We demonstrate an easy and scalable low-temperature process to convert porous ternary complex metal oxide nanoparticles from solution-synthesized core/shell metal oxide nanoparticles by thermal annealing. The final products demonstrate superior electrochemical properties with a large capacity and high stability during fast charging/discharging cycles for potential applications as advanced lithium-ion battery (LIB) electrode materials. In addition, a new breakdown mechanism was observed on these novel electrode materials.
Bismuth telluride (Bi2Te3) is one of the most important commercial thermoelectric materials. In recent years, the discovery of topologically protected surface states in Bi chalcogenides has paved the way for their application in nanoelectronics. Determination of the fracture toughness plays a crucial role for the potential application of topological insulators in flexible electronics and nanoelectromechanical devices. Using depth-sensing nanoindentation tests, we investigated for the first time the fracture toughness of bulk single crystals of Bi2Te3 topological insulators, grown using the Bridgman-Stockbarger method. Our results highlight one of the possible pitfalls of the technology based on topological insulators.
In this study, a potentially universal new strategy is reported for the large-scale, low-cost fabrication of visible-light-active highly ordered heteronanostructures based on the spontaneous photoelectric-field-enhancement effect inherent in pyramidal morphology. The hierarchical vertically oriented arrayed structures comprise an active molecular co-catalyst at the apex of a visible-light-active large band gap semiconductor for low-cost solar water splitting in a neutral aqueous medium without the use of a sacrificial agent.
Formic acid oxidation is an important electrocatalytic reaction in protonexchange membrane (PEM) fuel cells, in which both active sites and species adsorption/activation play key roles. In this study, we have developed hollow Pd-Ag alloy nanostructures with high active surface areas for application to electrocatalytic formic acid oxidation. When a certain amount of Ag is incorporated into a Pd lattice, which is already a highly active material for formic acid oxidation, the electrocatalytic activity can be significantly boosted. As indicated by theoretical simulations, coupling between Pd and Ag induces polarization charges on Pd catalytic sites, which can enhance the adsorption of HCOO* species. As a result, the designed electrocatalysts can achieve reduced Pd usage and enhanced catalytic properties at the same time. This study represents an approach that simultaneously fabricates hollow structures to increase the number of active sites and utilizes interatomic interactions to tune species adsorption/activation towards improved electrocatalytic performance.
Isothermal methods, such as helicase-dependent amplification (HDA), have an advantage over polymerase chain reaction for DNA amplification owing to their ease of operation. Here, we developed a new HDA method that is nanoparticle-assisted, termed nanoHDA. This method uses gold nanoparticles (AuNPs) to improve the sensitivity and specificity of the isothermal method. In HDA, the denaturation of DNA templates is mediated by helicases, but this method is limited by the low denaturation efficiency of helicases. In this report, AuNPs with preferential affinity for single-stranded DNA (ssDNA) were utilized to improve the denaturation efficiency of helicases. The same affinity property of nanoparticles can also enhance specificity by suppressing primer-dimer formation. This nanoHDA method was employed to genotype the KRAS gene in genomic DNA samples from colorectal cancer patients, as achieved by the hybridization of nanoHDA amplicons using the NanoBioArray chip.
Sandwich-type ordered mesoporous carbon/graphene nanocomposites were successfully synthesized using 2D ordered mesoporous silica/graphene nanocomposites as the hard template and an ionic liquid as a N-rich carbon source. We used an ionic liquid of 1-(3-cyanopropyl)-3-methylimidazolium dicyanamide containing nitrile groups (–CN) in the cation and anion as a carbon precursor for the preparation of the nanocomposites. Nitriles do not decompose under thermal treatment in an inert gas atmosphere, but leave significant amounts of N-rich carbon materials. The nanocomposites had a large surface area (1,316 m2·g–1), an average pore diameter of 5.9 nm, and high electrical conductivity. The nanocomposite electrode showed a high specific capacitance of 190 F·g–1 at 0.5 A·g–1 in 1 M TEABF4/AN electrolyte and a good rate capability between 0 and 2.7 V for supercapacitor (or ultracapacitor) applications.
Sandwich structured graphene-wrapped FeS-graphene nanoribbons (G@FeS-GNRs) were developed. In this composite, FeS nanoparticles were sandwiched between graphene and graphene nanoribbons. When used as anodes in lithium ion batteries (LIBs), the G@FeS-GNR composite demonstrated an outstanding electrochemical performance. This composite showed high reversible capacity, good rate performance, and enhanced cycling stability owing to the synergy between the electrically conductive graphene, graphene nanoribbons, and FeS. The design concept developed here opens up a new avenue for constructing anodes with improved electrochemical stability for LIBs.
