In situ synthesis of CNTs/Fe–Ni/TiO2 nanocomposite by fluidized bed chemical vapor deposition and the synergistic effect in photocatalysis

Carbon nanotube (CNTs)/Fe–Ni/TiO₂ nanocomposite photocatalysts have been synthesized by an in situ fluidized bed chemical vapor deposition (FBCVD) method. The composite photocatalysts were characterized by XRD, Raman spectroscopy, BET, FESEM, TEM, UV–vis spectroscopy, and XPS. The results showed that the CNTs were grown in situ on the surface of TiO₂. Fe(III) in TiO₂ showed no chemical changes in the growth of CNTs. Ni(II) was partly reduced to metal Ni in the FBCVD process, and the metal Ni acted as a catalyst for the growth of CNTs. The photocatalytic activities of CNTs/Fe–Ni/TiO₂ decreased with the rise of the FBCVD reaction temperature. For the sample synthesized at low FBCVD temperature (500 °C), more than 90% and nearly 50% of methylene blue were removed under UV irradiation in 180 min and under visible light irradiation in 300 min, respectively. The probable mechanism of synergistic enhancement of photocatalysis on the CNTs/Fe–Ni/TiO₂ nanocomposite is proposed.     

One-dimensional titania nanotubes annealed at various temperatures for the photocatalytic degradation of low concentration gaseous pollutants

In this study, one-dimensional titania nanotubes (TNTs) were synthesized using a combined process of chemical and hydrothermal treatments, and their activities for the photocatalytic reactions of selected gaseous pollutants at sub-ppm levels were determined. Additionally, the properties of the TNTs were examined using selected spectroscopic methods. The annealed TNTs showed higher photocatalytic activities for the four target compounds than did the unannealed TNTs. For all the target compounds except benzene, the effect of the annealing temperature on the degradation efficiency was difficult to determine because all degradation efficiencies were very high. However, for benzene, which decomposed with a low efficiency, the degradation activities of the TNTs increased as the treatment temperature was increased from 250 to 300 °C, while they decreased slightly when the temperature was increased from 300 to 400 °C. These findings confirm the presence of an optimal annealing temperature for the synthesis of TNTs. Moreover, the average degradation extents for benzene, toluene, ethylbenzene, and o-xylene decreased from 92%, 96%, 99%, and 98% to 77%, 86%, 92%, and 94%, respectively, as the airstream flow rate increased within the range of 1–4 L/min. The average degradation extents decreased from 12%, 75%, 87%, and 88% to 3%, 29%, 46%, and 51%, respectively, as the input concentration increased from 0.4 to 1.9 ppm. Overall, these findings suggest that one-dimensional TNTs can be effectively utilized for the degradation of gaseous pollutants under optimal operational conditions.     

Mechanics of hydrogen storage in carbon nanotubes

A continuum mechanics model is established for hydrogen storage in single- and multi-wall carbon nanotubes (CNTs) and the bundle of single-wall CNTs. The model accounts for the deformation of CNTs, and van der Waals interactions among hydrogen molecules and between hydrogen and carbon atoms. The analytical expressions of hydrogen storage (number of hydrogen molecules per unit volume) in CNTs are obtained, and are validated by atomistic simulations. CNTs are categorized as tiny, small, medium and large CNTs; tiny CNTs cannot achieve the goals of hydrogen storage (62 kg/m³ and 6.5 wt% of hydrogen set by the US Department of Energy) without fracture; small CNTs are strained during hydrogen storage; medium CNTs can achieve the above goals without the strain and do not self collapse; and large CNTs may self collapse upon the release of hydrogen.     

Carbon nanotubes coated with platinum nanoparticles as anode of biofuel cell

A hybrid system of carbon nanotubes (CNTs) coated with poly (amidoamine) (PAMAM) dendrimer-encapsulated platinum nanoparticles (Pt-DENs) and glucose oxidase (GOx) was prepared through the layer-by-layer (LbL) self-assembly approach and then used as anode in enzyme-based biofuel cells (BFCs). The assembly process was monitored by ζ-potential measurement, and the as-resulted Pt-DENs/CNTs nanocomposites were characterized by transmission electron microscopy (TEM). The performance of electrodes modified by Pt-DENs/CNTs was also investigated by electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV). We found that the Pt-DENs/CNTs could enhance the electron transfer between the redox centers in enzyme and the electrode surfaces. Furthermore, by employing the Pt-DENs/CNTs modified electrodes as anode, the enzyme-based BFCs operated in a solution containing glucose generated an open-circuit voltage of approximately 640.0 mV and a maximum current density of about 90.0 μA/cm², suggesting that Pt-DENs/CNTs may serve as an alternative anode to previously used noble metals in BFC applications.     

