Tetrahydrofuran-functionalized multi-walled carbon nanotubes as effective support for Pt and PtSn electrocatalysts of fuel cells

A novel and simple method to functionalize multi-walled carbon nanotubes (MWCNTs) is developed using tetrahydrofuran (THF) solvent as the functionalization and anchoring agent. The effectiveness of the method is demonstrated by the synthesis of uniformly distributed Pt and PtSn nanoparticles on THF-functionalized MWCNTs. Transmission electron microscopy and X-ray diffraction results indicate that Pt and PtSn nanoparticles with a narrow particle size distribution and an average particle size of ∼4 nm are synthesized on THF-functionalized MWCNTs. The lattice parameter of PtSn/MWCNTs increases with the Sn content, indicating the successful formation of PtSn binary nanoparticles. The results demonstrate the applicability and effectiveness of the THF-functionalized MWCNTs as effective catalyst supports in the development of highly dispersed and active Pt and Pt-based electrocatalysts for low temperature fuel cells. The successful functionalization of MWCNTs by THF also indicates that there could be a strong σ-π interaction between the MWCNTs and the THF.     

Synthesis and characterization of functionalized carbon nanotubes with different wetting behaviors and their influence on the wetting properties of carbon nanotubes/polymethylmethacrylate coatings

The synthesis and characterization of hydrophobic functionalized multi-wall carbon nanotubes (MWCNTs) were investigated and their influence on the wetting properties of organic coatings and composites was studied. Functionalization was performed using oxidation, 1,3-dipolar cycloaddition, and silanization. Silanization was conducted using three hydrophobic silane precursors: 1H,1H,2H,2H-perfluorodecyltrimethoxysilane, 1H,1H,2H,2H-perfluorooctyltrimethoxysilane, and triethoxyoctylsilane. Functionalization was directly confirmed and characterized by Fourier transform infrared spectroscopy, thermal gravimetric analysis, and scanning electron microscopy. The water contact angle of the functionalized MWCNTs was 40–142° for different surface functionalities and the functionalized MWCNTs were incorporated into an acidic solution of polymethylmethacrylate. The effect of surface functionality and the concentration of the functionalized MWCNTs on the wetting properties of these composites were studied by measuring the water contact angle. Under optimum conditions, composite surfaces with water contact angles greater than 110° were obtained. Atomic force microscopy was used to determine the topography of the surface and energy dispersion spectroscopy was used to determine the distribution of the functionalized MWCNTs in the composite film. It was shown that the hydrophobic functionalized MWCNTs migrated to the surface; this was more pronounced for the more hydrophobic MWCNTs.     

掺氮碳纳米管的结构、制备及其催化应用

将氮原子掺入到碳纳米管的晶格中,使碳纳米管表面碱性增强,从而改变了碳纳米管表面的吸附性能;掺杂在碳纳米管晶格中的氮原子的高电子云密度还导致碳纳米管在电子、材料和催化方面具有独特的性能.介绍了掺氮碳纳米管结构特征和制备方法,综述了近年来在催化中的应用.     

A comparison of reinforcement efficiency of various types of carbon nanotubes in polyacrylonitrile fiber

Polyacrylonitrile (PAN)/carbon nanotubes (CNTs) composite fibers were spun from solutions in dimethyl acetamide (DMAc), using single wall (SWNTs), double wall (DWNTs), multi wall (MWNTs) carbon nanotubes, and vapor grown carbon nanofibers (VGCNFs). In each case, CNT content was 5 wt% with respect to the polymer. Structure, morphology, and properties of the composite fibers have been characterized using X-ray diffraction, Raman spectroscopy, scanning and transmission electron microscopy, tensile tests, dynamic mechanical tests, as well as thermal shrinkage. While all nanotubes contributed to property improvements, maximum increase in modulus (75%) and reduction in thermal shrinkage (up to 50%) was observed in the SWNT containing composites, and the maximum improvement in tensile strength (70%), strain to failure (110%), and work of rupture (230%) was observed in the MWNTs containing composites. PAN orientation is higher in the composite fiber (orientation factor up to 0.62) than in the control PAN fiber (orientation factor 0.52), and the PAN crystallite size in the composite fiber is up to 35% larger than in the control PAN (3.7 nm), while the overall PAN crystallinity diminished slightly. Nanotube orientation in the composite fibers is significantly higher (0.98 for SWNTs, 0.88 for DWNTs, and 0.91 for MWNTs and VGCNFs) than the PAN orientation (0.52-0.62). Improvement in low strain properties (modulus and shrinkage) was attributed to PAN interaction with the nanotube, while the improvement in high strain properties (tensile strength, elongation to break, and work of rupture) at least in part is attributed to the nanotube length. Property improvements have been analyzed in terms of nanotube surface area and orientation.     

