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Title: In situ/Operando studies of electrocatalysts using hard X-ray spectroscopy

Journal Article · · Journal of Electron Spectroscopy and Related Phenomena
 [1];  [2];  [3];  [2];  [2]
  1. Synchrotron SOLEIL, Gif-sur-Yvette (France)
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Molecular Biophysics and Integrated Bioimaging Div.
  3. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Molecular Biophysics and Integrated Bioimaging Div.; SLAC National Accelerator Lab., Menlo Park, CA (United States). Linac Coherent Light Source (LCLS)

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 evolving 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.

Research Organization:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
Sponsoring Organization:
USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
AC02-05CH11231; GM110501; GM55302; RGP0063/2013-310; AC02-76SF00515; RGP0063/2013 310
OSTI ID:
1378359
Alternate ID(s):
OSTI ID: 1423211; OSTI ID: 1495733
Journal Information:
Journal of Electron Spectroscopy and Related Phenomena, Journal Name: Journal of Electron Spectroscopy and Related Phenomena; ISSN 0368-2048
Publisher:
ElsevierCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 45 works
Citation information provided by
Web of Science

References (66)

Powering the planet: Chemical challenges in solar energy utilization journal October 2006
The Future of Energy Supply: Challenges and Opportunities journal January 2007
Determination of photoelectrochemical water oxidation intermediates on haematite electrode surfaces using operando infrared spectroscopy journal July 2016
An Investigation of Thin-Film Ni–Fe Oxide Catalysts for the Electrochemical Evolution of Oxygen journal August 2013
Catalysts at work: From integral to spatially resolved X-ray absorption spectroscopy journal July 2009
Kinetics of CO Poisoning in Simulated Reformate and Effect of Ru Island Morphology on PtRu Fuel Cell Catalysts As Determined by Operando X-ray Absorption Near Edge Spectroscopy journal July 2007
In Situ X-Ray Absorption Near-Edge Structure Evidence for Quadrivalent Nickel in Nickel Battery Electrodes journal January 1996
The structure of interfacial water on gold electrodes studied by x-ray absorption spectroscopy journal October 2014
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
Water Oxidation by Amorphous Cobalt-Based Oxides: Volume Activity and Proton Transfer to Electrolyte Bases journal January 2014
Calcium Manganese(III) Oxides (CaMn 2 O 4x  H 2 O) as Biomimetic Oxygen-Evolving Catalysts journal March 2010
A Bifunctional Nonprecious Metal Catalyst for Oxygen Reduction and Water Oxidation journal October 2010
In Situ Formation of an Oxygen-Evolving Catalyst in Neutral Water Containing Phosphate and Co2+ journal August 2008
Nanostructured Cobalt Oxide Clusters in Mesoporous Silica as Efficient Oxygen-Evolving Catalysts journal February 2009
Nickel-borate oxygen-evolving catalyst that functions under benign conditions journal May 2010
Nickel–Iron Oxyhydroxide Oxygen-Evolution Electrocatalysts: The Role of Intentional and Incidental Iron Incorporation journal April 2014
Structure and Valency of a Cobalt−Phosphate Water Oxidation Catalyst Determined by in Situ X-ray Spectroscopy journal October 2010
Structure–Activity Correlations in a Nickel–Borate Oxygen Evolution Catalyst
  • Bediako, D. Kwabena; Lassalle-Kaiser, Benedikt; Surendranath, Yogesh
  • Journal of the American Chemical Society, Vol. 134, Issue 15 https://doi.org/10.1021/ja301018q
journal April 2012
Water oxidation by amorphous cobalt-based oxides: in situ tracking of redox transitions and mode of catalysis journal January 2015
On the chemical state of Co oxide electrocatalysts during alkaline water splitting journal January 2013
Diffraction and Spectroscopic Studies of the Cobaltic Acid System HCoC 2 –DCoO 2 journal March 1969
Water Oxidation by Electrodeposited Cobalt Oxides-Role of Anions and Redox-Inert Cations in Structure and Function of the Amorphous Catalyst journal February 2012
Intermediate-Range Structure of Self-Assembled Cobalt-Based Oxygen-Evolving Catalyst journal April 2013
Elucidating the Domain Structure of the Cobalt Oxide Water Splitting Catalyst by X-ray Pair Distribution Function Analysis journal June 2012
First turnover analysis of water-oxidation catalyzed by Co-oxide nanoparticles journal January 2015
Time-resolved observations of water oxidation intermediates on a cobalt oxide nanoparticle catalyst journal February 2014
Surface Proton Hopping and Fast-Kinetics Pathway of Water Oxidation on Co 3 O 4 (001) Surface journal July 2016
Reversible amorphization and the catalytically active state of crystalline Co3O4 during oxygen evolution journal October 2015
Dynamical changes of a Ni-Fe oxide water splitting catalyst investigated at different pH journal March 2016
Discovering Ce-rich oxygen evolution catalysts, from high throughput screening to water electrolysis journal January 2014
Identification of Highly Active Fe Sites in (Ni,Fe)OOH for Electrocatalytic Water Splitting journal January 2015
Oxygen Evolution Reaction Dynamics, Faradaic Charge Efficiency, and the Active Metal Redox States of Ni–Fe Oxide Water Splitting Electrocatalysts journal April 2016
