Magnetoadsorptive Particles Enabling the Centrifugation‐Free,Preparative‐Scale Separation,and Sorting of Single‐Walled Carbon Nanotubes

A novel magnetic composition of the high surface area particles with amide chemical functionality, Sephacryl S‐200, is reported enabling the preparative‐scale (1 L, ≈5–10 mg) separation of metallic and semiconducting single‐walled carbon nanotubes (SWNT) from completely unpurified and uncentrifuged nanotube stocks. Sephacryl S‐200 has previously been utilized in separating semiconducting SWNT (s‐SWNT) on the laboratory scale. Significantly, use of these magnetic derivative particles in absorptive separation of SWNT allows the unprecedented and industrially scalable purification of both metallic SWNT (m‐SWNT) as well as s‐SWNT directly from uncentrifuged, ultrasonicated surfactant‐based SWNT solutions by simple and scalable magnetic separation. These particles also allowed for the systematic study on the effect of SWNT–polymer interaction time on the resulting SWNT “payloads.” Ultimately, high ‐purity m‐SWNT and s‐SWNT products are independently achieved by controlling the SWNT–polymer interaction time and relative concentrations, as well as SWNT sonication conditions. Furthermore, by controlling these factors, single‐chirality (6,5) s‐SWNT can be isolated with 92% purity directly from unpurified stocks. Thermogravimetric analysis indicates a total process SWNT yield of 1.2% and 1.7% for m‐SWNT and s‐SWNT, respectively. These results demonstrate the potential for a preparative method for separating carbon nanotubes based on electronic properties.     

Resin‐Derived Ni3S2/Carbon Nanocomposite for Advanced Rechargeable Aqueous Zn‐Based Batteries

The exploration of high‐energy and stable cathode materials is highly desirable and challenging for the development of advanced Zn‐based batteries. In this work, a facile pyrolysis method is reported to synthetize Ni₃S₂/carbon nanocomposite as high‐performance cathode by employing ion exchange resin as a precursor. Attributing to the abundant active sites and enhanced conductivity from well binding between Ni₃S₂ and carbon, a markedly high capacity of 234.3 mA h g^?1 is obtained for this Ni₃S₂/carbon at a high current density of 6.9 A g^?1. Moreover, a Zn‐based battery is demonstrated by using the Ni₃S₂/carbon as a cathode and Zn plate as an anode, which delivers a maximum power density of 58.6 kW kg^?1, together with a peak energy density of 356 W h kg^?1 and 93.7% capacity retention after 5000 charging–discharging cycles. This simple synthetic strategy to achieve robust Ni‐based composite electrodes may open up new opportunities to design other transition metal–based electrodes for energy storage applications.     

Angle‐multiplexed optical printing of biomimetic hierarchical 3D textures

Multi scale hierarchical structures underpin mechanical, optical, and wettability behavior in nature. Here we present a novel approach which can be used to mimic the natural hierarchical patterns in a quick and easy maskless fabrication. By using two‐beam interference lithography with angle‐multiplexed exposures and scanning, we have successfully printed large‐area complex structures having a cascading resolution and 3D surface profiles. By precisely controlling the exposure dose we have demonstrated a capability to create different 3D textured surfaces having comparable aspect ratio with period spanning from 4 μm to 300 nm (more than one order of magnitude) and the height spanning from 0.9 μm to 40 nm, respectively. Up to three levels of biomimetic hierarchical structures were obtained that show several natural phenomena: superhydrophobicity, iridescence, directionality of reflectivity, and polarization at different colors.

     

3D HSQC-HSQMBC—increasing the resolution of long-range proton–carbon correlation experiments

A 3D HSQC-HSQMBC experiment is proposed for increasing the separation of proton–carbon long-range correlation cross peaks, the lack of which is occasionally seen in corresponding 2D experiments. It is aimed at complex molecules with many protonated carbons exhibiting a narrow spread of ¹³C chemical shifts e.g., complex carbohydrates. It does not yield long-range correlation of quaternary carbons. An extra indirectly detected ¹H dimension of this experiment provides additional separation of long-range correlation cross peaks by utilising the chemical shifts of protons directly attached to ¹³C. Evolution of single-quantum coherences throughout the entire pulse sequence ensures that the cross peaks are inphase pure absorption singlets in both indirectly detected dimensions, thus maximising the resolution and sensitivity of the experiment. Partial signal cancellation can be expected due to the antiphase character of peaks in the directly detected dimension. The intensity of cross peaks depends on the length of a single long-range evolution interval and values of both active and passive long-range coupling constants of each carbon. The 3D HSQC-HSQMBC experiment provided high quality long-range correlation spectra of a 2 mg pentasaccharide sample in 27 h. The technique can also be used for measurement of long-range heteronuclear coupling constants from pure antiphase multiplets in the directly detected dimension.     

