Selection principle for various modes of spatially nonuniform electrochemical oscillations

The pattern selection principle for various modes of spatially nonuniform oscillation was investigated by taking a current oscillation of negative differential resistance type, appearing in H2O2 reduction on platinum (Pt) ring electrodes, as a model system. In experiments, various modes of spatiotemporal oscillation, such as a spatially uniform oscillation, standing wave oscillation, and rotating wave oscillation, appeared depending on the applied potential and the distance between the Pt-ring electrode and the reference electrode. A simple mathematical model for the spatiotemporal patterns at the electrode surface was proposed. Numerical calculations and nonlinear bifurcation analysis based on the proposed model reproduced all the essential features of the experimental results and clarified the pattern selection principle.     

Clar valence bond representation of pi-bonding in carbon nanotubes

The application of the Clar aromatic sextet valence bond (VB) model to extended, defect-free single-walled carbon nanotubes (CNTs) with roll-up vectors (m, n) provides a real space model of their electronic structure. If m - n = 3k, where k is an integer, then all pi-electrons can be represented by aromatic sextets, and the CNT is fully benzenoid; the converse is also true. Since m - n = 3k is known to be a necessary criterion for conductivity in CNTs, only fully benzenoid CNTs are metallic, and only potentially metallic CNTs are fully benzenoid. This behavior contrasts with that of planar polycyclic aromatic hydrocarbons, in which the fully benzenoid structures are known to have large HOMO-LUMO gaps. For CNTs that are not fully benzenoid, e.g., m - n = 3k + l, where l = 1 or 2 and k is an integer, a seam of double bonds wraps about an otherwise benzenoid CNT at the chiral angle - 60 degrees or the chiral angle, respectively. Nucleus-independent chemical shift calculations on hydrogen-terminated CNT segments support this, and show that the magnetic manifestation of aromatic sextets is not due to electron correlation. The resonance hybrid of the Clar VB structures corresponds to patterns occasionally observed in scanning tunneling microscopy images of CNTs.     

Hydrogen bond dynamics and microscopic structure of confined water inside carbon nanotubes

We have investigated the density and temperature dependences of microscopic structure and hydrogen bond dynamics of water inside carbon nanotubes (CNTs) using molecular dynamics simulation. The CNTs are treated as rigid, and smoothly truncated extended simple point charge water model is adopted. The results show that as the overall density increases, the atomic density profiles of water inside CNTs become sharper, the peaks shift closer to the wall, and a new peak of hydrogen atomic density appears between the first (outermost) and second layer. The intermittent hydrogen bond correlation function C(HB)(t) of water inside CNTs decays slower than that of bulk water, and the rate of decay decreases as the tube diameter decreases. C(HB)(t) clearly decays more slowly for the first layer of water than for other regions inside CNTs. The C(HB)(t) of the interlayer hydrogen bonds decays faster than those of the other regions and even faster than that of the bulk water. On the other hand, the hydrogen bond lifetimes of the first layer are shorter than those of the inner layer(s). Interlayer hydrogen bond lifetimes are clearly shorter than those of the constituent layers. As a whole, the hydrogen bond lifetimes of water inside CNTs are shorter than those of bulk water, while the relaxation of C(HB)(t) is slower for the confined water than for bulk water. In other words, hydrogen bonds of water inside CNTs break more easily than those of bulk water, but the water molecules remain in each other's vicinity and can easily reform the bonds.     

