Temperature dependence of two types of dissolution of platinum in acid media. An electrochemical nanogravimetric study

Smooth and platinized platinum electrodes in contact with sulfuric acid solutions were studied using electrochemical quartz crystal nanobalance (EQCN) technique at different temperatures.Two types of dissolution processes have been observed. A platinum loss was detected during the reduction of platinum oxide, the extent of which depends on the positive potential limit and the scan rate, and to a lesser extent on the temperature. The platinum dissolution during the electroreduction of oxide is related either to the mechanical detachment of Pt atoms which were loosely bounded due to the interfacial place exchange of the oxygen and platinum atoms in the oxide region or to the reduction of Pt(IV) formed at higher positive potentials resulting in soluble Pt²⁺ species. At elevated temperatures two competitive processes take place at high positive potentials: a dissolution of platinum and platinum oxide formation. The presence of dissolved platinum in the solution has been detected by two different methods.These phenomena are of importance regarding the long-term stability of proton exchange fuel cells.     

Electrodeposition and dissolution of yttrium-hexacyanoferrate layers

The electrodeposition and dissolution of yttrium-hexacyanoferrate [YHCNFe(II)] were investigated by electrochemical quartz crystal microbalance technique (EQCM). The electrodeposition was carried out by potential cycling or stepping from solutions of Y(NO₃)₃ and K₃[Fe^III(CN)₆] of different concentrations. The ratio of the reactants was also varied. No deposition was found in dilute solutions (c < 10⁻³ mol dm⁻³). The increase of concentrations led to an intense deposition of YHCNFe(II) in the course of reduction of [Fe^III(CN)₆]³⁻. At high concentrations of the reactants a coagulation deposition of YHCNFe(III) at open-circuit has also been detected. During the reduction the first phase is the nucleation which requires saturation or oversaturation in respect to the reacting species near the gold surface. The growth phase is much faster than the formation of nuclei, and its rate depends on the concentration and the concentration ratio of the species. The composition of the deposits has been determined by total reflection X-ray fluorescence (TXRF) spectrometry. From the molar ratio of atomic constituents (K, Y and Fe) of the slightly soluble deposit (solubility: 5 × 10⁻⁵ mol dm⁻³) formed after reduction of Fe(III) a formula K_0.46Y_1.18[Fe^II(CN)₆] can be derived. This value is in good accordance with the molar mass calculated from the results of EQCM experiments which also revealed that the deposit contains ca. 2 mol H₂O/mol YHCNFe(II). The solubility of YHCNFe(III) is substantially higher (s = 2 × 10⁻³ mol dm⁻³), and according to the results of TXRF measurements, its composition is Y[Fe^III(CN)₆]. The reoxidation of YHCNFe(II) takes place in two steps. The first one is a partial oxidation which is accompanied by the desorption of K⁺ ions from the layer. During further oxidation a fast dissolution occurs due to the high solubility of YHCNFe(III).     

Electrochemical quartz crystal microbalance study of formation and redox transformations of poly(diphenylamine)

The electropolymerization of diphenylamine (DPA) dissolved in 2 mol dm⁻³ H₂SO₄ has been studied on a gold electrode by cyclic electrochemical quartz crystal microbalance measurements. Similar experiments have been accomplished with DPA microcrystals attached to a gold electrode, in the presence of aqueous acidic media. In both cases the redox transformations of the poly(diphenylamine) films formed on Au have been investigated in solutions of different pHs. The cyclic voltammograms and the mass changes refer to two closely spaced redox reactions resulting in the formation of cation radicals and dications, respectively. The irregular, broad shape of the voltammetric waves may be explained by presence of other electrochemically active sites beside the linear diphenylbenzidine structure. The results indicate a pH and potential-dependent relative contribution of anions and hydrogen ions to the overall ion exchange process. The expulsion of protons is the predominant ion transport process at the beginning of the oxidation and the incorporation of anions occurs at a later stage of oxidation. The sorption/desorption of solvent molecules also contributes to the mass change observed during the redox transformations of the polymer.     

