Showing papers on "Copper published in 2015"

Selective Electrochemical Reduction of Carbon Dioxide to Ethylene and Ethanol on Copper(I) Oxide Catalysts

Abstract: The selective electroreduction of carbon dioxide to C2 compounds (ethylene and ethanol) on copper(I) oxide films has been investigated at various electrochemical potentials. Aqueous 0.1 M KHCO3 was used as electrolyte. A remarkable finding is that the faradic yields of ethylene and ethanol can be systematically tuned by changing the thickness of the deposited overlayers. Films 1.7–3.6 μm thick exhibited the best selectivity for these C2 compounds at −0.99 V vs RHE, with faradic efficiencies (FE) of 34–39% for ethylene and 9–16% for ethanol. Less than 1% methane was formed. A high C2H4/CH4 products’ ratio of up to ∼100 could be achieved. Scanning electron microscopy, X-ray diffraction, and in situ Raman spectroscopy revealed that the Cu2O films reduced rapidly and remained as metallic Cu0 particles during the CO2 reduction. The selectivity trends exhibited by the catalysts during CO2 reduction in phosphate buffer, and KHCO3 electrolytes suggest that an increase in local pH at the surface of the electrode i...

An Aqueous Zinc‐Ion Battery Based on Copper Hexacyanoferrate

Abstract: A new zinc-ion battery based on copper hexacyanoferrate and zinc foil in a 20 mM solution of zinc sulfate, which is a nontoxic and noncorrosive electrolyte, at pH 6 is reported. The voltage of this novel battery system is as high as 1.73 V. The system shows cyclability, rate capability, and specific energy values near to those of lithium-ion organic batteries based on Li4 Ti5 O12 and LiFePO4 at 10 C. The effects of Zn(2+) intercalation and H2 evolution on the performance of the battery are discussed in detail. In particular, it has been observed that hydrogen evolution can cause a shift in pH near the surface of the zinc electrode, and favor the stabilization of zinc oxide, which decreases the performance of the battery. This mechanism is hindered when the surface of zinc becomes rougher.

A two-dimensional π–d conjugated coordination polymer with extremely high electrical conductivity and ambipolar transport behaviour

Abstract: Currently, studies on organic two-dimensional (2D) materials with special optic-electronic properties are attracting great research interest. However, 2D organic systems possessing promising electrical transport properties are still rare. Here a highly crystalline thin film of a copper coordination polymer, Cu-BHT (BHT = benzenehexathiol), is prepared via a liquid-liquid interface reaction between BHT/dichloromethane and copper(II) nitrate/H2O. The morphology and structure characterization reveal that this film is piled up by nanosheets of 2D lattice of [Cu-3(C6S6)](n), which is further verified by quantum simulation. Four-probe measurements show that the room temperature conductivity of this material can reach up to 1,580 S cm (-1), which is the highest value ever reported for coordination polymers. Meanwhile, it displays ambipolar charge transport behaviour and extremely high electron and hole mobilities (99 cm(2) V (-1) s (-1) for holes and 116 cm(2) V (-1) s (-1) for electrons) under field-effect modulation.

Targeting copper in cancer therapy: ‘Copper That Cancer’

Abstract: Copper is an essential micronutrient involved in fundamental life processes that are conserved throughout all forms of life. The ability of copper to catalyze oxidation-reduction (redox) reactions, which can inadvertently lead to the production of reactive oxygen species (ROS), necessitates the tight homeostatic regulation of copper within the body. Many cancer types exhibit increased intratumoral copper and/or altered systemic copper distribution. The realization that copper serves as a limiting factor for multiple aspects of tumor progression, including growth, angiogenesis and metastasis, has prompted the development of copper-specific chelators as therapies to inhibit these processes. Another therapeutic approach utilizes specific ionophores that deliver copper to cells to increase intracellular copper levels. The therapeutic window between normal and cancerous cells when intracellular copper is forcibly increased, is the premise for the development of copper-ionophores endowed with anticancer properties. Also under investigation is the use of copper to replace platinum in coordination complexes currently used as mainstream chemotherapies. In comparison to platinum-based drugs, these promising copper coordination complexes may be more potent anticancer agents, with reduced toxicity toward normal cells and they may potentially circumvent the chemoresistance associated with recurrent platinum treatment. In addition, cancerous cells can adapt their copper homeostatic mechanisms to acquire resistance to conventional platinum-based drugs and certain copper coordination complexes can re-sensitize cancer cells to these drugs. This review will outline the biological importance of copper and copper homeostasis in mammalian cells, followed by a discussion of our current understanding of copper dysregulation in cancer, and the recent therapeutic advances using copper coordination complexes as anticancer agents.

