Enhanced OER catalytic activity of single metal atoms supported by the pentagonal NiN2 monolayer: insight from density functional theory calculations.

Two-dimensional material-supported single metal atom catalysts have been extensively studied and proved effective in electrocatalytic reactions in recent years. In this work, we systematically investigate the OER catalytic properties of single metal atoms supported by the NiN2 monolayer. Several typical transition metals with high single atom catalytic activity, such as Fe, Co, Ru, Rh, Pd, Ir, and Pt, were selected as catalytic active sites. The energy calculations show that transition metal atoms (Fe, Co, Ru, Rh, Pd, Ir, and Pt) are easily embedded in the NiN2 monolayer with Ni vacancies due to the negative binding energy. The calculated OER overpotentials of Fe, Co, Ru, Rh, Pd, Ir and Pt embedded NiN2 monolayers are 0.92 V, 0.47 V, 1.13 V, 0.66 V, 1.25 V, 0.28 V, and 0.94 V, respectively. Compared to the 0.57 V OER overpotential of typical OER noble metal catalysts IrO2, Co@NiN2 and Ir@NiN2 exhibit high OER catalytic activity due to lower overpotential, especially for Ir@NiN2. The high catalytic activity of the Ir embedded NiN2 monolayer can be explained well by the d-band center model. It is found that the adsorption strength of the embedded TM atoms with intermediates follows a linear relationship with their d-band centers. Besides, the overpotential of the Ir embedded NiN2 monolayer can be further reduced to 0.24 V under -2% biaxial strain. Such findings are expected to be employed in more two-dimensional material-supported single metal atom catalyzed reactions.

A Malicious Code Detection Method Based on Stacked Depthwise Separable Convolutions and Attention Mechanism.

To address the challenges of weak model generalization and limited model capacity adaptation in traditional malware detection methods, this article presents a novel malware detection approach based on stacked depthwise separable convolutions and self-attention, termed CoAtNet. This method combines the strengths of the self-attention module's robust model adaptation and the convolutional networks' powerful generalization abilities. The initial step involves transforming the malicious code into grayscale images. These images are subsequently processed using a detection model that employs stacked depthwise separable convolutions and an attention mechanism. This model effectively recognizes and classifies the images, automatically extracting essential features from malicious software images. The effectiveness of the method was validated through comparative experiments using both the Malimg dataset and the augmented Blended+ dataset. The approach's performance was evaluated against popular models, including XceptionNet, EfficientNetB0, ResNet50, VGG16, DenseNet169, and InceptionResNetV2. The experimental results highlight that the model surpasses other malware detection models in terms of accuracy and generalization ability. In conclusion, the proposed method addresses the limitations of traditional malware detection approaches by leveraging stacked depthwise separable convolutions and self-attention. Comprehensive experiments demonstrate its superior performance compared to existing models. This research contributes to advancing the field of malware detection and provides a promising solution for enhanced accuracy and robustness.

Precisely modulated 2D PdCu alloy nanodendrites as highly active peroxidase mimics for the elimination of biofilms.

Pd-based nanomaterials are good candidates for antibacterial applications because of their high catalytic activity and good biocompatibility. Nonetheless, there is still much work to do to improve the catalytic activity of Pd nanomaterials as antibacterial agents, particularly for anti-biofilms. In this work, Cu was introduced into Pd to form a series of 2D PdCu alloy nanodendrites (PdCu NDs) as high-performance peroxidase mimics based on flexible control of compositions. Remarkably, catalytic kinetics show that the composition-dependent synergy in the PdCu NDs strongly enhances the peroxidase-like activity. The detailed theoretical study reveals that the tuning of the electrostatic adsorption and dissociative chemisorption of the H2O2 molecule on PdCu ND surfaces by the precise introduction of Cu plays a key role in obtaining superior peroxidase-like catalytic activity. Significantly, the distinct peroxidase-like properties of the fine-tuned PdCu NDs endow them with excellent biofilm elimination capability via the generation of hydroxyl radicals. This work offers a great opportunity to design noble metal nanozymes with enhanced performance, which might advance the development of nanozymes as a new class of highly efficient antibacterial agents.

