Mechanical Robustness Enhanced Flexible Antennas Using Ti3C2 MXene and Nanocellulose Composites for Noninvasive Glucose Sensing.

Electromagnetic sensors with flexible antennas as sensing elements have attracted increasing attention in noninvasive continuous glucose monitoring for diabetic patients. The significant radiation performance loss of flexible antennas during mechanical deformation impairs the reliability of glucose monitoring. Here, we present flexible ultrawideband monopole antennas composed of Ti3C2 MXene and cellulose nanofibril (CNF) composite films for continuous glucose monitoring. The flexible MXene/CNF antenna with 20% CNF content can obtain a gain of up to 3.33 dBi and a radiation efficiency of up to 65.40% at a frequency range from 2.3 to 6.0 GHz. Compared with the pure MXene antenna, this antenna offers a comparable radiation performance and a lower performance loss in mechanical bending deformation. Moreover, the MXene/CNF antenna shows a stable response to fetal bovine serum/glucose, with a correlation of >0.9 at the reference glucose levels, and responds sensitively to the variations in blood glucose levels during human trials. The proposed strategy enhancing the mechanical robustness of MXene-based flexible antennas makes metallic two-dimensional nanomaterials more promising in wearable electromagnetic sensors.

Prediction of nonlayered oxide monolayers as flexible high-κ dielectrics with negative Poisson's ratios.

During the last two decades, two-dimensional (2D) materials have been the focus of condensed matter physics and material science due to their promising fundamental properties and (opto-)electronic applications. However, high-κ 2D dielectrics that can be integrated within 2D devices are often missing. Here, we propose nonlayered oxide monolayers with calculated exfoliation energy as low as 0.39 J/m2 stemming from the ionic feature of the metal oxide bonds. We predict 51 easily or potentially exfoliable oxide monolayers, including metals and insulators/semiconductors, with intriguing physical properties such as ultra-high κ values, negative Poisson's ratios and large valley spin splitting. Among them, the most promising dielectric, GeO2, exhibits an auxetic effect, a κ value of 99, and forms type-I heterostructures with MoSe2 and HfSe2, with a band offset of ~1 eV. Our study opens the way for designing nonlayered 2D oxides, offering a platform for studying the rich physics in ultra-thin oxides and their potential applications in future information technologies.

Transition from semiconductor to conductor of a Mg2N electride induced by strain.

Electrides are a class of materials in which electrons are not bound to atoms but are similar to anions in crystals. To date, there are more than 300 electrides that have been discovered by first-principles. Alkaline-earth metal nitrides (AE2N, AE = Be, Mg, Ca, Sr, and Ba) are an important component of electride materials. Ca2N, Sr2N, and Ba2N structures have been identified and synthesized in previous research studies. Furthermore, the structures of Be2N (R3̄m symmetry) and Mg2N (R3m symmetry) were recently identified. For Mg2N, it has zero-dimension (0D) interstitial localized electrons and band structure with semiconductor properties, which is significantly different from the other AE2N structures (two-dimension electrides and metal properties). Consequently, Mg2N was systematically studied in this work. We found that the pristine Mg2N was an indirect band gap semiconductor with a band gap of 0.243 eV. It transitioned to a metal when 2% stretch stress was applied to the c-axis. Moreover, at 5% stretch stress, the structure exhibited 2D interstitial localized electrons with the superconducting transition temperature (Tc) of 0.3 K. These studies thus provide a deeper understanding of the physicochemical properties of Mg2N as an electride.

Dual-band achromatic metalens-assisted grating couplers for wavelength demultiplexing.

The design of grating couplers (GCs) that can (de)multiplex and couple arbitrarily defined spatial light into photonic devices is crucial for miniaturized integrated chips. However, traditional GCs have a limited optical bandwidth due to their wavelength's dependency on the coupling angle. In this paper, we propose a device that addresses this limitation by combining a dual-broadband achromatic metalens (ML) with two focusing GCs. By controlling the frequency dispersion, the waveguide-mode-based ML achieves excellent dual-broadband achromatic convergence and separates broadband spatial light into opposing directions at normal incidence. The focused and separated light field matches the grating diffractive mode field and is then coupled into two waveguides by the GCs. This ML-assisted GCs device exhibits a good broadband property with -3 dB bandwidths of 80 nm at 1.31 µm (CE ∼ -6 dB) and 85 nm at 1.51 µm (CE ∼ -5 dB), which almost covers the entire designed working bands, representing an improvement over traditional spatial light-GC coupling. This device can be integrated into optical transceivers and dual-band photodetectors to enhance the bandwidth of wavelength (de)multiplexing.

