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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 289 records · Page 16

CyRRL (Cyber Resilient Reinforcement Learning for grid voltage control) [SWR-24-115]

This codebase contains a multi-agent, actor-critic reinforcement learning implementation for cyber-resilient grid voltage control. It uses a 123-bus OpenDSS system as the environment, with three-phase power flow translating nodal power injections into solved nodal voltages. The reward function penalizes deviations from nominal voltage as well as reactive power dispatch, while encouraging agents to take actions that result in fast convergence to nominal conditions. The codebase models false data injection attacks and includes functionality for training, testing, hyper-parameter tuning, and visualization.

Murphy, Sinnott [National Renewable Energy Laborat↗

Real-Time Atomic-Scale Structural Analysis Resolves the Amorphous to Crystalline CaCO 3 Mechanism Controversy

Amorphous calcium carbonate (ACC) occurs as a precursor to geological and biogenic calcium carbonate (CaCO 3 ), yet its transformation pathways and reaction mechanisms remain inconsistent and controversial. In this study, we investigated the transformation of ACC to calcite under both solution and dry conditions, in the presence and absence of impurity ions, utilizing operando time-resolved synchrotron X-ray diffraction (TRXRD) and reactive transport modeling. Results demonstrate that TRXRD techniques allow us to differentiate dissolution-reprecipitation versus solid-state transformation mechanisms for amorphous to crystalline phase transitions. Specifically, we observe that in environments with abundant water, ACC transforms to calcite through a dissolution-reprecipitation mechanism. This features an activation energy of 63 ± 2 kJ/mol and unit cell volume contraction during calcite crystal growth. Conversely, under water-limited conditions, ACC to calcite transformation proceeds via a solid-state transformation mechanism, with an activation energy of 210 ± 2 kJ/mol, three times greater than the dissolution-reprecipitation route, and a unit cell expansion during crystalline calcite growth. Further, to illustrate the magnitude of these effects, the rates of calcite growth were similar during dissolution-reprecipitation at 3 °C [0.00207(35) s –1 ] and solid-state transformation at 280 °C [0.00134(11) s –1 ]. Moreover, the incorporation of an impurity, strontium, significantly retards the rate of calcite growth while expanding its unit cell but whose incorporation is history dependent. Reactive transport modeling of the dissolution–precipitation kinetics suggests that ACC must be dissolving as compact aggregates. These various transformation mechanisms drive diverse geological and biological carbonate formations, impacting their use as paleoenvironmental markers and functional materials synthesis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Aerosol Optical Tweezers Elucidate the Chemistry, Acidity, Phase Separations, and Morphology of Atmospheric Microdroplets

Aerosol particles represent unique chemical environments because of their high surface area-to-volume ratio that promotes the effects of interfacial chemistry in confined environments. Properties such as viscosity, diffusivity, water content, pH, and morphology—following liquid–liquid phase separation—can strongly alter how a particle interacts with condensable vapors and reactive trace gases, thus modifying its continual evolution and environmental effects. Our understanding of this chemical evolution of atmospheric particulate matter and its environmental impacts is largely limited by our ability to directly observe how these critical particle properties respond to the addition or reactive uptake of new chemical components. Aerosol optical tweezers (AOT) stably trap particles in focused laser beams, providing positional control and the retrieval of many of these critical properties required to understand and predict the chemistry of aerosolized microdroplets. The analytical power of the AOT stems from the retrieval of the cavity-enhanced Raman spectrum induced by the trapping laser. Analysis of the whispering gallery modes (WGMs) that resonate as a standing wave around the droplet’s interface, provide high accuracy measurements of the droplet’s size, refractive index (and thus a measurement of composition), and can distinguish between core–shell, partially engulfed, and homogeneous morphologies. In this study, we have advanced the ability to determine the properties of the core and shell phases in biphasic droplets, including obtaining high-accuracy pH measurements. These capabilities were applied to perform AOT physical chemistry experiments on authentic secondary organic aerosol (SOA) produced directly in the AOT chamber by ozonolysis of terpene vapors. The propensity of the SOA to phase separate as a shell from a wide range of nonpolar to polar core phases was observed, along with the discovery of a stable emulsified state of SOA particles in an aqueous salt droplet. Micron-thick SOA shells did not impede the gain or loss of water or squalane from the core to the surrounding air, indicating no significant diffusional limitations to condensational growth or partitioning even under dry conditions. These experiments formed the foundation of a new framework that predicts how the phase-separated morphology of complex aerosols containing organic carbon evolves during continual atmospheric oxidation processes. Increases in oxidation state will quickly drive conversion from a partially engulfed to core–shell morphology that has dramatically different chemical reactivity since the core phase is completely concealed by the shell. The recent advances in the experimental capabilities of the AOT technique such as presented here enable novel experimental methodologies that provide insights into the chemistry and multidimensional properties of aerosol microdroplets, and how these coevolve and respond to continual chemical reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

