Electrocatalysis at Organic-Metal Interfaces: Identification of Structure-Reactivity Relationships for CO 2 Reduction at Modified Cu Surfaces.

Autor: Buckley AK; Department of Chemistry , University of California , Berkeley , California 94720 , United States., Lee M; Department of Chemistry and Chemical Biology , Cornell University , Ithaca , New York 14853 , United States., Cheng T; Joint Center for Artificial Photosynthesis and Materials and Process Simulation Center , California Institute of Technology , Pasadena , California 91125 , United States.; Institute of Functional Nano & Soft Materials (FUNSOM), Jiangsu Key Laboratory for Carbon-Based Functional Materials & Devices, Joint International Research Laboratory of Carbon-Based Functional Materials and Devices , Soochow University , 199 Renai Road , Suzhou , 215123 , Jiangsu , PR China., Kazantsev RV, Larson DM, Goddard WA III; Joint Center for Artificial Photosynthesis and Materials and Process Simulation Center , California Institute of Technology , Pasadena , California 91125 , United States., Toste FD; Department of Chemistry , University of California , Berkeley , California 94720 , United States., Toma FM
Jazyk: angličtina
Zdroj: Journal of the American Chemical Society [J Am Chem Soc] 2019 May 08; Vol. 141 (18), pp. 7355-7364. Date of Electronic Publication: 2019 Apr 29.
DOI: 10.1021/jacs.8b13655
Abstrakt: The limited selectivity of existing CO 2 reduction catalysts and rising levels of CO 2 in the atmosphere necessitate the identification of specific structure-reactivity relationships to inform catalyst development. Herein, we develop a predictive framework to tune the selectivity of CO 2 reduction on Cu by examining a series of polymeric and molecular modifiers. We find that protic species enhance selectivity for H 2 , hydrophilic species enhance formic acid formation, and cationic hydrophobic species enhance CO selectivity. ReaxFF reactive molecular dynamics simulations indicate that the hydrophilic/hydrophobic modifiers influence the formation of surface hydrides, which yield formic acid or H 2 . These observations offer insights into how these modifiers influence catalytic behavior at the non-precious Cu surface and may aid in the future implementation of organic structures in CO 2 reduction devices.
Databáze: MEDLINE
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