Hierarchical and Porous Structures of Carbon Nanotubes-Anchored MOF Derivatives Bridged by Carbon Nanocoils as Lightweight and Broadband Microwave Absorbers.

High-performance microwave absorption (MA) materials have attracted more and more attention because they can effectively prevent microwave radiation and interference from electronic devices. Herein, a new type of MA composite is constructed by introducing carbon nanotubes (CNTs)-anchored metal-organic framework derivatives (MOFDs) into a conductive carbon nanocoil (CNC) network, denoted as CNC/CNT-MOFD. The CNC/MOFD shows a wide effective absorption band of 6.7 GHz under a filling ratio of only 9% in wax-matrix. This is attributed to the hierarchical and porous structures of MOFD bridged by the uniformly dispersed conductive CNC network and the cross-polarization induced by the 3D spiral CNCs. Besides, the as-grown 1D CNTs improve space utilization, porosity, and polarization loss of the composites, resulting in the increase of imaginary permittivity, which further realizes impedance matching and energy attenuation. The Ni nanoparticles in layers of MOFD and at the tips of CNTs generate magnetic loss, promoting the low-frequency absorption ability. Resultantly, RCS values of the optimized composite in all tested theta (θ) ranges are less than -25 dB m2 at 9.5 GHz, effectively reducing the probability of the target detected by the radar.

Boosting Conductive Loss and Magnetic Coupling Based on "Size Modulation Engineering" toward Lower-Frequency Microwave Absorption.

The rational design of absorber size is a promising strategy for obtaining excellent electromagnetic wave (EMW) absorption performance. However, achieving controllable tuning of the material size through simple methods is challenging and the associated EMW attenuation mechanisms are still unclear. In this study, the sizes of metal-organic frameworks (MOFs) are successfully tailored by changing the growth time and the molar ratio of iron (Fe)/organic ligands. The lateral and vertical lengths of MOFs vary in the range of 200 nm to 2 µm and 100 nm to 1 µm, respectively. Both experiments and simulations confirm that the decrease of MOF size favors the formation of more conductive networks, which is beneficial for improving the conductivity loss. Meanwhile, the micromagnetic simulation reveals that the magnetic coupling can be effectively enhanced by the decrease of MOF size, which is conducive to the improvement of magnetic loss, especially in low-frequency range. The reflection loss of Fe-based MOFs with optimized size reaches -46.4 dB at 6.2 GHz with an effective absorption bandwidth of 3.1 GHz. This work illustrates the important role of size effect in EMW dissipation and provides an effective strategy for enhancing the low-frequency EMW absorption performance.

Revealing the linear relationship between electrical, thermal, mechanical and structural properties of carbon nanocoils.

The special helical morphologies and polycrystalline-amorphous internal structures differ carbon nanocoils (CNCs) from carbon nanotubes or carbon nanofibers, but bring difficulties in illuminating the correlations between physical and structural properties. In this paper, we measure the electrical conductivity (σ), thermal diffusivity (α) and Young's modulus (E) of single CNCs at the same time, using a transient electrothermal technique and an electromechanical vibration technique. Based on the statistical results of 8 single CNC samples, a linear correlation between the three parameters is uncovered, expressed as σ = 0.052(α - 2.5) × 104 S m-1, E = (-10.38σ + 14.04) GPa and E = (-0.59α + 16.08) GPa, where the unit of α is 10-7 m2 s-1. Concise proportional relations between the three parameters and average graphite grain size (ld) are deduced, expressed as σ = Ald(C1 - T)-1, α = Bld(C2 + T)-1 and E = -Dld + E0. The proportional relation between physical parameters and ld demonstrates the confinement originated from the nano-grain system.

Synthesis of a highly efficient 3D graphene-CNT-MnO2-PANI nanocomposite as a binder free electrode material for supercapacitors.