Coexistence of circular dichroism and asymmetric transmission in Babinet-complementary metamaterials.

Chiral metamaterials with circular dichroism (CD) or asymmetric transmission (AT) draw enormous attention for their attractive applications in polarization transformers, circular polarizers, and biosensing. In this study, a feasible trilayer chiral metamaterials (TCM) is designed and investigated in theory and simulation. The proposed TCM is composed of a nanoslit layer and a Babinet-complementary nanorod layer separated by a nanoslit spacer. Owing to symmetry breaking by the tilted nanoslit in metal film, the TCM shows simultaneous CD and AT effects in the near-infrared region. The simulated electric charge distributions prove that the chirality arises from the excitation of asymmetric electric dipole resonant modes due to the coupling of adjacent unit cells. Moreover, CD and AT can be tuned by the tilted angle of the nanoslit and the thickness of the spacer, the fitting functions of which are consistent with the theoretical formulas based on transmittance matrix analysis. The proposed nanostructure offers a potential strategy for manipulating metamaterials with simultaneous CD and AT effects, allowing a multitude of exciting applications such as ultra-sensitive polarization transformer and biosensor.

Rational Design of LLZO/Polymer Solid Electrolytes for Solid-State Batteries.

Hybrid composite electrolytes incorporate polymer matrixes and garnet filler attract the focus of concern for all-solid-state batteries, which possess high ionic conductivity, superior electrochemical stability, and wide electrochemical window of ceramic electrolyte advantages, and exhibit excellent flexibility and tensile shear strength from polymer electrolyte benefits. Hence, the unique structure design of solid-state electrolytes resolves the existing defects that the use of either single garnet or polymer electrolytes implemented into battery devices. This review summarizes Li7 La3 Zr2 O12 (LLZO)/polymer solid composite electrolytes (SCEs), comprising LLZO/polymer SCEs with various structures and different ratios of LLZO fillers, LLZO/polymer with different kinds of polymers matrix and hybrid lithium-salt, and Li+ transport pathways within the LLZO/polymers SCEs interface. The purpose here is to propose the viewpoints and challenges of LLZO/polymer SCEs to promote the development of next-generation solid electrolytes.

Enhanced terahertz sensitivity for glucose detection with a hydrogel platform embedded with Au nanoparticles.

We presented a strategy for enhancing the sensitivity of terahertz glucose sensing with a hydrogel platform pre-embedded with Au nanoparticles. Physiological-level glucose solutions ranging from 0 to 0.8 mg/mL were measured and the extracted absorption coefficients can be clearly distinguished compared to traditional terahertz time domain spectroscopy performed directly on aqueous solutions. Further, Isotherm models were applied to successfully describe the relationship between the absorption coefficient and the glucose concentration (R2 = 0.9977). Finally, the origin of the sensitivity enhancement was investigated and verified to be the pH change induced by the catalysis of Au nanoparticles to glucose oxidation.

Aqueous Electrolytes with Hydrophobic Organic Cosolvents for Stabilizing Zinc Metal Anodes.

Rechargeable aqueous zinc (Zn) batteries are promising for large-energy storage because of their low cost, high safety, and environmental compatibility, but their implementation is hindered by the severe irreversibility of Zn metal anodes as exemplified by water-induced side reactions (H2 evolution and Zn corrosion) and dendrite growth. Here, we find that the introduction of a hydrophobic carbonate cosolvent into a dilute aqueous electrolyte exhibits a much stronger ability to address the reversible issues facing Zn anodes than that with hydrophilic ones. Among the typical carbonates (ethylene carbonate, propylene carbonate, dimethyl carbonate, and diethyl carbonate (DEC)), DEC as the most hydrophobic additive enables the strongest breaking of water's H-bond network and replaces the solvating H2O in a Zn2+-solvation sheath, which significantly reduces the water activity and its decomposition. Additionally, DEC molecules preferentially adsorb onto the Zn surface to create an H2O-poor electrical double layer and render a dendrite-free Zn2+-plating behavior. The formulated hybrid 2 m Zn(OTf)2 + 7 m DEC electrolyte endows the Zn electrode with an ability to achieve high cycling stability (over 3500 h at 5 mA cm-2 with 2.5 mA h cm-2) and supports the stable operation of Zn||V2O5·nH2O full battery. This efficient strategy with hydrophobic cosolvent suggests a promising direction for designing aqueous battery chemistries.

Enhanced sensitivity of dilute aqueous adrenaline solution with an asymmetric hexagonal ring structure in the terahertz frequencies.

