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At least 325 records · Page 18
All sourcesNASA NTRSDOE OSTI
NASA NTRS1984

Far-infrared spectroscopy of the galactic center - Neutral and ionized gas in the central 10 parsecs of the Galaxy

The present mapping of the 3P1-3P2 fine structure line emission from neutral atomic oxygen near the galactic center shows the emission to be extended over more than 12 pc along the galactic plane, centered on the position of Sgr A West. The rotational velocity of the O I gas at R of about 1 corresponds to a mass within the central parsec of about 3 million solar masses. The forbidden O I line probably arises in a predominantly neutral atomic region immediately outside the ionized central parsec of the Galaxy. Gas temperatures are greater than 100 K, and the total integrated luminosity radiated in the line, which is about 100,000 solar luminosities, substantially contributes to the cooling of the gas. The 3P1-3P0 fine structure line of the O III forbidden line has also been detected at 88 microns toward Sgr A West, coming from high density ionized gas.

Genzel, R.↗
DOE OSTI2021

In situ EXAFS study of Sr adsorption on TiO 2 (110) under high ionic strength wastewater conditions

In order to provide important details concerning the adsorption reactions of Sr, batch reactions and a set of both ex situ and in situ Grazing Incidence X-ray Absorption Fine Structure (GIXAFS) adsorption experiments were completed on powdered TiO 2 and on rutile(110), both reacted with either SrCl 2 or SrCO 3 solutions. TiO 2 sorption capacity for strontium (Sr) ranges from 550 ppm (SrCl 2 solutions, second order kinetics) to 1400 ppm (SrCO 3 solutions, first order kinetics), respectively, and is rapid. Sr adsorption decreased as a function of chloride concentration but significantly increased as carbonate concentrations increased. In the presence of carbonate, the ability of TiO 2 to remove Sr from the solution increases by a factor of ~4 due to rapid epitaxial surface precipitation of an SrCO 3 thin film, which registers itself on the rutile(110) surface as a strontianite-like phase (d-spacing 2.8 Å). Extended X-ray Absorption Fine Structure (EXAFS) results suggest the initial attachment is via tetradental inner-sphere Sr adsorption. Moreover, adsorbates from concentrated SrCl 2 solutions contain carbonate and hydroxyl species, which results in both inner- and outer-sphere adsorbates and explains the reduced Sr adsorption in these systems. These results not only provide new insights into Sr kinetics and adsorption on TiO 2 but also provide valuable information concerning potential improvements in effluent water treatment models and are pertinent in developing treatment methods for rutile-coated structural materials within nuclear power plants.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2023

Improved quasiparticle self-consistent electronic band structure and excitons in β – LiGaO 2

The band structure of β–LiGaO 2 is calculated using the quasiparticle self-consistent QSGWˆ method where the screened Coulomb interaction Wˆ is evaluated including electron-hole interaction ladder diagrams and G is the one-electron Green's function. Improved convergence compared to previous calculations leads to a significantly larger band gap of about 7.0 eV. However, exciton binding energies are found to be large and lead to an exciton gap of about 6.0 eV if also a zero-point-motion correction of about –0.4 eV is included. Furthermore, these results are in excellent agreement with recent experimental results on the onset of absorption. Besides the excitons observed thus far, the calculations indicate the existence of a Rydberg-like series of exciton excited states, which is however modified from the classical Wannier exciton model by the anisotropies of the material and the more complex mixing of Bloch states in the excitons resulting from the Bethe-Salpeter equation. The exciton fine structure and the exciton wave functions are visualized and analyzed in various ways.

36 MATERIALS SCIENCE↗
NASA NTRS1992

Infrared line diagnostics of active galactic nuclei

The CLOUDY photoionization code of Ferland (1991) is employed to predict intensities and ratios of the near-, mid-, and far-IR ionic fine-structure lines from AGN of the LINER and Seyfert types, and starbursts. The depths of varying the important model parameters, including ionization parameter, density, and optical depth, are investigated. The way in which detailed IR spectroscopy can reveal the presence of density inhomogeneities and abundance anomalies is shown, and the slope of the ionizing continuum and the amount of reddening and the reddening law are determined. The predictions of the present model and others are compared to the observed line ratios of the starburst galaxy M82 and of the Galactic center. No single-zone model adequately predicted all of the observed lines, but a simple combination of a starburst plus photodissociation region of higher density have a good fit for M82. The present model predictions are used to estimate the detectability of IR fine-structure lines in various active galaxies.

