Search Menu
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information
Search Scholarly Publications

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

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. As a result, mechanistic models for the the reaction of the pyridinium with carbon dioxide are considered.

Authors:
 [1];  [2];  [2];  [2];  [3];  [2];  [2]
+ Show Author Affiliations
  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)
Publication Date:
Research Org.:
Princeton Univ., NJ (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division
Contributing Org.:
Princeton University
OSTI Identifier:
1418444
Grant/Contract Number:  
SC0002133
Resource Type:
Accepted Manuscript
Journal Name:
Topics in Catalysis
Additional Journal Information:
Journal Volume: 58; Journal Issue: 1; Journal ID: ISSN 1022-5528
Publisher:
Springer
Country of Publication:
United States
Language:
English
Subject:
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

Citation Formats

Barton Cole, Emily E., Baruch, Maor F., L’Esperance, Robert P., Kelly, Michael T., Lakkaraju, Prasad S., Zeitler, Elizabeth L., and Bocarsly, Andrew B. Substituent Effects in the Pyridinium Catalyzed Reduction of CO2 to Methanol: Further Mechanistic Insights. United States: N. p., 2014. Web. doi:10.1007/S11244-014-0343-Z.
Copy to clipboard
Barton Cole, Emily E., Baruch, Maor F., L’Esperance, Robert P., Kelly, Michael T., Lakkaraju, Prasad S., Zeitler, Elizabeth L., & Bocarsly, Andrew B. Substituent Effects in the Pyridinium Catalyzed Reduction of CO2 to Methanol: Further Mechanistic Insights. United States. https://doi.org/10.1007/S11244-014-0343-Z
Copy to clipboard
Barton Cole, Emily E., Baruch, Maor F., L’Esperance, Robert P., Kelly, Michael T., Lakkaraju, Prasad S., Zeitler, Elizabeth L., and Bocarsly, Andrew B. Sat . "Substituent Effects in the Pyridinium Catalyzed Reduction of CO2 to Methanol: Further Mechanistic Insights". United States. https://doi.org/10.1007/S11244-014-0343-Z. https://www.osti.gov/servlets/purl/1418444.
Copy to clipboard
@article{osti_1418444,
title = {Substituent Effects in the Pyridinium Catalyzed Reduction of CO2 to Methanol: Further Mechanistic Insights},
author = {Barton Cole, Emily E. and Baruch, Maor F. and L’Esperance, Robert P. and Kelly, Michael T. and Lakkaraju, Prasad S. and Zeitler, Elizabeth L. and Bocarsly, Andrew B.},
abstractNote = {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.},
doi = {10.1007/S11244-014-0343-Z},
journal = {Topics in Catalysis},
number = 1,
volume = 58,
place = {United States},
year = {Sat Nov 15 00:00:00 EST 2014},
month = {Sat Nov 15 00:00:00 EST 2014}
}
Copy to clipboard
Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1007/S11244-014-0343-Z
Copyright Statement
Other availability
Search WorldCat Search WorldCat to find libraries that may hold this journal
Citation Metrics:
Cited by: 35 works
Citation information provided by
Web of Science
Save / Share:
Export Metadata
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.

Works referenced in this record:

A decade of weather extremes
journal, March 2012

Electrochemical Reduction of Carbon Dioxide in Water: Analysis of Reaction Mechanism on Ruthenium-Titanium-Oxide
journal, January 1992

  • Bandi, A.
  • Journal of The Electrochemical Society, Vol. 139, Issue 6
  • DOI: 10.1149/1.2069464

Electrochemical Reduction of Carbon Dioxide to Methane, Methanol, and CO on Ru Electrodes
journal, January 1985

  • Frese, K. W.
  • Journal of The Electrochemical Society, Vol. 132, Issue 1
  • DOI: 10.1149/1.2113780

Reduction of carbon dioxide on ruthenium oxide and modified ruthenium oxide electrodes in 0.5 M NaHCO3
journal, January 1997

  • Popić, J. P.; Avramov-Ivić, M. L.; Vuković, N. B.
  • Journal of Electroanalytical Chemistry, Vol. 421, Issue 1-2, p. 105-110
  • DOI: 10.1016/S0022-0728(96)04823-1

A new homogeneous electrocatalyst for the reduction of carbon dioxide to methanol at low overpotential
journal, July 1994

  • Seshadri, Gayatri; Lin, Chao; Bocarsly, Andrew B.
  • Journal of Electroanalytical Chemistry, Vol. 372, Issue 1-2, p. 145-150
  • DOI: 10.1016/0022-0728(94)03300-5

Selective Solar-Driven Reduction of CO 2 to Methanol Using a Catalyzed p-GaP Based Photoelectrochemical Cell
journal, May 2008

