Green synthesis of iron-doped graphene quantum dots: an efficient nanozyme for glucose sensing.

Single-atom nanozymes with well-defined atomic structures and electronic coordination environments can effectively mimic the functions of natural enzymes. However, the costly and intricate preparation processes have hindered further exploration and application of these single-atom nanozymes. In this study, we presented a synthesis technique for creating Fe-N central single-atom doped graphene quantum dot (FeN/GQDs) nanozymes using a one-step solvothermal process, where individual iron atoms form strong bonds with graphene quantum dots through nitrogen coordination. Unlike previous studies, this method significantly simplifies the synthesis conditions for single-atom nanozymes, eliminating the need for high temperatures and employing environmentally friendly precursors derived from pineapple (ananas comosus) leaves. The resulting FeN/GQDs exhibited peroxidase-like catalytic activity and kinetics comparable to that of natural enzymes, efficiently converting H2O2 into hydroxyl radical species. Leveraging their excellent peroxide-like activity, FeN/GQDs nanozymes have been successfully applied to construct a colorimetric biosensor system characterized by remarkably high sensitivity for glucose detection. This achievement demonstrated a promising approach to designing single-atom nanozymes with both facile synthesis procedures and high catalytic activity, offering potential applications in wearable sensors and personalized health monitoring.

Are MXenes suitable for soft multifunctional composites?

MXenes are a family of two-dimensional (2D) nanomaterials known for their high electrical and thermal conductivity, as well as high aspect ratios. Recent research has focused on dispersing MXenes within compliant polymer matrices, aiming to create flexible and stretchable composites that harness MXenes' exceptional conductivity and aspect ratios. Experimental findings demonstrate the potential of MXene polymer composites (MXPCs) as flexible electrical, thermal conductors, and high dielectric materials, with promising applications in soft matter engineered systems. However, the 2D structure of MXene inclusions and their relatively large elastic modulus can impart increased stiffness to the polymer matrix, posing limitations on the mechanical flexibility of these functional materials. Here, we introduce a modeling platform to predict the mechanics and functionality of MXene elastomer composites and assess their suitability as soft multifunctional materials. Our investigation primarily focuses on understanding the influence of MXenes' size, layered structure, and percolation arrangements on the effective properties of the resulting composites. Through our model, we successfully determined the elastic modulus, thermal conductivity, and dielectric constant of MXene elastomer composites, and our results exhibit strong agreement with those obtained through finite element analysis. By utilizing this framework, we can theoretically identify the necessary microstructures of MXenes and guide the experiments, enabling the creation of MXPCs with the desired synergistic mechanical and functional properties.

Thermally Stable Poly(vinylidene fluoride) for High-Performance Printable Piezoelectric Devices.

Piezoelectric polymers, such as poly(vinylidene fluoride) (PVDF) and its copolymers, can achieve large strains and high work density under external electrical fields. These materials are highly desirable in the development of electronic devices and intelligent structures. Here, we demonstrate that dehydrofluorination (DHF) can provide a versatile chemical modification of the PVDF homopolymer that yields thermally stable ferroelectricity. The DHF process significantly increases the fraction of planar chain conformation in the PVDF and results in higher piezoelectric coupling with a wider processing temperature range, compared to traditionally processed PVDF. The efficacy of DHF in promoting planar chain conformation is demonstrated through molecular simulation and further proven by experimental characterization. The induced piezoelectric phases by DHF were able to be preserved through high temperature treatments up to 200 °C. The dehydrofluorinated PVDF exhibits improved electromechanical coupling with a high piezoelectric strain coefficient of d31 = 25.12 ± 1.13 pC/N, which can be further improved to 35.12 ± 0.69 pC/N by common mechanical drawing. This high piezoelectric voltage coefficient leads to an excellent actuation and energy harvesting behavior with a power density of 21.96 mW/cm3 in a flexible undrawn PVDF energy harvester, which is 3.13 times higher than conventionally drawn PVDF. The versatile and scalable method for preparing PVDF polymers with high piezoelectric coupling will enable new manufacturing processes not currently compatible with PVDF homopolymers.

Soft and Stretchable Thermoelectric Generators Enabled by Liquid Metal Elastomer Composites.