Quantitative detection of neurotransmitters in aqueous environment is crucial for the early diagnosis of many neurological disorders. Terahertz waves, as a non-contact and non-labeling tool, have demonstrated large potentials in quantitative biosensing. Although the detection of trace-amount analyte has been achieved with terahertz metamaterials in the recent decades, most studies have been focused on dried samples. Here, a hexagonal asymmetric metamaterial sensor was designed and fabricated for aqueous solution sensing with terahertz waves in the reflection geometry. An absorption enhancement of 43 was determined from the simulation. Dilute adrenaline solutions ranging from 30 µM to 0.6 mM were measured on our sensor using a commercial terahertz time-domain spectroscopy system, and the effective absorption was found to be linearly correlated with the concentration (R2 = 0.81). Furthermore, we found that as the concentration becomes higher (>0.6 mM), a non-linear relationship starts to take place, which confirmed the previous theory on the extended solvation shell that can be probed on the picosecond scale. Our sensor, without the need of high-power and stable terahertz sources, has enabled the detection of subtle absorption changes induced by the solvation dynamics.

Mechanical Behavior and Constitutive Model Characterization of Optically Clear Adhesive in Flexible Devices.

Optically clear adhesive (OCA) has been widely used in flexible devices, where wavy stripes that cause troublesome long-term reliability problems often occur. The complex mechanical behavior of OCA should be studied, as it is related to the aforementioned problems. Therefore, it is necessary to establish reasonable mechanical constitutive models for deformation and stress control. In this work, hyperelastic and viscoelastic mechanical tests were carried out systematically and relative constitutive models of OCA material were established. We found that temperature has a great influence on OCA's mechanical properties. The stress and modulus both decreased rapidly as the temperature increased. In the static viscoelasticity test, the initial stress at 85 °C was only 12.6 kPa, 57.4% lower than the initial stress at 30 °C. However, in the dynamic test, the storage modulus monotonically decreased from 1666.3 MPa to 0.6628 MPa as the temperature rose, and the decline rate reached the maximum near the glass transition temperature (Tg = 0 °C). The test data and constitutive models can be used as design references in the manufacturing process, as well as for product reliability evaluation.

Computational Auxiliary for the Progress of Sodium-Ion Solid-State Electrolytes.

All-solid-state sodium batteries (ASSBs) have attracted ever-increasing attention due to their enhanced safety, high energy density, and the abundance of raw materials. One of the remaining key issues for the practical ASSB is the lack of good superionic and electrochemical stable solid-state electrolytes (SEs). Design and manufacturing specific functional materials used as high-performance SEs require an in-depth understanding of the transport mechanisms and electrochemical properties of fast sodium-ion conductors on an atomic level. On account of the continuous progress and development of computing and programming techniques, the advanced computational tools provide a powerful and convenient approach to exploit particular functional materials to achieve that aim. Herein, this review primarily focuses on the advanced computational methods and ion migration mechanisms of SEs. Second, we overview the recent progress on state-of-the-art solid sodium-ion conductors, including Na-ß-alumina, sulfide-type, NASICON-type, and antiperovskite-type sodium-ion SEs. Finally, we outline the current challenges and future opportunities. Particularly, this review highlights the contributions of the computational studies and their complementarity with experiments in accelerating the study progress of high-performance sodium-ion SEs for ASSBs.

Accumulation and passive sampling of bisphenol analogues using triolein-embedded cellulose acetate membrane in waters.

Bisphenol analogues (BPs) are emerging contaminants that have been widely detected in water environments. The presence of substituted hydrophilic and hydrophobic groups in the molecule may lead to unclear performance in passive sampling. This study tested the accumulation capacity and passive sampling of fifteen BPs in a triolein-embedded cellulose acetate membrane (TECAM) passive sampler. In a dynamic accumulation experiment, twelve hydrophobic BPs accumulated in the TECAM with concentrations ranging from 251 ng g-1 to 6283 ng g-1, and three hydrophilic BPs did not accumulate during the 72 h exposure duration. BPs accumulations were determined by the hydrophilic and hydrophobic substituent groups in molecule structures. The estimated passive sampling parameters showed correlations to both the log Kow values and chemical structures, and compared to other contaminants, such as organophosphorus flame retardants. Environmental factors, including flow rate, temperature, salinity, and pH, that affect the accumulation of BPs in the TECAM were tested, and the flow rate was found to be an important factor affecting the uptake rate. The isotropic exchange kinetics for BPs in the TECAM were verified, and the results indicated that BPs can be calibrated with performance reference compounds (PRCs) in field applications. Finally, a field deployment of TECAM in river waters successfully estimated the time-weighted concentrations of two hydrophobic BPs. To address the inherent weaknesses of TECAM in sampling hydrophilic and moderately hydrophobic BPs, future studies should explore alternative passive samplers, such as hydrophilic-lipophilic balance sorbent-embedded cellulose acetate membranes, to sample BPs in surface waters.

