Light-Driven Reduction of CO2 to CO in Water with a Cobalt Molecular Catalyst and an Organic Sensitizer: Difference between revisions
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{{ | {{DOI|doi=10.1021/acscatal.3c00036}} | ||
{{BaseTemplate}} | {{BaseTemplate}} | ||
== Catalyst == | === Abstract === | ||
<chemform smiles="C1C2C3C=CC=C4C5C=CC=C6C7C=CC=CN=7[Co+2](O)(O)(N=34)(N=56)N=2C=CC=1.Cl([O-])(=O)(=O)=O.Cl([O-])(=O)(=O)=O" inchi="1S/C20H14N4.2ClHO4.Co.2H2O/c1-3-13-21-15(7-1)17-9-5-11-19(23-17)20-12-6-10-18(24-20)16-8-2-4-14-22-16;2*2-1(3,4)5;;;/h1-14H;2*(H,2,3,4,5);;2*1H2/q;;;+2;;/p-2" inchikey="OZQYFMFOIFRRLI-UHFFFAOYSA-L" height="200px" width="300px" float="none"></chemform><chemform smiles="[Co+2]([Cl-])[Cl-]" inchi="1S/2ClH.Co/h2*1H;/q;;+2/p-2" inchikey="GVPFVAHMJGGAJG-UHFFFAOYSA-L" height=" | |||
==== Summary ==== | |||
A photochemical reduction of CO<sub>2</sub> to CO was shown using the cobalt complex {{#moleculelink:|link=OZQYFMFOIFRRLI-UHFFFAOYSA-L|image=false|width=300|height=200}} as a catalyst in combination with the organic, water soluble triazatriangulenium photosensitizer {{#moleculelink:|link=DORDHQADTWICIT-UHFFFAOYSA-N|image=false|width=300|height=200}}. Turnover numbers (TONs) up to 19000 and selectivity of 93% for CO were reached in acetonitrile with 20% of water. The experiments were conducted under visible-light irradiation (λ > 450 nm) using tertiary amines or BIH as sacrificial reductants (see section SEDs below). The photoreduction could also be shown in pure water. | |||
==== Advances and special progress ==== | |||
The photoreduction of CO<sub>2</sub> to CO could be shown in 100% water with a TON of 2600 and a selectivity of 94% without any noble metals or rare materials. | |||
==== Additional remarks ==== | |||
In initial experiments, CO and formate were first produced with a total TON >3700 upon irradiation in CO<sub>2</sub>-saturated CH<sub>3</sub>CN solution with visible light. The addition of water enhanced the catalysis and directed it toward CO production (19,000 TON, 93% selectivity). | |||
=== 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 cobalt complex as a catalyst. The catalytic system performs best (referring to the TON of CO production) in acetonitrile with 20% water using BIH and TEOA. | |||
==== Catalyst ==== | |||
<chemform smiles="C1C2C3C=CC=C4C5C=CC=C6C7C=CC=CN=7[Co+2](O)(O)(N=34)(N=56)N=2C=CC=1.Cl([O-])(=O)(=O)=O.Cl([O-])(=O)(=O)=O" inchi="1S/C20H14N4.2ClHO4.Co.2H2O/c1-3-13-21-15(7-1)17-9-5-11-19(23-17)20-12-6-10-18(24-20)16-8-2-4-14-22-16;2*2-1(3,4)5;;;/h1-14H;2*(H,2,3,4,5);;2*1H2/q;;;+2;;/p-2" inchikey="OZQYFMFOIFRRLI-UHFFFAOYSA-L" height="200px" width="300px" float="none"></chemform><chemform smiles="[Co+2]([Cl-])[Cl-]" inchi="1S/2ClH.Co/h2*1H;/q;;+2/p-2" inchikey="GVPFVAHMJGGAJG-UHFFFAOYSA-L" height="100px" width="150px" float="none"> | |||
-INDIGO-11172313372D | -INDIGO-11172313372D | ||
| Line 23: | Line 37: | ||
</chemform> | </chemform> | ||
