Optimization of cuprous oxide nanocrystals deposition on multiwalled carbon nanotubes

Cu (I) phenyl acetylide was used as a source of copper to achieve a homogeneous distribution of Cu₂O nanocrystals (10–80 nm) decorated on multiwalled carbon nanotubes (MWCNTs) having an average diameter of 10 nm. Pristine MWCNTs were first oxygen-functionalized by treating them with a mixture of concentrated (H₂SO₄/HNO₃ : 3/1) acids and the products were characterized by X-ray powder diffraction, transmission and scanning electron microscopy, energy dispersive X-ray analysis, X-ray photoelectron spectroscopy and thermogravimetric analysis. An easy, efficient and one-step impregnation method was followed to produce copper-containing nanoparticles on the MWCNTs. The copper-treated MWCNTs dried at room temperature were seen to be well decorated by copper-containing nanoparticles on their outer surface. The MWCNTs were then heat-treated at 400 °C in a nitrogen atmosphere to produce a homogeneous distribution of cuprous oxide nanocrystals on their surface. By varying the ratio of copper to oxygen-functionalized MWCNTs, Cu₂O nanocrystals decorated on MWCNTs with different copper content can be obtained.     

Formation mechanisms of nanocomposite layers based on multiwalled carbon nanotubes and non-stoichiometric tin oxide

Nanocomposite layers based on multiwalled carbon nanotubes (MWCNTs) and non-stoichiometric tin oxide (SnO _x ) have been grown by magnetron deposition and CVD methods. In the case of the CVD method, the study of the structure and phase composition of obtained nanocomposite layers has shown that a tin oxide “superlattice” is formed in the MWCNT layer volume, fixed by SnO _x islands on the MWCNT surface. During magnetron deposition, the MWCNT surface is uniformly coated with tin oxide islands, which causes a change in properties of individual nanotubes. Electrical measurements have revealed the sensitivity of nanocomposite layers to (NO₂)⁻ molecule adsorption, which is qualitatively explained by a change in the conductivity of the semiconductor fraction of p-type MWCNTs.     

Photoinduced growth of Cu nanoparticles on ZnO from CuCl<Subscript>2</Subscript> in methanol

Cu nanoparticles were formed on surface of nano-ZnO by UV light induced photoreduction of CuCl₂ in methanol solution suspended with ZnO nanoparticles. By controlling the reaction conditions, the average size of the produced copper nanocrystal can be fine-tuned in the range of 10–200 nm. At constant UV irradiation, the Cu nanocrystals gradually grew up as the initial concentration of copper cation was increased, showing that the in situ formed Cu nanoparticles act as a bridge to facilitate the transferring of photoexcited electrons from ZnO surface to Cu²⁺ in solution. A Redox property was also proved for the Cu nanoparticles.     

Ultrasound-assisted facile one-pot synthesis of ternary MWCNT/MnO2/rGO nanocomposite for high performance supercapacitors with commercial-level mass loadings

Commercial application of supercapacitors (SCs) requires high mass loading electrodes simultaneously with high energy density and long cycle life. Herein, we have reported a ternary multi-walled carbon nanotube (MWCNT)/MnO₂/reduced graphene oxide (rGO) nanocomposite for SCs with commercial-level mass loadings. The ternary nanocomposite was synthesized using a facile ultrasound-assisted one-pot method. The symmetric SC fabricated with ternary MWCNT/MnO₂/rGO nanocomposite demonstrated marked enhancement in capacitive performance as compared to those with binary nanocomposites (MnO₂/rGO and MnO₂/MWCNT). The synergistic effect from simultaneous growth of MnO₂ on the graphene and MWCNTs under ultrasonic irradiation resulted in the formation of a porous ternary structure with efficient ion diffusion channels and high electrochemically active surface area. The symmetric SC with commercial-level mass loading electrodes (∼12 mg cm⁻²) offered a high specific capacitance (314.6 F g⁻¹) and energy density (21.1 W h kg⁻¹ at 150 W kg⁻¹) at a wide operating voltage of 1.5 V. Moreover, the SC exhibits no loss of capacitance after 5000 charge−discharge cycles showcasing excellent cycle life.     

