Curvature induced L-defects in water conduction in carbon nanotubes

We conduct molecular dynamics simulations to study the effect of the curvature induced static dipole moment of small open-ended single-walled carbon nanotubes (CNTs) immersed in water. This dipole moment generates a nonuniform electric field, changing the energy landscape in the CNT and altering the water conduction process. The CNT remains practically filled with water at all times, whereas intermittent filling is observed when the dipole term is not included. In addition, the dipole moment induces a preferential orientation of the water molecules near the end regions of the nanotube, which in turn causes a reorientation of the water chain in the middle of the nanotube. The most prominent feature of this reorientation is an L-defect in the chain of water molecules inside the CNT. The analysis of the water energetics and structural characteristics inside and in the vicinity of the CNT helps to identify the role of the dipole moment and to suggest possible mechanisms for controlled water and proton transport at the nanoscale.     

N‐Type Superconductivity in an Organic Mott Insulator Induced by Light‐Driven Electron‐Doping

The presence of interface dipoles in self‐assembled monolayers (SAMs) gives rise to electric‐field effects at the device interfaces. SAMs of spiropyran derivatives can be used as photoactive interface dipole layer in field‐effect transistors because the photochromism of spiropyrans involves a large dipole moment switching. Recently, light‐induced p‐type superconductivity in an organic Mott insulator, κ‐(BEDT‐TTF)₂Cu[N(CN)₂]Br (κ‐Br: BEDT‐TTF = bis(ethylenedithio)tetrathiafulvalene) has been realized, thanks to the hole carriers induced by significant interface dipole variation in the spiropyran‐SAM. This report explores the converse situation by designing a new type of spiropyran monolayer in which light‐induced electron‐doping into κ‐Br and accompanying n‐type superconducting transition have been observed. These results open new possibilities for novel electronics utilizing a photoactive SAMs, which can design not only the magnitude but also the direction of photoinduced electric‐fields at the device interfaces.     

Dendrite‐Free Zinc Deposition Induced by Multifunctional CNT Frameworks for Stable Flexible Zn‐Ion Batteries

The current boom of safe and renewable energy storage systems is driving the recent renaissance of Zn‐ion batteries. However, the notorious tip‐induced dendrite growth on the Zn anode restricts their further application. Herein, the first demonstration of constructing a flexible 3D carbon nanotube (CNT) framework as a Zn plating/stripping scaffold is constituted to achieve a dendrite‐free robust Zn anode. Compared with the pristine deposited Zn electrode, the as‐fabricated Zn/CNT anode affords lower Zn nucleation overpotential and more homogeneously distributed electric field, thus being more favorable for highly reversible Zn plating/stripping with satisfactory Coulombic efficiency rather than the formation of Zn dendrites or other byproducts. As a consequence, a highly flexible symmetric cell based on the Zn/CNT anode presents appreciably low voltage hysteresis (27 mV) and superior cycling stability (200 h) with dendrite‐free morphology at 2 mA cm^?2, accompanied by a high depth of discharge (DOD) of 28%. Such distinct performance overmatches most of recently reported Zn‐based anodes. Additionally, this efficient rechargeability of the Zn/CNT anode also enables a substantially stable Zn//MnO₂ battery with 88.7% capacity retention after 1000 cycles and remarkable mechanical flexibility.     

Dynamic Self‐Assembly of Magnetic/Polymer Composites in Rotating Frames of Reference

Small ferromagnetic particles suspended in a rotating viscous polymer and subjected to an external static magnetic field dynamically self‐assemble into open‐lattice, periodic structures. Depending on the orientation of the magnetic field with respect to the system's axis of rotation, these structures range from arrays of parallel plates to single, double, triple, or even quaternary helices. Dynamic self‐assembly in this rotating frame of reference can be explained by an interplay between magnetic, dipole–dipole, viscous drag, and centripetal forces. Once formed, the dynamic aggregates can be made permanent by thermally curing the polymer matrix.     