Metal-N4@Graphene as Multifunctional Anchoring Materials for Na-S Batteries: First-Principles Study.

Developing highly efficient anchoring materials to suppress sodium polysulfides (NaPSs) shuttling is vital for the practical applications of sodium sulfur (Na-S) batteries. Herein, we systematically investigated pristine graphene and metal-N4@graphene (metal = Fe, Co, and Mn) as host materials for sulfur cathode to adsorb NaPSs via first-principles theory calculations. The computing results reveal that Fe-N4@graphene is a fairly promising anchoring material, in which the formed chemical bonds of Fe-S and N-Na ensure the stable adsorption of NaPSs. Furthermore, the doped transition metal iron could not only dramatically enhance the electronic conductivity and the adsorption strength of soluble NaPSs, but also significantly lower the decomposition energies of Na2S and Na2S2 on the surface of Fe-N4@graphene, which could effectively promote the full discharge of Na-S batteries. Our research provides a deep insight into the mechanism of anchoring and electrocatalytic effect of Fe-N4@graphene in sulfur cathode, which would be beneficial for the development of high-performance Na-S batteries.

Spatial pattern analysis reveals multiple sources of organophosphorus flame retardants in coastal waters.

Organophosphorus flame retardants (PFRs) are a group of emerging contaminants which have been detected in worldwide waters. However, source of various PFRs in the large-scale area like coastal water environment have not been clearly revealed. In this study, fifteen PFRs in coast of Guangdong-Hong Kong-Macao Greater Bay area (GBA), China were investigated, and a method of spatial pattern analysis was firstly used for pollution source identification. Seawater samples from different segments of GBA coast were analyzed and thirteen PFRs were quantified with total concentrations ranging from 32.7 to 1032.7 ng L-1. GBA coasts have been seriously polluted by PFRs. A hierarchical cluster analysis of the PFR concentrations in different GBA sites showed significant spatial distributions for different types of PFRs. A series of correlation analysis between PFRs distributions and spatial pattern of GBA socio-economic indicators were performed, and multiple sources including human settlement, wastewater, manufacture, construction industry, vehicles, and shipping transport were found to be correlated to PFRs pollutions in the coasts. This study indicates that spatial pattern analysis based on statistical analysis would be a promising method of analyzing environmental data and exploring pollution source in large-scale area.

Benchmark Investigation of Band-Gap Tunability of Monolayer Semiconductors under Hydrostatic Pressure with Focus-On Antimony.

In this paper, the band-gap tunability of three monolayer semiconductors under hydrostatic pressure was intensively investigated based on first-principle simulations with a focus on monolayer antimony (Sb) as a semiconductor nanomaterial. As the benchmark study, monolayer black phosphorus (BP) and monolayer molybdenum disulfide (MoS2) were also investigated for comparison. Our calculations showed that the band-gap tunability of the monolayer Sb was much more sensitive to hydrostatic pressure than that of the monolayer BP and MoS2. Furthermore, the monolayer Sb was predicted to change from an indirect band-gap semiconductor to a conductor and to transform into a double-layer nanostructure above a critical pressure value ranging from 3 to 5 GPa. This finding opens an opportunity for nanoelectronic, flexible electronics and optoelectronic devices as well as sensors with the capabilities of deep band-gap tunability and semiconductor-to-metal transition by applying mechanical pressure.

Boosting Lithium Storage in Free-Standing Black Phosphorus Anode via Multifunction of Nanocellulose.

Layer-structured black phosphorus (BP) demonstrating high specific capacity has been viewed as a very promising anode material for future high-energy-density Li-ion batteries (LIBs). However, its practical application is hindered by large volume change of BP and poor mechanical stability of BP anodes by traditional slurry casting technology. Here, a free-standing flexible anode composed of BP nanosheets and nanocellulose (NC) nanowires is fabricated via a facile vacuum-assisted filtration approach. The constructed free-standing BP@NC composite anode offers three-dimensional (3D) mixed-conducting network for Li+/e- transports. The substrate of NC film has a certain flexibility up to 10.2% elongation that can restrain the volume change of BP and electrode during operation. In addition, molecular dynamic (MD) simulation and density function theory (DFT) show the greatly enhanced Li+ diffusion in BP@NC composite where the Li ions receive less repulsive force at the interface of BP interlayer and nanocellulose. Benefiting from above multifunction of nanocellulose, the BP@NC composite exhibits high capacities of 1020.1 mAh g-1 at 0.1 A g-1 after 230 cycles and 994.4 mAh g-1 at 0.2 A g-1 after 400 cycles, corresponding to high capacity retentions of 87.1% and 84.9%, respectively. Our results provide a low-cost and effective strategy to develop advanced electrodes for next-generation rechargeable batteries.