Spinoglio, Luigi↗
NASA NTRS1994

Atomic data from the iron project. 3: Rate coefficients for electron impact excitation of boron-like ions: Ne VI, Mg VIII, Al IX, Si X, S XII, Ar XIV, Ca XVI and Fe XXII

Collison strengths and maxwellian averaged rate coefficients have been calculated for the 105 transitions among all 15 fine structure levels of the 8 LS terms 2s(sup 2) 2 P(P-2(sup 0 sub 1/, 3/2)), 2s2p(sup 2)(P-4(sub 1/2,3/2,5/2), D-2(sub 3/2, 5/2), S-2(sub 1/2), P-2(sub 1/2, 3/2)), 2p(sup 3)(S-4(sup 0)(sub 3/2), D-2(sup 0 sub 3/2, 5/2), P-2(sup 0 sub 1/2, 3/2)) in highly- charged B-like Ne, Mg, Al, Si, S, Ar, Ca and Fe. Rate coefficients have been tabulated at a wide range of temperatures, depending on the ion charge and abundance in plasma sources. Earlier work for O IV has also been extended to include the high temperature range. A brief discussion of the calculations, sample results, and comparison with earlier works is also given. While much of the new data should be applicable to UV spectral diagnostics, the new rates for the important ground state fine structure transition P-2(sup 0 sub 1/2)-P-2(sup 0 sub 3/2) should result in significant revision of the IR cooling rates in plasmas where B-like ions are prominent constituents, since the new rate coefficients are generally higher by several factors compared with the older data.

Zhang, Hong Lin↗
NASA NTRS2002

Lightning Return-Stroke Current Waveforms Aloft, From Measured Field Change, Current, and Channel Geometry

Direct current measurements are available near the attachment point from both natural cloud-to-ground lightning and rocket-triggered lightning, but little is known about the rise time and peak amplitude of return-stroke currents aloft. We present, as functions of height, current amplitudes, rise times, and effective propagation velocities that have been estimated with a novel remote-sensing technique from data on 24 subsequent return strokes in six different lightning flashes that were triggering at the NASA Kennedy Space Center, FL, during 1987. The unique feature of this data set is the stereo pairs of still photographs, from which three-dimensional channel geometries were determined previously. This has permitted us to calculate the fine structure of the electric-field-change (E) waveforms produced by these strokes, using the current waveforms measured at the channel base together with physically reasonable assumptions about the current distributions aloft. The computed waveforms have been compared with observed E waveforms from the same strokes, and our assumptions have been adjusted to maximize agreement. In spite of the non-uniqueness of solutions derived by this technique, several conclusions seem inescapable: 1) The effective propagation speed of the current up the channel is usually significantly (but not unreasonably) faster than the two-dimensional velocity measured by a streak camera for 14 of these strokes. 2) Given the deduced propagation speed, the peak amplitude of the current waveform often must decrease dramatically with height to prevent the electric field from being over-predicted. 3) The rise time of the current wave front must always increase rapidly with height in order to keep the fine structure of the calculated field consistent with the observations.

Willett, J. C.↗
NASA NTRS1995

Lightning-channel morphology by return-stroke radiation field waveforms

Simultaneous video and wideband electric field recordings of 32 cloud-to-ground lightning flashes in Florida were analyzed to show the formation of new channels to ground can be detected by examination of the return-stroke radiation fields alone. The return-stroke E and dE/dt waveforms were subjectively classified according to their fine structure. Then the video images were examined field by field to identify each waveform with a visible channel to ground. Fifty-five correlated waveforms and channel images were obtained. Of these, all 34 first-stroke waveforms (multiple jagged E peaks, noisy dE/dt), 8 of which were not radiated by the chronologically first stroke in the flash, came from new channels to ground (not previously seen on video). All 18 subsequent-stroke waveforms (smoothly rounded E and quiet dE/dt after initial peak) were radiated by old channels (illuminated by a previous stroke). Two double-ground waveforms (two distinct first-return-stroke pulses separated by tens of microseconds or less) coincided with video fields showing two new channels. One `anomalous-stroke' waveform (beginning like a first stroke and ending like a subsequent) was produced by a new channel segment to ground branching off an old channel. This waveform classification depends on the presence or absence of high-frequency fine structure. Fourier analysis shows that first-stroke waveforms contain about 18 dB more spectral power in the frequency interval from 500 kHz to at least 7 MHz than subsequent-stroke waveforms for at least 13 microseconds after the main peak.

