Ultrafast Synthesis of Transition Metal Phosphides in Air via Pulsed Laser Shock.

Transition metal phosphide nanoparticles (TMP NPs) represent a promising class of nanomaterials in the field of energy; however, a universal, time-saving, energy-efficient, and scalable synthesis method is currently lacking. Here, a facile synthesis approach is first introduced using a pulsed laser shock (PLS) process mediated by metal-organic frameworks, free of any inert gas protection, enabling the synthesis of diverse TMP NPs. Additionally, through thermodynamic calculations and experimental validation, the phase selection and competition behavior between phosphorus and oxygen have been elucidated, dictated by the redox potential and electronegativity. The resulting composites exhibit a balanced performance and extended durability. When employed as electrocatalysts for overall water splitting, the as-constructed electrolyzer achieves a low cell voltage of 1.54 V at a current density of 10 mA cm-2. This laser method for phosphide synthesis provides clear guidelines and holds potential for the preparation of nanomaterials applicable in catalysis, energy storage, biosensors, and other fields.

A clean transfer approach to prepare centimetre-scale black phosphorus crystalline multilayers on silicon substrates for field-effect transistors.

Recently reported direct growth of highly crystalline centimetre-sized black phosphorus (BP) thin films on mica substrates by pulsed laser deposition (PLD) has attracted considerable research interest. However, an effective and general transfer method to incorporate them into (opto-)electronic devices is still missing. Here, we show a wet transfer method utilizing ethylene-vinyl acetate (EVA) and an ethylene glycol (EG) solution to transfer high-crystalline large-area PLD-BP films onto SiO2/Si substrates. The transferred films were used to fabricate BP-based bottom-gate field-effect transistor (FET) arrays exhibiting good uniformity and continuity, with carrier mobility and current switching ratios comparable to those obtained in as-grown BP films on mica substrates. Our work presents a promising transfer strategy for scalable integration of on-substrate grown 2D BP into devices with more complex structures and further investigation of material properties.

Direct observation of intrinsic room-temperature ferroelectricity in 2D layered CuCrP2S6.

Multiferroic materials have ignited enormous interest owing to their co-existence of ferroelectricity and ferromagnetism, which hold substantial promise for advanced device applications. However, the size effect, dangling bonds, and interface effect in traditional multiferroics severely hinder their potential in nanoscale device applications. Recent theoretical and experimental studies have evidenced the possibility of realizing two-dimensional (2D) multiferroicity in van der Waals (vdW) layered CuCrP2S6. However, the incorporation of magnetic Cr ions in the ferroelectric framework leads to antiferroelectric and antiferromagnetic orderings, while macroscopic spontaneous polarization is always absent. Herein, we report the direct observation of robust out-of-plane ferroelectricity in 2D vdW CuCrP2S6 at room temperature with a comprehensive investigation. Modification of the ferroelectric polarization states in 2D CuCrP2S6 nanoflakes is experimentally demonstrated. Moreover, external electric field-induced polarization switching and hysteresis loops are obtained in CuCrP2S6 down to ~2.6 nm (4 layers). By using atomically resolved scanning transmission electron microscopy, we unveil the origin of the emerged room-temperature ferroelectricity in 2D CuCrP2S6. Our work can facilitate the development of multifunctional nanodevices and provide important insights into the nature of ferroelectric ordering of this 2D vdW material.

Achieving reinforcement learning in a three-active-terminal neuromorphic device based on a 2D vdW ferroelectric material.

Currently, for most three-terminal neuromorphic devices, only the gate terminal is active. The inadequate modes and freedom of modulation in such devices greatly hinder the implementation of complex neural behaviors and brain-like thinking strategies in hardware systems. Taking advantage of the unique feature of co-existing in-plane (IP) and out-of-plane (OOP) ferroelectricity in two-dimensional (2D) ferroelectric α-In2Se3, we construct a three-active-terminal neuromorphic device where any terminal can modulate the conductance state. Based on the co-operation mode, controlling food intake as a complex nervous system-level behavior is achieved to carry out positive and negative feedback. Specifically, reinforcement learning as a brain-like thinking strategy is implemented due to the coupling between polarizations in different directions. Compared to the single modulation mode, the chance of the agent successfully obtaining the reward in the Markov decision process is increased from 68% to 82% under the co-operation mode through the coupling effect between IP and OOP ferroelectricity in 2D α-In2Se3 layers. Our work demonstrates the practicability of three-active-terminal neuromorphic devices in handling complex tasks and advances a significant step towards implementing brain-like learning strategies based on neuromorphic devices for dealing with real-world challenges.

