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Title: Predicted Structures of the Active Sites Responsible for the Improved Reduction of Carbon Dioxide by Gold Nanoparticles

Abstract

Gold (Au) nanoparticles (NPs) are known experimentally to reduce carbon dioxide (CO2) to carbon monoxide (CO), with far superior performance to Au foils. To obtain guidance in designing improved CO2 catalysts, we want to understand the nature of the active sites on Au NPs. Here, we employed multiscale atomistic simulations to computationally synthesize and characterize a 10 nm thick Au NP on a carbon nanotube (CNT) support, and then we located active sites from quantum mechanics (QM) calculations on 269 randomly selected sites. The standard scaling relation is that the formation energy of *COOH (ΔE*COOH) is proportional to the binding energy of *CO (Ebinding*CO); therefore, decreasing ΔE*COOH to boost the CO2 reduction reaction (CO2RR) causes an increase of Ebinding*CO that retards CO2RR. We show that the NPs have superior CO2RR because there are many sites at the twin boundaries that significantly break this scaling relation.

Authors:
ORCiD logo [1];  [1]; ORCiD logo [1]; ORCiD logo [1]
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  1. California Inst. of Technology (CalTech), Pasadena, CA (United States)
Publication Date:
Research Org.:
California Institute of Technology (CalTech), Pasadena, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1467601
Grant/Contract Number:  
SC0004993
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry Letters
Additional Journal Information:
Journal Volume: 8; Journal Issue: 14; Journal ID: ISSN 1948-7185
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Cheng, Tao, Huang, Yufeng, Xiao, Hai, and Goddard, III, William A. Predicted Structures of the Active Sites Responsible for the Improved Reduction of Carbon Dioxide by Gold Nanoparticles. United States: N. p., 2017. Web. doi:10.1021/acs.jpclett.7b01335.
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Cheng, Tao, Huang, Yufeng, Xiao, Hai, & Goddard, III, William A. Predicted Structures of the Active Sites Responsible for the Improved Reduction of Carbon Dioxide by Gold Nanoparticles. United States. https://doi.org/10.1021/acs.jpclett.7b01335
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Cheng, Tao, Huang, Yufeng, Xiao, Hai, and Goddard, III, William A. Tue . "Predicted Structures of the Active Sites Responsible for the Improved Reduction of Carbon Dioxide by Gold Nanoparticles". United States. https://doi.org/10.1021/acs.jpclett.7b01335. https://www.osti.gov/servlets/purl/1467601.
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@article{osti_1467601,
title = {Predicted Structures of the Active Sites Responsible for the Improved Reduction of Carbon Dioxide by Gold Nanoparticles},
author = {Cheng, Tao and Huang, Yufeng and Xiao, Hai and Goddard, III, William A.},
abstractNote = {Gold (Au) nanoparticles (NPs) are known experimentally to reduce carbon dioxide (CO2) to carbon monoxide (CO), with far superior performance to Au foils. To obtain guidance in designing improved CO2 catalysts, we want to understand the nature of the active sites on Au NPs. Here, we employed multiscale atomistic simulations to computationally synthesize and characterize a 10 nm thick Au NP on a carbon nanotube (CNT) support, and then we located active sites from quantum mechanics (QM) calculations on 269 randomly selected sites. The standard scaling relation is that the formation energy of *COOH (ΔE*COOH) is proportional to the binding energy of *CO (Ebinding*CO); therefore, decreasing ΔE*COOH to boost the CO2 reduction reaction (CO2RR) causes an increase of Ebinding*CO that retards CO2RR. We show that the NPs have superior CO2RR because there are many sites at the twin boundaries that significantly break this scaling relation.},
doi = {10.1021/acs.jpclett.7b01335},
journal = {Journal of Physical Chemistry Letters},
number = 14,
volume = 8,
place = {United States},
year = {Tue Jul 04 00:00:00 EDT 2017},
month = {Tue Jul 04 00:00:00 EDT 2017}
}
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Publisher's Version of Record
https://doi.org/10.1021/acs.jpclett.7b01335
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    Works referencing / citing this record:

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