Tailoring the photocatalytic activity of nanoparticulate zinc oxide by transition metal oxide doping

The successful use of nanoparticulate ZnO in applications such as UV-screening agents or photocatalyst for the destruction of chemical waste requires the development of techniques for controlling its photocatalytic activity. In this study, we have investigated transition metal doping as a means of achieving this goal. Powders of ZnO, Mn_xZn_1−xO, and Co_xZn_1−xO were synthesised by a three-stage process consisting of high-energy mechanical milling, heat treatment, and washing. The photocatalytic activity of these powders was evaluated using the spin-trapping technique with electron paramagnetic resonance spectroscopy. It was found that the photocatalytic activity of Co_xZn_1−xO progressively decreased with the doping level. In contrast, the activity of Mn_xZn_1−xO initially increased with doping up to a level of 2 mol% and thereafter declined. These results demonstrate that doping with transition metal oxides can be used to tailor the photocatalytic properties of nanoparticulate ZnO.

Silicone coated metal oxide particles

A process for applying a silicone coating to metal oxide particles is described. The process comprises the steps of: preparing a mixture of an aqueous suspension of metal oxide particles and an aqueous solution of water-soluble organosilicon monomers; and, adding a pH-lowering agent to the mixture so as to initiate polymerisation of the water-soluble organosilicon monomers and form silicone coated metal oxide particles. The process does not require the use of an organic solvent.

Mechanically alloyed and spark plasma sintered aluminium/precious metal oxide composite materials

Air-atomised pure aluminium powder with additions of 10 at.% of AgO, PtO₂ or PdO was mechanically alloyed (MAed) by using a vibrational ball mill, and MAed powders were consolidated into bulk materials by a spark plasma sintering (SPS) process. Mechano-chemical reactions among pure Al, precious metal oxide and stearic acid, added as a process control agent, during the mechanical alloying (MA) process and subsequent heat treatments were investigated by X-ray diffraction. The mechanical properties of MAed powders obtained under various heat treatment conditions and those of the SPS materials were evaluated by hardness tests. Mechano-chemical reactions occurred in Al/precious metal oxide composite powders during 36 ks of the MA process to form AlAg₂, Pt and Al₃Pd₂ for the Al-AgO, Al-PtO₂ and Al-PdO systems, respectively. Further solid-state reactions in MAed powders have been observed after heating at 373 K to 873 K for 7.2 ks. The hardness of MAed powders initially increased significantly after heating at 373 K and then generally decreased with increasing heating temperatures. The full density was obtained for the SPS materials under the conditions of an applied pressure of 49 MPa at 873 K for 3.6 ks. All the SPS materials exhibited hardness values of over 200 HV in the as-fabricated state.

Bi-functional oxygen electrocatalysts based on Palladium oxide-Ruthenium oxide composites

Bi-functional oxygen electrodes are an enabling component for rechargeable metal-air batteries and regenerative fuel cells, both of which are regarded as the next-generation energy devices with zero emission. Nonetheless, at the present, no single metal oxide component can catalyze both oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) with high performance which leads to large overpotential between ORR and OER. This work strives to address this limitation by studying the bi-functional electrocatalytic activity of the composite of a good ORR catalyst compound (e.g. palladium oxide, PdO) and a good OER catalyst compound (e.g. ruthenium oxide, RuO2) in alkaline solution (0.1M KOH) utilizing a thin-film rotating disk electrode technique. The studied compositions include PdO, RuO2, PdO/RuO2 (25wt.%/75wt.%), PdO/RuO2 (50wt.%/50wt.%) and PdO/RuO2 (75wt.%/25wt.%). The lowest overpotential (e.g. E (2 mA cm−2) - E (-2 mA cm−2)) of 0.82 V is obtained for PdO/RuO2 (25wt.%/75wt.%) (versus Ag|AgCl (3M NaCl) reference electrode).

Inverse opal structure of SnO2 and SnO2 : Zn for gas sensing

In the present work, we propose a low cost synthetic sol-gel route that allows to produce high quality oxide nanostructures with inverse opal architecture which, transferred on alumina substrates provided with Pt interdigitated contacts and heater, are tested as gas sensing devices. An opal template of sintered monodisperse polystyrene spheres was filled with alcoholic solutions of metal oxide precursors and transferred on the alumina substrate. The polystyrene template was removed by thermal treatment, leading to the simultaneous sintering of the oxide nanoparticles. Beside SnO₂, a binary oxide well known for gas sensing application, a Zn containing ternary solid solution (SnO₂:Zn, with Zn 10% molar content) was taken into account for sensor preparation. The obtained high quality macro and meso-porous structures, characterized by different techniques, were tested for pollutant (CO, NO₂) and interfering (methanol) gases, showing that very good detection can be reached through the increase of surface area offered by the inverse opal structure and the tailoring of the chemical composition. The electrical characterization performed on the tin dioxide based sensors shows an enhancement of the relative response towards NO₂ at low temperatures in comparison with conventional SnO₂ sensors obtained with sputtering technique. The addition of Zn increases the separation between the operating temperatures for reducing and oxidizing gases and results in a further enhancement of the selectivity to NO₂ detection.

