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At least 379 records · Page 21
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Ultrafast X-ray Absorption Spectroscopy Reveals Excited-State Dynamics of B 12 Coenzymes Controlled by the Axial Base

Polarized time-resolved X-ray absorption spectroscopy at the Co K-edge is used to probe the excited-state dynamics and photolysis of base-off methylcobalamin and the excited-state structure of base-off adenosylcobalamin. For both molecules, the final excited-state minimum shows evidence for an expansion of the cavity around the Co ion by ca. 0.04 to 0.05 Å. The 5-coordinate base-off cob(II)alamin that is formed following photodissociation has a structure similar to that of the 5-coordinate base-on cob(II)alamin, with a ring expansion of 0.03 to 0.04 Å and a contraction of the lower axial bond length relative to that in the 6-coordinate ground state. Here these data provide insights into the role of the lower axial ligand in modulating the reactivity of B 12 coenzymes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Brewster angle-cavity ringdown spectroscopy for low temperature plasma measurements in multiphases

Here we report on the development of a Brewster angle-cavity ringdown spectroscopy (BA-CRDS) system for low temperature plasma diagnostics. The system can measure gas species in solutions, with a detection limit (minimum detectable absorbance) of 9.1 × 10 -5 , which is equivalent to a detection limit of 0.04 parts per billion for measuring OH radicals in water at 308 nm. With higher reflectivity ringdown mirrors and improved design of a Brewster angle cell, the detection limit can potentially be up to 10 -6 or lower. In this exploratory study, the absorption cross sections of HgBr 2 and H 2 O 2 in the aqueous phase at 256 nm are measured to be (1.8 ± 0.1) × 10 -18 cm 2 and (5.2 ± 0.5) × 10 -20 cm 2 , respectively. Furthermore, temporal profiles of absorbance from distilled water, HgBr 2 , and H 2 O 2 solutions when interacting with a helium atmospheric plasma jet are individually characterized at different plasma powers, gas flow rates, and/or solute concentrations. The observed linear temporal profiles of absorbance from the plasma-interacted water suggest formation of H 2 O 2 from plasma-generated OH radicals, while the nonlinear temporal profiles from the plasma-treated HgBr 2 solutions reveal possible removal of HgBr 2 by OH radicals. Our results demonstrate that the new BA-CRDS system is a powerful tool for quantification of reactive plasma species in multiphases or other complex settings.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2023

Scrutinizing formally Ni IV centers through the lenses of core spectroscopy, molecular orbital theory, and valence bond theory

Nickel K- and L 2,3 -edge X-ray absorption spectra (XAS) are discussed for 16 complexes and complex ions with nickel centers spanning a range of formal oxidation states from II to IV. K-edge XAS alone is shown to be an ambiguous metric of physical oxidation state for these Ni complexes. Meanwhile, L 2,3 -edge XAS reveals that the physical d-counts of the formally Ni IV compounds measured lie well above the d 6 count implied by the oxidation state formalism. The generality of this phenomenon is explored computationally by scrutinizing 8 additional complexes. The extreme case of NiF 6 2- is considered using high-level molecular orbital approaches as well as advanced valence bond methods. The emergent electronic structure picture reveals that even highly electronegative F-donors are incapable of supporting a physical d 6 Ni IV center. The reactivity of Ni IV complexes is then discussed, highlighting the dominant role of the ligands in this chemistry over that of the metal centers.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Impact of Solution Chemistry on Growth and Structural Features of Mo-Substituted Spinel Iron Oxides

