skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Simultaneous detection of electronic structure changes from two elements of a bifunctional catalyst using wavelength-dispersive X-ray emission spectroscopy and in situ electrochemistry.

Abstract

Multielectron catalytic reactions, such as water oxidation, nitrogen reduction, or hydrogen production in enzymes and inorganic catalysts often involve multimetallic clusters. In these systems, the reaction takes place between metals or metals and ligands to facilitate charge transfer, bond formation/breaking, substrate binding, and release of products. In this study, we present a method to detect X-ray emission signals from multiple elements simultaneously, which allows for the study of charge transfer and the sequential chemistry occurring between elements. Kβ X-ray emission spectroscopy (XES) probes charge and spin states of metals as well as their ligand environment. A wavelength-dispersive spectrometer based on the von Hamos geometry was used to disperse Kβ signals of multiple elements onto a position detector, enabling an XES spectrum to be measured in a single-shot mode. This overcomes the scanning needs of the scanning spectrometers, providing data free from temporal and normalization errors and therefore ideal to follow sequential chemistry at multiple sites. We have applied this method to study MnOx-based bifunctional electrocatalysts for the oxygen evolution reaction (OER) and the oxygen reduction reaction (ORR). In particular, we investigated the effects of adding a secondary element, Ni, to form MnNiOx and its impact on the chemical states andmore » catalytic activity, by tracking the redox characteristics of each element upon sweeping the electrode potential. The detection scheme we describe here is general and can be applied to time-resolved studies of materials consisting of multiple elements, to follow the dynamics of catalytic and electron transfer reactions.« less

Authors:
; ; ; ; ; ; ; ; ; ; ; ; ; ;
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1512186
DOE Contract Number:  
AC02-05CH11231
Resource Type:
Journal Article
Journal Name:
Physical Chemistry Chemical Physics. PCCP (Print)
Additional Journal Information:
Journal Volume: 17; Journal Issue: 14; Journal ID: ISSN 1463-9076
Country of Publication:
United States
Language:
English

Citation Formats

Gul, Sheraz, Ng, Jia Wei Desmond, Alonso-Mori, Roberto, Kern, Jan, Sokaras, Dimosthenis, Anzenberg, Eitan, Lassalle-Kaiser, Benedikt, Gorlin, Yelena, Weng, Tsu-Chien, Zwart, Petrus H, Zhang, Jin Z, Bergmann, Uwe, Yachandra, Vittal K, Jaramillo, Thomas F, and Yano, Junko. Simultaneous detection of electronic structure changes from two elements of a bifunctional catalyst using wavelength-dispersive X-ray emission spectroscopy and in situ electrochemistry.. United States: N. p., 2015. Web. doi:10.1039/c5cp01023c.
Gul, Sheraz, Ng, Jia Wei Desmond, Alonso-Mori, Roberto, Kern, Jan, Sokaras, Dimosthenis, Anzenberg, Eitan, Lassalle-Kaiser, Benedikt, Gorlin, Yelena, Weng, Tsu-Chien, Zwart, Petrus H, Zhang, Jin Z, Bergmann, Uwe, Yachandra, Vittal K, Jaramillo, Thomas F, & Yano, Junko. Simultaneous detection of electronic structure changes from two elements of a bifunctional catalyst using wavelength-dispersive X-ray emission spectroscopy and in situ electrochemistry.. United States. doi:10.1039/c5cp01023c.
Gul, Sheraz, Ng, Jia Wei Desmond, Alonso-Mori, Roberto, Kern, Jan, Sokaras, Dimosthenis, Anzenberg, Eitan, Lassalle-Kaiser, Benedikt, Gorlin, Yelena, Weng, Tsu-Chien, Zwart, Petrus H, Zhang, Jin Z, Bergmann, Uwe, Yachandra, Vittal K, Jaramillo, Thomas F, and Yano, Junko. Wed . "Simultaneous detection of electronic structure changes from two elements of a bifunctional catalyst using wavelength-dispersive X-ray emission spectroscopy and in situ electrochemistry.". United States. doi:10.1039/c5cp01023c.
@article{osti_1512186,
title = {Simultaneous detection of electronic structure changes from two elements of a bifunctional catalyst using wavelength-dispersive X-ray emission spectroscopy and in situ electrochemistry.},
author = {Gul, Sheraz and Ng, Jia Wei Desmond and Alonso-Mori, Roberto and Kern, Jan and Sokaras, Dimosthenis and Anzenberg, Eitan and Lassalle-Kaiser, Benedikt and Gorlin, Yelena and Weng, Tsu-Chien and Zwart, Petrus H and Zhang, Jin Z and Bergmann, Uwe and Yachandra, Vittal K and Jaramillo, Thomas F and Yano, Junko},
abstractNote = {Multielectron catalytic reactions, such as water oxidation, nitrogen reduction, or hydrogen production in enzymes and inorganic catalysts often involve multimetallic clusters. In these systems, the reaction takes place between metals or metals and ligands to facilitate charge transfer, bond formation/breaking, substrate binding, and release of products. In this study, we present a method to detect X-ray emission signals from multiple elements simultaneously, which allows for the study of charge transfer and the sequential chemistry occurring between elements. Kβ X-ray emission spectroscopy (XES) probes charge and spin states of metals as well as their ligand environment. A wavelength-dispersive spectrometer based on the von Hamos geometry was used to disperse Kβ signals of multiple elements onto a position detector, enabling an XES spectrum to be measured in a single-shot mode. This overcomes the scanning needs of the scanning spectrometers, providing data free from temporal and normalization errors and therefore ideal to follow sequential chemistry at multiple sites. We have applied this method to study MnOx-based bifunctional electrocatalysts for the oxygen evolution reaction (OER) and the oxygen reduction reaction (ORR). In particular, we investigated the effects of adding a secondary element, Ni, to form MnNiOx and its impact on the chemical states and catalytic activity, by tracking the redox characteristics of each element upon sweeping the electrode potential. The detection scheme we describe here is general and can be applied to time-resolved studies of materials consisting of multiple elements, to follow the dynamics of catalytic and electron transfer reactions.},
doi = {10.1039/c5cp01023c},
journal = {Physical Chemistry Chemical Physics. PCCP (Print)},
issn = {1463-9076},
number = 14,
volume = 17,
place = {United States},
year = {2015},
month = {4}
}

