Nature of the First Electron Transfer in Electrochemical Ammonia Activation in a Nonaqueous Medium
Name
RevisedManuscript.pdf
Description
Published version
Size
2.52 MB
Format
Adobe PDF
Checksum (MD5)
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Author(s)
Schiffer, Zachary J.
Lazouski, Nikifar
Corbin, Nathan
Manthiram, Karthish
Date Issued
March 2019
Journal
Journal of Physical Chemistry C
Publisher
American Chemical Society (ACS)
Citation
Schiffer, Zachary et al. "Nature of the First Electron Transfer in Electrochemical Ammonia Activation in a Nonaqueous Medium." Journal of Physical Chemistry C 123, 15 (April 2019): 9713-9720 © 2019 American Chemical Society
Version
Author's final manuscript
Abstract
Decreasing costs of renewable sources of electricity will increase the viability of electrochemical processes in chemical manufacturing. To this end, improved understanding of electrochemical N-H bond activation is essential to develop electrochemical routes for producing nitrogen-containing chemicals. In this work, we investigate electrochemical ammonia activation in acetonitrile, a prototypical nonaqueous solvent for electro-organic syntheses. Nonaqueous environments are desirable for electro-organic syntheses due to large electrochemical stability windows and high solubility for organic products. We find that ammonia oxidation in acetonitrile proceeds through an outer-sphere mechanism involving an initial electron transfer as the rate-determining step, likely producing an ammonia radical cation. Density functional theory calculations explain a low transfer coefficient and suggest possible subsequent reaction steps. Structural factors involved in lowering of the transfer coefficient provide insights that are applicable to a wider range of small-molecule activation chemistries.
MIT Department
Massachusetts Institute of Technology. Department of Chemical Engineering
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DOI of Published Version
https://doi.org/10.1021/ACS.JPCC.9B00669
