Study of adsorption of citrate on Pt by CV and EQCM

Citrates are frequently used as additives in the electrodeposition of metals such as manganese in order to improve deposit characteristics and process efficiency. Nevertheless, few studies have been reported on the mechanism of citrate adsorption. This paper presents the results of a study of citrate adsorption onto platinum from solutions of various citrate concentrations in 0.1 M HClO₄. Simultaneous observations with an electrochemical quartz crystal microbalance (EQCM) and cyclic voltammetry (CV) indicate that with increasing concentrations, up to 10⁻² M, the fractional surface coverage by citrate rises to 13% in the region of hydrogen UPD, and the anodic formation of PtO is inhibited and reduced by as much as 43%. Combination of EQCM with cathodic linear-sweep voltammetry shows the interactions of citrate with platinum oxidation and hydrogen UPD. Thus, this approach reveals changes in additive adsorption with potential and indicates in particular the influence of the additive on the adsorption and desorption of hydrogen as a step in understanding metal deposition.     

An EQCM study of the deposition and doping/dedoping behavior of polypyrrole from phosphoric acid solutions

The potentiostatic deposition of polypyrrole (PPy) from 0.1 M aqueous phosphoric acid solution and the doping/dedoping behavior of the resulting films have been investigated by the electrochemical quartz crystal microbalance (EQCM) technique. The change of the complex shear modulus during the film growth and during the doping/dedoping were calculated using the acoustic impedance method. It was found that the films contain only ca. 1 wt% water in the oxidized state which is in accordance with their relatively high storage modulus of 38 MPa and low loss tangent of 0.05. Comparing H₃PO₄ (pH 1) and NaH₂PO₄ (pH 8) it was found that the doping/dedoping in the latter is accompanied by a strong increase of the surface roughness which is a direct result of cation exchange present at pH 8.     

Effect of Cu(II) ligands on electroless copper deposition rate in formaldehyde solutions: An EQCM study

The electroless copper deposition rate for 6 Cu^II complexes decreases in the ligand sequence: nitrilotriacetic acid (NTA) > N,N,N′,N′-tetrakis-(2-hydroxypropyl)-ethylenediamine (Quadrol) > glycerol > L(+)-tartrate ~ sucrose > -tartrate. Both Cu^II complex stability and specific ligand effects were found to influence the Cu deposition process. The specific ligand effects are most obvious in the case of Quadrol (high kinetic activity at a high Cu^II complex stability), glycerol and sucrose (additional reaction of Cu₂O formation by interaction of Cu^II with ligand). According to the EQCM data for 11 Cu^II complexes (including data from the former study) the higher kinetic activity is demonstrated by complexes with ligands containing amino groups; this factor is more important for Cu deposition rate than copper complex stability. A potential dependence of the Cu reduction partial current on the electrode potential has been extracted from the EQCM data in the complete electroless plating bath. An increase in Cu^II reduction rate was found to occur in electroless plating solution for Cu^II complexes with NTA and Quadrol compared with that in formaldehyde-free solutions. Possible reasons for the acceleration of the partial Cu^II reduction reaction and the overall process kinetics are discussed using a hypothetical reaction sequence involving intermediate copper oxy-species and active Cu* formation as well as development of the preferred Cu surface structure.     

In situ FTIRS and EQCM studies of glycine adsorption and oxidation on Au(1 1 1) electrode in alkaline solutions

Dissociative adsorption and oxidation of glycine on Au(1 1 1) single crystal electrodes in alkaline solutions were studied in the present paper using cyclic voltammetry (CV), in situ FTIR spectroscopy (FTIRS) and electrochemical quartz crystal microbalance (EQCM). In situ FTIRS results demonstrated that adsorbates derived from glycine dissociative adsorption are adsorbed cyanide anions (CN_ad⁻). The CN_ad⁻ species are stable on Au(1 1 1) surface in the potential region from −0.8 to 0.0 V, and can be oxidized when electrode potential is increased above 0.1 V. The oxidation of CN_ad⁻ releases surface active sites for further glycine oxidation. The products of CN_ad⁻ oxidation were determined by in situ FTIRS as cyanate (OCN⁻), aurous cyanide (AuCN) and aurous di-cyanide (Au(CN)₂⁻). The formation of Au(CN)₂⁻ may initiate a dissolution of Au(1 1 1) surface atoms, which has been confirmed by a loss of surface mass determined in EQCM studies. It has revealed also that at high electrode potential region glycine may be split on Au(1 1 1) surface to form AuCH₂NH₂ and AuCOO⁻ adsorbates. Further oxidation of these species yielded CO₂ and -NH₂, and the AuCH₂NH₂ may be also combined with surface Au oxide to form methylamine. The CO₂ species produced in glycine oxidation are all retained in alkaline solutions to generate carbonate (CO₃²⁻) and bicarbonate (HCO₃⁻) species that were clearly determined by in situ FTIRS studies.     

