Light-Driven Reduction of CO2 to CO in Water with a Cobalt Molecular Catalyst and an Organic Sensitizer: Difference between revisions

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== Catalyst ==
=== Abstract ===
 
==== Summary ====
A photochemical reduction of CO2 to CO was shown using the cobalt complex [[Molecule:100826|100826]] as a catalyst in combination with the organic, water soluble triazatriangulenium photosensitizer [[Molecule:100498|100498]]. Turnover numbers (TONs) up to 19000 and selectivity of 93% for CO were reached in acetonitrile with 20% of water. The experiments were conducted under visible-light irradiation (λ > 450 nm) using tertiary amines or BIH as sacrificial electron donors (see section SEDs below).
 
==== Advances and special progress ====
The photoreduction of CO2 to CO could be shown in 100% water with a TON of 2600 and a selectivity of 94% without any noble metals or rare materials.
 
==== Additional remarks ====
 
=== Content of the published article in detail ===
The article contains results for the reduction of CO2 to CO under visible-light catalysis using a cobalt complex as a catalyst. The catalytic system performs best (referring to the TON of CO production) for CO as a feedstock.
 
==== Catalyst ====
<chemform smiles="C1C2C3C=CC=C4C5C=CC=C6C7C=CC=CN=7[Co+2](O)(O)(N=34)(N=56)N=2C=CC=1.Cl([O-])(=O)(=O)=O.Cl([O-])(=O)(=O)=O" inchi="1S/C20H14N4.2ClHO4.Co.2H2O/c1-3-13-21-15(7-1)17-9-5-11-19(23-17)20-12-6-10-18(24-20)16-8-2-4-14-22-16;2*2-1(3,4)5;;;/h1-14H;2*(H,2,3,4,5);;2*1H2/q;;;+2;;/p-2" inchikey="OZQYFMFOIFRRLI-UHFFFAOYSA-L" height="200px" width="300px" float="none"></chemform><chemform smiles="[Co+2]([Cl-])[Cl-]" inchi="1S/2ClH.Co/h2*1H;/q;;+2/p-2" inchikey="GVPFVAHMJGGAJG-UHFFFAOYSA-L" height="200px" width="300px" float="none">
<chemform smiles="C1C2C3C=CC=C4C5C=CC=C6C7C=CC=CN=7[Co+2](O)(O)(N=34)(N=56)N=2C=CC=1.Cl([O-])(=O)(=O)=O.Cl([O-])(=O)(=O)=O" inchi="1S/C20H14N4.2ClHO4.Co.2H2O/c1-3-13-21-15(7-1)17-9-5-11-19(23-17)20-12-6-10-18(24-20)16-8-2-4-14-22-16;2*2-1(3,4)5;;;/h1-14H;2*(H,2,3,4,5);;2*1H2/q;;;+2;;/p-2" inchikey="OZQYFMFOIFRRLI-UHFFFAOYSA-L" height="200px" width="300px" float="none"></chemform><chemform smiles="[Co+2]([Cl-])[Cl-]" inchi="1S/2ClH.Co/h2*1H;/q;;+2/p-2" inchikey="GVPFVAHMJGGAJG-UHFFFAOYSA-L" height="200px" width="300px" float="none">
   -INDIGO-11172313372D
   -INDIGO-11172313372D
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</chemform>
</chemform>


== Photosensitizer ==
==== Photosensitizer ====
<chemform smiles="C12C3N(CCCC)C4C5[C+]1C1C(N(CCCC)C=5C=CC=4)=CC=CC=1N(CCCC)C=2C=CC=3.[P-](F)(F)(F)(F)(F)F" inchi="1S/C31H36N3.F6P/c1-4-7-19-32-22-13-10-15-24-28(22)31-29-23(32)14-11-16-25(29)34(21-9-6-3)27-18-12-17-26(30(27)31)33(24)20-8-5-2;1-7(2,3,4,5)6/h10-18H,4-9,19-21H2,1-3H3;/q+1;-1" inchikey="DORDHQADTWICIT-UHFFFAOYSA-N" height="200px" width="300px" float="none">
<chemform smiles="C12C3N(CCCC)C4C5[C+]1C1C(N(CCCC)C=5C=CC=4)=CC=CC=1N(CCCC)C=2C=CC=3.[P-](F)(F)(F)(F)(F)F" inchi="1S/C31H36N3.F6P/c1-4-7-19-32-22-13-10-15-24-28(22)31-29-23(32)14-11-16-25(29)34(21-9-6-3)27-18-12-17-26(30(27)31)33(24)20-8-5-2;1-7(2,3,4,5)6/h10-18H,4-9,19-21H2,1-3H3;/q+1;-1" inchikey="DORDHQADTWICIT-UHFFFAOYSA-N" height="200px" width="300px" float="none">
   -INDIGO-11172313202D
   -INDIGO-11172313202D
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</chemform>
</chemform>


== Investigations ==
==== Investigations ====
{{#experimentlist:|form=Photocatalytic_CO2_conversion_experiments|name=Visible-Light Driven CO2 Reduction with 1/TATA+/BIH + TEOA under Various Conditions|importFile=}}
{{#experimentlist:|form=Photocatalytic_CO2_conversion_experiments|name=Visible-Light Driven CO2 Reduction with 1/TATA+/BIH + TEOA under Various Conditions|importFile=}}


