Electrochemical and surface characterisation of gold nanoparticle decorated multi-walled carbon nanotubes

A novel type of gold nanoparticle/multi-walled carbon nanotube (AuNP/MWCNT) composite electrodes is presented. The electrochemical reduction of oxygen on these hybrid electrodes was studied using the rotating disk electrode (RDE) method. The AuNP/MWCNT nanocomposites were prepared by sputter deposition of gold in argon atmosphere on MWCNTs followed by heat-treatment of the catalyst at different temperatures. High-resolution scanning electron microscopy (HR-SEM), glancing incidence angle X-ray powder diffraction (GIXRD) and small-angle X-ray scattering (SAXS) techniques were employed to characterise the surface structure and morphology of catalyst materials. Au nanoparticles with diameter around 20 nm were dispersed at the tips and on the sidewalls of nanotubes. Electrochemical measurements were performed to demonstrate the electrocatalytic properties of the composite catalysts towards O₂ reduction in acid media. The successful preparation of AuNP/MWCNT nanocomposites by magnetron sputtering opens up the possibility of making an efficient dispersion of nanoparticles for electrocatalyst design.     

Ru decorated Pt nanoparticles by a modified polyol process for enhanced catalytic activity for methanol oxidation

Ru decorated Pt nanoparticles on carbon nanotubes (MWCNTs) were prepared by a modified polyol synthesis method for enhanced catalytic activity for methanol oxidation. The characterizations for the electrocatalysts were carried out by transmission electron microscopy (TEM), X-ray diffraction (XRD), cyclic voltammetry (CV) and chronoamperometry (CA). The modified polyol synthesis method promoted position-controlled nucleation and growth of Ru atoms near Pt, and resulted in improved durability against catalyst poisoning compared to PtRu/MWCNTs prepared by common polyol method. This concept also allowed a high loading and dispersion of the catalyst on the carbon supports with few agglomerations of catalyst nanoparticles, resulting in high catalytic activity.     

Deposition of silver nanoparticles on carbon nanotube by chemical reduction method: Evaluation of surface,thermal and optical properties

Silver was stabilized on multi-walled carbon nanotubes (MWCNTs) by chemical-reduction technique using N,N-dimethylformamide (DMF) as a reducing agent. The influence of silver on the performance of carbon nanotubes (CNTs) was investigated by employing Fourier-transform infrared spectra (FTIR), Raman spectroscopy (RAS), thermal gravimetric analysis (TGA), zeta potential measurement, scanning electron microscope (SEM), electron dispersive X-ray spectrometer (EDX), transmission electron microscopy (TEM), and reflectance spectroscopy (RS). FTIR as well as RS methods evidenced the synthesis procedure using chemical reduction method was successful. Performing TGA of the samples under oxygen atmosphere demonstrated that the silver nanoparticles (Ag NPs) generated on MWCNTs surface can decrease the thermal stability of the particles by the catalytic oxidation of CNTs. In contrary, the thermal stability of the MWCNTs has improved under nitrogen atmosphere. EDX results showed the presence of Ag, Au and Co on the surface of deposited sample. The synthesised silver multi-walled carbon nanotubes (Ag–MWCNTs) were found to have higher UV reflection activity compared with untreated particles. The Ag–CNTs can be used in producing anti-UV composites.     

Effects of additives on palladium nanocrystals supported on multiwalled carbon nanotubes and their electrocatalytic properties toward formic acid oxidation

Carbon nanotubes are believed to be powerful materials for constructing novel hybrid composites with desirable functionalities and applications in many fields. Therefore, a better understanding of the functionalization of multiwalled carbon nanotubes (MWCNTs) holds the key to a better performance of the hybrid properties. In this paper, with a series of aromatic bifunctional molecule additives, modified MWCNTs were used as composite supports for synthesizing nanostructured palladium catalysts for formic acid oxidation. The additives contain anthranilic acid, o-phenylenediamine, salicylic acid, catechol, and phthalic acid. The influence of the different bifunctional groups (such as –NH₂, –OH, –COOH, and their mixed groups) on the morphologies, particle sizes, and electrical properties of Pd nanocrystals was intensively studied. Transmission electron microscopy measurement demonstrates that the palladium nanoparticles were well dispersed on the surface of MWCNTs with a relatively narrow particle size distribution in the presence of the additives. Cyclic voltammetry and chronoamperometry tests demonstrate that the functional groups of the additives play an important role in electrocatalytic activity and stability for formic acid oxidation, and the influence law of various functional groups on electrocatalytic activity and stability is also investigated in this paper. We hope it can provide certain theoretical guidance meaning and practical reference value in future studies.     

