In situ characterization of cofacial Co(IV) centers in Co4O4 cubane: Modeling the high-valent active site in oxygen-evolving catalysts

Brodsky, Casey N.; Hadt, Ryan G.; Hayes, Dugan; Reinhart, Benjamin J.; Li, Nancy; Chen, Lin X.; Nocera, Daniel G.

doi:10.1073/pnas.1701816114

Title: In situ characterization of cofacial Co(IV) centers in Co₄O₄ cubane: Modeling the high-valent active site in oxygen-evolving catalysts

Journal Article · Mon Mar 27 00:00:00 EDT 2017 · Proceedings of the National Academy of Sciences of the United States of America

DOI:https://doi.org/10.1073/pnas.1701816114· OSTI ID:1373381

Brodsky, Casey N. ^[1]; Hadt, Ryan G. ^[2]; Hayes, Dugan ^[2]; Reinhart, Benjamin J. ^[2]; Li, Nancy ^[1]; Chen, Lin X. ^[3];

^[1]

Harvard Univ., Cambridge, MA (United States). Dept. of Chemistry and Chemical Biology
Argonne National Lab. (ANL), Argonne, IL (United States). Chemical Sciences and Engineering Division
Argonne National Lab. (ANL), Argonne, IL (United States). Chemical Sciences and Engineering Division; Northwestern Univ., Evanston, IL (United States). Dept. of Chemistry

The Co₄O₄cubane is a representative structural model of oxidic cobalt oxygen-evolving catalysts (Co-OECs). The Co-OECs are active when residing at two oxidation levels above an all-Co(III) resting state. This doubly oxidized Co(IV)₂state may be captured in a Co(III)₂(IV)₂cubane. We demonstrate that the Co(III)₂(IV)₂cubane may be electrochemically generated and the electronic properties of this unique high-valent state may be probed by in situ spectroscopy. Intervalence charge-transfer (IVCT) bands in the near-IR are observed for the Co(III)₂(IV)₂cubane, and spectroscopic analysis together with electrochemical kinetics measurements reveal a larger reorganization energy and a smaller electron transfer rate constant for the doubly versus singly oxidized cubane. Spectroelectrochemical X-ray absorption data further reveal systematic spectral changes with successive oxidations from the cubane resting state. Electronic structure calculations correlated to experimental data suggest that this state is best represented as a localized, antiferromagnetically coupled Co(IV)₂dimer. The exchange coupling in the cofacial Co(IV)₂site allows for parallels to be drawn between the electronic structure of the Co₄O₄cubane model system and the high-valent active site of the Co-OEC, with specific emphasis on the manifestation of a doubly oxidized Co(IV)₂center on O–O bond formation.

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States); Harvard Univ., Cambridge, MA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division; National Science Foundation (NSF)

Grant/Contract Number:: AC02-06CH11357; SC0017619

OSTI ID:: 1373381

Alternate ID(s):: OSTI ID: 1599216

Journal Information:: Proceedings of the National Academy of Sciences of the United States of America, Vol. 114, Issue 15; ISSN 0027-8424

Publisher:: National Academy of SciencesCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 84 works

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
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Title: In situ characterization of cofacial Co(IV) centers in Co4O4 cubane: Modeling the high-valent active site in oxygen-evolving catalysts

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Title: In situ characterization of cofacial Co(IV) centers in Co₄O₄ cubane: Modeling the high-valent active site in oxygen-evolving catalysts