Bulk CO oxidation on platinum electrodes vicinal to the Pt(111) surface

Bulk CO oxidation has been studied on platinum stepped surfaces belonging to the series Pt(S)[n(111) × (111)], using a hanging meniscus rotating disk electrode (HMRDE) configuration. The general shape of the voltammograms is not significantly affected by the presence of the steps. However, the curves shift towards negative values as the step density increases. Thus, in the positive-going scan, a linear relationship is observed for the dependence of the potential for the ignition peak vs the step density for surfaces with terraces wider than five atoms, shorter terraces deviate from this behavior. In the negative-going scan, a similar situation is observed for the potential where the current drops to zero. In this case, Pt(111) electrode also deviates from the expected behavior because of the formation of the ordered bisulfate adlayer on the electrode. The anion readsorption process is also observed by recording the HRMDE voltammograms at a high scan rate. All these results have been analyzed in light of a common mechanism, discussing the possible role of the steps in the stability and reactivity of the CO adlayer. In memoriam of Francisco C. Nart, an excellent scientist, colleague, and friend.     

Adsorption isotherm of CO on Pt(111) electrodes.

We have determined, for the first time, the equilibrium CO coverage of Pt(111) electrodes at room temperature in 0.1 M H(2)SO(4) as a function of the CO partial pressure using CO-stripping cyclic voltammetry. Fourier-transform infrared (FT-IR) spectroscopy was used to confirm qualitatively the coverage values obtained.     

In-situ IR spectroscopy with a gas diffusion cell CO adsorption and oxidation on Pt

A gas diffusion cell allowing ready access of reactant to the electrode through the thin electrolyte layer has been used to obtain in-situ infra-red spectra from adsorbed CO on Pt under conditions of sustained reaction. The potential dependence of CO oxidation and adsorption and the inhibition of CO oxidation by adsorbed CO have been investigated.     

CO oxidation on Pt-modified Rh(111) electrodes.

The CO electro-oxidation reaction was studied on platinum-modified Rh(111) electrodes in 0.5 M H2SO4 using cyclic voltammetry and chronoamperometry. The Pt-Rh(111) electrodes were generated during voltammetric cycles at 50 mV s(-1) in a 30 microM H2PtCl6 and 0.5 M H2SO4 solution. Surfaces generated by n deposition cycles were investigated (Ptn-Rh(111) with n=2, 4, 6, 8, 10, and 16). The blank cyclic voltammograms of these surfaces are characterized by a pronounced sharpening of the hydrogen/(bi)sulfate adsorption/desorption peaks, typical for Rh(111), and the appearance of contributions between 0.1 and 0.4 V, which were ascribed to hydrogen/(bi)sulfate adsorption/desorption on the deposited platinum. At higher potentials, the surface oxidation of Rh(111) is enhanced by the presence of platinum. The structure of the Pt-modified electrodes was investigated by STM imaging. At low Pt coverages (Pt2-Rh(111)), monoatomically high islands are formed, which grow three dimensionally as the number of deposition cycles increases. After eight cycles, the monolayer islands have grown in diameter and range from mono- to multiatomic height. At even higher Pt coverage (Pt16-Rh(111)), the islands grow to particles of approx. 10 nm in diameter, which are 5-6 atoms high. The CO stripping voltammetry on these surfaces is characterized by two peaks: A low-potential, structure-insensitive peak, ascribed to CO reacting at the platinum monolayer islands, whose onset is shifted 150, 250, and 100 mV negatively with respect to pure Rh(111), Pt(111), and polycrystalline Pt, respectively, indicating the enhanced CO electro-oxidation properties of the Pt overlayer system. A peak at higher potentials displays strong structure sensitivity (particle-size effect) and was ascribed to CO reacting on the islands of multiatomic height. Current-time transients recorded on the surface with the highest amount of monolayer islands (Pt4-Rh(111)) also indicate enhanced CO-oxidation kinetics. Comparison of the Pt4-Rh(111) current-time transients recorded at 0.635, 0.675, and 0.750 V versus RHE (reversible hydrogen electrode) with those of pure Rh(111) and Pt(111) shows greatly reduced reaction times. A Cottrellian decay at long times indicates surface-diffusion-limited CO oxidation on the bare Rh(111) surface, while the peak visible at short times is indicative of CO reacting at the monolayer platinum islands. The results presented here show that, as indicated by density functional theory (DFT) calculations, the CO-adlayer oxidation for this system is enhanced compared to both pure Rh and Pt.     

