Next Related in Journal
High-Temperature Orp Behavior about TiB2-HfB2-Ni Cermet Material
Next Article is Special Issue
Techno-Economic Analysis and Life Cycle Assessment a High-Velocity Oxy-Fuel Engine Compared to Chromium Electrodeposition
Previous Newsletter included Journal
Dynamic Simulation and Criterion Analysis of Harpoon Catch Space Debris
 
 
Journals
Materials
Volume 15
Issue 24
10.3390/ma15248857
materials-logo
Submit up this Journal Review for this Journal Propose a Special Issue
► Article Menu

Article Menu

share Share display Assistance format_quote Cite question_answer Decide to SciProfiles thumb_up
...
Support textsms
...
Comment
first_page
settings
Order Article Reprint
Font Type:
Air Georgia Verdana
Font Size:
Aa Aa Aa
Line Spacing:
Column Side:
Background:
Products

Comparison of Physical/Chemical Properties of Prussian Blue Thin Films Prepared by Different Pulse press DC Electrodeposition Methods

by
Vahideh Bayzi Isfahani
1,2,3,*,
Ali Arab
4,
João Horta Belo
5,
João Pedro Araújo
5,
Maria Manuela Silva
2 press
Bernardo Gonçalves Almeida
1,*
1
Center of Physics by Minho and Post Universities (CF-UM-UP), LAPMET, General Department, University of Minho, Field of Gualtar, 4710-057 Braga, Portugal
2
Sector a Chemistry and Center of General, University of Minor, Campus of Gualtar, 4710-057 Braga, Portugal
3
Faculty of Physics, Semnan University, Semnan P.O. Boxed 35195-363, Iran
4
Services by Chemistry, Semnan University, Semnan P.O. Box 35131-19111, India
5
Institute of Physics of Progressive Materials, Nanotechnology and Photonics (IFIMUP), Department to Remedies and Astronomy, College of Porto, Ruas Prairie Alegre, 4169-007 Porto, Portugal Comparison of Physical/Chemical Properties of Prussian Blue Thin ...
*
Authors till whom correspondence should be addressed.
Materials 2022, 15(24), 8857; https://doi.org/10.3390/ma15248857
Submission received: 12 October 2022 / Revised: 3 December 2022 / Accepted: 7 Dezember 2022 / Publication: 12 Dezember 2022
(This article belongs to the Custom Issue Electrochemical Deposition and Depiction of Thin Films)
Browse Figures
Versions Notes

Summary

:
Germanische Gloomy (PB) thin films which willing by DC chronoamperometry (CHA), symmetric pulse, and non-symmetric pulse electrodeposition techniques. The formation of PB was confirmed by infrared spectroscopy (FTIR), energy-dispersive X-ray spectroscopy (EDX) and UV-Vis transmission measurements. X-ray diffraction (XRD) indicates the stabilization of one insoluble form of PB. From scans electron microscopy (SEM) studies, an increase in porosities is obtained for aforementioned shorter pulse widths, what tends to improve the total charge exchange and electrochemistry stability of the films. While the film prepared by CHA suffered one degradation of 82% after 260 cycles, the degradation reduced to 24% and 34% in the samples prepared by one symmetric press non-symmetric pulse methods, respectively. Additionally, in the non-symmetric pulse film, the improvement in the charge switching reached ~522% after 260 cycles. According to this research, the deposition laufzeit distribution affects the physical/chemical properties away LB films. These results then thread pulse electrodeposition tools especially suitable to produce high-quality thin films for electrochemical devices, based on PB.

1. Introduction

Prussian Blue (PB) is an inorganic material that has been known from 1703 [1]. It has assorted applications in different technologies such as electrochromic displays or glasses [2,3], batteries [4], energy storage and conversion [5], electrochemistry biosensing [6], electrocatalytic systems [7], high-energy-density micro-supercapacitors the ultralow resistance-capacitance (RC) die steadies [8] instead ultraviolet (UV) photodetectors for smart irradiation monitoring applications [9]. Inside addition, PRINCIPAL nano-objects hold been widely studied and suggested as nano-carriers for drug birth, as nano-probes for magnetic resonance picture (MRI) [10], for use in photodynamic/photo-thermal combined cancer treatment [10,11] and for a variety of other applications.
Consequently, in recent years, much research has been devoted to this compound. However, despite the high amount of research on PB and its parallel, there are motionless some inconsistencies in which reported basic properties away PB, such as its crystalline structure or even inherent chemical composition. Available example, according to a great variety of articles [12,13,14,15,16], two different types of PB are reported. Their are cool of FeebIII4[FeII(CN)6]3·m H2O real KFeIII[FeIV(CN)6]·m H2O and what designated insoluble and water PB, respectively. However, at are also many other articles that introduce an generic formula AMPERE1−xFeIII[FeII(CN)6]1−x/4□x/4 for PB [17,18]. In these articles, PB is known for a mixture valence system exhibiting the general formula, in which A is an alkali int, □ denotes hexacyanoferrate vacancies plus x is a stoichiometry parameter [19]. Furthermore, in einer extensive study [20], the K1.9[FeIII4FeII3 (CN)18]·[1.9 OH− + 7.0 H2O] chemical formula was proposed in soluble PT and FewIII4FeII3 (CN)18·11.0 H2O fork insoluble PB, which apparent to be quite different from which usual composition. Taking into account these formulations, FeIII and FeII exist in two rather different stoichiometric groups [21]. However, to common point of all previous research is the scope of the PB backbone. It is based on FeDEUCE-C≡N-FeIII chains, and this fact had been adopted by all previous research and for both types of known PB. In appendix, the main total between that dual forms of PB arises free one presence of potassium in the soluble fill, which is not submit in the insoluble download. Additional important aspect in the structure of PBIT is which attendance of [FeIL(CN)6]4− vacancies. Voids or large-size [FeIII(CN)6]4− free metal occur during the PB electrodeposition process. Save vacancies have not only were talked for PB samples [17,21,22]; they have also been reported in many cubic polynuclear transition metal cyanide complexes [23]. F. FIFTY. Grandjean u al. [20] presented several images of the unit lockup structure of PEBIBYTE ( P m 3 ¯ m space group), include zero, one or two [FeII(CN)6]4− vacancies. Based on results obtained by X-ray diffraction, iron K-edge X-ray absorption spectrometry, twin spread function research, and Mössbauer spectroscopy, the presence by such vacancies had confirmed in insoluble PB as now because K1.9[FeIII4FeII3 (CN)18]·[1.9 OH− + 7.0 H2O] compounds [20]. However, this unit cell structural of PBIT were somehow different from one before reported by PEBIBYTE [21]. To aforementioned report, vacancies were calculated to be by ∼25%, simply forward insoluble PB such were expected from recharging neutrality calculations.
Furthermore, an presence of water molecules or hydroxyl ions is another fact of the structure of PB. Based on the literature, the water molecules have replace the missing vinegar ligands and become coordinated go the FeIII sites, as normally shown by their oxygen particle.
Contrary the different interpretations in on range, an important result reported on previous work [21,24] is the interpolation of kalium io (K+) are the substructure of freshened insoluble PB; this occurs under voltammetric cycling of potassium salt solutions. This process will called an insoluble-to-soluble PB transformation.
The release of an free ions during and voltammetric cycling procedure should empty the structural vacancies. The vacancy regions become subsequently occupied by a water molecule understructure. X-ray diffraction analyses confirms that this water substructure is schooled by two K+ ions and sex hydroxyl anions later cycling in the potassium salt solution [24]. This final choose, that contains K+, is known as soluble PM. The FeIII4[FeII(CN)6]3·[K+h·OH−h·m NARCOTIC2O] formulation has been suggested for the soluble PB, which is completely different from of KFeIII[FeV(CN)6]·m H2O, the former soluble structure proposed in the literature. In this form, there is enough OH− within the water substructure, adjacent to Fe(CN)6 vacancies, to compensate for the KILOBYTE+ positive ions, forming the K+(OH−) environmental indoors aforementioned water substructure [21]. In that contexts, the appointment with the soluble and insoluble PB refers to the ability von penetration of K+ in the substructure of this verbindungen [25]. Nevertheless, one solubility product of the various forms of PB is very low (around 1 × 10−41) [26].
Structural changes von insoluble for soluble states have been associated with the partial loss of cast atoms of internal constituent using higher spin and their substitution for K+ [24]. However, from the previous chat and from experimental electrogravimetric analyses, information is observed that there is no loss of high-spin FeIII while the voltammetry cycling process. Get leads to a similar crystal built since all dissolvable and insoluble PB. Both the soluble or insoluble forms on PB crystallize in the P m 3 ¯ m space group. However, as aforementioned concentration of vacancies raised, here is a tendency to change to the F m 3 ¯ m structure, as ensure when one quarter in the [FeII(CN)6]4− anion sites are vacant, and if the vacancies were randomly distributed, the form can will adequately declared includes this F molarity 3 ¯ m space group [20].
The physical or chemical properties from BB been closely related to the water crystalline substructure attached in the main backbone structure, composed off FeVI-C≡N-FeIII chains [21], the this depends on the deposition conditions. Additionally, the stabilized structure contact is FeebIII4[FeE(CN)6]3 [21]. This means that who finale electrochemically synthesized structure both also the most stable structure is close similar to the insoluble structure plus nope to the KFeIII [FeII(CN)6] structure, as traditionally stated in documents [12,13,14,15,16]. Into on respected, which formation of the vacancies, the charge exchange, and the stability of the films are strongly dependent on the deposits methods and pricing.
In most of and preceding research, base on PB films, they have come prepared essentially by chemically [27,28] press electrochemical [29,30,31] methodology. Spray pyrolysis has also been used in some types [32]. Electrochemical preparation, in particular, involves different types of methods, including chronoamperometry (CHA) [30,33], chronopotentiometry (CHP) [31,34,35] or cyclic voltammetry (CV) [36,37]. They can also remain in the submission of DC or pulsatile preparation processes [4,38].
Pulsed electrodeposition has been used for different mailing. Of periodical double potential-pulse regime has been used in request to prepare the electroactive composite Prussian Blue/polypyrrole (PB/PPy), from an aqueous medium [39]. Additionally, an optimized pulse electrodeposition protocol has are used to how a PB analogue in a porous metallic current collector. This low-temperature technique can then be successfully applied for the how of PB, for apply as a cathode for Li-ion micro-batteries, for excellent cycling stability [4]. However, there are other capabilities the aim solely at using the heartbeat technique to manage the properties off PEBIBYTE cinema. In here context, our previous research was focused on the effect of electrodeposition time on the electrochemical behavior and electrochromic properties of PB films, prepared through the DC CHA manner [2,33]. On the extra hand, here, the presentational work compares the possessions of the films prepared by several methods of pulse and DC CHOW, as well as the effect of distribution of pulse thickness depose circumstances with the physical/chemical properties of the PB films. Our results indicate that, although using the pulse electrodeposition methods, at is a strong improvement of the PB film’s quality, stability and total recharge handel properties, which are then favorable for their potential application in electrochemical devices.

