Self-assembled ultrafine hierarchical ZnS treelike nanoarchitectures

Ultrafine hierarchical tree-shaped nanoarchitectures of ZnS were synthesized by a H₂-assisted thermal evaporation and condensation technique. Morphology and composition of the ZnS deposit were studied by means of field emission scanning electron microscopy, high-resolution transmission electron microscopy and energy dispersive X-ray spectroscopy. The deposit was found to consist of a layer of oriented submicrorods partly covered by microsheets and randomly oriented submicrowires, and three-dimensional treelike nanoarchitectures grew epitaxially on various submicrorods, microsheets, and submicrowires. The growth of the nanostructures is a spontaneous and self-assembled process. Vapor-solid (VS) growth mechanism is proposed for the formation of the treelike nanostructures because catalyst was not introduced during the synthesis process. This novel hierarchical ZnS nanoarchitecture may offer great potential for applications, including three-dimensional nanoelectronics and high efficient spatial resolved photon detector.     

Dumbbells,Trikes and Quads: Organic–Inorganic Hybrid Nanoarchitectures Based on “Clicked” Gold Nanoparticles

The controlled assembly of gold nanoparticles in terms of the spatial arrangement and number of particles is essential for many future applications like electronic devices, sensors and labeling. Here an approach is presented to build up oligomers of mono functionalized gold nanoparticles by the use of 1,3‐bipolar azide alkyne cycloaddition click chemistry. The gold nanoparticles of 1.3 nm diameter are stabilized by one dendritic thioether ligand comprising an alkyne function. Together with di‐, tri‐ and tetra‐azide linker molecules the gold nanoparticle can be covalently coupled by a wet chemical protocol. The reaction is tracked with IR and UV–vis spectroscopy and the yielded organic‐inorganic hybrid structures are analyzed by transmission electron microscopy. To evaluate the success of this click chemistry reaction statistical analysis of the formed oligomers is performed. The geometric and spatial arrangements of the found oligomers match perfectly the calculated values for the used linker molecules. Dimers, trimers and tetramers could be identified after the reaction with the corresponding linker molecule. The results of this model reaction suggest that the used click chemistry protocol is working well with mono functionalized gold nanoparticles.     

Chemical Design of Palladium‐Based Nanoarchitectures for Catalytic Applications

Palladium (Pd) plays an important role in numerous catalytic reactions, such as methanol and ethanol oxidation, oxygen reduction, hydrogenation, coupling reactions, and carbon monoxide oxidation. Creating Pd‐based nanoarchitectures with increased active surface sites, higher density of low‐coordinated atoms, and maximized surface coverage for the reactants is important. To address the limitations of pure Pd, various Pd‐based nanoarchitectures, including alloys, intermetallics, and supported Pd nanomaterials, have been fabricated by combining Pd with other elements with similar or higher catalytic activity for many catalytic reactions. Herein, recent advances in the preparation of Pd‐based nanoarchitectures through solution‐phase chemical reduction and electrochemical deposition methods are summarized. Finally, the trend and future outlook in the development of Pd nanocatalysts toward practical catalytic applications are discussed.     

Lithiophilic and Antioxidative Copper Current Collectors for Highly Stable Lithium Metal Batteries

Designing copper (Cu) current collectors is a convenient way to stabilize lithium (Li) metal anodes. However, Cu current collectors and their derived Li/Cu anodes still face several obstacles, including lithiophobic and oxidizable Cu surface, cumbersome anode fabrication process, and low Li utilization. Here, a formate-treatment strategy is presented to reconstruct Cu current collectors with a passivation layer covered Cu(110) surface. This method can easily be generalized to increase the lithiophilicity and oxidation resistibility of Cu current collectors. Using the formate-treated Cu nanowire network as an anode current collector, the full cell consisting of a LiFePO₄ cathode and Li/Cu anode with a low negative/positive capacity ratio delivers an excellent cycling performance with 74.8% capacity retention after 1000 cycles at 1 C. In addition, a concept of an upper current collector is introduced to simplify the manufacturing procedure of Li/Cu anodes. This work provides new insights into the design and construction of high-performance Li/Cu anodes.     

