Local structure study of the Fe ions in mixed-valence iron(II)-iron(III) metal formate frameworks

Piskorska‐Hommel, E.; Ciupa-Litwa, Aneta

doi:10.1016/j.poly.2022.115963

Cited by 7 publications

(28 citation statements)

References 50 publications

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“…The Fe L edge spectrum of AC‐1 reveals two peaks at 710.6 eV and 712.3 eV, confirming the presence of mixed valent Fe 2+ and Fe 3+ species (Figure 3f) [54–62] . The higher intensity of the peak at 709.7 eV in AC‐2 indicates the presence of higher amount of Fe 3+ in AC‐2 (Figure 3f).…”

Section: Resultsmentioning

confidence: 66%

“…However, Fe K‐EXAFS oscillation indicates a different oscillation showing the different coordination environment of Fe in AC‐2 and AC‐1 (Figure S21b) [55, 60, 61, 65–67] . Thus, XANES and EXAFS spectra concluded the coexistence of the high valent Fe 3+ /Co 3+ with cationic (Co/Fe) vacancies in AC‐2 [55, 60, 61, 65–67] …”

Section: Resultsmentioning

confidence: 96%

“…The contraction of the Fe−O bond also suggests the higher coordination number in Fe−O first shell. Apart from the dominant peak at 1.50 Å in AC‐1, another peak around 2.64 Å indicates the Fe−Fe distance (Figure 3h) [55, 60, 61, 65–67] . Further, the peak ≈2 Å was assigned to the Fe=O bond (coordination number ≈4), originated from the disordered structure of AC‐2 (Figure 3h) [66, 68] .…”

Section: Resultsmentioning

confidence: 97%

“…[55][56][57][58][59][60][61] The pre-edge peak intensity is low and also the peak intensity is observed between Fe 3 O 4 and α-Fe 2 O 3 indicating the presence of octahedral coordinated Fe 2 + and Fe 3 + species in AC-1 (Figure 3e). [55][56][57][59][60][61] The comparison of the main absorption peak in the Fe K-edge XANES spectra reveals a positive shift towards higher energy for AC-2 confirming the presence of a higher amount of Fe 3 + species (Figure 3e). [55][56][57][58] The Fe L edge spectrum of AC-1 reveals two peaks at 710.6 eV and 712.3 eV, confirming the presence of mixed valent Fe 2 + and Fe 3 + species (Figure 3f).…”

Section: Structural Characterization Of the Active Catalystsmentioning

confidence: 99%

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Deciphering Ligand Controlled Structural Evolution of Prussian Blue Analogues and Their Electrochemical Activation during Alkaline Water Oxidation

et al. 2022

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Herein, we have demonstrated the control over the structure of precatalysts to tune the properties of the active catalysts and their water oxidation activity. The reaction of K 3 [Fe(CN) 6 ] and Na 2 [Fe(CN) 5 (NO)] with Co(OH) 2 @CC produced precatalysts PC-1 and PC-2, respectively, with distinct structural and electronic features. The replacement of the À CN group with strong π-acceptor À NO modulates the electronic and atomic structure of PC-2. As a result, a facile electrochemical transformation of PC-2 into active catalyst FeÀ Co-(OH) 2 -Co(O)OH (AC-2) has been attained only in 15 CV cycles while 600 CV cycles are required for the electrochemical activation of PC-1 into AC-1. The X-ray absorption studies reveal the contraction of the CoÀ O and FeÀ O bond in AC-2 because of the presence of a higher amount of Co 3 + and Fe 3 + than in AC-1. The high valent Co 3 + and Fe 3 + modulates the electronic properties of AC-2 and assists in the OÀ O bond formation, leading to the improved water oxidation activity.

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Section: Resultsmentioning

confidence: 66%

Section: Resultsmentioning

confidence: 96%

Section: Resultsmentioning

confidence: 97%

Section: Structural Characterization Of the Active Catalystsmentioning

confidence: 99%

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Deciphering Ligand Controlled Structural Evolution of Prussian Blue Analogues and Their Electrochemical Activation during Alkaline Water Oxidation

et al. 2022

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“…Chemie accompanied by the increment in the oxidation state of Fe (Fe 3 + ) (Figure 3h). [55,60,61,[65][66][67] The contraction of the FeÀ O bond also suggests the higher coordination number in FeÀ O first shell. Apart from the dominant peak at 1.50 Å in AC-1, another peak around 2.64 Å indicates the FeÀ Fe distance (Figure 3h).…”

Section: Methodsmentioning

confidence: 97%

Deciphering Ligand Controlled Structural Evolution of Prussian Blue Analogues and Their Electrochemical Activation during Alkaline Water Oxidation

et al. 2022

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Novel Heterostructure‐Based CoFe and Cobalt Oxysulfide Nanocubes for Effective Bifunctional Electrocatalytic Water and Urea Oxidation

Mariappan,

Mannu,

Ranjith

et al. 2024

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The development of effective oxygen evolution reaction (OER) and urea oxidation reaction (UOR) on heterostructure electrocatalysts with specific interfaces and characteristics provides a distinctive character. In this study, heterostructure nanocubes (NCs) comprising inner cobalt oxysulfide (CoOS) NCs and outer CoFe (CF) layered double hydroxide (LDH) are developed using a hydrothermal methodology. During the sulfidation process, the divalent sulfur ions (S2−) are released from the breakdown of the sulfur source and react with the Co‐precursors on the surface leading to the transformation of CoOH nanorods into CoOS nanocubes. Further, X‐ray photoelectron spectroscopy (XPS) and X‐ray absorption spectroscopy (XAS) analyses reveal that the interactions at the interface of the CF@CoOS NCs significantly altered the electronic structure, thus enhancing the electrocatalytic performance. The optimal catalysts exhibited effective OER and UOR activities, the attained potentials are 1.51 and 1.36 V. This remarkable performance is attributable to the induction of electron transfer from the CoFe LDH to CoOS, which reduces the energy barrier of the intermediates for the OER and UOR. Furthermore, an alkaline water and urea two‐cell electrolyzer assembled using CF@CoOS‐2 NCs and Pt/C as the anode and cathode requires a cell voltage of 1.63 and 1.56 V along with a durability performance.

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Local structure study of the Fe ions in mixed-valence iron(II)-iron(III) metal formate frameworks

Cited by 7 publications

References 50 publications

Deciphering Ligand Controlled Structural Evolution of Prussian Blue Analogues and Their Electrochemical Activation during Alkaline Water Oxidation

Deciphering Ligand Controlled Structural Evolution of Prussian Blue Analogues and Their Electrochemical Activation during Alkaline Water Oxidation

Deciphering Ligand Controlled Structural Evolution of Prussian Blue Analogues and Their Electrochemical Activation during Alkaline Water Oxidation

Novel Heterostructure‐Based CoFe and Cobalt Oxysulfide Nanocubes for Effective Bifunctional Electrocatalytic Water and Urea Oxidation

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