Kinetic study of nitrate reduction on Pt(1 1 0) electrode in perchloric acid solution

The kinetics of electrocatalytic reduction of nitrate on Pt(1 1 0) in perchloric acid was studied with cyclic voltammetry at a very low sweep rate of 1 mV s⁻¹, where pseudo-steady state condition was assumed to be achieved at each electrode potential. Stationary current-potential curves in perchloric acid in the absence of nitrate showed two peaks at 0.13 V and 0.23 V (RHE) in the so-called adsorbed hydrogen region. The nitrate reduction proceeded in the potential region of the latter peak in the pH range studied. The reaction orders with respect to NO₃⁻ and H⁺ were observed to be close to 0 and 1, respectively. The former value means that the adsorbed NO₃⁻ at a saturated coverage is one of the reactants in the rate-determining step (rds). The latter value means that hydrogen species is also a reactant above or on the rds. The Tafel slope of nitrate reduction was −66 mV per decade, which is taken to be approximately −59 mV per decade, indicating that the rds is a pure chemical reaction following electron transfer. We discuss two possible reaction schemes including bimolecular and monomolecular reactions in the rds to explain the kinetics and suggest that the reactants in the rds are adsorbed hydrogen and adsorbed NO₃⁻ with the assistance of the results in our recent report for nitrate reduction on Pt(S)[n(1 1 1) × (1 1 1)] electrodes: the nitrate reduction mechanism can be classified within the framework of the Langmuir-Hinshelwood mechanism.     

Adsorption of phosphate species on poly-oriented Pt and Pt(1 1 1) electrodes over a wide range of pH

The adsorption of phosphate anions from phosphate solutions at poly-oriented and single-crystal platinum electrodes, primarily Pt(1 1 1), was studied over a wide range of pH by cyclic voltammetry. The features observed at the poly-oriented Pt electrode in phosphate solution may be related to the different crystalline facets, the (1 1 1) orientation presenting the most significant behavior in terms of phosphate adsorption. On the reversible hydrogen electrode (RHE) scale, the phosphate adsorption strength decreases with increasing alkalinity of the solution. Qualitatively, three different pH regions can be distinguished. At pH < 6 only a broad reversible peak is observed, corresponding to the adsorption of H₂PO₄⁻ and further deprotonation to adsorbed HPO₄⁻. For 6 < pH < 11 a butterfly feature followed by one or two anodic peaks (depending on scan rate) is observed, ascribed to the adsorption of HPO₄⁻ followed by its subsequent deprotonation to adsorbed PO₄³⁻. The splitting into two or three voltammetric features, and the irreversibility of the two features at more positive potential, is ascribed to the deprotonation reaction leading to a surface species (i.e. phosphate) which needs to change its surface coordination. At pH > 11 a reversible pre-wave and a sharp spike are observed, ascribed to the co-adsorption of phosphate and hydroxide.     

Surface X-ray scattering of high index plane of platinum containing kink atoms in solid-liquid interface: Pt(3 1 0) = 3(1 0 0)-(1 1 0)

Surface structure of Pt(3 1 0) = 3(1 0 0)-(1 1 0), which contains kink atoms in the step, has been determined with the use of in situ surface X-ray scattering (SXS) in the double layer region (0.50 V(RHE)) in 0.1 M HClO₄. Clean Pt(3 1 0) surface has pseudo (1 × 1) structure on which lateral displacements of 2-9% and 0.3-1% are found along a and b directions, respectively, whereas the surfaces of Pt(1 1 0) = 2(1 1 1)-(1 1 1) and Pt(3 1 1) = 2(1 0 0)-(1 1 1) are reconstructed to (1 × 2) according to previous reports. Interlayer spacing between the first and the second layers d₁₂ is contracted about 5% compared with the bulk spacing, whereas those between underlying layers are expanded down to fourth layer. Fully adsorbed CO has no effect on the surface structure of Pt(3 1 0). This result differs from that on Pt(1 1 1), where d₁₂ is expanded after CO adsorption.     

