Rapid synthesis of porous honeycomb Cu/Pd through a hydrogen-bubble templating method

A rapid electrochemical method based on using a clean hydrogen-bubble template to form a bimetallic porous honeycomb Cu/Pd structure has been investigated. The addition of palladium salt to a copper-plating bath under conditions of vigorous hydrogen evolution was found to influence the pore size and bulk concentration of copper and palladium in the honeycomb bimetallic structure. The surface was characterised by X-ray photoelectron spectroscopy, which revealed that the surface of honeycomb Cu/Pd was found to be rich with a Cu/Pd alloy. The inclusion of palladium in the bimetallic structure not only influenced the pore size, but also modified the dendritic nature of the internal wall structure of the parent copper material into small nanometre-sized crystallites. The chemical composition of the bimetallic structure and substantial morphology changes were found to significantly influence the surface-enhanced Raman spectroscopic response for immobilised rhodamine B and the hydrogen-evolution reaction. The ability to create free-standing films of this honeycomb material may also have many advantages in the areas of gas- and liquid-phase heterogeneous catalysis.

Formation of nanostructured porous Cu-Au surfaces : the influence of cationic sites on (electro)-catalysis

The fabrication of nanostructured bimetallic materials through electrochemical routes offers the ability to control the composition and shape of the final material that can then be effectively applied as (electro)-catalysts. In this work a clean and transitory hydrogen bubble templating method is employed to generate porous Cu–Au materials with a highly anisotropic nanostructured interior. Significantly, the co-electrodeposition of copper and gold promotes the formation of a mixed bimetallic oxide surface which does not occur at the individually electrodeposited materials. Interestingly, the surface is dominated by Au(I) oxide species incorporated within a Cu2O matrix which is extremely effective for the industrially important (electro)-catalytic reduction of 4-nitrophenol. It is proposed that an aurophilic type of interaction takes place between both oxidized gold and copper species which stabilizes the surface against further oxidation and facilitates the binding of 4-nitrophenol to the surface and increases the rate of reaction. An added benefit is that very low gold loadings are required typically less than 2 wt% for a significant enhancement in performance to be observed. Therefore the ability to create a partially oxidized Cu–Au surface through a facile electrochemical route that uses a clean template consisting of only hydrogen bubbles should be of benefit for many more important reactions.

Lateral charge propagation effects during the galvanic replacement of electrodeposited MTCNQ (M= Cu, Ag) microstructures with gold and its influence on catalysed electron transfer reactions

The galvanic replacement of isolated electrodeposited semiconducting CuTCNQ microstructures on a glassy carbon (GC) substrate with gold is investigated. It is found that anisotropic metal nanoparticles are formed which are not solely confined to the redox active sites on the semiconducting materials but are also observed on the GC substrate which occurs via a lateral charge propagation mechanism. We also demonstrate that this galvanic replacement approach can be used for the formation of isolated AgTCNQ/Au microwire composites which occurs via an analogous mechanism. The resultant MTCNQ/Au (M = Cu, Ag) composite materials are characterized by Raman, spectroscopy, X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and investigated for their catalytic properties for the reduction of ferricyanide ions with thiosulphate ions in aqueous solution. Significantly it is demonstrated that gold loading, nanoparticle shape and in particular the MTCNQ–Au interface are important factors that influence the reaction rate. It is shown that there is a synergistic effect at the CuTCNQ/Au composite when compared to AgTCNQ/Au at similar gold loadings.

A vibrational spectroscopic study of the arsenate mineral bayldonite (Cu,Zn)3Pb(AsO3OH)2(OH)2 : a comparison with other basic arsenates

We have studied the vibrational spectra of the mineral bayldonite, a hydroxy arsenate of copper and lead of formula Cu3Pb(AsO3OH)2(OH)2 from the type locality, the Penberthy Croft Mine, St Hilary, Mount's Bay District, Cornwall, England.and relate the spectra to the mineral structure. Raman bands at 896 and 838 cm-1are assigned to the (AsO4)3- ν1 symmetric stretching mode and the second to the (AsO4)3- ν3 antisymmetric stretching mode. It is noted that the position of the symmetric stretching mode is at a higher position than the antisymmetric stretching mode. It is proposed that the Raman bands at 889 and 845 cm-1 are symmetric and antisymmetric stretching modes of the (HOAsO3)2- units. Raman bands of bayldonite at 490 and 500 cm-1 are assigned to the (AsO4)3- ν4 bending modes. Raman bands for bayldonite are noted at 396, 408 and 429 cm-1 and are assigned to the (AsO4)3- ν2 bending modes. A comparison is made with spectra of the other basic copper arsenate minerals, namely cornubite, olivenite, cornwallite.

