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.
Rapid development of flexible electronic devices is promoting the design of flexible energy-storage devices. Lithium-sulfur (Li-S) batteries are considered as promising candidates for high energy density energy-storage devices. Therefore, flexible Li-S batteries are desired. In this study, we fabricated composite films of freestanding reduced graphene oxide nanotubes wrapped sulfur nanoparticles (RGONTs@S) by pressing RGONTs@S composite foams, which were synthesized by combining cold quenching with freeze-drying and a subsequent reduction process. These RGONTs@S composite films can serve as self-supporting cathodes for Li-S batteries without additional binders and conductive agents. Their interconnected tubular structure allows easy electron transport throughout the network and helps to confine the polysulfides produced during the charge/discharge process. As a result, the RGONTs@S composite films exhibited a high initial specific capacity, remarkable cycling stability, and excellent rate capability. More importantly, the RGONTs@S composite films can serve as electrodes in flexible Li-S batteries. As a proof of concept, soft-packaged Li-S batteries were assembled using these electrodes and they displayed stable electrochemical performance at different bending states.
Cyclic penta-twinned noble metal nanocrystals exhibit promising properties due to their unique geometric and electronic structures. However, the controlled synthesis of cyclic penta-twinned nanostructures, especially of noble metals with a high cohesive energy (e.g., Rh), is very difficult, and the corresponding growth mechanism is not fully understood. Herein, we report a facile one-pot hydrothermal approach for the synthesis of cyclic penta-twinned Rh icosahedral nanocrystals. It was found that apart from regulating the surface free energy by changing the concentration or category of the capping agents, the solvent might influence the adsorption ability of the surfactant on the Rh crystal surface, which results in a change in the surface free energy and thus allows the formation of Rh cyclic penta-twinned nanostructures. In addition, due to their unique electronic and geometric structures, the Rh icosahedral nanocrystals exhibit superior catalytic activity and stability for the electrooxidation of ethanol as compared to single-crystal Rh tetrahedral nanocrystals and commercial Rh black.
In this paper, we demonstrate that for colloidal CdSe/CdS nanoplatelets, a rectangular shape induces emission asymmetry, in terms of both polarization and emission patterns. Polarimetry and emission pattern analyses are combined to provide information on the orientation of the transition dipoles involved in the nanoplatelet emission. It is shown that for rectangular nanoplatelets, the emission is polarized and the emission patterns are anisotropic, whereas they remain nonpolarized and isotropic for square nanoplatelets. This can be appropriately described by the dielectric antenna effect induced by the elongated shape of the rectangular platelet.
In this work, we developed a novel triboelectricity-assisted polymer-free method for the transfer of large-area chemical vapor deposited graphene films. With the assistance of electrostatic forces from friction-generated charges, graphene sheets were successfully transferred from copper foils to flexible polymer substrates. Characterization results confirmed the presence of high quality graphene with less defects and contaminations, compared to graphene transferred by conventional poly(methyl methacrylate)-mediated processes. In addition, the graphene samples possessed outstanding electrical transport capabilities and mechanical stability, when studied as electron transfer matrixes in graphene/ZnO hybrid flexible photodetectors. Our results showed a broad application potential for this transfer method in future flexible electronics and optoelectronics.
Multistep plasmonic nanostructures can induce the deep modulation of electromagnetic-field interactions on the nanoscale for positioning hotspots, and this generation of enhanced fields is important in many optical applications. In this article, a new strategy is proposed for fabricating a plasmonic doublestacked nanocone (DSC) nanostructure. In the DSC structure, a tunable plasmonic hybrid mode proceeds from the strong coupling of the plasmonic resonance of a fundamental cavity mode with a localized surface plasmon gap mode. In the nanostructure, the far-field response is deeply modulated and the hottest spots can be effectively positioned on the top surface of the DSC nanostructure. A controllable and cost-effective mask-reconfiguration technique for manufacturing the multiscale nanostructure is developed, which guarantees the generation of the introduced crucial stage on the DSC nanostructure. To evaluate the features of the plasmonic resonance, the DSC nanostructure is used as a surface-enhanced Raman scattering (SERS) substrate for detecting 4-mercaptopyridine molecules under specific excitation conditions. Its good performance, with an average measured SERS enhancement factor as high as 108, demonstrates its strong plasmonic-mode hybridization and extreme field enhancement.
