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Title: Positional effects of second-sphere amide pendants on electrochemical CO 2 reduction catalyzed by iron porphyrins

Abstract

The development of catalysts for electrochemical reduction of carbon dioxide offers an attractive approach to transforming this greenhouse gas into value-added carbon products with sustainable energy input. Inspired by natural bioinorganic systems that feature precisely positioned hydrogen-bond donors in the secondary coordination sphere to direct chemical transformations occurring at redox-active metal centers, we now report the design, synthesis, and characterization of a series of iron tetraphenylporphyrin (Fe-TPP) derivatives bearing amide pendants at various positions at the periphery of the metal core. Proper positioning of the amide pendants greatly affects the electrocatalytic activity for carbon dioxide reduction to carbon monoxide. In particular, derivatives bearing proximal and distal amide pendants on the ortho position of the phenyl ring exhibit significantly larger turnover frequencies (TOF) compared to the analogous para-functionalized amide isomers or unfunctionalized Fe-TPP. Analysis of TOF as a function of catalyst standard reduction potential enables first-sphere electronic effects to be disentangled from second-sphere through-space interactions, suggesting that the ortho-functionalized porphyrins can utilize the latter second-sphere property to promote CO 2 reduction. Indeed, the distally-functionalized ortho-amide isomer shows a significantly larger through-space interaction than its proximal ortho-amide analogue. These data establish that proper positioning of secondary coordination sphere groups is an effectivemore » design element for breaking electronic scaling relationships that are often observed in electrochemical CO 2 reduction.The development of catalysts for electrochemical reduction of carbon dioxide offers an attractive approach to transforming this greenhouse gas into value-added carbon products with sustainable energy input.« less

Authors:
 [1];  [1];  [2];  [1]; ORCiD logo [1]
  1. Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  2. Univ. of California, Berkeley, CA (United States)
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1422003
Alternate Identifier(s):
OSTI ID: 1465425
Grant/Contract Number:  
AC02-05CH11231; 101528-002
Resource Type:
Published Article
Journal Name:
Chemical Science
Additional Journal Information:
Journal Volume: 9; Journal Issue: 11; Related Information: © 2018 The Royal Society of Chemistry.; Journal ID: ISSN 2041-6520
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Nichols, Eva M., Derrick, Jeffrey S., Nistanaki, Sepand K., Smith, Peter T., and Chang, Christopher J. Positional effects of second-sphere amide pendants on electrochemical CO2 reduction catalyzed by iron porphyrins. United States: N. p., 2018. Web. doi:10.1039/c7sc04682k.
Nichols, Eva M., Derrick, Jeffrey S., Nistanaki, Sepand K., Smith, Peter T., & Chang, Christopher J. Positional effects of second-sphere amide pendants on electrochemical CO2 reduction catalyzed by iron porphyrins. United States. doi:10.1039/c7sc04682k.
Nichols, Eva M., Derrick, Jeffrey S., Nistanaki, Sepand K., Smith, Peter T., and Chang, Christopher J. Wed . "Positional effects of second-sphere amide pendants on electrochemical CO2 reduction catalyzed by iron porphyrins". United States. doi:10.1039/c7sc04682k.
@article{osti_1422003,
title = {Positional effects of second-sphere amide pendants on electrochemical CO2 reduction catalyzed by iron porphyrins},
author = {Nichols, Eva M. and Derrick, Jeffrey S. and Nistanaki, Sepand K. and Smith, Peter T. and Chang, Christopher J.},
abstractNote = {The development of catalysts for electrochemical reduction of carbon dioxide offers an attractive approach to transforming this greenhouse gas into value-added carbon products with sustainable energy input. Inspired by natural bioinorganic systems that feature precisely positioned hydrogen-bond donors in the secondary coordination sphere to direct chemical transformations occurring at redox-active metal centers, we now report the design, synthesis, and characterization of a series of iron tetraphenylporphyrin (Fe-TPP) derivatives bearing amide pendants at various positions at the periphery of the metal core. Proper positioning of the amide pendants greatly affects the electrocatalytic activity for carbon dioxide reduction to carbon monoxide. In particular, derivatives bearing proximal and distal amide pendants on the ortho position of the phenyl ring exhibit significantly larger turnover frequencies (TOF) compared to the analogous para-functionalized amide isomers or unfunctionalized Fe-TPP. Analysis of TOF as a function of catalyst standard reduction potential enables first-sphere electronic effects to be disentangled from second-sphere through-space interactions, suggesting that the ortho-functionalized porphyrins can utilize the latter second-sphere property to promote CO2 reduction. Indeed, the distally-functionalized ortho-amide isomer shows a significantly larger through-space interaction than its proximal ortho-amide analogue. These data establish that proper positioning of secondary coordination sphere groups is an effective design element for breaking electronic scaling relationships that are often observed in electrochemical CO2 reduction.The development of catalysts for electrochemical reduction of carbon dioxide offers an attractive approach to transforming this greenhouse gas into value-added carbon products with sustainable energy input.},
doi = {10.1039/c7sc04682k},
journal = {Chemical Science},
number = 11,
volume = 9,
place = {United States},
year = {2018},
month = {2}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI: 10.1039/c7sc04682k

Citation Metrics:
Cited by: 12 works
Citation information provided by
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Figures / Tables:

Fig. 1 Fig. 1: Titration of 3,5-[bis(trifluoromethyl)phenyl]amide to Fe-TPP under CO2 showing current increases with increasing concentrations of amide. Conditions: 0.1 M TBAPF6 in DMF, 1 mM Fe-TPP.