Enhancing anti-tumor effect of ultrasensitive bimetallic RuCu nanoparticles as radiosensitizers with dual enzyme-like activities.

Radiotherapy (RT), through the generation of reactive oxygen species (ROS) and DNA damage to tumor cells caused by high-energy irradiation, has been a widely applied cancer treatment strategy in clinic. However, the therapeutic effect of traditional RT is restricted by the insufficient radiation energy deposition and the side effects on normal tissues. Recently, multifunctional nano-formulations and synergistic therapy has been developed as attractive strategies for used to enhancing the efficacy and safety of RT. Herein, we show that a bimetallic nanozyme (copper-modified ruthenium nanoparticles, RuCu NPs), containing the high atomic number (Z) element Ru as a novel radiosensitizer, offers an ideal solution to RT sensitization, with ultrasensitive peroxidase (POD)-like activity and catalase (CAT)-like activity. Density functional theory (DFT) calculations also clarified the optimal POD-like catalytic ratio of RuCu NPs and further revealed the mechanism of its supper catalytic activity. Under X-ray exposure, RuCu NPs coated with poly(ethylene glycol) (PEG) exhibited simultaneously improved the ROS production and relieved tumor hypoxia in the acid tumor microenvironment (TME), and demonstrated remarkable therapeutic efficacy in the MDA-MB-231 breast cancer model. Our results provide a proof-of-concept for a RT sensitization strategy, which combine the intrinsic nature of high-Z element and the advantages of nanozymes to overcome the tricky drawbacks existed in radiotherapy, and further open a new direction of exploring novel nanozyme-based strategies for tumor catalytic therapy and synergistic radiotherapy.

Macrophage-Targeted Sonodynamic/Photothermal Synergistic Therapy for Preventing Atherosclerotic Plaque Progression Using CuS/TiO2 Heterostructured Nanosheets.

Sonodynamic therapy (SDT) and photothermal therapy (PTT) are two effective strategies for the treatment of atherosclerotic plaques. However, the low yield of reactive oxygen species (ROS) of conventional organic sonosensitizers and the low biosafety of hyperthermia limit the therapeutic efficacy of SDT and PTT. Herein, we report copper sulfide/titanium oxide heterostructure nanosheets modified with hyaluronic acid (HA) and PEG (HA-HNSs) for low-intensity sonodynamic and mild-photothermal synergistic therapy for early atherosclerotic plaques. CuS/TiO2 heterostructure nanosheets (HNSs) show high electron-hole separation efficiency and superior sonodynamic performance, because it has high surface energy crystal facets as well as a narrow band. Moreover, HNSs exhibit intense absorbance in the NIR-II region, which endows the nanosheets with excellent photothermal performance. With a further modification of HA, HA-HNSs can selectively target intraplaque proinflammatory macrophages through CD44-HA interaction. Because SDT reduces the expression of heat shock protein 90 and PTT facilitates the sonocatalytic process, the combination of SDT and PTT based on HA-HNSs could synergistically induce proinflammatory macrophage apoptosis. More importantly, the synergistic therapy prevents the progression of early atherosclerotic plaque by removing lesional macrophages and mitigating inflammation. Taken together, this work provides a macrophage-targeting sonodynamic/photothermal synergistic therapy, which is an effective translational clinical intervention for early atherosclerotic plaques.

Highly sensitive and fast-response ethanol sensing of porous Co3O4 hollow polyhedra via palladium reined spillover effect.