Yolk/shell (Y–S) hybrid nanoarchitectures, owing to the interior voids created for individualized catalyst applications, have emerged as new candidates for effectively isolating catalytic species. However, the well-defined hollow interiors with flexible core and shell compositions—such as noble-metal cores, metal-oxide cores, and widespread semiconductor shells—and a flexible anisotropic shape are far from the requirements. In particular, the introduction of catalytic noble metals or metal-oxide nanocrystals (NCs) with isotropic or anisotropic shapes into various hollow semiconductor structures with well-defined morphologies has been rarely reported but is urgently needed. Herein, we propose a strategy involving the careful sulfuration of as-prepared cavity-free core/shell NCs or metal-oxide NCs followed by phosphine-initialized cation-exchange reactions for preparing metal@semiconductor and metal oxide@semiconductor (II-VI) Y–S NCs. The geometry, size, and conformations of the core and shell are fully and independently considered. New and unprecendented metal@semiconductor and metal oxide@semiconductor (II-VI) Y–S NCs are prepared via widespread phosphine-initialized cation-exchange reactions.
Manipulating the polarization of light at the nanoscale is essential for the development of nano-optical devices. Owing to its corrugated honeycomb structure, two-dimensional (2D) layered black phosphorus (BP) exhibits outstanding in-plane optical anisotropy with distinct linear dichroism and optical birefringence in the visible region, which are superior characteristics for ultrathin polarizing optics. Herein, taking advantage of polarized Raman spectroscopy, we demonstrate that layered BP with a nanometer thickness can remarkably alter the polarization state of a linearly-polarized laser and behave as an ultrathin optical polarization element in a BP-Bi2Se3 stacking structure by inducing the exceptionally polarized Raman scattering of isotropic Bi2Se3. Our findings provide a promising alternative for designing novel polarization optics based on 2D anisotropic materials, which can be easily integrated in microsized all-optical and optoelectronic devices.
Catalytic hydrogenation is an important process in the chemical industry. Traditional catalysts require the effective cleavage of hydrogen molecules on the metal-catalyst surface, which is difficult to achieve with non-noble metal catalysts. In this work, we report a new hydrogenation method based on water/proton reduction, which is completely different from the catalytic cleavage of hydrogen molecules. Active hydrogen species and photo-generated electrons can be directly applied to the hydrogenation process with Cu1.94S-Zn0.23Cd0.77S semiconductor heterojunction nanorods. Nitrobenzene, with a variety of substituent groups, can be efficiently reduced to the corresponding aniline without the addition of hydrogen gas. This is a novel and direct pathway for hydrogenation using non-noble metal catalysts.
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.
A thermal emitter composed of a frequency-selective surface metamaterial layer and a hexagonal boron nitride-encapsulated graphene filament is demonstrated. The broadband thermal emission of the metamaterial (consisting of ring resonators) was tailored into two discrete bands, and the measured reflection and emission spectra agreed well with the simulation results. The high modulation frequencies that can be obtained in these devices, coupled with their operation in air, confirm their feasibility for use in applications such as gas sensing.
This paper offers a comprehensive overview on the role of nanostructures in the development of advanced anode materials for application in both lithium and sodium-ion batteries. In particular, this review highlights the differences between the two chemistries, the critical effect of nanosize on the electrode performance, as well as the routes to exploit the inherent potential of nanostructures to achieve high specific energy at the anode, enhance the rate capability, and obtain a long cycle life. Furthermore, it gives an overview of nanostructured sodium- and lithium-based anode materials, and presents a critical analysis of the advantages and issues associated with the use of nanotechnology.
We have studied the magnetic and electrical transport properties of epitaxial NiAs-type CrTe thin films grown on SrTiO3(111) substrates. Unlike rectangle hysteresis loops obtained from magnetic measurements, we have identified intriguing extra bump/dip features from anomalous Hall experiments on the films with thicknesses less than 12 nm. This observed Hall anomaly is phenomenologically consistent with the occurrence of a topological Hall effect(THE) in chiral magnets with a skyrmion phase. Furthermore, the THE contribution can be tuned by the film thickness, showing the key contribution of asymmetric interfaces in stabilizing Néel-type skyrmions. Our work demonstrates that a CrTe thin film on SrTiO3(111) substrates is a good material candidate for studying real-space topological transport.
Rechargeable metal-iodine batteries are an emerging attractive electrochemical energy storage technology that combines metallic anodes with halogen cathodes. Such batteries using aqueous electrolytes represent a viable solution for the safety and cost issues associated with organic electrolytes. A hybrid-electrolyte battery architecture has been adopted in a lithium-iodine battery using a solid ceramic membrane that protects the metallic anode from contacting the aqueous electrolyte. Here we demonstrate an eco-friendly, low-cost zinc-iodine battery with an aqueous electrolyte, wherein active I2 is confined in a nanoporous carbon cloth substrate. The electrochemical reaction is confined in the nanopores as a single conversion reaction, thus avoiding the production of I3? intermediates. The cathode architecture fully utilizes the active I2, showing a capacity of 255 mAh·g?1 and low capacity cycling fading. The battery provides an energy density of ～ 151 Wh·kg?1 and exhibits an ultrastable cycle life of more than 1,500 cycles.
