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

Latest revision as of 11:41, 21 November 2025

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 MeCN, 2 μM of the catalyst 100968, 200 μM of the photosensitizer Ru(bpy)3, 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 stir plate 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).

	cat	cat conc [µM]	PS	PS conc [mM]	e-D	e-D conc [M]	solvent A	additives	TON CO	TON H2
1.	Molecule:100968	2	Ru(bpy)3	0.2	BIH	0.1	MeCN		15520	86
2.	Molecule:100968	0.2	Ru(bpy)3	0.2	BIH	0.1	MeCN		30349	1013
3.			Ru(bpy)3	0.2	BIH	0.1	MeCN		43	52
4.	Molecule:100968	2			BIH	0.1	MeCN		112	0
5.	Molecule:100968	2	Ru(bpy)3	0.2			MeCN		150	0
6.	Molecule:100968	2	Ru(bpy)3	0.2	BIH	0.1	MeCN		6	0
7.	Molecule:100968	2	Ru(bpy)3	0.2	BIH	0.1	MeCN	Ar	0	222
8.	Molecule:100968	2	Molecule:100971	0.2	BIH	0.1	MeCN		12749	163
9.	Molecule:100968	0.2	Molecule:100971	0.2	BIH	0.1	MeCN		28712	6527
10.	Molecule:100968	2	Ir(ppy)3	0.2	BIH	0.1	MeCN		18502	141
11.	Molecule:100968	2	Molecule:100970	0.2	BIH	0.1	MeCN		6710	0

Investigation-Name: CO2 Reduction under diverse conditions with diverse sensitizers

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

	cat	cat conc [µM]	PS	PS conc [mM]	e-D	e-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

Tags: photochemical CO2 reduction, photocatalysis, homogeneous catalysis, iron complex catalyst, cobalt complex catalyst, tpyPY2Me ligand, Ru(bpy)3 photosensitizer, acridinium photosensitizer, Ir(ppy)3 photosensitizer, BIH sacrificial electron donor, phenol proton source, MeCN solvent, blue LED irradiation, metal–ligand exchange coupling, charge delocalization, turnover number determination, gas chromatography analysis

Investigations

CO2 Reduction under diverse conditions with diverse sensitizers (Molecular process, Photocatalytic CO2 conversion experiments)
Results Co2+ experiments taken from SI (Molecular process, Photocatalytic CO2 conversion experiments)

DOI	10.1021/acscatal.2c02072
Authors	Patricia De La Torre, Jeffrey S. Derrick, Andrew Snider, Peter T. Smith, Matthias Loipersberger, Martin Head-Gordon, Christopher J. Chang,
Submitted	01.07.2022
Published online	01.07.2022
Licenses	https://doi.org/10.15223/policy-029, https://doi.org/10.15223/policy-037, https://doi.org/10.15223/policy-045,
Subjects	-
Go to literature page