Polymer adsorption in the grafting reactions of hydroxyl terminal polymers with multi-walled carbon nanotubes

Melt stirring of non-functional polymers such as poly(ethylene oxide) dimethylether (PEO-Me) and polystyrene (PS-H) with multiwalled carbon nanotubes (MWNTs) in the absence of solvent for 48 h induced a substantial amount of polymer adsorption on the MWNTs. The chloroform extraction of the reaction products using centrifugation yielded black colored solutions exhibiting UV absorbance corresponding to the presence of MWNTs. The adsorption of polymer was confirmed on the surfaces of solvent washed residual and recovered MWNTs from the reactions using thermogravimetric analysis (TGA) and FT-IR spectroscopy. Covalent grafting reactions carried out using hydroxyl-terminated PEO-OH and PS-OH with acid chloride containing MWNTs under identical melt stirring condition produced similar results. The presence of polymer on the residual and recovered MWNTs irrespective of the nature of the terminal groups indicates that the adsorption of polymers poses a problem in accurately determining the grafting efficiency. FT IR spectra of the PEO-g-MWNTs shows a substantial shift in CH stretching vibrations indicating a plausible weak intermolecular interaction with π electrons of the MWNTs.     

Influence of carbon nanotubes on thermal and electrical conductivity of zirconia-based composite

Carbon nanotubes (CNTs) are widely used in ceramic-matrix composites (CMC) as a filler. An individual carbon nanotube exhibits extremely high thermal conductivity, however, the influence of CNTs on the thermal conductivity of CMCs is moderate. In contrast, even a small quantity of CNTs significantly increases the electrical conductivity of CMCs. The present paper studies this contradictory influence for ZrO₂-CNTs composites with 3, 5, 10 and 20 vol% multi-wall carbon nanotubes (MWCNTs). Their thermal and electrical conductivity was studied by the laser flash method and electrochemical impedance spectroscopy. The analysis reveals that the moderate influence of MWCNTs on the thermal conductivity of composites originates from the similar thermal conductivity of MWCNTs in a bundle and zirconia. On the other hand, the substantial difference in the electrical conductivity of MWCNTs and zirconia leads to an exponential increase in the electrical conductivity of the ZrO₂-CNTs composite even with small additions of nanotubes.     

烷基桥联丁基磺酸磺化木质素的制备及其在分散碳纳米管中的应用

利用1,4-丁磺酸内酯作为磺化剂,1,6-二溴己烷作为烷基化桥联剂对碱木质素进行改性,通过一步反应制备了兼有烷基磺酸基和烷基链的交联结构的新型聚合物--烷基桥联丁基磺酸磺化木质素 (AASLS),并系统研究了AASLS在碳纳米管(CNT)悬浮液体系的分散性能。结果表明,当分散剂质量掺量为2%时,AASLS分散的CNT悬浮液在660 nm处的吸收高于由聚苯乙烯磺酸钠(PSS)和聚乙烯吡咯烷酮(PVP)分散的CNT悬浮液,悬浮稳定性更高;透射电镜测试结果进一步表明AASLS的掺入有效解决了CNT的团聚问题;拉曼光谱表明,通过AASLS的非共价功能化修饰,CNT的I₁₃₅₀/I₁₅₈₀值有效降低;电化学测试表明AASLS与CNT形成的复合物在酸性电解液中可进行准可逆的氧化反应。     

Easy synthesis of carbon nanotubes with polypyrrole nanotubes as the carbon precursor

An easy synthesis route for carbon nanotubes with polypyrrole nanotubes as a carbon precursor has been developed. Polypyrrole nanotubes were fabricated via a reactive self-degraded template method. Carbon nanotubes were further obtained by pyrolysis of the polypyrrole nanotube at 900 °C under a nitrogen atmosphere. The resultant carbon nanotube structure was found to be amorphous carbon on the basis of XRD, Raman spectra and high-resolution transmission electron microscopy (HRTEM) studies.     

