Chiral discrimination within disordered adlayers on metal surfaces

Using a novel non-linear optical technique enantiomeric excess within a translationally disordered overlayer on a metal surface has been monitored for the first time.

Near-field distribution of optical transmission of periodic subwavelength holes in a metal film

Optical transmission of a two-dimensional array of subwavelength holes in a metal film has been numerically studied using a differential method. Transmission spectra have been calculated showing a significant increase of the transmission in certain spectral ranges corresponding to the excitation of the surface polariton Bloch waves on a metal surface with a periodic hole structure. Under the enhanced transmission conditions, the near-field distribution of the transmitted light reveals an intensity enhancement greater than 2 orders of magnitude in localized (similar to 40 nm) spots resulting from the interference of the surface polaritons Bragg scattered by the holes in an array.

Resolution of an ancient surface science anomaly: Work function change induced by N adsorption on W{100}

For many decades it has been assumed that an adsorbate centered above a metal surface and with a net negative charge should increase the work function of the surface. However, despite their electronegativity, N adatoms on W{100} cause a significant work function decrease. Here we present a resolution of this anomaly. Using density functional theory, we demonstrate that while the N atom carries a negative charge, of overriding importance is a reduction in the surface overspill electron density into the vacuum, when that charge is engaged in bonding to the adatom. This novel interpretation is fundamentally important in the general understanding of work function changes induced by atomic adsorbates.

A review of the selective reduction of NOx, with hydrocarbons under lean-burn conditions with non-zeolitic oxide and platinum group metal catalysts

Research on the selective reduction of NOx with hydrocarbons under lean-burn conditions using non-zeolitic oxides and platinum group metal (PGM) catalysts has been critically reviewed. Alumina and silver-promoted alumina catalysts have been described in detail with particular emphasis on an analysis of the various reaction mechanisms that have been put forward in the literature. The influence of the nature of the reducing agent, and the preparation and structure of the catalysts have also been discussed and rationalised for several other oxide systems. It is concluded for non-zeolitic oxides that species that are strongly adsorbed on the surface, such as nitrates/nitrites and acetates, could be key intermediates in the formation of various reduced and oxidised species of nitrogen, the further reaction of which leads eventually to the formation of molecular nitrogen. For the platinum group metal catalysts, the different mechanisms that have been proposed in the literature have been critically assessed. It is concluded that although there is indirect, mainly spectroscopic, evidence for various reaction intermediates on the catalyst surface, it is difficult to confirm that any of these are involved in a critical mechanistic step because of a lack of a direct quantitative correlation between infrared and kinetic measurements. A simple mechanism which involves the dissociation of NO on a reduced metal surface to give N(ads) and O(ads), with subsequent desorption of N-2 and N2O and removal of O(ads) by the reductant can explain many of the results with the platinum group metal catalysts, although an additional contribution from organo-nitro-type species may contribute to the overall NOx reduction activity with these catalysts.

Enhancing the Efficiency of Slit-Coupling to Surface-Plasmon Polariton via Dispersion Engineering

We describe a simple method for enhancing the efficiency of coupling from a free-space transverse-magnetic (TM) plane-wave mode into a surface-plasmon-polariton (SPP) mode. The coupling structure consists a metal film with a dielectric-filled slit and a planar, dielectric layer on the slit-exit side of the metal film. By varying the dielectric layer thickness, the wavevector of the SPP mode on the metal surface can be tuned to match the wavevector magnitude of the modes emanating from the slit exit, enabling high-efficiency radiation coupling into the SPP mode at the slit exit. An optimal dielectric layer thickness of approximately 100 nm yields a visible-frequency SPP coupling efficiency approximately 4 times greater than the SPP coupling efficiency without the dielectric layer. Commensurate coupling enhancement is observed spanning the free-space wavelength range 400 nm < or = lambda(0) < or = 700 nm. We map the dependence of the SPP coupling efficiency on the slit width, the dielectric-layer thickness, and the incident wavelength to fully characterize this SPP coupling methodology

Density functional theory study of the interaction between CO and on a Pt surface:CO/Pt(111), O/Pt(111), and CO/O/Pt(111)

