Nanogap Electrochemistry of Adsorption-Coupled Electron Transfer

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In this project funded by the Chemical Measurement and Imaging Program, with co-funding from the Chemical Structure, Dynamics, and Mechanisms-A Program, of the Division of Chemistry, Professor Shigeru Amemiya of the University of Pittsburgh is developing new electrochemical methods that allow for the separate study of electron transfer and coupled adsorption events at novel nanometer-sized electrodes. This project focuses on gaining an advanced understanding of adsorption-coupled electron transfer, which plays a vital role in numerous electrochemical energy devices, such as fuel cells, batteries, solar cells, and supercapacitors. Reliable determination of rate and energy parameters is possible due to the creation of new research tools. Students from underrepresented groups gain interdisciplinary training in the research and undergraduate laboratory environments, as a result of their participating in cross-cutting research. This project is focused on the quantitative study of adsorption-coupled electron transfer as the key step of electrochemical technologies that span electrocatalysis, electrodeposition, and electroanalysis. New nanoelectrochemical methods developed in the Amemiya laboratory provide an opportunity to kinetically resolve adsorption-coupled electron transfer into its elementary steps. Specifically, nanogap voltammetry with a scanning electrochemical microscope affords a path to separately determine the dynamics of inner-sphere and outer-sphere electron transfer, surface adsorption, and even coupled chemical reactions. Reliable reaction parameters can be obtained by employing clean electrodes that maintain vacuum-level surface cleanliness in air and solution, as a result of new methods developed by Professor Amemiya's research group.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.