Specific adsorption of formate ions at the mercury—aqueous solution interface

Adsorption on polarized Hg electrode of formate ions from aqueous solutions of pure HCOONa using differential capacity measurements was studied. Anion specific adsorption was indicated by the cathodic shift of potential of zero charge with increase in bulk-electrolyte activity. Variation of charge due to surface excess of sodium ions (Γ ₊ Z₊ F) and of charge due to specifically adsorbed formate ions (q¹), with electrode charge (q^M) indicated super-equivalent adsorption of formate ions at all positive charges and for all concentrations studied. Esin—Markov coefficient was found to be unreliable criterion of the occurence of specific adsorption. Logarithmic form of constant charge adsorption isotherms were found to be followed. The plots of φ^{M ? 2}vs q¹ at constant q^M were not linear and resembled those for F^?, BF₄^? and CH₃COO^? ions; which is attributed to relatively weak specific adsorption of anions.     

Evaluation of the pseudocapacitance in RuO2 with a RuO2/GC thin film electrode

The pseudocapacitance of nanocrystalline RuO₂ with BET surface area of 42 m² g⁻¹ was evaluated using a RuO₂ modified Glassy Carbon (RuO₂/GC) thin film electrode. The charge storage behavior of the RuO₂/GC thin film electrode was studied from fast to slow scan cyclic voltammetry between various potential windows. The utilization of the thin film electrode method for nanocrystalline RuO₂ with known specific surface area allowed a semi-quantitative understanding of the electric double-layer capacitance (C_dl), adsorption related charge (C_ad), and the irreversible redox related charge (C_irr) per unit mass and surface area of RuO₂. Comparison of the cyclic voltammograms between different voltage windows revealed that the contribution from C_irr is especially dominant below 0.4 V (versus RHE) at slow scan rates.     

Specific adsorption of acetate ions at the mercury—lithium acetate (AQ) interface

Specific adsorption of acetate ions at the mercury—lithium acetate (aq) interface has been investigated using both differential capacity and electrocapillary measurements. Variation of charge due to surface excess of lithium ions (q⁺) and of charge due to specifically adsorbed acetate ions (q^?1 with electrode charge (q^M) have been discussed. Such discussion inferred superequivalent adsorption of acetate ions at all positive charges for concentrations of lithium acetate ≥0.20 M whereas Esin-Markov plots predicted the absence of specific adsorption; the prediction of Esin-Markov plots has been shown to be faulty under certain conditions. The plots of φ^M-2vsq^?1 at constant q^M for acetate ion resembled the corresponding plots for F^? and BF^?₄ ions; the slope of these plots is negative up to coverages corresponding to 0.20 M lithium acetate. The identification of the isotherm parameter, (?φ^M-2/?q^?1)_q^M with the reciprocal of inner layer capacity at constant charge (_^?1Cⁱ) has been questioned.     

Bond formation in electrosorbates—II electrosorption and double layer properties in non-aqueous solvents

According to the principles outlined in Part I, electrosorption valencies of various systems are summarized for non-aqueous solvents. γ/z-values of ions adsorbed electrostatically can be taken as geometric factors, g, which characterize the relative penetration of the ions into the double layer. For different solvents, g increases with increasing double layer thickness, d, or decreasing minimum double layer capacity, C_min. The partial charge transfer, ?γ/z, is discussed in dependence on the difference, |Δχ|, of the electronegativities of the metal and of the adsorbed substances. Corresponding to the analysis for water, γ/z was plotted in dependence on |Δχ| for methanol and DMF as solvents. Complete charge transfer is observed in methanol for |Δχ| < 0·3, and electrostatic adsorption without charge transfer takes place for large |Δχ|-values. In the mean range of |Δχ|, eg in iodide systems, partial charge transfer takes place in all solvents. The influence of the solvation properties of the solvent on the partial charge transfer can be discussed qualitatively only. It is concluded that strong solvent-ion interaction facilitates the electrostatic adsorption, but increasing charge transfer is enhanced by a decreasing solvent-ion interaction, eg in case of anion adsorption from aprotic solvents.     