Rapid and ultrasensitive detection of SARS-CoV-2 spike protein based on upconversion luminescence biosensor for COVID-19 point-of-care diagnostics.

Here, we firstly introduce a detection system consisting of upconversion nanoparticles (UCNPs) and Au nanorods (AuNRs) for an ultrasensitive, rapid, quantitative and on-site detection of SARS-CoV-2 spike (S) protein based on Förster resonance energy transfer (FRET) effect. Briefly, the UCNPs capture the S protein of lysed SARS-CoV-2 in the swabs and subsequently they are bound with the anti-S antibodies modified AuNRs, resulting in significant nonradiative transitions from UCNPs (donors) to AuNRs (acceptors) at 480 nm and 800 nm, respectively. Notably, the specific recognition and quantitation of S protein can be realized in minutes at 800 nm because of the low autofluorescence and high Yb-Tm energy transfer in upconversion process. Inspiringly, the limit of detection (LOD) of the S protein can reach down to 1.06 fg mL-1, while the recognition of nucleocapsid protein is also comparable with a commercial test kit in a shorter time (only 5 min). The established strategy is technically superior to those reported point-of-care biosensors in terms of detection time, cost, and sensitivity, which paves a new avenue for future on-site rapid viral screening and point-of-care diagnostics.

Facile Atomic-Level Tuning of Reactive Metal-Support Interactions in the Pt QDs@ HF-Free MXene Heterostructure for Accelerating pH-Universal Hydrogen Evolution Reaction.

Supported metallic nanoparticles render highly tunable physical and chemical properties to mixed-dimensionality materials in electrocatalysts. However, some supports are susceptible to being dissolved in acidic solution or are unstable in ambient air. The development of high-performance catalysts has been facing the major hurdles of the sluggish activity in alkaline solution and requesting high energy to stabilize the nanoparticles on their supports, challenging the pH-universality and the applicability of the supported metallic nanoparticles. Here, a one-step strategy is proposed to modulate the growth of Pt quantum dots (QDs) on HF-free MXene under atomic-level by a low-temperature metal-support interaction reaction. By controllable tailoring in the morphology and strain induced by terminations, Pt (111) QDs with a sub-nanoscale size of 1.15 nm are grown as 0D/1D heterostructure to overcome the restrictions of employing reduction gas and high annealing temperature. The catalyst exhibits a low overpotential of 33.3 mV for acidic solution, while 65.1 mV for alkaline solution at a specific current density of 10 mA cm-2 . This study not only paves a scalable pathway to developing cost-efficient catalysts in moderate conditions, but also demonstrates an effective surface modulation strategy for 0D/1D heterostructures.

One-Step, DNA-Programmed, and Flash Synthesis of Anisotropic Noble Metal Nanostructures on MXene.

Precise morphological control over anisotropic noble metal nanoparticles (ANPs) is one of the key issues in the nano-research field owing to their unique optoelectronic, magnetic, mechanical, and catalytic properties. Although nanostructures fabricated by the directed assembly of adsorbate have been widely demonstrated recently, facile yet universal synthesis of nanocrystal with tunable morphologies, green templates, no seeds, and high yield remains challenging. Herein, we develop a versatile method, allowing for the rapid, one-step, seedless, surfactant-free synthesis of a noble metal nanostructure with tunable anisotropy on MXene in a sequence-dependent manner through a single-DNA molecular regulator. Based on the mild reducibility of MXene and the selective affinity of the DNA to the specific facets in the crystals, oriented aggregations and the growth of ANPs (Au, Pt, Pd) can be achieved and the resulting asymmetric morphology from polyhedrons, or flowers, or nanoplates to dendrites is observed. The ability to align such ANPs on the MXene surface is expected to lead to improved photothermal effect and surface-enhanced Raman scattering. Furthermore, our work makes the fabrication of the ANPs or ANP-MXene heterostructure easier, stimulating further explorations of physical, chemical, and biological applications.