Willett, J. C.↗
NASA NTRS2005

The Far-Infrared Emission Line and Continuum Spectrum of the Seyfert Galaxy NGC 1068

We report on the analysis of the first complete far-infrared spectrum (43-197 microns) of the Seyfert 2 galaxy NGC 1068 as observed with the Long Wavelength Spectrometer (LWS) onboard the Infrared Space Observatory (ISO). In addition to the 7 expected ionic fine structure emission lines, the OH rotational lines at 79, 119 and 163 microns were all detected in emission, which is unique among galaxies with full LWS spectra, where the 119 micron line, where detected, is always in absorption. The observed line intensities were modelled together with IS0 Short Wavelength Spectrometer (SWS) and optical and ultraviolet line intensities from the literature, considering two independent emission components: the AGN component and the starburst component in the circumnuclear ring of approximately 3kpc in size. Using the UV to mid-IR emission line spectrum to constrain the nuclear ionizing continuum, we have confirmed previous results: a canonical power-law ionizing spectrum is a poorer fit than one with a deep absorption trough, while the presence of a big blue bump is ruled out. Based on the instantaneous starburst age of 5 Myr constrained by the Br gamma equivalent width in the starburst ring, and starburst synthesis models of the mid- and far-infrared fine-structure line emission, a low ionization parameter (U=10(exp -3.5)) and low densities (n=100 cm (exp -3)) are derived. Combining the AGN and starburst components, we succeed in modeling the overall UV to far-IR atomic spectrum of SGC 1068, reproducing the line fluxes to within a factor 2.0 on average with a standard deviation of 1.4. The OH 119 micron emission indicates that the line is collisionally excited, and arises in a warm and dense region. The OH emission has been modeled using spherically symmetric, non-local, non-LTE radiative transfer models. The models indicate that the bulk of the emission arises from the nuclear region, although some extended contribution from the starburst is not ruled out. The OH abundance in the nuclear region is expected to be approximately 10(exp -5), characteristic of X-ray dominated regions.

Spinoglio, Luigi↗
DOE OSTI2025

Nitrate-To-Ammonia Electroconversion at Neutral pH on Polycrystalline Vanadium Sulfide Derived from Vanadium Disulfide

The electrochemical nitrate reduction reaction (NO3RR) offers a pathway to produce NH3 for fuel and fertilizer from waste NO3-. In this work, a polycrystalline vanadium sulfide (VSx), which is derived from solvothermally grown and annealed VS2, is shown to exhibit excellent NO3RR activity (2.3 +- 0.6 mg.cm-2 geo..h-1 @ -0.92 VRHE) and Faradaic efficiency to NH4+ (69 +- 6% at -0.69 VRHE) in buffered neutral pH electrolyte containing 0.1 M NO3-. A variety of characterization techniques are leveraged to support the VSx assignment, including X-ray photoelectron spectroscopy, near-edge X-ray absorption fine structure spectroscopy, selected area electron diffraction, and X-ray diffraction measurements. The VS2 annealing step reduces the oxide character and generates VSx, which, based on the improved NO3RR activity, results in the creation of active sites for NO3- binding. To help shed light on NO3RR on VSx, VS2 is used as a model system, and a grand-canonical density functional theory (GC-DFT) investigation of VS2 shows strong evidence that S vacancies are active sites for NO3RR, where NO3- outcompetes H+ for adsorption at the S-vacancy sites. Moreover, GC-DFT results highlight a thermodynamically favorable reaction to generate NH4+ in an aqueous electrolyte at relevant cathodic potentials. As an annealed material, VSx may contain undersaturated V sites, which show an electronic structure similar to the theoretically calculated S-vacancy site of VS2, and these sites may contribute to the observed increase in NO3RR activity and selectivity for NH4+ on VSx versus unannealed VS2. Finally, kinetic isotope effect measurements suggest that the kinetic rate-limiting step of the NO3RR on VSx is not proton-coupled, indicating it may be the first electron transfer to adsorbed NO3*.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1983