The effect of crystallizing solution chemistry on the chemistry of subsequently as-grown materials was investigated for Mo-substituted iron oxides prepared by thermally activated co-precipitation. In the presence of Mo ions, we find that varying the oxidation state of the iron precursor from Fe(II) to Fe(III) causes a progressive loss of atomic long-range order with the stabilization of 2-4 nm particles for the sample prepared with Fe(III). The oxidation state of the Fe precursor also affects the distribution of Fe and Mo cations within the spinel structure. Increasing the Fe precursor oxidation state gives decreased Fe-ion occupation and increased Mo-ion occupation of tetrahedral sites, as revealed by the extended X-ray absorption fine structure. The stabilization of Mo within tetrahedral sites appears to be unexpected, considering the octahedral preferred coordination number of Mo(VI). The analysis of the atomic structure of the sample prepared with Fe(III) indicates a local ordering of vacancies and that the occupation of tetrahedral sites by Mo induces a contraction of the interatomic distances within the polyhedra as compared to Fe atoms. Moreover, the occupancy of Mo into the thermodynamic site preference of a Mo dopant in Fe 2 O 3 assessed by density functional theory calculations points to a stronger preference for Mo substitution at octahedral sites. Hence, we suggest that the synthetized compound is thermodynamically metastable, that is, kinetically trapped. Such a state is suggested to be a consequence of the tetrahedral site occupation by Mo ions. The population of these sites, known to be reactive sites enabling particle growth, is concomitant with the stabilization of very small particles. Furthermore, we confirmed our hypothesis by using a blank experiment without Mo ions, further supporting the impact of tetrahedral Mo ions on the growth of iron oxide nanoparticles. Our findings provide new insights into the relationships between the Fechemistry of the crystallizing solution and the structural features of the as-grown Mo-substituted Fe-oxide materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

How the choice of exchange–correlation functional affects DFT-based simulations of the hydrated electron

Hydrated electrons are anionic species that are formed when an excess electron is introduced into liquid water. Building an understanding of how hydrated electrons behave in solution has been a long-standing effort of simulation methods, of which density functional theory (DFT) has come to the fore in recent years. The ability of DFT to model the reactive chemistry of hydrated electrons is an attractive advantage over semi-classical methodologies; however, relatively few density functional approximations (DFAs) have been used for the hydrated electron simulations presented in the literature. Here, we simulate hydrated electron systems using a series of exchange–correlation (XC) functionals spanning Jacob’s ladder. We calculate a variety of experimental and other observables of the hydrated electron and compare the XC functional dependence for each quantity. We find that the formation of a stable localized hydrated electron is not necessarily limited to hybrid XC functionals and that some hybrid functionals produce delocalized hydrated electrons or electrons that react with the surrounding water at an unphysically fast rate. Here, we further characterize how different DFAs impact the solvent structure and predicted spectroscopy of the hydrated electron, considering several methods for calculating the hydrated electron’s absorption spectrum for the best comparison between structures generated using different density functionals. None of the dozen or so DFAs that we investigated are able to correctly predict the hydrated electron’s spectroscopy, vertical detachment energy, or molar solvation volume.

Ab-initio molecular dynamics↗
DOE OSTI2025

Structural and electronic changes in L⁢i 2 ⁢Ru⁢O 3 induced by lithium intercalation

Despite extensive research on oxide battery cathodes that transcend classical cationic redox activity, the detailed interplay between structural transformations and electronic redox processes remains insufficiently understood. We report a detailed study of the sequential structural and electronic changes in Li 2 RuO 3 upon lithium intercalation, characterized by powder x-ray and neutron diffraction alongside Ru and O K-edge x-ray absorption spectroscopy (XAS), and guided by operando synchrotron x-ray diffraction. During delithiation, Li 2 RuO 3 evolves from a well-defined monoclinic state to a complex trigonal phase via multiple intermediate structures, marked by significant changes in Ru-O bond distances that closely track the transition from a classical cationic redox to an unconventional process centered at oxygen states. Armed with high-quality atomic structural descriptions, computational models of the O K-edge XAS closely reproduce the experimentally observed spectral shifts. Lastly, we relate observations of electrochemical hysteresis with concurrent changes in the pathways of structural and electronic transitions. In conclusion, our results not only clarify the mechanisms underpinning voltage hysteresis in a model for lattice oxygen redox but also underscore the importance of structural fidelity in modeling redox behavior when this type of complex reactivity is present.

