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At least 721 records · Page 40
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Decoupling of particles and dissolved iron downstream of Greenlandic glacier outflows

Glaciers can be a significant and locally dominant source of iron (Fe), a biologically essential micronutrient, in high latitude coastal seas. The vast majority of this glacial Fe delivery is associated with particles, yet the speciation of the solid-phase Fe and specifically the relationships that govern exchange between particulate and dissolved Fe phases in these environments are poorly described. Here, in this work, we performed measurements of in situ dissolved Fe (dFe) along meltwater and particle plumes in three transects around Disko Bay and Ameralik Fjord (West Greenland). Measurements of dFe were combined with Fe K-edge X-ray absorption spectroscopy analysis of ~40 suspended sediment samples obtained from the same transects and from select depth profiles down to 300 m. We observed relatively constant dFe levels (4 to 10 nM for nearly all dFe measurements) across fjords with widely varying particulate Fe(II) contents (from 20 to 90% Fe(II)), indicating that dFe concentrations had little dependence on the oxidation state of Fe in the suspended sediment. Particulate Fe data were grouped by underlying bedrock geology, with suspended sediment consisting of 80-90% biotite-like Fe(II) in fjords with Precambrian shield geology and poorly-ordered Fe(III) particles (<20-30% Fe(II)) in one fjord with suspended sediments derived from tertiary basalts. Our characterization data indicated no significant change in the average Fe oxidation state and bonding environment of particles along the fjord transects, implying that Fe(II) in biotite-like coordination is not a readily labile Fe form on this spatial scale. Finally, our results suggest that dFe in these glacially-modified coastal waters is buffered at a relatively constant low nM concentration due to factors other than particle Fe mineralogy and that glacier-derived Fe phases are relatively inert on this spatial scale.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2025

Tuning Solvation Dynamics of Electrolytes at Their Eutectic Point Through Halide Identity

Deep eutectic solvents (DESs) are regarded as highly promising solvent systems for redox flow batteries. DESs, composed of choline halides (ChX, X = F − , Cl − , Br − , I − ) and ethylene glycol (EG), exhibit distinct physicochemical properties at their eutectic points, including halide-dependent phase behavior, viscosity, polarity, conductivity, and solvation dynamics. In this study, we investigate the effects of the halide identity on the solvation properties of ChX:EG mixtures at varying mol % of ChX salt content. The solvatochromic polarity based on ET(30) measurements indicates higher polarity for larger halides (I − > Br − ) than for smaller halides (Cl − > F − ), which exhibit larger compensating solvation shells. The ionic conductivity follows the trend of the solvent fluidity (the inverse of the viscosity), namely ChCl > ChBr > ChI > ChF, influenced by the ion mobility and solvodynamic radii. Measurements of the liquidus temperatures (T L ) reveal that the system with ChCl exhibits the deepest eutectic point (at ~20 mol % ChCl), while ChBr and ChI have shallower minima at ~10 mol % ChBr and ~3 mol % ChI, respectively. ChF does not display a eutectic transition but instead appears to readily supercool at salt concentrations above 30 mol % ChF. Consistent with the phase transition measurements, femtosecond transient absorption spectroscopy shows that in the ChCl system, the solvation dynamics become faster with an increasing salt concentration up to ~16.67 mol %, after which the dynamics slow down with further increases in the salt content. The ChF-based system exhibits similar behavior, though with slower dynamics. In contrast, the solvation dynamics of the systems containing ChBr and ChI monotonously slow down with an increasing salt concentration, in agreement with the phase transition measurements, which show that the eutectic points occur at low salt concentrations. These measurements suggest that the solvent composition and, in particular, the identity of the halide anion play a significant role in the solvation behavior of these ethylene-glycol-based DESs, offering a foundation for tuning the DES properties for specific applications.

