Efficient C-N coupling in electrocatalytic urea generation on copper carbonate hydroxide electrocatalysts

Urea generation through electrochemical CO_(2) and NO_(3)~-co-reduction reaction(CO_(2)NO_(3)RR)is still limited by either the low selectivity or yield rate of urea.Herein,we report copper carbonate hydroxide(Cu_2(OH)_2CO_(3))as an efficient CO_(2)NO_(3)RR electrocatalyst with an impressive urea Faradaic efficiency of45.2%±2.1%and a high yield rate of 1564.5±145.2μg h~(-1)mg_(cat)~(-1).More importantly,H_(2) evolution is fully inhibited on this electrocatalyst over a wide potential range between-0.3 and-0.8 V versus reversible hydrogen electrode.Our thermodynamic simulation reveals that the first C-N coupling follows a unique pathway on Cu_2(OH)_2CO_(3) by combining the two intermediates,~*COOH and~*NHO.This work demonstrates that high selectivity and yield rate of urea can be simultaneously achieved on simple Cu-based electrocatalysts in CO_(2)NO_(3)RR,and provide guidance for rational design of more advanced catalysts.

Cu,N codoped carbon nanosheets encapsulating ultrasmall Cu nanoparticles for enhancing selective 1,2-propanediol oxidation

In the selective oxidation of biomass-based 1,2-propanediol(PDO)with oxygen as the terminal oxidant,it is challenging to improve the lactic acid(LA)selectivity for nonnoble metal nanoparticles(NPs)due to their limited oxygen reduction rate and easy C-C cleavage.Given the high economic feasibility of nonnoble metals,i.e.,Cu,in this work,copper and nitrogen codoped porous carbon nanosheets encapsulating ultrafine Cu nanoparticles(Cu@Cu-N-C)were developed to realize highly selective of PDO oxidation to LA.The carbon-encapsulated ultrasmall Cu^(0)NPs in Cu@Cu-N-C have high PDO dehydrogenation activity while N-coordinated Cu(Cu-N)sites are responsible for the high oxygen reduction efficacy.Therefore,the performance of catalytic PDO conversion to LA is optimized by a proposed pathway of PDO→hydroxylacetone→lactaldehyde→LA.Specifically,the enhanced LA selectivity is 88.5%,and the PDO conversion is up to 75.1%in an O_(2)-pressurized reaction system(1.0 MPa O_(2)),superior to other Cu-based catalysts,while in a milder nonpressurized system(O_(2)flow rate of 100 mL min-1),a remarkable LA selectivity(94.2%)is obtained with 39.8%PDO conversion,2.2 times higher than that of supported Au nanoparticles(1%Au/C).Moreover,carbon encapsulation offers Cu@Cu-N-C with strong leaching resistance for better recycling.

Direct Patterning of Carbon Nanotube via Stamp Contact Printing Process for Stretchable and Sensitive Sensing Devices

Flexible and wearable sensing devices have broad application prospects in bio-monitoring such as pulse measurement,motion detection and voice recognition.In recent years,many significant improvements had been made to enhance the sensor’s performance including sensitivity,flexibility and repeatability.However,it is still extremely complicated and difficult to prepare a patterned sensor directly on a flexible substrate.Herein,inspired by typography,a lowcost,environmentally friendly stamping method for the mass production of transparent conductive carbon nanotube(CNT)film is proposed.In this dry transfer strategy,a porous CNT block was used as both the seal and the ink;and Ecoflex film was served as an object substrate.Welldesigned CNT patterns can be easily fabricated on the polymer substrate by engraving the target pattern on the CNT seal before the stamping process.Moreover,the CNT film can be directly used to fabricate ultrathin(300μm)strain sensor.This strain sensor possesses high sensitivity with a gauge factor(GF)up to 9960 at 85%strain,high stretchability(>200%)and repeatability(>5000 cycles).It has been used to measure pulse signals and detect joint motion,suggesting promising application prospects in flexible and wearable electronic devices.

