Elucidation of the Co state with strong charge-transfer effects in charged LiCoO by resonant soft X-ray emission spectroscopy at the Co L edge.

To understand the electronic-structure change of LiCoO, a widely used cathode material in Li-ion batteries, during charge-discharge, we performed soft X-ray absorption spectroscopy (XAS) and resonant soft X-ray emission spectroscopy (RXES) of the Co L edge in combination with charge-transfer multiplet calculations. The RXES profile significantly changed for the charged state at 4.2 V Li/Li, corresponding to the oxidation reaction from a Co low-spin state for the initial state, while the XAS profile exhibited small changes.

Operando Soft X-ray Absorption of LaMn Co O Perovskites for CO Oxidation.

We employed operando soft X-ray absorption spectroscopy (XAS) to monitor the changes in the valence states and spin properties of LaMn Co O catalysts subjected to a mixture of CO and O at ambient pressure. Guided by simulations based on charge transfer multiplet theory, we quantitatively analyze the Mn and Co 2p XAS as well as the oxygen K-edge XAS spectra during the reaction process. The Mn sites are particularly sensitive to the catalytic reaction, displaying dynamics in their oxidation state.

In Situ X-ray Absorption Spectroscopy of LaFeO and LaFeO/LaNiO Thin Films in the Electrocatalytic Oxygen Evolution Reaction.

We study the electrocatalytic oxygen evolution reaction using in situ X-ray absorption spectroscopy (XAS) to track the dynamics of the valence state and the covalence of the metal ions of LaFeO and LaFeO/LaNiO thin films. The active materials are 8 unit cells grown epitaxially on 100 nm conductive LaSrMnO layers using pulsed laser deposition (PLD). The perovskite layers are supported on monolayer CaNbO nanosheet-buffered 100 nm SiN membranes.

Spin polarized electron dynamics enhance water splitting efficiency by yttrium iron garnet photoanodes: a new platform for spin selective photocatalysis.

This work presents a spectroscopic and photocatalytic comparison of water splitting using yttrium iron garnet (YFeO, YIG) and hematite (α-FeO) photoanodes. Despite similar electronic structures, YIG significantly outperforms widely studied hematite, displaying more than an order of magnitude increase in photocurrent density. Probing the charge and spin dynamics by ultrafast, surface-sensitive XUV spectroscopy reveals that the enhanced performance arises from (1) reduced polaron formation in YIG compared to hematite and (2) an intrinsic spin polarization of catalytic photocurrents in YIG.

Electron population dynamics in resonant non-linear x-ray absorption in nickel at a free-electron laser.

Free-electron lasers provide bright, ultrashort, and monochromatic x-ray pulses, enabling novel spectroscopic measurements not only with femtosecond temporal resolution: The high fluence of their x-ray pulses can also easily enter the regime of the non-linear x-ray-matter interaction. Entering this regime necessitates a rigorous analysis and reliable prediction of the relevant non-linear processes for future experiment designs. Here, we show non-linear changes in the -edge absorption of metallic nickel thin films, measured with fluences up to 60 J/cm.

Anomalous Impact of Mechanochemical Treatment on the Na-ion Conductivity of Sodium Closo-Carbadodecaborate Probed by X-Ray Raman Scattering Spectroscopy.

Solid-state sodium ion conductors are crucial for the next generation of all-solid-state sodium batteries with high capacity, low cost, and improved safety. Sodium closo-carbadodecaborate (NaCB H ) is an attractive Na-ion conductor owing to its high thermal, electrochemical, and interfacial stability. Mechanical milling has recently been shown to increase conductivity by five orders of magnitude at room temperature, making it appealing for application in all-solid-state sodium batteries.

Modulation-doping a correlated electron insulator.

Correlated electron materials (CEMs) host a rich variety of condensed matter phases. Vanadium dioxide (VO) is a prototypical CEM with a temperature-dependent metal-to-insulator (MIT) transition with a concomitant crystal symmetry change. External control of MIT in VO-especially without inducing structural changes-has been a long-standing challenge.

Magnetic excitations beyond the single- and double-magnons.

A photon carrying one unit of angular momentum can change the spin angular momentum of a magnetic system with one unit (ΔM = ±1) at most. This implies that a two-photon scattering process can manipulate the spin angular momentum of the magnetic system with a maximum of two units. Herein we describe a triple-magnon excitation in α-FeO, which contradicts this conventional wisdom that only 1- and 2-magnon excitations are possible in a resonant inelastic X-ray scattering experiment.