Li, Haifeng [Univ. of Illinois, Chicago, IL (Unite↗
DOE OSTI2023

Structure and Site Evolution of Framework Ni Species in MIL-127 MOFs for Propylene Oligomerization Catalysis

A mixed-valence oxotrimer metal–organic framework (MOF), Ni-MIL-127, with a fully coordinated nickel atom and two iron atoms in the inorganic node, generates a missing linker defect upon thermal treatment in helium (>473 K) to engender an open coordination site on nickel which catalyzes propylene oligomerization devoid of any cocatalysts or initiators. This catalyst is stable for ~20 h on stream at 500 kPa and 473 K, unprecedented for this chemistry. The number of missing linkers on synthesized and activated Ni-MIL-127 MOFs is quantified using temperature-programmed oxidation, 1 H nuclear magnetic resonance spectroscopy, and X-ray absorption spectroscopy to be ~0.7 missing linkers per nickel; thus, a majority of Ni species in the MOF framework catalyze propylene oligomerization. In situ NO titrations under reaction conditions enumerate ~62% of the nickel atoms as catalytically relevant to validate the defect density upon thermal treatment. Propylene oligomerization rates on Ni-MIL-127 measured at steady state have activation energies of 55–67 kJ mol –1 from 448 to 493 K and are first-order in propylene pressures from 5 to 550 kPa. Density functional theory calculations on cluster models of Ni-MIL-127 are employed to validate the plausibility of the missing linker defect and the Cossee–Arlman mechanism for propylene oligomerization through comparisons between apparent activation energies from steady-state kinetics and computation. Here this study illustrates how MOF precatalysts engender defective Ni species which exhibit reactivity and stability characteristics that are distinct and can be engineered to improve catalytic activity for olefin oligomerization.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Millisecond timescale reactions observed via X-ray spectroscopy in a 3D microfabricated fused silica mixer

Determination of electronic structures during chemical reactions remains challenging in studies which involve reactions in the millisecond timescale, toxic chemicals, and/or anaerobic conditions. Here, a three-dimensionally (3D) microfabricated microfluidic mixer platform that is compatible with time-resolved X-ray absorption and emission spectroscopy (XAS and XES, respectively) is presented. This platform, to initiate reactions and study their progression, mixes a high flow rate (0.50–1.5 ml min –1 ) sheath stream with a low-flow-rate (5–90 µl min –1 ) sample stream within a monolithic fused silica chip. The chip geometry enables hydro­dynamic focusing of the sample stream in 3D and sample widths as small as 5 µm. The chip is also connected to a polyimide capillary downstream to enable sample stream deceleration, expansion, and X-ray detection. In this capillary, sample widths of 50 µm are demonstrated. Further, convection–diffusion-reaction models of the mixer are presented. The models are experimentally validated using confocal epifluorescence microscopy and XAS/XES measurements of a ferricyanide and ascorbic acid reaction. The models additionally enable prediction of the residence time and residence time uncertainty of reactive species as well as mixing times. Residence times (from initiation of mixing to the point of X-ray detection) during sample stream expansion as small as 2.1 ± 0.3 ms are also demonstrated. Importantly, an exploration of the mixer operational space reveals a theoretical minimum mixing time of 0.91 ms. The proposed platform is applicable to the determination of the electronic structure of conventionally inaccessible reaction intermediates.

3D microfabrication↗
DOE OSTI2020

Consequences of 131 I Transmutation in Gas Phase Radioiodine Molecules and Adsorbed on Graphite Surface

