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

Latest revision as of 16:51, 17 January 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 catalyst100968, 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

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+ 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.
+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====
@@ Line 15: / 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">
+<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.FC(S([O-])(=O)=O)(F)F.FC(S([O-])(=O)=O)(F)F" inchikey="NIRWJCRVFQKYDZ-UHFFFAOYSA-L" inchi="1S/C27H21N5.C2H3N.2CHF3O3S.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;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">
-   -INDIGO-11172400022D
+   -INDIGO-01102515192D
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 M  V30 BEGIN CTAB
-M  V30 COUNTS 36 44 0 0 0
+M  V30 COUNTS 52 58 0 0 0
 M  V30 BEGIN ATOM
 M  V30 1 C -3.23952 -0.911479 0.0 0
@@ Line 58: / 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
 M  V30 BEGIN BOND
@@ Line 104: / Line 120: @@
 M  V30 43 1 35 36
 M  V30 44 10 34 19
+M  V30 45 1 37 38
+M  V30 46 1 38 39
+M  V30 47 1 38 40
+M  V30 48 1 38 41
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+M  V30 50 2 41 43
+M  V30 51 1 41 44
+M  V30 52 1 45 46
+M  V30 53 1 46 47
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+M  V30 57 2 49 51
+M  V30 58 1 49 52
 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">
+</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">
-   -INDIGO-11172400032D
+   -INDIGO-01102515192D
   0  0  0  0  0  0  0  0  0  0 V3000
 M  V30 BEGIN CTAB
-M  V30 COUNTS 36 44 0 0 0
+M  V30 COUNTS 52 58 0 0 0
 M  V30 BEGIN ATOM
 M  V30 1 C -3.23952 -0.911479 0.0 0
@@ Line 150: / Line 180: @@
 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 3.45897 1.925 0.0 0
+M  V30 38 C 4.325 2.425 0.0 0
+M  V30 39 F 4.325 3.425 0.0 0
+M  V30 40 F 3.825 1.55897 0.0 0
+M  V30 41 S 5.19103 1.925 0.0 0
+M  V30 42 O 5.89813 2.63211 0.0 0
+M  V30 43 O 6.19103 1.925 0.0 0
+M  V30 44 O 5.19103 0.925 0.0 0 CHG=-1
+M  V30 45 F 3.85897 -0.575 0.0 0
+M  V30 46 C 4.725 -0.075 0.0 0
+M  V30 47 F 4.725 0.925 0.0 0
+M  V30 48 F 4.225 -0.941025 0.0 0
+M  V30 49 S 5.59103 -0.575 0.0 0
+M  V30 50 O 6.29813 0.132107 0.0 0
+M  V30 51 O 6.59103 -0.575 0.0 0
+M  V30 52 O 5.59103 -1.575 0.0 0 CHG=-1
 M  V30 END ATOM
 M  V30 BEGIN BOND
@@ Line 196: / Line 242: @@
 M  V30 43 1 35 36
 M  V30 44 10 34 19
+M  V30 45 1 37 38
+M  V30 46 1 38 39
+M  V30 47 1 38 40
+M  V30 48 1 38 41
+M  V30 49 2 41 42
+M  V30 50 2 41 43
+M  V30 51 1 41 44
+M  V30 52 1 45 46
+M  V30 53 1 46 47
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 M  V30 END BOND
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@@ Line 493: / Line 553: @@
-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}}
+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
@@ Line 500: / Line 560: @@
 === 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.
+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}}

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

Latest revision as of 16:51, 17 January 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 16:51, 17 January 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