Electrochemical responses of carbon nanotubes-based films printed on polymer substances

The electrochemical responses of novel thin films, which consist of multiwalled carbon nanotubes (MWCNTs) printed on polymer substrates, were investigated towards ferrocyanide/ferricyanide, [Fe(CN)₆]^3?/4? redox couple in aqueous potassium chloride solutions. With this respect, MWCNT-based films were fabricated through transfer of water-dispersed MWCNTs onto the polymer substances polyethylene terephthalate (MWCNT-PET) and polycarbonate (MWCNT-PC) by means of mass flexographic printing process. For the electrochemical studies, the techniques of cyclic voltammetry and electrochemical impedance spectroscopy were employed. The findings reveal that the MWCNT-PC films exhibit better stability in solution, less oxidation overpotential, greater oxidation current density, and larger capacitance compared to MWCNT-PET films. In addition, the MWCNT-PC films provide fewer barriers for electron transfer process and faster electrode kinetics compared to MWCNT-PET films. The results are very promising and open the possibility of using mass-printing techniques for the construction of printed MWCNT-polymer films for electrochemical applications.     

Electrochemical Studies on Substituted Iron-Hexacyanoiron(III) Bi-Layered Thin Films at Glassy Carbon Electrode/Electrolyte Interface

Thin films (30–50 nm) of bilayered HCM (hexacyanometalates) were prepared using direct electrodeposition or electrochemically driven insertion-substitution of PB (Prussian Blue) or InHCF (Indium Hexacyanoferrate) or K..In _x [Fe{CN}₆] _y , as starting material. The redox behavior of the immobilized counter/central ions at GCE/electrolyte interface have been investigated in aqueous KCl (pH 1) electrolytes using dynamic voltammetric techniques. Studies show that when the counter Fe or In ion is replaced by expandable partially filled d orbits elements such as Ru³⁺ a redox wave of the inserted counter ion is observed. Furthermore, the substitution of Fe as a counter ion with other poly-valent cations was found to be reversible if PB was the starting material. Studies were extended to include the EC (electrochemical) behavior of related HCM compounds such as K...Al _x [Fe{CN}₆] _y K, Ni _x [Fe{CN}₆] _y Cu _x [Fe{CN}₆] _y , K..Zn _x [Fe{CN}₆] _y and, K..Ru[Fe{CN}₆]₃. Unlike studied 3d cations, GCE modified with thin films of copper-hexacyanoiron (III) KCu _x [Fe{CN}₆] _y or CHF showed two redox waves with E^o _f 0.6, 0.9 V vs Ag/AgCl. Studies showed that even immobilized Cu ions were capable of catalyzing the oxidation of hydrazine and sulfite. The mechanism for electro-oxidation is also included.     

Magnetic and Mössbauer studies of cyanide-bridged bimetallic assembly [Mn(cyclam)][Fe(CN)6]·3H2O

Cyanide-bridged bimetallic assembly [Mn(cyclam)][Fe(CN)₆]·3H₂O (cyclam=1,4,8,11-tetraazacyclotetradecane) was synthesized from the reaction of trans-[MnCl₂(cyclam)]Cl with K₃Fe(CN)₆. A linear chain structure consisting of alternating [Mn(cyclam)]³⁺ and [Fe(CN)₆]³⁻ units was indicated by the IR and Mössbauer spectra. The variable-temperature magnetization and Mössbauer measurements revealed that this complex exhibited a long-range ordering below 6.8 K. The magnetic behavior of the complex was based on intrachain ferromagnetic and interchain antiferromagnetic interactions.     

Synthesis and characterization of conducting polypyrrole-containing iron complexes

Electrochemical or chemical oxidation of pyrrole-containing complex anions of iron cyanide or iron chloride results in the formation of films or powders of conducting polypyrroles. Freshly prepared films exhibit an additional IR band at ca 1630–1640 cm⁻¹, slowly disappearing in air and not observed in previously studies polypyrrole-based systems. It is possible that this new band is associated with the existence of a CN bond in dehydrogenated pyrrole rings which are transformed into regular pyrrole rings, probably due to the protonation reaction occurring in air and simultaneous bond rearrangement. The polypyrrole structure favours the presence of Fe(CN)₆⁴⁻ over Fe(CN)₆³⁻ since the former is the only iron species detected by Mössbauer spectroscopy in electrochemically prepared samples. It is also the dominant iron species in the samples oxidized chemically. The polypyrrole-containing Fe(CN)₆⁴⁻ is more ordered than those containing monovalent anions, as evidence by X-ray diffraction studies. High-spin eron complexes can be inserted into polypyrrole during electrochemical oxidation of pyrrole in non-aqueous solutions containing LiCl/FeCl₃. The inserted species exhibit Mössbauer parameters characteristic of slightly distorted FeCl₄⁻.     

