Rhenium(I) trinuclear rings as highly efficient redox photosensitizers for photocatalytic CO2 reduction: Difference between revisions
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===Abstract=== | ===Abstract=== | ||
==== Summary==== | ==== Summary==== | ||
A photochemical reduction of CO<sub>2</sub> to CO or formic acid was shown using the bipyridine-based rhenium, ruthenium and manganese catalysts {{#moleculelink:|link=NZCMNMSVXYOMGS-UHFFFAOYSA-N|image=false|width=300|height=200}}, {{#moleculelink: |link=XUQJAKJUMNDNTK-UHFFFAOYSA-L|image=false|width=300|height=200}} or {{#moleculelink: |link=OMERWMHUIAGAOR-UHFFFAOYSA-N|image=false|width=300|height=200}} in combination with cyclic rhenium-based trinuclear redox photosensitizers. Turnover numbers (TONs) of up to 290 for formic acid were reached in DMA with the ruthenium complex {{#moleculelink: |link=XUQJAKJUMNDNTK-UHFFFAOYSA-L|image=false|width=300|height=200}} and photosensitizer {{#moleculelink: |link=JLRZSCLFGATQEH-UHFFFAOYSA-T|image=false|width=300|height=200}}. For CO production, TONs of up to 98 were obtained in DMF with the rhenium complex {{#moleculelink:|link=NZCMNMSVXYOMGS-UHFFFAOYSA-N|image=false|width=300|height=200}} and photosensitizer {{#moleculelink:|link=LKSLWZSWOWNWCR-UHFFFAOYSA-T|image=false|width=300|height=200}}. The experiments were conducted under visible-light irradiation (λ = 436 nm) using TEOA as sacrificial electron donor (see section SEDs below). | A photochemical reduction of CO<sub>2</sub> to CO or formic acid was shown using the bipyridine-based rhenium, ruthenium and manganese catalysts {{#moleculelink:|link=NZCMNMSVXYOMGS-UHFFFAOYSA-N|image=false|width=300|height=200}}, {{#moleculelink: |link=XUQJAKJUMNDNTK-UHFFFAOYSA-L|image=false|width=300|height=200}} or {{#moleculelink: |link=OMERWMHUIAGAOR-UHFFFAOYSA-N|image=false|width=300|height=200}} in combination with cyclic rhenium-based trinuclear redox photosensitizers. Turnover numbers (TONs) of up to 290 for formic acid were reached in DMA with the ruthenium complex {{#moleculelink: |link=XUQJAKJUMNDNTK-UHFFFAOYSA-L|image=false|width=300|height=200}} and photosensitizer {{#moleculelink: |link=JLRZSCLFGATQEH-UHFFFAOYSA-T|image=false|width=300|height=200}}. For CO production, TONs of up to 98 were obtained in DMF with the rhenium complex {{#moleculelink:|link=NZCMNMSVXYOMGS-UHFFFAOYSA-N|image=false|width=300|height=200}} and photosensitizer {{#moleculelink: |link=LKSLWZSWOWNWCR-UHFFFAOYSA-T|image=false|width=300|height=200}}. The experiments were conducted under visible-light irradiation (λ = 436 nm) using TEOA as sacrificial electron donor (see section SEDs below). | ||
====Advances and special progress==== | ====Advances and special progress==== | ||
Re(I)-based trinuclear photosensitizers were developed and allowed for high product selectivities for CO or formic acid in CO<sub>2</sub> reduction attempts with different bipyridine-based catalysts. | Re(I)-based trinuclear photosensitizers were developed and allowed for high product selectivities for CO or formic acid in CO<sub>2</sub> reduction attempts with different bipyridine-based catalysts. | ||
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M V30 END CTAB | M V30 END CTAB | ||
M END | M END | ||
