New Photosensitizers Based on Heteroleptic Cu(I) Complexes and CO2 Photocatalytic Reduction with (Ni(II)(cyclam))Cl2: Difference between revisions
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===Abstract=== | ===Abstract=== | ||
====Summary==== | ====Summary==== | ||
A photochemical reduction of CO<sub>2</sub> was shown using the nickel catalyst {{#moleculelink:|link=IZFLGDSTXHVTSZ-UHFFFAOYSA-L|image=false|width=300|height=200}} and the copper-based photosensitizers {{#moleculelink:|link=OGUFRAGOGOMEFL-UHFFFAOYSA-P|image=false|width=300|height=200}}, {{#moleculelink:|link=XIYWTOURLVMHSU-UHFFFAOYSA-R|image=false|width=300|height=200}}, {{#moleculelink:|link=LMWHUTMATFLCSY-UHFFFAOYSA-R|image=false|width=300|height=200}} and{{#moleculelink:|link=WFPHYLSMKQIDJB-UHFFFAOYSA-R|image=false|width=300|height=200}}. Turnover numbers (TONs) of 8.1 for CO were reached in acetonitrile/TEOA for complex {{#moleculelink:|link=LMWHUTMATFLCSY-UHFFFAOYSA-R|image=false|width=300|height=200}} after 4 hours. Employing the other synthesized photosensitizers {{#moleculelink:|link=OGUFRAGOGOMEFL-UHFFFAOYSA-P|image=false|width=300|height=200}}, {{#moleculelink:|link=XIYWTOURLVMHSU-UHFFFAOYSA-R|image=false|width=300|height=200}} or {{#moleculelink:|link=WFPHYLSMKQIDJB-UHFFFAOYSA-R|image=false|width=300|height=200}}, TONs of 4.3 to 4.9 were obtained. The experiments were conducted under visible-light irradiation (λ = 420 nm) using BIH as sacrificial electron donor (see section SEDs below). | |||
====Advances and special progress==== | ====Advances and special progress==== | ||
The first example of Cu(I)-based photosensitizers used for photocatalytic CO<sub>2</sub> reduction in combination with {{#moleculelink:|link=IZFLGDSTXHVTSZ-UHFFFAOYSA-L|image=false|width=300|height=200}} was successfully reported, demonstrating the usability of a fully noble-metal free CO<sub>2</sub> reduction system. The TONs are consistent with previously reported results on noble-metal based photosensitizers. | |||
====Additional remarks==== | ====Additional remarks==== | ||
The developed heteroleptic photosensitizer complexes showed a high stability in acetonitrile and no ligand release or formation of the homoleptic complexes was detected in UV/Vis stability studies. | |||
===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 CO under visible-light catalysis using a nickel complex as catalyst and copper-based photosensitizers. The catalytic system performs best (referring to the TON of CO production) in acetonitrile/TEOA with photosensitizer {{#moleculelink:|link=LMWHUTMATFLCSY-UHFFFAOYSA-R|image=false|width=300|height=200}}. | |||
====Catalysts==== | ====Catalysts==== | ||
<chemform smiles="" inchi="" inchikey="IZFLGDSTXHVTSZ-UHFFFAOYSA-L" height="200px" width="300px" float="none"></chemform> | <chemform smiles="" inchi="" inchikey="IZFLGDSTXHVTSZ-UHFFFAOYSA-L" height="200px" width="300px" float="none"></chemform> | ||
| Line 1,040: | Line 1,048: | ||
In this study, the experiments were done with the sacrificial electron donor {{#moleculelink:|link=VDFIVJSRRJXMAU-UHFFFAOYSA-N|image=false|width=300|height=200}}. | In this study, the experiments were done with the sacrificial electron donor {{#moleculelink:|link=VDFIVJSRRJXMAU-UHFFFAOYSA-N|image=false|width=300|height=200}}. | ||
====Additives==== | ====Additives==== | ||
In this study, {{#moleculelink:|link= | In this study, {{#moleculelink:|link=GSEJCLTVZPLZKY-UHFFFAOYSA-N|image=false|width=300|height=200}} was used as a proton donor. For one experiment, {{#moleculelink:|link=GETQZCLCWQTVFV-UHFFFAOYSA-N|image=false|width=300|height=200}} was employed instead. The catalyst {{#moleculelink:|link=YZGSKMIIVMCEFE-UHFFFAOYSA-N|image=false|width=300|height=200}} was used for a control experiment.[[Category:Publication]] | ||
Latest revision as of 09:07, 16 April 2024
Abstract[edit | edit source]
Summary[edit | edit source]
A photochemical reduction of CO2 was shown using the nickel catalyst Ni(cyclam)Cl2 and the copper-based photosensitizers 100906, 100907, 100908 and100909. Turnover numbers (TONs) of 8.1 for CO were reached in acetonitrile/TEOA for complex 100908 after 4 hours. Employing the other synthesized photosensitizers 100906, 100907 or 100909, TONs of 4.3 to 4.9 were obtained. The experiments were conducted under visible-light irradiation (λ = 420 nm) using BIH as sacrificial electron donor (see section SEDs below).
