Systematic Doping of Cobalt into Layered Manganese Oxide Sheets Substantially Enhances Water Oxidation Catalysis
Abstract
The effect on the electrocatalytic oxygen evolution reaction (OER) of cobalt incorporation into the metal oxide sheets of the layered manganese oxide birnessite was investigated. Birnessite and cobalt-doped birnessite were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, and conductivity measurements. A cobalt:manganese ratio of 1:2 ended in the most active catalyst for the OER. Specifically, the overpotential (η) for the OER was 420 mV, significantly lower than the η = 780 mV associated with birnessite in the absence of Co. Moreover, the Tafel slope for Co/birnessite was 81 mV/dec, in comparison to a Tafel slope of greater than 200 mV/dec for birnessite. For chemical water oxidation catalysis, an 8-fold turnover number (TON) was achieved (h = 70 mmol of O2/mol of metal). Density functional theory (DFT) calculations predict that cobalt modification of birnessite resulted in a raising of the valence band edge and occupation of that edge by holes with enhanced mobility during catalysis. Inclusion of extra cobalt beyond the ideal 1:2 ratio was detrimental to catalysis due to disruption of the layered structure of the birnessite phase.
- Publication Date:
- Research Org.:
- Temple Univ., Philadelphia, PA (United States). Energy Frontier Research Center (EFRC) Center for the Computational Design of Functional Layered Materials (CCDM); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); National Institutes of Health (NIH)
- OSTI Identifier:
- 1470025
- Grant/Contract Number:
- SC0012575
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Inorganic Chemistry
- Additional Journal Information:
- Journal Volume: 57; Journal Issue: 2; Related Information: CCDM partners with Temple University (lead); Brookhaven National Laboratory; Drexel University; Duke University; North Carolina State University; Northeastern University; Princeton University; Rice University; University of Pennsylvania; 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; 74 ATOMIC AND MOLECULAR PHYSICS; 36 MATERIALS SCIENCE
Citation Formats
McKendry, Ian G., Thenuwara, Akila C., Shumlas, Samantha L., Peng, Haowei, Aulin, Yaroslav V., Chinnam, Parameswara Rao, Borguet, Eric, Strongin, Daniel R., and Zdilla, Michael J. Systematic Doping of Cobalt into Layered Manganese Oxide Sheets Substantially Enhances Water Oxidation Catalysis. United States: N. p., 2018.
Web. doi:10.1021/acs.inorgchem.7b01592.
McKendry, Ian G., Thenuwara, Akila C., Shumlas, Samantha L., Peng, Haowei, Aulin, Yaroslav V., Chinnam, Parameswara Rao, Borguet, Eric, Strongin, Daniel R., & Zdilla, Michael J. Systematic Doping of Cobalt into Layered Manganese Oxide Sheets Substantially Enhances Water Oxidation Catalysis. United States. https://doi.org/10.1021/acs.inorgchem.7b01592
McKendry, Ian G., Thenuwara, Akila C., Shumlas, Samantha L., Peng, Haowei, Aulin, Yaroslav V., Chinnam, Parameswara Rao, Borguet, Eric, Strongin, Daniel R., and Zdilla, Michael J. Thu .
"Systematic Doping of Cobalt into Layered Manganese Oxide Sheets Substantially Enhances Water Oxidation Catalysis". United States. https://doi.org/10.1021/acs.inorgchem.7b01592. https://www.osti.gov/servlets/purl/1470025.
@article{osti_1470025,
title = {Systematic Doping of Cobalt into Layered Manganese Oxide Sheets Substantially Enhances Water Oxidation Catalysis},
author = {McKendry, Ian G. and Thenuwara, Akila C. and Shumlas, Samantha L. and Peng, Haowei and Aulin, Yaroslav V. and Chinnam, Parameswara Rao and Borguet, Eric and Strongin, Daniel R. and Zdilla, Michael J.},
abstractNote = {The effect on the electrocatalytic oxygen evolution reaction (OER) of cobalt incorporation into the metal oxide sheets of the layered manganese oxide birnessite was investigated. Birnessite and cobalt-doped birnessite were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, and conductivity measurements. A cobalt:manganese ratio of 1:2 ended in the most active catalyst for the OER. Specifically, the overpotential (η) for the OER was 420 mV, significantly lower than the η = 780 mV associated with birnessite in the absence of Co. Moreover, the Tafel slope for Co/birnessite was 81 mV/dec, in comparison to a Tafel slope of greater than 200 mV/dec for birnessite. For chemical water oxidation catalysis, an 8-fold turnover number (TON) was achieved (h = 70 mmol of O2/mol of metal). Density functional theory (DFT) calculations predict that cobalt modification of birnessite resulted in a raising of the valence band edge and occupation of that edge by holes with enhanced mobility during catalysis. Inclusion of extra cobalt beyond the ideal 1:2 ratio was detrimental to catalysis due to disruption of the layered structure of the birnessite phase.},
doi = {10.1021/acs.inorgchem.7b01592},
journal = {Inorganic Chemistry},
number = 2,
volume = 57,
place = {United States},
year = {Thu Jan 04 00:00:00 EST 2018},
month = {Thu Jan 04 00:00:00 EST 2018}
}
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