Highly active catalysts for the oxygen evolution reaction (OER) are required for the development of photoelectrochemical devices that generate hydrogen efficiently from water using solar energy. Here, we identify the origin of a 500-fold OER activity enhancement that can be achieved with mixed (Ni,Fe)oxyhydroxides (Ni(1-x)Fe(x)OOH) over their pure Ni and Fe parent compounds, resulting in one of the most active currently known OER catalysts in alkaline electrolyte. Operando X-ray absorption spectroscopy (XAS) using high energy resolution fluorescence detection (HERFD) reveals that Fe(3+) in Ni(1-x)Fe(x)OOH occupies octahedral sites with unusually short Fe-O bond distances, induced by edge-sharing with surrounding [NiO6] octahedra. Using computational methods, we establish that this structural motif results in near optimal adsorption energies of OER intermediates and low overpotentials at Fe sites. By contrast, Ni sites in Ni(1-x)Fe(x)OOH are not active sites for the oxidation of water.

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Identification of Highly Active Fe Sites in (Ni,Fe)OOH for Electrocatalytic Water Splitting

Rechargeable battery technologies have ignited major breakthroughs in contemporary society, including but not limited to revolutions in transportation, electronics, and grid energy storage The remarkable development of rechargeable batteries is largely attributed to in-depth efforts to improve battery electrode and electrolyte materials There are, however, still intimidating challenges of lower cost, longer cycle and calendar life, higher energy density, and better safety for large scale energy storage and vehicular applications Further progress with rechargeable batteries may require new chemistries (lithium ion batteries and beyond) and better understanding of materials electrochemistry in the various battery technologies In the past decade, advancement of battery materials has been complemented by new analytical techniques that are capable of probing battery chemistries at various length and time scales Synchrotron X-ray techniques stand out as one of the most effective methods that allow for near

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Synchrotron X-ray Analytical Techniques for Studying Materials Electrochemistry in Rechargeable Batteries

The ability to manipulate quantum dot (QD) surfaces is foundational to their technological deployment. Surface manipulation of metal halide perovskite (MHP) QDs has proven particularly challenging in comparison to that of more established inorganic materials due to dynamic surface species and low material formation energy; most conventional methods of chemical manipulation targeted at the MHP QD surface will result in transformation or dissolution of the MHP crystal. In previous work, we have demonstrated record-efficiency QD solar cells (QDSCs) based on ligand-exchange procedures that electronically couple MHP QDs yet maintain their nanocrystalline size, which stabilizes the corner-sharing structure of the constituent PbI64– octahedra with optoelectronic properties optimal for solar energy conversion. In this work, we employ a variety of spectroscopic techniques to develop a molecular-level understanding of the MHP QD surface chemistry in this system. We individually target both the anionic (oleate) and ...

Targeted Ligand-Exchange Chemistry on Cesium Lead Halide Perovskite Quantum Dots for High-Efficiency Photovoltaics

Supported single atoms provide an opportunity to design new heterogeneous catalysts while optimizing the utilization of noble metals. However, identification of the active single-atom structure is required for understanding the reaction mechanism and guiding catalyst design. Here, we use in situ infrared spectroscopy, operando X-ray absorption spectroscopy and quantum chemical calculations to identify the active single-atom complex as well as the resting state of the Ir/MgAl2O4 catalysts during the low-temperature CO oxidation. In contrast to poisoning of iridium nanoparticles by CO, here we show that the formation of Ir(CO) on single atoms results in a different reaction mechanism and high activity for low-temperature CO oxidation. This is due to the ability of single atoms to coordinate with multiple ligands, where Ir(CO) provides an interfacial site for facile O2 activation between Ir and Al and lowers the reaction barrier between gas-phase CO(g) and *O in Ir(CO)(O) through an Eley–Rideal mechanism. Single-atom catalysts are receiving much attention, but insights into their active sites or the differences in reactivity with conventional nanoparticles are still controversial. Now, operando studies on CO oxidation with Ir/MgAl2O4 accompanied by computational investigations reveal important features of this class of catalyst.

