Persistence and Amalgamation Types of CN Stretching Mode in Oxidation Process of Prussian Blue Analogues

Moriya, Toshiaki; Shibata, Takayuki; Fukuzumi, Yuya; Niwa, Hideharu; Moritomo, Yutaka

doi:10.7566/jpsj.89.064708

Cited by 3 publications

(4 citation statements)

References 30 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The larger bandwidth of CN ligands in [Fe II (CN) 6 ] 4− , leading to a persistent stretching mode rather than amalgamation types, results in stronger polarization. 7 Research on the electronic structure using soft X-ray absorption spectroscopy showed the valence orbitals of metal cyano bond in trivalent lanthanide PBAs had stronger covalent properties than in tetravalent actinide PBAs. 8 The crystal structure of PBAs shows, in addition to the cubic phase, that there are two other structures, monoclinic and rhombohedral phases, attributed to the amount of alkali metal cations and interstitial waters.…”

Section: ■ Structure and Propertiesmentioning

confidence: 99%

“…The larger bandwidth of CN ligands in [Fe II (CN) 6 ] 4– , leading to a persistent stretching mode rather than amalgamation types, results in stronger polarization . Research on the electronic structure using soft X-ray absorption spectroscopy showed the valence orbitals of metal cyano bond in trivalent lanthanide PBAs had stronger covalent properties than in tetravalent actinide PBAs …”

Section: Structure and Propertiesmentioning

confidence: 99%

See 1 more Smart Citation

Recent Advances of Prussian Blue-Based Wearable Biosensors for Healthcare

et al. 2021

View full text Add to dashboard Cite

Section: ■ Structure and Propertiesmentioning

confidence: 99%

Section: Structure and Propertiesmentioning

confidence: 99%

Recent Advances of Prussian Blue-Based Wearable Biosensors for Healthcare

et al. 2021

View full text Add to dashboard Cite

“…The empirical rule tells us that Fe takes divalent (trivalent) if ν CN < 2135 cm -1 ( ν CN > 2145 cm -1 ). On the other hands, Moriya et al performed in situ IR spectroscopy of Co- and Mn-PBAs 32 . They clarified the persistent and/or amalgamation type behavior of the CN - stretching mode during the oxidization process.…”

Section: Introductionmentioning

confidence: 99%

In situ IR spectroscopy during oxidation process of cobalt Prussian blue analogues

Niwa

Moriya

Shibata

et al. 2021

Sci Rep

Self Cite

View full text Add to dashboard Cite

Cobalt Prussian blue analogues (Co-PBA; NaxCo[Fe(CN)6]y), consisting of cyano-bridged transition metal network, –Fe–CN–Co–NC–Fe–, are promising cathode materials for Na-ion secondary batteries. In the oxidation process, oxidization of Fe and/or Co are compensated by Na+ deintercalation. Here, we investigated the oxidization process of three Co-PBAs by means of in situ infrared absorption (IR) spectroscopy. With use of an empirical rule of the frequencies of the CN− stretching mode in ferrocyanide ([FeII(CN)6]4−) and ferricyanide ([FeIII(CN)6]3−), the oxidation processes of Co-PBAs were determined against the Fe concentration (y) and temperature (T). We will discuss the interrelation between the oxidation processes and Fe concentration (y).

show abstract

“…We note that the oscillator strength is different between the [ + Fe 2 (CN) 6 ] -4 and [ + Fe 3 (CN) 6 ] -3 modes. 26) Then, it is difficult to compare the spectral weights of the two modes. Therefore, we chose the spectral weight ratios ( + I HT 2 / + I LT 2 and + + I I HT 3 LT…”

mentioning

confidence: 99%

Extended charge-transfer model for Na_xCo[Fe(CN)₆]_0.82

Moritomo¹,

Tachihara²,

Iwaizumi³

et al. 2021

Jpn. J. Appl. Phys.

Self Cite

View full text Add to dashboard Cite

Cobalt Prussian blue analogues (Na x Co[Fe(CN)6] y ; x ∼ 4 y − 3 ) whose valences are close to Co 3 + and Fe 2 + show characteristic phase transitions triggered by cooperative charge transfer (CT) from Fe 2 + to Co 3 + . Here, we extended the cooperative CT to the entire region of sodium concentration ( 0 ≤ x ≤ 4 y − 2 ). We systematically investigated (1) upper ( T c u ) and lower ( T c l ) critical temperature, (2) variation of the [ Fe 2 + (CN)6] 4 − ([ Fe 3 + (CN)6] 3 − ) concentration, and (3) spectral weight ( I ET ) due to electron transfer from Fe 2 + to Co 3 + of thin films of Na x Co[Fe(CN)6]0.82 against x. In a wide x region from 0.00 to 0.57, we observed first-order phase transition triggered by the cooperative CT. The extended CT model reproduces the x-dependent behavior of the [FeII(CN)6] 4 − ([FeIII(CN)6] 3 − ) concentration and I ET , except for the high-x region above x ∼ 0.9 .

show abstract

Persistence and Amalgamation Types of CN Stretching Mode in Oxidation Process of Prussian Blue Analogues

Cited by 3 publications

References 30 publications

Recent Advances of Prussian Blue-Based Wearable Biosensors for Healthcare

Recent Advances of Prussian Blue-Based Wearable Biosensors for Healthcare

In situ IR spectroscopy during oxidation process of cobalt Prussian blue analogues

Extended charge-transfer model for Na_xCo[Fe(CN)₆]_0.82

Contact Info

Product

Resources

About

Persistence and Amalgamation Types of CN Stretching Mode in Oxidation Process of Prussian Blue Analogues

Cited by 3 publications

References 30 publications

Recent Advances of Prussian Blue-Based Wearable Biosensors for Healthcare

Recent Advances of Prussian Blue-Based Wearable Biosensors for Healthcare

In situ IR spectroscopy during oxidation process of cobalt Prussian blue analogues

Extended charge-transfer model for Na x Co[Fe(CN)6]0.82

Contact Info

Product

Resources

About

Extended charge-transfer model for Na_xCo[Fe(CN)₆]_0.82