Observation of O–O Bond Forming Step of Molecular Co4O4 Cubane Catalyst for Water Oxidation by Rapid-Scan FT-IR Spectroscopy

Liu, Hongfei; Frei, Heinz

doi:10.1021/acscatal.9b03281

Title: Observation of O–O Bond Forming Step of Molecular Co₄O₄ Cubane Catalyst for Water Oxidation by Rapid-Scan FT-IR Spectroscopy

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Abstract

Monitoring of water oxidation by the established Co cubane catalyst Co₄O₄(OAc)₄(py)₄ (abbrev. Co₄O₄, OAc = acetate, py = pyridine) by time-resolved rapid-scan ATR FT-IR spectroscopy revealed the O–O bond forming intermediate by its O–O stretch mode at 833 cm^–1. The catalysis was either driven in alkaline solution by a visible light sensitizer or in hydroxide (OH^–) containing acetonitrile solution using the one-electron oxidized cubane as the sole source of charge. Finally, the μ-peroxido structure of the intermediate was established by ¹⁸O isotopic labeling, and its catalytic relevancy and role in the O₂ evolving cycle were revealed by the kinetic relationship with decreasing cubium ([Co₄O₄]⁺) and recovery of the Co₄O₄ complex.

Authors:

Liu, Hongfei ^[1];

^[1]

Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

Publication Date:: Mon Jan 13 00:00:00 EST 2020

Research Org.:: Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES); Swiss National Science Foundation (SNSF)

OSTI Identifier:: 1582635

Grant/Contract Number:: AC02-05CH11231; P2ZHP2_168445

Resource Type:: Accepted Manuscript

Journal Name:: ACS Catalysis

Additional Journal Information:: Journal Volume: 10; Journal Issue: 3; Journal ID: ISSN 2155-5435

Publisher:: American Chemical Society (ACS)

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; water oxidation catalysis; cobalt oxide; cubane; time-resolved FT-IR; peroxo intermediate; O-O bond formation

Citation Formats


                    Liu, Hongfei, and Frei, Heinz. Observation of O–O Bond Forming Step of Molecular Co4O4 Cubane Catalyst for Water Oxidation by Rapid-Scan FT-IR Spectroscopy.  United States: N. p., 2020. 
Web.  doi:10.1021/acscatal.9b03281.

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                    Liu, Hongfei, & Frei, Heinz. Observation of O–O Bond Forming Step of Molecular Co4O4 Cubane Catalyst for Water Oxidation by Rapid-Scan FT-IR Spectroscopy.  United States.  https://doi.org/10.1021/acscatal.9b03281

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                    Liu, Hongfei, and Frei, Heinz. Mon .  
"Observation of O–O Bond Forming Step of Molecular Co4O4 Cubane Catalyst for Water Oxidation by Rapid-Scan FT-IR Spectroscopy".  United States.  https://doi.org/10.1021/acscatal.9b03281.  https://www.osti.gov/servlets/purl/1582635.

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@article{osti_1582635,

  title        = {Observation of O–O Bond Forming Step of Molecular Co4O4 Cubane Catalyst for Water Oxidation by Rapid-Scan FT-IR Spectroscopy},

  author       = {Liu, Hongfei and Frei, Heinz},

  abstractNote = {Monitoring of water oxidation by the established Co cubane catalyst Co4O4(OAc)4(py)4 (abbrev. Co4O4, OAc = acetate, py = pyridine) by time-resolved rapid-scan ATR FT-IR spectroscopy revealed the O–O bond forming intermediate by its O–O stretch mode at 833 cm–1. The catalysis was either driven in alkaline solution by a visible light sensitizer or in hydroxide (OH–) containing acetonitrile solution using the one-electron oxidized cubane as the sole source of charge. Finally, the μ-peroxido structure of the intermediate was established by 18O isotopic labeling, and its catalytic relevancy and role in the O2 evolving cycle were revealed by the kinetic relationship with decreasing cubium ([Co4O4]+) and recovery of the Co4O4 complex.},

  doi          = {10.1021/acscatal.9b03281},

  journal      = {ACS Catalysis},

  number       = 3,

  volume       = 10,

  place        = {United States},

  year         = {Mon Jan 13 00:00:00 EST 2020},

  month        = {Mon Jan 13 00:00:00 EST 2020}

}

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Title: Observation of O–O Bond Forming Step of Molecular Co4O4 Cubane Catalyst for Water Oxidation by Rapid-Scan FT-IR Spectroscopy

Abstract

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Title: Observation of O–O Bond Forming Step of Molecular Co₄O₄ Cubane Catalyst for Water Oxidation by Rapid-Scan FT-IR Spectroscopy