Far-IR spectroscopy of the galactic center: Neutral and ionized gas in the central 10 pc of the galaxy

The 3P1 - 3P2 fine structure line emission from neutral atomic oxygen at 63 microns in the vicinity of the galactic center was mapped. The emission is extended over more than 4' (12 pc) along the galactic plane, centered on the position of Sgr A West. The line center velocities show that the O I gas is rotating around the galactic center with an axis close to that of the general galactic rotation, but there appear also to be noncircular motions. The rotational velocity at R is approximately 1 pc corresponds to a mass within the central pc of about 3 x 10(6) solar mass. Between 1 and 6 pc from the center the mass is approximately proportional to radius. The (O I) line probability arises in a predominantly neutral, atomic region immediately outside of the ionized central parsec of out galaxy. Hydrogen densities in the (O I) emitting region are 10(3) to 10(6) cm(-3) and gas temperatures are or = 100 K. The total integrated luminosity radiated in the line is about 10(5) solar luminosity, and is a substantial contribution to the cooling of the gas. Photoelectric heating or heating by ultraviolet excitation of H2 at high densities (10(5) cm(-3)) are promising mechanisms for heating of the gas, but heating due to dissipation of noncircular motions of the gas may be an alternative possibility. The 3P1 - 3P0 fine structure line of (O III) at 88 microns toward Sgr A West was also detected. The (O III) emission comes from high density ionized gas (n 10(4) cm(-3)), and there is no evidence for a medium density region (n 10(3) cm(-3)), such as the ionized halo in Sgr A West deduced from radio observations. This radio halo may be nonthermal, or may consist of many compact, dense clumps of filaments on the inner edges of neutral condensations at R or = 2 pc.

Hollenbach, D. J.↗
NASA NTRS1994

Carbon recombination lines as a diagnostic of photodissociation regions

We have observed the C91 alpha radio recombination line toward the Orion H II region. This narrow (approximately 3-5 km per sec full width at half maximum (FWHM)) line is spatially very extended (approximately 8 arcmin or 1 pc). These charateristics compare well with the observed characteristics of the C II fine structure line at 158 microns. Thus, the C91 alpha line originates in the predominantly neutral photodissociation regions separating the H II region from the molecular cloud. We have developed theoretical models for the C II radio recombination lines from photodissociation regions. The results show that the I(C91 alpha)/I(C158) intensity ratio is a sensitive function of the temperature and density of the emitting gas. We have also extended theoretical models for photodissociation regions to include the C II recombination lines. Comparison with these models show that, in the central portion of the Orion region, the C91 alpha line originates in dense (10(exp 6) per cu cm), warm (500-1000 K) gas. Even at large projected distances (approximately 1 pc), the inferred density is still high (10(exp 5) per cu cm) and implies extremely high thermal pressures. As in the case of the (C II) 158 microns line, the large extent of the C91 alpha line shows that (FUV) photons can penetrate to large distances from the illuminating source. The decline of the intensity of the incident radiation field with distance from Theta(sup 1) C seems to be dominated by geometrical dilution, rather than dust extinction. Finally, we have used our models to calculate the intensity of the 9850 A recombination line of C II. The physical conditions inferred from this line are in good agreement with those determined from the radio recombination and the far-infrared fine-structure lines. We show that the ratio of the 9850 A to the C91 alpha lines is a very good probe of very high density clumps.

