Raman evidence of the interaction between multiwalled carbon nanotubes and nanostructured TiO2

Nanocomposites of carbon nanotubes and titanium dioxide (TiO₂) have attracted much attention due to their photocatalytic properties. Although many examples in the literature have visualized these nanocomposites by electron microscopic images, spectroscopic characterization is still lacking with regard to the interaction between the carbon nanotube and TiO₂. In this work, we show evidence of the attachment of nanostructured TiO₂ to multiwalled carbon nanotubes (MWNTs) by Raman spectroscopy. The nanostructured TiO₂ was characterized by both full‐width at half‐maximum (FWHM) and the Raman shift of the TiO₂ band at ca 144 cm⁻¹, whereas the average diameter of the crystallite was estimated as approximately 7 nm. Comparison of the Raman spectra of the MWNTs and MWNTs/TiO₂ shows a clear inversion of the relative intensities of the G and D bands, suggesting a substantial chemical modification of the outermost tubes due to the attachment of nanostructured TiO₂. To complement the nanocomposite characterization, scanning electronic microscopy and X‐ray diffraction were performed. Copyright © 2011 John Wiley & Sons, Ltd.     

Synthesis and characterization of polycaprolactone-grafted carbon nanotubes via click reaction

Polycaprolactone (PCL) was covalently grafted on the surface of carbon nanotubes by a simple click reaction of propargyl-terminated PCL (propargyl-PCL) and carbon nanotubes (CNTs) containing azide groups (MWNT-N₃). Propargyl-PCL was synthesized by the ring-opening polymerization of ε-caprolactone using propargyl alcohol and stannous octoate. MWNT-N₃ was prepared from MWNT having 2-bromoisobutyryl groups (MWNT-Br) with sodium azide by azidation. The melting temperature of propargyl-PCL was shifted to the high temperature in PCL-grafted MWNT. The thermal stability of PCL-grafted MWNT was enhanced as compared to that of propargyl-PCL. PCL was coated on the surface of MWNT with a high density of PCL chains, which showed good solubility of PCL-grafted MWNT in organic solvents. PCL-grafted MWNT was characterized with FT-IR, ¹H NMR, Raman, differential scanning calorimetry, thermogravimetric analysis, and scanning electron microscopy.     

Effect of multi-walled carbon nanotubes loaded with Ag nanoparticles on the photocatalytic degradation of rhodamine B under visible light irradiation

Multi-walled carbon nanotubes loaded with Ag nanoparticles (Ag/MWNTs) were prepared by two methods (direct photoreduction and thermal decomposition). The photocatalytic activity of Ag/MWNTs for the degradation of rhodamine B (RhB) under visible light irradiation was investigated in detail. The adsorption and photocatalytic activity tests indicated that the MWNTs served as both an adsorbent and a visible light photocatalyst. The photocatalytic activity of MWNTs was remarkably enhanced when the Ag nanoparticles were loaded on the surface of MWNTs. Moreover, the visible light photocatalytic activity of Ag/MWNTs depended on the synthetic route. On the basis of the experimental results, a possible visible light photocatalytic degradation mechanism was discussed.     

Preparation, characterization and photocatalytic activity of the neodymium-doped TiO2 nanotubes

A series of Nd-TiO₂ powders have been prepared by the sol-gel technique with neodymium nitrate and tetra-n-butyl titanium as raw materials, and then Nd-TiO₂ nanotubes were fabricated by the hydrothermal method with a 10 mol l⁻¹ NaOH solution. The as-prepared Nd-TiO₂ nanotubes were characterized by TEM, XRD, DRS, and XPS, and their photocatalytic activity was also tested in the case of the degradation of methyl orange in water. TEM photograph showed that Nd-TiO₂ nanotubes were about 10-20 nm in diameter, with the lengths range from 100 to 300 nm. TiO₂ nanotubes contained anatase and rutile crystallites. However, 0.3% Nd-TiO₂ nanotubes contained anatase crystallites, and only little rutile crystallites, so it is shown that neodymium doping hindered the phase transformation from anatase into rutile. Nd doping increased the visible-light absorption ability of Nd-TiO₂ nanotubes, and a red shift for Nd-TiO₂ nanotubes appeared when compared to TiO₂ nanotubes. XPS analysis showed that two types of oxygen existed on the photocatalyst surface, including metal-O and hydroxyl group, and more hydroxyl group was on the surface of 2% Nd-TiO₂ nanotubes than on the surface of TiO₂ nanotubes. Nd doping enhanced the photocatalytic activities of Nd-TiO₂ nanotubes, and 0.3% Nd-TiO₂ nanotubes exhibited the highest photocatalytic activity.     