Works referenced in this record:

Temperature- and pressure-induced spin-state transitions in LaCoO 3
journal, January 2006


ATHENA , ARTEMIS , HEPHAESTUS : data analysis for X-ray absorption spectroscopy using IFEFFIT
journal, June 2005


Why is Gold such a Good Catalyst for Oxygen Reduction in Alkaline Media?
journal, November 2012

  • Quaino, P.; Luque, N. B.; Nazmutdinov, R.
  • Angewandte Chemie International Edition, Vol. 51, Issue 52
  • DOI: 10.1002/anie.201205902

Probing the 3d Spin Momentum with X-ray Emission Spectroscopy:  The Case of Molecular-Spin Transitions
journal, June 2006

  • Vankó, György; Neisius, Thomas; Molnár, Gábor
  • The Journal of Physical Chemistry B, Vol. 110, Issue 24
  • DOI: 10.1021/jp0615961

Manganese Oxide Octahedral Molecular Sieves: Preparation, Characterization, and Applications
journal, April 1993


Direct Detection of Oxygen Ligation to the Mn4Ca Cluster of Photosystem II by X-ray Emission Spectroscopy
journal, December 2009

  • Pushkar, Yulia; Long, Xi; Glatzel, Pieter
  • Angewandte Chemie International Edition, Vol. 49, Issue 4
  • DOI: 10.1002/anie.200905366

Experimental and Computational X-ray Emission Spectroscopy as a Direct Probe of Protonation States in Oxo-Bridged Mn IV Dimers Relevant to Redox-Active Metalloproteins
journal, October 2013

  • Lassalle-Kaiser, Benedikt; Boron, Thaddeus T.; Krewald, Vera
  • Inorganic Chemistry, Vol. 52, Issue 22
  • DOI: 10.1021/ic400821g

Anisotropic valence→core x-ray fluorescence from a [Rh(en)3][Mn(N)(CN)5]⋅H2O single crystal: Experimental results and density functional calculations
journal, February 2002

  • Bergmann, U.; Bendix, J.; Glatzel, P.
  • The Journal of Chemical Physics, Vol. 116, Issue 5
  • DOI: 10.1063/1.1419062

Nanostructured Manganese Oxide Supported onto Particulate Glassy Carbon as an Active and Stable Oxygen Reduction Catalyst in Alkaline-Based Fuel Cells
journal, January 2014

  • Ng, Jia Wei Desmond; Gorlin, Yelena; Nordlund, Dennis
  • Journal of The Electrochemical Society, Vol. 161, Issue 7
  • DOI: 10.1149/2.014407jes

Review of the structure and the electrochemistry of nickel hydroxides and oxy-hydroxides
journal, January 1982


Room temperature femtosecond X-ray diffraction of photosystem II microcrystals
journal, June 2012

  • Kern, J.; Alonso-Mori, R.; Hellmich, J.
  • Proceedings of the National Academy of Sciences, Vol. 109, Issue 25, p. 9721-9726
  • DOI: 10.1073/pnas.1204598109

An Investigation of Thin-Film Ni–Fe Oxide Catalysts for the Electrochemical Evolution of Oxygen
journal, August 2013

  • Louie, Mary W.; Bell, Alexis T.
  • Journal of the American Chemical Society, Vol. 135, Issue 33
  • DOI: 10.1021/ja405351s

Electrocatalytic performance of Ni modified MnOx/C composites toward oxygen reduction reaction and their application in Zn–air battery
journal, February 2014


Kβ Mainline X-ray Emission Spectroscopy as an Experimental Probe of Metal–Ligand Covalency
journal, June 2014

  • Pollock, Christopher J.; Delgado-Jaime, Mario Ulises; Atanasov, Mihail
  • Journal of the American Chemical Society, Vol. 136, Issue 26
  • DOI: 10.1021/ja504182n