Natta, A.↗
NASA NTRS2003

The [C II] 158 Micron Line in Ultraluminous Infrared Galaxies Revisited

We present a study of the [C II] 157.74 micron fine-structure line in a sample of 15 ultraluminous infrared (IR) galaxies (IR luminosity L(sub IR greater than or equal to 10(exp 12)L.; ULIRGs) using the Long Wavelength Spectrometer (LWS) on the Infrared Space Observatory (ISO). We confirm the observed order of magnitude deficit (compared to normal and starburst galaxies) in the strength of the [C II] line relative to the far-infrared (FIR) dust continuum emission found in our initial report, but here with a sample that is twice as large. This result suggests that the deficit is a general phenomenon affecting 4 out of 5 ULIRGs. We present an analysis using observations of generally acknowledged photodissociation region (PDR) tracers ([C II], [OI] 63 and 145 micron, and FIR continuum emission), which suggests that a high ultraviolet flux G(sub 0) incident on a moderate density n PDR could explain the deficit. However, comparisons with other ULIRG observations, including CO (1-0), [C I] (1-0), and 6.2 micron polycyclic aromatic hydrocarbon (PAH) emission, suggest that high G(sub 0)/n PDRs alone cannot produce a self-consistent solution that is compatible with all of the observations. We propose that non-PDR contributions to the FIR continuum can explain the apparent [C II] deficiency. Here, unusually high G(sub 0) and/ or n physical conditions in ULIRGs as compared to those in normal and starburst galaxies are not required to explain the [C II] deficit. Dust-bounded photoionization regions, which generate much of the FIR emission but do not contribute significant [C II] emission, offer one possible physical origin for this additional non-PDR component. Such environments may also contribute to the observed suppression of FIR fine-structure emission from ionized gas and PAHs, as well as the warmer FIR colors found in ULIRGs. The implications for observations at higher redshifts are also revisited.

Luhman, M. L.↗
DOE OSTI2024

Catalytic Water Electrolysis by Co–Cu–W Mixed Metal Oxides: Insights from X-ray Absorption Spectroelectrochemistry

Mixed metal oxides (MMOs) are a promising class of electrocatalysts for the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER). Despite their importance for sustainable energy schemes, our understanding of relevant reaction pathways, catalytically active sites, and synergistic effects is rather limited. Here, we applied synchrotron-based X-ray absorption spectroscopy (XAS) to explore the evolution of the amorphous Co–Cu–W MMO electrocatalyst, shown previously to be an efficient bifunctional OER and HER catalyst for water splitting. Ex situ XAS measurements provided structural environments and the oxidation state of the metals involved, revealing Co 2+ (octahedral), Cu + / 2+ (tetrahedral/square-planar), and W 6+ (octahedral) centers. Operando XAS investigations, including X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS), elucidated the dynamic structural transformations of Co, Cu, and W metal centers during the OER and HER. The experimental results indicate that Co 3+ and Cu 0 are the active catalytic sites involved in the OER and HER, respectively, while Cu 2+ and W 6+ play crucial roles as structure stabilizers, suggesting strong synergistic interactions within the Co–Cu–W MMO system. In conclusion, these results, combined with the Tafel slope analysis, revealed that the bottleneck intermediate during the OER is Co 3+ hydroperoxide, whose formation is accompanied by changes in the Cu–O bond lengths, pointing to a possible synergistic effect between Co and Cu ions. Our study reveals important structural effects taking place during MMO-driven OER/HER electrocatalysis and provides essential experimental insights into the complex catalytic mechanism of emerging noble-metal-free MMO electrocatalysts for full water splitting.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Deciphering the Solvent Effect for the Solvation Structure of Ca 2+ in Polar Molecular Liquids

Although the crystal structures for many inorganic compounds are readily available, researchers are still working hard to understand the relations between the structures and chemical properties of solutions because most of the chemical reactions take place in solutions. A huge amount of effort has been put toward modeling the ion solvation structure from the perspectives of both experiments and theories. In this study, the solvation structures of Ca 2+ ions in aqueous and alcoholic solutions at different concentrations were carefully evaluated by Ca K-edge X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) analyses. Further, density functional theory (DFT) calculations were also performed to correlate the results with the experimental data and then further extended to other similar systems. It was found that the number of coordinating solvent molecules decreases with increasing Ca 2+ concentration and increasing solvent molecule sizes. From the EXAFS data, it was observed that the first solvation shell of Ca 2+ splits into two Ca-O distances in a methanol solution and the counter ion Cl - might also be within the first shell at high concentrations. For the first time, the effects of solvents with different polarities and sizes on the ion solvation environment were systematically evaluated.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

In Situ Determination of Speciation and Local Structure of NaCl–SrCl 2 and LiF–ZrF 4 Molten Salts