Biochemistry & Molecular Biology↗
DOE OSTI2020

Hybridization effect on the x-ray absorption spectra for actinide materials: Application to PuB 4

Studying the local moment and 5 f -electron occupations sheds insight into the electronic behavior in actinide materials. X-ray absorption spectroscopy (XAS) has been a powerful tool to reveal the valence electronic structure when assisted with theoretical calculations. However, the analysis currently taken in the community on the branching ratio of the XAS spectra generally does not account for the hybridization effects between local f orbitals and conduction states. In this paper, we discuss an approach which employs the density functional theory plus Gutzwiller rotationally invariant slave boson method to obtain a local Hamiltonian for the single-impurity Anderson model, and calculates the XAS spectra by the exact diagonalization (ED) method. A customized numerical routine was implemented for the ED XAS part of the calculation. By applying this technique to the recently discovered 5 f -electron topological Kondo insulator Pu B 4 , we determined the signature of 5 f -electronic correlation effects in the theoretical x-ray spectra. Furthermore, we found that the Pu 5 f - 6 d hybridization effect provides an extra channel to mix the j = 5 / 2 and 7 / 2 orbitals in the 5 f valence. As a consequence, the resulting electron occupation number and spin-orbit coupling strength deviate from the intermediate-coupling regime.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Elucidation of complex triplet excited state dynamics in Pd(ii) biladiene tetrapyrroles

Pd(II) biladienes have been developed over the last five years as non-aromatic oligotetrapyrrole complexes that support a rich triplet photochemistry. In this work, we have undertaken the first detailed photophysical interrogation of three homologous Pd(II) biladienes bearing different combinations of methyl- and phenyl-substituents on the frameworks’ sp 3 -hybridized meso-carbon (i.e., the 10-position of the biladiene framework). These experiments have revealed unexpected excited-state dynamics that are dependent on the wavelength of light used to excite the biladiene. More specifically, transient absorption spectroscopy revealed that higher-energy excitation (λ exc ~ 350–500 nm) led to an additional lifetime (i.e., an extra photophysical process) compared to experiments carried out following excitation into the lowest-energy excited states (λ exc = 550 nm). Each Pd(II) biladiene complex displayed an intersystem crossing lifetime on the order of tens of ps and a triplet lifetime of ~20 μs, regardless of the excitation wavelength. However, when higher-energy light is used to excite the complexes, a new lifetime on the order of hundreds of ps is observed. The origin of the ‘extra’ lifetime observed upon higher energy excitation was revealed using density functional theory (DFT) and time-dependent DFT (TDDFT). These efforts demonstrated that excitation into higher-energy metal-mixed-charge-transfer excited states with high spin–orbit coupling to higher energy metal-mixed-charge-transfer triplet states leads to the additional excitation deactivation pathway. Furthermore, the results of this work demonstrate that Pd(II) biladienes support a unique triplet photochemistry that may be exploited for development of new photochemical schemes and applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

In situ and operando investigation of the dynamic morphological and phase changes of a selenium-doped germanium electrode during (de)lithiation processes

To understand the effect of selenium doping on the good cycling performance and rate capability of a Ge 0.9 Se 0.1 electrode, the dynamic morphological and phase changes of the Ge 0.9 Se 0.1 electrode were investigated by synchrotron-based operando transmission X-ray microscopy (TXM) imaging, X-ray diffraction (XRD), and X-ray absorption spectroscopy (XAS). The TXM results show that the Ge 0.9 Se 0.1 particle retains its original shape after a large volume change induced by (de)lithiation and undergoes a more sudden morphological and optical density change than pure Ge. The difference between Ge 0.9 Se 0.1 and Ge is attributed to a super-ionically conductive Li–Se–Ge network formed inside Ge 0.9 Se 0.1 particles, which contributes to fast Li-ion pathways into the particle and nano-structuring of Ge as well as buffering the volume change of Ge. The XRD and XAS results confirm the formation of a Li–Se–Ge network and reveal that the Li–Se–Ge phase forms during the early stages of lithiation and is an inactive phase. The Li–Se–Ge network also can suppress the formation of the crystalline Li 15 Ge 4 phase. Finally, these in situ and operando results reveal the effect of the in situ formed, super-ionically conductive, and inactive network on the cycling performance of Li-ion batteries and shed light on the design of high capacity electrode materials.