57 Fe nuclear resonance vibrational spectroscopic studies of tetranuclear iron clusters bearing terminal iron( III )–oxido/hydroxido moieties

57 Fe nuclear resonance vibrational spectroscopy (NRVS) has been applied to study a series of tetranuclear iron ([Fe 4 ]) clusters based on a multidentate ligand platform (L 3− ) anchored by a 1,3,5-triarylbenzene linker and pyrazolate or (tertbutylamino)pyrazolate ligand (PzNH t Bu − ). These clusters bear a terminal Fe(III)–O/OH moiety at the apical position and three additional iron centers forming the basal positions. The three basal irons are connected with the apical iron center via a μ 4 -oxido ligand. Detailed vibrational analysis via density functional theory calculations revealed that strong NRVS spectral features below 400 cm −1 can be used as an oxidation state marker for the overall [Fe 4 ] cluster core. The terminal Fe(III)–O/OH stretching frequencies, which were observed in the range of 500–700 cm −1 , can be strongly modulated (energy shifts of 20–40 cm −1 were observed) upon redox events at the three remote basal iron centers of the [Fe 4 ] cluster without the change of the terminal Fe(III) oxidation state and its coordination environment. Therefore, the current study provides a quantitative vibrational analysis of how the remote iron centers within the same iron cluster exert exquisite control of the chemical reactivities and thermodynamic properties of the specific iron site that is responsible for small molecule activation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Implementation of Perturbation Theory and Sensitivity Capabilities in Griffin

Griffin is a Multiphysics Object-Oriented Simulation Environment (MOOSE) based reactor Multiphysics analysis application, jointly developed by Argonne and Idaho National Laboratories under the DOE-NE NEAMS program. This fiscal year, capabilities for reactivity and sensitivity evaluation using perturbation methods were implemented and verified. The First Order Perturbation Method (FOPT) was employed to compute reactivity worth resulting from small perturbations in input parameters, while the Generalized Perturbation Theory (GPT) was used to evaluate sensitivities of a range of response types, including reaction rate ratio, k-eigenvalue, neutron generation time, and effective delayed neutron fraction. These perturbation methods enable users to quantify how response quantities change due to a perturbation in a input parameter without explicitly performing an additional transport simulation for each perturbed state. In particular, the GPT formulation accounts for indirect effects arising from flux changes by solving generalized inhomogeneous equations, for which a Neumann series-based iterative solution method was developed and implemented in Griffin. The implemented reactivity and sensitivity evaluation capabilities were verified using two test problems: an infinite homogeneous system and a two-dimensional hexagonal core. The results showed excellent agreement with reference solutions obtained by a direct method based on finite difference approximation as well as GPT-based results from the PERSENT code, confirming the accuracy of both reactivity and sensitivity evaluations. Additionally, preliminary uncertainty quantification (UQ) results were obtained by combining the sensitivity values computed using GPT and external covariance data, demonstrating that the implemented sensitivity results can be reliably used for uncertainty calculations. To further demonstrate the generality and practical strength of the implementation, the sensitivity evaluation capability was successfully applied to the Empire microreactor with a geometrically complex design that poses significant modeling challenges. The results confirm that Griffin enables sensitivity evaluations even for irregular and highly heterogeneous reactor configurations, thereby establishing a foundation for UQ applications in advanced reactor designs and analyses.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Plutonium Co-precipitation with Calcite

