mean Square (Rq). Three oxidation methods were applied: short, extended, and a repeated HF and H₂O₂ oxidation process. Preliminary results show promising reductions in carbon contamination and surface defects.

Romero, Juan [Fermilab]↗

Oxygen Evolution on Iron Oxide Nanoparticles: The Impact of Crystallinity and Size on the Overpotential

The oxygen evolution reaction (OER) is a critical reaction in electrolysis and photoelectrolysis of water to generate and store clean energy. Therefore, the development of low-cost and efficient electrocatalysts for the OER is of great scientific and technological importance. Although promising iron oxide-based electrocatalysts have been recently developed for the OER, an in-depth experimental and theoretical analysis of the OER mechanism on iron oxide-based electrocatalysts is still needed to provide guidelines to optimize the performance of iron oxide-based electrocatalysts further. To address this need, we synthesized a series of monodisperse iron oxide nanoparticles to analyze their intrinsic OER activities. Using nanoparticles of the same size but different crystallinity, we show that amorphous iron oxide nanoparticles have better OER activity than crystalline ones. The size effect studies further revealed that the edge/defect sites are the active sites for the OER. Density functional theory calculations demonstrated that the edge/defect sites provide bridge sites to adsorb OER intermediates, resulting in low OER overpotential. These calculations confirm that the high OER activity of amorphous nanoparticles results from a high concentration of defect sites on their surface. These results provide novel strategies to increase the performance of iron oxide-based and likely other oxide-based OER electrocatalysts.

Electrochemistry↗

Controlling Oxidation of Nb in Oxygen Abundant Environments.

Superconducting Radio Frequency (SRF) cavities, the core of modern particle accelerators, rely on high-purity niobium (Nb) to achieve high quality factors and accelerating gradients. However, native oxidation in ambient conditions introduces a complex oxide layer with increased surface defects and contamination, particularly from carbon. This research explores a controlled oxidation processes in an oxygen-abundant environment to try to control this complex oxide stack, with the goal of improving surface purity and uniformity. Using standard surface preparation techniques—including electropolishing, vacuum baking, and sonication—followed by a custom oxidation protocol, we compared structural and chemical changes through Confocal Microscopy, Scanning Electron Microscopy (SEM), and X-Ray Photoelectron Spectroscopy (XPS). Results show that iterative oxidation cycles can significantly reduce carbon-related defects, even without baking. Aditionally, baked samples with a specific oxidation technique demonstrated a measurable 25\% decrease in carbide formation.

Romero, Juan [Fermilab]↗

Quantification of Oxygen Vacancies in SrFe0.5Cr0.5O3−δ Thin Films: Correlating Lattice Expansion with Oxidation State Variability

Oxygen vacancies (VO), even in the dilute regime, can significantly impact the physical and chemical properties of complex oxides. It is however challenging to reliably detect and adequately quantify such defects in thin film samples where the VO concentration and distribution may further vary in response to interfacial strain. Here, we present a method to quantify VO concentrations in SrFe0.5Cr0.5O3−δ (SFCO) epitaxial thin films. Through coherent Bragg rod analysis, X-ray absorption spectroscopy, and theoretical modeling, we systematically correlate the c-axis lattice expansion detected in SFCO films with a VO concentration gradient. Our results reveal a nearly linear relationship between oxygen off-stoichiometry and out-of-plane lattice expansion in coherently strained SFCO films, with δ increasing from 0.32 to 0.52 and the lattice expanding by ∼1.0%. Moreover, a significant decrease in Cr oxidation state (from Cr5+ to Cr3+) is observed as the VO concentration increases, while the Fe oxidation state remains fixed at Fe3+. Our findings provide a reliable way to quantify oxygen stoichiometry in complex oxides, offering a pathway to design materials with precisely tailored structure–property relationships.