Electrochemical formation of Cu/Ag surfaces and their applicability as heterogeneous catalysts

In this work the electrochemical formation of porous Cu/Ag materials is reported via the simple and quick method of hydrogen bubble templating. The bulk and surface composition ratio between Ag and Cu was varied in a systematic manner and was readily controlled by the concentration of precursor metal salts in the electrolyte. The incorporation of Ag within the Cu scaffold only affected the formation of well-defined pores at high Ag loading whereas the internal pore wall structure gradually transformed from dendritic to cube like and finally needle like structures, which was due to the concomitant formation of Cu2O within the structure. The materials were characterised by scanning electron microscopy (SEM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). Their surface properties were further investigated by surface enhanced Raman spectroscopy (SERS) and electrochemically probed by recording the hydrogen evolution reaction (HER) which is highly sensitive to the nature of the surface. The effect of surface composition was then investigated for its influence on two catalytic reactions namely the reduction of ferricyanide ions with thiosulphate ions and the reduction of 4-nitrophenol with NaBH4 in aqueous solution where it was found that the presence of Ag had a beneficial effect in both cases but more so in the case of nitrophenol reduction. It is believed that this material may have many more potential applications in the area of catalysis, electrocatalysis and photocatalysis.

Electrochemical and photochemical routes to semiconducting transition metal-tetracyanoquinodimethane coordination polymers

TCNQ·− radical anions (TCNQ = 7,7,8,8,-tetracyanoquinodimethane) form a wide range of semiconducting coordination polymers when coordinated to transition metals. Some such as CuTCNQ and AgTCNQ exhibit molecular switching and memory storage properties; others have intriguing magnetic properties and for example may behave as molecular magnets at low temperature. In this review, the electro- and photo-chemical synthesis and characterization of this important class of material is reviewed. In particular, the electrochemistry and the redox properties of TCNQ derivatives of coordination polymers based on Cu, Ag, Mn, Fe, Co, Ni, Zn and Cd transition metals are surveyed, with an emphasis on the mechanistic aspects of their electrochemical formation via nucleation–growth processes. Given that TCNQ is an extremely good electron acceptor, readily forming TCNQ•− and TCNQ2-, electrochemical reduction of TCNQ in the presence of a transition metal ion provides an ideal method for synthesis of metal-TCNQ materials by electrocrystallization from organic solvents and ionic liquids or solid-solid transformation using TCNQ modified electrodes from aqueous media containing transition metal electrolytes. The significance of the reversible formal potential (E0f) in these studies is discussed. The coupling of electrocrystallisation on electrode surfaces and microscopic characterization of the electrodeposited materials reveals a wide range of morphologies and phases which strongly influence their properties and applications. Since TCNQ also can be photo-reduced in the presence of suitable electron donors, analogous photochemical approaches to the synthesis of TCNQ-transition metal derivatives are available. The advantages of electrochemical and photochemical methods of synthesis relative to chemical synthesis are outlined.

Vibrational spectroscopic study of the sulphate mineral glaucocerinite (Zn,Cu)10Al6(SO4)3(OH)32⋅18H2O – a natural layered double hydroxide

We have studied the molecular structure of the mineral glaucocerinite (Zn,Cu)5Al3(SO4)1.5(OH)16�9(H2O) using a combination of Raman and infrared spectroscopy. The mineral is one of the hydrotalcite supergroup of natural layered double hydroxides. The Raman spectrum is characterised by an intense Raman band at 982 cm�1 with a low intensity band at 1083 cm�1. These bands are attributed to the sulphate symmetric and antisymmetric stretching mode. The infrared spectrum is quite broad with a peak at 1020 cm�1. A series of Raman bands at 546, 584, 602, 625 and 651 cm�1 are assigned to the m4 (SO4)2� bending modes. The observation of multiple bands provides evidence for the reduction in symmetry of the sulphate anion from Td to C2v or even lower symmetry. The Raman band at 762 cm�1 is attributed to a hydroxyl deformation mode associated with AlOH units. Vibrational spectroscopy enables aspects of the molecular structure of glaucocerinite to be determined.

