Visible-Light-Driven Conversion of CO2 to CH4 with an Organic Sensitizer and an Iron Porphyrin Catalyst: Difference between revisions
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{{DOI|doi=10.1021/jacs.8b09740}} | |||
{{ | |||
=== | === Abstract === | ||
=== | ==== Summary ==== | ||
< | A photochemical reduction of CO<sub>2</sub> to CO and CH<sub>4</sub> was shown using the iron porphyrin catalyst {{#moleculelink:|link=LKNRTBVZMCBYCY-NGWNFTKISA-I|image=false|width=300|height=200}} in combination with the phenoxazine photosensitizers {{#moleculelink:|link=HPIOBCHPZVAATK-UHFFFAOYSA-N|image=false|width=300|height=200}} and {{#moleculelink:|link=IGGSSEOAGCUGDJ-UHFFFAOYSA-N|image=false|width=300|height=200}}. Turnover numbers (TONs) up to 149 for CO and 29 for CH<sub>4</sub> 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 ==== | |||
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 ==== | |||
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 === | |||
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 ==== | |||
<chemform smiles="C1C=C2C(C3C=CC([N+](C)(C)C)=CC=3)=C3C=CC4C(C5C=CC([N+](C)(C)C)=CC=5)=C5N6~[Fe+3](~[Cl-])7(~N2C=1C(C1C=CC([N+](C)(C)C)=CC=1)=C1N7=C(C(C2C=CC([N+](C)(C)C)=CC=2)=C6C=C5)C=C1)N3=4.[Cl-].[Cl-].[Cl-].[Cl-]" inchi="1S/C56H60N8.5ClH.Fe/c1-61(2,3)41-21-13-37(14-22-41)53-45-29-31-47(57-45)54(38-15-23-42(24-16-38)62(4,5)6)49-33-35-51(59-49)56(40-19-27-44(28-20-40)64(10,11)12)52-36-34-50(60-52)55(48-32-30-46(53)58-48)39-17-25-43(26-18-39)63(7,8)9;;;;;;/h13-36H,1-12H3;5*1H;/q+2;;;;;;+5/p-5/b53-45-,53-46-,54-47-,54-49-,55-48-,55-50-,56-51-,56-52-;;;;;;" inchikey="LKNRTBVZMCBYCY-NGWNFTKISA-I" height="200px" width="300px" float="none"> | |||
-INDIGO-11282314292D | |||
-INDIGO- | |||
0 0 0 0 0 0 0 0 0 0 0 V3000 | 0 0 0 0 0 0 0 0 0 0 0 V3000 | ||
| Line 232: | Line 88: | ||
M V30 63 C 4.34205 -10.4999 0.0 0 | M V30 63 C 4.34205 -10.4999 0.0 0 | ||
M V30 64 C 3.13494 -10.341 0.0 0 | M V30 64 C 3.13494 -10.341 0.0 0 | ||
M V30 65 Fe 8.425 -5.075 0.0 0 | M V30 65 Fe 8.425 -5.075 0.0 0 CHG=3 | ||
M V30 66 Cl 9. | M V30 66 Cl 9.33211 -3.94289 0.0 0 CHG=-1 | ||
M V30 67 Cl 13. | M V30 67 Cl 13.95 -7.55 0.0 0 CHG=-1 | ||
M V30 68 Cl | M V30 68 Cl 2.875 -7.65 0.0 0 CHG=-1 | ||
M V30 69 Cl | M V30 69 Cl 2.975 -2.325 0.0 0 CHG=-1 | ||
M V30 70 Cl | M V30 70 Cl 13.8 -2.275 0.0 0 CHG=-1 | ||
M V30 END ATOM | M V30 END ATOM | ||
M V30 BEGIN BOND | M V30 BEGIN BOND | ||
| Line 322: | Line 178: | ||
</chemform> | </chemform> | ||
=== | ==== Photosensitizers ==== | ||
<chemform smiles="C1C=CC2N(C3C=C4C=CC=CC4=CC=3)C3C=CC=CC=3N(C3C=C4C=CC=CC4=CC=3)C=2C=1" inchi="1S/C32H22N2/c1-3-11-25-21-27(19-17-23(25)9-1)33-29-13-5-7-15-31(29)34(32-16-8-6-14-30(32)33)28-20-18-24-10-2-4-12-26(24)22-28/h1-22H" inchikey="HPIOBCHPZVAATK-UHFFFAOYSA-N" height="200px" width="300px" float="none"> | <chemform smiles="C1C=CC2N(C3C=C4C=CC=CC4=CC=3)C3C=CC=CC=3N(C3C=C4C=CC=CC4=CC=3)C=2C=1" inchi="1S/C32H22N2/c1-3-11-25-21-27(19-17-23(25)9-1)33-29-13-5-7-15-31(29)34(32-16-8-6-14-30(32)33)28-20-18-24-10-2-4-12-26(24)22-28/h1-22H" inchikey="HPIOBCHPZVAATK-UHFFFAOYSA-N" height="200px" width="300px" float="none"> | ||
-INDIGO- | -INDIGO-11092309282D | ||
0 0 0 0 0 0 0 0 0 0 0 V3000 | 0 0 0 0 0 0 0 0 0 0 0 V3000 | ||
| Line 330: | Line 186: | ||
M V30 COUNTS 34 40 0 0 0 | M V30 COUNTS 34 40 0 0 0 | ||
M V30 BEGIN ATOM | M V30 BEGIN ATOM | ||
M V30 1 C | M V30 1 C 8.77818 -2.39419 0.0 0 | ||