The adsorption of trifluoromethanesulfonate anions at the mercury/electrolyte interface

Recently, there has been much interest in the use of trifluoromethanesulfonic acid as an electrolyte in advanced fuel cell systems because of the enhanced rate of oxygen reduction in this medium. In order to elucidate this characteristic from a double layter point of view, the present work was undertaken to study the adsorption of trifluoromethanesulfonate ions on mercury electrodes. Differential capacities and potentials of zero charge were measured in constant ionic strength solutions of composition X M CF₃SO₃ K + (1-X) M KF at 25°C. Analysis of the results shows that the extent of specific adsorption of CF₃SO₃^? anions is small, and the anions even desorb from the surface at sufficiently positive electrode charges. The structure of the inner layer is elucidated, and an isotherm for the adsorption of CF₃SO₃^? based on electrostatic models of the double layer is derived. The results indicate that at the potentials for the electroreduction of oxygen CF₃SO₃^? anions will not interfere with the adsorption of the reactant and of intermediates, allowing faster rates to be achieved.     

The mechanism of electrode process in the system silver/silver cyanide complexes

The electrode's surface inhomogeneity was taken into account studying the mechanism of process. The effect of CN⁻ adsorption and partial surface coverage was investigated by electrochemical fast Fourier transform (FFT) impedance spectroscopy (0.03-3900 Hz). The isopotential solutions (E₀=−0.350 V) as well as solutions containing constant silver cyanide complex concentration (0.05 M) and different free cyanide ion concentrations (from 0.01 to 1.0 M) were studied. The exchange current density, re-calculated for only active area, gives electrochemical reaction order (R_CN=1.8 for α=0.5, and R_CN=2 for α=0.6) which is independent from CN⁻ concentration and from the composition of complexes prevailing in the bulk of electrolyte. The value of R_CN close to 2, obtained in a series of isopotential solutions confirms that in all cases the complex ions Ag(CN)₂⁻ take direct part in the charge transfer step.     

Infiltrated La0.5Ba0.5CoO3-δ in La0.8Sr0.2Ga0.8Mg0.2O2.8 scaffolds as cathode material for IT-SOFC

The electrochemical response of infiltrated La_0.5Ba_0.5CoO_3-δ (LBC) in porous La_0.8Sr_0.2Ga_0.8Mg_0.2O_2.8 (LSGM) has been investigated. The thermal expansion coefficient (TEC) of the resulting electrode was measured, obtaining α?=?12.5?×?10^?6 K^?1, a value similar to that of LSGM. The polarization resistance (Rp) and the processes involved in the oxygen reduction reaction (ORR) for the new electrode were studied and analyzed through complex impedance spectroscopy measurements as a function of temperature and oxygen partial pressure (pO₂), using a symmetrical cell. The value of Rp for the infiltrated LBC turned out to be lower than that measured for an electrode prepared with a composite LBC-LSGM (1:1?wt%) by an order of magnitude, for the temperature range 750?°C ≤ T?≤?900?°C, and about 5 times lower for the temperature range 450?°C≤ T?≤?650?°C. At 600?°C, the LBC infiltrated cathode exhibits a polarization resistance R_p =?0.22?Ω?cm², in air. The complex impedance spectra show two processes, one identified as low frequency (LF),with a characteristic frequency of 10?Hz, and the other as intermediate frequency (IF), with a range between 0.05 and 2000?Hz. The LF process could be associated to the diffusion of oxygen in the gas phase through the pores of the electrode. Its resistance, R_LF =?0.01?Ωc?m²_, was found to be independent of the temperature and half of that obtained for the LBC composite cathode. On the other hand, the IF process is related to charge transfer at the electrode surface and the electrode-electrolyte interface. The LBC cobaltite infiltrated in the LSGM scaffolds offers an adequate thermal expansion coefficient and good electrocatalytic activity for the ORR.     

