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Title: Role of Hydroxyl Groups on the Stability and Catalytic Activity of Au Clusters on a Rutile Surface

Abstract

Hydroxyls are present as surface terminations of transition metal oxides under ambient conditions and may modify the properties of supported catalysts. We perform first-principles density functional theory calculations to investigate the role of hydroxyls on the catalytic activity of supported gold clusters on TiO₂ (rutile). We find that they have a long-range effect increasing the adhesion of gold clusters on rutile. While hydroxyls make one gold atom more electronegative, a more complex charge-transfer scenario is observed on larger clusters which are important for catalytic applications. This enhances the molecular adsorption and coadsorption energies of CO and O₂, thereby increasing the catalytic activity of gold clusters for CO oxidation, consistent with reported experiments. Hydroxyls at the interface between gold and rutile surface are most important to this process, even when not directly bound to gold. As such, accurate models of catalytic processes on gold and other catalysts should include the effect of surface hydroxyls.

Authors:
 [1];  [2];  [3]
  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Science
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Science and Computer Science & Mathematics Division
  3. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Materials Science & Technology Division
Research Org.:
Energy Frontier Research Centers (EFRC); Fluid Interface Reactions, Structures and Transport Center (FIRST)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1065769
DOE Contract Number:  
DOE-ERKCC61
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Physical Chemistry Letters; Journal Volume: 2; Journal Issue: 22; Related Information: FIRST partners with Oak Ridge National Laboratory (lead); Argonne National Laboratory; Drexel University; Georgia State University; Northwestern University; Pennsylvania State University; Suffolk University; Vanderbilt University; University of Virginia
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; catalysis (heterogeneous), solar (fuels), energy storage (including batteries and capacitors), hydrogen and fuel cells, electrodes - solar, mechanical behavior, charge transport, materials and chemistry by design, synthesis (novel materials)

Citation Formats

Ganesh, P., Kent, P. R. C., and Veith, Gabriel M. Role of Hydroxyl Groups on the Stability and Catalytic Activity of Au Clusters on a Rutile Surface. United States: N. p., Web. doi:10.1021/jz2013177.
Ganesh, P., Kent, P. R. C., & Veith, Gabriel M. Role of Hydroxyl Groups on the Stability and Catalytic Activity of Au Clusters on a Rutile Surface. United States. doi:10.1021/jz2013177.
Ganesh, P., Kent, P. R. C., and Veith, Gabriel M. . "Role of Hydroxyl Groups on the Stability and Catalytic Activity of Au Clusters on a Rutile Surface". United States. doi:10.1021/jz2013177.
@article{osti_1065769,
title = {Role of Hydroxyl Groups on the Stability and Catalytic Activity of Au Clusters on a Rutile Surface},
author = {Ganesh, P. and Kent, P. R. C. and Veith, Gabriel M.},
abstractNote = {Hydroxyls are present as surface terminations of transition metal oxides under ambient conditions and may modify the properties of supported catalysts. We perform first-principles density functional theory calculations to investigate the role of hydroxyls on the catalytic activity of supported gold clusters on TiO₂ (rutile). We find that they have a long-range effect increasing the adhesion of gold clusters on rutile. While hydroxyls make one gold atom more electronegative, a more complex charge-transfer scenario is observed on larger clusters which are important for catalytic applications. This enhances the molecular adsorption and coadsorption energies of CO and O₂, thereby increasing the catalytic activity of gold clusters for CO oxidation, consistent with reported experiments. Hydroxyls at the interface between gold and rutile surface are most important to this process, even when not directly bound to gold. As such, accurate models of catalytic processes on gold and other catalysts should include the effect of surface hydroxyls.},
doi = {10.1021/jz2013177},
journal = {Journal of Physical Chemistry Letters},
number = 22,
volume = 2,
place = {United States},
year = {},
month = {}
}