Investigation on mechanical behaviour of AM60 magnesium alloys

Purpose: In this work, tension, impact, bend and fatigue tests were conducted in an AM60 magnesium alloy. The effects of environmental temperature and loading rates on impact and tension behavior of the alloy were also investigated. Design/methodology/approach: The tests were conducted using an Instron universal testing machine. The loading speed was changed from 1 mm/min to 300 mm/min to gain a better understanding of the effect of strain rate. To understand the failure behavior of this alloy at different environmental temperatures, Charpy impact test was conducted in a range of temperatures (-40~35°C). Plane strain fracture toughness (KIC) was evaluated using compact tension (CT) specimen. To gain a better understanding of the failure mechanisms, all fracture surfaces were observed using scanning electron microscopy (SEM). In addition, fatigue behavior of this alloy was estimated using tension test under tension-tension condition at 30 Hz. The stress amplitude was selected in the range of 20~50 MPa to obtain the S-N curve. Findings: The tensile test indicated that the mechanical properties were not sensitive to the strain rates applied (3.3x10-4~0.1) and the plastic deformation was dominated by twining mediated slip. The impact energy is not sensitive to the environmental temperature. The plane strain fracture toughness and fatigue limit were evaluated and the average values were 7.6 MPa.m1/2 and 25 MPa, respectively. Practical implications: Tested materials AM60 Mg alloy can be applied among others in automotive industry aerospace, communication and computer industry. Originality/value: Many investigations have been conducted to develop new Mg alloys with improved stiffness and ductility. On the other hand, relatively less attention has been paid to the failure mechanisms of Mg alloys, such as brittle fracture and fatigue, subjected to different environmental or loading conditions. In this work, tension, impact, bend and fatigue tests were conducted in an AM60 magnesium alloy.

Nanostructured high strength Mg-5%Al-x%Nd alloys prepared by mechanical alloying

Nanostructured high strength Mg-5%Al-x%Nd alloys were prepared by mechanical alloying. Microstructural characterization reveled average crystalline size to be about 30 nm after mechanical alloying while it increased to about 90 nm after sintering and extrusion. Mechanical properties showed increase in 0.2% yield stress, ultimate tensile strength was attributed to reduction in gain size as well as to the enhanced diffusion after mechanical activation. Although ultra high yield stress was observed from the specimen with 5% Nd, its ductility was reduced to about 1.6%.

In-situ combustion synthesis of ultrafine TiB2 particles reinforced Cu matrix composite

Due to the lower strength of pure copper (Cu), ceramic particulate or whisker reinforced Cu matrix composites have attracted wide interest in recent years [1–3]. These materials exhibit a combination of excellent thermal and electrical conductivities, high strength retention at elevated temperatures, and high microstructural stability [3]. The potential applications include various electrodes, electrical switches, and X-ray tube components [4].

Fabrication and microstructure of mechanically alloyed Mg-Al-Nd alloys

In this work, nanocrystalline Mg-Al-Nd alloys were fabricated using mechanical alloying method. Phase structure of the extrided rods was examined using X-ray diffraction (XRD) and the microstructures were observed using transmission electronic microscopy (TEM). High yield strength was obtained in the alloys with a high Nd content due to grain refinement and Nd rich precipitate phase.