Interaction of BSA protein with copper evaluated by electrochemical impedance spectroscopy and quartz crystal microbalance

The interaction of bovine serum albumin (BSA) protein with copper in phosphate buffer solution has been studied by a combination of electrochemical impedance spectroscopy (EIS) close to the open circuit potential, with simultaneous monitoring by the electrochemical quartz crystal microbalance (EQCM), in order to throw light on BSA adsorption. Copper films were electroplated onto gold quartz crystals and mounted in the EQCM. Experiments were conducted in the presence and absence of dissolved oxygen and of BSA and the results show the influence of O₂ on the protein/metal interaction and also show specific interactions between BSA and copper. The good reproducibility obtained in these experiments suggests future application to other systems and which should lead to a better understanding of the use of such types of protein as corrosion inhibitors.     

Electrosorption of hydrogen into palladium-rhodium alloys

Hydrogen electrosorption into Pd-Rh alloys has been studied in acidic solutions (0.5 M H₂SO₄) using cyclic voltammetry and chronoamperometry. Pd-Rh electrodes were prepared as thin alloy electrodeposits on Au wires. The influence of electrode potential on the amount of electrosorbed hydrogen was investigated. One can distinguish potential regions of α- and β-phase existence as well as the region of α-β phase transition. For alloys containing less than 20 at.% Rh in the bulk the hydrogen-to-metal ratio, H/(Pd + Rh), is greater than for pure Pd. The maximum value of the H/(Pd + Pt) ratio is 0.80 for an alloy containing in the bulk 94 at.% Pd and 6 at.% Rh. Due to a smaller lattice parameter of the Pd-Rh alloy with respect to pure Pd the α-β phase transition occurs at lower potentials than in Pd. The hysteresis is observed in chronoamperometric absorption and desorption experiments; the effect of hysteresis decreases with the increase in Rh content. Additionally, preliminary results are presented concerning the electrochemical quartz crystal microbalance measurements of hydrogen absorption/desorption into/from Pd-Rh alloys in comparison with Pd.     

Investigations of ultrathin polypyrrole films: Formation and effects of doping/dedoping processes on its optical properties by electrochemical surface plasmon resonance (ESPR)

In the present work an investigation of the effects of the electropolymerization mode on the optical properties associated to the doping/dedoping processes of nanometric films of polypyrrole (PPy) is reported, monitoring in situ and in real time using simultaneously surface plasmon resonance and electrochemical techniques (ESPR). The electropolymerization of pyrrole was performed by potentiostatic, potentiodynamic and galvanostatic methods and the use of the ESPR technique showed that the electropolymerization mode is essential to the stability of polymer and the reversibility of its optical properties during the doping and dedoping processes. Thus, the optical properties of oxidized and reduced film were obtained by nonlinear least square fitting using Fresnel equations for a four-layer system. Then, the values of the real and imaginary parts of the complex dielectric constant for PPy fims were correlated with the polymer doping level. Finally, quartz crystal microbalance measurements were also applied to obtain correlation between doping/dedoping processes and the changes in the real and imaginary parts of the dielectric constant of the polypyrrole film, showing that the doping and dedoping processes in the polypyrrole film can act directly on its optical properties while the ESPR technique can give the same information indirectly.     

An electrochemical quartz crystal microbalance study into the deposition of manganese dioxide

An electrochemical quartz crystal microbalance (EQCM) has been used to study the effects of electrolyte composition (MnSO₄ and H₂SO₄ concentrations) and anodic current density on the electrodeposition of manganese dioxide. The EQCM, in tandem with the electrode voltage during deposition, has been used to characterize features of the deposition mechanism such as the relative lifetime of the Mn(III) intermediate, the rate of soluble Mn(III) hydrolysis to form MnOOH, and the porosity of the resultant manganese dioxide deposit as a function of crystal nucleation. The connection between the results obtained here and commercial electrodeposition of manganese dioxide were also discussed.     

利用石英晶体微量天平测定紫杉醇在二氧化碳中的溶解度

A quartz crystal microbalance (QCM) is used to determine the phase equilibrium of paclitaxel-carbon dioxide system in the pressure range of 0-11 MPa and at temperatures of 35 °C,40 °C and 45 °C.The experimental results indicated that gaseous CO2 could be absorbed poorly into paclitaxel.The swelling of paclitaxel film in CO2 was observed before paclitaxel dissolved into supercritical carbon dioxide (ScCO2) with the increase of pressure.It was found that ScCO2 was not a good solvent for paclitaxel.The mole fraction of paclitaxel in ScCO2 was in the range of (4.5×10-9)-(7.8×10-9) under all our experimental conditions.Therefore,a much higher pressure than the CO2 supercritical point and/or a cosolvent must be used in any processes wherever paclitaxel dissolution in ScCO2 is required.     

