Toward Self-Powered Sensing and Thermal Energy Harvesting in High-Performance Composites via Self-Folded Carbon Nanotube Honeycomb Structures.

The development of high-performance self-powered sensors in advanced composites addresses the increasing demands of various fields such as aerospace, wearable electronics, healthcare devices, and the Internet-of-Things. Among different energy sources, the thermoelectric (TE) effect which converts ambient temperature gradients to electric energy is of particular interest. However, challenges remain on how to increase the power output as well as how to harvest thermal energy at the out-of-plane direction in high-performance fiber-reinforced composite laminates, greatly limiting the pace of advance in this evolving field. Herein, we utilize a temperature-induced self-folding process together with continuous carbon nanotube veils to overcome these two challenges simultaneously, achieving a high TE output (21 mV and 812 nW at a temperature difference of 17 °C only) in structural composites with the capability to harvest the thermal energy from out-of-plane direction. Real-time self-powered deformation and damage sensing is achieved in fabricated composite laminates based on a thermal gradient of 17 °C only, without the need of any external power supply, opening up new areas of autonomous self-powered sensing in high-performance applications based on TE materials.

Enhancing the Interfacial Shear Strength and Tensile Strength of Carbon Fibers through Chemical Grafting of Chitosan and Carbon Nanotubes.

Multi-scale "rigid-soft" material coating has been an effective strategy for enhancing the interfacial shear strength (IFSS) of carbon fibers (CFs), which is one of the key themes in composite research. In this study, a soft material, chitosan (CS), and a rigid material, carbon nanotubes (CNTs), were sequentially grafted onto the CFs surface by a two-step amination reaction. The construction of the "rigid-soft" structure significantly increased the roughness and activity of the CFs surface, which improved the mechanical interlocking and chemical bonding between the CFs and resin. The interfacial shear strength (IFSS) of the CS- and CNT-modified CFs composites increased by 186.9% to 123.65 MPa compared to the desized fibers. In addition, the tensile strength of the modified CFs was also enhanced by 26.79% after coating with CS and CNTs. This strategy of establishing a "rigid-soft" gradient modulus interfacial layer with simple and non-destructive operation provides a valuable reference for obtaining high-performance CFs composites.

Ultrathin Two-Dimensional Metal-Organic Framework Nanosheets with Activated Ligand-Cluster Units for Enhanced SERS.

Ultrathin two-dimensional (2D) metal-organic framework (MOF) nanosheets (MOFNs) comprise an emerging family of attractive materials with excellent potential for use in different catalytic, electrochemical, and sensing applications owing to their striking features such as ultrathin thickness, a large surface area, and highly ordered network structures. However, to the best of our knowledge, the ligand-cluster units activated through exfoliation into the MOFNs have rarely been realized, which is indeed crucial for surface-enhanced Raman scattering (SERS) analysis. Herein, we emphasize that the activated ligand-cluster units are based on the accessible coordination sites at the exposed cluster nodes accompanied by a complete excitation of the ligand-cluster units under incident photons, which make MOFNs highly effective SERS substrates, significantly outperforming their bulk counterparts. The SERS enhancement of MOFNs is further illustrated by an efficient integration of the inherent ligand-cluster charge-transfer (LCCT) transitions in MOFNs into interfacial charge-transfer processes through an "L"-type charge-transfer (CT) pathway, as further evidenced by an ultrahigh degree (0.98) of CT contributed to the SERS enhancement. This study provides an efficient strategy of exfoliating MOFs into ultrathin nanosheets for the design of highly efficient MOF-based SERS substrates.

Silica Aerogels with Self-Reinforced Microstructure for Bioinspired Hydrogels.