== Photosensitizer == | ==== Photosensitizer ==== | ||
<chemform smiles="C12C3N(CCCC)C4C5[C+]1C1C(N(CCCC)C=5C=CC=4)=CC=CC=1N(CCCC)C=2C=CC=3.[P-](F)(F)(F)(F)(F)F" inchi="1S/C31H36N3.F6P/c1-4-7-19-32-22-13-10-15-24-28(22)31-29-23(32)14-11-16-25(29)34(21-9-6-3)27-18-12-17-26(30(27)31)33(24)20-8-5-2;1-7(2,3,4,5)6/h10-18H,4-9,19-21H2,1-3H3;/q+1;-1" inchikey="DORDHQADTWICIT-UHFFFAOYSA-N" height="200px" width="300px" float="none"> | <chemform smiles="C12C3N(CCCC)C4C5[C+]1C1C(N(CCCC)C=5C=CC=4)=CC=CC=1N(CCCC)C=2C=CC=3.[P-](F)(F)(F)(F)(F)F" inchi="1S/C31H36N3.F6P/c1-4-7-19-32-22-13-10-15-24-28(22)31-29-23(32)14-11-16-25(29)34(21-9-6-3)27-18-12-17-26(30(27)31)33(24)20-8-5-2;1-7(2,3,4,5)6/h10-18H,4-9,19-21H2,1-3H3;/q+1;-1" inchikey="DORDHQADTWICIT-UHFFFAOYSA-N" height="200px" width="300px" float="none"> | ||
-INDIGO-11172313202D | -INDIGO-11172313202D | ||
| Line 124: | Line 138: | ||
</chemform> | </chemform> | ||
== Investigations == | ==== Investigations ==== | ||
{{#experimentlist:|form=Photocatalytic_CO2_conversion_experiments|name=Visible-Light Driven CO2 Reduction with 1/TATA+/BIH + TEOA under Various Conditions|importFile=}} | {{#experimentlist:|form=Photocatalytic_CO2_conversion_experiments|name=Visible-Light Driven CO2 Reduction with 1/TATA+/BIH + TEOA under Various Conditions|importFile=}} | ||
{{#experimentlist:|form=Photocatalytic_CO2_conversion_experiments|name=Photocatalytic CO2 Reduction by 1 (2 μM) in CO2-Saturated Aqueous CH3CN Solutions|importFile=}} | {{#experimentlist:|form=Photocatalytic_CO2_conversion_experiments|name=Photocatalytic CO2 Reduction by 1 (2 μM) in CO2-Saturated Aqueous CH3CN Solutions|importFile=}} | ||
== Sacrificial electron donor == | ==== Sacrificial electron donor ==== | ||
In this study, the experiments were done with the sacrificial reductants TEOA ([[Molecule:100507|100507]]), BIH ([[Molecule:100508|100508]]), and TEA ([[Molecule:100505|100505]]). | |||
==== Additives ==== | |||
In this study, some experiments were conducted under argon atmosphere or with the addition of Hg. | |||
[[Category:Photocatalytic CO2 conversion to CO]][[Category:Publication]] | |||
Latest revision as of 10:04, 22 May 2024
Abstract[edit | edit source]
Summary[edit | edit source]
A photochemical reduction of CO2 to CO was shown using the cobalt complex [Co(qpy)(H2O)2][ClO4]2 as a catalyst in combination with the organic, water soluble triazatriangulenium photosensitizer 100797. Turnover numbers (TONs) up to 19000 and selectivity of 93% for CO were reached in acetonitrile with 20% of water. The experiments were conducted under visible-light irradiation (λ > 450 nm) using tertiary amines or BIH as sacrificial reductants (see section SEDs below). The photoreduction could also be shown in pure water.
Advances and special progress[edit | edit source]
The photoreduction of CO2 to CO could be shown in 100% water with a TON of 2600 and a selectivity of 94% without any noble metals or rare materials.
