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Title: On the Structure Sensitivity of Formic Acid Decomposition on Cu Catalysts

Abstract

Catalytic decomposition of formic acid (HCOOH) has attracted substantial attention since HCOOH is a major by-product in biomass reforming, a promising hydrogen carrier, and also a potential low temperature fuel cell feed. Despite the abundance of experimental studies for vapor-phase HCOOH decomposition on Cu catalysts, the reaction mechanism and its structure sensitivity is still under debate. In this work, self-consistent, periodic density functional theory calculations were performed on three model surfaces of copper—Cu(111), Cu(100) and Cu(211), and both the HCOO (formate)-mediated and COOH (carboxyl)-mediated pathways were investigated for HCOOH decomposition. The energetics of both pathways suggest that the HCOO-mediated route is more favorable than the COOH-mediated route on all three surfaces, and that HCOOH decomposition proceeds through two consecutive dehydrogenation steps via the HCOO intermediate followed by the recombinative desorption of H 2. On all three surfaces, HCOO dehydrogenation is the likely rate determining step since it has the highest transition state energy and also the highest activation energy among the three catalytic steps in the HCOO pathway. The reaction is structure sensitive on Cu catalysts since the examined three Cu facets have dramatically different binding strengths for the key intermediate HCOO and varied barriers for the likely rate determiningmore » step—HCOO dehydrogenation. Cu(100) and Cu(211) bind HCOO much more strongly than Cu(111), and they are also characterized by potential energy surfaces that are lower in energy than that for the Cu(111) facet. Coadsorbed HCOO and H represents the most stable state along the reaction coordinate, indicating that, under reaction conditions, there might be a substantial surface coverage of the HCOO intermediate, especially at under-coordinated step, corner or defect sites. Therefore, under reaction conditions, HCOOH decomposition is predicted to occur most readily on the terrace sites of Cu nanoparticles. Finally, as a result, we hereby present an example of a fundamentally structure-sensitive reaction, which may present itself as structure-insensitive in typical varied particle-size experiments.« less

Authors:
 [1];  [1];  [1]
  1. Univ. of Wisconsin, Madison, WI (United States). Dept. of Chemical and Biological Engineering
Publication Date:
Research Org.:
Univ. of Wisconsin, Madison, WI (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Contributing Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL); Argonne National Lab. (ANL), Argonne, IL (United States). Center for Nanoscale Materials; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)
OSTI Identifier:
1398775
Grant/Contract Number:  
FG02-05ER15731; AC02-06CH11357; AC02-05CH11231
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Topics in Catalysis
Additional Journal Information:
Journal Volume: 59; Journal Issue: 17-18; Journal ID: ISSN 1022-5528
Publisher:
Springer
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; HCOOH decomposition; Structure sensitivity; DFT; Catalysis; Copper

Citation Formats

Li, Sha, Scaranto, Jessica, and Mavrikakis, Manos. On the Structure Sensitivity of Formic Acid Decomposition on Cu Catalysts. United States: N. p., 2016. Web. doi:10.1007/s11244-016-0672-1.
Li, Sha, Scaranto, Jessica, & Mavrikakis, Manos. On the Structure Sensitivity of Formic Acid Decomposition on Cu Catalysts. United States. doi:10.1007/s11244-016-0672-1.
Li, Sha, Scaranto, Jessica, and Mavrikakis, Manos. Wed . "On the Structure Sensitivity of Formic Acid Decomposition on Cu Catalysts". United States. doi:10.1007/s11244-016-0672-1. https://www.osti.gov/servlets/purl/1398775.
@article{osti_1398775,
title = {On the Structure Sensitivity of Formic Acid Decomposition on Cu Catalysts},
author = {Li, Sha and Scaranto, Jessica and Mavrikakis, Manos},
abstractNote = {Catalytic decomposition of formic acid (HCOOH) has attracted substantial attention since HCOOH is a major by-product in biomass reforming, a promising hydrogen carrier, and also a potential low temperature fuel cell feed. Despite the abundance of experimental studies for vapor-phase HCOOH decomposition on Cu catalysts, the reaction mechanism and its structure sensitivity is still under debate. In this work, self-consistent, periodic density functional theory calculations were performed on three model surfaces of copper—Cu(111), Cu(100) and Cu(211), and both the HCOO (formate)-mediated and COOH (carboxyl)-mediated pathways were investigated for HCOOH decomposition. The energetics of both pathways suggest that the HCOO-mediated route is more favorable than the COOH-mediated route on all three surfaces, and that HCOOH decomposition proceeds through two consecutive dehydrogenation steps via the HCOO intermediate followed by the recombinative desorption of H2. On all three surfaces, HCOO dehydrogenation is the likely rate determining step since it has the highest transition state energy and also the highest activation energy among the three catalytic steps in the HCOO pathway. The reaction is structure sensitive on Cu catalysts since the examined three Cu facets have dramatically different binding strengths for the key intermediate HCOO and varied barriers for the likely rate determining step—HCOO dehydrogenation. Cu(100) and Cu(211) bind HCOO much more strongly than Cu(111), and they are also characterized by potential energy surfaces that are lower in energy than that for the Cu(111) facet. Coadsorbed HCOO and H represents the most stable state along the reaction coordinate, indicating that, under reaction conditions, there might be a substantial surface coverage of the HCOO intermediate, especially at under-coordinated step, corner or defect sites. Therefore, under reaction conditions, HCOOH decomposition is predicted to occur most readily on the terrace sites of Cu nanoparticles. Finally, as a result, we hereby present an example of a fundamentally structure-sensitive reaction, which may present itself as structure-insensitive in typical varied particle-size experiments.},
doi = {10.1007/s11244-016-0672-1},
journal = {Topics in Catalysis},
number = 17-18,
volume = 59,
place = {United States},
year = {Wed Aug 03 00:00:00 EDT 2016},
month = {Wed Aug 03 00:00:00 EDT 2016}
}

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