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Title: X-ray spectroscopy of energy materials under in situ / operando conditions

Authors:
; ; ; ; ;
Publication Date:
Sponsoring Org.:
USDOE
OSTI Identifier:
1249958
Grant/Contract Number:
AC02-05CH11231
Resource Type:
Journal Article: Publisher's Accepted Manuscript
Journal Name:
Journal of Electron Spectroscopy and Related Phenomena
Additional Journal Information:
Journal Volume: 200; Journal Issue: C; Related Information: CHORUS Timestamp: 2017-10-03 21:57:39; Journal ID: ISSN 0368-2048
Publisher:
Elsevier
Country of Publication:
Netherlands
Language:
English

Citation Formats

Crumlin, Ethan J., Liu, Zhi, Bluhm, Hendrik, Yang, Wanli, Guo, Jinghua, and Hussain, Zahid. X-ray spectroscopy of energy materials under in situ / operando conditions. Netherlands: N. p., 2015. Web. doi:10.1016/j.elspec.2015.06.008.
Crumlin, Ethan J., Liu, Zhi, Bluhm, Hendrik, Yang, Wanli, Guo, Jinghua, & Hussain, Zahid. X-ray spectroscopy of energy materials under in situ / operando conditions. Netherlands. doi:10.1016/j.elspec.2015.06.008.
Crumlin, Ethan J., Liu, Zhi, Bluhm, Hendrik, Yang, Wanli, Guo, Jinghua, and Hussain, Zahid. Wed . "X-ray spectroscopy of energy materials under in situ / operando conditions". Netherlands. doi:10.1016/j.elspec.2015.06.008.
@article{osti_1249958,
title = {X-ray spectroscopy of energy materials under in situ / operando conditions},
author = {Crumlin, Ethan J. and Liu, Zhi and Bluhm, Hendrik and Yang, Wanli and Guo, Jinghua and Hussain, Zahid},
abstractNote = {},
doi = {10.1016/j.elspec.2015.06.008},
journal = {Journal of Electron Spectroscopy and Related Phenomena},
number = C,
volume = 200,
place = {Netherlands},
year = {Wed Apr 01 00:00:00 EDT 2015},
month = {Wed Apr 01 00:00:00 EDT 2015}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record at 10.1016/j.elspec.2015.06.008

Citation Metrics:
Cited by: 20works
Citation information provided by
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  • Cited by 10
  • X-ray absorption fine structure (XAFS) measurements are widely used for the analysis of electronic structure. Generally, XAFS in the soft X-ray region is measured under vacuum, but chemical structures under vacuum are typically different from those under operando conditions, where chemical species exhibit their function. Here, we developed an XAFS measurement instrument, as a step toward operando fluorescent, which yields XAFS measurement using synchrotron radiation in the soft X-ray region. We applied this method to analyze the local electronic structure of the sulfur atoms in L-cysteine in different pH solutions. In water at pH 7, the hydrogen atom does notmore » dissociate from the thiol (-SH) group in L-cysteine, which forms a structure surrounded by and interacting with water molecules. The XAFS spectrum of L-cysteine in solution was altered by changing the pH. At pH 9, the hydrogen atom dissociated and a thiolate anion was formed. Although the -SH group was oxidized to SO{sub 4}{sup 2−} when L-cysteine was adsorbed on a metal surface and dried, no oxidation was observed in solution. This may be because the water molecules were densely packed and protected the -SH group from oxidation. Our results show that this instrument aimed toward operando fluorescence XAFS measurements in the soft X-ray region is useful for structural analysis of sulfur atoms in organic molecules in air and in solution. The instrument will be applied to the structural analysis of materials containing elements that have absorption edges in soft X-ray region, such as phosphorus and alkali metals (potassium and cesium). It will be also particularly useful for the analysis of samples that are difficult to handle under vacuum and materials that have specific functions in solution.« less
  • An in situ flow electrochemical cell has been designed and fabricated to allow better seal under UHV chamber thus to achieve a good signal to noise ratio in fluorescence yield detection of X-ray absorption spectra for spectroelectrochemical study. The cell also stabilizes the thin silicon nitride membrane window in an effective manner so that the liquid cell remains intact during X-ray absorption experiments. With the improved design of the liquid cell, electrochemical experiments such as cyclic voltammetry have been performed for 10 cycles with a good stability of sample window. Also an operando electrochemical experiment during photoelectrochemistry has been performedmore » on n-type hematite electrode deposited on silicon nitride window. The experiment allows us to observe the formation of two extra electronic transitions before pre edge of O K-edge spectra.« less
  • This review focuses on the use of X-ray absorption and emission spectroscopy techniques using hard X-rays to study electrocatalysts under in situ/operando conditions. The importance and the versatility of methods in the study of electrodes in contact with the electrolytes are described, when they are being cycled through the catalytic potentials during the progress of the oxygen-evolution, oxygen reduction and hydrogen evolution reactions. The catalytic oxygen evolution reaction is illustrated with examples using three oxides, Co, Ni and Mn, and two sulfides, Mo and Co. These are used as examples for the hydrogen evolution reaction. A bimetallic, bifunctional oxygen evolvingmore » and oxygen reducing Ni/Mn oxide is also presented. The various advantages and constraints in the use of these techniques and the future outlook are discussed.« less