TiO2-loaded activated carbon fiber: Hydrothermal synthesis,adsorption properties and photo catalytic activity under visible light irradiation

TiO₂-loaded activated carbon fibers (ACF) were prepared by a hydrothermal method. The samples were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectrometry and UV–vis diffuse reflectance spectra (DRS). SEM images showed that the TiO₂ nanoparticles were deposited on the surface of ACF, and the particle size and loading amount of TiO₂ were varied by changing the initial concentration of tetrabutyl titanate (TBOT). The results of an ash experiment showed that the loading amounts of TiO₂ were 18.4%, 43.3%, 52.5%, 75.1%, and 91.1% for initial concentrations of TBOT of 0.07, 014, 0.21, 0.28, and 0.35 mol/L, respectively. Physical interactions played an important role in the formation of TiO₂/ACF composite fibers that absorb UV and visible light. Compared with those of ACF, improved adsorption and photocatalytic activity toward Rhodamine B (RhB) were observed for TiO₂/ACF composite fiber. The Rhodamine B could be removed efficiently by TiO₂/ACF composite fibers, and the TiO₂ loading amount had a significant effect on the photocatalytic activity of TiO₂/ACF composite fibers.     

Visible light-driven photocatalysis of W,N co-doped TiO2

W, N co-doped TiO2 nanoparticles were synthesized by a sol-gel method. The prepared samples were characterized by X-ray diffraction （XRD）, field emission scanning electron microscopy （FE-SEM）, trans- mission electron microscopy （TEM）, Fourier transform infrared spectroscopy （FT-1R）, X-ray photoelectron spectroscopy （XPS） and diffuse reflectance spectrophotometry （DRS）. The results showed that the co- doped photocatalysts were essentially uniform spherical particles with the smallest particle size of 22.5 nm. Compared to un-doped TiO2, N-TiO2 and P-25, the absorption edge of the W, N co-doped TiO2 shifted to longer wavelength and its photocatalytic activity for degradation of methyl orange （MO） under Xe-lamp （350W） was higher.     

A study on the bending stiffness of single-walled carbon nanotubes and related issues

Single-walled carbon nanotubes (SWCNTs) are usually modeled as elastic tubes and their bending stiffness D is often related to their axial stretching modulus E (Young's modulus) as in mechanics of materials (i.e. D=EI where I is the moment of inertia of the tube). However, recent studies show that large discrepancies may exist when this relationship is used to predict Young's modulus of carbon nanotubes (CNTs) through bending dominated deformations. In the present paper, the bending stiffness of SWCNTs and some related issues are investigated by the combined use of the molecular-mechanics (M-M) model and the deformation mapping technique. Based on the analysis results, the contradictions mentioned above can be explained well. Furthermore, an analytical expression for the bending stiffness of SWCNTs is also presented. It shows that the bending stiffness of a SWCNT is approximately proportional to the cube of its radius which agrees well with the existing molecular dynamics simulation and continuum theory based results.     

An atomistic-based continuum theory for carbon nanotubes: analysis of fracture nucleation

Carbon nanotubes (CNTs) display unique properties and have many potential applications. Prior theoretical studies on CNTs are based on atomistic models such as empirical potential molecular dynamics (MD), tight-binding methods, or first-principles calculations. Here we develop an atomistic-based continuum theory for CNTs. The interatomic potential is directly incorporated into the continuum analysis through constitutive models. Such an approach involves no additional parameter fitting beyond those introduced in the interatomic potential. The atomistic-based continuum theory is then applied to study fracture nucleation in CNTs by modelling it as a bifurcation problem. The results agree well with the MD simulations.     

