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Dramatic Increase in the Oxygen Reduction Reaction for Platinum Cathodes from Tuning the Solvent Dielectric Constant

Fortunelli, Alessandro and Goddard, William A., III and Sha, Yao and Yu, Ted H. and Sementa, Luca and Barcaro, Giovanni and Andreussi, Oliviero (2014) Dramatic Increase in the Oxygen Reduction Reaction for Platinum Cathodes from Tuning the Solvent Dielectric Constant. Angewandte Chemie International Edition, 53 (26). pp. 6669-6672. ISSN 1433-7851. http://resolver.caltech.edu/CaltechAUTHORS:20140603-152723913

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Abstract

Hydrogen fuel cells (FC) are considered essential for a sustainable economy based on carbon-free energy sources, but a major impediment are the costs. First-principles quantum mechanics (density functional theory including solvation) is used to predict how the energies and barriers for the mechanistic steps of the oxygen reduction reaction (ORR) over the fcc(111) platinum surface depend on the dielectric constant of the solvent. The ORR kinetics can be strongly accelerated by decreasing the effective medium polarizability from the high value it has in water. Possible ways to realize this experimentally are suggested. The calculated volcano structure for the dependence of rate on solvent polarization is considered to be general, and should be observed in other electrochemical systems.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://onlinelibrary.wiley.com/doi/10.1002/anie.201403264/abstractPublisherArticle
http://dx.doi.org/10.1002/anie.201403264DOIArticle
http://onlinelibrary.wiley.com/doi/10.1002/anie.201403264/suppinfoRelated ItemSupporting Information
ORCID:
AuthorORCID
Fortunelli, Alessandro0000-0001-5337-4450
Goddard, William A., III0000-0003-0097-5716
Yu, Ted H.0000-0003-3202-0981
Additional Information:© 2014 Wiley-Vch Verlag GmbH & Co. Article first published online: 14 May 2014. This work was supported by a Short-Term Mission (STM) funded by Italian Consiglio Nazionale delle Ricerche (CNR), the National Science Foundation (grant number CBET-1067848, Caltech) and by the Caltech and Taiwan Energy Exchange (CTEE) collaborative project funded by the National Science Council of Taiwan (grant number NSC 102-3113-P-008-001).The facilities of the Materials and Process Simulation Center used in this study were established with grants from DURIP-ONR, DURIP-ARO, and NSF-CSEM.
Funders:
Funding AgencyGrant Number
Consiglio Nazionale delle Ricerche (CNR)UNSPECIFIED
NSFCBET-1067848
National Science Council (Taipei)NSC 102-3113-P-008-001
Office of Naval Research (ONR)UNSPECIFIED
Army Research Office (ARO)UNSPECIFIED
Record Number:CaltechAUTHORS:20140603-152723913
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20140603-152723913
Official Citation:Fortunelli, A., Goddard, W. A., Sha, Y., Yu, T. H., Sementa, L., Barcaro, G. and Andreussi, O. (2014), Dramatic Increase in the Oxygen Reduction Reaction for Platinum Cathodes from Tuning the Solvent Dielectric Constant. Angew. Chem. Int. Ed., 53: 6669–6672. doi: 10.1002/anie.201403264
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:46064
Collection:CaltechAUTHORS
Deposited By: Ruth Sustaita
Deposited On:03 Jun 2014 22:50
Last Modified:31 Mar 2017 01:50

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