Hierarchical morphology of carbon single-walled nanotubes during sonication in an aliphatic diamine

Dispersion of single-walled carbon nanotubes (SWNTs) by sonication into diamine curing agents is studied as a means to improve the dispersion of SWNTs in cured epoxy. Cured and uncured specimens are analyzed by light microscopy, electron microscopy, light scattering (LS), ultra small-angle X-ray scattering (USAXS), electrical conductivity and Raman spectroscopy. A flexible diamine (D2000) forms a stable SWNT suspension leading to good homogeneity in both the diamine and the cured epoxy. High resolution transmission electron microscopy (TEM) shows that small ropes of SWNTs (mostly under 15 nm) are present despite the sample's visual homogeneity. Further morphological investigation of cured and uncured D2000 resins using light and small-angle X-ray scattering indicates that the SWNTs are networked into fractal clusters that electrically percolate at low SWNTs loadings (0.05 wt%).     

Synthesis of water-soluble single-walled carbon nanotubes by RAFT polymerization

Water-soluble single-walled carbon nanotubes (SWNTs) were synthesized by grafting poly(acrylamide) (PAM) from the surface of SWNT via reversible addition-fragmentation chain transfer (RAFT) polymerization. The RAFT agents were covalently attached to the SWNTs by functionalizing SWNTs with in situ generated diazonium compounds. The product was characterized by means of FT-IR, Raman, ¹H NMR, TGA and TEM. The results showed that PAM chains had successfully grafted from SWNT by RAFT polymerization. The amount of PAM grown from SWNT increased with the polymerization time. The acrylamide conversion increased linearly with the polymerization time, indicating the “living” characteristics of the RAFT polymerization. TEM was utilized to image PAM-g-SWNT, showing relatively uniform polymer coatings present on the surface of individual, debundled nanotubes.     

Electrocatalytic reduction of dioxygen by cobalt porphyrin-modified glassy carbon electrode with single-walled carbon nanotubes and nafion in aqueous solutions

Cobalt porphyrin (CoP)-modified glassy carbon electrode (GCE) with single-walled carbon nanotubes (SWNTs) and Nafion demonstrated a higher electrocatalytic activity for the reduction of dioxygen in 0.1 M H₂SO₄ solution. Cyclic and hydrodynamic voltammetry at the CoP-SWNTs/GCE-modified electrodes in O₂-saturated aqueous solutions was used to study the electrocatalytic pathway. Compared with the CoP/GCE-modified electrodes, the reduction potential of dioxygen at the CoP-SWNTs/GCE-modified electrodes was shifted to the positive direction and the limiting current was greatly increased. Especially, the Co(TMPP)-SWNTs/GCE-modified electrode was catalyzed effectively by the 4e⁻ reduction of dioxygen to water, because hydrodynamic voltammetry revealed the transference of approximately four electrons for dioxygen reduction and the minimal generation of hydrogen peroxide in the process of dioxygen reduction.     

Studies of single-walled carbon nanotubes-induced hepatotoxicity by NMR-based metabonomics of rat blood plasma and liver extracts

The toxicological effects of single-walled carbon nanotubes (SWCNTs) were investigated after intratracheal instillation in male Wistar rats over a 15-day period using metabonomic analysis of ¹H (nuclear magnetic resonance) NMR spectra of blood plasma and liver tissue extracts. Concurrent liver histopathology examinations and plasma clinical chemistry analyses were also performed. Significant changes were observed in clinical chemistry features, including alkaline phosphatase, total protein, and total cholesterol, and in liver pathology, suggesting that SWCNTs clearly have hepatotoxicity in the rat. ¹H NMR spectra and pattern recognition analyses from nanomaterial-treated rats showed remarkable differences in the excretion of lactate, trimethylamine oxide, bilineurin, phosphocholine, amylaceum, and glycogen. Indications of amino acid metabolism impairment were supported by increased lactate concentrations and decreased alanine concentrations in plasma. The rise in plasma and liver tissue extract concentrations of choline and phosphocholine, together with decreased lipids and lipoproteins, after SWCNTs treatment indicated a disruption of membrane fluidity caused by lipid peroxidation. Energy, amino acid, and fat metabolism appeared to be affected by SWCNTs exposure. Clinical chemistry and metabonomic approaches clearly indicated liver injury, which might have been associated with an indirect mechanism involving nanomaterial-induced oxidative stress.     