Highly sensitive and fast detection of volatile organic compounds (VOCs) in industrial and living environments is an urgent need. The combination of distinctive structure and noble metal modification is an important strategy to achieve high-performance gas sensing materials. In addition, it is urgent to clarify the chemical state and function of noble metals on the surface of the sensing material during the actual sensing process. In this work, Pd modified Co3O4 hollow polyhedral (Pd/Co3O4 HP) is developed through one-step pyrolysis of a Pd doped MOF precursor. At an operating temperature of 150 °C, the Pd/Co3O4 HP gas sensor can achieve 1.6 times higher sensitivity than that of Co3O4 HP along with fast response (12 s) and recovery speed (25 s) for 100 ppm ethanol vapor. Near-ambient pressure X-ray photoelectron spectroscopy (NAPXPS) was used to monitor the dynamic changes in the surface state of Pd/Co3O4 HP. The NAPXPS results reveal that the oxidation and reduction of Pd in the ethanol sensing process are attributed to a spillover effect of oxygen and ethanol, respectively. This work opens up an effective approach to investigate spillover effects in a sensing mechanism of noble metal modified oxide semiconductor sensors.

Construction of Novel Bimetallic Oxyphosphide as Advanced Anode for Potassium Ion Hybrid Capacitor.

Potassium ion hybrid capacitors (PIHCs) have attracted considerable interest due to their low cost, competitive power/energy densities, and ultra-long lifespan. However, the more sluggish insertion kinetics of battery-type anodes than capacitor-type cathodes in PIHCs seriously limits their practical application. Therefore, developing advanced anodes with high capacitor and suitable K+ intercalation is imperative and significant. A novel core-shell structure of NiCo oxide/NiCo oxyphosphide (NCOP) nanowires are designed and constructed in this study via efficient and facile strategy. Combining the merits of the core-shell structure and the massive active sites in the oxyphosphide layer, the as-prepared NCOP composites manifest highly reversible capacitors and outstanding rate capability. Meanwhile, the insertion and conversion potassium storage mechanisms of the NCOP are successfully revealed through in situ X-ray diffraction and density functional theory calculations, respectively. Furthermore, the PIHC was assembled with NCOP anode and borocarbonitride cathode, which displays a large energy density and high-power density, along with an exceptional capacity retention of ≈90% over 10 000 cycles at 1.0 A g-1 . This work provides the anion regulation strategy for modifying the transition metal oxide and constructing the advancing electrode materials for next-generation energy storage and beyond.

Photoacoustic and magnetic resonance imaging-based gene and photothermal therapy using mesoporous nanoagents.

The integration of photothermal therapy (PTT) with gene therapy (GT) in a single nanoscale platform demonstrates great potential in cancer therapy. Porous iron oxide nanoagents (PIONs) are widely used as magnetic nanoagents in the drug delivery field and also serve as a photothermal nanoagent for photothermal therapy. However, the therapeutic efficacy of PIONs-mediated GT has not been studied. The long noncoding RNA (lncRNA) CRYBG3 (LNC CRYBG3), a lncRNA induced by heavy ion irradiation in lung cancer cells, has been reported to directly bind to globular actin (G-actin) and cause degradation of cytoskeleton and blocking of cytokinesis, thus indicating its potential for use in GT by simulating the effect of heavy ion irradiation and functioning as an antitumor drug. In the present study, we investigated the possibility of combining PIONs-mediated PTT and LNC CRYBG3-mediated GT to destroy non-small cell lung cancer (NSCLC) cells both in vitro and in vivo. The combination therapy showed a high cancer cell killing efficacy, and the cure rate was better than that achieved using PTT or GT alone. Moreover, as a type of magnetic nanoagent, PIONs can be used for magnetic resonance imaging (MRI) and photoacoustic imaging (PAI) both in vitro and in vivo. These findings indicate that the new combination therapy has high potential for cancer treatment.

Macrophage-Mediated Porous Magnetic Nanoparticles for Multimodal Imaging and Postoperative Photothermal Therapy of Gliomas.

