Multifunctioning of carboxylic-cellulose nanocrystals on the reinforcement of compressive strength and conductivity for acrylic-based hydrogel.

Simultaneously having competitive compressive properties, fatigue-resistant stability, excellent conductivity and sensitivity has still remained a challenge for acrylic-based conductive hydrogels, which is critical in their use in the sensor areas where pressure is performed. In this work, an integrated strategy was proposed for preparing a conductive hydrogel based on acrylic acid (AA) and sodium alginate (SA) by addition of carboxylic-cellulose nanocrystals (CNC-COOH) followed by metal ion interaction to reinforce its compressive strength and conductivity simultaneously. The CNC-COOH played a multifunctional role in the hydrogel by well-dispersing SA and AA in the hydrogel precursor solution for forming a uniform semi-interpenetrating network, providing more hydrogen bonds with SA and AA, more -COOH for metal ion interactions to form uniform multi-network, and also offering high modulus to the final hydrogel. Accordingly, the as-prepared hydrogels showed simultaneous excellent compressive strength (up to 3.02 MPa at a strain of 70 %) and electrical conductivity (6.25 S m-1), good compressive fatigue-resistant (93.2 % strength retention after 1000 compressive cycles under 50 % strain) and high sensitivity (gauge factor up to 14.75). The hydrogel strain sensor designed in this work is capable of detecting human body movement of pressing, stretching and bending with highly sensitive conductive signals, which endows it great potential for multi-scenario strain sensing applications.

Solvent-Free Ultrafast Construction of Se-Deficient Heterojunctions of Bimetallic Selenides toward Flexible Sodium-Ion Full Batteries.

Flexible quasi-solid-state sodium ion batteries featuring their low-cost, high safety and excellent mechanical strength have attracted widespread interest in the field of wearable electronic devices. However, the development of such batteries faces great challenges including the construction of interfacial compatible flexible electrode materials and addressing the high safety demands of electrolyte. Here selenium-vacancies regulated bimetallic selenide heterojunctions anchored on waste cotton cloth-derived flexible carbon cloth (FCC) with robust interfacial C-Se-Co/Fe chemical bonds as a flexible anode material (CCFSF) is proposed by ultrafast microwave pyrolysis method. Rich selenium vacancies and CoSe2 /FeSe2-x heterostructures are synchronously formed that can significantly improve ionic and electronic diffusion kinetics. Additionally, a uniform carbon layer coating on the surface of Se-deficient heterostructures endows it with outstanding structural stability. The flexible cathode (PB@FCC) is also fabricated by directly growing Prussian blue nanoparticles on the FCC. Furthermore, an advanced flexible quasi-solid-state Na-ion pouch cell is assembled by coupling CCFSF anode, PB@FCC cathode with P(VDF-HFP)-based gel polymer electrolyte. The full cell not only demonstrates excellent energy storage performance but also robust mechanical flexibility and safety. The present work offers an effective avenue to achieve high safety flexible energy storage device, promoting the development of flexible wearable electronic devices.

Effect of Selective Metallic Defects on Catalytic Performance of Alloy Nanosheets.

Defects in the crystal structure of nanomaterials are important for their diverse applications. As, defects in 2D framework allow surface confinement effects, efficient molecular accessibility, high surface-area to volume-ratio and lead to higher catalytic activity, but it is challenging to expose defects of specific metal on the surface of 2D alloy and find the correlation between defective structure and electrocatalytic properties with atomic precision. Herein, the work paves the way for the controlled synthesis of ultrathin porous Ir-Cu nanosheets (NSs) with selectively iridium (Ir) rich defects to boost their performance for acidic oxygen evolution reaction (OER). X-ray absorption spectroscopy reveals that the oxidized states of Ir in defects of porous NSs significantly impact the electronic structure and decline the energy barrier. As a result, porous Ir-Cu/C NSs deliver improved OER activity with an overpotential of 237 mV for reaching 10 mA cm-2 and exhibit significantly higher mass activity than benchmark Ir/C under acidic conditions. Therefore, the present work highlights the concept of constructing a selective noble metal defect-rich open structure for catalytic applications.

