The vibrational spectra of the cyanide ligand revisited: the ν(CN) infrared and Raman spectroscopy of Prussian blue and its analogues

Kettle, S. F. A.; Diana, Eliano; Marchese, Edoardo; Boccaleri, Enrico; Stanghellini, P. L.

doi:10.1002/jrs.2944

Cited by 93 publications

(65 citation statements)

References 105 publications

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“…The peaks in the region between 2070–2200 cm −1 , however, are related to the electronic features of PB: PB cyanide ligands are coordinated to iron ions with different oxidation state ( F e I I I − C N − F e I I ) that influences the wavenumber of the vibrational stretching mode. When a modification in the oxidation state of iron occurs, as in case of laser‐induced excitation, these vibrational modes change, giving rise to peaks with different characteristics …”

Section: Discussionmentioning

confidence: 99%

Raman spectroscopy of the photosensitive pigment Prussian blue

Moretti

Gervais

2018

J Raman Spectroscopy

140

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Prussian blue is a pigment highly sensitive to electromagnetic radiation, visible light included. This photosensitivity, associated with a complex redox behavior, causes a vulnerability even to Raman lasers, with the possibility of sample alteration or irreversible damage. In this study, we systematically explored the influence of the laser wavelength and laser power on different types of Prussian blue pigments, soluble and insoluble. The use of different laser wavelengths does not influence the position of the characteristic peak, though it affects the signal‐to‐noise ratio. The latter can be improved by increasing the number of accumulations and/or the acquisition time. Furthermore, we evaluated a safe level of Raman laser excitation or “safe zone” with laser power between 0.005 and 0.06 mW, where Raman analysis can be performed without laser‐induced artifacts or damage for the sample. These artifacts may affect the characteristic spectral signature of the two different Prussian blue, leading to a wrong identification of the pigments. Moreover, artifacts can also hide features arisen from fading in objects presenting non‐visible alterations of Prussian blue.

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Section: Discussionmentioning

confidence: 99%

Raman spectroscopy of the photosensitive pigment Prussian blue

Moretti

Gervais

2018

J Raman Spectroscopy

140

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“…From higher to lower frequencies, they are assigned to A 1g , E g , F 1g and F 2g modes from O h symmetry. 68,69 The bands are only observed at the L/L interface, in the presence of CNTs: when the CNT signal falls away, so do those due to the [Fe (CN) 6 ] 4-. Therefore, CNTs are enhancing C≡N modes that are normally observed only in saturated solutions, while the studied system is within the mmol L -1 range and far from saturation.…”

Section: Resultsmentioning

confidence: 99%

“…While present in an ionic species such as [Fe (CN) 6 ] 4-, lower energy free CN -modes are observed, whereas when the second metallic center coordinates to the ion via the nitrogen atom of the CN ligands to produce PB, a rigid structure is formed, shifting CN modes to higher frequencies. 56,68,69 The degree of defects and incomplete bonding also dictate the band positions. Therefore, the more ferric ions coordinate to N to form an organized cubic structure, the more CN modes shift.…”

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confidence: 99%

Electrodeposition of Prussian Blue/Carbon Nanotube Composites at a Liquid‑Liquid Interface

