HCOOH decomposition on Pt(111): A DFT study

Scaranto, Jessica; Mavrikakis, Manos

doi:10.1016/j.susc.2015.09.023

Title: HCOOH decomposition on Pt(111): A DFT study

Journal Article · Tue Oct 13 00:00:00 EDT 2015 · Surface Science

DOI:https://doi.org/10.1016/j.susc.2015.09.023· OSTI ID:1406904

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

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

Formic acid (HCOOH) decomposition on transition metal surfaces is important for hydrogen production and for its electro-oxidation in direct HCOOH fuel cells. HCOOH can decompose through dehydrogenation leading to formation of CO₂ and H₂ or dehydration leading to CO and H₂O; because CO can poison metal surfaces, dehydrogenation is typically the desirable decomposition path. Here we report a mechanistic analysis of HCOOH decomposition on Pt(111), obtained from a plane wave density functional theory (DFT-PW91) study. We analyzed the dehydrogenation mechanism by considering the two possible pathways involving the formate (HCOO) or the carboxyl (COOH) intermediate. We also considered several possible dehydration paths leading to CO formation. We studied HCOO and COOH decomposition both on the clean surface and in the presence of other relevant co-adsorbates. The results suggest that COOH formation is energetically more difficult than HCOO formation. In contrast, COOH dehydrogenation is easier than HCOO decomposition. Here, we found that CO₂ is the main product through both pathways and that CO is produced mainly through the dehydroxylation of the COOH intermediate.

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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)

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:: 1406904

Alternate ID(s):: OSTI ID: 1251783

Journal Information:: Surface Science, Vol. 648, Issue C; ISSN 0039-6028

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 46 works

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36 MATERIALS SCIENCE
Pt(111)
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Decomposition
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Title: HCOOH decomposition on Pt(111): A DFT study

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