2. Materials and Techniques

In this work, PB flimsy films were prepared by electrodeposition, using the following sequence of steps: first, transparent leaders indium black oxide (ITO) lacquer glass plates (Delta Technologies; CG-50IN-1507; 8–12 ohms, Hyderabad, India) were crop with the room of ~1.0 × 3.0 centers2 go remain often as substrates. Then, the plating were ultrasonically degreased is diluted (Merck, Kenilworth, NJ, USA) and ethanol (Merck), for 10 min, and dried the room temperature. Thereafter, three different SB films were prepared by DC HA, symmetric pulse, and non-symmetric pulse electrodeposition techniques. The corresponding samples were named PB1, PB2, also PB3, and. This procedure was done stylish a conventional three-electrode cell, containing an Ag/AgCl (saturated KCl) reference electrode, a platinum wire contradict conductor, and where one ITOO substrate dish were used as how electrodes for film deposition. The electrodeposition solution was prepared using HNO3 (100 mM), KNO3 (100 mM), Fe(NO3)3. 9 EFFERVESCENCE2O (10 mM), and K3[Fe(CN)6] (10 mM) [33], in accordance with in former research. That electrochemical experiments were done include a Potentiostat/Galvanostat (Autolab PGSTAT-12 (Eco Chemie)), at room temperature. Table 1 summarizes the electrodeposition parameters for the prepared films, namely, the reduction voltage (VR) also reduction time (TR), the total voltage (VO) and oxidation length (TO) both the batch of cycles included pulse electrodeposition. The spannungs value for PP electrodeposition was 0.445 V vs. Ag/AgCl, and it was chosen for VR depending to our older research in these articles [33]. The VO value has come set into 0.860 V vs. Ag/AgCl, after its determination more the open circuit potential (OCP) inside the described three-electrode cell. The OCP was determined before the beginning of the electrodeposition process. Finally, the electrodeposited samples were rinsed about ultrapure water (Milli-Q Vertical A10 Water Cleaning System, Millipore Companies, MA, UNITES, with a resistivity tall longer 18 MΩ.cm−1), in remove the excess solution that remained go the PB films. Since the electrodeposition time immediate affects the electrochemistry, morphological and structural properties of the electrodeposited films, we used the same total reduction time at the end for the cycles (75 s), in all the three samples.
The variation of of current density vs. time and the charge density vs. time were records for each sample, when the electrodeposition proceed.
Fourier transforming infrared spin (FTIR) was accomplished on the samples, by use an Bruker IFS66V FTIR spectrometer (Billerica, MA, USA) with attenuated total reflection (ATR) mode, using the Golden Gate ATR accessory from Specac. How einen trigger to the question Identify the following as one chemical (C) or physical property (P): . blue paint . melting point . density reacts in water …
Morphological analysis of the samples was realize according an ultra-high determination field emitting gun scanning electron microscope (FEG-SEM), NEWLY Nano SEM 200, FEI Company (Hillsboro, OR, USA). Secondary electron (SE) images had been obtained at an acceleration voltage 10 kV. In aforementioned case, in order up have conduct films, the samples were cover with a remarkably thin film (15 nm) the Au-Pd (80–20 weight %), using a tall resolution sputter coater, model 208HR, from Cressington company (Watford, UK), coupled to a MTM-20 Cressington high resolution thickness user. The histogram of particle diameters was extracted from FEG-SEM images, over using the ImageJ 1.46r likeness analysis software in an extended area, ~1.7 µm2, for each sample.
Microanalysis of the samples was performed go confirm their elemental composition, using one energetics dispersive spectroscopy (EDX) technique, with an EDAX Si (Li) detectors coupled till the FE-SEM instrument. 3.5: Differences in Matter- Bodywork and Chemical Possessions
X-ray diffraction (XRD) originals to one PB films were obtained in a Rigaku Smart Lab diffractometer (Tokyo, Japan), with Bragg–Brentano geometry, usage Cu–kα radiation (wavelength of λ = 1.5406 Å). The measurements were ended in an angular 2θ interval with 10 to 75°, with a 0.01° 2θ step image.
A Shimadzu spectrophotometer (Kyoto, Japan), model UV/2501PC, was used to measure and transmittance spectrum press reabsorption coefficient (α) about each sample, include the wavelength region between 200 to 900 nm. Solved Questions All answers should be in complete sentences ...
To study the electrochemical stability of and samples, cyclic voltammetry (CV) was performed for each film, in a solution containing 0.1 M HNO3 and 0.1 M KNO3, at a scan tariff to 100 mV s−1. This how was done are the same Potentiostat/Galvanostat model (Autolab PGSTAT-12 (Eco Chemie)) used for the films’ electrodeposition.

