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Modeling Dioxygen Reduction at Multicopper Oxidase Cathodes

Agbo, Peter and Heath, James R. and Gray, Harry B. (2014) Modeling Dioxygen Reduction at Multicopper Oxidase Cathodes. Journal of the American Chemical Society, 136 (39). pp. 13882-13887. ISSN 0002-7863. http://resolver.caltech.edu/CaltechAUTHORS:20140926-091054210

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Abstract

We report a general kinetics model for catalytic dioxygen reduction on multicopper oxidase (MCO) cathodes. Our rate equation combines Butler–Volmer (BV) electrode kinetics and the Michaelis–Menten (MM) formalism for enzymatic catalysis, with the BV model accounting for interfacial electron transfer (ET) between the electrode surface and the MCO type 1 copper site. Extending the principles of MM kinetics to this system produced an analytical expression incorporating the effects of subsequent intramolecular ET and dioxygen binding to the trinuclear copper cluster into the cumulative model. We employed experimental electrochemical data on Thermus thermophilus laccase as benchmarks to validate our model, which we suggest will aid in the design of more efficient MCO cathodes. In addition, we demonstrate the model’s utility in determining estimates for both the electronic coupling and average distance between the laccase type-1 active site and the cathode substrate.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/ja5077519DOIArticle
http://pubs.acs.org/doi/abs/10.1021/ja5077519PublisherArticle
http://pubs.acs.org/doi/suppl/10.1021/ja5077519PublisherSupporting Information
http://dx.doi.org/10.1021/jacs.5b11603DOICorrection
http://pubs.acs.org/doi/10.1021/jacs.5b11603PublisherCorrection
ORCID:
AuthorORCID
Heath, James R.0000-0001-5356-4385
Additional Information:© 2014 American Chemical Society. Received: July 29, 2014. Publication Date (Web): September 4, 2014. We thank Fan Liu, Joseph Varghese, and Jay Winkler for helpful discussions and the Beckman Institute Molecular Materials Research Center for access to equipment. This research was funded by the NSF CCI Solar Fuels Program (CHE-1305124) and a Perkins Grant (JRH.PERKINS3-1-GRANT.PERKINS3). The authors declare no competing financial interest.
Group:CCI Solar Fuels
Funders:
Funding AgencyGrant Number
NSFCHE-1305124
Perkins FoundationJRH.PERKINS3-1- GRANT.PERKINS3
Record Number:CaltechAUTHORS:20140926-091054210
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20140926-091054210
Official Citation:Modeling Dioxygen Reduction at Multicopper Oxidase Cathodes Peter Agbo, James R. Heath, and Harry B. Gray Journal of the American Chemical Society 2014 136 (39), 13882-13887
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:50053
Collection:CaltechAUTHORS
Deposited By: Jason Perez
Deposited On:26 Sep 2014 22:49
Last Modified:25 Apr 2017 04:02

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