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Research Article Open access CC BY 4.0

Hydrogen-Bonding Secondary Coordination Sphere Effect on CO2 Reduction

Anamarija Briš, Davor Margetić

Organics · pp. 277–288 · Published 5 Jun 2023

10.3390/org4020022

Abstract

Great efforts of the scientific community are focused on the development of catalysts for the reduction of carbon dioxide (CO2) to useful molecules such as carbon monoxide, formic acid, methanol, ethanol, methane, ethylene, or acetate. Various metal porphyrin complexes were synthesized and studied to develop highly active and selective catalysts. While the substituents on the porphyrin core (the primary coordination sphere) determine the reactivity of the metal, the introduction of the secondary coordination is important for the binding and activation of CO2. In this review, selected examples of iron porphyrin catalysts with a secondary coordination sphere capable of stabilizing intermediates of the CO2 reduction process by hydrogen bonding are presented.

Coordination sphere Porphyrin Catalysis Carbon monoxide Chemistry Formic acid Methanol Coordination complex

References (33)

  1. 1 Carbon Dioxide (2023, March 06). National Oceanic and Atmospheric Administration, Available online: https://climate.nasa.gov/.
  2. 2 Kinzel, 2021, Transition Metal Complexes as Catalysts for the Electroconversion of CO2: An Organometallic Perspective [DOI]
  3. 3 Pappijn, 2020, Challenges and Opportunities of Carbon Capture and Utilization: Electrochemical Conversion of CO2 to Ethylene [DOI]
  4. 4 Francke, 2018, Homogeneously Catalyzed Electroreduction of Carbon Dioxide−Methods, Mechanisms, and Catalysts [DOI]
  5. 5 Li, 2021, How to Go Beyond C1 Products with Electrochemical Reduction of CO2 [DOI]
  6. 6 Zhang, 2017, Energy-Related Small Molecule Activation Reactions: Oxygen Reduction and Hydrogen and Oxygen Evolution Reactions Catalyzed by Porphyrin- and Corrole-Based Systems [DOI]
  7. 7 Amanullah, 2022, Recent Developments in the Synthesis of Bio-Inspired Iron Porphyrins for Small Molecule Activation [DOI]
  8. 8 Dorniak, 2021, Recent Progress in (Photo-)-Electrochemical Conversion of CO2 With Metal Porphyrinoid-Systems [DOI]
  9. 9 Bhugun, 1996, Catalysis of the Electrochemical Reduction of Carbon Dioxide by Iron(0) Porphyrins. Synergistic Effect of Lewis Acid Cations [DOI]
  10. 10 Lei, 2022, Electrocatalytic CO2 Reduction: From Discrete Molecular Catalysts to Their Integrated Catalytic Materials [DOI]
  11. 11 Amanullah, 2021, Biochemical and Artificial Pathways for the Reduction of Carbon Dioxide, Nitrite and the Competing Proton Reduction: Effect of 2nd Sphere Interactions in Catalysis [DOI]
  12. 12 Gotico, 2021, Shaping the Electrocatalytic Performance of Metal Complexes for CO2 Reduction [DOI]
  13. 13 Nichols, 2019, Secondary-Sphere Effects in Molecular Electrocatalytic CO2 Reduction [DOI]
  14. 14 Costentin, 2012, A Local Proton Source Enhances CO2 Electroreduction to CO by a Molecular Fe Catalyst [DOI]
  15. 15 Azcarate, 2016, Dissection of Electronic Substituent Effects in Multielectron−Multistep Molecular Catalysis. Electrochemical CO2-to-CO Conversion Catalyzed by Iron Porphyrins [DOI]
  16. 16 Azcarate, 2016, Through-Space Charge Interaction Substituent Effects in Molecular Catalysis Leading to the Design of the Most Efficient Catalyst of CO2-to-CO Electrochemical Conversion [DOI]
  17. 17 Hammouche, 1988, Catalysis of the Electrochemical Reduction of Carbon Dioxide by Iron(“0”) Porphyrins [DOI]
  18. 18 Mondal, 2015, Intermediates Involved in the 2e−/2H+ Reduction of CO2 to CO by Iron(0) Porphyrin [DOI]
  19. 19 Nichols, 2018, Positional Effects of Second-Sphere Amide Pendants on Electrochemical CO2 Reduction Catalyzed by Iron Porphyrins [DOI]
  20. 20 Margarit, 2019, Carbon Dioxide Reduction by Iron Hangman Porphyrins [DOI]
  21. 21 Guo, 2020, Unexpected Effect of Intramolecular Phenolic Group on Electrocatalytic CO2 Reduction [DOI]
  22. 22 Guo, 2022, Iron Porphyrin with Appended Guanidyl Group for Significantly Improved Electrocatalytic Carbon Dioxide Reduction Activity and Selectivity in Aqueous Solutions [DOI]
  23. 23 Sen, 2019, Role of 2nd Sphere H-bonding Residues in Tuning the Kinetics of CO2 Reduction to CO by Iron Porphyrin Complexes [DOI]
  24. 24 Gotico, 2019, Second-Sphere Biomimetic Multipoint Hydrogen-Bonding Patterns to Boost CO2 Reduction of Iron Porphyrins [DOI]
  25. 25 Gotico, 2020, Atropisomeric Hydrogen Bonding Control for CO2 Binding and Enhancement of Electrocatalytic Reduction at Iron Porphyrins [DOI]
  26. 26 Derrick, 2022, Templating Bicarbonate in the Second Coordination Sphere Enhances Electrochemical CO2 Reduction Catalyzed by Iron Porphyrins [DOI]
  27. 27 Liu, 2020, Construction of Secondary Coordination Sphere Boosts Electrochemical CO2 Reduction of Iron Porphyrins [DOI]
  28. 28 Amanullah, 2021, Activating the Fe(I) State of Iron Porphyrinoid with Second-Sphere Proton Transfer Residues for Selective Reduction of CO2 to HCOOH via Fe(III/II)−COOH Intermediate(s) [DOI]
  29. 29 Guo, 2022, Role-Specialized Division of Labor in CO2 Reduction with Doubly-Functionalized Iron Porphyrin Atropisomers [DOI]
  30. 30 Ramuglia, 2021, An Iron Porphyrin Complex with Pendant Pyridine Substituents Facilitates Electrocatalytic CO2 Reduction via Second Coordination Sphere Effects [DOI]
  31. 31 Narouz, 2022, Multifunctional Charge and Hydrogen-Bond Effects of Second- Sphere Imidazolium Pendants Promote Capture and Electrochemical Reduction of CO2 in Water Catalyzed by Iron Porphyrins [DOI]
  32. 32 Costentin, 2013, Catalysis of the Electrochemical Reduction of Carbon Dioxide [DOI]
  33. 33 Gotico, 2020, Recent Advances in Metalloporphyrin-Based Catalyst Design Towards Carbon Dioxide Reduction: From Bio-Inspired Second Coordination Sphere Modifications to Hierarchical Architectures [DOI]

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