Evolution of Oxygen–Metal Electron Transfer and Metal Electronic States During Manganese Oxide Catalyzed Water Oxidation Revealed with In Situ Soft X-Ray Spectroscopy

Marc F. Tesch, Shannon A. Bonke, Travis E. Jones, Maryam N. Shaker, Jie Xiao, Katarzyna Skorupska, Rik Mom, Jens Melder, Philipp Kurz, Axel Knop-Gericke, Robert Schlögl, Rosalie K. Hocking, Alexandr N. Simonov

Research output: Contribution to journalArticleResearchpeer-review

5 Citations (Scopus)

Abstract

Manganese oxide (MnOx) electrocatalysts are examined herein by in situ soft X-ray absorption spectroscopy (XAS) and resonant inelastic X-ray scattering (RIXS) during the oxidation of water buffered by borate (pH 9.2) at potentials from 0.75 to 2.25 V vs. the reversible hydrogen electrode. Correlation of L-edge XAS data with previous mechanistic studies indicates MnIV is the highest oxidation state involved in the catalytic mechanism. MnOx is transformed into birnessite at 1.45 V and does not undergo further structural phase changes. At potentials beyond this transformation, RIXS spectra show progressive enhancement of charge transfer transitions from oxygen to manganese. Theoretical analysis of these data indicates increased hybridization of the Mn−O orbitals and withdrawal of electron density from the O ligand shell. In situ XAS experiments at the O K-edge provide complementary evidence for such a transition. This step is crucial for the formation of O2 from water.

Original languageEnglish
Pages (from-to)3426-3432
Number of pages7
JournalAngewandte Chemie - International Edition
Volume58
Issue number11
DOIs
Publication statusPublished - 1 Jan 2019

Keywords

  • in situ spectroscopy
  • manganese oxide
  • resonant inelastic X-ray scattering
  • soft X-ray absorption spectroscopy
  • water electrooxidation

Cite this

Tesch, Marc F. ; Bonke, Shannon A. ; Jones, Travis E. ; Shaker, Maryam N. ; Xiao, Jie ; Skorupska, Katarzyna ; Mom, Rik ; Melder, Jens ; Kurz, Philipp ; Knop-Gericke, Axel ; Schlögl, Robert ; Hocking, Rosalie K. ; Simonov, Alexandr N. / Evolution of Oxygen–Metal Electron Transfer and Metal Electronic States During Manganese Oxide Catalyzed Water Oxidation Revealed with In Situ Soft X-Ray Spectroscopy. In: Angewandte Chemie - International Edition. 2019 ; Vol. 58, No. 11. pp. 3426-3432.
@article{3611c92670d54305a47d27af7cb253be,
title = "Evolution of Oxygen–Metal Electron Transfer and Metal Electronic States During Manganese Oxide Catalyzed Water Oxidation Revealed with In Situ Soft X-Ray Spectroscopy",
abstract = "Manganese oxide (MnOx) electrocatalysts are examined herein by in situ soft X-ray absorption spectroscopy (XAS) and resonant inelastic X-ray scattering (RIXS) during the oxidation of water buffered by borate (pH 9.2) at potentials from 0.75 to 2.25 V vs. the reversible hydrogen electrode. Correlation of L-edge XAS data with previous mechanistic studies indicates MnIV is the highest oxidation state involved in the catalytic mechanism. MnOx is transformed into birnessite at 1.45 V and does not undergo further structural phase changes. At potentials beyond this transformation, RIXS spectra show progressive enhancement of charge transfer transitions from oxygen to manganese. Theoretical analysis of these data indicates increased hybridization of the Mn−O orbitals and withdrawal of electron density from the O ligand shell. In situ XAS experiments at the O K-edge provide complementary evidence for such a transition. This step is crucial for the formation of O2 from water.",
keywords = "in situ spectroscopy, manganese oxide, resonant inelastic X-ray scattering, soft X-ray absorption spectroscopy, water electrooxidation",
author = "Tesch, {Marc F.} and Bonke, {Shannon A.} and Jones, {Travis E.} and Shaker, {Maryam N.} and Jie Xiao and Katarzyna Skorupska and Rik Mom and Jens Melder and Philipp Kurz and Axel Knop-Gericke and Robert Schl{\"o}gl and Hocking, {Rosalie K.} and Simonov, {Alexandr N.}",
year = "2019",
month = "1",
day = "1",
doi = "10.1002/anie.201810825",
language = "English",
volume = "58",
pages = "3426--3432",
journal = "Angewandte Chemie - International Edition",
issn = "1433-7851",
publisher = "Wiley-Blackwell",
number = "11",