Electrochemical properties of compacts of nano-and microdisperse diamond powders in aqueous electrolytes

The electrochemical behavior of compacts of micro-and nanodisperse diamond powders were studied by using model redox K₃[Fe(CN)₆]-K₄[Fe(CN)₆] and Ce(SO₄)₂-Ce₂(SO₄)₃ systems in aqueous electrolytes. The current-voltage curves for compacts of microdisperse diamonds and the kinetics of reactions on these compacts in a solution of the [Fe(CN)₆]^3-/4- system are similar to those obtained by using a metal electrode. For nanodisperse diamonds, the same reactions are essentially irreversible.     

Mössbauer studies of photochemical reaction products of Ru(bpy)3 2+ iron cyanide double complexes

The reductive and the oxidative electron-transfer photochemical reaction system of light-irradiated the mix solutions of Ru(bpy)₃ ²⁺ with [Fe(CN)₆]^4–, [Fe(CN)₆]^3–, [Fe(CN)₅NO]^2– and PB (Prussian Blue) have been studied. The double complexes which isolated from the precipitates of the photochemical reaction have been identified by means of Mössbauer spectroscopy. In order to clarify the chemical states of these isolated double complexes, we have (prepared and) studied Mössbauer spectra of the double complexes such as [Ru(bpy)₃]₃[Fe(CN)₆]₂.14H₂O, [Ru(bpy)₃]₂[Fe(CN)₆].10H₂O, [Ru(bpy)₃][Fe(CN)₅NO].4H₂O, and [Ru(bpy)₃][PB]₂.xH₂O.     

Direct growth of single crystalline ReO3 nanorods on a tungsten (W) microwire for enhanced electron-transfer reaction kinetics

We report the direct growth of highly single crystalline rhenium trioxide (ReO₃) nanorods on a tungsten (W) microwire electrode via the physical vapor transport process without any catalyst. In our growth mode, ReO₃ nanocubes were initially formed on the surface of a tungsten (W) microwire electrode and further they were anisotropically grown along the [001] crystallographic direction. Furthermore, we performed the fundamental electrochemical experiments so that from cyclic voltammetric measurements, ReO₃ nanorods on a W microwire exhibit a good capacitance and Nernstian behavior for a Fe(CN)₆³⁻/Fe(CN)₆⁴⁻ redox couple in 1 M KNO₃ aqueous solution, indicating a promising electrode material for electrochemical applications.     

一种新型的染料敏化紫外光电池

利用浸渍提拉法制备了纳米TiO₂多孔膜.采用紫外光源,以[Fe(CN)₆]^3-/[Fe(CN)₆]^4-溶液为电解质,分别以两种染料敏化纳米TiO₂膜为光阳极制成了一种新型的紫外光电池,探讨了该电池的伏安特性曲线.电池最大电压为0.36 mV,最大电流密度为0.02 μA/cm²,同时对染料敏化电极的光电转换机理进行了初步讨论.     

Changes in the chemical state and concentration of iron in carbon nanotubes obtained by the CVD method and exposed to pulsed ion irradiation

Data on the distribution of iron in nitrogen-containing multiwall carbon nanotubes (N-MWCNTs) and changes in its chemical state and concentration under different parameters of irradiation by a pulsed ion beam are obtained by methods of transmission electron microscopy, X-ray photoelectron spectroscopy, and energy dispersion analysis. It is shown that the irradiation of N-MWCNTs with an energy density of 0.5 J/cm² lead to the formation, on their lateral surfaces, of structures with a size of 2–10 nm, consisting of metallic iron encapsulated in a carbon shell. An increase in the energy density to 1–1.5 J/cm² leads to a substantial removal of iron clusters from the tips of carbon nanotubes and a reduction in the amount of iron in the bulk of the N-MWCNT layer.