Ab initio total energy calculations within the Density Functional Theory framework were carried out for Pt(111), Pt(111)-p(2x2)-CO, Pt(111)-p(2x2)-O, and Pt(111)-p(2x2)-(CO+O) to provide an insight into the interaction between CO and O on metal surfaces, an important issue in CO oxidation, and also in promotion and poisoning effects of catalysis. The geometrical structures of these systems were optimized with respect to the total energy, the results of which agree with existing experimental values very well. It is found that (i) the local structures of Pt(111)-p(2x2)-(CO+O), such as the bond lengths of C-O, C-Pt, and O-Pt (chemisorbed O atom with Pt), are almost the same as that in Pt(111)-p(2x2)-CO and Pt(111)-p(2x2)-O, respectively, (ii) the total valence charge density distributions in Pt(111)-p(2x2)-(CO+O) are very similar to that in Pt(111)-p(2x2)-CO, except in the region of the chemisorbed oxygen atom, and also nearly identical to that in Pt(111)-p(2x2)-O, apart from in the region of the chemisorbed CO, and (iii) the chemisorption energy of CO on a precovered Pt(111)-p(2x2)-O and the chemisorption energy of O on a precovered Pt(111)-p(2x2)CO are almost equal to that in Pt(111)-p(2x2)-CO and Pt(111)-p(2x2)-O, respectively. These results indicate that the interaction between CO and chemisorbed oxygen on a metal surface is mainly shore range in nature. The discussions of Pt-CO and Pt-O bonding and the interaction between CO and the chemisorbed oxygen atom on Pt(111) are augmented by local densities of states and real space distributions of quantum states.

Swellable polymer films containing Au nanoparticles for point-of-care therapeutic drug monitoring using surface-enhanced Raman spectroscopy

Large (10 × 10 cm) sheets of surface-enhanced Raman spectroscopy (SERS) active polymer have been prepared by stabilising metal nanoparticle aggregates within dry hydroxyethylcellulose (HEC) films. In these films the aggregates are protected by the polymer matrix during storage but in use they are released when aqueous analyte droplets cause the films to swell to their gel form. The fact that these "Poly-SERS" films can be prepared in bulk but then cut to size and stored in air before use means that they provide a cost effective and convenient method for routine SERS analysis. Here we have tested both Ag and Au Poly-SERS films for use in point-of-care monitoring of therapeutic drugs, using phenytoin as the test compound. Phenytoin in water could readily be detected using Ag Poly-SERS films but dissolving the compound in phosphate buffered saline (PBS) to mimic body fluid samples caused loss of the drug signal due to competition for metal surface sites from Cl^- ions in the buffer solution. However, with Au Poly-SERS films there was no detectable interference from Cl^- and these materials allowed phenytoin to be detected at 1.8 mg L^-1, even in PBS. The target range of detection of phenytoin in therapeutic drug monitoring is 10-20 mg L^-1. With the Au Poly-SERS films, the absolute signal generated by a given concentration of phenytoin was lower for the films than for the parent colloid but the SERS signals were still high enough to be used for therapeutic monitoring, so the cost in sensitivity for moving from simple aqueous colloids to films is not so large that it outweighs the advantages which the films bring for practical applications, in particular their ease of use and long shelf life.

Use of a rotating disc reactor to investigate the heterogeneously catalysed oxidation of cinnamyl alcohol in toluene and ionic liquids

To evaluate the effect of mass transfer limitations in the three-phase oxidation of cinnamyl alcohol carried out in toluene and an ionic liquid (1-butyl-3-methyl-imidazolium bis(trifluoromethylsulphonyl)imide), studies have been performed in a rotating disc reactor and compared with those carried out in a stirred tank reactor where mass transfer effects are considered negligible. High catalyst efficiencies are found in the stirred tank reactor with the use of both ionic liquid and toluene, although there is a decrease in rate for the ionic liquid reactions. In contrast, internal pore diffusion limits the reaction in both solvents in the rotating disc reactor. This mass transfer resistance reduces the problem of overoxidation of the metal surface when the reaction is carried out in toluene, leading to significantly higher rates of reaction than expected, although at the cost of decreased selectivity.