Stretchable thermoelectric generators (TEGs) capable of harvesting electrical energy from body heat under cold weather conditions have the potential to make wearable electronic and robotic systems more lightweight and portable by reducing their dependency on on-board batteries. However, progress depends on the integration of soft conductive materials for robust electrical wiring and thermal management. The use of thermally conductive soft elastomers is especially important for conforming to the body, absorbing body heat, and maintaining a temperature gradient between the two sides of the TEGs in order to generate power. Here, we introduce a soft-matter TEG architecture composed of electrically and thermally conductive liquid metal embedded elastomer (LMEE) composites with integrated arrays of n-type and p-type Bi2Te3 semiconductors. The incorporation of a LMEE as a multifunctional encapsulating material allows for the seamless integration of 100 thermoelectric semiconductor elements into a simplified material layup that has a dimension of 41.0 × 47.3 × 3.0 mm. These stretchable thermoelectric devices generate voltages of 59.96 mV at Δ10 °C, 130 mV at Δ30 °C, and 278.6 mV and a power of 86.6 µW/cm2 at Δ60 °C. Moreover, they do not electrically or mechanically fail when stretched to strains above 50%, making them well-suited for energy harvesting in soft electronics and wearable computing applications.

Liquid metal nanocomposites.

Liquid metal (LM) has attracted tremendous interest over the past decade for its enabling combination of high electrical and thermal conductivity and low mechanical compliance and viscosity. Efforts to harness LM in electronics, robotics, and biomedical applications have largely involved methods to encapsulate the liquid so that it can support functionality without leaking or smearing. In recent years, there has been increasing interest in LM "nanocomposites" in which either liquid metal is mixed with metallic nanoparticles or nanoscale droplets of liquid metal are suspended within a soft polymer matrix. Both of these material systems represent an important step towards utilizing liquid metal for breakthrough applications. In this minireview, we present a brief overview of recent progress over the past few years in methods to synthesize LM nanomaterials and utilize them as transducers for sensing, actuation, and energy harvesting. In particular, we focus on techniques for stable synthesis of LM nanodroplets, suspension of nanodroplets within various matrix materials, and methods for incorporating metallic nanoparticles within an LM matrix.

Solution processable liquid metal nanodroplets by surface-initiated atom transfer radical polymerization.

Eutectic gallium indium (EGaIn) is a liquid metal alloy at room temperature. EGaIn microdroplets can be incorporated into elastomers to fabricate highly stretchable, mechanically robust, soft multifunctional composites with high thermal stability1 and electrical conductivity2-4 that are suitable for applications in soft robotics and self-healing electronics5-7. However, the current methods of preparation rely on mechanical mixing, which may lead to irregularly shaped micrometre-sized droplets and an anisotropic distribution of properties8. Therefore, procedures for the stabilization of sub-micrometre-sized droplets of EGaIn and compatibilization in polymer matrices and solvents have attracted significant attention9-12. Here we report the synthesis of EGaIn nanodroplets stabilized by polymeric ligand encapsulation. We use a surface-initiated atom transfer radical polymerization initiator to covalently functionalize the oxide layer on the surface of the EGaIn nanodroplets13 with poly(methyl methacrylate) (PMMA), poly(n-butyl acrylate) (PBMA), poly(2-dimethylamino)ethyl methacrylate) (PDMAEMA) and poly(n-butyl acrylate-block-methyl methacrylate) (PBA-b-PMMA). These nanodroplets are stable in organic solvents, in water or in polymer matrices up to 50 wt% concentration, enabling direct solution-casting into flexible hybrid materials. The liquid metal can be recovered from dispersion by acid treatment. The nanodroplets show good mechanical, thermal and optical properties, with a remarkable suppression of crystallization and melting temperatures (down to -80 °C from 15 °C).

A Liquid-Metal-Elastomer Nanocomposite for Stretchable Dielectric Materials.

Stretchable high-dielectric-constant materials are crucial for electronic applications in emerging domains such as wearable computing and soft robotics. While previous efforts have shown promising materials architectures in the form of dielectric nano-/microinclusions embedded in stretchable matrices, the limited mechanical compliance of these materials significantly limits their practical application as soft energy-harvesting/storage transducers and actuators. Here, a class of liquid metal (LM)-elastomer nanocomposites is presented with elastic and dielectric properties that make them uniquely suited for applications in soft-matter engineering. In particular, the role of droplet size is examined and it is found that embedding an elastomer with a polydisperse distribution of nanoscale LM inclusions can enhance its electrical permittivity without significantly degrading its elastic compliance, stretchability, or dielectric breakdown strength. In contrast, elastomers embedded with microscale droplets exhibit similar improvements in permittivity but a dramatic reduction in breakdown strength. The unique enabling properties and practicality of LM-elastomer nanocomposites for use in soft machines and electronics is demonstrated through enhancements in performance of a dielectric elastomer actuator and energy-harvesting transducer.

