Exchange Coupling Determines Metal-Dependent Efficiency for Iron- and Cobalt-Catalyzed Photochemical CO2 Reduction: Difference between revisions
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General details for the experimental setup: Conducted inside a 25 mL borosilicate culture tube with a stir bar, a rubber septum, and an aluminum crimped top. The reaction vessel contained 5 mL of {{#moleculelink:|link=WEVYAHXRMPXWCK-UHFFFAOYSA-N|image=false|width=300|height=200}}, 2 μM of the catalyst{{#moleculelink:|link=NIRWJCRVFQKYDZ-UHFFFAOYSA-L|image=false|width=300|height=200}}, 200 μM of the photosensitizer {{#moleculelink:|link=HNVRWFFXWFXICS-UHFFFAOYSA-N|image=false|width=300|height=200}}, 100 mM {{#moleculelink:|link=VDFIVJSRRJXMAU-UHFFFAOYSA-N|image=false|width=300|height=200}} (112 mg), and 1 M phenol (470 mg). The reaction tubes were sparged with CO<sub>2</sub> for 10 min, followed by injection of a gaseous internal standard (0.1 mL of C<sub>2</sub>H<sub>6</sub>). The reactions were placed on a stir plate 13 cm from two Kessil blue LED lamps (440 nm) for 15 or 30 min at a time and maintained at ambient temperature using a fan. Analysis of the headspace by Gas Chromatography (GC).{{#experimentlist:|form=Photocatalytic_CO2_conversion_experiments|name=CO2 Reduction under diverse conditions with diverse sensitizers|importFile=Exchange Coupling Determines Metal-Dependent Efficiency for Iron- and Cobalt-Catalyzed Photochemical CO2 Reduction_2.xlsx}} | General details for the experimental setup: Conducted inside a 25 mL borosilicate culture tube with a stir bar, a rubber septum, and an aluminum crimped top. The reaction vessel contained 5 mL of {{#moleculelink:|link=WEVYAHXRMPXWCK-UHFFFAOYSA-N|image=false|width=300|height=200}}, 2 μM of the catalyst {{#moleculelink:|link=NIRWJCRVFQKYDZ-UHFFFAOYSA-L|image=false|width=300|height=200}}, 200 μM of the photosensitizer {{#moleculelink:|link=HNVRWFFXWFXICS-UHFFFAOYSA-N|image=false|width=300|height=200}}, 100 mM {{#moleculelink:|link=VDFIVJSRRJXMAU-UHFFFAOYSA-N|image=false|width=300|height=200}} (112 mg), and 1 M phenol (470 mg). The reaction tubes were sparged with CO<sub>2</sub> for 10 min, followed by injection of a gaseous internal standard (0.1 mL of C<sub>2</sub>H<sub>6</sub>). The reactions were placed on a stir plate 13 cm from two Kessil blue LED lamps (440 nm) for 15 or 30 min at a time and maintained at ambient temperature using a fan. Analysis of the headspace by Gas Chromatography (GC).{{#experimentlist:|form=Photocatalytic_CO2_conversion_experiments|name=CO2 Reduction under diverse conditions with diverse sensitizers|importFile=Exchange Coupling Determines Metal-Dependent Efficiency for Iron- and Cobalt-Catalyzed Photochemical CO2 Reduction_2.xlsx}} | ||
The values in Table 2 include TOF numbers given in TON/min | The values in Table 2 include TOF numbers given in TON/min | ||
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====Additives==== | ====Additives==== | ||
Different sources of protons were used, e.g. {{#moleculelink:|link=ISWSIDIOOBJBQZ-UHFFFAOYSA-N|image=false|width=300|height=200}}, {{#moleculelink:|link=RHQDFWAXVIIEBN-UHFFFAOYSA-N|image=false|width=300|height=200}} and {{#moleculelink:|link=WXNZTHHGJRFXKQ-UHFFFAOYSA-N|image=false|width=300|height=200}} | Different sources of protons were used, e.g. {{#moleculelink:|link=ISWSIDIOOBJBQZ-UHFFFAOYSA-N|image=false|width=300|height=200}}, {{#moleculelink:|link=RHQDFWAXVIIEBN-UHFFFAOYSA-N|image=false|width=300|height=200}} and {{#moleculelink:|link=WXNZTHHGJRFXKQ-UHFFFAOYSA-N|image=false|width=300|height=200}} | ||
{{Tags|tags=photochemical CO2 reduction, photocatalysis, homogeneous catalysis, iron complex catalyst, cobalt complex catalyst, tpyPY2Me ligand, Ru(bpy)3 photosensitizer, acridinium photosensitizer, Ir(ppy)3 photosensitizer, BIH sacrificial electron donor, phenol proton source, MeCN solvent, blue LED irradiation, metal–ligand exchange coupling, charge delocalization, turnover number determination, gas chromatography analysis}} | |||
Latest revision as of 11:41, 21 November 2025
Abstract[edit | edit source]
Summary[edit | edit source]
A photochemical reduction of CO2 to CO was shown using an Fe2+ and Co2+ complex as catalysts in combination with different photosensitizers. The authors examined the efficiency for photocatalytic CO2RR pending on metal−ligand exchange coupling as an example of charge delocalization. The iron complex 100968 and cobalt complexes100969, both bearing the redox-active ligand tpyPY2Me were tested in comparison. It was found that the two-electron reduction of the Co(tpyPY2Me)]2+ catalyst 100969 occurs at potentials 770 mV more negative than the Fe(tpyPY2Me)]2+ analogue100968 due to maximizing the exchange coupling in the latter compound.
