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

Latest revision as of 15:19, 22 November 2024

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).

	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

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

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

"Molecule:" can not be assigned to a declared number type with value 1009792."Molecule:" can not be assigned to a declared number type with value 1009819.

	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

Experiment-Name: Table 2 Co catalyst testing

"Molecule:" can not be assigned to a declared number type with value 1009792."Molecule:" can not be assigned to a declared number type with value 1009819.

	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

Experiment-Name: testtest2

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)
Iron-Catalyzed Photochemical CO2 Reduction under diverse conditions (Molecular process, Photocatalytic CO2 conversion experiments)
Iron-Catalyzed Photochemical CO2 Reduction under diverse conditions error (Molecular process, Photocatalytic CO2 conversion experiments)
Table 2 Co catalyst testing (Molecular process, Photocatalytic CO2 conversion experiments)
Table 2 Conversion with Co catalyst (Molecular process, Photocatalytic CO2 conversion experiments)
Table 2 conversion with Co catalyst (Molecular process, Photocatalytic CO2 conversion experiments)
testtest2 (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 497: / Line 497: @@
 The values in Table 2 include TOF numbers given in TON/h
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+{{#experimentlist:|form=Photocatalytic_CO2_conversion_experiments|name=Table 2 Co catalyst testing|importFile=Exchange Coupling Determines Metal-Dependent Efficiency for Iron- and Cobalt-Catalyzed Photochemical CO2 Reduction_Table2.xlsx}}
+{{#experimentlist:|form=Photocatalytic_CO2_conversion_experiments|name=testtest2|importFile=Exchange Coupling Determines Metal-Dependent Efficiency for Iron- and Cobalt-Catalyzed Photochemical CO2 Reduction_Table2.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.
+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====
 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 <chemform smiles="C1C=C(Cl)C=CC=1O" inchi="1S/C6H5ClO/c7-5-1-3-6(8)4-2-5/h1-4,8H" inchikey="WXNZTHHGJRFXKQ-UHFFFAOYSA-N" height="200px" width="300px" float="none">
+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}}
-  -INDIGO-11172415362D
-  0  0  0  0  0  0  0  0  0  0 V3000
-M  V30 BEGIN CTAB
-M  V30 COUNTS 8 8 0 0 0
-M  V30 BEGIN ATOM
-M  V30 1 C 4.00985 -6.67507 0.0 0
-M  V30 2 C 5.74015 -6.67459 0.0 0
-M  V30 3 C 4.87664 -6.17497 0.0 0
-M  V30 4 C 5.74015 -7.67553 0.0 0
-M  V30 5 C 4.00985 -7.68002 0.0 0
-M  V30 6 C 4.87882 -8.17503 0.0 0
-M  V30 7 O 4.87725 -5.17497 0.0 0
-M  V30 8 Cl 4.88268 -9.17503 0.0 0
-M  V30 END ATOM
-M  V30 BEGIN BOND
-M  V30 1 2 3 1
-M  V30 2 2 4 2
-M  V30 3 1 1 5
-M  V30 4 1 2 3
-M  V30 5 2 5 6
-M  V30 6 1 6 4
-M  V30 7 1 3 7
-M  V30 8 1 6 8
-M  V30 END BOND
-M  V30 END CTAB
-M  END
-</chemform>

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

Latest revision as of 15:19, 22 November 2024

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 15:19, 22 November 2024

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