Phase and Defect Engineering of MoSe2 Nanosheets for Enhanced NIR-II Photothermal Immunotherapy.

Inducing immunogenic cell death (ICD) during photothermal therapy (PTT) has the potential to effectively trigger photothermal immunotherapy (PTI). However, ICD induced by PTT alone is often limited by inefficient PTT, low immunogenicity of tumor cells, and a dysregulated redox microenvironment. Herein, we develop MoSe2 nanosheets with high-percentage metallic 1T phase and rich exposed active Mo centers through phase and defect engineering of MoSe2 as an effective nanoagent for PTI. The metallic 1T phase in MoSe2 nanosheets endows them with strong PTT performance, and the abundant exposed active Mo centers endow them with high activity for glutathione (GSH) depletion. The MoSe2-mediated high-performance PTT synergizing with efficient GSH depletion facilitates the release of tumor-associated antigens to induce robust ICD, thus significantly enhancing checkpoint blockade immunotherapy and activating systemic immune response in mouse models of colorectal cancer and triple-negative metastatic breast cancer.

A novel label-free dual-mode aptasensor based on the mutual regulation of silver nanoclusters and MoSe2 nanosheets for reliable detection of ampicillin.

Current methods for the rapid detection of trace antibiotics in the environment remains problems of low accuracy and false negative or false positive, making the development of fast, and accurate, and reliable methods for antibiotic testing a major challenge that needs to be addressed. Herein, we developed a novel label-free colorimetric and fluorescent dual-mode aptasensor assembled by the strong interaction of layered MoSe2 nanosheets (MoSe2 NSs) with ampicillin (AMP) aptamer functionalized silver nanoclusters (Apt-AgNCs) that specifically bind AMP to allow the sensitive and selective detection of AMP. Apt-AgNCs could be adsorbed on the surface of MoSe2 NSs via van der Waals force to form a nanocomposite, Apt-AgNCs/MoSe2 NSs. Interestingly, Apt-AgNCs/MoSe2 NSs act together to construct dual mode aptasensor through modulation of the intrinsic peroxidase activity of MoSe2 NSs and the fluorescence of Apt-AgNCs. In the presence of AMP, Apt-AgNCs could specifically bind AMP, triggering desorption from the MoSe2 NSs surface, leading to a decrease in the peroxidase activity of the system with the recovery in Apt-AgNCs fluorescence. The dual-signal aptasensor exhibited good linear colorimetric and fluorescence responses in the AMP concentration ranges of 0.115-2.00 µM and 6-100 nM, respectively. Furthermore, the aptasensor was successfully measured AMP levels in commercially-bought milk and lake water with satisfactory results. Unlike single-signal aptasensors, the constructed dual-signal aptasensor could not only improve the detection precision, but also reduce the false positive or false negative results. These promising results suggest that the dual-readout strategy as demonstrated is general mode for the detection of other antibiotics or compounds using various aptamers functionalized AgNCs in concert with MoSe2 NSs.

Enhanced photocatalytic hydrogen evolution by piezoelectric effects based on MoSe2/Se-decorated CdS nanowire edge-on heterostructure.

The build-in electric field by the construction of heterojunction is one of the most promising strategies to suppress the recombination of photogenerated carriers. Here, we reported a piezo-photocatalytic system composed of Se-decorated CdS nanowires and few-layered edge-on MoSe2 nanosheets for efficient H2 generation by two-pot hydrothermal synthesis. The few-layered MoSe2 exposed abundant edge sites for hydrogen evolution reaction (HER). The activity of 20-MoSe2/CdS0.95Se0.05 (20-MS/CSS, with 20 mol% of MoSe2 loading) nanocomposite casted a remarkable photocatalytic HER performance, with a rate of 47.3 mmol h-1 g-1. Moreover, MoSe2 nanosheets deformed to generate the piezoelectric polarization field under magnetic stirring, which rendered efficient separation of photogenerated carriers, resulting in a piezo-photocatalytic synergistic effect. As a result, the HER of 20-MS/CSS at 900 rpm for piezo-photocatalysis was 59.1 mmol h-1 g-1, which was 1.25 times that of 20-MS/CSS for photocatalysis. Meanwhile, the photoelectrochemical measurements further visualized the piezo-photoelectric synergy. This study exposes a new way for utilizing mechanical energy to improve photocatalytic performance, and achieving high piezo-photocatalysis.