Modulus difference-induced embedding strategy to construct iontronic pressure sensor with high sensitivity and wide linear response range.

Sensitivity and linearity are two crucial indices to assess the sensing capability of pressure sensors; unfortunately, the two mutually exclusive parameters usually result in limited applications. Although a series of microengineering strategies including micropatterned, multilayered, and porous approach have been provided in detail, the conflict between the two parameters still continues. Here, we present an efficient strategy to resolve this contradiction via modulus difference-induced embedding deformation. Both the microscopic observation and finite element simulation results confirm the embedding deformation behavior ascribed to the elastic modulus difference between soft electrode and rigid microstructures. The iontronic pressure sensor with high sensitivity (35 kPa-1) and wide linear response range (0-250 kPa) is further fabricated and demonstrates the potential applications in monitoring of high-fidelity pulse waveforms and human motion. This work provides an alternative strategy to guide targeted design of all-around and comprehensive pressure sensor.

Skin-Inspired Hair-Epidermis-Dermis Hierarchical Structures for Electronic Skin Sensors with High Sensitivity over a Wide Linear Range.

The quest for both high sensitivity and a wide linear range in electronic skin design is perpetual; unfortunately, these two key parameters are generally mutually exclusive. Although limited success in attaining both high sensitivity and a wide linear range has been achieved via material-specific or complicated structure design, addressing the conflict between these parameters remains a critical challenge. Here, inspired by the human somatosensory system, we propose hair-epidermis-dermis hierarchical structures based on a reduced graphene oxide/poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) aerogel to reconcile this contradiction between high sensitivity and a wide linear range. This hierarchical structure enables an electronic skin (e-skin) sensor linear sensing range up to 30 kPa without sacrificing the high sensitivity (137.7 kPa-1), revealing an effective strategy to overcome the above-mentioned conflict. In addition, the e-skin sensor also exhibits a low detection limit (1.1 Pa), fast responsiveness (∼80 ms), and excellent stability and reproducibility (over 10 000 cycles); as a result, the e-skin platform is capable of detecting small air flow and monitoring human pulse and even sound-induced vibrations. This structure may boost the ongoing research on the structural design and performance regulation of emerging flexible electronics.

Adsorption and desorption mechanisms on graphene oxide nanosheets: Kinetics and tuning.

A knowledge of the adsorption and desorption behavior of sorbates on surface adsorptive site (SAS) is the key to optimizing the chemical reactivity of catalysts. However, direct identification of the chemical reactivity of SASs is still a challenge due to the limitations of characterization techniques. Here, we present a new pathway to determine the kinetics of adsorption/desorption on SASs of graphene oxide (GO) based on total internal reflectance fluorescence microscopy. The switching on and off of the fluorescent signal of SAS lit by carbon dots (CDs) was used to trace the adsorption process and desorption process. We find that sodium pyrophosphate (PPi) could increase the adsorption equilibrium of CDs thermodynamically and promote the substrate-assisted desorption pathway kinetically. At the single turnover level, it was disclosed that the species that can promote desorption may also be an adsorption promoter. Such discovery provides significant guidance for improving the chemical reactivity of the heterogeneous catalyst.

Stretchable, self-healable integrated conductor based on mechanical reinforced graphene/polyurethane composites.