High Selectivity for Ethylene from Carbon Dioxide Reduction over Copper Nanocube Electrocatalysts

Abstract: Nanostructured surfaces have been shown to greatly enhance the activity and selectivity of many different catalysts. Here we report a nanostructured copper surface that gives high selectivity for ethylene formation from electrocatalytic CO2 reduction. The nanostructured copper is easily formed in situ during the CO2 reduction reaction, and scanning electron microscopy (SEM) shows the surface to be dominated by cubic structures. Using online electrochemical mass spectrometry (OLEMS), the onset potentials and relative selectivity toward the volatile products (ethylene and methane) were measured for several different copper surfaces and single crystals, relating the cubic shape of the copper surface to the greatly enhanced ethylene selectivity. The ability of the cubic nanostructure to so strongly favor multicarbon product formation from CO2 reduction, and in particular ethylene over methane, is unique to this surface and is an important step toward developing a catalyst that has exclusive selectivity for multicarbon products.

Copper-catalysed azide-alkyne cycloadditions (CuAAC): an update.

Abstract: The reactions of organic azides and alkynes catalysed by copper species represent the prototypical examples of click chemistry. The so-called CuAAC reaction (copper-catalysed azide-alkyne cycloaddition), discovered in 2002, has been expanded since then to become an excellent tool in organic synthesis. In this contribution the recent results described in the literature since 2010 are reviewed, classified according to the nature of the catalyst precursor: copper(I) or copper(II) salts or complexes, metallic or nano-particulated copper and several solid-supported copper systems.

Understanding the pathway of antibacterial activity of copper oxide nanoparticles

Abstract: This work investigates the role of oxidation state in the antibacterial activity of copper oxide nanoparticles (NPs). The findings add strong support to a contact killing mechanism of copper oxides (CuO and Cu2O) through which bacteria initially suffer severe damage to the cell envelope. Then further damage ensues by an independent pathway of each copper oxide nanoparticle. Formation of copper(I)–peptide complex from cuprous oxide (Cu2O) and free radical generation from cupric oxide (CuO) were identified as key sources of toxicity towards E.coli. Cu2O rapidly inactivated Fumarase A, an iron sulphur cluster enzyme suggesting the cuprous state of copper binding to the proteins. This inactivation was not noticed in CuO. The percentage of biocidal/bacteriostatic activity is closely related to the oxidation state of the copper oxides. In the case of E.coli, Cu2O nanoparticles showed more efficient antibacterial activity and higher affinity to the bacterial cells. CuO nanoparticles produced significant ROS in terms of super oxides while Cu2O did not. The diminishing defective emission peaks of Cu2O after incubation with microbes strongly suggest the formation of protein complexes. This work is carried out to enable better understanding of the mechanistic pathways of copper oxide nanoparticles.

Manipulating the Hydrocarbon Selectivity of Copper Nanoparticles in CO2 Electroreduction by Process Conditions

Abstract: The formation of ethylene in CO2 electroreduction over rough copper electrodes is often explained by the presence of specific surface crystal steps, edges and defects. We demonstrate that an identical electrode covered with copper nanoparticles can yield either predominantly ethylene or methane, depending on the electrolyte concentration and applied CO2 pressure. Calculations of the pH near the electrode surface suggest that ethylene formation is favored by a relatively high (local) pH. Furthermore, the conditions leading to the formation of significant amounts of methane result in rapid deterioration of hydrocarbon production rates, whereas electrode performance in conditions favoring ethylene production can be sustained for hours. This study substantially alters the mechanistic interpretation of formation of ethylene over rough copper surfaces and implies that applied process conditions inducing pH variations near the electrode surface need to be taken into consideration.

FTIR and synchronous fluorescence heterospectral two-dimensional correlation analyses on the binding characteristics of copper onto dissolved organic matter.

Abstract: Dissolved organic matter (DOM) is known to form strong complexes with heavy metals and thus governs the distribution, toxicity, bioavailability, and ultimate fate of heavy metals in the environment. The relevant aspects of metal-organic interactions remain unclear because the metal binding functionalities in DOM are substantially nonuniform and the availability of the models is limited. In this work, two-dimensional correlation spectroscopy (2DCOS) integrated with synchronous fluorescence and infrared absorption spectroscopy was used to explore the binding process of copper to DOM. A series of heterogeneous binding sites in humic acid (HA), a representative DOM, and the subsequent subtle changes of these sites within the molecular interactions were elucidated by the 2DCOS method. The band assignments and the correspondence between the results obtained by two spectral probes (synchronous fluorescence and infrared absorption spectra) were verified by hetero-2DCOS. Our results showed that, during the copper binding process, the carboxyl and polysaccharide groups gave the fastest responses to copper binding. Then fluorescence quenching of fluorescent humic-like moieties occurred with a vibrational change of the related functionalities, i.e., phenolic and aryl carboxylic groups, which further induces the fluorescence quenching of fulvic-like fractions. Finally, small amounts of amide and aliphatic groups participated in the copper binding after the fluorescence of the protein-like fraction decreased. With these promising results, a comprehensive picture of structural changes of HA during the copper binding process was developed, highlighting the superior potential of 2D heterospectral correlation spectroscopy in studying complex interactions in the environment.