Direct Z-scheme MoSe2/TiO2 heterostructure with improved piezoelectric and piezo-photocatalytic performance.

Nano-semiconductor materials coupled with piezoelectric effect have received extensive attention due to their wide application in catalysis. In this work, few-layered MoSe2 nanosheets were grown vertically on TiO2 nanorods (TNr) to synthesize a direct Z-scheme heterojunction, exhibiting efficient piezocatalytic and piezo-photocatalytic performance. The MoSe2/TNr heterostructure exhibited superior piezoelectric degradation efficiency, successfully removing over 98% of RhB within 360 s under continuous magnetic stirring in dark. Compared with piezocatalysis, the piezo-photocatalytic system possessed higher degradation efficiency and cycle stability. Furthermore, a piezo-photoelectric synergistic effect of nanocomposites was observed by current outputs. Under stirring conditions, the current density of depleted MoSe2/TNr and MoSe2 nanosheets were respectively 6.3 µA/cm2 and 5.5 µA/cm2. When light and stirring were applied, the MoSe2/TNr current density increased twice to 13.2 µA/cm2, while the MoSe2 nanosheets didn't exhibit improvement. Through the direct Z-scheme heterojunction of MoSe2/TNr, photoexcitation and piezoelectric polarization work together to effectively replenish carriers under light irradiation, and then rapidly separate free charges through piezopotential. This work broadens the application prospects of piezocatalysis and piezo-photocatalysis in renewable energy harvesting and water purification.

Anderson-Type Polyoxometalate-Assisted Synthesis of Defect-Rich Doped 1T/2H-MoSe2 Nanosheets for Efficient Seawater Splitting and Mg/Seawater Batteries.

Designing high-performance hydrogen evolution reaction (HER) catalysts is crucial for seawater splitting. Herein, we demonstrate a facile Anderson-type polyoxometalate-assisted synthesis route to prepare defect-rich doped 1T/2H-MoSe2 nanosheets. As demonstrated, the optimized defect-rich doped 1T/2H-MoSe2 nanosheets display low overpotentials of 116 and 274 mV to gain 10 mA cm-2 in acidic and simulated seawater for the HER, respectively. A magnesium (Mg)/seawater battery was fabricated with the defect-rich doped 1T/2H-MoSe2 nanosheet cathode, displaying the highest power density of up to 7.69 mW cm-2 and stable galvanostatic discharging over 24 h. The theoretical and experimental investigations show that the superior HER and battery performances of the heteroatom-doped MoSe2 nanosheets are attributed to both the improved intrinsic catalytic activity (effective activation of water and favorable subsequent hydrogen desorption) and the abundant active sites, benefiting from the favorable catalytic factors of the doped heteroatom, 1T phase, and defects. Our work presents an intriguing structural modulation strategy to design high-performance catalysts toward both HER and Mg/seawater batteries.

Highly sensitive and flexible pressure sensor based on two-dimensional MoSe2 nanosheets for online wrist pulse monitoring.