Understanding CO-stripping mechanism from NiUPD/Pt(1 1 0) in view of the measured nickel formal partial charge number upon underpotential deposition on platinum surfaces in sulphate media

We recently showed nickel-underpotential deposition (Ni-UPD) occurs on polycrystalline or single crystal platinum electrodes in acidic media. Whereas the decoupling of the nickel and hydrogen adsorption/desorption peaks is difficult for low pH, these processes can be better separated for higher pH values, typically pH > 3. However, even for platinum single crystals, high pH solutions do not enable to sufficiently separate nickel from hydrogen phenomena. As a result, electrochemistry alone cannot yield important information about Ni-UPD, such as the formal partial charge number (valency of electrosorption) and the role of the sulphate or hydrogen sulphate anions.So, we decided to couple cyclic voltammetry to electrochemical quartz crystal microbalance (EQCM). EQCM measurements enable to decorrelate the simultaneous hydrogen and nickel adsorption/desorption peaks, which we could not attempt solely with electrochemistry. The coupling between gravimetric and electrochemical measurements allows us to detect the contribution of the anions and thus to isolate that of nickel: nickel coverage can then be determined. Nearly 4/5 Ni_UPD monolayer (θ_Ni ≈ 0.8) over platinum is reached at nickel equilibrium potential for high pH solutions (5.5). The QCM and electrochemistry coupling further allows the determination of nickel formal partial charge number: ι_Ni,EQCM = 1.3 ± 0.13. Direct electrochemistry measurements (Swathirajan and Bruckenstein method) yield: ι_Ni,Pt(poly) = 1.5 ± 0.17. These two values are close, which validates the electrochemical method for the nickel/platinum system. In consequence, we used Swathirajan and Bruckenstein method for Pt(1 1 0)-(1 × 2) crystal and found: ι_{Ni,Pt(1 1 0)} ≈ 1.4 ± 0.1. Whatever the system (Ni_UPD/Pt(poly) or Ni_UPD/Pt(1 1 0)-(1 × 2)) or the experimental technique, nickel formal partial charge number is lower than nickel cation charge: ι_Ni < z_Ni = 2. In consequence, upon underpotential deposition on platinum surfaces, nickel cations discharge and then undergo additional charge exchange processes, such as anion (or water) adsorption, resulting in apparent partial nickel cation discharge. Moreover, Ni_UPD/Pt(1 1 0) surface displays high activity towards CO_ad oxidation reaction. We explain such positive effect by the possible existence of a bifunctional mechanism in which oxygenated-species-covered Ni_UPD adatoms provide the oxygen atom to CO_ad?Pt species, enabling its facile oxidation.     

MnxCu1−xCo2O4 used as bifunctional electrocatalyst in alkaline medium

Composite film electrodes containing mechanically mixed Mn_xCu_1−xCo₂O₄ (0 ≤ x ≤ 1) particles, carbon black Vulcan XC72R and poly(vinylidene fluoride-co-hexafluoropropylene) (PVdF-HFP) were formed on the glassy carbon disk surface of a rotating ring-disk electrode (RRDE) and studied for the oxygen reduction and evolution reactions (ORR and OER, respectively) in 1 M KOH solution. The electrocatalytic activities for both reactions were observed to depend strongly on the Mn content in CuCo₂O₄. An opposite trend was observed for the apparent and intrinsic electrocatalytic activities for the ORR; the simultaneous presence of Cu and Mn was found to be detrimental to the intrinsic charge density, but beneficial to the geometric charge density with a maximum for Mn_0.6Cu_0.4Co₂O₄. The latter was characterized by the highest total number of electrons exchanged per O₂ molecule, n, close to 4, greater k₁ (4e⁻ process)/k₂ (2e⁻ process) ratios, and by a unique and low Tafel slope (−41 mV dec⁻¹). The results obtained for the OER showed that the intrinsic electrocatalytic activity is determined by the number of active sites (Co⁴⁺) electrochemically formed at the oxide surface prior to the OER, from Co³⁺ cations. The partial substitution of Cu by Mn in CuCo₂O₄ was found to decrease the OER activity.     

Theoretical Study of NO2 Adsorption on a Transition-Metal Zeolite Model

Calculations for the study of NO₂ adsorption on a transition-metal-exchanged zeolite (M=Zn, Cu, Ni, Co, Fe) were carried out using an ab initio density functional theory and pseudopotential approaches. A tritetrahedral model (T3) was used to represent the structure of the zeolite. The density functional calculations predict that the bonding energy follows the order Zn>Ni>Cu>Fe>Co. Analysis of the electronic properties shows that only in the case of Cu and Ni ions does the d¹⁰-s¹d⁹ promotion favor interaction between the NO₂ molecule and the metallic center. The optimization results show that there is a charge transfer from the metallic ion to the NO₂ molecule, which produces a weakening of the N–O bond.     

