Phase textures of metal-oxide nanocomposites self-orchestrated by atomic diffusions through precursor alloys.

Metal-oxide nanocomposites (MONs) are of pivotal importance as electrode materials, yet lack a guiding principle to tune their phase texture. Here we report that the phase texture of MONs can be tuned at the nanoscale by controlling the nanophase separation of precursor alloys. In situ transmission electron microscopy (in situ TEM) has demonstrated that a MON material of platinum (Pt) and cerium oxide (CeO2) is obtained through promoted nanophase separation of a Pt5Ce precursor alloy in an atmosphere containing oxygen (O2) and carbon monoxide (CO). The Pt-CeO2 MON material comprised an alternating stack of nanometre-thick layers of Pt and CeO2 in different phase textures ranging from lamellae to mazes, depending on the O2 fraction in the atmosphere. Mathematical simulations have demonstrated that the phase texture of MONs originates from a balance in the atomic diffusions across the alloy precursor, which is controllable by the O2 fraction, temperature, and composition of the precursor alloys.

Photoinduced dynamics during electronic transfer from narrow to wide bandgap layers in one-dimensional heterostructured materials.

Electron transfer is a fundamental energy conversion process widely present in synthetic, industrial, and natural systems. Understanding the electron transfer process is important to exploit the uniqueness of the low-dimensional van der Waals (vdW) heterostructures because interlayer electron transfer produces the function of this class of material. Here, we show the occurrence of an electron transfer process in one-dimensional layer-stacking of carbon nanotubes (CNTs) and boron nitride nanotubes (BNNTs). This observation makes use of femtosecond broadband optical spectroscopy, ultrafast time-resolved electron diffraction, and first-principles theoretical calculations. These results reveal that near-ultraviolet photoexcitation induces an electron transfer from the conduction bands of CNT to BNNT layers via electronic decay channels. This physical process subsequently generates radial phonons in the one-dimensional vdW heterostructure material. The gathered insights unveil the fundamentals physics of interfacial interactions in low dimensional vdW heterostructures and their photoinduced dynamics, pushing their limits for photoactive multifunctional applications.

A liquid metal catalyst for the conversion of ethanol into graphitic carbon layers under an ultrasonic cavitation field.

Eutectic gallium indium (EGaIn) has drawn considerable research interest in potential liquid catalysis. Herein, we report that EGaIn liquid metal acts as a catalyst for the growth of a graphitic carbon layer from ethanol under ultrasonication. High-speed imaging demonstrated the formation of ultrasonic cavitation bubbles at the liquid metal/ethanol interface, which facilitated the pyrolysis of ethanol into graphitic carbon on the liquid metal surface.

Effect of electron beam irradiation in gas atmosphere during ETEM.

Transmission electron microscopy (TEM) is used to observe the atomic structures of materials. Environmental TEM (ETEM) is a method wherein a gas can be evaluated and it has been used to observe the dynamic reaction between materials and gases at the atomic level. An electron beam (EB), which has a sufficiently high energy (exceeding a few tens of kilovolts), can be used to ionize gas molecules. Subsequently, the ionized molecules might react with the materials during ETEM. Therefore, the current generated by the ions and electrons were measured to verify the presence of ions generated due to the ionization of the N2 gas atmosphere during EB irradiation in ETEM. The electron energy loss spectra (EELS) were acquired from the N2 gas atmosphere to estimate the types of ions generated. The results demonstrated that ions and electrons were generated in the N2 atmosphere during ETEM and EB irradiation. Moreover, the EELS analysis indicated that the generated ion was N2+. The material observation conducted using gas ETEM can detect the reaction between gases, ions, and materials.

Anisotropic Growth of Copper Nanorods Mediated by Cl- Ions.

Anisotropic growth to form Cu particles of rod and wire shapes has been obtained typically in a complex system that involves both organic capping agents and Cl- ions. However, the sole effect of Cl- ions on the formation of Cu wires has yet to be fully understood, especially in an organic system. This present work determines the effect of Cl- ions on the morphologies of Cu particles in an organic phase without any capping agents. The results revealed that anisotropic Cu rods could be grown with the sole presence of Cl- ions. The rods have the (011) facets as the long axis, the (111) facets as the tip, and the (100) facets as the side surface. By increasing the Cl- ion concentration, more Cu atoms contributed to the formation of Cu rods and the kinetic growth of the length and the diameter of the rods varied. This suggests that Cl- ions have preferential adsorption on the (100) Cu surfaces to promote the anisotropic growth of Cu. Meanwhile, the adsorption of Cl- to the (111) and (100) surfaces at high Cl- concentrations regulates the relative growth of the particle length and diameter.