Voltammetric study of halide ion adsorption on platinum in perchloric acid solutions

Periodic current/potential curves were taken potentiostatically at 30 mV/sec on smooth platinum in 1 N HClO₄ with different additions of HCl, HBr, and HI, in the potential range between hydrogen evolution and deposition of oxygen or of the respective halide ion. The effect of increasing halide ion concentration, starting at 10⁻⁶ M, on hydrogen adsorption and oxygen adsorption was studied systematically. Impedance measurements were made at 1000 c/s under the same conditions as the measurements of the current/potential curves. It is concluded from the dependence of the double layer capacitance upon the bulk concentration of halide ions in the double layer region that nearly a monolayer of adsorbed ions is present there for ₀c_Cl⁻ ≈ 10⁻² M, ₀c_Br ≈ 10⁻⁴ M, and ₀c_HI ≈ 10⁻⁵ M. The measurements at larger concentrations, especially for I⁻, show additional effects which are due to the deposition of halides and to the reverse reaction.     

Voltametry and EQCM study of copper oxidation in acidic solution in presence of chloride ions

Cyclic voltametry experiments coupled with electrochemical quartz crystal microbalance (EQCM) measurements showed the corrosion mechanism of electrodeposited copper in presence of chloride ions. The oxidation of copper in acidic solution containing high concentration of Cl⁻ begins with formation of Cu⁺ ions. The Cu⁺ concentration at the vicinity of the electrode increasing, the small solubility product of CuCl is then exceeded, leading to a CuCl precipitation on the gold covered quartz crystal used as working electrode. For highest anodic potentials, the oxidation of electrodeposited copper or CuCl precipitate phases could occur. A combination with structural techniques like SEM, EDAX, AFM and DRX gives insight into the morphology and the nature of these CuCl precipitates.     

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.     

Effect of Cl ions and benzylideneacetone/ethanol on the underpotential deposition of zinc in acidic media: cyclic voltammetry and EQCM studies

The influence of chloride ions and a benzylideneacetone (BDA)/ethanol (EtOH) mixture on the underpotential deposition (UPD) of Zn²⁺ ions on Pt electrodes in acidic media was investigated by cyclic voltammetry and electrochemical quartz crystal microbalance (EQCM). In the potential region of the UPD of H and Zn, the surface coverage of Zn adatoms on Pt was evaluated based on the correspondence between charge and mass for several different solutions. In the absence of Cl⁻ ions and BDA/EtOH, the maximum surface coverage of the Zn deposited by UPD was 0.29. In addition, in the presence of Cl⁻ ions, the UPD of Zn²⁺ ions occurred simultaneously with the adsorption of Cl⁻, and the presence of Cl⁻ did not modify the quantity of Zn deposited by UPD. In the presence of Cl⁻ ions and BDA/EtOH, the maximum surface coverage of the Zn deposited by UPD was 0.16. The partial inhibition of the UPD of Zn²⁺ ions is associated with the adsorption of BDA/EtOH or products of the decomposition of BDA/EtOH during the UPD process.     