In-situ infrared study of the adsorption and oxidation of oxalic acid at single-crystal and thin-film gold electrodes: a combined external reflection infrared and ATR-SEIRAS approach

The adsorption and oxidation of oxalic acid at gold electrodes were studied by in-situ infrared spectroscopy. External reflection experiments carried out with gold single-crystal electrodes were combined with internal reflection (ATR-SEIRAS) experiments with gold thin-film electrodes. These gold thin films, with a typical thickness of ca. 35 nm, were deposited on silicon substrates by argon sputtering. As previously reported for evaporated gold films, the voltammetric curves obtained in sulfuric acid solutions after electrochemical annealing show typical features related to the presence of wide bidimensional (111) domains with long-range order. The in-situ infrared data collected for solutions of pH 1 confirmed the potential-dependent adsorption of either oxalate (Au(100)) or a mixture of bioxalate and oxalate (Au(111), Au(110), and gold thin films) anions in a bidentate configuration. The better signal-to-noise ratio associated with the SEIRA effect in the case of the gold thin-film electrodes allows the observation of the carbonyl band for adsorbed bioxalate that was not detected in the external reflection experiments. Besides, additional bands are observed between 2000 and 3000 cm(-)(1) that can be tentatively related to the formation of hydrogen bonds between neighboring bioxalate anions. The intensities of these bands decrease with increasing solution pH values, disappearing for pH 3 solutions in which adsorbed oxalate anions are the predominant species. The analysis of the intensities of the nu(s)(O-C-O) and nu(C-OH) + delta(C-O-H) bands for adsorbed oxalate and bioxalate, respectively, suggests that the pK(a) for the surface equilibrium between these species is significantly lower than that for the solution equilibrium.     

Electrocatalytic properties of Pt(111), Pt(332), Pt(331) and Pt(110) single crystal electrodes towards ethylene glycol oxidation in sulphuric acid solutions

In the present paper four platinum single crystal electrodes, two basal planes of Pt(111) and Pt(110) and two stepped surfaces of Pt(332) and Pt(331), were prepared and used in the study of electro-oxidation of ethylene glycol (EG). All of these Pt single crystal electrodes belong to the [1 0] zone of crystallography, and exhibit on their surface (111) symmetry sites or certain combinations of terraces of (111) symmetry with steps of (111) symmetry type. It has been found that as a result of a favourable steric matching of surface sites the Pt(110) electrode manifested a higher activity both for EG dissociative adsorption and oxidation than that of the Pt(111) electrode. The stepped surfaces of Pt(332) and Pt(331) operated with certain combinations of characteristics of Pt(111) and Pt(110). The best electrocatalytic properties have been obtained with a Pt(331) electrode, and this is attributed both to the configuration of the atomic arrangement and to the stability of this surface.In summary, the above results show that the performance of a given Pt single crystal electrode in EG oxidation at a potential below 1.0 V may be evaluated by three factors.

1. (1) The ability to resist self-poisoning (AB) which describes the difficulty of EG dissociative adsorption on the electrode surface.

2. (2) The activity for EG oxidation (AC). In considering that the threshold potential for EG oxidation on all electrodes is at 0.3 V and that the self-poisoning is encountered in PGPS, the activity for EG oxidation may be reasonably characterized by the intensity of the peak current acquired in NGPS near 0.6 V, which corresponds to the maximum current of EG oxidation on an activated (non-poisoned) surface of the electrode.

3. (3) The stability of activity during potential cycling (SA) between 0.05 and 1.0 V, which describes the resistance to the decrease of intensity of the EG oxidation current during voltammetric cycling.