A coupled mechanical‐charge/dipole molecular dynamics finite element method,with multi‐scale applications to the design of graphene nano‐devices

A new Molecular Dynamics Finite Element Method (MDFEM) with a coupled mechanical‐charge/dipole formulation is proposed. The equilibrium equations of Molecular Dynamics (MD) are embedded exactly within the computationally more favourable Finite Element Method (FEM). This MDFEM can readily implement any force field because the constitutive relations are explicitly uncoupled from the corresponding geometric element topologies. This formal uncoupling allows to differentiate between chemical‐constitutive, geometric and mixed‐mode instabilities. Different force fields, including bond‐order reactive and polarisable fluctuating charge–dipole potentials, are implemented exactly in both explicit and implicit dynamic commercial finite element code. The implicit formulation allows for larger length and time scales and more varied eigenvalue‐based solution strategies. The proposed multi‐physics and multi‐scale compatible MDFEM is shown to be equivalent to MD, as demonstrated by examples of fracture in carbon nanotubes (CNT), and electric charge distribution in graphene, but at a considerably reduced computational cost. The proposed MDFEM is shown to scale linearly, with concurrent continuum FEM multi‐scale couplings allowing for further computational savings. Moreover, novel conformational analyses of pillared graphene structures (PGS) are produced. The proposed model finds potential applications in the parametric topology and numerical design studies of nano‐structures for desired electro‐mechanical properties (e.g. stiffness, toughness and electric field induced vibrational/electron‐emission properties). Copyright © 2014 John Wiley & Sons, Ltd.     

A Fluid Liquid‐Crystal Material with Highly Polar Order

An anomalously large dielectric permittivity of ≈10⁴ is found in the mesophase temperature range (MP phase) wherein high fluidity is observed for a liquid‐crystal compound having a 1,3‐dioxane unit in the mesogenic core (DIO). In this temperature range, no sharp X‐ray diffraction peak is observed at both small and wide Bragg angles, similar to that for a nematic phase; however, an inhomogeneous sandy texture or broken Schlieren one is observed via polarizing optical microscopy, unlike that for a conventional nematic phase. DIO exhibits polarization switching with a large polarization value, i.e., P = 4.4 µC cm^?2, and a parallelogram‐shaped polarization–electric field hysteresis loop in the MP phase. The inhomogeneously aligned DIO in the absence of an electric field adopts a uniform orientation along an applied electric field when field‐induced polarization switching occurs. Furthermore, sufficiently larger second‐harmonic generation is observed for DIO in the MP phase. Second‐harmonic‐generation interferometry clearly shows that the sense of polarization is inverted when the +/? sign of the applied electric field in MP is reversed. These results suggest that a unidirectional, ferroelectric‐like parallel polar arrangement of the molecules is generated along the director in the MP phase.     

A Silicon Nanowire as a Spectrally Tunable Light‐Driven Nanomotor

Over the last decades, scientists have endeavored to develop nanoscopic machines and envisioned that these tiny machines could be exploited in biomedical applications and novel material fabrication. Here, a visible‐/near‐infrared light‐driven nanomotor based on a single silicon nanowire is reported. The silicon nanomotor harvests energy from light and propels itself by the self‐electrophoresis mechanism. Due to the high efficiency, the silicon nanowire can be readily driven by visible and near‐infrared illumination at ultralow light intensity (≈3 mW cm^?2). The experimental study and numerical simulation also show that the detailed structure around the concentrated reaction center determines the migration behavior of the nanomotor. Importantly, due to the optical resonance inside the silicon nanowire, the spectral response of the nanowire‐based nanomotor can be readily modulated by the nanowire's diameter. Compared to other methods, light controlling potentially offers more freedom and flexibility, as light can be modulated not only with its intensity and direction, but also with the frequency and polarities. This nanowire motor demonstrates a step forward to harness the advantages of light, which opens up new opportunities for the realization of many novel functions such as multiple channels communication to nanorobots and controllable self‐assembly.     