Dynamics of single-walled carbon nanotube (SWNT)/polyisoprene (PI) nanocomposites in electric and mechanical fields

Relaxation dynamics of single-walled carbon nanotube (SWNT)/polyisoprene (PI) nanocomposites were examined by dielectric relaxation spectroscopy (DRS) and dynamic mechanical spectroscopy (DMS) over a wide range of frequency and temperature. Both functionalized (SWNT-f) and pristine (SWNT-p) nanotubes were used and their effect on dynamics compared. Functionalized (PISF) nanocomposites were characterized by an increase in the time scale of the normal mode process as a consequence of the strong surface interactions between the polymer matrix and the nanotubes. The exact opposite is seen in pristine (PISP) nanocomposites where a decrease in the time scale of the normal mode relaxation is observed and attributed to weaker surface interactions and the effect of confinement on dynamics. The segmental process in PISF or PISP is not affected by the presence of nanotubes. The temperature dependence of the average relaxation time for normal and segmental modes is of the Vogel-Fulcher-Tammann (VFT) type. A good agreement is observed in the time scale of processes measured by DRS and DMS in PISF nanocomposites. In PISP nanocomposites, however, the time scales obtained from DRS and DMS measurements are not in consistently good agreement and an explanation is offered in terms of confinement.     

单壁碳纳米管显著增强的ZnO可见光催化活性

利用醋酸锌为原料,采用溶胶-凝胶法制备了单壁碳纳米管（SWMTs）和氧化锌的纳米复合物（ZnO/SWNTs）。用X射线衍射光谱（XRD）、拉曼光谱、扫描电子显微镜（SEM）、透射电子显微镜（TEM）、热重分析（TGA）、傅里叶变换红外光谱（FT-IR）以及紫外-可见吸收光谱（UV-Vis）对复合物进行了表征。结果显示,粒径为10～20 nm的ZnO粒子均匀地负载在SWNTs表面,且在可见光区具有很好的光吸收性能。研究了ZnO/SWNTs光催化剂在太阳光照射下对甲基橙和亚甲基蓝的光催化降解情况。结果表明,复合物的催化活性明显高于ZnO。对于甲基橙,光照200 min后,降解率为99.8%,是纯ZnO（4.8%）的20倍;对于亚甲基蓝,仅光照20 min,降解率就达到了98.4%,是纯ZnO（4.0%）的25倍。     

Transparent conductive oxide films mixed with gallium oxide nanoparticle/single-walled carbon nanotube layer for deep ultraviolet light-emitting diodes

We propose a transparent conductive oxide electrode scheme of gallium oxide nanoparticle mixed with a single-walled carbon nanotube (Ga₂O₃ NP/SWNT) layer for deep ultraviolet light-emitting diodes using spin and dipping methods. We investigated the electrical, optical and morphological properties of the Ga₂O₃ NP/SWNT layers by increasing the thickness of SWNTs via multiple dipping processes. Compared with the undoped Ga₂O₃ films (current level 9.9 × 10^-9 A @ 1 V, transmittance 68% @ 280 nm), the current level flowing in the Ga₂O₃ NP/SWNT increased by approximately 4 × 10⁵ times and the transmittance improved by 9% after 15 times dip-coating (current level 4 × 10^-4 A at 1 V; transmittance 77.0% at 280 nm). These improvements result from both native high transparency of Ga₂O₃ NPs and high conductivity and effective current spreading of SWNTs.     

NO2 gas sensing properties of Au-functionalized porous ZnO nanosheets enhanced by UV irradiation

Porous ZnO nanosheets were synthesized by thermal evaporation. The morphology, crystal structure, and sensing properties of the ZnO nanosheets to NO₂ gas at room temperature under UV illumination were examined. Au nanoparticles with diameters of a few tens of nanometers were distributed over the ZnO nanosheets. The responses of the multiple networked nanosheet gas sensors were improved 1.8–3.3 fold by Au functionalization at NO₂ concentrations ranging from 1 to 5 ppm. Furthermore, the Au-functionalized ZnO nanosheet gas sensors showed a considerably enhanced response at room temperature under ultraviolet (UV) illumination. In addition, the mechanisms through which the gas sensing properties of ZnO nanosheets are enhanced by Au functionalization and UV irradiation are discussed.     

Synthesis of hydrophobic carbon nanotubes/reduced graphene oxide composite films by flash light irradiation

Carbon nanotubes/graphene composites have superior mechanical, electrical and electrochemistry properties with carbon nanotubes as a hydrophobicity boosting agent. Their extraordinary hydrophobic performance is highly suitable for electrode applications in lithium ion batteries and supercapacitors which often employ organic electrolytes. Also the hydrophobic features enable the oil enrichment for the crude oil separation from seawater. The ever reported synthesis routes towards such a composite either involve complicated multi-step reactions, e.g., chemical vapor depositions, or lead to insufficient extrusion of carbon nanotubes in the chemical reductions of graphene oxide, e.g., fully embedding between the compact graphene oxide sheets. As a consequence, the formation of standalone carbon nanotubes over graphene sheets remains of high interests. Herein we use the facile flash light irradiation method to induce the reduction of graphene oxides in the presence of carbon nanotubes. Photographs, micrographs, X-ray diffraction, infrared spectroscopy and thermogravimetric analysis all indicate that graphene oxides has been reduced. And the contact angle tests confirm the excellent hydrophobic performances of the synthesized carbon nanotube/reduced graphene oxide composite films. This one-step treatment represents a straightforward and high efficiency way for the reduction of carbon nanotubes/graphene oxides composites.

