Adsorption of 2-X-benzoic acids (X = fluoro, chloro, and bromo) on Au(1 0 0) electrode in acidic media studied by IRAS

Adsorption behaviors of 2-fluoro-, 2-chloro-, and 2-bromobenzoic acids on Au(1 0 0) electrode in 0.1 M HClO₄ have been investigated by using in situ reflection adsorption IR spectroscopy and differential capacity measurements. It is found for the 2-substitued benzoic acids that the flat lying adsorbed species is present at negative potentials, and the vertically adsorbed benzoate with both oxygen atoms oriented toward the metal surface is present at positive potentials. A new adsorbed state due to the vertical orientation was observed around 0.75 V only in 2-fluorobenzoic acid solution, as well as the case of benzoic acid. This indicates that the new band is due to the formation of an ordered adsorption layer of the vertical 2-fluorobenzoate, and the formation of the arrangement adsorption is dependent on the size of the adsorbed molecule.     

Two types of vertically adsorbed 3-pyridinecarboxylate on Au(1 1 1), Au(1 0 0) and Au(1 1 0) electrodes

3-Pyridinecarboxylic acid (3-PC) adsorbed on low index face electrodes in NaF solution were investigated using in situ Fourier transform-infrared (FTIR) spectroscopy and differential capacity measurements. Two types of vertically adsorbed 3-PC were confirmed on the electrodes, while flat-lying adsorbed species were not observed at the potentials measured. At negative potentials, 3-PC molecules adsorb vertically on the electrode via the lone pair electrons of the pyridine ring nitrogen atom, and at positive potentials, 3-PC adsorbs vertically via the two oxygen atoms of the carboxyl group.     

Adsorption behavior of terephthalic acid on Au(1 0 0), Au(1 1 1) and Au(1 1 0) electrodes in neutral solution

Adsorption of terephthalic acid on Au(1 0 0), Au(1 1 1) and Au(1 1 0) electrodes in neutral solution has been investigated using in situ Fourier transform infrared (FT-IR) spectroscopy, differential capacity measurements and scanning tunneling microscopy (STM). At negative potentials, the terephthalate anions in solution adsorb in a flat orientation onto the electrode via the π electrons of the aromatic ring. At positive potentials, the terephthalate anions adsorb in a vertical orientation via the oxygen atoms of one of the carboxyl groups as a form of dianion. At more positive potentials, the anions adsorb in a vertical orientation as a form of hydrogen terephthalate. For the three electrodes examined, the overtone and/or combination bands, due to vertically oriented hydrogen terephthalate, were observed at 2642 and 2517 cm⁻¹, respectively. For the Au(1 1 1) electrode, STM observations indicated a flat orientation in the form of terephthalic acid.     

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.     

Potential-induced lifting of the Au(1 0 0)-surface reconstruction studied with DFT

The potential-induced surface reconstruction of Au(1 0 0) was studied by a combination of density functional theory (DFT) and thermodynamic considerations. On the basis of realistic models for the reconstructed surface ((5 × 1) and (7 × 1) unitcells), in which a hexagonal overlayer was located above the bulk-truncated Au(1 0 0) surface, we found that applying an electric field causes a slight lifting of the overlayer, leading to a stronger surface buckling than without electric field. Using experimental cyclovoltammetry measurements we were able to relate the electric field applied in our calculations to the electrode potential. The resulting surface free energy curves showed a transition from the hexagonal-reconstructed surface phase to the non-reconstructed structure between +0.5 and +0.6 V (versus SCE-electrode) depending on the ion concentration in the electrolyte. Higher potentials values are required at lower electrolyte concentrations.     

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.     

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.     

The interface between Au(1 1 1) and an ionic liquid

The electrochemical interface between Au(1 1 1) and 1-butyl-3-methyl-imidazolium hexafluorophosphate has been studied by cyclic voltammetry and electrochemical impedance spectroscopy in a potential range, which might be considered to be the double-layer charging region for Au(1 1 1) is such an environment. The corresponding equivalent circuit is given by a capacity in parallel to a constant phase element (CPE). The high-frequency value of the capacity - that is, the double-layer capacitance - is about 6-7 μF/cm² over the whole potential range under study, whereas the CPE peaks at a potential, which coincides with the potential of zero total charge (pztc), as determined by immersion experiments. This latter element expresses the kinetics of the re-structuring of the interfacial region. In situ STM measurements reveal marked structural differences positive and negative of the pztc.     