Aerogel is a kind of high-performance lightweight open-porous solids with ultralow density, high specific surface area, and broad application in many emerging fields including biotechnology, energy, environment, aerospace, etc. A giant challenge remains in preventing of the hydrophilic aerogel framework shrinkage when replacing of solvent with air in its extremely abundant nanosized pores during its fabrication process in ambient conditions. In this work, started from a linear polymeric precursor with further condensation reaction, superhydrophilic silica aerogels with self-reinforced microstructure and the least volume shrinkage have been successfully obtained via ambient pressure drying process without use of any additives in the presence of a low surface tension solvent. The resulting superhydrophilic silica aerogels possess specific surface area up to 1065 m2/g, pore volume up to 2.17 cm3/g and density down to 84 mg/cm3, and these values are comparable to those of their counterparts obtained by supercritical CO2 drying process. Moreover, as an application demonstration, the bioinspired hydrogels with desirable mechanical flexibility and adhesive performance at extremely harsh environment (e.g., below -50 °C) have been successfully synthesized by mimicking carrier of a functional bioagent with the resulting superhydrophilic silica aerogel microparticles. Our work has made a significant step forward for future high-performance hydrophilic aerogels with self-enhanced microstructures and the resulting superhydrophilic aerogels have shown great potentials in making functional hydrogels with bionic properties.

Mass Formation of α-Cyclodextrin Hexagonal Rods by the Direct Solvent Evaporation Strategy.

The self-assembly of cyclodextrins (CDs) with various guest polymers and small molecules has been intensively investigated for several decades, and it has still increasingly attracted wide attention to construct well-defined microstructures for the uses in biomedicine, sensors, environments, and nanorobotics. While most of the self-assembly of CDs involves the presence of guests, we recently discovered that α-CDs and γ-CDs could be self-assembled between themselves without the incorporation of any guests simply by elevating the temperature of their N,N-dimethylformamide (DMF) solution. In this work, we further found that α-CDs could self-assemble or reorganize in DMF into hexagonal rods simply by directly drying out the α-CD DMF solution. The α-CDs were self-assembled in the guest-free solution triggered by solvent evaporation. The X-ray powder diffraction results confirmed that they possessed a columnar structure, combined with the absence of guests in the strategy, and the cavities of CDs were not filled with guest molecules, but some water molecules may exist. The rods could be formed in various concentrations from 0.001 to 0.08 g/mL with drying temperatures ranging from 80 to 140 °C. The finding of this work shows the exceptional possibility of CDs to form well-defined microstructures without the engagement of guest molecules.

Metal-free synthesis of phosphinoylchroman-4-ones via a radical phosphinoylation-cyclization cascade mediated by K2S2O8.

A variety of chroman-4-ones bearing phosphine oxide motifs were conveniently synthesized from readily available diphenylphosphine oxides and alkenyl aldehydes via a metal-free tandem phosphinoylation/cyclization protocol. The reaction utilizes K2S2O8 as oxidant and proceeds in DMSO/H2O at environmentally benign conditions with a broad substrate scope and afforded the title compounds in moderate yields.

Rational and wide-range tuning of CNT aerogel conductors with multifunctionalities.

Different from conventional conductors, elastic 3D nanoarchitectured conductors have shown promise in developing various flexible devices. However, rational design and control of their microstructures to achieve desired physicochemical properties is challenging and lacks comprehensive and profound investigation. In this study, we report an interesting quantitative correlation between density and physical properties when highly porous CNT aerogels are densified, enabling a wide-range tuning of CNT 3D networked structures with different functions. Upon densification by compressing the original thickness of a CNT aerogel by 100 fold, a linear double-logarithmic structure-property relationship in terms of both thickness and density is witnessed, with the resultant density increased by a factor of 100 from 3 to 286 mg cm-3, Young's modulus by 20 times (5.0-105 kPa), electrical conductivity by 400 times (0.4-163 s cm-1), and thermal conductivity by 140 times (0.048-6.7 W m-1 K-1). It can be thus inferred that the CNT aerogel can be regulated with desired mechanical, electrical and thermal properties in a quantitative manner over a wide range, making it promising as a multifunctional aerogel conductor. As a proof, two pieces of CNT aerogel conductors tailored with high conductivity and low thermal conductivity are employed to fabricate a flexible TE device using a simple all-carbon design, which yields a typical power density of 27.5 µW cm-2 and stable outputs under various deformations, demonstrating a potential strategy for design and fabrication of low-cost, flexible and portable power-generation devices.

Understanding the Mechanical and Conductive Properties of Carbon Nanotube Fibers for Smart Electronics.