XPS and flow-cell EQCM study of albumin adsorption on passivated chromium surfaces: Influence of potential and pH

The adsorption of albumin (BSA: bovine serum albumin) on passivated chromium surfaces was studied in deaerated sulphate solutions as a function of potential (in the passive state) and pH (from 4 to 10). In situ switch-flow cell EQCM measurements were coupled to ex situ XPS analyses. EQCM results showed that (i) the initial adsorption rate is about 3.3 ng cm⁻² s⁻¹ which corresponds to 3 × 10¹⁰ molecules cm⁻² s⁻¹, irrespective of the passive potential and pH, and (ii) the passive potential as well as the pH have no influence on the amount of adsorbed BSA (Δm = 440 ± 70 ng cm⁻² on the adsorption plateau). From the XPS N 1s and C 1s signals, which provide a fingerprint for the protein, it can be concluded that BSA is adsorbed on the Cr surface and is chemically intact. The XPS results show that (i) when increasing the passive potential, the oxide layer thickness increases (mean value: d_ox = 2.2 ± 0.2 nm), and (ii) the passive film is not modified by the adsorption of protein. From combined EQCM and XPS data, a full coverage of the Cr surface by the adsorbed proteins (γ = 1) is demonstrated at pH 4 (whatever the passive potential). The thickness of the continuous BSA layer (h_BSA) is 3.3 ± 0.3 nm, which corresponds to one monolayer “side-on”, i.e. oriented parallel to the surface. At pH 5.5 and 10, the adsorbed proteins form islands. The surface coverage is much lower (γ ∼ 0.5), and the height of the protein islands is significantly higher (h_BSA ∼ 6.5 nm). The results suggest a strong interaction (partially covalent) between the protein and the passivated chromium surface.     

Thermodynamic studies of phosphate adsorption on Pt(1 1 1) electrode surfaces in perchloric acid solutions

The thermodynamics of the so-called perfectly polarizable electrode was employed to analyze the total charge densities for a nearly defect-free Pt(1 1 1) electrode in a series of NaH₂PO₄ solutions with an excess of inert electrolyte (0.1 M HClO₄) at constant ionic strength and pH. Thermodynamic analysis using both electrode potential and charge density as independent electrical variables is described. The Gibbs excess, Gibbs energy of adsorption and charge numbers both at constant electrode potential and constant chemical potential for anion adsorption at the Pt(1 1 1) surface have been determined. The calculated electrosorption valencies and charge numbers at constant chemical potential are close to two electrons per adsorbed anion, suggesting that in the absence of co-adsorbed species, HPO₄²⁻ is the predominant adsorbed species. The maximum Gibbs excess of adsorbed hydrogenphosphate attains a value of ≈3.2 × 10¹⁴ ions cm⁻² which corresponds to a coverage of ≈0.22 ML.     

Ion transport investigations of polypyrroles doped with different anions by EQCM and CER techniques

The ion transfer in redox processes of conducting polypyrrole doped with various anions, such as 1-naphthalenesulfonate, 10-camphorsulfonate, p-toluenesulfonate, dodecylbenzenesulfonate was investigated by electrochemical quartz crystal microbalance (EQCM), contact electric resistance (CER), and cyclic voltamperometry in situ techniques. By using this setup, the doping levels of the synthesized PPy films and mobility of charge carries in these materials in KCl aqueous solution under linear potential scan were determined.     

Comparative voltammetric study of methanol oxidation and adsorption on noble metal electrodes in perchloric acid solutions

Periodic current/potential curves were measured potentiostatically on smooth electrodes of platinum, iridium, rhodium, and gold at 30 mV/s in perchloric acid solutions with different additions of methanol (10⁻³ M to 1 M). Information on methanol adsorption was obtained from impedance measurements at 1000 c/s by volcammetry with superimposed a.c. voltage. The current/potential curves look similar on Pt and Pd on the one hand, and on Ir and Rh on the other hand. There is no noticeable methanol oxidation on gold. The peak current of the first wave during the anodic sweep decreases considerably in the order Pt> Pd> Rh> Ir. The capacitive component of the impedance shows methanol adsorption in the hydrogen and double layer region. The shape of the current/potential curves and the methanol adsorption are strongly influenced on platinum metals by oxygen layers which are formed or reduced electrochemically during the sweeps in different potential ranges.     