The advancement of portable and flexible electronics that is integrated with multiple sensing functions has increasingly drawn considerable interest. The fabricated sensors would have the ability to sense multiple deformations like pressing, twisting and trivial vibrations such as pulses of wrist vibrations to mimic human skin. Presently, we implemented an easy, cost-effective and optimized fabrication technique for production of pressure sensors based on MoSe2 nanosheets coated on cellulose paper. The present sensor exhibits an incorporation of large pressure sensitivity of 18.42 kPa-1 in pressure range 0.001-0.5 kPa, 7.28 kPa-1 in pressure range 1-35 kPa and 2.63 kPa-1 in pressure range 40-100 kPa, working in broad pressure range (from 0.001 to 100 kPa) and long-term stability up to 200 deformation cycles at 2 kPa. The sensor showed excellent response towards the detection of vibrations of machines including cellular phone, compressor, etc. Besides, the sensor shows excellent environmental stability and exhibits immune piezo-resistive response to temperature variation.

2D CTAB-MoSe2 Nanosheets and 0D MoSe2 Quantum Dots: Facile Top-Down Preparations and Their Peroxidase-Like Catalytic Activity for Colorimetric Detection of Hydrogen Peroxide.

We report the facile and economic preparation of two-dimensional (2D) and 0D MoSe2 nanostructures based on systematic and non-toxic top-down strategies. We demonstrate the intrinsic peroxidase-like activity of these MoSe2 nanostructures. The catalytic processes begin with facilitated decomposition of H2O2 by using MoSe2 nanostructures as peroxidase mimetics. In turn, a large amount of generated radicals oxidizes 3,3,5,5-tetramethylbenzidine (TMB) to produce a visible color reaction. The enzymatic kinetics of our MoSe2 nanostructures complies with typical Michaelis-Menten theory. Catalytic kinetics study reveals a ping-pong mechanism. Moreover, the primary radical responsible for the oxidation of TMB was identified to be È®2- by active species-trapping experiments. Based on the peroxidase mimicking property, we developed a new colorimetric method for H2O2 detection by using 2D and 0D MoSe2 nanostructures. It is shown that the colorimetric sensing capability of our MoSe2 catalysts is comparable to other 2D materials-based colorimetric platforms. For instance, the linear range of H2O2 detection is between 10 and 250 µM by using 2D functionalized MoSe2 nanosheets as an artificial enzyme. Our work develops a systematic approach to use 2D materials to construct novel enzyme-free mimetic for a visual assay of H2O2, which has promising prospects in medical diagnosis and food security monitoring.

Flexible Vertical p-n Diode Photodetectors with Thin N-type MoSe2 Films Solution-Processed on Water Surfaces.

Two-dimensional (2D) nanosheets of transition metal dichalcogenides (TMDs) are of significant interest for potential photoelectronic applications. However, the fabrication of solution-processed arrays of mechanically flexible thin TMD films-based vertical type p-n junction photodetectors over a large area is a great challenge. Our method is based on controlled solvent evaporation of MoSe2 suspension spread on water surface. Single or few-layered MoSe2 nanosheets modified with the dispersant amine-terminated poly(styrene) (PS-NH2) were homogeneously deposited and stacked on water upon solvent evaporation, giving rise to uniform MoSe2/PS-NH2 composite films that can be readily transferred onto other substrates. A p-n junction vertical diode of Al/p-type Si/p-type poly(9,9-di- n-octylfluorenyl-2,7-diyl)/n-type MoSe2 composite/Au stacked from bottom to top exhibited characteristic rectifying current behavior upon voltage sweep with a rectification ratio of 103. Subsequent illumination of near-infrared light on the device resulted in a substantially enhanced dark current of approximately 103 times greater than that of the nonexposed device. The photodetection performance, that is, switching time, responsivity, and detectivity, were 100.0 ms, 2.5 AW-1, and 2.34 × 1014, respectively. Furthermore, the performance of mechanically flexible photodetectors devices was comparable with that of the devices fabricated on the hard Si substrate even after 1000 bending cycles at a bending diameter of 7.2 mm.

Ag filament induced nonvolatile resistive switching memory behaviour in hexagonal MoSe2 nanosheets.