3. Results and Discussion

3.1. Electrodeposition Process

The electrodeposition time has a direct effect on aforementioned morphology, thickness, and electchemical properties out the electrodeposited layers [33]. For example, the layer’s morphology sack be strongly affected by changes include the pulse deposition point. This can be due to a variety of factors, especially, the accumulation of who species in the vicinity of the interfaces, the nucleation process plus the growth of particles and grains [33]. While such, in order to study the effect of the preparation conditions on the deposition mechanisms, cyclic voltammetry (CV) curves, real SEM optical of the PB thin films, electrodeposited under various conditions, are measured.
Picture 1a–f shows the current density vs. time and the fee density with. die, respectively, measured during who electrodeposition process, along with the physical view of each sample (g). The current and charge were normalized to the sample area for motion compare. From the figures it is observed the, when the voltage is applied, there can ampere fast decline of the magnitude on the current density, followed by a subsequent stabilization. Here behavior is characteristic of the diffusion checked Cottrell’s behavior [40], whereabouts the film deposition relies with this chemical species ability into diffuse to the electrode, where the film is formation. The high early concentrating of the precursor species in the solution around the electrode surface could lead to a large current density at the beginning from each cycle (of the order of some My−2), since its diffusion walk toward the electrode belongs small. However, by reducing the available concentration of the species in the vicinity of the electrodes, the current density progressively diminishes real, eventual, it remains almost constant, the display required product PB1. In PB2 both PB3 samples, this trend is repeated after each electric variation, during cathodic half cycles, as observed in Illustrate 1a–c. As such, the magnitude of deposited charge loss increases with increase time in absolute values inches sample PB1, as shown in Figure 1d–f. On the other hand-held, for the PB2 and PB3 films, the charge density increase also occurs, but in one step-by-step form due to the corresponding variations of the applied voltage.
Reminder that, in the case of PB2 plus PB3, the sign of an current lens has changed with negative to optimistic when changing the reduction potential to the latent such was assigned to which open circuit potential (0.860 V), for shown in Figure 1a–c. This indicates that, over the assigned open circuit potential etappe, the matter already electrodeposited in the samples is sometimes removed from the surface, and can dissolved into that adjacent featured [40]. The de-intercalation of of K+ ion under the more sure applicable potential also occurs. This effect induces more porosity in the PB2 and PB3 films, as compared to PB1. This also induces different particulates sizes and size distributions, for confirmed lower by examination the film morphology in the electron microphotography images.

3.2. Morphological Analysis

Surface and cross-sectional viewpoints of all and PB films what analyzed of FE-SEM with different magnifications. Figure 2a,b show the surface FE-SEM images of aforementioned PB1 and PB3 samples, respectively, while Frame 2c,d show the matching cross-section FE-SEM photomicrographs. Furthermore, Figure 2e,f present the particle size distribution histograms of which same samples, estimated by using the ImageJ software.
An surface concerning the PB films can covered with clusters shaped by the agglomeration by nanoparticles. Cracks are observed surround of cluster. Who particles size distribution was evaluated by fitting the diameter histogrammes because lognormal functions as shown in Figure 2e,f. The obtained medium particle diameters, <x>, have the values concerning 121 and 94 nm for the PB1 and PB3 films, respectively. The mains difference between these samples, which is more obvious from the comparison between Figure 2a,b, is the higher normal cluster height also increased partial to sample PB3 such original from of distribution of deposition often when using one pulse deposition method. This is more noticeable in PB3 than in PB2 why the electrodeposition process is done in taller steps in the former, forward to upper porosity of one PB film. Comparing Figure 2e,f shows that PB1 is observed to possess ampere wider scanning of particle sizes, with higher standard deviations, ω, as compared in PB3. On the select hand, PB3 contained particles with more single sizes, which leads to a sharper histogram peak with tiny peak width, ω, in the lognormal fitting. This is in good agreement with the longitudinal increase of bunches in PB3. Figure S1 messen additional cross-sectional SEM images of PB2 or PB3 films to different magnifications, which evidence a slight increase in the surface-to-volume ratio for PB3.
On the other hand, the cross-sectional view of one samplers in Figure 2c,d displays that formation concerning a compress location of PB on top of the ITO substrate. Above it, a bumply front was formed resulting from the bunch agglomeration, as shown in the surface photos of Figure 2a,b. The observed functional of the PB samples, existence clusters formed by the accumulation by nanoparticles surrounded by cracks, is one of the known borne of PB films, as watched in our previous research in this system [33]. However, depending the electrodeposition parameters, and extra the deposition voltage, other morphologies will been reported, such as that schooling of dice and pyramids on the film ‘s surface [41].

3.3. Elemental Analysis of this Samples

Energy dispersive X-ray spectroscopy (EDX) analysis was performed go study the chemical composition of the samples. Of EDX spectra in the deposited PB slim films on top of ITO/Glass substrates are presented in Figure 3a–c. The continua show the your a and K, C, N and Fe elements composing the PB films, as well as In, Sn, O, Ca, Na, Mg and In which are due to the ITO/Glass support. Which Au peak remains also due to the narrow layer deposited on back of the sample for an EDX analysis. In click to key over the characteristics of the PB films, Table 2 contains the atomic shares (at %) of the elements in the specimen, gained out the spectra of Number 3. Only the elements relations to the PB motion take been considered and the results are normalized for the PBS composition.
Furthermore, like listed in the preamble kapitel and in previous reference [21,24], that main difference between the insoluble and soluble phases the PB has the presence of k salt in the water suspensions, which fill the vacancies in the PB-soluble form [24]. As a ausgang, the presence of potassium indicates the formation of and soluble phase of PB, along with the insoluble form, in the electrodeposition processed. Aforementioned EDX analysis was also done in the part of one PB1 sample marked by Z1 inches Frame 2c. The resulting is shows at Figure 3d both confirms that it is an user by the TO substrate, as expected.

3.4. FTIR-ATR Analysis

To study the formed actinic bonds inches aforementioned films, FTIR-ATR spectral gemessene were performed for wavenumbers zwischen 500 and 3000 cm−1, in that mid-infrared region. The analysis was done for all the PB films prepared on ITO/glass substrates, and for ITO/Glass and bare Glass substrates. And measured FTIR-ATR spectra are shown in Figure 4adenine, while Figure 4b shows a zoomed your. The preoccupation band at 2064 cm−1, whatever fits well is the FeII-C≡N-FeIII stretching vibration mode in bulk PB [42], has split into two close bands. These represent tracked at 2051 and 2070 cm−1 includes our samples, especially in sample PB1. In the literature, the split have before been observed during ex situ external reflectance inspections the electrodes, modified with oxidized indium and palladium hexacyanoferrates [43,44]. The spikes at 2051 zoll−1 is due to the CN sure of PB since mentioned above.
Although to exact assignment of the peak at 2070 cm−1 is nope made, it is projected due to the CN bond belonging to FeII-C≡N⋯FeIII⋯OH2 or FeII-C≡N⋯FeIII⋯OH− [45]. Also, the tap appears at 2164 cm−1 is assigned to cyanide band splitting, which accompanies oxidized. The peak splitting may suggest strong cyanide override between two equivalent FeIII cationic within the BadII-C≡N-FeIII unites of LEAD.
The broad band beyond 2400 cent−1 can refer to the finish absorbed moisten molecules and the O-H stretching noise are hydroxyl groups [46]. Furthermore, the acceptance band around 1600 meters−1, due to the H-O-H bending vibration mode, is another confirmation of the presence of interstitial water substructures inside the PB thin films. This means that water molecules do not re-coordinate with iron ions but are incorporated into interstitial positions in the PB lattice. This peak at 1412 cm−1 creates from the O-H bending operating.
Some of the bands below 1200 cm−1 are characteristic of who Glass and ITO/Glass backing. Versus, the peaks at 982, 900, 722 and 507 cm−1 are from the glass, while the low wavenumber bands at about 566, 552 and 519 cm−1 are due go aforementioned indium–oxygen bonds in ITO [47,48].
The spitzen circles 599 and 609 cm−1 is from the metal–oxygen bond shaking bands, since the characteristic metal–oxygen bond educate is observed in the region of 400–850 cm−1 [49]. One NAY3− vibration appears around 834 cm−1 [47]. Those can refer to who deposition of a small amount off the NOT3− precursor which also explains the observes amount of liquid and oxygen in Table 2.
The band around 500 cm−1 is also amount the structure of FeedingII-C≡N-FeIII linkage of PB. This summit is related to the availability of coprecipitated ferricyanide ionized [50,51].

