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Electrocatalysis at Organic–Metal Interfaces: Identification of Structure–Reactivity Relationships for CO_2 Reduction at Modified Cu Surfaces

Buckley, Aya K. and Lee, Michelle and Cheng, Tao and Kazantsev, Roman V. and Larson, David M. and Goddard, William A., III and Toste, F. Dean and Toma, Francesca M. (2019) Electrocatalysis at Organic–Metal Interfaces: Identification of Structure–Reactivity Relationships for CO_2 Reduction at Modified Cu Surfaces. Journal of the American Chemical Society, 141 (18). pp. 7355-7364. ISSN 0002-7863. https://resolver.caltech.edu/CaltechAUTHORS:20190506-093522029

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Abstract

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.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1021/jacs.8b13655DOIArticle
https://pubs.acs.org/doi/suppl/10.1021/jacs.8b13655PublisherSupporting Information
ORCID:
AuthorORCID
Cheng, Tao0000-0003-4830-177X
Goddard, William A., III0000-0003-0097-5716
Toste, F. Dean0000-0001-8018-2198
Toma, Francesca M.0000-0003-2332-0798
Alternate Title:Electrocatalysis at Organic–Metal Interfaces: Identification of Structure–Reactivity Relationships for CO2 Reduction at Modified Cu Surfaces
Additional Information:© 2019 American Chemical Society. Received: December 21, 2018; Published: March 31, 2019. This material was based upon work performed by the Joint Center for Artificial Photosynthesis, a DOE Energy Innovation Hub, supported through the Office of Science of the U.S. Department of Energy under Award No. DE-SC0004993. We acknowledge Dr. Jason K. Cooper, Dr. Adam Z. Weber, Ms. Philomena Weng, Dr. Anna Wuttig, Dr. Drew Higgins, and Prof. Miquel Salmeron for fruitful discussions. The authors declare no competing financial interest.
Group:JCAP
Funders:
Funding AgencyGrant Number
Department of Energy (DOE)DE-SC0004993
Other Numbering System:
Other Numbering System NameOther Numbering System ID
WAG1335
Issue or Number:18
Record Number:CaltechAUTHORS:20190506-093522029
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20190506-093522029
Official Citation:Electrocatalysis at Organic–Metal Interfaces: Identification of Structure–Reactivity Relationships for CO2 Reduction at Modified Cu Surfaces. Aya K. Buckley, Michelle Lee, Tao Cheng, Roman V. Kazantsev, David M. Larson, William A. Goddard III, F. Dean Toste, and Francesca M. Toma. Journal of the American Chemical Society 2019 141 (18), 7355-7364. DOI: 10.1021/jacs.8b13655
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:95235
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:06 May 2019 16:44
Last Modified:03 Oct 2019 21:11

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