Deciphering the Selectivity of the Electrochemical CO2 Reduction to CO by a Cobalt Porphyrin Catalyst in Neutral Aqueous Solution: Insights from DFT Calculations
Abstract Density functional theory (DFT) calculations were conducted to investigate the cobalt porphyrin‐catalyzed electro‐reduction of CO2 to CO in an aqueous solution. The results suggest that CoII−porphyrin (CoII−L) undertakes a ligand‐based reduction to generate the active species CoII−L⋅−, wher...
| Main Authors: | , , , , |
|---|---|
| Format: | Article |
| Language: | English |
| Published: |
Wiley-VCH
2023-02-01
|
| Series: | ChemistryOpen |
| Subjects: | |
| Online Access: | https://doi.org/10.1002/open.202200254 |
| _version_ | 1797896280412782592 |
|---|---|
| author | Yu‐Chen Cao Le‐Le Shi Dr. Man Li Prof. Dr. Bo You Prof. Dr. Rong‐Zhen Liao |
| author_facet | Yu‐Chen Cao Le‐Le Shi Dr. Man Li Prof. Dr. Bo You Prof. Dr. Rong‐Zhen Liao |
| author_sort | Yu‐Chen Cao |
| collection | DOAJ |
| description | Abstract Density functional theory (DFT) calculations were conducted to investigate the cobalt porphyrin‐catalyzed electro‐reduction of CO2 to CO in an aqueous solution. The results suggest that CoII−porphyrin (CoII−L) undertakes a ligand‐based reduction to generate the active species CoII−L⋅−, where the CoII center antiferromagnetically interacts with the ligand radical anion. CoII−L⋅− then performs a nucleophilic attack on CO2, followed by protonation and a reduction to give CoII−L−COOH. An intermolecular proton transfer leads to the heterolytic cleavage of the C−O bond, producing intermediate CoII−L−CO. Subsequently, CO is released from CoII−L−CO, and CoII−L is regenerated to catalyze the next cycle. The rate‐determining step of this CO2RR is the nucleophilic attack on CO2 by CoII−L⋅−, with a total barrier of 20.7 kcal mol−1. The competing hydrogen evolution reaction is associated with a higher total barrier. A computational investigation regarding the substituent effects of the catalyst indicates that the CoPor−R3 complex is likely to display the highest activity and selectivity as a molecular catalyst. |
| first_indexed | 2024-04-10T07:40:18Z |
| format | Article |
| id | doaj.art-af6c19801fd6497389e32adbe4d384de |
| institution | Directory Open Access Journal |
| issn | 2191-1363 |
| language | English |
| last_indexed | 2024-04-10T07:40:18Z |
| publishDate | 2023-02-01 |
| publisher | Wiley-VCH |
| record_format | Article |
| series | ChemistryOpen |
| spelling | doaj.art-af6c19801fd6497389e32adbe4d384de2023-02-23T11:56:36ZengWiley-VCHChemistryOpen2191-13632023-02-01122n/an/a10.1002/open.202200254Deciphering the Selectivity of the Electrochemical CO2 Reduction to CO by a Cobalt Porphyrin Catalyst in Neutral Aqueous Solution: Insights from DFT CalculationsYu‐Chen Cao0Le‐Le Shi1Dr. Man Li2Prof. Dr. Bo You3Prof. Dr. Rong‐Zhen Liao4Key Laboratory of Material Chemistry for Energy Conversion and Storage Ministry of Education Hubei Key Laboratory of Bioinorganic Chemistry and Materia Medica Hubei Key Laboratory of Materials Chemistry and Service Failure School of Chemistry and Chemical Engineering Huazhong University of Science and Technology Wuhan 430074 P. R. ChinaKey Laboratory of Material Chemistry for Energy Conversion and Storage Ministry of Education Hubei Key Laboratory of Bioinorganic Chemistry and Materia Medica Hubei Key Laboratory of Materials Chemistry and Service Failure School of Chemistry and Chemical Engineering Huazhong University of Science and Technology Wuhan 430074 P. R. ChinaKey Laboratory of Material Chemistry for Energy Conversion and Storage Ministry of Education Hubei Key Laboratory of Bioinorganic Chemistry and Materia Medica Hubei Key Laboratory of Materials Chemistry and Service Failure School of Chemistry and Chemical Engineering Huazhong University of Science and Technology Wuhan 430074 P. R. ChinaKey Laboratory of Material Chemistry for Energy Conversion and Storage Ministry of Education Hubei Key Laboratory of Bioinorganic Chemistry and Materia Medica Hubei Key Laboratory of Materials Chemistry and Service Failure School