The mobility of plutonium (Pu) in the environment is affected by Pu–mineral interactions, such as adsorption–desorption and structural incorporation. Calcite (CaCO 3 ) is a common secondary phase in near surface environments and a major component of many rocks and soils and is expected to form as an alteration product of cement-based materials planned for use in geological repositories. The reactivity of the calcite surface and its ability to tolerate significant variations in its chemical composition through substitution of Ca for other cations make calcite a potentially important sink for environmental contaminants. Here, single crystals of calcite were synthesized from aqueous solutions in equilibrium with air containing Pu as either Pu(VI) or Pu(IV) and characterized using a combination of laser ablation inductively coupled plasma mass spectrometry (LA–ICP–MS) and X-ray absorption spectroscopy (XAS). These data are used to assess the amount, structure, and oxidation state of Pu co-precipitated into calcite, providing insight into the potential for Pu sequestration in calcite precipitates. Overall, the XAS and LA–ICP–MS data support the co-precipitation of plutonyl [Pu(VI/V)] in the bulk calcite, although the exact nature of the co-precipitated Pu complex is difficult to elucidate in the synthesized material. Co-precipitated plutonyl could be incorporated in either distorted Ca lattice sites or defect sites, and we provide evidence to suggest that Pu(VI) is reduced mainly to Pu(V) in the precipitated solid. LA–ICP–MS additionally shows that the co-precipitation of Pu(VI/V) is favored over the co-precipitation of Pu(IV). Altogether, our results suggest that Pu sequestration in calcite under environmental conditions could immobilize Pu and isolate it from groundwater interactions in contaminated environments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Geochemical Modeling of Celestite (SrSO 4 ) Precipitation and Reactive Transport in Shales

Celestite (SrSO 4 ) precipitation is a prevalent example of secondary sulfate mineral scaling issues in hydraulic fracturing systems, particularly in basins where large concentrations of naturally occurring strontium are present. Herein, we present a validated and flexible geochemical model capable of predicting celestite formation under such unconventional environments. Simulations were built using CrunchFlow and guided by experimental data derived from batch reactors. These data allowed the constraint of key kinetic and thermodynamic parameters for celestite precipitation under relevant synthetic hydraulic fracturing fluid conditions. Effects of ionic strength, saturation index, and the presence of additives were considered in the combined experimental and modeling construction. This geochemical model was then expanded into a more complex system where interactions between hydraulic fracturing fluids and shale rocks were allowed to occur subject to diffusive transport. We find that the carbonate content of a given shale and the presence of persulfate breaker in the system strongly impact the location and extent of celestite formation. The results of this study provide a novel multicomponent reactive transport model that may be used to guide future experimental design in the pursuit of celestite and other sulfate mineral scale mitigation under extreme conditions typical of hydraulic fracturing in shale formations.

54 ENVIRONMENTAL SCIENCES↗

Hydrogen and Deuterium Reactivity with Carbon Surface Impurities on the TPBAR Getter Ni Plate Studied in situ with Environmental XPS

Tritium for the U.S. Department of Energy’s Tritium Readiness Program is produced in tritium-producing burnable absorber rods (TPBARs) inserted into light-water nuclear reactors. The rods are stainless-steel-clad tubes with a permeation barrier coating and internal components. The internal components have been designed and selected to produce and retain tritium. The TPBAR incorporates a Ni-plated Zircaloy-4 getter tube to capture tritium and prevent it from reaching the rod cladding and permeating into the environment. The role of the Ni coating is to protect the Zircaloy-4 getter from oxidation while allowing for maximum tritium permeability. Ubiquitous surface impurities on the Ni, such as carbon, could limit its protective functionality and permeability if they exist in relatively large concentrations. The reactivity of impurity carbon with permeating tritium can also result in tritiated hydrocarbon impurities on the gas phase. The goal of this work is to determine quantitatively the chemical state and reactivity of potential Ni coating impurities in actual TPBAR getter samples. Using Environmental X-ray Photoelectron Spectroscopy (eXPS), a very sensitive gas/surface chemistry diagnostic, we reveal in situ the source and evolution of carbon on the Ni surface at different hydrogen and deuterium pressure conditions, and how carbon reactivity may result in hydrocarbon gas-evolution at application-relevant temperatures.

