Surface structure effects on the electrochemical oxidation of ethanol on platinum single crystal electrodes

Ethanol oxidation has been studied on Pt(111), Pt(100) and Pt(110) electrodes in order to investigate the effect of the surface structure and adsorbing anions using electrochemical and FTIR techniques. The results indicate that the surface structure and anion adsorption affect significantly the reactivity of the electrode. Thus, the main product of the oxidation of ethanol on the Pt(111) electrode is acetic acid, and acetaldehyde is formed as secondary product. Moreover, the amount of CO formed is very small, and probably associated with the defects present on the electrode surface. For that reason, the amount of CO(2) is also small. This electrode has the highest catalytic activity for the formation of acetic acid in perchloric acid. However, the formation of acetic acid is inhibited by the presence of specifically adsorbed anions, such as (bi) sulfate or acetate, which is the result of the formation of acetic acid. On the other hand, CO is readily formed at low potentials on the Pt(100) electrode, blocking completely the surface. Between 0.65 and 0.80 V, the CO layer is oxidized and the production of acetaldehyde and acetic acid is detected. The Pt(110) electrode displays the highest catalytic activity for the splitting of the C-C bond. Reactions giving rise to CO formation, from either ethanol or acetaldehyde, occur at high rate at any potential. On the other hand, the oxidation of acetaldehyde to acetic acid has probably the lower reaction rate of the three basal planes.

Comment on "Influence of bulk properties on the surface structure of finite nuclei"

We comment on a recent paper by Uma Maheswari et al. in which it is claimed that quantal calculations of the half-infinite nuclear matter, in contrast to semiclassical approximations, exhibit an unusually strong dependence of the 90%10% surface thickness of the density profile on the Fermi momentum kF at saturation. This conclusion was carried over to the surface incompressibility. On the contrary we find essential agreement between semiclassical and quantal results and very weak dependence on kF of the quantities in question.

Surface structure and stability of PdZn and PtZn alloys: Density-functional slab model studies

Geometric parameters of binary (1:1) PdZn and PtZn alloys with CuAu-L10 structure were calculated with a density functional method. Based on the total energies, the alloys are predicted to feature equal formation energies. Calculated surface energies of PdZn and PtZn alloys show that (111) and (100) surfaces exposing stoichiometric layers are more stable than (001) and (110) surfaces comprising alternating Pd (Pt) and Zn layers. The surface energy values of alloys lie between the surface energies of the individual components, but they differ from their composition weighted averages. Compared with the pure metals, the valence d-band widths and the Pd or Pt partial densities of states at the Fermi level are dramatically reduced in PdZn and PtZn alloys. The local valence d-band density of states of Pd and Pt in the alloys resemble that of metallic Cu, suggesting that a similar catalytic performance of these systems can be related to this similarity in the local electronic structures.

Nontypable Haemophilus influenzae displays a prevalent surface structure molecular pattern in clinical isolates.

Non-typable Haemophilus influenzae (NTHi) is a Gram negative pathogen that causes acute respiratory infections and is associated with the progression of chronic respiratory diseases. Previous studies have established the existence of a remarkable genetic variability among NTHi strains. In this study we show that, in spite of a high level of genetic heterogeneity, NTHi clinical isolates display a prevalent molecular feature, which could confer fitness during infectious processes. A total of 111 non-isogenic NTHi strains from an identical number of patients, isolated in two distinct geographical locations in the same period of time, were used to analyse nine genes encoding bacterial surface molecules, and revealed the existence of one highly prevalent molecular pattern (lgtF+, lic2A+, lic1D+, lic3A+, lic3B+, siaA−, lic2C+, ompP5+, oapA+) displayed by 94.6% of isolates. Such a genetic profile was associated with a higher bacterial resistance to serum mediated killing and enhanced adherence to human respiratory epithelial cells.

Surface structure and stability of PdZn and PtZn alloys: Density-functional slab model studies

Geometric parameters of binary (1:1) PdZn and PtZn alloys with CuAu-L10 structure were calculated with a density functional method. Based on the total energies, the alloys are predicted to feature equal formation energies. Calculated surface energies of PdZn and PtZn alloys show that (111) and (100) surfaces exposing stoichiometric layers are more stable than (001) and (110) surfaces comprising alternating Pd (Pt) and Zn layers. The surface energy values of alloys lie between the surface energies of the individual components, but they differ from their composition weighted averages. Compared with the pure metals, the valence d-band widths and the Pd or Pt partial densities of states at the Fermi level are dramatically reduced in PdZn and PtZn alloys. The local valence d-band density of states of Pd and Pt in the alloys resemble that of metallic Cu, suggesting that a similar catalytic performance of these systems can be related to this similarity in the local electronic structures.