Advances and special progress[edit | edit source]
Additional remarks[edit | edit source]
Content of the published article in detail[edit | edit source]
Catalysts tested in this study[edit | edit source]
Photosensitizer[edit | edit source]
Ru(bpy)3
3,6-Diamino-10-methylacridinium
100971
Ir(ppy)3
Investigation[edit | edit source]
General details for the experimental setup: Conducted inside a 25 mL borosilicate culture tube with a stir bar, a rubber septum, and an aluminum crimped top. The reaction vessel contained 5 mL of MeCN, 2 μM of the catalyst 100968, 200 μM of the photosensitizer Ru(bpy)3, 100 mM BIH (112 mg), and 1 M phenol (470 mg). The reaction tubes were sparged with CO2 for 10 min, followed by injection of a gaseous internal standard (0.1 mL of C2H6). The reactions were placed on a stir plate 13 cm from two Kessil blue LED lamps (440 nm) for 15 or 30 min at a time and maintained at ambient temperature using a fan. Analysis of the headspace by Gas Chromatography (GC).
| cat | cat conc [µM] | PS | PS conc [mM] | e-D | e-D conc [M] | . | . | solvent A | additives | . | . | TON CO | TON H2 | . | . | |
|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|
| 1. | 2 | 0.2 | 0.1 | 15520 | 86 | |||||||||||
| 2. | 0.2 | 0.2 | 0.1 | 30349 | 1013 | |||||||||||
| 3. | 0.2 | 0.1 | 43 | 52 | ||||||||||||
| 4. | 2 | 0.1 | 112 | 0 | ||||||||||||
| 5. | 2 | 0.2 | 150 | 0 | ||||||||||||
| 6. | 2 | 0.2 | 0.1 | 6 | 0 | |||||||||||
| 7. | 2 | 0.2 | 0.1 | Ar | 0 | 222 | ||||||||||
| 8. | 2 | 0.2 | 0.1 | 12749 | 163 | |||||||||||
| 9. | 0.2 | 0.2 | 0.1 | 28712 | 6527 | |||||||||||
| 10. | 2 | 0.2 | 0.1 | 18502 | 141 | |||||||||||
| 11. | 2 | 0.2 | 0.1 | 6710 | 0 |
The values in Table 2 include TOF numbers given in TON/min
| cat | cat conc [µM] | PS | PS conc [mM] | e-D | e-D conc [M] | . | . | solvent A | . | . | . | . | . | . | |
|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|
| 1. | 2 | 0.2 | 0.1 | ||||||||||||
| 2. | 2 | 0.2 | 0.1 | ||||||||||||
| 3. | 2 | 0.2 | 0.05 | ||||||||||||
| 4. | 2 | 0.2 | 0.05 | ||||||||||||
| 5. | 2 | 0.2 | 0.05 | ||||||||||||
| 6. | 2 | 0.2 | 0.05 | ||||||||||||
| 7. | 2 | 0.2 | 0.05 | ||||||||||||
| 8. | 2 | 0.2 | 0.05 | ||||||||||||
| 9. | 2 | 0.2 | 0.05 |
Further Information[edit | edit source]
The results for the catalytic activity of the Co2+ compound 100969 in Table 2 were gained from the Supporting Information.
Sacrificial electron donor[edit | edit source]
In this study, the experiments were done with the sacrificial electron donor BIH (100508).
Additives[edit | edit source]
Different sources of protons were used, e.g. PhOH, TFE and 4-CHLOROPHENOL
Tags: photochemical CO2 reduction, photocatalysis, homogeneous catalysis, iron complex catalyst, cobalt complex catalyst, tpyPY2Me ligand, Ru(bpy)3 photosensitizer, acridinium photosensitizer, Ir(ppy)3 photosensitizer, BIH sacrificial electron donor, phenol proton source, MeCN solvent, blue LED irradiation, metal–ligand exchange coupling, charge delocalization, turnover number determination, gas chromatography analysis |
Investigations
- CO2 Reduction under diverse conditions with diverse sensitizers (Molecular process, Photocatalytic CO2 conversion experiments)
- Results Co2+ experiments taken from SI (Molecular process, Photocatalytic CO2 conversion experiments)