</chemform><chemform smiles="CC(C)(C)C1=CC2=N(~[Ru](~Cl)(~Cl)(~C#O)(~C#O)~N3=C2C=C(C(C)(C)C)C=C3)C=C1" inchikey="XUQJAKJUMNDNTK-UHFFFAOYSA-L" inchi="InChI=1S/C18H24N2.2CO.2ClH.Ru/c1-17(2,3)13-7-9-19-15(11-13)16-12-14(8-10-20-16)18(4,5)6;2*1-2;;;/h7-12H,1-6H3;;;2*1H;/q;;;;;+2/p-2" float="none" width="200" height="200"> | </chemform><chemform smiles="CC(C)(C)C1=CC2=N(~[Ru](~Cl)(~Cl)(~C#O)(~C#O)~N3=C2C=C(C(C)(C)C)C=C3)C=C1" inchikey="XUQJAKJUMNDNTK-UHFFFAOYSA-L" inchi="InChI=1S/C18H24N2.2CO.2ClH.Ru/c1-17(2,3)13-7-9-19-15(11-13)16-12-14(8-10-20-16)18(4,5)6;2*1-2;;;/h7-12H,1-6H3;;;2*1H;/q;;;;;+2/p-2" float="none" width="200" height="200" margin="0px 0px 0px 30px"> | ||
RDKit 2D | RDKit 2D | ||
| Line 150: | Line 150: | ||
M V30 END CTAB | M V30 END CTAB | ||
M END | M END | ||
</chemform><chemform smiles="C(C(C)(C)C)1C=C2C3C=C(C(C)(C)C)C=CN=3[Mn+]([C-]#[O+])([C-]#[O+])([C-]#[O+])(N#CC)N2=CC=1.F[P-](F)(F)(F)(F)F" inchikey="OMERWMHUIAGAOR-UHFFFAOYSA-N" inchi="1S/C18H24N2.C2H3N.3CO.F6P.Mn/c1-17(2,3)13-7-9-19-15(11-13)16-12-14(8-10-20-16)18(4,5)6;1-2-3;3*1-2;1-7(2,3,4,5)6;/h7-12H,1-6H3;1H3;;;;;/q;;;;;-1;+1" float="none" width="200" height="200"> | </chemform><chemform smiles="C(C(C)(C)C)1C=C2C3C=C(C(C)(C)C)C=CN=3[Mn+]([C-]#[O+])([C-]#[O+])([C-]#[O+])(N#CC)N2=CC=1.F[P-](F)(F)(F)(F)F" inchikey="OMERWMHUIAGAOR-UHFFFAOYSA-N" inchi="1S/C18H24N2.C2H3N.3CO.F6P.Mn/c1-17(2,3)13-7-9-19-15(11-13)16-12-14(8-10-20-16)18(4,5)6;1-2-3;3*1-2;1-7(2,3,4,5)6;/h7-12H,1-6H3;1H3;;;;;/q;;;;;-1;+1" float="none" width="200" height="200" margin="0px 0px 0px 30px"> | ||
-INDIGO-02192415212D | -INDIGO-02192415212D | ||
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====Investigation==== | ====Investigation==== | ||
{{#experimentlist:|form=Photocatalytic_CO2_conversion_experiments|name=Table 1}}{{#experimentlist:|form=Photocatalytic_CO2_conversion_experiments|name=Table 2}} | {{#experimentlist:|form=Photocatalytic_CO2_conversion_experiments|name=Table 1}} | ||
{{#experimentlist:|form=Photocatalytic_CO2_conversion_experiments|name=Table 2}} | |||
====Sacrificial Electron Donor ==== | ====Sacrificial Electron Donor ==== | ||
In this study, the experiments were done with the sacrificial electron donor TEOA ([[Molecule:100507|100507]]). | In this study, the experiments were done with the sacrificial electron donor TEOA ([[Molecule:100507|100507]]). | ||
| Line 642: | Line 643: | ||
In this study, no additives were tested. | In this study, no additives were tested. | ||
[[Category:Photocatalytic CO2 conversion to HCOOH]][[Category:Publication]] | [[Category:Photocatalytic CO2 conversion to HCOOH]][[Category:Publication]] | ||
{{Tags|tags=CO2 reduction, photochemical reduction, photocatalysis, visible-light catalysis, homogeneous catalysis, organometallic chemistry, rhenium catalyst, ruthenium catalyst, manganese catalyst, bipyridine complexes, trinuclear photosensitizer, rhenium photosensitizer, formic acid production, carbon monoxide production, solar fuels, sacrificial electron donor, TEOA, turnover number}} | |||
Latest revision as of 11:44, 21 November 2025
Abstract[edit | edit source]
Summary[edit | edit source]
A photochemical reduction of CO2 to CO or formic acid was shown using the bipyridine-based rhenium, ruthenium and manganese catalysts [Re(bpy)(CO)3(MeCN)][PF6], Ru(dtBubpy)(CO)2Cl2 or [Mn(dtBubpy)(CO)3(MeCN)][PF6] in combination with cyclic rhenium-based trinuclear redox photosensitizers. Turnover numbers (TONs) of up to 290 for formic acid were reached in DMA with the ruthenium complex Ru(dtBubpy)(CO)2Cl2 and photosensitizer 100877. For CO production, TONs of up to 98 were obtained in DMF with the rhenium complex [Re(bpy)(CO)3(MeCN)][PF6] and photosensitizer 100878. The experiments were conducted under visible-light irradiation (λ = 436 nm) using TEOA as sacrificial electron donor (see section SEDs below).
