Thermal expansion behavior of Cu/Cu2O cermets with different Cu structures

Cu/Cu₂O cermets were prepared with Cu₂O matrix imbedded with branch-like or spherical Cu powders. The coefficients of thermal expansion (CTE) of them were tested. The CTE curves can be divided into three segments. From 25 °C to 150 °C, CTEs were found to decrease with temperatures. The CTEs were influenced by the structure of the conductor phase. For cermets prepared with spherical Cu, the increase in CTEs was basically linear with temperatures above 150 °C. In contrast, cermets with same Cu content prepared with branch-like Cu had a CTE with an increasing rate as the temperature rose from 150 °C to 900 °C, and the increasing rates in these temperature range are much higher than those prepared with spherical Cu.     

Effects of supporting electrolyte on galvanic deposition of Cu2O crystals

The effects of introduced supporting electrolyte on the galvanic deposition of Cu₂O crystals have been investigated using scanning electron microscopy (SEM), energy-dispersive X-ray (EDX), X-ray diffraction (XRD). The results show that the chemical nature of supporting electrolytes plays very important roles in the galvanic deposition of Cu₂O crystals. The chloride stabilizes the (1 0 0) planes of Cu₂O crystals, resulting in the formation of cubic crystals, while nitrate, sulfate and fluoride stabilize the (1 1 1) planes of Cu₂O crystals, leading to the deposition of truncated octahedral and octahedral Cu₂O crystals. It provides a facile way to control the morphology of galvanically obtained Cu₂O crystals by indirectly adjusting the inorganic adsorption agents.     

Electrodeposited ZnO/Cu2O heterojunction solar cells

In this paper the fabrication and the characterization of heterojunction solar cells based on electrodeposited ZnO and Cu₂O is described. The effect of the electrodeposition conditions (pH and temperature) on the cell performance has been investigated. The cells made with a Cu₂O layer deposited at high pH (12) and moderate temperature (50 °C) have shown conversion efficiency as high as 0.41%.     

p-Type and n-type Cu2O semiconductor thin films: Controllable preparation by simple solvothermal method and photoelectrochemical properties

p-Type and n-type Cu₂O thin films were controllably prepared using a simple solvothermal method by adjusting pH value of the copper (II) acetate aqueous solution. Photoelectrochemical experiments show that the Cu₂O thin films synthesized in acid and alkaline (or neutral) media present n-type and p-type semiconductor character, respectively. Moreover, the films prepared at pH 5 have the best photoelectrochemical properties. The mechanism for the formation of these p-type and n-type Cu₂O films is discussed. The Cu₂O p–n homojunction fabricated in this study shows typical p–n junction character. This facile preparation method may be a promising way to prepare p–n homojunctions for semiconductor devices.     

Fabrication of nanometer-to-micron sized Cu2O single crystals by electrodeposition

Nanometer-to-micron sized cuprous oxide (Cu₂O) single crystals were fabricated on Au/Pd sputter-coated silicon wafer and stainless steel cathode substrates by electrodeposition in CuSO₄ at pH 4.0 at room temperature (25 °C) with no additives. The Cu₂O crystals were generally of an octahedral shape with sizes ranging from 100 nm to 400 nm on Si wafer, and 1 μm to 3 μm on stainless steel substrates respectively. Very small crystals of a spherical shape were also observed under low applied voltage. Transient crystal shapes observed on the cathode near the electrolyte surface suggest that growth slows down once {1 1 1} free surfaces are formed, and this explains the robust observation of the octahedral crystal shape. The effect of electrodeposition parameters such as deposition voltage and deposition time on the size of the crystals and their coverage on the substrates was investigated. Apart from the cathode, similar octahedral Cu₂O nanocrystals were also found to deposit on the Cu anode used. This work provides a method to fabricate Cu₂O crystals on both electrodes in a single step.     

A convenient method for preparing shape-controlled nanocrystalline Cu2O in a polyol or water/polyol system

A facile method capable of preparing well-dispersed Cu₂O nanocrystals with controllable shapes, such as rods, needles to other irregular shapes, has been developed. The different shapes of Cu₂O nanocrystals can be obtained simply by adjusting the composition of the reaction system. For example, if small amounts of poly(vinyl pyrrolidone) (PVP) was added in a mixture of Cu(NO₃)₂ and ethylene glycol, the needle-shaped nanocrystals could be formed. Interestingly further addition of small amounts of water in above system enabled us to obtain Cu₂O nanorods. Moreover the ratio of water/EG and the species of stabilizers played a crucial role in fine tuning the structure and size of as-prepared Cu₂O nanocrystals.     

