Examining iron complexes with organic ligands by laboratory XAFS

Motz, Damian; Praetz, Sebastian; Schlesiger, Christopher; Henniges, Jonathan; Böttcher, Florian; Hesse, Bernhard; Castillo‐Michel, Hiram; Mijatz, Steven; Malzer, Wolfgang; Kanngießer, Birgit; Vogt, C.

doi:10.1039/d2ja00351a

“…The performance of laboratory and synchrotron based XANES measurements for examining Fe complexes with organic ligands has been compared. 91 The laboratory instrument is based on a Highly Annealed Pyrolytic Graphite (HAPG) von Hamos spectrometer with the use of a cylindrically shaped crystal for combining high spectral resolution with a high solid angle of detection, modified to use a thinner HAPG crystal with a broader bending radius, which improves the spectral resolving power of the spectrometer. For validation, synchrotron XAFS measurements were performed at the μSR-XFM/μXAS beamline ID21 at the ESRF45 operating from 2.0 to 9.6 keV.…”

Section: Elemental Speciation Analysismentioning

confidence: 99%

Atomic spectrometry update: review of advances in elemental speciation

Clough,

Harrington,

Hill

et al. 2024

J. Anal. At. Spectrom.

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Operando Spectroelectrochemistry Unravels the Mechanism of CO₂ Electrocatalytic Reduction by an Fe Porphyrin

Salamé,

Hon Cheah,

Bonin

et al. 2024

Angewandte Chemie

0

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Iron porphyrins are molecular catalysts recognized for their ability to electrochemically and photochemically reduce carbon dioxide (CO2). The main reduction product is carbon monoxide (CO). CO holds significant industrial importance as it serves as a precursor for various valuable chemical products containing either a single carbon atom (C1), like methanol or methane, or multiple carbon atoms (Cn), such as ethanol or ethylene. Despite the long‐established efficiency of these catalysts, optimizing their catalytic activity and stability and comprehending the intricate reaction mechanisms remain a significant challenge. This article presents a comprehensive investigation of the mechanistic aspects of the selective electroreduction of CO2 to CO using an iron porphyrin substituted with four trimethylammonium groups in the para position [(pTMA)FeIII‐Cl]4+. By employing infrared and UV‐Visible spectroelectrochemistry, changes in the electronic structure and coordination environment of the iron center can be observed in real‐time as the electrochemical potential is adjusted, offering new insights into the reaction mechanisms. Catalytic species were identified, and evidence of a secondary reaction pathway was uncovered, potentially prompting a re‐evaluation of the nature of the catalytically active species.

show abstract

Operando Spectroelectrochemistry Unravels the Mechanism of CO₂ Electrocatalytic Reduction by an Fe Porphyrin

Salamé,

Hon Cheah,

Bonin

et al. 2024

Angew Chem Int Ed

1

0

View full text Add to dashboard Cite

Iron porphyrins are molecular catalysts recognized for their ability to electrochemically and photochemically reduce carbon dioxide (CO2). The main reduction product is carbon monoxide (CO). CO holds significant industrial importance as it serves as a precursor for various valuable chemical products containing either a single carbon atom (C1), like methanol or methane, or multiple carbon atoms (Cn), such as ethanol or ethylene. Despite the long‐established efficiency of these catalysts, optimizing their catalytic activity and stability and comprehending the intricate reaction mechanisms remain a significant challenge. This article presents a comprehensive investigation of the mechanistic aspects of the selective electroreduction of CO2 to CO using an iron porphyrin substituted with four trimethylammonium groups in the para position [(pTMA)FeIII‐Cl]4+. By employing infrared and UV‐Visible spectroelectrochemistry, changes in the electronic structure and coordination environment of the iron center can be observed in real‐time as the electrochemical potential is adjusted, offering new insights into the reaction mechanisms. Catalytic species were identified, and evidence of a secondary reaction pathway was uncovered, potentially prompting a re‐evaluation of the nature of the catalytically active species.

show abstract

Examining iron complexes with organic ligands by laboratory XAFS

Abstract: This paper presents the application of laboratory X-ray Absorption Fine Structure Spectroscopy (XAFS) in the field of iron coordination chemistry, especially for compounds with larger organic ligands and usually low...

Cited by 3 publications

References 55 publications

Atomic spectrometry update: review of advances in elemental speciation

Atomic spectrometry update: review of advances in elemental speciation

Operando Spectroelectrochemistry Unravels the Mechanism of CO₂ Electrocatalytic Reduction by an Fe Porphyrin

Operando Spectroelectrochemistry Unravels the Mechanism of CO₂ Electrocatalytic Reduction by an Fe Porphyrin

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Examining iron complexes with organic ligands by laboratory XAFS

Abstract: This paper presents the application of laboratory X-ray Absorption Fine Structure Spectroscopy (XAFS) in the field of iron coordination chemistry, especially for compounds with larger organic ligands and usually low...

Cited by 3 publications

References 55 publications

Atomic spectrometry update: review of advances in elemental speciation

Atomic spectrometry update: review of advances in elemental speciation

Operando Spectroelectrochemistry Unravels the Mechanism of CO2 Electrocatalytic Reduction by an Fe Porphyrin

Operando Spectroelectrochemistry Unravels the Mechanism of CO2 Electrocatalytic Reduction by an Fe Porphyrin

Contact Info

Product

Resources

About

Operando Spectroelectrochemistry Unravels the Mechanism of CO₂ Electrocatalytic Reduction by an Fe Porphyrin

Operando Spectroelectrochemistry Unravels the Mechanism of CO₂ Electrocatalytic Reduction by an Fe Porphyrin