25 ENERGY STORAGE↗
DOE OSTI2020

Iron and Phosphorus Geochemistry in High-Centered and Low-Centered Polygon Soils from the Barrow Environmental Observatory, Utqiagvik, Alaska, 2015

This dataset provides chemical characterization of soil cores obtained in triplicate from center and trough positions of a high-centered polygon and center, ridge, and trough positions of a low-centered polygon in the NGEE Arctic research area within the Barrow Environmental Observatory, Utqiagvik, Alaska. Photographs of the 15 collected cores are provided. Cores were collected to thaw depth in early October 2015 and subsequently divided into subsamples for analysis, which included bulk soil horizons (organic or mineral) and finer scale depth increments (minimum 4 cm thickness per increment). Bulk horizons and depth increments were characterized using sequential chemical extractions for Fe and P and with Fe K-edge x-ray absorption spectroscopy. Additional soil parameters such as loss-on-ignition, gravimetric water content, and carbon and nitrogen concentrations were also quantified for bulk horizons. This dataset includes four csv files, one pdf user guide, and one zip folder of *.jpg photos.The Next-Generation Ecosystem Experiments: Arctic (NGEE Arctic), was a research effort to reduce uncertainty in Earth System Models by developing a predictive understanding of carbon-rich Arctic ecosystems and feedbacks to climate. NGEE Arctic was supported by the Department of Energy's Office of Biological and Environmental Research.The NGEE Arctic project had two field research sites: 1) located within the Arctic polygonal tundra coastal region on the Barrow Environmental Observatory (BEO) and the North Slope near Utqiagvik (Barrow), Alaska and 2) multiple areas on the discontinuous permafrost region of the Seward Peninsula north of Nome, Alaska.Through observations, experiments, and synthesis with existing datasets, NGEE Arctic provided an enhanced knowledge base for multi-scale modeling and contributed to improved process representation at global pan-Arctic scales within the Department of Energy's Earth system Model (the Energy Exascale Earth System Model, or E3SM), and specifically within the E3SM Land Model component (ELM).

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2020

Robust framework and software implementation for fast speciation mapping

One of the greatest benefits of synchrotron radiation is the ability to perform chemical speciation analysis through X-ray absorption spectroscopies (XAS). XAS imaging of large sample areas can be performed with either full-field or raster-scanning modalities. A common practice to reduce acquisition time while decreasing dose and/or increasing spatial resolution is to compare X-ray fluorescence images collected at a few diagnostic energies. In this work, several authors have used different multivariate data processing strategies to establish speciation maps. Furthermore, the theoretical aspects and assumptions that are often made in the analysis of these datasets are focused on. A robust framework is developed to perform speciation mapping in large bulk samples at high spatial resolution by comparison with known references. Two fully operational software implementations are provided: a user-friendly implementation within the MicroAnalysis Toolkit software, and a dedicated script developed under the R environment. The procedure is exemplified through the study of a cross section of a typical fossil specimen. Additionally, the algorithm provides accurate speciation and concentration mapping while decreasing the data collection time by typically two or three orders of magnitude compared with the collection of whole spectra at each pixel. Whereas acquisition of spectral datacubes on large areas leads to very high irradiation times and doses, which can considerably lengthen experiments and generate significant alteration of radiation-sensitive materials, this sparse excitation energy procedure brings the total irradiation dose greatly below radiation damage thresholds identified in previous studies. This approach is particularly adapted to the chemical study of heterogeneous radiation-sensitive samples encountered in environmental, material, and life sciences.