Stretchable conductors are susceptible to wear through repeated deformation over time. Stretchable conductors with self-healing properties can increase longevity and reduce safety hazards. However, most current self-healing conductors can only repair either the conductive layer or the insulating layer. Meantime, high mechanical robustness and self-healing efficiency are exclusive especially at ambient conditions. Realizing a stretchable conductor with integral self-healing and ultra-high mechanical strength is challenging, because this requires good interfacial compatibility and adaptability of the conductive and insulating layers. We adapt a biphasic dynamic network strategy to add toughness to self-healing materials. The DOU (dimethylglyoxime-urethane polyurethane) dynamic bonds and hydrogen bonds in the soft phase enable high self-healing efficiency, while the graphene as a hard phase supports the material's superior mechanical properties. We have prepared an overall self-healing stretchable conductor through the soft phase as a self-encapsulating insulating layer. This all-solid (Tg = -49.5 °C) graphene/dimethylglyoxime-urethane polyurethane (Gr/DOU-PU) composites characteristic of both high mechanical strength (~6 MPa, ~1000%, ~48 MJ m-3), self-healing conductivity (~90%, 10 min, 25 °C) and conductivity (R□=47.8 Ω □-1, d = 0.4 mm). The conductor has excellent stability for flexible electronics and for building stress sensors.

Oxidized titanium carbide MXene-enabled photoelectrochemical sensor for quantifying synergistic interaction of ascorbic acid based antioxidants system.

Antioxidants can protect organization from damage by scavenging of free radicals. When two kinds of antioxidants are consumed together, the total antioxidant capacity might be enhanced via synergistic interactions. Herein, we develop a simple, direct, and effective strategy to quantify the synergistic interaction between ascorbic acid (AA) and other different antioxidants by photoelectrochemical (PEC) technology. MXene Ti3C2-TiO2 composites fabricated via hydrogen peroxide oxidation were applied as sensing material for the antioxidants interaction study. Under excitation of 470 nm wavelength, the photogenerated electrons transfer from the conduction band of TiO2 nanoparticles to the Ti3C2 layers, and the holes in TiO2 can oxidize antioxidants, leading to an enhanced photocurrent as the detection signal. This PEC sensor exhibits a good linear range to AA concentrations from 12.48 to 521.33 µM as well as obvious antioxidants capability synergism. In particular, the photocurrents of AA + gallic acid (GA) and AA + chlorogenic acid (CHA) mixtures at 476.19 µM increase 1.95 and 2.35 times respectively comparing with the sum of photocurrents of AA and GA or CHA. It is found that the synergistic effect is mainly depending on the fact that AA with the low redox potential (0.246 V vs NHE) can reduce other antioxidants radical to promote regeneration, improving the overall antioxidant performance. Moreover, it is proved that the greater redox potential of antioxidants, the more obvious the synergistic effect. In addition, the sensor was used to real sample assay, which provides available information towards food nutrition analysis, health products design and quality inspection.

Enhanced energy density of PVDF-based nanocomposites via a core-shell strategy.

In recent years, high energy density polymer capacitors have attracted a lot of scientific interest due to their potential applications in advanced power systems and electronic devices. Here, core-shell structured TiO2@SrTiO3@polydamine nanowires (TiO2@SrTiO3@PDA NWs) were synthesized via a combination of surface conversion reaction and in-situ polymerization method, and then incorporated into the poly(vinylidene fluoride) (PVDF) matrix. Our results showed that a small amount of TiO2@SrTiO3@PDA NWs can simultaneously enhance the breakdown strength and electric displacement of nanocomposite (NC) films, resulting in improved energy storage capability. The 5 wt% TiO2@SrTiO3@PDA NWs/PVDF NC demonstrates 1.72 times higher maximum discharge energy density compared to pristine PVDF (10.34 J/cm3 at 198 MV/m vs. 6.01 J/cm3 at 170 MV/m). In addition, the NC with 5 wt% TiO2@SrTiO3@PDA NWs also demonstrates an excellent charge-discharge efficiency (69% at 198 MV/m). Enhanced energy storage performance is due to hierarchical interfacial polarization among their multiple interfaces, the large aspect ratio as well as surface modification of the TiO2@SrTiO3 NWs. The results of this study provide guidelines and a foundation for the preparation of the polymer NCs with an outstanding discharge energy density.

Highly Stretchable Fiber-Based Potentiometric Ion Sensors for Multichannel Real-Time Analysis of Human Sweat.