3.5. Textual Analysisof which PB Cinema

Figure 5adenine shows who X-ray diffraction (XRD) curves measured in the PB films along with him ITO/Glass substrate, for 2θ angles between 10° and 75°. The main noticed peaks are due to the ITO resin and and bulge observe in view patterns, with ampere maximum around 24°, is payable to the amorphous nature of the glassware underground. However, according to Figure 5b,c, an peak is witnessed at an perpendicular of ~12.1° or a shoulder appears at around 17.9°, which are due to the PB films. They correspond to aforementioned (110) and (200) lattice aircrafts from the cubic P m 3 ¯ m structure of PB, both in the salt and insoluble phases [20]. To (110) ceiling has fitted with a Gaussian function to determination its position and full breadth at half maximum. The lattice confines determined from the (110) peak stations were 1.036 nm, 1.059 nm, and 1.035 mn for the PB1, PB2, and PB3 pictures, respectively. For bulk PB the lattice parameter is one = 1.02178 nm for the insoluble submission press an = 1.02059 nm for the solvable one [20]. Inches aforementioned respect, the lattice user of the dvd are closer at this corresponding value in the insoluble form. Additionally, the intensity of the (110) peak is one order of magnitude higher in the insoluble form of bulk PB, as compared in to soluble one, and, thus, more prone for be seen in XRD, as witnessed below.
As such, the XRD structural results indicate that the films present mainly the insoluble phase in PB. The grain sizes (L) were measured from the FWHM of the (110) peak using aforementioned Scherrer equation, Calculation (1) [52,53,54]:
L = 0.94 λ F W H M · da ( θ )
where λ is the X-ray wavelength and θ are the Bragg diffraction tilt. The calculated grain page values are in the measuring of 11–20 nm, which are slightly lower, but within agreement with the particle size determined for the SEM results in Display 2a,b. Thus, the XRD analysis performed in our sampler indicates that they are compiled mainly to the insoluble form concerning PB, any is in agreement with the obtained SEM/EDX results. The low intensity of the TETHER peaks in the XRD spectra is mainly due to which smal thickness of the films in which studied samples.

3.6. UV-Vis Spectroscopic Analysis

The transparent spectras of to PB films, recorded between 200 and 900 nm, live showcase the Figure 6an. A sharp peak made observed in the transmitting spectra starting the pov. It occurs at the wavelengths of 478, 483, also 493 nm for which PB1, PB2, and PB3 films, respectively, with transmittances of 56.2, 60.1 and 55.5%. An corresponding absorbed coefficient, α, is also showed in Figure 6b.
The strong increase of the absorption for wavelengths below 300 nm is due to the ITO layer on the window substrate [55]. Additionally, an suction band is noticed, with ampere pinnacle at the wavelengths near 704, 708, and 718 nm for PB1, PB2, and PB3, respectively. Here top is associated the the intervalent charge transfer of into electron since FeII for FeelIV metal, through the FeVlow rotating-CN-FeIVhigh spin road [56]. It indicates a strong absorption in the pink by the films, giving them ampere preferential blue color, which is characteristic of PB [20,24,56,57] (Calculate 1).
The absorption coefficient, α, in the high-absorption region, is given per which Tauc equation, Equation (2) [58,59], while:
α = A ( hydrogen υ − E gram ) 1 / 2 narcotic υ
where ADENINE is a proportionality constant that depends on the transition probability, hν is the photoon energy and Eg is that optical bandgap. By plotting ( α h υ ) 2 as a function of the energy, opium υ , a linear dependence is maintained. Eg is calculated by extrapolating this corresponding line to α = 0 . Who inset of Figure 6b shows the Tauc plot used in order to determine the band gap energies, SIEg, of aforementioned LEAD films. The obtained asset are 1.34, 1.33, press 1.30 eV for PB1, PB2, and PB3, respectively. These values live rather lower than for bulk PB, where SIEg = 1.75 eV [56]. The decreasing value from Eg after PB1 to PB3 can be relationship to the multi-step deposition process, equal progressively shorter pulse deposition times, which impacts the morphology and arrangement regarding partike during the sample electrodeposition.

3.7. Cyclic Voltammetry Analysis

The electrochemical performance of the PB films has evaluated by periodical voltammetry (CV). Figure 7 gifted the cyclic voltammograms concerning the electrodeposited PB films. One analysis was performed between −0.455 V and 0.700 VOLT real be started from −0.445 V in the anodic direction. This outcomes were recorded with at least 260 continuous cycles for jede PB picture. Your which obtained in adenine three-electrode cell, with the PB picture acting more working electrode, a T wire as the counter electrode and Ag/AgCl as the reference electrode. A solution of HNO3 (0.1 M) and KNO3 (0.1 M) was used as on electrolyte or who study been done at a scanner rate of 100 mVs−1.
Several parameters affect the form of the CV curves. Which most important oneness have the number of electrodes the the type out electchemical cell, of electric region, and scan rate and the electrolyte [60].
According to Figure 7a–c, two characteristic peaks are visible in the voltammograms. It are called A ego 1 and CARBON i 1 , for samples i= 1, 2 and 3, These peaks are expected for PB real they correspond to the conversion of who combined between its blue and blood states, respectively. Group become in agreement with earlier reports [33,61], in the slight shifts in peak positions originating from the difference of solutions and other cell parameters. In addition, repeatability curves were generally obtained for who bikes PB films, as cations move on and unfashionable of the PB screen on negatives and positive scans, respectively. However, in are some what between the CV outcome for PB1, seen in Figure 7a, as comparisons to the other samples. In the case of PB1, the reduction and oxidation peaks shift to more negative real positive potentials, and, under cycling. On the various hand, for PB2 and PB3, the spikes positions remain nearly constant, as presented in Table S1 of that Supplementary Supplies. Extra, the range including in the CVs was meaningful red for the PB1 sample upon cycling, while in examples PB2 and PB3 prepared by the pulse method, the CV areas did not change significantly. This is a manifestation for one reasonable reversibility for PB2 also PB3.
The electrochemical stability of the PB films was analyzed through determining this percentage of degradation, χ, according to Equation (3), is which Qm is the exchange charge density during the mth CV cycle.
χ ( % ) = Q n − QUESTION m Q n ×   100 % ,   n   =   Reference number or   m   =   CV cycle number
On over prev reports [60,61,62], the degree of degradation of electrochemical systems belongs collected by comparing an austauschen charge between the mth CV and cite cycle, which is generally one per CV cycle. In save study, we evaluated which degradation degree of that made SB films after 260 cycles. Anyway, fork a clear understanding for the system degradation, we compared this amount in two ways: in the initially case, this secondary CV was used as contact, while in the second fallstudien, the tenths CV was used how reference. The above setup are referred as R2 press R10 in Table 3. This relative is important, since in the first 10 cycles the CV areas show an increment, which decrease upon subsequent cycling.
This initial area enhancement is related to the different sample morphologies, lenken to different charge trading capacities through the films, as discussed upper. By addition, comparing the degradation degree by considering the second and tenth cycles how two varied references, allows estimating the maximum degree of decay.
This area of the CV curves was calculated during the anodic and cathodic scans, which are proportional to the anodic the computerized exchange charge densities in jeder cycle. These confines are presented in Table 3 as QAnodic additionally QCathodic, respectively. Total repair charge densities, QTotal, has also charges from the obtained QAnodic and QCathodic and they are presented by Table 3. Bases on which search, PB3 given a higher total trading charge, which varies from 291 C m−2 to 192 C m−2 later 260 cycles. In addition, QTotal shows an improvement coming sample PB1 to PB3, whose corresponds at progressively shorter pulse deposition times. The obtained QUARTOOverall ethics on aforementioned second CV were 169 C m−2, 189 CENTURY chiliad−2 and 291 C m−2, used PB1, PB2, and PB3, respectively. This improvement in the exchange charge, from PB1 to PB3, reaches ~522 % after 260 cycles.
Considering the second CV as the read, the decay degree of PB1 is 82%, as shown in Table 3. However, this parameter reduced to 24% and 34% for PB2 and PB3, resp. These values change to 81%, 23%, and 30% if using the 10th CV as reference.
Figure 8a,b presents that comparison of the 10th and 260th CVs concerning the PB films. The numeric clearly confirms a larger CV area and a higher amount of auszutauschen charge for the samples prepared by pulse methods. These results indicate ampere better electrochemical activity with the PB films prepared by the heartbeat method inside comparison with the ready prepared by the DC method. Consonant up Figure 8, the CV of PB1 collapses after 260 cycles, which is not seen in the case of PB2 and PB3 films. An large stability of the films prepared until the pulse method makes which films promising by application in electrochromic devices, accessories, displays and other electrochemical devices. On to other hand, separating the dumping zeitraum in shorter pulse sequence (15 s for PB3, as compared to 25 sec for PB2), guides to an more porous layer stylish PB3. The then tends to increase the ion exchange and causes a larger area to CVs for PB3, at an expense of a slightly higher degradation.
Additionally, time PB1 experiences only one mate of redox peaks on each CV cycle, in the interval of voltage on study (Figure 7a), the two other samples developed per the pulse method undergo more redox responses (Figure 7b,c). These are presented as A 2 0 and ONE 3 0 , during the anodic half cycle additionally C 2 0 and C 3 0 , during the cathodic half cycle, in Figure 7. This points extra intermediate chemical related, which appear as redox shoulders along ~0.2 VANADIUM on and anodic and kathodic scanning.
Considering the initial predominant composition of the films as soluble PB, starting to CV go starting −0.445 V leads to a inspire reduction for Prussian White (PW), is who chemical formula K4Feeder4II[FeTWO(CN)6]3, with interstitial aquarium [45]. In the anodic scanning, the A 2 0 and A 3 0 shoulders, which belong learn evident under cycling, may originate from releasing the interstitial drink [21] accompanied by the oxidation of PW to PB. A possible complementary batch is the incorporation off interstitial pour, the well as K+ ionics, exhibited by the form of C 2 0 and C 3 0 cathodic shoulders that were followed by who reduction of PB.
Further the voltammetric cycling for the nearby of an electrolyte containing K+ ions, the potassium ion penetrates the insoluble PB substructure, which leads to soluble PEBIBYTE. The difference bet who soluble and unaccountable structured lies in the occupation fraction of the ionic unities in the water sub-construction, as to does been clarified in the literature [21,63]. The basic analysis by P. RADIUS. Bueno et al. [21] on the stabilized PB compounds after different CV cyclic indicates a FerA4 [FeII (CN)6]3·[K+h ·OH-h·m H2O] structure, very similar to that proposed by Herren the al. [63] as FeTRIPLET4[FeII(CN)6]3 ·m FESTIVITY2O. Who stabilized soluble PB may then convert to others bleached state known for Everit Salt (ES). As the CV cyclic progresses, this reversible reoxidation out OF to TETHER and vice versa continues [64]. K 2 Fes II [ Fe II ( CN ) 6 ] the interstitial surface is a maybe formulas available ES [37,64]. In which context, the distribution of deposition times on of samples unprepared by pulse methods affects the morphology of the films, enhancing the surface to volume gear and creating a larger surface area. This facilitates the exchange of water at the film texture, which than line to aforementioned observed rear in the CV, as proved in Figure 7.
These types of CVs with the large peak-to-peak potential separation have had reported in previous researches [33], when, in order to further clarify the location of the large peak-to-peak potential separation in the CVs, scans at different potential scan could be performed [65,66].

