The widespread use of fuel cells is currently limited by the lack of efficient and cost-effective catalysts for the oxygen reduction reaction. Iron-based non-precious metal catalysts exhibit promising activity and stability, as an alternative to state-of-the-art platinum catalysts. However, the identity of the active species in non-precious metal catalysts remains elusive, impeding the development of new catalysts. Here we demonstrate the reversible deactivation and reactivation of an iron-based non-precious metal oxygen reduction catalyst achieved using high-temperature gas-phase chlorine and hydrogen treatments. In addition, we observe a decrease in catalyst heterogeneity following treatment with chlorine and hydrogen, using Mössbauer and X-ray absorption spectroscopy. Our study reveals that protected sites adjacent to iron nanoparticles are responsible for the observed activity and stability of the catalyst. These findings may allow for the design and synthesis of enhanced non-precious metal oxygen reduction catalysts with a higher density of active sites.

Using in situ synchrotron measurements of total reflection x-ray fluorescence, we find evidence of strontium surface segregation in (001)-oriented La0.7Sr0.3MnO3 thin films over a wide range of temperatures (25–900 °C) and oxygen partial pressures (pO2=0.15–150 Torr). The strontium surface concentration is observed to increase with decreasing pO2, suggesting that the surface oxygen vacancy concentration plays a significant role in controlling the degree of segregation. Interestingly, the enthalpy of segregation becomes less exothermic with increasing pO2, varying from −9.5 to −2.0 kJ/mol. In contrast, the La0.7Sr0.3MnO3 film thickness and epitaxial strain state have little impact on segregation behavior.

Electrodeposition of Cu, Cu/Ag, and Cu/Sn alloy films by using 3,5-diamino-1,2,4-triazole (DAT) as an electrodeposition inhibitor yields a high surface area Cu-based catalyst. All three Cu-based electrodes exhibit high Faradaic efficiency (FE) of CO2 reduction toward C2H4 production. The CuSn-DAT electrode exhibits the highest FE for CO (∼90% at −0.4 V) and C2H4 (∼60% at −0.8 V) production and high current density (∼−225 mA/cm2 at −0.8 V). In situ surface enhanced Raman spectroscopy (SERS) studies in a flow cell obtained from the three Cu-based samples show a correlation between the decreased oxide content on the Cu surface, increased presence of CO, and increased activity for CO and C2 production. The CuSn-DAT electrode has the lowest amount of Cu2O and exhibits the highest activity, whereas the Cu-DAT electrode has an increasing Cu2O content and exhibits lower activity as the potential is made negative. These results demonstrate that incorporation of different well-mixed alloy materials provides a way to tune CO2 reduction speciation.

Nonresonant x-ray Raman scattering ͑XRS͒ is the inelastic scattering of hard x rays from the K shell of low-Z elements or the less tightly bound shells of heavier elements. In the limit of low momentum transfer q, XRS is determined by the same transition matrix element as is measured by x-ray absorption spectroscopies. However, XRS at higher q can often access higher order multipole transitions which help separate the symmetry of various contributions to the local density of states. The main drawback of XRS is its low cross section-a problem that is compounded for a q-dependent study. To address this issue, we have constructed a multielement spectrometer to simultaneously measure XRS at ten different values of q. By means of example, we report new measurements of the XRS from the L-and K-edges of Mg. This instrument is now available to general users at the Advanced Photon Source as the lower energy resolution inelastic x-ray scattering ͑LERIX͒ spectrometer.

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In lithium ion batteries, decomposition of the electrolyte and its associated passivation of the electrode surface occurs at low potentials, resulting in an electronically insulating, but Li-ion conducting, solid electrolyte interphase (SEI). The products of the SEI and their chemical constituents/properties play an important role in the long-term stability and performance of the battery. Reactivity and the sub-keV core binding energies of lithium, carbon, oxygen, and fluorine species in the SEI present technical challenges in the spectroscopy of these compounds. Using an alternative approach, nonresonant inelastic x-ray scattering, we examine the near-edge spectra of bulk specimens of common SEI compounds, including LiF, Li(2)CO(3), LiOH, LiOH·H(2)O, and Li(2)O. By working at hard x-ray energies, we also experimentally differentiate the s- and p-symmetry components of lithium's unoccupied states using the evolution of its K edge with momentum transfer. We find good agreement with theoretical spectra calculated using a Bethe-Salpeter approach in all cases. These results provide an analytical and diagnostic foundation for better understanding of the makeup of SEIs and the mechanism of their formation.

Many complex oxides display an array of structural instabilities often tied to altered electronic behavior. For oxide heterostructures, several different interfacial effects can dramatically change the nature of these instabilities. Here, we investigate LaAlO3/SrTiO3 (001) heterostructures using synchrotron x-ray scattering. We find that when cooling from high temperature, LaAlO3 transforms from the \documentclass[12pt]{minimal}\begin{document}$Pm\bar{3}m$\end{document}Pm3¯m to the Imma phase due to strain. Furthermore, the first 4 unit cells of the film adjacent to the substrate exhibit a gradient in rotation angle that can couple with polar displacements in films thinner than that necessary for 2D electron gas formation.

Intrinsic and experimental mechanisms frequently lead to broadening of spectral features in excited-state spectroscopies. For example, intrinsic broadening occurs in x-ray absorption spectroscopy (XAS) measurements of heavy elements where the core-hole lifetime is very short. On the other hand, nonresonant x-ray Raman scattering (XRS) and other energy loss measurements are more limited by instrumental resolution. Here, we demonstrate that the Richardson-Lucy (RL) iterative algorithm provides a robust method for deconvolving instrumental and intrinsic resolutions from typical XAS and XRS data.For the K-edge XAS of Ag, we find nearly complete removal of ~9.3 eV FWHM broadening from the combined effects of the short core-hole lifetime and instrumental resolution. We are also able to remove nearly all instrumental broadening in an XRS measurement of diamond, with the resulting improved spectrum comparing favorably with prior soft x-ray XAS measurements. We present a practical methodology for implementing the RL algorithm to these problems, emphasizing the importance of testing for stability of the deconvolution process against noise amplification, perturbations in the initial spectra, and uncertainties in the core-hole lifetime.