Electrochemical sensing the genotoxicity of Cu2O nanocubes activated by hydrogen peroxide electro-generated on the surface of Au nanoparticles

In order to investigate the genotoxicity of Cu₂O nanocubes, a novel electrochemical biosensor was constructed by incorporating the mixture of Cu₂O nanocubes and Au nanoparticles (AuNPs) into a multi-membrane containing natural ds-DNA. The ds-DNA was damaged in situ in the membrane and the DNA damage was monitored by DPV with two electrochemical indicators, Co(phen)₃³⁺ and Ru(NH₃)₆³⁺. The mechanism studies showed that the nanoCu₂O and AuNPs had synergistic effects on DNA damage and the DNA damage reagent (OH) was generated via electro-Fenton (E-Fenton) reactions on the surface of Cu₂O nanocubes and Au nanoparticles. This method was very suitable to study the genotoxicity mechanisms of nanomaterials and it had potential application in studying some chemicals anti-oxidation property.     

Synthesis of pure Cu2O thin layers controlled by in-situ conductivity measurements

An easy synthesis route for cuprous oxide (Cu₂O) nanoparticles is reported via thermal annealing improved and controlled by in-situ conductivity measurements. The crystalline structure, phase transition, surface morphology and particle size/shape, were investigated through X-ray diffraction, a conductivity setup and scanning electron microscopy, respectively. X-ray diffraction patterns revealed that initial metallic Cu nanoparticles were transformed to Cu₂O nanoparticles with high purity, under specific conditions critically dependent on the temperature and annealing duration. This transformation was also dependent on the film thickness and atmospheric composition in the test chamber during the annealing process.     

Thin films of Cu2Sb and Cu9Sb2 as anode materials in Li-ion batteries

Thin Cu₂Sb films have been prepared by heat-treating Sb films, electrodeposited on Cu substrates. The influence of the electrodeposition conditions and the heat-treatment period on composition and morphology of the films were investigated (SEM and XRD) and the obtained films were tested as anode materials for Li-ion batteries. The Cu₂Sb material showed a stable capacity of 290 mAh g⁻¹ (close to the theoretical capacity of 323 mAh g⁻¹) during more than 60 cycles. The presence of 9-11% (w/w) Sb₂O₃ in the electrodeposited films resulted in smaller particles but also slowed down formation of Cu₂Sb during the heat-treatment step. The presence of Sb₂O₃ was found to decrease the cycling stability although structural reversibility of Cu₂Sb was obtained both with and without Sb₂O₃. Longer heat-treatments of pure Sb films resulted in the formation of Cu₉Sb₂ which was shown to be reduced at a lower potential than Cu₂Sb. The Cu₉Sb₂ was converted to Cu₂Sb during repeated cycling and the capacity of the latter Cu₂Sb material was found to be 230 mAh g⁻¹. While reduction of the materials was complicated by simultaneous formation of an SEI layer, three plateaus could be identified during the oxidation of Li₃Sb, indicating the presence of three separate one-electron oxidation reactions.     

Cu2O/rGO复合材料修饰阴极强化MFC产电脱氮性能及其机理

微生物燃料电池(MFC)在处理含硝酸盐(NO_3^--N)废水时具有同时产电和脱氮的潜力,寻找成本低且改善其产电脱氮性能的阴极修饰材料是MFC在含氮废水处理领域应用的关键。氧化亚铜/还原氧化石墨烯(Cu₂O/rGO)复合材料具有良好的电化学性能,在替代铂基材料提高MFC性能方面具有一定的应用前景。本研究通过还原法制备了Cu₂O/rGO复合材料,并对材料的结构和氧还原性能进行表征；同时,将其负载于阴极碳布后分析其电化学性能,并通过MFC的输出电压、功率密度和NO_3^--N的去除率探究Cu₂O/rGO阴极对MFC产电和脱氮性能的强化作用；通过对反硝化相关酶活性和胞外聚合物的测定,探究Cu₂O/rGO阴极强化MFC性能的机理。结果表明：Cu₂O/rGO复合材料具有大量的介孔结构,能够为电子传递提供更多的通道,并且Cu₂O/rGO复合材料具有良好的氧化还原可逆性；与Pt/C阴极相比,Cu₂O/rGO阴极的交换电流密度升高33.53%,电子转移阻力降低65.53%；Cu₂O/rGO-MFC在处理NO_3^-N废水时获得的最大平均输出电压(662.54 mV)、最大功率密度(26.27 mW/cm^₂)、平均库伦效率(32.02%)和NO_3^--N去除速率(83.33 mg NO_3^--N L/h)均高于Pt/C-MFC(485.33 mV,16.98 mW/cm^₂,7.38%,41.67 mg NO_3^--N L/h)；Cu₂O/rGO复合材料通过提高MFC阴极反硝化关键酶活性和类蛋白组分含量,改善了MFC的产电和脱氮性能。     

Metal-organic framework Cu3 (BTC)2(H2O)3 catalyzed Aldol synthesis of pyrimidine-chalcone hybrids

A typical metal organic framework, [Cu₃ (BTC)₂(H₂O)₃, BTC = 1,3,5-benzene tricarboxylate] has been used for the synthesis of pyrimidine-chalcones. We have explored a green synthesis of pyrimidine chalcones under Cu₃(BTC)₂ catalysis by Aldol condensation. Easy isolation of product, excellent yield, and recyclable catalyst makes this reaction eco-friendly. The technology was demonstrated to be applicable to the synthesis of a host of chemical hybrids.     

