Full Energy Range Resonant Inelastic X-ray Scattering of O2 and CO2: Direct Comparison with Oxygen Redox State in Batteries

The varying oxygen state plays key roles in the performance and stability of various electrochemical systems. However, the nature of the non-divalent state remains elusive with speculations under active debates. A direct comparison between these unconventional states on their full oxygen spectroscopic profile is critical but remains missing. Here, high-efficiency full energy range O-K mapping of resonant inelastic x-ray scattering (mRIXS) was collected from O2 (O0) and CO2 (O2-) gas molecules. The results are compared directly with Li2O2 (O1-) and more importantly, the oxidized oxygen (On-, 0-n-2) state in representative Na-ion and Li-ion battery electrodes. All the mRIXS features of O2 and CO2 are interpreted, and we focus on the contrasts of two characteristic features among all oxidized oxygen species, especially on the striking 523.7 eV emission feature. The full mRIXS profile reveals that oxygen redox states in batteries have distinct distributions along the excitation energy compared with Li2O2 and O2. This work provides not only the first full range mRIXS results of O2 and CO2, but also the direct comparison of four different oxygen states, i.e., O2-, O1-, On-(0-n-2), and O0. Our results indicate that the nature of the oxidized oxygen state in oxide electrodes is beyond a simple molecular configuration of either peroxide or O2.

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Full Energy Range Resonant Inelastic X-Ray Scattering of O2 and CO2: Direct Comparison with Oxygen Redox State in Batteries

10.26434/chemrxiv.11340170 ◽

2019 ◽

Author(s):

Zengqing Zhuo ◽

Yi-Sheng Liu ◽

Jinghua Guo ◽

Yi-de Chuang ◽

Feng Pan ◽

...

Keyword(s):

Energy Range ◽

High Efficiency ◽

Full Range ◽

Molecular Configuration ◽

X Ray ◽

Full Energy ◽

Oxide Electrodes ◽

X Ray Scattering ◽

Oxygen State ◽

Ray Scattering

The varying oxygen state plays key roles in the performance and stability of various electrochemical systems. However, the nature of the non-divalent state remains elusive with speculations under active debates. A direct comparison between these unconventional states on their full oxygen spectroscopic profile is critical but remains missing. Here, high-efficiency full energy range O-K mapping of resonant inelastic x-ray scattering (mRIXS) was collected from O2 (O0) and CO2 (O2-) gas molecules. The results are compared directly with Li2O2 (O1-) and more importantly, the oxidized oxygen (On-, 0-n-2) state in representative Na-ion and Li-ion battery electrodes. All the mRIXS features of O2 and CO2 are interpreted, and we focus on the contrasts of two characteristic features among all oxidized oxygen species, especially on the striking 523.7 eV emission feature. The full mRIXS profile reveals that oxygen redox states in batteries have distinct distributions along the excitation energy compared with Li2O2 and O2. This work provides not only the first full range mRIXS results of O2 and CO2, but also the direct comparison of four different oxygen states, i.e., O2-, O1-, On-(0-n-2), and O0. Our results indicate that the nature of the oxidized oxygen state in oxide electrodes is beyond a simple molecular configuration of either peroxide or O2.

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Oxides and Their Heterostructures Studied with X-Ray Absorption Spectroscopy and Resonant Inelastic X-Ray Scattering in the “Soft” Energy Range

Spectroscopy of Complex Oxide Interfaces - Springer Series in Materials Science ◽

10.1007/978-3-319-74989-1_11 ◽

2018 ◽

pp. 283-314 ◽

Cited By ~ 1

Author(s):

M. Salluzzo ◽

G. Ghiringhelli

Keyword(s):

Energy Range ◽

Absorption Spectroscopy ◽

X Ray ◽

X Ray Scattering ◽

X Ray Absorption ◽

Ray Scattering

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An endstation for resonant inelastic X-ray scattering studies of solid and liquid samples

Journal of Synchrotron Radiation ◽

10.1107/s1600577516016611 ◽

2017 ◽

Vol 24 (1) ◽

pp. 302-306 ◽

Cited By ~ 7

Author(s):

Zhong Yin ◽

Hans-Bernhard Peters ◽

Ulrich Hahn ◽

Josef Gonschior ◽

Daniel Mierwaldt ◽

...