The single crystalline nanostructure of organic semiconductors provides a very promising class of materials for applications in modern optoelectronic devices. However, morphology control and optoelectronic property modulation of high quality single crystalline samples remain a challenge. Here, we report the morphology-controlled growth of single crystalline nanorod arrays of perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA). We demonstrate that, unlike PTCDA film, PTCDA nanorods exhibits optical waveguide features, enhanced absorption, and Frenkel excitation emission in the visible region. Additionally, we measured the electrical properties of PTCDA nanorods, including the conductivity along the growth direction of the nanorod, which is roughly 0.61 S·m–1 (much higher than that of pure crystalline PTCDA films).
The oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are crucial processes for energy conversion/storage systems, such as fuel cells, metal–air batteries, and water splitting. However, both reactions are severely restricted by their sluggish kinetics, thus requiring highly active, cost-effective, and durable electrocatalysts. Herein, we develop novel bifunctional nanocatalysts through surface nanoengineering of dealloying-driven nanoporous gold (NPG). Pd overlayers were precisely deposited onto the NPG ligament surface by epitaxial layer-by-layer growth. More importantly, the obtained NPG-Pd overlayer nanocatalysts exhibit remarkably enhanced electrocatalytic activities toward both the ORR and OER in alkaline media, benchmarked against a stateof- the-art Pt/C catalyst. The improved electrocatalytic performance is rationalized by the unique three-dimensional nanoarchitecture of NPG, enhanced Pd utilization efficiency from precise control of the Pd overlayers, and change in electronic structure, as revealed by density functional theory calculations.
Three-dimensional (3D) graphene has recently attracted enormous attention for electrochemical energy storage applications. However, current methods suffer from an inability to simultaneously control and engineer the porosity and morphology of the graphene frameworks. Here, we report the designed synthesis of ordered mesoporous graphene spheres (OMGSs) by transformation of self-assembled Fe3O4 nanocrystal superlattices. The resultant OMGSs have an ultrathin framework comprising few-layered graphene, with highly ordered and interconnected mesoporosity and a high surface area. These advantageous structural and textural features, in combination with the excellent electrical conductivity of the graphitic frameworks, render the OMGSs an ideal and general platform for creating hybrid materials that are well suited for use as composite electrodes in lithium-ion batteries (LIBs). As a proof-of-concept demonstration, SnO2 and GeO2 nanoparticles are incorporated into the OMGSs to afford SnO2@OMGSs and GeO2@OMGSs, respectively, both of which exhibit outstanding lithium storage properties when used as LIB anodes.
Exploring lightweight microwave attenuation materials with strong and tunable wideband microwave absorption is highly desirable but remains a significant challenge. Herein, three-dimensional (3D) porous hybrid composites consisting of NiFe nanoparticles embedded within carbon nanocubes decorated on graphene oxide (GO) sheets (NiFe@C nanocubes@GO) as high-performance microwave attenuation materials have been rationally synthesized. The 3D porous hybrid composites are fabricated by a simple method, which involves one-step pyrolysis of NiFe Prussian blue analogue nanocubes in the presence of GO sheets. Benefiting from the unique structural features that exhibit good magnetic and dielectric losses as well as a proper impedance match, the resulting NiFe@C nanocubes@GO composites show excellent microwave attenuation ability. With a minimum reflection loss (RL) of–51 dB at 7.7 GHz at a thickness of 2.8 mm and maximum percentage bandwidth of 38.6% for RL <–10 dB at a thickness of 2.2 mm, the NiFe@C nanocubes@GO composites are superior to the previously reported state-of-the-art carbon-based microwave attenuation materials.
The persistent need for a sustainable energy economy has led researchers to focus on novel energy conversion and storage technologies, inspiring the discovery of smart material designs such as hierarchical nanocomposites. These nanocomposites have proven effective in the advancement of energy-based technologies. The synergistic properties of hierarchical nanocomposites composed of two types of two-dimensional layered materials, layered double hydroxides and graphene, have resulted in improved electrochemical as well as photocatalytic performance. Synthetic strategies and their effect on the electrochemical and photocatalytic performance of these nanocomposites as high-performance supercapacitors and water oxidation catalysts are discussed in detail in this review.
In-plane symmetry is an important contributor to the physical properties of two-dimensional layered materials, as well as atomically thin heterojunctions. Here, we demonstrate anisotropic/isotropic van der Waals (vdW) heterostructures of ReS2 and MoS2 monolayers, where interlayer coupling interactions and charge separation were observed by in situ Raman-photoluminescence spectroscopy, electrical, and photoelectrical measurements. We believe that these results could be helpful for understanding the fundamental physics of atomically thin vdW heterostructures and creating novel electronic and optoelectronic devices.