Electroreduction of nitrate ions on Pt(1 1 1) electrodes modified by copper adatoms

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 θ_Cu 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 < 0.3 V. Sulphate blocks the adsorption sites on the platinum surface and/or islands of epitaxial Cu(1 × 1) monolayer thus hindering the adsorption of nitrate anions and their reduction. The extent of inhibition weakly depends on the copper adatom coverage. Deposition of a small amount of bulk copper does not affect noticeably the rate of nitrate reduction.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 Cu_ad 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.     

In situ radiotracer and voltammetric study of the formation of surface adlayers in the course of Cr(VI) reduction on polycrystalline and (1 1 1) oriented platinum

This paper is focused on the in situ radiotracer and voltammetric studies of the induced HSO₄⁻/SO₄²⁻ adsorption at Pt(poly) and Pt(1 1 1) surfaces in 0.1 mol dm⁻³ HClO₄ solution in the course of Cr(VI) electroreduction. Besides this, the sorption behavior of HSO₄⁻/SO₄²⁻ ions on bare Pt(poly) and Pt(1 1 1) electrodes is compared and discussed. From the experimental results it can be stated that: (i) although the extent of bisulfate/sulfate adsorption is strongly dependent upon the crystallographic orientation of Pt surfaces, the maximum coverage on the Pt(1 1 1) does not exceed 0.2 monolayer; (ii) the Cr(VI) electroreduction on both poly- and (1 1 1) oriented platinum proceeds via a ce (chemical-electron-transfer) mechanism to yield Pt surfaces covered with intermediate surface adlayers containing Cr(VI) particles (and reduced Cr-containing adspecies) and ‘strongly bonded’ HSO₄⁻/SO₄²⁻ ions; (iii) while the coverage of platinum surfaces by the intermediate complexes formed in the course of Cr(VI) electroreduction at E > 0.20 V is basically independent of the crystallographic orientation of the Pt electrode, the onset for rapid Cr(VI) reduction is highly affected by the nature and crystallographic orientation of the electrode.     

Crystalline alloys produced by mercury electrodeposition on Pt(1 1 1) electrode at room temperature

In situ scanning tunneling microscopy (STM) and reflection high energy electron diffraction (RHEED) were used to characterize mercury film electrodeposited onto a Pt(1 1 1) electrode at room temperature. Depending on the amount of Hg deposit, two different growth modes were observed. At low Hg coverage, crystalline (0 0 0 1)Hg adlayer accompanied by 30°-rotated (1 1 1)-Pt patches was found on Pt(1 1 1). Deposition of multilayer Hg resulted in layered PtHg₂ and PtHg₄ amalgams, which grew epitaxially by aligning their (2 0 1) and planes, respectively, parallel to the Pt(1 1 1) substrate. The preference of these epitaxial relationships for the electrochemically formed Pt-Hg intermetallic compounds on Pt(1 1 1) could result from minimization of the surface energy.     

Potential of zero free charge of Pd overlayers on Pt(1 1 1)

Differential capacitance measurements of Pd overlayers on a Pt(1 1 1) electrode in dilute aqueous NaF solutions have been performed as a function of film thickness in order to determine the potential of zero free charge (pzfc). The pzfc of the first, pseudomorphic Pd monolayer on Pt(1 1 1) is −0.21 V versus SCE. By increasing the amount of deposited Pd, a clear shift of the pzfc to more positive values is observed. After deposition of an equivalent of 10 monolayers, the value approaches that of a massive Pd(1 1 1) electrode (−0.12 V versus SCE). The pzfc's for the various Pd coverages are correlated with surface structure information, derived from STM images (R. Hoyer, L.A. Kibler, D.M. Kolb, Electrochim. Acta 49 (2003) 63). Variations in the pzfc are discussed in the context of an electronic modification by the underlying substrate and are compared with corresponding data for Pd overlayers on Au(1 1 1).     

