HCOOH decomposition on Pt(111): A DFT study
Abstract
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.
- Authors:
-
- Univ. of Wisconsin-Madison, Madison, WI (United States)
- Publication Date:
- Research Org.:
- Energy Frontier Research Centers (EFRC) (United States). Institute for Atom-efficient Chemical Transformations (IACT); Univ. of Wisconsin, Madison, WI (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- Contributing Org.:
- 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)
- OSTI Identifier:
- 1406904
- Alternate Identifier(s):
- OSTI ID: 1251783
- Grant/Contract Number:
- FG02-05ER15731; AC02-06CH11357; AC02-05CH11231
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Surface Science
- Additional Journal Information:
- Journal Volume: 648; Journal Issue: C; Journal ID: ISSN 0039-6028
- Publisher:
- Elsevier
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE; Pt(111); Formic acid; Decomposition; Formate; Carboxyl; Density functional theory
Citation Formats
Scaranto, Jessica, and Mavrikakis, Manos. HCOOH decomposition on Pt(111): A DFT study. United States: N. p., 2015.
Web. doi:10.1016/j.susc.2015.09.023.
Scaranto, Jessica, & Mavrikakis, Manos. HCOOH decomposition on Pt(111): A DFT study. United States. https://doi.org/10.1016/j.susc.2015.09.023
Scaranto, Jessica, and Mavrikakis, Manos. Tue .
"HCOOH decomposition on Pt(111): A DFT study". United States. https://doi.org/10.1016/j.susc.2015.09.023. https://www.osti.gov/servlets/purl/1406904.
@article{osti_1406904,
title = {HCOOH decomposition on Pt(111): A DFT study},
author = {Scaranto, Jessica and Mavrikakis, Manos},
abstractNote = {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.},
doi = {10.1016/j.susc.2015.09.023},
journal = {Surface Science},
number = C,
volume = 648,
place = {United States},
year = {Tue Oct 13 00:00:00 EDT 2015},
month = {Tue Oct 13 00:00:00 EDT 2015}
}
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