Advances and special progress[edit | edit source]
The first example of Cu(I)-based photosensitizers used for photocatalytic CO2 reduction in combination with Ni(cyclam)Cl2 was successfully reported, demonstrating the usability of a fully noble-metal free CO2 reduction system. The TONs are consistent with previously reported results on noble-metal based photosensitizers.
Additional remarks[edit | edit source]
The developed heteroleptic photosensitizer complexes showed a high stability in acetonitrile and no ligand release or formation of the homoleptic complexes was detected in UV/Vis stability studies.
Content of the published article in detail[edit | edit source]
The article contains results for the reduction of CO2 to CO under visible-light catalysis using a nickel complex as catalyst and copper-based photosensitizers. The catalytic system performs best (referring to the TON of CO production) in acetonitrile/TEOA with photosensitizer 100908.
Catalysts[edit | edit source]
Photosensitizers[edit | edit source]
Investigations[edit | edit source]
| cat | cat conc [µM] | PS | PS conc [mM] | e-D | e-D conc [M] | solvent A | . | . | . | . | λexc [nm] | . | TON CO | . | |
|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|
| 1. | 0.1 | 1 | 0.02 | 420 nm (4 x 8 W) | 4.3 | ||||||||||
| 2. | 0.1 | 1 | 0.02 | 420 nm (4 x 8 W) | 4.9 | ||||||||||
| 3. | 0.1 | 1 | 0.02 | 420 nm (4 x 8 W) | 8.1 | ||||||||||
| 4. | 0.1 | 1 | 0.02 | 420 nm (4 x 8 W) | 4.6 | ||||||||||
| 5. | 0.1 | 1 | 0.01 | 420 nm (4 x 8 W) | 2.6 | ||||||||||
| 6. | 0.1 | 1 | 0.01 | 420 nm (4 x 8 W) | 3.5 | ||||||||||
| 7. | 0.1 | 1 | 0.01 | 420 nm (4 x 8 W) | 5.0 | ||||||||||
| 8. | 0.1 | 1 | 0.01 | 420 nm (4 x 8 W) | 1.8 | ||||||||||
| 9. | 0.1 | 1 | 0.01 | 420 nm (4 x 8 W) | 2.8 | ||||||||||
| 10. | 1 | 0.01 | 420 nm (4 x 8 W) | ||||||||||||
| 11. | 0.1 | 1 | 0.01 | 420 nm (4 x 8 W) | |||||||||||
| 12. | 0.1 | 1 | 420 nm (4 x 8 W) | ||||||||||||
| 13. | 0.1 | 1 | 0.01 | 420 nm (4 x 8 W) | |||||||||||
| 14. | 0.1 | 0.01 | 420 nm (4 x 8 W) | ||||||||||||
| 15. | 0.1 | 1 | 0.01 | dark | |||||||||||
| 16. | 0.1 | 1 | 0.01 | 420 nm (4 x 8 W) | |||||||||||
| 17. | 0.1 | 1 | 0.02 | 420 nm (4 x 8 W) | 7.3 | ||||||||||
| 18. | 0.1 | 1 | 0.02 | 420 nm (4 x 8 W) | 6.5 |
Investigation-Name: Photocatalytic CO2 reduction and control experiments
Sacrificial Electron Donor[edit | edit source]
In this study, the experiments were done with the sacrificial electron donor BIH.
Additives[edit | edit source]
In this study, TEOA was used as a proton donor. For one experiment, N(Me)3 was employed instead. The catalyst [Cu(ACN)4][BF4] was used for a control experiment.
Investigations
- Photocatalytic CO2 reduction and control experiments (Molecular process, Photocatalytic CO2 conversion experiments)