Bimetal‐Organic‐Framework Derivation of Ball‐Cactus‐Like Ni‐Sn‐P@C‐CNT as Long‐Cycle Anode for Lithium Ion Battery

Metal phosphides are a new class of potential high‐capacity anodes for lithium ion batteries, but their short cycle life is the critical problem to hinder its practical application. A unique ball‐cactus‐like microsphere of carbon coated NiP₂/Ni₃Sn₄ with deep‐rooted carbon nanotubes (Ni‐Sn‐P@C‐CNT) is demonstrated in this work to solve this problem. Bimetal‐organic‐frameworks (BMOFs, Ni‐Sn‐BTC, BTC refers to 1,3,5‐benzenetricarboxylic acid) are formed by a two‐step uniform microwave‐assisted irradiation approach and used as the precursor to grow Ni‐Sn@C‐CNT, Ni‐Sn‐P@C‐CNT, yolk–shell Ni‐Sn@C, and Ni‐Sn‐P@C. The uniform carbon overlayer is formed by the decomposition of organic ligands from MOFs and small CNTs are deeply rooted in Ni‐Sn‐P@C microsphere due to the in situ catalysis effect of Ni‐Sn. Among these potential anode materials, the Ni‐Sn‐P@C‐CNT is found to be a promising anode with best electrochemical properties. It exhibits a large reversible capacity of 704 mA h g^?1 after 200 cycles at 100 mA g^?1 and excellent high‐rate cycling performance (a stable capacity of 504 mA h g^?1 retained after 800 cycles at 1 A g^?1). These good electrochemical properties are mainly ascribed to the unique 3D mesoporous structure design along with dual active components showing synergistic electrochemical activity within different voltage windows.     

Ultra‐High Optical Absorption Efficiency from the Ultraviolet to the Infrared Using Multi‐Walled Carbon Nanotube Ensembles

The optical absorption efficiencies of vertically aligned multi‐walled (MW)‐carbon nanotube (CNT) ensembles are characterized in the 350?7000 nm wavelength range where CNT site densities > 1 × 10¹¹/cm² are achieved directly on metallic substrates. The site density directly impacts the optical absorption characteristics, and while high‐density arrays of CNTs on electrically insulating and non‐metallic substrates have been commonly reported, achieving high site‐densities on metals has been challenging and remains an area of active research. These absorber ensembles are ultra‐thin (<10 μm) and yet they still exhibit a reflectance as low as ～0.02%, which is 100 times lower than the reference; these characteristics make them potentially attractive for high‐sensitivity and high‐speed thermal detectors. In addition, the use of a plasma‐enhanced chemical vapor deposition process for the synthesis of the absorbers increases the portfolio of materials that can be integrated with such absorbers due to the potential for reduced synthesis temperatures. The remarkable ruggedness of the absorbers is also demonstrated as they are exposed to high temperatures in an oxidizing ambient environment, making them well‐suited for extreme thermal environments encountered in the field, potentially for solar cell applications. Finally, a phenomenological model enables the determinatiom of the extinction coefficients in these nanostructures and the results compare well with experiment.     

Monodisperse CNT Microspheres for High Permeability and Efficiency Flow‐Through Filtration Applications

Carbon nanotube (CNT)‐based filters have the potential to revolutionize water treatment because of their high capacity and fast kinetics in sorption of organic, inorganic, and biological pollutants. To date, CNT filters either rely on CNTs dispersed in liquids, which are difficult to recover and cause safety concerns, or on CNT buckypaper, which offers high efficiency, but suffers from an intrinsic trade‐off between filter permeability and capacity. Here, a new approach is presented that bypasses this trade‐off and achieves buckypaper‐like efficiency combined with filter‐column‐like permeability and capacity. For this, CNTs are first assembled into porous microspheres and then are packed into microfluidic column filters. These microcolumns exhibit large flow‐through filtration efficiencies, while maintaining membrane permeabilities an order of magnitude larger then CNT buckypaper and specific permeabilities double that of activated carbon for similar flowrates (232 000 L m^?2 h^?1 bar^?1, 1.23 × 10^?12 m²). Moreover, in a test to remove sodium dodecyl sulfate (SDS) from water, these microstructured CNT columns outperform activated carbon columns. This improved filtration efficiency and permeability is an important step toward a broader implementation of CNT‐based filtration devices.     