Effective Piezo-Phototronic Enhancement of Flexible Photodetectors Based on 2D Hybrid Perovskite Ferroelectric Single-Crystalline Thin-Films.

2D hybrid perovskites are very attractive for optoelectronic applications because of their numerous exceptional properties. The emerging 2D perovskite ferroelectrics, in which are the coupling of spontaneous polarization and piezoelectric effects, as well as photoexcitation and semiconductor behaviors, have great appeal in the field of piezo-phototronics that enable to effectively improve the performance of optoelectronic devices via modulating the electro-optical processes. However, current studies on 2D perovskite ferroelectrics focus on bulk ceramics that cannot endure irregular mechanical deformation and limit their application in flexible optoelectronics and piezo-phototronics. Herein, we synthesize ferroelectric EA4 Pb3 Br10 single-crystalline thin-films (SCFs) for integration into flexible photodetectors. The in-plane multiaxial ferroelectricity is evident within the EA4 Pb3 Br10 SCFs through systematic characterizations. Flexible photodetectors based on EA4 Pb3 Br10 SCFs are achieved with an impressive photodetection performance. More importantly, optoelectronic EA4 Pb3 Br10 SCFs incorporated with in-plane ferroelectric polarization and effective piezoelectric coefficient show great promise for the observation of piezo-phototronic effect, which is capable of greatly enhancing the photodetector performance. Under external strains, the responsivity of the flexible photodetectors can be modulated by piezo-phototronic effect with a remarkable enhancement up to 284%. Our findings shed light on the piezo-phototronic devices and offer a promising avenue to broaden functionalities of hybrid perovskite ferroelectrics.

Fluoride-Free 2D Niobium Carbide MXenes as Stable and Biocompatible Nanoplatforms for Electrochemical Biosensors with Ultrahigh Sensitivity.

Recently, 2D niobium carbide MXene has drawn vast attention due to its merits of large surface area, good metallic conductivity, and tunable band gap, making it desirable for various applications. However, the usage of highly toxic fluoride-containing etchant and quite long etching time in the conventional synthesis route has greatly hindered further exploration of MXene, especially restricting its biomedical application. Herein, novel fluoride-free Nb2CT x nanosheets are prepared by a facile strategy of electrochemical etching (E-etching) exfoliation. Taking advantage of rapid aluminum clearance, excellent chemical stability, and biocompatibility from the MXene by E-etching, fluoride-free Nb2CT x /acetylcholinesterase-based biosensors are constructed for phosmet detection with the limit of detection down to 0.046 ng mL-1. The fabricated Nb2CT x -based biosensor is superior to the counterpart from hydrofluoric acid-etched Nb2CT x , indicating that fluoride-free MXene can enhance the enzyme activity and electron transfer in the biosensor. The results prove that the fluorine-free MXene shows promise for developing biosensors with high performance of ultrahigh sensitivity and selectivity. It is highly expected that the fluoride-free MXene as a stable and biocompatible nanoplatform has great potential to be expanded to many other biomedical fields.

Efficient Energy Conversion and Storage Based on Robust Fluoride-Free Self-Assembled 1D Niobium Carbide in 3D Nanowire Network.

Owing to their high robustness and conductivity, 2D transition metal carbides and nitrides known as MXenes are considered as a promising material class for electrochemical catalysis, energy conversion, and storage applications. Nevertheless, conventional hazardous fluoride-based synthesis routes and the intense intralayer bonding restrict the development of MXenes. Herein, a fluoride-free, facile, and rapid method for synthesizing self-assembled 1D architecture from an MXene-based compound is reported. The MXene nanowire (NW) not only provides a robust connection to the flexible substrate but also effectively increases the electrochemically active surface area. The kinetics-favorable structure yields a boosted performance for the hydrogen/oxygen evolution reaction and the intake of the zinc ion. The 1D NW based on MXene compound maintains high stability in a quite low overpotential of 236 mV for 24 h without detachment from the substrate and manifests an exceptional high-power density of 420 W kg-1 over 150 cycles as a flexible aqueous zinc ion battery. This work paves a novel and non-toxic synthesis method for the 1D nanofiber structure from MXene composition and demonstrates its multifunctional applications for energy conversion and storage.

A General Wet Transferring Approach for Diffusion-Facilitated Space-Confined Grown Perovskite Single-Crystalline Optoelectronic Thin Films.