36 MATERIALS SCIENCE↗

Solvated Electrons Have Multiple Personalities in Molten Salts

P-Crosscut: Solvated Electrons Have Multiple Personalities in Molten Salts [EFRC – MSEE] Alejandro Ramos-Ballesteros;1 Hung H. Nguyen;2 Kazuhiro Iwamatsu;3 Santanu Roy;4 Vyacheslav Bryantsev;4 Michael E. Woods;1 Ruchi Gakhar;1 Phillip Halstenberg;4 Bobby Layne;5 Jay A. LaVerne;6 Claudio J. Margulis:2* and James F. Wishart5* 1Idaho National Laboratory; 2The University of Iowa; 3Hunter College; 4Oak Ridge National Laboratory; 5Brookhaven National Laboratory; 6University of Notre Dame Abstract: The solvated (eS–) is a powerful reducing agent and one of the primary products of molten salt radiolysis. In these extreme high-temperature environments, the eS– can initiate cascades of redox processes that significantly alter the physical and chemical properties of a molten salt, posing challenges for molten salt reactor (MSR) performance and longevity. Consequently, mastering the fundamental behavior of the eS– could enable the design of specific molten salt mixtures with tailored Lewis acidities for controlling the speciation and chemical reactivity of the eS–, thereby mitigating its overall impact on MSR technologies. Here, we use time-resolved electron pulse radiolysis techniques for determining chemical kinetics and transient absorption spectra, combined with ab initio molecular dynamics simulations to explore the influence of multivalent metal cations on the fundamental speciation and distribution of eS– coordination environments.

38 - RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCL↗

Isolating Detrital and Diagenetic Signals in Magnetic Susceptibility Records From Methane‐Bearing Marine Sediments

Abstract Volume‐dependent magnetic susceptibility (κ) is commonly used for paleoenvironmental reconstructions in both terrestrial and marine sedimentary environments where it reflects a mixed signal between primary deposition and secondary diagenesis. In the marine environment, κ is strongly influenced by the abundance of ferrimagnetic minerals regulated by sediment transport processes. Post‐depositional alteration by H 2 S, however, can dissolve titanomagnetite, releasing reactive Fe that promotes pyritization and subsequently decreases κ. Here, we provide a new approach for isolating the detrital signal in κ and identifying intervals of diagenetic alteration of κ driven by organoclastic sulfate reduction (OSR) and the anaerobic oxidation of methane (AOM) in methane‐bearing marine sediments offshore India. Using the correlation of a heavy mineral proxy from X‐ray fluorescence data (Zr/Rb) and κ in unaltered sediments, we predict the primary detrital κ signal and identify intervals of decreased κ, which correspond to increased total sulfur content. Our approach is a rapid, high‐resolution method that can identify overprinted κ resulting from pyritization of titanomagnetite due to H 2 S production in marine sediments. In addition, total organic carbon, total sulfur, and authigenic carbonate δ 13 C measurements indicate that both OSR and AOM can drive the observed κ loss, but AOM drives the greatest decreases in κ. Overall, our approach can enhance paleoenvironmental reconstructions and provide insight into paleo‐positions of the sulfate‐methane transition zone, past enhancements of OSR or paleo‐methane seepage, and the role of detrital iron oxide minerals on the marine sediment sulfur sink, with consequences influencing the development of chemosynthetic biological communities at methane seeps.

58 GEOSCIENCES↗

Concentration-dependent ion correlations impact the electrochemical behavior of calcium battery electrolytes.