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A comparative study on UV light activated porous TiO2 and ZnO film sensors for gas sensing at room temperature

In order to find a new approach for screening the photoactivated gas sensing materials with high sensitivity, a comparative study was carried out. With the simple technique of screen printing, TiO₂ and ZnO were used to fabricate the UV light activated gas sensors which were applied at room temperature. To facilitate the simultaneous measurements of the current transients of the two materials, they were printed on the same alumina substrate. Compared with ZnO, TiO₂ exhibited a superior performance to ethanol and formaldehyde gases. It was found that the responses of TiO₂ increased with the concentration of test gas and amounted to 224 and 1700 to 100 ppm ethanol and formaldehyde gases, respectively, while the responses of ZnO to 100 ppm ethanol and formaldehyde gases were 0.14 and 1.5, respectively. The mechanism of such a huge difference between TiO₂ and ZnO was discussed in detail. Furthermore, it is suggested that metal oxide semiconductor with lower photo-to-dark current ratio can achieve higher photoactivated gas sensitivity.     

Improvement in growth yield of single-walled carbon nanotubes with narrow chirality distribution by pulse plasma CVD

A pulse plasma chemical vapor deposition (CVD) technique was developed for improving the growth yield of single-walled carbon nanotubes (SWNTs) with a narrow chirality distribution. The growth yield of the SWNTs could be improved by repetitive short duration pulse plasma CVD, while maintaining the initial narrow chirality distribution. Detailed growth dynamics is discussed based on a systematic investigation by changing the pulse parameters. The growth of SWNTs with a narrow chirality distribution could be controlled by the difference in the nucleation time required using catalysts comprising relatively small or large particles as the key factor. The nucleation can be controlled by adjusting the pulse on/ofF time ratio and the total processing time.     

Local reactivity of diamond-like carbon modified PTFE membranes used in SO2 sensors

The local electrochemical activity of polytetrafluorethylene (PTFE) membranes coated with diamond-like carbon (DLC) was investigated using scanning electrochemical microscopy (SECM). During z-approach curves in the feedback mode of SECM unexpected local variations in the electron-transfer rate of [Fe(CN)₆]^3−/4− and [Ru(NH₃)₆]^3+/2+ were observed. This local heterogeneity of the electrochemical activity was further evaluated in a system adapted from SO₂ gas sensors. In this case, the Cu^2+/+ couple is used as dissolved reversible redox system. Reaction of SO₂ with Cu²⁺ yields Cu⁺ which is re-oxidized at the DLC-coated PTFE membrane. Gas permeation/tip-collection mode SECM experiments allowed visualizing the local pore distribution as sites where the SO₂ is permeating through the membrane and hence formation of Cu⁺ takes place.     

A Flexible,Highly Sensitive,and Selective Chemiresistive Gas Sensor Obtained by In Situ Photopolymerization of an Acrylic Resin in the Presence of MWCNTs

A new flexible polymeric gas sensor is developed by photocrosslinking poly(ethylene glycol) diacrylate resin (PEGDA) containing multi‐walled carbon nanotubes (MWCNTs) as conductive filler. The cured material shows a percolative threshold conductivity which changes when in contact with various gas analytes with different chemical and physical properties. The different behavior of the sensors toward the different gases is explained either on the basis of chemical affinity toward the polymeric matrix or due to the interactions that can occur between the analyte and the surface of the nanotubes in the case of the aromatic gas.     

Lactoperoxidase-mediated degradation of single-walled carbon nanotubes in the presence of pulmonary surfactant

Carbon nanotubes (CNTs) may elicit inflammatory responses following pulmonary exposure. Conversely, enzymatic biodegradation of CNTs by inflammatory cells has also been reported. The aim of this study was to study the degradation of oxidized single-walled CNTs (ox-SWCNTs) by lactoperoxidase (LPO), a secreted peroxidase present in the airways, and whether pulmonary surfactant affects this biodegradation. To this end, ox-SWCNTs were incubated in vitro with recombinant bovine LPO + H₂O₂ + NaSCN in the presence and absence of porcine lung surfactant (Curosurf®) and biodegradation was monitored using UV–Vis–NIR spectroscopy, Raman spectroscopy, and scanning electron microscopy. The interaction of recombinant LPO with bundles of ox-SWCNTs was confirmed by atomic force microscopy. Cell-free biodegradation of ox-SWCNTs was also observed ex vivo in murine bronchoalveolar lavage fluid in the presence of H₂O₂ + NaSCN. Our study provides evidence for biodegradation of ox-SWCNTs with a lung surfactant ‘bio-corona’ and expands the repertoire of mammalian peroxidases capable of biodegradation of ox-SWCNTs. These findings are relevant to inhalation exposure to these materials, as LPO serves as an important component of the airway defense system.