正丁醇在Pt及其修饰电极上氧化的EQCM研究

运用电化学石英晶体微天平 (EQCM)研究了正丁醇在Pt、Pt/Sbad和Pt/Sad电极上的电氧化过程 ,结果表明正丁醇的氧化与电极表面氧化物种有着密切的关系。Pt电极表面Sb修饰原子能在较低的电位下吸附氧 ,催化正丁醇的氧化在较低电位下进行。相反 ,Pt电极表面S修饰原子的氧化会消耗表面氧化物种 ,从而抑制正丁醇的电氧化。     

Regeneration of spent bleaching earth and its adsorption of copper (II) ions from aqueous solutions

This study was designed to provide a comprehensive investigation into heat and acid reactivation of spent bleaching earth (SBE) and adsorption of Cu(II) ions from aqueous solutions. Heat treatment was the master variable in SBE regeneration. Dilute acid treatment did not constitute an effective SBE reactivation protocol for this purpose. Solvent extraction of residual oil using excess methylethyl ketone followed by heating at 370 °C was, therefore, the most effective reactivation procedure. Highly adsorptive materials with > 98% removal of Cu(II) ions from solution were obtained. Thus, > 80% Cu adsorption was reversible at SBE silicate sites because of their higher proportion in the adsorbent.     

SERS and EQCM studies on the effect of allyl thiourea on copper dissolution and deposition in aqueous sulfuric acid

We investigated the effect of allyl thiourea (ATU) on both the electrodeposition and electrodissolution of copper in aqueous sulfuric acid by combining cyclic voltammetry (CV) with electrochemical quartz crystal microbalance (EQCM) studies and surface enhanced Raman spectroscopy (SERS). The results demonstrated that the two-electron transfer reaction is the predominant process for the copper dissolution–deposition process in 1.0 M H₂SO₄ solution not containing ATU in the potential range −0.65 to 0.05 V versus SCE. In comparison, the copper dissolution–deposition process in 1.0 M H₂SO₄ solution containing ATU corresponds to a one-electron transfer reaction. The spectral features observed from the SERS studies showed at molecular level that ATU can be adsorbed tilted to the copper electrode surface and that coordination occurs via the sulfur atom. The secondary amino group is nearer to the surface than the primary amino group. SO₄²⁻ and HSO₄⁻ can be coadsorbed on the protonated −NH (CH₂CHCH₂) groups.     

EQCM study of the ECL quenching of the tris(2,2′-bipyridyl)ruthenium(II)/tris-n-propylamine system at a Au electrode in the presence of chloride ions

Significant effect of chloride ions on the electrogenerated chemiluminescence (ECL) behavior of the ruthenium(II)tris(2,2′-bipyridine) (Ru(bpy)₃²⁺)/tri-n-propylamine (TPrA) system at a Au electrode was reported. At low concentrations (e.g., [Cl⁻] < 5 mM), the ECL was enhanced; at relatively high concentrations, however, the ECL intensity decreased with the increase of the [Cl⁻]. At [Cl⁻] = 90 mM, ∼50% and 100% ECL inhibition was observed for the first and the second ECL wave, respectively. The electrogenerated gold-chloride complexes (AuCl₂⁻ and AuCl₄⁻) which were verified using an electrochemical quartz-crystal microbalance (EQCM) method were found to be responsible for the ECL inhibition. This study suggests that care must be taken when a Au working electrode is used for ECL studies in chloride-containing buffer solutions (widely used in DNA probes) and/or with the commonly used chloride-containing reference electrodes since in these cases the ECL behavior may significantly disagree with that obtained using other electrodes and reaction media.     

Comparison between cyclic voltammetry and chronoamperometry when coupled with EQCM for the study of the SEI on a carbon film electrode

Cyclic voltammetry (CV) and chronoamperometry have been conducted with the electrochemical quartz crystal microbalance (EQCM) to characterize electron-beam deposited carbon film electrodes in LiClO₄-containing mixed electrolytes of ethylene carbonate (EC) and dimethyl carbonate (DMC). For a system whose electrolyte viscosity changes in the course of experiments, such as the above combination of electrode and electrolyte, the mass change per mole of electrons transferred (MPE) of the species on quartz crystals depends on the potential scan rate of CV. Chronoamperometry with a short period is more desirable for the estimation of the MPE of the solid electrolyte interphase (SEI) because the viscosity-induced frequency change, which hinders the correct MPE estimation, constitutes a small portion of the measured frequency change under this experimental condition.     