Advances and special progress[edit | edit source]
Re(I)-based trinuclear photosensitizers were developed and allowed for high product selectivities for CO or formic acid in CO2 reduction attempts with different bipyridine-based catalysts.
Additional remarks[edit | edit source]
Content of the published article in detail[edit | edit source]
The article contains results for the reduction of CO2 to CO or formic acid under visible-light catalysis using bipyridine-based complexes and rhenium-based trinuclear rings as photosensitizers. The catalytic system performs best in DMA for formic acid production (referring to the TON of formic acid production) and in DMF for CO production.
Catalyst[edit | edit source]
[Re(bpy)(CO)3(MeCN)][PF6]
Ru(dtBubpy)(CO)2Cl2
[Mn(dtBubpy)(CO)3(MeCN)][PF6]
Photosensitizer[edit | edit source]
Investigation[edit | edit source]
| cat | cat conc [µM] | PS | PS conc [mM] | solvent A | . | . | λexc [nm] | . | TON CO | . | . | . | |
|---|---|---|---|---|---|---|---|---|---|---|---|---|---|
| 1. | 50 | 0.05 | 436 | 27 | |||||||||
| 2. | 50 | 0.05 | 436 | 98 | |||||||||
| 3. | 50 | 0.05 | 436 | 22 | |||||||||
| 4. | 50 | 0.05 | 436 | 71 | |||||||||
| 5. | 0.05 | 436 | 6 | ||||||||||
| 6. | 0.05 | 436 | 8 | ||||||||||
| 7. | 50 | 0.05 | 436 | 20 | |||||||||
| 8. | 50 | 0.05 | 436 | 32 | |||||||||
| 9. | 50 | 0.05 | 436 | 11 | |||||||||
| 10. | 50 | 0.05 | 436 | 48 |
Investigation-Name: Table 1
| cat | cat conc [µM] | PS | PS conc [mM] | e-D | e-D conc [M] | solvent A | . | . | λexc [nm] | . | TON CO | TON H2 | TON HCOOH | . | . | . | |
|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|
| 1. | 50 | 0.05 | 436 | 20 | 72 | 290 | |||||||||||
| 2. | 50 | 0.05 | 0.03 | 436 | 16 | 49 | 280 | ||||||||||
| 3. | 50 | 0.05 | 436 | 32 | 85 | ||||||||||||
| 4. | 50 | 0.05 | 0.03 | 436 | 80 | 60 |
Investigation-Name: Table 2
Sacrificial Electron Donor[edit | edit source]
In this study, the experiments were done with the sacrificial electron donor TEOA (100507).
Additives[edit | edit source]
In this study, no additives were tested.
Tags: CO2 reduction, photochemical reduction, photocatalysis, visible-light catalysis, homogeneous catalysis, organometallic chemistry, rhenium catalyst, ruthenium catalyst, manganese catalyst, bipyridine complexes, trinuclear photosensitizer, rhenium photosensitizer, formic acid production, carbon monoxide production, solar fuels, sacrificial electron donor, TEOA, turnover number |