Development of growth cycle for antimony telluride film on Au (1 1 1) disk by electrochemical atomic layer epitaxy

Electrochemical deposition of Sb₂Te₃ thin film on Au (1 1 1) disk via the route of electrochemical atomic layer epitaxy (ECALE) is described in this paper. Electrochemical aspects of Te and Sb on Au, Te on Sb-covered Au, and Sb on Te-covered Au were studied by means of cyclic voltammetry and coulometry. The apparent variation of coverage for Te or Sb on hetero-covered substrate is explained by considering the thermodynamic process of compound formation. A steady ECALE deposition for Sb₂Te₃ compound could be attained after negatively adjusting the underpotential deposition (UPD) potentials of Sb and Te on Au in steps over the initial 40 cycles, and the potentials could be kept constant for the following deposition. A 200-cycle deposit, which was grown with the steady deposition potentials, was proved to be a single phase Sb₂Te₃ compound by X-ray diffraction analysis. The 2:3 stoichiometric ratio of the deposit was further verified by energy dispersive X-ray (EDX) quantitative analysis. The p-type semiconductive property was demonstrated by measurements of the Seebeck coefficient and the electrical resistivity with a value of 145 μV/K and 9.37 μΩm, respectively. The morphologies of deposits with various growth cycle numbers were observed with FE-SEM. The evolvement mechanism of the morphology was investigated. The results show that the morphology of deposit has changed after initial potential adjustment and numberless thin sheets appeared and grew uprightly during the continuous cycle process. Fourier transform infrared spectroscopy (FTIR) absorption measurements suggested a band gap of 0.26 eV in very good agreement with literature reports for Sb₂Te₃ single crystals.     

Oxidation of formaldehyde and ethanol on Au(1 1 1) and Au(1 1 1) modified by spontaneously deposited Ru in sulfuric acid solution

The oxidation of formaldehyde and ethanol on both pure Au(1 1 1) and Au(1 1 1) modified by approximately 0.3 monolayer (ML) of spontaneously deposited Ru was studied by cyclic voltammetry (CV) in 0.5 M H₂SO₄ solution containing either 0.25 M formaldehyde or 0.35 M ethanol. In situ scanning tunneling microscopy (STM) and CV were employed to characterize the Au(1 1 1) and Ru/Au(1 1 1) surfaces. The oxidation of HCHO on Ru/Au(1 1 1) commences at 0.1 V more negative potential than on pure Au(1 1 1). From 0.25 to 0.55 V vs. (Ag/AgCl), the reaction occurs with increasing current, showing a peak at a potential of 0.43 V. It is assumed that the increasing anodic activity of the Ru/Au(1 1 1) surface is associated with the oxidation of some reaction intermediates, facilitated by the presence of Ru in its metallic state. On the other hand, the oxidation of ethanol on Ru/Au(1 1 1) commences at 0.1 V more positive potential than on pure Au(1 1 1), and proceeds in the potential region from 0.2 to 0.5 V with significantly smaller currents, showing a peak at 0.43 V. This inhibiting effect is explained by the deactivation of the most active Au(1 1 1) step sites by high coverage with Ru islands. The appearance of a small peak at 0.43 V is most likely associated to the oxidation of some intermediates during ethanol oxidation at the Ru/Au step sites formed on the Au(1 1 1) terraces by the presence of a small coverage with Ru islands.     

Overpotential deposition of copper on an iodine-modified Au(1 1 1) electrode

Cyclic voltammetry, chronoamperometry and in situ electrochemical scanning tunneling microscopy were used to study the kinetics of nucleation and crystal growth during the initial stages of copper overpotential deposition (OPD) on a previously iodine-modified Au(1 1 1) electrode, from an aqueous solution 10⁻³ M CuSO₄ in 0.05 M H₂SO₄. The starting potential during step experiments was chosen in the region where the gold electrode was completely free of the copper deposit. The recorded current transients for copper deposition onto the iodine-modified Au(1 1 1) electrode surface appear to be very complex, with the unusual presence of two or more current maxima. A new method was used for quantitative evaluation of current transients that involves the transition UPD-OPD, developed by our group [M. Palomar-Pardavé, I. González, N. Batina, J. Phys. Chem. B 104 (2000) 3545], was used for the quantitative interpretation. Our results show that, within a single current transient, copper adsorption and two types of nucleation process: two-dimensional (2D) and three-dimensional (3D) limited by lattice incorporation of copper adatoms and diffusion of Cu(II) ion, respectively, take place simultaneously. STM images revealed the enhanced growth of 3D copper on edge of I-Au(1 1 1) during the early stages of deposition. Moreover, our results strongly suggest that the iodine adlayer is constantly present, even after the striping Cu that was overpotential deposited.     

