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Title: Covalent organic frameworks comprising cobalt porphyrins for catalytic CO 2 reduction in water

Abstract

Conversion of carbon dioxide (CO2) to carbon monoxide (CO) and other value-added carbon products is an important challenge for clean energy research. Here we report modular optimization of covalent organic frameworks (COFs), in which the building units are cobalt porphyrin catalysts linked by organic struts through imine bonds, to prepare a catalytic material for aqueous electrochemical reduction of CO2 to CO. The catalysts exhibit high Faradaic efficiency (90%) and turnover numbers (up to 290,000, with initial turnover frequency of 9400 hour-1) at pH 7 with an overpotential of –0.55 volts, equivalent to a 26-fold improvement in activity compared with the molecular cobalt complex, with no degradation over 24 hours. X-ray absorption data reveal the influence of the COF environment on the electronic structure of the catalytic cobalt centers.

Authors:
; ; ; ; ; ; ; ; ; ;
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Center for Gas Separations Relevant to Clean Energy Technologies (CGS)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1370752
DOE Contract Number:  
SC0001015
Resource Type:
Journal Article
Journal Name:
Science
Additional Journal Information:
Journal Volume: 349; Journal Issue: 6253; Related Information: CGS partners with University of California, Berkeley; University of California, Davis; Lawrence Berkeley National Laboratory; University of Minnesota; National Energy Technology Laboratory; Texas A&M University; Journal ID: ISSN 0036-8075
Publisher:
AAAS
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; membrane, carbon capture, materials and chemistry by design, synthesis (novel materials), synthesis (self-assembly), synthesis (scalable processing)

Citation Formats

Lin, S., Diercks, C. S., Zhang, Y. -B., Kornienko, N., Nichols, E. M., Zhao, Y., Paris, A. R., Kim, D., Yang, P., Yaghi, O. M., and Chang, C. J. Covalent organic frameworks comprising cobalt porphyrins for catalytic CO2 reduction in water. United States: N. p., 2015. Web. doi:10.1126/science.aac8343.
Lin, S., Diercks, C. S., Zhang, Y. -B., Kornienko, N., Nichols, E. M., Zhao, Y., Paris, A. R., Kim, D., Yang, P., Yaghi, O. M., & Chang, C. J. Covalent organic frameworks comprising cobalt porphyrins for catalytic CO2 reduction in water. United States. doi:10.1126/science.aac8343.
Lin, S., Diercks, C. S., Zhang, Y. -B., Kornienko, N., Nichols, E. M., Zhao, Y., Paris, A. R., Kim, D., Yang, P., Yaghi, O. M., and Chang, C. J. Thu . "Covalent organic frameworks comprising cobalt porphyrins for catalytic CO2 reduction in water". United States. doi:10.1126/science.aac8343.
@article{osti_1370752,
title = {Covalent organic frameworks comprising cobalt porphyrins for catalytic CO2 reduction in water},
author = {Lin, S. and Diercks, C. S. and Zhang, Y. -B. and Kornienko, N. and Nichols, E. M. and Zhao, Y. and Paris, A. R. and Kim, D. and Yang, P. and Yaghi, O. M. and Chang, C. J.},
abstractNote = {Conversion of carbon dioxide (CO2) to carbon monoxide (CO) and other value-added carbon products is an important challenge for clean energy research. Here we report modular optimization of covalent organic frameworks (COFs), in which the building units are cobalt porphyrin catalysts linked by organic struts through imine bonds, to prepare a catalytic material for aqueous electrochemical reduction of CO2 to CO. The catalysts exhibit high Faradaic efficiency (90%) and turnover numbers (up to 290,000, with initial turnover frequency of 9400 hour-1) at pH 7 with an overpotential of –0.55 volts, equivalent to a 26-fold improvement in activity compared with the molecular cobalt complex, with no degradation over 24 hours. X-ray absorption data reveal the influence of the COF environment on the electronic structure of the catalytic cobalt centers.},
doi = {10.1126/science.aac8343},
journal = {Science},
issn = {0036-8075},
number = 6253,
volume = 349,
place = {United States},
year = {2015},
month = {8}
}

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