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    Works referencing / citing this record:

    Dissection of Electronic Substituent Effects in Multielectron–Multistep Molecular Catalysis. Electrochemical CO 2 -to-CO Conversion Catalyzed by Iron Porphyrins
    journal, December 2016

    • Azcarate, Iban; Costentin, Cyrille; Robert, Marc
    • The Journal of Physical Chemistry C, Vol. 120, Issue 51
    • DOI: 10.1021/acs.jpcc.6b09947

    Catalysis of the Electrochemical Reduction of Carbon Dioxide by Iron(0) Porphyrins:  Synergystic Effect of Weak Brönsted Acids
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    • Bhugun, Iqbal; Lexa, Doris; Savéant, Jean-Michel
    • Journal of the American Chemical Society, Vol. 118, Issue 7
    • DOI: 10.1021/ja9534462

    De Novo 3D Structure Determination from Sub-milligram Protein Samples by Solid-State 100 kHz MAS NMR Spectroscopy
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    • Agarwal, Vipin; Penzel, Susanne; Szekely, Kathrin
    • Angewandte Chemie International Edition, Vol. 53, Issue 45
    • DOI: 10.1002/anie.201405730

    Rhenium bipyridine catalysts with hydrogen bonding pendant amines for CO 2 reduction
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    Studies of Cobalt-Mediated Electrocatalytic CO 2 Reduction Using a Redox-Active Ligand
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    • Lacy, David C.; McCrory, Charles C. L.; Peters, Jonas C.
    • Inorganic Chemistry, Vol. 53, Issue 10
    • DOI: 10.1021/ic403122j

    Frontiers, Opportunities, and Challenges in Biochemical and Chemical Catalysis of CO 2 Fixation
    journal, June 2013

    • Appel, Aaron M.; Bercaw, John E.; Bocarsly, Andrew B.
    • Chemical Reviews, Vol. 113, Issue 8
    • DOI: 10.1021/cr300463y

    Synthetic Heme-Dioxygen Complexes
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    • Momenteau, Michel; Reed, Christopher A.
    • Chemical Reviews, Vol. 94, Issue 3
    • DOI: 10.1021/cr00027a006

    Chemical catalysis of electrochemical reactions. Homogeneous catalysis of the electrochemical reduction of carbon dioxide by iron("0") porphyrins. Role of the addition of magnesium cations
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    • Hammouche, Mohamed; Lexa, Doris; Momenteau, Michel
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    • Accounts of Chemical Research, Vol. 42, Issue 12
    • DOI: 10.1021/ar9001679

    Electrocatalytic Oxygen Reduction by Iron Tetra-arylporphyrins Bearing Pendant Proton Relays
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    • Carver, Colin T.; Matson, Benjamin D.; Mayer, James M.
    • Journal of the American Chemical Society, Vol. 134, Issue 12
    • DOI: 10.1021/ja211987f

    Nickel(II)-cyclam: an extremely selective electrocatalyst for reduction of CO2 in water
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    • Beley, Marc; Collin, Jean-Paul; Ruppert, Romain
    • Journal of the Chemical Society, Chemical Communications, Issue 19
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    journal, November 2016


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    • Inorganic Chemistry, Vol. 27, Issue 25
    • DOI: 10.1021/ic00298a016

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    journal, April 2016

    • Chapovetsky, Alon; Do, Thomas H.; Haiges, Ralf
    • Journal of the American Chemical Society, Vol. 138, Issue 18
    • DOI: 10.1021/jacs.6b01980

    Cobalt Porphyrin Catalyzed Reduction of CO 2 . Radiation Chemical, Photochemical, and Electrochemical Studies
    journal, April 1998

    • Behar, D.; Dhanasekaran, T.; Neta, P.
    • The Journal of Physical Chemistry A, Vol. 102, Issue 17
    • DOI: 10.1021/jp9807017

    Molecular Designs for Controlling the Local Environments around Metal Ions
    journal, July 2015


    Visible-Light Photoredox Catalysis: Selective Reduction of Carbon Dioxide to Carbon Monoxide by a Nickel N -Heterocyclic Carbene–Isoquinoline Complex
    journal, September 2013

    • Thoi, V. Sara; Kornienko, Nikolay; Margarit, Charles G.
    • Journal of the American Chemical Society, Vol. 135, Issue 38
    • DOI: 10.1021/ja4074003

    Evaluation of attractive interactions in the second coordination sphere of iron complexes containing pendant amines
    journal, January 2019

    • Liao, Qian; Liu, Tianbiao; Johnson, Samantha I.
    • Dalton Transactions, Vol. 48, Issue 15
    • DOI: 10.1039/c9dt00708c

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