Alginate-Stabilized Gold Nanoparticles Prepared Using the Microwave-Induced Plasma-in-Liquid Process with Long-Term Storage Stability for Potential Biomedical Applications.

A one-step preparation of alginate-stabilized gold nanoparticles (Au NPs) using the microwave-induced plasma-in-liquid process (MWPLP) was reported. Effects of alginate with various concentrations on the preparation and properties of the synthesized Au NPs, including reaction rate, morphology, size, and optical absorption property, were studied. The introduction of alginate (1) accelerated the reaction rate, (2) prevented aggregation and precipitation due to long time discharge in MWPLP, and (3) provided long-term colloidal stability. An abnormal size change (from large to small) of Au NPs during particle growth, which was opposite to the typical change in bottom-up chemical reduction, was observed and a possible mechanism was proposed based on the dynamical and thermodynamical instability of particles during growth. The strategy of drying and redispersion of Au NPs in alginate solution was also studied. The drying and redispersion process had an imperceptible effect on the Au NPs. As a consequence, this strategy might be an effective technique for the long-term storage of Au NPs and other metal NPs. The alginate-stabilized Au NPs without the addition of toxic reducing or stabilizing agents can be appropriate to biomedical applications.

Nanoporous ultra-high-entropy alloys containing fourteen elements for water splitting electrocatalysis.

High-entropy alloys (HEAs) are near-equimolar alloys comprising five or more elements. In recent years, catalysis using HEAs has attracted considerable attention across various fields. Herein, we demonstrate the facile synthesis of nanoporous ultra-high-entropy alloys (np-UHEAs) with hierarchical porosity via dealloying. These np-UHEAs contain up to 14 elements, namely, Al, Ag, Au, Co, Cu, Fe, Ir, Mo, Ni, Pd, Pt, Rh, Ru, and Ti. Furthermore, they exhibit high catalytic activities and electrochemical stabilities in the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in acidic media, superior to that of commercial Pt/graphene and IrO2 catalysts. Our results offer valuable insights for the selection of elements as catalysts for various applications.

Highly Correlated Size and Composition of Pt/Au Alloy Nanoparticles via Magnetron Sputtering onto Liquid.

Pt/Au alloy nanoparticles (NPs) in a wide composition range have been synthesized by room-temperature simultaneous sputter deposition from two independent magnetron sources onto liquid PEG (MW = 600). The prepared NPs were alloyed with the face-centered cubic (fcc) structure. In addition, the particle sizes, composition, and shape are strongly correlated but can be tailored by an appropriate variation of the sputtering parameters. No individual particle but large agglomerates with partial alloy structure formed at Pt content of less than 16 atom %. Highly dispersed NPs with no agglomeration were observed in PEG when the quantity of Pt is more than 26 atom %. On the other hand, a small amount of Pt could terminate the agglomeration of Au when sputtering on the grids for transmission electron microscope observation. Our experiment and computer simulation carried out by two different methods indicate that the composition-dependent particle size of Pt/Au can be explained by the atomic concentration, formation energy of the cluster, and interaction between different metal atoms and the PEG molecule.

In situ TEM observation of liquid-state Sn nanoparticles vanishing in a SiO2 structure: a potential synthetic tool for controllable morphology evolution from core-shell to yolk-shell and hollow structures.

Precise design of hollow nanostructures can be realized via various approaches developed in the last two decades, endowing nanomaterials with unique structures and outstanding performances, showing their usefulness in a broad range of fields. Herein, we demonstrate the formation of SnO2@SiO2 hollow nanostructures, for the first time, by interaction between liquid state Sn cores and SiO2 shell structures inside Sn@SiO2 core-shell nanoparticles with real-time observation via in situ transmission electron microscopy (TEM). Based on the in situ results, designed transformation of the nanoparticle structure from core-shell Sn@SiO2 to yolk-shell Sn@SiO2 and hollow SnO2@SiO2 is demonstrated, showing the controllable structure of core-shell Sn@SiO2 nanoparticles via fixing liquid-state Sn inside a SiO2 shell which has a certain Sn containing capacity. The present approach expands the toolbox for the design and preparation of yolk-shell and hollow nanostructures, thus providing us with a new strategy for fabrication of more complicated nanostructures.

Selective Reduction Mechanism of Graphene Oxide Driven by the Photon Mode versus the Thermal Mode.