  • Barton, Emily E.; Rampulla, David M.; Bocarsly, Andrew B.
  • Journal of the American Chemical Society, Vol. 130, Issue 20
  • DOI: 10.1021/ja0776327

Electrochemistry of Aqueous Pyridinium: Exploration of a Key Aspect of Electrocatalytic Reduction of CO 2 to Methanol
journal, September 2013

  • Yan, Yong; Zeitler, Elizabeth L.; Gu, Jing
  • Journal of the American Chemical Society, Vol. 135, Issue 38
  • DOI: 10.1021/ja4064052

Electrochemistry of Acids on Platinum. Application to the Reduction of Carbon Dioxide in the Presence of Pyridinium Ion in Water
journal, November 2013

  • Costentin, Cyrille; Canales, Juan Carlos; Haddou, Baptiste
  • Journal of the American Chemical Society, Vol. 135, Issue 47
  • DOI: 10.1021/ja407988w

Using a One-Electron Shuttle for the Multielectron Reduction of CO2 to Methanol: Kinetic, Mechanistic, and Structural Insights
journal, August 2010

  • Barton Cole, Emily; Lakkaraju, Prasad S.; Rampulla, David M.
  • Journal of the American Chemical Society, Vol. 132, Issue 33, p. 11539-11551
  • DOI: 10.1021/ja1023496

Functional Role of Pyridinium during Aqueous Electrochemical Reduction of CO 2 on Pt(111)
journal, February 2013

  • Ertem, Mehmed Z.; Konezny, Steven J.; Araujo, C. Moyses
  • The Journal of Physical Chemistry Letters, Vol. 4, Issue 5
  • DOI: 10.1021/jz400183z

Electrochemical Reduction of Aqueous Imidazolium on Pt(111) by Proton Coupled Electron Transfer
journal, November 2014

Water Suppression That Works. Excitation Sculpting Using Arbitrary Wave-Forms and Pulsed-Field Gradients
journal, February 1995

  • Hwang, T. L.; Shaka, A. J.
  • Journal of Magnetic Resonance, Series A, Vol. 112, Issue 2
  • DOI: 10.1006/jmra.1995.1047

Theory of Stationary Electrode Polarography. Single Scan and Cyclic Methods Applied to Reversible, Irreversible, and Kinetic Systems.
journal, April 1964

  • Nicholson, R. S.; Shain, Irving
  • Analytical Chemistry, Vol. 36, Issue 4, p. 706-723
  • DOI: 10.1021/ac60210a007

Cyclic voltammetry theory for the disproportionation reaction and spherical diffusion
journal, May 1969

  • Olmstead, Michael L.; Nicholson, Richard S.
  • Analytical Chemistry, Vol. 41, Issue 6
  • DOI: 10.1021/ac60275a004

Electrocatalytic Carbon Dioxide Activation: The Rate-Determining Step of Pyridinium-Catalyzed CO2 Reduction
journal, February 2011

  • Morris, Amanda J.; McGibbon, Robert T.; Bocarsly, Andrew B.
  • ChemSusChem, Vol. 4, Issue 2, p. 191-196
  • DOI: 10.1002/cssc.201000379

Theoretical Insights into Pyridinium-Based Photoelectrocatalytic Reduction of CO 2
journal, April 2012

  • Keith, John A.; Carter, Emily A.
  • Journal of the American Chemical Society, Vol. 134, Issue 18
  • DOI: 10.1021/ja300128e

Comparison of DFT Methods for Molecular Orbital Eigenvalue Calculations
journal, March 2007

  • Zhang, Gang; Musgrave, Charles B.
  • The Journal of Physical Chemistry A, Vol. 111, Issue 8
  • DOI: 10.1021/jp061633o
    Sort by:
    [ × clear filter / sort ]

    Works referencing / citing this record:

    Sustainion Imidazolium-Functionalized Polymers for Carbon Dioxide Electrolysis
    journal, March 2017

    • Kutz, Robert B.; Chen, Qingmei; Yang, Hongzhou
    • Energy Technology, Vol. 5, Issue 6
    • DOI: 10.1002/ente.201600636

    Pyridinium-Facilitated CO 2 Electroreduction on Pt Nanowire: Enhanced Electrochemical Performance in CO 2 Conversion: Pyridinium-Facilitated CO2
    journal, September 2018

    • Rabiee, Arash; Nematollahi, Davood
    • Environmental Progress & Sustainable Energy, Vol. 38, Issue 1
    • DOI: 10.1002/ep.12975

    CO 2 electrochemical reduction at thiolate-modified bulk Au electrodes
    journal, January 2019

    • Fang, Yuxin; Cheng, Xun; Flake, John C.
    • Catalysis Science & Technology, Vol. 9, Issue 10
    • DOI: 10.1039/c9cy00506d
      Sort by:
      [ × clear filter / sort ]

      Similar Records in DOE PAGES and OSTI.GOV collections: