Disposable screen-printed bismuth electrode modified with multi-walled carbon nanotubes for electrochemical stripping measurements

Integrating the advantages of screen printing technology with the encouraging electroanalytical characteristic of metallic bismuth, we developed an ultrasensitive and disposable screen-printed bismuth electrode (SPBE) modified with multi-walled carbon nanotubes (MWCNTs) for electrochemical stripping measurements. Metallic bismuth powders and MWCNTs were homogeneously mixed with graphite-carbon ink to mass-prepare screen-printed bismuth electrode doped with multi-walled carbon nanotubes (SPBE/MWCNT). The electroanalytical performance of the prepared SPBE/MWCNT was intensively evaluated by measuring trace Hg(II) with square-wave anodic stripping voltammetry (SWASV). The results indicated that the SPBE modified with 2 wt% MWCNTs could offer a more sensitive response to trace Hg(II) than the bare SPBE. The stripping current obtained at SPBE/MWCNT was linear with Hg(II) concentration in the range from 0.2 to 40 μg/L (R(2) = 0.9976), with a detection limit of 0.09 μg/L (S/N = 3) under 180 s accumulation. The proposed "mercury-free" electrode, with extremely simple preparation and ultrahigh sensitivity, holds wide application prospects in both environmental and industrial monitoring.     

Controlled hydrothermal synthesis of bismuth oxyhalide nanobelts and nanotubes

Ternary bismuth oxyhalide crystalline nanobelts (such as Bi24O31Br10, Bi3O4Br, Bi12O17Br2, BiOCl, and Bi24O31Cl10) and nanotubes (such as Bi24O31Br10) have been synthesized by using convenient hydrothermal methods. The composition and morphologies of the bismuth oxyhalides could be controlled by adjusting some growth parameters, including reaction pH, time, and temperature. All the nanostructures were characterized by using various methods including X-ray diffraction, transmission electron microscopy, high-resolution TEM, electron diffraction, and energy-dispersive X-ray analysis. The possible reaction mechanism and growth of the crystals are discussed based on the experimental results.     

Use of a bismuth ion-selective electrode for investigation of bismuth complexes of citric and malic acids

A bismuth ion-selective electrode has been used to determine the nature and stability of the complexes formed by bismuth with citric acid and malic acid, by measurement of the response of the electrode to different total bismuth concentrations at various combinations of pH and total ligand concentration. The values found were beta(2) = 3 x 10(13) for Bi(Cit)(2)(3-) and beta(3) = 8 x 10(9) for Bi(Mal)(2)(3-).     

碳纳米管的功能化及其电化学性能

超级电容器作为一种新型的储能元件,以其快速储存、释放能量等优点,近年来成为各国科研工作的研究重点和焦点[1￣3],并在数据记忆存储系统、便携式仪器设备、后备电源、通讯设备、计算机、燃料电池、电动车混合电源等许多领域都有广泛的应用前景[4]。目前,超级电容器用的电极材     

Zigzag boron-carbon nanotubes with quasi-planar tetracoordinate carbons

Four kinds of novel zigzag boron-carbon nanotubes with quasi-planar tetracoordinate carbons (2m, 0, i) (m = 3-6; i = 1-4) have been constructed, and their structures, stabilities, and bonding properties have been investigated by B3LYP calculations. The results show that the novel nanotubes (m, 0, i) have the character of metal properties with quite small HOM-LUMO gaps. Structurally, there are big windows on the walls of nanotubes and they are promising in design for functional materials.     

Computer simulation of size effects and adsorption properties of one-wall carbon nanotubes (6,6)

Structure, electric and adsorption properties of carbon open-end nanotubes of (6,6) chirality consisting of 5–19 segments were studied by quantum-chemical methods AM1, PM3, LSDA/3-21G, B3LYP/6-31G. The size effects and adsorption properties of nanotubes are discussed.     

功能化碳纳米管的电化学性质及在6-巯基嘌呤分析检测中的应用

采用修饰单壁碳纳米管(SWNT、SWNT-COOH或SWNT-OH)及多壁碳纳米管(MWNT、MWNT-COOH或MWNT-OH)的石墨电极研究配位阴离子[Fe(CN)6]3-和配位阳离子[Co(phen)3]3+的电化学行为与吸附性能,借助[Co(phen)3]3+在碳纳米管(CNT)的强吸附特性制备[Co(phen)3]3+/CNT/C修饰电极,以其应用于6-MP的分析检测.结果表明:1)在CNT修饰电极上[Fe(CN)6]3-/4-呈现很好的氧化还原可逆性,而[Co(phen)3]3+则显示明显的吸附控制特征.2)[Co(phen)3]3+在多壁碳纳米管修饰电极上的吸附量较单壁碳纳米管大,但经羧基化或羟基化后,吸附量减小,而且在羧基化表面的吸附量较羟基化的大.3)[Co(phen)3]3+与6-MP间存在明显的相互作用,其配位产物的还原峰电流与6-MP浓度呈线性关系.     