Adsorption of N,N′-dimethylthiourea at a mercury/aqueous solution of NaClO4 interface; dependence on the supporting electrolyte concentration

Adsorption of N,N′-dimethylthiourea (DMTU) on mercury electrode from 0.1, 1 and 5 M NaClO₄ was studied as the function of electrode charge density and adsorbate bulk concentration. In the study, the experimental data obtained from the measurements of differential capacity of double layer were used, the measurements of zero charge potential and surface tension at the zero charge potential. In each system studied the values of the relative surface excess increase with an increase of the concentration of N,N′-dimethylthiourea and NaClO₄. The adsorption parameters were obtained from the Frumkin, virial and modified Flory-Huggins isotherms. It was found that the values of free adsorption energy, interactions constants and integral capacity depends on the supporting electrolyte concentration. The strength of the surface bond formed between N,N′-dimethylthiourea and the electrode surface and the influence of water present on the electrode surface in the obtained results of calculations were discussed.     

Experimental determination of the thermodynamic parameters affecting the adsorption behaviour and dispersion effectiveness of PCE superplasticizers

For adsorption of three different allylether-based PCE superplasticizers on CaCO₃ surface, the thermodynamic parameters ΔH, ΔS and ΔG were determined experimentally. The GIBBS standard free energy of adsorption ΔG_0ads, the standard enthalpy of adsorption ΔH_0ads and the standard entropy of adsorption ΔS_0ads applying to an unoccupied CaCO₃ surface were obtained via a linear regression of ln K (equilibrium constant) versus 1 / T (VAN'T HOFF plot). Additionally, the thermodynamic parameters characteristic for a CaCO₃ surface loaded already with polymer (isosteric conditions) were determined using a modified CLAUSIUS-CLAPEYRON equation.For all PCE molecules, negative ΔG values were found, indicating that adsorption of these polymers is energetically favourable and a spontaneous process. Adsorption of PCEs possessing short side chains is mainly instigated by electrostatic attraction and a release of enthalpy. Contrary to this, adsorption of PCEs with long side chains occurs because of a huge gain in entropy. The gain in entropy results from the release of counter ions attached to the carboxylate groups of the polymer backbone and of water molecules and ions adsorbed on the CaCO₃ surface. With increased surface loading, however, ΔG_isosteric decreases and adsorption ceases when ΔG becomes 0. The presence of Ca²⁺ ions in the pore solution strongly impacts PCE adsorption, due to complexation of carboxylate groups and a reduced anionic charge amount of the molecule. In the presence of Ca²⁺, adsorption of allylether-based PCEs is almost exclusively driven by a gain in entropy. Consequently, PCEs should produce a strong entropic effect upon adsorption to be effective cement dispersants. Molecular architecture, anionic charge density and molecular weight as well as the type of anchor groups present in a superplasticizer determine whether enthalpy or entropy is the dominant force for superplasticizer adsorption.     

Voltammetric investigation of thallium adsorption on silver single crystal electrodes

The adsorption behaviour of Tl⁺ on Ag(100) and Ag(111) in 0.5 M NaClO₄ and Na₂SO₄ has been studied by voltammetric methods including flow-through thin layer voltammetry (FTTL) and single electrode thin layer voltammetry (STL). The Tl-deposits formed on both electrode substrates exhibit the ideal charge stoichiometry of metal monolayer adsorbates, indicating the absence of anion adsorption. The adsorption on Ag(100) can be characterized by an equilibrium Γ(E)-isotherm compatible with a stepwise formation of three stable sorption layers. The Tl-deposit on Ag(111) features the successive build up of two adsorbate layers. In case of incomplete formation of the first layer, however, a slow structural transformation occurs, involving a strong interaction with the Ag(111) substrate and accompanied by partial Tl-desorption. The complex behaviour of this system is interpreted in terms of internal strain within the Tl-superlattice structures.     