共聚物模板辅助合成高倍率性能多孔Li2FeSiO4@C/CNTs纳米复合正极材料

通过溶胶-凝胶法制备了Li₂FeSiO₄@C/CNTs(LFS@C/CNTs)纳米复合材料,其中三嵌段共聚物P123用作结构导向剂和碳源,碳纳米管作为导电线提高材料的导电性。LFS@C/CNTs不仅具有海绵状纳米孔,能够与电解液充分接触改善锂离子的传输路径,同时由非晶碳和碳纳米管构成的三维桥联导电网络利于电子的快速传递,提高了材料大电流充放电能力和循环稳定性。复合后的LFS@C/CNTs的高倍率性能相比LFS@C明显提高, 当CNTs的掺量为4%,电压窗口为1.5~4.5 V,0.1C电流密度下放电比容量为182 mAh·g^-1。在10C经70次循环后该材料的放电比容量能保持在117 mAh·g^-1,是LFS@C放电比容量(55 mAh·g^-1)的两倍。     

共聚物模板辅助合成高倍率性能多孔Li2FeSiO4@C/CNTs纳米复合正极材料

通过溶胶-凝胶法制备了Li₂FeSiO₄@C/CNTs(LFS@C/CNTs)纳米复合材料,其中三嵌段共聚物P123用作结构导向剂和碳源,碳纳米管作为导电线提高材料的导电性。LFS@C/CNTs不仅具有海绵状纳米孔,能够与电解液充分接触改善锂离子的传输路径,同时由非晶碳和碳纳米管构成的三维桥联导电网络利于电子的快速传递,提高了材料大电流充放电能力和循环稳定性。复合后的LFS@C/CNTs的高倍率性能相比LFS@C明显提高, 当CNTs的掺量为4%,电压窗口为1.5~4.5 V,0.1C电流密度下放电比容量为182 mAh·g^-1。在10C经70次循环后该材料的放电比容量能保持在117 mAh·g^-1,是LFS@C放电比容量(55 mAh·g^-1)的两倍。     

线性变位极谱研究 V:碲的吸附电流方程式

The mechanism of the electroreduction of Te(IV) has been studied, it is (TeO3)2- + 3H2O + 4e = (Teads)0 + 6OH- (1) (Teads)0 + H2O + 2e = (Hte)- + OH- (Teads)0 + 2e = Te2- The reaction scheme can generally be expressed as follows: ACcordingly, the equation of adsorptive current is give: i = 0.629 n2**2F**i/RT \n\(D0)1/2m2/3t7/6 \Pn\/(1+\Pn\)**2 (C0)* where \Pn\ = bAtA,7exp n2F/RT (E-E0)/& When \Pn\ = 1 the current reaches the maximum, ip = 0.157 n2**2F**2/RT \n\(D0)1/2m2/3t7/6(C0)* This equation shows that the peak current ip is proportional to m2/3t7/6, the ratio of potential change v and the concentration of the substance O being reduced. The half wave width, w1/2, can be obtained from the equation (6) in the form of the following expression W1/2 = 3.52RT/n2F The theoretical conclusions are in good agreement with experimental data for the adsorptive wave of tellurium in 0.25M NH3-NH4cl solution. The diffusion coefficient value determined agrees with that obtained by other polarographic method reported in the literature.     

Large-scale synthesis, characterization and microwave absorption properties of carbon nanotubes of different helicities

Carbon nanotubes of high helicity (H-HCNTs, Sample A) have been synthesized in large-scale by pyrolysis of acetylene at 450 °C over Fe nanoparticles derived from coprecipitation/hydrogen reduction method. With controlled introduction of hydrogen during acetylene pyrolysis, CNTs of low helicity (L-HCNTs, Sample B) and worm-like CNTs (Sample C) were obtained in large quantities. The yields of the CNTs products are high, especially that of H-HCNTs (ca. 7474%). The complex permittivity and permeability of Composites A, B, and C that contain Samples A, B and C (30 wt%) were measured in the 2-18 GHz frequency range. Good absorption of electromagnetic wave (reflection loss<−20 dB) was observed in the 7.18-10.68 and 7.5-10.7 GHz range over Composites B and C (2.0-3.0 mm thickness), respectively. Thus, through the suggested route, CNTs can be produced easily and selectively in large quantities. The lightweight materials can be utilized for microwave absorption.     