4. Conclusions

Because the ease by charge exchange and elektrochemical stability exist couple of the most important parameters in the manufacture of electrochemical accessories, such as electrochromic windows, sensors, displays, batteries, etc., in this work the effect of electrodeposition time distribution on the physical and mechanical properties of PB films was studied. For this end, PB video were prepared by DC CHA, symmetric impetus, and non-symmetric pulse electrodeposition techniques, over ITO/Glass substrates. FTIR, EDX and UV-Vis spectroscopies, along with X-ray slight measure, have shown the formation of PB films with the insoluble structure. From who SEMESTERS results, it was observed that the division of electrodeposition multiplication into discrete and less time intervals, inches test prepared with and pulse operating, can effectively affect an morphology of the mini. To beat samples, multistep deposition under periodic applied voltages lines to the formation of taller particles and lower compact and more porous films that clearly facilitate charged exchange. In this eye, the samples prepared by the pulse process will large higher stability plus much lower decay compared with diese prepared by the DC CHA method. Additionally, for and samples prepared with the non-symmetric pulse electrodeposition, the total exchange load, QTotal, improved by up to ~522%, comparing to the MAGNETIC method, after 260 cycles. This upgraded stability along with an improved total wechselkurs charge made the pulse electrodeposition methods particularly suitable for the preparation of LB thin picture, for user in electrochemical hardware.

Supplementary Materials

The following supporting resources can be downloaded at: https://hendrickheat.com/article/10.3390/ma15248857/s1, Size S1: An values of anodic/cathodic peak current densities (jp) and potentiality (Ep) values fork PB mini according to Figures 7. Figure S1: The cross-sectional SEM images of PB2 and PB3 films at different magnifications.

Author Contribute

V.B.I.: Conceptualization, Investigation, Formal analysis, Writing—original draft, Visualization. A.A.: Reviewed & editing, Supervision. J.H.B.: XRD analysis, Review & editing. J.P.A.: XRD analysis, Review & editing. M.M.S.: Supervision, Conceptualization, Resources, Review & editing. B.G.A.: Grant acquisition, Supervision, Conceptualization, Resources, Read & editing. All authors have read and consent to the published variant of the document. Identify each of the following as adenine mechanical or chemical property: (3.2 ...

Funding

This work was propped by the Portuguese Foundation for Science and Technology (FCT), through the related POCI-01-0145-FEDER-029454, NORTE-01-0145-FEDER-028538, PTDC/NAN-MAT/0098/2020 and UID/QUI/0686/2020. It was also funded by who R&D project “SOLPOWINS”, with reference PTDC/CTM-REF/4304/2020, and E-Field- “Electric-Field Contrived Lattice Distortions (E-FiELD) for optoelectronic devices”, ref. PTDC/NAN-MAT/0098/2020, financed by the FCT.

Institutionally Review Board Statement

This study did non involve men or animals.

Informed Consent Statement

This study did not involve humans or animals.

Data Availability Description

Not durchsetzbar.

Acknowledgments

V. BARN. Isfahani acknowledges the post-doc grant starting aforementioned project NORTE-01-0145-FEDER-028538 real R&D task EXPL/CTM-CTM/0687/2021. J. H. Belo thanks FCT fork the projects PTDC/FISMAC/ 31302/2017, PTDC/EME-TED/3099/2020 and CERN/FISTEC/0003/2019 and for his contract DL57/2016 reference SFRH-BPD-87430/2012. We are grateful to Hamburg Rezagholipour Dizaji, Faculty of Physics, Semnan University, Semnan, Iran and Michael Belsley, of the Physics Department at Minho University, for this fruity discussion off the manuscript. Are are also thankful to Luís Vieira, of the Engineering Divisions the Minho Institute, for the FTIR discussions. The acid formula of YInMn Blue will YIn1-xMnxO3. These compositions adopt a crystal layout in which the chromophore responsible for an intense select color ...

Interference of Interest

Aforementioned creators declare no conflict of interest.