X-ray emission and photoluminescence spectroscopy of nanostructured silica with implanted copper ions

Quartz glass samples and compacted SiO₂ nanopowders have been studied by x-ray emission (CuL _{2, 3} transition 3d4s → 2p _{1/2, 3/2}) and photoluminescence spectroscopy following pulsed Cu⁺ ion implantation (energy, 30 keV; pulse current up to 0.5 A; pulse duration, 400 μs; irradiation doses, 10¹⁵, 10¹⁶, and 2 × 10¹⁷ cm^?2). It has been established that ion irradiation gives rise to the formation of glassy and compacted SiO₂ samples of nanosized metallic and oxide phases in the structure. An analysis of CuL x-ray emission spectra has shown that copper nanoparticles are thermodynamically metastable and chemically active because ion beam bombardment transfers them readily to the oxide form. This results from the radiation-stimulated fracture of regular Si-O-Si bonds in amorphous SiO₂ and the formation of defective Si-Si bonds, followed by capture of oxygen by copper atoms. The enhanced degree of oxidation of copper ions in SiO₂ nanostructured pellets can be reduced by coimplantation and thermal annealing. Optical spectroscopy studies suggest that, in glasses and SiO₂ nanostructured pellets, there exist metallic Cu _n ⁰ nanoclusters, which at low temperatures exhibit quantum-confined photoluminescence with a characteristic stepped excitation spectrum.     

Synthesis and gas sensing characteristic based on metal oxide modification multi wall carbon nanotube composites

A new type of gas sensing material based on metal oxide modification multi wall carbon nanotube (MO/MWCNT) composites is presented since the interface between the composites enhance the carrier density so as to improve the gas sensitivity. Three kinds of MO/MWCNT composite materials, such as ZnO/MWCNT, SnO₂/MWCNT and TiO₂/MWCNT, have been acquired in situ growth using catalytic pyrolysis method. The MO nano particles have decorated on side of MWCNTs, whereas the introduction of SnO₂ nano particles makes part of MWCNT showing two-dimensional form of carbon nano-wall structure. Among four kinds of cathode of ZnO/MWCNTs, SnO₂/MWCNTs, TiO₂/MWCNTs and pure MWCNT composite film, TiO₂/MWCNTs composite has the lowest threshold electric field required to draw current of 12 μA has been found to be ∼1.2 V/μm, and also TiO₂/MWCNTs composite has the highest sensitivity of 16% to ethanol. The TiO₂/MWCNTs composite is superior to the others both in vacuum electron transportation and gas sensitivity.     

Ultrasound assisted synthesis of {[Cu2(BDC)2(dabco)].2DMF.2H2O} nanostructures in the presence of modulator; new precursor to prepare nano copper oxides

As a new precursor to prepare nano copper oxide, nanostructures of porous metal organic framework (MOF) {[Cu₂(BDC)₂(dabco)].2DMF.2H₂O} (1) have been synthesized in the presence of acetic acid as a modulator via sonochemical method. Different concentrations of metal ion, organic linkers, modulator reagent and also different sonication times were held to improve the quality of nanostructures. Ultrasound irradiation helps nucleation step of the oriented attachment of modulation method and nanoparticles with a few nanorods has been prepared. As prepared MOF was calcinated at 500 °C to prepare nano CuO and Cu₂O. Compound 1, CuO and Cu₂O nanostructures were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM) and X-ray powder diffraction (XRD).     

Preparation of Cu 2 O nanoparticles dispersed in NH 2 -terminated polyethyleneoxide matrix

Small Copper (I) oxide, Cu₂O, nanoparticles dispersed in diamine-terminated polyethyleneoxide (PEO-NH₂) matrix have been successfully prepared by vacuum evaporation of copper onto the molten PEO-NH₂. The obtained composite were characterized by TEM, electron diffraction, TG-DTA and FT-IR spectroscopy. The stable composite, in which the Cu₂O nanoparticles are stabilized through interaction between NH₂ chain end groups of PEO molecules and Cu₂O nanoparticles was obtained when the samples were heat-treated at 110 ^° C. The mean size of the Cu₂O nanoparticles increased from 2.5 to 3.5 nm in diameter upon increasing the amount of initial Cu deposition. The obtained composite material having a waxy texture was soluble in many solvents without aggregation and can be handled as a simple chemical compound for starting material in various applications. Received 29 November 2000     

A comparison of the magnetic and microwave absorption properties of Mn–Sn–Ti substituted strontium ferrite with and without multi-walled carbon nanotube