Investigation of photoelectrocatalytic activity of Cu2O nanoparticles for p-nitrophenol using rotating ring-disk electrode and application for electrocatalytic determination

A cuprous oxide (Cu₂O) nanoparticles modified Pt rotating ring-disk electrode (RRDE) was successfully fabricated, and the electrocatalytic determination of p-nitrophenol (PNP) using this electrode was developed. Cu₂O nanoparticles were obtained by reducing the copper-citrate complex with hydrazine hydrate (N₂H₄·H₂O) in a template-free process. The hydrodynamic differential pulse voltammetry (HDPV) technique was applied for in situ monitor the photoelectrochemical behavior of PNP under visible light using nano-Cu₂O modified Pt RRDE as working electrode. PNP undergoes photoelectrocatalytic degradation on nano-Cu₂O modified disk to give electroactive p-hydroxylamino phenol species which is compulsive transported and can only be detected at ring electrode at around 0.05 V with oxidation signal. The effects of illumination time, applied bias potential, rotation rates and pH of the reaction medium have been discussed. Under optimized conditions for electrocatalytic determination, the anodic current is linear with PNP concentration in the range of 1.0 × 10⁻⁵ to 1.0 × 10⁻³ M, with a detection limit of 1.0 × 10⁻⁷ M and good precision (RSD = 2.8%, n = 10). The detection limit could be improved to 1.0 × 10⁻⁸ M by given illumination time. The proposed nano-Cu₂O modified RRDE can be potentially applied for electrochemical detection of p-nitrophenol. And it also indicated that modified RRDE technique is a promising way for photoelecrocatalytic degradation and mechanism analysis of organic pollutants.     

Facile preparation of Cu2O microcrystals with morphologies of octahedron, half circular and rectangular plates by anodic dissolution of bulk Cu in alkaline aqueous solutions

In this work, a facile electrochemical route i.e., anodic dissolution of bulk Cu at 2.0 V or more (vs. SCE) in a NaOH solution containing NH₂OH·HCl, was introduced for the synthesis of clean Cu₂O microcrystals (Cu₂O MCs) with morphologies of octahedron, half circular plate, etc. The bulk Cu electrode can be facilely dispersed into Cu(OH)₄²⁻ in alkaline solutions with the help of intense O₂ releasing. In the presence of reductive NH₂OH·HCl, Cu(II) was quickly reduced to Cu(I). Due to the concentration gradient of Cu(I) and OH⁻ resulting from the electrochemical reaction and the selective adsorption of OH⁻ on different crystal facets, half circular plate Cu₂O MCs were for the first time, synthesized. By changing the NaOH concentration or applied potential, octahedron and rectangular plate Cu₂O MCs could also be obtained. Scanning electron microscope (SEM), transmission electron microscope (TEM), X-ray diffraction (XRD) techniques, etc. were used to characterize the oxides. The Cu₂O MCs were phase-pure cubic Cu₂O. This electrochemical route is simple, basically green and can be used to synthesize Cu₂O MCs with different morphologies.     

恒电流法制备Cu2O/TiO2复合纳米管阵列异质结光电极

通过在含F-离子的电解液中阳极氧化Ti薄片基底制备了TiO2纳米管阵列,随后通过恒电流沉积的方法在在TiO2纳米管阵列顶部原位电沉积了Cu2O纳米颗粒。场发射电子扫描显微镜显示TiO2纳米管这列被成功制备,通过恒电流电化学沉积后,TiO2纳米管阵列顶部出现大量纳米颗粒物质,并且随着沉积时间的延长,可以控制沉积物的量。通过X-射线衍射谱的特征衍射谱图我们可以发现TiO2锐钛矿的衍射峰以及相对较弱的Cu2O衍射峰,这说明Cu2O晶体的结晶度不高。在能谱（EDS）图中我们可以发现Ti、Cu、O三种元素,结合XRD以及FE-SEM结果我们可以指出,通过恒电流法确实可以在TiO2纳米管阵列顶部原位沉积Cu2O纳米颗粒。     

