Ultrasensitive electrochemical microRNA-21 detection based on MXene and ATRP photocatalytic strategy.

A Ti3C2TxMXene-based biosensor has been developed and the photocatalytic atom transfer radical polymerization (photo ATRP) amplification strategy applied to detect target miRNA-21 (tRNA). Initially, Ti3C2TxMXene nanosheets were synthesized from the Ti3AlC2 MAX precursor via selective aluminum etching. Then, functionalization of Ti3C2TxMXene nanosheets with 3-aminopropyl triethoxysilane (APTES) via silylation reactions to facilitate covalent bonding with hairpin DNA biomolecules specifically designed for tRNA detection. Upon binding with the tRNA, the hairpin DNA liberated the azide (N3) group, initiating a click reaction to affix to the photo ATRP initiator. Through the ATRP photoreaction, facilitated by an organic photoredox catalyst and light, a significant amount of ferrocenyl methyl methacrylate (FMMA) monomer was immobilized on the electrode. Therefore, the electrochemical signal is amplified. The electrochemical efficacy of the biosensor was assessed using square wave voltammetry (SWV). Under optimized conditions, the biosensor demonstrated remarkable sensitivity in detecting tRNA, with a linear detection range from 0.01 fM to 10 pM and a detection limit of 2.81 aM. The findings elucidate that the developed biosensor, in conjunction with the photo ATRP strategy, offers reproducibility, stability, and increased sensitivity, underscoring its potential applications within the experimental medical sector of the biomolecular industry.

Nacre-Inspired Strong MXene/Cellulose Fiber with Superior Supercapacitive Performance via Synergizing the Interfacial Bonding and Interlayer Spacing.

MXene fibers are promising candidates for weaveable and wearable energy storage devices because of their good electrical conductivity and high theoretical capacitance. Herein, we propose a nacre-inspired strategy for simultaneously improving the mechanical strength, volumetric capacitance, and rate performance of MXene-based fibers through synergizing the interfacial interaction and interlayer spacing between Ti3C2TX nanosheets. The optimized hybrid fibers (M-CMC-1.0%) with 99 wt % MXene loading exhibit an improved tensile strength of ∼81 MPa and a high specific capacitance of 885.0 F cm-3 at 1 A cm-3 together with an outstanding rate performance of 83.6% retention at 10 A cm-3 (740.0 F cm-3). As a consequence, the fiber supercapacitor (FSC) based on the M-CMC-1.0% hybrid delivers an output capacitance of 199.5 F cm-3, a power density of 1186.9 mW cm-3, and an energy density of 17.7 mWh cm-3, respectively, implying its promising applications as portable energy storage devices for future wearable electronics.

Identifying the Role of the Cationic Geometric Configuration in Spinel Catalysts for Polysulfide Conversion in Sodium-Sulfur Batteries.

An AB2X4 spinel structure, with tetrahedral A and octahedral B sites, is a paradigmatic class of catalysts with several possible geometric configurations and numerous applications, including polysulfide conversion in metal-sulfur batteries. Nonetheless, the influence of the geometric configuration and composition on the mechanisms of catalysis and the precise manner in which spinel catalysts facilitate the conversion of polysulfides remain unknown. To enable controlled exposure of single active configurations, herein, Cotd2+ and Cooh3+ in Co3O4 catalysts for sodium polysulfide conversion are in large part replaced by Fetd2+ and Feoh3+, respectively, generating FeCo2O4 and CoFe2O4. Through an examination of electrochemical activation energies, the characterization of symmetric cells, and theoretical calculations, we determine that Cooh3+ serves as the active site for the breaking of S-S bonds, while Cotd2+ functions as the active site for the formation of S-Na bonds. The current study underlines the subtle relationship between activity and geometric configurations of spinel catalysts, providing unique insights for the rational development of improved catalysts by optimizing their atomic geometric configuration.

Rheology Engineering for Dry-Spinning Robust N-Doped MXene Sediment Fibers toward Efficient Charge Storage.

MXene nanosheets are believed to be an ideal candidate for fabricating fiber supercapacitors (FSCs) due to their metallic conductivity and superior volumetric capacitance, while challenges remain in continuously collecting bare MXene fibers (MFs) via the commonly used wet-spinning technique due to the intercalation of water molecules and a weak interaction between Ti3 C2 TX nanosheets in aqueous coagulation bath that ultimately leads to a loosely packed structure. To address this issue, for the first time, a dry-spinning strategy is proposed by engineering the rheological behavior of Ti3 C2 TX sediment and extruding the highly viscose stock directly through a spinneret followed by a solvent evaperation induced solidification. The dry-spun Ti3 C2 TX fibers show an optimal conductivity of 2295 S cm-1 , a tensile strength of 64 MPa and a specific capacitance of 948 F cm-3 . Nitrogen (N) doping further improves the capacitance of MFs to 1302 F cm-3 without compromising their mechanical and electrical properties. Moreover, the FSC based on N-doped MFs exhibits a high volumetric capacitance of 293 F cm-3 , good stability over 10 000 cycles, excellent flexibility upon bending-unbending, superior energy/power densities and anti-self-discharging property. The excellent electrochemical and mechanical properties endow the dry-spun MFs great potential for future applications in wearable electronics.