Tribological application of carbon nanotubes in a metal-based composite coating and composites

Ni-P-carbon nanotube (CNT) composite coating and carbon nanotube/copper matrix composites were prepared by electroless plating and powder metallurgy techniques, respectively. The effects of CNTs on the tribological properties of these composites were evaluated. The results demonstrated that the Ni-P-CNT electroless composite coating exhibited higher wear resistance and lower friction coefficient than Ni-P-SiC and Ni-P-graphite composite coatings. After annealing at 673 K for 2 h, the wear resistance of the Ni-P-CNT composite coating was improved. Carbon nanotube/copper matrix composites revealed a lower wear rate and friction coefficient compared with pure copper, and their wear rates and friction coefficients showed a decreasing trend with increasing volume fraction of CNTs within the range from 0 to 12 vol.% due to the effects of the reinforcement and reduced friction of CNTs. The favorable effects of CNTs on the tribological properties are attributed to improved mechanical properties and unique topological structure of the hollow nanotubes.     

Synthesis of a novel sulfonated poly(amide‐imide) and its application in preparation of ultrafiltration PES membranes as a modifier

Sulfonated poly(amide‐imide) (SPAI) copolymer was synthesized, characterized, and blended into poly(ether sulfone) (PES)/dimethylacetamide casting solutions to prepare ultrafiltration membranes. Different weight ratios of the copolymer (0–10 wt %) were mixed in the PES casting solution. The analyses of contact angle and attenuated total reflection‐Fourier transform infrared spectra were used to study hydrophilicity and physicochemical properties of the membrane surface, respectively. The membranes were further characterized by scanning electron microscopy images, ultrafiltration performance, and fouling analyses. The outcomes showed that addition of the SPAI in the PES matrix improved considerably the membranes hydrophilicity. Moreover, with increasing SPAI concentration, the porosity, flux recovery ratio, and pure water permeability of the modified membranes were improved. The pure water flux was increased from 3.6 to 12.4 kg/m² h by increasing 2 wt % SPAI. The antifouling property of the modified PES membranes against bovine serum albumin, tested by a dead‐end filtration setup revealed that bovine serum albumin rejection of the obtained membrane was also enhanced and the antifouling properties of the blending membranes were improved. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46477.     

Scalable and number-controlled synthesis of carbon nanotubes by nanostencil lithography

Controlled synthesis and integration of carbon nanotubes (CNTs) remain important areas of study to develop practical carbon-based nanodevices. A method of controlling the number of CNTs synthesized depending on the size of the catalyst was characterized using nanostencil lithography, and the critical dimension for the nanoaperture produced on a stencil mask used for growing individual CNTs was studied. The stencil mask was fabricated as a nanoaperture array down to 40 nm in diameter on a low-stress silicon nitride membrane. An iron catalyst used to synthesize CNTs was deposited through submicron patterns in the stencil mask onto a silicon substrate, and the profile of the patterned iron catalyst was analyzed using atomic force microscopy. The feasibility toward a scalable, number-, and location-controlled synthesis of CNTs was experimentally demonstrated based on the diameter and geometry of the apertures in the stencil mask.     