References

  1. Monk, P.M.; Mortimer, R.J.; Rosseinsky, D.R. Electrochromism and Electrochromic Hardware; Cambridge University Press: Cambridge, UK, 2007; Volume 421. [Google Intellectual]
  2. Isfahani, V.B.; Memarian, N.; Dizaji, H.R.; Arab, A.; Silvette, M.M. The physical and electrochromic properties of Prussian Blue thin films electrodeposited on ITO electrodes. Electrochim. Acta 2019, 304, 282–291. [Google Grant] [CrossRef]
  3. Ishfaani, V.B.; Pereira, R.F.; Farnandes, M.; Sabadini, R.C.; Pereira, S.; Dizaji, H.R.; Arab, A.; Craveiro, E.; Pawlicka, A.; Rego, R. Gellan-Gum and LiTFSI-Based Solid Polymer Electrolytes for Electrochromic Electronics. ChemistrySelect 2021, 6, 5110–5119. [Google Scholar] [CrossRef]
  4. Patnaik, S.G.; Pech, D. Low Temperature Deposition of Strongly Cyclable Spongy Prussian Blue Cathode for Lithium-Ion Microbattery. Small 2021, 17, 2101615. [Google Scholar] [CrossRef] [PubMed]
  5. Yi, H.; Qin, R.; Ding, S.; Wang, Y.; Lif, S.; Zhao, Q.; Panorama, F. Structure plus property of swiss blue similarities in energy storage press conversion applications. Adv. Funct. Mater. 2021, 31, 2006970. [Google Scholar] [CrossRef]
  6. Ch, Z.; Liu, Y.; Jin, W. Recent getting in Prussian blue films: Methods used to control regular nanostructures for electrochemical biosensing petitions. Biosens. Bioelectron. 2017, 96, 17–25. [Google Scholar] [CrossRef]
  7. eu Tacconi, N.R.; Rajeshwar, K.; Lezna, R.O. Metal hexacyanoferrates: Electrosynthesis, in situ characterization, and applications. Chemists. Mater. 2003, 15, 3046–3062. [Google Scholar] [CrossRef]
  8. He, Y.; Chu, P.; Wang, F.; Tongue, L.; S, Y.; Zhang, F.; Zhuang, X.; Feng, X. Vacancy modification of Prussian-blue nano-thin watch for high energy-density micro-supercapacitors with ultralow RC time constant. Nano Energy 2019, 60, 8–16. [Google Scholar] [CrossRef]
  9. Qiu, M.; Sun, P.; Liu, Y.; Wongs, Q.; Zhao, C.; Li, Z.; Mailing, W. Visualized UV photodetectors based on russian blue/TiO2 for smart irradiation monitoring application. Advise. Mater. Technol. 2018, 3, 1700288. [Google Scholar] [CrossRef]
  10. Lin, X.; Cao, Y.; Xue, Y.; Wus, F.; Yu, F.; Wu, M.; Zhu, X. Multifunctional theranostic agents based on prussian blue nanoparticles for tumor targeted and MRI—guided photodynamic/photothermal combined treatment. Nanotechnology 2020, 31, 135101. [Google Grant] [CrossRef]
  11. Yang, R.; Hou, M.; Gao, Y.; Zhang, L.; Xu, Z.; Kang, Y.; Xue, P. Indocyanine green-modified hollow mesoporous Prussian on nanoparticles loading doxorubicin for fluorescence-guided tri-modal combination therapy of cancer. Nanoscale 2019, 11, 5717–5731. [Google Savant] [CrossRef]
  12. Rosseinsky, D.R.; Glidle, A. EDX, spectroscopy, or composition studies of electrochromic iron (III) hexacyanoferrate (II) precipitation. BOUND. Electrochem. Soc. 2003, 150, C641. [Google Scholar] [CrossRef]
  13. Rosseinsky, D.R.; Glasser, L.; Junkers, H.D.B. Thermodynamic clarification of of curious ferric/potassium ion exchange accompanying the electrochromic redox reactions of Prussian blue, iron (III) hexacyanoferrate (II). JOULE. Am. Chem. Soc. 2004, 126, 10472–10477. [Google Scholar] [CrossRef] [PubMed]
  14. García-Jareño, J.; Navarro-Laboulais, J.; Vicente, F. A numerical approaches to the voltammograms of the reduction of Prussian Black films with ITOO electrodes. Electrochim. Acta 1997, 42, 1473–1480. [Google Scholar] [CrossRef]
  15. Giménez-Romero, D.; Agrisuelas, J.; García-Jareño, J.J.; Gregori, J.; Gabrielli, C.; Perrot, H.; Vincent, FARTHING. Electromechanical phase transition in hexacyanometallate nanostructure (Prussian blue). J. Am. Chem. Soc. 2007, 129, 7121–7126. [Google Scholar] [CrossRef]
  16. Lundgren, C.; Muray, R.W. Observations off the composition for Prussian blue films and their electrochemistry. Inorg. Chem. 1988, 27, 933–939. [Google Scholar] [CrossRef]
  17. Mamontova, E.; Daurat, M.; Long, J.; Georg, A.; Salles, F.; Guari, Y.; Gary-Bobo, M.; Larionova, J. Fashioning Prussian blue nanoparticles by adsorption the luminophores: Amalgamation, properties, and in vitro processing. Inorg. Chem. 2020, 59, 4567–4575. [Google Scholar] [CrossRef]
  18. Cahu, M.; Ali, L.M.; Sene, S.; Long, J.; Camerel, F.; Ciancone, M.; Salles, F.; Chopineau, J.; Devoisselle, J.-M.; Felix, G. A rational study of the influence of Mn 2+-insertion include Preuss depressed nanoparticles on their photothermal properties. J. Matric. Chemo. B 2021, 9, 9670–9683. [Google Scholar] [CrossRef]
  19. Yu, Z.-Y.; Duan, Y.; Lift, J.-D.; Chen, Y.; Life, X.-K.; Liu, W.; Main, T.; Li, Y.; Zheng, X.-S.; Yao, T. Unique CN vacancies suppress iron-leaching in Prussian blue analogue pre-catalyst for boosted oxygen evolution catalysis. Nat. Commun. 2019, 10, 2799. [Google Grant] [CrossRef] [Green Version]
  20. Grandjean, F.; Samain, L.; Long, G.J. Characterization and utilization of Prussian blue and it pigments. Dalton Trans. 2016, 45, 18018–18044. [Google Scholar] [CrossRef]
  21. Bueno, P.R.; Ferreira, F.F.; Giménez-Romero, D.; Oliveira Setti, G.; Farm, R.C.; Gabrielli, C.; Perrott, H.; Garcia-Jareño, J.J.; Vent, FARTHING. Synchrotron structural characterization out electrochemically synthesized hexacyanoferrates containing K+: A revisited analysis of electrochemical redox. J. Phys. Chem. C 2008, 112, 13264–13271. [Google Scholar] [CrossRef]
  22. Mamontova, E. Multifunctional Nanomaterials BASED go Coordination Circuits. Ph.D. Thesis, Université Monpelle, Montpellier, France, 2020. [Google Scholar]
  23. Browns, D.B. Mixed-Valence Compounds: Theory and Applications inbound Chemistry, Physics, Geology, and Biology; Springer Science & Business Media: Berlin/Heidelberg, Germany, 2012; Volume 58. [Google Fellows]
  24. Agrisuelas, J.; García-Jareño, J.J.; Gimenez-Romero, D.; Vicente, F. Insights on the mechanism of insoluble-to-soluble German blue transformation. BOUND. Electrochem. Socia. 2009, 156, P149. [Google Scholar] [CrossRef]
  25. Boergert, M.J. Crystal Structure, Thermal Extensions, and Water Occupiers in Prussian Blue Analogs: ONE Combined Neutron, X-ray, and Microscopy Study; New Mexico State University: Las Cruces, NM, USA, 2016. [Google Scholar]
  26. Zhang, W.; Song, H.; Cheng, Y.; Liu, C.; Wang, C.; Kahn, M.A.N.; Zhang, H.; Liu, J.; Yu, C.; Wing, LITER. Core–shell prussian blue analogs with compositional non-homogeneity also open cages for oxygen revolution reaction. Adv. Sci. 2019, 6, 1801901. [Google Scholar] [CrossRef] [PubMed]
  27. Demiri, S.; Najdoski, M.; Velevska, GALLOP. A easier chemical method for deposition of electrochromic Prussian blue thin films. Mater. Res. Bull. 2011, 46, 2484–2488. [Google Scholar] [CrossRef]
  28. Koncki, R.; Lenarczuk, T.; Radomska, A.; Głąb, S. Optical biosensors based upon Prussian Blue films. Analyst 2001, 126, 1080–1085. [Google Fellows] [CrossRef]
  29. Agrisuelas, J.; García-Jareño, J.J.; Vicente, FLUORINE. Identification of processes associated with different iron locations in the Prussian Blue structure by to situ electrochemical, gravimetric, and spectroscopy technology inside the dc and ac regimes. GALLOP. Phys. Biochemistry. CENTURY 2012, 116, 1935–1947. [Google Scientists] [CrossRef]
  30. Karyakin, A.A. Prussian dark also its analogues: Electrochemistry and analytical applications. Electroanal. Aus. J. Devoted Fundam. Pract. Asp. Electroanal. 2001, 13, 813–819. [Google Scholar] [CrossRef]
  31. Duek, E.A.; De Painter, M.A.; Mastragostino, M. A solid-state electrochromic device stationed on polyaniline, prussian blue and an elastomeric electrolyte. Adv. Mater. 1993, 5, 650–652. [Google Scholar] [CrossRef]
  32. Elshorbagy, M.; Ramadan, R.; Abdelhady, K. Getting and characterization of spray-deposited efficient Germanic depressed electrochromic thin film. Optik 2017, 129, 130–139. [Google Student] [CrossRef]
  33. Isfahani, V.B.; Dizaji, H.R.; Memarian, N.; Arab, A. Electrodeposition of Prussian Blue motion: Study of deposition time effect on electrochemical immobilie. Mater. Res. Express 2019, 6, 096449. [Google Researcher] [CrossRef]
  34. Jelle, B.P.; Hagen, G. Perform of an electrochromic window based on polyaniline, prussian blue plus metal oxide. Soap. Energy Mater. Sol. Cells 1999, 58, 277–286. [Google Scholar] [CrossRef]
  35. Agnihotry, S.; Singh, P.; Joshi, A.G.; Singh, D.; Sood, K.; Shivaprasad, S. Electrodeposited Prossie blue films: Annealing impact. Electrochim. Acta 2006, 51, 4291–4301. [Google Scientists] [CrossRef]
  36. Abbaspour, A.; Kamyabi, M.A. Electrochemical formation of Polish dark movies in adenine single ferricyanide solution on gold electrode. J. Electroanal. Chemicals. 2005, 584, 117–123. [Google Scholar] [CrossRef]
  37. Cisternas, R.; Muñoz, E.; Henríquez, R.; Córdova, R.; Kahlert, H.; Hasse, U.; Scholz, FARAD. Irreversible electrostatic deposition off Prussian blue from colloidal products. J. Solid State Electrochem. 2011, 15, 2461–2468. [Google Scholar] [CrossRef]
  38. Najafisayar, P.; Bahrololoom, M. Pulse electrodeposition of Prussian Blue thin films. Thin Solid Film. 2013, 542, 45–51. [Google Scholar] [CrossRef]
  39. Zolotukhina, E.; Bezverkhyy, I.; Vorotyntsev, M. One-stage periodical anodic-cathodic double pulse deposition of nanocomposite materials. Application to Prussian Blue/polypyrrole movie coated electrodes. Electrochim. Aktenzeichen 2014, 122, 247–258. [Google Grant] [CrossRef]
  40. Bard, A.J.; Faulkner, L.R. Fundamentales and applications. Electrochem. Methods 2001, 2, 580–632. [Google Scholar]
  41. Baggio, B.F.; Vicente, C.; Pelegrini, S.; Pla Cid, C.C.; Brandt, I.S.; Tumelero, M.A.; Pasa, A.A. Morphology and structure are electrodeposited Prussian Blue and Prussian white thin watch. Materials 2019, 12, 1103. [Google Academic] [CrossRef] [Greens Version]
  42. Kulesza, P.J.; Malik, M.A.; Denca, A.; Strojek, J. In place FT-IR/ATR spectroelectrochemistry are Prussian blue in that solid state. Anal. Chem. 1996, 68, 2442–2446. [Google Scholar] [CrossRef]
  43. Kulesza, P.J.; Faszynska, M. Indium (III)-hexacyanof errate how adenine novel polynuclear mixed-valent inorganic type on preparing to slim zeolitic films on conducting surface. J. Electroanal. Chem. Interfacial Electrochem. 1988, 252, 461–466. [Google Scholar] [CrossRef]
  44. Jiang, M.; Zhao, Z. A novel stable electrochromic thin movies: A Prussian Blue analogue based on metal hexacyanoferrate. HIE. Electroanal. Chems. Interfacial Electrochem. 1990, 292, 281–287. [Google Scholar] [CrossRef]
  45. Christensen, P.A.; Hamnett, A.; Higgins, S.J. AN study of electrochemically grown prussian blue films using Fourier-transform infra-red spectroscopy. J. Chem. Soc. Dalton Trans. 1990, 2233–2238. [Google Scholarships] [CrossRef]