47 OTHER INSTRUMENTATION↗
DOE OSTI2025

Tuning Excited-State Charge Transfer Character in Cofacial Core-Substituted Perylenediimide Dimers

Understanding the interplay between excimer formation and symmetry-breaking charge separation is important for optimizing charge separation in organic photovoltaic materials. To explore this connection, we synthesized four 1,6,7,12-tetrakis( p -X-phenoxy)perylene-(3,4:9,10)-bisdicarboximide cofacially stacked dimers, where X = MeO, tert -butyl, Br, and CF 3 . Steady-state spectroscopy reveals H-type aggregation and excimer formation in all four dimers, while transient absorption spectroscopy shows relatively small changes in their excited-state absorptions. However, time-resolved fluorescence (TRF) spectroscopy shows that relaxation occurs from an initial Frenkel exciton-dominated excimer state to one in which charge transfer (CT) character contributes. Relaxation to the lower-lying state with CT character is attributed to a combination of structural and charge distribution changes elicited by varying the substituents. Finally, this study illustrates how subtle changes in charge distribution and structure can combine to influence the excited state dynamics that influence charge separation in molecular dimers.

fluorescence↗
DOE OSTI2022

Solid-phase Mn speciation in suspended particles along meltwater-influenced fjords of West Greenland

Manganese (Mn) is an essential micro-nutrient that can limit or, along with iron (Fe), co-limit phytoplankton growth in the ocean. Glacier meltwater is thought to be a key source of trace metals to high latitude coastal systems, but little is known about the nature of Mn delivered to glacially-influenced fjords and adjacent coastal waters. In this work, we combine in-situ dissolved Mn (dMn) measurements of surface waters with Mn K-edge X-ray absorption spectroscopy (XAS) data of suspended particles in four fjords of West Greenland. Data were collected from transects of up to 100 km in fjords with different underlying bedrock geology from 64 to 70°N. We found that dMn concentrations generally decreased conservatively with increasing salinity (from 80 to 120 nM at salinity < 8 to < 40 nM at salinities > 25). Dissolved Fe (dFe) trends in these fjords similarly declined with increasing distance from glacier outflows (declining from > 20 nM to < 8 nM). However, the dMn/dFe ratio increased rapidly likely due to the greater stability of dMn at intermediate salinities (i.e. 10–20) compared to rapid precipitation of dFe across the salinity gradient. The XAS data indicated a widespread presence of Mn(II)-rich suspended particles near fjord surfaces, with structures akin to Mn(II)-bearing phyllosilicates. However, a distinct increase in Mn oxidation state with depth and the predominance of birnessite-like Mn(IV) oxides was observed for suspended particles in a fjord with tertiary basalt geology. The similar dMn behaviour in fjords with different suspended particle Mn speciation (i.e., Mn(II)-bearing phyllosilicates and Mn(IV)-rich birnessite) is consistent with the decoupling of dissolved and particulate Mn and suggests that dMn concentrations on the scale of these fjords are controlled primarily by dilution of a freshwater dMn source rather than exchange between dissolved and particle phases. This work provides new insights into the Mn cycle in high latitude coastal waters, where small changes in the relative availabilities of dMn, dFe and macronutrients may affect the identity of the nutrient(s) proximally limiting primary production.

58 GEOSCIENCES↗
DOE OSTI2024

Speciation and Aqueous Dissolution of Macronutrients in Fire Ash: Variation across Ecosystems and the Effects on Nutrient Cycling

This study investigated the speciation and aqueous dissolution of macronutrients in fire ash from diverse ecosystems and speciation of ash and smoke from laboratory burning, exploring the variations and their causes. The speciation of phosphorus (P), calcium (Ca), and potassium (K) in fire ash from five globally distributed ecosystems was characterized by using X-ray absorption spectroscopy and sequential fractionation. Aqueous dissolution of the macronutrients was measured by batch experiments at acidic and alkaline pHs. The results showed that P existed mainly as Ca phosphates, Ca as double carbonates, calcite, and sulfates, and most K was associated with Ca carbonates. Mineralogy and the relative abundance of the species were primarily controlled by elemental stoichiometry and fire temperature. Differences in Ca and P speciation existed between ash and smoke from laboratory burning, possibly caused by the temperature difference and/or mass fractionation during burning. The rates, extents, and pH dependencies of macronutrient dissolution differed among macronutrients and depended on their speciation, with K being highly soluble and the P and Ca regulated by solution pH. The variability in ash macronutrient chemistry and ecosystemspecific fire ash loads resulted in varying loads and availability of individual macronutrient from fire among ecosystems. This study provides a mechanistic understanding of how fires transform the chemistry of macronutrients and affect macronutrient returns to soils across different ecosystems, which is essential for evaluating the disturbance to ecosystem nutrient cycling by fires.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2025

