Visible-Light-Driven Conversion of CO2 to CH4 with an Organic Sensitizer and an Iron Porphyrin Catalyst: Difference between revisions
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=== Abstract === | === Abstract === | ||
==== Summary ==== | |||
A photochemical reduction of CO2 to CO and CH4 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 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. | A photochemical reduction of CO2 to CO and CH4 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 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 === | ==== Advances and special progress ==== | ||
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. | 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 === | ==== Additional remarks ==== | ||
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. | 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. | ||
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=== Content of the published article === | === Content of the published article === | ||
The article contains additional information on CO-reduction with the same system as additional information. The system gives higher conversion rates to CH4 and is not added here yet. | The article contains additional information on CO-reduction with the same system as additional information. The system gives higher conversion rates to CH4 and is not added here yet. | ||
===Catalysts=== | |||
==== 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"> | <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-11282314292D | ||
| Line 177: | Line 180: | ||
</chemform> | </chemform> | ||
=== Photosensitizers=== | ==== 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-11092309282D | -INDIGO-11092309282D | ||
| Line 382: | Line 385: | ||
</chemform> | </chemform> | ||
=== Investigations === | ==== Investigations ==== | ||
{{#experimentlist:|form=Photocatalytic_CO2_conversion_experiments|name=Table 1}} | {{#experimentlist:|form=Photocatalytic_CO2_conversion_experiments|name=Table 1}} | ||
===Sacrificial Electron Donor === | |||
==== 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}}). | 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=== | ==== 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. | 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:Photocatalytic CO2 conversion to CH4]] | ||
Revision as of 09:17, 29 December 2023
Abstract
Summary
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
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
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 5,10-Di(2-naphthyl)-5,10-dihydrophenazine and 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
The article contains additional information on CO-reduction with the same system as additional information. The system gives higher conversion rates to CH4 and is not added here yet.
Catalysts
Photosensitizers
5,10-Di(2-naphthyl)-5,10-dihydrophenazine
3,7-Di((1,1'-biphenyl)-4-yl)-10-(naphthalen-1-yl)-10H-phenoxazine
Investigations
- REDIRECT Photocatalytic reduction of CO2
Investigation-Name: Table 1
Sacrificial Electron Donor
In this study, the experiments were done with the sacrificial electron donors DIPEA (DIPEA), TEOA (TEOA), BIH (BIH), and TEA (TEA).
Additives
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)
