J. Appl. Cryst.の発刊に際して

During the last decades, X-ray absorption spectroscopy (XAS) has become an indispensable method for probing the structure and composition of heterogeneous catalysts, revealing the nature of the active sites and establishing links between structural motifs in a catalyst, local electronic structure, and catalytic properties. Here we discuss the fundamental principles of the XAS method and describe the progress in the instrumentation and data analysis approaches undertaken for deciphering X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) spectra. Recent usages of XAS in the field of heterogeneous catalysis, with emphasis on examples concerning electrocatalysis, will be presented. The latter is a rapidly developing field with immense industrial applications but also unique challenges in terms of the experimental characterization restrictions and advanced modeling approaches required. This review will highlight the new insight that can be gained with XAS on complex real-world electrocatalysts including their working mechanisms and the dynamic processes taking place in the course of a chemical reaction. More specifically, we will discuss applications of in situ and operando XAS to probe the catalyst’s interactions with the environment (support, electrolyte, ligands, adsorbates, reaction products, and intermediates) and its structural, chemical, and electronic transformations as it adapts to the reaction conditions.

In Situ/Operando Electrocatalyst Characterization by X-ray Absorption Spectroscopy

As the main constituent of planetary cores, pure iron phase diagram under high pressure and temperature is of fundamental importance in geophysics and planetary science. However, previously reported iron‐melting curves show large discrepancies (up to 1000 K at the Earth's core–mantle boundary, 136 GPa), resulting in persisting high uncertainties on the solid‐liquid phase boundary. Here we unambiguously show that the observed differences commonly attributed to the nature of the used melting diagnostic are due to a carbon contamination of the sample as well as pressure overestimation at high temperature. The high melting temperature of pure iron under core‐mantle boundary (4250 ± 250 K), here determined by X‐ray absorption experiments at the Fe K‐edge, indicates that volatile light elements such as sulfur, carbon, or hydrogen are required to lower the crystallization temperature of the Earth's liquid outer core in order to prevent extended melting of the surrounding silicate mantle.

https://agupubs.onlinelibrary.wiley.com/doi/pdf/10.1029/2018GL079950

Solving Controversies on the Iron Phase Diagram Under High Pressure

Understanding Warm Dense Matter (WDM), the state of planetary interiors, is a new frontier in scientific research. There exists very little experimental data probing WDM states at the atomic level to test current models and those performed up to now are limited in quality. Here, we report a proof-of-principle experiment that makes microscopic investigations of materials under dynamic compression easily accessible to users and with data quality close to that achievable at ambient. Using a single 100 ps synchrotron x-ray pulse, we have measured, by K-edge absorption spectroscopy, ns-lived equilibrium states of WDM Fe. Structural and electronic changes in Fe are clearly observed for the first time at such extreme conditions. The amplitude of the EXAFS oscillations persists up to 500 GPa and 17000 K, suggesting an enduring local order. Moreover, a discrepancy exists with respect to theoretical calculations in the value of the energy shift of the absorption onset and so this comparison should help to refine the approximations used in models.

/pdf/probing-local-and-electronic-structure-in-warm-dense-matter-onp8g30zza.pdf

Probing local and electronic structure in Warm Dense Matter: single pulse synchrotron x-ray absorption spectroscopy on shocked Fe

In the past couple of decades, the laser-heated diamond anvil cell (combined with in situ techniques) has become an extensively used tool for studying pressure-temperature-induced evolution of various physical (and chemical) properties of materials. In this review, the general challenges associated with the use of the laser-heated diamond anvil cells are discussed together with the recent progress in the use of this tool combined with synchrotron X-ray diffraction and absorption spectroscopy.

A Practical Review of the Laser-Heated Diamond Anvil Cell for University Laboratories and Synchrotron Applications

The European Synchrotron Radiation Facility has recently made available to the user community a facility totally dedicated to Time-resolved and Extreme-conditions X-ray Absorption Spectroscopy – TEXAS. Based on an upgrade of the former energy-dispersive XAS beamline ID24, it provides a unique experimental tool combining unprecedented brilliance (up to 1014 photons s−1 on a 4 µm × 4 µm FWHM spot) and detection speed for a full EXAFS spectrum (100 ps per spectrum). The science mission includes studies of processes down to the nanosecond timescale, and investigations of matter at extreme pressure (500 GPa), temperature (10000 K) and magnetic field (30 T). The core activities of the beamline are centered on new experiments dedicated to the investigation of extreme states of matter that can be maintained only for very short periods of time. Here the infrastructure, optical scheme, detection systems and sample environments used to enable the mission-critical performance are described, and examples of first results on the investigation of the electronic and local structure in melts at pressure and temperature conditions relevant to the Earth's interior and in laser-shocked matter are given.

/pdf/the-time-resolved-and-extreme-conditions-xas-texas-facility-1xhjl1ae5c.pdf

The Time-resolved and Extreme-conditions XAS (TEXAS) facility at the European Synchrotron Radiation Facility: the energy-dispersive X-ray absorption spectroscopy beamline ID24

Knowledge on the temperature distribution in high pressure and temperature devices is important for the interpretation of data and can often not be obtained from experiments. Here, we report on the thermal characteristics of the most employed Paris–Edinburgh press assemblies for in-situ X-ray purposes using finite element calculations. The maximal horizontal T variations in the sample are found to be small and amount maximal 50 K at 2500 K. Temperature differences between the sample and the calibrant material are in the same order of magnitude only if the latter is placed well centred on the sample capsule. The present (pure thermal) calculations can only partly reproduce the discrepancies between experimentally determined input power to T relations (1000 K at 350 W) indicating that different deformation behaviours of assemblies may play a crucial role. Based on the obtained results we present an optimized assembly in terms of sample temperature and gradients.

Heat distribution in Paris–Edinburgh press assemblies through finite element simulations

Corrections to Table 2 of Nanao et al. [ J. Synchrotron Rad. (2022). 29, 581–590] are reported.

/pdf/id23-2-an-automated-and-high-performance-microfocus-beamline-k8n1z600.pdf

C. Clavel

Papers

The Time-resolved and Extreme-conditions XAS (TEXAS) facility at the European Synchrotron Radiation Facility: the energy-dispersive X-ray absorption spectroscopy beamline ID24

Heat distribution in Paris–Edinburgh press assemblies through finite element simulations

ID23-2: an automated and high-performance microfocus beamline for macromolecular crystallography at the ESRF. Corrigendum