The development of fiber-based smart electronics has provoked increasing demand for high-performance and multifunctional fiber materials. Carbon nanotube (CNT) fibers, the 1D macroassembly of CNTs, have extensively been utilized to construct wearable electronics due to their unique integration of high porosity/surface area, desirable mechanical/physical properties, and extraordinary structural flexibility, as well as their novel corrosion/oxidation resistivity. To take full advantage of CNT fibers, it is essential to understand their mechanical and conductive properties. Herein, the recent progress regarding the intrinsic structure-property relationship of CNT fibers, as well as the strategies of enhancing their mechanical and conductive properties are briefly summarized, providing helpful guidance for scouting ideally structured CNT fibers for specific flexible electronic applications.

Multifunctional Aramid Nanofiber/Carbon Nanotube Hybrid Aerogel Films.

Lightweight, robust, and thin aerogel films with multifunctionality are highly desirable to meet the technological demands of current society. However, fabrication and application of these multifunctional aerogel films are still significantly underdeveloped. Herein, we demonstrate a multifunctional aerogel film composed of strong aramid nanofibers (ANFs), conductive carbon nanotubes (CNTs), and hydrophobic fluorocarbon (FC) resin. The obtained hybrid aerogel film exhibits large specific surface area (232.8 m2·g-1), high electrical conductivity (230 S·m-1), and excellent hydrophobicity (contact angle of up to 137.0°) with exceptional Joule heating performance and supreme electromagnetic interference (EMI) shielding efficiency. The FC coating renders the hydrophilic ANF/CNT aerogel films hydrophobic, resulting in an excellent self-cleaning performance. The high electrical conductivity enables a low-voltage-driven Joule heating property and an EMI shielding effectiveness (SE) of 54.4 dB in the X-band at a thickness of 568 µm. The specific EMI SE is up to 33528.3 dB·cm2·g-1, which is among the highest values of typical metal-, conducting-polymer-, or carbon-based composites. This multifunctional aerogel film holds great promise for smart garments, electromagnetic wave shielding, and personal thermal management systems.

Electrochromic semiconductors as colorimetric SERS substrates with high reproducibility and renewability.

Electrochromic technology has been actively researched for displays, adjustable mirrors, smart windows, and other cutting-edge applications. However, it has never been proposed to overcome the critical problems in the field of surface-enhanced Raman scattering (SERS). Herein, we demonstrate a generic electrochromic strategy for ensuring the reproducibility and renewability of SERS substrates, which are both scientifically and technically important due to the great need for quantitative analysis, standardized production and low cost in SERS. This color-changing strategy is based on a unique quantitative relationship between the SERS signal amplification and the coloration degree within a certain range, in which the SERS activity of the substrate can be effectively inferred by judging the degree of color change. Our results may provide a first step toward the rational design of electrochromic SERS substrates with a high sensitivity, reproducibility, and renewability.

Erratum: 3D Printing Fiber Electrodes for an All-Fiber Integrated Electronic Device via Hybridization of an Asymmetric Supercapacitor and a Temperature Sensor.

[This corrects the article DOI: 10.1002/advs.201801114.].

3D Printing Fiber Electrodes for an All-Fiber Integrated Electronic Device via Hybridization of an Asymmetric Supercapacitor and a Temperature Sensor.

Wearable fiber-shaped electronic devices have drawn abundant attention in scientific research fields, and tremendous efforts are dedicated to the development of various fiber-shaped devices that possess sufficient flexibility. However, most studies suffer from persistent limitations in fabrication cost, efficiency, the preparation procedure, and scalability that impede their practical application in flexible and wearable fields. In this study, a simple, low-cost 3D printing method capable of high manufacturing efficiency, scalability, and complexity capability to fabricate a fiber-shaped integrated device that combines printed fiber-shaped temperature sensors (FTSs) with printed fiber-shaped asymmetric supercapacitors (FASCs) is developed. The FASCs device can provide stable output power to FTSs. Moreover, the temperature responsivity of the integrated device is 1.95% °C-1.

Growth of boron nitride nanotubes from magnesium diboride catalysts.