Additional remarks[edit | edit source]
In initial experiments, CO and formate were first produced with a total TON >3700 upon irradiation in CO2-saturated CH3CN solution with visible light. The addition of water enhanced the catalysis and directed it toward CO production (19,000 TON, 93% selectivity).
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 cobalt complex as a catalyst. The catalytic system performs best (referring to the TON of CO production) in acetonitrile with 20% water using BIH and TEOA.
Catalyst[edit | edit source]
Photosensitizer[edit | edit source]
Investigations[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 H2 | TON HCOOH | . | |
|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|
| 1. | 0.002 | 0.2 | 0.1 | 450 | 2332 | 106 | 1370 | ||||||||
| 2. | 0.2 | 0.1 | 450 | 0 | 0 | 0 | |||||||||
| 3. | 0.002 | 0.1 | 450 | 0 | 0 | 0 | |||||||||
| 4. | 0.002 | 0.2 | 450 | 950 | 86 | 316 | |||||||||
| 5. | 0.002 | 0.2 | 0.1 | 450 | 107 | 7 | 5 | ||||||||
| 6. | 0.002 | 0.2 | 0.1 | Argon atmosphere | 450 | 0 | 7 | 0 | |||||||
| 7. | 0.005 | 0.2 | 0.1 | 450 | 0 | 159 | 0 | ||||||||
| 8. | 0.002 | 0.2 | 0.1 | Hg (0.1 mL) | 450 | 1880 | 255 | 1973 |
Investigation-Name: Visible-Light Driven CO2 Reduction with 1/TATA+/BIH + TEOA under Various Conditions
| cat | cat conc [µM] | PS | PS conc [mM] | e-D | e-D conc [M] | . | . | solvent A | . | . | additives | λexc [nm] | TON CO | TON H2 | TON HCOOH | . | |
|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|
| 1. | 0.002 | 0.2 | 0.1 | 450 | 2332 | 106 | 1370 | ||||||||||
| 2. | 0.002 | 0.2 | 0.1 | 450 | 6228 | 304 | 2441 | ||||||||||
| 3. | 0.002 | 0.2 | 0.1 | 450 | 14691 | 283 | 1097 | ||||||||||
| 4. | 0.002 | 0.2 | 0.1 | 450 | 15822 | 220 | 1147 | ||||||||||
| 5. | 0.002 | 0.2 | 0.1 | 450 | 18989 | 227 | 1215 | ||||||||||
| 6. | 0.002 | 0.2 | 0.1 | Hg | 450 | 19646 | 226 | 415 | |||||||||
| 7. | 0.002 | 0.2 | 0.1 | 450 | 183 | 9 | 419 | ||||||||||
| 8. | 0.002 | 0.2 | 0.1 | 450 | 612 | 202 | 51 | ||||||||||
| 9. | 0.002 | 0.2 | 0.1 | 450 | 515 | 253 | 46 | ||||||||||
| 10. | 0.002 | 0.2 | 0.1 | 450 | 3171 | 498 | 179 | ||||||||||
| 11. | 0.002 | 0.2 | 0.1 | 450 | 6331 | 264 | 179 | ||||||||||
| 12. | 0.002 | 0.2 | 0.1 | Hg | 450 | 6286 | 304 | 97 |
Investigation-Name: Photocatalytic CO2 Reduction by 1 (2 μM) in CO2-Saturated Aqueous CH3CN Solutions
Sacrificial electron donor[edit | edit source]
In this study, the experiments were done with the sacrificial reductants TEOA (100507), BIH (100508), and TEA (100505).
Additives[edit | edit source]
In this study, some experiments were conducted under argon atmosphere or with the addition of Hg.
Investigations
- Photocatalytic CO2 Reduction by 1 (2 μM) in CO2-Saturated Aqueous CH3CN Solutions (Molecular process, Photocatalytic CO2 conversion experiments)
- BIH + TEOA under Various Conditions (Molecular process, Photocatalytic CO2 conversion experiments)