Metal–Oxide Interface Sites Created Using Atomic Layer Deposition and Tested for CO Oxidation

The performance of catalysts made out of Pt supported on TiO 2 thin films grown on SBA-15 (a silica mesoporous material) by atomic layer deposition (ALD) was characterized systematically by combining in situ infrared absorption spectroscopy (IR) with other techniques including electron microscopy and adsorption−desorption isothermal measurements. The titania films in the resulting high-surface-area catalysts were evenly distributed throughout the inner surface of the SBA-15 mesopores, and their thickness could be controlled at a submonolayer level, with 3 to 4 TiO 2 ALD cycles needed for the complete coverage of the silica sites. The titania films could be deposited either before or after adding the metal (Pt), which was dispersed in the form of small nanoparticles (NPs) approximately 4−6 nm in diameter, in order to exert some control on the density and nature of the Pt/TiO 2 interface sites. One important lesson deriving from this work is that such an order of deposition leads to significantly different catalysts in spite of the fact that most of their structural properties are similar. If the Pt is deposited on the titania films, the resulting metal NPs are slightly smaller than those grown on silica and display CO adsorption sites with lower surface Pt coordination numbers. On the other hand, when TiO 2 is deposited on the Pt/SBA-15 starting material, some titania grows on the metal and partially blocks its surface while also creating new interface sites where CO binds more weakly and displays lower C−O stretching frequencies. In terms of catalytic performance, the results from in situ IR CO site titration and kinetic measurements combined suggest a mechanism where CO first adsorbs on Pt atop sites and then migrates to Pt/TiO 2 interface sites, where oxidation takes place. Both types of sites appear to be similar in all the catalysts tested, but catalytic performance could be optimized by tuning their surface densities. Maximum catalytic activity was obtained when the TiO2 films were deposited first and with TiO 2 coverages of at least half a monolayer, that is, after at least 2 ALD cycles.

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

Significance of the structural configuration of B2 disorder in Co and Ti based Heusler alloys

We investigate here structural (at local and global levels) and transport properties for 𝑋 2 ⁢MnAl (𝑋= Co and Ti). Additionally, the magnetic properties were also studied for Ti 2 ⁢MnAl. Our x-ray diffraction results show that both the compounds stabilize in B2 disordered phase with cubic structure of 𝑃⁢𝑚⁢$\overline{3}$⁢𝑚 space group. Further, the structural configuration of the above disordered phase for both the compounds was identified using combined studies of x-ray absorption spectroscopy and multiple scattering calculations at the transition metal 𝐾 edges. Upon such identification, in the case of Co 2 ⁢Mn 1−𝑦⁢ Cr 𝑦 ⁢Al (𝑦= 0, 0.05, 0.1, 0.2) with change in 𝑦, we are able to establish a better connection quantitatively between the inverse of Mn-Co bonds and peak in the temperature-dependent resistivity. This highlights the crucial importance of a detailed understanding of the nature of B2 disorder. In the case of 𝑦=0, in the temperature range of study, the resistivity is driven by the functional form associated with (a) three-dimensional enhanced electron-electron Coulomb interaction scattering mechanism and (b) an unconventional one-magnon process. For Ti 2 ⁢MnAl, the transport shows metallic glasslike behavior at high temperature, while at low temperature it follows both the Cote-Meisel's model and quantum correction model. In this compound, the magnetic studies suggest the formation of superparamagnetic clusters in the paramagnetic matrix at low temperatures. Our density functional theory results are in line with the transport and magnetic properties. In literature, the spin polarization percentage (𝑃) for 𝑋= Co in B2 disordered phase is 76%. However, the present results emphasize the fact that in B2 disordered phase, the value of 𝑃 can range from 90% to 71% depending on the structural configuration introduced by swapping of the atomic positions of Mn and Al. For the compound under study, the value of percentage spin polarization obtained ranges between 82% to 85%. In addition, we also identify the origin of the difference in the shape of the Mn 3⁢𝑑 density of states for both the alloys. In conclusion, our results for 𝑋= Co alloy highlights the importance of identifying the specific structural configuration associated with a particular disorder category especially in the estimation of 𝑇 𝑐 and 𝑃 and for 𝑋= Ti, the physical properties can be tuned by varying the position of 𝐸 𝐹 and thereby its utilization in device applications.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Reaction Mechanism of Electrodeposited ε-MnO 2 : A Proton-Centered Pathway in Aqueous Zn-Ion Systems

