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Title: CO 2 Reduction Selective for C ≥2 Products on Polycrystalline Copper with N-Substituted Pyridinium Additives

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/CH 4 significantly greater than 100 have been observed with several additives. 13C-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. As a result, product selectivity can also be tuned from C ≥2 species to H 2 (~90%) while suppressing methane with certain N-heterocyclic additives.

Authors:
 [1];  [1];  [1];  [1]; ORCiD logo [1]
  1. California Institute of Technology, Pasadena, CA (United States)
Publication Date:
Research Org.:
California Institute of Technology, Pasadena, CA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1372119
Alternate Identifier(s):
OSTI ID: 1417626
Grant/Contract Number:
SC0004993
Resource Type:
Journal Article: Published Article
Journal Name:
ACS Central Science
Additional Journal Information:
Journal Volume: 3; Journal Issue: 8; Journal ID: ISSN 2374-7943
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Han, Zhiji, Kortlever, Ruud, Chen, Hsiang -Yun, Peters, Jonas C., and Agapie, Theodor. CO2 Reduction Selective for C≥2 Products on Polycrystalline Copper with N-Substituted Pyridinium Additives. United States: N. p., 2017. Web. doi:10.1021/acscentsci.7b00180.
Han, Zhiji, Kortlever, Ruud, Chen, Hsiang -Yun, Peters, Jonas C., & Agapie, Theodor. CO2 Reduction Selective for C≥2 Products on Polycrystalline Copper with N-Substituted Pyridinium Additives. United States. doi:10.1021/acscentsci.7b00180.
Han, Zhiji, Kortlever, Ruud, Chen, Hsiang -Yun, Peters, Jonas C., and Agapie, Theodor. Fri . "CO2 Reduction Selective for C≥2 Products on Polycrystalline Copper with N-Substituted Pyridinium Additives". United States. doi:10.1021/acscentsci.7b00180.
@article{osti_1372119,
title = {CO2 Reduction Selective for C≥2 Products on Polycrystalline Copper with N-Substituted Pyridinium Additives},
author = {Han, Zhiji and Kortlever, Ruud and Chen, Hsiang -Yun and Peters, Jonas C. and Agapie, Theodor},
abstractNote = {Electrocatalytic CO2 reduction to generate multicarbon products is of interest for applications in artificial photosynthetic schemes. This is a particularly attractive goal for CO2 reduction by copper electrodes, where a broad range of hydrocarbon products can be generated but where selectivity for C–C coupled products relative to CH4 and H2 remains an impediment. Herein we report a simple yet highly selective catalytic system for CO2 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 C2 and C3 products with a hydrocarbon ratio of C≥2/CH4 significantly greater than 100 have been observed with several additives. 13C-labeling studies verify CO2 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. As a result, product selectivity can also be tuned from C≥2 species to H2 (~90%) while suppressing methane with certain N-heterocyclic additives.},
doi = {10.1021/acscentsci.7b00180},
journal = {ACS Central Science},
number = 8,
volume = 3,
place = {United States},
year = {Fri Jul 21 00:00:00 EDT 2017},
month = {Fri Jul 21 00:00:00 EDT 2017}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record at 10.1021/acscentsci.7b00180

Citation Metrics:
Cited by: 8works
Citation information provided by
Web of Science

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  • 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 withmore » a hydrocarbon ratio of C ≥2/CH 4 significantly greater than 100 have been observed with several additives. 13C-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. As a result, product selectivity can also be tuned from C ≥2 species to H 2 (~90%) while suppressing methane with certain N-heterocyclic additives.« less
  • Direct conversion of carbon dioxide to multicarbon products remains as a grand challenge in electrochemical CO 2 reduction. Various forms of oxidized copper have been demonstrated as electrocatalysts that still require large overpotentials. Here in this paper, we show that an ensemble of Cu nanoparticles (NPs) enables selective formation of C 2–C 3 products at low overpotentials. Densely packed Cu NP ensembles underwent structural transformation during electrolysis into electrocatalytically active cube-like particles intermixed with smaller nanoparticles. Ethylene, ethanol, and n-propanol are the major C 2–C 3 products with onset potential at -0.53 V (vs. reversible hydrogen electrode, RHE) and Cmore » 2–C 3 faradaic efficiency (FE) reaching 50% at only -0.75 V. Thus, the catalyst exhibits selective generation of C 2–C 3 hydrocarbons and oxygenates at considerably lowered overpotentials in neutral pH aqueous media. In addition, this approach suggests new opportunities in realizing multicarbon product formation from CO 2, where the majority of efforts has been to use oxidized copper-based materials. Robust catalytic performance is demonstrated by 10 h of stable operation with C 2–C 3 current density 10 mA/cm 2 (at -0.75 V), rendering it attractive for solar-to-fuel applications. Lastly, Tafel analysis suggests reductive CO coupling as a rate determining step for C 2 products, while n-propanol (C 3) production seems to have a discrete pathway.« less
    Cited by 5
  • Direct conversion of carbon dioxide to multicarbon products remains as a grand challenge in electrochemical CO 2 reduction. Various forms of oxidized copper have been demonstrated as electrocatalysts that still require large overpotentials. Here in this paper, we show that an ensemble of Cu nanoparticles (NPs) enables selective formation of C 2–C 3 products at low overpotentials. Densely packed Cu NP ensembles underwent structural transformation during electrolysis into electrocatalytically active cube-like particles intermixed with smaller nanoparticles. Ethylene, ethanol, and n-propanol are the major C 2–C 3 products with onset potential at -0.53 V (vs. reversible hydrogen electrode, RHE) and Cmore » 2–C 3 faradaic efficiency (FE) reaching 50% at only -0.75 V. Thus, the catalyst exhibits selective generation of C 2–C 3 hydrocarbons and oxygenates at considerably lowered overpotentials in neutral pH aqueous media. In addition, this approach suggests new opportunities in realizing multicarbon product formation from CO 2, where the majority of efforts has been to use oxidized copper-based materials. Robust catalytic performance is demonstrated by 10 h of stable operation with C 2–C 3 current density 10 mA/cm 2 (at -0.75 V), rendering it attractive for solar-to-fuel applications. Lastly, Tafel analysis suggests reductive CO coupling as a rate determining step for C 2 products, while n-propanol (C 3) production seems to have a discrete pathway.« less
    Cited by 5
  • Cited by 62