The use of NH3 to promote the production of large-diameter single-walled carbon nanotubes with a narrow (n,m) distribution

We demonstrate here a simple and effective (n,m)-selective growth of single-walled carbon nanotubes (SWCNTs) in an aerosol floating catalyst chemical vapor deposition (CVD) process by introducing a certain amount of ammonia (NH(3)). Chiralities of carbon nanotubes produced in the presence of 500 ppm NH(3) at 880 °C are narrowly distributed around the major semiconducting (13,12) nanotube with over 90% of SWCNTs having large chiral angles in the range 20°-30°, and nearly 50% in the range 27°-29°. The developed synthesis process enables chiral-selective growth at high temperature for structurally stable carbon nanotubes with large diameters.     

Alkali-metal-supported bismuth polyhedra-principles and theoretical studies

We have quantum chemically investigated the structure, stability, and bonding mechanism in highly aggregated alkali-metal salts of bismuthanediide anions [RBi](2-) using relativistic density functional theory (DFT, at ZORA-BP86/TZ2P) in combination with a quantitative energy decomposition analysis (EDA). Our model systems are alkali-metal-supported bismuth polyhedra [(RBi)(n)M(2n-4)](4-) with unique interpenetrating shells of a bismuth polyhedron and an alkali-metal superpolyhedron. Furthermore, we have analyzed the trianionic inclusion complexes [M'@{(RBi)(n)M(2n-4)}](3-) involving an additional endohedral alkali-metal ion M'. The main objective is to assist the further development of synthetic approaches toward this class of compounds. Our analyses led to electron-counting rules relating, for example, the number of bonding orbitals (N(bond)) of the cage molecules [(RBi)(n)M(2n+Q)](Q) to the number of bismuth atoms (n(Bi)), alkali-metal atoms (n(M)), and net charge Q as N(bond) = n(Bi) + n(M) - Q (R = one-electron donor ligand; M = alkali metal; n = 4-12; Q = -4, -6, -8). Finally, on the basis of our findings, we predict the next members in the 5-fold symmetrical row of alkali-metallobismaspheres with a macroicosahedral arrangement.     

Protein nanotubes comprised of an alternate layer-by-layer assembly using a polycation as an electrostatic glue

We present the synthesis and structure of various protein nanotubes comprised of an alternate layer-by-layer (LbL) assembly using a polycation as an electrostatic glue. The nanotubes were fabricated by sequential LbL depositions of positively charged polycations and negatively charged proteins into a porous polycarbonate (PC) membrane, followed by release of the cylindrical core by quick dissolution of the template with CH(2)Cl(2). This procedure provides a variety of protein nanotubes without interlayer cross-linking. The three-cycle depositions of poly-L-arginine (PLA) and human serum albumin (HSA, M(w)=66.5 kDa) into the porous PC template (pore diameter, D(p)=400 nm) yielded well-defined (PLA/HSA)(3) nanotubes with an outer diameter of 419+/-29 nm and a wall thickness of 46+/-8 nm, revealed by scanning electron microscopy (SEM) and transmission electron microscopy (TEM) observations. The outer diameter of the tubules can be controlled by the pore size of the template (200-800 nm), whereas the wall thickness is always constant, independent of the D(p) value. The (PEI/HSA)(3) (PEI: polyethylenimine) nanotubes showed a slightly thin wall of 39+/-5 nm. CD spectra of the multilayered (PEI/HSA)(n) film on a flat quartz plate suggested that the secondary structure of HSA between the polycations was almost the same as that in aqueous solution. The three-cycle LbL depositions of PLA and ferritin (M(w)=460 kDa) or myoglobin (Mb, M(w)=1.7 kDa) into the porous PC membrane also gave cylindrical hollow structures. The wall thickness of the (PLA/ferritin)(3) and (PLA/Mb)(3) nanotubes were 55+/-5 nm and 31+/-4 nm; it depends on the globular size of the protein (ferritin>HSA>Mb). The individual ferritin molecule was clearly seen in the tubular walls by SEM and TEM measurements.     