Aqueous Zn/MnO 2 batteries have garnered significant interests owing to their abundance, high theoretical specific capacity, safety, and low cost. However, large-scale application of these systems is limited by the incomplete understanding of the MnO 2 reaction chemistry. The different crystal lattice structures among MnO 2 polymorphs contribute to the variations in reported reaction mechanisms. Among them, ε-MnO 2 polymorph, the dominant phase in electrolytic manganese dioxide (EMD), is notably observed during the charge cycles of aqueous Zn/MnO 2 batteries. Here, in this work, we investigate the electrochemical behavior of an ε-MnO 2 cathode synthesized via electrodeposition from a ZnSO 4 and MnSO 4 electrolyte, onto a 3-dimensional carbon cloth substrate. Proton intercalation emerges as the dominant charge storage mechanism, critically enabling the reversibility of ε-MnO 2 during cycling, as revealed by operando synchrotron X-ray diffraction and X-ray absorption spectroscopy. Additionally, a proton-coupled dissolution/redeposition pathway operates alongside minor Zn 2+ intercalation, as quantified by Rietveld refinement. Morphological and chemical heterogeneities are studied by transmission X-ray microscopy further validates this reaction mechanism. These mechanistic insights provide the foundation for rationally designing Zn/MnO 2 batteries with optimized proton dynamics and charge transfer, advancing these systems as a viable solution for safe, cost-effective grid-scale energy storage.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Multicode benchmark on simulated Ti K-edge x-ray absorption spectra of Ti-O compounds

X-ray absorption spectroscopy (XAS) is an element-specific materials characterization technique that is sensitive to structural and electronic properties. First-principles simulated XAS has been widely used as a powerful tool to interpret experimental spectra and draw physical insights. Recently, there has also been growing interest in building computational XAS databases to enable data analytics and machine learning applications. However, there are non-trivial differences among commonly used XAS simulation codes, both in underlying theoretical formalism and in technical implementation. Reliable and reproducible computational XAS databases require systematic benchmark studies. In this work, we benchmarked Ti K-edge XAS simulations of ten representative Ti-O binary compounds, which we refer to as the Ti-O-10 dataset, using three state-of-the-art codes: XSPECTRA, OCEAN and exciting. We systematically studied the convergence behavior with respect to the input parameters and developed a workflow to automate and standardize the calculations to ensure converged spectra. Our benchmark comparison considers a 35 eV spectral range starting from the K-edge onset, representative of widely used near-edge spectra. Quantitative comparison over this range is based on Spearman’s rank correlation score (r sp ). Our results show: (1) the two Bethe-Salpeter equation (BSE) codes (OCEAN and exciting) have excellent agreement with an average $r$ $sp$ of 0.998; (2) good agreement is obtained between the core-hole potential code (XSPECTRA) and BSE codes (OCEAN and exciting) with an average $r$ $sp$ of 0.990, and this smaller $r$ $sp$ reflects the noticeable differences in the main edge spectral shape that can be primarily attributed to the difference in the strength of the screened core-hole potential; (3) simulations from both methods overall reproduce well the main experimental spectral features of rutile and anatase, and the different treatments of the screened core-hole potential have visible impact on pre-edge intensities and the peak ratio of the main edge; (4) there exist moderate differences in the relative edge alignment of the three codes with a standard deviation of about 0.2 eV, which arise from multiple contributions including the frozen core approximation, final state effects, and different approximations used for the self-energy correction. In conclusion, our benchmark study provides important standards for first-principles XAS simulations with broad impact in data-driven XAS analysis.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Carrier gradients and the role of charge selective contacts in lateral heterojunction all back contact perovskite solar cells