Hierarchical nano-architectures comprised of ultrathin ternary selenide (CoNiSe2) nanorods were directly grown on nickel foam (NF). The integrated CoNiSe2/NF functions as a robust electrocatalyst with an extremely high activity and stability for emerging renewable energy technologies, and electrochemical oxygen and hydrogen evolution reactions (OER and HER, respectively). The overpotentials required to deliver a current density of 100 mA·cm?2 are as low as 307 and 170 mV for the OER and HER, respectively; therefore, the obtained CoNiSe2 is among the most promising earth-abundant catalysts for water splitting. Furthermore, our synthetic sample validates a two-electrode electrolyzer for reducing the cell voltage in the full water splitting reaction to 1.591 V to achieve a current density of 10 mA·cm?2, which offers a novel, inexpensive, integrated selenide/NF electrode for electrocatalytic applications.
Solar-to-H2 conversion is attracting much research attention as a potential approach to meet global renewable energy demands. Although significant advances have been made using metal-tipped colloidal cadmium chalcogenide zero-dimensional (0D) quantum dots and one-dimensional (1D) nanorod heterostructures in solar-to-H2 conversion, their efficiency may be further enhanced using an emerging class of colloidal cadmium chalcogenide nanocrystals, namely two-dimensional (2D) nanoplatelets (NPLs), because of their unique properties. In this review, we summarize the recent advances on exciton dissociation dynamics and light-driven H2 generation performance of colloidal nanoplatelet heterostructures. Following an introduction on the electronic structure of 2D NPLs, we discuss the dynamics of exciton dissociation by electron transfer to molecular acceptors. The exciton quenching dynamics of CdS NPL-Pt and CdSe NPL-Pt heterostructures are compared to highlight the effect of material properties on the relative contributions of the energy-transfer and electron-transfer pathways. Representative solar-to-H2 conversion performances of 2D NPL-metal heterostructures are discussed and compared with those of 1D nanorod-metal heterostructures. Finally, we discuss the challenges in further improving the solar-to-fuel conversion efficiencies of these systems.
Hexagonal ultrathin WO3 nano-ribbons (HUWNRs) of subnanometer thicknesses, 2–5 nm widths, and lengths of up to several micrometers were prepared by a solvothermal method. The as-prepared HUWNRs grow along the [001] direction, and the main exposed facet is the (120) crystal plane. The HUWNRs exhibit good electrochemical performance as an anode material in lithium ion batteries because of their unique structure. It is believed that these unique materials may be applied in many fields.
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.
Sodium-ion batteries have received remarkable attention as next-generation high-performance electrochemical energy storage devices because of their cost effectiveness and the broad geographical distribution of sodium. As a critical component of sodium-ion batteries, anode materials, especially nanostructured anodes, have a significant effect on the electrochemical performance of sodium-ion batteries. Recent research indicates that phosphorus and metal phosphides show great promise as anode candidates for sodium-ion batteries because of their low cost and relatively high theoretical gravimetric and volumetric specific capacities. In this review, we systematically summarize recent research progress on state-of-the-art nanostructured phosphorus and phosphides, including the synthetic strategies, Na-storage mechanisms, and the relationship between the nanostructure and electrochemical performance. Moreover, we present an overview of future challenges and opportunities based on current developments.
Nanosized metal (Pt or Pd)-decorated TiO2 nanofibers (NFs) were synthesized by a wet impregnation method. CdSe quantum dots (QDs) were then anchored onto the metal-decorated TiO2 NFs. The photocatalytic performance of these catalysts was tested for activation and reduction of CO2 under UV-B light. Gas chromatographic analysis indicated the formation of methanol, formic acid, and methyl formate as the primary products. In the absence of CdSe QDs, Pd-decorated TiO2 NFs were found to exhibit enhanced performance compared to Pt-decorated TiO2 NFs for methanol production. However, in the presence of CdSe, Pt-decorated TiO2 NFs exhibited higher selectivity for methanol, typically producing ～90 ppmg?1·h?1 methanol. The CO2 photoreduction mechanism is proposed to take place via a hydrogenation pathway from first principles calculations, which complement the experimental observations.
