Exchange Coupling Determines Metal-Dependent Efficiency for Iron- and Cobalt-Catalyzed Photochemical CO2 Reduction: Difference between revisions

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===A [[Category:Publication]] bs [[Category:Publication]] tract===
===Abstract===
[[Category:Publication]]
[[Category:Publication]]
====Summary ====
====Summary ====
A {{Annotation|property=Tag|value=photocatalytic CO2 reduction; voc4cat; voc4cat:0000099|display=photochemical reduction of CO2}} and {{Annotation|property=Tag|value=CO;;|display=CO}} to {{Annotation|property=Tag|value=methane; chebi; CHEBI:16183,CH4;;|display=methane}} was shown using the {{Annotation|property=Tag|value=nickel;;|display=nickel}} carbene complexes {{#moleculelink: |link=QDSMZTKUFVYRKR-UHFFFAOYSA-N|image=false|width=300|height=200}}, {{#moleculelink:|link=NWZXUODUJQGAHV-UHFFFAOYSA-N|image=false|width=300|height=200}}, and {{#moleculelink:|link=BQELNTZVSDPWHI-UHFFFAOYSA-N|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) up to 310000 for CO and 19000 for CH<sub>4</sub> and selectivities of 90% for CO<sub>2</sub> reduction products were reached for complex {{#moleculelink:|link=BQELNTZVSDPWHI-UHFFFAOYSA-N|image=false|width=300|height=200}} in {{Annotation|property=Tag|value=|display=acetonitrile}}. The experiments were conducted under visible-light irradiation using BIH as sacrificial electron donor (see section SEDs below).
A {{Annotation|property=Tag|value=photocatalytic CO2 reduction; voc4cat; voc4cat:0000099|display=photochemical reduction of CO2}} to {{Annotation|property=Tag|value=CO;;|display=CO}} was shown using an Fe2+ and Co2+ complex as catalysts in combination with different photosensitizers. The authors examined the efficiency for photocatalytic CO2RR pending on metal−ligand exchange coupling as an example of charge delocalization. The iron complex {{#moleculelink:|link=YJOFQAAXFUIRKO-UHFFFAOYSA-N|image=false|width=300|height=200}} and cobalt complexes{{#moleculelink:|link=GEWRDVXFGQMHJL-UHFFFAOYSA-N|image=false|width=300|height=200}}, both bearing the redox-active ligand tpyPY2Me  were tested in comparison. It was found that the two-electron reduction of the Co(tpyPY2Me)]2+ catalyst {{#moleculelink:|link=GEWRDVXFGQMHJL-UHFFFAOYSA-N|image=false|width=300|height=200}} occurs at potentials 770 mV more negative than the Fe(tpyPY2Me)]2+ analogue{{#moleculelink:|link=YJOFQAAXFUIRKO-UHFFFAOYSA-N|image=false|width=300|height=200}} due to maximizing the exchange coupling in the latter compound.  
====Advances and special progress====
====Advances and special progress====
====Additional remarks====
====Additional remarks====
The macrocyclic nickel carbene complex {{#moleculelink:|link=NWZXUODUJQGAHV-UHFFFAOYSA-N|image=false|width=300|height=200}} gave a higher carbon-selective reduction percentage than the related complexes {{#moleculelink:|link=BQELNTZVSDPWHI-UHFFFAOYSA-N|image=false|width=300|height=200}} and {{#moleculelink: |link=QDSMZTKUFVYRKR-UHFFFAOYSA-N|image=false|width=300|height=200}}. The conversion of CO<sub>2</sub> to CO and methane as well as the conversion of a CO/H<sub>2</sub> atmosphere to methane were investigated with complex {{#moleculelink:|link=NWZXUODUJQGAHV-UHFFFAOYSA-N|image=false|width=300|height=200}}.
 
===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 CH<sub>4</sub> and CO to CH<sub>4</sub> under visible-light catalysis using a nickel complex as a catalyst. The catalytic system performs best (referring to the TON of CH<sub>4</sub> production) in acetonitrile with a 1:1 CO/H<sub>2</sub> atmosphere.
 