Air‐Stable Copper‐Based P2‐Na7/9Cu2/9Fe1/9Mn2/3O2 as a New Positive Electrode Material for Sodium‐Ion Batteries

Abstract: An air-stable copper-based P2-Na7/9Cu2/9Fe1/9Mn2/3O2 is designed and synthesized by a simple solid-state method and investigated as a positive electrode material for sodium-ion batteries. The attractive long cycling stability is demonstrated by the capacity retention of 85% after 150 cycles at 1 C rate without phase transformation. The reversible Cu2+/Cu3+ redox couple in P2 phase oxides is proved for the first time.

Electrocatalytic Production of C3-C4 Compounds by Conversion of CO2 on a Chloride-Induced Bi-Phasic Cu2O-Cu Catalyst.

Abstract: Electrocatalytic conversion of carbon dioxide (CO2) has recently received considerable attention as one of the most feasible CO2 utilization techniques. In particular, copper and copper-derived catalysts have exhibited the ability to produce a number of organic molecules from CO2. Herein, we report a chloride (Cl)-induced bi-phasic cuprous oxide (Cu2O) and metallic copper (Cu) electrode (Cu2OCl) as an efficient catalyst for the formation of high-carbon organic molecules by CO2 conversion, and identify the origin of electroselectivity toward the formation of high-carbon organic compounds. The Cu2OCl electrocatalyst results in the preferential formation of multi-carbon fuels, including n-propanol and n-butane C3-C4 compounds. We propose that the remarkable electrocatalytic conversion behavior is due to the favorable affinity between the reaction intermediates and the catalytic surface.

4 Copper and Copper Alloys

Abstract: Copper was among the first metals to be put into utilitarian service. The Unified Numbering System (UNS) is the accepted alloy designation system in North America for wrought and cast coppers and copper alloys. Identification is by five-digit numbers preceded by the letter C. Preferred marine alloys include copper nickels, which exhibit the highest corrosion and erosion resistance among copper metals, and also offer relatively high strengths, and aluminum bronzes, which are stronger still, as well as ultrahigh-strength beryllium copper, inhibited aluminum brass, phosphor bronzes, arsenical admiralty brass, and nickel silvers. Copper alloys that perform well in seawater are also often acceptable for use with industrial and process. Copper casting alloys are widely used in the manufacture of plumbing, electrical, and mechanical products and for bearings and industrial valves and fittings. Copper nickels, aluminum bronzes, silicon bronzes, manganese bronzes, and tin and phosphor bronzes should be considered for such environments. Keywords: copper alloys; marine alloys; Unified Numbering System (UNS)

Highly Dispersed Copper Oxide Clusters as Active Species in Copper-Ceria Catalyst for Preferential Oxidation of Carbon Monoxide

Abstract: Copper-ceria is one of the very active catalysts for the preferential oxidation of carbon monoxide (CO-PROX) reaction, which is also a typical system in which the complexity of copper chemistry is clearly exhibited. In the present manuscript, copper–ceria catalysts with different Cu contents up to 20 wt % supported on CeO2 nanorods were synthesized by a deposition–precipitation (DP) method. The as-prepared samples were characterized by various structural and textural detections including X-ray diffraction (XRD), Vis-Raman, transmission electron microscopy (TEM), ex situ/in situ X-ray absorption fine structure (XAFS), and temperature-programmed reduction by hydrogen (H2-TPR). It has been confirmed that the highly dispersed copper oxide (CuOx) clusters, as well as the strong interaction of Cu-[Ox]-Ce structure, were the main copper species deposited onto the ceria surface. No separated copper phase was detected for both preoxidized and prereduced samples with the Cu contents up to 10 wt %. The fresh copper–...

Electrocatalytic water oxidation by a dinuclear copper complex in a neutral aqueous solution.