Cu2O催化甲醛乙炔化反应助剂效应

在液相还原法制备的纯Cu2O样品中,采用浸渍法分别引入Mg、Al、Fe助剂制备Cu2O-MgO、Cu2O-Al2O3、Cu2O-Fe2O3催化剂。采用XRD、FT-IR、TEM和H2-TPR等对催化剂进行表征,研究不同助剂的加入对甲醛乙炔化反应的影响。结果表明,不同助剂对催化剂的结晶度和可还原性能有较大影响,进而使甲醛乙炔化表现出不同的催化活性。相比MgO与Al2O3,Fe2O3的引入,使Cu2O结晶度明显下降,主要是由于Fe2O3与Cu2O之间产生强的相互作用,有利于乙炔亚铜活性物种的形成,从而表现出最优的催化性能。     

Cyclic durable high-capacity Sn/Cu6Sn5 composite thin film anodes for lithium ion batteries prepared by electron-beam evaporation deposition

Sn/Cu₆Sn₅ alloy composite thin films were directly prepared by electron-beam deposition for anodes of lithium ion batteries. The thin film was comprised of micro/sub-microcrystalline Sn and Cu₆Sn₅, where the polyhedral micro-sized Sn grains were uniformly dispersed in the loose Cu₆Sn₅ matrix. Lithiation reaction kinetics were confirmed to be controlled by a diffusion step and the diffusion coefficient of Li⁺ in the thin film anode was determined to be 1.91 × 10⁻⁷ cm²/s. The galvanostatic cycling behavior of Sn/Cu₆Sn₅ composite thin film anodes was studied under different conditions. Stable capacities of more than 370 mAh/g were obtained by discharging from 1.25 to 0.1 V. Structure changes and fading mechanism of the thin film electrodes was discussed based on SEM, XRD and EDX investigations. The present results demonstrated that the multi-phase composite structure can improve electrochemical performance of the Cu-Sn alloy thin film electrodes.     

Photocatalytic activity of Cu2O/TiO2, Bi2O3/TiO2 and ZnMn2O4/TiO2 heterojunctions

Cu₂O/TiO₂, Bi₂O₃/TiO₂ and ZnMn₂O₄/TiO₂ heterojunctions were studied for potential applications in water decontamination technology and their capacity to induce an oxidation process under VIS light. UV–vis spectroscopy analysis showed that the junctions-based Cu₂O, Bi₂O₃ and ZnMn₂O₄ are able to absorb a large part of visible light (respectively, up to 650, 460 and 1000 nm). This fact was confirmed in the case of Cu₂O/TiO₂ and Bi₂O₃/TiO₂ by photocatalytic experiments performed under visible light. A part of the charge recombination that can take place when both semiconductors are excited was observed when a photocatalytic experiment was performed under UV–vis illumination. Orange II, 4-hydroxybenzoic and benzamide were used as pollutants in the experiment. Photoactivity of the junctions was found to be strongly dependent on the substrate. The different phenomena that were observed in each case are discussed.     

Preparation and characterization of negative thermal expansion Sc2W3O12/Cu core-shell composite

A composite of Sc₂W₃O₁₂/Cu where Sc₂W₃O₁₂, the core, is coated by the Cu shell was synthesized using simple electroless plating method. As-prepared Sc₂W₃O₁₂/Cu composites were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive spectrometry (EDS) and thermomechanical analyzer (TMA) techniques. The study results show that the Pd-Sn activator was successfully formed on the surface of Sc₂W₃O₁₂ after the sensitization and activation. In the electroless plating process, Cu nanocrystals formed firstly, and then grew together to form a continuous coating. Sc₂W₃O₁₂/Cu core-shell composites exhibit a negative linear coefficient of thermal expansion CTE = −4.47 × 10⁻⁶ °C⁻¹ from room temperature to 200 °C.     

Chemical instability of Cu3(BTC)2 by reaction with thiols

In contrast to Fe(BTC) (BTC: 1,3,5-benzenetricarboxylate), the crystal structure of Cu₃(BTC)₂, a commercial metal organic framework widely used as solid catalyst, collapses when contacted with thiols under mild reaction conditions forming copper nanoparticles.     

CO2 hydrogenation to methanol over Cu/ZnO/ZrO2 catalysts prepared via a route of solid-state reaction

Cu/ZnO/ZrO₂ catalysts were prepared by a route of solid-state reaction and tested for the synthesis of methanol from CO₂ hydrogenation. The effects of calcination temperature on the physicochemical properties of as-prepared catalysts were investigated by N₂ adsorption, XRD, TEM, N₂O titration and H₂-TPR techniques. The results show that the dispersion of copper species decreases with the increase in calcination temperature. Meanwhile, the phase transformation of zirconia from tetragonal to monoclinic was observed. The highest activity was achieved over the catalyst calcined at 400 °C. This method is a promising alternative for the preparation of highly efficient Cu/ZnO/ZrO₂ catalysts.