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Title: On decomposition, degradation, and voltammetric deviation: the electrochemist's field guide to identifying precatalyst transformation

Abstract

What is the identity of the true electrocatalytic species? This basic question has plagued the molecular electrocatalysis community during its decades-long search for selective and efficient transition-metal based electrocatalysts for fuel forming reactions. Identifying when the added species is a precatalyst that transforms into the active catalyst in situ is an extraordinarily complex endeavor. Thankfully, the last decade has witnessed a resurgence of interest in understanding and controlling these transformations, leading to an expansion of the experimental toolkit available to probe catalyst identity. Here in this Tutorial Review, researchers will learn how the nature of the active catalyst can be uncovered using state-of-the-art electrochemical and spectroscopic methods. Analysis of catalytic voltammograms can quickly furnish qualitative evidence of precatalyst transformation and a library of these tell-tale signs is discussed, along with the chemical phenomena underpinning each feature. Complementary electrochemical and spectroscopic methods for identifying in situ generation of heterogeneous catalysts are also presented, outlining the conditions required for correct application with special emphasis on potential pitfalls when studying weakly-adsorbed material. Case studies are presented to showcase how these different probes can be integrated to develop a comprehensive picture of precatalyst transformation.

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]
  1. Univ. of North Carolina, Chapel Hill, NC (United States)
Publication Date:
Research Org.:
Univ. of North Carolina, Chapel Hill, NC (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1604867
Alternate Identifier(s):
OSTI ID: 1512813
Grant/Contract Number:  
SC0015303
Resource Type:
Accepted Manuscript
Journal Name:
Chemical Society Reviews
Additional Journal Information:
Journal Volume: 48; Journal Issue: 11; Journal ID: ISSN 0306-0012
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
08 HYDROGEN; 10 SYNTHETIC FUELS

Citation Formats

Lee, Katherine J., McCarthy, Brian D., and Dempsey, Jillian L. On decomposition, degradation, and voltammetric deviation: the electrochemist's field guide to identifying precatalyst transformation. United States: N. p., 2019. Web. doi:10.1039/C8CS00851E.
Lee, Katherine J., McCarthy, Brian D., & Dempsey, Jillian L. On decomposition, degradation, and voltammetric deviation: the electrochemist's field guide to identifying precatalyst transformation. United States. doi:10.1039/C8CS00851E.
Lee, Katherine J., McCarthy, Brian D., and Dempsey, Jillian L. Wed . "On decomposition, degradation, and voltammetric deviation: the electrochemist's field guide to identifying precatalyst transformation". United States. doi:10.1039/C8CS00851E. https://www.osti.gov/servlets/purl/1604867.
@article{osti_1604867,
title = {On decomposition, degradation, and voltammetric deviation: the electrochemist's field guide to identifying precatalyst transformation},
author = {Lee, Katherine J. and McCarthy, Brian D. and Dempsey, Jillian L.},
abstractNote = {What is the identity of the true electrocatalytic species? This basic question has plagued the molecular electrocatalysis community during its decades-long search for selective and efficient transition-metal based electrocatalysts for fuel forming reactions. Identifying when the added species is a precatalyst that transforms into the active catalyst in situ is an extraordinarily complex endeavor. Thankfully, the last decade has witnessed a resurgence of interest in understanding and controlling these transformations, leading to an expansion of the experimental toolkit available to probe catalyst identity. Here in this Tutorial Review, researchers will learn how the nature of the active catalyst can be uncovered using state-of-the-art electrochemical and spectroscopic methods. Analysis of catalytic voltammograms can quickly furnish qualitative evidence of precatalyst transformation and a library of these tell-tale signs is discussed, along with the chemical phenomena underpinning each feature. Complementary electrochemical and spectroscopic methods for identifying in situ generation of heterogeneous catalysts are also presented, outlining the conditions required for correct application with special emphasis on potential pitfalls when studying weakly-adsorbed material. Case studies are presented to showcase how these different probes can be integrated to develop a comprehensive picture of precatalyst transformation.},
doi = {10.1039/C8CS00851E},
journal = {Chemical Society Reviews},
number = 11,
volume = 48,
place = {United States},
year = {2019},
month = {5}
}

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