Ion interactions strongly determine the solvation environments of multivalent electrolytes even at concentrations below that required for practical battery-based energy storage. This statement is particularly true of electrolytes utilizing ethereal solvents due to their low dielectric constants. These solvents are among the most commonly used for multivalent batteries based on reactive metals (Mg, Ca) due to their reductive stability. Recent developments in multivalent electrolyte design have produced a variety of new salts for Mg2+ and Ca2+ that test the limits of weak coordination strength and oxidative stability. Such electrolytes have great potential for enabling full-cell cycling of batteries based on these working ions. However, the ion interactions in these electrolytes exhibit significant and non-intuitive concentration relationships. In this work, we investigate a promising exemplar, calcium tetrakis(hexafluoroisopropoxy)borate (Ca(BHFIP)(2)), in the ethereal solvents 1,2-dimethoxyethane (DME) and tetrahydrofuran (THF) across a concentration range of several orders of magnitude. Surprisingly, we find that effective salt dissociation is lower at relatively dilute concentrations (e.g. 0.01 M) than at higher concentrations (e.g. 0.2 M). Combined experimental and computational dielectric and X-ray spectroscopic analyses of the changes occurring in the Ca2+ solvation environment across these concentration regimes reveals a progressive transition from well-defined solvent-separated ion pairs to de-correlated free ions. This transition in ion correlation results in improvements in both conductivity and calcium cycling stability with increased salt concentration. Comparison with previous findings involving more strongly associating salts highlights the generality of this phenomenon, leading to important insight into controlling ion interactions in ether-based multivalent battery electrolytes.

Hahn, Nathan T.↗

Atomic-scale modeling of the dissolution of oxidized platinum nanoparticles in an explicit water environment

Pt nanoparticles (NPs) are currently being investigated for use in fuel cells; however, Pt NP oxidation as a function of size, morphology, and temperature is not well understood or currently quantified. In this study, the stability and dissolution of oxidized platinum NPs is examined via classical molecular dynamics in an explicit water environment. The NPs considered range in size from 1.35 to 2.92 nm in diameter and included five different monolayer (ML) coverages of O*. The simulations were performed at 300, 450, and 600 K with the many-body, reactive third-generation charge-optimized many-body or COMB3 potentials and examine the kinetics of NP dissolution in water. The Pt–O layer, which reduces the kinetic activity for Pt atom dissolution, is projected to make dissolution more favorable for O* MLs smaller than 0.5. The simulations further indicate that the Pt NPs' kinetic rates of dissolution are slowed by an increase in the number of adsorbed species caused by the dissociation of water molecules at the reconstructed facets of the Pt NPs. Furthermore, these findings quantify the effect of oxygen and temperature on the stability and dissolution of oxidized platinum NP in an explicit water environment similar to the conditions in fuel cells and electrocatalysis.

08 HYDROGEN↗

Towards ternary binders involving limestone additions — A review

The review summarises literature to examine the transition from portland limestone cement system to composite ternary binder systems involving limestone. Interest in limestone addition as an ideal component in multicomponent binder systems has surged as evident from the large volume of literature published in the recent past. A ternary blended system, with co-substitution of limestone, has the potential to complement the reaction of the supplementary cementitious materials (SCMs). The direct addition of limestone powder helps to attain higher substitution levels of portland cement clinker, improve early age properties, and supplement SCM's reactivity. However, the dilution of hydrates could hamper the long-term benefits. In this review, the interaction of fine limestone is classified and elaborated under two broad umbrellas: physical and chemical interactions. The physical interactions can manifest in three ways, namely, filler action, shearing action and improved packing, which alters reaction rate and extent at early ages. The chemical interactions also modify the reaction kinetics and phase assemblage due to nucleation of C-S-H on calcite surfaces, preservation of the ettringite phase and formation of carboaluminates. Two different forms of carboaluminate hydrates — hemicarboaluminate and mono-carboaluminate can be present in the hydrate matrix depending on the balance between carbonate ions and aluminates in the pore solution. Several factors such as replacement level, particle size, choice of SCM, its reactivity and reactive aluminates content, sulphate levels, curing temperature, and duration of curing can control the carboaluminate formation, reaction degree of SCMs and chemical interaction from limestone additions. A combination of physical and chemical effects makes fine limestone a potential material for co-substitution with aluminosilicate based SCMs, mainly fly ash, slag, and calcined clay. In this review, the factors affecting limestone-SCM composites are summarised based on a detailed literature survey. The effects of SCM-limestone cement composites on hydration kinetics, reaction chemistry, the reactivity of SCMs, the stability of hydrated phases, and contribution to the physical structure development and macroscopic properties by evaluating hydration and mechanical properties are discussed. The importance of AFm (Al{sub 2}O{sub 3}–Fe{sub 2}O{sub 3}-mono) phases in various deterioration mechanisms in concrete and their influence on performance characteristics in different exposure environment is critically appraised.