Aligning Solution‐Derived Carbon Nanotube Film with Full Surface Coverage for High‐Performance Electronics Applications

The main challenge for application of solution‐derived carbon nanotubes (CNTs) in high performance field‐effect transistor (FET) is how to align CNTs into an array with high density and full surface coverage. A directional shrinking transfer method is developed to realize high density aligned array based on randomly orientated CNT network film. Through transferring a solution‐derived CNT network film onto a stretched retractable film followed by a shrinking process, alignment degree and density of CNT film increase with the shrinking multiple. The quadruply shrunk CNT films present well alignment, which is identified by the polarized Raman spectroscopy and electrical transport measurements. Based on the high quality and high density aligned CNT array, the fabricated FETs with channel length of 300 nm present ultrahigh performance including on‐state current I_on of 290 µA µm^?1 (V_ds = ?1.5 V and V_gs = ?2 V) and peak transconductance g_m of 150 µS µm^?1, which are, respectively, among the highest corresponding values in the reported CNT array FETs. High quality and high semiconducting purity CNT arrays with high density and full coverage obtained through this method promote the development of high performance CNT‐based electronics.     

Carbon‐Nanotube–Polymer Nanocomposites for Field‐Emission Cathodes

The electron field‐emission (FE) characteristics of functionalized single‐walled carbon‐nanotube (CNT)–polymer composites produced by solution processing are reported. It is shown that excellent electron emission can be obtained by using as little as 0.7% volume fraction of nanotubes in the composite. Furthermore by tailoring the nanotube concentration and type of polymer, improvements in the charge transfer through the composite can be obtained. The synthesis of well‐dispersed randomly oriented nanotube–polymer composites by solution processing allows the development of CNT‐based large area cathodes produced using a scalable technology. The relative insensitivity of the cathode's FE characteristics to the electrical conductivity of the composite is also discussed.     

Alkali‐Metal‐Intercalated Percolation Network Regulates Self‐Assembled Electronic Aromatic Molecules

In the continuously growing field of correlated electronic molecular crystals, there is significant interest in addressing alkali‐metal‐intercalated aromatic hydrocarbons, in which the possibility of high‐temperature superconductivity emerges. However, searching for superconducting aromatic molecular crystals remains elusive due to their small shielding fraction volume. To exploit this potential, a design principle for percolation networks of technologically important film geometry is indispensable. Here the effect of potassium‐intercalation is shown on the percolation network in self‐assembled aromatic molecular crystals. It is demonstrated that one‐dimensional (1D) dipole pairs, induced by dipole interaction, regulate the conductivity, as well as the electronic and optical transitions, in alkali‐metal‐intercalated molecular electronic crystals. A solid‐solution growth methodology of aromatic molecular films with a broad range of stability is developed to uncover electronic and optical transitions of technological importance. The light‐induced electron interactions enhance the charge‐carrier itinerancy, leading to a switchable metal‐to‐insulator transition. This discovery opens a route for the development of aromatic molecular electronic solids and long‐term modulation of electronic efficacy in nanotechnologically important thin films.     

Nitrogen‐Enriched Carbon/CNT Composites Based on Schiff‐Base Networks: Ultrahigh N Content and Enhanced Lithium Storage Properties

To improve the electrochemical performance of carbonaceous anodes for lithium ion batteries (LIBs), the incorporation of both well‐defined heteroatom species and the controllable 3D porous networks are urgently required. In this work, a novel N‐enriched carbon/carbon nanotube composite (NEC/CNT) through a chemically induced precursor‐controlled pyrolysis approach is developed. Instead of conventional N‐containing sources or precursors, Schiff‐base network (SNW‐1) enables the desirable combination of a 3D polymer with intrinsic microporosity and ultrahigh N‐content, which can significantly promote the fast transport of both Li⁺ and electron. Significantly, the strong interaction between carbon skeleton and nitrogen atoms enables the retention of ultrahigh N‐content up to 21 wt% in the resultant NEC/CNT, which exhibits a super‐high capacity (1050 mAh g^?1) for 1000 cycles and excellent rate performance (500 mAh g^?1 at a current density of 5 A g^?1) as the anode material for LIBs. The NEC/CNT composite affords a new model system as well as a totally different insight for deeply understanding the relationship between chemical structures and lithium ion storage properties, in which chemistry may play a more important role than previously expected.     