Ti3 C2 TX MXene Ink Direct Writing Flexible Sensors for Disposable Paper Toys.

Flexible electronics have gained great attention in recent years owing to their promising applications in biomedicine, sustainable energy, human-machine interaction, and toys for children. Paper mainly produced from cellulose fibers is attractive substrate for flexible electronics because it is biodegradable, foldable, tailorable, and light-weight. Inspired by daily handwriting, the rapid prototyping of sensing devices with arbitrary patterns can be achieved by directly drawing conductive inks on flat or curved paper surfaces; this provides huge freedom for children to design and integrate "do-it-yourself (DIY)" electronic toys. Herein, viscous and additive-free ink made from Ti3 C2 TX MXene sediment is employed to prepare disposable paper electronics through a simple ball pen drawing. The as-drawn paper sensors possess hierarchical microstructures with interweaving nanosheets, nanoflakes, and nanoparticles, therefore exhibiting superior mechanosensing performances to those based on single/fewer-layer MXene nanosheets. As proof-of-concept applications, several popular children's games are implemented by the MXene-based paper sensors, including "You say, I guess," "Emotional expression," "Rock-Paper-Scissors," "Arm wrestling," "Throwing game," "Carrot squat," and "Grab the cup," as well as a DIY smart whisker for a cartoon mouse. Moreover, MXene-based paper sensors are safe and disposable, free from producing any e-waste and hazard to the environment.

A Review on the Prediction of Health State and Serving Life of Lithium-Ion Batteries.

The monitoring and prediction of the health status and the end of life of batteries during the actual operation plays a key role in the battery safety management. However, although many related studies have achieved exciting results, there are few systematic and comprehensive reviews on these prediction methods. In this paper, the current prediction models of remaining useful life of lithium-ion batteries are divided into mechanism-based models, semi-empirical models and data-driven models. Their advantages, technical obstacles, improvement methods and prediction performance are summarized, and the latest research results are shown by comparison. We highlight that the fusion models of convolution neural network, long short term memory network and so on, which have great practical application prospects because of their outstanding computing efficiency and strong modeling ability. Finally, we look forward to the future work in simplifying the model and improving its interpretability.

2D material-based peroxidase-mimicking nanozymes: catalytic mechanisms and bioapplications.

The boom in nanotechnology brings new insights into the development of artificial enzymes (nanozymes) with ease of modification, lower manufacturing cost, and higher catalytic stability than natural enzymes. Among various nanomaterials, two-dimensional (2D) nanomaterials exhibit promising enzyme-like properties for a plethora of bioapplications owing to their unique physicochemical characteristics of tuneable composition, ultrathin thickness, and huge specific surface area. Herein, we review the recent advances in several 2D material-based nanozymes, such as carbonaceous nanosheets, metal-organic frameworks (MOFs), transition metal dichalcogenides (TMDs), layered double hydroxides (LDHs), and transition metal oxides (TMOs), clarify the mechanisms of peroxidase (POD)-mimicking catalytic behaviors, and overview the potential bioapplications of 2D nanozymes.

A Capacitor-type Faradaic Junction for Direct Solar Energy Conversion and Storage.

Two-electrode solar rechargeable devices trigger intense attention due to their potential applications in solar energy conversion and storage. However, interface energy barriers lead to severe loss of output voltage and negligible dark discharge current. Therefore, external biases are required for dark discharge in these devices, limiting their practical applications. Herein, we report a new two-electrode device of Si/WO3 /H2 SO4(aq) /C that can work without bias. The device has the highest dark output power among all of the two-electrode solar rechargeable devices. The device based on a Si/WO3 junction indicates photoinduced adjustable interface barrier height during charge transfer, which can overcome the energy barrier and realize dark discharge without bias. Owing to the interface characteristics, the Si/WO3 is designated as a capacitor-type Faradaic junction.

Microstructure Design of Carbonaceous Fibers: A Promising Strategy toward High-Performance Weaveable/Wearable Supercapacitors.

