Mn-carbonyl molecular catalysts containing a redox-active phenanthroline-5,6-dione for selective electro- and photoreduction of CO2 to CO or HCOOH: Difference between revisions
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{{ | {{DOI|doi=10.1016/j.electacta.2017.04.080 }} | ||
[[Category:Photocatalytic CO2 conversion to HCOOH]] | [[Category:Photocatalytic CO2 conversion to HCOOH]] | ||
{{BaseTemplate}} | {{BaseTemplate}} | ||
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===Abstract=== | ===Abstract=== | ||
==== Summary==== | ==== Summary==== | ||
A photochemical reduction of CO<sub>2</sub> to CO was shown using the manganese complexes as catalyst in combination with the ruthenium-based photosensitizer {{#moleculelink:|link=SJFYGUKHUNLZTK-UHFFFAOYSA-L|image=false|width=300|height=200}}. Turnover numbers (TONs) | A photochemical reduction of CO<sub>2</sub> to CO or formic acid was shown using the manganese complexes {{#moleculelink:|link=KOYXLRUHHLMCRS-UHFFFAOYSA-M|image=false|width=300|height=200}} or {{#moleculelink:|link=JWEFEWAAUDGGIH-UHFFFAOYSA-N|image=false|width=300|height=200}} as catalyst in combination with the ruthenium-based photosensitizer {{#moleculelink:|link=SJFYGUKHUNLZTK-UHFFFAOYSA-L|image=false|width=300|height=200}}, comparing the results to the previously reported catalysts {{#moleculelink:|link=PGQIIBGFONEXSA-UHFFFAOYSA-M|image=false|width=300|height=200}} and {{#moleculelink:|link=ZUZWBGQHMPVNDY-UHFFFAOYSA-M|image=false|width=300|height=200}}. Turnover numbers (TONs) of 58 for formic acid were reached in acetonitrile with complex {{#moleculelink:|link=JWEFEWAAUDGGIH-UHFFFAOYSA-N|image=false|width=300|height=200}}. The experiments were conducted under visible-light irradiation (λ = 480 or 500 nm) using TEOA and BNAH as sacrificial electron donors (see section SEDs below). | ||
====Advances and special progress==== | ====Advances and special progress==== | ||
The efficiency of formic acid generation from CO<sub>2</sub> was improved compared to a previously reported manganese complex. The increased water solubility of one of the novel complexes may enable photo- or electrocatalytic CO<sub>2</sub> reduction in aqueous media. | |||
====Additional remarks==== | ====Additional remarks==== | ||
In electrochemical CO<sub>2</sub> reduction experiments, a high selectivity for CO formation was observed, contrary to the preferential formation of formic acid in the photocatalytic CO<sub>2</sub> reduction. | |||
===Content of the published article in detail=== | ===Content of the published article in detail=== | ||
The article contains results for the reduction of CO<sub>2</sub> to | The article contains results for the reduction of CO<sub>2</sub> to formic acid under visible-light catalysis using manganese complexes as catalysts. The catalytic system performs best (referring to the TON of formic acid production) in acetonitrile using catalyst {{#moleculelink:|link=JWEFEWAAUDGGIH-UHFFFAOYSA-N|image=false|width=300|height=200}}. | ||
==== Catalyst==== | ==== Catalyst==== | ||
<chemform smiles="C1C=CN2[Mn+]([Br-])([C-]#[O+])([C-]#[O+])([C-]#[O+])N3=CC=CC4C(=O)C(=O)C=1C=2C=43" inchikey="KOYXLRUHHLMCRS-UHFFFAOYSA-M" inchi="1S/C12H6N2O2.3CO.BrH.Mn/c15-11-7-3-1-5-13-9(7)10-8(12(11)16)4-2-6-14-10;3*1-2;;/h1-6H;;;;1H;/q;;;;;+1/p-1" float="none" width="200" height="200"> | <chemform smiles="C1C=CN2[Mn+]([Br-])([C-]#[O+])([C-]#[O+])([C-]#[O+])N3=CC=CC4C(=O)C(=O)C=1C=2C=43" inchikey="KOYXLRUHHLMCRS-UHFFFAOYSA-M" inchi="1S/C12H6N2O2.3CO.BrH.Mn/c15-11-7-3-1-5-13-9(7)10-8(12(11)16)4-2-6-14-10;3*1-2;;/h1-6H;;;;1H;/q;;;;;+1/p-1" float="none" width="200" height="200"> | ||
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In this study, the experiments were done with the sacrificial electron donors TEOA ([[Molecule:100507|100507]]) and BNAH ({{#moleculelink:|link=CMNUYDSETOTBDE-UHFFFAOYSA-N|image=false|width=300|height=200}}). | In this study, the experiments were done with the sacrificial electron donors TEOA ([[Molecule:100507|100507]]) and BNAH ({{#moleculelink:|link=CMNUYDSETOTBDE-UHFFFAOYSA-N|image=false|width=300|height=200}}). | ||
====Additives==== | ====Additives==== | ||
In this study, ascorbic acid was tested as an additive and control experiments under argon atmosphere were performed. | In this study, ascorbic acid was tested as an additive and control experiments under argon atmosphere were performed.[[Category:Publication]] | ||
Latest revision as of 13:48, 23 May 2024
Abstract[edit | edit source]
Summary[edit | edit source]
A photochemical reduction of CO2 to CO or formic acid was shown using the manganese complexes Mn(phdk)(CO)3Br or Mn(phdk)(CO)3(MeCN) as catalyst in combination with the ruthenium-based photosensitizer Ru(bpy)3Cl2, comparing the results to the previously reported catalysts Mn(phen)(CO)3Br and Mn(bpy)(CO)3Br. Turnover numbers (TONs) of 58 for formic acid were reached in acetonitrile with complex Mn(phdk)(CO)3(MeCN). The experiments were conducted under visible-light irradiation (λ = 480 or 500 nm) using TEOA and BNAH as sacrificial electron donors (see section SEDs below).