Effect of CNT incorporation on PAN/PPy nanofibers synthesized by electrospinning method

In this study, carbon nanotubes (CNTs) added polyacrylonitrile/polypyrrole (PAN/PPy) electrospun nanofibers were produced. Average diameters of the nanofibers were measured as 268 and 153 nm for 10 and 25 wt% of PPy contents, respectively. A relatively higher strain to failure values (23.3%) were observed for the low PPy content. When as-grown CNTs (1 and 4 wt%) were added into the PAN/PPy blends, disordered nanofibers were observed to form within the microstructure. To improve the interfacial properties of CNTs/PAN/PPy composites, CNTs were functionalized with H₂SO₄/HNO₃/HCl solution. The functionalized CNTs were well dispersed within the nanofibers and aligned along the direction of nanofibers. Therefore, beads formation on nanofibers decreased. The impedance of the nanofibers was found to decrease with the PPy content and CNT addition. These nanofibers had a great potential to be used as an electrochemical actuator or a tissue engineering scaffold.     

FUNDAMENTAL PROBLEMS IN FINITE ELEMENT SIMULATION OF WAVE MOTION

The transmitting boundary condition is written in a compact form, which can be direct-ly incorporated into finite elements. Basic characteristics of discretization are analyzed throughstudies on wave motion in a one-dimensional discrete model and their differences from those in thecorresponding continuum. Tbe analysis leads to identifying a frequency band within which thesimulation is possible, and to a suggestion of using the lumped-mass finite element model forthe simulation. Mechanism of the oscillation instability is then illuminated in the frequencydomain by amplification at the artificial boundary and multi-reflection of wave motion in afinite discrete model. Based on understanding of the mechanism, a modified transmittingboundary condition is devised for eliminating the instability. The special stability criterion forthe modified boundary is finally presented for the one-dimensional model.     

Dynamics of hyperthermal collisions of O(3P) with CO

The dynamics of O(3P) + CO collisions at a hyperthermal collision energy near 80 kcal mol-1 have been studied with a crossed molecular beams experiment and with quasi-classical trajectory calculations on computed potential energy surfaces. In the experiment, a rotatable mass spectrometer detector was used to monitor inelastically and reactively scattered products as a function of velocity and scattering angle. From these data, center-of-mass (c.m.) translational energy and angular distributions were derived for the inelastic and reactive channels. Isotopically labeled C18O was used to distinguish the reactive channel (16O + C18O 16OC + 18O) from the inelastic channel (16O + C18O 16O + C18O). The reactive 16OC molecules scattered predominantly in the forward direction, i.e., in the same direction as the velocity vector of the reagent O atoms in the c.m. frame. The c.m. translational energy distribution of the reactively scattered 16OC and 18O was very broad, indicating that 16OC is formed with a wide range of internal energies, with an average internal excitation of approximately 40% of the available energy. The c.m. translational energy distribution of the inelastically scattered C18O and 16O products indicated that an average of 15% of the collision energy went into internal excitation of C18O, although a small fraction of the collisions transferred nearly all the collision energy into internal excitation of C18O. The theoretical calculations, which extend previously published results on this system, predict c.m. translational energy and angular distributions that are in near quantitative agreement with the experimentally derived distributions. The theoretical calculations, thus validated by the experimental results, have been used to derive internal state distributions of scattered CO products and to probe in detail the interactions that lead to the observed dynamical behavior.     

