Hard X-ray spectroscopy: an exhaustive toolbox for mechanistic studies (?)

Schoch, Anke; Burkhardt, Lukas; Schoch, Roland; Stührenberg, Kai

doi:10.1039/c9fd00070d

Cited by 9 publications

(7 citation statements)

References 92 publications

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“…Non‐resonant X‐ray emission spectroscopy (XES) is a powerful technique for the study of occupied electron orbitals in the valence shell with elemental selectivity and under in situ conditions 1–8 . In XES, X‐ray photons with energy greater than the binding energy of an inner‐shell electron produce core‐hole vacancies.…”

Section: Introductionmentioning

confidence: 99%

Valence‐to‐core X‐ray emission spectroscopy of titanium compounds using energy dispersive detectors

et al. 2020

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X-ray emission spectroscopy (XES) of transition metal compounds is a powerful tool for investigating the spin and oxidation state of the metal centers. Valence-to-core (vtc) XES is of special interest, as it contains information on the ligand nature, hybridization, and protonation. To date, most vtc-XES studies have been performed with high-brightness sources, such as synchrotrons, due to the weak fluorescence lines from vtc transitions. Here, we present a systematic study of the vtc-XES for different titanium compounds in a laboratory setting using an X-ray tube source and energy dispersive microcalorimeter sensors. With a full-width at half-maximum energy resolution of approximately 4 eV at the Ti Kβ lines, we measure the XES features of different titanium compounds and compare our results for the vtc line shapes and energies to previously published and newly acquired synchrotron data as well as to new theoretical calculations. Finally, we report simulations of the feasibility of performing time-resolved vtc-XES studies with a laser-based plasma source in a laboratory setting. Our results show that microcalorimeter sensors can already perform high-quality measurements of vtc-XES features in a laboratory setting under static conditions and that dynamic measurements will be possible in the future after reasonable technological developments. 1 | INTRODUCTION Non-resonant X-ray emission spectroscopy (XES) is a powerful technique for the study of occupied electron orbitals in the valence shell with elemental selectivity and under in situ conditions. 1-8 In XES, X-ray photons with energy greater than the binding energy of an innershell electron produce core-hole vacancies. These core holes are quickly filled by the relaxation of less tightly bound electrons with concomitant X-ray fluorescence or

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Section: Introductionmentioning

confidence: 99%

Valence‐to‐core X‐ray emission spectroscopy of titanium compounds using energy dispersive detectors

et al. 2020

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“…Wei et al used EXAFS in combination with other spectroscopic and imaging techniques to observe the transition of noble metal nanoparticles (Pt, Pd, and Au–NPs) to thermally stable single atom catalyst when calcined above 900 °C under inert conditions . Similarly, review articles focused on atomically dispersed catalysts frequently highlight the significance of EXAFS in understanding the local structure of the active species, thus reemphasizing the relevance of using theory to model EXAFS data. ,− …”

Section: How Is Exafs Being Currently Used By the Catalysis Science C...mentioning

confidence: 99%

Bridging the Gap between the X-ray Absorption Spectroscopy and the Computational Catalysis Communities in Heterogeneous Catalysis: A Perspective on the Current and Future Research Directions

et al. 2022

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X-ray absorption spectroscopy (XAS) [extended X-ray absorption fine structure (EXAFS) and X-ray absorption near-edge structure (XANES)] is a key technique within the heterogeneous catalysis community to probe the structure and properties of the active site(s) for a diverse range of catalytic materials. However, the interpretation of the raw experimental data to derive an atomistic picture of the catalyst requires modeling and analysis; the EXAFS data are compared to a model, and a goodness of fit parameter is used to judge the best fit. This EXAFS modeling can often be nontrivial and time-consuming; overcoming or improving these limitations remains a central challenge for the community. Considering these limitations, this Perspective highlights how recent developments in analysis software, increased availability of reliable computational models, and application of data science tools can be used to improve the speed, accuracy, and reliability of EXAFS interpretation. In particular, we emphasize the advantages of combining theory and EXAFS as a unified technique that should be treated as a standard (when applicable) to identify catalytic sites and not two separate complementary methods. Building on the recent trends in the computational catalysis community, we also present a community-driven approach to adopt FAIR Guiding Principles for the collection, analysis, dissemination, and storage of XAS data. Written with both the experimental and theory audience in mind, we provide a unified roadmap to foster collaborations between the two communities.

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“…3 Similarly, review articles focused on atomically dispersed catalysts frequently highlight the significance of EXAFS in understanding the local structure of the active species, thus, reemphasizing the relevance of using theory to model EXAFS data. [73][74][75][76][77][78][79][80][81][82][83][84][85][86][87] A common feature in the studies by Lomachenko et al and Wei et al is that important information was obtained based on the changes in the average coordination environment around the absorbing atom. Since the experimental samples (e.g., Cu oxides or various nanoparticle catalysts) are not described by a unique or uniformly distributed arrangement of atoms, conventional EXAFS analysis provides qualitative insights that link experimental observations to structural changes in the catalysts.…”

Section: Identification Of the Local Coordination Environment From Ex...mentioning

confidence: 99%

Bridging the Gap between the X-ray Absorption Spectroscopy and the Computational Catalysis Communities in Heterogeneous Catalysis: A Perspective on the Current and Future Research Directions

Rana

Vila

Kulkarni

et al. 2022

Preprint

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X-ray absorption spectroscopy (XAS), (Extended X-ray Absorption Fine Structure (EXAFS) and X-ray Absorption Near-Edge Structure (XANES)), is a key technique within the heterogeneous catalysis community to probe the structure and properties of active site(s) for a diverse range of catalytic materials. However, the interpretation of the raw experimental data to derive an atomistic picture of the catalyst requires modeling and analysis; the EXAFS data are compared to a model and a goodness of fit parameter is used to judge the best fit. This EXAFS modeling can often be non-trivial and time-consuming; overcoming or improving these limitations remains a central challenge for the community. Considering these limitations, this Perspective highlights how recent developments in analysis software, increased availability of reliable computational models and application of data science tools can be used to improve the speed, accuracy, and reliability of EXAFS interpretation. In particular, we emphasize the advantages of combining theory and EXAFS as a unified technique that should be treated as a standard (when applicable) to identify catalytic sites and not two separate complementary methods. Building on the recent trends in the computational catalysis community, we also present a community-driven approach to adopt FAIR Guiding Principles for the collection, analysis, dissemination, and storage of XAS data. Written with both the experimental and theory audience in mind, we provide unified roadmap to foster collaborations between the two communities.

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Hard X-ray spectroscopy: an exhaustive toolbox for mechanistic studies (?)

Abstract: The hard X-ray spectroscopy methods XAS, valence-to-core XES and higher solution XANES offer unique insights into organometallic reaction mechanisms.

Cited by 9 publications

References 92 publications

Valence‐to‐core X‐ray emission spectroscopy of titanium compounds using energy dispersive detectors

Valence‐to‐core X‐ray emission spectroscopy of titanium compounds using energy dispersive detectors

Bridging the Gap between the X-ray Absorption Spectroscopy and the Computational Catalysis Communities in Heterogeneous Catalysis: A Perspective on the Current and Future Research Directions

Bridging the Gap between the X-ray Absorption Spectroscopy and the Computational Catalysis Communities in Heterogeneous Catalysis: A Perspective on the Current and Future Research Directions

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