Fiber-based supercapacitors (FSCs) possess great potential as an ideal type of power source for future weaveable/wearable electronics and electronic-textiles. The performance of FSCs is, without doubt, primarily determined by the properties of fibrous electrodes. Carbonaceous fibers, e.g., commercial carbon fibers, newly developed graphene fibers, and carbon nanotube fibers, are deemed as promising materials for weaveable/wearable supercapacitors owing to their exotic properties including high tensile strength and robustness, excellent electrical conductivity, good flexibility, and environmental stability. Nevertheless, bare carbonaceous fiber normally exhibits low capacitance originating from electric double-layer capacitance, which remains unsatisfactory for efficiently powering wearable and portable devices. Numerous efforts have been devoted to tailoring fiber properties by hybridizing pseudocapacitive materials, and impressive progress has been achieved thus far. Herein, the microstructures of pristine carbonaceous fibers are introduced in detail, and the recent advances in rational nano/microstructure design of their hybrids, which provides the feasibility to achieve the synergistic interaction between conductive agents and pseudocapacitive nanomaterials but are normally overlooked, are comprehensively reviewed. Besides, the challenges in developing high-performance fibrous electrodes are also elaborately discussed.

Rational Design of a Flexible CNTs@PDMS Film Patterned by Bio-Inspired Templates as a Strain Sensor and Supercapacitor.

Flexible devices integrated with sensing and energy storage functions are highly desirable due to their potential application in wearable electronics and human motion detection. Here, a flexible film is designed in a facile and low-cost leaf templating process, comprising wrinkled carbon nanotubes (CNTs) as the conductive layer and patterned polydimethylsiloxane (PDMS) with bio-inspired microstructure as a soft substrate. Assembled from wrinkled CNTs on patterned PDMS film, a strain sensor is realized to possess sensitive resistance response against various deformations, producing a resistance response of 0.34%, 0.14%, and 9.1% under bending, pressing, and 20% strain, respectively. Besides, the strain sensor can reach a resistance response of 3.01 when stretched to 44%. Furthermore, through the electro-deposition of polyaniline, the CNTs film is developed into a supercapacitor, which exhibits a specific capacitance of 176 F g-1 at 1 A g-1 and a capacitance retention of 88% after 10 000 cycles. In addition, the fabricated supercapacitor shows super flexibility, delivering a capacitance retention of 98% after 180° bending for 100 cycles, 95% after 45° twisting for 100 cycles, and 98% after 100% stretching for 400 cycles. The superior capacitance stability demonstrates that the design of wrinkled CNTs-based electrodes fixed by microstructures is beneficial to the excellent electrochemical performance.

Electrostatically Assembling 2D Nanosheets of MXene and MOF-Derivatives into 3D Hollow Frameworks for Enhanced Lithium Storage.

As an essential member of 2D materials, MXene (e.g., Ti3 C2 Tx ) is highly preferred for energy storage owing to a high surface-to-volume ratio, shortened ion diffusion pathway, superior electronic conductivity, and neglectable volume change, which are beneficial for electrochemical kinetics. However, the low theoretical capacitance and restacking issues of MXene severely limit its practical application in lithium-ion batteries (LIBs). Herein, a facile and controllable method is developed to engineer 2D nanosheets of negatively charged MXene and positively charged layered double hydroxides derived from ZIF-67 polyhedrons into 3D hollow frameworks via electrostatic self-assembling. After thermal annealing, transition metal oxides (TMOs)@MXene (CoO/Co2 Mo3 O8 @MXene) hollow frameworks are obtained and used as anode materials for LIBs. CoO/Co2 Mo3 O8 nanosheets prevent MXene from aggregation and contribute remarkable lithium storage capacity, while MXene nanosheets provide a 3D conductive network and mechanical robustness to facilitate rapid charge transfer at the interface, and accommodate the volume expansion of the internal CoO/Co2 Mo3 O8 . Such hollow frameworks present a high reversible capacity of 947.4 mAh g-1 at 0.1 A g-1 , an impressive rate behavior with 435.8 mAh g-1 retained at 5 A g-1 , and good stability over 1200 cycles (545 mAh g-1 at 2 A g-1 ).

A Solid-State Fibriform Supercapacitor Boosted by Host-Guest Hybridization between the Carbon Nanotube Scaffold and MXene Nanosheets.