Fitting Multiplet Simulations to L-Edge XAS Spectra of Transition-Metal Complexes Using an Adaptive Grid Algorithm.

A new methodology based on an adaptive grid algorithm followed by an analysis of the ground state from the fit parameters is presented to analyze and interpret experimental XAS L-edge data. The fitting method is tested first in a series of multiplet calculations for d-d systems and for which the solution is known. In most cases, the algorithm is able to find the solution, except for a mixed-spin Co complex, where it instead revealed a correlation between the crystal field and the electron repulsion parameters near spin-crossover transition points.

Insight into the Nature of the ZnO Promoter during Methanol Synthesis.

Despite the great commercial relevance of zinc-promoted copper catalysts for methanol synthesis, the nature of the Cu-ZnO synergy and the nature of the active Zn-based promoter species under industrially relevant conditions are still a topic of vivid debate. Detailed characterization of the chemical speciation of any promoter under high-pressure working conditions is challenging but specifically hampered by the large fraction of Zn spectator species bound to the oxidic catalyst support. We present the use of weakly interacting graphitic carbon supports as a tool to study the active speciation of the Zn promoter phase that is in close contact with the Cu nanoparticles using time-resolved X-ray absorption spectroscopy under working conditions.

Analyzing the Local Electronic Structure of CoO Using 2p3d Resonant Inelastic X-ray Scattering.

We present the cobalt 2p3d resonant inelastic X-ray scattering (RIXS) spectra of CoO. Guided by multiplet simulation, the excited states at 0.5 and 1.

Direct and real-time observation of hole transport dynamics in anatase TiO using X-ray free-electron laser.

Carrier dynamics affects photocatalytic systems, but direct and real-time observations in an element-specific and energy-level-specific manner are challenging. In this study, we demonstrate that the dynamics of photo-generated holes in metal oxides can be directly probed by using femtosecond X-ray absorption spectroscopy at an X-ray free-electron laser. We identify the energy level and life time of holes with a long life time (230 pico-seconds) in nano-crystal materials.

Hole Dynamics in Photoexcited Hematite Studied with Femtosecond Oxygen K-edge X-ray Absorption Spectroscopy.

Hematite (α-FeO) is a photoelectrode for the water splitting process because of its relatively narrow bandgap and abundance in the earth's crust. In this study, the photoexcited state of a hematite thin film was investigated with femtosecond oxygen K-edge X-ray absorption spectroscopy (XAS) at the PAL-XFEL in order to follow the dynamics of its photoexcited states. The 200 fs decay time of the hole state in the valence band was observed via its corresponding XAS feature.

Temperature-Driven Self-Doping in Magnetite.

Magnetite is one of the most fascinating materials exhibiting the enigmatic first-order Verwey transition which is conventionally manipulated through chemical doping. Here, we show that heating magnetite results in a spontaneous charge reordering and, consequently, a hole self-doping effect at the octahedral sublattice. Core-level x-ray spectroscopy measurements combined with theory uncovers that there are three regimes of self-doping that map the temperature dependence of the electrical conductivity and magnetism up to the Curie temperature.

Femtosecond Charge Density Modulations in Photoexcited CuWO.

Copper tungstate (CuWO) is an important semiconductor with a sophisticated and debatable electronic structure that has a direct impact on its chemistry. Using the PAL-XFEL source, we study the electronic dynamics of photoexcited CuWO. The Cu L X-ray absorption spectrum shifts to lower energy upon photoexcitation, which implies that the photoexcitation process from the oxygen valence band to the tungsten conduction band effectively increases the charge density on the Cu atoms.

Rational strain engineering of single-atom ruthenium on nanoporous MoS for highly efficient hydrogen evolution.

Maximizing the catalytic activity of single-atom catalysts is vital for the application of single-atom catalysts in industrial water-alkali electrolyzers, yet the modulation of the catalytic properties of single-atom catalysts remains challenging. Here, we construct strain-tunable sulphur vacancies around single-atom Ru sites for accelerating the alkaline hydrogen evolution reaction of single-atom Ru sites based on a nanoporous MoS-based Ru single-atom catalyst. By altering the strain of this system, the synergistic effect between sulphur vacancies and Ru sites is amplified, thus changing the catalytic behavior of active sites, namely, the increased reactant density in strained sulphur vacancies and the accelerated hydrogen evolution reaction process on Ru sites.

Spectroscopic characterization of electronic structures of ultra-thin single crystal LaSrMnO.

