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

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:
Grant/Contract Number:
SC0004993
Type:
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)
Research Org:
California Institute of Technology, Pasadena, CA (United States)
Sponsoring Org:
USDOE
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1372119
Alternate Identifier(s):
OSTI ID: 1417626

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., 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. 2017. "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 = {2017},
month = {7}
}