The difficulty in synthesizing boron nitride nanotubes (BNNTs) in a conventional horizontal tube furnace by chemical vapor deposition (CVD) may be ascribed to the failure to identify suitable catalysts and nucleation particles. This report demonstrates that magnesium diboride (MgB2) can effectively catalyze the growth of BNNTs in such a tube furnace from various boron sources, including boron oxide (B2O3), boric acid (H3BO3), and a mixture of boron (B) and calcium oxide (CaO). This catalyst is more efficient than the possible magnesium oxide (MgO) or magnesium nitride (Mg3N2) catalysts. MgB2 efficiently catalyzes the formation of BNNTs by maintaining a liquid state and showing a dissolving capacity for B2O3 at the growth temperature, thus satisfying the criteria for the vapor-liquid-solid (VLS) mechanisms of one-dimensional nanomaterials. First-principles simulations demonstrate that B2O3 can be dissolved into the MgB2 nanoparticle. We believe that the strong catalytic behavior of MgB2 can be attributed to its robust nucleation for BNNTs and dissolubility for B2O3.

Ammonium-tungstate-promoted growth of boron nitride nanotubes.

Ammonium tungstate ((NH4)10W12O41 · xH2O) is a kind of oxygen-containing ammonium salt. The following study proves that it can be successfully used as a metal oxide alternative to produce boron oxide (B2O2) by oxidizing boron (B) in a traditional boron oxide chemical vapor deposition (BOCVD) process. This special oxidant promotes the simplistic fabrication of boron nitride nanotubes (BNNTs) in a conventional horizontal tube furnace, an outcome which may have resulted from its strong oxidizability. The experimental results demonstrate that the mole ratio of B and (NH4)10W12O41 · xH2O is a key parameter in determining the formation, quality and quantity of BNNTs when stainless steel is employed as a catalyst. We also found that Mg(NO3)2 and MgO nanoparticles (NPs) can be used as catalysts to grow BNNTs with the same precursor. The BNNTs obtained from the Mg(NO3)2 catalyst were straighter than those obtained from the MgO NP catalyst. This could have been due to the different physical forms of the catalysts that were used.

Polyaniline-stabilized electromagnetic wave absorption composites of reduced graphene oxide on magnetic carbon nanotube film.

A multi-layered composite with exceptionally high electromagnetic wave-absorbing capacity and performance stability was fabricated via the facile electrophoresis of a reduced graphene oxide network on carbon nanotube (CNT)-Fe3O4-polyaniline (PANI) film. Minimum reflection loss (RL) of -53.2 dB and absorbing bandwidth of 5.87 GHz (< -10 dB) are achieved, surpassing most recently reported CNT- and graphene-based absorbers. In particular, comparing to the original composites, the minimum RL and bandwidth (< -10 dB) maintains 82.5% and 99.7%, respectively, after 20 h charge/discharge cycling, demonstrating high environmental suitability.

Active Manipulation of NIR Plasmonics: the Case of Cu2-xSe through Electrochemistry.

Active control of nanocrystal optical and electrical properties is crucial for many of their applications. By electrochemical (de)lithiation of Cu2-xSe, a highly doped semiconductor, dynamic and reversible manipulation of its NIR plasmonics has been achieved. Spectroelectrochemistry results show that NIR plasmon red-shifted and reduced in intensity during lithiation, which can be reversed with perfect on-off switching over 100 cycles. Electrochemical impedance spectroscopy reveals that a Faradaic redox process during Cu2-xSe (de)lithiation is responsible for the optical modulation, rather than simple capacitive charging. XPS analysis identifies a reversible change in the redox state of selenide anion but not copper cation, consistent with DFT calculations. Our findings open up new possibilities for dynamical manipulation of vacancy-induced surface plasmon resonances and have important implications for their use in NIR optical switching and functional circuits.

Semiconductor SERS enhancement enabled by oxygen incorporation.

Semiconductor-based surface-enhanced Raman spectroscopy (SERS) substrates represent a new frontier in the field of SERS. However, the application of semiconductor materials as SERS substrates is still seriously impeded by their low SERS enhancement and inferior detection sensitivity, especially for non-metal-oxide semiconductor materials. Herein, we demonstrate a general oxygen incorporation-assisted strategy to magnify the semiconductor substrate-analyte molecule interaction, leading to significant increase in SERS enhancement for non-metal-oxide semiconductor materials. Oxygen incorporation in MoS2 even with trace concentrations can not only increase enhancement factors by up to 100,000-fold compared with oxygen-unincorporated samples but also endow MoS2 with low limit of detection below 10-7 M. Intriguingly, combined with the findings in previous studies, our present results indicate that both oxygen incorporation and extraction processes can result in SERS enhancement, probably due to the enhanced charge-transfer resonance as well as exciton resonance arising from the judicious control of oxygen admission in semiconductor substrate.