A study on the electro-oxidation and electropolymerization of a new OPE linear molecule by EQCM and in situ FTIR spectroelectrochemistry

A novel symmetric conjugated oligo(phenylene-ethynylene) (OPE) linear molecule (1,4-bis(4-aminophenylethynyl)benzene); BAB) was synthesized by Sonogashira cross-coupling reactions. The structure and purity of the compound were confirmed by ¹H NMR, ¹³C NMR and infrared (IR) and mass spectrometry (MS). The electrochemical oxidation process and mechanism of BAB were investigated via in situ Fourier transform infrared (FTIR) spectroelectrochemistry and electrochemical quartz crystal microbalance (EQCM). The electrochemical oxidation mechanism of BAB was proposed. The studies revealed that the BAB concentration and oxidation potential had a significant influence on the growth of the polymer film. A densely packed polymer film, which exhibited nonelectroactivity, was formed when a high monomer concentration and a high oxidation potential were used. When the electropolymerization of BAB was conducted at a lower concentration, a new pair of redox peaks appeared, and the resultant thin film had better electroactivity. The in situ FTIR studies confirmed that BAB could be electro-oxidized into radical cations and then electropolymerized via para (N-N) and/or ortho (N-C) coupling reactions to form polymers with a larger conjugated π-electron system. The surface morphology of the poly-BAB was also investigated with atomic force microscopy (AFM) and scanning electron microscopy (SEM).     

Kinetics of dissociative adsorption of ethylene glycol on Pt(1 0 0) electrode surface in sulfuric acid solutions

The dissociative adsorption of ethylene glycol (EG) on Pt(1 0 0) electrode surface cooled in air after flame annealing was investigated by using programmed potential step technique and in situ FTIR spectroscopy. The stable adsorbates derived from EG dissociative adsorption on Pt(1 0 0) were determined by in situ FTIR spectroscopy as linear- and bridge-bonded CO. The quantitative results demonstrated that the average rate of dissociative adsorption of EG on Pt(1 0 0) surface varies with electrode potential, yielding a volcano-type distribution with a maximum value located near 0.10 V versus SCE. From the variation of the quantity of CO adsorbates generated in EG dissociative adsorption with the adsorption time t_ad, the initial rate (ν_i) of this surface reaction was evaluated quantitatively. The maximum value of ν_i has been determined to be 2.64 × 10⁻¹¹ mol cm⁻² s⁻¹ in a solution containing 2 × 10⁻³ mol L⁻¹ EG. The influence of the surface structure of Pt(1 0 0) electrode obtained by different pretreatment as well as of the specific adsorption of (bi)sulfate anions on the kinetics of EG dissociative adsorption has been also investigated and discussed. In comparison with a Pt(1 0 0) surface cooled in air atmosphere after flame treatment, the Pt(1 0 0) surface cooled in an Ar-H₂ stream or subjected to a treatment of fast potential cycling decreased significantly the initial rate ν_i of EG dissociative adsorption. Similar effect was also observed for the specific adsorption of (bi)sulfate anions. However, the maximum attainable coverage () of adsorbates derived from EG dissociative adsorption is not affected either by the surface structure of Pt(1 0 0) or by (bi)sulfate anions adsorption.     

On the p-doping of PEDOT layers in various ionic liquids studied by EQCM and acoustic impedance

Poly(3,4-ethylenedioxythiophene) (PEDOT) films have been polymerized in several ionic liquids on the polycrystalline gold electrode of an electrochemical quartz crystal microbalance (EQCM) at 25 °C and 85 °C. Under cyclic potential variation, the EQCM resonance frequency decreased in the anodic potential region, indicating that the p-doping process is accompanied by the incorporation of anions. Elastic shear moduli G′, G″ - calculated from acoustic impedance measurements - were about 10⁷ Pa, values that are 2 orders of magnitude higher than for PEDOT polymerized in acetonitrile solutions. This difference is explained by the stiffening of the film by incorporated charged species because of the absence of a neutral molecular solvent plasticizing the film.