In the case of nuclear power plant accidents, several radionuclides are being dispersed into the environment. In particular, the release of radioiodine 131 I represents a major health concern because of its absorption by the thyroid gland. To reduce the release of 131 I into the environment, capture materials, such as activated carbon, provide a mean to efficiently retain radioiodine-bound molecular species. Here, we use ab initio molecular dynamic calculations to investigate the effects of 131 I radioactive decay on the molecular stability of I 2 , acid iodine (HI, HIO, HIO 2 , and HIO 3 ), and methyl-iodine species in both gas phase and adsorbed on graphite. In gas phase, we found that I 2 is the least resistant to 131 I transmutation, followed by the HIO x family of molecules, then HI and CH 3 I which are the most resistant. However, the graphite surface is found to greatly favorize the fragmentation of adsorbed molecular species. While the identification of gas phase fragments can offer new chemical route to consider in chemical kinetics models, the formation reactive fragment products at the graphite surface can favorize their reaction with surface carbon atoms which overtime could reduce the number of adsorption sites of capture materials available, and hence, impacting their capture capability.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2014

Revised (Mixed-Effects) Estimation for Forest Burning Emissions of Gases and Smoke, Fire/Emission Factor Typology, and Potential Remote Sensing Classification of Types for Ozone and Black-Carbon Simulation

We summarize recent progress (a) in correcting biomass burning emissions factors deduced from airborne sampling of forest fire plumes, (b) in understanding the variability in reactivity of the fresh plumes sampled in ARCTAS (2008), DC3 (2012), and SEAC4RS (2013) airborne missions, and (c) in a consequent search for remotely sensed quantities that help classify forest-fire plumes. Particle properties, chemical speciation, and smoke radiative properties are related and mutually informative, as pictures below suggest (slopes of lines of same color are similar). (a) Mixed-effects (random-effects) statistical modeling provides estimates of both emission factors and a reasonable description of carbon-burned simultaneously. Different fire plumes will have very different contributions to volatile organic carbon reactivity; this may help explain differences of free NOx(both gas- and particle-phase), and also of ozone production, that have been noted for forest-fire plumes in California. Our evaluations check or correct emission factors based on sequential measurements (e.g., the Normalized Ratio Enhancement and similar methods). We stress the dangers of methods relying on emission-ratios to CO. (b) This work confirms and extends many reports of great situational variability in emissions factors. VOCs vary in OH reactivity and NOx-binding. Reasons for variability are not only fuel composition, fuel condition, etc., but are confused somewhat by rapid transformation and mixing of emissions. We use "unmixing" (distinct from mixed-effects) statistics and compare briefly to approaches like neural nets. We focus on one particularly intense fire the notorious Yosemite Rim Fire of 2013. In some samples, NOx activity was not so suppressed by binding into nitrates as in other fires. While our fire-typing is evolving and subject to debate, the carbon-burned delta(CO2+CO) estimates that arise from mixed effects models, free of confusion by background-CO2 variation, should provide a solid base for discussion. (c) We report progress using promising links we find between emissions-related "fire types" and promising features deducible from remote observations of plumes, e.g., single scatter albedo, Angstrom exponent of scattering, Angstrom exponent of absorption, (CO column density)/(aerosol optical depth).

Remote sensing↗
DOE OSTI2024

Polymer Layer-Accelerated CO 2 Absorption in Aqueous Amino Acid Solutions

Direct air capture (DAC) of CO 2 via solvent-based absorption is considered a promising negative-emission technology. However, the low concentration of CO 2 in the air and slow transport into the solvent make DAC notoriously challenging to implement without costly investments. In this study, we explore the fundamental role that the bulk and surface properties of CO 2 -permeable polymer membranes play in enhancing the efficiency of the solution sorption process in passive DAC of CO 2 . This work leverages various spectroscopic and computational studies to demonstrate that a hybrid system, comprising a reusable CO 2 -permeable polymer layer placed atop an aqueous amino acid (AA) solution, can outperform a pure aqueous AA system by 2-fold. Here we show how the enhanced solubility of CO 2 in the polymer layer can improve the transport of CO 2 into the aqueous phase, while the chemistry of the polymer can control the interfacial barrier for CO 2 permeation and the interfacial concentration of reactive AAs. The derived knowledge of the material properties achieved here can aid in the design of DAC systems with improved performance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Impact of Actinide Complexation on Ligand Radiolysis