Hossain, Mohammad Delower↗

Cobalt-substituted perovskite compounds for solid oxide electrochemical cells

Oxygen electrodes are provided, comprising a perovskite compound having Formula (I), Sr(Ti 1-x Fe x-y Co y )O 3-δ wherein 0.90 ≥ x ≥ 0.40 and 0.02 ≥ y ≥ 0.30. Electrochemical devices comprising such oxygen electrodes are also provided, comprising a counter electrode in electrical communication with the oxygen electrode, and a solid oxide electrolyte between the oxygen electrode and the counter electrode. Methods of using such electrochemical devices are also provided, comprising exposing the oxygen electrode to a fluid comprising O 2 under conditions to induce the reaction O 2 +4e − →2O 2− , or to a fluid comprising O 2− under conditions to induce the reaction 2O 2− →O 2 +4e − .

Zhang, Shan-Lin↗

Oxygen Loss in Layered Oxide Cathodes for Li-Ion Batteries: Mechanisms, Effects, and Mitigation

Layered lithium transition metal oxides derived from LiMO 2 (M = Co, Ni, Mn, etc.) have been widely adopted as the cathodes of Li-ion batteries for portable electronics, electric vehicles, and energy storage. Oxygen loss in the layered oxides is one of the major factors leading to cycling-induced structural degradation and its associated fade in electrochemical performance. Herein, we review recent progress in understanding the phenomena of oxygen loss and the resulting structural degradation in layered oxide cathodes. We first present the major driving forces leading to the oxygen loss and then describe the associated structural degradation resulting from the oxygen loss. Here, we follow this analysis with a discussion of the kinetic pathways that enable oxygen loss, and then we address the resulting electrochemical fade. Finally, we review the possible approaches toward mitigating oxygen loss and the associated electrochemical fade as well as detail novel analytical methods for probing the oxygen loss.

36 MATERIALS SCIENCE↗

Untangling the sequence of events during the S 2 → S 3 transition in photosystem II and implications for the water oxidation mechanism

In oxygenic photosynthesis, light-driven oxidation of water to molecular oxygen is carried out by the oxygen-evolving complex (OEC) in photosystem II (PS II). Recently, we reported the room-temperature structures of PS II in the four (semi)stable S-states, S 1 , S 2 , S 3 , and S 0 , showing that a water molecule is inserted during the S 2 → S 3 transition, as a new bridging O(H)-ligand between Mn1 and Ca. To understand the sequence of events leading to the formation of this last stable intermediate state before O 2 formation, we recorded diffraction and Mn X-ray emission spectroscopy (XES) data at several time points during the S 2 → S 3 transition. At the electron acceptor site, changes due to the two-electron redox chemistry at the quinones, Q A and Q B , are observed. At the donor site, tyrosine Y Z and His190 H-bonded to it move by 50 µs after the second flash, and Glu189 moves away from Ca. This is followed by Mn1 and Mn4 moving apart, and the insertion of O X (H) at the open coordination site of Mn1. This water, possibly a ligand of Ca, could be supplied via a “water wheel”-like arrangement of five waters next to the OEC that is connected by a large channel to the bulk solvent. XES spectra show that Mn oxidation (τ of ∼350 µs) during the S 2 → S 3 transition mirrors the appearance of O X electron density. This indicates that the oxidation state change and the insertion of water as a bridging atom between Mn1 and Ca are highly correlated.

59 BASIC BIOLOGICAL SCIENCES↗

Modeling Dynamic Evolution of Oxygen Vacancies in Solid Oxide Materials

SOEC is a promising H 2 generation technology for mitigating climate change. Novel material design and optimization strategies, such as oxygen vacancy chemistries, can enhance SOEC efficiency. In this study, Monte Carlo-ReaxFF and eReaxFF simulations were used to study oxygen vacancies (O v ) and electron migration in BZY20 solid oxide material. Our results shows that O v migrate towards the surface, increasing surface O v concentration by 10%. Yttrium restricts electron mobility and functions as an electron trapping site, while Zr accelerates electron mobility and migration. These insights could improve solid-state electrolytes’ electrochemical performance in renewable energy applications.

