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Title: On the nature of active sites for formic acid decomposition on gold catalysts

Abstract

Formic acid decomposition has been studied experimentally on supported gold nanoparticles with strong evidence showing the critical role of gold clusters in the subnanometer range in catalyzing the reaction. However, there is a lack of theoretical studies capable of explaining these experimental observations. In this work, without accounting for support effects, vapor phase formic acid decomposition was studied systematically on sub-nanometric gold clusters from Au 4 to Au 25, among which several candidate Au clusters were identified as a promising active site model for the Au/SiC catalysts. Combining theoretical and experimental results suggested that the active site on Au/SiC catalysts could be represented by an Au 18 cluster, on which the reaction rates calculated from the microkinetic model closely match the experimentally measured rates. On Au 18, formic acid decomposition proceeds through the same formate mediated pathway as that on extended Au surfaces (HCOOH → HCOO + H → CO 2 + 2H → CO 2 + H 2), with the reaction taking place on a triangular Au 3 site where the reactive Au atoms have a coordination number of 5. Despite the fact that other Au clusters among those studied, including Au17 and Au19 which also expose the samemore » triangular Au 3 site, they were not found to be an accurate representation of the active sites, suggesting an atom-specific activity of gold clusters for formic acid decomposition.« less

Authors:
ORCiD logo [1];  [1]; ORCiD logo [1]; ORCiD logo [1]
  1. Univ. of Wisconsin, Madison, WI (United States)
Publication Date:
Research Org.:
Univ. of Wisconsin, Madison, WI (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division
OSTI Identifier:
1570852
Alternate Identifier(s):
OSTI ID: 1511504
Grant/Contract Number:  
FG02-05ER15731; AC02-06CH11357; AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Catalysis Science and Technology
Additional Journal Information:
Journal Volume: 9; Journal Issue: 11; Journal ID: ISSN 2044-4753
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Li, Sha, Singh, Suyash, Dumesic, James A., and Mavrikakis, Manos. On the nature of active sites for formic acid decomposition on gold catalysts. United States: N. p., 2019. Web. doi:10.1039/c9cy00410f.
Li, Sha, Singh, Suyash, Dumesic, James A., & Mavrikakis, Manos. On the nature of active sites for formic acid decomposition on gold catalysts. United States. doi:10.1039/c9cy00410f.
Li, Sha, Singh, Suyash, Dumesic, James A., and Mavrikakis, Manos. Wed . "On the nature of active sites for formic acid decomposition on gold catalysts". United States. doi:10.1039/c9cy00410f.
@article{osti_1570852,
title = {On the nature of active sites for formic acid decomposition on gold catalysts},
author = {Li, Sha and Singh, Suyash and Dumesic, James A. and Mavrikakis, Manos},
abstractNote = {Formic acid decomposition has been studied experimentally on supported gold nanoparticles with strong evidence showing the critical role of gold clusters in the subnanometer range in catalyzing the reaction. However, there is a lack of theoretical studies capable of explaining these experimental observations. In this work, without accounting for support effects, vapor phase formic acid decomposition was studied systematically on sub-nanometric gold clusters from Au4 to Au25, among which several candidate Au clusters were identified as a promising active site model for the Au/SiC catalysts. Combining theoretical and experimental results suggested that the active site on Au/SiC catalysts could be represented by an Au18 cluster, on which the reaction rates calculated from the microkinetic model closely match the experimentally measured rates. On Au18, formic acid decomposition proceeds through the same formate mediated pathway as that on extended Au surfaces (HCOOH → HCOO + H → CO2 + 2H → CO2 + H2), with the reaction taking place on a triangular Au3 site where the reactive Au atoms have a coordination number of 5. Despite the fact that other Au clusters among those studied, including Au17 and Au19 which also expose the same triangular Au3 site, they were not found to be an accurate representation of the active sites, suggesting an atom-specific activity of gold clusters for formic acid decomposition.},
doi = {10.1039/c9cy00410f},
journal = {Catalysis Science and Technology},
number = 11,
volume = 9,
place = {United States},
year = {2019},
month = {5}
}

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Works referenced in this record:

Decomposition and Reforming of Formic Acid on Supported Au Catalysts: Production of CO-Free H2
journal, July 2011

  • Gazsi, A.; Bánsági, T.; Solymosi, F.
  • The Journal of Physical Chemistry C, Vol. 115, Issue 31, p. 15459-15466
  • DOI: 10.1021/jp203751w

From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999


Conversion of cellulose to hydrocarbon fuels by progressive removal of oxygen
journal, October 2010

  • Serrano-Ruiz, Juan Carlos; Braden, Drew J.; West, Ryan M.
  • Applied Catalysis B: Environmental, Vol. 100, Issue 1-2, p. 184-189
  • DOI: 10.1016/j.apcatb.2010.07.029

A climbing image nudged elastic band method for finding saddle points and minimum energy paths
journal, December 2000

  • Henkelman, Graeme; Uberuaga, Blas P.; Jónsson, Hannes
  • The Journal of Chemical Physics, Vol. 113, Issue 22, p. 9901-9904
  • DOI: 10.1063/1.1329672

Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996


Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996


Integrated Catalytic Conversion of γ-Valerolactone to Liquid Alkenes for Transportation Fuels
journal, February 2010


Size-dependent catalytic activity and geometries of size-selected Pt clusters on TiO2(110) surfaces
journal, January 2011

  • Watanabe, Yoshihide; Wu, Xingyang; Hirata, Hirohito
  • Catalysis Science & Technology, Vol. 1, Issue 8, p. 1490-1495
  • DOI: 10.1039/c1cy00204j

Accurate and simple analytic representation of the electron-gas correlation energy
journal, June 1992