Model catalyst studies of the strong metal-support interaction: Surface structure identified by STM on Pd nanoparticles on TiO2(110)

Model catalysts of Pd nanoparticles and films on TiO2 (I 10) were fabricated by metal vapour deposition (MVD). Molecular beam measurements show that the particles are active for CO adsorption, with a global sticking probability of 0.25, but that they are deactivated by annealing above 600 K, an effect indicative of SMSI. The Pd nanoparticles are single crystals oriented with their (I 11) plane parallel to the surface plane of the titania. Analysis of the surface by atomic resolution STM shows that new structures have formed at the surface of the Pd nanoparticles and films after annealing above 800 K. There are only two structures, a zigzag arrangement and a much more complex "pinwheel" structure. The former has a unit cell containing 7 atoms, and the latter is a bigger unit cell containing 25 atoms. These new structures are due to an overlayer of titania that has appeared on the surface of the Pd nanoparticles after annealing, and it is proposed that the surface layer that causes the SMSI effect is a mixed alloy of Pd and Ti, with only two discrete ratios of atoms: Pd/Ti of 1: 1 (pinwheel) and 1:2 (zigzag). We propose that it is these structures that cause the SMSI effect. (c) 2005 Elsevier Inc. All rights reserved.

The surface structure of BaO on Pt(111): (2x2)-reconstructed BaO(111)

The surface structure of BaO(111) has been determined using STM and computer modelling. The BaO(111) surface was prepared in thin film form on Pt(111) and presents a surface with twice the lattice parameter expected for that of the bulk termination, i.e. a (2 x 2) reconstruction. Computer modelling indicates that the bulk termination is unstable, but that the (2 x 2) reconstructed BaO(111) surface has a low surface energy and is hence a stable surface reconstruction. The (2 x 2) reconstruction consists of small, three-sided pyramids with (100) oriented sides and either oxygen or barium ions at the apices. Less regular surface reconstructions containing the same pyramids are almost equally stable, indicating that we may also expect less regular regions to appear with a fairly random distribution of these surface species. The simulations further suggest that a regular (4 x 4) reconstruction built up of bigger pyramids is even more energetically favourable, and some evidence is found for such a structure in the STM. (c) 2006 Elsevier B.V. All rights reserved.

Surface structure of thin asymmetric PS-b-PMMA diblock copolymers investigated by atomic force microscopy

Asymmetric poly(styrene-b-methyl methacrylate) (PS-b-PMMA) diblock copolymers of molecular weight M-n = 29,700g mol(-1) (M-PS = 9300 g mol(-1) M-PMMA = 20,100 g mol(-1), PD = 1.15, chi(PS) = 0.323, chi(PMMA) = 0.677) and M-n = 63,900 g mol(-1) (M-PS = 50,500 g mol(-1), M-PMMA = 13,400 g mol(-1), PD = 1.18, chi(PS) = 0.790, chi(PMMA) = 0.210) were prepared via reversible addition-fragmentation chain transfer (RAFT) polymerization. Atomic force microscopy (AFM) was used to investigate the surface structure of thin films, prepared by spin-coating the diblock copolymers on a silicon substrate. We show that the nanostructure of the diblock copolymer depends on the molecular weight and volume fraction of the diblock copolymers. We observed a perpendicular lamellar structure for the high molar mass sample and a hexagonal-packed cylindrical patterning for the lower molar mass one. Small-angle X-ray scattering investigation of these samples without annealing did not reveal any ordered structure. Annealing of PS-b-PMMA samples at 160 degrees C for 24 h led to a change in surface structure.

Surface structure and electronic properties of Pt-Fe/C nanocatalysts and their relation with catalytic activity for oxygen reduction

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Egg surface structure of the freshwater toadfish Thalassophryne amazonica (Teleostei: Batrachoididae) with information on its distribution and natural habitat

The egg surface structure of Thalassophryne amazonica, a freshwater toadfish from the Amazon basin is described. Eggs of this species show a remarkable, highly unusual system of parallel ridges and intermittent grooves that originate at the equator of the egg and lead to the micropylar pit, at which they end in a spiralling pattern. A similar egg surface structure has so far been described only from a group of Asian anabantoid percomorphs, obviously not closely related to Thalassophryne. This egg surface pattern may enhance fertilization success by guiding sperm to the micropyle. We review museum records for T amazonica, present an updated map of its occurrence in the Amazon basin, and provide information on its habitat.

