Density functional theory studies of HCOOH decomposition on Pd(111)

Scaranto, Jessica; Mavrikakis, Manos

doi:10.1016/j.susc.2015.11.020

Title: Density functional theory studies of HCOOH decomposition on Pd(111)

Journal Article · Wed Dec 02 00:00:00 EST 2015 · Surface Science

DOI:https://doi.org/10.1016/j.susc.2015.11.020· OSTI ID:1406902

Scaranto, Jessica ^[1]; Mavrikakis, Manos ^[1]

Univ. of Wisconsin-Madison, Madison, WI (United States)

Here, the investigation of formic acid (HCOOH) decomposition on transition metal surfaces is important to derive useful insights for vapor phase catalysis involving HCOOH and for the development of direct HCOOH fuel cells (DFAFC). Here we present the results obtained from periodic, self-consistent, density functional theory (DFT-GGA) calculations for the elementary steps involved in the gas-phase decomposition of HCOOH on Pd(111). Accordingly, we analyzed the minimum energy paths for HCOOH dehydrogenation to CO₂ + H₂ and dehydration to CO + H₂O through the carboxyl (COOH) and formate (HCOO) intermediates. Our results suggest that HCOO formation is easier than COOH formation, but HCOO decomposition is more difficult than COOH decomposition, in particular in presence of co-adsorbed O and OH species. Therefore, both paths may contribute to HCOOH decomposition. CO formation goes mainly through COOH decomposition.

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Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Institute for Atom-efficient Chemical Transformations (IACT); Univ. of Wisconsin, Madison, WI (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); 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)

Grant/Contract Number:: FG02-05ER15731; AC02-06CH11357; AC02-05CH11231

OSTI ID:: 1406902

Alternate ID(s):: OSTI ID: 1373614

Journal Information:: Surface Science, Vol. 650, Issue C; ISSN 0039-6028

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 61 works

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
36 MATERIALS SCIENCE
Density Functional Theory
Formic acid
Pd(111)
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Formate
Carboxyl

Title: Density functional theory studies of HCOOH decomposition on Pd(111)

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