Printed Nanocomposite Energy Harvesters with Controlled Alignment of Barium Titanate Nanowires.

Piezoelectric nanocomposites are commonly used in the development of self-powered miniaturized electronic devices and sensors. Although the incorporation of one-dimensional (1D) piezoelectric nanomaterials (i.e., nanowires, nanorods, and nanofibers) in a polymer matrix has led to the development of devices with promising energy harvesting and sensing performance, they have not yet reached their ultimate performance due to the challenges in fabrication. Here, a direct-write additive manufacturing technique is utilized to facilitate the fabrication of spatially tailored piezoelectric nanocomposites. High aspect ratio barium titanate (BaTiO3) nanowires (NWs) are dispersed in a polylactic acid (PLA) solution to produce a printable piezoelectric solution. The BaTiO3 NWs are arranged in PLA along three different axes of alignment via shear-induced alignment during a controlled printing process. The result of electromechanical characterizations shows that the nanowire alignment significantly affects the energy harvesting performance of the nanocomposites. The optimal power output can be enhanced by as much as eight times for printed nanocomposites with a tailored architecture of the embedded nanostructures. This power generation capacity is 273% higher compared to conventional cast nanocomposites with randomly oriented NWs. The findings of this study suggest that 3D printing of nanowire-based nanocomposites is a feasible, scalable, and rapid methodology to produce high-performance piezoelectric transducers with tailored micro- and nanostructures. This study offers the first demonstration of nanocomposite energy harvesters with spatially controlled filler orientation realized directly from a digital design.

EGaIn-Assisted Room-Temperature Sintering of Silver Nanoparticles for Stretchable, Inkjet-Printed, Thin-Film Electronics.

Coating inkjet-printed traces of silver nanoparticle (AgNP) ink with a thin layer of eutectic gallium indium (EGaIn) increases the electrical conductivity by six-orders of magnitude and significantly improves tolerance to tensile strain. This enhancement is achieved through a room-temperature "sintering" process in which the liquid-phase EGaIn alloy binds the AgNP particles (≈100 nm diameter) to form a continuous conductive trace. Ultrathin and hydrographically transferrable electronics are produced by printing traces with a composition of AgNP-Ga-In on a 5 µm-thick temporary tattoo paper. The printed circuit is flexible enough to remain functional when deformed and can support strains above 80% with modest electromechanical coupling (gauge factor ≈1). These mechanically robust thin-film circuits are well suited for transfer to highly curved and nondevelopable 3D surfaces as well as skin and other soft deformable substrates. In contrast to other stretchable tattoo-like electronics, the low-cost processing steps introduced here eliminate the need for cleanroom fabrication and instead requires only a commercial desktop printer. Most significantly, it enables functionalities like "electronic tattoos" and 3D hydrographic transfer that have not been previously reported with EGaIn or EGaIn-based biphasic electronics.

Isolation of Aramid Nanofibers for High Strength and Toughness Polymer Nanocomposites.

The development of nanoscale reinforcements that can be used to improve the mechanical properties of a polymer remains a challenge due to the long-standing difficulties with exfoliation and dispersion of existing materials. The dissimilar chemical nature of common nanofillers (e.g., carbon nanotubes, graphene) and polymeric matrix materials is the main reason for imperfect filler dispersion and, consequently, low mechanical performance of their composites relative to theoretical predictions. Here, aramid nanofibers that are intrinsically dispersible in many polymers are prepared from commercial aramid fibers (Kevlar) and isolated through a simple, scalable, and low-cost controlled dissolution method. Integration of the aramid nanofibers in an epoxy resin results in nanocomposites with simultaneously improved elastic modulus, strength, and fracture toughness. The improvement of these two mutually exclusive properties of nanocomposites is comparable to the enhancement of widely reported carbon nanotube reinforced nanocomposites but with a cost-effective and more feasible method to achieve uniform and stable dispersion. The results indicate the potential for aramid nanofibers as a new class of reinforcements for polymers.

Barium Titanate Film Interfaces for Hybrid Composite Energy Harvesters.