2D reduced graphene oxide–titania nanocomposites synthesized under different hydrothermal conditions for treatment of hazardous organic pollutants

Two-dimensional reduced graphene oxide–titania (RGO–TiO₂) composites were prepared using a single-step hydrothermal method under various hydrothermal reaction conditions. The morphological and surface characteristics of the RGO–TiO₂ composites and reference materials were determined. The RGO–TiO₂ composites showed photocatalytic activity for the decomposition of two target pollutants that was superior to both pure TiO₂ and RGO under fluorescent daylight lamp illumination. The photocatalytic activity of the RGO–TiO₂ composite increased as the hydrothermal treatment time increased from 1 to 24 h, but then it decreased as the time increased to 36 h, which indicated the presence of an optimal treatment time. RGO–TiO₂ composites activated by violet light-emitting diodes (LEDs) displayed lower decomposition efficiency than those activated by a daylight lamp, likely because of the lower light intensity of violet LEDs (0.2 mW/cm²) when compared with that of the daylight lamp (1.4 mW/cm²). However, the photocatalytic decomposition of the target pollutants using the RGO–TiO₂ composite was more energy-efficient using the violet LEDs. The photocatalytic reaction rates increased as the residence time decreased, whereas the reverse was true for the decomposition efficiency.     

Lithium-storage properties of SiO2 nanotubes@C using carbon nanotubes as templates

Silica-based anode material is the most concerned material at present, which has the advantages of good cycle stability, high theoretical specific capacity and abundant reserves. However, silica suffers from inherent low conductivity, severe volume expansion effect and low initial coulombic efficiency, which limits its application in lithium-ion batteries. Nanotubes structure can mitigate the volume expansion during lithiation/delithiation. In this article, silica nanotubes (SNTs) were prepared using carbon nanotubes (CNTs) as a template, and then the uniform carbon layer was coated on their surface by carbonization of citric acid. The hollow structure of nanotubes provides more sites for the insertion of Li⁺ during lithiation and additional channels for Li⁺ migration in the cycles, which improves the electrochemical performance. Conductivity can be enhanced by coating carbon layer. The specific capacity of the composite material is about 650 mAh g⁻¹ at 0.1 A g⁻¹ after 100 cycles. With a specific capacity of 400 mAh g⁻¹ even at 1 A g⁻¹ after 100 cycles. The silica-based material is a competitive anode material for lithium-ion batteries.     

Cooperative deformation of carboxyl groups in functionalized carbon nanotubes

Functionalized carbon nanotubes have tremendous potential for nanotechnology applications such as in the fabrication of polymeric carbon fibers. However, approaches to design carbon nanotube structures by using functional groups as glue and carbon nanotubes as stiff building blocks to reach superior mechanical strength and toughness at the fiber level with limited amount of materials remains poorly understood. Inspired by the outstanding mechanical properties of spider silk, here we present a bio-inspired structural model of carbon nanotube based fibers connected by weak hydrogen bonds (H-bonds) formed between functional carboxyl groups as the molecular interface. By applying shear loading, we study how the deformation of H-bonds in functional groups is affected by the structural organization of the carboxyl groups, as well as by the geometry of constituting carbon nanotubes. The analysis of H-bond deformation fields is used to compute the extent of significant deformation of inter-CNT bonds, defining a region of cooperativity. We utilize an exponential function (exp (?x/ξ)) to fit the deformation of H-bonds, with the cooperative region defined by the parameter ξ, and where a higher value of ξ represents a weaker exponential decay of displacements of carboxyl groups from the point where the load is applied. Hence, the parameter ξ characterizes the number of carboxyl groups that participate in the deformation of CNTs under shear loading. The cooperativity of deformation is used as a measure for the utilization of the chemical bonds facilitated by the functional groups. We find that for ultra-small diameter CNTs below 1 nm the external force deforms H-bonds significantly only within a relatively small region on the order of a few nanometers. We find that the mechanical properties of carbon nanotube fibers are affected by the organization of H-bonds in functional carboxyl groups. Both, the grouping of functional groups into clusters, and a specific variation of the clustering of functional groups along the CNT axis are shown to be potential strategies to improve the cooperativity of deformation. This allows for a more effective utilization of functional groups and hence, larger overlap lengths between CNTs in fibers. The effect of structural organization of functional groups is not only significant in very small diameter CNTs, but also in larger diameter CNTs as they are most commonly used for engineering applications. Notably larger-diameter CNTs naturally show a larger cooperative deformation range. Our model can be applied to other functional groups attached to CNTs, and could in principle also include strong bonds such as covalent or ionic bonds, or other weak bonds such van der Waals forces or dipole–dipole interactions.     