FeNi Layered Double‐Hydroxide Nanosheets on a 3D Carbon Network as an Efficient Electrocatalyst for the Oxygen Evolution Reaction

An efficient electrocatalyst for oxygen evolution has been prepared via the deposition of iron–nickel layered double‐hydroxide (FeNi‐LDH) nanosheets on 3D carbon network as the building scaffold in a one‐step hydrothermal process. It is found that upon the assembling of FeNi‐LDH nanosheets with graphene into the 3D cross‐linked hybrid, the FeNi‐LDH/graphene hybrid features a well‐improved catalytic activity towards the oxygen evolution reaction (OER) with a good stability during the long‐term cycling experiment. Moreover, the hybrid catalyst is also active in the oxygen reduction reaction (ORR), qualifying it as a new type of bifunctional catalyst that can work in metal–air batteries.     

3D Raman mapping of uniaxially loaded 6H‐SiC crystals

Raman spectroscopy is used to investigate the three‐dimensional stress distribution in 6H‐silicon carbide (SiC) specimens subjected to stresses up to 3.7 GPa along the c‐axis. Specifically, the relative Raman shift of the longitudinal optic phonon of 6H‐SiC is used to evaluate the local stress across the bulk crystal. For this purpose, an anvil device with opposed 6H‐SiC and sapphire specimens was used. After subjecting the anvils to uniaxial load, several series of two‐dimensional Raman maps were registered at different depths in the 6H‐SiC anvil. The analysis of the Raman spectra reveals an exponential decay of the stress as a function of the depth. A novel phenomenological Grüneisen‐like model is introduced here to account for such observation. On the contrary, the in‐plane stress analysis shows a radial Gaussian‐like distribution regardless the depth, a distinct behavior that is attributed to the appearance of shear stress components. The suitability of both models and their applicability to other materials are discussed, along with some future directions. Copyright © 2013 John Wiley & Sons, Ltd.     

3D processing map and hot deformation behaviour of a new type Al–Zn–Mg alloy

ABSTRACT

The thermal compression behaviour of Al–Zn–Mg alloy was studied on a thermal simulator machine at the temperature range of 380–540°C and strain rate range of 0.01–10?s^?1. The constitutive equation and 3D processing map of the alloys were established. The microstructure characteristics of the alloy were studied by metallographic observation, electron back-scatter diffraction (EBSD) analysis and transmission electron microscopy (TEM) microstructure analysis. The results show that the peak stress of high-temperature deformation of alloy decreases with the increase of deformation temperature and increases with the increase of strain rate. The dynamic recovery of the alloy occurs at the temperature range of 380–460°C and the strain rate range of 0.01–0.1?s^?1. The dynamic recrystallization of the alloy occurs at the temperature range of 460–500°C and the strain rate range of 0.01–0.1?s^?1. The alloy maintains fine and uniform recrystallized grains at a temperature range of 460–480°C and a strain rate range of 0.01–0.1?s^?1, which is suitable for hot working.     

Hybrid femtosecond laser microfabrication to achieve true 3D glass/polymer composite biochips with multiscale features and high performance: the concept of ship‐in‐a‐bottle biochip

True three‐dimensionally (3D) integrated biochips are crucial for realizing high performance biochemical analysis and cell engineering, which remain ultimate challenges. In this paper, a new method termed hybrid femtosecond laser microfabrication which consists of successive subtractive (femtosecond laser‐assisted wet etching of glass) and additive (two‐photon polymerization of polymer) 3D microprocessing was proposed for realizing 3D “ship‐in‐a‐bottle” microchip. Such novel microchips were fabricated by integrating various 3D polymer micro/nanostructures into flexible 3D glass microfluidic channels. The high quality of microchips was ensured by quantitatively investigating the experimental processes containing “line‐to‐line” scanning mode, improved annealing temperature (645°C), increased prebaking time (18 h for 1mm‐length channel), optimal laser power (1.9 times larger than that on the surface) and longer developing time (6 times larger). The ship‐in‐a‐bottle biochips show high capabilities to provide simultaneous filtering and mixing with 87% efficiency in a shorter distance and on‐chip synthesis of ZnO microflower particles.     

Facile Synthesis of Gd(OH)3‐Doped Fe3O4 Nanoparticles for Dual‐Mode T1‐ and T2‐Weighted Magnetic Resonance Imaging Applications