Catchment-specific element signatures in estuarine crocodiles (Crocodylus porosus) from the Alligator Rivers Region, northern Australia

The concentrations of Na, K, Ca, Mg, Ba, Sr, Fe, Al, Mn, Zn, Pb, Cu, Ni, Cr, Co, Se, U and Ti were determined in the osteoderms and/or flesh of estuarine crocodiles (Crocodylus porosus) captured in three adjacent catchments within the Alligator Rivers Region (ARR) of northern Australia. Results from multivariate analysis of variance showed that when all metals were considered simultaneously, catchment effects were significant (P≤0.05). Despite considerable within-catchment variability, linear discriminant analysis (LDA) showed that differences in elemental signatures in the osteoderms and/or flesh of C. porosus amongst the catchments were sufficient to classify individuals accurately to their catchment of occurrence. Using cross-validation, the accuracy of classifying a crocodile to its catchment of occurrence was 76% for osteoderms and 60% for flesh. These data suggest that osteoderms provide better predictive accuracy than flesh for discriminating crocodiles amongst catchments. There was no advantage in combining the osteoderm and flesh results to increase the accuracy of classification (i.e. 67%). Based on the discriminant function coefficients for the osteoderm data, Ca, Co, Mg and U were the most important elements for discriminating amongst the three catchments. For flesh data, Ca, K, Mg, Na, Ni and Pb were the most important metals for discriminating amongst the catchments. Reasons for differences in the elemental signatures of crocodiles between catchments are generally not interpretable, due to limited data on surface water and sediment chemistry of the catchments or chemical composition of dietary items of C. porosus. From a wildlife management perspective, the provenance or source catchment(s) of 'problem' crocodiles captured at settlements or recreational areas along the ARR coastline may be established using catchment-specific elemental signatures. If the incidence of problem crocodiles can be reduced in settled or recreational areas by effective management at their source, then public safety concerns about these predators may be moderated, as well as the cost of their capture and removal. Copyright © 2002 Elsevier Science B.V.

Plasma-driven self-organization of Ni nanodot arrays on Si(100)

The results of the combined experimental and numerical study suggest that nonequilibrium plasma-driven self-organization leads to better size and positional uniformity of nickel nanodot arrays on a Si(100) surface compared with neutral gas-based processes under similar conditions. This phenomenon is explained by introducing the absorption zone patterns, whose areas relative to the small nanodot sizes become larger when the surface is charged. Our results suggest that strongly nonequilibrium and higher-complexity plasma systems can be used to improve ordering and size uniformity in nanodot arrays of various materials, a common and seemingly irresolvable problem in self-organized systems of small nanoparticles. © 2008 American Institute of Physics.

Synthesis, mechanical and electrical properties of carbon microcoils and nanocoils

The results on the synthesis, mechanical and electrical properties of carbon microcoils and nanocoils (CMCs, CNCs) synthesized using catalytic CVD and Ni-P and Co-P catalyst alloys, respectively, are reported. SEM analysis reveals that the CMCs and CNCs have unique helical morphologies, and diameters of 5.0-9.0 μm and 450-550 nm, respectively. Moreover, CMCs with flat cross-section can be stretched to 3 times their original coil lengths. Current-voltage characteristics of a single microcoil have also been obtained. It is found that the CMCs have the electrical conductivity between 100 and 160 S/cm, whereas the electrical resistance increases by about 20% during the coil extension. Besides, the microcoils can produce light in vacuum when the test voltage reaches 10 V. The emission intensity increases as the voltage increases. The mechanical and electrical properties of CMCs and CNC make them potentially useful in many applications in micromagnetic sensors, mechanical microsprings and optoelectronics.

Effect of doping with Co and/or Cu on electronic structure and optical properties of ZnO

This paper reports on ab initio numerical simulations of the effect of Co and Cu dopings on the electronic structure and optical properties of ZnO, pursued to develop diluted magnetic semiconductors vitally needed for spintronic applications. The simulations are based upon the Perdew-Burke-Enzerh generalized gradient approximation on the density functional theory. It is revealed that the electrons with energies close to the Fermi level effectively transfer only between Cu and Co ions which substitute Zn atoms, and are located in the neighbor sites connected by an O ion. The simulation results are consistent with the experimental observations that addition of Cu helps achieve stable ferromagnetism of Co-doped ZnO. It is shown that simultaneous insertion of Co and Cu atoms leads to smaller energy band gap, redshift of the optical absorption edge, as well as significant changes in the reflectivity, dielectric function, refractive index, and electron energy loss function of ZnO as compared to the doping with either Co or Cu atoms. These highly unusual optical properties are explained in terms of the computed electronic structure and are promising for the development of the next-generation room-temperature ferromagnetic semiconductors for future spintronic devices on the existing semiconductor micromanufacturing platform.