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Theoretical Study of Solvent Effects on the Platinum-Catalyzed Oxygen Reduction Reaction

Sha, Yao and Yu, Ted H. and Liu, Yi and Merinov, Boris V. and Goddard, William A., III (2010) Theoretical Study of Solvent Effects on the Platinum-Catalyzed Oxygen Reduction Reaction. Journal of Physical Chemistry Letters, 1 (5). pp. 856-861. ISSN 1948-7185 . http://resolver.caltech.edu/CaltechAUTHORS:20100517-132958379

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Abstract

We report here density functional theory (DFT) studies (PBE) of the reaction intermediates and barriers involved in the oxygen reduction reaction (ORR) on a platinum fuel cell catalyst. Solvent effects were taken into account by applying continuum Poisson−Boltzmann theory to the bound adsorbates and to the transition states of the various reactions on the platinum (111) surface. Our calculations show that the solvent effects change significantly the reaction barriers compared with those in the gas-phase environment (without solvation). The O_2 dissociation barrier decreases from 0.58 to 0.27 eV, whereas the H + O → OH formation barrier increases from 0.73 to 1.09 eV. In the water-solvated phase, OH formation becomes the rate-determining step for both ORR mechanisms, O_2 dissociation and OOH association, proposed earlier for the gas-phase environment. Both mechanisms become significantly less favorable for the platinum catalytic surface in water solvent, suggesting that alternative mechanisms must be considered to describe properly the ORR on the platinum surface.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/jz9003153 DOIArticle
http://pubs.acs.org/doi/full/10.1021/jz9003153PublisherArticle
ORCID:
AuthorORCID
Yu, Ted H.0000-0003-3202-0981
Merinov, Boris V.0000-0002-2783-4262
Goddard, William A., III0000-0003-0097-5716
Additional Information:© 2010 American Chemical Society. Received Date: November 25, 2009. Accepted Date: January 26, 2010. Published on Web Date: February 15, 2010. This work was supported partially by the U.S. Department of Energy under Grant DE-AC02-06CH11357 and partially by Ford Motor Company (Dr. Pezhman Shirvanian). The facilities of the MSC used in this study were established with grants from DURIP-ONR and DURIP-ARO.
Funders:
Funding AgencyGrant Number
Department of Energy (DOE)DE-AC02-06CH11357
Ford Motor CompanyUNSPECIFIED
Office of Naval Research (ONR)UNSPECIFIED
Army Research Office (ARO)UNSPECIFIED
Record Number:CaltechAUTHORS:20100517-132958379
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20100517-132958379
Official Citation:Theoretical Study of Solvent Effects on the Platinum-Catalyzed Oxygen Reduction Reaction Yao Sha, Ted H. Yu, Yi Liu, Boris V. Merinov, William A. Goddard III The Journal of Physical Chemistry Letters 2010 1 (5), 856-861
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:18327
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:24 May 2010 02:47
Last Modified:21 Nov 2016 21:04

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