Reversal of Clar's Aromatic-Sextet Rule in Ultrashort Single-End-Capped [5,5] Carbon Nanotubes

The three-fold HOMO-LUMO gap oscillation, typical of finite length armchair carbon nanotubes (CNT), has a major effect on the magnetic response of ultrashort, single-end-capped [5,5] carbon nanotubes to a perturbing magnetic field parallel to the main symmetry axis. For the CNT's containing 40, 70, and 100 carbon atoms, for which 100 % of the C=C double bonds can be grouped into aromatic-sextets, i. e., fully or complete Clar networks, large paratropic (antiaromatic) global circulations around the cylindrical axis are predicted at the DFT level of calculation. Local and semi-global diatropic (aromatic) currents of strengths not larger than that of the benzene molecule are determined for a perpendicular perturbing magnetic field. CNTs of intermediate lengths do not display this enhanced antiaromatic response. The paratropic current flow clearly shows that these complete Clar networks can be viewed as stacked cycloparaphenylene belts, each providing a double annulene circuit as a consequence of the quinoidal resonance structure that results from their closure. Paradoxically, the fully aromatic Clar structure itself is responsible for the enhanced global antiaromaticity.     

Lattice dynamics of solid α-carbon monoxide

The lattice dynamics of α-CO is studied assuming a fully-ordered antiferro P2₁3 structure, using a potential model which includes electrostatic, dispersion and exchange interactions. The coupling of translational and librational motions leads to mixed modes at finite wave vectors and to anomalous acoustic dispersion. Anharmonic frequency shifts and the damping due to phonon—phonon interactions are evaluated for the zero wave vector modes. The single-particle potential wells for the high-frequency librational modes are investigated and suggest that translation—rotation coupling plays a primary role in the molecular reorientations.     

Preparation and properties of chitosan nanocomposites with nanofillers of different dimensions

In this work, the chitosan ternary nanocomposites with two-dimensional (2D) clay platelets and one-dimensional (1D) CNTs have been successfully prepared by a simple solution-intercalation/mixing method in acid media. It was found that the thermal degradation temperature of chitosan (at 50% weight loss) could be only improved in about 20-30 °C by adding 3 wt% either clay or CNTs, however, almost 80 °C increase of degradation temperature could be achieved by adding 2 wt% clay and 1 wt% CNTs together. Dynamic mechanical measurement demonstrated an obviously improved storage modulus for chitosan/clay-CNTs than that for the corresponding binary chitosan/clay or chitosan/CNT nanocomposites with the same total filler content (3 wt%). For the solvent vapor permeation properties, a largely improved benzene vapor barrier property was observed only in chitosan/clay-CNT ternary nanocomposites and depended on the ratio of clay to CNTs. XRD, SEM and TEM results showed that both clay and CNTs could be well dispersed in the ternary nanocomposites with the nanotubes located around the clay platelets. FTIR showed an improved interaction between the fillers and chitosan by using both clay and CNTs. A much enhanced solid-like behavior was observed in the ternary nanocomposites, compared with the corresponding binary nanocomposites with the same total filler content, as indicated by rheological measurement. The unique synergistic effect of two-dimensional (2D) clay platelets and one-dimensional (1D) CNTs on the property enhancement could be tentatively understood as due to a formation of much jammed filler network with 1D CNTs and 2D clay platelets combined together. Our work demonstrates a good example for the preparation of high performance polymer nanocomposites by using nanofillers with different dimensions together.     

Absolute humidity measurement utilizing alpha-ray absorption

Changes in air density due to humidity were measured by a scintillation detector with alpha-particles. The distance between the scintillator and an alpha-ray source of 241 Am, 3.7 MBq (100 microCi), was fixed at 25 mm which was a little shorter than the range of alpha-particles from the source. The measured absolute humidities were in a range of 7.9 g/m3 to 52.2 g/m3 at temperatures of 35 degrees C and 45 degrees C and under atmospheric pressure. The counting rate of alpha-particles in an absolute humidity of 31.7 g/m3 (80% in relative humidity) at 35 degrees C increased 28% compared with that in dry air. From experimental results and theoretical calculation, the counting rate difference between humid air and dry air was shown to be almost proportional to the absolute humidity in air. The absolute humidity can be measured with an accuracy of +/- 3 g/m3, that is +/- 5% in relative humidity at 45 degrees C.     