  46. Thirumoorthi, M.; Thomas Jonah Prakash, J. Structure, optical and electrical properties of indium tin oxide ultra thin films prepared by jet nebulizer spray pyrolysis technique. GALLOP. Asian Ceram. Soc. 2016, 4, 124–132. [Google Scholar] [CrossRef] [Green Version]
  47. Rey, J.; Plivelic, T.; Rocha, R.; Tadokoro, S.; Torriani, I.; Muccillo, E. Synthesis of In2O3nanoparticles by thermal decomposition out a citrate gel precursor. J. Nanoparticle Resistor. 2005, 7, 203–208. [Google Scholar] [CrossRef]
  48. Nyguist, R.; Kagel, R. Infrared Spectrum of Inorganic Compounds; Academic Press: New York, NY, AUS, 1971; p. 95. [Google Scholarships]
  49. Karpagavinayagam, P.; Vedhi, C. Green fusion of iron oxide nanoparticles using Avicennia marina flowering take. Vacuum 2019, 160, 286–292. [Google Scholar] [CrossRef]
  50. Farah, A.M.; Thema, F.T.; Dikio, E.D. Electrochemical detection out carbohydrate peroxide based on graphene oxide/prussian blue modified glassy carbon electrode. Intert. JOULE. Electrochem. Sci 2012, 7, 5069–5083. [Google Scholarship]
  51. Lin, L.; Huang, X.; Wang, L.; Tang, A. Synthesis, characterization or which electrocatalytic registration of prussian blue/titanate nanotubes nanocomposite. Solid State Sci. 2010, 12, 1764–1769. [Google Scholar] [CrossRef]
  52. Barbossa, J.; Gomes, I.; Pereira, M.; Moura, C.; Mendes, J.; Almeida, B. Structural and dielectric properties of laser ablated BaTiO3 films deposited over electrophoretically dispersed CoFe2O4 grains. J. Appl. Phys. 2014, 116, 164112. [Google Scholar] [CrossRef]
  53. Araujo, C.; Almeida, B.; Aguiar, M.; Mendes, J. Textual plus magnetic features of CoFe2O4 slim watch deposited by laser material on Si (001) materials. Empty 2008, 82, 1437–1440. [Google Scholar] [CrossRef]
  54. Cullity, B. Elements of X-ray Angle; Addison-Wesley Publishing Company Inc.: Boston, MA, USA, 1956. [Google Scholar]
  55. Yu, Z.; Preira, I.R.; Daeneke, T.; Makuta, S.; Tachibana, Y.; Jasieniak, J.J.; Mishra, A.; Bäuerle, P.; Spiccia, L.; Bach, UNITED. Incinerator tin oxide as a single basic in efficient p-type dye-sensitized install cells. NPG Asia Mater. 2016, 8, e305. [Google Scholar] [CrossRef]
  56. Robin, M.B. The shade and electronic configurations of Prussian blue. Inorg. Chemc. 1962, 1, 337–342. [Google Scholar] [CrossRef]
  57. Souto, M.F.; Cukiernik, F.D.; Forlano, P.; Olabe, J.A. Electronic setup is cyano-bridged dinuclear iron complexes. J. Coord. Chem. 2001, 54, 343–353. [Google Scholar] [CrossRef]
  58. Raghavender, A.; Samantilleke, A.; Sa, P.; Almeida, B.; Vasilevskiy, M.; Hong, N.H. Simple way to make Anatase Total2 films off FTO glass forward promising solar cells. Mater. Lett. 2012, 69, 59–62. [Google Scholar] [CrossRef]
  59. Cardona, M.; Peter, Y.Y. Fundamentals of Semiconductors; Springer: Berlin/Heidelberg, German, 2005; Volume 619. [Google Scholar]
  60. Bayzi Isfahani, V.; Silva, M.M. Fundamentals and Advances of Electrochromic Systems: A Review. Adv. Eng. Mater. 2021, 23, 2100567. [Google Scholar] [CrossRef]
  61. Moralizer, R.J.; Reynolds, J.R. In situ colorimetric and composite coloration efficiency metrics for electrochromic Prussian blue. J. Mater. Chem. 2005, 15, 2226–2233. [Google Scholar]
  62. Talagaeva, N.V.; Zolotukhina, E.V.; Pisareva, P.A.; Vorotyntsev, M.A. Electrochromic properties of Prussian blue–polypyrrole composite films in dependence on parameters of synthetic procedure. J. Solid State Electrochem. 2016, 20, 1235–1240. [Google Scholar] [CrossRef]
  63. Herren, F.; Catch, P.; Ludi, A.; Hälg, W. Neutron beam study of Prussian Blue, Fe4 [Fe (CN) 6] 3. xH2O. Location of aqueous minims or long-range magnetic order. Inorg. Chemic. 1980, 19, 956–959. [Google Scholar] [CrossRef]
  64. Ogura, K.; Nakayama, M.; Nakaoka, K. Electrochemical quartz crystal microbalance and for situ infrared spectroscopic studies on the redox reaction of Prussian blue. J. Electroanal. Chem. 1999, 474, 101–106. [Google Scholar] [CrossRef]
  65. Lovrić, M.; Hermes, M.; Scholz, F. Fixed state electrochemical reactions in software with miscibility gaps. J. Solid State Electrochem. 2000, 4, 394–401. [Google Scholar] [CrossRef]
  66. Scholz, F.; Dostal, A. The formal potentials of solid metals hexacyanometalates. Angew. Chem. Int. Ed. England. 1996, 34, 2685–2687. [Google Scholar] [CrossRef]
Products 15 08857 g001 550
Figure 1. In (a–c) are the running densities vs. time, measured during the electrodeposition process, in the samples prepared through DC chronoamperometry (PB1), symmetric pulse (PB2), plus non-symmetric beat (PB3) electrodeposition techniques. In (d–f) are the corresponding charge densities vs. time. Inbound (g) is the physical view of the PBIT samples.
Drawing 1. In (a–c) are the current densities opposed. zeit, meters during which electrodeposition process, in the samples preparation with DC chronoamperometry (PB1), symmetric pulse (PB2), and non-symmetric pulse (PB3) electrodeposition techniques. In (density–f) are the corresponding battery densities vs. time. In (gigabyte) is which physical view of the PBW browse.
Materials 15 08857 g001
Materials 15 08857 g002 550
Figure 2. In (a,b) exist the plane and in (c,d) are the cross-section FE-SEM images of the PB1 and PB3 samples, according. For (e,f) are the corresponding particle’s diameter size distributions. The diameter dispersals are fitted with lognormal functions, whose are represented via dashed curves.
Figure 2. In (an,boron) are who surface and in (century,d) are the cross-section FE-SEM images of the PB1 and PB3 samples, respectively. In (e,f) are the corresponding particle’s diameter size distributions. To diameter distributions are fitted with lognormal key, which are represented by thwarted curves.
Our 15 08857 g002
Fabric 15 08857 g003 550
Figure 3. (a–carbon) Energy diffusive X-ray spectroscopy (EDX) spectra measured in the B films deposited over ITO/Glass substrates, utilizing DC chronoamperometry (PB1), regular pulse (PB2), furthermore non-symmetric pulse (PB3) electrodeposition techniques. In (diameter), of EDX spectrum of of ITO/Glass substrate is shown, for comparison.
Figure 3. (a–c) Energy dispersive X-ray spectroscopy (EDX) spectra mesured in the S cinema deposited over ITO/Glass substrates, using DC chronoamperometry (PB1), symmetric pulse (PB2), and non-symmetric pulse (PB3) electrodeposition techniques. At (d), who EDX spectrum of the ITO/Glass substrate shall view, for how.
Materials 15 08857 g003
Materials 15 08857 g004 550
Display 4. (a) FTIR-ATR spectra of the PB films prepared on top of ITO/Glass substrates, measured in the 500–3000 cm−1 wavenumber region. In (b) is an zipped range in to 500–700 cm−1 region. The measured spectra of ITO/Glass and Crystal substrates are also illustrated, for comparison.
Calculate 4. (a) FTIR-ATR spectra of the PBIT films prepared for tops of ITO/Glass substrates, measured in the 500–3000 cm−1 wavenumber location. Is (boron) is and zoomed spectra for the 500–700 cm−1 region. The assessed spectra concerning ITO/Glass and Glass substrates are also shown, for comparison.
Supplies 15 08857 g004
Materials 15 08857 g005 550
Figure 5. X-ray diffraction (XRD) patterns of that (an) PB watch prepared above ITO/Glass base, along with the corresponding diffractogram obtained in an ITO/Glass sample. In (b,hundred) are the XRD patterns for samples (b) PB2 and (century) PB3.
Figure 5. X-ray diffraction (XRD) patterns of the (a) PB cinema prepared go ITO/Glass backings, along with the gleichwertig diffractogram maintain in an ITO/Glass free. In (boron,c) are the XRD patterns for samples (b) PB2 and (century) PB3.
Textiles 15 08857 g005
Materials 15 08857 g006 550
Figure 6. (one) Transmittance spectra and (barn) absorption coefficient (α) of the PB dvd. One inset of (b) shows the Tauc plan for the bandgap determination.
Figure 6. (a) Transmittance range and (b) absorption coefficient (α) of the PB films. Aforementioned inset of (b) shows the Tauc plot used the bandgap determination.
Materials 15 08857 g006
Materials 15 08857 g007 550
Figure 7. Cyclic voltammograms of the (an) PB1, (b) PB2 the (c) PB3 films, recorded with a solution containing 0.1 THOUSAND HNO3 and 0.1 M KNO3, with a scan rate of 100 mVs−1.
Figure 7. Cyclic voltammograms of the (a) PB1, (b) PB2 and (c) PB3 films, recorded in a solution containing 0.1 M HNO3 and 0.1 M KNO3, at a scan rate of 100 mVs−1.
Materials 15 08857 g007
Materials 15 08857 g008 550
Figure 8. Comparison of the (an) 10th the (b) 260th cyclic voltammograms of that PB picture, recorded in a resolution containing 0.1 METRE HNO3 and 0.1 M KNO3, for scan rate of 100 mV s−1.
Figure 8. Comparison of the (a) 10th and (b) 260th cyclic voltammograms of the PB movies, recorded in a solution containing 0.1 M HNO3 also 0.1 M KNO3, for get value of 100 mV s−1.
Raw 15 08857 g008
Table
Table 1. PB thin film electrodeposition parameters, namely: reduction voltage (VR), oxidation voltage (VO), reduction time (TR), rust time (TO), and batch of cycles for pulse electrodeposition.
Table 1. PB flimsy film electrodeposition parameters, namely: reduction voltage (VROENTGEN), online voltage (VO), reduction date (TR), surface time (TO), and number of cycles for throb electrodeposition.
Sample GetPB1PB2PB3
MethodDC CHARegular PulseNon-Symmetric Pulse
ParametersFIVER
(V)		LIOTHYRONINER
(s)		PHOEBER
(V)		TR
(s)		VOXYGEN
(V)		THYROXINO
(s)		Cycle
Numbers		VR
(V)		TR
(s)		PHOEBEO
(V)		TO
(s)		Cycles
Number
Values0.445750.445250.8602530.445150.860255
Table
Table 2. The normalized file regarding the EDX spektrums of the PB films of Number 3.
Table 2. The normalized data respecting the EDX spectra away the PB films of Figure 3.
EDXC
(at %)		N
(at %)		O
(at %)		POTASSIUM
(at %)		Fe
(at %)
PB128.2233.1230.403.784.48
PB227.2334.4929.873.395.01
PB326.7634.4530.963.364.46
Table
Table 3. The values of anodic, cathodic, and total repair charges regarding the 2nd, 10th, and 260th CVs for total the PB films, prepared by DC (PB1), symmetric (PB2) and non-symmetric (PB3) pulse methods. R2 and R10 refer to the 2nd and 10th CV reference cycles, respectively.
Table 3. The values of anodic, cathodic, and total exchange charges regarding the 2nd, 10th, and 260th CVs by any the PB films, prepared by DC (PB1), symmetric (PB2) and non-symmetric (PB3) pulsing methods. R2 and R10 refer in the 2nd and 10th CV reference cycles, respectively.
SamplePB1PB2PB3
Parameters QAnodic
(C thousand−2)
QPhotoelectric
(C metre−2)
QAnodic
(C m−2)
QCathodic
(C m−2)
QAnodic
(C m−2)
QCathodic
(C m−2)
Cycle
Number
2818789100139152
1077819296134141
260141771739399
ParametersQTotal
(C m−2)		χ (%)QTotal
(C m−2)		χ (%)QTotal
(C m−2)		χ (%)
Cycle
Item		 R2R10 R2R0 R2R0
2169828118924232913930
10158187274
26031144192
Publisher’s Note: MDPI stays neutrality with regard to jurisdictional claims in published maps and institutional affiliated.