Low-frequency electrical response to microbial induced sulfide precipitation

We investigated the sensitivity of low-frequency electrical measurements to microbe-induced metal sulfide precipitation. Three identical sand-packed monitoring columns were used; a geochemical column, an electrical column and a control column. In the first experiment, continuous upward flow of nutrients and metals in solution was established in each column. Cells of Desulfovibrio vulgaris (D. vulgaris) were injected into the center of the geochemical and electrical columns. Geochemical sampling and post-experiment destructive analysis showed that microbial induced sulfate reduction led to metal precipitation on bacteria cells, forming motile biominerals. Precipitation initially occurred in the injection zone, followed by chemotactic migration of D. vulgaris and ultimate accumulation around the nutrient source at the column base. Results from this experiment conducted with metals show (1) polarization anomalies, up to 14 mrad, develop at the bacteria injection and final accumulation areas, (2) the onset of polarization increase occurs concurrently with the onset of lactate consumption, (3) polarization profiles are similar to calculated profiles of the rate of lactate consumption, and (4) temporal changes in polarization and conduction correlate with a geometrical rearrangement of metal-coated bacterial cells. In a second experiment, the same biogeochemical conditions were established except that no metals were added to the flow solution. Polarization anomalies were absent when the experiment was replicated without metals in solution. We therefore attribute the polarization increase observed in the first experiment to a metal-fluid interfacial mechanism that develops as metal sulfides precipitate onto microbial cells and form biominerals. Temporal changes in polarization and conductivity reflect changes in (1) the amount of metal-fluid interfacial area, and (2) the amount of electronic conduction resulting from microbial growth, chemotactic movement and final coagulation. This polarization is correlated with the rate of microbial activity inferred from the lactate concentration gradient, probably via a common total metal surface area effect.

The energetics of tetrahydrocarbazole aromatization over Pd(111): A computational analysis

The carbazole moiety is a component of many important pharmaceuticals including anticancer and anti-HIV agents and is commonly utilized in the production of modern polymeric materials with novel photophysical and electronic properties. Simple carbazoles are generally produced via the aromatization of the respective tetrahydrocarbazole (THCZ). In this work, density functional theory calculations are used to model the reaction pathway of tetrahydrocarbazole aromatization over Pd(111). The geometry of each of the intermediate surface species has been determined and how each structure interacts with the metal surface addressed. The reaction energies and barriers of each of the elementary surface reactions have also been calculated, and a detailed analysis of the energetic trends performed. Our calculations have shown that the surface intermediates remain fixed to the surface via the aromatic ring in a manner similar to that of THCZ. Moreover, the aliphatic ring becomes progressively more planer with the dissociation of each subsequent hydrogen atom. Analysis of the reaction energy profile has revealed that the trend in reaction barriers is determined by the two factors: (i) the strength of the dissociating ring-H bond and (ii) the subsequent gain in energy due to the geometric relaxation of the aliphatic ring. (c) 2008 American Institute of Physics.

Insight into the key aspects of the regeneration process in the NOx storage reduction (NSR) reaction probed using fast transient kinetics coupled with isotopically labelled (NO)-N-15 over Pt and Rh-containing Ba/Al2O3 catalysts

For the first time, the coupling of fast transient kinetic switching and the use of an isotopically labelled reactant (15NO) has allowed detailed analysis of the evolution of all the products and reactants involved in the regeneration of a NOx storage reduction (NSR) material. Using realistic regeneration times (ca. 1 s) for Pt, Rh and Pt/Rh-containing Ba/Al2O3 catalysts we have revealed an unexpected double peak in the evolution of nitrogen. The first peak occurred immediately on switching from lean to rich conditions, while the second peak started at the point at which the gases switched from rich to lean. The first evolution of nitrogen occurs as a result of the fast reaction between H2 and/or CO and NO on reduced Rh and/or Pt sites. The second N2 peak which occurs upon removal of the rich phase can be explained by reaction of stored ammonia with stored NOx, gas phase NOx or O2. The ammonia can be formed either by hydrolysis of isocyanates or by direct reaction of NO and H2.