For the two basal planes studied, the AB and SA of Pt(111) are higher than those of Pt(110), but its AC is much lower than that of Pt(110). These differences are clearly related to the surface atomic arrangement of the two electrodes. As has been discussed above, the surface of Pt(111) is atomically smooth and stable during voltammetric cycling. The surface of Pt(110) presents, however, atomic steps and is reconstructed under experimental conditions, i.e. certain steric configurations are encountered on the Pt(110) surface. The high AC and the low AB may be assigned to a favourite stereographic matching during EG adsorption and oxidation on Pt(110).The two electrodes with stepped surfaces, Pt(332) and Pt(331), contain different densities of (110) sites, which are formed on the border between terrace and step, as shown in Fig. 8. The AB of these two electrodes has been observed at a moderate range between that of Pt(111) and the AB of Pt(110). With a majority of (111) sites on its surface, the electrode of Pt(332) operates at a relatively higher AC than Pt(111) does, and its SA is not as good as that of Pt(111) but is much better than the SA of a Pt(110) electrode. In all cases the highest AC and SA are obtained with a Pt(331) electrode. It may be seen from the profile of a (331) plane (shown by the cross-section of A-A in Fig. 8) that all atoms on the top of the surface participated in forming (110) sites, and the atom on the step has two functions — one is to form a (110) site with an atom located in the terrace of second layer and the other is to form a (111) site in the terrace of the same layer. It has been mentioned in the above discussions that the Pt(110) electrode keeps a higher AC due to favourite stereographic matching in EG adsorption and oxidation, but its SA is the worst, due to the instability of the surface. The highest AC and SA obtained with Pt(331) may be ascribed not only to the high density of (110) sites existing on the surface, but also to the stabilization of these (110) sites, and moreover, the synergy generated by the atomic arrangement of the Pt(331) surface may also contribute to the performance of the Pt(331) electrode.     

Chiral templating of surfaces: adsorption of (S)-2-methylbutanoic acid on Pt(111) single-crystal surfaces

The adsorption and thermal chemistry of (S)-(+)-2-methylbutanoic acid ((S)-2MBA) on Pt(111) single-crystal surfaces was characterized by using temperature programmed desorption (TPD) and reflection-adsorption infrared (RAIRS) spectroscopies. Particular emphasis was placed on the characterization of the chiral superstructures formed upon the deposition of the submonolayer coverages of enantiopure (S)-2-methylbutanoate species that are produced by thermal dehydrogenation of the (S)-2MBA. The enantioselectivity of the empty platinum sites left open on those structures were identified by their difference in behavior toward the adsorption of the two enantiomers of propylene oxide. It was found that a significant enhancement in adsorption is possible on surfaces with the same chirality of the probe molecule, specifically that the uptake of (S)-propylene oxide is larger than that of (R)-propylene oxide on (S)-2-methylbutanoate adsorbed layers. This contrasts with the lack of enantioselectivity previously reported for the same adsorbate on Pd(111). Detectable differences in adsorption energetics of (R)- vs (S)-propylene oxide on the (S)-2-methylbutanoate/Pt(111) overlayers were measured but deemed not to be the controlling factor in the enantioselectivity reported in this system.     

Kinetics of dissociative adsorption of formic acid on Pt(100), Pt(610), Pt(210) and Pt(110) single-crystal electrodes in perchloric acid solutions

The kinetics of dissociative adsorption of HCOOH on Pt(100), Pt(610), Pt(210) and Pt(110) single-crystal electrodes has been investigated. The oxidation of dissociative adsorbate (DA) derived from the dissociative adsorption of HCOOH was used as a probe reaction together with the potential-step technique of short time windows. The quantity Q_ad of DA produced at a given potential E_ad and in a defined time window t_ad of adsorption has been determined systematically. At fixed t_ad peaked curves of Q_ad versus E_ad in the potential range between −0.25 and 0.25 V/SCE have been obtained on all four electrodes. The maximum rate of dissociative adsorption of HCOOH decreases in the order Pt(110) Pt(210) Pt(610) Pt(100).     

Adsorption of anions on ultra-thin metal deposits on single-crystal electrodes: II: Voltammetric and radiochemical study of bisulfate adsorption on Pt(111) and Pt(poly) electrodes containing copper adatoms

The formation of ultra-thin metal deposits of copper on Pt(111) and polycrystalline platinum electrodes, as well as the adsorption of bisulfate on the copper-covered platinum surfaces, were studied by cyclic voltammetry and radioactive labeling. The highest charge obtained by voltammetry in the underpotential stripping range nearly corresponds to a close-packed monolayer of copper. The radioactive labeling data indicate that there are inactive and active copper adlayers toward bisulfate adsorption. The transition from inactive to active behavior is interpreted in terms of an increase in surface—bisulfate interactions at the expense of surface—perchlorate interactions. Based on recent X-ray absorption near-edge spectroscopy (XANES) analysis of copper deposition onto platinum, the site for bisulfate adsorption is most probably a Cu⁺ surface species. Combining this spectroscopic information with coulometry shows that an additional electron is confined to surface platinum atom(s) covered by the copper species. The copper film attains bulk copper properties when approximately 2.5 monolayers of copper are deposited.     