===Catalysts tested in this study===
===Catalysts tested in this study===
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M  V30 6 C -2.82207 -0.160195 0.0 0
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M  V30 11 C -1.56971 2.09366 0.0 0
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M  V30 13 C 0.59091 1.38473 0.0 0
M  V30 14 N 1.03281 0.647561 0.0 0
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M  V30 17 C 1.86772 2.15013 0.0 0
M  V30 18 C 1.00836 2.13601 0.0 0
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M  V30 26 C 1.66347 -1.86344 0.0 0
M  V30 27 C 2.33535 -2.34218 0.0 0
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M  V30 36 C -0.771725 3.46759 0.0 0
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M  V30 42 3 34 35
M  V30 43 1 35 36
M  V30 44 10 34 19
M  V30 END BOND
M  V30 END CTAB
M  END
</chemform> <chemform smiles="C1C=C2C3C=CC=C4C5C=CC=C6C7(C8C=CC=CN=8[Co+2](N#CC)(N8C7=CC=CC=8)(N=56)(N=34)N2=CC=1)C" inchi="1S/C27H21N5.C2H3N.Co/c1-27(24-14-3-6-18-29-24,25-15-4-7-19-30-25)26-16-9-13-23(32-26)22-12-8-11-21(31-22)20-10-2-5-17-28-20;1-2-3;/h2-19H,1H3;1H3;/q;;+2" inchikey="GEWRDVXFGQMHJL-UHFFFAOYSA-N" height="200px" width="300px" float="none">
  -INDIGO-11172400032D
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M  V30 2 C -2.79762 -1.64865 0.0 0
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M  V30 7 C -1.54526 0.605208 0.0 0
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M  V30 9 C -0.268449 1.37061 0.0 0
M  V30 10 C -0.710354 2.10778 0.0 0
M  V30 11 C -1.56971 2.09366 0.0 0
M  V30 12 C -1.98716 1.34238 0.0 0
M  V30 13 C 0.59091 1.38473 0.0 0
M  V30 14 N 1.03281 0.647561 0.0 0
M  V30 15 C 1.89217 0.661678 0.0 0
M  V30 16 C 2.30963 1.41296 0.0 0
M  V30 17 C 1.86772 2.15013 0.0 0
M  V30 18 C 1.00836 2.13601 0.0 0
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M  V30 43 1 35 36
M  V30 44 10 34 19
M  V30 END BOND
M  V30 END CTAB
M  END
</chemform>


=== Photosensitizer ===
=== Photosensitizer ===
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M  V30 41 10 32 37
M  V30 42 10 23 37
M  V30 43 10 13 37
M  V30 44 10 11 37
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M  V30 END BOND
M  V30 END CTAB
M  END
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  -INDIGO-11172411382D
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M  V30 BEGIN BOND
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M  V30 48 C 3.94977 -1.66581 0.0 0
M  V30 49 C 3.23334 -1.25673 0.0 0
M  V30 50 C 1.07052 3.15423 0.0 0
M  V30 51 F 1.47828 2.43705 0.0 0
M  V30 52 F 1.7877 3.562 0.0 0
M  V30 53 F 0.66275 3.87141 0.0 0
M  V30 54 C 1.07011 -3.16024 0.0 0
M  V30 55 F 0.651958 -3.87141 0.0 0
M  V30 56 F 1.78129 -3.57839 0.0 0
M  V30 57 F 1.48827 -2.44906 0.0 0
M  V30 END ATOM
M  V30 BEGIN BOND
M  V30 1 1 50 51
M  V30 2 1 50 52
M  V30 3 1 50 53
M  V30 4 1 11 50
M  V30 5 1 54 55
M  V30 6 1 54 56
M  V30 7 1 54 57
M  V30 8 1 35 54
M  V30 9 2 2 3
M  V30 10 1 3 4
M  V30 11 2 4 5
M  V30 12 1 5 6
M  V30 13 2 6 7
M  V30 14 1 7 2
M  V30 15 1 6 8
M  V30 16 2 8 9
M  V30 17 1 9 10
M  V30 18 2 10 11
M  V30 19 1 11 12
M  V30 20 2 12 13
M  V30 21 1 13 8
M  V30 22 2 14 15
M  V30 23 1 15 16
M  V30 24 2 16 17
M  V30 25 1 17 18
M  V30 26 2 18 19
M  V30 27 1 19 14
M  V30 28 1 18 20
M  V30 29 2 20 21
M  V30 30 1 21 22
M  V30 31 2 22 23
M  V30 32 1 23 24
M  V30 33 2 24 25
M  V30 34 1 25 20
M  V30 35 2 26 27
M  V30 36 1 27 28
M  V30 37 2 28 29
M  V30 38 1 29 30
M  V30 39 2 30 31
M  V30 40 1 31 26
M  V30 41 1 30 32
M  V30 42 2 32 33
M  V30 43 1 33 34
M  V30 44 2 34 35
M  V30 45 1 35 36
M  V30 46 2 36 37
M  V30 47 1 37 32
M  V30 48 10 17 1
M  V30 49 10 21 1
M  V30 50 10 37 1
M  V30 51 1 31 1
M  V30 52 1 14 38
M  V30 53 1 24 39
M  V30 54 1 7 40
M  V30 55 1 3 41
M  V30 56 1 27 42
M  V30 57 1 29 43
M  V30 58 1 38 44
M  V30 59 1 38 45
M  V30 60 1 38 46
M  V30 61 1 39 47
M  V30 62 1 39 48
M  V30 63 1 39 49
M  V30 64 1 5 1
M  V30 65 10 9 1
M  V30 END BOND
M  V30 BEGIN SGROUP
M  V30 1 SUP 1 ATOMS=(4 50 51 52 53) BRKXYZ=(9 0.000000 0.000000 0.000000 0.0-
M  V30 00000 0.000000 0.000000 0.000000 0.000000 0.000000) BRKXYZ=(9 0.000000-
M  V30  0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 0.0000-
M  V30 00) LABEL=CF3
M  V30 2 SUP 2 ATOMS=(4 54 55 56 57) BRKXYZ=(9 0.000000 0.000000 0.000000 0.0-
M  V30 00000 0.000000 0.000000 0.000000 0.000000 0.000000) BRKXYZ=(9 0.000000-
M  V30  0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 0.000000 0.0000-
M  V30 00) LABEL=CF3
M  V30 END SGROUP
M  V30 END CTAB
M  END
</chemform> <chemform smiles="" inchi="" inchikey="NSABRUJKERBGOU-UHFFFAOYSA-N" height="200px" width="300px" float="none"></chemform>


