Photochemical Reduction of Carbon Dioxide to Formic Acid using Ruthenium(II)-Based Catalysts and Visible Light: Difference between revisions
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[[Category:Photocatalytic CO2 conversion to HCOOH]] | [[Category:Photocatalytic CO2 conversion to HCOOH]] | ||
{{ | {{DOI|doi=10.1002/cctc.201500494 }} | ||
=== Abstract === | === Abstract === | ||
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=== 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> to formic acid under visible-light catalysis using ruthenium complexes as catalysts, the iridium complex [Ir(ppy)<sub>2</sub>(bpy)]PF<sub>6</sub> ({{#moleculelink:|link=RJJGJTKSOSSNNL-UHFFFAOYSA-N|image=false|width=300|height=200}}) as a photosensitizer and triethanolamine as the electron donor. The catalytic system performs best (referring to the TON of HCOOH production) with [Ru(bpy)<sub>2</sub>(Cl)(CO)]PF<sub>6</sub>{{#moleculelink: |link=WUXWMOMXGWJDBM-UHFFFAOYSA-M|image=false|width=300|height=200}} as photocatalyst. | ||
==== Catalysts ==== | ==== Catalysts ==== | ||
| Line 661: | Line 661: | ||
==== Investigations ==== | ==== Investigations ==== | ||
{{#experimentlist:|form=Photocatalytic_CO2_conversion_experiments|name= | {{#experimentlist: |form=Photocatalytic_CO2_conversion_experiments|name=CO2 reduction experiments}} | ||
{{#experimentlist:|form=Photocatalytic_CO2_conversion_experiments|name= | {{#experimentlist: |form=Photocatalytic_CO2_conversion_experiments|name=Optimization of concentrations}} | ||
{{#experimentlist:|form=Cyclic_Voltammetry_experiments|name=Table 3 - CV}} | {{#experimentlist:|form=Cyclic_Voltammetry_experiments|name=Table 3 - CV}} | ||
Latest revision as of 17:26, 14 March 2025
Abstract[edit | edit source]
Summary[edit | edit source]
A photochemical reduction of CO2 to formic acid was shown using a system containing an iridium-based photosensitizer, ruthenium photocatalyst and triethanolamine as the electron donor. Turnover numbers up to 526 and a selectivity of 80% towards formic acid were observed if the reaction was performed with [Ir(ppy)2(bpy)]PF6 ([Ir(ppy)2(bpy)][PF6]) as the photosensitizer and [Ru(bpy)2(Cl)(CO)]PF6 (100837) as the catalyst. The experiments were conducted under irradiation with Hg-lamp equipped with a λ=400–700 nm filter.
Advances and special progress[edit | edit source]
The employed photocatalytic system showed activity for the photoreduction of Na2CO3 to formic acid as well. A TON of 53 was observed after 5h reaction time.
Additional remarks[edit | edit source]
Experiments using different electron and proton donors such as triethylamine (TEA) and 1-benzyl-1,4-dihydronicotinamide (BNAH) were unsuccessful as the observed activities were lower than those obtained in the presence of TEOA.
Content of the published article in detail[edit | edit source]
The article contains results for the reduction of CO2 to formic acid under visible-light catalysis using ruthenium complexes as catalysts, the iridium complex [Ir(ppy)2(bpy)]PF6 ([Ir(ppy)2(bpy)][PF6]) as a photosensitizer and triethanolamine as the electron donor. The catalytic system performs best (referring to the TON of HCOOH production) with [Ru(bpy)2(Cl)(CO)]PF6100837 as photocatalyst.
