Multifunctional Charge and Hydrogen-Bond Effects of Second-Sphere Imidazolium Pendants Promote Capture and Electrochemical Reduction of CO2 in Water Catalyzed by Iron Porphyrins
Abstract
Abstract Microenvironments tailored by multifunctional secondary coordination sphere groups can enhance catalytic performance at primary metal active sites in natural systems. Here, we capture this biological concept in synthetic systems by developing a family of iron porphyrins decorated with imidazolium (im) pendants for the electrochemical CO 2 reduction reaction (CO 2 RR), which promotes multiple synergistic effects to enhance CO 2 RR and enables the disentangling of second‐sphere contributions that stem from each type of interaction. Fe‐ ortho ‐im(H) , which poises imidazolium units featuring both positive charge and hydrogen‐bond capabilities proximal to the active iron center, increases CO 2 binding affinity by 25‐fold and CO 2 RR activity by 2000‐fold relative to the parent Fe tetraphenylporphyrin ( Fe‐TPP ). Comparison with monofunctional analogs reveals that through‐space charge effects have a greater impact on catalytic CO 2 RR performance compared to hydrogen bonding in this context.
- Authors:
-
[1];
[1];
[1]
- Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division
- Publication Date:
- Research Org.:
- Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; National Institutes of Health (NIH); USDOE
- OSTI Identifier:
- 1963460
- Alternate Identifier(s):
- OSTI ID: 1885609
- Grant/Contract Number:
- AC02-05CH11231; NIH S10OD023532; NIH S10OD024998
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Angewandte Chemie (International Edition)
- Additional Journal Information:
- Journal Name: Angewandte Chemie (International Edition); Journal Volume: 61; Journal Issue: 37; Journal ID: ISSN 1433-7851
- Publisher:
- Wiley
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Carbon Dioxide Capture; Electrochemical Carbon Dioxide Reduction; Imidazolium; Iron Porphyrin; Second-Sphere Effect
Citation Formats
Narouz, Mina R., De La Torre, Patricia, An, Lun, and Chang, Christopher J. Multifunctional Charge and Hydrogen-Bond Effects of Second-Sphere Imidazolium Pendants Promote Capture and Electrochemical Reduction of CO2 in Water Catalyzed by Iron Porphyrins. United States: N. p., 2022.
Web. doi:10.1002/anie.202207666.
Narouz, Mina R., De La Torre, Patricia, An, Lun, & Chang, Christopher J. Multifunctional Charge and Hydrogen-Bond Effects of Second-Sphere Imidazolium Pendants Promote Capture and Electrochemical Reduction of CO2 in Water Catalyzed by Iron Porphyrins. United States. https://doi.org/10.1002/anie.202207666
Narouz, Mina R., De La Torre, Patricia, An, Lun, and Chang, Christopher J. Mon .
"Multifunctional Charge and Hydrogen-Bond Effects of Second-Sphere Imidazolium Pendants Promote Capture and Electrochemical Reduction of CO2 in Water Catalyzed by Iron Porphyrins". United States. https://doi.org/10.1002/anie.202207666. https://www.osti.gov/servlets/purl/1963460.
