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+ complexes as catalysts in combination with Ruxx as photosensitizer.  
 
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====
====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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=== Investigation ===
=== Investigation ===
{{#experimentlist:|form=Photocatalytic_CO2_conversion_experiments|name=Comparison of Fe and Co complexes|importFile=}}


===Further Information===
===Further Information===

Revision as of 23:57, 16 November 2024


Abstract

Summary

A photochemical reduction of CO2 to CO was shown using an Fe2+ and Co2+ complexes as catalysts in combination with Ruxx as photosensitizer.

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

Content of the published article in detail

Catalysts tested in this study

Photosensitizer

Investigation

Experiment 'Exchange Coupling Determines Metal-Dependent Efficiency for Iron- and Cobalt-Catalyzed Photochemical CO2 Reduction/Comparison of Fe and Co complexes' does not exist.

Further Information

The Supporting Information gives quantum yields for described experiments in Table 1.

Sacrificial electron donor

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

Additives

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