Copper is a highly promising catalyst for the electrochemical CO$_2$ reduction reaction (CO2RR) since it is the only pure metal that can form highly added-value products such as ethylene and ethanol. Since the CO2RR takes place in aqueous solution, the detailed atomic structure of the water-copper interface is essential for unraveling the key reaction mechanisms. In this study, we investigate copper-water interfaces exhibiting nanometer-scale roughnesses. We introduce two molecular dynamics protocols to create rough copper surfaces, which are subsequently brought into contact with water. From these interfaces, we sample additional training configurations from machine-learning-interatomic-potential-driven molecular dynamics simulations containing hundreds of thousands of atoms. An active learning workflow is developed to identify regions with high spatially resolved uncertainty and convert them into DFT-feasible cells through a modified amorphous matrix embedding approach. Finally, we analyze the local environments at the interface using unsupervised machine-learning techniques. Unique environments emerge on the rough copper surfaces absent from model systems, including stacking-fau
To understand the complex interplay of topography and surface chemistry in wetting, fundamental studies investigating both parameters are needed. Due to the sensitivity of wetting to miniscule changes in one of the parameters it is imperative to precisely control the experimental approach. A profound understanding of their influence on wetting facilitates a tailored design of surfaces with unique functionality. We present a multi-step study: The influence of surface chemistry is analyzed by determining the adsorption of volatile carbonous species (A) and by sputter deposition of metallic copper and copper oxides on flat copper substrates (B). A precise surface topography is created by laser processing. Isotropic topography is created by ps laser processing (C), and hierarchical anisotropic line patterns are produced by direct laser interference patterning (DLIP) with different pulse durations (D). Our results reveal that the long-term wetting response of polished copper surfaces stabilizes with time despite ongoing accumulation of hydrocarbons and is dominated by this adsorption layer over the oxide state of the substrate (Cu, CuO, Cu2O). The surfaces' wetting response can be preci
Thin films have found a wide variety of applications because of the substantial improvement in their properties as compared to bulk metals. Metal oxide thin films are increasingly being used in various fields and are especially important in functional applications. They can be either p- or n-type in nature depending on the materials, dopants, and preparation route. Copper oxide is an example of a p-type metal oxide, which finds application in solar cells, photo-electrochemical cells, gas sensors, supercapacitors, and thermoelectric touch detectors. Both copper (I) and copper (II) oxides can be grown with the lower valence state oxide stable at low temperature and the higher valence state obtained by annealing at higher temperatures. In this work, we modify the optical and electrical properties of copper oxide thin films, by doping of silver through a thermal evaporation process route. Copper is thermally evaporated onto the substrate and silver is co-evaporated during this process. The films are then annealed in ambient under various conditions to obtain copper oxide. Structural and functional comparison is made between undoped and silver doped copper oxide thin films, prepared und
Copper foil impurities are hampering scalable production of high-quality graphene by chemical vapor deposition (CVD). Here, we conduct a thorough study on the origin of these unavoidable contaminations at the surface of copper after the CVD process. We identify two distinct origins for the impurities. The first type is intrinsic impurities, originating from the manufacturing process of the copper foils, already present at the surface before any high-temperature treatment, or buried into the bulk of copper foils. The buried impurities diffuse towards the copper surface during high-temperature treatment and precipitate. The second source is external: silica contamination arising from the quartz tube that also precipitate on copper. The problem of the extrinsic silica contamination is readily solved upon using an adequate confinement the copper foil samples. The intrinsic impurities are much more difficult to remove since they appear spread in the whole foil. Nevertheless, electropolishing proves particularly efficient in drastically reducing the issue.
In this research, wettability control by area fraction of laser ablated surface of copper is presented. The functional surfaces with full wettability control from highly hydrophilic to super-hydrophobic were created on copper by nanosecond (ns) and picosecond (ps) laser irradiation. The area fraction and color change were evaluated by digital image processing of microscopic images of the laser-ablated copper surface. The control of the wetting angle from almost 0 degrees to 132 degrees was achieved for both ps and ns pulses by controlling the area fraction of the laser-ablated surface. Cassie, Cassie-Baxter, and Wenzel models were adopted to explain the experimental results. For the first time, the wettability and color of copper were controlled by controlling the area fraction of the laser-ablated surface. It is expected that the current results make an impact on the heat exchanger technology of water heat sinks, cooling units, atmospheric water generators, and fog harvesting and impact numerous applications from power plants to solar thermal water systems devices where highly-hydrophilic to super hydrophobic copper can be applied.