Fabrication and thermal conductivity of copper matrix composites reinforced by tungsten-coated carbon nanotubes

Carbon nanotubes （CNTs） were coated by tungsten using metal organic chemical vapor deposition. Magnetic stirring was employed to disperse the W-coated CNTs （W-CNTs） in a Cu matrix, and then, the mixed powders were consolidated by spark plasma sintering. The W-CNTs obtained a uniform dispersion within the Cu matrix when the W-CNT content was less than 5.0vo1%, but high content of W-CNTs （10vol%） resulted in the presence of clusters. The W-CNT/Cu composites containing low content of W-CNTs （〈5.0vol%） exhibited a higher thermal conductivity than the sintered pure Cu, while the CNT/Cu composites exhibited no increase in thermal conductivity after the incorporation of uncoated CNTs. The W-CNT content was found to play a crucial role in determining the thermal conductivity of the W-CNT/Cu composites. The thermal conductivity of the W-CNT/Cu composites increased first and then decreased with the W-CNT content increasing. When the W-CNT content was 2.5vo1%, the W-CNT/Cu composite obtained the maximum value of thermal conductivity. The thermal resistance of the （W-CNT）-Cu interface was predicted in terms of Maxwell-Gamett effective medium approximation, and its calculated value was about 3.0× 10-9 m2.K.W-l.

Photopromoted Carbonylation of Alkyl Bromides Catalyzed by Copper Salts under Ambient Conditions

Photopromoted carbonylation of alkyl bromides with carbon monoxide or carbon dioxide catalyzed by copper salts can be carried out under ambient conditions （atmospheric pressure and room temperature） and the corresponding ester was produced. The yield and the selectivity of the ester can be improved greatly by addition of sodium phosphate.

Friction and wear properties of copper matrix composites reinforced by tungsten-coated carbon nanotubes

Carbon nanotubes （CNTs） were coated by tungsten layer using metal organic chemical vapor deposition process with tungsten hexacarbonyl as a precursor. The W-coated CNTs （W-CNTs） were dispersed into Cu powders by magnetic stirring process and then the mixed powders were consolidated by spark plasma sintering to fabricate W-CNTs/Cu composites. The CNTs/Cu composites were fabricated using the similafprocesses. The friction coefficient and mass wear loss of W-CNTs/Cu and CNTs/Cu composites were studied. The results showed that the W-CNT content, interfacial bonding situation, and applied load could influence the friction coefficient and wear loss of W-CNTs/Cu com- posites. When the W-CNT content was 1.0 wt.%, the W-CNTs/Cu composites got the minimum friction coefficient and wear loss, which were decreased by 72.1% and 47.6%, respectively, compared with pure Cu specimen. The friction coefficient and wear loss of W-CNTs/Cu composites were lower than those of CNTs/Cu composites, which was due to that the interracial bonding at （W-CNTs）-Cu interface was better than that at CNTs-Cu interface. The friction coefficient of composites did not vary obviously with increasing applied load, while the wear loss of composites increased significantly with the increase of applied load.

Controllable fabrication of self-organized nano-multilayers in copper–carbon films

In order to clarify the influence of methane concentration and deposition time on self-organized nano-multilayers,three serial copper-carbon films have been prepared at various methane concentrations with different deposition times using a facile magnetron sputtering deposition system. The ratios of methane concentration(CH4/Ar+CH4) used in the experiments are 20%, 40%, and 60%, and the deposition times are 5 minutes, 20 minutes, and 40 minutes, respectively.Despite the difference in the growth conditions, self-organizing multilayered copper-carbon films are prepared at different deposition times by changing methane concentration. The film composition and microstructure are investigated by x-ray photoelectron spectroscopy(XPS), x-ray diffraction(XRD), field emission scanning electron microscopy(FESEM), and high-resolution transmission electron microscopy(HRTEM). By comparing the composition and microstructure of three serial films, the optimal growth conditions and compositions for self-organizing nano-multilayers in copper-carbon film are acquired. The results demonstrate that the self-organized nano-multilayered structure prefers to form in two conditions during the deposition process. One is that the methane should be curbed at low concentration for long deposition time,and the other condition is that the methane should be controlled at high concentration for short deposition time. In particular, nano-multilayered structure is self-organized in the copper-carbon film with copper concentration of 10-25 at.%.Furthermore, an interesting microstructure transition phenomenon is observed in copper-carbon films, that is, the nanomultilayered structure is gradually replaced by a nano-composite structure with deposition time and finally covered by amorphous carbon.