Functionalization of multiwall carbon nanotubes with nitrogen containing polyelectrolyte by a simple method

Commercially available multiwall carbon nanotubes (MWCNTs) have been functionalized with poly(diallyl dimethylammonium) chloride (PDDA), a nitrogen containing polyelectrolyte by a simple on-off ultrasonication method. The results obtained from Raman and X-ray photoelectron spectroscopy (XPS) studies confirm the functionalization of MWCNTs with PDDA. An up- shift in the positions of C1s XPS peak and a down-shift in the positions of the N1s XPS peak, has been observed along with an up-shift in the G-peak position in the Raman spectra, which suggest the occurrence of inter-molecular charge transfer from carbon atoms in MWCNTs to N⁺ centres in PDDA. The preliminary linear sweep voltammetry (LSV) results show good electrocatalytic activity of MWCNTs functionalized with nitrogen containing polyelectrolyte, which is comparable to the results with platinum based electrodes. Thus, MWCNTs non-covalently functionalized with a nitrogen containing polyelectrolyte (PDDA) by a simple on-off ultrasonication method could be advantageous for developing efficient metal-free electrocatalysts for the oxygen reduction reaction (ORR).     

Preparation of highly dispersed Pt-SnOx nanoparticles supported on multi-walled carbon nanotubes for methanol oxidation

To maximize the utilization of catalysts and thereby reduce the high price, a new strategy was developed to prepare highly dispersed Pt-SnO_x nanoparticles supported on 8-Hydroxyquinoline (HQ) functionalized multi-walled carbon nanotubes (MWCNTs). HQ functionalized MWCNTs (HQ-MWCNTs) provide an ideal support for improving the utilization of platinum-based catalysts, and the introduction of SnO_x to the catalyst prevents the CO poisoning effectively. The as-prepared catalysts are characterized by Transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and Raman spectroscopy. It is found that the HQ functionalization process preserves the integrity and electronic structure of MWCNTs, and the resulting Pt-SnO_x particles are well dispersed on the HQ-MWCNTs with an average diameter of ca. 2.2 nm. Based on the electrochemical properties characterized by cyclic voltammetry and chronoamperometry, the Pt-SnO_x/HQ-MWCNTs catalyst displays better electrocatalytic activity and stability for the methanol oxidation. It is worth mentioning that the forward peak current density of Pt-SnO_x/HQ-MWCNTs catalyst is ca. 1.9 times of that of JM commercial 20% Pt/C catalyst, which makes it the preferable catalyst for direct methanol fuel cells.     

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.     

Multiwalled carbon nanotube supported Pt–Sn–M (M = Ru,Ni, and Ir) catalysts for ethanol electrooxidation

In the present study, Pt–Sn–M (M = Ru, Ni, and Ir) nanocatalysts were supported on multiwalled carbon nanotube and their electrocatalytic activity for ethanol oxidation in membraneless fuel cells was investigated. The combination of monometallic Pt/MWCNTs, bi-metallic Pt–Sn/MWCNTs, and tri-metallic Pt–Sn–Ru/MWCNT, Pt–Sn–Ni/MWCNT, and Pt–Sn–Ir/MWCNT nanocatalysts were prepared by the ultrasonic assisted chemical reduction method. Transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy (EDX), and X-ray diffraction (XRD) were used for the catalyst characterization. The electrocatalytic activities of the catalysts were investigated in half-cell experiments using cyclic voltammetry (CV), CO stripping voltammetry, and chronoamperometry (CA). During the experiments performed on a single membraneless ethanol fuel cell (MLEFC), the Pt–Sn–Ir/MWCNTs exhibited a better catalytic activity from among all the catalysts prepared, with a power density of 39.25 mW cm^?2.     