Graphene based nanocomposites have been investigated intensively, as electrode materials for energy storage applications. In the current work, a graphene-CNT-MnO2-PANI (GCM@PANI) nanocomposite has been synthesized on 3D graphene grown on nickel foam, as a highly efficient binder free electrode material for supercapacitors. Interestingly, the specific capacitance of the synthesized electrode increases up to the first 1500 charge-discharge cycles, and is thus referred to as an electrode activation process. The activated GCM@PANI nanocomposite electrode exhibits an extraordinary galvanostatic specific capacitance of 3037 F g-1 at a current density of 8 A g-1. The synthesized nanocomposite exhibits an excellent cyclic stability with a capacitance retention of 83% over 12 000 charge-discharge cycles, and a high rate capability by retaining a specific capacitance of 84.6% at a current density of 20 A g-1. The structural and electrochemical analysis of the synthesized nanocomposite suggests that the astonishing electrochemical performance might be attributed to the growth of a novel PANI nanoparticle layer and the synergistic effect of CNT/MnO2 nanostructures.

Impact of Surface-Bound Small Molecules on the Thermoelectric Property of Self-Assembled Ag2Te Nanocrystal Thin Films.

Small molecules with functional groups can show different electron affinity and binding behavior on nanocrystal surface, which in principle could be used to alternate the electrical transport in self-assembled nanocrystal thin films. These small molecules can also serve for scattering the phonons to reduce the thermal conductivity. Here, we present our research on the thermoelectric characteristic of self-assembled silver telluride (Ag2Te) nanocrystal thin films that are fabricated by a layer-by-layer (LBL) dip-coating process. We perform investigations on the electrical conductivity and Seebeck coefficient on the Ag2Te nanocrystal thin films containing hydrazine, 1,2-ethanedithiol, and ethylenediamine between 300 and 400 K. We also use photothermal (PT) technique to obtain the thermal conductivity of the films at room temperature and estimate the thermoelectric figure of merit (ZT). The experimental results suggest that the surface-bound small molecules could serve as a beneficial component to build nanocrystal-based thermoelectric devices operating at low temperature.

Precise Crystal Orientation Identification and Twist-Induced Giant Modulation of Optical Anisotropy in 1T'-ReS2.

The ability to precisely identify crystal orientation as well as to nondestructively modulate optical anisotropy in atomically thin rhenium dichalcogenides is critical for the future development of polarization programmable optoelectronic devices, which remains challenging. Here, we report a modified polarized optical imaging (POI) method capable of simultaneously identifying in-plane (Re chain) and out-of-plane (c-axis) crystal orientations of the monolayer to few-layer ReS2, meanwhile, propose a nondestructive approach to modulate the optical anisotropy in ReS2 via twist stacking. The results show that parallel and near-cross POI are effective to independently identify the in-plane and out-of-plane crystal orientations, respectively, while regulating the twist angle allows for giant modulation of in-plane optical anisotropy from highly intrinsic anisotropy to complete optical isotropy in the stacked ReS2 bilayer (with either the same or opposite c-axes), as well modeled by linear electromagnetic theory. Overall, this study not only develops a simple optical method for precise crystal orientation identification but also offers an efficient light polarization control strategy, which is a big step toward the practical application of anisotropic van der Waals materials in the design of nanophotonic and optoelectronic devices.

A microfluidics vapor-membrane-valve generated by laser irradiation on carbon nanocoils.

We have investigated a micro vapor membrane valve (MVMV) for closing the microfluidic channels by laser irradiation on carbon nanocoils (CNCs) attached to the inner wall of the microchannels. The microchannel with MVMVs was found to exhibit a "closed" state without the supply of laser energy, which is explained on the basis of the theory of heat and mass transfer. Multiple MVMVs for sealing the channels can be generated in sequence and exist simultaneously at different irradiation sites, independently. The significant advantages of the MVMV generated by the laser irradiation on CNCs are the elimination of extrinsic energy required to maintain the microfluidic channel "closed" state and the simplification of the structure integrated into the microfluidic channels and fluid control circuitries. The CNC-based MVMV is a powerful tool for the investigations of the functions of microchannel switching and sealing on microfluidic chips in biomedicine, chemical analysis and other fields. The study of MVMVs will have great significance for biochemical and cytological analysis.

Fabrication and Conductive Mechanism Analysis of Stretchable Electrodes Based on PDMS-Ag Nanosheet Composite with Low Resistance, Stability, and Durability.

