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Title: Controlling selectivities in CO 2 reduction through mechanistic understanding

Abstract

Catalytic CO 2 conversion to energy carriers and intermediates is of utmost importance to energy and environmental goals. However, the lack of fundamental understanding of the reaction mechanism renders designing a selective catalyst inefficient. We performed operando FTIR/SSITKA experiments to understand the correlation between the kinetics of product formation and that of surface species conversion during CO 2 reduction over Pd/Al 2O 3 catalysts. We found that the rate-determining step for CO formation is the conversion of adsorbed formate, while that for CH 4 formation is the hydrogenation of adsorbed carbonyl. The balance of the hydrogenation kinetics between adsorbed formates and carbonyls governs the selectivities to CH 4 and CO. As a result, we demonstrated how this knowledge can be used to design catalysts to achieve high selectivities to desired products.

Authors:
 [1]; ORCiD logo [1];  [1]
  1. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1406770
Report Number(s):
PNNL-SA-123127
Journal ID: ISSN 2041-1723; KC0302010
Grant/Contract Number:  
AC05-76RL01830
Resource Type:
Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 8; Journal Issue: 1; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
54 ENVIRONMENTAL SCIENCES; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Wang, Xiang, Shi, Hui, and Szanyi, Janos. Controlling selectivities in CO2 reduction through mechanistic understanding. United States: N. p., 2017. Web. doi:10.1038/s41467-017-00558-9.
Wang, Xiang, Shi, Hui, & Szanyi, Janos. Controlling selectivities in CO2 reduction through mechanistic understanding. United States. doi:10.1038/s41467-017-00558-9.
Wang, Xiang, Shi, Hui, and Szanyi, Janos. Mon . "Controlling selectivities in CO2 reduction through mechanistic understanding". United States. doi:10.1038/s41467-017-00558-9. https://www.osti.gov/servlets/purl/1406770.
@article{osti_1406770,
title = {Controlling selectivities in CO2 reduction through mechanistic understanding},
author = {Wang, Xiang and Shi, Hui and Szanyi, Janos},
abstractNote = {Catalytic CO2 conversion to energy carriers and intermediates is of utmost importance to energy and environmental goals. However, the lack of fundamental understanding of the reaction mechanism renders designing a selective catalyst inefficient. We performed operando FTIR/SSITKA experiments to understand the correlation between the kinetics of product formation and that of surface species conversion during CO2 reduction over Pd/Al2O3 catalysts. We found that the rate-determining step for CO formation is the conversion of adsorbed formate, while that for CH4 formation is the hydrogenation of adsorbed carbonyl. The balance of the hydrogenation kinetics between adsorbed formates and carbonyls governs the selectivities to CH4 and CO. As a result, we demonstrated how this knowledge can be used to design catalysts to achieve high selectivities to desired products.},
doi = {10.1038/s41467-017-00558-9},
journal = {Nature Communications},
number = 1,
volume = 8,
place = {United States},
year = {2017},
month = {9}
}

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