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Title: Supramolecular Porphyrin Cages Assembled at Molecular–Materials Interfaces for Electrocatalytic CO Reduction

Abstract

Conversion of carbon monoxide (CO), a major one-carbon product of carbon dioxide (CO 2) reduction, into value-added multicarbon species is a challenge to addressing global energy demands and climate change. Here in this paper, we report a modular synthetic approach for aqueous electrochemical CO reduction to carbon-carbon coupled products via self-assembly of supramolecular cages at molecular-materials interfaces. Heterobimetallic cavities formed by face-to-face coordination of thiol-terminated metalloporphyrins to copper electrodes through varying organic struts convert CO to C2 products with high faradaic efficiency (FE = 83% total with 57% to ethanol) and current density (1.34 mA/cm 2) at a potential of -0.40 V vs RHE. The cage-functionalized electrodes offer an order of magnitude improvement in both selectivity and activity for electrocatalytic carbon fixation compared to parent copper surfaces or copper functionalized with porphyrins in an edge-on orientation.

Authors:
; ; ; ; ; ; ;  [1]; ORCiD logo [2]; ORCiD logo
  1. Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan, Shanxi 030001, China
  2. Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan, Shanxi 030001, China, Synfuels China, Beijing, 100195, China
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC); National Science Foundation (NSF)
OSTI Identifier:
1389889
Alternate Identifier(s):
OSTI ID: 1416929
Grant/Contract Number:  
101528-002; AC02-05CH11231
Resource Type:
Published Article
Journal Name:
ACS Central Science
Additional Journal Information:
Journal Name: ACS Central Science Journal Volume: 3 Journal Issue: 9; Journal ID: ISSN 2374-7943
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Gong, Ming, Cao, Zhi, Liu, Wei, Nichols, Eva M., Smith, Peter T., Derrick, Jeffrey S., Liu, Yi-Sheng, Liu, Jinjia, Wen, Xiaodong, and Chang, Christopher J. Supramolecular Porphyrin Cages Assembled at Molecular–Materials Interfaces for Electrocatalytic CO Reduction. United States: N. p., 2017. Web. doi:10.1021/acscentsci.7b00316.
Gong, Ming, Cao, Zhi, Liu, Wei, Nichols, Eva M., Smith, Peter T., Derrick, Jeffrey S., Liu, Yi-Sheng, Liu, Jinjia, Wen, Xiaodong, & Chang, Christopher J. Supramolecular Porphyrin Cages Assembled at Molecular–Materials Interfaces for Electrocatalytic CO Reduction. United States. doi:10.1021/acscentsci.7b00316.
Gong, Ming, Cao, Zhi, Liu, Wei, Nichols, Eva M., Smith, Peter T., Derrick, Jeffrey S., Liu, Yi-Sheng, Liu, Jinjia, Wen, Xiaodong, and Chang, Christopher J. Mon . "Supramolecular Porphyrin Cages Assembled at Molecular–Materials Interfaces for Electrocatalytic CO Reduction". United States. doi:10.1021/acscentsci.7b00316.
@article{osti_1389889,
title = {Supramolecular Porphyrin Cages Assembled at Molecular–Materials Interfaces for Electrocatalytic CO Reduction},
author = {Gong, Ming and Cao, Zhi and Liu, Wei and Nichols, Eva M. and Smith, Peter T. and Derrick, Jeffrey S. and Liu, Yi-Sheng and Liu, Jinjia and Wen, Xiaodong and Chang, Christopher J.},
abstractNote = {Conversion of carbon monoxide (CO), a major one-carbon product of carbon dioxide (CO2) reduction, into value-added multicarbon species is a challenge to addressing global energy demands and climate change. Here in this paper, we report a modular synthetic approach for aqueous electrochemical CO reduction to carbon-carbon coupled products via self-assembly of supramolecular cages at molecular-materials interfaces. Heterobimetallic cavities formed by face-to-face coordination of thiol-terminated metalloporphyrins to copper electrodes through varying organic struts convert CO to C2 products with high faradaic efficiency (FE = 83% total with 57% to ethanol) and current density (1.34 mA/cm2) at a potential of -0.40 V vs RHE. The cage-functionalized electrodes offer an order of magnitude improvement in both selectivity and activity for electrocatalytic carbon fixation compared to parent copper surfaces or copper functionalized with porphyrins in an edge-on orientation.},
doi = {10.1021/acscentsci.7b00316},
journal = {ACS Central Science},
number = 9,
volume = 3,
place = {United States},
year = {2017},
month = {9}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI: 10.1021/acscentsci.7b00316

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Cited by: 10 works
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Works referencing / citing this record:

In-Situ Nanostructuring and Stabilization of Polycrystalline Copper by an Organic Salt Additive Promotes Electrocatalytic CO 2 Reduction to Ethylene
journal, October 2019

  • Thevenon, Arnaud; Rosas-Hernández, Alonso; Peters, Jonas C.
  • Angewandte Chemie International Edition, Vol. 58, Issue 47
  • DOI: 10.1002/anie.201907935

In-Situ Nanostructuring and Stabilization of Polycrystalline Copper by an Organic Salt Additive Promotes Electrocatalytic CO 2 Reduction to Ethylene
journal, October 2019

  • Thevenon, Arnaud; Rosas-Hernández, Alonso; Peters, Jonas C.
  • Angewandte Chemie International Edition, Vol. 58, Issue 47
  • DOI: 10.1002/anie.201907935