@@ Line 7: / Line 7: @@
 [[Category:Publication]]
 ====Summary ====
-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+ complexes as catalysts in combination with Ruxx as photosensitizer.
+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 Fe<sup>2+</sup> and Co<sup>2+</sup> complex as catalysts in combination with different photosensitizers. The authors examined the efficiency for photocatalytic CO<sub>2</sub>RR pending on metal−ligand exchange coupling as an example of charge delocalization. The iron complex {{#moleculelink: |link=NIRWJCRVFQKYDZ-UHFFFAOYSA-L|image=false|width=300|height=200}} and cobalt complexes{{#moleculelink: |link=CSMKCVWSHRTJMD-UHFFFAOYSA-L|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=CSMKCVWSHRTJMD-UHFFFAOYSA-L|image=false|width=300|height=200}} occurs at potentials 770 mV more negative than the Fe(tpyPY2Me)]2+ analogue{{#moleculelink: |link=NIRWJCRVFQKYDZ-UHFFFAOYSA-L|image=false|width=300|height=200}} due to maximizing the exchange coupling in the latter compound.
+====Advances and special progress====
-metal−ligand exchange coupling as an example of charge delocalization that can determine the efficiency for photocatalytic CO2RR. A comparative evaluation of iron and cobalt complexes supported by the redox-active ligand tpyPY2Me establishes that the two-electron reduction of [Co(tpyPY2Me)]2+ ([Co]2+) occurs at potentials 770 mV more negative than the [Fe(tpyPY2Me)]2+ ([Fe]2+) analogue by maximizing the exchange coupling in the latter compound.
-====Advances and special progress====
 ====Additional remarks====
@@ Line 16: / Line 15: @@
 ===Catalysts tested in this study===
-<chemform smiles="C1C=C2C3C=CC=C4C5C=CC=C6C7(C8C=CC=CN=8[Fe+2](N#CC)(N8C7=CC=CC=8)(N=56)(N=34)N2=CC=1)C" inchi="1S/C27H21N5.C2H3N.Fe/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="YJOFQAAXFUIRKO-UHFFFAOYSA-N" height="200px" width="300px" float="none">
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 M  V30 1 C -3.23952 -0.911479 0.0 0
@@ Line 59: / Line 58: @@
 M  V30 35 C -0.188361 2.88423 0.0 0
 M  V30 36 C -0.771725 3.46759 0.0 0
+M  V30 37 F 4.59199 1.175 0.0 0
+M  V30 38 C 5.45801 1.675 0.0 0
+M  V30 39 F 5.45801 2.675 0.0 0
+M  V30 40 F 4.95801 0.808975 0.0 0
+M  V30 41 S 6.32404 1.175 0.0 0
+M  V30 42 O 7.03115 1.88211 0.0 0
+M  V30 43 O 7.32404 1.175 0.0 0
+M  V30 44 O 6.32404 0.175 0.0 0 CHG=-1
+M  V30 45 F 4.15897 -1.425 0.0 0
+M  V30 46 C 5.025 -0.925 0.0 0
+M  V30 47 F 5.025 0.075 0.0 0
+M  V30 48 F 4.525 -1.79103 0.0 0
+M  V30 49 S 5.89103 -1.425 0.0 0
+M  V30 50 O 6.59813 -0.717893 0.0 0
+M  V30 51 O 6.89103 -1.425 0.0 0
+M  V30 52 O 5.89103 -2.425 0.0 0 CHG=-1
 M  V30 END ATOM
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@@ Line 105: / Line 120: @@
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 M  V30 44 10 34 19
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 M  V30 END BOND
 M  V30 END CTAB
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-</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">
+</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.FC(S([O-])(=O)=O)(F)F.FC(S([O-])(=O)=O)(F)F" inchikey="CSMKCVWSHRTJMD-UHFFFAOYSA-L" inchi="1S/C27H21N5.C2H3N.2CHF3O3S.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;2*2-1(3,4)8(5,6)7;/h2-19H,1H3;1H3;2*(H,5,6,7);/q;;;;+2/p-2" float="none" width="200" height="200">
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@@ Line 151: / Line 180: @@
 M  V30 35 C -0.188361 2.88423 0.0 0
 M  V30 36 C -0.771725 3.46759 0.0 0
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+M  V30 40 F 3.825 1.55897 0.0 0
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@@ Line 492: / Line 551: @@
 === Investigation ===
-{{#experimentlist:|form=Photocatalytic_CO2_conversion_experiments|name=Iron-Catalyzed Photochemical CO2 Reduction under diverse conditions|importFile=Exchange Coupling Determines Metal-Dependent Efficiency for Iron- and Cobalt-Catalyzed Photochemical CO2 Reduction.xlsx}}
-===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 {{#moleculelink:|link=WEVYAHXRMPXWCK-UHFFFAOYSA-N|image=false|width=300|height=200}}, 2 μM of the catalyst {{#moleculelink:|link=NIRWJCRVFQKYDZ-UHFFFAOYSA-L|image=false|width=300|height=200}}, 200 μM of the photosensitizer {{#moleculelink:|link=HNVRWFFXWFXICS-UHFFFAOYSA-N|image=false|width=300|height=200}}, 100 mM {{#moleculelink:|link=VDFIVJSRRJXMAU-UHFFFAOYSA-N|image=false|width=300|height=200}} (112 mg), and 1 M phenol (470 mg). The reaction tubes were sparged with CO<sub>2</sub> for 10 min, followed by injection of a gaseous internal standard (0.1 mL of C<sub>2</sub>H<sub>6</sub>). The reactions were placed on a stir plate 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 Co<sup>2+</sup> compound {{#moleculelink: |link=CSMKCVWSHRTJMD-UHFFFAOYSA-L|image=false|width=300|height=200}} in Table 2 were gained from the Supporting Information.
 ====Sacrificial electron donor====
 In this study, the experiments were done with the sacrificial electron donor BIH ([[Molecule:100508|100508]]).
 ====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}}
+{{Tags|tags=photochemical CO2 reduction, photocatalysis, homogeneous catalysis, iron complex catalyst, cobalt complex catalyst, tpyPY2Me ligand, Ru(bpy)3 photosensitizer, acridinium photosensitizer, Ir(ppy)3 photosensitizer, BIH sacrificial electron donor, phenol proton source, MeCN solvent, blue LED irradiation, metal–ligand exchange coupling, charge delocalization, turnover number determination, gas chromatography analysis}}

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

Latest revision as of 11:41, 21 November 2025

Contents

Abstract[edit | edit source]

Summary[edit | edit source]

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]

Photosensitizer[edit | edit source]

Investigation[edit | edit source]

Further Information[edit | edit source]

Sacrificial electron donor[edit | edit source]

Additives[edit | edit source]

Investigations

Tags

Topics

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

Latest revision as of 11:41, 21 November 2025

Abstract[edit | edit source]

Summary[edit | edit source]

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]

Photosensitizer[edit | edit source]

Investigation[edit | edit source]

Further Information[edit | edit source]

Sacrificial electron donor[edit | edit source]

Additives[edit | edit source]

Investigations

Tags

Current site

Topics