A flexible and stretchable electrode based on polydimethylsiloxane (PDMS)-Ag nanosheet composite with low resistance and stable properties has been investigated. Under the synergistic effect of the excellent flexibility and stretchability of PDMS and the excellent electrical conductivity of Ag nanosheets, the electrode possesses a resistivity as low as 4.28 Ωm, a low resistance variation in the 0-50% strain range, a stable electrical conductivity over 1000 cycles, and a rapid recovery ability after failure caused by destructive large stretching. Moreover, the conductive mechanism of the flexible electrode during stretching is explained by combining experimental tests, theoretical models of contact point-tunneling effect, and finite element simulation. This research provides a simple and effective solution for the structure design and material selection of flexible electrodes, and an analytical method for the conductive mechanism of stretchable electrodes, which has potential for applications in flexible electronic devices, smart sensing, wearable devices, and other fields.

MOF-derived AuNS/LDH with high adsorption ability for surface enhanced Raman spectroscopy detection.

The sensitivity of surface enhanced Raman spectroscopy (SERS) depends on the construction of "hot spots" and the number of analyte molecules adsorbed onto the substrates. Herein, we have constructed a kind of SERS substrate based on gold nanostars (Au NSs) coated with nickel-cobalt layered double hydroxide (LDH) using a zeolitic imidazolate skeleton as sacrificial template via nickel ions etching. LDH was used as the absorption medium for target molecules, and concurrently prevented Au NSs from agglomeration to improve stability and uniformity of the substrate. Meanwhile, encapsulated Au NSs were used as the enhancement medium for Raman detection. The porous LDH shell around the Au NSs promoted the target molecules to approach the Au NSs, which was certified by the experimental results of UV-Vis absorption and simulation analysis using the density functional theory. The detection of Rhodamine 6G solution with a concentration of 10-9 M was realized by the AuNS/LDH, and the relative standard deviation of Raman signals was less than 10%. Therefore, this work provides a new idea and a suitable structure to improve SERS signal intensity by introducing adsorption medium into the SERS substrate.

Surface modification of helical carbon nanocoil (CNC) with N-doped and Co-anchored carbon layer for efficient microwave absorption.

Surface modification and composition control for nanomaterials are effective strategies for designing high-performance microwave absorbing materials (MWAMs). Herein, we have successfully fabricated Co-anchored and N-doped carbon layers on the surfaces of helical carbon nanocoils (CNCs) by wet chemical and pyrolysis methods, denoted as Co@N-Carbon/CNCs. It is found that pure CNCs show a very good microwave absorption performance under a filling ratio of only 6%, which is attributed to the uniformly dispersed conductive network and the cross polarization induced by the unique chiral and spiral morphology. The coating of N-doped carbon layers on CNCs further enriches polarization losses and the uniform anchoring of Co nanoparticles in these layers generates magnetic losses, which enhance the absorption ability and improve the low frequency performance. As compared with the pure CNCs-filling samples, the optimized Co@N-Carbon/CNCs-2.4 enhances the absorption capacity in the lower frequency range under the same thickness, and realizes the decreased thickness from 3.2 to 2.8 mm in the same X band, as well as the decreased thickness from 2.2 to 1.9 mm in the Ku band. Resultantly, a specific effective absorption wave value of 22 GHz g-1 mm-1 has been achieved, which enlightens the synthesis of ultrathin and light high-performance MWAMs.

Construction of a binder-free non-enzymatic glucose sensor based on Cu@Ni core-shell nanoparticles anchored on 3D chiral carbon nanocoils-nickel foam hierarchical scaffold.