This study presented a novel method to prepare hexagonal iron flakes with hexagonal close-packed structures (hcp) on the copper oxide sublayers. Also, it demonstrated that the size and structure of iron grains are functions of sublayer features. The sublayer was prepared by sputtering copper on the glass substrate and annealing it. As the annealing temperature of the copper sublayer increased, the oxygen percentage increased and copper oxide rods were formed. Hexagonal iron flakes were formed after sputtering iron on this sublayer. The XRD analysis showed that these hexagonal flakes have a close-packed hexagonal structure. This finding was further confirmed by the magnetic properties of the samples and by density functional theory (DFT) calculations.
The inclusion of small amounts of copper is often reported to enhance the mechanical and biointegrative performance of bioceramics towards tissue engineering applications. In this work, 3D scaffolds were additively manufactured by robocasting of precipitation derived copper doped diopside. Compositions were chosen in which magnesium sites in diopside were substituted by copper up to 3 at.%. Microstructure, mechanical performance, bioactivity, biodegradability, drug release, biocompatibility, in vitro angiogenesis and antibacterial activity were studied. Results indicate that copper is incorporated in the diopside structure and improves materials fracture toughness. Scaffolds with more than 80% porosity exhibited compressive strengths exceeding that of cancellous bone. All compositions showed bioactivity and drug release functionalities. However, only samples with 0 to 1 at.% copper substitution showed favorable proliferation of osteogenic sarcoma cells, human umbilical vein endothelial cells and fibroblasts, while larger amounts of copper had cytotoxic behavior. In vitro angiogenesis was significantly enhanced by low levels of copper. Copper containing materials showed anti Escheri
Superconducting radio-frequency (SRF) thin film cavities on copper substrates are employed in several particle accelerators. However, these SRF cavities historically featured a progressive performance degradation with the accelerating field that is still not completely understood. The degradation of cavity performance, which limits the use of this technology in accelerators where the real-estate gradient has to be maximized, is manifested by the presence of heat losses in the superconducting film. However, measuring the temperature on the outer surface of copper substrates is challenging due to the higher thermal conductivity of copper at low temperatures compared to niobium. This study describes how temperature variations on copper surfaces can be satisfactorily measured in view of superconducting thin film cavity applications at liquid helium temperatures. Furthermore, we explore how the thermal exchange between thermometers and copper surfaces, and thermometers and helium bath must be tuned with respect to each other in order to measure accurately temperature rises in the thin film. Our findings suggest that engineering the copper surfaces can improve heat transfer into the heli
Multiferroics are materials with a coexistence of magnetic and ferroelectric order allowing the manipulation of magnetism by applications of an electric field through magnetoelectric coupling effects. Here we propose an idea to design a class of multiferroics with a $d^9$ configuration using the magnetic order in copper-oxygen layers appearing in copper oxide high-temperature superconductors by inducing ferroelectricity. Copper-based charge transfer multiferroics SnCuO2 and PbCuO2 having the inversion symmetry breaking $P4mm$ polar space group are predicted to be such materials. The active inner s electrons in Sn and Pb hybridize with O $2p$ states leading the buckling in copper-oxygen layers and thus induces ferroelectricity, which is known as the lone pair mechanism. As a result of the $d^9$ configuration, SnCuO2 and PbCuO2 are charge transfer insulators with the antiferromagnetic ground state of the moment on Cu retaining some strongly correlated physical properties of parent compounds of copper oxide high-temperature superconductors. Our work reveals the possibility of designing multiferroics based on copper oxide high-temperature superconductors.
To assess the feasibility of in-situ plasma cleaning for copper cavities, a 13.56 MHz inductively coupled plasma platform with a built-in coil was developed at Tsinghua University. Experiments were conducted using this platform to optimize plasma discharge parameters and procedures specific to copper cavities. The results indicate that the "Ar/O + Ar/H method" significantly enhances the work function of the copper surface while reducing field enhancement effects induced by surface burrs. Consequently, this study confirms that in-situ plasma cleaning effectively mitigates field emission within copper cavities, thereby enhancing the stability and acceleration gradient of the accelerator system.