Husmann

Booth

Zarbin

et al. 2018

J. Braz. Chem. Soc.

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The iron complex hexacyanoferrate (Fe 4 [Fe(CN) 6 ] 3 ), known as Prussian Blue (PB), was electrodeposited over a free-standing carbon nanotube (CNT) film assembled at the interface between two immiscible liquids, water and 1,2-dichlorobenzene. Polarization of the interface achieved through a fixed potential or under potential variation enabled iron present inside CNTs to generate a stable CNT/PB composite. We report herein on the observation that the deposition of PB is dependent on both the pH and applied potential. It was found that aqueous phases containing K 3 [Fe(CN) 6 ] can decompose under an applied potential, while those containing K 4 [Fe(CN) 6 ] presented more stable behavior making it a suitable precursor for PB synthesis. The electrodeposition and modification of the interface was followed by in situ spectroelectrochemical Raman spectroscopy, which indicated that an increase in signal due to PB formation was acompanied by changes in the CNT bands due to modification of the CNT walls by decoration with PB, forming a composite structure. Keywords: liquid-liquid interface, Prussian Blue, carbon nanotubes, immiscible liquids IntroductionBiphasic liquid/liquid (L/L) systems have been used for a long time, either for the study of interfacial electron and ion transfer reactions or for the synthesis and assembly of micro and nano-sized materials.1,2 The interface between two immiscible liquids provides a defect-free environment suitable for controlled homogeneous particle deposition. Driven by the decrease in the L/L interfacial free energy, particles dispersed or synthesized in a biphasic system spontaneously migrate to the interface formed by the two liquids. [3][4][5] Due to the ease of formation and robust nature of L/L interfaces, they have been utilized in a wide range of different applications. The L/L system can be used simply as a means to assemble previously synthesized materials into organized arrays or thin films, such as carbon nanostructures or metal nanoparticles. 6,7 Alternatively, materials can be both synthesized and assembled by using the L/L interface as the region of contact between reactants located in the different phases. [8][9][10] As an alternative to spontaneous reactions occurring at the point of contact between the two phases, material deposition can also occur by electrochemical polarization of the interface. 11,12 In addition to standard synthetic parameters such as concentration, time or pH, the applied potential and polarization of the interface between the two immiscible electrolyte solutions (ITIES) governs the rate of ion and electron transfer between the phases, allowing significant control over synthetic procedures. 1,2,13,14 By combining these different approaches to utilize the L/L interface, composite structures can be prepared using one material as the support and/or nucleation site for the other. 15,16 Previously, it has been observed that particle or polymer formation was possible, under stirring, on the surface of carbon nanostructures present in a L/L sy...

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“…2, the spectrum of BiVO 4 /V 2 O 5 /Cohcc exhibits new bands in comparison of the film without Cohcc. The set of Raman bands at 2150-2230 cm -1 is characteristic for C ≡ N stretching vibration [33]. The presence of at least two bands at this region suggests that Co centers coexist at different oxidation states.…”

Section: Raman Spectroscopymentioning

confidence: 94%

Enhanced Photoelectrocatalytical Performance of Inorganic-Inorganic Hybrid Consisting BiVO4, V2O5, and Cobalt Hexacyanocobaltate as a Perspective Photoanode for Water Splitting

et al. 2019

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Thin layers of BiVO 4 /V 2 O 5 were prepared on FTO substrates using pulsed laser deposition technique. The method of cobalt hexacyanocobaltate (Cohcc) synthesis on the BiVO 4 /V 2 O 5 photoanodes consists of cobalt deposition followed by electrochemical oxidation of metallic Co in K 3 [Co(CN) 6 ] aqueous electrolyte. The modified electrodes were tested as photoanodes for water oxidation under simulated sunlight irradiation. Deposited films were characterized using UV-Vis spectroscopy, Raman spectroscopy, and scanning electron microscopy. Since the V 2 O 5 is characterized by a narrower energy bandgap than BiVO 4 , the presence of V 2 O 5 shifts absorption edge (ΔE =~0.25 eV) of modified films towards lower energies enabling the conversion of a wider range of solar radiation. The formation of heterojunction increases photocurrent of water oxidation measured at 1.2 V vs Ag/ AgCl (3 M KCl) to over 1 mA cm-2 , while bare BiVO 4 and V 2 O 5 exhibit 0.37 and 0.08 mA cm-2 , respectively. On the other hand, the modification of obtained layers with Cohcc shifts onset potential of photocurrent generation into a cathodic direction. As a result, the photocurrent enhancement at a wide range of applied potential was achieved.

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The vibrational spectra of the cyanide ligand revisited: the ν(CN) infrared and Raman spectroscopy of Prussian blue and its analogues

Cited by 93 publications

References 105 publications

Raman spectroscopy of the photosensitive pigment Prussian blue

Raman spectroscopy of the photosensitive pigment Prussian blue

Electrodeposition of Prussian Blue/Carbon Nanotube Composites at a Liquid‑Liquid Interface

Enhanced Photoelectrocatalytical Performance of Inorganic-Inorganic Hybrid Consisting BiVO4, V2O5, and Cobalt Hexacyanocobaltate as a Perspective Photoanode for Water Splitting

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