Because of the blood-brain barrier and the high infiltration of glioma cells, the diagnostic accuracy and treatment efficiency of gliomas are still facing challenges. There is an urgent need to explore the integration of diagnostic and therapeutic methods to achieve an accurate diagnosis, guide surgery, and inhibit postoperative recurrence. In this work, we developed a macrophage loaded with a photothermal nanoprobe (MFe3O4-Cy5.5), which is able to cross the blood-brain barrier and accumulate into deep gliomas to achieve multimodal imaging and guided glioma surgery purposes. With desirable probing depth and high signal-to-noise ratio, Fe3O4-Cy5.5 can perform fluorescence, photoacoustic, and magnetic resonance imaging, which can distinguish brain tumors from the surrounding normal tissues and accurately guide glioma resection. Meanwhile, Fe3O4-Cy5.5 can effectively induce local photothermal therapy and inhibit the recurrence of glioma after surgery. These results demonstrate that the macrophage-mediated Fe3O4-Cy5.5, which can achieve a multimodal diagnosis, accurate imaging-guided surgery, and effective photothermal therapy, is a promising nanoplatform for gliomas.

Smart Textiles Based on MoS2 Hollow Nanospheres for Personal Thermal Management.

Two-dimensional transition metal dichalcogenides are of particular interest in high-performance photothermal conversion, yet there remains a huge challenge in their practical application in smart textiles for healthcare, energy, and personal protection. Herein, we controllably prepared MoS2 hollow nanospheres with a high photothermal conversion efficiency of 36% via a microemulsion-hydrothermal method, which was further applied to construct photothermal fibers for personal thermal management after a hot-blast dip-drying process. Because of the prominent photothermal effect, the temperature of the photothermal fibers sharply increases from the room temperature value of 25.0 to 55.5 °C in 60 s under near-infrared illumination with a power density of 500 W/cm2. Furthermore, the photothermal fiber pad demonstrated an obvious temperature enhancement of 38.0 °C from a skin temperature of 22.0 °C after it was irradiated by natural sunlight for 60 s. Significantly, the antibacterial elimination rates of the photothermal fibers for Escherichia coli and Staphylococcus aureus are ∼99.9 and ∼99.8%, respectively. This strategy affords an avenue toward the practical application of photothermal materials in smart fibers for personal thermoregulation.

Size-Dependent Selectivity of Electrochemical CO2 Reduction on Converted In2 O3 Nanocrystals.

The size modulation of catalyst particles represents a useful dimension to tune catalytic performances by impacting not only their surface areas but also local electronic structures. It, however, has remained inadequately explored and poorly elucidated. Here, we report the interesting size-dependent selectivity of electrochemical CO2 reduction on In2 O3 nanocrystals. 5-nm nanoparticles and 15-nm nanocubes with focused size distribution are prepared via a facile solvothermal reaction in oleylamine by carefully controlling a set of experimental parameters. They serve as the precatalysts, and are reduced to In nanocrystals while largely inherit the original size feature during electrochemical CO2 reduction. Catalyst derived from 15-nm nanocubes exhibits greater formate selectivity (>95 %) at lower overpotential and negligible side reactions compared to bulk-like samples (indium foil and 200-nm cubes) as well as the catalyst derived from smaller 5-nm nanoparticles. This unique size dependence is rationalized as a result of the competition among different reaction pathways by our theoretical computations. Smaller is not always better in the catalyst design.

Hybridized Mechanical and Solar Energy-Driven Self-Powered Hydrogen Production.

Photoelectrochemical hydrogen generation is a promising approach to address the environmental pollution and energy crisis. In this work, we present a hybridized mechanical and solar energy-driven self-powered hydrogen production system. A rotatory disc-shaped triboelectric nanogenerator was employed to harvest mechanical energy from water and functions as a sufficient external power source. WO3/BiVO4 heterojunction photoanode was synthesized in a PEC water-splitting cell to produce H2. After transformation and rectification, the peak current reaches 0.1 mA at the rotation speed of 60 rpm. In this case, the H2 evolution process only occurs with sunlight irradiation. When the rotation speed is over 130 rpm, the peak photocurrent and peak dark current have nearly equal value. Direct electrolysis of water is almost simultaneous with photoelectrocatalysis of water. It is worth noting that the hydrogen production rate increases to 5.45 and 7.27 µL min-1 without or with light illumination at 160 rpm. The corresponding energy conversion efficiency is calculated to be 2.43% and 2.59%, respectively. All the results demonstrate such a self-powered system can successfully achieve the PEC hydrogen generation, exhibiting promising possibility of energy conversion.