     

Relation between 2p X-ray photoelectron and Kα X-ray emission spectra of manganese and iron oxides

The high resolution Mn and Fe Kα X-ray emission spectra (XES), and Mn and Fe 2p X-ray photoelectron spectra (XPS) for manganese and iron oxides were measured. The spectra were compared with those of [MnO₄]⁻, [Fe(CN)₆]⁴⁻ and [Fe(CN)₆]³⁻ ions. As the electronic structure of the latter compounds do not change with electron hole creation in the core levels, satellite peaks due to charge transfer are not observed in the 2p XPS spectra, and the peak profiles of metal 2p XPS and Kα XES are governed by the exchange splitting between 2p and valence electrons. The metal 2p XPS spectra of the oxides had satellite peaks, but the XES spectra had no satellites. FWHMs of the metal 2p_3/2 main peaks of the compounds being low spin states are smaller than those of metal Kα₁ XES spectra. However, FWHMs of Mn 2p_3/2 of the manganese oxide were nearly equal to those of Mn Kα₁ XES spectra, and those of Fe 2p_3/2 XPS spectra of the iron oxides are greater than those of Fe Kα₁ XES spectra.     

Electrochemical immune bioassay for the antigen–antibody interaction based on [Fe(CN)<Subscript>6</Subscript>]<Superscript>4-/3-</Superscript> and [AuCl<Subscript>4</Subscript>]<Superscript>-</Superscript> ions-derivated biomimetic interface

A simple and sensitive electrochemical immune bioassay for the detection of hepatitis B surface antigen (HBsAg), as a model, was developed based on [Fe(CN)₆]^4-/3- and [AuCl₄]^- ions-derivated biomimetic interface in this study. A layer of [Fe(CN)₆]^4-/3- film (i.e., Prussian blue, PB) was initially electrodeposited onto a glassy carbon electrode, and then [AuCl₄]^- ions were reduced under the potentiostat to form gold nanoparticles on the PB film. Finally, hepatitis B surface antibody (HBsAb) was adsorbed onto the nanogold surface. The performance and factors influencing the immunosensor were assessed and optimized. The proposed immunosensor exhibits a specific response to HBsAg in the range of 2.13–314.3 ng∙ml^-1 with a detection limit of 0.42 ng∙ml^-1. In addition, the developed immunosensor shows high sensitivity, good reproducibility, and long-term stability. Importantly, the ions-derivated biomimetic interface could be further extended for the immobilization of other proteins and biocompound.     

Electrochemical and surface characterisation of carbon-film-coated piezoelectric quartz crystals

The electrochemical properties of carbon films, of thickness between 200 and 500 nm, sputter-coated on gold- and platinum-coated 6 MHz piezoelectric quartz crystal oscillators, as new electrode materials have been investigated. Comparative studies under the same experimental conditions were performed on bulk electrodes. Cyclic voltammetry was carried out in 0.1 M KCl electrolyte solution, and kinetic parameters of the model redox systems Fe(CN)₆^3−/4− and [Ru(NH₃)₆]^3+/2+ as well as the electroactive area of the electrodes were obtained. Atomic force microscopy was used in order to examine the surface morphology of the films, and the properties of the carbon films and the electrode-solution interface were studied by electrochemical impedance spectroscopy. The results obtained demonstrate the feasibility of the preparation and development of nanometer thick carbon film modified quartz crystals. Such modified crystals should open up new opportunities for the investigation of electrode processes at carbon electrodes and for the application of electrochemical sensing associated with the EQCM.     

Laser induced breakdown spectroscopy surface analysis correlated with the process of nanoparticle production by laser ablation in liquids

