Pyranopterin Related Dithiolene Molybdenum Complexes as Homogeneous Catalysts for CO2 Photoreduction: Difference between revisions
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{{ | {{DOI|doi=10.1002/anie.201809084}} | ||
===Abstract=== | ===Abstract=== | ||
====Summary==== | ====Summary==== | ||
A photochemical reduction of CO<sub>2</sub> to formic acid or CO was shown using the novel dithiolene molybdenum complexes {{#moleculelink:|link=ZANCFLAGIYSVGM-UHFFFAOYSA-J|image=false|width=300|height=200}} and {{#moleculelink:|link=NXVSQECHHKIDOQ-UHFFFAOYSA-J|image=false|width=300|height=200}} in comparison to the previously reported complex {{#moleculelink:|link=SZEIOHNZAHLTPQ-UHFFFAOYSA-J|image=false|width=300|height=200}} as catalysts in combination with photosensitizer {{#moleculelink:|link=SJFYGUKHUNLZTK-UHFFFAOYSA-L|image=false|width=300|height=200}}. Turnover numbers (TONs) of up to 83 for formic acid and 40 for CO were reached in acetonitrile for complex {{#moleculelink:|link=NXVSQECHHKIDOQ-UHFFFAOYSA-J|image=false|width=300|height=200}}. The experiments were conducted under visible-light irradiation (λ = 400 nm) using BIH and TEOA as sacrificial electron donor (see section SEDs below). | A photochemical reduction of CO<sub>2</sub> to formic acid or CO was shown using the novel dithiolene molybdenum complexes {{#moleculelink:|link=ZANCFLAGIYSVGM-UHFFFAOYSA-J|image=false|width=300|height=200}} and {{#moleculelink:|link=NXVSQECHHKIDOQ-UHFFFAOYSA-J|image=false|width=300|height=200}} in comparison to the previously reported complex {{#moleculelink:|link=SZEIOHNZAHLTPQ-UHFFFAOYSA-J|image=false|width=300|height=200}} as catalysts in combination with photosensitizer {{#moleculelink:|link=SJFYGUKHUNLZTK-UHFFFAOYSA-L|image=false|width=300|height=200}}. Turnover numbers (TONs) of up to 83 for formic acid and 40 for CO were reached in acetonitrile for complex {{#moleculelink:|link=NXVSQECHHKIDOQ-UHFFFAOYSA-J|image=false|width=300|height=200}}. The experiments were conducted under visible-light irradiation (λ = 400 nm) using BIH and TEOA as sacrificial electron donor (see section SEDs below). | ||
====Advances and special progress==== | ====Advances and special progress==== | ||
Bioinspired dithiolene Mo-complexes as analogues of the active site of the FDH (formate dehydrogenase) were shown to be active as CO<sub>2</sub> photoreduction catalysts with formation of formic acid as the main product. | |||
====Additional remarks==== | ====Additional remarks==== | ||
The developed complex {{#moleculelink:|link=NXVSQECHHKIDOQ-UHFFFAOYSA-J|image=false|width=300|height=200}} shows a similar TON for formic acid production to the previously synthesized complex {{#moleculelink:|link=SZEIOHNZAHLTPQ-UHFFFAOYSA-J|image=false|width=300|height=200}}, however a strong increase in selectivity is observed. The previously reported complex mainly catalyzes the generation of hydrogen. | |||
===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 or formic acid under visible-light catalysis using molybdenum complexes and a ruthenium-based photosensitizer. The catalytic system performs best (referring to the TON of formic acid production) in acetonitrile with complex {{#moleculelink:|link=NXVSQECHHKIDOQ-UHFFFAOYSA-J|image=false|width=300|height=200}}. | The article contains results for the reduction of CO<sub>2</sub> to CO or formic acid under visible-light catalysis using molybdenum complexes and a ruthenium-based photosensitizer. The catalytic system performs best (referring to the TON of formic acid production) in acetonitrile with complex {{#moleculelink:|link=NXVSQECHHKIDOQ-UHFFFAOYSA-J|image=false|width=300|height=200}}. | ||
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====Additives==== | ====Additives==== | ||
In this study, no additives were tested. | In this study, no additives were tested. | ||
[[Category:Photocatalytic CO2 conversion to HCOOH]] | [[Category:Photocatalytic CO2 conversion to HCOOH]][[Category:Publication]] | ||
Latest revision as of 10:37, 11 April 2024
Abstract[edit | edit source]
Summary[edit | edit source]
A photochemical reduction of CO2 to formic acid or CO was shown using the novel dithiolene molybdenum complexes [K]2[MoO(Hqpdt)2] and [MoO(2Hqpdt)2][NBu4] in comparison to the previously reported complex [MoO(qpdt)2][NBu4]2 as catalysts in combination with photosensitizer Ru(bpy)3Cl2. Turnover numbers (TONs) of up to 83 for formic acid and 40 for CO were reached in acetonitrile for complex [MoO(2Hqpdt)2][NBu4]. The experiments were conducted under visible-light irradiation (λ = 400 nm) using BIH and TEOA as sacrificial electron donor (see section SEDs below).
Advances and special progress[edit | edit source]
Bioinspired dithiolene Mo-complexes as analogues of the active site of the FDH (formate dehydrogenase) were shown to be active as CO2 photoreduction catalysts with formation of formic acid as the main product.
Additional remarks[edit | edit source]
The developed complex [MoO(2Hqpdt)2][NBu4] shows a similar TON for formic acid production to the previously synthesized complex [MoO(qpdt)2][NBu4]2, however a strong increase in selectivity is observed. The previously reported complex mainly catalyzes the generation of hydrogen.
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 molybdenum complexes and a ruthenium-based photosensitizer. The catalytic system performs best (referring to the TON of formic acid production) in acetonitrile with complex [MoO(2Hqpdt)2][NBu4].
Catalyst[edit | edit source]
[K]2[MoO(Hqpdt)2]
[MoO(2Hqpdt)2][NBu4]
[MoO(qpdt)2][NBu4]2
Photosensitizer[edit | edit source]
Investigation[edit | edit source]
| 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. | 0.05 | 0.5 | 0.1 | 400 | 73 | 670 | 80 | |||||||||
| 2. | 0.05 | 0.5 | 0.1 | 400 | 13 | 51 | 31 | |||||||||
| 3. | 0.05 | 0.5 | 0.1 | 400 | 40 | 89 | 83 |
Sacrificial Electron Donor[edit | edit source]
In this study, the experiments were done with the sacrificial electron donors TEOA (TEOA) and BIH (BIH).
Additives[edit | edit source]
In this study, no additives were tested.
Investigations
- Table 1 (Molecular process, Photocatalytic CO2 conversion experiments)