Field-dipole orientation mechanism and higher order modes in atom guides

Abstract

In cavity quantum electrodynamics (CQED), cavity size, dipole position and dipole orientation are the main factors controlling cavity effects, for example, suppression and enhancement of spontaneous emission. However, the dynamical effects of dipole orientation in CQED have, to date, remained largely unexplored, with most treatments simply concentrating on two (or three) orthogonal directions to illustrate the variations of CQED effects with dipole orientation. No mechanism which determines the evolution of the dipole orientation has been put forward to describe typical situations where atoms move in the field of an excited cavity mode. We emphasize here that in the presence of a cavity mode, the average dipole orientation is automatically determined at every point to be parallel to the direction of the electric field vector of the cavity mode. Besides giving rise to a single value for the spontaneous emission rate, this mechanism is shown to have important consequences for the dynamics of atoms in atom guides. In particular, it determines the average trapping potential distributions and the average radiation forces which guide the atoms along a cylindrical cavity. The effects of the field-dipole orientation mechanism are illustrated with reference to typical situations involving sodium atoms in sub-micron cylindrical guides. The role of a higher order cavity mode of the cylinder in the dynamics is highlighted in terms of its influence on the rotational and vibrational motions in such guides.     

Variational‐based modeling of micro‐electro‐elasticity with electric field‐driven and stress‐driven domain evolutions

Recently, increasing interest in so‐called functional or smart materials with electromechanical coupling has been shown such as ferroelectric piezoceramics. These materials are characterized by microstructural properties, which can be changed by external stress and electric field stimuli, and hence find use as the active components in sensors and actuators. The electromechanical coupling effects result from the existence and rearrangement of microstructural domains with uniformly oriented electric polarization. The understanding and efficient simulation of these highly nonlinear and dissipative mechanisms, which occur on the microscale of ferroelectric piezoceramics, are a key challenge of the current research. This paper does not offer a substantially new physical model of these phenomena but a new mathematical modeling approach based on a rigorous exploitation of rate‐type variational principles. This provides a new insight in the structure of the coupled problem, where the governing field equations appear as the Euler equations of a variational statement. We outline a variational‐based micro‐electro‐elastic model for the microstructural evolution of both electrically and mechanically driven electric domains in ferroelectric ceramics, which also incorporates the surrounding free space. To this end, we extend recently developed multifield incremental variational principles of electromechanics from local to gradient‐extended dissipative response and specialize it by a Ginzburg–Landau‐type phase field model, where the thickness of the domain walls enters the formulation as a length scale. This serves as a natural starting point for a canonical compact, symmetric finite element implementation, considering the mechanical displacement, the microscopic polarization, and the electric potential induced by the polarization as the primary fields. The latter is defined on both the solid domain and a surrounding free space. Numerical simulations treat domain wall motions for electric field‐driven and stress‐driven loading processes, including the expansion of the electric potential into the free space. Copyright © 2012 John Wiley & Sons, Ltd.     

Hyperporous Sponge Interconnected by Hierarchical Carbon Nanotubes as a High‐Performance Potassium‐Ion Battery Anode

Recently, commercial graphite and other carbon‐based materials have shown promising properties as the anode for potassium‐ion batteries. A fundamental problem related to those carbon electrodes, significant volume expansion, and structural instability/collapsing caused by cyclic K‐ion intercalation, remains unsolved and severely limits further development and applications of K‐ion batteries. Here, a multiwalled hierarchical carbon nanotube (HCNT) is reported to address the issue, and a reversible specific capacity of 232 mAh g^?1, excellent rate capability, and cycling stability for 500 cycles are achieved. The key structure of the HCNTs consists of an inner CNT with dense‐stacked graphitic walls and a loose‐stacked outer CNT with more disordered walls, and individual HCNTs are further interconnected into a hyperporous bulk sponge with huge macropore volume, high conductivity, and tunable modulus. It is discovered that the inner dense‐CNT serves as a robust skeleton, and collectively, the outer loose‐CNT is beneficial for K‐ion accommodation; meanwhile the hyperporous sponge facilitates reaction kinetics and offers stable surface capacitive behavior. The hierarchical carbon nanotube structure has great potential in developing high‐performance and stable‐structure electrodes for next generation K and other metal‐ion batteries.     