=== Investigation ===
=== Investigation ===


===Further Information===
 
The Supporting Information gives quantum yields for described experiments in Table 1.
General details for the experimental setup: Conducted inside a 25 mL borosilicate culture tube with a stir bar, a rubber septum, and an aluminum crimped top. The reaction vessel contained 5 mL of CH3CN, 2 μM of the catalyst, 200 μM of the photosensitizer, 100 mM BIH (112 mg), and 1 M phenol (470 mg). The reaction tubes were sparged with CO2 for 10 min, followed by injection of a gaseous internal standard (0.1 mL of C2H6). The reactions were placed on a stirplate 13 cm from two Kessil blue LED lamps (440 nm) for 15 or 30 min at a time and maintained at ambient temperature using a fan. Analysis of the headspace by Gas Chromatography (GC).{{#experimentlist:|form=Photocatalytic_CO2_conversion_experiments|name=CO2 Reduction under diverse conditions with diverse sensitizers|importFile=Exchange Coupling Determines Metal-Dependent Efficiency for Iron- and Cobalt-Catalyzed Photochemical CO2 Reduction_2.xlsx}}
 
The values in Table 2 include TOF numbers given in TON/min
 
{{#experimentlist:|form=Photocatalytic_CO2_conversion_experiments|name=Results Co2+ experiments taken from SI|importFile=Exchange publication_table 2.xlsx}}
 
=== Further Information ===
The results for the catalytic activity of the Co2+ compound {{#moleculelink:|link=GEWRDVXFGQMHJL-UHFFFAOYSA-N|image=false|width=300|height=200}} in Table 2 were gained from the Supporting Information.  
====Sacrificial electron donor====
====Sacrificial electron donor====
In this study, the experiments were done with the sacrificial electron donor BIH ([[Molecule:100508|100508]]).
In this study, the experiments were done with the sacrificial electron donor BIH ([[Molecule:100508|100508]]).
====Additives====
====Additives====
Different sources of protons were used, e.g. {{#moleculelink:|link=ISWSIDIOOBJBQZ-UHFFFAOYSA-N|image=false|width=300|height=200}}, {{#moleculelink:|link=RHQDFWAXVIIEBN-UHFFFAOYSA-N|image=false|width=300|height=200}} and {{#moleculelink:|link=WXNZTHHGJRFXKQ-UHFFFAOYSA-N|image=false|width=300|height=200}}

Latest revision as of 23:34, 22 November 2024


Abstract[edit | edit source]

Summary[edit | edit source]

A photochemical reduction of CO2 to CO was shown using an Fe2+ and Co2+ complex as catalysts in combination with different photosensitizers. The authors examined the efficiency for photocatalytic CO2RR pending on metal−ligand exchange coupling as an example of charge delocalization. The iron complex 100968 and cobalt complexes100969, both bearing the redox-active ligand tpyPY2Me were tested in comparison. It was found that the two-electron reduction of the Co(tpyPY2Me)]2+ catalyst 100969 occurs at potentials 770 mV more negative than the Fe(tpyPY2Me)]2+ analogue100968 due to maximizing the exchange coupling in the latter compound.