Linkage isomerism is the coexistence of iso-compositional molecules or solids differing by connectivity of the metal to a ligand. In a crystalline solid state, the rotation is possible for asymmetric ligands, e.g., for cyanide ligand. Here we report on our observation of a phase transition in anhydrous RbMn[Fe(CN)₆] (nearly stoichiometric) and on the effect of linkage isomerism ensuing our interpretation of the results of Mössbauer study in which we observe the iron spin state crossover among two phases involved into this transition. The anhydrous RbMn[Fe(CN)₆] can be prepared via prolonged thermal treatment (1 week at at 80 °C) of the as-synthesized hydrated RbMn[Fe(CN)₆]·H₂O. The latter compound famous for its charge-transfer phase transition is a precursor in our case. As the temperature is raising above 80 °C (remaining below 100 °C) we observe RbMn[Fe(CN)₆] that inherited its F-43 m symmetry from RbMn[Fe(CN)₆]·H₂O transforming to a phase of the Fm-3 m symmetry. In the latter, more than half of Fe^3?+? ions are in high-spin state. We suggest a plausible way to explain the spin-crossover that is to allow the linkage isomerism by rotation of the cyanide ligands.     

Preparation and characterization of conducting polymer/silver hexacyanoferrate nanocomposite

In this work, we present an alternative route to prepare silver hexacyanoferrate(II)/polyaniline (PANI) composite thin films. Differently from the electrochemical method, used to synthesize the conducting polymer film on a electrode surface, this new chemical route makes use of dialysis membrane as a solid support to synthesize the silver hexacyanoferrate(III) compound, and subsequently uses this composite membrane as oxidizing agent to polymerize the aniline monomer. The spectroscopic (UV-vis and IR region) and electrochemical characterization (cyclic voltammetry) indicates that the polymeric composite remains optically active and conductive. The X-ray analysis shows that the composite membrane/Ag₃[Fe_III(CN)₆] has an crystalline structure that can be assigned to the Ag₃[Fe_III(CN)₆] structure, and after reaction with aniline solution it became less crystalline. Additionally the SEM measurements shown that the reaction of silver ions with hexacyanoferrate(III) across the membrane results in a well defined and aliened Ag₃[Fe_III(CN)₆] crystals and when this crystalline compound reacts with aniline monomer silver wire of 100 nm of diameter by 6 μm longer are formed together with the conducting polymer polyaniline/Ag_x[Fe_II(CN)₆] composite.     

Characterization of T-55 sorbent using 57Fe Mössbauer spectroscopy with a high velocity resolution

A new sorbent T-55 with mixed ferrocyanide surface modification developed for Cs⁺ sorption was characterized using Mössbauer spectroscopy with a high velocity resolution in comparison with K₂Ni[Fe(CN)₆] and K₄[Fe(CN)₆ samples. The main sorption active component of T-55 sorbent was determined as K₂Ni[Fe(CN)₆].     

Green synthesis of silver and gold nanoparticles using Rosa damascena and its primary application in electrochemistry

Biosynthesis and characterizations of nanoparticles have become an important branch of nanotechnology. In this paper, green synthesis of gold nanoparticles (AuNPs) and silver nanoparticles (AgNPs) using the flower extract of Rosa damascena as a reducing and stabilizing agent, has been discussed. This approach is simple, cost-effective and stable for a long time, reproducible at room temperature and in an eco-friendly manner to obtain a self-assembly of AuNPs and AgNPs. The resulting nanoparticles are characterized using UV–vis, TEM, XRD and FT-IR spectroscopic techniques. A modified glassy carbon electrode using AuNPs (AuNPs/GCE) was investigated by means of cyclic voltammetry in a solution of 0.1 M KCl and 5.0×10⁻³ M [Fe(CN)₆]^3−/4−. The results show that electronic transmission rate between the modified electrode and [Fe(CN)₆]^3−/4− increased.     

High-spin metal-cyanide clusters: species incorporating [Mn(salen)] complexes as a source of anisotropy

The use of N,N′-ethylenebis(salycylideneiminato) (salen) complexes of Mn^III in assembling high-spin metal-cyanide coordination clusters with significant magnetic anisotropy is demonstrated. The reaction of [Mn(salen)(H₂O)₂]⁺with [Cr(CN)₆]³⁻ in aqueous solution generates {Cr[CNMn(salen)(H₂O)]₆}[Cr(CN)₆]·6H₂O (1), a previously reported compound featuring a heptanuclear cluster with a distorted octahedral geometry. A fit to the variable-temperature magnetic susceptibility data for 1 revealed the presence of weak antiferromagnetic coupling of within the cluster, giving rise to an S=21/2 ground state. In addition, variable-field magnetization data collected at low temperatures revealed the presence of magnetic anisotropy in the ground state, with the best fit yielding zero-field splitting parameters of D=+0.19 cm⁻¹ and A reaction intended to produce a direct analogue of 1 by employing [Fe(CN)₆]³⁻ in place of [Cr(CN)₆]³⁻ instead gave an unusually complex compound of formula {Fe(CN)₄[CNMn(salen)(MeOH)]₂}{[Mn(salen)(H₂O)]₂}[Mn(salen)(H₂O)(MeOH)]₂[Fe(CN)₆]·4H₂O (2). The crystal structure and magnetic properties of this compound are reported.     

