Plasma-aided hydrogenation and Al-doping : increasing the conductivity and optical transparency of ZnO transparent conducting oxide

Plasma-assisted magnetron sputtering with varying ambient conditions has been utilised to deposit Al-doped ZnO (AZO) transparent conductive thin films directly onto a glass substrate at a low substrate temperature of 400 °C. The effects of hydrogen addition on electrical, optical and structural properties of the deposited AZO films have been investigated using X-ray diffractometry (XRD), scanning electron microscopy (SEM), Hall effect measurements and UV–vis optical transmission spectroscopy. The results indicate that hydrogen addition has a remarkable effect on the film transparency and conductivity with the greatest effects observed with a hydrogen flux of approximately 3 sccm. It has been demonstrated that the conductivity and the average transmittance in the visible range can increase simultaneously contrary to the effects observed by other authors. In addition, hydrogen incorporation further leads to the absorption edge shifting to a shorter wavelength due to the Burstein–Moss effect. These results are of particular relevance to the development of the next generation of optoelectronic and photovoltaic devices based on highly transparent conducting oxides with controllable electronic and optical properties.

Si quantum dots embedded in an amorphous SiC matrix : nanophase control by non-equilibrium plasma hydrogenation

Nanophase nc-Si/a-SiC films that contain Si quantum dots (QDs) embedded in an amorphous SiC matrix were deposited on single-crystal silicon substrates using inductively coupled plasma-assisted chemical vapor deposition from the reactive silane and methane precursor gases diluted with hydrogen at a substrate temperature of 200 °C. The effect of the hydrogen dilution ratio X (X is defined as the flow rate ratio of hydrogen-to-silane plus methane gases), ranging from 0 to 10.0, on the morphological, structural, and compositional properties of the deposited films, is extensively and systematically studied by scanning electron microscopy, high-resolution transmission electron microscopy, X-ray diffraction, Raman spectroscopy, Fourier-transform infrared absorption spectroscopy, and X-ray photoelectron spectroscopy. Effective nanophase segregation at a low hydrogen dilution ratio of 4.0 leads to the formation of highly uniform Si QDs embedded in the amorphous SiC matrix. It is also shown that with the increase of X, the crystallinity degree and the crystallite size increase while the carbon content and the growth rate decrease. The obtained experimental results are explained in terms of the effect of hydrogen dilution on the nucleation and growth processes of the Si QDs in the high-density plasmas. These results are highly relevant to the development of next-generation photovoltaic solar cells, light-emitting diodes, thin-film transistors, and other applications.

Catalytic role of pre-adsorbed CO in platinum-based catalysts : the reduction of SO 2 by CO on Pt l Au m (CO) n

Using density functional theory, we have investigated the catalytic properties of bimetallic complex catalysts PtlAum(CO)n (l + m = 2, n = 1–3) in the reduction of SO2 by CO. Due to the strong coupling between the C-2p and metal 5d orbitals, pre-adsorption of CO molecules on the PtlAum is found to be very effective in not only reducing the activation energy, but also preventing poisoning by sulfur. As result of the coupling, the metal 5d band is broadened and down-shifted, and charge is transferred from the CO molecules to the PtlAum. As SO2 is adsorbed on the catalyst, partial charge moves to the anti-σ bonding orbitals between S and O in SO2, weakening the S–O bond strength. This effect is enhanced by pre-adsorbing up to three CO molecules, therefore the S–O bonds become vulnerable. Our results revealed the mechanism of the excellent catalytic properties of the bimetallic complex catalysts.

Museums as urban catalysts : the role of urban design in flagship cultural development

A long-held urban redevelopment strategy has been the investment in flagship cultural projects—large-scale, iconic museums and arts centres that are intended to enhance the city image while catalyzing private sector investment and attracting tourists to the surrounding area. This paper concentrates on an aspect of the flagship cultural strategy that has received surprisingly little focused attention—the role that urban design and context play in realizing project outcomes. The analysis concentrates on two established flagship museums in Los Angeles and San Jose, California. The research demonstrates that certain urban design characteristics can negatively affect the ability of a project to attract visitors and generate commercial activity. However, at the same time, factors beyond the local context may be an overriding factor in project outcomes thus calling into question the concept of cultural catalyst.

