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

Cheng, Tao; Huang, Yufeng; Xiao, Hai; Goddard, III, William A.

doi:10.1021/acs.jpclett.7b01335

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

Journal Article · Tue Jul 04 00:00:00 EDT 2017 · Journal of Physical Chemistry Letters

DOI:https://doi.org/10.1021/acs.jpclett.7b01335· OSTI ID:1467601

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California Inst. of Technology (CalTech), Pasadena, CA (United States)

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.

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Research Organization:: California Institute of Technology (CalTech), Pasadena, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC)

Grant/Contract Number:: SC0004993

OSTI ID:: 1467601

Journal Information:: Journal of Physical Chemistry Letters, Vol. 8, Issue 14; ISSN 1948-7185

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 35 works

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Recent Progress in the Theoretical Investigation of Electrocatalytic Reduction of CO ₂ Tian, Ziqi; Priest, Chad; Chen, Liang Advanced Theory and Simulations, Vol. 1, Issue 5 https://doi.org/10.1002/adts.201800004	journal	April 2018
Tuning Gold Nanoparticles with Chelating Ligands for Highly Efficient Electrocatalytic CO 2 Reduction Cao, Zhi; Zacate, Samson B.; Sun, Xiaodong Angewandte Chemie, Vol. 130, Issue 39 https://doi.org/10.1002/ange.201805696	journal	August 2018
Electrochemical CO ₂ Reduction into Chemical Feedstocks: From Mechanistic Electrocatalysis Models to System Design Kibria, Md Golam; Edwards, Jonathan P.; Gabardo, Christine M. Advanced Materials, Vol. 31, Issue 31 https://doi.org/10.1002/adma.201807166	journal	December 2018
A Highly Active Star Decahedron Cu Nanocatalyst for Hydrocarbon Production at Low Overpotentials Choi, Chungseok; Cheng, Tao; Flores Espinosa, Michelle Advanced Materials https://doi.org/10.1002/adma.201805405	journal	December 2018
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