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Topics in Catalysis
Published in: Topics in Catalysis 1/2015

01-02-2015 | Original Paper

Substituent Effects in the Pyridinium Catalyzed Reduction of CO2 to Methanol: Further Mechanistic Insights

Authors: Emily E. Barton Cole, Maor F. Baruch, Robert P. L’Esperance, Michael T. Kelly, Prasad S. Lakkaraju, Elizabeth L. Zeitler, Andrew B. Bocarsly

Published in: Topics in Catalysis | Issue 1/2015

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Abstract

A series of substituted pyridiniums were examined for their catalytic ability to electrochemically reduce carbon dioxide to methanol. It is found that in general increased basicity of the nitrogen of the amine and higher LUMO energy of the pyridinium correlate with enhanced carbon dioxide reduction. The highest faradaic yield for methanol production at a platinum electrode was 39 ± 4 % for 4-aminopyridine compared to 22 ± 2 % for pyridine. However, 4-tertbutyl and 4-dimethylamino pyridine showed decreased catalytic behavior, contrary to the enhanced activity associated with the increased basicity and LUMO energy, and suggesting that steric effects also play a significant role in the behavior of pyridinium electrocatalysts. Mechanistic models for the the reaction of the pyridinium with carbon dioxide are considered.
previous article Reaction Mechanisms in the Direct Carboxylation of Alcohols for the Synthesis of Acyclic Carbonates
next article Electrochemical Reduction of Aqueous Imidazolium on Pt(111) by Proton Coupled Electron Transfer

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Appendix
Available only for authorised users
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Metadata
Title
Substituent Effects in the Pyridinium Catalyzed Reduction of CO2 to Methanol: Further Mechanistic Insights
Authors
Emily E. Barton Cole
Maor F. Baruch
Robert P. L’Esperance
Michael T. Kelly
Prasad S. Lakkaraju
Elizabeth L. Zeitler
Andrew B. Bocarsly
Publication date
01-02-2015
Publisher
Springer US
Published in
Topics in Catalysis / Issue 1/2015
Print ISSN: 1022-5528
Electronic ISSN: 1572-9028
DOI
https://doi.org/10.1007/s11244-014-0343-z

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Preface

Preface

Original Paper

Electrochemical Reduction of Aqueous Imidazolium on Pt(111) by Proton Coupled Electron Transfer

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