Modification of surfaces to enable dropwise condensation is a promising approach for achieving high condensation rates. In this work, we present an experimental study on condensation of water on copper surfaces coated with an ultrathin, 5 nm - 10 nm thick polydimethylsiloxane (PDMS) layer. This hydrophobic coating possesses a very low thermal resistance, which in combination with copper substrate enables achieving high condensation rates in heat transfer applications. The PDMS-coated copper substrates have been fabricated with a newly developed method, which involves turning, sanding, polishing, oxidation, and polymer coating steps. The measured static contact angle was 110°, and a the contact angle hysteresis was 2°. The achieved very low hysteresis is advantageous for promoting dropwise condensation. The surface showed no ageing effects during 100 repetitions of advancing and receding contact angle (ARCA) measurements. Condensation heat transfer on uncoated and PDMS-coated copper surfaces surfaces has been studied experimentally in a saturated water vapor atmosphere at 60°C. An enhancement factor for heat flux and heat transfer coefficient of up to 1.6 was found on PDMS-coated co
We investigate the non-local thermodynamic equilibrium (NLTE) analysis for \ion{Cu}{1} lines with the updated model atom that includes quantum-mechanical rate coefficients of Cu\,$+$\,H and Cu$^+$\,$+$\,H$^-$ inelastic collisions from the recent study of Belyaev et al. (2021). The influence of these data on NLTE abundance determinations has been performed for six metal-poor stars in a metallicity range of $-$2.59\,dex$\,\le$\,[Fe/H]\,$\le$\,$-$0.95\,dex. For \ion{Cu}{1} lines, the application of accurate atomic data leads to a decrease in the departure from LTE and lower copper abundances compared to that obtained with the Drawin's theoretical approximation. To verify our adopted copper atomic model, we also derived the LTE copper abundances of \ion{Cu}{2} lines for the sample stars. A consistent copper abundance from the \ion{Cu}{1} (NLTE) and \ion{Cu}{2} (LTE) lines has been obtained, which indicates the reliability of our copper atomic model. It is noted that the [Cu/Fe] ratios increase with increasing metallicity when $\sim$\,$-$2.0\,dex\,$<$\,[Fe/H]\,$<$\,$\sim$\,$-$1.0\,dex, favoring a secondary (metallicity-dependent) copper production.
Nanofluids are suspensions of nanoscale particles (such as metals and their oxides) in base fluids (such as water, oil, or alcohol), which can significantly enhance the heat transfer performance of the base fluid. However, when nanofluids are applied to heat pipes, it is common for nanoparticles to accumulate within the heat pipe's capillary wick, clogging it and increasing thermal resistance. This paper investigates the phenomenon of boiling of water and nanofluids enhanced by copper foam through experimental methods. When the liquid is injected into copper foam placed on a heating plate, some of the liquid is squeezed out along the boundary of the heated surface of the copper foam during boiling. This phenomenon is independent of gravity but related to the hydrophilicity or hydrophobicity of the heating surface. Based on these properties, we design a device to guide the squeezed-out liquid to other locations, offering a promising solution to the problem of nanoparticle accumulation in the heat pipe's capillary wick.
In the field of waste copper granules recycling, engineers should be able to identify all different sorts of impurities in waste copper granules and estimate their mass proportion relying on experience before rating. This manual rating method is costly, lacking in objectivity and comprehensiveness. To tackle this problem, we propose a waste copper granules rating system based on machine vision and deep learning. We firstly formulate the rating task into a 2D image recognition and purity regression task. Then we design a two-stage convolutional rating network to compute the mass purity and rating level of waste copper granules. Our rating network includes a segmentation network and a purity regression network, which respectively calculate the semantic segmentation heatmaps and purity results of the waste copper granules. After training the rating network on the augmented datasets, experiments on real waste copper granules demonstrate the effectiveness and superiority of the proposed network. Specifically, our system is superior to the manual method in terms of accuracy, effectiveness, robustness, and objectivity.
Results are presented from several samples taken from leaves of the Pardon Portico of Mosque-Cathedral of Cordoba, where an alteration on their surface was detected. Metal samples analyzed using X-ray microanalysis and powder x-ray diffraction were predominantly constituted by copper with some amounts of zinc attributed to brass, whereas other samples were also constituted by copper, tin and lead attributed to bronze. Surface samples were analyzed using the same techniques. In addition Fourier transform infrared spectroscopy was also used.The main compound identified in all the surface of the leaves is copper chloride hydroxide (atacamite). Lead chlorides have also been found. These data show that the sudden alteration that appears may be attributed to the use of some cleaning product containing chloride. Other compounds detected in the surface were gypsum, quartz and oxalates coming from environmental contamination.
