An integrated Re(I) photocatalyst and sensitizer that activates the formation of formic acid from reduction of CO2: Difference between revisions
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{{ | {{DOI|doi=10.1039/c9cc03943k}} | ||
[[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 | A photochemical reduction of CO<sub>2</sub> to formic acid was shown using the rhenium catalyst and sensitizer {{#moleculelink:|link=SQEHJZNRDJMTCB-UHFFFAOYSA-M|image=false|width=300|height=200}} in combination with the supplemental photosensitizer {{#moleculelink:|link=KLDYQWXVZLHTKT-UHFFFAOYSA-N|image=false|width=300|height=200}}. Turnover numbers (TONs) up to 2750 for formic acid were reached in dimethylacetamide. The experiments were conducted under visible-light irradiation (λ = 405 nm) with TEOA (see section SEDs below) as sacrificial electron donor. | ||
====Advances and special progress==== | ====Advances and special progress==== | ||
A | A unprecedented rhenium complex was used as an integrated photosensitizer/catalyst to generate formic acid from CO<sub>2</sub>; other rhenium catalysts only allow for the formation of CO as the reduction product. | ||
====Additional remarks==== | ====Additional remarks==== | ||
The | The complex {{#moleculelink:|link=SQEHJZNRDJMTCB-UHFFFAOYSA-M|image=false|width=300|height=200}} can act both as a photocatalyst and sensitizer, but its performance is considerably enhanced by the addition of {{#moleculelink:|link=KLDYQWXVZLHTKT-UHFFFAOYSA-N|image=false|width=300|height=200}} as supplemental photosensitizer. The variation of the catalyst concentration also showed a drastic influence on the performance of the catalytic system. | ||
=== 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 a rhenium complex as a catalyst. The catalytic system performs best (referring to the TON of formic acid production) in dimethylacetamide. | ||
=== Catalyst=== | === Catalyst=== | ||
<chemform smiles="C1C=C2C3C=CC=CN=3[Re+]([C-]#[O+])([C-]#[O+])3(N4C=CC=CC=4C4N3=CC=CC=4)N2=CC=1.S(C(F)(F)F)([O-])(=O)=O" inchi="1S/2C10H8N2.CHF3O3S.2CO.Re/c2*1-3-7-11-9(5-1)10-6-2-4-8-12-10;2-1(3,4)8(5,6)7;2*1-2;/h2*1-8H;(H,5,6,7);;;/q;;;;;+1/p-1" inchikey="SQEHJZNRDJMTCB-UHFFFAOYSA-M" height="200px" width="300px" float="none"> | <chemform smiles="C1C=C2C3C=CC=CN=3[Re+]([C-]#[O+])([C-]#[O+])3(N4C=CC=CC=4C4N3=CC=CC=4)N2=CC=1.S(C(F)(F)F)([O-])(=O)=O" inchi="1S/2C10H8N2.CHF3O3S.2CO.Re/c2*1-3-7-11-9(5-1)10-6-2-4-8-12-10;2-1(3,4)8(5,6)7;2*1-2;/h2*1-8H;(H,5,6,7);;;/q;;;;;+1/p-1" inchikey="SQEHJZNRDJMTCB-UHFFFAOYSA-M" height="200px" width="300px" float="none"> | ||
| Line 104: | Line 108: | ||
M END | M END | ||
</chemform> | </chemform> | ||
===Photosensitizer=== | |||
<chemform smiles="" inchi="" inchikey="KLDYQWXVZLHTKT-UHFFFAOYSA-N" height="200px" width="300px" float="none"></chemform> | |||
===Investigations=== | |||
{{#experimentlist:|form=Photocatalytic_CO2_conversion_experiments|name=Solvent effect study between DMA DMF and acetonitrile|importFile=}} | |||
{{#experimentlist:|form=Photocatalytic_CO2_conversion_experiments|name=Time profile in DMF|importFile=}}{{#experimentlist: |form=Photocatalytic_CO2_conversion_experiments|name=Study on the concentration of catalyst}} | |||
{{#experimentlist:|form=Photocatalytic_CO2_conversion_experiments|name=Effect of proton donor|importFile=}} | |||
====Sacrificial electron donor==== | ====Sacrificial electron donor==== | ||
In this study, the experiments were done with the sacrificial electron donor TEOA ([[Molecule:100507|100507]]). | In this study, the experiments were done with the sacrificial electron donor TEOA ([[Molecule:100507|100507]]). | ||
====Additives==== | ====Additives==== | ||
In this study, | In this study, the experiments were done with the additives water ({{#moleculelink:|link=XLYOFNOQVPJJNP-UHFFFAOYSA-N|image=false|width=300|height=200}}) and phenol ({{#moleculelink:|link=ISWSIDIOOBJBQZ-UHFFFAOYSA-N|image=false|width=300|height=200}}).[[Category:Publication]] | ||
Latest revision as of 10:37, 11 April 2024
Abstract[edit | edit source]
Summary[edit | edit source]
A photochemical reduction of CO2 to formic acid was shown using the rhenium catalyst and sensitizer [Re(bpy)2(CO)2][OTf] in combination with the supplemental photosensitizer [Ru(bpy)3][PF6]. Turnover numbers (TONs) up to 2750 for formic acid were reached in dimethylacetamide. The experiments were conducted under visible-light irradiation (λ = 405 nm) with TEOA (see section SEDs below) as sacrificial electron donor.
