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Title: In Situ Mass Spectrometric Monitoring of the Dynamic Electrochemical Process at the Electrode–Electrolyte Interface: a SIMS Approach

Abstract

The in situ molecular characterization of reaction intermediates and products at electrode-electrolyte interfaces is central to mechanistic studies of complex electrochemical processes, yet a great challenge. The coupling of electrochemistry (EC) and mass spectrometry (MS) has seen rapid development and found broad applicability in tackling challenges in analytical and bioanalytical chemistry. However, few truly in situ and real-time EC-MS studies have been reported at electrode-electrolyte interfaces. An innovative EC-MS coupling method named in situ liquid secondary ion mass spectrometry (SIMS) was recently developed by combining SIMS with a vacuum compatible microfluidic electrochemical device. Using this novel capability we report the first in situ elucidation of the electro-oxidation mechanism of a biologically significant organic compound, ascorbic acid (AA), at the electrode-electrolyte interface. The short-lived radical intermediate was successfully captured, which had not been detected directly before. Moreover, we demonstrated the power of this new technique in real-time monitoring of the formation and dynamic evolution of electrical double layers at the electrode-electrolyte interface. This work suggests further promising applications of in situ liquid SIMS in studying more complex chemical and biological events at the electrode-electrolyte interface.

Authors:
; ; ; ; ; ORCiD logo; ORCiD logo; ;
Publication Date:
Research Org.:
Pacific Northwest National Laboratory (PNNL), Richland, WA (US), Environmental Molecular Sciences Laboratory (EMSL)
Sponsoring Org.:
USDOE
OSTI Identifier:
1339805
Report Number(s):
PNNL-SA-122793
Journal ID: ISSN 0003-2700; 48143; 47299; 49188; KP1704020
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Resource Relation:
Journal Name: Analytical Chemistry; Journal Volume: 89; Journal Issue: 1
Country of Publication:
United States
Language:
English
Subject:
Environmental Molecular Sciences Laboratory

Citation Formats

Wang, Zhaoying, Zhang, Yanyan, Liu, Bingwen, Wu, Kui, Thevuthasan, Suntharampillai, Baer, Donald R., Zhu, Zihua, Yu, Xiao-Ying, and Wang, Fuyi. In Situ Mass Spectrometric Monitoring of the Dynamic Electrochemical Process at the Electrode–Electrolyte Interface: a SIMS Approach. United States: N. p., 2017. Web. doi:10.1021/acs.analchem.6b04189.
Wang, Zhaoying, Zhang, Yanyan, Liu, Bingwen, Wu, Kui, Thevuthasan, Suntharampillai, Baer, Donald R., Zhu, Zihua, Yu, Xiao-Ying, & Wang, Fuyi. In Situ Mass Spectrometric Monitoring of the Dynamic Electrochemical Process at the Electrode–Electrolyte Interface: a SIMS Approach. United States. doi:10.1021/acs.analchem.6b04189.
Wang, Zhaoying, Zhang, Yanyan, Liu, Bingwen, Wu, Kui, Thevuthasan, Suntharampillai, Baer, Donald R., Zhu, Zihua, Yu, Xiao-Ying, and Wang, Fuyi. Tue . "In Situ Mass Spectrometric Monitoring of the Dynamic Electrochemical Process at the Electrode–Electrolyte Interface: a SIMS Approach". United States. doi:10.1021/acs.analchem.6b04189.
@article{osti_1339805,
title = {In Situ Mass Spectrometric Monitoring of the Dynamic Electrochemical Process at the Electrode–Electrolyte Interface: a SIMS Approach},
author = {Wang, Zhaoying and Zhang, Yanyan and Liu, Bingwen and Wu, Kui and Thevuthasan, Suntharampillai and Baer, Donald R. and Zhu, Zihua and Yu, Xiao-Ying and Wang, Fuyi},
abstractNote = {The in situ molecular characterization of reaction intermediates and products at electrode-electrolyte interfaces is central to mechanistic studies of complex electrochemical processes, yet a great challenge. The coupling of electrochemistry (EC) and mass spectrometry (MS) has seen rapid development and found broad applicability in tackling challenges in analytical and bioanalytical chemistry. However, few truly in situ and real-time EC-MS studies have been reported at electrode-electrolyte interfaces. An innovative EC-MS coupling method named in situ liquid secondary ion mass spectrometry (SIMS) was recently developed by combining SIMS with a vacuum compatible microfluidic electrochemical device. Using this novel capability we report the first in situ elucidation of the electro-oxidation mechanism of a biologically significant organic compound, ascorbic acid (AA), at the electrode-electrolyte interface. The short-lived radical intermediate was successfully captured, which had not been detected directly before. Moreover, we demonstrated the power of this new technique in real-time monitoring of the formation and dynamic evolution of electrical double layers at the electrode-electrolyte interface. This work suggests further promising applications of in situ liquid SIMS in studying more complex chemical and biological events at the electrode-electrolyte interface.},
doi = {10.1021/acs.analchem.6b04189},
journal = {Analytical Chemistry},
number = 1,
volume = 89,
place = {United States},
year = {Tue Jan 03 00:00:00 EST 2017},
month = {Tue Jan 03 00:00:00 EST 2017}
}