Advances and special progress[edit | edit source]
The efficiency of formic acid generation from CO2 was improved compared to a previously reported manganese complex. The increased water solubility of one of the novel complexes may enable photo- or electrocatalytic CO2 reduction in aqueous media.
Additional remarks[edit | edit source]
In electrochemical CO2 reduction experiments, a high selectivity for CO formation was observed, contrary to the preferential formation of formic acid in the photocatalytic CO2 reduction.
Content of the published article in detail[edit | edit source]
The article contains results for the reduction of CO2 to formic acid under visible-light catalysis using manganese complexes as catalysts. The catalytic system performs best (referring to the TON of formic acid production) in acetonitrile using catalyst Mn(phdk)(CO)3(MeCN).
Catalyst[edit | edit source]
Mn(phdk)(CO)3Br
Mn(phdk)(CO)3(MeCN)
Mn(phen)(CO)3Br
Mn(bpy)(CO)3Br
Photosensitizer[edit | edit source]
Investigation[edit | edit source]
| cat | cat conc [µM] | PS | PS conc [mM] | e-D | e-D conc [M] | solvent A | . | . | . | additives | λexc [nm] | . | TON CO | TON HCOOH | . | |
|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|
| 1. | 100 | 0.1 | 480 | 8 | 52 | |||||||||||
| 2. | 100 | 0.1 | 480 | 15 | 58 | |||||||||||
| 3. | 100 | 0.1 | 480 | 9 | 48 | |||||||||||
| 4. | 100 | 0.1 | 480 | 47 | 15 | |||||||||||
| 5. | 100 | 0.1 | 500 | 7 | 40 | |||||||||||
| 6. | 100 | 0.1 | 457 | 7 | 34 | |||||||||||
| 7. | 2 | 100 | 0.1 | 480 | 5 | 18 | ||||||||||
| 8. | 200 | 0.1 | 480 | 8 | 52 | |||||||||||
| 9. | 100 | 0.1 | 480 | |||||||||||||
| 10. | 100 | 0.1 | 500 | |||||||||||||
| 11. | 100 | 480 | 3 | |||||||||||||
| 12. | 0.1 | 500 | ||||||||||||||
| 13. | 100 | 0.1 | Argon gas | 480 | ||||||||||||
| 14. | 100 | 0.1 | 480 | |||||||||||||
| 15. | 100 | 0.1 | 480 | |||||||||||||
| 16. | 100 | 0.1 | 480 | 21 | 22 | |||||||||||
| 17. | 100 | 0.1 | 480 | 2 | ||||||||||||
| 18. | 100 | 480 | 9 | 13 | ||||||||||||
| 19. | 100 | 0.1 | 480 | 17 | 4 | |||||||||||
| 20. | 100 | 0.1 | 480 | 6 | 39 | |||||||||||
| 21. | 100 | ascorbic acid/NaA | 480 | |||||||||||||
| 22. | 100 | ascorbic acid/NaA | 500 |
Sacrificial electron donor[edit | edit source]
In this study, the experiments were done with the sacrificial electron donors TEOA (100507) and BNAH (BNAH).
Additives[edit | edit source]
In this study, ascorbic acid was tested as an additive and control experiments under argon atmosphere were performed.
Investigations
- Table 1 (Molecular process, Photocatalytic CO2 conversion experiments)