Correlation between conductance and mass changes during p-doping of 2-methoxynaphthalene films

The redox response of 2-methoxynaphthalene films electrosynthesized in two different organic solvents, acetonitrile (ACN) and nitrobenzene (NB) has been studied by different in situ electrochemical techniques: the in situ conductance technique, electrochemical quartz crystal microbalance (EQCM) and electrochemical voltage spectroscopy (EVS). In situ measurements of conductance as a function of the potential during p-doping of 2-methoxynaphthalene films, electrosynthesized in TBAPF₆-ACN and TBAPF₆-NB, show that the conductance properties are strongly dependent on the solvent used during electrosynthesis, resulting in higher conductance values for films electrosynthesized in NB solutions. The EQCM technique has been used to correlate the frequency changes (mass changes) at the electrode surface with conductance changes during p-doping of the different films. The molar mass of the species involved in the charging-discharging reactions has been estimated from the EQCM results. For the determination of the electrochemical bandgap of the two different films, cyclic voltammetry (CV) and EVS were applied. Films electrosynthesized in NB solutions have a lower value of the bandgap (1.34 eV) than films electrosynthesized in ACN solutions (2.00 eV).     

A voltammetric and nanogravimetric study of Te underpotential deposition on Pt in perchloric acid medium

This work describes the study of Te underpotential deposition on Pt in acid media using cyclic voltammetry, rotating ring-disc electrode and electrochemical quartz crystal microbalance techniques. The voltammetric results indicate the presence of two dissolution peaks in the positive scan with a total charge density of 420 μC cm⁻². These phenomena are attributed to the deposition of one Te monolayer with the occupancy of two active Pt sites by each ad-atom. This is confirmed by rotating ring-disc electrode results. The electrochemical quartz crystal microbalance (EQCM) experiments yielded the small mass variation of −32 ng cm⁻² (while the theoretical one is −140.4 ng cm⁻² for a complete Te monolayer). This low value can be attributed to the simultaneous adsorption of water, perchlorate anions and the formation of platinum oxide.     

Adsorption and precipitation during the redox transformations of phenazine

The adsorption/desorption and deposition/dissolution phenomena occurring during the electrochemical transformations of phenazine (Ph) at a gold electrode in aqueous acidic solutions have been studied by cyclic and potential step electrochemical quartz crystal microbalance measurements. Phenazine exhibits two successive one-electron reduction steps in acidic media. In dilute phenazine solutions, the product of the first electron transfer is phenazylium cation radical () which adsorbs in the form of a phenazylium salt (ClO₄⁻, Cl⁻) at the electrode surface. The perchlorate salt is highly soluble and the electroreduction takes place via a loosely adsorbed state. In chloride containing solutions, multilayer adsorption is observed. The second electron transfer in dilute phenazine solutions results in the formation of 5,10-dihydrophenazine (PhH₂) in HClO₄, which desorbs from the electrode surface. In HCl solutions, a substantial portion of the fully reduced product, which is a charged dimer, remains on the surface. In more concentrated phenazine solutions in the potential region of the second reduction wave, a deposition process can be observed, which is due to the formation of the quinhydrone-analogue, phenazinehydrine charge-transfer complex. The formation of the charge-transfer complex obeys a second-order kinetics, however, the rate of the film growth is influenced by the simultaneous dissolution process. The increase of the acid concentration enhances the dissolution, and may prevent the film formation. In dilute phenazine solutions, both redox waves are reversible and likewise the adsorption/desorption processes. In concentrated solutions, the reoxidation of the phenazinehydrine film results in a complicated voltammetric response related to a dissolution-redeposition-dissolution sequence.     

