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Promoter effects of alkali metal cations on the electrochemical reduction of carbon dioxide

Resasco, Joaquin and Chen, Leanne D. and Clark, Ezra and Tsai, Charlie and Hahn, Christopher and Jaramillo, Thomas F. and Chan, Karen and Bell, Alexis T. (2017) Promoter effects of alkali metal cations on the electrochemical reduction of carbon dioxide. Journal of the American Chemical Society, 139 (32). pp. 11277-11287. ISSN 0002-7863. https://resolver.caltech.edu/CaltechAUTHORS:20170727-084953058

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[img] PDF (Figure S1: Product selectivities for electrochemical reduction of CO2 on Cu (100). Figure S2: Product selectivities as a function of cation size for electrochemical reduction of CO2 on Cu (100). Table S1: Faradaic efficiencies (%) for minor liquid...) - Supplemental Material
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Abstract

The electrochemical reduction of CO_2 is known to be influenced by the identity of the alkali metal cation in the electrolyte; however, a satisfactory explanation for this phenomenon has not been developed. Here we present the results of experimental and theoretical studies aimed at elucidating the effects of electrolyte cation size on the intrinsic activity and selectivity of metal catalysts for the reduction of CO_2. Experiments were conducted under conditions where the influence of electrolyte polarization is minimal in order to show that cation size affects the intrinsic rates of formation of certain reaction products, most notably for HCOO–, C_2H_4, and C_2H_5OH over Cu(100)- and Cu(111)-oriented thin films, and for CO and HCOO– over polycrystalline Ag and Sn. Interpretation of the findings for CO_2 reduction was informed by studies of the reduction of glyoxal and CO, key intermediates along the reaction pathway to final products. Density functional theory calculations show that the alkali metal cations influence the distribution of products formed as a consequence of electrostatic interactions between solvated cations present at the outer Helmholtz plane and adsorbed species having large dipole moments. The observed trends in activity with cation size are attributed to an increase in the concentration of cations at the outer Helmholtz plane with increasing cation size.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1021/jacs.7b06765DOIArticle
http://pubs.acs.org/doi/abs/10.1021/jacs.7b06765PublisherArticle
http://pubs.acs.org/doi/suppl/10.1021/jacs.7b06765PublisherSupporting Information
ORCID:
AuthorORCID
Chen, Leanne D.0000-0001-9700-972X
Hahn, Christopher0000-0002-2772-6341
Jaramillo, Thomas F.0000-0001-9900-0622
Chan, Karen0000-0002-6897-1108
Bell, Alexis T.0000-0002-5738-4645
Additional Information:© 2017 American Chemical Society. Received: June 29, 2017; Published: July 24, 2017. This material is 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 Number DE-SC0004993. J.R. gratefully acknowledges support of the National Science Foundation Graduate Research Fellowship Program (NSF GRFP) under Grant No. DGE-0802270. The authors would also like to acknowledge the allocation of computer time at the National Energy Research Scientific Computing Center, a DOE Office of Science User Facility supported by the Office of Science of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231. The authors declare no competing financial interest.
Group:JCAP
Funders:
Funding AgencyGrant Number
Department of Energy (DOE)DE-SC0004993
NSF Graduate Research FellowshipDGE-0802270
Department of Energy (DOE)DE-AC02-05CH11231
Issue or Number:32
Record Number:CaltechAUTHORS:20170727-084953058
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20170727-084953058
Official Citation:Promoter Effects of Alkali Metal Cations on the Electrochemical Reduction of Carbon Dioxide Joaquin Resasco, Leanne D. Chen, Ezra Clark, Charlie Tsai, Christopher Hahn, Thomas F. Jaramillo, Karen Chan, and Alexis T. Bell Journal of the American Chemical Society 2017 139 (32), 11277-11287 DOI: 10.1021/jacs.7b06765
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:79478
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:27 Jul 2017 15:57
Last Modified:09 Mar 2020 13:18

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