Enhanced hydrogen production activity over BiO_X–TiO_2 under solar irradiation:Improved charge transfer through bismuth oxide clusters

A series of titania nanoparticles and nanotubes deposited with various quantities of bismuth(Bi) were prepared via sol-gel and hydrothermal methods, respectively. They were then characterized using X-ray diffraction spectroscopy(XRD), X-ray photo electron spectroscopy(XPS), UV–Vis diffused reflectance spectra(DRS), photoluminescence spectra(PLS), transmission electron microscopy(TEM), energy dispersive analysis of X-rays(EDAX), and BET surface analysis. These catalysts were employed for the photocatalytic production of hydrogen from a mixture of pure water and glycerol under solar light irradiation. The presence of the Bi~((3+x)+) species was found to play a vital role in enhancing activity while minimizing electron hole recombination(relative to bare TiO_2). The nanotubes exhibited better activity than the nanoparticles of Bi-deposited TiO_2, showing the significance of the morphology; however, photocatalytic activity is predominantly dependent on the deposition of bismuth. The activity increased by approximately an order of magnitude at the optimum concentration of Bi deposited over TiO_2(2 wt%). The presence of the Bi~((3+x)+) species played a vital role in minimizing electron hole recombination, resulting in higher activity compared to bare TiO_2.     

The complexes of bismuth(III) and nitrilotriacetic acid

The reaction between bismuth(III) and nitrilotriacetic acid (NTA or H(3)X) has been investigated by ultraviolet spectrophotometry. It has been established that bismuth(III) and NTA form two complexes with compositions bismuth(III): NTA = 1:1 and 1:2. The absorption maxima are at 243 nm (1:1) and 271 nm (1:2), the molar absorptivities being 8.00 x 10(3) and 8.20 x 10(3) l.mole(-1).cm(-1) respectively. The stability constants (at mu = 1.0) are: log beta(BiX) = 17.53 +/- 0.06 and log beta(B)(2)(3-) = 26.56 +/- 0.07. The possibility of the analytical application of BiX is briefly discussed.     

Synthesis and characterization of nanostructured bismuth selenide thin films

Nanostructured bismuth selenide thin films have been successfully fabricated on a silicon substrate at low temperature by rational design of the precursor solution. Bi(2)Se(3) thin films were constructed of coalesced lamella in the thickness of 50-80 nm. The nucleation and growth process of Bi(2)Se(3) thin films, as well as the influence of solution chemistry on the film structure were investigated in detail. As one of the most promising thermoelectric materials, the thermoelectric properties of the prepared Bi(2)Se(3) thin films were also investigated. The power factor increased with increasing carrier mobility, coming from the enlarged crystallites and enhanced coalesced structure, and reached 1 μW cm(-1) K(-1).     

Aggregation behavior of single-walled carbon nanotubes in dilute aqueous suspension

The aggregation behavior of colloidal single-walled carbon nanotubes (SWNT) in dilute aqueous suspensions was investigated using a novel light scattering measurement technique. The aggregation of SWNT in three suspensions was examined: (1) nanotubes after acid treatment; (2) as-received nanotubes stabilized by a nonionic surfactant; and (3) acid-treated nanotubes with nonionic surfactant. Continuous light scattering measurements of the SWNT suspensions (probing the 38-436 nm length scale) made over two weeks showed that the nanotubes in each sample formed networks with fractal-like structures. The as-received nanotubes were stable over the measurement period, while the acid-treated nanotube suspension showed greater dispersion variability over time, yielding looser structures at large length scales and more compact structures at smaller length scales. The addition of surfactant to the acid-treated suspension significantly enhanced nanotube dispersion.     

B和N原子掺杂超长(3,3)单壁碳纳米管的从头算研究

用从头算的周期边界条件方法,建立了(3,3)型超长单壁碳纳米管的新模型.使用B3LYP/3-21G方法计算了B和N掺杂纳米管的结构参数、掺杂能量、能带结构以及能隙.研究表明,B和N原子掺杂的(3,3)型单壁碳纳米管具有直接带隙半导体特征,其α轨道计算所得能隙值分别为1.797和2.041 eV.     

