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We present a comprehensive study on the initial stages of silver electrodeposition on Pt (111), Au (111), and Au (100) single crystal surfaces in low-viscosity ionic liquids (ILs) containing dicyanamide anions: 1-butyl-1-methylpyrrolidinium dicyanamide [BMP][DCA] and 1-butyl-3-methylimidazolium dicyanamide [BMIm][DCA]. Electrochemical methods in combination with in situ scanning tunneling microscopy (STM) and ex situ atomic force microscopy (AFM) are employed to explore the Ag underpotential (upd) and overpotential (opd) deposition processes as well as the stability of the single crystal electrode surfaces in the absence of Ag+ ions. The substrate material is shown to significantly affect the mechanism of Ag deposit nucleation and growth in the ILs. While no Ag upd is detected on Pt (111), the formation of a Ag upd monolayer on a Au (111) electrode in both ILs is clearly visualized by in situ STM. The Ag adlayer formation on the Au electrodes in the underpotential regime facilitates Ag opd, which starts on Au (111) and Au (100) at much less negative potentials than on Pt (111). There is an excellent agreement between the electrochemical (voltammetry and chronoamperometry), AFM and STM data, demonstrating the nucleation and growth of individual Ag crystallites on Pt (111) according to the Volmer–Weber mechanism and the layer–by–layer growth of Ag deposit on Au (111) and Au (100). Only at high overpotentials, the Ag growth on the gold electrodes switches to the Stranski-Krastanov mode involving the appearance of 3D crystallites.

Nitrate electroreduction is studied on Pt(S)-[n(100)x(110)] stepped platinum single crystals with 2, 4, and 6 atoms wide terraces modified by copper adatoms. The electrodes were modified by electrodeposition of Cuad in a 0.1 M HClO4 + 0.020 M NaNO3 + 10−5 M Cu(ClO4)2 solution by cycling the potential in the range of 50–350 mV, simultaneously with nitrate reduction. The peak of dissolution of copper adatoms in the nitrate solution is shifted in the positive direction, as compared to the nitrate–free solution, due to the stabilization of copper adatoms by adsorbed NO. This shift is not observed for Pt(210) with the terrace width of only 2 atoms: an increase in the terrace width results in the growing peak shift. The rate of nitrate electroreduction on modified electrodes increases by up to two orders of magnitude and grows at low copper coverages at an increase in the terrace width in the sequence of Pt(210)

Neodymium is one of the most important rare earth elements due to its various applications, above all, in permanent magnets in consumer electronics and renewable power sources. Production of primary Nd is a rather complex and expensive process characterized by significant import dependency, which brings to the forefront Nd recovery from secondary sources. Electrowinning as one of the cheapest and processible solutions is not applicable for electropositive rare earths in aqueous systems but is a good option in the case of solutions based on ionic organic solvents. Nd electrodeposition and its induced codeposition with Fe are studied at room temperature in a fluorine-free dicyanamide ionic liquid (IL) using a complex set of electrochemical and physical (spectroscopic and microscopic) methods in dry solutions and in the presence of water. We show that the addition of water significantly promotes electrodeposition of individual metals in the respective single-component solutions but produces a hindering effect on the induced codeposition of Nd with Fe. We suggest an explanation for the acceleration of individual Nd and Fe in the presence of water based on the effects at the IL/electrode interface and for the inhibition of Nd-Fe deposition in the presence of water owing to the decelerating effect of formation of Nd oxide/hydroxide film. This is the first systematic study of the effect of water on the rare earth–transition metal codeposition in ILs providing information that can be essential for production of secondary rare earths and fabrication of novel lanthanide-based materials.