M V30 2 C | M V30 2 C 9.56568 -3.90185 0.0 0 | ||
M V30 3 C | M V30 3 C 9.60456 -2.93752 0.0 0 | ||
M V30 4 C | M V30 4 C 8.61934 -4.37665 0.0 0 | ||
M V30 5 C | M V30 5 C 7.8904 -2.83774 0.0 0 | ||
M V30 6 C | M V30 6 C 7.82432 -3.83054 0.0 0 | ||
M V30 7 N | M V30 7 N 10.4405 -4.45572 0.0 0 | ||
M V30 8 C | M V30 8 C 10.3497 -5.46354 0.0 0 | ||
M V30 9 N | M V30 9 N 8.53861 -5.38656 0.0 0 | ||
M V30 10 C | M V30 10 C 9.40329 -5.92975 0.0 0 | ||
M V30 11 C | M V30 11 C 11.1475 -6.01893 0.0 0 | ||
M V30 12 C | M V30 12 C 11.0882 -6.99925 0.0 0 | ||
M V30 13 C | M V30 13 C 9.37194 -6.91346 0.0 0 | ||
M V30 14 C | M V30 14 C 10.2086 -7.44687 0.0 0 | ||
M V30 15 C | M V30 15 C 12.461 -2.5947 0.0 0 | ||
M V30 16 C | M V30 16 C 13.1563 -4.13947 0.0 0 | ||
M V30 17 C | M V30 17 C 13.2531 -3.16277 0.0 0 | ||
M V30 18 C | M V30 18 C 12.2464 -4.57663 0.0 0 | ||
M V30 19 C | M V30 19 C 11.5263 -2.99434 0.0 0 | ||
M V30 20 C | M V30 20 C 11.3871 -4.00797 0.0 0 | ||
M V30 21 C | M V30 21 C 14.1585 -2.75442 0.0 0 | ||
M V30 22 C | M V30 22 C 14.9626 -3.33191 0.0 0 | ||
M V30 23 C | M V30 23 C 13.9726 -4.713 0.0 0 | ||
M V30 24 C | M V30 24 C 14.8674 -4.30484 0.0 0 | ||
M V30 25 C | M V30 25 C 6.72327 -5.34925 0.0 0 | ||
M V30 26 C 7. | M V30 26 C 7.54819 -6.86005 0.0 0 | ||
M V30 27 C | M V30 27 C 7.6063 -5.86467 0.0 0 | ||
M V30 28 C | M V30 28 C 6.65065 -7.33043 0.0 0 | ||
M V30 29 C 5. | M V30 29 C 5.83784 -5.84193 0.0 0 | ||
M V30 30 C | M V30 30 C 5.81243 -6.82289 0.0 0 | ||
M V30 31 C | M V30 31 C 6.62929 -8.31067 0.0 0 | ||
M V30 32 C | M V30 32 C 5.77649 -8.78437 0.0 0 | ||
M V30 33 C | M V30 33 C 4.95434 -7.29437 0.0 0 | ||
M V30 34 C | M V30 34 C 4.93734 -8.28253 0.0 0 | ||
M V30 END ATOM | M V30 END ATOM | ||
M V30 BEGIN BOND | M V30 BEGIN BOND | ||
| Line 527: | Line 383: | ||
</chemform> | </chemform> | ||
=== | ==== Investigations ==== | ||
{{#experimentlist: |form=Photocatalytic_CO2_conversion_experiments|name=Photocatalytic reduction of CO2}} | |||
{{#experimentlist:|form=Photocatalytic_CO2_conversion_experiments|name=Photocatalytic reduction of CO|importFile=}} | |||
==== Sacrificial Electron Donor ==== | |||
In this study, the experiments were done with the sacrificial electron donors DIPEA ({{#moleculelink:|link=JGFZNNIVVJXRND-UHFFFAOYSA-N|image=false|width=300|height=200}}), TEOA ({{#moleculelink:|link=GSEJCLTVZPLZKY-UHFFFAOYSA-N|image=false|width=300|height=200}}), BIH ({{#moleculelink:|link=VDFIVJSRRJXMAU-UHFFFAOYSA-N|image=false|width=300|height=200}}), and TEA ({{#moleculelink: |link=ZMANZCXQSJIPKH-UHFFFAOYSA-N|image=false|width=300|height=200}}). | |||
==== Additives ==== | |||
In this study, different additives were used. As depicted in the investigation table, water ({{#moleculelink:|link=XLYOFNOQVPJJNP-UHFFFAOYSA-N|image=false|width=300|height=200}},) phenol ({{#moleculelink:|link=ISWSIDIOOBJBQZ-UHFFFAOYSA-N|image=false|width=300|height=200}}), and trifluoroethanol ({{#moleculelink:|link=RHQDFWAXVIIEBN-UHFFFAOYSA-N|image=false|width=300|height=200}}) were used. | |||
[[Category:Photocatalytic CO2 conversion to CH4]][[Category:Publication]] | |||
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 |
Investigation-Name: Photocatalytic reduction of CO2
| 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 |
Investigation-Name: Photocatalytic reduction of CO
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)