Bimetallic nanostructures composited with carbonaceous materials are the potential contenders for quantitative glucose measurement owing to their unique nanostructures, high biomimetic activity, synergistic effects, good conductivity and chemical stability. In the present work, chemical vapors deposition technique has been employed to grow 3D carbon nanocoils (CNCs) with a chiral morphology on hierarchical macroporous nickel foam (NF) to get a CNCs/NF scaffold. Following, bimetallic Cu@Ni core-shell nanoparticles (CSNPs) are effectively coupled with this scaffold through a facile solvothermal route in order to fabricate a binder-free novel Cu@Ni CSNPs/CNCs/NF hybrid nanostructure. The constructed free-standing 3D hierarchical composite electrode guarantees highly efficient glucose redox activity due to core-shell synergistic effects, enhanced electrochemical active surface area, excellent electrochemical stability, improved conductivity with better ion diffusivity and accelerated reaction kinetics. Being a non-enzymatic glucose sensor, this electrode achieves highly swift response time of 0.1 s, ultra-high sensitivity of 6905 µA mM-1 cm-2, low limit of detection of 0.03 µM along with potential selectivity and good storage stability. Moreover, the proposed sensor is also tested successfully for the determination of glucose concentration in human serum samples under good recovery ranging from 96.6 to 102.1 %. The 3D Cu@Ni CSNPs/CNCs/NF composite electrode with unprecedented catalytic performance can be utilized as an ideal biomimetic catalyst in the field of non-enzymatic glucose sensing.

Novel Wearable Pyrothermoelectric Hybrid Generator for Solar Energy Harvesting.

Recently, wearable energy harvesting systems have been attracting great attention. As thermal energy is abundant in nature, developing wearable energy harvesters based on thermal energy conversion processes has been of particular interest. By integration of a high-efficient solar absorber, a pyroelectric film, and thermoelectric yarns, herein, we design a novel wearable solar-energy-driven pyrothermoelectric hybrid generator (PTEG). In contrast to those wearable pyroelectric generators and thermoelectric generators reported in previous works, our PTEG can enable effective energy harvesting from both dynamic temperature fluctuations and static temperature gradients. Under an illumination intensity of 1500 W/m2 (1.5 sun), the PTEG successfully charges two commercial capacitors to a sum voltage of 3.7 V in only 800 s, and the total energy is able to light up 73 LED light bulbs. The volumetric energy density over the two capacitors is calculated to be 67.8 µJ/cm3. The practical energy harvesting performance of the PTEG is further evaluated in the outdoor environment. The PTEG reported in this work not only demonstrates a rational structural design of high-efficient wearable energy harvesters but also paves a new pathway to integrate multiple energy conversion technologies for solar energy collection.

A flexible tissue-carbon nanocoil-carbon nanotube-based humidity sensor with high performance and durability.

A flexible humidity sensor based on a tissue-carbon nanocoil (CNC)-carbon nanotube (CNT) composite has been investigated. Taking advantage of the excellent water absorption of tissue and the electrical sensitivity of CNCs/CNTs to humidity, this humidity sensor obtains outstanding humidity sensing performance, including a wide sensing range of 10-90% RH, a maximum response value of 492% (ΔR/R0) at 90% RH, a maximum sensitivity of 6.16%/% RH, a good long-time stability of more than 7 days, a high humidity resolution accuracy of less than 1% RH and a fast response time of 275 ms. Furthermore, the sensor also exhibits robust bending (with a curvature of 0.322 cm-1) and folding (up to 500 times) durability, and after being made into a complex "thousand paper crane" shape it still provides stable humidity sensing performance. As a proof of concept, this humidity sensor demonstrates excellent responsivity to human breath monitoring, non-contact fingertip humidity detection, water boiling detection and air humidity monitoring, indicating great potential in the fields of wearable devices, weather forecasting systems and other intelligent humidity monitoring devices.

Flexible, Transparent and Highly Conductive Polymer Film Electrodes for All-Solid-State Transparent Supercapacitor Applications.

Lightweight energy storage devices with high mechanical flexibility, superior electrochemical properties and good optical transparency are highly desired for next-generation smart wearable electronics. The development of high-performance flexible and transparent electrodes for supercapacitor applications is thus attracting great attention. In this work, we successfully developed flexible, transparent and highly conductive film electrodes based on a conducting polymer, poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS). The PEDOT:PSS film electrodes were prepared via a simple spin-coating approach followed by a post-treatment with a salt solution. After treatment, the film electrodes achieved a high areal specific capacitance (3.92 mF/cm2 at 1 mA/cm2) and long cycling lifetime (capacitance retention >90% after 3000 cycles) with high transmittance (>60% at 550 nm). Owing to their good optoelectronic and electrochemical properties, the as-assembled all-solid-state device for which the PEDOT:PSS film electrodes were utilized as both the active electrode materials and current collectors also exhibited superior energy storage performance over other PEDOT-based flexible and transparent symmetric supercapacitors in the literature. This work provides an effective approach for producing high-performance, flexible and transparent polymer electrodes for supercapacitor applications. The as-obtained polymer film electrodes can also be highly promising for future flexible transparent portable electronics.