Keyword(s):

Energy Range ◽

Electronic Configuration ◽

Resolving Power ◽

Liquid Jet ◽

X Ray ◽

X Ray Scattering ◽

Liquid Samples ◽

Sample Chamber ◽

High Flexibility ◽

Ray Scattering

A novel experimental setup is presented for resonant inelastic X-ray scattering investigations of solid and liquid samples in the soft X-ray region for studying the complex electronic configuration of (bio)chemical systems. The uniqueness of the apparatus is its high flexibility combined with optimal energy resolution and energy range ratio. The apparatus enables investigation of chemical analyses, which reflects the chemical imprints. The endstation is composed of a main sample chamber, a sample holder for either solid or liquid jet delivery system, and a soft X-ray grating spectrometer for 210–1250 eV with a resolving power of ∼1000. It combines for the first time liquid jet technology with a soft X-ray spectrometer based on the variable line spacing principle. This setup was commissioned at the soft X-ray beamline P04 at PETRA III of the Deutsches Elektronen-Synchrotron in Hamburg which is currently the most brilliant storage-ring-based X-ray radiation source in the world. The first results of liquid and solid samples show that this setup allows the detection of photons across an energy range of ∼300 eV. This covers simultaneously the emission lines of life-important elements like carbon, nitrogen and oxygen in a shot-based procedure.

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Topics in the study of correlated systems with resonant inelastic X-ray scattering (RIXS) in the soft energy range

Journal of Electron Spectroscopy and Related Phenomena ◽

10.1016/s0368-2048(01)00248-1 ◽

2001 ◽

Vol 117-118 ◽

pp. 103-111

Author(s):

L. Braicovich

Keyword(s):

Energy Range ◽

Correlated Systems ◽

X Ray ◽

X Ray Scattering ◽

Ray Scattering

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Microtubule nucleation sequence studied by time-resolved x-ray scattering and electron microscopy

Proceedings, annual meeting, Electron Microscopy Society of America ◽

10.1017/s0424820100077402 ◽

1983 ◽

Vol 41 ◽

pp. 766-767

Author(s):

Eva-Maria Mandelkow ◽

Eckhard Mandelkow ◽

Joan Bordas

Keyword(s):

Electron Microscopy ◽

Dynamic Equilibrium ◽

Time Resolved ◽

X Ray ◽

Additional Information ◽

X Ray Scattering ◽

Low Concentrations ◽

Microtubule Growth ◽

Ray Patterns ◽

Ray Scattering

When a solution of microtubule protein is changed from non-polymerising to polymerising conditions (e.g. by temperature jump or mixing with GTP) there is a series of structural transitions preceding microtubule growth. These have been detected by time-resolved X-ray scattering using synchrotron radiation, and they may be classified into pre-nucleation and nucleation events. X-ray patterns are good indicators for the average behavior of the particles in solution, but they are difficult to interpret unless additional information on their structure is available. We therefore studied the assembly process by electron microscopy under conditions approaching those of the X-ray experiment. There are two difficulties in the EM approach: One is that the particles important for assembly are usually small and not very regular and therefore tend to be overlooked. Secondly EM specimens require low concentrations which favor disassembly of the particles one wants to observe since there is a dynamic equilibrium between polymers and subunits.

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Time-Resolved Cryo-Electron Microscopy of Oscillating Microtubules

Proceedings, annual meeting, Electron Microscopy Society of America ◽

10.1017/s0424820100181269 ◽

1990 ◽

Vol 48 (1) ◽

pp. 502-503

Author(s):

Eva-Maria Mandelkow ◽

Ron Milligan

Keyword(s):

Electron Microscopy ◽

Dynamic Instability ◽

Entire Solution ◽

Reaction Scheme ◽

Time Resolved ◽

X Ray ◽

X Ray Scattering ◽

A Chain ◽

Ray Scattering

Microtubules form part of the cytoskeleton of eukaryotic cells. They are hollow libers of about 25 nm diameter made up of 13 protofilaments, each of which consists of a chain of heterodimers of α-and β-tubulin. Microtubules can be assembled in vitro at 37°C in the presence of GTP which is hydrolyzed during the reaction, and they are disassembled at 4°C. In contrast to most other polymers microtubules show the behavior of “dynamic instability”, i.e. they can switch between phases of growth and phases of shrinkage, even at an overall steady state [1]. In certain conditions an entire solution can be synchronized, leading to autonomous oscillations in the degree of assembly which can be observed by X-ray scattering (Fig. 1), light scattering, or electron microscopy [2-5]. In addition such solutions are capable of generating spontaneous spatial patterns [6].In an earlier study we have analyzed the structure of microtubules and their cold-induced disassembly by cryo-EM [7]. One result was that disassembly takes place by loss of protofilament fragments (tubulin oligomers) which fray apart at the microtubule ends. We also looked at microtubule oscillations by time-resolved X-ray scattering and proposed a reaction scheme [4] which involves a cyclic interconversion of tubulin, microtubules, and oligomers (Fig. 2). The present study was undertaken to answer two questions: (a) What is the nature of the oscillations as seen by time-resolved cryo-EM? (b) Do microtubules disassemble by fraying protofilament fragments during oscillations at 37°C?

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