Electric transport properties of rare earth doped YbxCa1-xMnO3 ceramics (part III: Point defect chemistry)

A defect chemical model based on charge neutrality and laws of mass action is proposed to clarify the details of the chemistry of point defects for donor-doped Yb_xCa_1-xMnO₃. DC-conductivity measurements were carried out in a wide range of partial pressure of oxygen p(O₂) ≈ 10⁻¹ down to 10^-19 MPa at 750⁰C for the first time without disintegrating the ceramic sample through reduction. A comparison of the experimental observations and the theoretical defect chemical models clearly shows the possibilities for controlling charge carriers in dependence of partial pressure of oxygen p(O₂) and dopant concentration. The origin of a plateau state, of a drastic decrease in conductivity in the intermediate and reduction p(O₂) regimes are figured out, respectively. In addition, the kind and concentration of the electronic and ionic majority charge carriers are determined and formulated according to the proposed defect chemical model. Furthermore, phase transitions were studied in a wide range of p(O₂) at elevated temperatures     

Electrochemical and ex situ XRD investigations on (1−x)LiNiO2·xLi2TiO3 (0.05≤x≤0.5)

An attempt to understand the unusual electrochemical behaviors in (1−x)LiNiO₂·xLi₂TiO₃ (0.05≤x≤0.5), an excess initial charge capacity exceeding the oxidation of transitional metal to +4 accompanying the appearance of an irreversible initial charge plateau when x reached 0.075, was performed. The decreased charge-discharge polarization after charging to 4.6 and 4.8 V and increased columbic reversibility after charging to 4.6 V typically for x=0.1 and 0.2, in contrast to charging to 4.4 V, suggested that the excess initial charge capacity possibly did not come mainly from electrolyte decomposition; while ex situ XRD results in the sample with x=0.2 confirmed that Li⁺ were really extracted at the stage of the charge plateau, ruling out the possibility that electrolyte decomposition mainly accounted for the unusual electrochemical behaviors. It was inferred that the species responsible for charge compensation for the excess charge capacity must be oxygen ions in these materials, considering that Ni⁴⁺ and Ti⁴⁺ are generally impossible to be oxidized to a higher valence. Various electrochemical cycling experiments demonstrated that the sample for x=0.05 with high resistant ability to high voltage and temperature is very promising cathode material in view of observed capacity and cycleability from a viewpoint of application.     

Surface and photoelectrochemical studies of semiconducting MoS2

Redox reactions with Cu(NH₃)^2+/1+_x, Fe(CN)^3?/4? and I^?₃/I₂ were studied on |-C surfaces of MoS₂ using rdes. From electrophoretic measurements, the zpc was found to occur at pH 2. The role of potential-determining ions and the effects of specific adsorption of ions on the electrode behaviour have been discussed. The change of potential with pH was ? 30 mV/pH unit for MoS₂ electrode in contact with a solution saturated with molybdenum and S^2? ions. From the information available, an energy level diagram has been constructed. This diagram is in agreement with the observed behaviour that electron exchange for the first three redox couples occurs with the conduction band, except that the electron transfer from the reduced species, Fe(CN)^4?₆ and Fe²⁺, in the reverse direction (oxidation) is partly and totally restricted, respectively. The charge transfer behaviour in the cse of I^?₃/I₂ couple, appears to be much more complex, most probably involving adsorption of I^? on the surface.     

Bond formation in electrosorbates—I correlation between the electrosorption valency and pauling's electronegativity for aqueous solutions

the electrosorption valency, γ, which can be determined experimentally, is discussed in dependence on system-specific parameters. For correlation purposes, values at the potential of zero charge, ?N, and small coverages, θ ≈ 0·1, only are used, and mixed adsorption and phase formation must be excluded. Experimental data for 50 ionic systems in aqueous solutions are summarized. For homonucleus ions, a simple correlation between the ratio, γ/z, and the electronegativity difference, |χ_M?χS|, is established. This relationship can be described using a reasonable assumption on the geometric factor, g, and Pauling's formula for the charge transfer in diatomic molecules. It follows from this simple model as well as from the experimental data that covalent adsorption (γ/z ≈ 1, ? λ/z ≈ 1), takes place in the range, |Δχ| < 0·5, but ionic adsorption (γ/z < 0·2, λ ≈ 0) occurs at |Δχ| > 1·0. For 0·5 < |Δχ| < 1·0 the partial charge transfer (0 < ?λ/z < 1) with the formation of polarized bonds is important.Heteronucleus ions are discussed qualitatively. The influence of the geometric factor seems to be dominant for these ions.     