Superb electromagnetic wave-absorbing composites based on large-scale graphene and carbon nanotube films.

ABSTARCT: Graphene has sparked extensive research interest for its excellent physical properties and its unique potential for application in absorption of electromagnetic waves. However, the processing of stable large-scale graphene and magnetic particles on a micrometer-thick conductive support is a formidable challenge for achieving high reflection loss and impedance matching between the absorber and free space. Herein, a novel and simple approach for the processing of a CNT film-Fe3O4-large scale graphene composite is studied. The Fe3O4 particles with size in the range of 20-200 nm are uniformly aligned along the axial direction of the CNTs. The composite exhibits exceptionally high wave absorption capacity even at a very low thickness. Minimum reflection loss of -44.7 dB and absorbing bandwidth of 4.7 GHz at -10 dB are achieved in composites with one-layer graphene in six-layer CNT film-Fe3O4 prepared from 0.04 M FeCl3. Microstructural and theoretical studies of the wave-absorbing mechanism reveal a unique Debye dipolar relaxation with an Eddy current effect in the absorbing bandwidth.

Morphology-Controlled Synthesis of Hybrid Nanocrystals via a Selenium-Mediated Strategy with Ligand Shielding Effect: The Case of Dual Plasmonic Au-Cu2-xSe.

Integrating a plasmonic metal and a semiconductor at the nanoscale is of great importance for exploring their optical coupling properties. However, the synthesis and fine structural control of such nanostructures remain challenging. Herein we report the facile aqueous-phase Se-mediated overgrowth of metal selenides onto Au nanocrystals. Taking plasmonic Cu2-xSe as an example, the introduction of a Se template allows deposition of large Cu2-xSe crystalline grains onto Au nanocrystal seeds in various shapes, including spheres, rods, and plates. Moreover, the configuration of Au-Cu2-xSe hybrids can be tuned from core-shell to heterodimer structure by controlling the growth behavior of the Se template. Se overgrowth depends critically on the absorption strength of stabilizers on Au seeds: a strongly absorbing stabilizer inhibits isotropic overgrowth, which is in agreement with molecular dynamics simulations. The resultant Au-Cu2-xSe hybrid nanocrystals possess multiple surface plasmon resonance modes. Finally, our synthetic strategy can be extended to prepare other Au-metal selenide hybrids such as Au-Ag2Se and Au-CdSe with controllable morphologies.

Wrapping Aligned Carbon Nanotube Composite Sheets around Vanadium Nitride Nanowire Arrays for Asymmetric Coaxial Fiber-Shaped Supercapacitors with Ultrahigh Energy Density.

The emergence of fiber-shaped supercapacitors (FSSs) has led to a revolution in portable and wearable electronic devices. However, obtaining high energy density FSSs for practical applications is still a key challenge. This article exhibits a facile and effective approach to directly grow well-aligned three-dimensional vanadium nitride (VN) nanowire arrays (NWAs) on carbon nanotube (CNT) fiber with an ultrahigh specific capacitance of 715 mF/cm2 in a three-electrode system. Benefiting from their intriguing structural features, we successfully fabricated a prototype asymmetric coaxial FSS (ACFSS) with a maximum operating voltage of 1.8 V. From core to shell, this ACFSS consists of a CNT fiber core coated with VN@C NWAs as the negative electrode, Na2SO4 poly(vinyl alcohol) (PVA) as the solid electrolyte, and MnO2/conducting polymer/CNT sheets as the positive electrode. The novel coaxial architecture not only fully enables utilization of the effective surface area and decreases the contact resistance between the two electrodes but also, more importantly, provides a short pathway for the ultrafast transport of axial electrons and ions. The electrochemical results show that the optimized ACFSS exhibits a remarkable specific capacitance of 213.5 mF/cm2 and an exceptional energy density of 96.07 µWh/cm2, the highest areal capacitance and areal energy density yet reported in FSSs. Furthermore, the device possesses excellent flexibility in that its capacitance retention reaches 96.8% after bending 5000 times, which further allows it to be woven into flexible electronic clothes with conventional weaving techniques. Therefore, the asymmetric coaxial architectural design allows new opportunities to fabricate high-performance flexible FSSs for future portable and wearable electronic devices.