Lattice strain effects on CO oxidation on Pt(111)

Surface strain plays a major role in determining the rate limiting step and catalytic activity of platinum for CO oxidation.     

Study of the charge displacement at constant potential during CO adsorption on Pt(110) and Pt(111) electrodes in contact with a perchloric acid solution

A new electrochemical approach has been made, employing the current—time transient responses when a CO adlayer is formed at a platinum electrode at various controlled potentials where CO oxidation does not take place. The case of Pt(110) is compared with those of Pt(111) and Pt(111) disordered after ten cycles of oxygen adsorption—desorption. In order to avoid interference with anion-specific adsorption, the study was carried out in a perchloric acid solution. There is good agreement between the charge measured by voltammetry in the absence of CO and the charges measured during the current—time transients. This is indicative that the latter charges are produced by the displacement of the species at the interface as a result of CO adlayer formations. The sign of the current transient has been found to depend on the potential at which CO adsorption is carried out. This dependence may be related to the nature of species which are present in the interfacial region, providing new complementary information that voltammetry cannot yield.     

The effect of the cooling atmosphere in the preparation of flame-annealed Pt(111) electrodes on CO adlayer oxidation

The effect of the cooling atmosphere on the rate of CO adlayer oxidation on flame-annealed Pt(111) has been studied. Cooling of a flame-annealed Pt(111) electrode in air results in a higher amount of crystalline defects compared to Pt(111) cooled in a hydrogen–argon stream. Although the blank profiles in 0.5 M H₂SO₄ of Pt(111), cooled in air and under oxygen exclusion, are virtually identical, CO adlayer oxidation occurs at significantly lower overpotentials on the former electrode. Three voltammetric peaks are observed for subsaturated CO adlayer oxidation on Pt(111), cooled in Ar+H₂ mixture, while only two peaks develop in the case of a Pt(111) surface cooled in air. Random crystalline defects, introduced via cooling of a flame-annealed Pt(111) in air, enhance CO adlayer oxidation, and apparently also suppress the third high-potential peak observed on a quasi-perfect (111) surface. The high sensitivity of the saturated CO adlayer oxidation to the presence of crystalline defects on Pt(111) can hence be used as a straightforward, sensitive, though qualitative method to assess the degree of crystalline order of the electrode.     

Effect of deposited bismuth on the potential of maximum entropy of Pt(111) single-crystal electrodes

The effect of bismuth adsorption on the entropy of formation of the double layer on Pt(111) electrodes has been studied with the laser-induced temperature jump method. The coulostatic response to the temperature change induced by pulsed laser illumination allows the estimation of the sign and magnitude of the thermal coefficient of the potential drop at the interphase. This is related to the entropy of formation of the double layer, and the particular potential where this thermal coefficient becomes zero can be identified with the potential of maximum entropy of double-layer formation (pme). The effect of bismuth adsorption on the pme depends on the adatom coverage. At high coverages, a marked decrease of the pme is observed. This trend follows the change of the potential of zero charge expected from work function measurements, and it is likely due to the change in the orientation of solvent molecules induced by surface dipoles originated between the adatom and the substrate. At low coverage, the pme increases with the bismuth coverage. The disruption of the water structure due to the presence of the bismuth adatoms is tentatively proposed as the most likely explanation for this behavior.     

Mechanism of CO oxidation on Pt(111) in alkaline media

Electrochemical techniques, coupled with in situ scanning tunneling microscopy, have been used to examine the mechanism of CO oxidation and the role of surface structure in promoting CO oxidation on well-ordered and disordered Pt(111) in aqueous NaOH solutions. Oxidation of CO occurs in two distinct potential regions: the prepeak (0.25-0.70 V) and the main peak (0.70 V and higher). The mechanism of reaction is Langmuir-Hinshelwood in both regions, but the OH adsorption site is different. In the prepeak, CO oxidation occurs through reaction with OH that is strongly adsorbed at defect sites. Adsorption of OH on defects at low potentials has been verified using charge displacement measurements. Not all CO can be oxidized in the prepeak, since the Pt-CO bond strength increases as the CO coverage decreases. Below theta(CO) = 0.2 monolayer, CO is too strongly bound to react with defect-bound OH. Oxidation of CO at low coverage occurs in the main peak through reaction with OH adsorbed on (111) terraces, where the Pt-OH bond is weaker than on defects. The enhanced oxidation of CO in alkaline media is attributed to the higher affinity of the Pt(111) surface for adsorption of OH at low potentials in alkaline media as compared with acidic media.     