@article{osti_1963460,
title = {Multifunctional Charge and Hydrogen-Bond Effects of Second-Sphere Imidazolium Pendants Promote Capture and Electrochemical Reduction of CO2 in Water Catalyzed by Iron Porphyrins},
author = {Narouz, Mina R. and De La Torre, Patricia and An, Lun and Chang, Christopher J.},
abstractNote = {Abstract Microenvironments tailored by multifunctional secondary coordination sphere groups can enhance catalytic performance at primary metal active sites in natural systems. Here, we capture this biological concept in synthetic systems by developing a family of iron porphyrins decorated with imidazolium (im) pendants for the electrochemical CO 2 reduction reaction (CO 2 RR), which promotes multiple synergistic effects to enhance CO 2 RR and enables the disentangling of second‐sphere contributions that stem from each type of interaction. Fe‐ ortho ‐im(H) , which poises imidazolium units featuring both positive charge and hydrogen‐bond capabilities proximal to the active iron center, increases CO 2 binding affinity by 25‐fold and CO 2 RR activity by 2000‐fold relative to the parent Fe tetraphenylporphyrin ( Fe‐TPP ). Comparison with monofunctional analogs reveals that through‐space charge effects have a greater impact on catalytic CO 2 RR performance compared to hydrogen bonding in this context.},
doi = {10.1002/anie.202207666},
journal = {Angewandte Chemie (International Edition)},
number = 37,
volume = 61,
place = {United States},
year = {Mon Jul 25 00:00:00 EDT 2022},
month = {Mon Jul 25 00:00:00 EDT 2022}
}
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Works referenced in this record:
Atropisomeric Hydrogen Bonding Control for CO 2 Binding and Enhancement of Electrocatalytic Reduction at Iron Porphyrins
journal, October 2020
- Gotico, Philipp; Roupnel, Loïc; Guillot, Regis
- Angewandte Chemie International Edition, Vol. 59, Issue 50
Übergangsmetallkomplexe als Katalysatoren für die elektrische Umwandlung von CO 2 – eine metallorganische Perspektive
journal, January 2021
- Kinzel, Niklas W.; Werlé, Christophe; Leitner, Walter
- Angewandte Chemie, Vol. 133, Issue 21
Electrocatalytic CO 2 Reduction by Imidazolium-Functionalized Molecular Catalysts
journal, September 2017
- Sung, Siyoung; Kumar, Davinder; Gil-Sepulcre, Marcos
- Journal of the American Chemical Society, Vol. 139, Issue 40
Non-sensitized selective photochemical reduction of CO 2 to CO under visible light with an iron molecular catalyst
journal, January 2017
- Rao, Heng; Bonin, Julien; Robert, Marc
- Chemical Communications, Vol. 53, Issue 19
Atropisomeric Effects of Second Coordination Spheres on Electrocatalytic CO 2 Reduction
journal, August 2020
- Williams, Caroline K.; Lashgari, Amir; Tomb, Jenny A.
- ChemCatChem, Vol. 12, Issue 19
What would it take for renewably powered electrosynthesis to displace petrochemical processes?
journal, April 2019
- De Luna, Phil; Hahn, Christopher; Higgins, Drew
- Science, Vol. 364, Issue 6438
Electrochemical CO2 Reduction on Metal Electrodes
book, January 2008
- Hori, Y.; Vayenas, Constantinos G.; White, Ralph E.
- Modern Aspects of Electrochemistry, p. 89-189
Investigations of Two Bidirectional Carbon Monoxide Dehydrogenases from Carboxydothermus hydrogenoformans by Protein Film Electrochemistry
journal, September 2013
- Wang, Vincent C. -C.; Ragsdale, Stephen W.; Armstrong, Fraser A.
- ChemBioChem, Vol. 14, Issue 14
Life on carbon monoxide: X-ray structure of Rhodospirillum rubrum Ni-Fe-S carbon monoxide dehydrogenase
journal, October 2001
- Drennan, C. L.; Heo, J.; Sintchak, M. D.
- Proceedings of the National Academy of Sciences, Vol. 98, Issue 21
Amide linked conjugated porous polymers for effective CO2 capture and separation
journal, December 2016
- Manoranjan, Narmadha; Won, Da Hye; Kim, Jihan
- Journal of CO2 Utilization, Vol. 16
Ultraefficient homogeneous catalyst for the CO 2 -to-CO electrochemical conversion
journal, October 2014
- Costentin, Cyrille; Passard, Guillaume; Robert, Marc
- Proceedings of the National Academy of Sciences, Vol. 111, Issue 42
A guide to secondary coordination sphere editing
journal, January 2022
- Drover, Marcus W.
- Chemical Society Reviews, Vol. 51, Issue 6
Quick and Easy Method to Dramatically Improve the Electrochemical CO 2 Reduction Activity of an Iron Porphyrin Complex
journal, August 2021
- Kosugi, Kento; Kondo, Mio; Masaoka, Shigeyuki
- Angewandte Chemie International Edition, Vol. 60, Issue 40
Through-Space Charge Interaction Substituent Effects in Molecular Catalysis Leading to the Design of the Most Efficient Catalyst of CO 2 -to-CO Electrochemical Conversion
journal, December 2016
- Azcarate, Iban; Costentin, Cyrille; Robert, Marc
- Journal of the American Chemical Society, Vol. 138, Issue 51
Carbon Dioxide Activation at the Ni,Fe-Cluster of Anaerobic Carbon Monoxide Dehydrogenase
journal, November 2007
- Jeoung, J. -H.; Dobbek, H.