Nanostructured Nickel Phosphide as an Electrocatalyst for the Hydrogen Evolution Reaction journal June 2013
Transition metal carbides (WC, Mo2C, TaC, NbC) as potential electrocatalysts for the hydrogen evolution reaction (HER) at medium temperatures journal February 2015
Nanostructured Amorphous Nickel Boride for High-Efficiency Electrocatalytic Hydrogen Evolution over a Broad pH Range journal January 2016
Amorphous Cobalt Boride (Co 2 B) as a Highly Efficient Nonprecious Catalyst for Electrochemical Water Splitting: Oxygen and Hydrogen Evolution journal June 2016
Unsupported transition metal sulfide catalysts: From fundamentals to industrial application journal April 2007
Identification of Active Edge Sites for Electrochemical H2 Evolution from MoS2 Nanocatalysts journal July 2007
Structural and Electronic Study of an Amorphous MoS3 Hydrogen-Generation Catalyst on a Quantum-Controlled Photosensitizer journal September 2011
Hydrogen evolution catalyzed by MoS3 and MoS2 particles journal January 2012
Evidence from in Situ X-ray Absorption Spectroscopy for the Involvement of Terminal Disulfide in the Reduction of Protons by an Amorphous Molybdenum Sulfide Electrocatalyst journal December 2014
Growth and Activation of an Amorphous Molybdenum Sulfide Hydrogen Evolving Catalyst journal August 2013
Electrodeposited Cobalt-Sulfide Catalyst for Electrochemical and Photoelectrochemical Hydrogen Generation from Water journal November 2013
Operando Spectroscopic Analysis of an Amorphous Cobalt Sulfide Hydrogen Evolution Electrocatalyst journal June 2015
Engineering the surface structure of MoS2 to preferentially expose active edge sites for electrocatalysis journal October 2012
Building an appropriate active-site motif into a hydrogen-evolution catalyst with thiomolybdate [Mo3S13]2− clusters journal January 2014
Highly Active Electrocatalysis of the Hydrogen Evolution Reaction by Cobalt Phosphide Nanoparticles journal April 2014
Molybdenum phosphide: a new highly efficient catalyst for the electrochemical hydrogen evolution reaction journal January 2014
Molybdenum phosphide as an efficient electrocatalyst for the hydrogen evolution reaction journal January 2014
Homogeneously dispersed multimetal oxygen-evolving catalysts journal March 2016
A highly active and stable IrO x /SrIrO 3 catalyst for the oxygen evolution reaction journal September 2016
Simultaneous detection of electronic structure changes from two elements of a bifunctional catalyst using wavelength-dispersive X-ray emission spectroscopy and in situ electrochemistry journal January 2015
A multi-crystal wavelength dispersive x-ray spectrometer journal July 2012
High resolution 1s core hole X-ray spectroscopy in 3d transition metal complexes—electronic and structural information journal January 2005
Photon-in photon-out hard X-ray spectroscopy at the Linac Coherent Light Source journal April 2015
Formation of Copper Catalysts for CO 2 Reduction with High Ethylene/Methane Product Ratio Investigated with In Situ X-ray Absorption Spectroscopy journal April 2016
CO2 Reduction at Low Overpotential on Cu Electrodes Resulting from the Reduction of Thick Cu2O Films journal April 2012
Tailoring Copper Nanocrystals towards C 2 Products in Electrochemical CO 2 Reduction journal April 2016
Robust carbon dioxide reduction on molybdenum disulphide edges journal July 2014
[Mn(bipyridyl)(CO)3Br]: An Abundant Metal Carbonyl Complex as Efficient Electrocatalyst for CO2 Reduction journal September 2011
A Local Proton Source Enhances CO 2 Electroreduction to CO by a Molecular Fe Catalyst journal October 2012
Catalytic CO2 valorization into CH4 on Ni-based ceria-zirconia. Reaction mechanism by operando IR spectroscopy journal October 2013
Developing a Mechanistic Understanding of Molecular Electrocatalysts for CO 2 Reduction using Infrared Spectroelectrochemistry journal April 2014
Direct Observation of Two Electron Holes in a Hematite Photoanode during Photoelectrochemical Water Splitting journal August 2012
Detecting Non-bridging Oxygens: Non-Resonant Inelastic X-ray Scattering in Crystalline Lithium Borates journal September 2014
1s3p Resonant Inelastic X-ray Scattering of Cobalt Oxides and Sulfides journal October 2016

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Recent Progress in Defective Carbon‐Based Oxygen Electrode Materials for Rechargeable Zink‐Air Batteries journal April 2019
Electrochemical flow cell enabling operando probing of electrocatalyst surfaces by X-ray spectroscopy and diffraction journal January 2019
A Review of Electrocatalytic Reduction of Dinitrogen to Ammonia under Ambient Conditions journal May 2018
Undesired Bulk Oxidation of LiMn 2 O 4 Increases Overpotential of Electrocatalytic Water Oxidation in Lithium Hydroxide Electrolytes journal August 2019
Understanding the crucial role of local crystal order in the electrocatalytic activity of crystalline manganese oxide journal January 2018
Time-resolved X-ray absorption spectroelectrochemistry of redox active species in solution journal October 2019
An Unconventional Iron Nickel Catalyst for the Oxygen Evolution Reaction journal February 2019
Operando X-Ray Spectroscopic Techniques: A Focus on Hydrogen and Oxygen Evolution Reactions journal January 2020