Effect of ceria on copper／γ－alumina catalysts for carbon monoxide and n－hexane oxidation

In this paper, oxidation activity of CuO/γ-A12O3 catalysts and the addition of CeO2 on CuO/γ-A12O3 catalysts for oxidation reaction of n-hexane (n-C6H14 ) and carbon monoxide (CO ) were studied by means of the flow method techniques, XRD and TPD-MS. Experimental results indicated that (1) the addition of CeO2 improving disperse degree of CuO on CuO/γ-Al2O3 catalysts which caused a large increase in activity; (2) the addition of CeO2 may increase oxygen supplying ability and oxygen recovery ability of catalyst surface.

Improving the Electrical Contact Property of Single-Walled Carbon Nanotube Arrays by Electrodeposition

A parallel method for the fabrication of metal contacts on single-walled carbon nanotube(SWNT)arrays was presented and the electrical contact property was evaluated by a SWNT-field effect transistor structure. Copper and gold contacts were fabricated on both semiconducting SWNTs and metallic SWNTs by using a maskless electrodeposition process. The SWNT array remained a p-type semiconductor after the electrodeposition. The contact resistance between SWNT array and microelectrodes was reduced more than 50% by the established copper contacts. The source-drain current of the carbon nanotube field-effect transistor(CNT-FET)structure can be further increased from 7.9 μA to 9.2 μA when the copper contacts were replaced by gold ones,which is probably due to the better contact property to SWNT of gold contacts with fine grain size.

Integrated Behavior of Carbon and Copper Alloy Heat Sink Under Different Heat Loads and Cooling Conditions

An actively water-cooled limiter has been designed for the long pulse operation of an HT-7 device, by adopting an integrated structure-doped graphite and a copper alloy heat sink with a super carbon sheet serving as a compliant layer between them. The behaviors of the integrated structure were evaluated in an electron beam facility under different heat loads and cooling conditions. The surface temperature and bulk temperature distribution were carefully measured by optical pyrometers and thermocouples under a steady state heat flux of 1 to 5 MW/m^2 and a water flow rate of 3 m^3/h, 4.5 m^3/h and 6 m^3/h, respectively. It was found that the surface temperature increased rapidly with the heat flux rising, but decreased only slightly with the water flow rate rising. The surface temperature reached approximately 1200℃ at 5 MW/m^2 of heat flux and 6 m^3/h of water flow. The primary experimental results indicate that the integrated design meets the requirements for the heat expelling capacity of the HT-7 device. A set of numerical simulations was also completed, whose outcome was in good accord with the experimental results.

Microstructure and properties of pure iron/copper composite cladding layers on carbon steel

In the present study, pure iron/copper composite metal cladding was deposited onto carbon steel by tungsten inert gas welding. The study focused on interfacial morphological, microstructural, and mechanical analyses of the composite cladding layers. Iron liquid–solid-phase zones were formed at copper/steel and iron interfaces because of the melting of the steel substrate and iron. Iron concentrated in the copper cladding layer was observed to exhibit belt, globule, and dendrite morphologies. The appearance of iron-rich globules indicated the occurrence of liquid phase separation（LPS） prior to solidification, and iron-rich dendrites crystallized without the occurrence of LPS. The maximum microhardness of the iron/steel interface was lower than that of the copper/steel interface because of the diffusion of elemental carbon. All samples fractured in the cladding layers. Because of a relatively lower strength of the copper layer, a short plateau region appeared when shear movement was from copper to iron.