Electrochemical characterization of irreversibly adsorbed germanium on platinum stepped surfaces vicinal to Pt(1 0 0)

The electrochemical behavior of germanium irreversibly adsorbed at stepped surfaces vicinal to the Pt(1 0 0) pole is reported. The process taking part on the (1 0 0) terraces is evaluated from charge density measurements and calibration lines versus the terrace dimension are plotted. On the series Pt(2n − 1,1,1) having (1 1 1) monoatomic steps, the charge involved in the redox process undergone by the irreversibly adsorbed germanium is able to account for (n − 0.5) terrace atoms, thus suggesting some steric difficulties in the growth of the adlayer on the (1 0 0) terraces. Conversely, no steric problems are apparent in the series Pt(n,1,0) in which more open (1 0 0) steps are present on the (1 0 0) terraces. In this latter case the charge density under the germanium redox peaks is proportional to the number of terrace atoms. Some comparison is made with other stepped surfaces to understand the behavior and stability of germanium irreversibly adsorbed on the different platinum surface sites.     

Carbon monoxide oxidation on Au(1 1 1) surface decorated by spontaneously deposited Pt

Platinum is deposited spontaneously on Au(1 1 1) surface from 1 mM H₂PtCl₆ + 1 M HClO₄ solution using multiple deposition procedure. X-ray photoelectron spectroscopy (XPS) analysis has shown that after immersion into the Pt containing solution and rinsing with water, Pt(OH)₂ resides on the Au(1 1 1) substrate. Consecutive depositions as well as in situ scanning tunneling microscopy (STM) and electrochemical measurements are performed on previously electrochemically reduced Pt/Au(1 1 1) surfaces. Only homogeneous distribution of thus deposited Pt islands is observed by in situ STM. With subsequent depositions, the width of deposited Pt islands increases, but stays lower than 10 nm, while a significant increase of Pt islands height is observed, leading to moderate increase of the coverage. Cyclic voltammetry (CV) profiles of obtained Pt/Au(1 1 1) surfaces, and CO stripping curves are recorded in 0.5 M H₂SO₄ solution. CO oxidation takes place only at higher potentials shifting negatively with increasing coverage. This is discussed with respect to Pt islands width and height distributions and to the influence of the Au(1 1 1) substrate surface.     

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.     

Adenine adsorption on Au(1 1 1) and Au(1 0 0) electrodes: Characterisation, surface reconstruction effects and thermodynamic study

Adsorption of adenine on Au(1 1 1) and Au(1 0 0) electrodes is studied by cyclic voltammetry, impedance and chronoamperometric measurements in 0.1 M and 0.01 M KClO₄ and in 0.5 M NaF solutions. The experiments performed with flame-annealed electrodes at different contact potentials, scan potential limits and scan rates, suggest different adsorption behaviour on the unreconstructed and reconstructed surface domains. This is confirmed by comparing the results obtained with electrochemically annealed unreconstructed and with flame-annealed reconstructed surfaces. In both cases the initial electrode surface state is characterised by the E_pzc values. The adsorption on reconstructed surfaces takes place at more positive potentials than on the unreconstructed surfaces and induces the lifting of the reconstruction.The thermodynamic analysis is performed on the chronoamperometric data for adenine desorption on well characterised unreconstructed Au(1 1 1) surfaces. To this end a new methodology of the chronoamperometric experiments is introduced. Quantitative thermodynamic adsorption parameters such as surface tension, Gibbs surface excess, Gibbs energy of adsorption, potential versus Gibbs excess slope and electrosorption valency are determined. Weak chemisorption of adenine is inferred with a molecular orientation independent on the coverage and on the electrode potential. It is proposed that adsorbed adenine molecules adopt a tilted orientation at the surface to facilitate the coordination to the gold atoms.     