Covalent functionalization of multi-walled carbon nanotubes by lipase

Lipase from Candida rugosa was covalently anchored onto acid-treated multi-walled carbon nanotubes (MWNTs) through a self-catalytic mechanism. A variety of characterization techniques including FTIR, Raman spectroscopy, and XPS were employed to demonstrate the formation of the ester linkage between lipase and MWNTs. The MWNTs-lipase biocomposites showed significantly increased solubility in some common-used organic solvents, such as THF, DMF and chloroform. This study may offer a novel and facile route for covalent modification of carbon nanotubes, and expand the potential utilization of both lipases and MWNTs in the fields of biocatalyst and biosensor.     

Europium-doped mesoporous anatase with enhanced photocatalytic activity toward elimination of gaseous methanol

Mesoporous anatase doped with various amounts of Eu were synthesized via a sol-gel route using Pluronic P123 as template. The XRD and TEM results show that Eu doping favors the formation of anatase with smaller crystal size. The photocatalytic activity of the mesoporous anatase was tested in photocatalytic elimination of gaseous methanol. The photocatalysts exhibited higher activity than that of the commercial photocatalyst (Degussa, P25) under either ultraviolet or visible light irradiation. The superior activity of the mesoporous anatase may be attributed to the synergic effects of the surface area, crystal size and doped Eu species.     

Synthesis and characterization of bamboo-like CdS/TiO<Subscript>2</Subscript> nanotubes composites with enhanced visible-light photocatalytic activity

In order to efficiently use the visible light in the photocatalytic reaction, a novel bamboo-like CdS/TiO₂ nanotubes composite was prepared by a facile chemical reduction method, in which CdS nanoparticles located in the TiO₂ nanotubes. The composition and structure of this nanocomposite were characterized by TEM, HRTEM, XRD, XPS, FTIR and UV-vis spectroscopy. This CdS/TiO₂ nanotubes composite exhibited much higher visible-light photocatalytic activity for the degradation of methylene blue than pure TiO₂ nanotubes and CdS nanoparticles, and the highest photodegradation efficiency after 6 h irradiation can reach 84.5%. It is inferred that the unique structure of CdS/TiO₂ nanotubes composites acts an important role for the improvement of their photocatalytic activity.     

The enhanced photocatalytic activity of CdS/TiO2 nanocomposites by controlling CdS dispersion on TiO2 nanotubes

CdS/TiO₂ nanocomposites were prepared via a simple wet chemical method, and characterized through X-ray diffraction (XRD) and transmission electron microscopy (TEM). Their ability to degrade Acid Rhodamine B was investigated under visible light irradiation. The results indicate that CdS/TiO₂ nanocomposite with a mass ratio of 4:1(TiO₂:CdS) showed high photocatalytic activity and the CdS loaded on TiO₂ nanotube surface exhibited a hexagonal phase. The dispersion of CdS on TiO₂ nanotube surface had an important effect on the degradation efficiency of pollutant, which provides a strategy for practical industry application.     

Synthesis,characterization of Cr-doped TiO<Subscript>2</Subscript> nanotubes with high photocatalytic activity

Cr-doped TiO₂ nanotubes (Cr/TiO₂ NTs) with high photocatalytic activity were prepared by the combination of sol–gel process with hydrothermal treatment. XRD, TEM and UV–vis DRS techniques were employed for microstructural characterization. TEM images show that Cr/TiO₂ NTs are in good tubular structure and have diameter of about 10 nm. The Cr doping induces the shift of the absorption edge to the visible light range and the narrowing of the band gap. The photocatalytic experiment reveals that the photocatalytic performance of TiO₂ NTs can be improved by the doping of chromium ions.     

不同氮掺杂浓度碳纳米管的制备及其成键特性分析

采用化学气相沉积法,以吡啶为氮源,乙炔为碳源,制备出了不同氮掺杂含量的碳纳米管.使用透射电子显微镜(TEM)和X射线荧光光谱(XPS)对样品的形貌和成键特性进行了观察和分析.TEM测试发现随着掺杂量的增大,氮掺杂碳纳米管的竹节长度从120 nm减小为40 nm左右,同时管身变得更加弯曲,管壁变得粗糙.XPS测试发现氮元素在碳纳米管中以“吡啶”、“吡咯”和“石墨”三种C—N键合方式存在.结合三种价键的形成原因,分析了氮掺杂浓度对键合形式的影响,并根据价键的存在形式解释了碳纳米管形貌变化的原因. 关键词： 碳纳米管 氮掺杂 XPS     

Carbon-nanodot-coverage-dependent photocatalytic performance of carbon nanodot/TiO_2 nanocomposites under visible light