Identification of the active complex for CO oxidation over single-atom Ir-on-MgAl 2 O 4 catalysts

Through soft X-ray absorption spectroscopy, hard X-ray Raman scattering, and theoretical simulations, we provide the most in-depth and systematic study of the phase transformation and (de)lithiation effect on electronic structure in LixFePO4 nanoparticles and single crystals. Soft X-ray reveals directly the valence states of Fe 3d electrons in the vicinity of Fermi level, which is sensitive to the local lattice distortion, but more importantly offers detailed information on the evolution of electronic states at different electrochemical stages. The soft X-ray spectra of LixFePO4 nanoparticles evolve vividly with the (de)lithiation level. The spectra fingerprint the (de)lithiation process with rich information on Li distribution, valency, spin states, and crystal field. The high resolution spectra reveal a subtle but critical deviation from two-phase transformation in our electrochemically prepared samples. In addition, we performed both first principles calculations and multiplet simulations of the spectra and quantitatively determined the 3d valence states that are completely redistributed through (de)lithiation. This electronic reconfiguration was further verified by the polarization-dependent spectra collected on LiFePO4 single crystals, especially along the lithium diffusion direction. The evolution of the 3d states is overall consistent with the local lattice distortion and provides a fundamental picture of the (de)lithiation effects on electronic structure in the LixFePO4 system.

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Phase Transformation and Lithiation Effect on Electronic Structure of LixFePO4 : An In-Depth Study by Soft X-ray and Simulations

We present a multicrystal Johann-type hard x-ray spectrometer (∼5–18 keV) recently developed, installed, and operated at the Stanford Synchrotron Radiation Lightsource. The instrument is set at the wiggler beamline 6-2 equipped with two liquid nitrogen cooled monochromators – Si(111) and Si(311) – as well as collimating and focusing optics. The spectrometer consists of seven spherically bent crystal analyzers placed on intersecting vertical Rowland circles of 1 m of diameter. The spectrometer is scanned vertically capturing an extended backscattering Bragg angular range (88°–74°) while maintaining all crystals on the Rowland circle trace. The instrument operates in atmospheric pressure by means of a helium bag and when all the seven crystals are used (100 mm of projected diameter each), has a solid angle of about 0.45% of 4π sr. The typical resolving power is in the order of EΔE∼10000. The spectrometer's high detection efficiency combined with the beamline 6-2 characteristics permits routine studies of x-ray emission, high energy resolution fluorescence detected x-ray absorption and resonant inelastic x-ray scattering of very diluted samples as well as implementation of demanding in situ environments.

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A seven-crystal Johann-type hard x-ray spectrometer at the Stanford Synchrotron Radiation Lightsource

We present a new x-ray Raman spectroscopy end-station recently developed, installed, and operated at the Stanford Synchrotron Radiation Lightsource. The end-station is located at wiggler beamline 6-2 equipped with two monochromators-Si(111) and Si(311) as well as collimating and focusing optics. It consists of two multi-crystal Johann type spectrometers arranged on intersecting Rowland circles of 1 m diameter. The first one, positioned at the forward scattering angles (low-q), consists of 40 spherically bent and diced Si(110) crystals with 100 mm diameters providing about 1.9% of 4π sr solid angle of detection. When operated in the (440) order in combination with the Si (311) monochromator, an overall energy resolution of 270 meV is obtained at 6462.20 eV. The second spectrometer, consisting of 14 spherically bent Si(110) crystal analyzers (not diced), is positioned at the backward scattering angles (high-q) enabling the study of non-dipole transitions. The solid angle of this spectrometer is about 0.9% of 4π sr, with a combined energy resolution of 600 meV using the Si (311) monochromator. These features exceed the specifications of currently existing relevant instrumentation, opening new opportunities for the routine application of this photon-in/photon-out hard x-ray technique to emerging research in multidisciplinary scientific fields, such as energy-related sciences, material sciences, physical chemistry, etc.

D. Wenger

Papers

A seven-crystal Johann-type hard x-ray spectrometer at the Stanford Synchrotron Radiation Lightsource

A high resolution and large solid angle x-ray Raman spectroscopy end-station at the Stanford Synchrotron Radiation Lightsource