A two-dimensional nanocarbon, graphene, has attracted substantial interest due to its excellent properties. The reduction of graphene oxide (GO) has been investigated for the mass production of graphene used in practical applications. Different reduction processes produce different properties in graphene, affecting the performance of the final materials or devices. Therefore, an understanding of the mechanisms of GO reduction is important for controlling the properties of functional two-dimensional systems. Here, we determined the average structure of reduced GO prepared via heating and photoexcitation and clearly distinguished their reduction mechanisms using ultrafast time-resolved electron diffraction, time-resolved infrared vibrational spectroscopy, and time-dependent density functional theory calculations. The oxygen atoms of epoxy groups are selectively removed from the basal plane of GO by photoexcitation (photon mode), in stark contrast to the behavior observed for the thermal reduction of hydroxyl and epoxy groups (thermal mode). The difference originates from the selective excitation of epoxy bonds via an electronic transition due to their antibonding character. This work will enable the preparation of the optimum GO for the intended applications and expands the application scope of two-dimensional systems.

Preparation and Growth Mechanism of Pt/Cu Alloy Nanoparticles by Sputter Deposition onto a Liquid Polymer.

We use a green sputtering technique to deposit a Pt/Cu alloy target on liquid polyethylene glycol (PEG) to obtain well-dispersed and stable Pt29Cu71 alloy nanoparticles (NPs). The effects of sputtering current, rotation speed of the stirrer, sputtering time, sputtering period, and temperature of PEG on the particle size are studied systematically. Our key results demonstrate that the aggregation and growth of Pt/Cu alloy NPs occurred at the surface as well as inside the liquid polymer after the particles landed on the liquid surface. According to particle size analysis, a low sputtering current, high rotation speed for the stirrer, short sputtering period, and short sputtering time are found to be favorable for producing small-sized single crystalline alloy NPs. On the other hand, varying the temperature of the liquid PEG does not have any significant impact on the particle size. Thus, our findings shed light on controlling NP growth using the newly developed green sputtering deposition technique.

Topologically immobilized catalysis centre for long-term stable carbon dioxide reforming of methane.

Methane reforming at low temperatures is of growing importance to mitigate the environmental impact of the production of synthesis gas, but it suffers from short catalyst lifetimes due to the severe deposition of carbon byproducts. Herein, we introduce a new class of topology-tailored catalyst in which tens-of-nanometer-thick fibrous networks of Ni metal and oxygen-deficient Y2O3 are entangled with each other to form a rooted structure, i.e., Ni#Y2O3. We demonstrate that the rooted Ni#Y2O3 catalyst stably promotes the carbon-dioxide reforming of methane at 723 K for over 1000 h, where the performance of traditional supported catalysts such as Ni/Y2O3 diminishes within 100 h due to the precluded mass transport by accumulated carbon byproducts. In situ TEM demonstrates that the supported Ni nanoparticles are readily detached from the support surface in the reaction atmosphere, and migrate around to result in widespread accumulation of the carbon byproducts. The long-term stable methane reforming over the rooted catalyst is ultimately attributed to the topologically immobilized Ni catalysis centre and the synergistic function of the oxygen-deficient Y2O3 matrix, which successfully inhibits the accumulation of byproducts.

Sputter Deposition toward Short Cationic Thiolated Fluorescent Gold Nanoclusters: Investigation of Their Unique Structural and Photophysical Characteristics Using High-Performance Liquid Chromatography.

We herein present the preparation of short, bulky cationic thiolate (thiocholine)-protected fluorescent Au nanoclusters via sputter deposition over a liquid polymer matrix. The obtained Au nanoclusters showed near-infrared fluorescence and had an average core diameter of 1.7 ± 0.6 nm, which is too large compared to that of the reported fluorescent Au nanoclusters prepared via chemical means. We revealed the mechanism of formation of this unique material using single-particle electron microscopy, optical measurements, X-ray photoelectron spectroscopy (XPS), and high-performance liquid chromatography fractionations. The noncrystallized image was observed via single-particle high-angle annular dark-field scanning transmission electron microscopy observations and compared with chemically synthesized crystalline Au nanoparticle with the same diameter, which demonstrated the unique structural characteristic speculated via XPS. The size fractionation and size-dependent fluorescence measurement, together with other observations, indicated that the nanoclusters most probably contained a mixture of very small fluorescent species in their aggregated form and were derived from the sputtering process itself and not from the interaction between thiol ligands.

Nanoporous Nickel Composite Catalyst for the Dry Reforming of Methane.

The development of efficient catalysts with high activities and durabilities for use in the dry reforming of methane (DRM) is desirable but challenging. We report the development of a nanoporous nickel composite (nanoporous Ni/Y2O3) via a facile one-step dealloying technique, for use in the DRM. Focusing on the low-temperature DRM, our composite possessed remarkable activity and durability against coking compared with conventional particle-based Ni catalysts. This was attributed to the aluminum oxides present on the Ni surface, which suppress pore coarsening. In addition, the inert bundled Y2O3 nanowires are suitable for use as substrates for nanoporous Ni.

