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Title: Photocatalytic CO 2 Reduction by Trigonal-Bipyramidal Cobalt(II) Polypyridyl Complexes: The Nature of Cobalt(I) and Cobalt(0) Complexes upon Their Reactions with CO 2, CO, or Proton

Trigonal-bipyramidal Co(II) complexes are used for photochemical carbon dioxide (CO 2) reduction with Ru(bpy) 3 2+ 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 CO 2 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:
Report Number(s):
BNL-203518-2018-JAAM
Journal ID: ISSN 0020-1669
Grant/Contract Number:
SC0012704
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)
Research Org:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1433980

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., Web. doi: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. doi: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. 2018. "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. doi:10.1021/acs.inorgchem.8b00433.
@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}
}