- Science, Vol. 318, Issue 5855
Second-sphere hydrogen-bonding enhances heterogeneous electrocatalytic CO 2 to CO reduction by iron porphyrins in water
journal, January 2021
- Zhang, Chanjuan; Dragoe, Diana; Brisset, François
- Green Chemistry, Vol. 23, Issue 22
Bioinspiration in light harvesting and catalysis
journal, August 2020
- Proppe, Andrew H.; Li, Yuguang C.; Aspuru-Guzik, Alán
- Nature Reviews Materials, Vol. 5, Issue 11
Transition Metal Complexes as Catalysts for the Electroconversion of CO 2 : An Organometallic Perspective
journal, January 2021
- Kinzel, Niklas W.; Werlé, Christophe; Leitner, Walter
- Angewandte Chemie International Edition, Vol. 60, Issue 21
Homogeneous Photocatalytic Reduction of CO 2 to CO Using Iron(0) Porphyrin Catalysts: Mechanism and Intrinsic Limitations
journal, September 2014
- Bonin, Julien; Chaussemier, Marie; Robert, Marc
- ChemCatChem, Vol. 6, Issue 11
Visible-light Homogeneous Photocatalytic Conversion of CO 2 into CO in Aqueous Solutions with an Iron Catalyst
journal, October 2017
- Rao, Heng; Bonin, Julien; Robert, Marc
- ChemSusChem, Vol. 10, Issue 22
Climate change mitigation potential of carbon capture and utilization in the chemical industry
journal, May 2019
- Kätelhön, Arne; Meys, Raoul; Deutz, Sarah
- Proceedings of the National Academy of Sciences, Vol. 116, Issue 23
Second‐Sphere Biomimetic Multipoint Hydrogen‐Bonding Patterns to Boost CO 2 Reduction of Iron Porphyrins
journal, February 2019
- Gotico, Philipp; Boitrel, Bernard; Guillot, Régis
- Angewandte Chemie, Vol. 131, Issue 14
Second-Sphere Biomimetic Multipoint Hydrogen-Bonding Patterns to Boost CO 2 Reduction of Iron Porphyrins
journal, February 2019
- Gotico, Philipp; Boitrel, Bernard; Guillot, Régis
- Angewandte Chemie International Edition, Vol. 58, Issue 14
Local ionic liquid environment at a modified iron porphyrin catalyst enhances the electrocatalytic performance of CO 2 to CO reduction in water
journal, January 2018
- Khadhraoui, Asma; Gotico, Philipp; Boitrel, Bernard
- Chemical Communications, Vol. 54, Issue 82
Reversibility and efficiency in electrocatalytic energy conversion and lessons from enzymes
journal, August 2011
- Armstrong, F. A.; Hirst, J.
- Proceedings of the National Academy of Sciences, Vol. 108, Issue 34
Turnover Numbers, Turnover Frequencies, and Overpotential in Molecular Catalysis of Electrochemical Reactions. Cyclic Voltammetry and Preparative-Scale Electrolysis
journal, June 2012
- Costentin, Cyrille; Drouet, Samuel; Robert, Marc
- Journal of the American Chemical Society, Vol. 134, Issue 27, p. 11235-11242
Unexpected Solvent Effect in Electrocatalytic CO 2 to CO Conversion Revealed Using Asymmetric Metalloporphyrins
journal, September 2018
- Sinha, Soumalya; Warren, Jeffrey J.