Effects of mesostructured silica catalysts on the depolymerization of organosolv lignin fractionated from woody eucalyptus

Isolated and purified organosolv eucalyptus wood lignin was depolymerized at different temperatures with and without mesostructured silica catalysts (i.e., SBA-15, MCM-41, ZrO2-SBA-15 and ZrO2-MCM-41). It was found that at 300 oC for 1 h with a solid/liquid ratio of 0.0175/1 (w/v), the SBA-15 catalyst with high acidity gave the highest syringol yield of 23.0% in a methanol/water mixture (50/50, wt/wt). Doping with ZrO2 over these catalysts did not increase syringol yield, but increased the total amount of solid residue. Gas chromatography-mass spectrometry (GC-MS) also identified other main phenolic compounds such as 1-(4-hydroxy-3,5-dimethoxyphenyl)-ethanone, 1,2-benzenediol, and 4-hydroxy-3,5-dimethoxy-benzaldehyde. Analysis of the lignin residues with Fourier transform-Infrared spectroscopy (FT-IR) indicated decreases in the absorption bands intensities of OH group, C-O stretching of syringyl ring and aromatic C-H deformation of syringol unit, and an increase in band intensities associated with the guaiacyl ring, confirming the type of products formed.

Art and science as creative catalysts

Science, Art and Science Art collaborations are generally presented and understood in terms of their products. We argue that the process of Science art can be a significant, even principal benefit of these collaborations, even though it may be largely invisible to anyone other than the collaborators. Hosting the Centenary of Canberra Science Art Commission at the Commonwealth Scientific and Industrial Research Organisation (CSIRO) has shown us that while Science and Art pursue orthogonal dimensions of creativity and innovation, collaborators can combine these directions to access new areas of imagination and ideas.

Co-and Ca-phosphate-based catalysts for the depolymerization of organosolv eucalytpus lignin

Depolymerization of purified organosolv eucalyptus wood lignin by the heterogeneous catalysts, cobalt polyphosphate (CoP2O6) and calcium phosphate (β-CaP2O6) was investigated. A total syringol yield of 16.7% was achieved with β-CaP2O6 in a methanol/water (50/50, wt/wt) solvent system after depolymerization at 300 ºC for 1 h, showing selectivity of the catalyst.

Small gold nanoparticles as crystallization "catalysts": Effect of seed size and concentration on Au-ZnO hetero nanoparticles

This work reports the effect of seed nanoparticle size and concentration effects on heterogeneous crystal nucleation and growth in colloidal suspensions. We examined these effects in the Au nanoparticle-seeded growth of Au-ZnO hetero-nanocrystals under synthesis conditions that generate hexagonal, cone-shaped ZnO nanocrystals. It was observed that small (~ 4 nm) Au seed nanoparticles form one-to-one Au-ZnO hetero dimers and that Au nanoparticle seeds of this size can also act as crystallization ‘catalysts’ that readily promote the nucleation and growth of ZnO nanocrystals. Larger seed nanoparticles (~9 nm, ~ 11 nm) provided multiple, stable ZnO-nucleation sites, generating multi-crystalline hetero trimers, tetramers and oligomers.

Visible light enhanced oxidant free dehydrogenation of aromatic alcohols using Au-Pd alloy nanoparticle catalysts

We find that visible light irradiation of gold–palladium alloy nanoparticles supported on photocatalytically inert ZrO2 significantly enhances their catalytic activity for oxidant-free dehydrogenation of aromatic alcohols to the corresponding aldehydes at ambient temperatures. Dehydrogenation is also the dominant process in the selective oxidation of the alcohols to the corresponding aldehydes with molecular oxygen. The alloy nanoparticles strongly absorb light and exhibit superior catalytic and photocatalytic activity when compared to either pure palladium or gold nanoparticles. Analysis with a free electron gas model for the bulk alloy structure reveals that the alloying increases the surface charge heterogeneity on the alloy particle surface, which enhances the interaction between the alcohol molecules and the metal NPs. The increased surface charge heterogeneity of the alloy particles is confirmed with density function theory applied to small alloy clusters. Optimal catalytic activity was observed with a Au : Pd molar ratio of 1 : 186, which is in good agreement with the theoretical analysis. The rate-determining step of the dehydrogenation is hydrogen abstraction. The conduction electrons of the nanoparticles are photo-excited by the incident light giving them the necessary energy to be injected into the adsorbed alcohol molecules, promoting the hydrogen abstraction. The strong chemical adsorption of alcohol molecules facilitates this electron transfer. The results show that the alloy nanoparticles efficiently couple thermal and photonic energy sources to drive the dehydrogenation. These findings provide useful insight into the design of catalysts that utilize light for various organic syntheses at ambient temperatures.