Fabrication of metal-nanoparticle-modified semiconducting copper--and silver--TCNQ materials as substrates for the reduction of chromium (VI) using thiosulfate ions at ambient temperature

The formation of readily recoverable and reusable organic semiconducting Cu- and AgTCNQ (TCNQ=7,7,8,8-tetracyanoquinodimethane) microstructures decorated with Pt and Pd metallic nanoparticles is described for the effective reduction of CrVI ions in aqueous solution at room temperature using both formic acid and an environmentally friendly thiosulfate reductant. The M-TCNQ (M=metal) materials were formed by electrocrystallisation onto a glassy carbon surface followed by galvanic replacement in the presence of H2PtCl6 or PdCl2 to form the composite material. It was found that loading of the surface with nanoparticles could easily be controlled by changing the metal salt concentration. Significantly, the M-TCNQ substrates facilitated the formation of well-isolated metal nanoparticles on their surfaces under appropriate galvanic replacement conditions. The semiconductor–metal nanoparticle combination was also found to be critical to the catalyst performance, wherein the best-performing material was CuTCNQ modified by well-isolated Pt nanoparticles with both formic acid and thiosulfate ions as the reductant.

High-temperature growth of graphene films on copper foils by ethanol chemical vapour deposition

Chemical vapor deposition (CVD) is widely utilized to synthesize graphene with controlled properties for many applications, especially when continuous films over large areas are required. Although hydrocarbons such as methane are quite efficient precursors for CVD at high temperature (∼1000 °C), finding less explosive and safer carbon sources is considered beneficial for the transition to large-scale production. In this work, we investigated the CVD growth of graphene using ethanol, which is a harmless and readily processable carbon feedstock that is expected to provide favorable kinetics. We tested a wide range of synthesis conditions (i.e., temperature, time, gas ratios), and on the basis of systematic analysis by Raman spectroscopy, we identified the optimal parameters for producing highly crystalline graphene with different numbers of layers. Our results demonstrate the importance of high temperature (1070 °C) for ethanol CVD and emphasize the significant effects that hydrogen and water vapor, coming from the thermal decomposition of ethanol, have on the crystal quality of the synthesized graphene.

Taguchi optimized synthesis of graphene films by copper catalyzed ethanol decomposition

Taguchi method is for the first time applied to optimize the synthesis of graphene films by copper-catalyzed decomposition of ethanol. In order to find the most appropriate experimental conditions for the realization of thin high-grade films, six experiments suitably designed and performed. The influence of temperature (1000–1070 °C) and synthesis duration (1–30 min) and hydrogen flow (0–100 sccm) on the number of graphene layers and defect density in the graphitic lattice was ranked by monitoring the intensity of the 2D- and D-bands relative to the G-band in the Raman spectra. After critical examination and adjusting of the conditions predicted to give optimal results, a continuous film consisting of 2–4 nearly defect-free graphene layers was obtained.

Synthesis and spectroscopic characterization of copper zinc aluminum nanoferrite particles

Copper doped zinc aluminium ferrites are synthesized by the solid-state reaction route is cubic crystalline with unit cell parameter varying from 8.39 to 8.89 Å. TEM pictures clearly indicating that fundamental unit is composed of octahedral and tetrahedral blocks and joined strongly shown in (a). EPR spectra is compositional dependent at lower Al/Cu concentration EPR spectra is due to Fe3+ and at a higher content of Al/Cu the EPR spectra is due to Cu2+. Absence of EPR spectra at room temperature indicates that the sample is perfectly ferromagnetic. EPR results at low temperature indicate that the sample is paramagnetic, and that copper is placed in the tetragonal elongation (B) site with magnetically non-equivalent ions in the unit cell having strong exchange coupling between them. This is shown in (b). (a) TEM image of ferrite with x = 0.15. (b) EPR spectrum of ferrite with x = 0.75.