Fiber-shaped supercapacitors with improved specific capacitance and high rate capability are a promising candidate as power supply for smart textiles. However, the synergistic interaction between conductive filaments and active nanomaterials remains a crucial challenge, especially when hydrothermal or electrochemical deposition is used to produce a core (fiber)-shell (active materials) fibrous structure. On the other hand, although 2D pseudocapacitive materials, e.g., Ti3 C2 T x (MXene), have demonstrated high volumetric capacitance, high electrical conductivity, and hydrophilic characteristics, MXene-based electrodes normally suffer from poor rate capability owing to the sheet restacking especially when the loading level is high and solid-state gel is used as electrolyte. Herein, by hosting MXene nanosheets (Ti3 C2 T x ) in the corridor of a scrolled carbon nanotube (CNT) scaffold, a MXene/CNT fiber with helical structure is successfully fabricated. These features offer open spaces for rapid ion diffusion and guarantee fast electron transport. The solid-state supercapacitor based on such hybrid fibers with gel electrolyte coating exhibits a volumetric capacitance of 22.7 F cm-3 at 0.1 A cm-3 with capacitance retention of 84% at current density of 1.0 A cm-3 (19.1 F cm-3 ), improved volumetric energy density of 2.55 mWh cm-3 at the power density of 45.9 mW cm-3 , and excellent mechanical robustness.

Electrochemically Mediated Surface-Initiated de Novo Growth of Polymers for Amplified Electrochemical Detection of DNA.

The development of convenient and efficient strategies without involving any complex nanomaterials or enzymes for signal amplification is of great importance in bioanalytical applications. In this work, we report the use of electrochemically mediated surface-initiated atom transfer radical polymerization (SI-eATRP) as a novel amplification strategy based on the de novo growth of polymers (dnGOPs) for the electrochemical detection of DNA. Specifically, the capture of target DNA (tDNA) by the immobilized peptide nucleic acid (PNA) probes provides a high density of phosphate groups for the subsequent attachment of ATRP initiators onto the electrode surface by means of the phosphate-Zr4+-carboxylate chemistry, followed by the de novo growth of electroactive polymer via the SI-eATRP. De novo growth of long polymeric chains enables the labeling of numerous electroactive probes, which in turn greatly improves the electrochemical response. Moreover, it circumvents the slow kinetics and poor coupling efficiency encountered when nanomaterials or preformed polymers are used and features sufficient flexibility and simplicity in controlling the degree of signal amplification. Under optimal conditions, it allows a highly sensitive and selective detection of tDNA within a broad linear range from 0.1 fM to 0.1 nM (R2 = 0.996), with the detection limit down to 0.072 fM. Compared with the unamplified method, more than 1.2 × 106-fold sensitivity improvement in DNA detection can be achieved. By virtue of its simplicity, high efficiency, and cost-effectiveness, the proposed dnGOPs-based signal amplification strategy holds great potential in bioanalytical applications for the sensitive detection of biological molecules.

Interface/defect-tuneable macro and micro photoluminescence behaviours of trivalent europium ions in electrospun ZrO2/ZnO porous nanobelts.

It was demonstrated that suitable interfaces between two materials can enhance the separation of photogenerated carriers. In this study, ZrO2/ZnO interfaces with type I structure were designed and prepared by the electrospinning technique. The obtained ZrO2/ZnO:Eu3+ (ZZOE) composites are highly porous in the form of nanobelts with width of 600-700 nm, comprising ZnO and ZrO2 nanocrystals, and the Eu doping can hinder the t-m phase transition of ZrO2. By tuning the annealing temperature, the inner stress and defects can be well controlled to improve the photoluminescence (PL) of the ZZOE porous nanobelts. Macro- and micro-PL spectra indicated that the body oxygen vacancies benefit the PL from Eu3+ ions, whereas the surficial ones do not. The optimal parameters for the preparation of ZZOE porous nanobelts were also investigated. Finally, a charge transfer mechanism was proposed to illuminate the PLs from the ZZOE porous nanobelts.

Quantum dots derived from two-dimensional materials and their applications for catalysis and energy.

Quantum dots (QDs) derived from the atomically-thin two-dimensional (2D) sheets (graphene, transition metal dichalcogenide, graphitic carbon nitride, hexagonal boron nitride, and phosphorene) are emerging extraordinary zero-dimensional materials. Covering a broad spectrum of interesting optical, catalytic, electronic, chemical and electrochemical properties, these 2D-QDs promise a wide range of novel applications including imaging, sensing, cancer therapy, optoelectronics, display, catalysis, and energy. In this article, we discuss the synthesis methods and the properties of these 2D-QDs and emphasize their applications in electrocatalysis, photocatalysis, supercapacitors, batteries, and photovoltaics.

Interaction and charge transfer between isolated thylakoids and multi-walled carbon nanotubes.