Catalysts[edit | edit source]
Ru(bpy)2Cl2
Ru(bpy)2CO3
[Ru(bpy)2ClCO][PF6]
[Ru(bpy)(H2O)(CO)][PF6]
[Ru(bpy)(AcMe)2][PF6]
[Ru(bpy)2HCO][PF6]
Photosensitizer[edit | edit source]
Investigations[edit | edit source]
| cat | cat conc [µM] | PS | PS conc [mM] | e-D | solvent A | . | λexc [nm] | TON CO | TON H2 | TON HCOOH | . | |
|---|---|---|---|---|---|---|---|---|---|---|---|---|
| 1. | 25 | 0.025 | 400 - 700 | 1 | 2 | 13 | ||||||
| 2. | 25 | 0.025 | 400 - 700 | 2 | 4 | 21 | ||||||
| 3. | 25 | 0.025 | 400 - 700 | 13 | 8 | 62 | ||||||
| 4. | 25 | 0.025 | 400 - 700 | 8 | 8 | 34 | ||||||
| 5. | 25 | 0.025 | 400 - 700 | 7 | 9 | 40 | ||||||
| 6. | 25 | 0.025 | 400 - 700 | 3 | 4 | 27 |
| cat | cat conc [µM] | PS | PS conc [mM] | e-D | solvent A | . | λexc [nm] | TON CO | TON H2 | TON HCOOH | . | |
|---|---|---|---|---|---|---|---|---|---|---|---|---|
| 1. | 6.2 | 0.025 | 400 - 700 | 3 | 9 | 26 | ||||||
| 2. | 6.2 | 0.025 | 400 - 700 | 3 | 11 | 39 | ||||||
| 3. | 6.2 | 0.025 | 400 - 700 | 19 | 19 | 117 | ||||||
| 4. | 6.2 | 0.025 | 400 - 700 | 21 | 16 | 107 | ||||||
| 5. | 6.2 | 0.025 | 400 - 700 | 21 | 14 | 75 | ||||||
| 6. | 6.2 | 0.025 | 400 - 700 | 4 | 12 | 64 | ||||||
| 7. | 3.1 | 0.025 | 400 - 700 | 36 | 33 | 296 | ||||||
| 8. | 3.1 | 0.025 | 400 - 700 | 16 | 29 | 145 | ||||||
| 9. | 3.1 | 0.025 | 400 - 700 | 34 | 28 | 211 | ||||||
| 10. | 1.6 | 0.025 | 400 - 700 | 40 | 67 | 419 | ||||||
| 11. | 1.6 | 0.025 | 400 - 700 | 25 | 62 | 225 | ||||||
| 12. | 1.6 | 0.025 | 400 - 700 | 45 | 65 | 335 | ||||||
| 13. | 1.6 | 0.025 | 400 - 700 | 4 | 44 | 75 |
| analyte | E0,0 [V] | E1,2 [V] | Ered1 [V] | Eox1 [V] | Ered2 [V] | Eox2 [V] | Ered3 [V] | Eox3 [V] | solvent | electrolyte | . | . | WE | . | . | RE | . | |
|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|---|
| 1. | 0 | 0, -2.11; | 0 | 0 | 0 | 0 | 0 | 0 | glassy carbon | Ag/AgNO3 in MeCN | ||||||||
| 2. | 0 | 0.45, -1.97; | 0 | 0 | 0 | 0 | 0 | 0 | glassy carbon | Ag/AgNO3 in MeCN | ||||||||
| 3. | 0 | 1.22, -1.75; | 0 | 0 | 0 | 0 | 0 | 0 | glassy carbon | Ag/AgNO3 in MeCN | ||||||||
| 4. | 0 | 1.2, -1.61; | 0 | 0 | 0 | 0 | 0 | 0 | glassy carbon | Ag/AgNO3 in MeCN |
Sacrificial electron donor[edit | edit source]
In this study, the experiments were done with the sacrificial electron donor TEOA (100507).
Additives[edit | edit source]
No additives were used in the described experiments.
Investigations
- CO2 reduction experiments (Molecular process, Photocatalytic CO2 conversion experiments)
- Optimization of concentrations (Molecular process, Photocatalytic CO2 conversion experiments)
- Table 1 (Molecular process, Photocatalytic CO2 conversion experiments)
- Table 2 (Molecular process, Photocatalytic CO2 conversion experiments)
- Table 3 - CV (Assay, Cyclic Voltammetry experiments)