纳米碳管/铝基复合材料的制备及摩擦磨损性能研究

利用粉末冶金法制备纳米碳管/铝基复合材料,研究不同纳米碳管含量对复合材料硬度和稳态摩擦磨损行为的影响,采用扫描电子显微镜观察复合材料的磨损表面形貌,并对其磨损机制进行探讨.结果表明:随着纳米碳管质量分数的增加,复合材料的硬度呈现先增大而后减小的趋势,含质量分数为2%的纳米碳管复合材料硬度比铝增加约80%;复合材料的摩擦系数逐渐降低,磨损率先减小而后增大;含质量分数为1%的纳米碳管复合材料磨损机制为磨粒磨损和粘着磨损,而含质量分数为2%的纳米碳管复合材料以剥层磨损和疲劳磨损为主.     

The influence of mechanical deformation on the electrical properties of single wall carbon nanotubes

Recent experimental studies and atomistic simulations have shown that carbon nanotubes (CNTs) display strong interplay between the mechanical deformation and electrical properties. We have developed a simple and accurate method to determine atom positions in a uniformly deformed CNT via a continuum analysis based on the interatomic potential. A shift vector is introduced to ensure the equilibrium of atoms. Such an approach, involving only three variables for the entire CNT, agrees very well with the molecular mechanics calculations. We then study the effect of mechanical deformation on the band gap change of single wall CNTs under tension, torsion, and combined tension/torsion via the k-space tight-binding method. Prior studies without this shift vector lead to significant overestimation of the band gap change. It is established that the conducting CNTs may easily become semi-conducting ones subject to mechanical deformation, but the semi-conducting CNTs never become conducting ones upon deformation.     

单壁碳纳米管屈曲的原子/连续介质混合模型

用数学和力学研究所，上海 200072)//力学学报.--2004,36(6).--744～748 提供了一种运用原子/连续介质混合(hybrid atomic/continuum,HAC)方法解决纳米力学问题的思路. 通过在连续介质力学模型中引入利用分子力学方法获得物性参数，建立了预测单壁碳纳米管临界屈曲参数的HAC模型. 结果表明, HAC模型具有与连续介质力学模型可比拟的简洁性, 同时可表征纳米管微观结构特征对屈曲参数的影响. 计算结果表明，Zigzag纳米管的抗屈曲性能优于Armchair纳米管. 基于Tersoff-Brenner作用势的分子动力学结果证实了这一结论.     

硅基表面稀土改性碳纳米管/氨基硅烷自组装复合膜的摩擦磨损性能

配置稀土溶液对碳纳米管进行表面改性,采用自组装膜技术在单晶硅表面制备了稀土改性碳纳米管复合薄膜,考察了其表面形貌、化学组成和摩擦学性能。扫描电子显微镜观察发现单晶硅表面附着了大量不规则排列碳纳米管,X射线光电子能谱仪分析发现稀土元素与薄膜表面的磷酸基发生了化学反应,从而使碳纳米管组装到基片表面。UMT-2MT摩擦试验机测试结果表明在给定的试验条件下,复合薄膜的摩擦系数较低,随载荷和速度的增加变化不大。由于稀土改性碳纳米管复合薄膜的存在,与未处理碳纳米管复合薄膜、硅烷薄膜相比,基片表面摩擦系数显著降低,并表现出了优异的耐磨性及摩擦稳定性。     

Dispersion of multi-walled carbon nanotubes in PDMS/PB blend

In this study, the sequential dispersion of multi-walled carbon nanotubes (CNTs) in PDMS/PB (polydimethylsiloxane/polybutene) blends and the change of blend morphology by the dispersion of CNTs were investigated by rheological and morphological observations. The dispersion of CNTs into PDMS/PB blend was accomplished by the dilution of the CNT master (2?wt.% CNT in PDMS) in PDMS/PB blend using an extensional mixer. The morphological study shows that under the extensional flow, CNTs in the dispersed CNT master phase are mainly broken up by tip-streaming and the continuous pinching-off of PDMS drops during morphology evolution enhances the dispersion of CNT. It has been shown that CNTs can be disentangled as in the case of dispersing CNTs in a Boger fluid. Rheological data and TEM observations show that it is not simply a mixing of two phases and the CNTs in the master phase can be dispersed in the single CNT level.     