The facile hydrothermal synthesis of polyethyleneimine (PEI)‐coated iron oxide (Fe₃O₄) nanoparticles (NPs) doped with Gd(OH)₃ (Fe₃O₄‐Gd(OH)₃‐PEI NPs) for dual mode T₁‐ and T₂‐weighted magnetic resonance (MR) imaging applications is reported. In this approach, Fe₃O₄‐Gd(OH)₃‐PEI NPs are synthesized via a hydrothermal method in the presence of branched PEI and Gd(III) ions. The PEI coating onto the particle surfaces enables further modification of poly(ethylene glycol) (PEG) in order to render the particles with good water dispersibility and improved biocompatibility. The formed Fe₃O₄‐Gd(OH)₃‐PEI‐PEG NPs have a Gd/Fe molar ratio of 0.25:1 and a mean particle size of 14.4 nm and display a relatively high r₂ (151.37 × 10^?3m ^?1 s^?1) and r₁ (5.63 × 10^?3m ^?1 s^?1) relaxivity, affording their uses as a unique contrast agent for T₁‐ and T₂‐weighted MR imaging of rat livers after mesenteric vein injection of the particles and the mouse liver after intravenous injection of the particles, respectively. The developed Fe₃O₄‐Gd(OH)₃‐PEI‐PEG NPs may hold great promise to be used as a contrast agent for dual mode T₁‐ and T₂‐weighted self‐confirmation MR imaging of different biological systems.     

Density functional theory study of the bis‐3‐benzo‐crown ethers and their complexes with alkali metal cations Na+, K+, Rb+ and Cs+

The binding interactions of bis‐3‐benzo‐15‐crown‐5 ethers and bis‐3‐benzo‐18‐crown‐6 ethers (neutral hosts) with a series of alkali metal cations Na⁺, K⁺, Rb⁺ and Cs⁺ (charged guests) were investigated using quantum chemical density functional theory. Different optimized structures, binding energies and various thermodynamic parameters of free crown ethers and their metal cation complexes were obtained based on the Becke, three‐parameter, Lee–Yang–Parr functional using mixed basis set (C, H, O, Na⁺ and K⁺ using 6‐31 g, and the heavier cation Rb⁺ and Cs⁺ using effective core potentials). Natural bond orbital analysis is conducted on the optimized geometric structures. The main types of driving force host–guest interactions are investigated. The electron donating O offers a lone pair of electrons to the contacting LP* (1‐center valence antibond lone pair) orbitals of metal cations. The bis‐3‐benzocrown ethers are assumed to have sandwich‐like conformations, considering the binding energies to gauge the exact interactions with alkali cations. It is found that there are two different types of complexes: one is a tight ion pair and the other is a separated ion pair. Copyright © 2011 John Wiley & Sons, Ltd.     

Nitrogen‐Doped Carbon with Mesopore Confinement Efficiently Enhances the Tolerance,Sensitivity, and Stability of a Pt Catalyst for the Oxygen Reduction Reaction

Electrocatalysts for the oxygen reduction reaction (ORR) present some of the most challenging vulnerability issues reducing ORR performance and shortening their practical lifetime. Fuel crossover resistance, selective activity, and catalytic stability of ORR catalysts are still to be addressed. Here, a facile and in situ template‐free synthesis of Pt‐containing mesoporous nitrogen‐doped carbon composites (Pt‐m‐N‐C) is designed and specifically developed to overcome its drawback as an electrocatalyst for ORR, while its high activity is sustained. The as‐prepared Pt‐m‐N‐C catalyst exhibits high electrocatalytic activity, dominant four‐electron oxygen reduction pathway, superior stability, fuel crossover resistance, and selective activity to a commercial Pt/C catalyst in 0.1 m KOH aqueous solution. Such excellent performance benefits from in situ covalent incorporation of Pt nanoparticles with optimal size into N‐doped carbon support, dense active catalytic sites on surface, excellent electrical contacts between the catalytic sites and the electron‐conducting host, and a favorable mesoporous structure for the stabilization of the Pt nanoparticles by pore confinement and diffusion of oxygen molecules.     

Characterisation of carbonaceous materials using Raman spectroscopy: a comparison of carbon nanotube filters,single‐ and multi‐walled nanotubes,graphitised porous carbon and graphite

Multi‐walled carbon nanotube (MWCNT) filters have been recently synthesised which have specific molecular filtering capabilities and good mechanical strength. Optical and scanning electron microscopy (SEM) reveals the formation of highly aligned arrays of bundles of carbon nanotubes having lengths up to 500 µm. The Raman spectra of this material along with four other carbonaceous materials, commercially available single‐walled carbon nanotubes (SWCNTs) and MWCNTs, graphitised porous carbon (Carbotrap) and graphite have been recorded using two‐excitation wavelengths, 532 and 785 nm, and analysed for band positions and shape with special emphasis paid to the D‐, G‐ and G′‐bands. A major difference between the different MWCNT varieties analysed is that G‐bands in the MWCNT filters exhibit almost no dispersion, whereas the other MWCNTs show a noticeable dispersive behaviour with a change in the excitation wavelength. Spectral features similar to those of the MWCNT filter varieties were observed for the Carbotrap material. From the line shape analysis, the intensity ratio, I_D/I_G, of the more ordered MWCNT filter material using the integral G‐band turns out to be two times lower than that of the less ordered MWCNT filter product at both excitation wavelengths. This parameter can, therefore, be used as a measure of the degree of MWCNT alignment in filter varieties, which is well supported also by our SEM study. Copyright © 2008 John Wiley & Sons, Ltd.