Inductive and electrostatic effects on cobalt porphyrins for heterogeneous electrocatalytic carbon dioxide reduction
Name
c9cy00102f.pdf
Description
Published version
Size
2.24 MB
Format
Adobe PDF
Checksum (MD5)
19ed4ada7a3f3776f17ec2e49f2a8070
Author(s)
Zhu, Minghui
Yang, Deng-Tao
Ye, Ruquan
Zeng, Joy
Corbin, Nathan
Manthiram, Karthish
Date Issued
2019
Journal
Catalysis Science & Technology
Publisher
Royal Society of Chemistry (RSC)
Version
Final published version
Abstract
© 2019 The Royal Society of Chemistry. Electrochemical carbon dioxide reduction enables conversion of carbon dioxide into fuels and chemicals with renewable energy input. Cobalt-based molecular complexes have exhibited high selectivity, activity, and stability for transforming carbon dioxide into carbon monoxide. Through evaluating immobilized cobalt porphyrins functionalized with various peripheral substituents, we demonstrated that their activity is affected not only by the electronegativity of the substituents, but importantly, also by the charge of the substituents. The performance of immobilized cobalt porphyrins can be improved by introducing electron-donating and positively charged functional groups. Through kinetic studies, we were able to understand the mechanism by which electron-donating groups enhance the observed rates of carbon dioxide reduction and how cationic functionality may contribute towards electrostatic stabilization of the intermediate formed in the rate-determining step. Our methodology provides a robust and experimentally-verified method of computationally predicting the electronic effect of peripheral substitution and hence the catalytic activity of substituted porphyrins.
MIT Department
Massachusetts Institute of Technology. Department of Chemical Engineering
Terms of Use
Creative Commons Attribution 4.0 International license
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DOI of Published Version
https://doi.org/10.1039/c9cy00102f