Although the actinides boast many unique physical and chemical properties, their inherent susceptibility to radioactive decay are what make them truly interesting elements to study. The absorption of ionizing radiation from actinide decay leads to the formation of a variety of transient and steady-state radicals, ions, and molecular radiolysis products that can lead to significant changes in the surrounding environment, and ultimately dictate steady-state actinide redox distributions and the longevity of molecules designed for actinide complexation. Radiolysis of the latter leads to complexant destruction and the concomitant formation of degradation products that can complicate actinide studies and processes. However, the radiation chemistry of most actinide complexants have been studied in the absence of the actinides they were designed to complex, which can lead to inaccurate conclusions on longevity and degradation product distributions, as metal ion complexation has been historically shown to influence a ligand’s radiolytic behavior. Consequently, bridging this knowledge gap is important for actinide science. Here, I will discuss the impact of actinide complexation on the steady-state and time-resolved radiation-induced reactivity of a variety of complexants, including, tributyl phosphate (TBP) and N,N,N',N'-tetraoctyl diglycolamide (TODGA) .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

In-situ polarization modulation IRRAS investigation of ammonia electrooxidation on Pt-Ir and Pt-Ru nanoparticles prepared on engineered catalyst supports

The catalytic activity and surface reactivity of monometallic Pt and bimetallic Pt-Ir and Pt-Ru nanoparticles, supported on two distinct Engineered Catalyst Supports (ECSs), were investigated for the Ammonia Electrooxidation Reaction (AmER) in alkaline media. XRD measurements confirmed alloy formation between Pt-Ir and Pt-Ru nanoparticles, as indicated by the shift of the (111) reflection to higher 2θ values. Cyclic voltammetry, linear sweep voltammetry, and chronoamperometry experiments were conducted to assess the catalytic activity of the Pt, Pt-Ir, and Pt-Ru electrocatalysts. All bimetallic catalysts exhibited lower onset potentials compared to Pt. The differing Tafel slopes between Pt (74 mV dec⁻¹), Pt-Ir (152 mV dec⁻¹), and Pt-Ru (118–197 mV dec⁻¹) suggest that alloying Pt with Ir or Ru alters the reaction mechanisms. Furthermore, the bimetallic Pt-Ir and Pt-Ru catalysts demonstrated greater tolerance for concentrated ammonia solutions relative to Pt. In-situ Polarization Modulation Infrared Reflection Absorption Spectroscopy (PM-IRRAS) provided insights into the formation of N-H species, azide anions (N₃⁻), and N-O compounds. For the Pt-Ru catalyst, an additional peak around ~3600 cm⁻¹ was observed, corresponding to OH⁻ species. The PM-IRRAS results align with the Gerischer–Mauerer mechanism, indicating that partially dehydrogenated ammonia adsorbates act as active intermediates in the oxidation of ammonia over Pt-Ir and Pt-Ru catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2005

Gas-Phase Formation Rates of Nitric Acid and Its Isomers Under Urban Conditions

Ozone formation in urban smog is controlled by a complex set of reactions which includes radical production from photochemical processes, catalytic cycles which convert NO to NO2, and termination steps that tie up reactive intermediates in long-lived reservoirs. The reaction OH + NO2 + M -4 HONO2 + M (la) is a key termination step because it transforms two short-lived reactive intermediates, OH and NO2, into relatively long-lived nitric acid. Under certain conditions (low VOC/NOx), ozone production in polluted urban airsheds can be highly sensitive to this reaction, but the rate parameters are not well constrained. This report summarizes the results of new laboratory studies of the OH + NO2 + M reaction including direct determination of the overall rate constant and branching ratio for the two reaction channels under atmospherically relevant conditions.

