In situ STM study of underpotential deposition of bismuth on Au(1 1 0) in perchloric acid solution

The underpotential deposition (UPD) of Bi on Au(1 1 0) was investigated in HClO₄ solution using in situ scanning tunneling microscopy. The UPD of Bi occurred in three steps. A structure, in which Bi atoms formed dimers, was found for the first UPD adlayer. A (1 × 1) image was obtained by STM at the second UPD peak. For the third UPD peak, Bi atoms formed an incommensurate adlayer, and stripes of Bi were observed on terraces. After the third UPD, a structural reconstruction caused by adsorbed Bi was observed.     

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.     

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.     

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.     

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.     

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.     

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.     

Electrochemical characterization of kinked Pt(7 5 1) surface in acidic media

Kinked Pt(7 5 1) surface was prepared and its electrochemical behaviors under different pretreatment conditions in acidic media were investigated systematically by using cyclic voltammetry. The results demonstrated that the upper limit of potential scanning and cooling atmospheres after the Pt(7 5 1) having been flame-annealed significantly influence the voltammetric behavior of Pt(7 5 1) electrode. The electric charge of hydrogen adsorption-desorption slightly increases with increasing the upper limit of potential scanning. Different cooling atmospheres give rise impacts to the surface structure of Pt(7 5 1) electrode, but hardly change the amount of hydrogen adsorption-desorption sites on the electrode. In addition, the so-called third oxidation peak appears near −0.08 V in H₂SO₄ media and −0.05 V in HClO₄ solution because of the presence of (1 1 0) terrace sites on this surface, and a plausible mechanism for the formation of this current peak is discussed. The results are of importance in understanding the electroadsorption properties of the kinked Pt(7 5 1) surface, as well as in further exploration of this kinked electrode in electrocatalysis.     

Thermodynamic analysis of (bi)sulphate adsorption on a Pt(1 1 1) electrode as a function of pH

A complete thermodynamic study of (bi)sulphate adsorption on Pt(1 1 1) electrodes from solutions at four different pHs (pH 0.43, 2.1, 3.1 and 4.1) is reported. The effect of pH on the sum of the Gibbs excesses of sulphate and bisulphate species, standard Gibbs energies of adsorption and formal partial charge numbers is analyzed. The results provide relevant information on the nature of species involved in the different voltammetric features. The experiments at pH 0.43 were performed in a higher base electrolyte concentration (0.5 M), that allows the study of (bi)sulphate adsorption in a broader range of concentrations. Under these conditions, two adsorption steps are clearly defined, associated to two different voltammetric features, between 0.30 and 0.60 V and between 0.65 and 0.90 V (standard hydrogen scale, SHE). Once the pH is increased, a marked decrease in absolute value of the (bi)sulphate adsorption Gibbs energy is observed, concomitant with an increasing amount of OH co-adsorption.     

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.     

Electrosorbed carbon monoxide monolayers on Pt(1 1 1)

We review structures of high-density CO monolayers on Pt(1 1 1) surfaces in CO-saturated electrolytes or in gaseous CO at near atmospheric pressure, using surface X-ray scattering (SXS) and scanning tunneling microscopy (STM). In electrolytes, we confirmed the well-known (2 × 2)-3CO and (√19 × √19)-13CO structures and were able to study the transition between them. For gas-phase studies, we were able to stabilize extremely well-ordered CO monolayers by emersion transfer from an electrochemical cell. We found that the hexagonal close-packed (2 × 2)-3CO structure is the equilibrium phase at room temperature in ∼1 atm CO gas pressure. This commensurate (C) phase transforms continuously to an incommensurate (IC) phase at elevated temperature (a second-order phase transition). We also confirm that the (√19 × √19)-13CO structure is stable at lower CO partial pressure. This C phase transforms discontinuously to an IC phase (a first-order phase transition). A tentative phase diagram and a brief review of structure details of the (2 × 2)-3CO and (√19 × √19)-13CO phases will be presented.     

Resonance surface X-ray scattering technique to determine the structure of electrodeposited Pt ultrathin layers on Au(1 1 1) surface

It is demonstrated that resonance surface X-ray scattering (RSXS), in which incident X-ray energy close to the Pt L_III absorption edge (11.55 keV) is used, is very useful for the determination of the structure of electrodeposited Pt thin layers on a Au(1 1 1) surface. This technique was applied to characterize the structure of electrodeposited Pt layers on Au(1 1 1) substrates prepared under two extreme conditions, which are known to provide rough and atomically flat layers. Detailed structural information was obtained by RSXS measurements and it was confirmed that the structures of the Pt layers were as reported. Pt atoms of the atomically flat monolayer were found to be situated at the threefold hollow cubic closest packing (ccp) sites of the Au(1 1 1)-(1 × 1) surface.     

Oxygen electroreduction on Ag(1 1 1): The pH effect

The rotating ring disk method (RRDE) is applied to investigate the pH effect on oxygen reduction reaction (ORR) on Ag(1 1 1) single crystal surface in 0.1 M KOH and 0.1 M HClO₄. In 0.1 M KOH, the ORR proceeds through 4e⁻ reaction pathway with a very small (0.5-2.5%) peroxide formation in the entire potential range. In 0.1 M HClO₄ the onset potential for the ORR is shifted for ca. 400 mV toward the higher overpotentials compared to the 0.1 M KOH solution. At the low overpotentials, in 0.1 M HClO₄ the ORR proceeds entirely as a 2e⁻ process, i.e, 100% H₂O₂ formation. At higher overpotentials, the initial mixed a 2e⁻ and 4e⁻ reduction is followed by the potential region where the ORR proceeds entirely as a 4e⁻ process, with H₂O formation as a final product. The pH dependent shift in the onset of the ORR as well as the reaction pathway has been explained based on both: a thermodynamic analysis of pH independent rate determining step, and on the pH dependent change in availability of surface active sites and adsorption energies of molecular oxygen and reaction intermediates.     

