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

Shimoda, Tomoe; Morishima, Takeshi; Kodama, Koichi; Hirose, Takuji; Polyansky, Dmitry E.; Manbeck, Gerald F.; Muckerman, James T.; Fujita, Etsuko

doi:10.1021/acs.inorgchem.8b00433

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

Journal Article · 26 April 2018 · Inorganic Chemistry

DOI: https://doi.org/10.1021/acs.inorgchem.8b00433 · OSTI ID:1433980

Shimoda, Tomoe ^[1]; Morishima, Takeshi ^[2];

^[2]; Hirose, Takuji ^[2]; Polyansky, Dmitry E. ^[3];

^[3]; Muckerman, James T. ^[3];

^[3]

Brookhaven National Lab. (BNL), Upton, NY (United States); Saitama Univ., Saitama (Japan)
Saitama Univ., Saitama (Japan)
Brookhaven National Lab. (BNL), Upton, NY (United States)

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]⁺.

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Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: SC0012704

OSTI ID:: 1433980

Report Number(s):: BNL--203518-2018-JAAM

Journal Information:: Inorganic Chemistry, Journal Name: Inorganic Chemistry Journal Issue: 9 Vol. 57; ISSN 0020-1669

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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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

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