Air pollution↗
DOE OSTI2025

Molecular Modifications of Crystalline Poly(triazine imide) for Advancing Its Structure–Property Relationships in Light-Driven Catalysis

Carbon-nitride materials represent light-absorbing structures composed of earth-abundant elements capable of being leveraged for semiconductor photocatalysis at their surfaces. This study systematically investigates the addition of molecular modifiers to the synthesis of crystalline carbon nitrides to assess their effects on the materials’ structure, optical bandgap, and photocatalytic activity for hydrogen (H 2 ) and oxygen (O 2 ) evolution under ultraviolet and visible-light irradiation. Melamine and five pyrimidine-centered analogs were employed as building blocks to modify various heteroatoms within the polymeric framework. The modified materials were characterized with attention to the differences introduced by the monomeric modifiers and their influence on the resulting structures and compositions. The findings indicate that these changes significantly broaden the visible-light absorption range, albeit with the gradual loss of the bulk crystalline structure. As the loading of modifiers increased beyond 50%, a predominantly amorphous form of carbon nitride emerged. XPS, 13 C solid-state NMR, and SEM analyses corroborated the changes, which were attributed to modifications of the elemental composition and a reduced amount of Li cations and charge-balancing Cl anions owing to fewer binding sites in the intralayer cavities. In photocatalytic measurements under an ultraviolet 390 nm LED, and aided by photodeposited nanoparticle cocatalysts, the unmodified PTI-LiCl framework demonstrated the highest H 2 evolution rate (HER; 3.44 mmol·g –1 ·h –1 ) with an apparent quantum yield of 5.4%, along with total water splitting at rates of 163 μmol of H 2 ·g –1 ·h –1 and 75.6 μmol·O 2 g –1 ·h –1 . While PTI-LiCl showed trace activity under a visible-light 440 nm LED, all modified materials exhibited enhanced reactivity with as low as 5% molecular modifiers. The photocatalytic rates peaked at a 15% modification level when using 2,4,6-triaminopyrimidine, with rates of 33 μmol·g –1 ·h –1 for HER, along with 19.7 μmol of H 2 ·g –1 ·h –1 and 8.7 μmol of O 2 ·g –1 ·h –1 for total water splitting. Density functional theory calculations were used to probe electronic structure changes resulting from the modifications. Furthermore, these results elucidate the structural, optical, and electronic changes arising from the five selected molecular modifiers and their impact on the semiconductors’ photocatalytic properties.

Electrical conductivity↗
DOE OSTI2023

Lost and Found Opportunities Around the Chlorine Worth Study

Los Alamos National Laboratory performed a series of critical experiments in 2021 to examine the worth of chlorine in plutonium-fueled systems. This series of experiments has been dubbed the “Chlorine Worth Study,” and the evaluation of the experiments was presented to the International Criticality Safety Benchmark Evaluation Project (ICSBEP) Technical Review Group in April, 2023. The primary purpose of these experiments was to enable validation of aqueous solutions crediting neutron absorption in 35 Cl. An external, independent view of the events leading up to the design and execution of these experiments indicates a missed opportunity to leverage sensitivity/uncertainty (S/U) analysis to assert validation without the experiments by taking an additional margin for the lack of direct validation of chlorine. On the other hand, the execution of these experiments also presents a rare opportunity to examine the efficacy of the S/U approach and extract useful information about the evaluated chlorine covariance data. TSUNAMI-1D models of representative application solutions were created and used to generate sensitivity data. Varying plutonium and chlorine concentrations were considered to examine the impact of these differences on the chlorine sensitivities and uncertainties. The data-induced uncertainty in k eff resulting from chlorine was calculated directly from uncertainty information calculated in the TSUNAMI-1D sequence. In all cases, this uncertainty was less than 0.1 %Δk. This result could potentially be used to justify a reactivity margin to account for the validation gap related to chlorine in the validation set. On the other hand, given that the experiments were performed, the community should endeavor to extract as much value from them and their results as possible. The results can be used to examine the actual bias associated with chlorine in these systems once the evaluations have been released. These data can be compared with the data-induced uncertainty margin discussed above to test the sufficiency of the validation gap penalty. This result will provide an indication of the performance of the chlorine covariance data specifically and the S/U validation approach generally. More advanced S/U techniques may also be employed to determine reactivity sensitivities associated with the chlorine in the experiments, potentially generating a more robust test of the chlorine covariance data.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2024