Au/Cu Bimetallic Nanoparticles via Double-Target Sputtering onto a Liquid Polymer.

Alloy nanoparticles (NPs) of a bimetal system, Au/Cu, that form intermetallic compounds in a bulk state have been successfully produced using a double-target sputtering technique onto a low-cost and biocompatible liquid polymer (polyethylene glycol, PEG). The formation of an Au/Cu solid solution alloy in individual NPs was revealed by scanning transmission electron microscopy-energy-dispersive X-ray elemental mapping analysis. Altering the sputter currents for Au and Cu targets resulted in a tailored NP composition, but the particle sizes did not significantly vary. We found similar structures, sizes, and optical properties of Au/Cu NPs obtained by double-head sputtering on carbon-coated transmission electron microscopy grids or PEG and by Au/Cu alloy target sputtering. Random alloy formation occurred in matrix sputtering using double-target heads. This method is advantageous for manipulating the alloy composition through highly independent control of sputter parameters for each metal target.

Nanophase-separated Ni3Nb as an automobile exhaust catalyst.

Catalytic remediation of automobile exhaust has relied on precious metals (PMs) including platinum (Pt). Herein, we report that an intermetallic phase of Ni and niobium (Nb) (i.e., Ni3Nb) exhibits a significantly higher activity than that of Pt for the remediation of the most toxic gas in exhaust (i.e., nitrogen monoxide (NO)) in the presence of carbon monoxide (CO). When subjected to the exhaust-remediation atmosphere, Ni3Nb spontaneously evolves into a catalytically active nanophase-separated structure consisting of filamentous Ni networks (thickness < 10 nm) that are incorporated in a niobium oxide matrix (i.e., NbO x (x < 5/2)). The exposure of the filamentous Ni promotes NO dissociation, CO oxidation and N2 generation, and the NbO x matrix absorbs excessive nitrogen adatoms to retain the active Ni0 sites at the metal/oxide interface. Furthermore, the NbO x matrix immobilizes the filamentous Ni at elevated temperatures to produce long-term and stable catalytic performance over hundreds of hours.

Small Nanosized Oxygen-Deficient Tungsten Oxide Particles: Mechanistic Investigation with Controlled Plasma Generation in Water for Their Preparation.

Production of oxygen-deficient tungsten oxide nanoparticles with a diameter of around 10 nm have been successfully developed using a microwave-induced plasma in liquid technique. The prepared blue-green nanoparticles exhibit strong absorption in the visible region; thus, these could be efficient visible-light photocatalysts. The high-angle annular dark-field images revealed the dislocation of tungsten, which causes oxygen deficiencies.

Matrix Sputtering into Liquid Mercaptan: From Blue-Emitting Copper Nanoclusters to Red-Emitting Copper Sulfide Nanoclusters.

A modified magnetron sputtering technique using pentaerythritol tetrakis(3-mercaptopropionate) (PEMP) as a stabilizing agent and liquid dispersion medium was developed to generate photoluminescent copper nanoclusters. The results reveal that, over time, the as-prepared blue-emitting copper nanoclusters were converted to red-emitting copper sulfide nanoclusters. The formation of copper oxide as an intermediate during the conversion of copper to copper sulfide nanoclusters was demonstrated. Furthermore, based on the mechanism of formation of copper sulfide, the kinetics of the conversion process could be controlled via ultraviolet (UV) irradiation of the as-synthesized dispersion. These findings shed light on the formation and conversion of nanoclusters obtained via sputtering into liquid, demonstrating that the method is highly versatile for producing metal nanoclusters and compounds with tailorable composition and optical properties.

Plasma induced tungsten doping of TiO2 particles for enhancement of photocatalysis under visible light.

Here we report a novel method for modifying commercially available TiO2 nanoparticles by a microwave-induced plasma technique. After the plasma treatment TiO2 nanoparticles showed enhanced visible absorption due to the doped W atoms, and the photocatalytic methylene blue degradation above 440 nm was successfully improved.

In situ observation of carbon nanotube yarn during voltage application.

Carbon nanotube (CNT) yarns are fabricated by drawing (combined with spinning) from CNT forests and grown on a substrate. Three types of phenomena occur in these CNT yarns with increasing amounts of current: yarn rotation, catalyst evaporation, and breakage of the yarn. These phenomena result from the resistive heating occurring during the current flow, and have been observed in situ under vacuum by transmission electron microscopy. If these CNT yarns are applied to electronic circuits, the rotation and breakage may lead to circuit failure. However, catalyst evaporation is a useful method for purifying CNT yarns without additional treatments prior to yarn fabrication.