On the importance of an acid additive in the synthesis of pyrido[1,2-a]benzimidazoles by direct copper-catalyzed amination

Pyrido[1,2-a]benzimidazoles1, 2a are interesting compounds both from the viewpoint of medicinal chemistry2–7 (solubility,7 DNA intercalation3) and materials chemistry8 (fluorescence). Of note among the former is the antibiotic drug Rifaximin,5 which contains this heteroaromatic core. The classical synthetic approach for the assembly of pyrido[1,2-a]benzimidazoles is by [3+3] cyclocondensation of benzimidazoles containing a methylene group at C2 with appropriate bielectrophiles.2a However, these procedures are often low-yielding, involve indirect/lengthy sequences, and/or provide access to a limited range of products, primarily providing derivatives with substituents located on the pyridine ring (A ring, Scheme 1).2–4 Theoretically, a good alternative synthetic method for the synthesis of pyrido[1,2-a]benzimidazoles with substituents in the benzene ring (C ring) should be accessible by intramolecular transition-metal-catalyzed CN bond formation in N-(2-chloroaryl)pyridin-2-amines, based on chemistry recently developed in our research group.9 These substrates themselves are easily available through SNAr or selective Pd-catalyzed amination10 of 2-chloropyridine with 2-chloroanilines.11 If a synthetic procedure that eliminated the need for preactivation of the 2-position of the 2-chloroarylamino entity could be developed, this would be even more powerful, as anilines are more readily commercially available than 2-chloroanilines. Therefore the synthesis of pyrido[1,2-a]benzimidazoles (4) by a transition-metal-catalyzed intramolecular CH amination approach from N-arylpyridin-2-amines (3) was explored (Scheme 1).

Vibrational spectroscopy of the copper (II) disodium sulphate dihydrate mineral kröhnkite Na2Cu(SO4)2 · 2H2O

A natural single-crystal specimen of the kröhnkite from Chuquicamata, Chile, with the general formula Na2Cu(SO4)2 · 2H2O, was investigated by Raman and infrared spectroscopy. The mineral kröhnkite is found in many parts of the world's arid areas. Kröhnkite crystallizes in the monoclinic crystal system with point group 2/m and space group P21/c. It is an uncommon secondary mineral formed in the oxidized zone of copper deposits, typically in very arid climates. The Raman spectrum of kröhnkite dominated by a very sharp intense band at 992 cm−1 is assigned to the ν1 symmetric stretching mode and Raman bands at 1046, 1049, 1138, 1164, and 1177 cm−1 are assigned to the ν3 antisymmetric stretching vibrations. The infrared spectrum shows an intense band at 992 cm−1. The Raman bands at 569, 582, 612, 634, 642, 655, and 660 cm−1 are assigned to the ν4 bending modes. Three Raman bands observed at 429, 445, and 463 cm−1 are attributed to the ν2 bending modes. The observation that three or four bands are seen in the ν4 region of kröhnkite is attributed to the reduction of symmetry to C2v or less.

The effect of electrode material on the electrochemical formation of porous copper surfaces using hydrogen bubble templating

The electrodeposition of copper onto copper, gold, palladium and glassy carbon (GC) electrodes via a hydrogen bubble templating method is reported. It is found that the composition of the underlying electrode material significantly influences the morphology of the copper electrodeposit. Highly ordered porous structures are achieved with Cu and Au electrodes, however on Pd this order is disrupted and a rough randomly oriented surface is formed whereas on GC a bubble templating effect is not observed. Chronopotentiograms recorded during the electrodeposition process allows bubble formation and detachment from the surface to be monitored where distinctly different potential versus time profiles are observed at the different electrodes. The porous Cu surfaces are characterised with scanning electron microscopy, X-ray diffraction and cyclic voltammetric measurements recorded under alkaline conditions. The latter demonstrates that there are active sites present on electrodeposited copper whose coverage and reactivity depend on the underlying electrode material. The most active Cu surface is achieved at a Pd substrate for both the hydrogen evolution reaction and the catalytic reduction of ferricyanide ions with thiosulphate ions. This demonstrates that the highly ordered porous structure on the micron scale which typifies the morphology that can be achieved with the hydrogen bubbling template method is not required in producing the most effective material.

Copper-capped carbon nanocones on silicon : plasma-enabled growth control

Controlled self-organized growth of vertically aligned carbon nanocone arrays in a radio frequency inductively coupled plasma-based process is studied. The experiments have demonstrated that the gaps between the nanocones, density of the nanocone array, and the shape of the nanocones can be effectively controlled by the process parameters such as gas composition (hydrogen content) and electrical bias applied to the substrate. Optical measurements have demonstrated lower reflectance of the nanocone array as compared with a bare Si wafer, thus evidencing their potential for the use in optical devices. The nanocone formation mechanism is explained in terms of redistribution of surface and volumetric fluxes of plasma-generated species in a developing nanocone array and passivation of carbon in narrow gaps where the access of plasma ions is hindered. Extensive numerical simulations were used to support the proposed growth mechanism.