The preparation of multi-walled carbon nanotubes with a Ni-P coating by an electroless deposition process

The multi-walled carbon nanotubes (MWCNTs, mean diameter: 100-200 nm) with nickel-phosphorous (Ni-P) coatings were obtained by an electroless deposition process. To prepare the MWCNTs covered with continual Ni-P layers, a pre-treatment procedure comprised of acid-cleaning, sensitization and activation has been developed. The resulting MWCNTs have a uniform distribution of the Ni-P layers coated on the MWCNTs with the fibrous appearance maintained. X-ray diffraction (XRD) and transmission electron microscopy (TEM) observations revealed that the as-coated MWCNTs were comprised of the amorphous Ni-P layers and inner carbon nanotubes covered with the Ni-P layers. These amorphous Ni-P-coated MWCNTs were used as precursors for preparing MWCNTs with nanocrystalline Ni-P(crystalline Ni and Ni₃P intermetallic compound) layers by the heat-treatment above 400 °C, which were determined by differential scanning calorimeter (DSC) and XRD studies. The results of this work provide an effective electrochemical method for preparing powdery MWCNTs with Ni-P layer as new composite materials from the aqueous solution.     

The density control of carbon nanotubes using spin-coated nanoparticle and its application to the electron emitter with triode structure

The density-controlled carbon nanotubes (CNTs) were grown on the iron nanoparticles by using the freeze–dry method. The iron-acetate [Fe(II)(CH₃COO)₂] solution was used for the preparation of the catalytic iron nanoparticles. The density of CNTs was controlled in order to achieve the enhancement in the field emission process. Furthermore, the patterning of the iron nanoparticle catalyst layer for the fabrication of electronic devices was simply achieved by using an alkaline solution, TMAH (tetramethylammonium hydroxide). We applied this patterning process of catalyst layer to the formation of the electron emitter with under-gate type triode structure.     

碳纳米管表面改性及其应用于复合材料的研究现状

对碳纳米管进行表面改性可提高碳纳米管的表面活性、分散能力和与基体材料之间的相容性,从而提高其在复合材料中的增强效果。本文介绍了碳纳米管表面改性的方法,分为物理法和化学法,物理法主要有高能机械研磨法、高能球磨法和超声振动法;化学法主要有酸处理法、偶联剂法、化学镀法、高能射线辐照法和原子转移自由基聚合法。在实际应用中常将几种改性方法联合使用,使得到的改性产物性能更稳定,性质更多样化。同时,介绍了改性后的碳纳米管在各种复合材料中的应用现状。并指出了对碳纳米管进行改性的两个重点：一是尽量保持碳纳米管的本身结构完整性;二是提高碳纳米管在基体中的分散性。     

Inclusion of carbon nanotubes in a hydroxyapatite sol–gel matrix

In this study, the inclusion of multi-walled carbon nanotubes as the second phase in the hydroxyapatite matrix, in order to improve the mechanical strength, has been performed via the sol–gel process. The stability of carbon nanotube sol with the changes of pH and dispersant values (sodium dodecyl sulfate) was evaluated by zeta potential analysis. The results indicated that synthesis of hydroxyapatite particles in the presence of the carbon nanotubes had the best result in homogenization of the carbon nanotube dispersion and faster crystallization of hydroxyapatite. The crystallization of hydroxyapatite phase was investigated with differential scanning calorimetry (DSC) and X-ray diffraction and the microstructure of the obtained composite powder was studied by electron microscopy.     

Electrospinning preparation of a graphene oxide nanohybrid proton‐exchange membrane for fuel cells

Proton‐exchange membrane (PEM) is a core component of fuel cells that provides a channel for proton migration and transport. Prevailing PEMs fabricated using well‐established casting techniques have several limitations such as low proton conductivity, high fuel permeability, and poor stability. To overcome these shortcomings, this article introduces a graphene oxide (GO)‐based nanohybrid Nafion nanofiber membrane prepared using a facile electrospinning technique. On the one hand, electrospinning nanofibers provide efficient transport paths for protons, which tremendously enhance the proton conductivity. On the other hand, GO doping in PEM improves the self‐humidification, stabilities (mechanical, thermal, and chemical), and proton conductivity and reduces the fuel permeability. In this research, nanofiber membranes were obtained from Nafion solutions containing 0, 0.1, and 0.2 wt % GO via electrospinning. The morphology, structure, mechanical properties, proton conductivity, water uptake, and swelling properties of the membranes were studied. The results demonstrated that the comprehensive performance of PEM was significantly improved. The new findings may promote the wide application of PEM fuel cells. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46443.     