Abstract: Electrocatalytic water oxidation using the oxidatively robust 2,7-[bis(2-pyridylmethyl)aminomethyl]-1,8-naphthyridine ligand (BPMAN)-based dinuclear copper(II) complex, [Cu2(BPMAN)(μ-OH)](3+), has been investigated. This catalyst exhibits high reactivity and stability towards water oxidation in neutral aqueous solutions. DFT calculations suggest that the O-O bond formation takes place by an intramolecular direct coupling mechanism rather than by a nucleophilic attack of water on the high-oxidation-state Cu(IV)=O moiety.

An exploration of binder jetting of copper

Abstract: Purpose – The purpose of this paper is to explore the use of binder jetting to fabricate high-purity copper parts. The ability to fabricate geometrically complex copper shapes would have implications on the design and manufacture of components for thermal management systems and structural electronics. Design/methodology/approach – To explore the feasibility of processing copper via binder jetting, the authors followed an established material development process that encompasses powder selection and tuning process parameters in printing and thermal cycles. Specifically, the authors varied powder size and sintering cycles to explore their effects on densification. Findings – Three differently sized copper powders were successfully printed, followed by sintering in a reducing atmosphere. It was found that a 15-μm-diameter powder with a sintering cycle featuring a 1,080°C maximum temperature provides the most dense (85 per cent) and pure (97 per cent) final copper parts of the parameters tested. Research limi...

Efficient Electrocatalytic Water Oxidation by a Copper Oxide Thin Film in Borate Buffer

Abstract: A robust water oxidation catalyst based on copper oxide was prepared by facile electrodeposition of Cu2+ from borate buffer solution under near neutral conditions. The Cu–Bi thin film exhibits high activity and long-term stability in Cu2+-free pH 9 borate buffer. A steady current density of 1.2 mA/cm2 was sustained for at least 10 h at 1.3 V versus NHE without iR compensation, which sets a new benchmark for copper-based OEC.

High thermoelectric performance in copper telluride

Abstract: Recently, Cu2-δS and Cu2-δSe were reported to have an ultralow thermal conductivity and high thermoelectric figure of merit zT. Thus, as a member of the copper chalcogenide group, Cu2-δTe is expected to possess superior zTs because Te is less ionic and heavy. However, the zT value is low in the Cu2Te sintered using spark plasma sintering, which is typically used to fabricate high-density bulk samples. In addition, the extra sintering processes may change the samples’ compositions as well as their physical properties, especially for Cu2Te, which has many stable and meta-stable phases as well as weaker ionic bonding between Cu and Te as compared with Cu2S and Cu2Se. In this study, high-density Cu2Te samples were obtained using direct annealing without a sintering process. In the absence of sintering processes, the samples’ compositions could be well controlled, leading to substantially reduced carrier concentrations that are close to the optimal value. The electrical transports were optimized, and the thermal conductivity was considerably reduced. The zT values were significantly improved—to 1.1 at 1000 K—which is nearly 100% improvement. Furthermore, this method saves substantial time and cost during the sample’s growth. The study demonstrates that Cu2-δX (X=S, Se and Te) is the only existing system to show high zTs in the series of compounds composed of three sequential primary group elements. A time-saving procedure for boosting the performance of experimental thermoelectric energy harvesters has been developed by a team in China. Recently, copper sulfide (CuS) and copper selenide (CuSe) compounds have garnered interest as thermoelectric generators because their extraordinarily low thermal conductivities enable highly efficient conversion of temperature swings into electricity. However, copper telluride (CuTe) compounds, which have even lower lattice thermal conductivities than CuS or CuSe compounds, have so far displayed only moderate thermoelectric capacities. Xun Shi at the Chinese Academy of Sciences and co-workers solved this mystery by eliminating the spark plasma sintering procedure normally used to produce high-density CuS and CuSe thermoelectrics. The researchers raised the thermoelectric efficiency by a few times by directly annealing CuTe crystals. They attribute this increase to better control over carrier concentrations in the samples’ crystal structure. Enhanced thermoelectric figure of merit in the fully densified Cu2Te bulk materials by direct annealing method.

Extracellular biosynthesis of copper and copper oxide nanoparticles by Stereum hirsutum , a native white-rot fungus from Chilean forests

Abstract: The white-rot fungus Stereum hirsutum was studied to evaluate its applicability for use in the biosynthesis of copper/copper oxide nanoparticles under different pHconditions and in the presence of three different copper salts (CuCl2, CuSO4, and Cu(NO3)2). The nanoparticle formation was evaluated by UV-visible spectroscopy, electron microscopy (TEM), X-ray diffraction analysis (XRD), and Fourier transforms infrared spectroscopy (FTIR). The nanoparticles biosynthesis in presence of all copper salts demonstrated higher formation with 5 mM CuCl2 under alkaline conditions. TEM analysis confirmed that the nanoparticles were mainly spherical (5 to 20 nm). The presence of amine groups attached to nanoparticles was confirmed by FTIR, which suggests that extracellular protein of fungus is responsible for the formation of the nanoparticles. Therefore, the white-rot fungus S. hirsutum was found to exhibit potential for use in the synthesis of copper/copper oxide nanoparticles.