13 HYDRO ENERGY↗

Heat Integration Optimization and Dynamic Modeling Investigation for Advancing the Coal-Direct Chemical Looping Process

The purpose of the project is to address the optimization and startup operation of a modular coal direct chemical looping (CDCL) combustion system integrated with a steam cycle for power generation to reduce the risks involved in further scale-up of the technology. The modular reactor design of the CDCL process provides flexibility in the fabrication of the reactor and in its operating capacity (i.e. turndown ratio) at the cost of a more complex heat exchange network (HEN) design and integration. To address the technology gaps and advance the efficiency and economic feasibility of the CDCL technology, the project will perform a detailed and comprehensive analysis of the integration of a modular CDCL reactor system and a steam cycle system under both static and transient conditions via HEN process performance simulations and system dynamic modeling, respectively. The scope of work consists of 1) Experimental and computational studies of the CDCL combustor reactor 2) Comprehensive static (i.e. steady-state) system HEN design analysis in CDCL 550 MWe commercial unit for power generation and 3) Dynamic modeling of site specific design of 10MWe CDCL large pilot plant. The project team has successfully developed and validated a kinetic model for the oxidation of oxygen carriers in the combustor using the unreacted shrinking core model (UCSM). The model is capable of capturing the oxidation kinetics of fully or partially reduced oxygen carrier particles. A computational fluid dynamics (CFD) model is developed to simulate the hydrodynamics, heat transfer, and chemical reaction occurring in the CDCL combustor. The model is developed in MFIX and ANSYS Fluent. Key aspects of CDCL combustor operation, including heat transfer, oxygen carrier oxidation, and the transport of oxygen carrier particles, are simulated using this CFD model. The HEN for a commercial scale 550 MWe CDCL power plant is simulated and optimized using ASPEN Plus. Practical design considerations are incorporated based on industrial experiences. The performance and cost for the commercial CDCL plant is updated based on these analyses. A dynamic model for the 10 MWe CDCL pilot plant is developed in ProTRAX simulation software. The model is based on the pilot plant design developed in project DE-FE0027654 “10 MWe CDCL Large Pilot Plang – Pre-FEED Study” and the steam cycle data obtained from Dover Light & Power plant. The transient behaviors during pilot plant load variation are simulated using the dynamic model.

01 COAL, LIGNITE, AND PEAT↗

Atomic-Scale Interface for Pt Nanoparticles on SrTiO 3 (001)

The interfacial structure formed by Pt nanoparticles grown epitaxially on a SrTiO 3 (001) surface by pulsed laser deposition was studied by X-ray standing-wave (XSW) excited core-level photoelectron emission. The XSW-generated 3D atomic map of the Pt and interfacial oxygens for the oxidized Pt/SrTiO 3 interface differs significantly from that of the as-deposited interface. After oxidation, the Pt atoms shifted upward and their atomic occupation at fcc-like sites evolved as the oxidation temperature increased. Interfacial oxygen atoms were differentiated from bulk O atoms by the chemical shift in the binding energy of their 1s electrons. After oxidation, the interfacial oxygen atoms rearranged to form a TiO 2 bilayer at the interface. Furthermore, these results provide a more complete description of the strong metal–support interaction process at the interface.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Spin-Selective Oxygen Evolution Reaction in Chiral Iron Oxide Nanoparticles: Synergistic Impact of Inherent Magnetic Moment and Chirality

Electron spin polarization is identified as a promising avenue for enhancing the oxygen evolution reaction (OER), which is the bottleneck that limits the energy efficiency of water-splitting. Here, in this work, we report that both ferrimagnetic (f-Fe 3 O 4 ) and superparamagnetic iron oxide (s-Fe 3 O 4 ) catalysts can exhibit external magnetic field (Hext)-induced OER enhancement, and the activity is proportional to their intrinsic magnetic moment. Additionally, the chirality-induced spin selectivity (CISS) effect was utilized in synergy with Hext to get a maximum enhancement of up to 89% improvement in current density (at 1.8 V vs RHE) with a low onset potential of 270 mV in s-Fe 3 O 4 catalysts. Spin polarization and the resultant spin selectivity suppress the production of H 2 O 2 and promote the formation of ground state triplet O 2 during the OER. Furthermore, the design of chiral s-Fe 3 O 4 with synergistic spin potential effect demonstrates a high spin polarization of ∼42%, as measured using conductive atomic force microscopy (c-AFM).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Engineering Active Surface Oxygen Sites of Cubic Perovskite Cobalt Oxides toward Catalytic Oxidation Reactions

