Inductive and electrostatic effects on cobalt porphyrins for heterogeneous electrocatalytic carbon dioxide reduction

Research output: Journal Publications and Reviews (RGC: 21, 22, 62)21_Publication in refereed journalpeer-review

30 Scopus Citations
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Author(s)

  • Minghui Zhu
  • Deng-Tao Yang
  • Joy Zeng
  • Nathan Corbin
  • Karthish Manthiram

Detail(s)

Original languageEnglish
Pages (from-to)974-980
Journal / PublicationCatalysis Science & Technology
Volume9
Issue number4
Online published21 Jan 2019
Publication statusPublished - 21 Feb 2019
Externally publishedYes

Abstract

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.

Citation Format(s)

Inductive and electrostatic effects on cobalt porphyrins for heterogeneous electrocatalytic carbon dioxide reduction. / Zhu, Minghui; Yang, Deng-Tao; Ye, Ruquan; Zeng, Joy; Corbin, Nathan; Manthiram, Karthish.

In: Catalysis Science & Technology, Vol. 9, No. 4, 21.02.2019, p. 974-980.

Research output: Journal Publications and Reviews (RGC: 21, 22, 62)21_Publication in refereed journalpeer-review