The role of Li doping in layered/layered Na x Li y Ni 0.4 Fe 0.2 Mn 0.4 O 2 intergrowth electrodes for sodium ion batteries

Here, the layered NaTMO 2 (TM = Ni, Fe, Mn) materials with the O3-type structure are attractive as positive electrodes for sodium ion batteries because of their high theoretical capacity. Additionally, Li doping in these materials has been shown to offer substantial enhancements to their electrochemical properties by promoting the formation of intergrowth structures, which are combinations of specific phases. However, the mechanism by which the intergrowth modifies the electrochemical properties is often unclear. Systematic variation of Li content in Na x Li y Ni 0.4 Fe 0.2 Mn 0.4 O 2 (NFM-Li y ) was conducted to identify its role in structural modification and electrochemical performance. Li contents of 0.15 and greater generate a layered/layered Na-O3/Li-O’3 intergrowth structure. 7 Li and 23 Na nuclear magnetic resonance and x-ray absorption spectroscopy identify that when the total solubility for alkali ions in the layered structure is exceeded, Li continues to form the Li-O’3 phase while the excess Na forms residual sodium compounds such as Na 2 O. Higher Li content is associated with improved capacity retention in the initial cycles from the superior stability of the mechanically linked NaO3/Li-O’3 structure that suppresses the P3 to OP2 phase transition during charge. However, high Li contents are associated with increased rates of parasitic side reactions that reduce long-term cycling stability. These side reactions are associated with the instability of the cathode-electrolyte interphase, which can be partially mitigated by atomic layer deposition (ALD) coating with alumina, which significantly enhances the capacity retention and Coulombic efficiency over many cycles. Overall, we find that the layered/layered Na-O3/Li-O’3 intergrowth structure is able to provide structural stability and suppress undesired phase transformations but is overwhelmed by the increased reactivity of the surface if not protected by surface coating.

25 ENERGY STORAGE↗
DOE OSTI2022

Characterization of plasma catalytic decomposition of methane: role of atomic O and reaction mechanism

In this work, we investigated atmospheric pressure plasma jet (APPJ)-assisted methane oxidation over a Ni-SiO 2 /Al 2 O 3 catalyst. We evaluated possible reaction mechanisms by analyzing the correlation of gas phase, surface and plasma-produced species. Plasma feed gas compositions, plasma powers, and catalyst temperatures were varied to expand the experimental parameters. Real-time Fourier-transform infrared spectroscopy was applied to quantify gas phase species from the reactions. The reactive incident fluxes generated by plasma were measured by molecular beam mass spectroscopy using an identical APPJ operating at the same conditions. A strong correlation of the quantified fluxes of plasma-produced atomic oxygen with that of CH 4 consumption, and CO and CO 2 formation implies that O atoms play an essential role in CH 4 oxidation for the investigated conditions. With the integration of APPJ, the apparent activation energy was lowered and a synergistic effect of 30% was observed. We also performed in-situ diffuse reflectance infrared Fourier-transform spectroscopy to analyze the catalyst surface. The surface analysis showed that surface CO abundance mirrored the surface coverage of CH n at 25 °C. This suggests that CH n adsorbed on the catalyst surface as an intermediate species that was subsequently transformed into surface CO. We observed very little surface CH n absorbance at 500 °C, while a ten-fold increase of surface CO and stronger CO 2 absorption were seen. This indicates that for a nickel catalyst at 500 °C, the dissociation of CH 4 to CHn may be the rate-determining step in the plasma-assisted CH 4 oxidation for our conditions. We also found the CO vibrational frequency changes from 2143 cm –1 for gas phase CO to 2196 cm –1 for CO on a 25 °C catalyst surface, whereas the frequency of CO on a 500 °C catalyst was 2188 cm –1 . Here, the change in CO vibrational frequency may be related to the oxidation of the catalyst.

methane oxidation↗