Charge separation in photosynthetic light reactions has gained much interest in an attempt to fabricate biological photovoltaic devices through integration of photosynthetic material and conducting electrodes. Direct interaction between thylakoids, as representatives of photosynthetic materials, and multi-walled carbon nanotubes (MWCNTs) is expected to increase charge transfer. Thylakoids are isolated from spinach leaf chloroplasts and pristine MWCNTs are dispersed in Triton X-100 (TX-100) as a surfactant to retain their electronic properties through non-covalent interactions. The Raman and UV-Vis spectra suggest close interactions between the thylakoids and the MWCNTs. Stable thylakoids including the embedded protein subunits and light harvesting antennas can be detected from the non-shifted 680 nm absorbance peak. The 50% fluorescence quenching in the MWCNTs-thylakoids preparation as compared to thylakoids alone using single wavelength excitation suggests charge transfer between the thylakoids and the MWCNTs.

Heteroatom-doped graphene materials: syntheses, properties and applications.

Heteroatom doping can endow graphene with various new or improved electromagnetic, physicochemical, optical, and structural properties. This greatly extends the arsenal of graphene materials and their potential for a spectrum of applications. Considering the latest developments, we comprehensively and critically discuss the syntheses, properties and emerging applications of the growing family of heteroatom-doped graphene materials. The advantages, disadvantages, and preferential doping features of current synthesis approaches are compared, aiming to provide clues for developing new and controllable synthetic routes. We emphasize the distinct properties resulting from various dopants, different doping levels and configurations, and synergistic effects from co-dopants, hoping to assist a better understanding of doped graphene materials. The mechanisms underlying their advantageous uses for energy storage, energy conversion, sensing, and gas storage are highlighted, aiming to stimulate more competent applications.

Hybrid fibers made of molybdenum disulfide, reduced graphene oxide, and multi-walled carbon nanotubes for solid-state, flexible, asymmetric supercapacitors.

One of challenges existing in fiber-based supercapacitors is how to achieve high energy density without compromising their rate stability. Owing to their unique physical, electronic, and electrochemical properties, two-dimensional (2D) nanomaterials, e.g., molybdenum disulfide (MoS2 ) and graphene, have attracted increasing research interest and been utilized as electrode materials in energy-related applications. Herein, by incorporating MoS2 and reduced graphene oxide (rGO) nanosheets into a well-aligned multi-walled carbon nanotube (MWCNT) sheet followed by twisting, MoS2 -rGO/MWCNT and rGO/MWCNT fibers are fabricated, which can be used as the anode and cathode, respectively, for solid-state, flexible, asymmetric supercapacitors. This fiber-based asymmetric supercapacitor can operate in a wide potential window of 1.4 V with high Coulombic efficiency, good rate and cycling stability, and improved energy density.

Fabrication of ultralong hybrid microfibers from nanosheets of reduced graphene oxide and transition-metal dichalcogenides and their application as supercapacitors.

Two-dimensional materials have attracted increasing research interest owing to their unique electronic, physical, optical, and mechanical properties. We thus developed a general strategy for the fabrication of ultralong hybrid microfibers from a mixture of reduced graphene oxide and transition-metal dichalcogenides (TMDs), including MoS2 , TiS2 , TaS2 , and NbSe2 . Furthermore, we prepared fiber-based solid-state supercapacitors as a proof-of-concept application. The performance of thus-prepared supercapacitors was greatly improved by the introduction of the TMDs.

Rational electrolyte design and electrode regulation for boosting high-capacity Zn-iodine fiber-shaped batteries with four-electron redox reactions.

Aqueous Zn ion-based fiber-shaped batteries (AZFBs) with the merits of high flexibility and safety have received much attention for powering wearable electronic devices. However, the relatively low specific capacity provided by cathode materials limits their practical application. Herein, we first propose a simple strategy for fabricating high-capacity Zn-iodine fiber-shaped batteries with a high concentration electrolyte and a reduced graphene oxide fiber (GF) cathode. It was found that oxygen functional groups in the graphene sheet demonstrate strong interaction with polyiodides but hinder electron conductivity; thus, the optimal balance between the specific capacity and coulombic efficiency of the GF electrode can be a function of the surface properties at different hydrothermal temperatures. Besides, the regulated high concentration electrolyte effectively suppresses the diffusion of polyiodides, which is attributed to the constrained freedom of water. More importantly, a four-electron redox mechanism was experimentally revealed through in situ Raman spectra. As a result, this fiber-shaped battery delivers a superior high reversible capacity of 390 mA h cm-3 at 1 A cm-3, an excellent rate performance of 125.7 mA h cm-3 at a high current density of 8 A cm-3 and outstanding cycling life with 82% capacitance retention after 2500 cycles.