Polarization sensitive in situ infrared spectroscopy: the adsorption of simple ions at platinum electrodes

The application of a simplified spectrometric setup to the investigation of the electrochemical double layer using polarization sensitive in situ infrared spectroscopy is described. As examples, the adsorption of carbon monoxide, thiocyanate, and cyanate at platinum electrodes are investigated. Results are compared with previously published data. Differences are explained in terms of different experimental conditions, they are not caused by differences between the employed methods.     

Formic acid oxidation at platinized platinum electrodes: Part IV. Effect of preadsorbed sulfur and related studies

A study has been made of the effect of preadsorbed sulfur layer on the anodic oxidation of formic acid at a platinized platinum electrode. It is shown that, in the presence of the preadsorbed s sulfur layer, the oxidation process obeys the following rate expression,i=nFkc^αg(θ_s) exp(α_anF?r/RT)where α≈0.75 and α_an≈0.5. This is explained in terms of the following rate-determining step,

${\left(HCOOH\right)}_{ads}\to \underset{*}{C}OOH+H^{+}+e$

and involves the adsorption of formic acid on the sulfur-covered electrode surface. A strong catalytic effect of the sulfur layer is observed; the function g(θ_S) is greater than unity at all θ_S and exhibits two maxima at г_S values of 0.3 and 0.6. It is suggested that these effects arise from a coverage-dependent variation of bond strength between adsorbed sulfur and platinum. Evidence is adduced that the adsorption of sulfur from H₂S solutions involves 2-site adsorption at low coverages and 1-site adsorption at higher coverages. Possibility of multilayer adsorption under appropriate conditions is also discussed in the light of the results obtained.     

Electrochemistry of platinum single crystal surfaces: Part II. Structural effect on formic acid oxidation and poison formation on Pt (111), (100) and (110)

The geometrical arrangement of sites favourable for formic acid oxidation and the poison formation reaction is determined using low index platinum single crystal planes. For this determination, the least number of sites required for the reactions to occur, which was obtained in the study of electrocatalysis by adatoms, was used, that is three adjacent sites are required for formic acid oxidation and four adjacent sites are required for poison formation.The triplet of sites on a unit lattice of Pt (111) and that on a unit lattice of Pt (100) plane are equally very favourable for the main oxidation reaction, but that on a unit lattice of Pt (110) is not so favourable as those on the former two planes. The oxidation rate is more than one order of magnitude lower on the latter than on the former triplets.The poison formation reaction proceeds at a very high rate on the (100) and the (110) planes. The geometrical arrangement of four sites on a square unit lattice of the (100) plane and on a rectangular unit lattice of the (110) plane are favourable for the poison formation reaction, but that on a hexagonal unit lattice of the (111) plane is not so favourable as the former two.     

Vibrational sum frequency generation studies of the (2 x 2)-->(radical19 x radical19) phase transition of CO on Pt(111) electrodes

The potential-dependent (2x2)-3CO-->(radical19x radical19)R23.4 degrees-13CO adlayer phase transition on Pt(111) with 0.1M H(2)SO(4) electrolyte was studied using femtosecond broadband multiplex sum frequency generation (SFG) spectroscopy combined with linear scan voltammetry. Across the phase boundary the SFG atop intensity jumps, and at the same time the SFG spectrum of threefold CO sites is transformed into a bridge site spectrum with a small decrease in integrated SFG intensity. The SFG atop intensity jump and three fold-to-bridge intensity drop are noticeably different from what would be expected for these structures on the basis of coverage alone. This occurs because the SFG signal is sensitive to both the coverage and changes in the local field that result from a changing adlayer structure. We derive an equation that allows us to correct the SFG intensities for these effects using information derived from infrared absorption-reflection spectroscopy (IRAS) and second-harmonic generation (SHG) measurements. With this correction, the SFG results agree well with what would be expected for a transition between perfect adlattices. A small (approximately 20%) discrepancy in the SFG determination of atop coverage is attributed to either a small amount of surface disorder or uncertainties in the SFG, SHG, and IRAS measurements. SFG is also used to examine the reversibility hysteresis and kinetics of the phase transition and its dependence on electrolyte composition. The phase transition is reversible with an approximately 150 mV anodic overpotential and the forward (2x2)-->(radical19x radical19) transition is slower than the reverse. Repeated cycles of phase transition indicate that the 25 microm electrolyte layer used here does not appreciably distort the potential-coverage relationships.