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 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 {{#moleculelink:|link= | 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 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 {{#moleculelink: |link=NIRWJCRVFQKYDZ-UHFFFAOYSA-L|image=false|width=300|height=200}} and cobalt complexes{{#moleculelink:|link=GEWRDVXFGQMHJL-UHFFFAOYSA-N|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=GEWRDVXFGQMHJL-UHFFFAOYSA-N|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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===Catalysts tested in this study=== | ===Catalysts tested in this study=== | ||
<chemform smiles="C1C=C2C3C=CC=C4C5C=CC=C6C7(C8C=CC=CN=8[Fe+2](N#CC)(N8C7=CC=CC=8)(N=56)(N=34)N2=CC=1)C" inchi="1S/C27H21N5.C2H3N.Fe/c1-27(24-14-3-6-18-29-24,25-15-4-7-19-30-25)26-16-9-13-23(32-26)22-12-8-11-21(31-22)20-10-2-5-17-28-20;1-2-3;/h2-19H,1H3;1H3;/q;;+2 | <chemform smiles="C1C=C2C3C=CC=C4C5C=CC=C6C7(C8C=CC=CN=8[Fe+2](N#CC)(N8C7=CC=CC=8)(N=56)(N=34)N2=CC=1)C.FC(S([O-])(=O)=O)(F)F.FC(S([O-])(=O)=O)(F)F" inchikey="NIRWJCRVFQKYDZ-UHFFFAOYSA-L" inchi="1S/C27H21N5.C2H3N.2CHF3O3S.Fe/c1-27(24-14-3-6-18-29-24,25-15-4-7-19-30-25)26-16-9-13-23(32-26)22-12-8-11-21(31-22)20-10-2-5-17-28-20;1-2-3;2*2-1(3,4)8(5,6)7;/h2-19H,1H3;1H3;2*(H,5,6,7);/q;;;;+2/p-2" float="none" width="200" height="200"> | ||
-INDIGO- | -INDIGO-01102515192D | ||
0 0 0 0 0 0 0 0 0 0 0 V3000 | 0 0 0 0 0 0 0 0 0 0 0 V3000 | ||
M V30 BEGIN CTAB | M V30 BEGIN CTAB | ||
M V30 COUNTS | M V30 COUNTS 52 58 0 0 0 | ||
M V30 BEGIN ATOM | M V30 BEGIN ATOM | ||
M V30 1 C -3.23952 -0.911479 0.0 0 | M V30 1 C -3.23952 -0.911479 0.0 0 | ||
| Line 58: | Line 58: | ||
M V30 35 C -0.188361 2.88423 0.0 0 | M V30 35 C -0.188361 2.88423 0.0 0 | ||
M V30 36 C -0.771725 3.46759 0.0 0 | M V30 36 C -0.771725 3.46759 0.0 0 | ||
M V30 37 F 4.59199 1.175 0.0 0 | |||
M V30 38 C 5.45801 1.675 0.0 0 | |||
M V30 39 F 5.45801 2.675 0.0 0 | |||
M V30 40 F 4.95801 0.808975 0.0 0 | |||
M V30 41 S 6.32404 1.175 0.0 0 | |||
M V30 42 O 7.03115 1.88211 0.0 0 | |||
M V30 43 O 7.32404 1.175 0.0 0 | |||
M V30 44 O 6.32404 0.175 0.0 0 CHG=-1 | |||
M V30 45 F 4.15897 -1.425 0.0 0 | |||
M V30 46 C 5.025 -0.925 0.0 0 | |||
M V30 47 F 5.025 0.075 0.0 0 | |||
M V30 48 F 4.525 -1.79103 0.0 0 | |||
M V30 49 S 5.89103 -1.425 0.0 0 | |||
M V30 50 O 6.59813 -0.717893 0.0 0 | |||
M V30 51 O 6.89103 -1.425 0.0 0 | |||
M V30 52 O 5.89103 -2.425 0.0 0 CHG=-1 | |||
M V30 END ATOM | M V30 END ATOM | ||
M V30 BEGIN BOND | M V30 BEGIN BOND | ||
| Line 104: | Line 120: | ||
M V30 43 1 35 36 | M V30 43 1 35 36 | ||
M V30 44 10 34 19 | M V30 44 10 34 19 | ||
M V30 45 1 37 38 | |||
M V30 46 1 38 39 | |||
M V30 47 1 38 40 | |||
M V30 48 1 38 41 | |||
M V30 49 2 41 42 | |||
M V30 50 2 41 43 | |||
M V30 51 1 41 44 | |||
M V30 52 1 45 46 | |||
M V30 53 1 46 47 | |||
M V30 54 1 46 48 | |||
M V30 55 1 46 49 | |||
M V30 56 2 49 50 | |||
M V30 57 2 49 51 | |||
M V30 58 1 49 52 | |||
M V30 END BOND | M V30 END BOND | ||
M V30 END CTAB | M V30 END CTAB | ||
Revision as of 15:19, 10 January 2025
Abstract
Summary
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 complexesMolecule with key GEWRDVXFGQMHJL-UHFFFAOYSA-N does not exist., 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 Molecule with key GEWRDVXFGQMHJL-UHFFFAOYSA-N does not exist. 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
Additional remarks
Content of the published article in detail
Catalysts tested in this study
Photosensitizer
Ru(bpy)3
3,6-Diamino-10-methylacridinium
100971
Ir(ppy)3
Investigation
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 CH3CN, 2 μM of the catalyst, 200 μM of the photosensitizer, 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 stirplate 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
The results for the catalytic activity of the Co2+ compound Molecule with key GEWRDVXFGQMHJL-UHFFFAOYSA-N does not exist. in Table 2 were gained from the Supporting Information.
Sacrificial electron donor
In this study, the experiments were done with the sacrificial electron donor BIH (100508).
Additives
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)
