Synthesis and Unique Behaviors of High-Purity HEA Nanoparticles Using Femtosecond Laser Ablation.

High-entropy alloys (HEAs) are a class of metal alloys consisting of four or more molar equal or near-equal elements. HEA nanomaterials have garnered significant interest due to their wide range of applications, such as electrocatalysis, welding, and brazing. Their unique multi-principle high-entropy effect allows for the tailoring of the alloy composition to facilitate specific electrochemical reactions. This study focuses on the synthesis of high-purity HEA nanoparticles using the method of femtosecond laser ablation synthesis in liquid. The use of ultrashort energy pulses in femtosecond lasers enables uniform ablation of materials at significantly lower power levels compared to longer pulse or continuous pulse lasers. We investigate how various femtosecond laser parameters affect the morphology, phase, and other characteristics of the synthesized nanoparticles. An innovative aspect of our solution is its ability to rapidly generate multi-component nanoparticles with a high fidelity as the input multi-component target material at a significant yielding rate. Our research thus focuses on a novel synthesis of high-entropy alloying CuCoMn1.75NiFe0.25 nanoparticles. We explore the characterization and unique properties of the nanoparticles and consider their electrocatalytic applications, including high power density aluminum air batteries, as well as their efficacy in the oxygen reduction reaction (ORR). Additionally, we report a unique nanowire fabrication phenomenon achieved through nanojoining. The findings from this study shed light on the potential of femtosecond laser ablation synthesis in liquid (FLASiL) as a promising technique for producing high-purity HEA nanoparticles.

Multifunctional Dental Adhesives Formulated with Silane-Coated Magnetic Fe3O4@m-SiO2 Core-Shell Particles to Counteract Adhesive Interfacial Breakdown.

The process of bonding to dentin is complex and dynamic, greatly impacting the longevity of dental restorations. The tooth/dental material interface is degraded by bacterial acids, matrix metalloproteinases (MMPs), and hydrolysis. As a result, bonded dental restorations face reduced longevity due to adhesive interfacial breakdown, leading to leakage, tooth pain, recurrent caries, and costly restoration replacements. To address this issue, we synthesized and characterized a multifunctional magnetic platform, CHX@SiQuac@Fe3O4@m-SiO2, to provide several beneficial functions. The platform comprises Fe3O4 microparticles and chlorhexidine (CHX) encapsulated within mesoporous silica, which was silanized by an antibacterial quaternary ammonium silane (SiQuac). This platform simultaneously targets bacterial inhibition, stability of the hybrid layer, and enhanced filler infiltration by magnetic motion. Comprehensive experiments include X-ray diffraction, FT-IR, VSM, EDS, N2 adsorption-desorption (BET), transmission electron microscopy, scanning electron microscopy, thermogravimetric analysis, and UV-vis spectroscopy. Then, CHX@SiQuac@Fe3O4@m-SiO2 was incorporated into an experimental adhesive resin for dental bonding restorations, followed by immediate and long-term antibacterial assessment, cytotoxicity evaluation, and mechanical and bonding performance. The results confirmed the multifunctional nature of CHX@SiQuac@Fe3O4@m-SiO2. This work outlined a roadmap for (1) designing and tuning an adhesive formulation containing the new platform CHX@SiQuac@Fe3O4@m-SiO2; (2) assessing microtensile bond strength to dentin using a clinically relevant model of simulated hydrostatic pulpal pressure; and (3) investigating the antibacterial outcome performance of the particles when embedded into the formulated adhesives over time. The results showed that at 4 wt % of CHX@SiQuac@Fe3O4@m-SiO2-doped adhesive under the guided magnetic field, the bond strength increased by 28%. CHX@SiQuac@Fe3O4@m-SiO2 enhanced dentin adhesion in the magnetic guide bonding process without altering adhesive properties or causing cytotoxicity. This finding presents a promising method for strengthening the tooth/dental material interface's stability and extending the bonded restorations' lifespan.

Synthesis, Characterization, and Applications of Nanomaterials for Energy Conversion and Storage.

Ever since the commencement of the Industrial Revolution in Great Britain in the mid-18th century, the annual global energy consumption from various fossil fuels, encompassing wood, coal, natural gas, and petroleum, has demonstrated an exponential surge over the past four centuries [...].

Photovoltaic amorphous feroxyhyte nanostructures synthesized by atmospheric AC microplasma.