- Inorganic Chemistry, Vol. 57, Issue 20
Unexpected Effect of Intramolecular Phenolic Group on Electrocatalytic CO 2 Reduction
journal, March 2020
- Guo, Kai; Li, Xialiang; Lei, Haitao
- ChemCatChem, Vol. 12, Issue 6
Role of 2 nd sphere H-bonding residues in tuning the kinetics of CO 2 reduction to CO by iron porphyrin complexes
journal, January 2019
- Sen, Pritha; Mondal, Biswajit; Saha, Dibyajyoti
- Dalton Transactions, Vol. 48, Issue 18
Through‐Space Electrostatic Interactions Surpass Classical Through‐Bond Electronic Effects in Enhancing CO 2 Reduction Performance of Iron Porphyrins
journal, January 2021
- Khadhraoui, Asma; Gotico, Philipp; Leibl, Winfried
- ChemSusChem, Vol. 14, Issue 5
A Thiourea Tether in the Second Coordination Sphere as a Binding Site for CO 2 and a Proton Donor Promotes the Electrochemical Reduction of CO 2 to CO Catalyzed by a Rhenium Bipyridine-Type Complex
journal, September 2018
- Haviv, Eynat; Azaiza-Dabbah, Dima; Carmieli, Raanan
- Journal of the American Chemical Society, Vol. 140, Issue 39
Visible-light-driven methane formation from CO2 with a molecular iron catalyst
journal, July 2017
- Rao, Heng; Schmidt, Luciana C.; Bonin, Julien
- Nature, Vol. 548, Issue 7665
Dissection of Light‐Induced Charge Accumulation at a Highly Active Iron Porphyrin: Insights in the Photocatalytic CO 2 Reduction
journal, February 2022
- Pugliese, Eva; Gotico, Philipp; Wehrung, Iris
- Angewandte Chemie International Edition, Vol. 61, Issue 14
Quick and Easy Method to Dramatically Improve the Electrochemical CO 2 Reduction Activity of an Iron Porphyrin Complex
journal, August 2021
- Kosugi, Kento; Kondo, Mio; Masaoka, Shigeyuki
- Angewandte Chemie, Vol. 133, Issue 40
Atropisomeric Hydrogen Bonding Control for CO 2 Binding and Enhancement of Electrocatalytic Reduction at Iron Porphyrins
journal, October 2020
- Gotico, Philipp; Roupnel, Loïc; Guillot, Regis
- Angewandte Chemie, Vol. 132, Issue 50
Progress and Perspectives of Electrochemical CO 2 Reduction on Copper in Aqueous Electrolyte
journal, April 2019
- Nitopi, Stephanie; Bertheussen, Erlend; Scott, Soren B.
- Chemical Reviews, Vol. 119, Issue 12
Pendant Hydrogen-Bond Donors in Cobalt Catalysts Independently Enhance CO 2 Reduction
journal, February 2018
- Chapovetsky, Alon; Welborn, Matthew; Luna, John M.
- ACS Central Science, Vol. 4, Issue 3
Activating the Fe(I) State of Iron Porphyrinoid with Second-Sphere Proton Transfer Residues for Selective Reduction of CO 2 to HCOOH via Fe(III/II)–COOH Intermediate(s)
journal, August 2021
- Amanullah, Sk; Saha, Paramita; Dey, Abhishek
- Journal of the American Chemical Society, Vol. 143, Issue 34
Opportunities and Challenges in CO 2 Reduction by Gold- and Silver-Based Electrocatalysts: From Bulk Metals to Nanoparticles and Atomically Precise Nanoclusters
journal, January 2018
- Zhao, Shuo; Jin, Renxi; Jin, Rongchao
- ACS Energy Letters, Vol. 3, Issue 2
Double Hangman Iron Porphyrin and the Effect of Electrostatic Nonbonding Interactions on Carbon Dioxide Reduction
journal, February 2020
- Margarit, Charles G.; Asimow, Naomi G.; Gonzalez, Miguel I.
- The Journal of Physical Chemistry Letters, Vol. 11, Issue 5
Carbon Dioxide Reduction by Iron Hangman Porphyrins
journal, June 2018
- Margarit, Charles G.; Schnedermann, Christoph; Asimow, Naomi G.
- Organometallics, Vol. 38, Issue 6
Molecular catalysis of CO 2 reduction: recent advances and perspectives in electrochemical and light-driven processes with selected Fe, Ni and Co aza macrocyclic and polypyridine complexes
journal, January 2020
- Boutin, E.; Merakeb, L.; Ma, B.
- Chemical Society Reviews, Vol. 49, Issue 16
Selective and Efficient Photocatalytic CO 2 Reduction to CO Using Visible Light and an Iron-Based Homogeneous Catalyst
journal, November 2014
- Bonin, Julien; Robert, Marc; Routier, Mathilde
- Journal of the American Chemical Society, Vol. 136, Issue 48
Determining the Overpotential of Electrochemical Fuel Synthesis Mediated by Molecular Catalysts: Recommended Practices, Standard Reduction Potentials, and Challenges
journal, August 2021
- Stratakes, Bethany M.; Dempsey, Jillian L.; Miller, Alexander J. M.