Thermodynamic approach to the double layer capacity of a Pt(1 1 1) electrode in perchloric acid solutions

A thermodynamic method based on the work done by Frumkin and Petrii [A.N. Frumkin, O.A. Petrii, Electrochim. Acta 20 (1975) 347], to calculate the so-called double layer capacity for a Pt(1 1 1) electrode is proposed. The analysis requires careful measurement of the total charge density versus potential curves for a series of solutions with composition (0.1 − x) M KClO₄ + x M HClO₄. A method in which the total charge densities are determined by integration of cyclic voltammograms recorded in solutions with or without chloride is described. Following this procedure the double layer capacity curves were calculated. The double layer capacity curves displayed three peaks that were tentatively assigned to the solvent reorientation, onset of OH adsorption and completion of the OH adlayer. In the hydrogen adsorption region, the double layer capacity values were 14 ± 5 μF/cm², in good agreement with previous estimates reported in the literature by using other approaches.     

XPS study of irreversibly adsorbed arsenic on a Pt(1 1 1) electrode

The chemical composition of an irreversibly adsorbed layer of arsenic on Pt(1 1 1) in sulfuric acid solution has been studied by X-ray photoelectron spectroscopy (XPS). From the chemical shift of the As 3d level, a change in the valence state from As(0) to As(III) with positive-going electrode potential is deduced, the total amount of As on the surface remaining constant. The As coverage derived from XPS is around 0.33 ML, which is in agreement with the charge under the current peak in the cyclic voltammogram. From the coadsorption of anions, accompanying the valence transition of As, As(III) is assumed to exist as As(OH)₃ on the surface.     

Electrodeposition of Ag and Pd on a reconstructed Au(1 1 1) electrode surface studied by in situ scanning tunneling microscopy

Electrochemical deposition of Ag and potential-induced structural change of the deposited Ag layer on a reconstructed surface of Au(1 1 1) electrode were followed by in situ scanning tunneling microscope (STM). A uniform Ag monolayer was formed on a reconstructed Au(1 1 1) surface in a 50-mM H₂SO₄ solution at +0.3 V (vs. Ag/AgCl) after adding a solution containing Ag₂SO₄ so that the concentration of Ag⁺ in the STM cell became ca. 2 μM. No characteristic height corrugation such as the Au reconstruction was observed on the surface, indicating that the lifting of the substrate Au reconstruction occurred by Ag deposition. The formed Ag monolayer was converted to a net-like shaped Ag nano-pattern of biatomic height when the potential was stepped from +0.3 to −0.2 V in the solution containing 2 μM Ag⁺. This result indicates that the substrate Au(1 1 1)-(1 × 1) surface was converted to the reconstructed surface even in the presence of Ag adlayer. Quite different structure was observed for Pd deposition on a reconstructed surface of Au(1 1 1) electrode at +0.3 V and the origin for this difference between Ag and Pd deposition is discussed.     

Structure and electrochemical characterization of electrolytic Ni + Mo + Si composite coatings in an alkaline solution

Ni + Mo + Si coatings were obtained by nickel deposition from a bath containing suspension of molybdenum and silicon powders. These coatings were obtained in galvanostatic conditions, at the current density of j_dep = −0.100 A cm⁻². For determination of the influence of phase composition and surface morphology of obtained coatings on changes of corrosion resistance, these coatings were modified in argon atmosphere by thermal treatment at the temperature of 1100 °C during 1 h. A scanning electron microscope was used for surface morphology characterization of the coatings. Chemical composition of obtained coatings was determined by X-ray fluorescence spectroscopy method. Phase composition investigations were conducted by X-ray diffraction method. It was found that the obtained coatings are composed of three phase structures, i.e., nickel, molybdenum and silicon. Phase composition for the Ni + Mo + Si coatings after thermal treatment is markedly different. The main peaks corresponding to the Ni and Mo coexist with the new ones corresponding to new phases: Mo₅Si₃, NiSi, Mo₂Ni₃Si and Ni₆Mo₆C_1.06.Electrochemical corrosion resistance investigations were carried out in the 5 M KOH, using potentiodynamic and electrochemical impedance spectroscopy methods. On the basis of these investigations it was found that Ni + Mo + Si coatings after thermal treatment are more resistant in alkaline solution than Ni + Mo + Si as-deposited coatings. The reason of this is presence of silicides in the coatings.     