3D Nanoprinting of Perovskites

As competing with the established silicon technology, organic–inorganic metal halide perovskites are continually gaining ground in optoelectronics due to their excellent material properties and low‐cost production. The ability to have control over their shape, as well as composition and crystallinity, is indispensable for practical materialization. Many sophisticated nanofabrication methods have been devised to shape perovskites; however, they are still limited to in‐plane, low‐aspect‐ratio, and simple forms. This is in stark contrast with the demands of modern optoelectronics with freeform circuitry and high integration density. Here, a nanoprecision 3D printing is developed for organic–inorganic metal halide perovskites. The method is based on guiding evaporation‐induced perovskite crystallization in mid‐air using a femtoliter ink meniscus formed on a nanopipette, resulting in freestanding 3D perovskite nanostructures with a preferred crystal orientation. Stretching the ink meniscus with a pulling process enables on‐demand control of the nanostructure's diameter and hollowness, leading to an unprecedented tubular‐solid transition. With varying the pulling direction, a layer‐by‐layer stacking of perovskite nanostructures is successfully demonstrated with programmed shapes and positions, a primary step for additive manufacturing. It is expected that the method has the potential to create freeform perovskite nanostructures for customized optoelectronics.     

DNA Minicircles Connected via G‐Quadruplex Interaction Modules

G‐quadruplexes are becoming reliable alternative interaction modules for the construction of DNA nanoarchitectures due to their prompt inducibility by salts. In this Full Paper, we report the design and synthesis of two different DNA minicircles equipped with G‐rich appendixes that can self‐hybridize into a G‐quadruplex, which acts as a DNA recruiter and glue. Both minicircles, one containing a hairpin‐like G‐rich region and the other an open tuning‐fork‐like G‐rich region, have the potential to form DNA G‐nanoconstructs but only the tuning‐fork minicircle does so. Incubation of the tuning‐fork minicircle with Na⁺ and Ni²⁺ results in the formation of minicircle dimers, while K⁺ and Sr²⁺ unexpectedly induce the formation of multimers. Moreover, a catenated DNA nanoconstruct is obtained when the components of the hairpin minicircle are incubated with K⁺ or Na⁺ and assembled in a stepwise sequence. All nanoconstructs are visualized by atomic force microscopy.     

Extraordinarily Stretchable All‐Carbon Collaborative Nanoarchitectures for Epidermal Sensors

Multifunctional microelectronic components featuring large stretchability, high sensitivity, high signal‐to‐noise ratio (SNR), and broad sensing range have attracted a huge surge of interest with the fast developing epidermal electronic systems. Here, the epidermal sensors based on all‐carbon collaborative percolation network are demonstrated, which consist 3D graphene foam and carbon nanotubes (CNTs) obtained by two‐step chemical vapor deposition processes. The nanoscaled CNT networks largely enhance the stretchability and SNR of the 3D microarchitectural graphene foams, endowing the strain sensor with a gauge factor as high as 35, a wide reliable sensing range up to 85%, and excellent cyclic stability (>5000 cycles). The flexible and reversible strain sensor can be easily mounted on human skin as a wearable electronic device for real‐time and high accuracy detecting of electrophysiological stimuli and even for acoustic vibration recognition. The rationally designed all‐carbon nanoarchitectures are scalable, low cost, and promising in practical applications requiring extraordinary stretchability and ultrahigh SNRs.     

Subtractive Structural Modification of Morpho Butterfly Wings

Different from studies of butterfly wings through additive modification, this work for the first time studies the property change of butterfly wings through subtractive modification using oxygen plasma etching. The controlled modification of butterfly wings through such subtractive process results in gradual change of the optical properties, and helps the further understanding of structural optimization through natural evolution. The brilliant color of Morpho butterfly wings is originated from the hierarchical nanostructure on the wing scales. Such nanoarchitecture has attracted a lot of research effort, including the study of its optical properties, its potential use in sensing and infrared imaging, and also the use of such structure as template for the fabrication of high‐performance photocatalytic materials. The controlled subtractive processes provide a new path to modify such nanoarchitecture and its optical property. Distinct from previous studies on the optical property of the Morpho wing structure, this study provides additional experimental evidence for the origination of the optical property of the natural butterfly wing scales. The study also offers a facile approach to generate new 3D nanostructures using butterfly wings as the templates and may lead to simpler structure models for large‐scale man‐made structures than those offered by original butterfly wings.