Prediction of the terahertz absorption features with a straightforward molecular dynamics method.

In this paper, we provide a straightforward method to predict the terahertz absorption spectrum based on a fixed charge model with classic molecular dynamics calculations. The absorption features in the frequency range between 1 and 3.4 THz of stearic acid B-form and between 1 and 2.7 THz of C-form were successfully calculated. Most of the absorption peaks from the simulation correspond well with those from the measurements. By calculating the spatial and time-dependent energy accumulation in the molecular system, the core idea of our calculation method is further validated. Compared with the ab initio calculations, our method provides a computationally inexpensive way to accurately predict the locations of absorption features. With regard to the traditional molecular dynamic simulations, our method is able to extract the spatial distribution of the energy accumulation as well as the local motions in the molecular system.

Electrochemical Analysis for Enhancing Interface Layer of Spinel LiNi0.5Mn1.5O4 Using p-Toluenesulfonyl Isocyanate as Electrolyte Additive.

LiNi0.5Mn1.5O4 (LNMO) is a potential cathode material for lithium-ion batteries with outstanding energy density and high voltage plateau (>4.7 V). However, the interfacial side reaction between LNMO and the liquid electrolyte seriously causes capacity fading during cycling at the high voltage. Here, p-toluenesulfonyl isocyanate (PTSI) is used as the electrolyte additive to overcome the above problem of LNMO. The results show that the specific capacity of LNMO/Li cell with 0.5 wt.% PTSI at the first cycle is effectively enhanced by 36.0 mAh/g and has better cycling performance than that without PTSI at 4.98 V. Also, a stable solid electrolyte interface (SEI) film derived from PTSI is generated on the electrode surface, which could alleviate the strike of hydrofluoric acid (HF) caused by electrolyte decomposition. These results are explained by the molecular structure of PTSI, which contains SO3. The S=O groups can delocalize the nitrogen nucleus to block the reactivity of PF5.

Correlation between saturated fatty acid chain-length and intermolecular forces determined with terahertz spectroscopy.

We measured crystalline (C-form) saturated fatty acids with even carbon numbers ranging from 12 to 20 using temperature dependent terahertz time-domain spectroscopy (THz-TDS). Absorption features between 0.5 and 3 THz were identified at temperatures from 96 K to 293 K, and a systematic red-shift was obvserved with the increasing carbon chain length. The origins of these absorption bands were uncovered using state-of-the-art ab initio density functional theory (DFT) calculations. Similar vibrational motions in the absorption bands of the different materials highlight the unique role that THz-TDS has for probing weak non-covalent interactions in these materials. Our results showcase the utility of the terahertz region, which is beyond the scope of related vibrational techniques, providing direct evidence of the effect of chain length on the intermolecular interactions of these molecules.

Optimal Quantity of Nano-Silicon for Electrospun Silicon/Carbon Fibers as High Capacity Anodes.

In this study, silicon/carbon composite nanofibers (Si@CNFs) were prepared as electrode materials for lithium-ion batteries via a simple electrospinning method and then subjected to heat treatment. The morphology and structure of these materials were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The results show that the structure provides good electrical conductivity and affords sufficient space to accommodate volume expansion during charging/discharging. Furtherly, electrochemical performance tests show that the optimized Si@CNFs have an initial reversible capacity of 1,820 mAh g-1 at a current density of 400 mA g-1 and capacity retention of 80.7% after 100 cycles at a current density of 800 mA g-1. Interestingly, the optimized Si@CNFs have a superior capacity of 1,000 mAh g-1 (400 mA g-1) than others, which is attributed to the carbon substrate nanofiber being able to accommodate the volume expansion of Si. The SEI resistance generated by the Si@CNFs samples is smaller than that of the Si nanoparticles, which confirms that SEI film generated from the Si@CNFs is much thinner than that from the Si nanoparticles. In addition, the connected carbon substrate nanofiber can form a fiber network to enhance the electronic conductivity.