A multi-crystal wavelength dispersive x-ray spectrometer
journal, July 2012

  • Alonso-Mori, Roberto; Kern, Jan; Sokaras, Dimosthenis
  • Review of Scientific Instruments, Vol. 83, Issue 7
  • DOI: 10.1063/1.4737630

Big as well as light weight portable, Mn3O4 based symmetric supercapacitive devices: Fabrication, performance evaluation and demonstration
journal, October 2012


High resolution 1s core hole X-ray spectroscopy in 3d transition metal complexes—electronic and structural information
journal, January 2005


Manganese Nitride Complexes in Oxidation States III, IV, and V: Synthesis and Electronic Structure
journal, September 2012

  • Kropp, Henning; King, Amanda E.; Khusniyarov, Marat M.
  • Journal of the American Chemical Society, Vol. 134, Issue 37
  • DOI: 10.1021/ja306647c

A carbon-free, precious-metal-free, high-performance O2 electrode for regenerative fuel cells and metal–air batteries
journal, January 2014

  • Ng, Jia Wei Desmond; Tang, Maureen; Jaramillo, Thomas F.
  • Energy & Environmental Science, Vol. 7, Issue 6
  • DOI: 10.1039/c3ee44059a

Taking snapshots of photosynthetic water oxidation using femtosecond X-ray diffraction and spectroscopy
journal, July 2014

  • Kern, Jan; Tran, Rosalie; Alonso-Mori, Roberto
  • Nature Communications, Vol. 5, Issue 1
  • DOI: 10.1038/ncomms5371

Transformation of Birnessite to Buserite, Todorokite, and Manganite under Mild Hydrothermal Treatment
journal, January 1987


From spinel Mn3O4 to layered nanoarchitectures using electrochemical cycling and the distinctive pseudocapacitive behavior
journal, March 2007

  • Dai, Yang; Wang, Ke; Xie, Jingying
  • Applied Physics Letters, Vol. 90, Issue 10
  • DOI: 10.1063/1.2711286

Sol−Gel Synthesis of Layered Birnessite-Type Manganese Oxides
journal, February 1997

  • Ching, Stanton; Petrovay, Diana J.; Jorgensen, Matthew L.
  • Inorganic Chemistry, Vol. 36, Issue 5
  • DOI: 10.1021/ic961088d

Evaluation of Several Carbon-Supported Nanostructured Ni-Doped Manganese Oxide Materials for the Electrochemical Reduction of Oxygen
journal, January 2011

  • Garcia, Amanda C.; Herrera, Alberto Diaz; Ticianelli, Edson A.
  • Journal of The Electrochemical Society, Vol. 158, Issue 3
  • DOI: 10.1149/1.3528439

Simultaneous Femtosecond X-ray Spectroscopy and Diffraction of Photosystem II at Room Temperature
journal, February 2013


Electrochemical and Spectroscopic Evidence on the Participation of Quadrivalent Nickel in the Nickel Hydroxide Redox Reaction
journal, January 1989

  • Corrigan, Dennis A.; Knight, Sandra L.
  • Journal of The Electrochemical Society, Vol. 136, Issue 3, p. 613-619
  • DOI: 10.1149/1.2096697

In Situ X-ray Absorption Spectroscopy Investigation of a Bifunctional Manganese Oxide Catalyst with High Activity for Electrochemical Water Oxidation and Oxygen Reduction
journal, June 2013

  • Gorlin, Yelena; Lassalle-Kaiser, Benedikt; Benck, Jesse D.
  • Journal of the American Chemical Society, Vol. 135, Issue 23
  • DOI: 10.1021/ja3104632

X-ray Emission Spectroscopy Evidences a Central Carbon in the Nitrogenase Iron-Molybdenum Cofactor
journal, November 2011


Preparation of a new crystal form of manganese dioxide: λ-MnO2
journal, September 1981


Energy-dispersive X-ray emission spectroscopy using an X-ray free-electron laser in a shot-by-shot mode
journal, November 2012

  • Alonso-Mori, R.; Kern, J.; Gildea, R. J.
  • Proceedings of the National Academy of Sciences, Vol. 109, Issue 47, p. 19103-19107
  • DOI: 10.1073/pnas.1211384109

IFEFFIT  : interactive XAFS analysis and FEFF fitting
journal, March 2001


Characterization of Redox States of Nickel Hydroxide Film Electrodes by In Situ Surface Raman Spectroscopy
journal, January 1988

  • Desilvestro, Johann
  • Journal of The Electrochemical Society, Vol. 135, Issue 4
  • DOI: 10.1149/1.2095818

High-resolution manganese x-ray fluorescence spectroscopy. Oxidation-state and spin-state sensitivity
journal, April 1994

  • Peng, G.; deGroot, F. M. F.; Haemaelaeinen, K.
  • Journal of the American Chemical Society, Vol. 116, Issue 7
  • DOI: 10.1021/ja00086a024

Highly Swollen Layered Nickel Oxide with a Trilayer Hydrate Structure
journal, January 2008

  • Yang, Xiaojing; Takada, Kazunori; Itose, Masayuki
  • Chemistry of Materials, Vol. 20, Issue 2
  • DOI: 10.1021/cm702981a