Plasma-enabled growth of separated, vertically aligned copper-capped carbon nanocones on silicon

The formation of vertically aligned, clearly separated, copper-capped carbon nanocones with a length of up to 500 nm and base diameter of about 150 nm via three-stage process involving magnetron sputtering, N2 plasma treatment, and CH4 + N2 plasma growth is studied. The width of gaps between the nanocones can be controlled by the gas composition. The nanocone formation mechanism is explained in terms of strong passivation of carbon in narrow gaps, where the access of plasma ions is hindered and the formation of large Cn H2n+2 molecules is possible. This plasma-enabled approach can be used to fabricate nanoelectronic, nanofluidic, and optoelectronic components and devices. © 2010 American Institute of Physics.

Nanostructured copper oxide semiconductors : a perspective on materials, synthesis methods and applications

The oxides of copper (CuxO) are fascinating materials due to their remarkable optical, electrical, thermal and magnetic properties. Nanostructuring of CuxO can further enhance the performance of this important functional material and provide it with unique properties that do not exist in its bulk form. Three distinctly different phases of CuxO, mainly CuO, Cu2O and Cu4O3, can be prepared by numerous synthesis techniques including, vapour deposition and liquid phase chemical methods. In this article, we present a review of nanostructured CuxO focusing on their material properties, methods of synthesis and an overview of various applications that have been associated with nanostructured CuxO.

Price linkages in the copper futures, primary, and scrap markets

This study investigates how markets for different levels of copper purity are interrelated by testing the long-run price linkage and causalities among the copper futures, primary, copper scrap, and brass scrap markets. It is expected that copper markets that deal with high purity levels, such as the futures, primary, and copper scrap markets, have a long-run relationship. However, brass scrap markets where copper with a lower purity is traded may not have a price linkage with other copper markets. The results reveal that a long-run relationship holds between the futures, primary, and copper scrap markets but the brass scrap market does not have a long-run relationship with the other markets. From the short-run and long-run causality tests, we determine that the futures market plays an important role in transmitting price information to other copper markets while such information flow is not found for the brass scrap market.

A vibrational spectroscopic study of the copper bearing silicate mineral luddenite

The molecular structure of the copper–lead silicate mineral luddenite has been analysed using vibrational spectroscopy. The mineral is only one of many silicate minerals containing copper. The intense Raman band at 978 cm−1 is assigned to the ν1 (A1g) symmetric stretching vibration of Si5O14 units. Raman bands at 1122, 1148 and 1160 cm−1 are attributed to the ν3 SiO4 antisymmetric stretching vibrations. The bands in the 678–799 cm−1 are assigned to OSiO bending modes of the (SiO3)n chains. Raman bands at 3317 and 3329 cm−1 are attributed to water stretching bands. Bands at 3595 and 3629 cm−1 are associated with the stretching vibrations of hydroxyl units suggesting that hydroxyl units exist in the structure of luddenite.

Interface of graphane with copper : a van der Waals density-functional study

Various forms of hydrogenated graphene have been produced to date by several groups, while the synthesis of pure graphane has not been achieved yet. The study of the interface between graphane, in all its possible hydrogenation configurations, and catalyst metal surfaces can be pivotal to assess the feasibility of direct CVD growth methods for this material. We investigated the adhesion of graphane to a Cu(111) surface by adopting the vdW-DF2-C09 exchange-correlation functional, which is able to describe dispersion forces. The results are further compared with the PBE and the LDA exchange-correlation functionals. We calculated the most stable geometrical configurations of the slab/graphane interface and evaluated how graphane's geometrical parameters are modified. We show that dispersion forces play an important role in the slab/graphane adhesion. Band structure calculations demonstrated that in the presence of the interaction with copper, the band gap of graphane is not only preserved, but also enlarged, and this increase can be attributed to the electronic charge accumulated at the interface. We calculated a substantial energy barrier at the interface, suggesting that CVD graphane films might act as reliable and stable insulating thin coatings, or also be used to form compound layers in conjunction with metals and semiconductors.