In situ carbon coating for enhanced chemical stability of copper nanowires

Copper nanowires(CuNWs)are promising electrode materials,especially for used in flexible and transparent electrodes,due to their advantages of earth-abundant,low-cost,high conductivity and flexibility.However,the poor stability of CuNWs against oxidation and chemic-al corrosion seriously hinders their practical applications.Herein,we propose a facile strategy to improve the chemical stability of CuNWs by in situ coating of carbon protective layer on top of them through hydrothermal carbonization method.The influential factors on the growth of carbon film including the concentration of the glucose precursor(carbon source),hydrothermal temperature,and hydrothermal time are sys-tematically studied.By tailoring these factors,carbon layers with thickness of 3-8 nm can be uniformly grown on CuNWs with appropriate glucose concentration around 80 mg·mL−1,hydrothermal temperature of 160-170°C,and hydrothermal time of 1-3 h.The as-prepared carbon-coated CuNWs show excellent resistance against corrosion and oxidation,and are of great potential to use broadly in various optoelectronic devices.

Robust copper nanocrystal/nitrogen-doped carbon monoliths as carbon monoxide-resistant electrodes for methanol oxidation reaction

Noble metal-based electrocatalysts present high activities for methanol oxidation reaction(MOR),but are limited by their high cost,low stability and poor resistance to carbon monoxide(CO) poisoning.The development of active and stable non-noble metal electrocatalysts for MOR is desired,but remains a challenge.Herein,we report a simple strategy to make copper nanocrystal/nitrogen-doped carbon(Cu/N-C)monoliths,which can serve as active and robust electrodes for MOR.Copper nanocrystals were electrochemically deposited onto a conductive polyaniline hydrogel and calcined to form Cu/N-C monolith,where the active copper nanocrystals are protected by nitrogen-doped carbon.Owing to their extremely high electrical conductivity(1.25 × 10^(5) S cm^(-1)) and mechanical robustness,these Cu/N-C monoliths can be directly used as electrodes for MOR,without using substrates or additives.The optimal Cu/N-C(FT)@500 monolith shows a high MOR activity of 189 mA cm^(-2) at 0.6 V vs.SCE in alkaline methanol solution,superior to most of reported Cu-based MOR catalysts.Cu/N-C(FT)@500 also presents a better stability than Pt/C catalyst in the long-term MOR test at high current densities.Upon carbon monoxide(CO) poisoning,Cu/N-C(FT)@500 retains 96% of its MOR activity,far exceeding the performance of Pt/C catalyst(61% retention).Owing to its facile synthesis,outstanding activity,high stability and mechanical robustness,Cu/N-C(FT)@500 monolith is promising as a low-cost,efficient and CO-resistant electrocatalyst for MOR.

Catalytic ozonation of phenol and oxalic acid with copper-loaded activated carbon

A novel heterogeneous catalytic ozonation process in water treatment was studied,with a copper-loaded activated carbon(Cu/AC) that was prepared by an incipient wetness impregnation method at low temperature and tested as a catalyst in the ozonation of phenol and oxalic acid.Cu/AC was characterized using XRD,BET and SEM techniques.Compared with ozonation alone,the presence of Cu/AC in the ozonation processes significantly improves the degradation of phenol or oxalic acid.With the introduction of the hydroxyl radical scavenger,i.e.,turt-butanol alcohol(t-BuOH),the degradation efficiency of both phenol and oxalic acid in the Cu/AC catalyzed ozonation process decreases by 22% at 30 min.This indicates that Cu/AC accelerates ozone decomposition into certain concentration of hydroxyl radicals.The amount of Cu(Ⅱ) produced during the reaction of Cu/AC-catalyzed ozonation of phenol or oxalic acid is very small,which shows that the two processes are both heterogeneous catalytic ozonation reactions.

Effect of tempering temperature on the mechanical properties and microstructure of an copper-bearing low carbon bainitic steel

The effect of tempering temperature on the microstructure and mechanical properties of ultra-high strength, copperbearing, low-carbon bainitic steel has been investigated in the experiment. The results showed that the microstructure was mainly the laths of bainite in the as-quenched steel. The bainitic laths were restored and combined after the steel tempered at various tempera- tures. There were rnartensite/austenite （M/A） islands and numerous dislocations within and between the bainitic laths, while very t-me precipitates of ε-Cu were also observed within the laths. With increasing the tempered temperature from 400 to 600℃, the yield strength （YS） increased from 877 to 957 MPa, whereas the ultimate tensile strength （UTS） decreased from 1020 to 985 MPa. The Charpy V-notch （CVN） varied from 68.5 to 42 J, and the value was minimal for the steel tempered at 500℃. 2008 University of Science and Technology Beijing. All rights reserved.