In this work, a comparison of magnetic and microwave properties between Mn–Sn–Ti substituted SrM ferrite and nanocomposite of Mn–Sn–Ti substituted SrM ferrite–20% volume multi-walled carbon nanotube (MWCNT) has been done. Phase characterization and crystal structure of the synthesized nanoparticles were tested by X-ray diffraction (XRD). Field emission scanning electron microscopy (FESEM), Fourier transform infrared spectrometry (FTIR) analysis approved that the SrFe_12−x(MnSn_0.5Ti_0.5)_x/2O₁₉ nanoparticles were attached on the external surfaces of the MWCNTs. Mӧssbauer spectroscopy (M_S) showed the occupancy by non-magnetic Mn²⁺–Sn⁴⁺–Ti⁴⁺ cations into the hexagonal lattice structure. Magnetic properties were evaluated by a vibrating sample magnetometer (VSM). The results also indicated that saturation magnetization and coercivity were decreased with an increase in x content and also MWCNTs addition. Microwave absorption properties were investigated by a vector network analyzer (VNA). It was found that with an addition of 20 volume percentage of MWCNTs, the saturation magnetization coupled with coercivity decrease, but reflection loss (RL) increase broadly. Also it proved that with an increase in the thickness of absorption the frequency band shifts from K_u (12–18 GHz) to X (8–12 GHz) band.     

Formation of well-packed TiO<Subscript>2</Subscript> nanoparticles on multiwall carbon nanotubes using CVD method to fabricate high sensitive gas sensors

Titanium oxide nanoparticles were coated on multiwall carbon nanotubes (MWCNTs) using an atmospheric pressure chemical vapor deposition (CVD) to achieve highly compact nanoparticles of about 5 nm on CNT structure. The CNTs with a diameter of about 50 nm were grown by plasma enhanced CVD. Gas sensitivity of the fabricated structure was investigated and compared with TiO₂/CNT composite-based gas sensors. The effect of the structural interaction between the nanoparticles and the CNT wall on sensing mechanism of the as-prepared gas sensors was investigated. Ultrasensitive gas sensors were obtained by TiO₂/CNT nanostructures with strong interaction between the MWCNT and the TiO₂ nanoparticles. The measurements show high chemical activity and exceptional electrical response of the as-prepared structure being exposed to gases. Scanning and transmission electron microscopy and X-ray diffraction analysis were used to obtain structural information.     

Surface‐enhanced Raman scattering and fluorescence emission of gold nanoparticle–multiwalled carbon nanotube hybrids

Multiwalled carbon nanotubes (MWCNTs) are grafted with gold (Au) nanoparticles of different sizes (1–12 and 1–20 nm) to form Au–MWCNT hybrids. The Au nanoparticles pile up at defect sites on the edges of MWCNTs in the form of chains. The micro‐Raman scattering studies of these hybrids were carried using visible to infrared wavelengths (514.5 and 1064 nm). Enhanced Raman scattering and fluorescence is observed at an excitation wavelength of 514.5 nm. It is found that the graphitic (G) mode intensity enhances by 10 times and down shifts by approximately 3 cm⁻¹ for Au–MWCNT hybrids in comparison with pristine carbon nanotubes. This enhancement in G mode due to surface‐enhanced Raman scattering effect is related to the interaction of MWCNTs with Au nanoparticles. The enhancement in Raman scattering and fluorescence for large size nanoparticles for Au–MWCNTs hybrids is corroborated with localized surface plasmon polaritons. The peak position of localized surface plasmons of Au nanoparticles shifts with the change in environment. Further, no enhancement in G mode was observed at an excitation wavelength of 1064 nm. However, the defect mode (D) mode intensity enhances, and peak position is shifted by approximately 40 cm⁻¹ to lower side at the same wavelength. The enhanced intensity of D mode at 1064 nm excitation wavelength is related to the double resonance phenomenon and shift in the particular mode occurs due to more electron phonon interactions near Fermi level. Copyright © 2012 John Wiley & Sons, Ltd.     