Despite long-term efforts for exploring antibacterial agents or drugs, it remains challenging how to potentiate antibacterial activity and meanwhile minimize toxicity hazards to the environment. Here, we experimentally show that the functionality of reduced graphene oxide (rGO) through copper ions displays selective antibacterial activity significantly stronger than that of rGO itself and no toxicity to mammalian cells. Remarkably, this antibacterial activity is two orders of magnitude greater than the activity of its surrounding copper ions. We demonstrate that the rGO is functionalized through the cation-$π$ interaction to massively adsorb copper ions to form a rGO-copper composite in solution and result in an extremely low concentration level of surrounding copper ions (less than ~0.5 $μM$). These copper ions on rGO are positively charged and strongly interact with negatively charged bacterial cells to selectively achieve antibacterial activity, while rGO exhibits the functionality to not only actuate rapid delivery of copper ions and massive assembly onto bacterial cells but also result in the valence shift in the copper ions from Cu$^{2+}$ into Cu$^{+}$ which greatly enhances
We investigate the electronic transport properties of copper-graphene composites using a density-functional framework. Conduction in composites by varying the interface distance of a copper/graphene/copper (Cu/G/Cu) interface models was studied. The electronic density of states reveals increasing contributions from both copper and carbon atoms near the Fermi level with decreasing Cu-G interfacial distance. Electronic conductivity of the models computed using the Kubo-Greenwood formula showed the conductivity increases with decreasing Cu-G distance. We also find that the conductivity saturates below a threshold Cu-G distance. By computing the space-projected conductivity of the Cu/G/Cu models, we show that the graphene forms a bridge to the electronic conduction at small copper-graphene distances, thereby enhancing the conductivity.
We report on the effect of ligand exchange of copper sulphide selenide as well as copper selenide nanocrystals with the organic pi-system Cobalt beta-tetraaminophthalocyanine and analyse changes in the structural, optical as well as electric properties of thin films of these hybrid materials. A strong ligand interaction with the surface of the nanocrystals is revealed by UV-vis absorption and Raman spectroscopy. Grazing-incidence small-angle X-ray scattering studies show a significant contraction in the interparticle distance upon ligand exchange. For copper-deficient copper selenide, this contraction has a negligible effect on electric transport, while for copper-deficient copper sulphide selenide, the conductivity increases by eight orders of magnitude and results in metal-like temperature-dependent transport. We discuss these differences in the light of varying contributions of electronic vs. ionic transport in the two materials and highlight their effect on the stability of the transport properties under ambient conditions. With photocurrent measurements, we demonstrate high optical responsivities of 200-400 A W-1 for the phthalocyanine-capped copper sulphide selenide and empha
The molecular responses of macrophages to copper-based nanoparticles have been investigated via a combination of proteomic and biochemical approaches, using the RAW264.7 cell line as a model. Both metallic copper and copper oxide nanoparticles have been tested, with copper ion and zirconium oxide nanoparticles used as controls. Proteomic analysis highlighted changes in proteins implicated in oxidative stress responses (superoxide dismutases and peroxiredoxins), glutathione biosynthesis, the actomyosin cytoskeleton, and mitochondrial proteins (especially oxidative phosphorylation complex subunits). Validation studies employing functional analyses showed that the increases in glutathione biosynthesis and in mitochondrial complexes observed in the proteomic screen were critical to cell survival upon stress with copper-based nanoparticles; pharmacological inhibition of these two pathways enhanced cell vulnerability to copper-based nanoparticles, but not to copper ions. Furthermore, functional analyses using primary macrophages derived from bone marrow showed a decrease in reduced glutathione levels, a decrease in the mitochondrial transmembrane potential, and inhibition of phagocytosis
We propose an innovative, easy-to-implement approach to synthesize large-area singlecrystalline graphene sheets by chemical vapor deposition on copper foil. This method doubly takes advantage of residual oxygen present in the gas phase. First, by slightly oxidizing the copper surface, we induce grain boundary pinning in copper and, in consequence, the freezing of the thermal recrystallization process. Subsequent reduction of copper under hydrogen suddenly unlocks the delayed reconstruction, favoring the growth of centimeter-sized copper (111) grains through the mechanism of abnormal grain growth. Second, the oxidation of the copper surface also drastically reduces the nucleation density of graphene. This oxidation/reduction sequence leads to the synthesis of aligned millimeter-sized monolayer graphene domains in epitaxial registry with copper (111). The as-grown graphene flakes are demonstrated to be both single-crystalline and of high quality.