Carbon nanodots(CDs) with visible absorption band and TiO_2 are integrated to enhance the photosensitivity of TiO_2.The CD/TiO_2 nanocomposites show obvious CD-coverage-dependent photocatalytic performance. The CD/TiO_2 nanocomposites with moderate CD coverge exhibit the highest photocatalytic activity after being irradiated with visible light, which is more excellent than that of TiO_2. Too little CD coverage could result in poor visible light absorption, which limits the photocatalytic performance of CD/TiO_2 nanocomposites. While, too much CD coverage weakens the photocatalytic activity of CD/TiO_2 nanocomposites by restraining the extraction of conduction band electrons within TiO_2 to generate active oxygen radicals and the electron transfer(ET) process from CDs to TiO_2. These results indicate that rational regulation of CD coverage and the realization of efficient ET process are important means to optimize the photocatalytic performance of CD/TiO_2 nanocomposites.     

钛碳化物改性碳纳米管的场发射性能

通过在碳纳米管(CNTs)表面沉积钛薄膜并经过高温真空退火处理,在CNTs表面形成了低功函数的钛碳化物.研究了钛碳化物改性CNTs的场发射性能,并利用X射线光电子能谱(XPS)对改性碳管进行了结构表征.实验结果表明,高温真空退火可使沉积在CNTs表面的钛原子与碳原子发生化学反应生成钛碳化物;经钛碳化物改性处理的CNTs的场发射性能明显改善,开启电场由改性前的121降低到104V/μm,当电场强度为234V/μm时,场发射电流密度由改性前的23增大到改性后的13.5mA/cm²,同时,CNTs的表面抗离子轰击能力增强,发射稳定性改善.对钛碳化物改性增强CNTs薄膜场发射性能的机理进行了分析. 关键词： 碳纳米管 钛碳化物 场发射 结构表征     

Microstructure and photocatalytic activity of titanium dioxide nanoparticles

Titanium dioxide nanoparticles with an average diameter of about 10 nm are fabricated using a sintering method. The degradation of methyl orange indicates that the photocatalytic efficiency is greatly enhanced, which is measured to be 62.81%. Transmission electron microscopy is used to investigate the microstructure of TiO 2 nanoparticles in order to correlate their photocatalytic properties. High-resolution transmission electron microscopy examinations show that all the nanoparticles belong to the anatase phase, and pure edge dislocations exist in some nanoparticles. The great enhancement of photocatalytic efficiency is attributed to two factors, the quantum size effect and the surface defects in the nanoparticles.     

Visible-light photocatalytic behavior of two different N-doped TiO2

The visible-light photocatalytic behavior of two different N-doped TiO₂ correlated with their physicochemical properties was investigated. The results show that N-TiO₂-1, prepared by a novel TiO₂ with unique defect structure, is more active in visible-light photocatalytic oxidation of C₃H₆ than N-TiO₂-2, prepared by standard P25-TiO₂ (Degussa). The specific rate constant of the former is ca. 5 times that of the latter. One model of photoactive center (V_o-NO-Ti) in anatase phase responsible for the visible-light photocatalytic activity is proposed. The higher the V_o-NO-Ti concentration is, the better the visible-light photocatalytic activity is.     

From ceramic–matrix nanocomposites to the synthesis of carbon nanotubes

The selective reduction in H₂ of oxide solid solutions produces nanocomposite powders in which transition metal nanoparticles are dispersed inside and on the surface of the oxide matrix grains. When using a H₂/CH₄ reducing atmosphere, the metal nanoparticles that form on the surface of the oxide grains act as catalysts for the CH₄ decomposition and, because of their small size at high temperatures (>800^○C), favor the in-situ nucleation and growth of single-wall and thin multiwall carbon nanotubes. This article reviews our results on the synthesis and characterization of M-MgAl₂O₄ (M=Fe, Fe/Co, Fe/Ni) nanocomposite powders, without and with carbon nanotubes, emphasizing the information that can be derived from Mössbauer spectroscopy as a complement to other characterization techniques.     

Synthesis of multi-walled carbon nanotubes using CoMnMgO catalysts through catalytic chemical vapor deposition

The Co Mg O and Co Mn Mg O catalysts are prepared by a co-precipitation method and used as the catalysts for the synthesis of carbon nanotubes（CNTs） through the catalytic chemical vapor deposition（CCVD）. The effects of Mn addition on the carbon yield and structure are investigated. The catalysts are characterized by temperature programmed reduction（TPR） and X-ray diffraction（XRD） techniques, and the synthesized carbon materials are characterized by transmission electron microscopy（TEM） and thermo gravimetric analysis（TG）. TEM measurement indicates that the catalyst Co Mg O enclosed completely in the produced graphite layer results in the deactivation of the catalyst. TG results suggest that the Co Mn Mg O catalyst has a higher selectivity for CNTs than Co Mg O. Meanwhile, different diameters of CNTs are synthesized by Co Mn Mg O catalysts with various amounts of Co content, and the results show that the addition of Mn avoids forming the enclosed catalyst, prevents the formation of amorphous carbon, subsequently promotes the growth of CNTs, and the catalyst with decreased Co content is favorable for the synthesis of CNTs with a narrow diameter distribution.The Co Mn Mg O catalyst with 40% Co content has superior catalytic activity for the growth of carbon nanotubes.     