Unraveling the role of surface oxygen sites in transition metal oxides during catalytic reactions has always been the focus of environmental and energy chemistry research. For this work, active surface oxygen sites of cubic perovskite cobalt oxide were engineered to comprehend their crucial role and catalytic mechanism at the molecular level. By removing those inert Sr/La–O termination layers, active oxygen sites were exposed on the Co terminated surface of Sr 0.6 La 0.4 CoO 3–δ that furnished the dominant catalytic process of CO oxidation via the Mars–van Krevelen (MvK) mechanism. The fabrication of five-coordinate cobalt ions and the enhanced covalency of Co–O bonds not only optimize the surface electronic structure of Co 3d–O 2p, but also supply active surface oxygen sites, which effectively oxidizes CO to CO 2 with a significantly improved oxidation performance and stability as evidenced by soft/hard XAS, XPS, and O 2 -TPD. Furthermore, online isotopic 18 O 2 mass spectrometry, in situ DRIFTS, and theoretical simulation demonstrate that the activity of surface oxygen sites enhances the kinetics of the MvK reaction, while unsaturated coordination sites from five-coordinate cobalt ions primarily contribute to the activated oxygen molecules and the stable catalytic cycle. The results reported here provide a deep insight into the comprehension of the relationships among active oxygen sites, surface electronic structure, and the reaction mechanism of transition metal oxides necessary for catalytic oxidation reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Unraveling Fundamental Activity–Stability Relationships in Rutile Oxides

The oxygen evolution reaction (OER) is a key anodic half-cell reaction that accompanies several critical electrochemical reduction reactions of interest to a variety of applications. Despite steady advances in understanding and qualitatively predicting OER activity and selectivity trends, a comprehensive description or prediction of material aqueous (in)stability and degradation mechanisms remains elusive, even though these processes critically influence device lifetime and economic feasibility. In this work, we investigate the interplay, or lack thereof, between OER activity and material aqueous stability across rutile oxides, with a particular focus on iridium oxide (IrO 2 ). By applying a Born–Haber cycle, we calculate the thermodynamic driving force for metal dissolution as a function of the applied bias and electrolyte conditions. We apply interpretable machine learning techniques, including principal component analysis and symbolic regression, to analyze trends across rutile oxides and find that key thermodynamic descriptors for OER activity and surface stability are only very weakly correlated. Instead, the local atomic environment─especially electronic structure signatures for interactions between the active site and its neighbors─plays a more important role in predicting material stability. Leveraging these insights, we investigate the impact of doping IrO 2 with a range of transition metals and show that the stability of Ir active sites can be tuned largely independently of its predicted OER activity. These insights lay the foundation for material design to improve stability with respect to corrosion, with the ultimate aim to enhance long-term stability without sacrificing catalytic performance in the OER.

evolution reactions↗

Theoretical understanding of stability of the oxygen electrode in a proton-conductor based solid oxide electrolysis cell

The oxygen electrode in a proton-conductor based solid oxide cells is often a triple-conducting material that enables the transport and exchange of electrons (e - ), oxygen ions (O 2- ), and protons (H + ), thus expanding active areas to enhance the oxygen electrode activity. In this work, a theoretical model was developed to understand stability of tri-conducting oxygen electrode by studying chemical potentials of neutral species (i.e., μ o 2 , μ H 2 , and μ H 2 O ) as functions of transport properties, operating parameters, and cell geometry. Our theoretical understanding shows that (1): In a conventional oxygen-ion based solid oxide cell, a high μ o 2 (thus high oxygen partial pressure) exists in the oxygen electrode during the electrolysis mode, which may lead to the formation of cracks at the electrode/electrolyte interface. Further, while in a proton-conductor based solid oxide cell, the μ o 2 is reduced significantly, suppressing the crack formation, and resulting in improved performance stability (2). In a typical proton-conductor based solid oxide electrolyzer, the dependence of μ o 2 on the Faradaic efficiency is negligible. Hence, approaches to block the electronic current can improve the electrolysis efficiency while achieving stability (3). The difference of the μ o 2 (thus p o 2 ) between the oxygen electrode and gas phase can be reduced by using higher ionic conducting components and improving electrode kinetics, which lead to further improvement of electrode stability.

