TY - JOUR
T1 - Nanoscale Scanning Electrochemical Cell Microscopy and Correlative Surface Structural Analysis to Map Anodic and Cathodic Reactions on Polycrystalline Zn in Acid Media
AU - Shkirskiy, V.
AU - Yule, L. C.
AU - Daviddi, E.
AU - Bentley, C. L.
AU - Aarons, J.
AU - West, G.
AU - Unwin, P. R.
PY - 2020/3
Y1 - 2020/3
N2 - Scanning electrochemical cell microscopy (SECCM) is used to map anodic and cathodic processes on polycrystalline zinc in 10 mM H2SO4, at the nanoscale. Electrochemical maps are correlated directly with structural data from electron backscatter diffraction applied to the same regions of the surface, and density functional theory (DFT) calculations are used to rationalize the data. Preliminary data on droplet stability with SECCM point measurements indicated that there was a significant spreading of the meniscus cell with an air atmosphere, attributed to changes in pH during the oxygen reduction reaction, compromising the lateral resolution of the SECCM measurement. Experiments with an argon atmosphere, as well as the application of a hydrophobic n-dodecane oil layer on the Zn interface, prevented spreading. Electrochemical maps of polycrystalline Zn surface under an Ar atmosphere indicated that the hydrogen evolution reaction (HER) and Zn electrodissolution on individual low-index grains decreased in the order (1¯21¯0) ≫ (011¯0) > (0001). DFT calculations revealed a correlation between experimental values of current associated with HER and Zn dissolution reactions and the predicted hydrogen adsorption and Zn dissolution energies on individual facets, respectively. This work further advances SECCM as a technique for probing electrified interfaces and demonstrates its applicability to reactive metals.
AB - Scanning electrochemical cell microscopy (SECCM) is used to map anodic and cathodic processes on polycrystalline zinc in 10 mM H2SO4, at the nanoscale. Electrochemical maps are correlated directly with structural data from electron backscatter diffraction applied to the same regions of the surface, and density functional theory (DFT) calculations are used to rationalize the data. Preliminary data on droplet stability with SECCM point measurements indicated that there was a significant spreading of the meniscus cell with an air atmosphere, attributed to changes in pH during the oxygen reduction reaction, compromising the lateral resolution of the SECCM measurement. Experiments with an argon atmosphere, as well as the application of a hydrophobic n-dodecane oil layer on the Zn interface, prevented spreading. Electrochemical maps of polycrystalline Zn surface under an Ar atmosphere indicated that the hydrogen evolution reaction (HER) and Zn electrodissolution on individual low-index grains decreased in the order (1¯21¯0) ≫ (011¯0) > (0001). DFT calculations revealed a correlation between experimental values of current associated with HER and Zn dissolution reactions and the predicted hydrogen adsorption and Zn dissolution energies on individual facets, respectively. This work further advances SECCM as a technique for probing electrified interfaces and demonstrates its applicability to reactive metals.
UR - http://www.scopus.com/inward/record.url?scp=85083673378&partnerID=8YFLogxK
U2 - 10.1149/1945-7111/ab739d
DO - 10.1149/1945-7111/ab739d
M3 - Article
AN - SCOPUS:85083673378
VL - 167
JO - Journal of the Electrochemical Society
JF - Journal of the Electrochemical Society
SN - 0013-4651
IS - 4
M1 - 041507
ER -