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Title: In situ Infrared Spectroelectrochemistry for Understanding Structural Transformations of Precisely Defined Ions at Electrochemical Interfaces

Abstract

Understanding the intrinsic properties of electroactive species at electrode-electrolyte interfaces (EEIs) is essential to the rational design of high-performance solid-state energy conversion and storage systems. In situ spectroscopy combined with cyclic voltammetry (CV) provides insights into structural changes of electroactive species at functioning EEIs. Ion soft-landing enables precisely-controlled deposition of massand charge-selected ions onto electrode surfaces thereby avoiding the contamination inherent with conventional electrode preparation techniques. In this contribution, we describe a new approach for the simultaneous electrochemical and spectroscopic characterization of soft-landed ions at operating solid-state EEIs. The technique exploits a specially-fabricated three-electrode cell that is compatible with in situ infrared reflection absorption spectroscopy (IRRAS) characterization of the softlanded ions. Keggin polyoxometalate (POM) anions, PW12O40 3-, were selected as a model system for these experiments due to their multielectron redox activity, structural stability, and well-characterized IRRAS spectrum. In situ CV measurements indicated continuous multielectron transfer processes of the soft-landed PW12O40 3- anions over a large potential range of -2.1 to -0.3 V. A distinct shift in the wavenumber of the terminal W=Ot stretching vibration in the IRRAS spectra was observed during the multielectron reduction process. The results demonstrate the capabilities of the in situ spectroelectrochemical approach for examining structuralmore » changes of well-defined electroactive species during electron transfer processes at operating solid-state EEIs.« less

Authors:
 [1]; ORCiD logo [2]; ORCiD logo [2];  [1]
  1. Purdue University
  2. BATTELLE (PACIFIC NW LAB)
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1558424
Report Number(s):
PNNL-SA-137370
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Journal Name:
Analytical Chemistry
Additional Journal Information:
Journal Volume: 90; Journal Issue: 18
Country of Publication:
United States
Language:
English

Citation Formats

Su, Pei, Prabhakaran, Venkateshkumar, Johnson, Grant E., and Laskin, Julia. In situ Infrared Spectroelectrochemistry for Understanding Structural Transformations of Precisely Defined Ions at Electrochemical Interfaces. United States: N. p., 2018. Web. doi:10.1021/acs.analchem.8b02440.
Su, Pei, Prabhakaran, Venkateshkumar, Johnson, Grant E., & Laskin, Julia. In situ Infrared Spectroelectrochemistry for Understanding Structural Transformations of Precisely Defined Ions at Electrochemical Interfaces. United States. doi:10.1021/acs.analchem.8b02440.
Su, Pei, Prabhakaran, Venkateshkumar, Johnson, Grant E., and Laskin, Julia. Tue . "In situ Infrared Spectroelectrochemistry for Understanding Structural Transformations of Precisely Defined Ions at Electrochemical Interfaces". United States. doi:10.1021/acs.analchem.8b02440.
@article{osti_1558424,
title = {In situ Infrared Spectroelectrochemistry for Understanding Structural Transformations of Precisely Defined Ions at Electrochemical Interfaces},
author = {Su, Pei and Prabhakaran, Venkateshkumar and Johnson, Grant E. and Laskin, Julia},
abstractNote = {Understanding the intrinsic properties of electroactive species at electrode-electrolyte interfaces (EEIs) is essential to the rational design of high-performance solid-state energy conversion and storage systems. In situ spectroscopy combined with cyclic voltammetry (CV) provides insights into structural changes of electroactive species at functioning EEIs. Ion soft-landing enables precisely-controlled deposition of massand charge-selected ions onto electrode surfaces thereby avoiding the contamination inherent with conventional electrode preparation techniques. In this contribution, we describe a new approach for the simultaneous electrochemical and spectroscopic characterization of soft-landed ions at operating solid-state EEIs. The technique exploits a specially-fabricated three-electrode cell that is compatible with in situ infrared reflection absorption spectroscopy (IRRAS) characterization of the softlanded ions. Keggin polyoxometalate (POM) anions, PW12O40 3-, were selected as a model system for these experiments due to their multielectron redox activity, structural stability, and well-characterized IRRAS spectrum. In situ CV measurements indicated continuous multielectron transfer processes of the soft-landed PW12O40 3- anions over a large potential range of -2.1 to -0.3 V. A distinct shift in the wavenumber of the terminal W=Ot stretching vibration in the IRRAS spectra was observed during the multielectron reduction process. The results demonstrate the capabilities of the in situ spectroelectrochemical approach for examining structural changes of well-defined electroactive species during electron transfer processes at operating solid-state EEIs.},
doi = {10.1021/acs.analchem.8b02440},
journal = {Analytical Chemistry},
number = 18,
volume = 90,
place = {United States},
year = {2018},
month = {9}
}