Inverse opal nanoassemblies : novel architectures for gas sensors the SnO2:Zn case

A novel technique is here presented, based on inverse opal metal oxide structures for the production of high quality macro and meso-porous structures for gas sensing. Taking advantage of a sol-gel templated approach. different mixed semiconducting oxides with high surface area, commonly used in chemical sensing application, were synthesized. In this work we report the
comparison between SnO₂ and SnO₂:Zn. As witnessed by Scanning and Transmission Electron Microscopy (SEM and TEM) analyses and by Powder x-ray Diffraction (PX RD), highly ordered meso-porous structures were formed with oxide crystalline size never exceeding 20 nm . The filled templates. in form of thick films, were bound to allumina substrate with Pt interdigitated contacts
and Pt heater, through in situ calcination, in order to perform standard electrical characterization. Pollutant gases like CO and NO₂ and methanol. as interfering gas, were used for the targeted electrical gas tests. All samples showed low detection limits towards both reducing and oxidizing species in low temperature measurements. Moreover, the addition of high molar percentages of Zn( II) affected the beha viour of electrical response improv ing the se lecti vity of the proposed system.

Process for the production of ultrafine powders

A process for the production of ultrafine powders consisting of individual particles with sizes in the range of 1 nm to 200 nm, which is based on the mechanical milling of two or more non-reacting powders. The process includes subjecting a suitable precursor metal compound and a non-reactant diluent phased to mechanical milling which through the process of mechanical activation reduces the microstructure of the mixture of the form of nano-sized grains of the metal compound uniformly dispersed in the diluent phase. Heat treating the milled powder converts the nano-sized grains of the precursor metal compound into a desired metal oxide phase. Alternatively, the precursor metal compound may itself be an oxide phase which has the requisite milling properties to form nanograins when milled with a diluent. An ultrafine powder is produced by removing the diluent phase such that nano-sized grains of the desired metal oxide phase are left behind. The process facilitates a significant degree of control over the particle size and size distribution of the particles in the ultrafine powder by controlling the parameters of mechanical activation and heat treatment.

Development and application of electroanalytical field-based chemical monitoring systems

The development and application of a novel combination of electrochemical techniques and computerized field-based battery-operated instrumentation is investigated. Low-power complementary metal oxide semiconductor technology has been utilized for the development of the field data acquisition systems and the instrumental performance of the complete analytical system is critically evaluated.

Ultrasensitive hydrogen sensor based on Pd0-loaded SnO2 electrospun nanofibers at room temperature

Pd0-loaded SnO2 nanofibers have been successfully synthesized with different loaded levels via electrospinning process, sintering technology, and in situ reduction. This simple strategy could be expected to extend for the fabrication of similar metal?oxide loaded nanofibers using different precursors. The morphological and structural characteristics of the resultant product were investigated by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), and X-ray photoelectron spectra (XPS). To demonstrate the usage of such Pd0-loaded SnO2 nanomaterial, a chemical gas sensor has been fabricated and investigated for H2 detection. The sensing performances versus Pd0-loaded levels have been investigated in detail. An ultralow limit of detection (20 ppb), high response, fast response and recovery, and selectivity have been obtained on the basis of the sensors operating at room temperature. The combination of SnO2 crystal structure and catalytic activity of Pd0-loaded gives a very attractive sensing behavior for applications as real-time monitoring gas sensors.

Synthesis and growth mechanism of Thin-film TiO2 nanotube arrays on focused-ion-beam micropatterned 3D isolated regions of titanium on silicon

In this paper, the fabrication and growth mechanism of net-shaped micropatterned self-organized thin-film TiO2 nanotube (TFTN) arrays on a silicon substrate are reported. Electrochemical anodization is used to grow the nanotubes from thin-film titanium sputtered on a silicon substrate with an average diameter of ?30 nm and a length of ?1.5 ?m using aqueous and organic-based types of electrolytes. The fabrication and growth mechanism of TFTN arrays from micropatterned three-dimensional isolated islands of sputtered titanium on a silicon substrate is demonstrated for the first time using focused-ion-beam (FIB) technique. This work demonstrates the use of the FIB technique as a simple, high-resolution, and maskless method for high-aspect-ratio etching for the creation of isolated islands and shows great promise toward the use of the proposed approach for the development of metal oxide nanostructured devices and their integration with micro- and nanosystems within silicon-based integrated-circuit devices.

