Rhenium(I) trinuclear rings as highly efficient redox photosensitizers for photocatalytic CO2 reduction
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Abstract
Summary
A photochemical reduction of CO2 to CO or formic acid was shown using the bipyridine-based catalysts [Re(bpy)(CO)3(MeCN)][PF6], Ru(dtBubpy)(CO)2Cl2 or -missing link parameter-in combination with the ruthenium-based photosensitizer [Ru(dmb)3][PF6]2 or Ru(bpy)3. Turnover numbers (TONs) of up to 157 and selectivities up to 85% for formate were reached in DMF. The experiments were conducted under visible-light irradiation (λ = 480 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 or formic acid under visible-light catalysis using a manganese complex and a ruthenium-based photosensitizer. The catalytic system performs best (referring to the TON of formate production) in DMF.
Catalyst
[Re(bpy)(CO)3(MeCN)][PF6] Ru(dtBubpy)(CO)2Cl2
Photosensitizer
Investigation
cat | cat conc [µM] | PS | PS conc [mM] | solvent A | . | . | λexc [nm] | . | TON CO | . | . | . | |
---|---|---|---|---|---|---|---|---|---|---|---|---|---|
1. | 0.05 | 0.05 | 436 | 27 | |||||||||
2. | 0.05 | 0.05 | 436 | 98 | |||||||||
3. | 0.05 | 0.05 | 436 | 22 | |||||||||
4. | 0.05 | 0.05 | 436 | 71 | |||||||||
5. | 0.05 | 436 | 6 | ||||||||||
6. | 0.05 | 436 | 8 | ||||||||||
7. | 0.05 | 0.05 | 436 | 20 | |||||||||
8. | 0.05 | 0.05 | 436 | 32 | |||||||||
9. | 0.05 | 0.05 | 436 | 11 | |||||||||
10. | 0.05 | 0.05 | 436 | 48 |
cat | cat conc [µM] | PS | PS conc [mM] | e-D | e-D conc [M] | solvent A | . | . | λexc [nm] | . | TON CO | TON H2 | TON HCOOH | . | . | . | |
---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|
1. | 0.05 | 0.05 | 436 | 20 | 72 | 290 | |||||||||||
2. | 0.05 | 0.05 | 0.03 | 436 | 16 | 49 | 280 | ||||||||||
3. | 0.05 | 0.05 | 436 | 32 | 85 | ||||||||||||
4. | 0.05 | 0.05 | 0.03 | 436 | 80 | 60 |
Sacrificial Electron Donor
In this study, the experiments were done with the sacrificial electron donor TEOA (100507).
Additives
In this study, no additives were tested.