In this work, electroreduction of nitrate anions on bare and copper-modified platinum nanoparticles (Pt NPs) supported on glassy carbon is studied using cyclic voltammetry. Two types of Pt NPs are chosen for this purpose: unshaped (polyoriented) NPs and cubic NPs displaying the preferential (100) orientation of faces. The modification of cubic and polyoriented Pt NPs by copper adatoms with submonolayer coverages is performed in a controlled way in solutions containing small concentrations of Cu 2 + ions, 10 − 5 M. Nitrate reduction is studied first in copper-free solutions and then in the presence of 10 − 5 M Cu 2 + . The transmission electron microscopy and voltammetric measurements of the cubic NPs indicate the presence of a significant amount of Pt(100) terraces on the surface of these NPs. In perchloric acid solutions containing 0.02 M NaNO 3 and 10 − 5 M Cu 2 + , accumulation of copper adatoms on the NPs results in a fast increase in the currents of nitrate electroreduction. These reduction currents on the cubic NPs are up to three times higher than on the polyoriented NPs at Cu coverages of 0.20–0.35. The comparison of the data on Pt NPs with the data for single crystal electrodes with (100) terraces of different width (Pt(610), Pt(210)) shows that the behavior of NPs can be simulated on the basis of the data for single crystal faces with wide (cubic NPs) and narrow (unshaped NPs) (100) terraces. Thus, cubic NPs manifest rather a high electrocatalytic activity in the studied reaction of nitrate anion electroreduction, which is typical for single crystal surfaces with relatively wide Pt(100) terraces. At the same time, in comparison with macro single crystalline electrodes, these NPs are characterized by sufficiently higher stability, larger specific surface area, and flexibility in application.

The initial stages of Cu deposition at low overpotentials have been studied on the Pt(100) and Pt(111) basal faces and stepped surfaces Pt(610), Pt(410) of platinum single crystal electrodes. The process includes formation of a Cuad adlayer, an epitaxial monolayer of a two dimensional phase and three dimensional copper crystallites on the (100) terraces, while on the Pt(111) face the two dimensional Cu layer is absent as in this case 3-fold coordination of deposited Cu atoms probably cannot provide sufficient decrease in surface energy of the system. At high enough cathodic overpotentials, the 3D-phase of copper is formed on the monolayer of copper adatoms Pt(111)-Cuad. The Stranski-Krastanov mechanism of nucleation and growth is realized on all the studied electrodes. Financial support from the Russian Foundation for Basic Research (project no. 14-03-00530), MINECO (CTQ2013-44083-P) and Generalitat Valenciana (PrometeoII/2014/013) (Feder, Spain) is gratefully acknowledged.

Pulsed (square–wave) electrodeposition of platinum nanocrystallites with a high concentration of (100) regions from a H2PtCl6 solution with different background anions is studied. The effect of the background electrolyte is shown, namely, a more perfect cubic faceting of crystallites obtained in the 0.1 M HClO4 solution as compared to 0.5 M H2SO4. A procedure for deposit formation (secondary growth) with intermediate pulsed treatment in acid is suggested that does not involve application of high negative/positive overpotentials (no additional increasing of the mobility of platinum atoms). This allows preserving the crystallite structure and improving the overall deposit structure. In addition to conventional methods of fine surface structure determination on the basis of the hydrogen UPD region in cyclic voltammograms in sulfuric acid and SEM, we propose analysis of the Pt(100) terrace concentration/width based on the characteristic peak of nitrate ion reduction in voltammograms in perchloric acid. Stepped Pt single crystals with (100) terraces of different width are used for comparison. The effect of solution temperature on formation of faceted crystallites is shown and the optimum deposition temperature is determined: the optimum temperature in perchloric acid solution is 40 °C, while an increase in the temperature in sulfuric acid solutions results under the chosen conditions in deposition acceleration and an increase in the amount of surface defects.