Remarkably enhanced photocatalytic activity by sulfur-doped titanium dioxide in nanohybrids with carbon nanotubes

TiO₂ doped S nanohybrids with carbon nanotubes (CNTs) were synthesized with CNTs, thiourea and TiO₂ nanoparticles. The result indicated that the TiO₂ nanoparticles with about 8 nm in size are attached on the sidewall of CNTs. The nanohybrids material can absorb at longer wavelength and the absorption even covers the whole range of visible region than that only TiO₂ nanoparticles. Application of the catalysts to photocatalytic degradation of methylene blue (MB) was tested under visible light irradiation. The result suggests that a high MB degradation activity of S-TiO₂/CNTs due to a reduce band gap of TiO₂ when S is doped, and the decrease in the possibility of electron–hole recombination by CNTs. In addition, the density functional-theory (DFT) calculations of the electronic band structures and density of states (DOS) to understand the bonding states between TiO₂ and CNTs, proved that the TiO₂/CNTs system is stable.     

Electrical, dielectric and surface wetting properties of multi-walled carbon nanotubes/nylon-6 nanocomposites

This paper reports that the multi-walled carbon nanotubes(MWCNT)/nylon-6 (PA6) nanocomposites with different MWCNT loadingshave been prepared by a simple melt-compounding method. Theelectrical, dielectric, and surface wetting properties of theCNT/PA6 composites have been studied. The temperature dependence ofthe conductivity of the CNT/PA6 composite with 10.0 wt{\%} CNTloading ($\sigma _{\rm RT} \sim 10^{-4}$ S/cm) are measured, andafterwards a charge-energy-limited tunnelling model (ln $\sigma (T)\sim T^{-1/2})$ is found. With increasing CNT weight percentage from0.0 to 10.0 wt%, the dielectric constant of the CNT/PA6composites enhances and the dielectric loss tangent increases twoorders of magnitude. In addition, water contact angles of theCNT/PA6 composites increase and the composites with CNT loadinglarger than 2.0 wt%even become hydrophobic. The obtainedresults indicate that the electrical and surface properties of thecomposites have been significantly enhanced by the embedded carbonnanotubes.     

Synthesis of superconductor MgCNi3 with carbon nanotubes

MgCNi3, an intermetallic compound superconductor with a cubic perovskite crystal structure, has been synthesized using fine Mg and Ni powders and carbon nanotubes （CNTs） as starting materials by the conventional powder metallurgy method. The composition, microstructure and superconductivity are characterized using x-ray diffraction （XRD）, energy dispersive x-ray （EDX） analysis, scanning electron microscopy （SEM）, and superconducting quantum interference device （SQUID） magnetometer. The results indicate that the phases of the synthesized samples are MgCNi3 （major phase） and traces of C and MgO. The MgCNi3 particle sizes range from several hundreds of nanometres to several micrometres. The onset superconducting transition temperature Tc of the MgCNi3 sample is about 7.2 K. The critical current density Jc is about 3.44 × 10^4 A/cm^2 calculated according to the Bean model from the magnetization hysteresis loop of the slab MgCNi3 sample at 5 K and zero applied field.     

Rare earth oxide-doped titania nanocomposites with enhanced photocatalytic activity towards the degradation of partially hydrolysis polyacrylamide

Rare-earth oxide-doped titania nanocomposites (RE³⁺/TiO₂, where RE = Eu³⁺, Pr³⁺, Gd³⁺, Nd³⁺, and Y³⁺) were prepared by a one-step sol-gel-solvothermal method. The products exhibited anatase phase structure, mesoporosity, and interesting surface compositions with three oxygen species and two titanium species. The products were used as the photocatalysts to degrade a partially hydrolysis polyacrylamide (HPAM) under UV-light irradiation, a very useful polymer in oil recovery. For comparison, Degussa P25 and as-prepared pure TiO₂ were also tested under the same conditions. The enhanced photocatalytic activity was obtained on as-prepared Eu³⁺ (Gd³⁺, Pr³⁺)/TiO₂ composites, and the reasons were explained. Finally, the degradation pathway of HPAM over the RE³⁺/TiO₂ composite was put forward based on the intermediates produced during the photocatalysis procedure.