Synthesis of Ultrathin Copper Nanowires Using Tris(trimethylsilyl)silane for High-Performance and Low-Haze Transparent Conductors.

Abstract: Colloidal metal nanowire based transparent conductors are excellent candidates to replace indium–tin–oxide (ITO) owing to their outstanding balance between transparency and conductivity, flexibility, and solution-processability. Copper stands out as a promising material candidate due to its high intrinsic conductivity and earth abundance. Here, we report a new synthetic approach, using tris(trimethylsilyl)silane as a mild reducing reagent, for synthesizing high-quality, ultrathin, and monodispersed copper nanowires, with an average diameter of 17.5 nm and a mean length of 17 μm. A study of the growth mechanism using high-resolution transmission electron microscopy reveals that the copper nanowires adopt a five-fold twinned structure and evolve from decahedral nanoseeds. Fabricated transparent conducting films exhibit excellent transparency and conductivity. An additional advantage of our nanowire transparent conductors is highlighted through reduced optical haze factors (forward light scattering) due to t...

Single-step deposition of high-mobility graphene at reduced temperatures

Abstract: Current methods of chemical vapour deposition (CVD) of graphene on copper are complicated by multiple processing steps and by high temperatures required in both preparing the copper and inducing subsequent film growth. Here we demonstrate a plasma-enhanced CVD chemistry that enables the entire process to take place in a single step, at reduced temperatures (o420C), and in a matter of minutes. Growth on copper foils is found to nucleate from arrays of well-aligned domains, and the ensuing films possess sub-nanometre smoothness, excellent crystalline quality, low strain, few defects and roomtemperature electrical mobility up to (6.0±1.0) � 10 4 cm 2 V � 1 s � 1 , better than that of large,

A thermally regenerative ammonia-based battery for efficient harvesting of low-grade thermal energy as electrical power

Abstract: Thermal energy was shown to be efficiently converted into electrical power in a thermally regenerative ammonia-based battery (TRAB) using copper-based redox couples [Cu(NH3)42+/Cu and Cu(II)/Cu]. Ammonia addition to the anolyte (2 M ammonia in a copper-nitrate electrolyte) of a single TRAB cell produced a maximum power density of 115 ± 1 W m−2 (based on projected area of a single copper mesh electrode), with an energy density of 453 W h m−3 (normalized to the total electrolyte volume, under maximum power production conditions). Adding a second cell doubled both the voltage and maximum power. Increasing the anolyte ammonia concentration to 3 M further improved the maximum power density to 136 ± 3 W m−2. Volatilization of ammonia from the spent anolyte by heating (simulating distillation), and re-addition of this ammonia to the spent catholyte chamber with subsequent operation of this chamber as the anode (to regenerate copper on the other electrode), produced a maximum power density of 60 ± 3 W m−2, with an average discharge energy efficiency of ∼29% (electrical energy captured versus chemical energy in the starting solutions). Power was restored to 126 ± 5 W m−2 through acid addition to the regenerated catholyte to decrease pH and dissolve Cu(OH)2 precipitates, suggesting that an inexpensive acid or a waste acid could be used to improve performance. These results demonstrated that TRABs using ammonia-based electrolytes and inexpensive copper electrodes can provide a practical method for efficient conversion of low-grade thermal energy into electricity.

Cu Vacancies Boost Cation Exchange Reactions in Copper Selenide Nanocrystals

Abstract: We have investigated cation exchange reactions in copper selenide nanocrystals using two different divalent ions as guest cations (Zn2+ and Cd2+) and comparing the reactivity of close to stoichiometric (that is, Cu2Se) nanocrystals with that of nonstoichiometric (Cu2–xSe) nanocrystals, to gain insights into the mechanism of cation exchange at the nanoscale. We have found that the presence of a large density of copper vacancies significantly accelerated the exchange process at room temperature and corroborated vacancy diffusion as one of the main drivers in these reactions. Partially exchanged samples exhibited Janus-like heterostructures made of immiscible domains sharing epitaxial interfaces. No alloy or core–shell structures were observed. The role of phosphines, like tri-n-octylphosphine, in these reactions, is multifaceted: besides acting as selective solvating ligands for Cu+ ions exiting the nanoparticles during exchange, they also enable anion diffusion, by extracting an appreciable amount of selen...