The carrier screening effect occurs commonly in dielectric materials. It reduces the electric potential gradient, thus negatively affecting the functionality of resistive random access memory (RRAM) devices. An Au/ZnO film/Al-doped ZnO device fabricated in this work exhibited no resistive switching (RS), which was attributed to the carrier screening effect. Therefore, annealing was used for alleviating the screening effect, significantly enhancing the RS property. In addition, different on/off ratios were obtained for various bias values, and the screening effect was accounted for by investigating electron transport mechanisms. Furthermore, different annealing temperatures were employed to modulate the free carrier concentration in ZnO films to alleviate the screening effect. The maximal on/off ratio reached 105 at an annealing temperature of 600 °C, yielding the lowest number of free carriers and the weakest screening effect in ZnO films. This work investigates the screening effect in RS devices. The screening effect not only modulates the characteristics of memory devices but also provides insight into the mechanism of RS in these devices.
Multi-shelled CoFe2O4 hollow microspheres with a tunable number of layers (1–4) were successfully synthesized via a facile one-step method using cyclodextrin as a template, followed by calcination. The structural features, including the shell number and shell porosity, were controlled by adjusting the synthesis parameters to produce hollow spheres with excellent capacity and durability. This is a straightforward and general strategy for fabricating metal oxide or bimetallic metal oxide hollow microspheres with a tunable number of shells.
RuCu nanocages and core–shell Cu@Ru nanocrystals with ultrathin Ru shells were first synthesized by a one-pot modified galvanic replacement reaction. The construction of bimetallic nanocrystals with fully exposed precious atoms and a high surface area effectively realizes the concept of high atom-efficiency. Compared with the monometallic Ru/C catalyst, both the RuCu nanocages and Cu@Ru core–shell catalysts supported on commercial carbon show superior catalytic performance for the regioselective hydrogenation of quinoline toward 1,2,3,4-tetrahydroquinoline. RuCu nanocages exhibit the highest activity, achieving up to 99.6% conversion of quinoline and 100% selectivity toward 1,2,3,4-tetrahydroquinoline.
By means of vibrational spectroscopy and density functional theory (DFT), we investigate CO adsorption on phosphorene-based systems. We find stable CO adsorption at room temperature on both phosphorene and bulk black phosphorus. The adsorption energy and vibrational spectrum are calculated for several possible configurations of the CO overlayer. We find that the vibrational spectrum is characterized by two different C–O stretching energies. The experimental data are in good agreement with the prediction of the DFT model and reveal the unusual C–O vibrational band at 165–180 meV, activated by the lateral interactions in the CO overlayer.
In this study, leaf-like one-dimensional InAs nanostructures were grown by the metal–organic chemical vapor deposition method. Detailed structural characterization suggests that the nanoleaves contain relatively low-energy {122} or {133} mirror twins acting as their midribs and narrow sections connecting the nanoleaves and their underlying bases as petioles. Importantly, the mirror twins lead to identical lateral growth of the twinned structures in terms of crystallography and polarity, which is essential for the formation of lateral symmetrical nanoleaves. It has been found that the formation of nanoleaves is driven by catalyst energy minimization. This study provides a biomimic of leaf found in nature by fabricating a semiconductor nanoleaf.
Two-dimensional ZrS2 materials have potential for applications in nanoelectronics because of their theoretically predicted high mobility and sheet current density. Herein, we report the thickness and temperature dependent transport properties of ZrS2 multilayers that were directly deposited on hexagonal boron nitride (h-BN) by chemical vapor deposition. Hysteresis-free gate sweeping, metalinsulator transition, and T–γ (γ ~ 0.82–1.26) temperature dependent mobility were observed in the ZrS2 films.
Recently, the synthesis of ultrathin nanostructures has attracted increasing interest because of their unique structure and properties. In this work, we report the synthesis of sub-2.0-nm Ru and composition-tunable RuPt nanowire networks using an environmentally friendly aqueous method. The structures were characterized using transmission electron microscopy (TEM), high-resolution TEM, X-ray diffraction (XRD), and energy-dispersive X-ray (EDX) spectroscopy. Moreover, the combined utilization of sodium n-dodecyl sulfate and potassium fluoride was determined to play a key role in the formation of these ultrathin nanostructures. The electrocatalytic properties of the sub-2.0-nm RuPt nanowire networks were investigated for methanol oxidation in an acidic medium. The nanostructures displayed composition-dependent properties, and compared with commercial Ru50Pt50/C, the as-synthesized Ru56Pt44 ultrathin nanowire network exhibited enhanced stability.