PbS Quantum Dots/2D Nonlayered CdS xSe1- x Nanosheet Hybrid Nanostructure for High-Performance Broadband Photodetectors.

Two-dimensional (2D) nonlayered nanomaterials have attracted extensive attention for electronic and optoelectronic applications recently because of their distinct properties. In this work, we first employed a facile one-step method to synthesize 2D nonlayered cadmium sulfide selenide (CdS xSe1- x, x = 0.33) nanosheets with a highly crystalline structure and then we introduced a generic spin-coating approach to fabricate hybrid nanomaterials composed of PbS quantum dots (QDs) and 2D CdS xSe1- x nanosheets and demonstrated their potential for high-performance broadband photodetectors. Compared with pure 2D CdS xSe1- x nanosheet photodetectors, the photoelectric performance of the PbS/CdS xSe1- x hybrid nanostructure is enhanced by 3 orders of magnitude under near-infrared (NIR) light illumination and maintains its performance in the visible (Vis) range. The photodetector exhibits a broadband response range from Vis to NIR with an ultrahigh light-to-dark current ratio (3.45 × 106), a high spectral responsivity (1.45 × 103 A/W), and high detectivity (1.05 × 1015 Jones). The proposed QDs/2D nonlayered hybrid nanostructure-based photodetector paves a promising way for next-generation high-performance broadband optoelectronic devices.

Synthesis of BiPO4/Bi2S3 Heterojunction with Enhanced Photocatalytic Activity under Visible-Light Irradiation.

BiPO4/Bi2S3 photocatalysts were successfully synthesized by a simple two-step hydrothermal process, which involved the initial formation of BiPO4 rod and then the attachment of Bi2S3 through ion exchange. The as-synthesized products were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and UV-vis diffuse reflectance spectra (UV-vis DRS). It was found that BiPO4 was regular rods with smooth surfaces. However, BiPO4/Bi2S3 heterojunction had a rough surface, which could be attributed to the attachment of Bi2S3 on the surface of BiPO4 rods. The BiPO4/Bi2S3 composite exhibited better photocatalytic performance than that of pure BiPO4 and Bi2S3 for the degradation of methylene blue (MB) and Rhodamine B (RhB) under visible light. The enhanced photocatalytic performance could be ascribed to synergistic effect of BiPO4/Bi2S3 heterojunction, in which the attached Bi2S3 nanoparticles could improve visible-light absorption and the BiPO4/Bi2S3 heterojunction suppressed the recombination of photogenerated electron-hole pairs. Our work suggested that BiPO4/Bi2S3 heterojunction could be a potential photocatalyst under visible light.

Simple fabrication of N-doped mesoporous TiO2 nanorods with the enhanced visible light photocatalytic activity.

N-doped mesoporous TiO2 nanorods were fabricated by a modified and facile sol-gel approach without any templates. Ammonium nitrate was used as a raw source of N dopants, which could produce a lot of gasses such as N2, NO2, and H2O in the process of heating samples. These gasses were proved to be vitally important to form the special mesoporous structure. The samples were characterized by the powder X-ray diffraction, X-ray photoelectron spectrometer, nitrogen adsorption isotherms, scanning electron microscopy, transmission electron microscopy, and UV-visible absorption spectra. The average length and the cross section diameter of the as-prepared samples were ca. 1.5 µm and ca. 80 nm, respectively. The photocatalytic activity was evaluated by photodegradation of methylene blue (MB) in aqueous solution. The N-doped mesoporous TiO2 nanorods showed an excellent photocatalytic activity, which may be attributed to the enlarged surface area (106.4 m2 g-1) and the narrowed band gap (2.05 eV). Besides, the rod-like photocatalyst was found to be easy to recycle.