3,4-二羟基苯甲酸-BrO3——Fe(phen)32+-H2SO4体系中的振荡现象

在Belousov-Zhabotinsky(BZ)反应中,Br^-通常起控制作用,初始加入少量的Br^-可抑制振荡。     

Dielectrophoretically patterned carbon nanotubes to sort microparticles

This article compares the operation of a dielectrophoretic (DEP) platform before and after pattering carbon nanotubes (CNTs) between its microelectrodes. The diverse performance of the DEP system is assessed by separating 1 and 5 μm polystyrene particles. In the absence of CNTs, both particles can only be trapped by operating the system at low medium conductivities, (<10⁻³ S/m) and frequencies (<75 kHz). Alternatively, applying CNTs to the system, some CNTs coat the surface of particles and increase their overall conductivity and permittivity, whereas the rest of them are patterned between the microelectrodes and induce strong DEP forces at their free ends, which can effectively trap the coated particles. The first development extends the range of medium conductivities and frequencies at which the trapping of both particles is achievable, whereas the second development facilitates the selective deposition of particles along the surface of curved microelectrodes. Setting the medium conductivity to 2×10⁻³ S/m and the frequency to 20 MHz, most of 5 μm particles are trapped at the entry region of the first microelectrode pair, whereas most of 1 μm particles are trapped at the tips, and this distinction facilitates their separation. The trapping of 1 μm particles can be improved by decreasing the frequency to 1.5 MHz. This study demonstrates how the integration of CNTs into microfluidic systems enables them to operate beyond their capabilities.     

Hydrogen bonding in potassium hydrogen carbonate studied by compton scattering on single crystals

Compton spectra excited by ²⁴¹Am radiation have been measured on thin single-crystal slices with the scattering vector oriented parallel and perpendicular to the pair of hydrogen bonds in the (HCO₃) dimers as well as to the plane of the dimers. the reciprocal form factors extracted from the spectra are strongly anisotropic with two extra zero passages in the direction of the hydrogen bonds. the results are in very satisfactory agreement with theoretical data that are calculated for the dimer with and without additional point charges simulating the neighboring ions in the crystal. The calculations have been done with Gaussian basis sets of double-zeta quality within the Hartree–Fock approximation. The theoretical reciprocal form factors of the monomer HCO and the dimer show only small differences in the directions perpendicular to the hydrogen bonds, whereas the differences in the hydrogen bond direction are remarkable and account for the experimentally observed features. In comparison to this effect the influence of the neighboring ions by their charges is much smaller, which is even true when taking into account the influence of the neighboring dimers in the crystalline stack in more detail by symmetrical orthogonalization of the combined wave functions. The same orthogonalization procedure applied to a pair of monomers in the spatial arrangement of the dimer yields a reciprocal form factor that in the experimentally reliable range above 1.8 Å accounts for most of the dimerization effect in the direction of the hydrogen bonds. Thus also for this prototype of paired hydrogen bonds (cf., carboxylic acids, DNA, and RNA), it confirms our earlier experimental finding on liquid water now unambiguously, namely that, in the same way as the cohesion in ionic crystals, hydrogen bond formation in bulk matter is distinctly dominated by electrostatic attraction, which is compensated by repulsion owing to the Pauli principle.     

V2O5-anchored carbon nanotubes for enhanced electrochemical energy storage

Functionalized multiwalled carbon nanotubes (CNTs) are coated with a 4-5 nm thin layer of V(2)O(5) by controlled hydrolysis of vanadium alkoxide. The resulting V(2)O(5)/CNT composite has been investigated for electrochemical activity with lithium ion, and the capacity value shows both faradaic and capacitive (nonfaradaic) contributions. At high rate (1 C), the capacitive behavior dominates the intercalation as 2/3 of the overall capacity value out of 2700 C/g is capacitive, while the remaining is due to Li-ion intercalation. These numbers are in agreement with the Trasatti plots and are corroborated by X-ray photoelectron spectroscopy (XPS) studies on the V(2)O(5)/CNTs electrode, which show 85% of vanadium in the +4 oxidation state after the discharge at 1 C rate. The cumulative high-capacity value is attributed to the unique property of the nano V(2)O(5)/CNTs composite, which provides a short diffusion path for Li(+)-ions and an easy access to vanadium redox centers besides the high conductivity of CNTs. The composite architecture exhibits both high power density and high energy density, stressing the benefits of using carbon substrates to design high performance supercapacitor electrodes.     