Electrochemical growth and dissolution of Ni on bimetallic Pd/Au(1 1 1) substrates

In this work we study the electrochemical growth and dissolution of a Ni on Pd-Au(1 1 1) bimetallic surfaces using in situ scanning tunnelling microscopy. We also compare Ni deposition on monometallic electrodes, i.e. Au(1 1 1) and Pd(1ML)/Au(1 1 1), using electrochemical characterizations. Results evidence that the first Ni monolayer grows preferentially on Au(1 1 1) in a wide potential range, and that a full Ni monolayer covering the entire Pd-Au surface can be selectively dissolved from Pd islands. No such selectivity is observed upon growth of subsequent Ni atomic planes. We demonstrate that the Ni-substrate interactions play a key role in the above mentioned selectivity. The binding energy of Ni to Pd is found to be 80 meV smaller than of Ni to Au. The sign and the amplitude of this difference are discussed in light of the d band filling of the Pd-Au(1 1 1) bimetallic surface and the presence of adsorbed H on Pd before deposition.     

CO monolayer oxidation on stepped Pt(S) [(n − 1)(1 0 0) × (1 1 0)] surfaces

The electrochemical oxidation of CO has been studied on Pt(S)[(n − 1)(1 0 0) × (1 1 0)] electrodes to investigate the effect of the step density in the reaction. This series shows two different trends for long (n ≥ 7) and short terraces. For long terraces, the voltammetric peak shifts towards higher potential as the step density increases, unlike the behaviour observed for other stepped surfaces, which exhibit the opposite behaviour in agreement with the Smoluchowski effect. For short terraces, the “normal” behaviour is observed, that is, as the step density increases the peak shifts towards lower potentials. Chronoamperometric measurements were used to determine rate constants and Tafel slopes using the mean field Langmuir-Hinselwood kinetics. Rate constants follow the same trends as the peak potentials in voltammetry. A Tafel slope of 75 ± 4 mV has been obtained for the surfaces with long terraces whereas a value of the surfaces with short terraces showed a value of 100-120 mV is obtained. This change of slopes is interpreted as a change in the electrochemical behaviour of the species involved in the mechanism, probably, a change in the adsorption isotherm of adsorbed OH. Pt(5 1 0) electrode exhibits an intermediate behaviour between those of long and short terraces with two different peaks that can be associated with both behaviours previously described.     

Rhodium deposition onto a 4-mercaptopyridine SAM on Au(1 1 1)

The application of a recently developed method for the deposition of Pd and Pt on top of a SAM, has been successfully extended to Rh, thus proving the versatility of the new concept. Experimental evidence from cyclic voltammetry, in situ STM and ex situ X-ray photoemission spectroscopy is presented for the deposition of monoatomic high rhodium islands onto a 4-mercaptopyridine self-assembled monolayer on a Au(1 1 1) electrode. By repetitive complexation of the Rh ions to the ring-nitrogen and reduction in a Rh-ion free solution, an almost completely covered SAM is obtained. The consequences of making contacts for molecular electronics are briefly discussed.     

X-ray absorption spectroscopy characterization of Zn underpotential deposition on Au(1 1 1) from phosphate supporting electrolyte

Zn K-edge X-ray absorption spectroscopy (XAS) has been used to investigate the structure of Zn monolayers prepared on Au(1 1 1) electrodes via underpotential deposition (UPD) from phosphate supporting electrolyte. Theoretical modeling of the XAS data indicates that the Zn adatoms adopt a commensurate (√3 × √3)R30° (θ_sc = 0.33) adlayer structure and reside within the 3-fold hollow sites of the Au(1 1 1) surface. Meanwhile, phosphate counter-ions co-adsorb on the UPD adlayer and bridge between the Zn adatoms in a (√3 × √3)R30° (θ_sc = 0.33) configuration, with each phosphorous atom residing above a vacant 3-fold hollow site of the Au(1 1 1). Significantly, this surface structure is invariant between the electrochemical potential for UPD adlayer formation and the onset of bulk Zn electrodeposition. Analysis of the Zn K-edge absorption onset also presents the possibility that the Zn adatoms do not fully discharge during the process of UPD, which had been proposed in prior voltammetric studies of the phosphate/Zn(UPD)/Au(1 1 1) system.     