Feroxyhite (δ-FeOOH) nanomaterials were successfully synthesized through the atmospheric AC microplasma method at room temperature from ferrous sulfate aqueous solutions. Various syntheses conditions, including electric voltage, electric field strength, ferrous concentration, hydrogen peroxide concentration, and reaction duration, were systematically investigated. The synthesized products were characterized through x-ray diffraction, UV-vis absorption spectroscopy, photoluminescence spectroscopy, infra-red spectroscopy, and electron microscopy. The bandgap of the produced materials were strongly dependent of the ferrous concentration while the product ratio was dependent on all experimental conditions. The synthesis mechanism was thoroughly discussed. The synthesized nanomaterials were amorphous nanospheres, showing superparamagnetic properties at room temperature. The synthesized oxyhydroxide is a potential photovoltaic material besides its reported applications in photocatalysts and supercapacitors. The application of this synthesis technique could be extended to synthesize other oxy-hydroxide nanomaterials for renewable energy applications facilely, scalablely, cost-effectively, and environmentally.

Electromagnetic Radiation Effects on MgO-Based Magnetic Tunnel Junctions: A Review.

Magnetic tunnel junctions (MTJs) have been widely utilized in sensitive sensors, magnetic memory, and logic gates due to their tunneling magnetoresistance. Moreover, these MTJ devices have promising potential for renewable energy generation and storage. Compared with Si-based devices, MTJs are more tolerant to electromagnetic radiation. In this review, we summarize the functionalities of MgO-based MTJ devices under different electromagnetic irradiation environments, with a focus on gamma-ray radiation. We explore the effects of these radiation exposures on the MgO tunnel barriers, magnetic layers, and interfaces to understand the origin of their tolerance. This review enhances our knowledge of the radiation tolerance of MgO-based MTJs, improves the design of these MgO-based MTJ devices with better tolerances, and provides information to minimize the risks of irradiation under various irradiation environments. This review starts with an introduction to MTJs and irradiation backgrounds, followed by the fundamental properties of MTJ materials, such as the MgO barrier and magnetic layers. Then, we review and discuss the MTJ materials and devices' radiation tolerances under different irradiation environments, including high-energy cosmic radiation, gamma-ray radiation, and lower-energy electromagnetic radiation (X-ray, UV-vis, infrared, microwave, and radiofrequency electromagnetic radiation). In conclusion, we summarize the radiation effects based on the published literature, which might benefit material design and protection.

Magnetic-Responsive Photosensitizer Nanoplatform for Optimized Inactivation of Dental Caries-Related Biofilms: Technology Development and Proof of Principle.

Conventional antibiotic therapies for biofilm-trigged oral diseases are becoming less efficient due to the emergence of antibiotic-resistant bacterial strains. Antimicrobial photodynamic therapy (aPDT) is hampered by restricted access to bacterial communities embedded within the dense extracellular matrix of mature biofilms. Herein, a versatile photosensitizer nanoplatform (named MagTBO) was designed to overcome this obstacle by integrating toluidine-blue ortho (TBO) photosensitizer and superparamagnetic iron oxide nanoparticles (SPIONs) via a microemulsion method. In this study, we reported the preparation, characterization, and application of MagTBO for aPDT. In the presence of an external magnetic field, the MagTBO microemulsion can be driven and penetrate deep sites inside the biofilms, resulting in an improved photodynamic disinfection effect compared to using TBO alone. Besides, the obtained MagTBO microemulsions revealed excellent water solubility and stability over time, enhanced the aPDT performance against S. mutans and saliva-derived multispecies biofilms, and improved the TBO's biocompatibility. Such results demonstrate a proof-of-principle for using microemulsion as a delivery vehicle and magnetic field as a navigation approach to intensify the antibacterial action of currently available photosensitizers, leading to efficient modulation of pathogenic oral biofilms.

Magnetic motion of superparamagnetic iron oxide nanoparticles- loaded dental adhesives: physicochemical/biological properties, and dentin bonding performance studied through the tooth pulpal pressure model.