Hybrid perovskite single-crystalline thin films are promising for making high-performance perovskite optoelectronic devices due to their superior physical properties. However, it is still challenging to incorporate them into multilayer devices because of their on-substrate growth. Here, a wet transfer method is used in transferring perovskite single-crystalline films perfectly onto various target substrates. More importantly, large millimeter-scaled single-crystalline films can be obtained via a diffusion-facilitated space-confined growth method as thin as a few hundred nanometers, which are capable of sustaining excellent crystalline quality and morphology after the transferring process. The availability of these crystalline films offers us a convenient route to further investigate their intrinsic properties of hybrid perovskites. We also demonstrate that the wet transfer method can be used for scalable fabrication of perovskite single-crystalline film-based photodetectors exhibiting a remarkable photoresponsivity. It is expected that this transferring strategy would promise broad applications of perovskite single-crystalline films for more complex perovskite devices.

Universal Strategy for HF-Free Facile and Rapid Synthesis of Two-dimensional MXenes as Multifunctional Energy Materials.

Two-dimensional MXenes are promising for various energy-related applications such as energy storage devices and electrocatalysis of water-splitting. MXenes prepared from hydrofluoric (HF) acid etching have been widely reported. Nonetheless, the acute toxicity of HF acid impedes the large-scale fabrication of MXenes and their wide utilization in energy-related applications. It is thus greatly encouraging to explore a more innocuous protocol for MXenes synthesis. Thereby, a universal strategy based on thermal-assisted electrochemical etching route is developed to synthesize MXenes (e.g., Ti2CT x, Cr2CT x, and V2CT x). Furthermore, the cobalt ion doped MXenes show an exceptionally enhanced capability of hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) activity, demonstrating their multifunctionalities, which is comparable to the commercialized catalysts. Moreover, we successfully exploited our MXenes as cathodes for the novel aqueous rechargeable battery, with proficient retention and excellent electrical output performance. This work paves a nontoxic and HF-free route to prepare various MXenes and demonstrates practical applications of the materials.

Valence Engineering via Selective Atomic Substitution on Tetrahedral Sites in Spinel Oxide for Highly Enhanced Oxygen Evolution Catalysis.

A major challenge that prohibits the practical application of single/double-transition metal (3d-M) oxides as oxygen evolution reaction (OER) catalysts is the high overpotentials during the electrochemical process. Herein, our theoretical calculation shows that Fe will be more energetically favorable in the tetrahedral site than Ni and Co, which can further regulate their electronic structure of binary NiCo spinel oxides for optimal adsorption energies of OER intermediates and improved electronic conductivity and hence boost their OER performance. X-ray absorption spectroscopy study on the as-synthesized NiCoFe oxide catalysts indicates that Fe preferentially dopes into tetrahedral sites of the lattice, which induces high proportions of Ni3+ and Co2+ on the octahedral sites (the active sites in OER). Consequently, this material exhibits a significantly enhanced OER performance with an ultralow overpotential of 201 mV cm-2 at 10 mA cm-2 and a small Tafel slope of 39 mV dec-1, which are much superior to state-of-the-art Ni-Co based catalysts.

Electrochemically assisted flexible lanthanide upconversion luminescence sensing of heavy metal contamination with high sensitivity and selectivity.

Heavy metal contamination in water can pose lethal threats to public health; therefore it is highly desired to develop a rapid and sensitive sensor for monitoring water quality. Owing to their superior optical features, upconversion nanoparticles (UCNPs) are widely explored to detect metal ions based on resonance energy transfer to dye quenchers. However, these schemes heavily rely on the optical properties of the molecules, which limits the flexibility of the probe design. Herein, a flexible carbon fiber cloth/UCNP composite probe was fabricated for sensing copper(ii) (Cu2+) ions and an electrochemical (E-chem) technique was implemented for the first time to enhance its sensing performance. By applying 0.3 V on the composite probe, Cu2+ ions can be effectively accumulated through oxidation, yielding a remarkable improvement in the selectivity and sensitivity. A more outstanding detection limit of the sensor was achieved at 82 ppb under the E-chem assistance, with 300-fold enhancement compared to the detection without the E-chem effect. This sensing approach can be an alternative to molecular quenchers and open up new possibilities for simple, rapid and portable sensing of metal ions.