Electrodeposition of copper on Ru(0 0 0 1) in sulfuric acid solution: Growth kinetics and nucleation behavior

The electrodeposition of Cu on Ru(0 0 0 1) from 0.1 M CuSO₄/0.5 M H₂SO₄ solution has been studied by cyclic voltammetry, current-time transient measurements, and by in situ electrochemical atomic force microscopy (EC-AFM). Cyclic voltammetry measurements show that the as-prepared Ru(0 0 0 1) electrode exhibits a UPD peak, while EC-AFM data indicate a broadly terraced surface with step heights of atomic dimensions. Kinetic data show that the electrodeposition/nucleation process is not well described by 3D or 2D nucleation models. The EC-AFM data show that at potentials near the OPD/UPD threshold, Cu crystallites exhibit pronounced growth anisotropy, with lateral dimensions greatly exceeding vertical dimensions. AFM data also show that deposition at more cathodic potentials result in smaller crystallites.     

Effects of concentration and temperature on the formation process of decanethiol self-assembled monolayer on Au(1 1 1) followed by electrochemical reductive desorption

The formation process of self-assembled monolayer (SAM) of decanethiol (C10SH) on Au(1 1 1) single crystal electrode has been investigated for wide range of C10SH concentration (0.1-500 μM) and temperature (253-298 K). The amount and quality of C10SH SAM were determined from area and position, respectively, of reductive desorption peak of the SAM modified Au(1 1 1) electrode measured in 0.5 M KOH aqueous solution. The kinetic analysis indicates that SAM formation proceeded by two steps, diffusion-limited physisorption followed by chemisorption.     

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.     

The adsorption of Sn on Pt(1 1 1) and its influence on CO adsorption as studied by XPS and FTIR

The coverage of Sn on Pt(1 1 1) which is obtained by electrochemical deposition from 5×10⁻⁵ M Sn²⁺ in 0.5 M H₂SO₄ has been determined by XPS for different deposition times. Complete suppression of hydrogen adsorption corresponds to a coverage of ?_max=0.35 (Sn to surface Pt atoms).Co-adsorption of CO with Sn on Pt(1 1 1) has been studied by FTIR spectroscopy. The IR spectra of the stretching vibration of CO can be interpreted in terms of the vibrational signature of the Pt(1 1 1)/CO system and no vibrational bands associated with CO on Sn are detected. At high Sn coverages, the 1840 cm⁻¹ band associated with bridge-bonded CO and the 2070 cm⁻¹ band assigned to on-top CO are present, however, no hollow site adsorption which is characterized by the 1780 cm⁻¹ band is revealed within the resolution of the experiment. This vibrational signature corresponds to a less compressed adlayer compared to the (2×2)-3CO saturation structure on Pt(1 1 1). At lower Sn coverages, signatures from both the compressed and the less compressed CO adlayer structures are seen in the spectra. From earlier structural and electrochemical studies it is known that Sn is adsorbed in 2D islands and influences CO molecules in its neighbourhood electronically. This leads to a disappearance of the IR band from CO adsorbed in the hollow site at high Sn coverages and to higher population of the weakly adsorbed state of CO for all Sn-modified surfaces, i.e. a relative increase of the amount of CO oxidised at low potentials. In addition to this electronic effect, Sn also exerts a co-catalytic effect at low Sn coverages on that part of CO which is adsorbed at a larger distance from Sn due to a bi-functional mechanism. The IR spectra shows for the Sn-modified Pt(1 1 1) surface that the transition from the compressed CO adlayer which is characterized by the hollow site adsorption of CO to the less compressed one which exhibits a characteristic band associated with bridge-bonded CO occurs already at 250 mV instead of 400 mV.