Electroless Plating of Carbon Nanotubes with Copper

A simple chemical method was employed to coat carbon nanotubes with a layer of copper. Due to the hydrophobic nature, large surface curvature, small diameter and large aspect ratio, it is difficult to gain continuous electroless plating layer on the surface of carbon nanotubes. In this paper, a series methods (oxidization, sensitization and activation) are used to add active sites before electroless plating, and the adjustment of the traditional composition of copper electroless plating bath and operating condition can decelerate electroless plating rate. The samples before and after coating were analyzed using transmission electron microscopy and energy-dispersive X-ray spectroscopy. The results showed that the surface of carbon nanotubes was successfully coated with continuous layer of copper, which lays a good foundation for applying carbon nanotubes in composites.

Catalytic effect of activated carbon on bioleaching of low-grade primary copper sulfide ores

The catalytic effect of activated carbon on the bioleaching of low-grade primary copper sulfide ores using mixture of Acidithiobacillus ferrooxidans and Acidithiobacillus thiooxidans was investigated. The results show that the addition of activated carbon can greatly accelerate the rate and efficiency of copper dissolution from low-grade primary copper sulfide ores. The solution with the concentration of 3.0 g/L activated carbon is most beneficial to the dissolution of copper. The resting time of the mixture of activated carbon and ores has an impact on the bioleaching of low-grade primary copper sulfide ores. The 2 d resting time is most favorable to the dissolution of copper. The enhanced dissolution rate and efficiency of copper can be attributed to the galvanic interaction between activated carbon and chalcopyrite. The addition of activated carbon obviously depresses the dissolution of iron and the bacterial oxidation of ferrous ions in solution. The lower redox potentials are more favorable to the copper dissolution than the higher potentials for low-grade primary copper sulfide ores in the presence of activated carbon.

Enhanced degradation of reactive dyes using a novel carbon ceramic electrode based on copper nanoparticles and multiwall carbon nanotubes

A novel carbon ceramic electrode consisting of Cu NPs and MWCNT was developed to treat reactive orange 84(RO84) wastewater using ultrasound-assisted electrochemical degradation. The proposed electrode generated more hydroxyl radicals than non-nanoparticle electrodes did. In addition, a new electrochemical sensor was applied to determine residue RO84 in an aqueous medium during discoloration. This sensor is based on a glassy carbon electrode modified with gold nanourchins and graphene oxide and can detect RO84 concentration in the range of 1.0–1200 μmol·L^-1 with the detection limit of 0.03 μmol·L^-1. The degradation effects of the modified electrode on RO84 were evaluated systematically with different initial pH values, time durations, and amounts of Cu NPs and MWCNT. The results suggested that the removal efficiency of RO84 was approximately 83% after120 min of electrolysis in a phosphate buffer with pH 8.0 using a carbon ceramic electrode made with 4.0 wt%Cu NPs and 4.0 wt% MWCNT. The possible mechanism of RO84 degradation was monitored by gas chromatography–mass spectrometry, and degradation pathways were proposed.

Thermo-physical Properties of Continuous Carbon Fiber Reinforced Copper Matrix Composites

Continuous carbon fiber reinforced copper matrix composites with 70%(volume fraction) of carbon fibers prepared by squeeze casting technique have been used for investigation of the coefficient of thermal expansion(CTE) and thermal conductivity.Thermo-physical properties have been measured in both,longitudinal and transversal directions to the fiber orientation.The results showed that Cf/Cu composites may be a suitable candidate for heat sinks because of its good thermo-physical properties e.g.the low CTE(4.18×10-6/K) in longitudinal orientation and(14.98×10-6/K) in transversal orientation at the range of 20-50℃,a good thermal conductivity(87.2 W/m·K) in longitudinal orientation and(58.2 W/m·K) in transversal orientation.Measured CTE and thermal conductivity values are compared with those predicted by several well-known models.Eshelby model gave better results for prediction of the CTE and thermal conductivity of the unidirectional composites.