In situ grown carbon nanotubes on carbon paper as integrated gas diffusion and catalyst layer for proton exchange membrane fuel cells

In situ grown carbon nanotubes (CNTs) on carbon paper as an integrated gas diffusion layer (GDL) and catalyst layer (CL) were developed for proton exchange membrane fuel cell (PEMFC) applications. The effect of their structure and morphology on cell performance was investigated under real PEMFC conditions. The in situ grown CNT layers on carbon paper showed a tunable structure under different growth processes. Scanning electron microscopy (SEM) and Brunauer–Emmett–Teller (BET) demonstrated that the CNT layers are able to provide extremely high surface area and porosity to serve as both the GDL and the CL simultaneously. This in situ grown CNT support layer can provide enhanced Pt utilization compared with the carbon black and free-standing CNT support layers. An optimum maximum power density of 670 mW cm⁻² was obtained from the CNT layer grown under 20 cm³ min⁻¹ C₂H₄ flow with 0.04 mg cm⁻² Pt sputter-deposited at the cathode. Furthermore, electrochemical impedance spectroscopy (EIS) results confirmed that the in situ grown CNT layer can provide both enhanced charge transfer and mass transport properties for the Pt/CNT-based electrode as an integrated GDL and CL, in comparison with previously reported Pt/CNT-based electrodes with a VXC72R-based GDL and a Pt/CNT-based CL. Therefore, this in situ grown CNT layer shows a great potential for the improvement of electrode structure and configuration for PEMFC applications.     

碳纳米管的应用研究进展

介绍了碳纳米管的性能,综述了近年来碳纳米管的应用及其研究进展。     

Self-assembled monolayers of pyridylthio-functionalized carbon nanotubes used as a support to immobilize cytochrome c

Self-assembled monolayers (SAMs) of pyridylthio-functionalized multiwalled carbon nanotubes (pythio-MWNTs) have been constructed on the gold substrate surface, which were used as a support to immobilize cytochrome c (Cyt c). The assembly processes of the SAMs and adsorption of Cyt c were monitored by using quartz crystal microbalance (QCM). Based on the frequency change of the QCM resonator, the surface coverage for the SAMs of pythio-MWNTs was estimated to be about 5.2 μg/cm², and that of the Cyt c adsorbed was about 0.29 μg/cm². For the gold electrode modified by the SAMs of pythio-MWNTs-Cyt c, a quasi-reversible redox wave was recorded with the cathodic and anodic potentials at about −0.55 and −0.28 V vs Ag/AgCl, respectively. Compositions and morphologies of the SAMs before and after immobilization of Cyt c were characterized by X-ray photoelectron spectroscopy, Raman spectroscopy, scanning electron microscopy, and atomic force microscopy.     

One-pot synthesis of glucose functionalized multi-walled carbon nanotubes: Dispersion in hydroxylated poly(amide-imide) composites and their thermo-mechanical properties

Multi-wall carbon nanotubes (MWCNTs) were functionalized with glucose using a covalent, non-specific functionalization approach. Fourier-transformed infrared spectroscopy, X-ray diffraction (XRD), thermogravimetric analysis (TGA), field emission scanning electron microscopy (FE-SEM), and transmission electron microscopy (TEM) confirmed that glucose structures were covalently attached to CNTs. Hydroxylated poly(amide-imide) (PAI)-based composites were developed by dispersing of glucose-functionalized MWCNTs (MWCNTs-Gl) as reinforcement in different concentrations varying from 5 to 15 wt.%. Nanocomposites have slightly higher degree of crystallinity than neat PAI and their thermo-oxidative stability was significantly affected by the addition of MWCNTs-Gl. According to mechanical tensile tests, the tensile strength and the Young's modulus of the MWCNT-Gl/PAI composites were increased with increasing MWCNTs-Gl content. The tensile strength remarkably increased from 81 to 129 MPa, which was about 59% higher than that of the neat PAI, with the addition of MWCNT-Gl contents within 15 wt.% and the elongation at break decreased about 0.2% at a 5 wt.% loading of MWCNT-Gl in comparison with the pure PAI film.