Optical, electrochemical and electrogravimetric behavior of poly(1-methoxy-4-(2-ethyl-hexyloxy)-p-phenylene vinylene) (MEH-PPV) films

Poly(1-methoxy-4-(2-ethyl-hexyloxy)-p-phenylene vinylene) (MEH-PPV) films spin-cast from chloroform solution were characterized by cyclic voltammetry, in situ spectroelectrochemistry, and electrochemical quartz crystal microbalance (EQCM) measurements. The MEH-PPV films exhibited two well-defined redox waves during p- and n-electrochemical doping, and a mass gain at the end of each cycle that is characteristic of the movement of ions and solvent into and out the film. The electronic energy gap of MEH-PPV was estimated as 2.35 eV from the anodic and cathodic onset potentials obtained by cyclic voltammetry, in good agreement with the value of optical energy gap determined from the absorption edge, 2.21 eV. The films also showed a reversible and stable electrochromic transition at a positive range of applied potentials from reddish-orange (neutral form) to brownish-green (oxidized form).     

Investigation of interfacial processes at tetraruthenated zinc porphyrin films using electrochemical surface plasmon resonance and electrochemical quartz crystal microbalance

In the present work we describe the investigation of interfacial and superficial processes on tetraruthenated zinc porphyrin (ZnTRP) films immobilized on gold electrode surface. In situ and real time measurements employing electrochemical surface plasmon resonance (ESPR) and electrochemical quartz crystal microbalance (EQCM) have given new insights into the electrochemical oxidation of ferrocyanide and phenolic compounds (acetaminophen, dopamine, and catechol) on ZnTRP modified electrodes. The decrease of diode like behavior in the presence of such phenolic species in contrast with ferrocyanide was clearly assigned to the inclusion of those species in the porphyrin film, creating new conduction pathways connecting the gold electrode surface with the film/solution interface. In fact, there are evidences that they can intercalate in the film (catechol > dopamine > acetaminophen), whereas ferrocyanide is completely excluded. Accordingly, the molecular size may play a fundamental role in such a process.     

The influence of lead upd on the oxidation of glucose at platinum electrodes an electrochemical quartz crystal microbalance study

The oxidation of glucose at Pt electrodes with upd deposits of Pb in acid media has been investigated using the electrochemical quartz crystal microbalance (EQCM). Glucose alone has a small effect on the mass response but changes in upd Pb coverage have a large effect. This allows changes in upd Pb coverage to be followed easily despite the fact that the associated current is largely obscured in the cyclic voltammogram. Cyclic voltammetry at low glucose concentrations shows a multiple peak structure in the double layer region of potential at low upd coverages that is charged to the more familiar single peak as upd coverage increases. Mass responses also reveal some blockage of Pb upd by glucose or species derived from it during cyclic voltammetry. Data from mass transients show that the deliberate formation of poisons prior to addition of Pb²⁺ ions to the electrolyte results in a substantial suppression of upd coverage especially between −0.1 and 0.1 V (sce). Finally, mass transients accompanying injections of Pb²⁺ in the presence of glucose in the electrolyte reveal the suppression of adsorption of Pb²⁺ cations on an oxidised Pt surface by species derived from glucose.     

Electrochemical behavior of thin polycrystalline rhodium layers studied by cyclic voltammetry and quartz crystal microbalance

Electrochemical behavior of thin polycrystalline Rh layers has been studied in 0.5 M H₂SO₄ solution by cyclic voltammetry (CV) and the electrochemical quartz crystal microbalance (EQCM). The properties of surface oxide formed on freshly electrodeposited Rh are different than on electrochemically aged Rh. The analysis of frequency changes in both hydrogen and oxygen regions is presented. It is suggested that hydrogen desorption occurs simultaneously with the adsorption of HSO₄⁻ ions, whose maximum surface coverage reaches ca. 8%. The EQCM results indicate that RhO is the main species formed during Rh surface oxidation. Metal dissolution proceeds during electrode cycling to sufficiently high potentials. The amount of dissolved metal increases with an increase in potential and a decrease in scan rate.     