Carbon nanocoils decorated with a porous NiCo2O4 nanosheet array as a highly efficient electrode for supercapacitors.

Well-organized substrate materials are of considerable significance in the development of energy-efficient pseudocapacitor electrodes. Herein, functionalized three-dimensional (3D) carbon nanocoils on nickel foam (CNCs/NF) have been used as the substrate to grow faradaic nickel cobaltite (NiCo2O4) via a solvothermal method. The arrays of NiCo2O4 were assembled by interconnected ultrathin nanosheets with random inter-particle pores. The number of electroactive sites increased specifically because of the porous feature of NiCo2O4 nanosheets and the 3D structure of CNCs/NF. Moreover, the CNCs/NF network aided the electrolyte ions in diffusing deeply within the architecture. The NiCo2O4/CNCs/NF composite exhibited an outstanding specific capacitance of 2821 F g-1 at the current density of 1 A g-1, a remarkable rate capability (82.4%) and long cyclic stability (91.7% after 3000 cycles). Such encouraging electrochemical performance was attributed mainly to the synergistic interactions of NiCo2O4 arrays and CNCs/NF substrate that helped achieve efficient redox reactions, enhanced ion diffusivity and excellent electron conductivity. In summary, this binder-free NiCo2O4/CNCs/NF composite electrode paves a way towards the synthesis of highly efficacious electrodes for supercapacitors.

Highly Flexible, Stretchable, and Self-Powered Strain-Temperature Dual Sensor Based on Free-Standing PEDOT:PSS/Carbon Nanocoils-Poly(vinyl) Alcohol Films.

The wearable and self-powered sensors with multiple functions are urgently needed for energy saving devices, economical convenience, and artificial human skins. It is a meaningful idea to convert excess heat sources into power supplies for wearable sensors. In this report, we have fabricated a series of free-standing self-powered temperature-strain dual sensors based on poly(3,4-ethylenedioxythiophene) polystyrenesulfonate (PEDOT:PSS)/carbon nanocoils (CNCs)-poly(vinyl) alcohol composite films by a simple drop casting method. The Seebeck coefficients of the composite films were measured to be 19 µV/K. The sensor, with the addition of CNCs, showed a superior sensing performance to that without CNCs. PEDOT:PSS is used to provide a thermoelectric power to detect temperature changes and strain deformations. The minimum detect limit for the temperature difference was 0.3 K. Under a constant temperature gradient of 30 K, strains from 1 to 10% were detected without any external power supply. The films can be easily made into an array to detect the temperature of the fingers and motions of the wrist by attaching it to the human wrist directly. For the first time, due to the independent action of the thermoelectric material and strain sensing material, the thermoelectric voltage which is generated by a constant temperature difference is maintained under different strains. This kind of free-standing self-powered multifunctional sensors has great application prospects in the fields of healthcare and artificial intelligence in the future.

Tip-to-tip assembly of urchin-like Au nanostar at water-oil interface for surface-enhanced Raman spectroscopy detection.

Au Nanostar (NS) monolayer as a surface enhanced Raman scattering (SERS) substrate has been synthesized by self-assembly at a water-oil interface. It is confirmed from the experiment and simulation results that the Au NS monolayer includes lots of "hot spots" at or between the tips of the Au NSs, enhancing the local electromagnetic fields and giving rise to strong SERS signals sequentially. The limit of detection is determined to be down to 4.2 × 10-12 M for rhodamine 6G. Furthermore, the Au NS monolayer can detect multiple molecules, including thiabendazole, methylene blue, 4-mercaptobenzoic acid, and p-amino thiophenol, indicating that the SERS substrate composed of Au NS monolayer has potential applications in analytical chemistry, food safety, and environmental safety.

Self-healing and anti-freezing graphene-hydrogel-graphene sandwich strain sensor with ultrahigh sensitivity.