Advances and special progress[edit | edit source]
A unprecedented rhenium complex was used as an integrated photosensitizer/catalyst to generate formic acid from CO2; other rhenium catalysts only allow for the formation of CO as the reduction product.
Additional remarks[edit | edit source]
The complex [Re(bpy)2(CO)2][OTf] can act both as a photocatalyst and sensitizer, but its performance is considerably enhanced by the addition of [Ru(bpy)3][PF6] as supplemental photosensitizer. The variation of the catalyst concentration also showed a drastic influence on the performance of the catalytic system.
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 a rhenium complex as a catalyst. The catalytic system performs best (referring to the TON of formic acid production) in dimethylacetamide.
Catalyst[edit | edit source]
Photosensitizer[edit | edit source]
Investigations[edit | edit source]
| cat | cat conc [µM] | PS | PS conc [mM] | e-D | solvent A | . | . | λexc [nm] | . | TON H2 | TON HCOOH | . | |
|---|---|---|---|---|---|---|---|---|---|---|---|---|---|
| 1. | 0.8 | 405 nm | 1.75 | 12.5 | |||||||||
| 2. | 0.8 | 405 nm | 2 | 15 | |||||||||
| 3. | 0.8 | 405 nm | 1.5 | 2.5 | |||||||||
| 4. | 0.8 | 405 nm | 10.3 | ||||||||||
| 5. | 0.8 | 0.8 | 405 nm | 1.5 | 52 | ||||||||
| 6. | 0.8 | 405 nm | 0.8 | 10.8 | |||||||||
| 7. | 0.8 | 0.8 | 405 nm | 2.8 | 66 | ||||||||
| 8. | 0.8 | 0.8 | 405 nm | ||||||||||
| 9. | 0.8 | 0.8 | 405 nm | 2.8 | 11.5 |
Investigation-Name: Solvent effect study between DMA DMF and acetonitrile
| cat | cat conc [µM] | PS | PS conc [mM] | e-D | solvent A | . | . | λexc [nm] | . | TON H2 | TON HCOOH | . | |
|---|---|---|---|---|---|---|---|---|---|---|---|---|---|
| 1. | 0.2 | 0.2 | 405 nm | 0 | 0 | ||||||||
| 2. | 0.2 | 0.2 | 405 nm | 1 | 12.5 | ||||||||
| 3. | 0.2 | 0.2 | 405 nm | 2.5 | 19.5 | ||||||||
| 4. | 0.2 | 0.2 | 405 nm | 4.5 | 50.5 | ||||||||
| 5. | 0.2 | 0.2 | 405 nm | 6 | 59.5 | ||||||||
| 6. | 0.2 | 0.2 | 405 nm | 8.5 | 69.25 |
Investigation-Name: Time profile in DMF
| cat | cat conc [µM] | PS | PS conc [mM] | e-D | solvent A | . | . | λexc [nm] | . | TON H2 | TON HCOOH | . | . | . | . | |
|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|
| 1. | 1 | 405 | 10.3 | |||||||||||||
| 2. | 1 | 1 | 405 | 1.5 | 52 | |||||||||||
| 3. | 0.5 | 1 | 405 | 15 | 115 | |||||||||||
| 4. | 0.2 | 1 | 405 | 24 | 275 | |||||||||||
| 5. | 0.1 | 1 | 405 | 38 | 428 | |||||||||||
| 6. | 0.05 | 1 | 405 | 50 | 535 | |||||||||||
| 7. | 0.02 | 1 | 405 | 225 | 1480 | |||||||||||
| 8. | 0.01 | 1 | 405 | 375 | 2750 |
Investigation-Name: Study on the concentration of catalyst
| cat | PS | e-D | solvent A | . | . | additives | λexc [nm] | . | TON H2 | TON HCOOH | . | |
|---|---|---|---|---|---|---|---|---|---|---|---|---|
| 1. | water | 405 nm | 4.25 | 25 | ||||||||
| 2. | water | 405 nm | 5.75 | 25.75 | ||||||||
| 3. | phenol | 405 nm | 5.25 | 27 | ||||||||
| 4. | phenol | 405 nm | 5.75 | 19 | ||||||||
| 5. | water | 405 nm | 2 | 12.5 | ||||||||
| 6. | water | 405 nm | 2.75 | 14.5 | ||||||||
| 7. | phenol | 405 nm | 1 | 10.25 | ||||||||
| 8. | phenol | 405 nm | 16.25 | 11.25 | ||||||||
| 9. | water | 405 nm | 3.25 | 20.5 | ||||||||
| 10. | water | 405 nm | 3.5 | 24 | ||||||||
| 11. | phenol | 405 nm | 7.75 | 30 | ||||||||
| 12. | phenol | 405 nm | 9 | 34.75 |
Investigation-Name: Effect of proton donor
Sacrificial electron donor[edit | edit source]
In this study, the experiments were done with the sacrificial electron donor TEOA (100507).
Additives[edit | edit source]
In this study, the experiments were done with the additives water (H2O) and phenol (PhOH).
Investigations
- Effect of proton donor (Molecular process, Photocatalytic CO2 conversion experiments)
- Solvent effect study between DMA DMF and acetonitrile (Molecular process, Photocatalytic CO2 conversion experiments)
- Study on the concentration of catalyst (Molecular process, Photocatalytic CO2 conversion experiments)
- Time profile in DMF (Molecular process, Photocatalytic CO2 conversion experiments)