Electrochemical properties of undoped CVD diamond films

The electrochemical properties of undoped diamond polycrystalline films grown on tungsten wire substrates using methanol as a precursor are described. The diamond film quality was changed by introducing sp²-bonded non-diamond carbon impurity through adjustment of the methanol-to-hydrogen (C/H) source gas ratio used for diamond growth.The electrodes were characterized by Raman spectroscopy, scanning electronic microscopy (SEM) and cyclic voltammetry (CV).Diamond coated tungsten wires were then used as a working electrode to ascertain their electrochemical behavior in electrolytic medium. Electrochemical windows of these films were found to be suitable in the potential range of [−2.5 V, +2.2 V] vs. Ag/AgCl in acid medium (0.1 M KCl).The electrochemical behavior was evaluated also using the Fe(CN)₆^3−/4−redox couple.The results demonstrate that the grain boundaries and sp²-hybridized carbon impurity can have a significant influence on electrochemical window of undoped diamond electrodes. It was observed that with increasing sp² carbon impurity concentration the electrochemical window decreases.     

Synthesis and electrochemical characterization of nitrogen-doped and nitrogen–phosphorus-doped multi-walled carbon nanotubes

Nitrogen-doped and nitrogen–phosphorus-doped multi-walled carbon nanotubes (N-MWCNTs and N–P-MWCNTs, respectively) were fabricated by chemical vapor deposition and characterized using scanning electron microscopy and transmission electron microscopy in combination with energy dispersive X-ray spectroscopy and Raman spectroscopy. The electrochemical response of N-MWCNTs and N–P-MWCNTs towards ferrocyanide/ferricyanide was initially studied. The findings exhibit weakening of electrochemical response and sensitivity of nanotubes with phosphorus doping, and thus, within the composite films tested, those consist exclusively of N-MWCNTs exhibit the greatest electrocatalytic activity. N–P-MWCNT film was further applied for individual electrochemical analysis of ascorbic acid (AA), uric acid (UA), and dopamine (DA), and lower limits of detections of 11.6, 7.8, and 1.9 μM were estimated, respectively. The findings demonstrate that AA does not interfere with UA, but considerable interference of AA in analysis of DA was observed. Thus, the simultaneous analysis of AA, UA, and DA on N–P-MWCNTs appears to be restricted.     

Formation of thin oxide and sulphide films on polycrystalline molybdenum foils: characterization by XPS and surface potential variations

By combining XPS and measurements of surface potential variation ΔΦ, the surface evolution of polycrystalline Mo sample has been studied during several processes of oxidation and sulphidation from room temperature up to 400°C. The chemical states of Mo, O and S have been identified from their core level binding energies, whereas the ΔΦ variation reflects changes in the work function during formation of the films. Oxidation by O₂ at 400°C produces an oxygen-deficient MoO₃ film which is further transformed by immersion in water with the formation of lower Mo oxidation states (mainly Mo^IV and Mo^III). Direct immersion of the metal in water results in the progressive growth of a highly hydroxylated and hydrated oxide film with the predominance of a MoO₂ structure after prolonged immersion. Thick Mo sulphide films (thickness >; 112 Å) are obtained by immersion of the foil in a thiomolybdate solution and further UHV annealing or by H₂S sulphidation of the preoxidized metal. In the sulphided films, the presence of both S²⁻ and S₂²⁻ species has been detected, the distribution of which influences the ΔΦ variation according to: ΔΦ (mV) = 550 − 13.75[S₂²⁻(%)]. It has also been found that the ΔΦ values of the films decrease in the order: ΔΦ[MoO₃] > ΔΦ[MoS₂] > ΔΦ[MoS₃] > ΔΦ[Mo⁰].