08 HYDROGEN↗

10 MWE CDCL Large Pilot Plant – pre-FEED Study

Coal Direct Chemical Looping (CDCL) is an advanced oxy-combustion technology that has the potential to substantially reduce the energy penalty and the cost of electricity (COE) for coal-fired power generation with CO₂ capture. The Babcock & Wilcox Company (B&W) and The Ohio State University (OSU) have been collaborating on the development of an iron oxide oxygen-carrier based chemical looping technology for clean power generation with inherent carbon capture. In this process, coal is dried and pulverized prior to being transported into a moving-bed reducer. In the reducer, coal reacts with the oxygen-carrier particles, forming combustion byproducts, predominantly CO₂ and H₂O, while reducing the iron oxide oxidation state from Fe₂O₃ to a mixture of FeO and Fe. The reduced state particles are then transported to a combustor reactor and re-oxidized with air. Following the oxidation, the oxygen-carrier particles are regenerated, and a large amount of heat is released for steam production. The produced steam is sent to a turbine for electricity generation. Meanwhile, the CO₂–rich stream leaving the reducer is cooled, cleaned, and compressed for subsequent pipeline transportation and sequestration. By combining air separation and fuel conversion into a single system, the CDCL technology enables the intensification of oxy-combustion processes by eliminating the energy and cost intensive cryogenic air separation unit and thereby results in higher overall plant efficiencies and lower COE’s. The use of a moving-bed reducer results in high conversions of volatile hydrocarbons and high CO₂ purity, which reduces the cost of downstream CO₂ purification for sequestration or utilization. The Babcock & Wilcox Company in collaboration with The Ohio State University, Johnson & Matthey, The Electric Power Research Institute, and Dover Light & Power completed a Preliminary Front-End Engineering and Design (Pre-FEED) study of a 10 MWe coal-direct chemical looping (CDCL) pilot plant. The planned system is a modular 10 MWe CDCL large pilot facility consisting in 4 modules of 2.5 MWe each, working in parallel and to be hosted within the current structure at the City of Dover’s Municipal Power Plant. The CDCL system can achieve auto-thermal operation and includes a sub-critical steam cycle for power generation. The pilot system was designed to demonstrate full commercial operation at a reduced scale. The coal distribution per plan area is a representative slice of larger commercial arrangements. The system includes a CO₂ recycle system, but it does not include a compression system. The large pilot includes all the environmental control equipment and oxygen carrier and ash handling systems. As part of the project, the Team performed laboratory testing and carried out multiple pilot test campaigns to obtain design and performance information at the 250 kWth CDCL pilot facility at the Babcock & Wilcox Company’s Research Center. The Team demonstrated sustained operations at designed coal inputs, high coal conversion, high CO₂ purity, heat generation on the combustor, low carbon carryover between reactors and low particle attrition. Emissions generated in the reducer reactor were identified as SO₂ and NO x . The commercial manufacturing cost of oxygen carrier particle was evaluated by JM. A particle manufacturing report was generated and submitted to the DOE. Based on the results from the pilot tests and the pre-FEED design efforts, a techno-economic analysis was performed. The study shows that the CDCL process is a promising carbon-friendly technology capable of producing electricity with high efficiency. The estimated COE of the supercritical CDCL plant is $83.3 / MWh, which meets DOE’s target of less than 30% increase in COE when compared to a supercritical PC plant without CO₂ capture. This is the lowest among the existing carbon capture technologies (post-combustion and oxy-combustion) for fossil fuel power plant. CDCL is evaluated to be the most promising technology for carbon capture from the economic aspect.

01 COAL, LIGNITE, AND PEAT↗