Hydrogels with specially designed structures and adjustable properties have been considered as smart materials with multi-purpose application prospects, especially in the field of flexible sensors. However, most hydrogel-based sensors have low sensitivity, which inevitably affects their promotion in the market. Herein, a strain sensor comprising a poly(vinyl alcohol)/poly(acrylic acid) (PVA/PAA) hybrid hydrogel sandwiched between two graphene layers was successfully constructed in a facile way, and it exhibited many excellent properties including extremely high sensitivity. The incorporation of glycerol ensured the good flexibility and anti-freezing performance of the hydrogel-based sensor even at -15 °C. The dynamic coordination bonds in the hydrogel-based sensor endowed it with excellent self-healing properties. In particular, the sandwich-structured hydrogel sensor showed a very high gauge factor (GF) value of 39 at the strain of 50%, which is much higher than those of most ordinary hydrogel-based strain sensors. A super stable signal value after 5000 strain cycles and a very short response time of 274 ms guaranteed the long-term usability and sensitivity of the hydrogel-based sandwich sensor. More importantly, the hydrogel-based sandwich sensor could detect both large and tiny human motions accurately and instantly in a series of real-time monitoring experiments, showing great potential for intelligent wearable electronic devices.

Supramolecular assemblies of carbon nanocoils and tetraphenylporphyrin derivatives for sensing of catechol and hydroquinone in aqueous solution.

Non-enzymatic electrochemical detection of catechol (CC) and hydroquinone (HQ), the xenobiotic pollutants, was carried out at the surface of novel carbon nanocoils/zinc-tetraphenylporphyrin (CNCs/Zn-TPP) nanocomposite supported on glassy carbon electrode. The synergistic effect of chemoresponsive activity of Zn-TPP and a large surface area and electron transfer ability of CNCs lead to efficient detection of CC and HQ. The nanocomposite was characterized by using FT-IR, UV/vis. spectrophotometer, SEM and energy dispersive X-ray spectroscopy (EDS). Cyclic voltammetry, differential pulse voltammetry (DPV) and electrochemical impedance spectroscopy were used for the electrochemical studies. CNCs/Zn-TPP/GCE nanosensor displayed a limit of detection (LOD), limit of quantification (LOQ) and sensitivity for catechol as 0.9 µM, 3.1 µM and 0.48 µA µM-1 cm-2, respectively in a concentration range of 25-1500 µM. Similarly, a linear trend in the concentration of hydroquinone detection was observed between 25 and 1500 µM with an LOD, LOQ and sensitivity of 1.5 µM, 5.1 µM and 0.35 µA µM-1 cm-2, respectively. DPV of binary mixture pictured well resolved peaks with anodic peak potential difference, ∆Epa(CC-HQ), of 110 mV showing efficient sensing of CC and HQ. The developed nanosensor exhibits stability for up to 30 days, better selectivity and good repeatability for eight measurements (4.5% for CC and 5.4% for HQ).

Structural Engineering of Hierarchical Aerogels Comprised of Multi-dimensional Gradient Carbon Nanoarchitectures for Highly Efficient Microwave Absorption.

Recently, multilevel structural carbon aerogels are deemed as attractive candidates for microwave absorbing materials. Nevertheless, excessive stack and agglomeration for low-dimension carbon nanomaterials inducing impedance mismatch are significant challenges. Herein, the delicate "3D helix-2D sheet-1D fiber-0D dot" hierarchical aerogels have been successfully synthesized, for the first time, by sequential processes of hydrothermal self-assembly and in-situ chemical vapor deposition method. Particularly, the graphene sheets are uniformly intercalated by 3D helical carbon nanocoils, which give a feasible solution to the mentioned problem and endows the as-obtained aerogel with abundant porous structures and better dielectric properties. Moreover, by adjusting the content of 0D core-shell structured particles and the parameters for growth of the 1D carbon nanofibers, tunable electromagnetic properties and excellent impedance matching are achieved, which plays a vital role in the microwave absorption performance. As expected, the optimized aerogels harvest excellent performance, including broad effective bandwidth and strong reflection loss at low filling ratio and thin thickness. This work gives valuable guidance and inspiration for the design of hierarchical materials comprised of dimensional gradient structures, which holds great application potential for electromagnetic wave attenuation.