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Quantitative Electrochemical Measurements Using In Situ ec-S/TEM Devices

Published online by Cambridge University Press:  11 March 2014

Raymond R. Unocic ,
Robert L. Sacci ,
Gilbert M. Brown ,
Gabriel M. Veith ,
Nancy J. Dudney ,
Karren L. More ,
Franklin S. Walden II ,
Daniel S. Gardiner ,
John Damiano  and
David P. Nackashi
Raymond R. Unocic*
Affiliation:
Oak Ridge National Laboratory, Center for Nanophase Materials Sciences, Oak Ridge, TN 37831, USA
Robert L. Sacci
Affiliation:
Oak Ridge National Laboratory, Materials Science and Technology Division, Oak Ridge, TN 37831, USA
Gilbert M. Brown
Affiliation:
Oak Ridge National Laboratory, Chemical Sciences Division, Oak Ridge, TN 37831, USA
Gabriel M. Veith
Affiliation:
Oak Ridge National Laboratory, Materials Science and Technology Division, Oak Ridge, TN 37831, USA
Nancy J. Dudney
Affiliation:
Oak Ridge National Laboratory, Materials Science and Technology Division, Oak Ridge, TN 37831, USA
Karren L. More
Affiliation:
Oak Ridge National Laboratory, Center for Nanophase Materials Sciences, Oak Ridge, TN 37831, USA
Franklin S. Walden II
Affiliation:
Protochips Inc., Raleigh, NC 27606, USA
Daniel S. Gardiner
Affiliation:
Protochips Inc., Raleigh, NC 27606, USA
John Damiano
Affiliation:
Protochips Inc., Raleigh, NC 27606, USA
David P. Nackashi
Affiliation:
Protochips Inc., Raleigh, NC 27606, USA
*
*Corresponding Author. unocicrr@ornl.gov
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Abstract

Insight into dynamic electrochemical processes can be obtained with in situ electrochemical-scanning/transmission electron microscopy (ec-S/TEM), a technique that utilizes microfluidic electrochemical cells to characterize electrochemical processes with S/TEM imaging, diffraction, or spectroscopy. The microfluidic electrochemical cell is composed of microfabricated devices with glassy carbon and platinum microband electrodes in a three-electrode cell configuration. To establish the validity of this method for quantitative in situ electrochemistry research, cyclic voltammetry (CV), choronoamperometry (CA), and electrochemical impedance spectroscopy (EIS) were performed using a standard one electron transfer redox couple [Fe(CN)6]3−/4−-based electrolyte. Established relationships of the electrode geometry and microfluidic conditions were fitted with CV and chronoamperometic measurements of analyte diffusion coefficients and were found to agree with well-accepted values that are on the order of 10−5 cm2/s. Influence of the electron beam on electrochemical measurements was found to be negligible during CV scans where the current profile varied only within a few nA with the electron beam on and off, which is well within the hysteresis between multiple CV scans. The combination of experimental results provides a validation that quantitative electrochemistry experiments can be performed with these small-scale microfluidic electrochemical cells provided that accurate geometrical electrode configurations, diffusion boundary layers, and microfluidic conditions are accounted for.

Keywords

in situ ec-S/TEMelectrochemistrymicrofluidic electrochemical cellsmicroelectrodes
Type
In Situ Special Section
Information
Microscopy and Microanalysis , Volume 20 , Issue 2 , April 2014 , pp. 452 - 461
Copyright
© Microscopy Society of America 2014 

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