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

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:
 [1] ;  [1]
  1. Univ. of Wisconsin-Madison, Madison, WI (United States)
Publication Date:
Grant/Contract Number:
FG02-05ER15731; AC02-06CH11357; AC02-05CH11231
Type:
Accepted Manuscript
Journal Name:
Surface Science
Additional Journal Information:
Journal Volume: 648; Journal Issue: C; Journal ID: ISSN 0039-6028
Publisher:
Elsevier
Research Org:
Univ. of Wisconsin-Madison, Madison, WI (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Contributing Orgs:
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)
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
OSTI Identifier:
1406904
Alternate Identifier(s):
OSTI ID: 1251783