An evolutionary algorithm for the surface structure problem

Many macroscopic properties: hardness, corrosion, catalytic activity, etc. are directly related to the surface structure, that is, to the position and chemical identity of the outermost atoms of the material. Current experimental techniques for its determination produce a “signature” from which the structure must be inferred by solving an inverse problem: a solution is proposed, its corresponding signature computed and then compared to the experiment. This is a challenging optimization problem where the search space and the number of local minima grows exponentially with the number of atoms, hence its solution cannot be achieved for arbitrarily large structures. Nowadays, it is solved by using a mixture of human knowledge and local search techniques: an expert proposes a solution that is refined using a local minimizer. If the outcome does not fit the experiment, a new solution must be proposed again. Solving a small surface can take from days to weeks of this trial and error method. Here we describe our ongoing work in its solution. We use an hybrid algorithm that mixes evolutionary techniques with trusted region methods and reuses knowledge gained during the execution to avoid repeated search of structures. Its parallelization produces good results even when not requiring the gathering of the full population, hence it can be used in loosely coupled environments such as grids. With this algorithm, the solution of test cases that previously took weeks of expert time can be automatically solved in a day or two of uniprocessor time.

SVis: A computational steering visualization environment for surface structure determination

The arrangement of atoms at the surface of a solid accounts for many of its properties: Hardness, chemical activity, corrosion, etc. are dictated by the precise surface structure. Hence, finding it, has a broad range of technical and industrial applications. The ability to solve this problem opens the possibility of designing by computer materials with properties tailored to specific applications. Since the search space grows exponentially with the number of atoms, its solution cannot be achieved for arbitrarily large structures. Presently, a trial and error procedure is used: an expert proposes an structure as a candidate solution and tries a local optimization procedure on it. The solution relaxes to the local minimum in the attractor basin corresponding to the initial point, that might be the one corresponding to the global minimum or not. This procedure is very time consuming and, for reasonably sized surfaces, can take many iterations and much effort from the expert. Here we report on a visualization environment designed to steer this process in an attempt to solve bigger structures and reduce the time needed. The idea is to use an immersive environment to interact with the computation. It has immediate feedback to assess the quality of the proposed structure in order to let the expert explore the space of candidate solutions. The visualization environment is also able to communicate with the de facto local solver used for this problem. The user is then able to send trial structures to the local minimizer and track its progress as they approach the minimum. This allows for simultaneous testing of candidate structures. The system has also proved very useful as an educational tool for the field.

Protein deposition at polymer surfaces:the bulk and surface structure-property effects of hydrogels

The primary objective of this research has been to investigate the interfacial phenomenon of protein adsorption in relation to the bulk and surface structure-property effect s of hydrogel polymers. In order to achieve this it was first necessary to characterise the bulk and surface properties of the hydrogels, with regard to the structural chemistry of their component monomers. The bulk properties of the hydrogels were established using equilibrium water content measurements, together with water-binding studies by differential scanning calorimetry (D.S.C.). Hamilton and captive air bubble-contact angle techniques were employed to characterise the hydrogel-water interface and from which by a mathematical derivation, the interfacial free energy (ðsw) and the surface free energy components (ð psv, ðdsv, ðsv) were obtained. From the adsorption studies using the radio labelled iodinated (125I) proteins of human serum albumin (H.S.A.) and human fibrinogen (H.Fb.), it was Found that multi-layered adsorption was occurring and that the rate and type of this adsorption was dependent on the physico-chemical behaviour of the adsorbing protein (and its bulk concentration in solution), together with the surface energetics of the adsorbent polymer. A potential method for the invitro evaluation of a material's 'biocompatibility' was also investigated, based on an empirically observed relationship between the adsorption of albumin and fibrinogen and the 'biocompatibility' of polymeric materials. Furthermore, some consideration was also given to the biocompatibility problem of proteinaceous deposit formation on hydrophilic soft' contact lenses and in addition a number of potential continual wear contact lens formulations now undergoing clinical trials,were characterised by the above techniques.