Metal-free reduction of CO2 to formate using a photochemical organohydride-catalyst recycling strategy: Difference between revisions

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{{DOI|doi=10.1038/s41557-023-01157-6}}
{{DOI|doi=10.1038/s41557-023-01157-6}}
[[Category:Photocatalytic CO2 conversion to CH4]][[Category:Publication]]
[[Category:Publication]]
{{BaseTemplate}}
{{BaseTemplate}}
===Abstract===
===Abstract===
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====Additional remarks====
====Additional remarks====
Derivatives in which the carbazole and benzimidazolium moieties were covalently connected were tested as a combined catalyst/photosensitizer, but showed a lower activity in catalyzing CO<sub>2</sub> reduction.
===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 HCOO<sup>-</sup> under visible-light catalysis using {{#moleculelink:|link=RDSICPYJALLFAN-UHFFFAOYSA-M|image=false|width=300|height=200}} as a catalyst. The catalytic system performs best (referring to the TON of formic acid production) in MeCN/H<sub>2</sub>O.
The article contains results for the reduction of CO<sub>2</sub> to HCOO<sup>-</sup> under visible-light catalysis using {{#moleculelink:|link=RDSICPYJALLFAN-UHFFFAOYSA-M|image=false|width=300|height=200}} as a catalyst. The catalytic system performs best (referring to the TON of formic acid production for the catalyst) in MeCN/H<sub>2</sub>O with photosensitizer {{#moleculelink:|link=SEAGXMGVRJVEBS-UHFFFAOYSA-N|image=false|width=300|height=200}}.
====Catalyst====
====Catalyst====
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<chemform smiles="C1C=CC2N(C)C(C)=[N+](C)C=2C=1.[I-]" inchi="1S/C10H13N2.HI/c1-8-11(2)9-6-4-5-7-10(9)12(8)3;/h4-7H,1-3H3;1H/q+1;/p-1" inchikey="RDSICPYJALLFAN-UHFFFAOYSA-M" height="200px" width="300px" float="none">
Line 50: Line 52:
M  V30 END CTAB
M  V30 END CTAB
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====Photosensitizer====
====Photosensitizer====
Line 118: Line 120:
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  -INDIGO-05152410562D
 
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====Investigation====
====Investigation====
{{#experimentlist:|form=Photocatalytic_CO2_conversion_experiments|name=photocatalytic CO2 conversion under different conditions|importFile=}}
====Sacrificial electron donor====
====Sacrificial electron donor====
In this study, the experiments were done with the sacrificial electron donor ascorbic acid {{#moleculelink:|link=PPASLZSBLFJQEF-UHFFFAOYSA-M|image=false|width=300|height=200}}. The use of BIH was tested, but found to yield worse results.
In this study, the experiments were done with the sacrificial electron donor ascorbic acid {{#moleculelink:|link=PPASLZSBLFJQEF-UHFFFAOYSA-M|image=false|width=300|height=200}}. The use of BIH was tested, but found to yield worse results.
====Additives====
====Additives====
In this study, potassium carbonate was added as a base.
In this study, potassium carbonate was added as a base. Control experiments under argon and with other bases were performed.
[[Category:Photocatalytic CO2 conversion to HCOOH]]

Latest revision as of 12:49, 17 May 2024


Abstract[edit | edit source]

Summary[edit | edit source]

A photochemical reduction of CO2 to formic acid was shown using 1,2,3-Trimethylbenzimidazolium iodide as catalyst in combination with the organic carbazole-based photosensitizer 3,6-bis(dimethylamino)-9-phenyl-9H-carbazole. Turnover numbers (TONs) of 6080 for the catalyst and 8820 for the photosensitizer and an exclusive selectivity for formic acid were reached in MeCN/H2O. The experiments were conducted under visible-light irradiation (λ = 400 nm) using ascorbic acid as sacrificial electron donor (see section SEDs below) and potassium carbonate as a base.

Advances and special progress[edit | edit source]

A transition-metal free process for the efficient photocatalytic reduction of CO2 to formic acid was described. The use of an organohydride catalyst allowed for a high selectivity for formate without noteworthy formation of H2 or CO.

Additional remarks[edit | edit source]

Derivatives in which the carbazole and benzimidazolium moieties were covalently connected were tested as a combined catalyst/photosensitizer, but showed a lower activity in catalyzing CO2 reduction.

Content of the published article in detail[edit | edit source]

The article contains results for the reduction of CO2 to HCOO- under visible-light catalysis using 1,2,3-Trimethylbenzimidazolium iodide as a catalyst. The catalytic system performs best (referring to the TON of formic acid production for the catalyst) in MeCN/H2O with photosensitizer 3,6-bis(dimethylamino)-9-phenyl-9H-carbazole.

Catalyst[edit | edit source]

1,2,3-Trimethylbenzimidazolium iodide BIH

Photosensitizer[edit | edit source]

3,6-bis(dimethylamino)-9-phenyl-9H-carbazole 3,6-bis(dimethylamino)carbazole 3,6-Bis(diphenylamino)-9-phenyl-9H-carbazole Ir(ppy)3

Investigation[edit | edit source]

catcat conc [µM]PSPS conc [mM]e-De-D conc [M]solvent A...λexc [nm].TON CO...
1.

Molecule:100951

2.5

Molecule:100952

0.005

Molecule:100861

0.05

MeCN

4002750
2.

Molecule:100951

2.5

Molecule:100950

0.005

Molecule:100861

0.05

MeCN

4006510
3.

Molecule:100951

2.5

Molecule:100953

0.005

Molecule:100861

0.05

MeCN

4008820
4.

Molecule:100951

2.5

Ir(ppy)3

0.005

Molecule:100861

0.05

MeCN

4007380
5.

Molecule:100951

2.5


Molecule:100861

0.05

MeCN

4000
6.

Molecule:100951

0.05

Molecule:100950

0.5

Molecule:100861

0.05

MeCN

40061
7.


Molecule:100950

0.5

Molecule:100861

0.05

MeCN

4000
8.

Molecule:100951

0.05

Molecule:100950

0.05

Molecule:100861

0.05

MeCN

400710
9.

Molecule:100951

0.05

Molecule:100950

0.005

Molecule:100861

0.05

MeCN

400860
10.

Molecule:100951

0.005

Molecule:100950

0.005

Molecule:100861

0.05

MeCN

4000

Sacrificial electron donor[edit | edit source]

In this study, the experiments were done with the sacrificial electron donor ascorbic acid L-ascorbate, sodium. The use of BIH was tested, but found to yield worse results.

Additives[edit | edit source]

In this study, potassium carbonate was added as a base. Control experiments under argon and with other bases were performed.

Investigations

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