Ab initio molecular dynamics of solvation effects on reactivity at electrified interfaces

Journal Article · Mon Aug 08 00:00:00 EDT 2016 · Proceedings of the National Academy of Sciences of the United States of America

DOI:https://doi.org/10.1073/pnas.1604590113· OSTI ID:1579289

Herron, Jeffrey A. ^[1]; Morikawa, Yoshitada ^[2]; Mavrikakis, Manos ^[1]

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1. Department of Chemical and Biological Engineering, University of Wisconsin–Madison, Madison, WI 53706,
2. Division of Precision Science &, Technology and Applied Physics, Osaka University, Osaka 565-0871, Japan

Significance Low-temperature fuel cells are efficient energy conversion devices that face a number of hurdles toward commercialization, including difficulties in storing hydrogen. Methanol represents a liquid-phase fuel alternative to hydrogen, yet the high cost of Pt-based catalysts limits fuel cells’ economic viability. Toward improved, lower-cost catalyst design, a fundamental understanding of the methanol electrooxidation reaction mechanism is necessary. Density functional theory calculations have become invaluable in elucidating these reaction mechanisms, although the complex reaction environment including solvation of a charged electrode has been a challenge to model. Using ab initio molecular dynamics, via the Blue Moon Ensemble, we have investigated methanol electrooxidation on a solvated and charged Pt(111) surface to understand the effect of solvation and charge on the reaction energetics.

• Research Organization: Univ. of Wisconsin, Madison, WI (United States)
• Sponsoring Organization: USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF); USDOE Office of Science (SC), Biological and Environmental Research (BER)
• Contributing Organization: EMSL, a National scientific user facility at Pacific Northwest National Laboratory (PNNL); the Center for Nanoscale Materials at Argonne National Laboratory (ANL); and the National Energy Research Scientific Computing Center (NERSC); Pacific Northwest National Laboratory (PNNL) (EMSL); Argonne National Laboratory (ANL) (CNM); Lawrence Berkeley National Laboratory (LBNL) (NERSC)
• Grant/Contract Number: FG02-05ER15731; AC02-06CH11357; AC02-05CH11231
• OSTI ID: 1579289
• Alternate ID(s): OSTI ID: 1405318; OSTI ID: 1994811
• Journal Information: Proceedings of the National Academy of Sciences of the United States of America, Journal Name: Proceedings of the National Academy of Sciences of the United States of America Vol. 113 Journal Issue: 34; ISSN 0027-8424
• Publisher: Proceedings of the National Academy of Sciences
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
AIMD
DFT
methanol
Pt(111)
electrocatalysis
density functional theory