}

Tesch, MF, Bonke, SA, Jones, TE, Shaker, MN, Xiao, J, Skorupska, K, Mom, R, Melder, J, Kurz, P, Knop-Gericke, A, Schlögl, R, Hocking, RK & Simonov, AN 2019, 'Evolution of Oxygen–Metal Electron Transfer and Metal Electronic States During Manganese Oxide Catalyzed Water Oxidation Revealed with In Situ Soft X-Ray Spectroscopy', Angewandte Chemie - International Edition, vol. 58, no. 11, pp. 3426-3432. https://doi.org/10.1002/anie.201810825

Evolution of Oxygen–Metal Electron Transfer and Metal Electronic States During Manganese Oxide Catalyzed Water Oxidation Revealed with In Situ Soft X-Ray Spectroscopy. / Tesch, Marc F.; Bonke, Shannon A.; Jones, Travis E.; Shaker, Maryam N.; Xiao, Jie; Skorupska, Katarzyna; Mom, Rik; Melder, Jens; Kurz, Philipp; Knop-Gericke, Axel; Schlögl, Robert; Hocking, Rosalie K.; Simonov, Alexandr N.

In: Angewandte Chemie - International Edition, Vol. 58, No. 11, 01.01.2019, p. 3426-3432.

Research output: Contribution to journalArticleResearchpeer-review

TY - JOUR

T1 - Evolution of Oxygen–Metal Electron Transfer and Metal Electronic States During Manganese Oxide Catalyzed Water Oxidation Revealed with In Situ Soft X-Ray Spectroscopy

AU - Tesch, Marc F.

AU - Bonke, Shannon A.

AU - Jones, Travis E.

AU - Shaker, Maryam N.

AU - Xiao, Jie

AU - Skorupska, Katarzyna

AU - Mom, Rik

AU - Melder, Jens

AU - Kurz, Philipp

AU - Knop-Gericke, Axel

AU - Schlögl, Robert

AU - Hocking, Rosalie K.

AU - Simonov, Alexandr N.

PY - 2019/1/1

Y1 - 2019/1/1

N2 - Manganese oxide (MnOx) electrocatalysts are examined herein by in situ soft X-ray absorption spectroscopy (XAS) and resonant inelastic X-ray scattering (RIXS) during the oxidation of water buffered by borate (pH 9.2) at potentials from 0.75 to 2.25 V vs. the reversible hydrogen electrode. Correlation of L-edge XAS data with previous mechanistic studies indicates MnIV is the highest oxidation state involved in the catalytic mechanism. MnOx is transformed into birnessite at 1.45 V and does not undergo further structural phase changes. At potentials beyond this transformation, RIXS spectra show progressive enhancement of charge transfer transitions from oxygen to manganese. Theoretical analysis of these data indicates increased hybridization of the Mn−O orbitals and withdrawal of electron density from the O ligand shell. In situ XAS experiments at the O K-edge provide complementary evidence for such a transition. This step is crucial for the formation of O2 from water.

AB - Manganese oxide (MnOx) electrocatalysts are examined herein by in situ soft X-ray absorption spectroscopy (XAS) and resonant inelastic X-ray scattering (RIXS) during the oxidation of water buffered by borate (pH 9.2) at potentials from 0.75 to 2.25 V vs. the reversible hydrogen electrode. Correlation of L-edge XAS data with previous mechanistic studies indicates MnIV is the highest oxidation state involved in the catalytic mechanism. MnOx is transformed into birnessite at 1.45 V and does not undergo further structural phase changes. At potentials beyond this transformation, RIXS spectra show progressive enhancement of charge transfer transitions from oxygen to manganese. Theoretical analysis of these data indicates increased hybridization of the Mn−O orbitals and withdrawal of electron density from the O ligand shell. In situ XAS experiments at the O K-edge provide complementary evidence for such a transition. This step is crucial for the formation of O2 from water.

KW - in situ spectroscopy

KW - manganese oxide

KW - resonant inelastic X-ray scattering

KW - soft X-ray absorption spectroscopy

KW - water electrooxidation

UR - http://www.scopus.com/inward/record.url?scp=85061211699&partnerID=8YFLogxK

U2 - 10.1002/anie.201810825

DO - 10.1002/anie.201810825

M3 - Article

VL - 58

SP - 3426

EP - 3432

JO - Angewandte Chemie - International Edition

JF - Angewandte Chemie - International Edition

SN - 1433-7851

IS - 11

ER -