Visible-Light-Driven Conversion of CO2 to CH4 with an Organic Sensitizer and an Iron Porphyrin Catalyst: Difference between revisions
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==== Advances and special progress ==== | ==== Advances and special progress ==== | ||
This article contains the first demonstration for the reduction of CO<sub>2</sub> to CH<sub>4</sub> (complete 8e''<sup>–</sup>''/8H<sup>+</sup> reduction) by a combination of an earth-abundant metal catalyst and an organic dye. So far, similar systems were shown to induce 2e<sup>–</sup>/2H<sup>+</sup> reduction of CO<sub>2</sub> to CO or formic acid. | |||
==== Additional remarks ==== | ==== Additional remarks ==== | ||
Methane was produced continuously (even after irradiation up to 4 days). The 8e''<sup>–</sup>''/8H<sup>+</sup> reduction efficiency strongly depends on the redox properties of the organic photosensitizer and acidity of the proton source. In additional experiments, CO was used as the gas resource. The system consisting of iron porphyrin catalyst {{#moleculelink:|link=LKNRTBVZMCBYCY-NGWNFTKISA-I|image=false|width=300|height=200}} in combination with the phenoxazine photosensitizer {{#moleculelink:|link=IGGSSEOAGCUGDJ-UHFFFAOYSA-N|image=false|width=300|height=200}} was able to produce CH<sub>4</sub> with a TON of 80 (85% selectivity, quantum yield: 0.47%). | Methane was produced continuously (even after irradiation up to 4 days). The 8e''<sup>–</sup>''/8H<sup>+</sup> reduction efficiency strongly depends on the redox properties of the organic photosensitizer and acidity of the proton source. In additional experiments, CO was used as the gas resource. The system consisting of iron porphyrin catalyst {{#moleculelink:|link=LKNRTBVZMCBYCY-NGWNFTKISA-I|image=false|width=300|height=200}} in combination with the phenoxazine photosensitizer {{#moleculelink:|link=IGGSSEOAGCUGDJ-UHFFFAOYSA-N|image=false|width=300|height=200}} was able to produce CH<sub>4</sub> with a TON of 80 (85% selectivity, quantum yield: 0.47%). | ||
=== Content of the published article in detail === | === Content of the published article in detail === | ||
The article contains results for the reduction of | The article contains results for the reduction of CO<sub>2</sub> and CO as feedstock gases. The catalytic system performs best (referring to the TON of CH<sub>4</sub> production) for CO as a feedstock. | ||
==== Catalysts ==== | ==== Catalysts ==== | ||
Latest revision as of 14:33, 16 August 2024
Abstract[edit | edit source]
Summary[edit | edit source]
A photochemical reduction of CO2 to CO and CH4 was shown using the iron porphyrin catalyst Fe(pTMAPP)Cl5 in combination with the phenoxazine photosensitizers 5,10-Di(2-naphthyl)-5,10-dihydrophenazine and 3,7-Di((1,1'-biphenyl)-4-yl)-10-(naphthalen-1-yl)-10H-phenoxazine. Turnover numbers (TONs) up to 149 for CO and 29 for CH4 were reached. The experiments were conducted under visible-light irradiation (λ > 435 nm) with a tertiary amine (see section SEDs below) as sacrificial electron donor.
Advances and special progress[edit | edit source]
This article contains the first demonstration for the reduction of CO2 to CH4 (complete 8e–/8H+ reduction) by a combination of an earth-abundant metal catalyst and an organic dye. So far, similar systems were shown to induce 2e–/2H+ reduction of CO2 to CO or formic acid.
Additional remarks[edit | edit source]
Methane was produced continuously (even after irradiation up to 4 days). The 8e–/8H+ reduction efficiency strongly depends on the redox properties of the organic photosensitizer and acidity of the proton source. In additional experiments, CO was used as the gas resource. The system consisting of iron porphyrin catalyst Fe(pTMAPP)Cl5 in combination with the phenoxazine photosensitizer 3,7-Di((1,1'-biphenyl)-4-yl)-10-(naphthalen-1-yl)-10H-phenoxazine was able to produce CH4 with a TON of 80 (85% selectivity, quantum yield: 0.47%).
Content of the published article in detail[edit | edit source]
The article contains results for the reduction of CO2 and CO as feedstock gases. The catalytic system performs best (referring to the TON of CH4 production) for CO as a feedstock.
Catalysts[edit | edit source]
Photosensitizers[edit | edit source]
5,10-Di(2-naphthyl)-5,10-dihydrophenazine
3,7-Di((1,1'-biphenyl)-4-yl)-10-(naphthalen-1-yl)-10H-phenoxazine
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 CH4 | TON H2 | . | |
|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|
| 1. | 0.01 | 1 | 0.1 | > 435 | 50 | 8 | 8 | |||||||||
| 2. | 0.01 | 1 | 0.1 | TFE | > 435 | 71 | 14 | 10 | ||||||||
| 3. | 0.01 | 1 | 0.1 | TFE | > 435 | 140 | 29 | 23 |
| cat | cat conc [µM] | PS | PS conc [mM] | e-D | e-D conc [M] | solvent A | additives | . | . | λexc [nm] | . | TON CH4 | TON H2 | . | |
|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|
| 1. | 0.01 | 1 | 0.1 | Visible light (>435) | 10 | 21 | |||||||||
| 2. | 0.01 | 1 | 0.1 | TFE | Visible light (>435) | 45 | 7 | ||||||||
| 3. | 0.01 | 1 | 0.1 | TFE | Visible light (>435) | 21 | 9 | ||||||||
| 4. | 0.01 | 1 | 0.1 | TFE | Visible light (>435) | 39 | 7 | ||||||||
| 5. | 0.01 | 1 | 0.1 | TFE | Visible light (>435) | 46 | 8 | ||||||||
| 6. | 0.01 | 1 | 0.1 | TFE | Visible light (>435) | 80 | 14 | ||||||||
| 7. | 0.01 | 1 | 0.1 | TFE | Visible light (>435) | 27 | 17 | ||||||||
| 8. | 0.01 | 1 | 0.1 | TFE | Visible light (>435) | 17 | 37 | ||||||||
| 9. | 0.01 | 1 | 0.1 | water | Visible light (>435) | 10 | 5 | ||||||||
| 10. | 0.01 | 1 | 0.1 | water | Visible light (>435) | 12 | 6 | ||||||||
| 11. | 0.01 | 1 | 0.1 | PhOH | Visible light (>435) | 26 | 44 |
Sacrificial Electron Donor[edit | edit source]
In this study, the experiments were done with the sacrificial electron donors DIPEA (DIPEA), TEOA (TEOA), BIH (BIH), and TEA (TEA).
Additives[edit | edit source]
In this study, different additives were used. As depicted in the investigation table, water (H2O,) phenol (PhOH), and trifluoroethanol (TFE) were used.
Investigations
- Photocatalytic reduction of CO (Molecular process, Photocatalytic CO2 conversion experiments)
- Photocatalytic reduction of CO2 (Molecular process, Photocatalytic CO2 conversion experiments)