Dispersion of multi-walled carbon nanotubes in poly（p-phenylene） thin films and their electrical characteristics

Dispersion of multi-walled carbon nanotubes in poly（p-phenylene） composite exposed to toluene was experimentally investigated. 3 mg of multi-walled carbon nanotubes with nominal size of 20 nm was compounded with 30 mg of poly（p-phenylene） with the presence of terpineol as binding initiator. To investigate an optimal condition for homogenizing all constituents, ultrasonication with an output power of 750W was employed with compounding time of 3, 10, 20 and 30 min. With FTIR analyses, it could be confirmed that homogeneous composite of multi-walled carbon nanotubes and poly（p-phenylene） could be prepared. SEM analyses were also conducted to examine the dispersion of multi-walled carbon nanotubes in the polymer matrix. Then intrinsic electrical resistance of the composites after being exposed to toluene was also investigated. It was found that the composite film prepared with ultrasonication for 20 min could provide sufficiently sensitive response with respect to varied concentration of toluene.     

Viscosity and dynamics of nanorod (carbon nanotubes, cellulose whiskers, stiff polymers and polymer fibers) suspensions

The zero shear viscosity and the dynamic behaviors of different nanorod dispersions (carbon nanotubes (CNTs), cellulose whiskers, polymer nanofibers, crosslinked polymer nanofibers, and stiff polymers such as poly(γ-benzyl-α-l-glutamate) (PBLG)) were compared and discussed from literature data. Their Brownian dynamic behaviors have always been discussed in the frame of the Doi–Edwards theory. In agreement with this theory, the straight rigid rods (CNTs, cellulose whisker, polymer nanofibers) obey a master curve in the reduced viscosity (or rotary diffusivity) c power laws on viscosity (η ₀ ∝ φ ³) and diffusivity (D _r ∝ ? ^?2). On the contrary, stiff polymer chains and crosslinked polymer fibers at temperature above T _g exhibit different and two distinct dynamic behaviors. Despite their deviation from the ideal rigidity, surprisingly it can be noted that stiff polymers such as PBLG have been extremely used in the literature to verify the Doi–Edwards theory. Finally, flexible crosslinked chains at T > T _g , do not obey the Doi–Edwards theory, and their dynamics are close to the physics of polymer solutions in terms of power laws.     

Rheological characterization of carbon nanotubes/poly(ethylene oxide) composites

Rheological properties of poly(ethylene oxide) nanocomposites embedded with carbon nanotubes (CNTs) were investigated in the present study. It was found that the CNT nanocomposites had a higher effective filler volume fraction than the real filler volume fraction, which yielded a drastic enhancement of shear viscosity. As the CNT loading in the nancomposites increases, non-Newtonian behavior was observed at the low-shear-rate region in the steady shear experiments. Oscillatory dynamic shear experiments showed that more addition of the CNTs led to stronger solidlike and nonterminal behaviors. To identify a dispersion state of the CNTs, field emission scanning electron spectroscopy and transmission electron microscopy were adopted and thermal analysis was also performed by using differential scanning calorimetry. The existence of percolated network structures of the CNTs even at a low CNT loading was verified by rheological properties and electrical conductivities.     

Liquid phase heterogeneous photocatalytic ozonation of phenol in liquid–solid fluidized bed: Simplified kinetic modeling

The isotherms of original AC (activated carbon) and photocatalysts (TiO₂-AC) calcined at 500 °C for phenol were measured. The results showed a reversible adsorption of phenol onto both kinds of particles at 25 °C, and could be fitted well to the Freundlich adsorption equation for the dilute solution. Five oxidation processes, namely O₃, O₃/UV, O₃/UV/AC, O₂/UV/TiO₂ and O₃/UV/TiO₂, for phenol degradation in fluidized bed were evaluated and compared, and the photocatalytic ozonation was found to give the highest phenol conversion because of the combined actions of homogenous ozonation in the liquid phase, heterogeneous ozonation on the surface of the catalyst support, i.e. activated carbon, and heterogeneous photocatalytic oxidation on the TiO₂ catalyst surface. With the simplified kinetic model, photolytic ozonation was confirmed to predominantly take place on the particle surface in comparison with the heterogeneous and homogeneous photolytic ozonation. Additionally, the heterogeneous photocatalytic oxidation constant was found to be enhanced by 3.73 times in photocatlaytic ozonation process with ozone as the scavenger compared to the photocatalytic oxidation process with oxygen as the scavenger.