The limited durability of dentin bonding harshly shortens the lifespan of resin composites restorations. The controlled, dynamic movement of materials through non-contacting forces provides exciting opportunities in adhesive dentistry. We, herein, describe comprehensive investigations of a new dental adhesive with superparamagnetic iron oxide nanoparticles (SPIONs) sensitive to magnetic fields for bonding optimization. This contribution outlines a roadmap of (1) designing and tuning of an adhesive formulation containing SPIONs to enhance penetrability into etched dentin guided by magnetic-field; (2) employing a clinically relevant model of simulated hydrostatic pulpal pressure on the microtensile bond to dentin; and (3) investigating a potential antibacterial effect of the formulated adhesives, and their biocompatibility. SPION-concentration-dependency chemical and mechanical behavior was shown via the degree of conversion, ultimate tensile strength, and micro shear bond strength to dentin. The effects of SPIONs carried on a dental adhesive on the bonding strength to dentin are studied in depth by combining experiments with in vitro simulated model. The results show that under the guided magnetic field, 0.07 wt.% of SPIONs-doped adhesive increased the bond strength that surpasses the reduction caused by hydrostatic pulpal pressure. Using a magnetic guide workflow during the bonding procedures, SPIONs-doped adhesives improved dentin's adhesion without changing adhesives' physicochemical properties. This outcome addresses the key challenge of poor resin infiltration of dentin's conventional total etching during the bonding procedure. The real-time magnetic motion of dental adhesives may open new paths to enhance resin-based restorations' longevity. STATEMENT OF SIGNIFICANCE: In this study, dental adhesives containing superparamagnetic iron oxide nanoparticles (SPIONs) were developed to enhance penetrability into dentin guided by a magnetic field. The adhesives were screened for physical, chemical, antibacterial properties, and cytotoxicity. For the first time, simulated pulpal pressure was used concurrently with the magnetic field to simulate a clinical setting. This approach showed that it is feasible to overcome pulpal pressure jeopardization on bond strength when SPIONs and a magnetic field are applied. The magnetic-responsive adhesives had great potential to improve bond strength, opening new paths to enhance resin-based restorations' longevity without affecting adhesives' biological properties. The use of magnetic-responsive particles and magnetically assisted motion is a promising strategy to improve the sealing ability of dental adhesives.

Vacancy ordering induced topological electronic transition in bulk Eu2ZnSb2.

Metal-semiconductor transitions from changes in edge chirality from zigzag to armchair were observed in many nanoribbon materials, especially those based on honeycomb lattices. Here, this is generalized to bulk complex Zintl semiconductors, exemplified by Eu2ZnSb2 where the Zn vacancy ordering plays an essential role. Five Eu2ZnSb2 structural models are proposed to guide transmission electron microscopy imaging. Zigzag vacancy ordering models show clear metallicity, while the armchair models are semiconducting with indirect bandgaps that monotonously increase with the relative distances between neighboring ZnSb2 chains. Topological electronic structure changes based on cation ordering in a Zintl compound point toward tunable and possibly switchable topological behavior, since cations in these are often mobile. Thus, their orderings can often be adjusted by temperature, minor alloying, and other approaches. We explain the electronic structure of an interesting thermoelectric and point the way to previously unidentified types of topological electronic transitions in Zintl compounds.

Enhanced Thermoelectric Performance of Zintl Phase Ca9Zn4+xSb9 by Beneficial Disorder on the Selective Cationic Site.

Zintl phase compounds Ca9Zn4+xSb9 have promising thermoelectric properties due to their complex crystal structure and tunable interstitial Zn. In this work, we prepared nominal Ca9Zn4+xSb9 (x = 0.5, 0.6, 0.7, and 0.8) using ball milling and hot pressing. Further decreased lattice thermal conductivity was obtained by isoelectronic substitution of Eu on the selective Ca site, which is farther away from the framework of [Zn4+xSb9]δ- for the smaller disturbance of carrier transport. Together with the intensively enhanced carrier mobility, which is attributed to the decreased effective mass and the increased interstitial Zn by inclusion of Eu, an increased peak ZT value to ∼1.05 at 773 K and an enhanced average ZT value to ∼0.73 from 300 to 823 K were achieved in Ca6.75Eu2.25Zn4.7Sb9.

Individually grown cobalt nanowires as magnetic force microscopy probes.

AC electric fields were utilized in the growth of individual high-aspect ratio cobalt nanowires from simple salt solutions using the Directed Electrochemical Nanowire Assembly method. Nanowire diameters were tuned from the submicron scale to 40 nm by adjusting the AC voltage frequency and the growth solution concentration. The structural properties of the nanowires, including shape and crystallinity, were identified using electron microscopy. Hysteresis loops obtained along different directions of an individual nanowire using vibrating sample magnetometry showed that the magnetocrystalline anisotropy energy has the same order of magnitude as the shape anisotropy energy. Additionally, the saturation magnetization of an individual cobalt nanowire was estimated to be close to the bulk single crystal value. A small cobalt nanowire segment was grown from a conductive atomic force microscope cantilever tip that was utilized in magnetic force microscopy (MFM) imaging. The fabricated MFM tip provided moderate quality magnetic images of an iron-cobalt thin-film sample.