Carbon nanotubes supported Cu-Ni bimetallic catalysts and their properties for the direct synthesis of dimethyl carbonate from methanol and carbon dioxide

Multi-walled carbon nanotubes (MWCNTs) supported Cu-Ni bimetallic catalysts for the direct synthesis of dimethyl carbonate (DMC) from CH₃OH and CO₂ were synthesized and investigated. The supporting materials and the synthesized catalysts were fully characterized using FTIR, scanning electron microscopy (SEM), transmission electron microscopy (TEM), temperature-programmed reduction (TPR), X-ray diffraction (XRD) and X-ray photoelectron spectrum (XPS) techniques. The catalytic activities were investigated by performing micro-reactions. The experimental results showed that the metal phase and Cu-Ni alloy phase in the catalyst were partially formed during the calcination and activation step. Active metal particles were dispersed homogeneously on the surface of the MWCNTs. Cu-Ni/MWCNTs catalysts were efficient for the direct synthesis of DMC. The highest conversion of CH₃OH was higher than 4.3% and the selectivity of DMC was higher than 85.0% under the optimal catalytic conditions of 120 °C and around 1.2 MPa. The high catalytic activity of Cu-Ni/MWCNTs in DMC synthesis can be attributed to the synergetic effects of metal Cu, Ni and Cu-Ni alloy in the activation of CH₃OH and CO₂, the unique structure of MWCNTs and the interaction between the metal particles and the supports.     

Sulfur grown around carbon nanotubes as a cathode material for Li/S battery

Sulfur/multi-walled carbon nanotubes (MWCNTs) composites have been successfully prepared by an in situ growth strategy as a cathode material for lithium/sulfur battery. The microstructure and morphology of the sulfur/MWCNTs composites are characterized by means of X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). From the results, it is found that the nano-sulfur (shell) grows around the MWCNTs (core) and is well-dispersed over the whole surface of the MWCNTs. Tested by coin type cells, the composite materials exhibited the sulfur utilization approaching to 78% for the first cycle, the capacity retention closing to 84% after 100 cycles at various rates. The excellent electrochemical performance could be attributed to the nano-size sulfur and the homogeneous distribution of sulfur on MWCNTs matrix, resulting from this novel in situ growth method, which not only enhances the reactive activity of sulfur during charge–discharge processes but also provides stable electrical and ionic transfer channels.     

Multi-walled carbon nanotube supported Pd and Pt nanoparticles with high solution affinity for effective electrocatalysis

Multi-walled carbon nanotubes (MWCNTs) are easily wrapped with a functional biopolymer—polydopamine (Pdop) through self-polymerization of dopamine in a mild basic solution. The MWCNTs@Pdop exhibits long term dispersivity in water for at least one month. The Pdop has large capacity to coordinate [PdCl₄]²⁻ and [PtCl₆]²⁻ that upon reduction transform to corresponding metal nanoparticles. The nanoparticles strongly adhere to Pdop layer and can be used for the electrooxidation of haydrazine and methanol, respectively. Compared to Pd and Pt supported on unmodified MWCNTs, the Pd and Pt nanoparticle decorated on MWCNTs@Pdop exhibit much higher electrocatalytic activity and enhanced stability.     

Immobilization of platinum nanoparticles on 3,4-diaminobenzoyl-functionalized multi-walled carbon nanotube and its electrocatalytic activity

Abstract  

Multi-walled carbon nanotubes (MWCNTs) are functionalized at the sp² C–H defect sites with 3,4-diaminobenzoic acid by a “direct” Friedel–Crafts acylation reaction in a mild polyphosphoric acid/phosphorous pentoxide medium. Owing to enhanced surface polarity, the resulting 3,4-diaminobenzoyl-functionalized MWCNTs (DAB-MWCNT) are highly dispersible in polar solvents, such as ethanol, N-methyl-2-pyrrolidone, and methanesulfonic acid. The absorption and emission properties of DAB-MWCNT in solution state are qualitatively shown to be sensitive to the pH in the environment. The DAB-MWCNT is used as a stable platform on which to deposit platinum nanoparticles (PNP). The PNP/DAB-MWCNT hybrid displays high electrocatalytic activity with good electrochemical stability for an oxygen reduction reaction under an alkaline condition.     

