Anodic stripping voltammetry with photochemical preconcentration at nanocrystalline TiO2 films: Detection of Ag+ and Hg2+

Nanocrystalline TiO2 deposited on conducting glass plates is shown to be an excellent material for preconcentration of silver and mercury, via photochemical reaction, prior to their detection by anodic stripping voltammetry (ASV). During the first stage of growth in the photoreduction of silver or mercury, 3D nuclei are formed on the TiO2 film. As the deposition proceeds micrometer size agglomerates grow on the surface. The conical morphology of the silver nuclei grown on a (110) rutile single crystal in the initial stages of growth suggests that there is a preferential deposition of silver at the centre of the growing nuclei. When the nuclei size reach a critical value (ca. 400 nm diameter, 40 nm height) the morphology changes to a globular shape without any preferential site for deposition on the surface of the silver nucleus. It was observed that micromolar concentrations of silver or mercury can be detected by anodic stripping voltammetry and relatively large amounts of these metals (micrometer scale nuclei) can be loaded on the nanocrystalline TiO2 film surface. The latter opens the possibility of analytical applications of nanocrystalline TiO2 electrodes for the selective detection of silver or mercury via photochemical anodic stripping voltammetry.

An investigation into the effect of thickness of titanium dioxide and gold-silver nanoparticle titanium dioxide composite thin-films on photocatalytic activity and photo-induced oxygen production in a sacrificial system

Thin films of titanium dioxide and titanium dioxide with incorporated gold and silver nanoparticles were deposited onto glass microscope slides, steel and titanium foil coupons by two sol-gel dip-coating methods. The film's photocatalytic activity and ability to evolve oxygen in a sacrificial solution were assessed. It was found that photocatalytic activity increased with film thickness (from 50 to 500 nm thick samples) for the photocatalytic degradation of methylene blue in solution and resazurin redox dye in an intelligent ink dye deposited on the surface. Contrastingly, an optimum film thickness of similar to 200 nm for both composite and pure films of titanium dioxide was found for water oxidation, using persulfate (S2O82-) as a sacrificial electron acceptor. The nanoparticle composite films showed significantly higher activity in oxygen evolution studies compared with plain TiO2 films.

Selective hydrogenation of acetylene in ethylene rich feed streams at high pressure over ligand modified Pd/TiO2

The selective hydrogenation of acetylene from ethylene rich streams was conducted at high pressure and in the presence of CO over two 1 wt% loaded Pd/TiO2 catalysts with differing dispersions. Although, the more poorly dispersed sample did not result in high acetylene conversion only a small proportion of the total available ethylene was hydrogenated to ethane. The more highly dispersed sample was able to remove acetylene to a level below the detection limit but this was at the expense of significant proportion (ca. 30%) of the available ethylene. Modification of the catalysts by exposure to triphenyl phosphine or diphenyl sulfide and subsequent reduction at 393 K led to improved performance with increased conversion of acetylene and decreased propensity to hydrogenate ethylene resulting in an overall net gain in ethylene. The higher dispersed sample which had been ligand modified provided the best results overall and in particular for the diphenyl sulfide treated sample which was able to completely eliminate acetylene and still obtain a net gain in ethylene. The differences observed are thought to be due to the creation of appropriate active ensembles of Pd atoms which are able to accommodate acetylene but have limited ability to adsorb ethylene. Sub-surface hydrogen formation was suppressed, but not eliminated, by exposure to modifier.

Inkjet printing of resistively loaded FSS for microwave absorbers

Inkjet printing is proposed as a means to create the resistively loaded elements of a frequency selective surface (FSS) which suppresses radar backscatter when placed above a metal ground plane. Spectral transmission and reflection measurements from 9 to 18 GHz show that the dot density of the printed features and the volume ratio of an aqueous vehicle and nano-silver (Ag) ink mixture can be selected to obtain surface resistances in the range 1.2-200 Ω/sq.

Ring-opening polymerisation of silver-diphosphine [M2L3] coordination cages to give [M2L3](infinity) coordination polymers

[M2L3] coordination cages and linear [M2L3]infinity polymers of the rigid, bridging diphosphines bis(diphenylphosphino)acetylene (dppa) and trans-1,2-bis(diphenylphosphino)ethylene (dppet) with silver(I) salts have been investigated in the solution and solid states. Unlike flexible diphosphines, 1:1 dppa/AgX mixtures do not selectively form discrete [Ag2(diphos)2(X)2] macrocycles; instead dynamic mixtures of one-, two- and three-coordinate complexes are formed. However, 3:2 dppa/AgX ratios (X = SbF6. BF4, O3SCF3 or NO3) do lead selectively to new [M2L3] triply bridged cage complexes [Ag2(dppa)3(X)2] 1a-d (X = SbF6 a, BF4 b, O3SCF3 c, NO3 d), which do not exhibit Ag-P bond dissociation at room temperature on the NMR time scale (121 MHz). Complexes la-d were characterised by X-ray crystallography and were found to have small internal cavities, helical conformations and multiple intramolecular aromatic interactions. The nucleophilicity of the anion subtly influences the cage shape: Increasing nucleophilicity from SbF6 (1a) through BF4 (1b) and O3SCF3 (1c) to NO3 (1d) increases the pyramidal distortion at the AgP3 centres, stretching the cage framework (with Ag...Ag distances increasing from 5.48 in 1a to 6.21 A in 1d) and giving thinner internal cavities. Crystal packing strongly affected the size of the helical twist angle, and no correlation between this parameter and the Ag-Ag distance was observed. When crystalline 1c was stored in its supernatant for 16 weeks, conversion occured to the isostoichiometric [M2L3]infinity coordination polymer [Ag(dppa)2Ag(dppa)(O3SCF3)2]infinity (1c'). X-ray crystallography revealed a structure with ten-membered Ag2(dppa)2 rings linked into infinite one-dimensional chains by a third dppa unit. The clear structural relationship between this polymer and the precursor cage 1c suggests a novel example of ring-opening polymerisation. With dppet, evidence for discrete [M2L3] cages was also found in solution, although 31P NMR spectroscopy suggested some Ag-P bond dissociation. On crystallisation, only the corresponding ring-opened polymeric structures [M2L3]infinity could be obtained. This may be because the greater steric bulk of dppet versus dppa destabilises the cage and favours the ring-opening polymerisation.

Surface plasmon polariton propagation across a gentle silver step

Surface plasmon polaritons (SPPs) are excited with light of wavelength lambda (1) = 632.8 nm on or near a gentle Ag/Ag step structure using focused beam, prism coupling and detected using a bare, sharpened fibre tip. The tip-sample separation is controlled by means of an evanescent optical field at wavelength lambda (2) = 543.5 nm in a photon scanning tunnelling microscope (PSTM). The SPP propagation properties are first characterised on both the thin and thick sections of the Ag film structure either side of the step, both macroscopically, using attenuated total reflection, and microscopically from the PSTM images; the two techniques yield very good agreement. It is found that the SPP propagation length is similar to 10-11 mum across the step in each direction (thick to thin and vice versa) as observed in the PSTM images. Thus, with reference to the propagation lengths of 14.2 and 11.7 mum for the thick and thin planar parts of the Ag film respectively, it is concluded that the SPPs negotiate the step reasonably successfully. Importantly, also, it is shown that images may be produced, displaying SPPs with either an artificially enhanced (similar to 15-20 mum) or truncated (5-8 mum) propagation length across the step. Consideration of such images leads us to suggest the possibility that the photon tunnelling occurs in a local water environment. (C) 2001 Elsevier Science B.V. All rights reserved.