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

Journal Article · · Topics in Catalysis
 [1];  [2];  [2];  [2];  [3];  [2];  [2]
  1. Princeton Univ., Princeton, NJ (United States); Monmouth Junction, NJ (United States)
  2. Princeton Univ., Princeton, NJ (United States)
  3. Princeton Univ., Princeton, NJ (United States); Georgian Court Univ., Lakewood, NJ (United States)
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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. As a result, mechanistic models for the the reaction of the pyridinium with carbon dioxide are considered.

Research Organization:
Princeton Univ., NJ (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division
Contributing Organization:
Princeton University
Grant/Contract Number:
SC0002133
OSTI ID:
1418444
Journal Information:
Topics in Catalysis, Vol. 58, Issue 1; ISSN 1022-5528
Publisher:
SpringerCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 35 works
Citation information provided by
Web of Science

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Using a One-Electron Shuttle for the Multielectron Reduction of CO2 to Methanol: Kinetic, Mechanistic, and Structural Insights
  • Barton Cole, Emily; Lakkaraju, Prasad S.; Rampulla, David M.
  • Journal of the American Chemical Society, Vol. 132, Issue 33, p. 11539-11551 https://doi.org/10.1021/ja1023496
journal August 2010
Functional Role of Pyridinium during Aqueous Electrochemical Reduction of CO 2 on Pt(111) journal February 2013
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Cited By (3)

Sustainion Imidazolium-Functionalized Polymers for Carbon Dioxide Electrolysis journal March 2017
Pyridinium-Facilitated CO 2 Electroreduction on Pt Nanowire: Enhanced Electrochemical Performance in CO 2 Conversion: Pyridinium-Facilitated CO2 journal September 2018
CO 2 electrochemical reduction at thiolate-modified bulk Au electrodes journal January 2019

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
25 ENERGY STORAGE
14 SOLAR ENERGY
pyridinium catalyzed co2 reduction
co2 to methanol conversion
electrochemical co2 reduction
carbon-dioxide