Thermal and Mechanical Properties of Epoxy/Carbon Fiber Composites Reinforced with Multi-walled Carbon Nanotubes

Multi-scale hybrid composite laminates of epoxy/carbon fiber (CF) reinforced with multi-walled carbon nanotubes (MWCNTs) were fabricated in an autoclave. For laminate fabrication, 0.5 wt% of pristine MWCNTs or silane-functionalized MWNCTs (f-MWCNTs) were dispersed into a diglycidyl ether of bisphenol-A epoxy system and applied on the woven carbon fabric. The neat epoxy/CF composite and the MWCNTs-reinforced epoxy/CF hybrid composites were characterized by thermogravimetric analysis (TGA), thermomechanical analysis (TMA), tensile testing, and field emission scanning electron microscopy (FE-SEM). A significant improvement in initial decomposition temperature and glass transition temperature of epoxy/CF composite was observed when reinforced with 0.5 wt% of f-MWCNTs. The coefficient of thermal expansion (CTE), measured by TMA, diminished by 22% compared to the epoxy/CF composite, indicating an improvement in dimensional stability of the hybrid composite. No significant improvement in tensile properties of either MWCNTs/epoxy/CF composites was observed compared to those of the neat epoxy/CF composite.     

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.     

Synthesis and magnetic properties of size-controlled FeNi alloy nanoparticles attached on multiwalled carbon nanotubes

FeNi alloy nanoparticles with controllable sizes were attached on the multiwalled carbon nanotubes by adjusting the atomic ratio of metal to carbon in the mixed solution of nitrate with Fe:Ni=1:1 (atomic ratio) via wet chemistry. Transmission electron microscopy (TEM) and high-resolution TEM indicated that quasi-spherical FeNi alloy nanoparticles with sizes in the range 12-25 nm are obtained. FeNi alloy composed of major face center cubic (fcc) and minor body center cubic (bcc) structures, which is proved by the X-ray powder diffraction (XRD). Magnetization measured by vibrating sample magnetometer demonstrated that both the coercive force and saturation magnetizations decrease as the size of the FeNi alloy nanoparticles decreased. The chemical method is promising for fabricating FeNi alloy nanoparticles attached on carbon nanotubes for magnetic storage and ultra high-density magnetic recording applications.     

Comparison of different types of polypyrimidine/CNTs/Pt hybrids in fuel cell catalysis

In this paper, we mainly studied the preparation of platinum-containing composite materials with carbon nanotubes wrapped by polypyrimidine-conjugated polymers and the performance of the composites. The polymer-based carbon nanotubes/Pt catalysts were prepared successfully and confirmed by infrared spectroscopy, XPS, XRD, and TEM images. The performance of polypyrimidine/multi-walled carbon nanotubes (MWCNTs)/Pt and polypyrimidine/double-walled carbon nanotubes (DWCNTs)/Pt was compared with the polypyrimidine/single-walled carbon nanotubes (SWCNTs)/Pt. The amount of the loaded Pt on the polypyrimidine/MWCNTs and polypyrimidine/DWCNTs was calculated to be 50.5 wt% and 52.7 wt% respectively. The effective specific surface area of the polypyrimidine/MWCNTs/Pt (45.7 m²/g) and polypyrimidine/DWCNTs/Pt (42.47 m²/g) was observed by electrochemical cyclic voltammetry. These studies strongly imply that the MWCNTs were better candidates than DWCNTs and SWCNTs in the application of polypyrimidine/CNT materials as catalyst for fuel cells.     

Surface modification of indium tin oxide films by amino ion implantation for the attachment of multi-wall carbon nanotubes

Amino ion implantation was carried out at the energy of 80 keV with fluence of 5 × 10¹⁵ ions cm⁻² for indium tin oxide film (ITO) coated glass, and the existence of amino group on the ITO surface was verified by X-ray photoelectron spectroscopy analysis and Fourier transform infrared spectra. Scanning electron microscopy images show that multi-wall carbon nanotubes (MWCNTs) directly attached to the amino ion implanted ITO (NH₂/ITO) surface homogeneously and stably. The resulting MWCNTs-attached NH₂/ITO (MWCNTs/NH₂/ITO) substrate can be used as electrode material. Cyclic voltammetry results indicate that the MWCNTs/NH₂/ITO electrode shows excellent electrochemical properties and obvious electrocatalytic activity towards uric acid, thus this material is expected to have potential in electrochemical analysis and biosensors.     