Herein, we present a study on the initial stages of chromium electrodeposition on platinum and gold single-crystal surfaces from an ionic liquid containing dicyanamide anions. We employed conventional electrochemical techniques in combination with in situ and ex situ scanning probe microscopy (in situ scanning tunneling microscopy (STM), ex situ atomic force microscopy (AFM)) and ex situ X-ray photoemission spectroscopy (XPS). Cr electrodeposition was carried out from Cr(II) and Cr(III) solutions of low (10 mM) and high (250 mM) Cr concentrations. The microscopic and spectroscopic approaches clearly demonstrate the formation of a Cr deposit, although the voltammetric responses are difficult to interpret. The absence of a pronounced Cr dissolution peak in the backward scan of the cyclic voltammograms and a relatively low amount of Cr deposit (as confirmed by AFM) suggest the passivation of Cr and the substrate during deposition, thus hindering both further deposition of Cr and its anodic dissolution.

Kinetics and mechanism of nitrate ion reduction on Pt(1 1 1) and Cu-modified Pt(1 1 1) electrodes have been studied by means of cyclic voltammetry, potentiostatic current transient technique and in situ FTIRS in solutions of perchloric and sulphuric acids to elucidate the role of the background anion. Modification of platinum surface with copper adatoms or small amount of 3D-Cu crystallites was performed using potential cycling between 0.05 and 0.3 V in solutions with low concentration of copper ions, this allowed us to vary coverage θCu smoothly. Following desorption of copper during the potential sweep from 0.3 to 1.0 V allowed us to estimate actual coverage of Pt surface with Cu adatoms. Another manner of the modification was also applied: copper was electrochemically deposited at several constant potentials in solutions containing 10−5 or 10−4 M Cu2+ and 5 mM NaNO3 with registration of current transients of copper deposition and nitrate reduction. It has been found that nitrate reduction at the Pt(1 1 1) surface modified by copper adatoms in sulphuric acid solutions is hindered as compared to pure platinum due to induced sulphate adsorption at E Nitrate reduction on copper-modified Pt(1 1 1) electrodes in perchloric acid solutions occurs much faster as compared to pure platinum. The steady-state currents are higher by 4 and 2 orders of magnitude at the potentials of 0.12 and 0.3 V, respectively. The catalytic effect of copper adatoms is largely caused by the facilitation of nitrate adsorption on the platinum surface near Cuad and/or on the islands of the Cu(1 × 1) monolayer (induced nitrate adsorption). Hydrogen adatoms block the adsorption sites on platinum for NO3− anion adsorption and inhibit reactions of nitrate reduction even at moderate surface coverage. The products of nitrate reduction in sulphuric and perchloric acids are essentially the same (NO and ammonia) irrespective of the presence or absence of Cu on the platinum surface.

The variation of electrode nature and surface structure (the use of stepped single crystal faces with controlled width of (1 1 1) terraces and monoatomic steps of (1 0 0) or (1 1 0) orientation) allows to determine peculiarities of co-adsorption of acetonitrile molecules, hydrogen adatoms and (bi)sulfate anions. It has been shown that first of all acetonitrile blocks adsorption sites at the steps. Anion adsorption at terraces of stepped platinum surfaces in 0.5 M H2SO4 solution with additions of acetonitrile depends on terrace width and the step orientation. This demonstrates the important role of structural factors in competitive adsorption processes. The decrease in adsorption of hydrogen and anions on narrow terraces is substantially due to the influence of acetonitrile molecules placed at the steps or nearby sites. At E < 1.0 V, electrochemical conversion of acetonitrile has not been detected at single crystal Pt surfaces. However, acetonitrile oxidation might proceed on polycrystalline platinum followed by product desorption. On Au(1 1 1) surface acetonitrile adsorption is considerably weaker than that on platinum electrodes.