Adsorption of camphor and 2,2′-bipyridine on Bi(1 1 1) electrode surface

Impedance spectroscopy and in situ STM methods have been used for investigation of the camphor and 2,2′-bipyridine (2,2′-BP) adsorption at the electrochemically polished Bi(1 1 1) electrode from weakly acidified Na₂SO₄ supporting electrolyte solution. The influence of electrode potential on the adsorption kinetics of camphor and 2,2′-BP on Bi(1 1 1) has been demonstrated. In the region of maximal adsorption, i.e. capacitance pit in the differential capacitance versus electrode potential curve, the heterogeneous adsorption and diffusion steps are the rate determining stages for camphor and 2,2′-BP adsorption at the Bi(1 1 1) electrode. It was found that for camphor | Bi(1 1 1) interface the stable adsorbate adlayer detectable by using the in situ STM method has been observed only at the positively charged electrode surface, where the weak co-adsorption of SO₄²⁻ anions and camphor molecules is possible. At the weakly negatively charged Bi(1 1 1) electrode surface there are only physically adsorbed camphor molecules forming the compact adsorption layer. The in situ STM data in a good agreement with impedance data indicate that a very well detectable 2,2′-BP adsorption layer is formed at Bi(1 1 1) electrode in the wide region of charge densities around the zero charge potential.     

Biosorption of Zn(II) from Seawater Solution by the Microalgal Biomass of Tetraselmis marina AC16-MESO

Biosorption refers to a physicochemical process where substances are removed from the solution by a biological material (live or dead) via adsorption processes governed by mechanisms such as surface complexation, ion exchange, and precipitation. This study aimed to evaluate the adsorption of Zn²⁺ in seawater using the microalgal biomass of Tetraselmis marina AC16-MESO “in vivo” and “not alive” at different concentrations of Zn²⁺ (0, 5, 10, and 20 mg L⁻¹) at 72 h. Analysis was carried out by using the Langmuir isotherms and by evaluating the autofluorescence from microalgae. The maximum adsorption of Zn²⁺ by the Langmuir model using the Q_max parameter in the living microalgal biomass (Q_max = 0.03051 mg g⁻¹) was more significant than the non-living microalgal biomass of T. marine AC16-MESO (Q_max = 0.02297 mg g⁻¹). Furthermore, a decrease in fluorescence was detected in cells from T. marina AC16-MESO, in the following order: Zn²⁺ (0 < 20 < 5 < 10) mg L⁻¹. Zn²⁺ was adsorbed quickly by living cells from T. marine AC16-MESO compared to the non-living microalgal biomass, with a decrease in photosystem II activities from 0 to 20 mg L⁻¹ Zn²⁺ in living cells.     

Adsorption of asparagine on the gold electrode and air/solution interface

The adsorption of asparagine (Asn) on a gold electrode from 0.1 M LiClO₄ aqueous solutions was investigated. The experimental data obtained from ac impedance measurements were analyzed to determine the dependence of adsorption parameters, i.e. the standard Gibbs energy of adsorption (ΔG⁰), maximal value of surface excess concentration (Γ_max) of Asn and parameter of interactions in the adsorbed layer (A) on the electrode potential. The relatively large value of Gibbs energy of adsorption (∼ −47 kJ mol⁻¹) gives the evidence of a very strong adsorption of Asn at the polycrystalline Au electrode. The comparison of the adsorption behavior of Asn at the air/solution and the Au/solution interfaces points out to the significant electronic interactions of adsorbate molecules with the Au electrode, since the adsorption of Asn on a free surface (from the same solutions) is very week. The analysis of the electrochemical data as well as the infrared reflection absorption spectroscopy (IRAS) results reveal that Asn molecules are anchored to the Au surface through oxygen atoms of the carboxylate group COO⁻ and through the amide carbonyl group.