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Title: Photocatalytic CO2 Reduction by Trigonal-Bipyramidal Cobalt(II) Polypyridyl Complexes: The Nature of Cobalt(I) and Cobalt(0) Complexes upon Their Reactions with CO2, CO, or Proton

Abstract

Trigonal-bipyramidal Co(II) complexes are used for photochemical carbon dioxide (CO2) reduction with Ru(bpy)32+ as a photosensitizer, tri-p-tolylamine (TTA) as a reversible quencher, and triethylamine (TEA) as a sacrificial electron donor to produce carbon monoxide and dihydrogen. Here, the CO2 reduction is slow because of the large structural changes, spin flipping in the cobalt catalytic intermediates, and an uphill reaction for reduction to catalytically active Co(0) by the photoproduced [Ru(bpy)3]+.

Authors:
 [1];  [2]; ORCiD logo [2];  [2];  [3]; ORCiD logo [3];  [3]; ORCiD logo [3]
  1. Brookhaven National Lab. (BNL), Upton, NY (United States); Saitama Univ., Saitama (Japan)
  2. Saitama Univ., Saitama (Japan)
  3. Brookhaven National Lab. (BNL), Upton, NY (United States)
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1433980
Report Number(s):
BNL-203518-2018-JAAM
Journal ID: ISSN 0020-1669
Grant/Contract Number:  
SC0012704
Resource Type:
Accepted Manuscript
Journal Name:
Inorganic Chemistry
Additional Journal Information:
Journal Volume: 57; Journal Issue: 9; Journal ID: ISSN 0020-1669
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY

Citation Formats

Shimoda, Tomoe, Morishima, Takeshi, Kodama, Koichi, Hirose, Takuji, Polyansky, Dmitry E., Manbeck, Gerald F., Muckerman, James T., and Fujita, Etsuko. Photocatalytic CO2 Reduction by Trigonal-Bipyramidal Cobalt(II) Polypyridyl Complexes: The Nature of Cobalt(I) and Cobalt(0) Complexes upon Their Reactions with CO2, CO, or Proton. United States: N. p., 2018. Web. https://doi.org/10.1021/acs.inorgchem.8b00433.
Shimoda, Tomoe, Morishima, Takeshi, Kodama, Koichi, Hirose, Takuji, Polyansky, Dmitry E., Manbeck, Gerald F., Muckerman, James T., & Fujita, Etsuko. Photocatalytic CO2 Reduction by Trigonal-Bipyramidal Cobalt(II) Polypyridyl Complexes: The Nature of Cobalt(I) and Cobalt(0) Complexes upon Their Reactions with CO2, CO, or Proton. United States. https://doi.org/10.1021/acs.inorgchem.8b00433
Shimoda, Tomoe, Morishima, Takeshi, Kodama, Koichi, Hirose, Takuji, Polyansky, Dmitry E., Manbeck, Gerald F., Muckerman, James T., and Fujita, Etsuko. Thu . "Photocatalytic CO2 Reduction by Trigonal-Bipyramidal Cobalt(II) Polypyridyl Complexes: The Nature of Cobalt(I) and Cobalt(0) Complexes upon Their Reactions with CO2, CO, or Proton". United States. https://doi.org/10.1021/acs.inorgchem.8b00433. https://www.osti.gov/servlets/purl/1433980.
@article{osti_1433980,
title = {Photocatalytic CO2 Reduction by Trigonal-Bipyramidal Cobalt(II) Polypyridyl Complexes: The Nature of Cobalt(I) and Cobalt(0) Complexes upon Their Reactions with CO2, CO, or Proton},
author = {Shimoda, Tomoe and Morishima, Takeshi and Kodama, Koichi and Hirose, Takuji and Polyansky, Dmitry E. and Manbeck, Gerald F. and Muckerman, James T. and Fujita, Etsuko},
abstractNote = {Trigonal-bipyramidal Co(II) complexes are used for photochemical carbon dioxide (CO2) reduction with Ru(bpy)32+ as a photosensitizer, tri-p-tolylamine (TTA) as a reversible quencher, and triethylamine (TEA) as a sacrificial electron donor to produce carbon monoxide and dihydrogen. Here, the CO2 reduction is slow because of the large structural changes, spin flipping in the cobalt catalytic intermediates, and an uphill reaction for reduction to catalytically active Co(0) by the photoproduced [Ru(bpy)3]+.},
doi = {10.1021/acs.inorgchem.8b00433},
journal = {Inorganic Chemistry},
number = 9,
volume = 57,
place = {United States},
year = {2018},
month = {4}
}

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Works referencing / citing this record:

Reduction of CO 2 by a masked two-coordinate cobalt( i ) complex and characterization of a proposed oxodicobalt( ii ) intermediate
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  • Roy, Lisa; Al-Afyouni, Malik H.; DeRosha, Daniel E.
  • Chemical Science, Vol. 10, Issue 3
  • DOI: 10.1039/c8sc02599a

Reduction of CO 2 by a masked two-coordinate cobalt( i ) complex and characterization of a proposed oxodicobalt( ii ) intermediate
journal, January 2019

  • Roy, Lisa; Al-Afyouni, Malik H.; DeRosha, Daniel E.
  • Chemical Science, Vol. 10, Issue 3
  • DOI: 10.1039/c8sc02599a

Effect of metal ion substitution on the catalytic activity of a pentanuclear metal complex
journal, January 2020

  • Akai, Takuya; Kondo, Mio; Lee, Sze Koon
  • Dalton Transactions, Vol. 49, Issue 5
  • DOI: 10.1039/c9dt04684d

Heterogeneous photocatalytic performances of CO 2 reduction based on the [Emim]BF 4 + TEOA + H 2 O system
journal, January 2019

  • Lin, Jinliang; Li, Youfeng; Xie, Bo
  • RSC Advances, Vol. 9, Issue 61
  • DOI: 10.1039/c9ra06235a

CO 2 reduction using paper-derived carbon electrodes modified with copper nanoparticles
journal, January 2019

  • Gomez, Federico J. V.; Chumanov, George; Silva, Maria Fernanda
  • RSC Advances, Vol. 9, Issue 58
  • DOI: 10.1039/c9ra07430a