36 MATERIALS SCIENCE↗

Evolution and persistence of SiO emission in nanosecond laser ablation plumes

Analyzing laser-produced plasmas in a controlled oxygen-containing environment provides insight into the formation and evolution of molecular species through gas-phase oxidation. This study explores the role of ambient pressure and oxygen availability in forming SiO molecular species in laser ablation plumes. The self-emission emanating during the reactive ablation of Si targets was characterized by optical emission spectroscopy and optical time-of-flight techniques. Our results showed that the SiO species formation was greatly influenced by both the ambient pressure and oxygen availability. The intensity and the persistence of SiO emission bands are lower at higher oxygen concentrations, indicating they are depopulated by the formation of more complex silicon oxides. The oxygen partial pressure effects on plume chemistry showed that SiO formation is favored even with a minimal oxygen concentration in the environment.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Activity–Based Protein Profiling of Bile Salt Hydrolysis in the Human Gut Microbiome with Beta–Lactam or Acrylamide–Based Probes

Microbial bile salt hydrolases (BSHs) found in the intestine catalyze the deconjugation of taurine– and glycine–linked bile salts produced in the liver. The resulting bile salts are biological detergents and are critical in aiding lipophilic nutrient digestion. Therefore, the activity of BSHs in the gut microbiome is directly linked to human metabolism and overall health. Bile salt metabolism has also been associated with disease phenotypes such as liver and colorectal cancer. In order to reshape the gut microbiome to optimize bile salt metabolism, tools to characterize and quantify these processes must exist to enable a much–improved understanding of how metabolism goes awry in the face of disease, and how it can be improved through an altered lifestyle and environment. Furthermore, it is necessary to attribute metabolic activity to specific members and BSHs within the microbiome. To this end, we have developed activity–based probes with two different reactive groups to target bile salt hydrolases. Finally, these probes bind similarly to the authentic bile salt substrates, and we demonstrate enzyme labeling of active bile salt hydrolases by using purified protein, cell lysates, and in human stool.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Protein-activated atomic layer deposition for robust crude-oil-repellent hierarchical nano-armored membranes

Atomic layer deposition (ALD) offers unique capabilities to fabricate atomically engineered porous materials with precise pore tuning and multi-functionalization for diverse applications like advanced membrane separations towards sustainable energy-water systems. However, current ALD technique is inhibited on most non-polar polymeric membranes due to lack of accessible nucleation sites. Here, in this study, we report a facile method to efficiently promote ALD coating on hydrophobic surface of polymeric membranes via novel protein activation/sensitization. As a proof of concept, TiO 2 ALD-coated membranes activated by bovine serum albumin exhibit remarkable superhydrophilicity, ultralow underwater crude oil adhesion, and robust tolerance to rigorous environments including acid, alkali, saline, and ethanol. Most importantly, excellent cyclable crude oil-in-water emulsion separation performance can be achieved. The mechanism for activation/sensitization is rooted in reactivity for a particular set of amino acids. Furthermore, the universality of protein-sensitized ALD is demonstrated using common egg white, promising numerous potential usages in biomedical engineering, environmental remediation, lowcarbon manufacturing, catalysis, and beyond.