Rational Design of Cobalt-Iron Selenides for Highly Efficient Electrochemical Water Oxidation.

Exploring active, stable, earth-abundant, low-cost, and high-efficiency electrocatalysts is highly desired for large-scale industrial applications toward the low-carbon economy. In this study, we apply a versatile selenizing technology to synthesize Se-enriched Co1-xFexSe2 catalysts on nickel foams for oxygen evolution reactions (OERs) and disclose the relationship between the electronic structures of Co1-xFexSe2 (via regulating the atom ratio of Co/Fe) and their OER performance. Owing to the fact that the electron configuration of the Co1-xFexSe2 compounds can be tuned by the incorporated Fe species (electron transfer and lattice distortion), the catalytic activity can be adjusted according to the Co/Fe ratios in the catalyst. Moreover, the morphology of Co1-xFexSe2 is also verified to strongly depend on the Co/Fe ratios, and the thinner Co0.4Fe0.6Se2 nanosheets are obtained upon selenization treatment, in which it allows more active sites to be exposed to the electrolyte, in turn promoting the OER performance. The Co0.4Fe0.6Se2 nanosheets not only exhibit superior OER performance with a low overpotential of 217 mV at 10 mA cm-2 and a small Tafel slope of 41 mV dec-1 but also possess ultrahigh durability with a dinky degeneration of 4.4% even after 72 h fierce water oxidation test in alkaline solution, which outperforms the commercial RuO2 catalyst. As expected, the Co0.4Fe0.6Se2 nanosheets have shown great prospects for practical applications toward water oxidation.

Recent Advances of Graphitic Carbon Nitride-Based Structures and Applications in Catalyst, Sensing, Imaging, and LEDs.

The graphitic carbon nitride (g-C3N4) which is a two-dimensional conjugated polymer has drawn broad interdisciplinary attention as a low-cost, metal-free, and visible-light-responsive photocatalyst in the area of environmental remediation. The g-C3N4-based materials have excellent electronic band structures, electron-rich properties, basic surface functionalities, high physicochemical stabilities and are "earth-abundant." This review summarizes the latest progress related to the design and construction of g-C3N4-based materials and their applications including catalysis, sensing, imaging, and white-light-emitting diodes. An outlook on possible further developments in g-C3N4-based research for emerging properties and applications is also included.

Achieving high power factor and output power density in p-type half-Heuslers Nb1-xTixFeSb.

Improvements in thermoelectric material performance over the past two decades have largely been based on decreasing the phonon thermal conductivity. Enhancing the power factor has been less successful in comparison. In this work, a peak power factor of ∼106 µW⋅cm-1⋅K-2 is achieved by increasing the hot pressing temperature up to 1,373 K in the p-type half-Heusler Nb0.95Ti0.05FeSb. The high power factor subsequently yields a record output power density of ∼22 W⋅cm-2 based on a single-leg device operating at between 293 K and 868 K. Such a high-output power density can be beneficial for large-scale power generation applications.

Higher thermoelectric performance of Zintl phases (Eu0.5Yb0.5)1-xCaxMg2Bi2 by band engineering and strain fluctuation.

Complex Zintl phases, especially antimony (Sb)-based YbZn0.4Cd1.6Sb2 with figure-of-merit (ZT) of ∼1.2 at 700 K, are good candidates as thermoelectric materials because of their intrinsic "electron-crystal, phonon-glass" nature. Here, we report the rarely studied p-type bismuth (Bi)-based Zintl phases (Ca,Yb,Eu)Mg2Bi2 with a record thermoelectric performance. Phase-pure EuMg2Bi2 is successfully prepared with suppressed bipolar effect to reach ZT ∼ 1. Further partial substitution of Eu by Ca and Yb enhanced ZT to ∼1.3 for Eu0.2Yb0.2Ca0.6Mg2Bi2 at 873 K. Density-functional theory (DFT) simulation indicates the alloying has no effect on the valence band, but does affect the conduction band. Such band engineering results in good p-type thermoelectric properties with high carrier mobility. Using transmission electron microscopy, various types of strains are observed and are believed to be due to atomic mass and size fluctuations. Point defects, strain, dislocations, and nanostructures jointly contribute to phonon scattering, confirmed by the semiclassical theoretical calculations based on a modified Debye-Callaway model of lattice thermal conductivity. This work indicates Bi-based (Ca,Yb,Eu)Mg2Bi2 is better than the Sb-based Zintl phases.