{{#experimentlist:|form=Photocatalytic_CO2_conversion_experiments|name=Photocatalytic CO2 Reduction by 1 (2 μM) in CO2-Saturated Aqueous CH3CN Solutions|importFile=}}
{{#experimentlist:|form=Photocatalytic_CO2_conversion_experiments|name=Photocatalytic CO2 Reduction by 1 (2 μM) in CO2-Saturated Aqueous CH3CN Solutions|importFile=}}


== Sacrificial electron donor ==
==== Sacrificial electron donor ====
<chemform smiles="" inchi="" inchikey="VDFIVJSRRJXMAU-UHFFFAOYSA-N" height="200px" width="300px" float="none"></chemform>
<chemform smiles="" inchi="" inchikey="VDFIVJSRRJXMAU-UHFFFAOYSA-N" height="200px" width="300px" float="none"></chemform>
==== Additives ====

Revision as of 13:24, 9 January 2024


Abstract

Summary

A photochemical reduction of CO2 to CO was shown using the cobalt complex 100826 as a catalyst in combination with the organic, water soluble triazatriangulenium photosensitizer 100498. Turnover numbers (TONs) up to 19000 and selectivity of 93% for CO were reached in acetonitrile with 20% of water. The experiments were conducted under visible-light irradiation (λ > 450 nm) using tertiary amines or BIH as sacrificial electron donors (see section SEDs below).

Advances and special progress

The photoreduction of CO2 to CO could be shown in 100% water with a TON of 2600 and a selectivity of 94% without any noble metals or rare materials.

Additional remarks

Content of the published article in detail

The article contains results for the reduction of CO2 to CO under visible-light catalysis using a cobalt complex as a catalyst. The catalytic system performs best (referring to the TON of CO production) for CO as a feedstock.

Catalyst

[Co(qpy)(H2O)2][ClO4]2 CoCl2

Photosensitizer

100797

Investigations

catcat conc [µM]PSPS conc [mM]e-De-D conc [M]solvent A..additivesλexc [nm]TON COTON H2TON HCOOH.
1.

[Co(qpy)(H2O)2][ClO4]2

0.002

Molecule:100797

0.2

BIH

0.1

MeCN

45023321061370
2.


Molecule:100797

0.2

BIH

0.1

MeCN

450000
3.

[Co(qpy)(H2O)2][ClO4]2

0.002


BIH

0.1

MeCN

450000
4.

[Co(qpy)(H2O)2][ClO4]2

0.002

Molecule:100797

0.2


MeCN

45095086316
5.

[Co(qpy)(H2O)2][ClO4]2

0.002

Molecule:100797

0.2

BIH

0.1

MeCN

45010775
6.

[Co(qpy)(H2O)2][ClO4]2

0.002

Molecule:100797

0.2

BIH

0.1

MeCN

Argon atmosphere450070
7.

CoCl2

0.005

Molecule:100797

0.2

BIH

0.1

MeCN

45001590
8.

[Co(qpy)(H2O)2][ClO4]2

0.002

Molecule:100797

0.2

BIH

0.1

MeCN

Hg (0.1 mL)45018802551973
catcat conc [µM]PSPS conc [mM]e-De-D conc [M]..solvent A..additivesλexc [nm]TON COTON H2TON HCOOH.
1.

[Co(qpy)(H2O)2][ClO4]2

0.002

Molecule:100797

0.2

BIH

0.1

MeCN

45023321061370
2.

[Co(qpy)(H2O)2][ClO4]2

0.002

Molecule:100797

0.2

BIH

0.1

MeCN

45062283042441
3.

[Co(qpy)(H2O)2][ClO4]2

0.002

Molecule:100797

0.2

BIH

0.1

MeCN

450146912831097
4.

[Co(qpy)(H2O)2][ClO4]2

0.002

Molecule:100797

0.2

BIH

0.1

MeCN

450158222201147
5.

[Co(qpy)(H2O)2][ClO4]2

0.002

Molecule:100797

0.2

BIH

0.1

MeCN

450189892271215
6.

[Co(qpy)(H2O)2][ClO4]2

0.002

Molecule:100797

0.2

BIH

0.1

MeCN

Hg45019646226415
7.

[Co(qpy)(H2O)2][ClO4]2

0.002

Molecule:100797

0.2

BIH

0.1

MeCN

4501839419
8.

[Co(qpy)(H2O)2][ClO4]2

0.002

Molecule:100797

0.2

BIH

0.1

MeCN

45061220251
9.

[Co(qpy)(H2O)2][ClO4]2

0.002

Molecule:100797

0.2

BIH

0.1

MeCN

45051525346
10.

[Co(qpy)(H2O)2][ClO4]2

0.002

Molecule:100797

0.2

BIH

0.1

MeCN

4503171498179
11.

[Co(qpy)(H2O)2][ClO4]2

0.002

Molecule:100797

0.2

BIH

0.1

MeCN

4506331264179
12.

[Co(qpy)(H2O)2][ClO4]2

0.002

Molecule:100797

0.2

BIH

0.1

MeCN

Hg450628630497

Sacrificial electron donor

BIH

Additives

Investigations