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.     

A first principles analysis of the electro-oxidation of CO over Pt(1 1 1)

First principle density functional theoretical calculations carried out within a constant potential half-cell formalism were used to model the electro-oxidation of CO over Pt(1 1 1). The method involves tuning the potential by the addition or removal of electrons from the system. The free energy for different adsorbed species within the double-layer is analyzed over a range of different potentials to establish the lowest energy states and the reaction energies that connect these states. The potentials are calculated based on a novel double-reference approach [J.S. Filhol, M. Neurock, Angew. Chem. Int. Ed. 45 (2006) 402] discussed earlier. The potential-dependent reaction energies are reported for the elementary steps of water activation in the presence of co-adsorbed CO and CO oxidation over the model Pt(1 1 1) surface. The potential-dependent activation barriers are computed for the key elementary steps in CO oxidation to develop a detailed reaction energy profile as a function of electrode potential. The results suggest that the coupling of co-adsorbed CO and OH controls the rate. Water activation, however, is necessary to supply a critical coverage of the surface OH oxidant.     

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.     

Kinetics of adenine adsorption on Au(1 1 1) electrodes: An impedance study

The adsorption/desorption kinetics of adenine on Au(1 1 1) electrodes is studied by Electrochemical Impedance Spectroscopy (EIS) in 0.5 M NaF solutions at four adenine concentrations. The experimental procedure is designed in order to obtain impedance data unaffected by surface reconstruction on the entire potential region of adsorption. The frequency dispersion of the impedance at potentials of the adsorption region has been analysed according to the Frumkin-Melik-Gaykazyan adsorption theory without any “a priori” assumption about the potential dependence of the adsorption rate constant. The analysis provides the values of the adsorption capacitance, C_ad, adsorption resistance, R_ad and the Warburg coefficient, σ_ad, at every potential, and from them the relaxations times τ_H and τ_D. A mixed adsorption-diffusion control has been detected and the specific rate constant of adsorption has been obtained in a wide potential region.     

Vibrational Stark tuning rates from periodic DFT calculations: CO/Pt(1 1 1)

DFT periodic calculations have been used to study the influence of an external electric field on the adsorption of CO on Pt(1 1 1). Particular attention has been focused on the determination of the CO and metal-CO vibrational Stark tuning rates. Stark tuning rates have been calculated at various CO coverages; a linear dependence between the CO Stark tuning rate and the CO surface coverage has been found. We have calculated a value of 68.94 cm⁻¹/(V/Å) for the zero-coverage limit CO Stark tuning rate, in good agreement with the experimental value of 75 ± 9 cm⁻¹/(V/Å). Like the CO Stark tuning rate, the metal-CO vibrational Stark tuning rate also increases as CO surface coverage decreases. In addition, we have found (at 0.25 ML) that the CO Stark tuning rate is similar at different adsorption sites, being only slightly larger at high-coordinated sites. CO vibrational Stark tuning rates of 45.58, 47.96, 47.61 and 48.49 cm⁻¹/(V/Å) have been calculated for ontop, bridge, hcp and fcc hollow sites, respectively. Calculations at high coverage using a (2 × 2)-3CO model yield a CO Stark tuning rate of 21.08 and 25.93 cm⁻¹/(V/Å) for ontop and three-fold hollow CO, respectively. These results show that the CO Stark tuning rate for CO adsorbed at high coordinated sites is only slightly larger than that at ontop sites. This result is in contradiction with experiments, which reported larger CO Stark tuning rates at high-coordinates sites than at ontop sites. Furthermore, the calculated metal-CO stretch is larger for ontop sites than for high-coordinated sites; this result is in disagreement with previous DFT cluster model calculations. Unfortunately, there is not experimental information available to support either result. Finally, we have also studied the CO adsorption site preference dependence on electric fields. We have found that CO adsorbs preferentially at high coordinated sites at more negative fields, and at ontop sites at more positive fields, in agreement with previous experiments and DFT cluster model calculations.     

Alloy formation during the electrochemical growth of a Ag-Cd ultrathin film on Au(1 1 1)

The electrodeposition of a Ag/Cd ultrathin film on a Au(1 1 1) surface and the formation of a surface alloy during this process have been studied using classical electrochemical techniques and in situ Scanning Tunneling Microscopy (STM). The films were obtained from separate electrolytes containing Ag⁺ or Cd²⁺ ions and from a multicomponent solution containing both ions. First, the polarization conditions were adjusted in order to form a Ag film by overpotential deposition. Afterwards, a Cd monolayer was formed onto this Au(1 1 1)/Ag modified surface by underpotential deposition. The voltammetric behavior of the Cd UPD and the in situ STM images indicated that the ultrathin Ag films were uniformly deposited and epitaxially oriented with respect to the Au(1 1 1) surface. Long time polarization experiments showed that a significant Ag-Cd surface alloying accompanied the formation of the Cd monolayer on the Au(1 1 1)/Ag modified surface, independent of the Ag film thickness. In the case of an extremely thin Ag layer (1 Ag ML) the STM images and long time polarization experiments revealed a solid state diffusion process of Cd, Ag, and Au atoms which can be responsible for the formation of different Ag-Cd or Au-Ag-Cd alloy phases.