La~2NiO~4催化制备纳米碳管

制备了四方结构复合氧化物La~2NiO~4,并以其为催化剂前体,甲烷和一氧化碳为碳,合成出大量高纯度的纳米碳管。XRD结果表明La~2NiO~4经还原后,在La~2O~3的隔离作用下Ni晶粒实现纳米级均匀分散。利用TEM,HRTEM,SEM,XRD,Raman等手段对所制备的纳米碳管进行了观察和表征。所制备的纳米碳管管径均匀、石墨化程度较高,该法制备纳米碳管工艺简单、产量较高,产品易于纯化。     

Ultrasonic approach for formation of erbium oxide nanoparticles with variable geometries

Ultrasound (20 kHz, 29 W·cm(-2)) is employed to form three types of erbium oxide nanoparticles in the presence of multiwalled carbon nanotubes as a template material in water. The nanoparticles are (i) erbium carboxioxide nanoparticles deposited on the external walls of multiwalled carbon nanotubes and Er(2)O(3) in the bulk with (ii) hexagonal and (iii) spherical geometries. Each type of ultrasonically formed nanoparticle reveals Er(3+) photoluminescence from crystal lattice. The main advantage of the erbium carboxioxide nanoparticles on the carbon nanotubes is the electromagnetic emission in the visible region, which is new and not examined up to the present date. On the other hand, the photoluminescence of hexagonal erbium oxide nanoparticles is long-lived (μs) and enables the higher energy transition ((4)S(3/2)-(4)I(15/2)), which is not observed for spherical nanoparticles. Our work is unique because it combines for the first time spectroscopy of Er(3+) electronic transitions in the host crystal lattices of nanoparticles with the geometry established by ultrasound in aqueous solution of carbon nanotubes employed as a template material. The work can be of great interest for "green" chemistry synthesis of photoluminescent nanoparticles in water.     

One-step solvothermal synthesis of single-crystalline TiOF2 nanotubes with high lithium-ion battery performance

Single-crystalline TiOF(2) nanotubes were prepared by a one-step solvothermal method. The nanotubes are rectangular in shape with a length of 2-3?μm, width of 200-300?nm, and wall thickness of 40-60?nm. The formation of TiOF(2) nanotubes is directly driven by the interaction between TiF(4) and oleic acid in octadecane to form the 1D nanorods, and this is followed by a mass diffusion process to form the hollow structures. The synthesis approach can be extended to grow TiOF(2) nanoparticles and nanorods. Compared with TiO(2), which is the more commonly considered anode material in lithium-ion batteries, TiOF(2) has the advantages of a lower Li-intercalation voltage (e.g., to help increase the total voltage of the battery cell) and higher specific capacities. The TiOF(2) nanotubes showed good Li-storage properties with high specific capacities, stable cyclabilities, and good rate capabilities.     

Reaction between copper(I)-thiourea and bismuth(III)-thiourea complexes in presence of iodide. New spot-tests for copper(II) and bismuth(III)

New and very simple spot tests are described for the detection of Bi(III), Cu(II) and I(-) ions with limits of detection of 3, 8, and 75 mug/0.05 ml respectively. Tests are also described for such combinations as Bi(III) + I(-); Bi(III) + Cu(II); and Bi(III) + Cu(II) + I(-). All the tests are based on the formation of an orange or red-orange precipitate of bismuth(III)-copper(I)-iodide-thiourea complex, for which the formula [Bi(tu)(3)I(3).Cu(tu)(3)I] (where tu = thiourea) is proposed. This complex is produced in various ways by the interaction of Bi(III), Cu(II), and I(-) ions with thiourea. Most cations and anions do not interfere, but Tl(I), Cs(I), SO(2-)(3), S(2)O(2-)(3), EDTA, and oxidizing ions such as NO(-)(2), IO(-)(3), IO(-)(4), BrO(-)(3), and MnO(-)(4) do. The complex hexakis(thioureato)sulphatomonoaquodicopper(I) [Cu(2)(tu)(6)SO(4).H(2)O] is proposed as a new spot-test reagent for Bi(III) and I(-) ions, although the sensitivity for the latter is poor.     

聚3-甲基噻吩及聚3-己基噻吩修饰钛酸盐纳米管的光电化学性能研究

采用水热法制备了钛酸盐纳米管, 并将钛酸盐纳米管制备成纳米结构电极进行光电化学研究. 钛酸盐纳米管产生阳极光电流, 具有n-型半导体特性. 结果表明, 聚3-甲基噻吩[poly(3-methylthiophene), PMeT]、聚3-己基噻吩[poly(3-hexylthiophene), P3HT]修饰钛酸盐纳米管后产生的光电流均较纯钛酸盐纳米管的光电流高, 且使产生光电流的波长向长波区移动. 钛酸盐纳米管/PMeT、钛酸盐纳米管/P3HT的光电转换效率分别达11.40%, 0.91%(未校正光子损失). 钛酸盐纳米管/PMeT的光电转换效率较钛酸盐纳米管/P3HT的光电转换效率高10.5%. 钛酸盐纳米管/PMeT、钛酸盐纳米管/P3HT中存在p-n异质结, 在一定条件下p-n异质结的存在有利于光生电子/空穴的分离.