Realizing photovoltaic devices that achieve the full potential of the metal halide perovskite material will require improved insight regarding the role of selective contacts and how key interfaces operate when mobile defects are present. However, measuring interface properties in typical device stacks where the perovskite layer is thin and sandwiched between two contacts has been a challenge. Here, we fabricate p-i-n and p-n lateral heterojunctions with nickel oxide/titanium oxide all back contacts, permitting us to employ a comprehensive analysis approach, including ultraviolet and X-ray photoemission spectroscopy (UPS/XPS), angle-resolved X-ray absorption spectroscopy (XAS), Kelvin probe force microscopy (KPFM), surface photovoltage (SPV), hyperspectral imaging (HSI), and time-resolved fluorescence lifetime imaging microscopy (TR-FLIM) to discern the role of selective contacts. Specifically, we tune the selectivity of the contacts, changing the gradient in the carrier concentration across the surface of the active layer, which is connected to carrier extraction at the buried interface, and thus the device functionality.

25 ENERGY STORAGE↗
DOE OSTI2019

Quantification of Anionic Redox Chemistry in a Prototype Na-Rich Layered Oxide

Harnessing anionic redox reactions is of prime importance for boosting the capacity of sodium-ion batteries (NIBs). However, quantifying the cyclability of anionic redox reactions is still challenging. Herein, we conduct a qualitative and quantitative investigation of the cationic and anionic redox reactions of a prototype Na-rich layered oxide, namely, Na 3 RuO 4 , by a combination of bulk-sensitive X-ray absorption spectroscopy and full-range mapping of resonant inelastic X-ray scattering. We unequivocally reveal that both Ru cations and oxygen anions are involved in the charge compensation process of Na 3 RuO 4 . Ru redox is highly reversible over extended electrochemical cycles, while the cyclability of lattice oxygen redox gradually decreases with the retention of only 36% after 30 cycles, which is mainly responsible for the capacity fading of Na 3 RuO 4 . Finally, our findings provide deeper insights into the complex oxygen redox mechanism, which plays a decisive role for designing high-energy Na-rich electrode materials for NIBs.

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

Atom Efficiency of Pd Sites for Methane Combustion: Single Atom Catalysts Versus Nanocatalysts

Methane combustion is an important reaction for energy production and methane removal from the atmosphere. This reaction highly relies on the use of noble metal Pd-based catalysts, which therefore drives the pursuit of catalysts with high atomic dispersion and activity. In this work, Pd/ceria catalysts dominated with Pd single atoms or nanosized Pd clusters (∼1 nm) are prepared and characterized by combining high-resolution high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM), in situ diffuse reflectance infrared Fourier-transform spectroscopy (DRIFTS), and Raman and X-ray absorption spectroscopy (XAS) techniques. By comparing the turnover frequencies (TOF; per every Pd atom) of Pd/ceria single atom catalysts and nanocatalysts, it is found that the atom efficiency of Pd is increased by 10 ∼30 times from single atom catalysts to nanocatalysts. For Pd single atom catalysts, although their activity can be tuned by changing the local structures, the intrinsic activity and number of active sites need to be further improved by engineering the surfaces of supports. For nanosized Pd species, despite the high TOF, the Pd atoms in the bulk structure are not directly participating in the catalytic reaction. Furthermore, this work highlights the importance of increasing the intrinsic activity of individual noble atoms, as well as the homogeneity of their local structures. For Pd/ceria systems reported in this work, our results indicate that from the application point of view, at the current stage, it is not practical to replace Pd nanocatalysts with single atom catalysts for methane combustion.

Pd↗