Electronic excitations and optical response of metal nanocomposites under heavy ion implantation

The optical transmission and ion-induced luminescence under implantation of copper ions into quartz glass (a-SiO₂) have been measured to study the processes of formation of copper nanoparticles. It is shown that in situ measurements are more informative in comparison with the ordinary approach—investigation of the properties of ion-implanted nanocomposites only after implantation. A series of experiments was performed to prove that the ion-induced luminescence band at 545–550 nm is due to Cu⁺ ions dissolved in a-SiO₂. The combined use of in situ optical techniques makes it possible to monitor the states of implanted copper (metal nanoparticles and dissolved atoms) by the change in the optical absorption near the surface plasmon resonance of nanoparticles and by the intensity of ion-induced luminescence of Cu⁺ states in solid solution. It is shown that the optical bands of defects, dissolved copper, and nanoparticles can be separated within a simple linear approximation. Near the surface plasmon resonance and defect bands, ion-induced transient optical absorption has been revealed. The transient optical absorption near the surface plasmon resonance is explained by the temperature effect. The relationship between the electronic excitation, radiation-induced optical response, and the kinetics of nanoparticle formation is analyzed. Several stages of nanoparticle formation have been established: accumulation of implanted copper in solid solution, nucleation of nanoparticles, coalescence, growth of nanoparticles, and saturation of nanocomposites.     

Adsorption and photocatalytic degradation of methylene blue on Zn1−xCuxS nanoparticles prepared by a simple green method

Nanoparticles of Zn_1−xCu_xS with various dopant contents (0 ≤ x ≤ 0.15) were prepared in water by refluxing for 90 min at about 95 °C. Powder X-ray diffraction (XRD) patterns of the nanoparticles demonstrate that loading of Cu²⁺ ions does not change the crystal structure of ZnS. Scanning electron microscopy (SEM) images demonstrate that size of the nanoparticles decreases with increasing Cu²⁺ ions. UV-Vis diffuse reflectance spectra (DRS) of the nanoparticles show significant absorption in visible light region. Adsorption capacity of the nanoparticles for methylene blue (MB) increases with mole fraction of copper ions. Photocatalytic activity of the nanoparticles toward photodegradation of MB was evaluated under visible light irradiation. The results indicate that Zn_0.85Cu_0.15S nanoparticles exhibit highest photocatalytic activity among the prepared samples. Moreover, effects of refluxing time applied for preparation of the nanoparticles and calcination temperature were investigated.     

Nanoscale Kirkendall Effect and Oxidation Kinetics in Copper Nanocrystals Characterized by Real‐Time,In Situ Optical Spectroscopy

The low‐temperature oxidation of ≈10 nm diameter copper nanocrystals is characterized using in situ UV–vis absorbance spectroscopy and observed to lead to hollow copper oxide shells. The kinetics of the oxidation of solid Cu nanocrystals to hollow Cu₂O nanoparticles is monitored in real‐time via the localized surface plasmon resonance response of the copper. A reaction‐diffusion model for the formation of hollow nanoparticles is fit to the measured time for complete Cu nanocrystal oxidation, and is used to quantify the diffusion coefficient of Cu in Cu₂O and the activation energy of the oxidation process. The diffusivity measured here in single‐crystalline nanoscale systems is 1–5 orders of magnitude greater than in comparable systems in the bulk, and have an Arrhenius dependence on temperature with an activation energy for diffusion of 37.5 kJ mol^?1 for 85 °C ≤ T ≤ 205 °C. These diffusion parameters are measured in some of the smallest metal systems and at the lowest oxidation temperatures yet reported, and are enabled by the unique nanoscale single‐crystalline material and the in situ characterization technique.     

Preparation of Cu2O nanowires by thermal oxidation-plasma reduction method

Facial synthesis of cuprous oxide (Cu₂O) nanowires by directly heating copper substrates is difficult; however, in this study, it was successfully done by thermal oxidation followed by a plasma reduction process. The preparation of CuO nanowires with an average diameter of 76.2?nm supported on the surface of copper substrate was conducted first in air at 500?°C for 3?hrs, and then the CuO nanowires were reduced into Cu₂O in 15?min using either radio frequency (RF) N₂ plasma or microwave (MW) N₂ plasma. The characteristics of CuO and Cu₂O nanowires were analyzed using XRD, FE-SEM, and TEM. The results showed that Cu₂O nanowires can be successfully reduced from CuO nanowires by a simple, promising, and fast nitrogen plasma process. Moreover, in RF plasma, narrower and longer Cu₂O nanowires can be produced as compared to MW plasma, because energetic N-containing species can reduce the nanowires at a relatively lower temperature.     