Magnetic carbon nanotubes synthesis by Fenton's reagent method and their potential application for removal of azo dye from aqueous solution

We report a simple and easy method to fabricate magnetic carbon nanotubes (CNTs) by Fenton's reagent method without the addition of any cations. H(2)O(2) was added slowly into the FeSO(4) solution mixed with purified CNTs, and the resulting reactants were placed into a quartz tube to undergo heat treatment under a nitrogen/hydrogen flow. Iron oxide (Fe(2)O(3)) nanoparticles were uniformly dispersed on CNTs without any pretreatment such as strong acid or covalent functionalization processes. The as-produced magnetic CNTs were used as an adsorbent for removal of methyl orange (MO) dye from aqueous solutions. Adsorption experiments indicated that the magnetic CNTs have good adsorption capacity (q(e)) of MO (28 mg/g). The Freundlich isotherm model fitted the experiment data better than the Langmuir isotherm mode. The mean energy of adsorption was calculated as 3.72 kJ/mol based on the Dubinin-Radushkevich model, which suggests that the removal process was dominated by physical adsorption. Kinetic regression results showed that the adsorption kinetics was more accurately represented by a pseudo second-order model. Intra-particle diffusion was involved in the adsorption process, but it was not the only rate-controlling step. More importantly, a new photocatalytic regeneration technology can be enabled by the high nanoscale iron oxide loading (50%). The magnetic CNT adsorbents could be effectively and quickly separated by applying an external magnetic field and regenerated by UV photocatalysis. Therefore, CNTs/λ-Fe(2)O(3) hybrid is a promising magnetic nanomaterial for preconcentration and separation of organic pollutants for environmental remediation.     

Sensitive Determination of Terbutaline Using a Platform Based on Nanoparticles of Europium Oxide and Carbon Nanotubes

This study presents a sensitive voltammetric determination of terbutaline (TER) on a platform based on carbon nanotubes (CNTs) and europium oxide nanoparticles (Eu₂O₃NPs) coated glassy carbon electrodes (GCEs). An ultrasonic bath was performed for the preparation of composite material. The material was characterized by energy dispersive X‐ray spectroscopy (EDX), X‐ray diffraction method (XRD) and scanning electron microscopy (SEM). The Eu₂O₃NPs/CNTs/GCE system was assessed for the oxidation of terbutaline (TER). A broad oxidation peak was appeared at 0.71 V using a bare GCE. However, the voltammetry of TER has been improved at a GCE coated with CNTs and a well‐defined anodic peak exhibited at 0.61 V. Furthermore, the nanoparticles of Eu₂O₃ and CNTs coated GCE has greatly improved the electrochemical behaviour of TER and a sharp peak was appeared at 0.59 V. Cyclic voltammetry at Eu₂O₃NPs/CNTs/GCE also reveals a high catalytic effect for the oxidation of TER with an oxidation peak that is distinctly enhanced compared to GCE and CNTs/GCE. Eu₂O₃ nanoparticles were utilized to enhance the surface area of GCE and then improve the sensitivity of the procedure. The response of TER was linear over a concentration range of 2.0×10^?8 M ?9.5×10^?6 M with an LOD of 3.7×10^?9 M. Square wave voltammetric analysis of tablets by Eu₂O₃NPs/CNTs/GCE yielded a recovery of 99.2 % with an RSD% of 3.2. The modified electrode (EuO₂NPs/CNTs/GCE) provides accuracy and precision to the analysis of samples.