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.     

Potential dependent adsorption behaviour of thiothymine derivatives on the Au(1 1 1) electrode

The adsorption behaviour of 2-thiothymine and 4-thiothymine on a Au(1 1 1) single crystal electrode has been studied using cyclic voltammetry and X-ray photo electron spectroscopy. For both thio derivatives the adsorption region is restricted due to the onset of reversible oxidization to 2,2′-bis(1H-5-methylpyrimidin-4-one-2-yl)-disulphide or 4,4′-bis(1H-5-methylpyrimidin-2-one-4-yl)-disulphide at anodic potentials. Two different orientations of adsorbed 2-thiothymine have been observed. Between −350 mV and −700 mV versus Ag/Ag⁺ the molecule is solely chemisorbed via its sulphur atom and adopts an upright orientation towards the surface. However at more negative potentials 2-thiothymine is reoriented into a slightly tilted position interacting via its S, N and O atoms with the surface. In contrast, 4-thiothymine exhibits only one adsorption geometry. Between −300 mV and −700 mV versus Ag/Ag⁺ it is chemisorbed via sulphur and nitrogen adopting a slightly tilted position. At −950 mV versus Ag/Ag⁺ 4-thiothymine is irreversibly reduced. The sulphur substituent is eliminated and covers the substrate.     

Dependence of electrocatalytic activity on film thickness for the hydrogen evolution reaction of Pd overlayers on Au(1 1 1)

The hydrogen evolution reaction has been studied for ultrathin Pd overlayers of various thickness on Au(1 1 1) in 0.1 M H₂SO₄. A clear correlation of the electrocatalytic activity as expressed by the exchange current density and the binding energy of adsorbed hydrogen has been found. While hydrogen is bound strongest on the second Pd monolayer (ML), the respective catalytic activity is poorest for all the surface structures under study. The exchange current density increases in the order 2 ML Pd < 1 ML Pd < bulk Pd (more than 2 ML). The electronic ligand effect, a geometric effect due to pseudomorphic growth and the surface defect density belong to the most crucial parameters in relations between structure of the electrode surface and its electrocatalytic activity. The experimental results are supported by an excellent agreement with theoretical predictions.     

Redox behavior of hemin at p-GaAs(1 0 0) electrode

Electrochemical behavior of hemin on p-GaAs(1 0 0) electrodes was examined by cyclic voltammetry (CV) and impedance spectroscopy (EIS) in phosphate buffer solutions (PBS) at pH 7.45. CV investigations in 0.6 mM hemin in PBS revealed a pair of reversible peaks at −0.44 and −0.32 V vs. SCE resulting in stable adsorbed species. EIS spectra analysis pointed out that these adsorbed species bring significant changes in the semiconductor surface state population and the potential drop distribution between the semiconductor space charge region and the Helmholtz layer.     

Ethanol electro-oxidation over Pt(h k l): Comparative study on the reaction intermediates probed by FTIR and SFG spectroscopies

We have investigated the adsorbed intermediates of ethanol electro-oxidation at Pt(1 1 1), Pt(1 0 0) and Pt(1 1 0) using FTIR and SFG spectroscopies. Mainly, we focus on the CO formation. The aim of the present work is to compare the responses coming from two different surface probes: FTIR spectroscopy and SFG spectroscopy. Between 1800 cm⁻¹ and 2300 cm⁻¹, our FTIR and SFG results are in good agreement. Specifically in the case of the ethanol/Pt(1 1 1) interface, the SFG spectroscopy presents higher sensibility to the interface response compared to the FTIR spectroscopy.