Molecular Catalysis of the Electrochemical and Photochemical Reduction of CO2 with Earth-Abundant Metal Complexes. Selective Production of CO vs HCOOH by Switching of the Metal Center: Difference between revisions
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{{ | {{DOI|doi=10.1021/jacs.5b06535}} | ||
[[Category:Photocatalytic CO2 conversion to HCOOH]] | [[Category:Photocatalytic CO2 conversion to HCOOH]] | ||
{{BaseTemplate}} | {{BaseTemplate}} | ||
===Abstract=== | ===Abstract=== | ||
==== Summary==== | ==== Summary==== | ||
A photochemical reduction of CO<sub>2</sub> to CO or formic acid was shown using the iron | A photochemical reduction of CO<sub>2</sub> to CO or formic acid was shown using the iron complex {{#moleculelink:|link=XTLBRFNUSVMBAM-DQIPMIPLSA-K|image=false|width=300|height=200}} or the cobalt complex {{#moleculelink:|link=UEQRGEGBADTDNK-YBRXSBAKSA-L|image=false|width=300|height=200}} as catalysts in combination with the iridium-based photosensitizer {{#moleculelink:|link=NSABRUJKERBGOU-UHFFFAOYSA-N|image=false|width=300|height=200}}. Turnover numbers (TONs) of 270 for CO with the cobalt complex and 5 for formic acid with the iron complex were reached in acetonitrile. The experiments were conducted under visible-light irradiation (λ > 460 nm) using TEA as sacrificial electron donor (see section SEDs below). | ||
====Advances and special progress==== | ====Advances and special progress==== | ||
The authors could demonstrate that switching the metal center has a major influence on the outcome of CO<sub>2</sub> reduction, enabling the generation of either CO or formic acid depending on the employed metal. For the cobalt complex, CO<sub>2</sub> reduction was possible both under electrochemical conditions and photochemically with a photosensitizer under visible light. | |||
====Additional remarks==== | ====Additional remarks==== | ||
In electrocatalytic experiments with the cobalt catalyst {{#moleculelink:|link=UEQRGEGBADTDNK-YBRXSBAKSA-L|image=false|width=300|height=200}} and E = -1.5 V vs SCE, CO formation with high faradaic yields of 82% was possible. | |||
===Content of the published article in detail=== | ===Content of the published article in detail=== | ||
The article contains results for the reduction of CO<sub>2</sub> to CO and formic acid under visible-light catalysis using iron complexes as catalysts. The catalytic system performs best (referring to the TON of CO production) in | The article contains results for the reduction of CO<sub>2</sub> to CO and formic acid under visible-light catalysis using iron or cobalt complexes as catalysts. The catalytic system performs best (referring to the TON of CO production) in acetonitrile with the cobalt catalyst. | ||
====Catalyst==== | ====Catalyst==== | ||
<chemform smiles="C1C2C(C)=N3[Fe+3]([Cl-])([Cl-])456N(CCN4CCN5CC3)=C(C)C(N=26)=CC=1.Cl([O-])(=O)(=O)=O" inchi="1S/C15H23N5.ClHO4.2ClH.Fe/c1-12-14-4-3-5-15(20-14)13(2)19-11-9-17-7-6-16-8-10-18-12;2-1(3,4)5;;;/h3-5,16-17H,6-11H2,1-2H3;(H,2,3,4,5);2*1H;/q;;;;+3/p-3/b18-12+,19-13+;;;;" inchikey="XTLBRFNUSVMBAM-DQIPMIPLSA-K" height="200px" width="300px" float="none"> | <chemform smiles="C1C2C(C)=N3[Fe+3]([Cl-])([Cl-])456N(CCN4CCN5CC3)=C(C)C(N=26)=CC=1.Cl([O-])(=O)(=O)=O" inchi="1S/C15H23N5.ClHO4.2ClH.Fe/c1-12-14-4-3-5-15(20-14)13(2)19-11-9-17-7-6-16-8-10-18-12;2-1(3,4)5;;;/h3-5,16-17H,6-11H2,1-2H3;(H,2,3,4,5);2*1H;/q;;;;+3/p-3/b18-12+,19-13+;;;;" inchikey="XTLBRFNUSVMBAM-DQIPMIPLSA-K" height="200px" width="300px" float="none"> | ||
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In this study, the experiments were done with the sacrificial electron donor TEA ([[Molecule:100505|100505]]). | In this study, the experiments were done with the sacrificial electron donor TEA ([[Molecule:100505|100505]]). | ||
====Additives==== | ====Additives==== | ||
In this study, no additives were tested. | In this study, no additives were tested.[[Category:Publication]] | ||
Latest revision as of 09:57, 22 May 2024
Abstract[edit | edit source]
Summary[edit | edit source]
A photochemical reduction of CO2 to CO or formic acid was shown using the iron complex [Fe(pabop)Cl2][CLO4] or the cobalt complex [Co(pabop)][ClO4]2 as catalysts in combination with the iridium-based photosensitizer Ir(ppy)3. Turnover numbers (TONs) of 270 for CO with the cobalt complex and 5 for formic acid with the iron complex were reached in acetonitrile. The experiments were conducted under visible-light irradiation (λ > 460 nm) using TEA as sacrificial electron donor (see section SEDs below).
Advances and special progress[edit | edit source]
The authors could demonstrate that switching the metal center has a major influence on the outcome of CO2 reduction, enabling the generation of either CO or formic acid depending on the employed metal. For the cobalt complex, CO2 reduction was possible both under electrochemical conditions and photochemically with a photosensitizer under visible light.
Additional remarks[edit | edit source]
In electrocatalytic experiments with the cobalt catalyst [Co(pabop)][ClO4]2 and E = -1.5 V vs SCE, CO formation with high faradaic yields of 82% was possible.
Content of the published article in detail[edit | edit source]
The article contains results for the reduction of CO2 to CO and formic acid under visible-light catalysis using iron or cobalt complexes as catalysts. The catalytic system performs best (referring to the TON of CO production) in acetonitrile with the cobalt catalyst.
Catalyst[edit | edit source]
[Fe(pabop)Cl2][CLO4]
[Co(pabop)][ClO4]2
Photosensitizer[edit | edit source]
Investigation[edit | edit source]
| cat | cat conc [µM] | PS | PS conc [mM] | e-D | solvent A | . | . | λexc [nm] | . | TON CO | TON HCOOH | . | |
|---|---|---|---|---|---|---|---|---|---|---|---|---|---|
| 1. | 0.05 | 0.2 | >460 | 270 | |||||||||
| 2. | 0.05 | 0.2 | >420 | 5 |
Sacrificial electron donor[edit | edit source]
In this study, the experiments were done with the sacrificial electron donor TEA (100505).
Additives[edit | edit source]
In this study, no additives were tested.
Investigations
- Table 1 (Molecular process, Photocatalytic CO2 conversion experiments)