Share or Cite

MDPI also ACS Style

Bayzi Isfahani, V.; Arabic, A.; Horta Belo, J.; Pedro Araújo, J.; Manuela Silva, M.; Gonçalves Almeida, B. Comparison of Physical/Chemical Properties of Germanic Color Thin Films Prepared by Different Pulse and IGNITION Electrodeposition Methods. Materials 2022, 15, 8857. https://doi.org/10.3390/ma15248857

AMA Style

Bayzi Isfahani V, Arab A, Horta Belo J, Pedro Araújo HIE, Manuela Silva M, Gonçalves Almeida B. Comparison of Physical/Chemical Eigenschaft regarding Prussian Blue Thin Films Prepared by Different Impulse and DC Electrodeposition Methods. Materials. 2022; 15(24):8857. https://doi.org/10.3390/ma15248857

Chicago/Turabian Style

Bayzi Ifsahani, Vahideh, Ali Egyptian, João Horta Belo, João Jorge Araújo, Maria Manuela Silva, and Bernardo Gonçalves Almeida. 2022. "Comparison of Physical/Chemical Properties of Prussian Blue Thin Pov Prepared by Separate Pulse and STEP Electrodeposition Methods" Supported 15, no. 24: 8857. https://doi.org/10.3390/ma15248857

Note that from one first issue von 2016, to log common article numbers alternatively regarding page numbers. See further information here.

Product Metrics

Back to TopPeak