Energy harvesting utilizing piezoelectric materials has become an attractive approach for converting mechanical energy into electrical power for low-power electronics. Structural composites are ideally suited for energy scavenging due to the large amount of mechanical energy they are subjected to. Here, a multifunctional composite with embedded sensing and energy harvesting is developed by integrating an active interface into carbon fiber reinforced polymer composites. By modifying the composite matrix, both rigid and flexible multifunctional composites are fabricated. Through electromechanical testing of a cantilever beam of the rigid composite, it reveals a power density of 217 pW/cc from only 1 g root-mean-square acceleration when excited at its resonant frequency of 47 Hz. Electromechanical sensor testing of the flexible multifunctional composite reveals an average voltage generation of 23.5 mV/g at its resonant frequency of 96 Hz. This research introduces a route for integrating nonstructural functionality into structural fiber composites by utilizing BaTiO3 coated woven carbon fiber fabrics with power scavenging and passive sensing capabilities.

Conformal BaTiO3 Films with High Piezoelectric Coupling through an Optimized Hydrothermal Synthesis.

Two-dimensional (2D) ferroelectric films have vast applications due to their dielectric, ferroelectric, and piezoelectric properties that meet the requirements of sensors, nonvolatile ferroelectric random access memory (NVFeRAM) devices, and micro-electromechanical systems (MEMS). However, the small surface area of these 2D ferroelectric films has limited their ability to achieve higher memory storage density in NVFeRAM devices and more sensitive sensors and transducer. Thus, conformally deposited ferroelectric films have been actively studied for these applications in order to create three-dimensional (3D) structures, which lead to a larger surface area. Most of the current methods developed for the conformal deposition of ferroelectric films, such as metal-organic chemical vapor deposition (MOCVD) and plasma-enhanced vapor deposition (PECVD), are limited by high temperatures and unstable and toxic organic precursors. In this paper, an innovative fabrication method for barium titanate (BaTiO3) textured films with 3D architectures is introduced to alleviate these issues. This fabrication method is based on converting conformally grown rutile TiO2 nanowire arrays into BaTiO3 textured films using a simple two-step hydrothermal process which allows for thickness-controlled growth of conformal films on patterned silicon wafers coated with fluorine-doped tin oxide (FTO). Moreover, the processing parameters have been optimized to achieve a high piezoelectric coupling coefficient of 100 pm/V. This high piezoelectric response along with high relative dielectric constant (εr = 1600) of the conformally grown textured BaTiO3 films demonstrates their potential application in sensors, NVFeRAM, and MEMS.

Lead-free 0.5Ba(Zr0.2Ti0.8)O3-0.5(Ba0.7Ca0.3)TiO3 nanowires for energy harvesting.

Lead-free piezoelectric nanowires (NWs) show strong potential in sensing and energy harvesting applications due to their flexibility and ability to convert mechanical energy to electric energy. Currently, most lead-free piezoelectric NWs are produced through low yield synthesis methods and result in low electromechanical coupling, which limit their efficiency as energy harvesters. In order to alleviate these issues, a scalable method is developed to synthesize perovskite type 0.5Ba(Zr0.2Ti0.8)O3-0.5(Ba0.7Ca0.3)TiO3 (BZT-BCT) NWs with high piezoelectric coupling coefficient. The piezoelectric coupling coefficient of the BZT-BCT NWs is measured by a refined piezoresponse force microscopy (PFM) testing method and shows the highest reported coupling coefficient for lead-free piezoelectric nanowires of 90 ± 5 pm V(-1). Flexible nanocomposites utilizing dispersed BZT-BCT NWs are fabricated to demonstrate an energy harvesting application with an open circuit voltage of up to 6.25 V and a power density of up to 2.25 µW cm(-3). The high electromechanical coupling coefficient and high power density demonstrated with these lead-free NWs produced via a scalable synthesis method shows the potential for high performance NW-based devices.

Morphology-controlled ZnO nanowire arrays for tailored hybrid composites with high damping.

Hybrid fiber reinforced composites using a nanoscale reinforcement of the interface have not reached their optimal performance in practical applications due to their complex design and the challenging assembly of their multiscale components. One promising approach to the fabrication of hybrid composites is the growth of zinc oxide (ZnO) nanowire arrays on the surface of carbon fibers to provide improved interfacial strength and out of plane reinforcement. However, this approach has been demonstrated mainly on fibers and thus still requires complex processing conditions. Here we demonstrate a simple approach to the fabrication of such composites through the growth of the nanowires on the fabric. The fabricated composites with nanostructured graded interphase not only exhibit remarkable damping enhancement but also stiffness improvement. It is demonstrated that these two extremely important properties of the composite can be controlled by tuning the morphology of the ZnO nanowires at the interface. Higher damping and flexural rigidity of these composites over traditional ones offer practical high-performance composites.