Understanding the local environment of the metal atoms in salt melts is important for modeling the properties of melts and predicting their behavior and thus helping enable the development of technologies such as molten salt reactors and solar-thermal power systems and new approaches to recycling rare-earth metals. Toward that end, we have developed an in situ approach for measuring the coordination of metals in molten salt coupling X-ray absorption spectroscopy (XAS) and Raman spectroscopy. Our approach was demonstrated for two salt mixtures (1.9 and 5 mol % SrCl 2 in NaCl, 0.8 and 5 mol % ZrF 4 in LiF) at up to 1100 °C. Near-edge (X-ray absorption near-edge structure, XANES) and extended X-ray absorption fine structure (EXAFS) spectra were measured. The EXAFS response was modeled using ab initio FEFF calculations. Strontium’s first shell is observed to be coordinated with chlorine (Sr 2+ –Cl – ) and zirconium’s first shell is coordinated by fluorine (Zr 4+ –F – ), both having coordination numbers that decrease with increasing temperature. Multiple zirconium complexes are believed to be present in the melt, which may interfere and distort the EXAFS spectra and result in an anomalously low zirconium first shell coordination number. Finally, the use of boron nitride (BN) powder as a salt diluent for XAFS measurements was found to not interfere with measurements and thus can be used for investigations of such systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Effect of oxidation on the release of multiple metals from industrially polluted sediments and synchrotron-based evidence of Cu–S dynamic association

Disposal operations for industrially polluted sediments are usually accompanied by disturbance and resuspension, which can induce metal remobilization and secondary pollution. Evaluating the risk of metal release under various redox conditions is fundamental for predicting contaminant mobilization and guiding remediation measures. An abandoned oxidation pond, Yanjia Lake, China, was selected as a typical industrially polluted site. Re-suspension experiments were carried out by mixing polluted sediments with lake water under oxic or anoxic conditions, then investigating the effect of oxidation conditions on the release of multiple metals. Metal concentrations and aqueous chemistry in the overlying water were monitored. Synchrotron-based methods, including X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS), were used to characterize oxidation states and coordination conditions of metals in sediments. The release of metals, including Cr, Co, Ni, Cu, Zn, Se, Mo, Sn, Cd, and Pb, was enhanced under oxic vs. anoxic conditions. The XANES analysis revealed that elevated Cr and Zn concentrations under oxic conditions likely resulted from the oxidation of Cr(III) and oxidizing dissolution of ZnS, respectively. K-edge Cu XANES, S XANES, and Cu EXAFS analyses reconstructed the Cu–S association, indicating that S-related oxidation promoted Cu release and Cu–O partly replaced Cu–S in the sediment after a 7-day oxic treatment. The release of most metals was promoted under oxic conditions, resulting from the oxidation of sulfides and metals as indicated by aqueous and synchrotron-based evidence. The risk of secondary pollution is greatly enhanced under oxic conditions, which suggests that measures should be taken to minimize the redox disturbance during sediment remediation. This information can guide the management of sediments in Yanjia Lake and other contaminated sites with similar properties.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2023

Temporal Ni K-Edge X-ray Absorption Spectroscopy Study Reveals the Kinetics of the Ni Redox Behavior of the Iron-Nickel Oxide Bimetallic OER Catalyst

Operando X-ray absorption spectroscopy (XAS) can be utilized to probe the phase and structural changes of FeNiOx and similar transition metal oxide electrocatalysts during electrocatalytic reactions. However, capturing the temporal changes occurring in the operando chemistry of electrocatalysts has been little studied. Here, in this work, we successfully capture the time-resolved changes at the Ni K-edge for both the X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) regions of an aqueous phase synthesized FeNiO x bimetallic nanoparticle electrocatalyst. During a stepped voltage experiment, the temporal change in the Ni K-edge was observed as the applied voltage was stepped from 0.7 to 0.8 V versus the silver/silver chloride reference electrode, and the change observed is associated with the Ni redox transition from the 2+ to 3+/4+ oxidation state. Individual XAS spectra were obtained in 90 s, and a total of 9 scans post voltage step showed a unique transition from a hydroxide to an oxyhydroxide phase. The shift in absorption edge energy position and the changes in spectral shape for individual scans explain the typically observed broadening of the Ni K-edge XANES spectrum during time-averaged operando XAS, and a kinetic analysis revealed a first-order observed rate constant, |k obs |, of 0.00426 s –1 and a half-life (t 1/2 ) of 163 s. Multivariate curve resolution-alternating least squares analysis followed by linear combination fitting analysis for time-averaged versus time-resolved Ni K-edge changes upon voltage step show distinct differences in estimated contributions from Ni 2+ oxide/hydroxide phases. Detailed EXAFS modeling shows the phase transition from hydroxide to oxyhydroxide on top of the unchanged metallic core.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