- ChemElectroChem, Vol. 8, Issue 22
Hybrid Catalysts for Artificial Photosynthesis: Merging Approaches from Molecular, Materials, and Biological Catalysis
journal, March 2020
- Smith, Peter T.; Nichols, Eva M.; Cao, Zhi
- Accounts of Chemical Research, Vol. 53, Issue 3
Efficient and selective molecular catalyst for the CO 2 -to-CO electrochemical conversion in water
journal, May 2015
- Costentin, Cyrille; Robert, Marc; Savéant, Jean-Michel
- Proceedings of the National Academy of Sciences, Vol. 112, Issue 22
A Local Proton Source Enhances CO 2 Electroreduction to CO by a Molecular Fe Catalyst
journal, October 2012
- Costentin, Cyrille; Drouet, Samuel; Robert, Marc
- Science, Vol. 338, Issue 6103
Two Pathways for Electrocatalytic Oxidation of Hydrogen by a Nickel Bis(diphosphine) Complex with Pendant Amines in the Second Coordination Sphere
journal, June 2013
- Yang, Jenny Y.; Smith, Stuart E.; Liu, Tianbiao
- Journal of the American Chemical Society, Vol. 135, Issue 26
Templating Bicarbonate in the Second Coordination Sphere Enhances Electrochemical CO 2 Reduction Catalyzed by Iron Porphyrins
journal, June 2022
- Derrick, Jeffrey S.; Loipersberger, Matthias; Nistanaki, Sepand K.
- Journal of the American Chemical Society, Vol. 144, Issue 26
Homogeneously Catalyzed Electroreduction of Carbon Dioxide—Methods, Mechanisms, and Catalysts
journal, January 2018
- Francke, Robert; Schille, Benjamin; Roemelt, Michael
- Chemical Reviews, Vol. 118, Issue 9
Selectivity in Electrochemical CO 2 Reduction
journal, January 2022
- Saha, Paramita; Amanullah, Sk; Dey, Abhishek
- Accounts of Chemical Research, Vol. 55, Issue 2
Urea-Based Multipoint Hydrogen-Bond Donor Additive Promotes Electrochemical CO 2 Reduction Catalyzed by Nickel Cyclam
journal, July 2018
- Nichols, Eva M.; Chang, Christopher J.
- Organometallics, Vol. 38, Issue 6
Homogeneous Molecular Catalysis of Electrochemical Reactions: Manipulating Intrinsic and Operational Factors for Catalyst Improvement
journal, November 2018
- Costentin, Cyrille; Savéant, Jean-Michel
- Journal of the American Chemical Society, Vol. 140, Issue 48
Pendant Acid–Base Groups in Molecular Catalysts: H-Bond Promoters or Proton Relays? Mechanisms of the Conversion of CO 2 to CO by Electrogenerated Iron(0)Porphyrins Bearing Prepositioned Phenol Functionalities
journal, August 2014
- Costentin, Cyrille; Passard, Guillaume; Robert, Marc
- Journal of the American Chemical Society, Vol. 136, Issue 33
Switching Catalyst Selectivity via the Introduction of a Pendant Nitrophenyl Group
journal, January 2022
- Johnson, Eric M.; Liu, Jeffrey J.; Samuel, Adam D.
- Inorganic Chemistry, Vol. 61, Issue 3
Positional effects of second-sphere amide pendants on electrochemical CO 2 reduction catalyzed by iron porphyrins
journal, January 2018
- Nichols, Eva M.; Derrick, Jeffrey S.; Nistanaki, Sepand K.
- Chemical Science, Vol. 9, Issue 11
Electrocatalytic and homogeneous approaches to conversion of CO 2 to liquid fuels
journal, January 2009
- Benson, Eric E.; Kubiak, Clifford P.; Sathrum, Aaron J.
- Chem. Soc. Rev., Vol. 38, Issue 1
Synergistic Effects of Imidazolium-Functionalization on fac -Mn(CO) 3 Bipyridine Catalyst Platforms for Electrocatalytic Carbon Dioxide Reduction
journal, March 2019
- Sung, Siyoung; Li, Xiaohui; Wolf, Lucienna M.
- Journal of the American Chemical Society, Vol. 141, Issue 16
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
Electronically Modified Cobalt Aminopyridine Complexes Reveal an Orthogonal Axis for Catalytic Optimization for CO 2 Reduction
journal, August 2020
- Chapovetsky, Alon; Liu, Jeffrey J.; Welborn, Matthew
- Inorganic Chemistry, Vol. 59, Issue 18