Wearable potentiometric ion sensors are attracting attention for real-time ion monitoring in biological fluids. One of the key challenges lies in keeping the analytical performances under a stretchable state. Herein, we report a highly stretchable fiber-based ion-selective electrode (ISE) prepared by coating an ion-selective membrane (ISM) on a stretchable gold fiber electrode. The fiber ISE ensures high stretchability up to 200% strain with only 2.1% increase in resistance of the fiber electrode. Owing to a strong attachment between the ISM and gold fiber electrode substrate, the ISE discloses favorable stability and potential repeatability. The Nernst slope of the ion response fluctuates from 59.2 to 57.4 mV/dec between 0 and 200% strain. Minor fluctuation of the intercept (E0) (±4.97 mV) also results. The ISE can endure 1000 cycles at the maximum stretch. Sodium, chloride, and pH fiber sensors were fabricated and integrated into a hairband for real-time analysis of human sweat. The result displays a high accuracy compared with ex situ analysis. The integrated sensors were calibrated before and just after on-body measurements, and they offer reliable results for sweat analysis.

Rational Construction of 2D Fe3 O4 @Carbon Core-Shell Nanosheets as Advanced Anode Materials for High-Performance Lithium-Ion Half/Full Cells.

Transition metal oxides have vastly limited practical application as electrode materials for lithium-ion batteries (LIBs) due to their rapid capacity decay. Here, a versatile strategy to mitigate the volume expansion and low conductivity of Fe3 O4 by coating a thin carbon layer on the surface of Fe3 O4 nanosheets (NSs) was employed. Owing to the 2D core-shell structure, the Fe3 O4 @C NSs exhibit significantly improved rate performance and cycle capability compared with bare Fe3 O4 NSs. After 200 cycles, the discharge capacity at 0.5 A g-1 was 963 mA h g-1 (93 % retained). Moreover, the reaction mechanism of lithium storage was studied in detail by ex situ XRD and HRTEM. When coupled with a commercial LiFePO4 cathode, the resulting full cell retains a capacity of 133 mA h g-1 after 100 cycles at 0.1 A g-1 , which demonstrates its superior energy storage performance. This work provides guidance for constructing 2D metal oxide/carbon composites with high performance and low cost for the field of energy storage.

Tough, Ultralight, and Water-Adhesive Graphene/Natural Rubber Latex Hybrid Aerogel with Sandwichlike Cell Wall and Biomimetic Rose-Petal-Like Surface.

Graphene aerogel (GA) as a rising multifunctional material has demonstrated great potential for energy storage and conversion, environmental remediation, and high-performance sensors or actuators. However, the commercial use of GA is obstructed by its fragility and high cost. Herein, by a simple stirring-induced foaming of the mixed aqueous solutions of natural rubber latex (NRL) and graphene oxide liquid crystal (GOLC), we obtained tough, ultralight (4.6 mg cm-3), high compressibility (>90%), and water-adhesive graphene/NRL hybrid aerogel (GA/NRL). Of particular note, the NRL particles are conformally wrapped by graphene layers to form a sandwichlike cell wall with a biomimetic rose-petal-like surface. These distinct hierarchical structures endow GA/NRL not only with high toughness to bear impact, torsion (>90°), and even ultrasonication but also with strong adhesion to water. As proof of concept, the utilization of the as-prepared GA/NRL for collecting water droplets suspended in moist air and its improved solar-thermal harvest capacity have been demonstrated. This facile, green, and cost-effective strategy opens a new route for tailoring the microstructure and functionality of GA, which will facilitate its large-scale production and commercial application.

N-Doped Graphene Oxide Decorated with PtCo Nanoparticles for Immobilization of Double-Stranded Deoxyribonucleic Acid and Investigation of Clenbuterol-Induced DNA Damage.