The study highlights the importance of the relative rates of regeneration and storage in determining the overall performance of the catalysts. The performance of the monometallic 1.1%Rh/Ba/Al2O3 catalyst at 250 and 350 °C was found to be dependent on the rate of NOx storage, since the rate of regeneration was sufficient to remove the NOx stored in the lean phase. In contrast, for the monometallic 1.6%Pt/Ba/Al2O3 catalyst at 250 °C, the rate of regeneration was the determining factor with the result that the amount of NOx stored on the catalyst deteriorated from cycle to cycle until the amount of NOx stored in the lean phase matched the NOx reduced in the rich phase. On the basis of the ratio of exposed metal surface atoms to total Ba content, the monometallic 1.6%Pt/Ba/Al2O3 catalyst outperformed the Rh-containing catalysts at 250 and 350 °C even when CO was used as a reductant.

CO oxidation on Pd(100) and Pd(111): A comparative study of reaction pathways and reactivity at low and medium coverages

We have performed density functional theory calculations with the generalized gradient approximation to investigate CO oxidation on a close-packed transition metal surface, Pd(lll), and a more open surface, Pd(100), aiming to shed light on surface structure effects on reaction pathways and reactivity, an important issue in catalysis. Reaction pathways on both surfaces at two different coverages have been studied. It is found that the reaction pathways on both surfaces possess crucial common features despite the fact that they have different surface symmetries. Having determined reaction barriers in these systems, we find that the reaction on Pd(lll) is strongly coverage dependent. Surface coverages, however, have little effect on the reaction on Pd(100). Calculations also reveal that the low coverage reactions are structure sensitive while the medium coverage reactions are not. Detailed discussions on these results are given.

Micro- and Nano-scale Tribo-Corrosion of Cast CoCrMo

Previous studies have established that some of the wear damage seen on cast CoCrMo joint surface is caused by entrained third-body hard particles. In this study, wet-cell micro-indentation and nano-scratch tests have been carried out with the direct aim of simulating wear damage induced by single abrasive particles entrained between the surfaces of cast CoCrMo hip implants. In situ electrochemical current noise measurements were uniquely performed to detect and study the wear-induced corrosion as well as the repassivation kinetics under the micro-/nano-scale tribological process. A mathematical model has been explored for the CoCrMo repassivation kinetics after surface oxide film rupture. Greater insights into the nature of the CoCrMo micro-/nano-scale wear-corrosion mechanisms and deformation processes are determined, including the identification of slip band formation, matrix/carbide deformation, nanocrystalline structure formation and strain-induced phase transformation. The electrochemical current noise provides evidence of instantaneous transient corrosion activity at the wearing surface resulting from partial oxide rupturing and stripping, concurrent with the indent/scratch.

A LEED STRUCTURAL STUDY OF THE CO INDUCED RECONSTRUCTION OF PD(110) - EVIDENCE FOR A MISSING ROW STRUCTURE

Molecularly adsorbed CO on Pd{110} has been shown (R. Raval et al., Chem. Phys. Lett. 167 (1990) 391, ref. [1]) to induce a substantial reconstruction of the surface in the coverage range 0.3 <theta less-than-or-equal-to 0.75. Throughout this coverage range, the adsorbate-covered reconstructed surface exhibits a (4 x 2) LEED pattern. However, the exact nature of the reconstruction remains uncertain. We have conducted a LEED I(E) "fingerprinting" analysis of the CO/Pd{110}-(4 x 2) structure in order to establish the type of reconstruction induced in the metal surface. This study shows that the LEED I(E) profiles of the integral order and appropriate half-order beams of the CO/Pd{110}-(4 x 2) pattern closely resemble the I(E) profiles theoretically calculated for a Pd{110}-(1 x 2) missing-row structure. Additionally, there is a strong resemblance to the experimental LEED I(E) profiles for the Cs/Pd{110}-(1 x 2) structure which has also been shown to exhibit the missing-row structure. On the basis of this evidence we conclude that the CO/Pd{110}-(4 x 2) LEED pattern arises from a missing-row reconstruction of the Pd{110} surface which gives rise to a strong underlying (1 x 2) pattern plus a poorly ordered CO overlayer which produces weak, diffuse fourth-order spots in the LEED pattern.