Free-Standing Self-Assemblies of Gallium Nitride Nanoparticles: A Review.

Gallium nitride (GaN) is an III-V semiconductor with a direct band-gap of 3 . 4 e V . GaN has important potentials in white light-emitting diodes, blue lasers, and field effect transistors because of its super thermal stability and excellent optical properties, playing main roles in future lighting to reduce energy cost and sensors to resist radiations. GaN nanomaterials inherit bulk properties of the compound while possess novel photoelectric properties of nanomaterials. The review focuses on self-assemblies of GaN nanoparticles without templates, growth mechanisms of self-assemblies, and potential applications of the assembled nanostructures on renewable energy.

Well-oriented epitaxial gold nanotriangles and bowties on MoS2 for surface-enhanced Raman scattering.

We report on epitaxial growth of Au nanotriangles (AuNTs) and bowties consisting of opposing tip-to-tip AuNTs with a few-nanometer gap on n-layer MoS2. These AuNTs exhibit well-defined crystallographic orientations with the average size determined by the MoS2 thickness. Monolayer (1L) MoS2 shows the weakest coalescence, corroborating the layer-dependent interactions among Au and n-layer MoS2. High-resolution transmission electron microscopy characterization confirms the lattice directing of thin MoS2 sheets on the AuNT formation with [111]Au||[001]MoS2 and <211>Au||<210>MoS(2). By introducing misfit dislocation arrays, the system with an 8.8% lattice misfit is stress-free. In particular, subwavelength-sized gold bowtie nanoantennas can be easily found on the MoS2 surface with a spacing gap down to 3 nm and a density up to 1.6 × 10(13) m(-2). This technique is low cost, time-saving and free of impurities compared to the conventional lithography technologies. Meanwhile, the equilateral AuNTs can enhance Raman signals of thin MoS2 sheets far stronger than that by ordinary gold films, indicating the potential use of AuNTs as SERS substrates for SERS applications.

Li3VO4 anchored graphene nanosheets for long-life and high-rate lithium-ion batteries.

Li3VO4 nanoparticles embedded in graphene nanosheets (Li3VO4@GNS) were obtained using a sol-gel method. The composite presents excellent high-rate performance with a stable capacity of 133 mA h g(-1) at 50 C and long-life performance with a capacity retention rate of 63.1% after 5000 cycles at 5 C.

Nanostructured YbAgCu4 for potentially cryogenic thermoelectric cooling.

We have studied the thermoelectric properties of nanostructured YbAgCu4 materials. A high power factor of ∼131 µW cm(-1) K(-2) has been obtained at 22 K for nanostructured samples prepared by ball milling the arc melted ingot into nanopowder and hot pressing the nanopowder. The implementation of nanostructuring method decreased the thermal conductivity at 42 K by 30-50% through boundary scattering comparing with the previously reported value of polycrystalline YbAgCu4. A peak dimensionless thermoelectric figure-of-merit, ZT, of 0.11 has been achieved at 42 K, which may find potential applications for cryogenic cooling below 77 K. The nanostructuring approach can be extended to other heavy Fermion materials to achieve high power factor and low thermal conductivity and ultimately higher ZT.

Thermoelectric performance of Ni compensated cerium and neodymium double filled p-type skutterudites.

We have synthesized Ni compensated Ce and Nd double filled p-type skutterudites CexNdxFe3.7Ni0.3Sb12 with x = 0.35, 0.40, 0.45, and 0.5 by a melting-quenching-annealing method. The samples were made by directly hot pressing the hand ground powder at 650 °C for 5 minutes at a pressure of about 80 MPa. Since Ni has two more electrons than Fe, a lower power factor and a stronger bipolar effect in thermal conductivity are expected at higher temperature. In the experiments, we have demonstrated that by suitably tuning the Fe-Ni ratio and filler concentration, we can achieve both a higher power factor (∼35 µW cm(-1) K(-2) at 535 °C) and a lower thermal conductivity (∼2.1 W m(-1) K(-1) at room temperature and ∼2.7 W m(-1) K(-1) at 535 °C) in Ce0.4Nd0.4Fe3.7Ni0.3Sb12. A peak thermoelectric figure-of-merit of ∼1.1 at 475 °C is achieved in Ce0.4Nd0.4Fe3.7Ni0.3Sb12.