We demonstrate here a facile hydrothermal-assisted formation of PtCo alloy nanoparticles (NPs) and their simultaneous anchoring on the graphitic surface of N-doped graphene oxide (NGO). Doping induced nanopores in the carbon surface to facilitate the uniform and homogeneous anchoring of alloy nanoparticles. It was revealed that the formation of PtCo NPs on an NGO interface plodded excellent tendency toward double-stranded deoxyribonucleic acid (dsDNA). The dsDNA immobilization was enabled by the presence of several oxidation states of Pt and Co. The same property was further used to monitor the direct detection of dsDNA damage induced by clenbuterol via screen-printed carbon electrodes. Cyclic voltammetric and electrochemical impedance spectroscopic characterization traced well the dsDNA attachment on the modified electrode surface. Differential pulsed voltammetry was further used as a tool to monitor the characteristic guanine peak before and after incubating with clenbuterol used as a damage probe for the dsDNA. The findings can further be appurtenant in exploring dsDNA immobilization protocols and developing analytical methods for determination of various dsDNA damaging agents.

MoS2/ZnO-Heterostructures-Based Label-Free, Visible-Light-Excited Photoelectrochemical Sensor for Sensitive and Selective Determination of Synthetic Antioxidant Propyl Gallate.

Propyl gallate (PG) as one of the important synthetic antioxidants is widely used in the prevention of oxidative deterioration of oils during processing and storage. Determination of PG has received extensive concern because of its possible toxic effects on human health. Herein, we report a photoelectrochemical (PEC) sensor based on ZnO nanorods and MoS2 flakes with a vertically constructed p-n heterojunction. In this system, the n-type ZnO and p-type MoS2 heterostructures exhibited much better optoelectronic behaviors than their individual materials. Under an open circuit potential (zero potential) and visible light excitation (470 nm), the PEC sensor exhibited extraordinary response for PG determination, as well as excellent anti-inference properties and good reproducibility. The PEC sensor showed a wide linear range from 1.25 × 10-7 to 1.47 × 10-3 mol L-1 with a detection limit as low as 1.2 × 10-8 mol L-1. MoS2/ZnO heterostructure with proper band level between MoS2 and ZnO could make the photogenerated electrons and holes separated more easily, which eventually results in great improvement of sensitivity. On the other hand, formation of a five membered chelating ring structure of Zn(II) with adjacent oxygen atoms of PG played significant roles for selective detection of PG. Moreover, the PEC sensor was successfully used for PG analysis in different samples of edible oils. It demonstrated the ability and reliability of the MoS2/ZnO-based PEC sensor for PG detection in real samples, which is beneficial for food quality monitoring and reducing the risk of overuse of PG in foods.

Breathable and Skin-Mountable Strain Sensor with Tunable Stretchability, Sensitivity, and Linearity via Surface Strain Delocalization for Versatile Skin Activities' Recognition.

Metal film/elastomer-based strain sensors usually exhibit small rupture strain (<5%) because of the strain localization and necking effect of the metal film under tension. To achieve both high stretchability and wide linear region is still challenging for metal film-based strain sensors. Here, we propose a low-cost yet effective strategy for fabricating ultrathin, breathable, and skin-mountable strain sensors with high sensitivity (gauge factor from 7.2 to 474.8), high stretchability (up to 140%), and good linearity by regulating the surface strain delocalization in the metal film on elastomer substrate. On the basis of this phenomenon of strain delocalization, the sensitivity and linearity are further enhanced based on a novel diffraction-induced Au film with gradient thickness. Meanwhile, by means of the strain redistribution and Poisson effect, a novel biaxial strain sensor is designed for recognition of complex human motion. On the basis of the enhanced stretchability, linearity, skin-mountable, and breathable properties, the low-cost metal film-based strain sensors can be broadened as disposable wearables for human motion detection, emotional expression recognition, human interaction, and virtual reality.

Direct generation of Ag nanoclusters on reduced graphene oxide nanosheets for efficient catalysis, antibacteria and photothermal anticancer applications.