Preparation, characterization and photocatalytic activity of multi-walled carbon nanotube-supported tungsten trioxide composites

Multi-walled carbon nanotube (MWCNT)-supported tungsten trioxide (WO₃) composite catalysts were prepared by liquid-phase process. WO₃ nanoparticles grew on the inner and outer surface of MWCNTs. Their photocatalytic activities in the degradation of the Rhodamine B Dye were studied. The effects of mass ratio of MWCNTs to WO₃ were discussed. X-ray diffraction, field emission transmission electron microscopy, thermogravimetric-differential thermal analysis and ultraviolet-visible light absorption spectra were carried out to characterize the composite catalysts. The results indicated that the optimum mass ratio of MWCNTs to WO₃ is 5:100.     

Size-selected copper oxide nanoparticles synthesized by laser ablation

Size-tuned copper oxide nanoparticles with sizes of 9, 12, and 15 nm were fabricated by laser ablation and on-line size selection using a differential mobility analyzer at a gas pressure of 666 Pa. The dependence of the particle properties on the in situ annealing temperatures and selection sizes was investigated. The crystalline phases of the nanoparticles fabricated at temperatures below 973 K were assigned to monoclinic cupric oxide (CuO) which converted into cubic cuprous oxide (Cu₂O) when the annealing temperature was above 1,173 K. This indicates that the crystalline phases can be easily controlled by changing the annealing temperature. TEM images confirmed that well-crystallized and well-dispersed CuO and Cu₂O nanoparticles with narrow size distributions were obtained using this method. This fabrication process is useful and promising for the future investigation of the intrinsic size-dependent properties of CuO and Cu₂O.     

Nanotitania-coated multi-walled carbon nanotube composite by facile colloidal processing route for photocatalytic applications

Multi-walled carbon nanotubes (MWCNTs) and titanium dioxide nanocomposites (MWCNTs/TiO₂) were fabricated by a simple novel colloidal processing route and tested as a photocatalyst for degradation of methylene blue under UV irradiation. The novel idea behind this work is to make MWCNTs and TiO₂ nanoparticle suspensions separately highly oppositely charged and utilize the electrostatic force of attraction between two entities to deposit nanotitania onto MWCNTs surface. Particle charge detector, scanning electron microscopy, transmission electron microscope, energy dispersive X-rays, X-rays diffraction (XRD), and Raman spectroscopy were used to characterize the composite. XRD and Raman spectroscopic analysis showed the crystalline structure of deposited TiO₂ over MWCNTs surface structure as anatase phase. It was found that MWCNTs/TiO₂ composite structure have much higher photocatalytic activity compared to TiO₂ nanoparticles. The composite material developed may find potential applications in the degradation of organic pollutants in aqueous medium under UV irradiation.     

In situ investigation of morphological and phase changes during thermal annealing and oxidation of carbon-encapsulated copper nanoparticles

In situ electron microscope and X-ray investigations of the morphological and phase characteristics of copper nanoparticles encapsulated in a carbon shell were carried out. It was found that oxidation of the copper nanoparticles starts at a temperature of 200 °C. The formation of oxide phases occurs on the surface of the carbon shells, with the Cu₂O phase appearing first followed by the formation of the CuO phase. Upon heating to just below its melting point, the copper sublimes resulting in the formation of hollow carbon nanocapsules. Treatment of the initial or oxidized encapsulated copper nanoparticles with nitric acid and annealing can be used to obtain hollow carbon nanocapsules.     

Optical characterization of thin thermal oxide films on copper by ellipsometry

A complete optical characterization in the visible region of thin copper oxide films has been performed by ellipsometry. Copper oxide films of various thicknesses were grown on thick copper films by low temperature thermal oxidation at 125 °C in air for different time intervals. The thickness and optical constants of the copper oxide films were determined in the visible region by ellipsometric measurements. It was found that a linear time law is valid for the oxide growth in air at 125 °C. The spectral behaviour of the optical constants and the value of the band gap in the oxide films determined by ellipsometry in this study are in agreement with the behaviour of those of Cu₂O, which have been obtained elsewhere through reflectance and transmittance methods. The band gap of copper oxide, determined from the spectral behaviour of the absorption coefficient was about 2 eV, which is the generally accepted value for Cu₂O. It was therefore concluded that the oxide composition of the surface film grown on copper is in the form of Cu₂O (cuprous oxide). It was also shown that the reflectance spectra of the copper oxide–copper structures exhibit behaviour expected from a single layer antireflection coating of Cu₂O on Cu. Received: 19 July 2001 / Accepted: 27 July 2001 / Published online: 17 October 2001