Advances and special progress[edit | edit source]

Additional remarks[edit | edit source]

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

Catalysts tested in this study[edit | edit source]

100968 100969

Photosensitizer[edit | edit source]

Ru(bpy)3 3,6-Diamino-10-methylacridinium 100971 Ir(ppy)3

Investigation[edit | edit source]

General details for the experimental setup: Conducted inside a 25 mL borosilicate culture tube with a stir bar, a rubber septum, and an aluminum crimped top. The reaction vessel contained 5 mL of CH3CN, 2 μM of the catalyst, 200 μM of the photosensitizer, 100 mM BIH (112 mg), and 1 M phenol (470 mg). The reaction tubes were sparged with CO2 for 10 min, followed by injection of a gaseous internal standard (0.1 mL of C2H6). The reactions were placed on a stirplate 13 cm from two Kessil blue LED lamps (440 nm) for 15 or 30 min at a time and maintained at ambient temperature using a fan. Analysis of the headspace by Gas Chromatography (GC).

catcat conc [µM]PSPS conc [mM]e-De-D conc [M]..solvent Aadditives..TON COTON H2..
1.

Molecule:100968

2

Ru(bpy)3

0.2

BIH

0.1

MeCN

1552086
2.

Molecule:100968

0.2

Ru(bpy)3

0.2

BIH

0.1

MeCN

303491013
3.


Ru(bpy)3

0.2

BIH

0.1

MeCN

4352
4.

Molecule:100968

2


BIH

0.1

MeCN

1120
5.

Molecule:100968

2

Ru(bpy)3

0.2


MeCN

1500
6.

Molecule:100968

2

Ru(bpy)3

0.2

BIH

0.1

MeCN

60
7.

Molecule:100968

2

Ru(bpy)3

0.2

BIH

0.1

MeCN

Ar0222
8.

Molecule:100968

2

Molecule:100971

0.2

BIH

0.1

MeCN

12749163
9.

Molecule:100968

0.2

Molecule:100971

0.2

BIH

0.1

MeCN

287126527
10.

Molecule:100968

2

Ir(ppy)3

0.2

BIH

0.1

MeCN

18502141
11.

Molecule:100968

2

Molecule:100970

0.2

BIH

0.1

MeCN

67100

The values in Table 2 include TOF numbers given in TON/min

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

Molecule:100969

2

Ru(bpy)3

0.2

BIH

0.1

MeCN

2.

Molecule:100969

2

Molecule:100971

0.2

BIH

0.1

MeCN

3.

Molecule:100969

2

Ir(ppy)3

0.2

BIH

0.05

MeCN

4.

Molecule:100969

2

Molecule:100971

0.2

BIH

0.05

MeCN

5.

Molecule:100969

2

Ru(bpy)3

0.2

BIH

0.05

MeCN

6.

Molecule:100969

2

Molecule:100971

0.2

TEA

0.05

MeCN

7.

Molecule:100969

2

Molecule:100971

0.2

TEA

0.05

MeCN

8.

Molecule:100969

2

Molecule:100971

0.2

TEA

0.05

MeCN

9.

Molecule:100969

2

Molecule:100971

0.2

TEA

0.05

MeCN

Investigation-Name: Results Co2+ experiments taken from SI

Further Information[edit | edit source]

The results for the catalytic activity of the Co2+ compound 100969 in Table 2 were gained from the Supporting Information.

Sacrificial electron donor[edit | edit source]

In this study, the experiments were done with the sacrificial electron donor BIH (100508).

Additives[edit | edit source]

Different sources of protons were used, e.g. PhOH, TFE and 4-CHLOROPHENOL

Investigations

Tags

TagContains tags that describe the content of the page.: photocatalytic CO2 reduction (Ontology: voc4cat, OBOID: voc4cat:0000099), TagContains tags that describe the content of the page.: CO

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