Influence of organic additives on the initial stages of copper electrodeposition on polycrystalline platinum

Effects of two additives, thiourea and saccharin, on copper electrodeposition from acid sulphate solutions were investigated by different electrochemical methods (cyclic voltammetry, chronoamperometry, and electrochemical quartz crystal microbalance) as well as by different observation techniques (scanning electron microscopy and atomic force microscopy). The morphology of copper coating obtained with thiourea leads to a smooth and bright deposit whereas it is only slightly modified by saccharin. The electrochemical reactions of copper electrodeposition were modified by the formation of complexes between thiourea and copper. However, in presence of saccharin, the kinetics and morphology of copper coating remain unchanged. From X-ray photoelectron spectroscopy analysis, thiourea was found to react with copper or copper ions by strong bond formation between the sulphur atoms of thiourea molecule and copper. This is the evidence of the adsorption of thiourea on the coating. Moreover, the thiourea action starts in the initial stages, allowing a homogeneous nuclei size and a large nuclei density. Finally, the nucleation mechanism of electrodeposition appears to be modified according to the additives used.     

Ion, solvent and polymer dynamics in polyaniline conducting polymer films

We describe the application of a new model for the visualization of mobile species (ion and solvent) transfers accompanying redox switching of electroactive films. The system studied was polyaniline, for which the mobile species population changes were determined from redox-driven film mass changes using a thickness shear mode acoustic wave resonator. Acoustic admittance data were used to establish conditions under which the resonator frequency response could be interpreted gravimetrically. Charge and frequency changes accompanying the first redox transition of polyaniline films exposed to aqueous perchloric acid were then used to determine the film's ion and solvent populations. The data are best described by a mechanism in which the early stages of film oxidation are associated with proton transfer (exit) and the latter stages with perchlorate transfer (entry) to satisfy electroneutrality; solvent enters throughout film oxidation and exits throughout film reduction. The alternative of a single ion satisfying electroneutrality throughout would require the rather less likely situation of a non-monotonic solvent flux. Application of the model's diagnostic criteria indicates that the film solvent population is in equilibrium on the timescale of slow scan voltammetry, but shows thermodynamic non-idealities. Hysteresis in the film ion population signals failure of the redox state to maintain equilibrium with the applied potential.     

EQCM study of polypyrrole modified electrodes doped with Keggin-type heteropolyanion for cation detection

The incorporation of a Keggin-type heteropolyanion, the phosphotungstate ([PW₁₂O₄₀]³⁻), into polypyrrole has been achieved during the electrochemical preparation of the polymer films in aqueous solution. The redox behaviour of these modified electrodes is described by using cyclic voltammetry (CV) and electrochemical quartz crystal microbalance (EQCM). The data allowed to estimate the doping level that indicates the extent of the heteropolyanion insertion. It is found that the polymer films, in aqueous solution, exhibit sensibility to cations, namely to Na⁺.     

Application of the electrochemical quartz crystal microbalance technique to copper sonoelectrochemistry: Part 1. Sulfate-based electrolytes

The applicability of the electrochemical quartz crystal microbalance technique in an ultrasonic field created by an ultrasound probe is demonstrated for the electrodeposition of copper. Cyclic voltammetry and potentiostatic depositions in acidic sulfate-based copper electrolytes were performed at different ultrasonic intensities. The electrochemical quartz crystal microbalance was operated in ultrasonic fields with intensities up to 30 W cm⁻². For cyclic voltammetry, potential resolved and averaged (apparent) current efficiencies were calculated from mass and charge data in function of the amplitude of the ultrasonic horn. Ultrasound slightly affected the current efficiencies during copper deposition in cyclic voltammetry, but did not change the efficiencies during dissolution. During potentiostatic depositions the current efficiency increased from 84% to almost 100% upon application of ultrasound. Morphology of deposits prepared by potentiostatic depositions was analyzed by scanning electron microscopy, and found to be different at high ultrasonic intensities.     

Electrodeposition of CdS from acidic aqueous thiosulfate solution—Invesitigation of the mechanism by electrochemical quartz microbalance technique

Electrochemical quartz crystal microbalance was used to study mechanism of cathodic electrodeposition of CdS from acidic aqueous solutions containing 0.01 M Cd(ClO₄)₂ and 0.1 M Na₂S₂O₃ as a source of sulfur. Experiments were performed by means of cyclic voltammetry and potentiostatic method. A comparison of gravimetric and current responses at pH 3 and 4 allowed for determination of the potential range in which side reactions of reduction of SO₃²⁻ and H⁺ ions compete most strongly with formation of CdS. The film thickness was determined by means of two methods: from AFM profiles and EQCM measurements.