The corrosion inhibition of aluminium alloy 7075-T651 with cerium and Mischmetal di phenyl phosphate

Previous studies have shown that cerium diphenyl phosphate (Cedpp) 3 is a very effective inhibitor of corrosion of aluminium alloys in chloride solutions. This paper describes the results of further studies using electrochemical and constant immersion corrosion tests to compare the effectiveness of Ce(dpp) 3 and Mischmetal diphenyl phosphate Mm(dpp) 3 as inhibitors of corrosion pitting on AA7075-T651 aluminium alloy. The results shows that both Ce(dpp) 3 and Mm(dpp) 3 are excellent inhibitors of pitting corrosion of this alloy in very aggressive environments of continuously aerated 0.1M and 1.0M sodium chloride (NaCl) solutions. Polarisation tests indicate that these compounds act as a cathodic inhibitors by reducing the rate of the oxygen reduction reaction, which results in a decreased corrosion current density and a separation of the corrosion potential from the pitting potential. This inhibition is thought to be due to the formation of a surface film consisting of rare earth metal oxide, aluminium oxide and a cerium-aluminium organo-phosphate complex. Surface analysis data from scanning electron microscopy and X-ray Energy Dispersive Spectroscopy show the complex nature of this protective film. This work further develops our understanding about the mechanisms through which these complex films form, and how inhibition occurs in the presence of these compounds.

Binding affinities of amino acid analogues at the charged aqueous titania interface : implications for titania-binding peptides

Despite the extensive utilization of biomolecule-titania interfaces, biomolecular recognition and interactions at the aqueous titania interface remain far from being fully understood. Here, atomistic molecular dynamics simulations, in partnership with metadynamics, are used to calculate the free energy of adsorption of different amino acid side chain analogues at the negatively-charged aqueous rutile TiO2 (110) interface, under conditions corresponding with neutral pH. Our calculations predict that charged amino acid analogues have a relatively high affinity to the titania surface, with the arginine analogue predicted to be the strongest binder. Interactions between uncharged amino acid analogues and titania are found to be repulsive or weak at best. All of the residues that bound to the negatively-charged interface show a relatively stronger adsorption compared with the charge-neutral interface, including the negatively-charged analogue. Of the analogues that are found to bind to the titania surface, the rank ordering of the binding affinities is predicted to be "arginine" > "lysine" ≈ aspartic acid > "serine". This is the same ordering as was found previously for the charge-neutral aqueous titania interface. Our results show very good agreement with available experimental data and can provide a baseline for the interpretation of peptide-TiO2 adsorption data.

Highly sensitive SnO2 nanofiber chemiresistors with a low optimal operating temperature: synergistic effect of Cu2+/Au co-doping

Metal oxide chemiresistors (MOCs) with a low optimal operating temperature, high sensitivity and fast response/recovery are highly promising for various applications, but remain challenging to realize. Herein, we demonstrate that SnO2 nanofibers after being co-doped with Cu2+ and Au show considerably enhanced sensing performances at an unexpectedly decreased operating temperature. A synergistic effect occurs when the two dopants are introduced together. Co-doping may form a novel strategy to the development of ultrasensitive MOCs working at a low optimal temperature. This journal is © the Partner Organisations 2014.

In situ prepared V2O5/graphene hybrid as a superior cathode material for lithium-ion batteries

Developing synthetic methods for graphene based cathode materials, with low cost and in an environmentally friendly way, is necessary for industrial production. Although the precursor of graphene is abundant on the earth, the most common precursor of graphene is graphene oxide (GO), and it needs many steps and reagents for transformation to graphite. The traditional approach for the synthesis of GO needs many chemicals, thus leading to a high cost for production and potentially great amounts of damage to the environment. In this study, we develop a simple wet ball-milling method to construct a V2O5/graphene hybrid structure in which nanometre-sized V2O5 particles/aggregates are well embedded and uniformly dispersed into the crumpled and flexible graphene sheets generated by in situ conversion of bulk graphite. The combination of V2O5 nanoparticles/aggregates and in situ graphene leads the hybrid to exhibit a markedly enhanced discharge capacity, excellent rate capability, and good cycling stability. This study suggests that nanostructured metal oxide electrodes integrated with graphene can address the poor cycling issues of electrode materials that suffer from low electronic and ionic conductivities. This simple wet ball-milling method can potentially be used to prepare various graphene based hybrid electrodes for large scale energy storage applications.