Exchange Coupling Determines Metal-Dependent Efficiency for Iron- and Cobalt-Catalyzed Photochemical CO2 Reduction: Difference between revisions
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====Summary ==== | ====Summary ==== | ||
A {{Annotation|property=Tag|value=photocatalytic CO2 reduction; voc4cat; voc4cat:0000099|display=photochemical reduction of CO2}} to {{Annotation|property=Tag|value=CO;;|display=CO}} was shown using an | A {{Annotation|property=Tag|value=photocatalytic CO2 reduction; voc4cat; voc4cat:0000099|display=photochemical reduction of CO2}} to {{Annotation|property=Tag|value=CO;;|display=CO}} was shown using an Fe<sup>2+</sup> and Co<sup>2+</sup> complex as catalysts in combination with different photosensitizers. The authors examined the efficiency for photocatalytic CO<sub>2</sub>RR pending on metal−ligand exchange coupling as an example of charge delocalization. The iron complex {{#moleculelink: |link=NIRWJCRVFQKYDZ-UHFFFAOYSA-L|image=false|width=300|height=200}} and cobalt complexes{{#moleculelink: |link=CSMKCVWSHRTJMD-UHFFFAOYSA-L|image=false|width=300|height=200}}, 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 {{#moleculelink: |link=CSMKCVWSHRTJMD-UHFFFAOYSA-L|image=false|width=300|height=200}} occurs at potentials 770 mV more negative than the Fe(tpyPY2Me)]2+ analogue{{#moleculelink: |link=NIRWJCRVFQKYDZ-UHFFFAOYSA-L|image=false|width=300|height=200}} due to maximizing the exchange coupling in the latter compound. | ||
====Advances and special progress==== | ====Advances and special progress==== | ||
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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 | 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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=== Further Information === | === Further Information === | ||
The results for the catalytic activity of the | The results for the catalytic activity of the Co<sup>2+</sup> compound {{#moleculelink: |link=CSMKCVWSHRTJMD-UHFFFAOYSA-L|image=false|width=300|height=200}} in Table 2 were gained from the Supporting Information. | ||
====Sacrificial electron donor==== | ====Sacrificial electron donor==== | ||
In this study, the experiments were done with the sacrificial electron donor BIH ([[Molecule:100508|100508]]). | In this study, the experiments were done with the sacrificial electron donor BIH ([[Molecule:100508|100508]]). | ||
====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}} | ||
Latest revision as of 16:51, 17 January 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 catalyst100968, 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 |
Investigation-Name: CO2 Reduction under diverse conditions with diverse sensitizers
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 |
Investigation-Name: Results Co2+ experiments taken from SI
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
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)