In this work, hexagonal MoSe2 nanosheets were prepared by hydrothermal process. Next, the resistive switching memory behaviour of single MoSe2 nanosheets was further investigated. We observed that MoSe2 nanosheets based memory device show reproducible and stable bipolar resistive switching memory characteristics. Through the analysis for conductive mechanism, the formation and rupture of nanoscale Ag filament inside the MoSe2 nanosheets is suggested to explain the memory behaviour.

Stable 1T-MoSe2 and Carbon Nanotube Hybridized Flexible Film: Binder-Free and High-Performance Li-Ion Anode.

Two-dimensional stable metallic 1T-MoSe2 with expanded interlayer spacing of 10.0 Å in situ grown on SWCNTs film is fabricated via a one-step solvothermal method. Combined with X-ray absorption near-edge structures, our characterization reveals that such 1T-MoSe2 and single-walled carbon nanotubes (abbreviated as 1T-MoSe2/SWCNTs) hybridized structure can provide strong electrical and chemical coupling between 1T-MoSe2 nanosheets and SWCNT film in a form of C-O-Mo bonding, which significantly benefits a high-efficiency electron/ion transport pathway and structural stability, thus directly enabling high-performance lithium storage properties. In particular, as a flexible and binder-free Li-ion anode, the 1T-MoSe2/SWCNTs electrode exhibits excellent rate capacity, which delivers a capacity of 630 mAh/g at 3000 mA/g. Meanwhile, the strong C-O-Mo bonding of 1T-MoSe2/SWCNTs accommodates volume alteration during the repeated charge/discharge process, which gives rise to 89% capacity retention and a capacity of 971 mAh/g at 300 mA/g after 100 cycles. This synthetic route of a multifunctional MoSe2/SWCNTs hybrid might be extended to fabricate other 2D layer-based flexible and light electrodes for various applications such as electronics, optics, and catalysts.

Carbon-Stabilized Interlayer-Expanded Few-Layer MoSe2 Nanosheets for Sodium Ion Batteries with Enhanced Rate Capability and Cycling Performance.

Sodium ion batteries (SIBs) have been considered as a promising alternative to lithium ion batteries, owing to the abundant reserve and low-cost accessibility of the sodium source. To date, the pursuit of high-performance anode materials remains a great challenge for the SIBs. In this work, carbon-stabilized interlayer-expanded few-layer MoSe2 nanosheets (MoSe2@C) have been fabricated by an oleic acid (OA) functionalized synthesis-polydopamine (PDA) stabilization-carbonization strategy, and their structural, morphological, and electrochemical properties have been carefully characterized and compared with the carbon-free MoSe2. When evaluated as anode for sodium ion half batteries, the MoSe2@C exhibits a remarkably enhanced rate capability of 367 mA h g-1 at 5 A g-1, a high reversible discharge capacity of 445 mA h g-1 at 1 A g-1, and a long-term cycling stability over 100 cycles. To further explore the potential applications, the MoSe2@C is assembled into sodium ion full batteries with Na3V2(PO4)3 (NVP) as cathode materials, showing an impressively high reversible capacity of 421 mA h g-1 at 0.2 A g-1 after 100 cycles. Such results are primarily attributed to the unique carbon-stabilized interlayer-expanded few-layer MoSe2 nanosheets structure, which facilitates the permeation of electrolyte into the inner of MoSe2 nanosheets, promoting charge transfer efficiency among MoSe2 nanosheets, and accommodating the volume change from discharge-charge cycling.

Ultrathin MoSe2 Nanosheets Decorated on Carbon Fiber Cloth as Binder-Free and High-Performance Electrocatalyst for Hydrogen Evolution.

MoSe2 nanosheets with ultrathin thickness and rich defects were grown on the surface of carbon fiber cloth by a facile solvent-thermal method. The active area and conductivity of the MoSe2 catalyst were increased simultaneously because of the NH4F etching effect and its incorporation with carbon fiber cloth. As a result, the MoSe2-based catalysts exhibited excellent HER activity including small onset potential, large exchange current density and small Tafel slope, which is superior to most of MoSe2-based catalysts reported previously.