There is considerable interest in understanding the catalytical, antibacterial, and photo-thermal properties of Ag nanoparticles. Herein, a simple, scalable and effective method is explored to generate Ag nanoclusters (∼3.57 nm) directly on reduced graphene oxide (rGO) (denoted as AgNC/GSH-rGO) using glutathione (GSH) as a green and mild co-reduction agent. Due to the good electrical conductivity of rGO, the extremely small particle size of Ag nanoclusters and the synergistic effect between Ag nanoclusters and rGO, high catalytic activity for reduction of 4-nitrophenol is achieved for AgNC/GSH-rGO at a very low Ag nanoclusters loading of 8.67 wt% on rGO. The conversion could reach 96.69% in 16 min and the apparent rate constant based on rGO is derived to be 0.55 min-1 when the concentration of AgNC/GSH-rGO is 0.04 mg mL-1. Moreover, the AgNC/GSH-rGO nanohybrids are also proven to be an efficient antibacterial and photothermal ablation agent for avoiding wound infection and cancer therapy applications.

Hierarchical Nickel-Cobalt-Based Transition Metal Oxide Catalysts for the Electrochemical Conversion of Biomass into Valuable Chemicals.

The upgrading of biomass into sustainable and valuable fine chemicals is an alternative to the use of state-of-the-art petrochemicals. The conversion of 5-hydroxymethylfurfural (HMF) biomass derivative into 2,5-furandicarboxylic acid (FDCA) has been recognized as an economical and green approach to replace the current polyethylene terephthalate based plastic industry. However, this reaction mostly relies on noble-metal-based catalysts for the sluggish aerobic oxidation of alcohol groups. In this work, we report a series of hierarchical Ni-Co-based transition metal oxide catalysts for HMF oxidation by electrocatalysis. Comprehensive material characterization and electrochemical evaluation have been performed. A 90 % FDCA yield, nearly 100 % Faradaic efficiency, and robust stability were achieved for NiCo2 O4 nanowires. As non-precious-metal catalysts, Ni-Co-based transition metal oxides may open up new potential materials for highly efficient electrochemical biomass upgrading.

Controllable synthesis of coloured Ag0/AgCl with spectral analysis for photocatalysis.

Broad spectrum absorption of semiconductor photocatalysts is an essential requirement to achieve the best values of solar energy utilization. Here, through precise surface state adjustment, coaxial tri-cubic Ag0/AgCl materials with distinct apparent colours (blue and fuchsia) were successfully fabricated. The reasons for the different colour generation of the Ag0/AgCl materials were investigated by performing corresponding spectrum analysis. It was revealed that Ag0/AgCl-blue and Ag0/AgCl-fuchsia crystals could efficiently boost the photon energy harvesting, spanning from the UV to near-infrared spectral region (250-800 nm), and achieved 2.6 and 5.4 times the wastewater degradation efficiency of AgCl-white. Simultaneously, these two fresh coloured candidates were demonstrated to have preferable photocatalytic CO2 photoreduction capability, with yields of ∼3.6 (Ag0/AgCl-fuchsia) and 2.6 (Ag0/AgCl-blue) times that of AgCl-white. It is expected that this work will provide a beneficial perspective for understanding the solar absorption feature at both the major structure modulation and particular surface state regulation level.

One-Step Synthesis of Boron Nitride Quantum Dots: Simple Chemistry Meets Delicate Nanotechnology.

Herein, a conceptually new and straightforward aqueous route is described for the synthesis of hydroxyl- and amino-functionalized boron nitride quantum dots (BNQDs) with quantum yields (QY) as high as 18.3 % by using a facile bottom-up approach, in which a mixture of boric acid and ammonia solution was hydrothermally treated in one pot at 200 °C for 12 h. The functionalized BNQDs, with excellent photoluminescence properties, could be easily dispersed in an aqueous medium and applied as fluorescent probes for the detection of ferrous (Fe2+ ) and ferric (Fe3+ ) ions with excellent selectivity and low detection limits. The mechanisms for the hydrothermal reaction and fluorescence quenching were also simulated by using density functional theory (DFT), which confirmed the feasibility and advantages of this strategy. It provides a scalable and eco-friendly method for preparation of BNQDs with good dispersability and could also be generalized to the synthesis of other 2D quantum dots and nanoplates.