36 MATERIALS SCIENCE↗

CO 2 Hydrogenation to Methanol over Inverse ZrO 2 /Cu(111) Catalysts: The Fate of Methoxy under Dry and Wet Conditions

Understanding the surface chemistry of CH 3 O species is essential for the production of methanol by CO 2 hydrogenation over Cu-based heterogeneous catalysts, as it facilitates the rational design of more efficient conversion processes. Recent research has identified inverse ZrO 2 /Cu catalysts as highly active and selective systems for the transformation of CO 2 to methanol with a performance that can be better than that of commercial Cu/ZnO catalysts. Here, we employed synchrotron-based ambient pressure X-ray photoelectron spectroscopy (AP-XPS) and calculations based on density functional theory (DFT) to understand the fate of CH 3 O groups under dry and wet environments. AP-XPS spectra revealed that under CO 2 hydrogenation conditions, formate and methoxy are two key intermediates to produce methanol. Furthermore, there are three different types of reactive sites on the surface: One is active for methoxy adsorption, which is stable and responsible for the methanol synthesis; Another one transforms CO 2 into CO; and a third one is active for CO 2 and methoxy dissociation, leading to C and methane formation. The theoretical calculations indicate that CH 3 OH readily dissociates to CH 3 O species following a highly exothermic (ΔE = -20.99 kcal/mol) and barrierless process. The water produced by the reverse water-gas shift reaction (CO 2 + H 2 → H 2 O + CO) can prevent the decomposition of CH 3 O species. We discovered that by introducing a tiny amount of water vapor (2 × 10 -6 Torr) into the reaction chamber, the energy barrier for the reaction CH 3 O(ads) + H(ads) → CH 3 OH(gas) is dramatically reduced. AP-XPS and computational modelling showed that water is quite capable of extracting adsorbed methoxy to form gaseous methanol. With this in mind, one could boost the methanol selectivity by adding appropriate amounts of water or steam, which is an inexpensive and feasible solution for industrial operations.

36 MATERIALS SCIENCE↗

Electrochemical Corrosion and Catalysis Dynamics of Tin Oxide during Water Oxidation

Metal oxide corrosion severely limits anodic electrocatalysis, particularly at high potentials in acidic environments, where degradation pathways remain poorly defined. This study establishes explicit connections between corrosion and electrocatalysis on tin oxide during water oxidation by examining the roles of lattice defects, reactive oxygen species, interfacial pH variations, and speciation of corroded tin in acid. We first demonstrate the presence of structural defects such as oxygen vacancies and substoichiometric Sn(II) species by integrating electron paramagnetic resonance spectroscopy, ultraviolet photoelectron spectroscopy, and Mott–Schottky analysis. Kohn–Sham density functional theory calculations reveal that explicit water structures thermodynamically stabilize reaction intermediates and lower reaction overpotentials. Moreover, we propose that water dissociation leads to hydrogen-bonding networks formed by H* and OH* intermediates, which may span the entire catalyst surface and decrease the interfacial pH to drive corrosion. In contrast, the electrochemical generation of reactive oxygen species is shown to play a minor role in catalyst corrosion during water oxidation using inductively coupled plasma mass spectrometry coupled with selective chemical scavengers. Square-wave voltammetry combined with rotating ring-disk electrodes is used to reveal that under open-circuit conditions, only Sn(IV) cations chemically dissolve from tin oxide, while both Sn(IV) and Sn(II) species electrochemically corrode during water oxidation. Our results unveil a dynamic and complicated interplay between corrosive and catalytic pathways on metal oxide electrocatalysts: a decrease in interfacial pH due to water oxidation exacerbates Sn(II)/Sn(IV) corrosion. Subsequently, the electrochemical corrosion of Sn(II)/Sn(IV) facilitates product formation from lattice oxygen, while the redeposition of corroded Sn(II) as Sn(IV) can enable oxygen exchange with water. By elucidating the roles of defects and interfacial chemistry, this work provides a roadmap for engineering improved electrocatalysts that balance activity and stability, a critical step toward scalable and durable energy technologies.

36 MATERIALS SCIENCE↗