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CO_2 Reduction Selective for C_(≥2) Products on Polycrystalline Copper with N-Substituted Pyridinium Additives

Han, Zhiji and Kortlever, Ruud and Chen, Hsiang-Yun and Peters, Jonas C. and Agapie, Theodor (2017) CO_2 Reduction Selective for C_(≥2) Products on Polycrystalline Copper with N-Substituted Pyridinium Additives. ACS Central Science, 3 (8). pp. 853-859. ISSN 2374-7943. PMCID PMC5571460. http://resolver.caltech.edu/CaltechAUTHORS:20170724-131758454

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Abstract

Electrocatalytic CO_2 reduction to generate multicarbon products is of interest for applications in artificial photosynthetic schemes. This is a particularly attractive goal for CO_2 reduction by copper electrodes, where a broad range of hydrocarbon products can be generated but where selectivity for C–C coupled products relative to CH_4 and H_2 remains an impediment. Herein we report a simple yet highly selective catalytic system for CO_2 reduction to C_(≥2) hydrocarbons on a polycrystalline Cu electrode in bicarbonate aqueous solution that uses N-substituted pyridinium additives. Selectivities of 70–80% for C_2 and C_3 products with a hydrocarbon ratio of C_(≥2)/CH4significantly greater than 100 have been observed with several additives. ^(13)C-labeling studies verify CO_2 to be the sole carbon source in the C_(≥2) hydrocarbons produced. Upon electroreduction, the N-substituted pyridinium additives lead to film deposition on the Cu electrode, identified in one case as the reductive coupling product of N-arylpyridinium. Product selectivity can also be tuned from C_(≥2) species to H_2 (∼90%) while suppressing methane with certain N-heterocyclic additives.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1021/acscentsci.7b00180DOIArticle
http://pubs.acs.org/doi/abs/10.1021/acscentsci.7b00180PublisherArticle
http://pubs.acs.org/doi/suppl/10.1021/acscentsci.7b00180PublisherSupporting Information
https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5571460/PubMed CentralArticle
ORCID:
AuthorORCID
Peters, Jonas C.0000-0002-6610-4414
Agapie, Theodor0000-0002-9692-7614
Additional Information:© 2017 American Chemical Society. ACS AuthorChoice - This is an open access article published under an ACS AuthorChoice License, which permits copying and redistribution of the article or any adaptations for non-commercial purposes. Received: April 26, 2017; Published: July 21, 2017. NMR and XPS spectra were collected at the NMR Facility (Division of CCE) and Molecular Materials Research Center (Beckman Institute) of the California Institute of Technology, respectively. 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. The authors declare no competing financial interest.
Group:JCAP
Funders:
Funding AgencyGrant Number
Department of Energy (DOE)DE-SC0004993
PubMed Central ID:PMC5571460
Record Number:CaltechAUTHORS:20170724-131758454
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20170724-131758454
Official Citation:CO2 Reduction Selective for C≥2 Products on Polycrystalline Copper with N-Substituted Pyridinium Additives Zhiji Han, Ruud Kortlever, Hsiang-Yun Chen, Jonas C. Peters, and Theodor Agapie ACS Central Science 2017 3 (8), 853-859 DOI: 10.1021/acscentsci.7b00180
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:79307
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:24 Jul 2017 20:26
Last Modified:31 Aug 2017 18:00

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