The kinetics of copper underpotential deposition on stepped Pt(hkl) electrodes with controlled width of (111) terraces in acidic solutions of copper sulfate with 0–200 mM of acetonitrile (AcN) has been studied by means of cyclic voltammetry. In the presence of AcN Cu UPD process is hindered both at (100) steps and (111) terraces of Pt(171515) and Pt(755) faces due to blocking of the electrode surface with organic molecules, strongly adsorbed at the steps and nearby ones. The decoration of (110) steps with copper adatoms is slightly accelerated for Pt(775) electrode in the solution with 0.04 mM AcN. Increase in AcN concentration leads to inhibition of the UPD process. The difference in behavior of the stepped platinum electrodes is controlled by competitive adsorption of AcN, (bi)sulfate and Cu atoms at the step sites. AcN adsorption at (100) steps is stronger as compared with (110) ones. Keywords: Copper, Stepped single crystal, Adsorption, Acetonitrile

Kinetics and mechanism of underpotential (UPD) and overpotential Cu deposition (OPD) on Pt(1 1 1), Pt(7 7 5) and Au(1 1 1) electrodes in sulfate solutions of different acidities (pH 0.3–3.7) are studied. In weakly acid solutions, the rates of both Cu UPD and OPD processes are higher as compared with acid solution of copper sulfate (pH 0.3) due to the enhanced concentration of active centers (copper oxides Cu xO) for 2-D and 3-D phase transitions and accelerated discharge of copper ions. The maximum rate of ( √ 3 × √ 3) R 30 ◦ formation is observed at

The catalytic and adsorption properties of platinum microparticles incorporated into polyaniline films were investigated using methanol oxidation in acidic solutions as a test reaction. The potential dependences of the specific reaction rates — the stationary oxidation currents referred to the unit of the true platinum surface were measured for different amounts of incorporated platinum (25–750 μg cm −2 ). The methanol adsorption kinetics and the dependence of the surface coverage on methanol concentration were established. The results of adsorption measurements were compared with catalytic effects. It was found that the extent of the catalytic effects and their mechanism depend on the amounts of the microdeposits and their distribution in the polymer layer. For moderate and high platinum loadings (60–750 μg cm −2 ) the specific reaction rates are higher than those on platinized platinum and increase with increasing loadings up to the reaction rate on smooth platinum. At the same time the reaction mechanism for these electrodes remains the same. It seems that the catalytic effects on such electrodes are influenced by structural peculiarities of the deposits. For low platinum loadings (25–35 μg cm −2 ) a change in the ratio of the rate of different steps can be observed as methanol adsorption becomes markedly inhibited and limits the overall reaction rate.

A long-term study of Cu UPD and OPD kinetics on the Pt(111) electrode by cyclic voltammetry and potentiostatic current transient techniques has shown that copper oxides CuxO could be considered as the active centers of the adlayer growth and further bulk copper deposition. These species are formed by a slow surface reaction between the adsorbed oxygen and copper atoms or ions at potentials E 0.55 V versus NHE. An enhanced rate of copper cations reduction on the positively charged Pt surface in the vicinity of electronegative CuxO species caused by the local electrostatic effects in the electric double layer could be the reason for the accelerating action of these active centers. © 2001 Elsevier Science Ltd. All rights reserved.

The influences of the Cu adatoms and Cu + ions on the initial stages of copper electrodeposition on polycrystalline Pt in acidified copper sulphate solution have been studied by cyclic voltammetry, potentiostatic current transients, rotating ring-disk electrode ( rrde ), and in situ scanning tunnelling microscopy (STM). It has been established that during the long-time polarization of the platinum electrode, at potentials close to the copper equilibrium potential, the concentration of Cu + ions in the vicinity of the electrode increases and a Cu microdeposit if formed. The dissolution of the microdeposit occurs very slowly and takes several minutes of potential cycling in the range of 0.27–1.25 V. While the microdeposit is present on the platinum, the electrode surface is more active with respect to upd and bulk copper deposition. The combination of electrochemical and in situ STM results indicates that formation of surface alloy occurs during electrodeposition of copper on polycrystalline platinum.

Poly( p -phenylene) (PPP) films deposited from benzene in concentrated H 2 SO 4 emulsion reveal a highly crystalline structure under TEM, SEM and XDA in contrast to nearly completely amorphous films deposited from C 6 H 5 NO 2 medium. Possible effects of solvent and electrolyte specificity on the morphology and mechanical properties of PPP films are discussed in view of these results.