Mn-carbonyl molecular catalysts containing a redox-active phenanthroline-5,6-dione for selective electro- and photoreduction of CO2 to CO or HCOOH
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Abstract
Summary
A photochemical reduction of CO2 to CO was shown using the manganese complexes as catalyst in combination with the ruthenium-based photosensitizer Ru(bpy)3Cl2 (100787). Turnover numbers (TONs) over xx and a selectivity of xx% for CO were reached in xx. The experiments were conducted under visible-light irradiation (λ = xx nm) using TEOA and BNAH as sacrificial electron donors (see section SEDs below).
Advances and special progress
Additional remarks
Content of the published article in detail
The article contains results for the reduction of CO2 to CO under visible-light catalysis using manganese complexes as catalysts. The catalytic system performs best (referring to the TON of CO production) in xx.
Catalyst
Mn(phdk)(CO)3Br (100691)
Mn(phdk)(CO)3(MeCN) (100693)
Mn(phen)(CO)3Br (100708)
Mn(bpy)(CO)3Br (100752)
Photosensitizer
Investigation
| cat | cat conc [µM] | PS | PS conc [mM] | e-D | e-D conc [M] | solvent A | . | . | . | additives | λexc [nm] | . | TON CO | TON HCOOH | . | . | ||
|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|
| (edit) | 1. | Mn(phdk)(CO)3Br | Ru(bpy)3Cl2 | 100 | BNAH | 0.1 | MeCN | 480 | 8 | 52 | ||||||||
| (edit) | 2. | Mn(phdk)(CO)3(MeCN) | Ru(bpy)3Cl2 | 100 | BNAH | 0.1 | MeCN | 480 | 15 | 58 | ||||||||
| (edit) | 3. | Mn(phdk)(CO)3(MeCN) | Ru(bpy)3Cl2 | 100 | BNAH | 0.1 | MeCN | 480 | 9 | 48 | ||||||||
| (edit) | 4. | Mn(bpy)(CO)3Br | Ru(bpy)3Cl2 | 100 | BNAH | 0.1 | MeCN | 480 | 47 | 15 | ||||||||
| (edit) | 5. | Mn(phdk)(CO)3(MeCN) | Ru(bpy)3Cl2 | 100 | BNAH | 0.1 | MeCN | 500 | 7 | 40 | ||||||||
| (edit) | 6. | Mn(phdk)(CO)3(MeCN) | Ru(bpy)3Cl2 | 100 | BNAH | 0.1 | MeCN | 457 | 7 | 34 | ||||||||
| (edit) | 7. | Mn(phdk)(CO)3(MeCN) | 2 | Ru(bpy)3Cl2 | 100 | BNAH | 0.1 | MeCN | 480 | 5 | 18 | |||||||
| (edit) | 8. | Mn(phdk)(CO)3(MeCN) | Ru(bpy)3Cl2 | 200 | BNAH | 0.1 | MeCN | 480 | 8 | 52 | ||||||||
| (edit) | 9. | Mn(phdk)(CO)3(MeCN) | Ru(bpy)3Cl2 | 100 | BNAH | 0.1 | MeCN | 480 | ||||||||||
| (edit) | 10. | Mn(phdk)(CO)3(MeCN) | Ru(bpy)3Cl2 | 100 | BNAH | 0.1 | MeCN | 500 | ||||||||||
| (edit) | 11. | Mn(phdk)(CO)3(MeCN) | Ru(bpy)3Cl2 | 100 | MeCN | 480 | 3 | |||||||||||
| (edit) | 12. | Mn(phdk)(CO)3(MeCN) | BNAH | 0.1 | MeCN | 500 | ||||||||||||
| (edit) | 13. | Mn(phdk)(CO)3Br | Ru(bpy)3Cl2 | 100 | BNAH | 0.1 | MeCN | Argon gas | 480 | |||||||||
| (edit) | 14. | Ru(bpy)3Cl2 | 100 | BNAH | 0.1 | MeCN | 480 | |||||||||||
| (edit) | 15. | Ru(bpy)3Cl2 | 100 | BNAH | 0.1 | MeCN | 480 | |||||||||||
| (edit) | 16. | Mn(phdk)(CO)3Br | Ru(bpy)3Cl2 | 100 | BNAH | 0.1 | DMF | 480 | 21 | 22 | ||||||||
| (edit) | 17. | Mn(phdk)(CO)3Br | Ru(bpy)3Cl2 | 100 | BNAH | 0.1 | DMF | 480 | 2 | |||||||||
| (edit) | 18. | Mn(phdk)(CO)3Br | Ru(bpy)3Cl2 | 100 | DMF | 480 | 9 | 13 | ||||||||||
| (edit) | 19. | Mn(phen)(CO)3Br | Ru(bpy)3Cl2 | 100 | BNAH | 0.1 | DMF | 480 | 17 | 4 | ||||||||
| (edit) | 20. | Mn(bpy)(CO)3Br | Ru(bpy)3Cl2 | 100 | BNAH | 0.1 | DMF | 480 | 6 | 39 | ||||||||
| (edit) | 21. | Mn(phdk)(CO)3(MeCN) | Ru(bpy)3Cl2 | 100 | H2O | ascorbic acid/NaA | 480 | |||||||||||
| (edit) | 22. | Mn(phdk)(CO)3(MeCN) | Ru(bpy)3Cl2 | 100 | H2O | ascorbic acid/NaA | 500 |
Investigation-Name: Table 1
Sacrificial electron donor
In this study, the experiments were done with the sacrificial electron donors TEOA (100507) and BNAH (BNAH (100509)).
Additives
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)