of Chemistry and Chemical Engineering Huazhong University of Science and Technology Wuhan 430074 P. R. ChinaKey Laboratory of Material Chemistry for Energy Conversion and Storage Ministry of Education Hubei Key Laboratory of Bioinorganic Chemistry and Materia Medica Hubei Key Laboratory of Materials Chemistry and Service Failure School of Chemistry and Chemical Engineering Huazhong University of Science and Technology Wuhan 430074 P. R. ChinaAbstract Density functional theory (DFT) calculations were conducted to investigate the cobalt porphyrin‐catalyzed electro‐reduction of CO2 to CO in an aqueous solution. The results suggest that CoII−porphyrin (CoII−L) undertakes a ligand‐based reduction to generate the active species CoII−L⋅−, where the CoII center antiferromagnetically interacts with the ligand radical anion. CoII−L⋅− then performs a nucleophilic attack on CO2, followed by protonation and a reduction to give CoII−L−COOH. An intermolecular proton transfer leads to the heterolytic cleavage of the C−O bond, producing intermediate CoII−L−CO. Subsequently, CO is released from CoII−L−CO, and CoII−L is regenerated to catalyze the next cycle. The rate‐determining step of this CO2RR is the nucleophilic attack on CO2 by CoII−L⋅−, with a total barrier of 20.7 kcal mol−1. The competing hydrogen evolution reaction is associated with a higher total barrier. A computational investigation regarding the substituent effects of the catalyst indicates that the CoPor−R3 complex is likely to display the highest activity and selectivity as a molecular catalyst.https://doi.org/10.1002/open.202200254CO2 reductioncobalt-porphyrindensity functional calculationsreaction mechanismsselectivity |
| spellingShingle | Yu‐Chen Cao Le‐Le Shi Dr. Man Li Prof. Dr. Bo You Prof. Dr. Rong‐Zhen Liao Deciphering the Selectivity of the Electrochemical CO2 Reduction to CO by a Cobalt Porphyrin Catalyst in Neutral Aqueous Solution: Insights from DFT Calculations ChemistryOpen CO2 reduction cobalt-porphyrin density functional calculations reaction mechanisms selectivity |
| title | Deciphering the Selectivity of the Electrochemical CO2 Reduction to CO by a Cobalt Porphyrin Catalyst in Neutral Aqueous Solution: Insights from DFT Calculations |
| title_full | Deciphering the Selectivity of the Electrochemical CO2 Reduction to CO by a Cobalt Porphyrin Catalyst in Neutral Aqueous Solution: Insights from DFT Calculations |
| title_fullStr | Deciphering the Selectivity of the Electrochemical CO2 Reduction to CO by a Cobalt Porphyrin Catalyst in Neutral Aqueous Solution: Insights from DFT Calculations |
| title_full_unstemmed | Deciphering the Selectivity of the Electrochemical CO2 Reduction to CO by a Cobalt Porphyrin Catalyst in Neutral Aqueous Solution: Insights from DFT Calculations |
| title_short | Deciphering the Selectivity of the Electrochemical CO2 Reduction to CO by a Cobalt Porphyrin Catalyst in Neutral Aqueous Solution: Insights from DFT Calculations |
| title_sort | deciphering the selectivity of the electrochemical co2 reduction to co by a cobalt porphyrin catalyst in neutral aqueous solution insights from dft calculations |
| topic | CO2 reduction cobalt-porphyrin density functional calculations reaction mechanisms selectivity |
| url | https://doi.org/10.1002/open.202200254 |
| work_keys_str_mv | AT yuchencao decipheringtheselectivityoftheelectrochemicalco2reductiontocobyacobaltporphyrincatalystinneutralaqueoussolutioninsightsfromdftcalculations AT leleshi decipheringtheselectivityoftheelectrochemicalco2reductiontocobyacobaltporphyrincatalystinneutralaqueoussolutioninsightsfromdftcalculations AT drmanli decipheringtheselectivityoftheelectrochemicalco2reductiontocobyacobaltporphyrincatalystinneutralaqueoussolutioninsightsfromdftcalculations AT profdrboyou decipheringtheselectivityoftheelectrochemicalco2reductiontocobyacobaltporphyrincatalystinneutralaqueoussolutioninsightsfromdftcalculations AT profdrrongzhenliao decipheringtheselectivityoftheelectrochemicalco2reductiontocobyacobaltporphyrincatalystinneutralaqueoussolutioninsightsfromdftcalculations |