We have successfully fabricated high quality single crystalline LaSrMnO (LSMO) film in the freestanding form that can be transferred onto silicon wafer and copper mesh support. Using soft x-ray absorption (XAS) and resonant inelastic x-ray scattering (RIXS) spectroscopy in transmission and reflection geometries, we demonstrate that the x-ray emission from Mn 3s-2p core-to-core transition (3sPFY) seen in the RIXS maps can represent the bulk-like absorption signal with minimal self-absorption effect around the Mn L-edge. Similar measurements were also performed on a reference LSMO film grown on the SrTiO substrate and the agreement between measurements substantiates the claim that the bulk electronic structures can be preserved even after the freestanding treatment process.

Self-Activated Catalytic Sites on Nanoporous Dilute Alloy for High-Efficiency Electrochemical Hydrogen Evolution.

Design and synthesis of effective electrocatalysts for hydrogen evolution reaction (HER) in wide pH environments are critical to reduce energy losses in water electrolyzers. Here, by using a self-activation strategy, we construct an atomic nickel (Ni) decorated nanoporous iridium (Ir) catalyst, which can create the reaction-favorable chemical environment and maximize the electrochemical active surface area (ECSA), enabling efficient HER over a wide pH range. By using X-ray absorption spectroscopy and theoretical calculations, the atomic Ni sites are identified as the synergistic sites, which not only accelerate the water dissociation under operation conditions but also activate the surface Ir sites thus leading to the efficient H generation.

Saturation and self-absorption effects in the angle-dependent 2p3d resonant inelastic X-ray scattering spectra of Co.

Angle-dependent 2p3d resonant inelastic X-ray scattering spectra of a LaCoO single crystal and a 55 nm LaCoO film on a SrTiO substrate are presented. Theoretical calculation shows that, with ∼20 meV resolved Co 2p3d resonant inelastic X-ray scattering (RIXS), the excited states of the isotropic A(O) ground state are split by 3d spin-orbit coupling, which can be distinguished via their angular dependence. However, strong self-absorption and saturation effects distort the spectra of the LaCoO single crystal and limit the observation of small angular dependence.

Tensor description of X-ray magnetic dichroism at the Fe L-edges of FeO.

A procedure to build the optical conductivity tensor that describes the full magneto-optical response of the system from experimental measurements is presented. Applied to the Fe L-edge of a 38.85 nm FeO/SrTiO (001) thin-film, it is shown that the computed polarization dependence using the conductivity tensor is in excellent agreement with that experimentally measured.

Intramolecular crossover from unconventional diamagnetism to paramagnetism of palladium ions probed by soft X-ray magnetic circular dichroism.

The case of palladium(II) ions in molecular polyoxopalladates highlights the importance of accounting not only for nearest neighbour atoms or ions in order to understand, model or predict magnetic characteristics. Here, using site-specific soft X-ray magnetic circular dichroism (XMCD), the effects of different bond lengths, delocalization of 4d electrons, and 4d spin-orbit coupling on the electronic and magnetic properties are investigated and three different states identified: Conventional diamagnetism in a square-planar O coordination environment, paramagnetism caused by four additional out-of-plane oxygen anions, and an unusual diamagnetic state in the diamagnetic/paramagnetic crossover region modified by significant mixing of states and facilitated by the substantial 4d spin-orbit coupling. The two diamagnetic states can be distinguished by characteristic XMCD fine structures, thereby overcoming the common limitation of XMCD to ferro-/ferrimagnetic and paramagnetic materials in external magnetic fields.

Dynamic active-site generation of atomic iridium stabilized on nanoporous metal phosphides for water oxidation.

Designing efficient single-atom catalysts (SACs) for oxygen evolution reaction (OER) is critical for water-splitting. However, the self-reconstruction of isolated active sites during OER not only influences the catalytic activity, but also limits the understanding of structure-property relationships. Here, we utilize a self-reconstruction strategy to prepare a SAC with isolated iridium anchored on oxyhydroxides, which exhibits high catalytic OER performance with low overpotential and small Tafel slope, superior to the IrO.

Oxygen K-edge X-ray Absorption Spectra.

We review oxygen K-edge X-ray absorption spectra of both molecules and solids. We start with an overview of the main experimental aspects of oxygen K-edge X-ray absorption measurements including X-ray sources, monochromators, and detection schemes. Many recent oxygen K-edge studies combine X-ray absorption with time and spatially resolved measurements and/or operando conditions.