Functional multi-walled carbon nanotube/polyaniline composite films as supports of platinum for formic acid electrooxidation

Embedding of carbon nanotubes in conducting polymeric matrices for various nanocomposites material is now a popular area. In this article, a concise chemical method has been described for the preparation of homogeneous nanocomposite of multi-walled carbon nanotube (MWNT)/polyaniline (PANI) by electrochemical codeposition. For this we functionalized the MWNTs via the diazotization reaction. This helped to disperse the nanotubes in aniline. The composite films were dispersed Pt by electrodeposition technique. The presence of MWNTs and platinum in the composite films was confirmed by XRD analysis and transmission electron microscopy (TEM). Four-point probe investigations revealed that the MWNT/PANI composite films exhibited a good conductivity. Cyclic voltammograms (CV) showed that Pt-modified MWNT/PANI composite films perform higher electrocatalytic activity and better long-term stability than Pt-modified pure PANI film toward formic acid oxidation. The results imply that the MWNT/PANI composite films as a promising support material improves the electrocatalytic activity for formic acid oxidation greatly.     

An efficient composite growing N-doped TiO<Subscript>2</Subscript> on multi-walled carbon nanotubes through sol–gel process

High-activity, visible-light-driven photocatalysts were prepared by forming N-doped TiO₂ on multi-walled carbon nanotubes (MWCNTs). The use of MWCNTs as the support in a N-doped TiO₂ system favored electron trapping, because the recombination process could be retarded, thus promoting photocatalytic activity. The prepared photocatalysts were systematically characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Brunaure–Emmett–Teller (BET) spectroscopy, and UV–Vis diffuse reflectance spectroscopy (UV–Vis/DRS). The results indicated that the N-doped TiO₂ coated on MWCNTs improved the surface area and slightly modified the optical properties of the composite. The activities of the photocatalysts were probed by photodegradation of methanol in the presence of visible light irradiation. The experimental results revealed that the strong interphase linkage between the MWCNTs and the N-doped TiO₂ played a significant role in improving photocatalytic activity. However, the mechanical process for MWCNT–TiO_2-x N _x mixtures showed lower activity than just pure N-doped TiO₂. In this study, N-doped TiO₂ precursors coated with pretreated MWCNTs during a sol–gel process could effectively form a MWCNT–TiO_2-x N _x composite. The composite showed excellent activity and effectively enhanced the efficiency of N-doped TiO₂ under the visible light region.     

Synthesis and comparative study of optical and electrical properties of Au-doped carbon nanotubes prepared in different reaction media

We introduce the synthesis, characterization and physical properties of gold (Au) doped multiwalled carbon nanotubes (MWCNTs) in different reaction media. In order to dope MWCNTs with Au nanoparticles (NPs), first functionalized carbon nanotubes (f-MWCNTs) were prepared. The reduction of gold (III) chloride trihydrate for synthesizing Au NPs in the presence of f-MWCNTs was performed by using sodium citrate as a reducing agent. The produced nanocomposites were characterized using FTIR, XRD and TEM analyses to explore their chemical structures and morphologies. All of the samples have been characterized by TGA and resultantly, the composite made into ethylene glycol exhibited the most concentration of Au NPs into the composite network. This work probes the optical characteristics, such as UV–vis absorption, and optical band gap. Hall effect analyses declared some pleasing variations in electrical characteristics. Remarkably, the n-type doping of Au NPs in the p-type MWCNTs’ network led to a downshift of the Fermi level. This process increased the doped samples electrical conductivity. The results indicated that modification of MWCNTs with Au NPs has generally an important role in decreasing the band gap and increasing the electrical activity of MWCNTs. Our research outcomes provide a new vision into how different reaction media could affect the characteristics of MWCNT/Au nanocomposites. We discovered that ethylene glycol could be considered as a perfect reaction medium for preparation of high-quality doped CNTs with excellent physical properties. Our effort opens up the door to far more investigations on the role of the reaction medium in products’ characteristics.