A Facile One‐Step Approach for Constructing Multidimensional Ordered Nanowire Micropatterns via Fibrous Elastocapillary Coalescence

Nanowire (NW) based micropatterns have attracted research interests for their applications in electric microdevices. Particularly, aligning NWs represents an important process due to the as‐generated integrated physicochemical advantages. Here, a facile and general strategy is developed to align NWs using fibrous elastocapillary coalescence of carbon nanotube arrays (ACNTs), which enables constructing multidimensional ordered NW micropatterns in one step without any external energy input. It is proposed that the liquid film of NW solution is capable of shrinking unidirectionally on the top of ACNTs, driven by the dewetting‐induced elastocapillary coalescence of the ACNTs. Consequently, the randomly distributed NWs individually rotate and move into dense alignment. Meanwhile, the aggregating and bundling of ACNTs is helpful to produce carbon nanotube (CNT) yarns connecting neighboring bundles. Thus, a micropatterned NW network composed of a top‐layer of horizontally aligned NWs and an under‐layer of vertical ACNT bundles connected by CNT yarns is prepared, showing excellent performance in sensing external pressure with a sensitivity of 0.32 kPa^?1. Moreover, the aligned NWs can be transferred onto various substrates for constructing electronic circuits. The strategy is applicable for aligning various NWs of Ag, ZnO, Al₂O₃, and even living microbes. The result may offer new inspiration for fabricating NW‐based functional micropatterns.     

Meshfree co‐rotational formulation for two‐dimensional continua

In this paper, a meshfree co‐rotational formulation for two‐dimensional continua is proposed. In a co‐rotational formulation, the motion of a body is separated into rigid motion and strain‐producing deformation. Traditionally, this has been done in the setting of finite elements for beams and shell‐type elements. In the present work every node in a meshfree discretized domain has its own co‐rotating coordinate system. Three key ingredients are established in order to apply the co‐rotational formulation: (i) the relationship between global and local variables, (ii) the angle of rotation of a typical co‐rotating coordinate system, and (iii) a variationally consistent tangent stiffness matrix. An algorithm for the co‐rotational formulation based on load control is provided. Maximum‐entropy basis functions are used to discretize the domain and stabilized nodal integration is implemented to construct the global system of equations. Numerical examples are presented to demonstrate the validity of the meshfree co‐rotational formulation. Copyright © 2009 John Wiley & Sons, Ltd.     

Nanomanufacturing of RGO‐CNT Hybrid Film for Flexible Aqueous Al‐Ion Batteries

A highly electrically conductive film‐type current collector is an essential part of batteries. Apart from the metal‐based current collectors, lightweight and highly conductive carbon materials such as reduced graphene oxide (RGO) and carbon nanotubes (CNTs) show great potential as current collectors. However, traditional RGO manufacturing usually requires a long time and high energy, which decreases the product yielding rate and manufacturing efficiency. Moreover, the performance of the manufactured RGO needs to be further improved. In this work, CNT and GO are evenly mixed into GO‐CNT, which can be directly reduced into RGO‐CNT by Joule heating at 2936 K within less than 1 min. The fabricated RGO‐CNT achieves a high electrical conductivity of 2750 S cm^?1, and realizes a 10⁶‐fold increase. The assembled flexible aqueous Al‐ion battery with RGO‐CNT as the current collector exhibits impressive electrochemical performance in terms of superior cycling stability and exceptional rate capability, and excellent mechanical ability regarding the tolerance to mechanical damage such as bending, folding, piercing, and cutting without detrimental consequences.